Coating agents, coating films, and laminates

Abstract

This invention provides a coating agent that can be applied to various substrates, exhibits excellent conductivity, and allows for the production of a coating film using an in-line coating method that is advantageous in terms of production efficiency. [Solution] A coating agent containing a conductive polymer, an acid-modified polyolefin resin, and an aqueous medium, wherein the proportion of organic solvent in the aqueous medium is 50% by mass or less. A method for producing a laminate having a coating film layer and a resin substrate layer, characterized by stretching a resin substrate coated with a coating agent containing a conductive polymer, an acid-modified polyolefin resin, and an aqueous medium in which the proportion of organic solvent is 50% by mass or less in at least one direction.

Description

[Technical Field]

[0001] The present invention relates to a coating agent capable of forming a coating film with excellent conductivity. [Background technology]

[0002] In recent years, the increasing integration density of electrical and electronic components and semiconductor devices has led to numerous problems with product damage caused by dust and static electricity. To reduce the impact of dust and static electricity on products during the assembly, transportation, and packaging processes of various components used in the manufacture of such products, conductive materials are used to impart conductivity to the materials used in assembly, transportation, and packaging for antistatic purposes.

[0003] One method for imparting conductivity to various materials is to apply a coating agent containing conductive components to various substrates to form a coating film (conductive layer). For example, π-conjugated conductive polymers are attracting attention as materials for forming conductive layers because they have excellent conductivity and transparency. Patent Document 1 discloses a coating agent that uses poly(3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) as a π-conjugated conductive polymer and adds a butadiene-based olefin (latex) as a binder to improve adhesion to the substrate. Patent Document 2 discloses a coating agent that uses PEDOT / PSS as a π-conjugated conductive polymer and has a polyolefin resin added as a binder to improve adhesion to the substrate. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 6-295016 [Patent Document 2] Japanese Patent Publication No. 2024-8377 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, while the coating obtained using the conductive coating agent disclosed in Patent Document 1 has antistatic properties before and after stretching, the substrate was limited to polyethylene terephthalate (PET). Furthermore, although the coating obtained using the conductive coating agent disclosed in Patent Document 2 uses a polyolefin resin to improve adhesion between the coating and the substrate, the majority of the solvent is an organic solvent such as methanol. Therefore, it could not be said that it was intended for coating films and the like using so-called in-line film-making equipment that does not generally have explosion-proof specifications.

[0006] In view of the problems of the prior art described above, the present invention aims to provide a water-based coating agent that can produce coating films and the like with high production efficiency by applying a coating film that adheres to various substrates and has antistatic properties to in-line film-making equipment that does not require explosion-proof specifications in the coating process. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors discovered that a water-based coating agent containing a conductive polymer and an acid-modified polyolefin resin solves the above problems, and thus arrived at the present invention. In other words, the gist of the present invention is as follows:

[0008] (1) A coating agent comprising a conductive polymer, an acid-modified polyolefin resin, and an aqueous medium, wherein the proportion of organic solvent in the aqueous medium is 50% by mass or less. (2) The coating agent according to (1), wherein the conductive polymer is a π-conjugated conductive polymer. (3) The coating agent according to (1), wherein the conductive polymer is poly(3,4-ethylenedioxythiophene). (4) The coating agent according to (1), further comprising a conductive polymer dopant. (5) The coating agent according to (4), wherein the dopant is polystyrene sulfonic acid. (6) A coating agent according to any of (1) to (5), wherein the main component of the olefin component constituting the acid-modified polyolefin resin is the ethylene component. (7) A coating agent according to any one of (1) to (6), wherein the proportion of organic solvent in the aqueous medium is 20% by mass or less. (8) A coating agent according to any of (1) to (6), which substantially does not contain an organic solvent. (9) A coating film obtained from any of the coating agents described in (1) to (8). (10) A laminate having a resin substrate layer and a coating layer as described in (9). (11) A laminate comprising at least three layers, having one or more additional layers on top of the resin substrate layer or coating layer of the laminate described in (10). (12) A method for producing a laminate having a coating layer and a resin substrate layer, characterized by stretching a resin substrate coated with a coating agent containing a conductive polymer, an acid-modified polyolefin resin, and an aqueous medium in which the proportion of an organic solvent is 50% by mass or less, in at least one direction. [Effects of the Invention]

[0009] According to the coating agent of the present invention, a coating film that can be applied to various substrates and exhibits excellent conductivity can be obtained by an in-line coating method that is advantageous in terms of production efficiency. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below. The coating agent of the present invention contains a conductive polymer, an acid-modified polyolefin, and an aqueous medium, wherein the proportion of the organic solvent in the aqueous medium is 50% by mass or less.

[0011] <Conductive polymer> The conductive polymer constituting the coating agent of the present invention is not particularly limited, but it is preferable that the main chain is composed of a π-conjugated system. Examples include polypyrrole-based conductive polymers, polythiophene-based conductive polymers, polyacetylene-based conductive polymers, polyphenylene-based conductive polymers, polyphenylene-vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophene-vinylene-based conductive polymers, and copolymers thereof. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophene-based conductive polymers, and polyaniline-based conductive polymers are preferred, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferred.

[0012] 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), and poly(3-iodine). Poly(3-Cyanothiophene), Poly(3-Phenylthiophene), Poly(3,4-Dimethylthiophene), Poly(3,4-Dibutylthiophene), Poly(3-Hydroxythiophene), Poly(3-Methoxythiophene), Poly(3-Ethoxythiophene), Poly(3-Butoxythiophene), Poly(3-Hexyloxythiophene), Poly(3-Heptyloxythiophene), Poly(3-Octyloxythiophene), Poly(3-Decyloxythiophene), Poly(3-Dodecyl Poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene), poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-didecyloxythiophene), poly(3,4-di Examples include dodecyloxythiophene, poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butylenedioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3-methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), and poly(3-methyl-4-carboxybutylthiophene).

[0013] Examples of the polypyrrole-based conductive polymer 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).

[0014] Examples of the polyaniline-based conductive polymer 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) (PEDOT) is particularly preferable from the viewpoints of conductivity, transparency, and heat resistance. The π-conjugated conductive polymer may be used alone, or may be used in combination of two or more types thereof.

[0015] <Dopant> It is preferable to use a compound that functions as a dopant in combination with the conductive polymer to form a conductive complex. Polystyrene sulfonic acid (PSS) functions as a dopant for the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer. In this case, it is considered that at least a part of the sulfonic acid groups of polystyrene sulfonic acid coordinates to the π-conjugated conductive polymer. As the conductive complex, a combination of PEDOT / PSS is preferable.

[0016] The weight average molecular weight of polystyrene sulfonic acid is preferably from 20,000 to 1,000,000, more preferably from 100,000 to 500,000. In this specification, the mass-average molecular weight is determined by gel permeation chromatography, with polystyrene used as the standard substance.

[0017] The content of polystyrene sulfonic acid in the conductive composite is preferably in the range of 1 part by mass or more and 10,000 parts by mass or less per 10 parts by mass of the π-conjugated conductive polymer, more preferably in the range of 10 parts by mass or more and 1,000 parts by mass or less, and even more preferably in the range of 100 parts by mass or more and 500 parts by mass or less. The conductive composite may contain one type of polystyrene sulfonic acid, or two or more types.

[0018] Examples of commercially available conductive polymers that can be used in the present invention include "SELFTRON S" and "SELFTRON H" from Tosoh Corporation, the Bellazole series from Soken Chemical Co., Ltd., "OrgaconN N1001", ASI-210, and the ICP series from Agfa Materials Japan, the Denatron Type-P series from Nagase ChemteX Corporation, the Clevios series from Heraeus, and the Sepulzida series from Shin-Etsu Chemical Co., Ltd.

[0019] <Conductive additive> The coating solution of the present invention may contain a conductive additive along with a conductive polymer or conductive composite. The conductive additive is a compound that further improves the conductivity of the coating film formed by the coating agent. Examples of conductive additives include sugars, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxyl groups, compounds having one or more hydroxyl groups and one or more carboxyl groups, amide group compounds, imide compounds, lactam compounds, compounds having glycidyl groups, as well as aprotic organic solvents such as dimethyl sulfoxide, dimethylformamide, and N-methyl-2-pyrrolidone. These may be used individually or in combination of two or more.

