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

Abstract

To provide a production method of a conductive laminate capable of reducing a surface resistance value of a conductive layer by treating a coated film of a conductive polymer-containing liquid under a heating and humidifying condition, a conductive polymer-containing liquid suitable for use in the production method thereof, and a production method of the same.SOLUTION: A conductive polymer-containing liquid includes: a conductive compound body containing a π-conjugated conductive polymer and a polyanion; a binder constituent; and a high conductivity agent. The conductive polymer-containing liquid is used for producing a conductive laminate by performing the following processes 1-3 in sequence: a process 1 of coating a substrate with a conductive polymer-containing liquid, and drying a coated film to form a conductive layer and obtain a conductive laminate A; a process 2 of keeping the conductive laminate A under a heating and humidifying condition of 60°C or higher and 85°C or lower, and 60% RH or higher and 85% RH or lower for 10 days or more and 30 days or less to obtain a conductive laminate B; and a process 3 of keeping the conductive laminate B under a non-humidified heating condition of 60°C or higher and 85°C or lower for 10 days or more and 30 days or less to obtain a conductive laminate C.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In a π-conjugated conductive polymer whose main chain is composed of a π-conjugated system, a polyanion having an anion group dopes to form a conductive complex, resulting in dispersibility in water. By coating a conductive polymer-containing liquid (sometimes referred to as a conductive polymer dispersion) containing the conductive complex on a film substrate or the like, a conductive film provided with a conductive layer can be produced. Further, for the purpose of enhancing the wettability of the conductive polymer-containing liquid with respect to the film substrate or enhancing the conductivity of the conductive layer to be formed, an epoxy compound may be reacted with the conductive complex. For example, Patent Document 1 discloses a method for improving the conductivity of a conductive complex by reacting a cyclic epoxy compound.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] It is required to further lower the surface resistance value of a conductive layer formed by curing a coating film of a conventional conductive polymer-containing liquid. The present invention provides a method for producing a conductive laminate capable of reducing the surface resistance value of a conductive layer by treating a coating film of a conductive polymer-containing liquid under heating and humidifying conditions, a conductive polymer-containing liquid suitable for use in the production method, and a method for producing the same.

Means for Solving the Problems

[0005] [1] A conductive polymer-containing liquid comprising a conductive composite containing a π-conjugated conductive polymer and a polyanion, a binder component, and a conductivity enhancer, which is used for the purpose of manufacturing a conductive laminate by sequentially performing the following steps 1 to 3. (Step 1) A step of obtaining a conductive laminate A by applying the conductive polymer-containing liquid to at least a part of the surface of a substrate to form a coating film, and drying the coating film to form a conductive layer. (Step 2) A step of obtaining a conductive laminate B by holding the conductive laminate A provided with the substrate and the conductive layer under heating and humidifying conditions of 60°C or higher and 85°C or lower and 60% RH or higher and 85% RH or lower for 10 days or more and 30 days or less. (Step 3) A step of obtaining a conductive laminate C by holding the conductive laminate B under heating conditions of 60°C or higher and 85°C or lower and non-humidifying for 10 days or more and 30 days or less, and drying the conductive layer. [2] The conductive polymer-containing liquid according to [1], wherein the surface resistance value B (unit: Ω / sq.) of the conductive layer provided in the conductive laminate B is lower than the surface resistance value A (unit: Ω / sq.) of the conductive layer provided in the conductive laminate A. [3] The conductive polymer-containing liquid according to [1] or [2], wherein the surface resistance value C (unit: Ω / sq.) of the conductive layer provided in the conductive laminate C is lower than the surface resistance value A (unit: Ω / sq.) of the conductive layer provided in the conductive laminate A. [4] The conductive polymer-containing liquid according to any one of [1] to [3], wherein the surface resistance value B (unit: Ω / sq.) of the conductive layer provided in the conductive laminate B is lower than the surface resistance value C (unit: Ω / sq.) of the conductive layer provided in the conductive laminate C. [5] The conductive polymer-containing liquid according to any one of [1] to [4], wherein the conductivity enhancer is one or more selected from compounds having two or more hydroxy groups, compounds having two or more carboxy groups, compounds having an amide group, and nitrogen-containing aromatic compounds. [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] The conductive polymer-containing liquid according to any one of [1] to [6], wherein the conductive composite is modified by reaction with one or more selected from an epoxy compound, an amine compound, and a quaternary ammonium compound. [8] A method for producing a conductive laminate, comprising obtaining the conductive laminate C by sequentially performing the above steps 1 to 3 using the conductive polymer-containing liquid according to any one of [1] to [7]. [9] The method for producing a conductive laminate according to [8], wherein the substrate is a film substrate.

[10] A method for producing the conductive polymer-containing liquid according to [7], comprising: adding one or more selected from an epoxy compound, an amine compound, and a quaternary ammonium compound to a raw material liquid containing a conductive composite containing a π-conjugated conductive polymer and a polyanion and an aqueous dispersion medium; recovering a reaction product of the added compound and the conductive composite; and obtaining a conductive polymer-containing liquid by mixing the reaction product, a solvent, a binder component, and a conductivity enhancer.

Advantages of the Invention

[0006] According to the method for producing a conductive laminate using the conductive polymer-containing liquid of the present invention, a conductive laminate having a conductive layer with a low surface resistance value can be produced. The conductive polymer-containing liquid of the present invention is useful for use in the above method for producing a conductive laminate. According to the method for producing a conductive polymer-containing liquid of the present invention, the above conductive polymer-containing liquid can be easily produced.

[0007] The present invention is considered to contribute to SDGs Goal 12 "Responsibility to Produce, Responsibility to Use".

[0008] In this specification and the claims, the lower and upper limit values of the numerical range indicated by "~" are included in the numerical range.

Mode for Carrying Out the Invention

[0009] ≪Conductive Polymer-Containing Liquid≫ The first aspect of the present invention is a conductive polymer-containing liquid containing a conductive composite including a π-conjugated conductive polymer and a polyanion, a binder component, and a conductivity enhancer. The conductive polymer-containing liquid of this aspect is preferably used in the method for manufacturing a conductive laminate described later. In the conductive polymer-containing liquid of this aspect, the conductive composite may be in a dispersed state or a dissolved state. In this specification, unless otherwise specified, the dispersed state and the dissolved state are not distinguished.

[0010] <π-Conjugated Conductive Polymer> The π-conjugated conductive polymer is not particularly limited as long as it has the effects of the present invention as long as it is an organic polymer whose main chain is composed of a π-conjugated system. For example, 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 can be mentioned. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes, and polyaniline-based conductive polymers are preferable, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferable.

[0011] Examples of 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), poly(3-iodothiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxy-thiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxy-thiophene), 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-didodecyloxythiophene), 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 π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferred in terms of conductivity, transparency, and heat resistance. The π-conjugated conductive polymer contained in the conductive composite may be one type or two or more types.

[0012] <Polyanion> A polyanion is a polymer having two or more monomer units having an anion group in the molecule. The anion group of this polyanion functions as a dopant for the π-conjugated conductive polymer and can improve the conductivity of the π-conjugated conductive polymer. The anion group of the polyanion is preferably a sulfo group or a carboxy group. Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylate esters having a sulfo group, polymethacrylate esters having a sulfo group (for example, poly(4-sulfobutyl methacrylate), polysulfoethyl methacrylate, polymethacryloyloxybenzene sulfonic acid), polymers having a sulfo group such as poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, and polymers having a carboxy group such as polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropane carboxylic acid), polyisoprene carboxylic acid. These may be homopolymers or copolymers of two or more types. Among these polyanions, polymers having a sulfo group are preferred and polystyrene sulfonic acid is more preferred because they can achieve higher conductivity. The polyanion may be of one type or two or more types.

[0013] The polyanion forms a conductive composite by doping a π-conjugated conductive polymer. However, in the polyanion that forms the conductive composite, some anion groups are not doped into the π-conjugated conductive polymer and have surplus anion groups that do not participate in the doping. Since this surplus anion group is a hydrophilic group, the conductive composite has high water dispersibility and low organic solvent dispersibility. When the number of all anion groups of the polyanion that forms the conductive composite is set to 100 mol%, the surplus anion groups are preferably 30 mol% or more and 90 mol% or less, and more preferably 45 mol% or more and 75 mol% or less.

[0014] The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less, more preferably 10 parts by mass or more and 700 parts by mass or less, and still more preferably 100 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer. If the content ratio of the polyanion is equal to or higher than the lower limit value, the doping effect on the π-conjugated conductive polymer tends to be stronger and the conductivity becomes higher. On the other hand, if the content of the polyanion is equal to or lower than the upper limit value, the π-conjugated conductive polymer can be sufficiently contained, so that sufficient conductivity can be ensured.

[0015] The content of the conductive composite with respect to the total mass of the conductive polymer-containing liquid of this embodiment can be, for example, 0.01% by mass or more and 10.0% by mass or less, preferably 0.05% by mass or more and 5.0% by mass or less, more preferably 0.1% by mass or more and 2.0% by mass or less, and still more preferably 0.5% by mass or more and 1.0% by mass or less. When it is equal to or higher than the lower limit value of the above range, the conductivity of the formed conductive layer becomes higher. When it is equal to or lower than the upper limit value of the above range, the dispersibility of the conductive composite in the conductive polymer-containing liquid can be enhanced, and a uniform conductive layer can be formed.

