JP2008147035A - Electroconductive layered product and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electroconductive layered product which is transparent and is superior in electroconductivity and to provide a method of manufacturing it. <P>SOLUTION: The electroconductive layered product 10 has a transparent substrate 11, a metallic electrode layer 12 formed on at least one face of the transparent substrate 11, and an electroconductive polymer layer 13 formed on a surface of the metallic electrode layer 12, wherein the electroconductive polymer layer 13 is a layer that is composed of an electroconductive polymer solution having pH 4 to 10, obtained by subjecting an electroconductive polymer mixed liquid containing π-conjugated electroconductive polymers, a dopant comprising acid, and water to a neutralization process. The method of manufacturing the electroconductive layered product comprises the steps of forming the metallic electrode layer 12 on the transparent substrate 11 and applying an electroconductive polymer solution on the metallic electrode layer 12 to form the electroconductive polymer layer 13, wherein the solution having pH 4 to 10, obtained by subjecting an electroconductive polymer mixed liquid containing the π-conjugated system electroconductive polymers, the dopant comprising the acid, and the water to a neutralization process, is used as the electroconductive polymer solution. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a conductive laminate used for a coordinate input device, an image display device, a dye-sensitized solar cell, and the like, and a method for manufacturing the same.

For a coordinate input device, an image display device, a dye-sensitized solar cell, and the like, a conductive laminate having both conductivity and transparency is used.
Since the conductive laminate is required to be thin, lightweight, and flexible, a conductive layer (hereinafter referred to as an ITO conductive layer) made of indium tin oxide (hereinafter referred to as ITO) on a polyethylene terephthalate film. ) May be used.
However, since the ITO conductive layer has a high refractive index and light is easily reflected on the surface, it has a low light transmittance and is yellowish. For example, when used in an image display device, the color tone of the image is low. changed. In addition, the ITO conductive layer may be altered and blackened due to an electrochemical reaction. From these things, the electroconductive laminated body provided with the ITO electroconductive layer had the problem that visibility was low.
In addition, the ITO conductive layer has low flexibility, and when it is bent, the ITO conductive layer cracks, so that the conductivity may be lowered.
Therefore, Patent Document 1 proposes a conductive laminate having a transparent substrate, an ITO conductive layer, and a conductive polymer layer formed by applying a polyaniline solution to the ITO conductive layer.
In Patent Document 2, a conductive laminate having a transparent substrate, an ITO conductive layer, and a conductive polymer layer formed by applying a poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid solution. The body has been proposed.
In the conductive laminates described in Patent Documents 1 and 2, since the transparent conductive layer is composed of two layers of the ITO conductive layer and the conductive polymer layer, the conductivity when a crack occurs in the ITO conductive layer. Degradation, deterioration of the ITO conductive layer, and color tone change of the image due to the ITO conductive layer are suppressed.
Japanese National Patent Publication No. 11-506849 JP-A-2005-19056

However, the conductive laminates described in Patent Documents 1 and 2 may have insufficient conductivity.
This invention is made | formed in view of the said situation, It aims at providing the electroconductive laminated body which is transparent and excellent in electroconductivity, and its manufacturing method.

  When the present inventors investigated the cause of insufficient conductivity of the conductive laminates described in Patent Documents 1 and 2, the conductive polymer layer containing the acid-containing dopant became acidic by the adsorbed water. The inventors have found that this is caused by deterioration of a metal electrode layer such as an ITO conductive layer. And based on the knowledge, it further examined and invented the following electroconductive laminated bodies and its manufacturing method.

The present invention includes the following configurations.
[1] It has a transparent substrate, a metal electrode layer formed on at least one surface of the transparent substrate, and a conductive polymer layer formed on the surface of the metal electrode layer,
The conductive polymer layer is formed from a conductive polymer solution having a pH of 4 to 10 obtained by neutralizing a conductive polymer mixed solution containing a π-conjugated conductive polymer, an acid dopant and water. A conductive laminate, characterized by being a layer.
[2] The conductive laminate according to [1], wherein the dopant is a polyanion.
[3] having a step of forming a metal-based electrode layer on a transparent substrate and a step of forming a conductive polymer layer by applying a conductive polymer solution on the metal-based electrode layer;
As the conductive polymer solution, a pH 4 to 10 solution obtained by neutralizing a conductive polymer mixed solution containing a π-conjugated conductive polymer, an acid dopant and water is used. A method for producing a conductive laminate.
[4] The process according to [3], wherein the neutralization treatment is a treatment of adding one or more neutralizing agents selected from the group consisting of aliphatic amines, aromatic amines, and quaternary amines. The electroconductive laminated body of description.
[5] The method for producing a conductive laminate according to [3] or [4], wherein the dopant is a polyanion.