[0020] The content of the conductive additive is not particularly limited, but is more preferably 1 to 30 parts by mass, and even more preferably 5 to 10 parts by mass, per 100 parts by mass of the conductive composite.

[0021] Examples of sugars include sucrose, fructose, glucose, ribose, maltose, galactose, mannose, fucose, xylose, trehalose, lactose, erythritol, cellobiose, isomaltose, xylitol, maltitol, sorbitol, mannitol, and inositol.

[0022] Examples of nitrogen-containing aromatic cyclic compounds include pyridines and their derivatives containing one nitrogen atom, imidazoles and their derivatives containing two nitrogen atoms, pyrimidines and their derivatives, pyrazines and their derivatives, and triazines and their derivatives containing three nitrogen atoms. From the viewpoint of solvent solubility, pyridines and their derivatives, imidazoles and their derivatives, and pyrimidines and their derivatives are preferred.

[0023] Specific examples of pyridines and their derivatives include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, N-vinylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 3-cyano-5-methylpyridine, 2-pyridinecarboxylic acid, 6-methyl-2-pyridinecarboxylic acid, 4-pyridinecarboxyaldehyde, 4-aminopyridine, 2,3-diaminopyridine, 2,6-diaminopyridine, 2,6-diamino-4-methylpyridine, 4-hydroxypyridine, 4-pyridinemethanol, 2,6-dihydroxypyridine, 2,6-pyridinedimethanol, and 6-hydroxynicotine. Examples include methyl acid, 2-hydroxy-5-pyridinemethanol, ethyl 6-hydroxynicotinate, 4-pyridinemethanol, 4-pyridineethanol, 2-phenylpyridine, 3-methylquinoline, 3-ethylquinoline, quinolinol, 2,3-cyclopentenopyridine, 2,3-cyclohexanopyridine, 1,2-di(4-pyridyl)ethane, 1,2-di(4-pyridyl)propane, 2-pyridinecarboxaldehyde, 2-pyridinecarboxylic acid, 2-pyridinecarbonitrate, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, and 3-pyridinesulfonic acid.

[0024] Specific examples of imidazoles and their derivatives include imidazole, 2-methylimidazole, 2-propylimidazole, 2-undecylimidazole, 2-phenylimidazole, N-methylimidazole, N-vinylimidazole, N-allyliimidazole, 1-(2-hydroxyethyl)imidazole (N-hydroxyethylimidazole), 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-methylimidazole Examples include anoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 4,5-imidazole dicarboxylic acid, 4,5-imidazole dicarboxylic acid dimethyl, benzimidazole, 2-aminobenzimidazole, 2-aminobenzimidazole-2-sulfonic acid, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole, and 2-(2-pyridyl)benzimidazole.

[0025] Specific examples of pyrimidines and their derivatives include 2-amino-4-chloro-6-methylpyrimidine, 2-amino-6-chloro-4-methoxypyrimidine, 2-amino-4,6-dichloropyrimidine, 2-amino-4,6-dihydroxypyrimidine, 2-amino-4,6-dimethylpyrimidine, 2-amino-4,6-dimethoxypyrimidine, 2-aminopyrimidine, 2-amino-4-methylpyrimidine, 4,6-dihydroxypyrimidine, 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,4,6-triaminopyrimidine, 2,4-dimethoxypyrimidine, 2,4,5-trihydroxypyrimidine, and 2,4-pyrimidinediol.

[0026] Specific examples of pyrazines and their derivatives include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5-methylpyrazinecarboxylic acid, pyrazineamide, 5-methylpyrazineamide, 2-cyanopyrazine, aminopyrazine, 3-aminopyrazine-2-carboxylic acid, 2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, and 2,3-diethylpyrazine.

[0027] Specific examples of triazines and their derivatives include 1,3,5-triazine, 2-amino-1,3,5-triazine, 3-amino-1,2,4-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4,6-triamino-1,3,5-triazine, 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, and 2,4,6-tri-2-pyridine-1,3 Examples include ,5-triazine, 3-(2-pyridine)-5,6-bis(4-phenylsulfonic acid)-1,2,4-triazine disodium, 3-(2-pyridine)-5,6-diphenyl-1,2,4-triazine, 3-(2-pyridine)-5,6-diphenyl-1,2,4-triazine-ρ,ρ'-disulfonic acid disodium, and 2-hydroxy-4,6-dichloro-1,3,5-triazine.

[0028] Examples of compounds having two or more hydroxyl groups include polyhydric aliphatic alcohols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, polyethylene glycol, D-glucose, D-glucitol, isoprene glycol, dimethylolpropionic acid, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, thiodiethanol, glucose, tartaric acid, D-glucaric acid, and glutaconic acid; and high molecular weight alcohols such as cellulose, polysaccharides, and sugar alcohols.1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 2,3-dihydroxy-1-pentadecylbenzene, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,4-dihydroxybenzophenone, 2,6-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 2,4'-dihydroxydiphenylsulfone, 2,2',5,5'-tetrahydroxydiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenyl Sulfone, hydroxyquinone carboxylic acid and its salts, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 1,4-hydroquinone sulfonic acid and its salts, 4,5-hydroxybenzene-1,3-disulfonic acid and its salts, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-dihydroxyna Phthalene-2,6-dicarboxylic acid, 1,6-dihydroxynaphthalene-2,5-dicarboxylic acid, 1,5-dihydroxynaphthoic acid, 1,4-dihydroxy-2-naphthoic acid phenyl ester, 4,5-dihydroxynaphthalene-2,7-disulfonic acid and its salts, 1,8-dihydroxy-3,6-naphthalenedisulfonic acid and its salts, 6,7-dihydroxy-2-naphthalenesulfonic acid and its salts, 1,2,3-trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene, 5-methyl-1,2,3-trihydroxybenzene Examples include aromatic compounds such as benzoin, 5-ethyl-1,2,3-trihydroxybenzene, 5-propyl-1,2,3-trihydroxybenzene, trihydroxybenzoic acid, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzoaldehyde, trihydroxyanthraquinone, 2,4,6-trihydroxybenzene, tetrahydroxy-p-benzoquinone, tetrahydroxyanthraquinone, methyl garlicate (methyl gallate), ethyl garlicate (ethyl gallate), and potassium hydroquinonesulfonate.

[0029] Compounds having one or more hydroxyl groups and one or more carboxyl groups include tartaric acid, glyceric acid, dimethylolbutanoic acid, dimethylolpropanoic acid, D-glucaric acid, and glutaconic acid.

[0030] Examples of amide compounds include acetamide, malonamide, succinamide, maleamide, fumaamide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-fluamide, formamide, N-methylformamide, propionamide, propioamide, butylamide, isobutylamide, palmitoamide, stearylamide, oleamide, oxamide, glutaramide, adipamide, cinnamamide, glycolamide, lactamide, glyceramide, tartaramide, citrullamide, glyoxylamide, pyruamide, acetacetamide, dimethylacetamide, benzylamide, anthranilamide, ethylenediaminetetraacetamide, diacetamide, triacetamide, dibenzamide, trybenzamide, rhodanine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea, 1,3-dimethylurea, 1,3-diethylurea, and their derivatives.

[0031] Acrylamides can also be used as amide compounds. Examples of acrylamides include 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, and N-methylolmethacrylamide.

[0032] Examples of imide compounds include phthalimide and phthalimide derivatives, succinimide and succinimide derivatives, benzimide and benzimide derivatives, maleimide and maleimide derivatives, and naphthalimide and naphthalimide derivatives.