[0016] The content of the π-conjugated conductive polymer with respect to the total mass of the conductive polymer-containing liquid of this embodiment can be, for example, 0.01% by mass or more and 2.0% by mass or less. The content of the polyanion with respect to the total mass of the conductive polymer-containing liquid of this embodiment can be, for example, 0.03% by mass or more and 10% by mass or less. The content ratio of the π-conjugated conductive polymer:polyanion contained in the conductive polymer-containing liquid of this embodiment is preferably (1:2) to (1:5) on a mass basis, more preferably (1:2) to (1:4), and still more preferably (1:2) to (1:3).

[0017] The conductive composite contained in the conductive polymer-containing liquid of this embodiment may be modified by reaction with one or more selected from epoxy compounds, amine compounds, and quaternary ammonium compounds. At least a part of the surplus anion groups that do not participate in the doping of the polyanion contained in the conductive composite is modified by the above reaction, and any of the substituents (A) to (C) described later is formed. The conductive composite having the substituents (A) to (C) has increased hydrophobicity and improved dispersibility in an organic solvent.

[0018] <Binder component> The conductive polymer-containing liquid of this embodiment contains a binder component. By containing the binder component, the strength of the conductive layer to be formed is improved, and it can particularly withstand the standing treatment under the heating and humidifying conditions described later and the subsequent drying treatment under the non-humidifying heating conditions.

[0019] The binder component is a resin or its precursor other than the π-conjugated conductive polymer and the polyanion, and is a thermoplastic resin, or a curable monomer or oligomer that cures during the formation of the conductive layer. The thermoplastic resin directly becomes the binder resin, and the resin formed by curing of the curable monomer or oligomer becomes the binder resin. Only one kind of binder component may be contained, or two or more kinds may be contained.

[0020] Specific examples of the binder resin derived from the binder component include, for example, epoxy resin, acrylic resin, polyester resin, polyurethane resin, polyimide resin, polyether resin, melamine resin, silicone, and the like.

[0021] When the conductive polymer-containing liquid of this embodiment contains an aqueous dispersion medium, a water-dispersible resin is preferable as the binder resin, and a water-dispersible emulsion resin is more preferable. The water-dispersible resin is an emulsion resin or a water-soluble resin.

[0022] Specific examples of the water-dispersible emulsion resin include acrylic resin, polyester resin, polyurethane resin, polyimide resin, melamine resin, etc., and those emulsified by an emulsifier.

[0023] Since the strength of the coating film obtained by applying the conductive polymer-containing liquid of this embodiment to a substrate is high, the binder resin preferably contains a resin having an epoxy group, more preferably contains an acrylic resin having an epoxy group, and even more preferably contains an emulsion of an acrylic resin having an epoxy group.

[0024] Since the strength of the coating film obtained by applying the conductive polymer-containing liquid of this embodiment to a substrate is high, the binder resin preferably contains a polyester resin, and more preferably contains an emulsion of a polyester resin. In particular, when applying to a polyester film substrate, it is preferable to contain a polyester resin or its emulsion because the adhesion of the coating film to the substrate is increased. When the above acrylic resin and polyester resin are used in combination, it is preferable because the strength and adhesion of the coating film are further enhanced.

[0025] Specific examples of the water-soluble resin include acrylic resin, polyester resin, polyurethane resin, polyimide resin, melamine resin, and those having 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 1 g or more, preferably 5 g or more, more preferably 10 g or more in 100 g of distilled water at 25°C. Acid groups such as carboxy groups and sulfo groups possessed by the water-dispersible resin may form a salt with a cation such as sodium ion or potassium ion.

[0026] When the conductive polymer-containing liquid of this embodiment sufficiently contains an organic solvent, a binder component having low solubility in water can be contained.

[0027] The binder component may be a curable monomer or oligomer, which may be a thermosetting monomer or oligomer, or a photocurable monomer or oligomer. Here, an oligomer is a polymer having a mass average molecular weight of less than 10,000. Examples of the curable monomer include acrylic monomers (acrylic compounds), epoxy monomers, organosiloxanes, and the like. Examples of the curable oligomer include acrylic oligomers (acrylic compounds), epoxy oligomers, silicone oligomers (curable silicones), and the like. When an acrylic monomer or acrylic oligomer is used as the binder component, it can be easily cured by heating or light irradiation. When an organosiloxane or silicone oligomer is used as the binder component, releasability (non-tackiness) can be imparted to the conductive layer.

[0028] When a curable monomer or oligomer is included, it is preferably further included with a curing catalyst. For example, when a thermosetting monomer or oligomer is included, it is preferably included with a thermal polymerization initiator that generates radicals by heating, and when a photocurable monomer or oligomer is included, it is preferably included with a photoinitiator that generates radicals by light irradiation. Also, when an organosiloxane or silicone oligomer is included, it is preferably included with a platinum catalyst for curing.

[0029] The content ratio of the binder component contained in the conductive polymer-containing liquid of this embodiment is preferably 100 parts by mass or more and 20,000 parts by mass or less, more preferably 500 parts by mass or more and 10,000 parts by mass or less, and even more preferably 1,000 parts by mass or more and 5,000 parts by mass or less, based on 100 parts by mass of the conductive composite. If it is above the lower limit value of the above range, the film-forming property and film strength when coating the conductive polymer-containing liquid of this embodiment on a substrate can be improved. If it is below the upper limit value of the above range, a decrease in conductivity due to a decrease in the content ratio of the conductive composite can be suppressed.

[0030] <High conductivity agent> The conductive polymer-containing liquid of this embodiment contains a conductivity improver. By containing a conductivity improver, the conductivity of the conductive layer to be formed can be improved, and in particular, the conductivity can be remarkably improved by the standing treatment under the heating and humidifying conditions described later. Here, the above-described π-conjugated conductive polymer, polyanion, binder resin, and organic solvent are not classified as conductivity improvers.

[0031] The conductivity improver is preferably at least one compound selected from the group consisting of saccharides, compounds having two or more hydroxy groups, compounds having two or more carboxy groups, compounds having one or more hydroxy groups and one or more carboxy groups, compounds having an amide group, compounds having an imide group, nitrogen-containing aromatic compounds (nitrogen-containing aromatic compounds), lactam compounds, and compounds having a glycidyl group. Here, hydroxy groups and carboxy groups are distinguished. The conductivity improver contained in the conductive polymer-containing liquid of this embodiment may be one type or two or more types.

[0032] Examples of the compound having two or more hydroxy groups (polyhydric alcohol) include thiodiglycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol), gallic acid, gallic acid alkyl esters, and the like.

[0033] Examples of the compound having two or more carboxy groups (polyvalent carboxylic acid) include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, and sulfur-containing carboxylic acids such as thiodipropionic acid.

[0034] The compound having an amide group (amide compound) is a monomolecular compound having an amide bond represented by -CO-NH- (the CO part is a double bond) in the molecule. Specifically, for example, acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-fluoroamide, formamide, N-methylformamide, propionamide, propiolamide, butylamide, isobutylamide, palmitamide, stearylamide, oleamide, oxamide, glutaramide, adipamide, cinnamide, glycolamide, lactamide, glyceramide, tartramide, citramide, glyoxylamide, pyruvamide, acetoacetamide, dimethylacetamide, benzylamide, anthranilamide, ethylenediaminetetraacetamide, diacetamide, triacetamide, dibenzamide, tribenzamide, rhodanine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea, 1,3-dimethylurea, 1,3-diethylurea and their derivatives, and acrylamides such as N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide, 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide.

[0035] Examples of the nitrogen-containing aromatic compound (an aromatic compound in which at least one nitrogen atom forms a ring structure) include pyrrole, indole, imidazole, 2-methylimidazole, 2-propylimidazole, N-methylimidazole, N-propylimidazole, N-butylimidazole, 1-(2-hydroxyethyl)imidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 2-aminobenzimidazole, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole, 2-(2-pyridyl)benzimidazole, pyridine, pyrimidine, pyrazine, and derivatives thereof such as their alkyl-substituted products (e.g., substituted products with alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, etc.), halogen-substituted products (e.g., substituted products with halogen groups such as fluoro, chloro, bromo, etc.), and nitrile-substituted products.

[0036] The content of the high-conductivity agent relative to the total mass of the conductive polymer-containing liquid of this embodiment is preferably 0.001% by mass or more and 10% by mass or less, more preferably 0.01% by mass or more and 1.0% by mass or less, and even more preferably 0.02% by mass or more and 0.2% by mass or less. When it is within the above-mentioned preferred range, the effect of improving conductivity by adding the high-conductivity agent can be further obtained.

[0037] The content ratio of the high-conductivity agent contained in the conductive polymer-containing liquid of this embodiment is preferably 10 parts by mass or more and 10,000 parts by mass or less, more preferably 30 parts by mass or more and 1,000 parts by mass or less, and even more preferably 50 parts by mass or more and 2,000 parts by mass or less with respect to 100 parts by mass of the conductive composite. When it is within the above-mentioned preferred range, the effect of improving conductivity by adding the high-conductivity agent can be further obtained.