The conductive laminate of the present invention is transparent and excellent in conductivity. Further, the conductive laminate of the present invention is one in which a decrease in conductivity when a crack occurs in the metal-based electrode layer, alteration of the metal-based electrode layer, and color change due to the metal-based electrode layer are suppressed.
According to the method for producing a conductive laminate of the present invention, a conductive laminate that is transparent and excellent in conductivity can be produced.

"Conductive laminate"
One embodiment of the conductive laminate of the present invention will be described.
FIG. 1 shows a conductive laminate according to this embodiment. The conductive laminate 10 includes a transparent substrate 11, a metal electrode layer 12 formed on the transparent substrate 11, and a conductive polymer layer 13 formed on the metal electrode layer 12.

(Transparent substrate)
Examples of the transparent substrate 11 include inorganic substrates such as glass and quartz, and organic substrates such as a transparent resin film. A transparent resin film is preferable in terms of excellent flexibility and transparency. Examples of the resin constituting the transparent resin film include polyethylene terephthalate, polybutylene terephthalate, polystyrene, polyvinyl chloride, polycarbonate, and polyvinylidene fluoride. Among these, polyethylene terephthalate is more preferable from the viewpoint of excellent heat resistance, dimensional stability, and transparency.

  The thickness of the transparent substrate 11 is preferably 25 to 5000 μm, and more preferably 50 to 2500 μm. If the thickness of the transparent base material 11 is 25 μm or more, the handleability is improved, and the durability of the conductive laminate 10 is further increased if the thickness is 5000 μm or less.

(Metal electrode layer)
Examples of the material constituting the metal-based electrode layer 12 include metals such as gold, silver, copper, nickel, tin, and zinc, metal oxides such as tin oxide, zinc oxide, indium oxide, and titanium oxide, and these thin films or A laminate is used.
From these points, metal oxides such as indium oxide are preferred because they are superior in transparency and excellent in stability.

When the metal electrode layer 12 is made of metal, the thickness of the metal electrode layer 12 is 0.1 to 500 nm, and preferably 1 to 200 nm. If the thickness of the metal electrode layer 12 made of metal is 0.1 nm or more, the conductivity of the conductive laminate 10 can be sufficiently secured, and if it is 500 nm or less, the transparency of the metal electrode layer 12 is ensured. Can be secured.
When the metal electrode layer 12 is composed of a metal oxide, the thickness of the metal electrode layer 12 is preferably 0.1 to 500 nm, and more preferably 1 to 200 nm. If the thickness of the metal electrode layer 12 made of a metal oxide is 0.1 nm or more, the conductivity of the conductive laminate 10 can be sufficiently secured, and if it is 500 nm or less, the metal electrode layer 12 Transparency can be sufficiently secured.

(Conductive polymer layer)
The conductive polymer layer 13 was formed from a conductive polymer solution in which a conductive polymer mixed solution containing a π-conjugated conductive polymer, an acid-containing dopant and water was subjected to neutralization described later. Is a layer. That is, the conductive polymer layer 13 contains a π-conjugated conductive polymer and a neutralized product of a dopant composed of an acid as essential components. In addition, the conductive polymer layer 13 may contain a conductivity improver, other dopants, other resin components, additives, and the like as optional components.

[Π-conjugated conductive polymer]
The π-conjugated conductive polymer is not particularly limited as long as the main chain is an organic polymer composed of a π-conjugated system. For example, polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, Examples thereof include polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of stability in air, polypyrroles, polythiophenes and polyanilines are preferred.