[0033] Examples of imide compounds include aliphatic imide compounds and aromatic imide compounds. Aliphatic imide compounds are further classified into saturated aliphatic imide compounds, which do not have unsaturated bonds between carbon atoms in the molecule, and unsaturated aliphatic imide compounds, which do have unsaturated bonds between carbon atoms in the molecule. Examples of saturated aliphatic imide compounds include cyclohexane-1,2-dicarboximide, allantoin, hydantoin, barbituric acid, alloxane, glutarimide, succinimide, 5-butylhydantoic acid, 5,5-dimethylhydantoin, 1-methylhydantoin, 1,5,5-trimethylhydantoin, 5-hydantoin acetate, N-hydroxy-5-norbornene-2,3-dicarboximide, semicarbazide, α,α-dimethyl-6-methylsuccinimide, bis[2-(succinimideoxycarbonyloxy)ethyl]sulfone, α-methyl-α-propylsuccinimide, and cyclohexylimide. Examples of unsaturated aliphatic imide compounds include 1,3-dipropyleneurea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimidobutane, 1,6-bismaleimidohexane, 1,8-bismaleimidooctane, and N-carboxyheptylmaleimide.

[0034] Examples of lactam compounds include pentano-4-lactam, 4-pentanelactam-5-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidinone, hexano-6-lactam, and 6-hexanelactam.

[0035] Examples of compounds containing a glycidyl group include glycidyl compounds such as ethyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl phenyl ether, bisphenol A diglycidyl ether, glycidyl acrylate ether, and glycidyl methacrylate ether.

[0036] In the coating agent of the present invention, the amount of conductive composite is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, and particularly preferably 40 to 200 parts by mass, per 100 parts by mass of acid-modified polyolefin resin.

[0037] <Acid-modified polyolefin resin> Acid-modified polyolefin resin is a copolymer containing an unsaturated carboxylic acid component and an olefin component as copolymer components. The coating agent of the present invention contains an acid-modified polyolefin resin in which the polyolefin resin is acid-modified with an unsaturated carboxylic acid component, and therefore can form a coating film with excellent stretchability, heat resistance, and adhesion to the resin substrate.

[0038] The unsaturated carboxylic acid component consists of unsaturated carboxylic acids and their anhydrides. Specifically, examples of unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, as well as half-esters and half-amides of unsaturated dicarboxylic acids. These may be used individually or in combination of two or more. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferred, with acrylic acid and maleic anhydride being particularly preferred.

[0039] The content of unsaturated carboxylic acid components in the acid-modified polyolefin resin is not particularly limited, and for example, it can range from 0.05 to 20% by mass. However, from the viewpoint of stable dispersion in an aqueous medium and improving the adhesion and heat resistance of the resulting coating film, it is preferably 0.1 to 18% by mass, more preferably 0.2 to 10% by mass, even more preferably 0.5 to 8% by mass, even more preferably 0.5 to 6% by mass, and particularly preferably 1 to 5% by mass.

[0040] Examples of olefin components constituting acid-modified polyolefin resins include alkenes having 2 to 12 carbon atoms, such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. These may be used individually or in combination of two or more. Of these, alkenes having 2 to 8 carbon atoms are preferred, 1-octene, propylene, and ethylene are more preferred, and 1-octene and ethylene are even more preferred in terms of antistatic performance.

[0041] The acid-modified polyolefin resin preferably has a weight-average molecular weight of 15,000 to 200,000, more preferably 15,000 to 150,000, and even more preferably 20,000 to 100,000.

[0042] The olefin component content in acid-modified polyolefin resin is typically 45% by mass or more, but from the viewpoint of improving the adhesion, heat resistance, and dielectric properties of the resulting coating film, it is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0043] Acid-modified polyolefin resins are preferably made to contain a (meth)acrylic acid ester component, from the viewpoint of improving adhesion to the resin substrate. The content of the (meth)acrylic acid ester component in the acid-modified polyolefin resin is not particularly limited, and for example, it is in the range of 0 to 30% by mass, but from the viewpoint of improving the adhesion and dielectric properties of the resulting coating film, it is preferably 3 to 25% by mass, more preferably 4 to 22% by mass, even more preferably 5 to 20% by mass, and particularly preferably 6 to 18% by mass.

[0044] Examples of (meth)acrylic acid ester components include esters of (meth)acrylic acid with an alcohol having 1 to 30 carbon atoms, and among these, esters of (meth)acrylic acid with an alcohol having 1 to 20 carbon atoms are preferred due to their availability. Specifically, examples of (meth)acrylic acid ester components include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate. These may be used individually or in combination of two or more. Of these, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl acrylate, and octyl acrylate are preferred from the viewpoint of improving adhesion to the resin substrate, ethyl acrylate and butyl acrylate are more preferred, and ethyl acrylate is particularly preferred. In this invention, "(meth)acrylic acid" means "acrylic acid or methacrylic acid."

[0045] Furthermore, the acid-modified polyolefin resin may contain other components in an amount of 10% by mass or less of the above-mentioned components. Examples of other components include alkenes with more than 12 carbon atoms, cyclic hydrocarbons such as norbornene, maleic acid esters such as dimethyl maleate, diethyl maleate, and dibutyl maleate, (meth)acrylamides, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl versatate, as well as vinyl alcohol obtained by saponifying vinyl esters with basic compounds, etc., 2-hydroxyethyl acrylate, glycidyl (meth)acrylate, (meth)acrylonitrile, styrene, substituted styrene, carbon monoxide, and sulfur dioxide. These may be used individually or in combination of two or more.

[0046] Furthermore, the acid-modified polyolefin resin may contain an N-substituted amide structure in which the hydroxyl group of the carboxyl group is replaced with an N,N-dimethylamino group, an N,N-diethylamino group, or the like.

[0047] The melting point of the acid-modified polyolefin resin is not particularly limited, but from the viewpoint of increasing cohesive force and fluidity and improving the adhesion of the resulting coating film to the resin substrate, 50 to 150°C is preferred, 60 to 130°C is more preferred, and 70 to 110°C is even more preferred.

[0048] Examples of acid-modified polyolefin resins include ethylene-(meth)acrylic acid copolymer resin, ethylene-maleic anhydride copolymer resin, ethylene-propylene-butene-maleic anhydride copolymer resin, propylene-maleic anhydride copolymer resin, propylene-butene-maleic anhydride copolymer resin, α-olefin-ethylene-maleic anhydride copolymer resin, α-olefin-ethylene-(meth)acrylic acid copolymer resin, acid-modified polyethylene, acid-modified polypropylene, acid-modified ethylene-propylene copolymer, acid-modified ethylene-butene copolymer, acid-modified propylene-butene copolymer, and acid-modified ethylene-propylene-butene copolymer. Furthermore, the acid-modified polyolefin resin may be chlorinated in the range of 5 to 40% by mass. These may be used individually or in combination of two or more.

[0049] The method for synthesizing the polyolefin resin used in the present invention is not particularly limited, but it is preferable not to use emulsifiers or compounds having protective colloidal properties. Generally, the polyolefin resin is obtained by high-pressure radical copolymerization of the monomers constituting the polyolefin resin in the presence of a radical generator. Alternatively, the unsaturated carboxylic acid, or its anhydride, may be graft copolymerized (graft modified).

[0050] As acid-modified polyolefin resins, commercially available products such as the Bondine series from Arkema, the Bestplast series from Evonik Japan, the Primacol series from Dow Chemical, the Yumex series from Sanyo Chemical Industries, the Admer series from Mitsui Chemicals, and the Toyo Tac series from Toyobo can be used. In addition, commercially available water-based products can also be used, such as the Superclon series from Nippon Paper Chemicals, the Zaixen series from Sumitomo Seika, the Chemipearl series from Mitsui Chemicals, and the Hardlen series from Toyobo.

[0051] <Aqueous medium> The aqueous medium constituting the coating agent of the present invention refers to water or a liquid mainly composed of water. The use of an aqueous medium is preferable from an environmental standpoint and can be used in in-line coating equipment that does not generally include explosion-proof specifications.

[0052] The aqueous medium in the coating agent of the present invention, by containing an organic solvent, can improve wettability (coating properties) and film-forming properties on the substrate. Furthermore, by adding an organic solvent during the aqueous dispersion of the acid-modified polyolefin resin, aqueous dispersion can be promoted and the size of the dispersed particles can be reduced.

[0053] The organic solvent is preferably water-soluble from the viewpoint of promoting aqueous dispersion and dispersion stability, preferably having a solubility of 10 g / L or more in water at 20°C, more preferably 20 g / L or more, and even more preferably 50 g / L or more.

[0054] However, from the viewpoint of application to in-line coating equipment, the content of organic solvents in the aqueous medium must be 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less, and most preferably substantially absent.