[0038] [Dispersion medium] Since the conductive polymer-containing liquid of this embodiment can easily disperse the conductive composite in the liquid, it preferably contains a dispersion medium. Examples of the dispersion medium include water, an organic solvent, and a mixture of water and an organic solvent. The highly conductive agent shall not be regarded as belonging to the dispersion medium.

[0039] Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, etc. Specific examples will be described later. The organic solvent may be used alone or in combination of two or more.

[0040] Since the unmodified conductive composite has high dispersibility in water, the dispersion medium for the unmodified conductive composite is preferably an aqueous dispersion medium containing water. The content ratio of water to the total mass of the aqueous dispersion medium contained in the conductive polymer-containing liquid of this embodiment can be, for example, 50% by mass or more and 100% by mass or less, preferably 60% by mass or more and 100% by mass or less, and more preferably 70% by mass or more and 100% by mass or less. As the dispersion medium other than water, monohydric alcohol is preferred. Since the modified conductive composite having substituents (A) to (C) described later has increased hydrophobicity, the dispersion medium for the modified conductive composite is preferably an organic solvent.

[0041] (Other additives) The conductive polymer-containing liquid of this embodiment may contain other additives. The additives are not particularly limited as long as the effects of the present invention can be obtained. For example, surfactants, inorganic conductive agents, defoaming agents, coupling agents, antioxidants, ultraviolet absorbers, etc. can be used. Examples of the surfactant include nonionic, anionic, and cationic surfactants, and nonionic surfactants are preferred from the viewpoint of storage stability. Also, polymer surfactants such as polyvinylpyrrolidone may be added. Examples of the inorganic conductive agent include metal ions, conductive carbon, etc. Note that metal ions can be generated by dissolving a metal salt in water. Examples of the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil, etc. Examples of the coupling agent include silane coupling agents having a vinyl group or an amino group. Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, saccharides, etc. 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, benzoate-based ultraviolet absorbers, etc. When the conductive polymer-containing liquid of this embodiment contains the above additives, the content ratio can be appropriately determined according to the type of the additive. For example, it can be in the range of 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer and the total polyanion.

[0042] <<Manufacturing method (1) of conductive polymer-containing liquid>> The conductive polymer-containing liquid of the first embodiment can be produced by a production method including, for example, the polymerization step described below. The polymerization step is a step of obtaining a conductive polymer-containing liquid containing the conductive composite containing the π-conjugated conductive polymer and the polyanion, and the aqueous dispersion medium by polymerizing a monomer that forms the π-conjugated conductive polymer in a reaction liquid containing the polyanion and the aqueous dispersion medium. By adding a binder component and a conductivity enhancer to the conductive polymer-containing liquid obtained in the polymerization step, the conductive polymer-containing liquid of the first embodiment is obtained.

[0043] The weight average molecular weight (Mw) of the polyanion used in the polymerization step is preferably 80,000 or more and 1,000,000 or less, more preferably 100,000 or more and 800,000 or less, and even more preferably 150,000 or more and 600,000 or less. Here, the weight average molecular weight is the average molecular weight on a mass basis measured by gel permeation chromatography (GPC) using pullulan of a known weight average molecular weight as a standard substance. When the weight average molecular weight is within the above-preferred range, the conductivity of the conductive layer is further enhanced. Before subjecting the aqueous solution of the polyanion to GPC, it is preferable to filter it through a membrane filter with an average pore size of 0.2 μm for the purpose of removing impurities and the like contained in the aqueous solution, and use the filtrate for GPC measurement.

[0044] As a method for synthesizing a polyanion with a specific weight average molecular weight, for example, a method of adjusting the addition amount of an oxidizing agent for polymerizing the monomers constituting the polyanion can be mentioned. Specifically, increasing the concentration of the oxidizing agent can reduce the weight average molecular weight of the polyanion formed by the polymerization of the monomers. By this method, for example, polystyrenesulfonic acid with a weight average molecular weight Mw of 100,000 or more and 1,000,000 or less can be obtained.

[0045] [Polymerization step] A reaction solution containing the monomer forming the π-conjugated conductive polymer and the polyanion in an arbitrary content ratio is prepared, and the monomer is polymerized to form a π-conjugated conductive polymer. In the reaction solution, the polyanion naturally dopes the π-conjugated conductive polymer, and a conductive composite composed of the π-conjugated conductive polymer and the polyanion is formed.

[0046] A catalyst may be added to the reaction solution. The catalyst is not particularly limited as long as it can promote the polymerization of the monomer, and examples thereof include transition metal compounds such as ferric chloride, ferrous sulfate, ferric nitrate, and cupric chloride. Among them, it is preferable to use a catalyst containing iron because the polymerization of the monomer proceeds stably at room temperature.

[0047] It is preferable to contain an oxidizing agent in the reaction solution together with the catalyst. The oxidizing agent can polymerize the monomer. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. It is preferable that the oxidizing agent is added slowly to the mixed solution S1 containing the monomer, the polyanion, and the catalyst as an oxidizing agent solution previously dissolved in ion-exchanged water to initiate polymerization. The concentration of the oxidizing agent solution is preferably 1.0% by mass or more and 3.0% by mass or less.

[0048] The standard reaction time required until the reaction is completed is 4 to 12 hours, and it is preferable that the reaction is completed in 6 to 10 hours. The completion of the polymerization reaction can be known by confirming that the monomer forming the π-conjugated system conductive polymer has disappeared by gas chromatography.

[0049] The content ratio of the monomer to the polyanion contained in the mixed solution S1 is preferably (1:2) to (1:5) on a mass basis, more preferably (1:2) to (1:4), and even more preferably (1:2) to (1:3). When it is equal to or higher than the lower limit value of the above range, the doping effect by the polyanion is sufficiently exhibited, and the dispersion stability of the conductive composite is further improved. When it is equal to or lower than the upper limit value of the above range, a conductive polymer-containing liquid capable of forming a conductive layer excellent in conductivity can be easily obtained.

[0050] The content of the monomer with respect to the total mass of the mixed solution S1 is preferably, for example, 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 5.0% by mass or less, and even more preferably 0.3% by mass or more and 1.0% by mass or less. When it is within the above range, the polymerization reaction can proceed stably, so the complexation with the polyanion present in the reaction system easily proceeds.

[0051] The content of the polyanion with respect to the total mass of the mixed solution S1 is preferably set based on the content ratio with respect to the monomer. For example, it is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 8.0% by mass or less, and even more preferably 0.6% by mass or more and 4.0% by mass or less.

[0052] (Removal of catalyst and oxidizing agent) When using a reaction solution to which a catalyst and an oxidizing agent are added, it is preferable to remove the catalyst and the oxidizing agent from the conductive polymer-containing solution obtained after the reaction. Examples of the removal method include, for example, a method of bringing the conductive polymer-containing solution into contact with an ion exchange resin to adsorb the catalyst and the oxidizing agent onto the ion exchange resin, and a method of removing the catalyst and the oxidizing agent by ultrafiltration of the conductive polymer-containing solution while replacing the aqueous dispersion medium. Among these, the method using an ion exchange resin is preferable because it is simple. It is preferable to use a combination of a cation exchange resin and an anion exchange resin as the ion exchange resin.

[0053] (Dispersion treatment) The conductive polymer-containing solution obtained in the polymerization step may be stirred to perform a dispersion treatment of the conductive composite. The stirring method is not particularly limited, and it may be stirring with a weak shearing force such as a stirrer, or stirring may be performed using a disperser with a high shearing force such as a high-pressure homogenizer. However, from the viewpoint of enhancing the dispersibility, it is preferable to use a high-pressure homogenizer or the like.

[0054] Through the above polymerization step, a conductive polymer-containing solution containing a π-conjugated conductive polymer and a polyanion, and the aqueous dispersion medium is obtained. Furthermore, by adding a binder component and a high-conductivity agent by a conventional method and mixing them, a target conductive polymer-containing solution is obtained.

[0055] ≪Manufacturing method of conductive polymer-containing solution (2)≫ The second aspect of the present invention is a step of adding at least one selected from an epoxy compound, an amine compound, and a quaternary ammonium compound to a raw material solution containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, and an aqueous dispersion medium (reaction step), a step of recovering the reaction product of the added compound and the conductive composite (recovery step), and a step of obtaining a conductive polymer-containing solution by mixing the reaction product, a solvent, a binder component, and a high-conductivity agent (mixing step).

[0056] [Reaction step] As the raw material liquid, the conductive polymer-containing liquid obtained by the above production method (1) (hereinafter sometimes referred to as a conductive polymer dispersion) can be applied. By adding one or more selected from an epoxy compound, an amine compound, and a quaternary ammonium compound to the conductive polymer dispersion, a reaction product containing the conductive composite can be precipitated. Anionic groups such as sulfonic acid groups in the reaction product precipitated in this step are hydrophobized by the reaction of the added compound to form any of the following substituents (A) to (C).

[0057] An excess of anionic groups that do not participate in the doping of the polyanion are sometimes hereinafter referred to as "some anionic groups". The following substituent (A) is formed by the reaction of some anionic groups with an epoxy compound. The following substituent (B) is formed by the reaction of some anionic groups with an amine compound. The following substituent (C) is formed by the reaction of some anionic groups with a quaternary ammonium compound.