  Specific examples of the π-conjugated 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-methyl) -4-hexyloxypyrrole), poly (thiophene), poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexyl) Thiophene), 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-dibutyl) Thiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3 -Ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3-methyl-4-methoxythiophene), poly (3,4-ethylenedioxythiophene), poly (3-methyl-4-ethoxy) Thiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene), polyaniline , Poly (2-methylaniline), poly (3-isobutyla) Phosphorus), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid), and the like.

  Even if the π-conjugated conductive polymer remains unsubstituted, sufficient conductivity and compatibility with the binder resin can be obtained, but in order to further improve conductivity and compatibility, an alkyl group, a carboxyl group, It is preferable to introduce a functional group such as a sulfo group, an alkoxyl group, or a hydroxyl group into the π-conjugated conductive polymer.

  The content of the π-conjugated conductive polymer in the conductive polymer layer 13 is preferably 0.5 to 90% by mass, and more preferably 1 to 80% by mass. If the content of the π-conjugated conductive polymer is 0.5% by mass or more, the conductivity can be further increased, and if it is 90% by mass or less, the conductive polymer layer 13 can be easily formed.

[Dopant]
Examples of the dopant made of an acid include a proton acid, a Lewis acid, an organic carboxylic acid, an organic sulfonic acid, and a polyanion.
Examples of the protonic acid include inorganic acids and organic acids. Furthermore, examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, borohydrofluoric acid, hydrofluoric acid, and perchloric acid. Moreover, organic carboxylic acid, organic sulfonic acid, etc. are mentioned as an organic acid.
Examples of the Lewis acid include PF ₅ , AsF ₅ , SbF ₅ , BF ₅ , BCl ₅ , BBr ₅ , SO _{3 and the} like.

  As the organic carboxylic acid, aliphatic, aromatic, cycloaliphatic or the like containing one or more carboxyl groups can be used. For example, formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, nitroacetic acid, And triphenylacetic acid.

  As the organic sulfonic acid, aliphatic, aromatic, cycloaliphatic or the like containing one or more sulfo groups can be used. Examples of those containing one sulfo group include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1-nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, 1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid, 2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoromethane Sulfonic acid, colistin methanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 2-amino-5-naphthol-7-sulfone Acid, 3-aminopropanesulfonic acid, N-cyclohexyl-3- Minopropanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzene Sulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, dipropylbenzenesulfone Acid, butylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, 4-amino-2-chlorotolue -5-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-amino-5-methoxy-2-methylbenzenesulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, 4 -Amino-2-methylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-acetamido-3-chlorobenzenesulfonic acid 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, 4-amino- 1-naphthalenesulfonic acid, 8-chloronaphthalene-1 Acid, naphthalenesulfonic acid-formalin polycondensate, a sulfonic acid compound containing a sulfo group such as melamine sulfonic acid-formalin polycondensates, and the like.

  Examples of those containing two or more sulfo groups include ethanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, decanedisulfonic acid, m-benzenedisulfonic acid, o-benzenedisulfonic acid, p-benzenedisulfonic acid, and toluenedisulfonic acid. Xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, dimethylbenzene disulfonic acid, diethylbenzene disulfonic acid, dibutylbenzene sulfonic acid, naphthalene disulfonic acid, Methyl naphthalene disulfonic acid, ethyl naphthalene disulfonic acid, dodecyl naphthalene disulfonic acid, pentadecyl naphthalene disulfonic acid, butyl naphthalene disulfonic acid, 2-amino-1,4-benze Disulfonic acid, 1-amino-3,8-naphthalenedisulfonic acid, 3-amino-1,5-naphthalenedisulfonic acid, 8-amino-1-naphthol-3,6-disulfonic acid, 4-amino-5-naphthol- 2,7-disulfonic acid, anthracene disulfonic acid, butylanthracene disulfonic acid, 4-acetamido-4'-isothio-cyanatostilbene-2,2'-disulfonic acid, 4-acetamido-4'-isothiocyanatostilbene-2 , 2'-disulfonic acid, 4-acetamido-4'-maleimidyl stilbene-2,2'-disulfonic acid, 1-acetoxypyrene-3,6,8-trisulfonic acid, 7-amino-1,3 6-naphthalene trisulfonic acid, 8-aminonaphthalene-1,3,6-trisulfonic acid, 3-amino-1,5,7-naphth Rent Li sulfonic acid and the like.