[0055] Examples of organic solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol (IPA), n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, and cyclohexanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and dioxane; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, and 3-methyl acetate. Examples include esters such as silbutyl, methyl propionate, ethyl propionate, diethyl carbonate, and dimethyl carbonate; glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol ethyl ether acetate; and also 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoethyl acetate, 1,2-dimethylglycerin, 1,3-dimethylglycerin, or trimethylglycerin.

[0056] <Basic compounds> The aqueous medium in the present invention may contain a basic compound. In the aqueous medium, the carboxyl groups of the acid-modified polyolefin resin are neutralized by the basic compound, and the electrorepulsive force between the generated carboxyl anions prevents aggregation between the fine particles of the acid-modified polyolefin resin, thereby providing dispersion stability in the aqueous medium. Any basic compound that can neutralize the carboxyl groups is acceptable, but from the viewpoint of maintaining good antistatic performance, it is preferable to use a volatile compound. Examples include ammonia, triethylamine, N,N-dimethylethanolamine, isopropylamine, aminoethanol, dimethylaminoethanol, diethylaminoethanol, ethylamine, diethylamine, isobutylamine, dipropylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, n-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, 2,2-dimethoxyethylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, pyrrole, or pyridine.

[0057] The content of the basic compound is preferably 0.5 to 10 times the equivalent amount relative to the carboxyl groups in the acid-modified polyolefin resin, more preferably 0.8 to 5 times the equivalent amount, and particularly preferably 0.9 to 3.0 times the equivalent amount. If the content of the basic compound is less than 0.5 times the equivalent amount, the effect of adding the basic compound is not observed, while if the content exceeds 10 times the equivalent amount, the stability of the aqueous dispersion may decrease.

[0058] The method for producing the coating agent of the present invention is not particularly limited, but a simple and preferred method is to mix an aqueous dispersion in which an acid-modified polyolefin resin is dispersed in an aqueous medium with an aqueous dispersion of a conductive polymer. The order of mixing is not particularly limited. In addition, for example, if the dispersion of a conductive composite such as PEDOT / PSS is acidic, a pH adjuster (such as an amine) can be added to make it alkaline, and then it can be mixed with the aqueous dispersion of the acid-modified polyolefin resin. Aqueous dispersions of acid-modified polyolefin resins or dispersions of conductive polymers may be commercially available.

[0059] The method for obtaining an aqueous dispersion of acid-modified polyolefin resin is not particularly limited, but for example, a method can be employed in which the acid-modified polyolefin resin, an organic solvent, water, and optionally a basic compound are heated and stirred in a preferably airtight container. The heating temperature is preferably 80 to 200°C, and the stirring time is preferably 5 to 120 minutes. After this, a step may be included to remove the organic solvent added to promote aqueous dispersion.

[0060] Methods for adjusting the solid content concentration of the aqueous dispersion obtained in this way include, for example, removing the aqueous medium by distillation or diluting it with water to achieve a desired solid content concentration.

[0061] As described above, the polyolefin resin is dispersed or dissolved in an aqueous medium to obtain a homogeneous aqueous dispersion. Here, "homogeneous liquid" means that, visually, no areas of localized differences in solid content concentration, such as precipitation, phase separation, or skinning, can be found in the aqueous dispersion.

[0062] <Additives> The coating agent of the present invention may contain aqueous dispersions of other polymers, metal ions, inorganic particles, or crosslinking agents to further improve its performance depending on the purpose.

[0063] The aqueous dispersions of other polymers are not particularly limited. For example, aqueous dispersions of polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinyl alcohol, polyvirinidene chloride, ethylene-(meth)acrylic acid copolymer, long-chain alkyl-containing acrylic resin, styrene-maleic acid resin, styrene-butadiene resin, butadiene resin, polyolefin resin, acrylonitrile-butadiene resin, poly(meth)acrylonitrile resin, (meth)acrylamide resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyester resin, modified nylon resin, urethane resin, phenolic resin, silicone resin, epoxy resin, etc. Two or more of these may be mixed in any proportion.

[0064] The coating agent of the present invention may contain a crosslinking agent. By including a crosslinking agent, the components of the acid-modified polyolefin are crosslinked, improving various properties such as release properties, heat resistance, cohesive force, water resistance, solvent resistance, and release properties. As the crosslinking agent, compounds having multiple functional groups that react with the acid-modified polyolefin in their molecule can be used, and examples include oxazoline compounds, carbodiimide compounds, epoxy compounds, isocyanate compounds, melamine compounds, urea compounds, zirconium salt compounds, and silane coupling agents. Furthermore, multiple crosslinking agents may be used simultaneously. From the viewpoint of reactivity, or when adhesion to the substrate after heat treatment is required for the resulting resin layer, at least one crosslinking agent selected from oxazoline compounds and carbodiimide compounds is suitable.

[0065] The oxazoline compound is not particularly limited as long as it has two or more oxazoline groups in its molecule. Examples include compounds having oxazoline groups such as 2,2'-bis(2-oxazoline), 2,2'-ethylene-bis(4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline), and bis(2-oxazolinylcyclohexane) sulfide, as well as oxazoline group-containing polymers. One or more of these can be used. Examples of commercially available oxazoline group-containing polymers include the Epocross series from Nippon Shokubai Co., Ltd., specifically the water-soluble types "WS-500" and "WS-700"; and the emulsion types "K-1010E," "K-1020E," "K-1030E," "K-2010E," "K-2020E," and "K-2030E."

[0066] When a crosslinking agent is used, its content is preferably 0.01 to 80 parts by mass, more preferably 0.1 to 50 parts by mass, and even more preferably 0.5 to 30 parts by mass, per 100 parts by mass of the acid-modified polyolefin resin.

[0067] The coating agent of the present invention may further contain various additives as needed, such as surfactants, leveling agents, defoaming agents, anti-smudge agents, pigment dispersants, ultraviolet absorbers, weathering agents, antioxidants, and flame retardants.

[0068] The content of nonvolatile components in the coating agent of the present invention can be appropriately selected depending on the coating conditions, the desired thickness and performance of the coating film, etc., and is not particularly limited, but in terms of maintaining an appropriate viscosity and exhibiting good film-forming properties, it is preferably 1 to 60% by mass, more preferably 3 to 55% by mass, even more preferably 5 to 50% by mass, and particularly preferably 10 to 45% by mass.

[0069] From the viewpoint of coatability on a substrate, the viscosity of the coating agent of the present invention is preferably 1 to 2000 mPa·s, more preferably 3 to 1000 mPa·s, and even more preferably 5 to 500 mPa·s.

[0070] <Other conductive materials> The coating agent of the present invention may further contain conductive materials other than conductive polymers for the purpose of improving conductivity. The type of conductive material is not particularly limited, and examples include carbon-based materials and metal oxides.

[0071] The type of carbon-based material is not particularly limited and includes carbon nanotubes, fullerenes, graphene, carbon fibers, and carbon black, but carbon nanotubes are preferred because they provide high conductivity.

[0072] Examples of carbon nanotubes include single-walled carbon nanotubes and multi-walled carbon nanotubes.

[0073] The average diameter of the carbon nanotubes is not particularly limited, but is preferably 0.5 to 100 nm.

[0074] The average length of the carbon nanotubes is not particularly limited, but is preferably between 0.1 and 1000 μm.

[0075] When adding carbon-based materials, the amount added is preferably 10 to 200 parts by mass per 100 parts by mass of acid-modified polyolefin resin.

[0076] Examples of metal oxides include tin oxide, antimond-doped tin oxide, tin-doped indium oxide, zinc oxide, titanium oxide, tungsten oxide, molybdenum oxide, and vanadium oxide.

[0077] The shape of the metal oxide is, for example, particle size. Its size is not particularly limited, but since transparency increases as the particle size decreases, the average particle size is preferably 200 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less.

[0078] When metal oxides are added, the content is preferably 30 to 1500 parts by mass per 100 parts by mass of the resin containing carboxyl groups.

[0079] By simultaneously incorporating metal oxides and carbon-based materials, transparency may be improved compared to when only carbon-based materials are included. Furthermore, solvent resistance may also be improved.