[0058] (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).

[0059] [Chemical formula]

[0060] [In formula (A1), R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom or an arbitrary substituent. ]

[0061] [Chemical formula]

[0062] [In formula (A2), m is an integer of 2 or more, and a plurality of R 5 , a plurality of R 6 , a plurality of R 7 , and a plurality of R 8 are each independently a hydrogen atom or an arbitrary substituent, and a plurality of R 5 may be the same or different, a plurality of R 6 may be the same or different, a plurality of R 7 may be the same or different, a plurality of R 8 may be the same or different.]

[0063] In formulas (A1) and (A2), the left - hand bond represents that the substituent (A) is substituted with a proton of an anionic group such as a sulfonic acid group.

[0064] In formula (A1), as arbitrary substituents of R 1 , R 2 , R 3 , and R 4 , there may be mentioned an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the like. R 1 and R 3 may combine to form a ring which may have a substituent. For example, when R 1 and R 3 are the above - mentioned hydrocarbon groups, and a divalent hydrocarbon group obtained by removing any one hydrogen atom of the monovalent hydrocarbon group of R 1 and a divalent hydrocarbon group obtained by removing any one hydrogen atom of the monovalent hydrocarbon group of R 3 are bonded to each other at the carbon atoms from which the hydrogen atoms have been removed to form a ring. In formula (A2), as arbitrary substituents of R 5 , R 6 , R 7 , and R 8 , there may be mentioned an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the like. R 5 and R 7It may combine to form a ring which may have a substituent. Examples of forming a ring are the same as described above. Here, "which may have a substituent" includes both the case of substituting a hydrogen atom (-H) with a monovalent group and the case of substituting a methylene group (-CH 2 -) with a divalent group. Examples of the monovalent group as a substituent include an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a trialkoxysilyl group (trimethoxysilyl group, etc.), and the like. Examples of the divalent group as a substituent include an oxygen atom (-O-), -C(=O)-, -C(=O)-O-, and the like. 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 at least the above lower limit value, the hydrophobicity of the conductive composite becomes sufficiently high. When m is at most the above upper limit value, it is possible to suppress the case where the hydrophobicity becomes too high or the conductivity decreases.

[0065] The epoxy compound is a compound having one or more epoxy groups in one molecule (epoxy group-containing compound). In terms of preventing aggregation or gelation, the epoxy compound is preferably a compound having one epoxy group in one molecule. One type or two or more types of epoxy compounds that react with the partial anion group may be used.

[0066] Examples of monofunctional epoxy compounds having one epoxy group in the 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, ethyl 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-glycidyloxypropyltrimethoxysilane, epoxy succinic 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, 4-tert-butylbenzoic acid glycidyl, 2,2,2-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)perfluorooctanesulfonamide, (2S,3S)-1,2-epoxy-3-(tert-butoxycarbonylamino)-4-phenylbutane, (R)-glycidyl 3-nitrobenzenesulfonate, glycidyl 3-nitrobenzenesulfonate, parthenolide, N-glycidylphthalimide, endrin, dieldrin, 4-glycidyloxycarbazole, [oxiranylmethyl] 7,7-dimethyloctanoate, 1,2-epoxy-4-vinylcyclohexane, higher alcohol glycidyl ethers having 10 to 16 carbon atoms, etc. may be mentioned.,

[0067] As the higher alcohol glycidyl ether, one or more of higher alcohol glycidyl ethers having 10 to 16 carbon atoms are preferable, one or more of higher alcohol glycidyl ethers having 12 to 14 carbon atoms are more preferable, and at least one of C12 (12 carbon atoms) higher alcohol glycidyl ether and C13 (13 carbon atoms) higher alcohol glycidyl ether is even more preferable.

[0068] Examples of the polyfunctional epoxy compound 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, isocyanuric acid triglycidyl, 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, 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, ethylene oxide lauryl alcohol glycidyl ether, and the like.

[0069] Since the epoxy compound has high dispersibility in an organic solvent, it preferably has a molecular weight of 50 or more and 2000 or less. Further, since the epoxy compound has high dispersibility in a low - polarity hydrocarbon - based solvent or ester - based solvent, the epoxy compound preferably has 4 or more and 120 or less carbon atoms, more preferably 7 or more and 100 or less carbon atoms, still more preferably 10 or more and 80 or less carbon atoms, and particularly preferably 15 or more and 50 or less carbon atoms.

[0070] (Substituent B) The substituent (B) is presumed to be a group represented by the following formula (B).

[0071] -HN + R 11 R 12 R 13 ···(B) [In formula (B), R 11 ~R 13 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, provided that at least one of R 11 ~R 13 is a hydrocarbon group which may have a substituent.]

[0072] In the substituent (B), the leftmost bond represents that the negative charge of the anion group, for example, the negative charge of the sulfonic acid group "-SO 3 - ", is bonded to the positive charge of the amine compound.

[0073] R 11 ~R 13 in the chemical formula (B) is a hydrogen atom or a hydrocarbon group which may have a substituent. R 11 ~R 13 in the chemical formula (B) is a substituent derived from the amine compound described below. The hydrocarbon group in the chemical formula (B) includes 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, an octyl group and the like. Examples of the substituent of the aliphatic hydrocarbon group include a phenyl group, a hydroxyl group and the like. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group and the like. Examples of the substituent of the aromatic hydrocarbon group include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group and the like.

[0074] The amine compound is at least one selected from the group consisting of a primary amine, a secondary amine and a tertiary amine. The amine compound that reacts with a part of the anion groups may be one kind or two or more kinds. Examples of the primary amine include aniline, toluidine, benzylamine, ethanolamine and the like. Examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine, and the like. Examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, trinaphthylamine, and the like. Among the amine compounds, since the conductivity of the conductive composite of this embodiment can be enhanced, a tertiary amine is preferred, and at least one of trioctylamine and tributylamine is more preferred.

[0075] Since the dispersibility in an organic solvent, particularly the dispersibility in a low-polarity hydrocarbon solvent or ester solvent is high, 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. The upper limit value of the carbon number of the substituent on this nitrogen atom is not particularly limited, and in consideration of the solubility and reactivity in the solvent, for example, 50 or less is preferred, 40 or less is more preferred, and 30 or less is even more preferred. Also, the R 11 ~R 13 The total carbon number of is preferably 6 to 33, more preferably 9 to 30, and even more preferably 12 to 27. The carbon numbers of the substituents on the nitrogen atom may be the same or different.

[0076] When the partial anionic group has a substituent (A) and a substituent (B), the mass ratio represented by [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 becomes easier to balance dispersibility and conductivity. The mass of [substituent (A)] can be calculated by [(the mass of reaction product A obtained by reacting with an epoxy compound)-(the mass of the conductive composite before reacting with the epoxy compound)]. The mass of [substituent (B)] can be calculated from [(the mass of reaction product B obtained by reacting the reaction product A with an amine compound)-(the mass of the reaction product A)].

[0077] (Substituent C) The substituent (C) is presumed to be a group represented by the following formula (C).

[0078] -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.]

[0079] In the substituent (C), the leftmost bond represents that the negative charge of the anionic group, for example, the negative charge of the sulfonic acid group "-SO 3 - ", is bonded to the positive charge of the quaternary ammonium cation.

[0080] R 11 ~R 14 in chemical formula (C) is a hydrocarbon group which may have a substituent. R 11 ~R 14 in chemical formula (C) is a substituent derived from a quaternary ammonium compound. The hydrocarbon group in chemical formula (C) includes 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, an octyl group, etc. Examples of the substituent of the aliphatic hydrocarbon group include a phenyl group, a hydroxyl group, etc. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, etc. Examples of the substituent of the aromatic hydrocarbon group include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, etc.

[0081] Since the quaternary ammonium compound has high dispersibility in an organic solvent and improved conductivity, it preferably has a substituent having 3 or more carbon atoms on the nitrogen atom, more preferably has a substituent having 5 or more carbon atoms, and even more preferably has a substituent having 7 or more carbon atoms on the nitrogen atom. The upper limit value of the carbon number of each substituent on this nitrogen atom is not particularly limited, and in consideration of solubility and reactivity in a solvent, for example, 40 or less is preferable, 30 or less is more preferable, and 20 or less is even more preferable. Further, the R 11 ~R 14 The total carbon number of is preferably 8 to 44, more preferably 12 to 40, and even more preferably 16 to 36. The carbon numbers of each substituent on the nitrogen atom may be the same or different.

[0082] 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 the counter anion of the ammonium cation include halogen ions such as bromine ions and chlorine ions, and hydroxy ions.

[0083] When the conductive composite has substituent (A) and substituent (C), the mass ratio represented by [substituent (A)]:[substituent (C)] (hereinafter, also referred to as A / C 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 / C ratio is within the above range, it becomes easier to balance the dispersibility and conductivity. The mass of [substituent (A)] can be calculated by [(the mass of reaction product A obtained by reacting with an epoxy compound) - (the conductive composite before reacting with the epoxy compound)]. The mass of [substituent (C)] can be calculated from [(the mass of reaction product C obtained by reacting the reaction product A with a quaternary ammonium compound) - (the mass of the reaction product A)].