-Polyanion Polyanion includes, for example, substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted polyester, and anionic group And a polymer composed of a structural unit having only an anionic group and a structural unit having no anionic group.

A polyalkylene is a polymer whose main chain is composed of repeating methylenes.
Polyalkenylene is a polymer composed of structural units containing one unsaturated double bond (vinyl group) in the main chain.
As polyimide, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2 ′-[4,4′-di (dicarboxyphenyloxy) phenyl] propane dianhydride And polyimides from acid anhydrides such as oxydiamine, paraphenylenediamine, metaphenylenediamine, benzophenonediamine and the like.
Examples of the polyamide include polyamide 6, polyamide 6,6, polyamide 6,10 and the like.
Examples of the polyester include polyethylene terephthalate and polybutylene terephthalate.

  When the polyanion has a substituent, examples of the substituent include an alkyl group, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a phenyl group, a phenol group, an ester group, and an alkoxyl group. In view of solubility in organic solvents, heat resistance, compatibility with resins, and the like, alkyl groups, hydroxyl groups, phenol groups, and ester groups are preferred.

Examples of the alkyl group include alkyl groups such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, and dodecyl, and cycloalkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl. It is done.
Examples of the hydroxyl group include a hydroxyl group bonded to the main chain of the polyanion directly or via another functional group. Examples of the other functional group include an alkyl group having 1 to 7 carbon atoms and a carbon group having 2 to 7 carbon atoms. An alkenyl group, an amide group, an imide group, etc. are mentioned. Hydroxyl groups are substituted at the ends or in these functional groups.
Examples of the amino group include an amino group bonded to the main chain of the polyanion directly or via another functional group. Examples of the other functional group include an alkyl group having 1 to 7 carbon atoms and an alkyl group having 2 to 7 carbon atoms. An alkenyl group, an amide group, an imide group, etc. are mentioned. The amino group is substituted at the end or in these functional groups.
Examples of the phenol group include a phenol group bonded directly or via another functional group to the main chain of the polyanion. Examples of the other functional group include an alkyl group having 1 to 7 carbon atoms and an alkyl group having 2 to 7 carbon atoms. An alkenyl group, an amide group, an imide group, etc. are mentioned. The phenol group is substituted at the end or in these functional groups.

Examples of the polyalkylene having a substituent include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, poly (3,3,3-trifluoropropylene), polyacrylonitrile, polyacrylate, polystyrene and the like. it can.
Specific examples of polyalkenylene include propenylene, 1-methylpropenylene, 1-butylpropenylene, 1-decylpropenylene, 1-cyanopropenylene, 1-phenylpropenylene, 1-hydroxypropenylene, 1-butenylene, 1-methyl-1-butenylene, 1-ethyl-1-butenylene, 1-octyl-1-butenylene, 1-pentadecyl-1-butenylene, 2-methyl-1-butenylene, 2-ethyl-1-butenylene, 2- Butyl-1-butenylene, 2-hexyl-1-butenylene, 2-octyl-1-butenylene, 2-decyl-1-butenylene, 2-dodecyl-1-butenylene, 2-phenyl-1-butenylene, 2-butenylene, 1-methyl-2-butenylene, 1-ethyl-2-butenylene, 1-octyl-2-butenylene 1-pentadecyl-2-butenylene, 2-methyl-2-butenylene, 2-ethyl-2-butenylene, 2-butyl-2-butenylene, 2-hexyl-2-butenylene, 2-octyl-2-butenylene, 2- Decyl-2-butenylene, 2-dodecyl-2-butenylene, 2-phenyl-2-butenylene, 2-propylenephenyl-2-butenylene, 3-methyl-2-butenylene, 3-ethyl-2-butenylene, 3-butyl 2-butenylene, 3-hexyl-2-butenylene, 3-octyl-2-butenylene, 3-decyl-2-butenylene, 3-dodecyl-2-butenylene, 3-phenyl-2-butenylene, 3-propylenephenyl- 2-butenylene, 2-pentenylene, 4-propyl-2-pentenylene, 4-propyl-2-pentenylene, 4- Tyl-2-pentenylene, 4-hexyl-2-pentenylene, 4-cyano-2-pentenylene, 3-methyl-2-pentenylene, 4-ethyl-2-pentenylene, 3-phenyl-2-pentenylene, 4-hydroxy- Examples thereof include polymers containing one or more structural units selected from 2-pentenylene, hexenylene and the like.