[0080] <coating film> The coating film of the present invention is obtained from the coating agent of the present invention and can be obtained by coating a substrate such as a film, nonwoven fabric, insulating resin substrate, or metal foil such as copper foil using a known method. Examples of coating methods include gravure roll coating, reverse roll coating, wire bar coating, lip coating, die coating, air knife coating, curtain flow coating, spray coating, dipping coating, and brush coating. After uniformly coating the substrate surface, a uniform coating film can be formed by subjecting it to a heat treatment for drying as necessary, thereby adhering it closely to the substrate surface. As a heating device, a normal hot air circulation type oven or infrared heater can be used. The drying temperature is selected appropriately considering economics and other factors, but from the viewpoint of improving adhesion, it is preferably 60 to 250°C, more preferably 80 to 150°C, and particularly preferably 100 to 130°C. The drying time is selected appropriately considering the coating film thickness and drying temperature, but from the viewpoint of productivity and improving adhesion, it is preferably in the range of 1 second to 900 seconds, and more preferably 5 seconds to 600 seconds.

[0081] The thickness of the coating film of the present invention is not particularly limited, but is preferably 0.005 to 5 μm, more preferably 0.01 to 2 μm, and even more preferably 0.1 to 1 μm. A coating film formed to have a thickness within the above range exhibits excellent thickness uniformity. Furthermore, since the coating film of the present invention exhibits excellent conductivity even as a thin film, it is possible to achieve both conductivity and transparency.

[0082] To adjust the thickness of the coating film, it is preferable to appropriately select the equipment and operating conditions used for coating, as well as to use a coating agent with a concentration suitable for the desired thickness. The concentration of the coating agent can be adjusted by the composition of the mixture during preparation, or it may be adjusted by appropriately diluting or concentrating the prepared coating agent.

[0083] <Laminate> The laminate of the present invention is formed by laminating a coating film obtained from the coating agent of the present invention onto a resin substrate. Further layers can be formed on the surface of the resin substrate or the coating film layer. The coating film of the present invention can be used as the outermost layer, or so-called topcoat layer, and when another layer is formed on this coating film layer, the coating film layer can be used as an adhesive layer or a primer layer (undercoat layer). Examples of other layers to be laminated include an ink layer such as UV ink, an acrylic coating agent layer, an adhesive layer, and a resin film layer such as polyethylene film.

[0084] <Resin substrate> The resin substrate used in the laminate of the present invention is not particularly limited in terms of resin type, but thermoplastic resins are preferred, and examples include polyamide resins such as polyamide 6, polyamide 66, polyamide MXD6, polyamide 9T, and polyamide 10T; acrylic polymers such as polymethyl (meth)acrylate and (meth)acrylic polymers having a ring structure in the main chain; polyesters such as polyethylene terephthalate and polybutylene terephthalate; cyclic olefin polymers such as norbornene polymers; cellulose polymers such as cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate; polyolefin polymers such as polyethylene and polypropylene; polycarbonate; polystyrene; vinyl chloride polymers; ABS resin; and AS resin.

[0085] The resin film is preferably a stretched film. Stretching may be uniaxial, sequential, or biaxial. Uniaxial stretching may be longitudinal stretching (stretching in the winding direction of the resin film) or transverse stretching (stretching in the width direction of the resin film). In the case of longitudinal stretching, it may be free-end uniaxial stretching, where the width direction of the resin film is freely adjustable, or fixed-end uniaxial stretching, where the width direction of the resin film is fixed. Sequential stretching may be performed longitudinally followed by transverse stretching, or transversely followed by longitudinal stretching. Biaxial stretching may be simultaneous biaxial stretching, where longitudinal and transverse stretching are performed at the same time. Furthermore, stretching may be performed in the thickness direction of the resin film or obliquely to the roll of the resin film. The stretching method, stretching temperature, and stretching ratio can be appropriately selected according to the optical properties, mechanical strength, etc., of the desired resin film.

[0086] The method for forming a coating film on the surface of a resin substrate is not particularly limited, but an in-line coating method in which the coating film is formed on the surface of the resin film when the resin substrate is manufactured as a resin film can be preferably employed. The coating agent of the present invention is suitable for this coating method and has the advantage of increasing production efficiency by simplifying the manufacturing process.The in-line coating method may be performed, for example, in the stretching process of the resin film described above, by applying a coating agent to the unstretched resin film and drying it to form a film; or by applying a coating agent to the unstretched resin film and drying it to form a film, then uniaxially stretching the unstretched resin film with the film formed on it in the longitudinal or transverse direction, and then fixing the stretch by subsequent heating; or by applying a coating agent to the unstretched resin film and drying it to form a film, then uniaxially stretching the unstretched resin film with the film formed on it in the longitudinal or transverse direction, and then fixing the stretch by subsequent heating; or by uniaxially stretching the unstretched resin film in the longitudinal or transverse direction, applying a coating agent to the film and drying it to form a film, and then fixing the stretch by heating; The process may be carried out by first stretching the resin film, fixing the stretch by subsequent heating, applying a coating agent to the film and drying to form a coating, then further stretching the resin film with the coating formed on it in a direction perpendicular to the uniaxial stretch, and then fixing the stretch by subsequent heating; or by first stretching the unstretched resin film uniaxially in the longitudinal or transverse direction, fixing the stretch by subsequent heating, then further stretching it in a direction perpendicular to the uniaxial stretch, then applying a coating agent and drying to form a coating, and then fixing the stretch by subsequent heating; or by first forming a coating on the unstretched resin film by applying a coating agent and drying, then simultaneously biaxially stretching the unstretched resin film with the coating formed on it, and then fixing the stretch by subsequent heating; or by simultaneously biaxially stretching the unstretched resin film, fixing the stretch by subsequent heating, and then applying a coating agent and drying to form a coating, thereby obtaining a laminate.

[0087] From the viewpoint of improving adhesion to the coating film, the resin film may be subjected to corona discharge treatment in advance, or an adhesion improver may be used.

[0088] The laminate of the present invention can be used, for example, in packaging materials for semiconductors and electronic components, semiconductor elements, surface protection films, removable labels, carrier tapes, masking tapes, polarizing plates, transparent touch panels and displays, light-emitting diodes, magnetic recording materials, electrophotographic recording materials, magnetic tapes, solar cells, secondary batteries, fuel cells, computer components, mobile phone components, automotive components, and the like. [Examples]

[0089] The present invention will be specifically described below with reference to examples. However, the present invention is not limited thereto.

[0090] The laminates obtained in the examples and comparative examples were evaluated as follows. Comparative Examples 2 and 3 were evaluated by forming a coating of a predetermined thickness on a base film using a bar coater.

[0091] 1.Surface resistivity (conductivity) In accordance with JIS K6911, the surface resistivity of the coating film surface of the laminate was measured using a digital ultra-high resistance / micro-current meter (Advantest R8340 model) at a temperature of 20°C and a humidity of 60% RH, and the conductivity was evaluated according to the following criteria. ◎: Surface resistivity is 1 × 10⁻⁶ 6 Ω / □ or less ○: Surface resistivity is 1 × 10⁻⁶ 6 Ω / □ exceeding 1×10 8 Ω / □ or less △: Surface resistivity is 1 × 10⁻⁶ 8 Ω / □ exceeding 1×10 9 Ω / □ or less ×: Surface resistivity is 1 × 10 9 Ω / □ exceeding

[0092] 2. Solvent resistance The laminate was immersed in toluene at 20°C for 1 hour. After the treated laminate was thoroughly dried, the solvent resistance was evaluated by visual inspection for changes in appearance (peeling) and measurement of surface resistivity according to the following criteria. ○: No change in the coating, and the increase in surface resistivity is less than 10 times. △: No change in the coating, but the surface resistivity increases by more than 10 times. ×: The paint film peels off.

[0093] 3. Water resistance evaluation The paint film was rubbed several times with a damp cloth, and its condition was visually evaluated. ○: No change △: The paint film becomes cloudy. ×: The coating film is completely dissolved.