[0084] When adding one or more epoxy compounds to the conductive polymer dispersion, the addition amount of the epoxy compound is preferably 10 parts by mass or more and 10000 parts by mass or less, more preferably 100 parts by mass or more and 5000 parts by mass or less, and even more preferably 500 parts by mass or more and 3000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer and the total polyanion contained in the conductive polymer dispersion. When it is at or above the lower limit value of the above range, the hydrophobicity of the conductive composite becomes sufficiently high, and the dispersibility in the organic solvent is improved. When it is at or below the upper limit value of the above range, it is possible to prevent a decrease in conductivity due to unreacted epoxy compounds. When adding the epoxy compound, it may be heated to promote the reaction. The heating temperature is preferably 40°C or higher and 100°C or lower.

[0085] When adding one or more amine compounds to the conductive polymer dispersion, the addition amount of the amine compound is preferably 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less, and even more preferably 100 parts by mass or more and 2000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer and the total polyanion contained in the conductive polymer dispersion. When it is equal to or higher than the lower limit value of the above range, the hydrophobicity of the conductive composite becomes sufficiently high, and the dispersibility in an organic solvent is improved. When it is equal to or lower than the upper limit value of the above range, it is possible to prevent a decrease in conductivity due to the unreacted amine compound.

[0086] When adding one or more quaternary ammonium compounds to the conductive polymer dispersion, the addition amount of the quaternary ammonium compound is preferably 1 part by mass or more and 10,000 parts by mass or less, more preferably 10 parts by mass or more and 5,000 parts by mass or less, and still more preferably 50 parts by mass or more and 2,000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer and all polyanions contained in the conductive polymer dispersion. When it is equal to or higher than the lower limit value of the above range, the hydrophobicity of the conductive composite becomes sufficiently high, and the dispersibility in an organic solvent is improved. When it is equal to or lower than the upper limit value of the above range, it is possible to prevent a decrease in conductivity due to the unreacted quaternary ammonium compound. The quaternary ammonium compound shows good reactivity with an addition amount less than that of the amine compound by a reaction mechanism similar to that of the amine compound. The conductivity of the conductive layer containing the conductive composite modified by the quaternary ammonium compound tends to be superior to that in the case of being modified by the amine compound.

[0087] Before adding one or more selected from an epoxy compound, an amine compound, and a quaternary ammonium compound to the conductive polymer dispersion, or simultaneously with or after the addition, an organic solvent may be added. As the organic solvent, a water-soluble organic solvent is preferable. Examples of the water-soluble organic solvent include alcohol solvents, ketone solvents, and ester solvents. The organic solvent to be added may be one type or two or more types.

[0088] When adding both an epoxy compound and an amine compound or a quaternary ammonium compound to the conductive polymer dispersion, the addition order is not particularly limited. Since it is easy to handle the synthetic intermediate (reaction intermediate), it is preferable to first add the epoxy compound and react it, and then add the amine compound or the quaternary ammonium compound and react it.

[0089] [Recovery process] The method for recovering the precipitated reaction product is not particularly limited, and it can be recovered, for example, by filtration treatment, decantation, or the like.

[0090] The amount of moisture contained in the recovered reaction product is preferably as small as possible, and most preferably contains no moisture at all. However, from a practical point of view, it may contain moisture in the range of 10% by mass or less. Examples of methods for reducing the amount of moisture include, for example, a method of washing away the reaction product with an organic solvent, a method of drying the reaction product, and the like.

[0091] [Washing process] There may be a washing process for washing the reaction product recovered in the recovery process. By this washing process, residual water, unreacted epoxy compound, unreacted amine compound or quaternary ammonium compound, and hydrolysis products of the epoxy compound are removed. The organic solvent for washing is preferably one that can be washed while minimizing the dissolution of the reaction product. For this reason, as the organic solvent for washing, an alcohol-based solvent is preferable. The organic solvent contained in the organic solvent for washing may be one type or two or more types. The washing method is not particularly limited. For example, the reaction product may be washed by pouring the organic solvent for washing from above the reaction product, or the reaction product may be washed by stirring in the organic solvent for washing.

[0092] [Mixing process] The solvent (dispersion medium) for dispersing the reaction product preferably contains an organic solvent. When the conductive polymer-containing liquid contains a hydrophobized conductive composite, the content of the organic solvent with respect to the total mass of the solvent is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and even more preferably 90% by mass or more and 100% by mass or less.

[0093] The content of the reaction product relative to the total mass of the conductive polymer-containing liquid obtained in this process can be, for example, 0.01% by mass or more and 10.0% by mass or less, preferably 0.05% by mass or more and 5.0% by mass or less, more preferably 0.1% by mass or more and 2.0% by mass or less, and even more preferably 0.5% by mass or more and 1.0% by mass or less. When it is at least the lower limit value of the above range, the conductivity of the conductive layer formed by applying the conductive polymer-containing liquid can be further improved. When it is at most the upper limit value of the above range, the dispersibility of the reaction product in the conductive polymer-containing liquid can be enhanced, and a uniform conductive layer can be formed.

[0094] <Organic solvent> Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents, hydrocarbon solvents, nitrogen atom-containing compound solvents, etc. The organic solvent may be of one type or two or more types.

[0095] The organic solvent may be a water-soluble organic solvent or a water-insoluble organic solvent. A water-soluble organic solvent is an organic solvent with a solubility of 1 g or more in 100 g of water at 20°C, and a water-insoluble organic solvent is an organic solvent with a solubility of less than 1 g in 100 g of water at 20°C. As the water-soluble organic solvent, one or more selected from alcohol solvents are preferred.

[0096] Examples of the alcohol solvent include monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether; and dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol. Examples of the ether solvent include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, etc. Examples of the ketone solvents include, for example, diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol and the like. Examples of the ester solvents and hydrocarbon solvents will be described later. Examples of the nitrogen atom-containing compound solvents include, for example, N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like. Examples of the solvents not classified above include, for example, dimethyl sulfoxide.

[0097] (Ester solvents) The ester solvents are ester group-containing compounds having an ester group (-C(=O)-O-). When the conductive composite is modified by reaction with an epoxy compound and an amine compound or a quaternary ammonium compound, it is preferable that the organic solvent contains an ester solvent because the dispersibility of the conductive composite is further enhanced. From the viewpoint of enhancing the dispersibility of the conductive composite, it is preferable to contain one or more ester solvents represented by the following formula 1z. Formula 1z: R 21 -C(=O)-O-R 22 [In the formula, R 21 represents a hydrogen atom, a methyl group or an ethyl group, and R 22 represents a linear or branched alkyl group having 1 to 6 carbon atoms.]

[0098] From the viewpoint of enhancing the dispersibility of the conductive composite, R 21 is preferably a methyl group or an ethyl group, and more preferably a methyl group. Also, the carbon number of R 22 is preferably 2 to 5, and more preferably 2 to 4.

[0099] Examples of the ester solvents include, for example, ethyl acetate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate and the like.

[0100] The content of the ester solvent contained in the organic solvent is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and may be 100% by mass, based on the total mass of the organic solvent. When the content of the ester solvent is within the above range, the dispersibility of the conductive composite can be enhanced.

[0101] When the conductive polymer-containing liquid of this aspect contains an ester solvent, one or more organic solvents other than the ester solvent may be further contained. Examples of the organic solvents other than the ester solvent include hydrocarbon solvents, ketone solvents, alcohol solvents, nitrogen atom-containing compound solvents, etc., which will be described later.

[0102] (Hydrocarbon solvent) When the conductive composite contained in the conductive polymer-containing liquid of this aspect is modified by reaction with an epoxy compound and an amine compound or a quaternary ammonium compound, it is preferable that a hydrocarbon solvent is contained as the dispersion medium because the wettability with respect to the plastic film substrate is increased and a low-polarity binder component can be easily added.

[0103] Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of the aliphatic hydrocarbon solvents include pentane, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, etc. Examples of the aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, etc. Among them, toluene is preferable because of the high dispersibility of the conductive composite. Also, when a silicone compound is added as the binder component, at least one of heptane and toluene is preferable because of the excellent solubility of the silicone compound.

[0104] In addition to the hydrocarbon solvent, it is preferable to further contain methyl ethyl ketone because the dispersibility of the conductive composite becomes higher. For example, with respect to 100 parts by mass of the hydrocarbon solvent, the amount of methyl ethyl ketone is preferably 20 parts by mass or more and 120 parts by mass or less, more preferably 30 parts by mass or more and 100 parts by mass or less, and even more preferably 40 parts by mass or more and 80 parts by mass or less.

[0105] The content of the hydrocarbon solvent is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and may even be 100% by mass, based on the total mass of the organic solvent. When the content of the hydrocarbon solvent is within the above range, the dispersibility of the conductive composite can be enhanced.

[0106] When the conductive polymer-containing liquid of this embodiment contains a hydrocarbon solvent, one or more organic solvents other than the hydrocarbon solvent may be further contained. Examples of the organic solvent other than the hydrocarbon solvent include the ketone-based solvents, alcohol-based solvents, ester-based solvents, nitrogen atom-containing compound-based solvents, etc. described above.

[0107] Among these, it is preferable that the organic solvent is one or more selected from alcohol-based solvents, ketone-based solvents, and ester-based solvents, and more preferably one or more selected from isopropanol, methyl ethyl ketone, and ethyl acetate. By using these suitable organic solvents, the dispersibility of the conductive composite contained in the conductive polymer-containing liquid can be further enhanced.