Examples of the anion group of the _{^{polyanion, -O-SO 3 - X +}} , -SO 3 - X +, -COO - X + (. X + is the hydrogen ion in each of the formulas, represents an alkali metal ion), and the like.
That is, the polyanion is a polymer acid containing a sulfo group and / or a carboxyl group. Among these, from the viewpoint of doping effects on the π-conjugated conductive _{^{polymer, -SO 3 - X +, -COO}} - X + are preferable.
Moreover, it is preferable that this anion group is arrange | positioned in the principal chain of a polyanion adjacently or at fixed intervals.

  Among the polyanions, polyisoprene sulfonic acid, a copolymer containing polyisoprene sulfonic acid, a polysulfoethyl methacrylate, a copolymer containing polysulfoethyl methacrylate, and poly (4-sulfone) are preferable in view of solvent solubility and conductivity. Butyl methacrylate), copolymers containing poly (4-sulfobutyl methacrylate), polymethallyloxybenzene sulfonic acid, copolymers containing polymethallyloxybenzene sulfonic acid, polystyrene sulfonic acid, copolymer containing polystyrene sulfonic acid A coalescence or the like is preferable.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

The content of the dopant is preferably in the range of 0.1 to 10 mol, and more preferably in the range of 1 to 7 mol, with respect to 1 mol of the π-conjugated conductive polymer. When the content of the dopant is less than 0.1 mol, the doping effect on the π-conjugated conductive polymer tends to be weak, and the conductivity may be insufficient. On the other hand, when the dopant content is more than 10 mol, the content of the π-conjugated conductive polymer is reduced, and it is difficult to obtain sufficient conductivity.
In particular, when the dopant is a polyanion, the content of the polyanion is preferably in the range of 0.1 to 10 mol, and in the range of 1 to 7 mol, with respect to 1 mol of the π-conjugated conductive polymer. It is more preferable. When the polyanion content is less than 0.1 mol, the doping effect on the π-conjugated conductive polymer tends to be weak, and the conductivity may be insufficient. In addition, the dispersibility and solubility in the solvent are reduced, making it difficult to obtain a uniform dispersion. On the other hand, when the polyanion content is more than 10 mol, the content of the π-conjugated conductive polymer is decreased, and it is difficult to obtain sufficient conductivity.

[Conductivity improver]
The conductivity improver interacts with the π-conjugated conductive polymer or the dopant of the π-conjugated conductive polymer to further improve the conductivity of the π-conjugated conductive polymer.
Examples of the conductivity improver include, for example, a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxyl groups, a compound having two or more carboxyl groups, one or more hydroxyl groups, and one or more carboxyls. Examples thereof include a compound having a group, a compound having an amide group, a compound having an imide group, a lactam compound, and a compound having a glycidyl group.

-Nitrogen-containing aromatic cyclic compound Examples of the nitrogen-containing aromatic cyclic compound include pyridine and derivatives thereof, imidazole and derivatives thereof, pyrimidine and derivatives thereof, pyrazine and derivatives thereof, triazine and derivatives thereof, and the like.

  Specific examples of pyridine derivatives include 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, and 3-cyano-5. -Methylpyridine, 2-pyridinecarboxylic acid, 6-methyl-2-pyridinecarboxylic acid, 2,6-pyridine-dicarboxylic acid, 4-pyridinecarboxaldehyde, 4-aminopyridine, 2,3-diaminopyridine, 2,6 -Diaminopyridine, 2,6-diamino-4-methylpyridine, 4-hydroxypyridine, 2,6-dihydroxypyridine, methyl 6-hydroxynicotinate, 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-pyridinecarbonitrile, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridine Examples thereof include dicarboxylic acid and 3-pyridinesulfonic acid.