[0094] 4. Alkali resistance evaluation A NaOH aqueous solution, adjusted to pH 12.0 at 20°C, was heated and stirred. A metal plate coated with this solution was then immersed in it for 3 minutes. Afterwards, it was rinsed with water, and the condition of the coating was visually evaluated. The NaOH aqueous solution was evaluated under two temperature conditions: 45°C and 60°C. ○: No change △: The paint film becomes cloudy. ×: The coating dissolves or peels off.

[0095] 5. Evaluation of coating adhesion Adhesion tests were conducted on the surface of the laminated coating according to the method of JIS K5400 8.5.2. The coating was cut to create 100 grid sections of 1 mm x 1 mm, and these were peeled off using adhesive tape. The number of sections that remained intact within the 100 grid sections was counted, and the adhesion of the coating was evaluated according to the following criteria. ◎: 100 〇:95 or more and 99 or less △: 85 or more and 94 or less ×: 84 or less

[0096] 6. Inline Court Suitability Assessment The content of organic solvents in the aqueous medium of the coating agent was evaluated according to the following criteria: ○: Less than 10% by mass △: 10% by mass or more and less than 50% by mass ×: 50% by mass or more

[0097] 7. Transparency of the laminate The total light transmittance of the laminate was measured in accordance with JIS K7361-1 using a turbidimeter (NDH4000 model, manufactured by Nippon Denshoku Industries Co., Ltd.). Air was used as the background for the measurement.

[0098] 8. Viscosity of the coating agent The rotational viscosity (mPa·s) at a temperature of 25°C was measured using a digital B-type viscometer (manufactured by Eiko Seiki Co., Ltd., DV2TLVTJ0·MODELG).

[0099] The following materials were used as raw materials and substrates for the coating agent.

[0100] 1. Antistatic ingredients PEDOT / PSS aqueous dispersion (A-1): Manufactured by Agfa Materials Japan Ltd., ASI-210, solids content 13% by mass PEDOT / PSS aqueous dispersion (A-2): Manufactured by Agfa Materials Japan Ltd., Orgacon N1001, solids content 8% by mass Tin oxide-based antistatic coating agent (A-3): Manufactured by Unitika Ltd., AT-8135-20, Solvent: Water, Solid content concentration 11% by mass

[0101] 2. Aqueous dispersion of acid-modified polyolefin resin <Production of aqueous dispersion (E-1) of acid-modified polyolefin resin (B-1)> A stirrer equipped with a sealed, pressure-resistant 1L glass container with a heater was used. 100g of acid-modified polyolefin resin (B-1) [ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene 92% by mass, ethyl acrylate 6% by mass, maleic anhydride 2% by mass, melting point 105°C], 80g of isopropanol (IPA), 4.0g of N,N-dimethylethanolamine, and 220g of water were charged into the glass container and heated and stirred at 130°C for 60 minutes. After that, the mixture was cooled to room temperature while stirring, and then 150g of water was added. Water and isopropanol were removed under reduced pressure using an evaporator to obtain an aqueous dispersion of acid-modified polyolefin resin (E-1) (solid content concentration 20% by mass). The composition of the acid-modified polyolefin resin was 1The analysis was performed using a 1H-NMR analyzer (Varian, 300 MHz) with orthodichlorobenzene (d4) as the solvent at 120°C.

[0102] <Production of aqueous dispersion (E-2) of acid-modified polyolefin resin (B-2)> (Preparation of acid-modified polyolefin (B-2)) Homopolypropylene resin with an isotactic structure (MFR = 0.1 g / 10 min - 170°C, 2160 g) was subjected to thermal depolymerization treatment at 360°C for 80 minutes under atmospheric pressure and nitrogen gas aeration. 1000 g of the resulting polypropylene resin was placed in a jacketed reactor, purged with nitrogen, and heated to 180°C to melt it. Then, 125 g of maleic anhydride was added and mixed uniformly. 125 g of xylene in which 6.3 g of dicumyl peroxide was dissolved was added dropwise, and the reaction was carried out with stirring at 180°C for 3 hours. After that, the xylene was removed under reduced pressure, and the resulting reaction product was added to 3 kg of acetone to solidify the resin. This resin was finely cut and processed into pellets. These pelletized resins were used as the "base resin". 100 g of this base resin was mixed with 300 g of acetone and stirred at 50°C for 1 hour to wash the resin. After recovering the resin from the washing solution, the same method was repeated two more times to wash the resin. After recovering the resin from the washing solution, this resin was further mixed with 300 g of a washing solution consisting of acetone and dimethylaminoethanol [acetone / dimethylaminoethanol = 90 / 10 (mass ratio)] and stirred at 50°C for 1 hour to wash the resin and remove free maleic anhydride. This resin was dried under reduced pressure in a vacuum dryer to obtain acid-modified polyolefin resin (B-2).

[0103] (Manufacturing of aqueous dispersions) Using a stirrer equipped with a sealed, pressure-resistant 1L glass container with a heater, 75.0g of acid-modified polyolefin resin (B-2), 30.0g of isopropanol, 170.0g of tetrahydrofuran, 15.0g of dimethylaminoethanol, and 210.0g of distilled water were placed in the glass container and stirred at a rotation speed of 300 rpm. No resin sediment was observed at the bottom of the container, and it was confirmed that the resin was suspended. Maintaining this state, the heater was turned on after 10 minutes to heat the mixture. The system temperature was then maintained at 150°C and stirred for another 60 minutes, after which the heater was turned off and the mixture was allowed to cool naturally. Once the internal temperature had cooled to 80°C, the container was opened, and the raw materials consisting of 60.0g tetrahydrofuran, 10.0g dimethylaminoethanol, and 50.0g distilled water were added. The container was then sealed, the heater was turned on, and the mixture was reheated (re-heated) with the stirring blades rotating at 300 rpm. After stirring for another 60 minutes while maintaining the internal temperature at 140°C, the heater output was adjusted to maintain an internal temperature of 80°C. Once the internal temperature had cooled to 80°C, the pressure inside the system was gradually reduced using a vacuum pump to remove isopropanol, tetrahydrofuran, and water. After removing more than 400g of tetrahydrofuran, isopropanol, and water, the heater was turned off, and when the internal temperature reached 35°C, water was added to adjust the concentration of the acid-modified polyolefin resin (B-2) in the aqueous dispersion to 20% by mass. This was then pressure filtered through a 180-mesh stainless steel filter to obtain a homogeneous aqueous dispersion of acid-modified polypropylene resin (E-2).

[0104] <Production of aqueous dispersion (E-3) of acid-modified polyolefin resin (B-3)> A stirrer equipped with a sealed, pressure-resistant 1L glass container with a heater was used. 100g of acid-modified polyolefin resin (B-3) [ethylene-propylene-maleic anhydride copolymer, ethylene 33% by mass, propylene 62% by mass, maleic anhydride 5% by mass], 93.0g of tetrahydrofuran, 2.0g of cyclohexane, 30.6g of triethylamine, and 129.4g of distilled water were placed in the glass container, and the mixture was stirred at a rotation speed of 300 rpm. While maintaining this state, the heater was turned on to heat the mixture, and the system temperature was maintained at 110°C for 60 minutes while stirring. After that, the mixture was cooled to room temperature (approximately 25°C) while being stirred in a water bath, and 165.0g of distilled water and 3.2g of N,N-dimethylethanolamine (hereinafter referred to as DMEA) were added. The obtained aqueous dispersion was placed in a 1 L round-bottom flask and the pressure was reduced using an evaporator while the flask was placed in a water bath heated to 60°C, and 243.2 g of aqueous medium was removed by distillation. After cooling, the liquid components in the flask were pressure filtered (air pressure 0.2 MPa) through a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain an aqueous dispersion of acid-modified polyolefin resin (E-1) (solid content concentration 20% by mass). The composition of the acid-modified polyolefin resin was 1 The analysis was performed using a 1H-NMR analyzer (Varian, 300 MHz) with orthodichlorobenzene (d4) as the solvent at 120°C.