[0108] (Dispersion treatment) After adding the solvent to the reaction product, the conductive polymer-containing liquid may be stirred to perform a dispersion treatment. The stirring method is not particularly limited, and it may be stirring with a weak shearing force such as a stirrer, or stirring may be performed using a disperser with a high shearing force such as a high-pressure homogenizer. However, from the viewpoint of enhancing the dispersibility, it is preferable to use a high-pressure homogenizer or the like.

[0109] By the above method, a conductive polymer-containing liquid containing a conductive composite including a π-conjugated system conductive polymer and a polyanion and the aqueous dispersion medium is obtained. Furthermore, by adding a binder component and a conductivity enhancer by a conventional method and mixing them, a target conductive polymer-containing liquid is obtained.

[0110] ≪Conductive laminate≫ The third aspect of the present invention is a conductive laminate including a base material and a conductive layer formed of a cured layer of the conductive polymer-containing liquid of the first aspect on at least a part of the surface of the base material. The conductive laminate of this aspect can be manufactured by the manufacturing method of the fourth aspect described later.

[0111] [Conductive layer] The formation range of the conductive layer may be the entire surface of any surface of the base material or a part thereof. In the conductive film, it is preferable that a conductive layer having a substantially uniform thickness is formed on substantially the entire surface of one surface or the other surface of the film base material. When the conductive layer is formed only on a part of the surface of the base material, for example, the conductive layer may be a fine conductive pattern such as a circuit or an electrode, or the region where the conductive layer is provided and the region where it is not provided may exist on the same surface and be roughly divided.

[0112] As the average thickness of the conductive layer, for example, 10 nm or more and 100 μm or less is preferable, 20 nm or more and 50 μm or less is more preferable, and 30 nm or more and 30 μm or less is further preferable. If the average thickness of the conductive layer is equal to or greater than the lower limit value, high conductivity can be exhibited, and if it is equal to or less than the upper limit value, the adhesion of the conductive layer to the base material is further improved. The average thickness of the conductive layer is a value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

[0113] [Base material] The base material may be a base material made of an insulating material or a base material made of a conductive material. The shape of the base material is not particularly limited, and examples thereof include shapes mainly having a plane such as a film and a substrate. Examples of the insulating material include glass, synthetic resin, ceramics, and the like. Examples of the conductive material include metal, conductive metal oxide, carbon, and the like.

[0114] (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 resin. Examples of the synthetic resin include 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 elastomer, polyester-based elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propionate, and the like. From the viewpoint of enhancing the adhesion between the film substrate and the conductive layer, the synthetic resin for the film substrate is preferably a polyester resin, and among them, polyethylene terephthalate is preferred.

[0115] 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 surface treatment such as corona discharge treatment, plasma treatment, flame treatment, etc. in order to further improve the adhesion of the conductive layer.

[0116] 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. If the average thickness of the film substrate is equal to or greater than the lower limit value, it becomes difficult to break, and if it is equal to or less than the upper limit value, sufficient flexibility as a film can be ensured. The average thickness of the film substrate is a value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

[0117] (Glass substrate) Examples of the glass substrate include an alkali-free glass substrate, a soda-lime glass substrate, a borosilicate glass substrate, a fused silica glass substrate, etc. When the substrate contains an alkali component, the conductivity of the conductive layer tends to decrease. Therefore, among the above glass substrates, an alkali-free glass is preferred. Here, the alkali-free glass refers to a glass composition in which the content of the alkali component is 0.1% by mass or less based on the total mass of the glass composition.

[0118] The average thickness of the glass substrate is preferably 100 μm or more and 3000 μm or less, more preferably 100 μm or more and 1000 μm or less. If the average thickness of the glass substrate is at least the lower limit value, it is less likely to be damaged, and if it is at most the upper limit value, it can contribute to thinning of the conductive laminate. The average thickness of the glass substrate is a value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

[0119] ≪Method for manufacturing a conductive laminate≫ The fourth aspect of the present invention is a method for manufacturing a conductive laminate by using the conductive polymer-containing liquid of the first aspect and sequentially performing the following steps 1 to 3.

[0120] (Step 1) This step is a step of obtaining a conductive laminate A by applying the conductive polymer-containing liquid to at least a part of the surface of the substrate to form a coating film, and drying the coating film to form a conductive layer.

[0121] Since the description of the substrate is the same as above, the overlapping description is omitted here.

[0122] As a method of applying (coating) the conductive polymer-containing liquid onto an arbitrary surface of the substrate, for example, methods using coaters such as 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, screen coater, etc., methods using sprayers such as air spray, airless spray, rotor damping, etc., dipping methods such as dip, etc. can be applied.

[0123] The coating amount of the conductive polymer-containing liquid on the substrate is not particularly limited, but considering uniform coating without unevenness and conductivity and film strength, as a solid content, it is preferably in the range of 0.01 g / m 2 or more and 10.0 g / m 2 or less.

[0124] As the thickness of the coating film immediately after applying the conductive polymer-containing liquid to the substrate, for example, it is preferably 0.1 μm or more and 500 μm or less, more preferably 1 μm or more and 100 μm or less, and even more preferably 5 μm or more and 50 μm or less. The thickness of the above coating film can be adjusted, for example, by changing the gauge number of the bar coater.

[0125] A conductive layer can be formed by drying the coating film of the conductive polymer-containing liquid applied to the substrate, removing at least a part of the dispersion medium, and curing it. Examples of the method of drying the coating film include heat drying, vacuum drying, etc. As heat drying, for example, methods such as hot air heating and infrared heating can be adopted. When applying heat drying, the heating temperature is appropriately set according to the dispersion medium used, but usually it is in the range of 50°C or more and 200°C or less. Here, the heating temperature is the set temperature of the drying device. As a suitable drying time in the above heating temperature range, it is preferably 0.5 minutes or more and 30 minutes or less, and more preferably 1 minute or more and 15 minutes or less. After drying, UV irradiation may be performed to cure the binder component contained in the coating film.

[0126] By drying the coating film, a conductive laminate A having a conductive layer formed on any surface of the substrate is obtained. As the average thickness of the conductive layer of the conductive laminate A, for example, 10 nm or more and 100 μm or less is preferable, 20 nm or more and 50 μm or less is more preferable, and 30 nm or more and 30 μm or less is even more preferable. If the average thickness of the conductive layer is equal to or greater than the lower limit value, high conductivity can be exhibited, and if it is equal to or less than the upper limit value, the adhesion of the conductive layer to the substrate is further improved. The average thickness of the conductive layer is a value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

[0127] The surface resistance value A of the conductive laminate A is, for example, 1.0×10 6 Ω / □ or more and 10.0×10 10 Ω / □ or less.

[0128] (Step 2) In this step, the conductive laminate A obtained in the previous step is held under heating and humidifying conditions of 60°C or more and 85°C or less and 60% RH or more and 85% RH or less for 10 days or more and 30 days or less to obtain a conductive laminate B. The range of the heating temperature is preferably 60°C or more and 85°C or less, more preferably 70°C or more and 85°C or less, and even more preferably 75°C or more and 85°C or less. The range of the relative humidity during heating is preferably 60% RH or more and 85% RH or less, more preferably 70% RH or more and 85% RH or less, and even more preferably 75% RH or more and 85% RH or less. When the conductive laminate A is placed under the above heating and humidifying conditions and held in a state where the conductive layer is exposed to the humidity in the atmosphere, the holding period is preferably 10 days or more and 30 days or less, more preferably 10 days or more and 20 days or less, and even more preferably 10 days or more and 15 days or less. Note that 1 day means 24 hours.

[0129] By exposing the conductive layer to humidity under the above heating and humidifying conditions, the conductivity of the conductive layer can be significantly improved. Although the details of this mechanism are not yet understood, it is presumed that the conductive layer absorbs a small amount of moisture, and the molecular motion of the contained components such as the conductive composite increases due to heating, resulting in an improvement in the molecular conformation and relative arrangement in the conductive layer, thereby increasing the conductivity.

[0130] As a specific method for placing the conductive laminate A under the above heating and humidifying conditions to obtain the conductive laminate B, for example, a method of using a commercially available thermo-hygrostat equipped with a sample chamber capable of controlling temperature and humidity can be mentioned. The heating temperature and humidity during the holding of the conductive laminate can be controlled as the set temperature and humidity of the sample chamber.

[0131] The surface resistance value B of the conductive laminate B is not particularly limited as long as it is lower than the surface resistance value A. For example, it can be 1.0×10 3 Ω / □ or more and 10.0×10 8 Ω / □ or less.

[0132] The value of the ratio represented by surface resistance value A / surface resistance value B can be, for example, in the range of 3 or more and 10000 or less, 10 or more and 5000 or less, 20 or more and 1000 or less, or 30 or more and 100 or less.