[0105] <Production of aqueous dispersion (E-4) of acid-modified polyolefin resin (B-4)> Using a stirrer equipped with a heatable, sealable pressure-resistant 1 L glass container, 30.0 g of acid-modified polyolefin resin B-4) [ethylene-octene-maleic anhydride copolymer, 60% by mass of ethylene, 38% by mass of octene, 2% by mass of maleic anhydride], 90.0 g of tetrahydrofuran, 15.0 g of triethylamine, 2.4 g of N,N-dimethylethanolamine, and 165.0 g of distilled water were charged into the glass container, and heated and stirred for 60 minutes at a rotation speed of the stirring blade of 300 rpm and an internal system temperature of 120°C. Thereafter, after cooling to room temperature while stirring, the entire amount of the obtained dispersion was transferred to a 1 L eggplant flask. While this dispersion was placed in a water bath heated to 60°C, solvent was removed under reduced pressure using an evaporator, and 74 g of an aqueous medium was distilled off. Subsequently, after adding 93.6 g of distilled water to the dispersion in the eggplant flask, solvent was removed under reduced pressure using an evaporator while the flask was placed in a water bath heated to 60°C, and 82 g of an aqueous medium was distilled off. After cooling, the dispersion in the eggplant flask was pressure-filtered (air pressure 0.2 MPa) through a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave), to obtain a uniform aqueous dispersion E-1 (solid content concentration 12.5% by mass).

[0106] <Production of aqueous dispersion (E-5) of acid-modified polyolefin resin (B-5)> A stirrer equipped with a heatable, sealable pressure-resistant 1 L glass container was used. 100 g of acid-modified polyolefin resin (B-5) [ethylene-methyl acrylate-maleic anhydride copolymer, 80% by mass of ethylene, 18% by mass of methyl acrylate, 2% by mass of maleic anhydride], 80 g of isopropanol (IPA), 4.0 g of N,N-dimethylethanolamine, and 220 g of water were charged into the glass container, and heated and stirred at 130°C for 60 minutes. Thereafter, after cooling to room temperature while stirring, 150 g of water was added, and water and isopropanol were distilled off under reduced pressure using an evaporator, to obtain an aqueous dispersion (E-1) of acid-modified polyolefin resin (solid content concentration 20% by mass). The composition of the acid-modified polyolefin resin was 1 Measurement was performed at 120°C using orthodichlorobenzene (d4) as a solvent with an H-NMR analyzer (manufactured by Varian Inc., 300 MHz).

[0107] <Manufacturing of aqueous dispersion (E-6) of acid-modified polyolefin resin (B-6)> Using a stirrer equipped with a sealed, pressure-resistant 1L glass container with a heater, 60.0g of acid-modified polyolefin resin (B-8) [propylene-butene-maleic anhydride copolymer, 77% by mass of propylene, 19% by mass of butene, 4% by mass of maleic anhydride], 45.0g of ethylene glycol monobutyl ether (manufactured by Wako Pure Chemical Industries, Ltd.), 8.0g of N,N-dimethylethanolamine, and 137.0g of distilled water were placed in the glass container and stirred at a rotation speed of 300 rpm. No resin sedimentation was observed at the bottom of the container, and it was confirmed that the resin was suspended. Maintaining this state, the heater was turned on after 10 minutes to heat the mixture. The system temperature was then maintained at 160°C and stirred for another 60 minutes. Subsequently, the mixture was cooled by air cooling until the internal temperature reached 80°C. The container was then opened, and 45.0 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), 5.0 g of N,N-dimethylethanolamine, and 30.0 g of distilled water were added. The container was then sealed, and the mixture was stirred for another 60 minutes at a rotation speed of 300 rpm, maintaining the internal temperature at 140°C. After cooling to room temperature (approximately 25°C) by air cooling while stirring at a rotation speed of 300 rpm, the mixture was pressure filtered (air pressure 0.2 MPa) through a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a slightly turbid aqueous dispersion E-6.

[0108] <Manufacturing of aqueous dispersion (E-7) of acid-modified polyolefin resin (B-7)> Using a stirrer equipped with a sealed, pressure-resistant 1L glass container with a heater, 60.0g of acid-modified polyolefin resin (B-7) [ethylene-propylene-maleic anhydride copolymer, ethylene 8% by mass, propylene 88% by mass, maleic anhydride 4% by mass], 45.0g of ethylene glycol monobutyl ether (manufactured by Wako Pure Chemical Industries, Ltd.), 8.0g of N,N-dimethylethanolamine, and 137.0g of distilled water were placed in the glass container, and the mixture was stirred at a rotation speed of 300 rpm. No resin sedimentation was observed at the bottom of the container, and it was confirmed that the resin was suspended. Maintaining this state, the heater was turned on after 10 minutes to heat the mixture. The internal temperature was then maintained at 160°C and the mixture was stirred for another 60 minutes. After that, the mixture was cooled by air cooling until the internal temperature reached 80°C, opened, and 45.0g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), 5.0g of N,N-dimethylethanolamine, and 30.0g of distilled water were added. The mixture was then sealed and stirred for another 60 minutes at a rotation speed of 300 rpm, maintaining the system temperature at 140°C. After cooling to room temperature (approximately 25°C) by air cooling while stirring at 300 rpm, it was pressure filtered (air pressure 0.2 MPa) through a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a slightly turbid aqueous dispersion E-7.

[0109] The composition of the polyolefin resin is shown in Table 1.

[0110] [Table 1]

[0111] 3. Conductive additives (C-1): D-sorbitol, manufactured by Tokyo Chemical Industry Co., Ltd. (C-2): Ethylene glycol, manufactured by Tokyo Chemical Industry Co., Ltd.

[0112] 5. The resin films used as the base material are as follows: PET film: Unstretched PET (300 μm thickness) PP film: Unoriented PP (thickness 300 μm) Nylon film: Unoriented nylon (300 μm thickness) PPS film: Unstretched PPS (thickness 300 μm)

[0113] Example 1 A coating agent with a solid content of 15% by mass and free of organic solvents was produced by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 100. The coating agent obtained above was applied to an unstretched PET film with a thickness of 300 μm, which had been uniaxially stretched at a longitudinal stretching ratio of 4.0 times. The coating agent was applied using a bar coater to a film such that the coating thickness after drying was 2.0 μm, and a film was formed by drying. Subsequently, the resin film with this film formed on it was further stretched in a direction perpendicular to the uniaxial stretching at a stretching ratio of 4.0 times, and the stretch was fixed by heating for 30 seconds to obtain a laminate.

[0114] Example 2 A coating agent with a solid content of 13% by mass was prepared by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 100, and adding isopropanol (IPA) to an aqueous medium of 20% by mass. A coating film was formed and stretched in the same manner as in Example 1 to obtain a laminate.

[0115] Example 3 A coating agent free of organic solvents was prepared by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 50. A coating film was formed and stretched in the same manner as in Example 1 to obtain a laminate.

[0116] Example 4 A coating agent free of organic solvents was prepared by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 500. A coating film was formed and stretched in the same manner as in Example 1 to obtain a laminate.

[0117] Example 5 A coating agent free of organic solvents was prepared by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 100. A coating film was formed in the same manner as in Example 1, except that the thickness was changed to 0.2 μm after drying, and a stretching operation was performed to obtain a laminate.

[0118] Example 6 A coating agent free of organic solvents was prepared by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 100. A coating film was formed in the same manner as in Example 1, and then the stretching operation was performed by changing the stretching ratio to simultaneous biaxial stretching of 3.3 times in the longitudinal direction and 3.0 times in the transverse direction, and a laminate was obtained.

[0119] Example 7 A coating agent free of organic solvents was prepared by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 100. Under the conditions of Example 1, the longitudinal stretching ratio was changed to 3.3 times, and the prepared coating agent was applied to the stretched film. After forming a coating film in the same manner as above, the film was further stretched in the transverse direction at 3.0 times, and the stretch was fixed by heating for 30 seconds to obtain a laminate.

[0120] Example 8 A coating agent free of organic solvents was prepared by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 100. A coating film was formed in the same manner as in Example 1, except that the thickness was changed to 10.0 μm after drying, and a stretching operation was performed to obtain a laminate.

[0121] Example 9 A coating agent free of organic solvents was prepared by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 100. A coating film was formed in the same manner as in Example 1, except that the resin substrate was changed to a 300 μm thick CPP film. The stretching temperature was changed to 140°C, and the stretching operation was performed to obtain a laminate.

[0122] Example 10 A coating agent free of organic solvents was prepared by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 100. A coating film was formed in the same manner as in Example 1, except that the resin substrate was changed to a nylon film with a thickness of 300 μm. The stretching temperature was changed to 190°C, and the stretching operation was performed to obtain a laminate.

[0123] Example 11 A coating agent free of organic solvents was prepared by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 100. A coating film was formed in the same manner as in Example 1, except that the resin substrate was changed to a PPS film with a thickness of 300 μm. The stretching temperature was changed to 90°C, and the stretching operation was performed to obtain a laminate.

[0124] Examples 12 and 13 A coating agent free of organic solvents was prepared by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 100. A laminate was obtained by performing a stretching operation in the same manner as in Example 1, with only the drying conditions changed.

[0125] Examples 14-19 Except for changing the aqueous dispersion (E-1) used in Example 1 to aqueous dispersions (E-2) to (E-7), a coating agent was obtained in the same manner as in Example 1, and a coating film was formed and stretched in the same manner as in Example 1 to obtain a laminate.

[0126] Example 20 In Example 1, a coating agent was obtained in the same manner as in Example 1, except that instead of 100 parts by mass of solids in the aqueous dispersion (E-1), a mixture of aqueous dispersion (E-1) and aqueous dispersion (E-4) was used so that each had 50 parts by mass of solids. A coating film was then formed and stretched in the same manner as in Example 11 to obtain a laminate.

[0127] Examples 21, 23 A coating agent was obtained in the same manner as in Example 1, except that an oxazoline-based crosslinking agent WS-700 (manufactured by Nippon Shokubai Co., Ltd., solid content concentration 30% by mass) was added to an aqueous dispersion (E-1) or (E-4) in the same manner as in Example 1, with a solid content of 20 parts by mass per 100 parts by mass of acid-modified polyolefin (B-1) or (B-4) in the dispersion. A coating film was then formed and stretched in the same manner as in Example 1 to obtain a laminate.

[0128] Example 22 A coating agent was obtained in the same manner as in Example 1, except that oxazoline-based crosslinking agent R-600 (manufactured by Kusumoto Chemical Co., Ltd., solid content concentration 33% by mass) was added to 100 parts by mass of acid-modified polyolefin (B-1) in an aqueous dispersion (E-1) so that the solid content was 30 parts by mass. A coating film was formed and stretched in the same manner as in Example 1 to obtain a laminate.

[0129] Examples 24, 25 A water-based dispersion (E-1) and PEDOT / PSS (A-1) were mixed to a solid content mass ratio of 100 / 100. To 200 parts by mass of the solid content of the mixture, 5 parts by mass of either a stretching aid (C-1) or (C-2) was added to produce a coating agent. A coating film was then formed and stretched in the same manner as in Example 1 to obtain a laminate.

[0130] Example 26 A coating agent was obtained in the same manner as in Example 1, except that PEDOT / PSS(A-2) was used instead of PEDOT / PSS(A-1). A coating film was formed and stretched in the same manner as in Example 1 to obtain a laminate.

[0131] Comparative Example 1 A coating agent was prepared in the same manner as in Example 1, except that it did not contain an aqueous dispersion, and a stretching operation was performed in the same manner to obtain a laminate.

[0132] Comparative Example 2 A coating agent with a solid content concentration of 15% by mass was prepared by mixing an aqueous dispersion (E-1) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 100, and then adding IPA to the aqueous medium at a concentration of 70% by mass.

[0133] Comparative Example 3 A coating agent was prepared by mixing an aqueous dispersion (E-2) and PEDOT / PSS (A-1) so that the solid content mass ratio was 100 / 100, and then adding IPA to the aqueous medium at a concentration of 70% by mass.

[0134] Comparative Example 4 A coating agent with a solid content of 11% by mass was prepared by mixing an aqueous dispersion (E-1) and a tin oxide-based antistatic coating agent (A-3) so that the solid content mass ratio was 100 / 100, and by adding IPA to an aqueous medium at a concentration of 20% by mass. A lamination was obtained by performing a stretching operation in the same manner as in Example 1.

[0135] Comparative Examples 5-7 Using only the antistatic component PEDOT / PSS(A-1) as the coating agent, a laminate was obtained by performing a stretching operation in the same manner as in Example 1.

[0136] Tables 2-4 show the composition of the coating agents used in the examples and comparative examples, and their evaluation results.

[0137] [Table 2]

[0138] [Table 3]

[0139] [Table 4]

[0140] The coatings formed using the coating agents obtained in Examples 1-25 could be applied by in-line coating, exhibited good adhesion to the resin substrate, and had antistatic properties after stretching. Furthermore, the coatings had excellent solvent resistance, water resistance, and alkali resistance.

[0141] A comparison of Examples 1 and 2 shows that adding a small amount of organic solvent to improve wettability does not change the performance.

[0142] A comparison of Example 3 with Examples 1 and 4 shows that the antistatic performance improves as the amount of conductive composite added as an antistatic component increases.

[0143] A comparison of Examples 1, 5, and 8 shows that the antistatic performance improves with increasing film thickness, and that the antistatic performance does not change even when the stretching ratio is increased.

[0144] Examples 1, 6, and 7 show that the antistatic performance does not change depending on the stretching method (uniaxial stretching, sequential biaxial stretching, and simultaneous biaxial stretching).

[0145] Examples 1 and 9-11 show that the adhesion and antistatic performance do not change depending on the resin substrate.

[0146] A comparison of Examples 1, 12-13 shows that the antistatic performance does not change with variations in drying time and temperature.

[0147] Examples 1, 14-20 show that when polyethylene-based resins (B-1, B-4, B-5, a mixture of B-1 and B-4) are used as the olefin component of the acid-modified polyolefin resin, the antistatic performance is superior to when polypropylene-based resins (B-2, B-3, B-6, B-7) are used.

[0148] A comparison between Example 1 and Example 21 or Example 23, and a comparison between Example 16 and Example 22, shows that the antistatic performance does not change with the addition of a crosslinking agent.

[0149] A comparison of Examples 1, 24, and 25 shows that the antistatic performance is improved by adding additives.

[0150] A comparison of Examples 1 and 26 shows that the performance does not change even when the conductive composite is modified. Comparative Example 1, compared to Example 1, shows no difference in antistatic properties or adhesion, but is inferior in solvent resistance, water resistance, and alkali resistance.

[0151] Comparative Examples 2 and 3 showed no difference in antistatic properties or adhesion compared to Example 1, but were unsuitable for inline coating due to their higher organic solvent ratio.

[0152] A comparison between Example 1 and Comparative Example 4 shows that when a tin-based antistatic agent is used, the antistatic performance is inferior to that of Example 1.

[0153] Comparative Examples 5-7 do not contain acid-modified polyolefin resin, but compared to Examples 9-11, it can be seen that adhesion is inferior when using substrates other than PET.

Claims

1. A coating agent containing a conductive polymer, an acid-modified polyolefin resin, and an aqueous medium, wherein the proportion of organic solvent in the aqueous medium is 50% by mass or less.

2. The coating agent according to claim 1, wherein the conductive polymer is a π-conjugated conductive polymer.

3. The coating agent according to claim 1, wherein the conductive polymer is poly(3,4-ethylenedioxythiophene).

4. Furthermore, the coating agent according to claim 1, further comprising a conductive polymer dopant.

5. The coating agent according to claim 4, wherein the dopant is polystyrene sulfonic acid.

6. The coating agent according to claim 1, wherein the main component of the olefin component constituting the acid-modified polyolefin resin is an ethylene component.

7. The coating agent according to claim 1, wherein the proportion of the organic solvent in the aqueous medium is 20% by mass or less.

8. The coating agent according to claim 1, which is substantially free of organic solvents.

9. A coating film obtained from the coating agent described in claim 1.

10. A laminate having a resin substrate layer and a coating film layer according to claim 9.

11. A laminate comprising at least three layers, wherein one or more other layers are located on the resin substrate layer or coating layer of the laminate according to claim 10.

12. A method for producing a laminate having a coating layer and a resin substrate layer, characterized by stretching a resin substrate coated with a coating agent containing a conductive polymer, an acid-modified polyolefin resin, and an aqueous medium in which the proportion of an organic solvent is 50% by mass or less, in at least one direction.

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