[0133] (Step 3) In this step, the conductive laminate B obtained in the previous step is held for 10 days or more and 30 days or less under heating conditions of 60°C or more and 85°C or less and non-humidified, and the conductive layer is dried to obtain a conductive laminate C. The range of the heating temperature is preferably 60°C or more and 85°C or less, more preferably 70°C or more and 85°C or less, and even more preferably 80°C or more and 85°C or less. In this step, the above heat treatment is performed without humidification. The humidity at 25°C in the environment where this step is performed is preferably, for example, 50%RH or more and 65%RH or less. Place the conductive laminate B under the above non-humidifying heating conditions, and the period for holding the conductive layer in a state of being exposed to the temperature in the atmosphere is preferably 10 days or more and 30 days or less, more preferably 10 days or more and 20 days or less, and even more preferably 10 days or more and 15 days or less. Note that 1 day means 24 hours.

[0134] By drying the conductive layer under the above non-humidifying heating conditions, the conductivity of the conductive layer can be maintained in an improved state. Although the details of this mechanism are not yet understood, by drying and removing the moisture absorbed by the conductive layer in this step, the preferred conformations and relative arrangements of the molecules in the conductive layer formed in step 2 are maintained as much as possible, and as a result of drying and hardening and fixing, it is presumed that the conductivity can be maintained at a high level.

[0135] As a specific method for placing the conductive laminate B under the above non-humidifying heating conditions to obtain the conductive laminate C, for example, a method of using a commercially available thermostat equipped with a sample chamber whose temperature can be controlled can be mentioned. The heating temperature during the holding of the conductive laminate can be controlled as the set temperature of the sample chamber.

[0136] The surface resistance value C of the conductive laminate C is not particularly limited as long as it is lower than the surface resistance value A. For example, it can be 1.0×10 4 Ω / □ or more and 10.0×10 8 Ω / □ or less.

[0137] The value of the ratio represented by surface resistance value A / surface resistance value C can be, for example, in the range of 3 or more and 10000 or less, 10 or more and 5000 or less, 20 or more and 1000 or less, or 30 or more and 100 or less, etc.

[0138] The surface resistance value C tends to be higher than the surface resistance value B. Although the details of this mechanism are not yet understood, it is presumed that the surface resistance value B has high conductivity because the conductive layer contains moisture. The value of the ratio represented by surface resistivity C / surface resistivity B may be, for example, in the range of 1.1 or more and 100 or less, in the range of 1.2 or more and 50 or less, in the range of 1.3 or more and 20 or less, or in the range of 1.4 or more and 10 or less, etc.

Example

[0139] (Production Example 1) Production of polystyrene sulfonic acid 206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and while stirring at 80°C, a solution of 1.14 g of ammonium persulfate oxidizing agent previously dissolved in 10 ml of water was added dropwise over 20 minutes, and this solution was stirred for 12 hours. To the obtained sodium polystyrene sulfonate solution, 1000 ml of sulfuric acid diluted to 10 mass% was added, and approximately 1000 ml of the solvent of the obtained polystyrene sulfonic acid solution was removed by ultrafiltration. Next, 2000 ml of ion-exchanged water was added to the residue, and approximately 2000 ml of the solvent was removed by ultrafiltration to wash the polystyrene sulfonic acid. This washing operation was repeated 3 times. The water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

[0140] (Production Example 2) Synthesis of PEDOT-PSS A solution obtained by dissolving 0.5 g of 3,4-ethylenedioxythiophene and 1.5 g of polystyrene sulfonic acid in 15.0 g of ion-exchanged water was mixed at 20°C. Next, 89.5 g of ion-exchanged water was added. The obtained mixed solution was kept at 20°C, and while stirring, a solution obtained by dissolving 0.03 g of ferric sulfate in 4.97 g of ion-exchanged water and a solution obtained by dissolving 1.1 of ammonium persulfate in 8.9 g of ion-exchanged water were slowly added, and the obtained reaction solution was stirred for 24 hours to react. By the above reaction, a conductive polymer-containing liquid containing a conductive composite (PEDOT-PSS) containing poly(3,4-ethylenedioxythiophene), which is a π-conjugated system conductive polymer, and polystyrene sulfonic acid, and water as a dispersion medium was obtained. To this conductive polymer-containing liquid, 13.2 g of Duolite C255LFH (manufactured by Sumika Chemtex Corporation, cation exchange resin) and 13.2 g of Duolite A368S (manufactured by Sumika Chemtex Corporation, anion exchange resin) were added, and the mixture was filtered to remove the ion exchange resins, obtaining a conductive polymer-containing liquid from which the oxidizing agent and the catalyst had been removed. The solid content (non-volatile component) of the obtained conductive polymer-containing liquid was 1.3% by mass.

[0141] (Production Example 3) Reaction with an amine compound To 100 g of the conductive polymer-containing liquid obtained in Production Example 2, 50 g of isopropanol and 10 g of trioctylamine were added, and the mixture was stirred for 1 hour to react trioctylamine with some of the sulfonic acid groups of the conductive composite. As a result, all of the reaction products floated on the upper layer of the reaction solution. This reaction solution was filtered to obtain a powder of the reaction product of the conductive composite and trioctylamine. Isopropanol was added to this powder to make a 500 g mixture, which was dispersed using a high-pressure homogenizer to obtain 500 g of a conductive polymer-containing liquid (solid content 0.6% by mass).

[0142] (Production Example 4) Reaction with an epoxy compound To 100 g of the conductive polymer-containing liquid obtained in Production Example 2, 25 g of an epoxy compound (manufactured by Kyoeisha Chemical Co., Ltd., Epolite M-1230, C12,13 mixed higher alcohol glycidyl ether) was added, and the mixture was heated and stirred at 60 °C for 4 hours to react the epoxy compound with some of the sulfonic acid groups of the conductive composite. As a result, reaction products precipitated. These precipitates were filtered to recover the reaction product of the conductive composite and the epoxy compound. Methyl ethyl ketone was added to this reaction product to make a 300 g mixture, which was dispersed using a high-pressure homogenizer to obtain 300 g of a conductive polymer-containing liquid (solid content 0.5% by mass).

[0143] (Production Example 5) Reaction with an epoxy compound and an amine compound To 100 g of the conductive polymer-containing liquid obtained in Production Example 2, 25 g of an epoxy compound (Epolite M-1230, C12,13 mixed higher alcohol glycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd.) was added, and the mixture was heated and stirred at 60 °C for 4 hours. Next, 50 g of isopropanol and 10 g of trioctylamine were added and stirred for 1 hour, whereby the epoxy compound and trioctylamine reacted with some of the sulfonic acid groups of the conductive composite. As a result, a reaction product precipitated. This precipitate was filtered to obtain a reaction product of the conductive composite, the epoxy compound, and trioctylamine. Ethyl acetate was added to this reaction product to make a 800 g mixed solution, which was dispersed using a high-pressure homogenizer to obtain 800 g of a conductive polymer-containing liquid (solid content: 0.3 mass%).

[0144] (Example 1) To 60 g of the conductive polymer-containing liquid obtained in Production Example 2, 40 g of Plaskote RZ105 (aqueous dispersion polyester, solid content: 25 mass%, manufactured by Gohsei Chemical Industry Co., Ltd.) and 0.25 g of methyl gallate were added. To this solution, 900 g of methanol was further added, and the resulting conductive polymer-containing liquid was applied onto a PET film using a #4 bar coater and dried at 120 °C for 1 minute to obtain a conductive film. The results of measuring the surface resistance value A of this conductive film are shown in Table 1. Next, the conductive film whose surface resistance value A was measured was left standing for 10 days under humidification conditions of a temperature of 85 °C and a humidity of 85% RH, and then the surface resistance value B was measured in the same manner as above. Furthermore, the conductive film whose surface resistance value B was measured was left standing for 10 days under non-humidification conditions of 85 °C, and then the surface resistance value C was measured in the same manner as above. Each measured value of the surface resistance value (unit: Ω / sq.) is shown in Table 1.

[0145] The surface resistance value of the conductive layer of the conductive film was measured using a resistivity meter (Hi-Rester manufactured by Nitto Seiko Analytic Co., Ltd.) under the condition of an applied voltage of 10 V. In the table, "1.0E+05" means "1.0×10 5 ", and the same applies to others.

[0146] (Example 2) A conductive polymer-containing solution was obtained in the same manner as in Example 1, except that the amount of methyl gallate added was changed to 0.5 g in Example 1. A conductive film was produced, and each surface resistance value was measured.

[0147] (Example 3) A conductive polymer-containing solution was obtained in the same manner as in Example 1, except that the amount of methyl gallate added was changed to 1.0 g in Example 1. A conductive film was produced, and each surface resistance value was measured.

[0148] (Example 4) A conductive polymer-containing solution was obtained in the same manner as in Example 1, except that the amount of methyl gallate added was changed to 2.0 g in Example 1. A conductive film was produced, and each surface resistance value was measured.

[0149] (Example 5) A conductive polymer-containing solution was obtained in the same manner as in Example 1, except that 1.0 g of thiodipropionic acid was added instead of 0.25 g of methyl gallate in Example 1. A conductive film was produced, and each surface resistance value was measured.

[0150] (Example 6) A conductive polymer-containing solution was obtained in the same manner as in Example 1, except that 1.0 g of imidazole was added instead of 0.25 g of methyl gallate in Example 1. A conductive film was produced, and each surface resistance value was measured.

[0151] (Example 7) A conductive polymer-containing solution was obtained in the same manner as in Example 1, except that 1.0 g of thiodiglycol was added instead of 0.25 g of methyl gallate in Example 1. A conductive film was produced, and each surface resistance value was measured.

[0152] (Example 8) A conductive polymer-containing solution was obtained in the same manner as in Example 1, except that 1.0 g of sorbitol was added instead of 0.25 g of methyl gallate in Example 1. A conductive film was produced, and each surface resistance value was measured.

[0153] (Example 9) A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 1.0 g of hydroxyethyl acrylamide was added instead of 0.25 g of methyl gallate. A conductive film was produced, and each surface resistance value was measured.

[0154] (Example 10) A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 40 g of Plascote RZ105 was replaced with 40 g of Plascote RZ570 (manufactured by Gohsei Chemical Co., Ltd., water-dispersible polyester, solid content 25% by mass). A conductive film was produced, and each surface resistance value was measured.

[0155] (Example 11) A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 60 g of Plascote RZ105 was added to 40 g of the conductive polymer-containing liquid obtained in Production Example 2. A conductive film was produced, and each surface resistance value was measured.

[0156] (Example 12) A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 20 g of Plascote RZ105 was added to 80 g of the conductive polymer-containing liquid obtained in Production Example 2. A conductive film was produced, and each surface resistance value was measured.

[0157] (Example 13) A conductive film was produced in the same manner as in Example 1, except that the conductive film for which the surface resistance value A was measured in Example 1 was left standing for 10 days under humidification conditions of a temperature of 60°C and a humidity of 60% RH, and then the surface resistance value B was measured. Each surface resistance value was measured. Note that Examples 1 to 12 exemplified above and Examples 14 to 19 to be exemplified later are reference examples.

[0158] (Example 14) A conductive film was produced in the same manner as in Example 1, except that the conductive film for which the surface resistance value B was measured in Example 1 was left standing for 10 days under non-humidification conditions of 60°C, and then the surface resistance value C was measured in the same manner as above. Each surface resistance value was measured.

[0159] (Example 15) The conductive film for which the surface resistance value A was measured in Example 1 was left standing for 30 days under humidification conditions of a temperature of 85°C and a humidity of 85% RH, and then the surface resistance value B was measured in the same manner as above. A conductive film was produced in the same manner as in Example 1 except for this, and each surface resistance value was measured.

[0160] (Example 16) The conductive film for which the surface resistance value B was measured in Example 1 was left standing for 30 days under non-humidification conditions of 85°C, and then the surface resistance value C was measured in the same manner as above. A conductive film was produced in the same manner as in Example 1 except for this, and each surface resistance value was measured.

[0161] (Comparative Example 1) A conductive polymer-containing liquid was obtained in the same manner as in Example 1 except that methyl gallate was not added, a conductive film was produced, and its surface resistance value was measured.

[0162] (Comparative Example 2) A conductive polymer-containing liquid was obtained in the same manner as in Example 1 except that methyl gallate and Plascote RZ105 were not added, a conductive film was produced, and its surface resistance value was measured.

[0163]

Table 1

[0164] (Example 17) To 98 g of the conductive polymer-containing liquid obtained in Production Example 3, 2 g of pentaerythritol triacrylate, 0.08 g of Irgacure 184 (photoinitiator, manufactured by BASF), and 0.1 g of methyl gallate were added. The obtained conductive polymer-containing liquid was applied onto a PET film using a #8 bar coater, dried at 100°C for 1 minute, and irradiated with ultraviolet rays of 400 mJ to obtain a conductive film. Table 2 shows the results of measuring the surface resistance values A to C for this conductive film in the same manner as in Example 1.

[0165] (Comparative Example 3) A conductive polymer-containing liquid was obtained in the same manner as in Example 17 except that methyl gallate was not added, and a conductive film was produced and its surface resistance value was measured.

[0166] (Comparative Example 4) A conductive polymer-containing liquid was obtained in the same manner as in Example 17 except that pentaerythritol triacrylate and Irgacure 184 were not added, and a conductive film was produced and its surface resistance value was measured.

[0167]

Table 2

[0168] (Example 18) To 98 g of the conductive polymer-containing liquid obtained in Production Example 4, 2 g of pentaerythritol triacrylate, 0.08 g of Irgacure 184 (photoinitiator, manufactured by BASF), and 0.1 g of methyl gallate were added. The obtained conductive polymer-containing liquid was applied onto a PET film using a #8 bar coater, dried at 100 °C for 1 minute, and irradiated with ultraviolet rays of 400 mJ to obtain a conductive film. The results of measuring the surface resistance values A to C of this conductive film in the same manner as in Example 1 are shown in Table 3.

[0169] (Comparative Example 5) A conductive polymer-containing liquid was obtained in the same manner as in Example 18 except that methyl gallate was not added, and a conductive film was produced and its surface resistance value was measured.

[0170] (Comparative Example 6) A conductive polymer-containing liquid was obtained in the same manner as in Example 18 except that pentaerythritol triacrylate and Irgacure 184 were not added, and a conductive film was produced and its surface resistance value was measured.

[0171]

Table 3

[0172] (Example 19) To 98 g of the conductive polymer-containing liquid obtained in Production Example 5, 2 g of pentaerythritol triacrylate, 0.08 g of Irgacure 184 (a photoinitiator, manufactured by BASF), and 0.1 g of methyl gallate were added. The obtained conductive polymer-containing liquid was applied onto a PET film using a #8 bar coater, dried at 100°C for 1 minute, and irradiated with ultraviolet rays of 400 mJ to obtain a conductive film. The results of measuring surface resistance values A to C for this conductive film in the same manner as in Example 1 are shown in Table 4.

[0173] (Comparative Example 7) A conductive polymer-containing liquid was obtained in the same manner as in Example 19 except that methyl gallate was not added, a conductive film was produced, and its surface resistance value was measured.

[0174] (Comparative Example 8) A conductive polymer-containing liquid was obtained in the same manner as in Example 19 except that pentaerythritol triacrylate and Irgacure 184 were not added, a conductive film was produced, and its surface resistance value was measured.

[0175]

Table 4

Claims

1. The conductive polymer-containing liquid contains a conductive complex containing a π-conjugated conductive polymer and a polyanion, a binder component, and a conductivity enhancing agent, and is used for the purpose of producing a conductive laminate by carrying out the following steps 1 to 3 in order: The surface resistance value B (unit: Ω / □) of the following conductive layer of the following conductive laminate B is is lower than the surface resistance value A (unit: Ω / □) of the conductive layer of the conductive laminate A described below, The surface resistance value C (unit: Ω / □) of the following conductive layer of the following conductive laminate C is The surface resistance value A (unit: Ω / □) of the conductive layer of the conductive laminate A is lower than that of the conductive layer A. Liquid containing conductive polymer. (Step 1) A step of obtaining a conductive laminate A by applying the conductive polymer-containing liquid to at least a part of the surface of a substrate to form a coating film and drying the coating film to form a conductive layer. (Step 2) A step of obtaining a conductive laminate B by maintaining the conductive laminate A including the substrate and the conductive layer under heated and humidified conditions of 60° C. or higher and 85° C. or lower and 60% RH or higher and lower than 70% RH for 10 days or longer and 30 days or shorter. (Step 3) A process of obtaining a conductive laminate C by maintaining the conductive laminate B under heating conditions of 60° C. to 85° C. and non-humidified for 10 to 30 days to dry the conductive layer.

2. The surface resistance value B (unit: Ω / □) of the conductive layer of the conductive laminate B is The conductive polymer-containing liquid according to claim 1 , wherein the conductive polymer-containing liquid has a surface resistance C (unit: Ω / □) lower than that of the conductive layer of the conductive laminate C.

3. 3. The conductive polymer-containing liquid according to claim 1, wherein the highly conductive agent is at least one selected from the group consisting of a compound having two or more hydroxy groups, a compound having two or more carboxy groups, a compound having an amide group, and a nitrogen-containing aromatic compound.

4. The conductive polymer-containing liquid according to any one of claims 1 to 3, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene), or the polyanion is polystyrenesulfonic acid.

5. The conductive polymer-containing liquid according to any one of claims 1 to 4, wherein the conductive complex is modified by a reaction with one or more compounds selected from the group consisting of an epoxy compound, an amine compound, and a quaternary ammonium compound.

6. The conductive polymer-containing liquid described in claim 1, wherein the highly conductive agent is gallic acid or a gallic acid alkyl ester.

7. The conductive polymer-containing liquid described in claim 6, wherein the binder component is a water-dispersible polyester resin.

8. A method for producing a conductive laminate, comprising: obtaining the conductive laminate C by sequentially carrying out the steps 1 to 3 using the conductive polymer-containing liquid according to any one of claims 1 to 7.

9. The method for producing a conductive laminate according to claim 8 , wherein the substrate is a film substrate.

10. A method for producing a conductive polymer-containing liquid according to claim 5, comprising the steps of: adding at least one compound selected from the group consisting of the epoxy compound, the amine compound, and the quaternary ammonium compound to a raw material liquid containing the conductive complex containing the π-conjugated conductive polymer and the polyanion and an aqueous dispersion medium; recovering a reaction product of the added compound and the conductive composite; and mixing the reaction product, a solvent, the binder component, and the highly-conductive agent to obtain the conductive polymer-containing liquid.

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