  Specific examples of imidazole derivatives include 2-methylimidazole, 2-propylimidazole, 2-undecylimidazole, 2-phenylimidazole, N-methylimidazole, 1- (2-hydroxyethyl) imidazole, 2-ethyl-4. -Methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 4,5-imidazole dicarboxylic acid, dimethyl 4,5-imidazole dicarboxylate, benzimidazole, 2-aminobenzimidazole, 2-aminobenzene 'S imidazol-2-sulfonic acid, 2-amino-1-methyl-base lens imidazole, 2-hydroxy-base lens imidazole, 2- (2-pyridyl) base lens and imidazole.

  Specific examples of derivatives of pyrimidine 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, Examples include 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,4,6-triaminopyrimidine, 2,4-dimethoxypyrimidine, 2,4,5-trihydroxypyrimidine, 2,4-pyrimidinediol and the like.

  Specific examples of pyrazine derivatives include 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-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, 2,3-diethylpyrazine, etc. Can be mentioned.

  Specific examples of the derivatives of triazine include 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, 2,4,6-tri-2-pyridine- 1,3,5-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 salt, 2-hydroxy-4,6 -Dichloro-1,3,5-triazine and the like The

-Compound having two or more hydroxyl groups Examples of the compound having two or more hydroxyl groups include propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, diglycerin, D-glucose, D-glucitol, isoprene glycol, dimethylolpropionic acid, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol Polyhydric aliphatic alcohols such as dipentaerythritol, thiodiethanol, glucose, tartaric acid, D-glucaric acid, glutaconic acid;
Polymer alcohols such as polyvinyl alcohol, cellulose, polysaccharides, 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'-dihydroxydiphenylsulfone, hydroxyquinonecarboxylic acid and its salts, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6- Dihydroxybenzoic acid, 3,5-di Droxybenzoic acid, 1,4-hydroquinonesulfonic 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-dihydroxynaphthalene-2,6-dicarboxylic acid, 1,6-dihydroxynaphthalene-2,5-dicarboxylic acid, 1,5-dihydroxy Naphthoic 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 1,2,3-trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene, 5-methyl-1,2,3-trihydroxybenzene, 5-ethyl-1,2,3-tri Hydroxybenzene, 5-propyl-1,2,3-trihydroxybenzene, trihydroxybenzoic acid, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzaldehyde, trihydroxyanthraquinone, 2,4,6-trihydroxybenzene, tetra Aromatic compounds such as hydroxy-p-benzoquinone, tetrahydroxyanthraquinone, methyl garlic acid (methyl gallate), ethyl garlic acid (ethyl gallate), potassium hydroquinone sulfonate, and the like.

・ Compounds having two or more carboxyl groups As compounds having two or more carboxyl groups, maleic acid, fumaric acid, itaconic acid, citraconic acid, malonic acid, 1,4-butanedicarboxylic acid, succinic acid, tartaric acid, Aliphatic carboxylic acid compounds such as adipic acid, D-glucaric acid, glutaconic acid and citric acid;
Phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride, 5-sulfoisophthalic acid, 5-hydroxyisophthalic acid, methyltetrahydrophthalic anhydride, 4,4'-oxydiphthalic acid, biphenyltetracarboxylic dianhydride, benzophenone tetra Aromatic carboxylic acid compounds in which at least one carboxyl group is bonded to an aromatic ring, such as carboxylic dianhydride, naphthalene dicarboxylic acid, trimellitic acid, pyromellitic acid; diglycolic acid, oxydipropion Examples include acids, thiodiacetic acid (thiodiacetic acid), thiodipropionic acid, iminodiacetic acid, and iminobutyric acid.

・ Compounds having one or more hydroxyl groups and one or more carboxyl groups As compounds having one or more hydroxyl groups and one or more carboxyl groups, tartaric acid, glyceric acid, dimethylolbutanoic acid, dimethylolpropanoic acid , D-glucaric acid, glutaconic acid and the like.

Amide Compound A compound having an amide group is a monomolecular compound having an amide bond represented by —CO—NH— (the CO moiety is a double bond) in the molecule. That is, as the amide compound, for example, a compound having functional groups at both ends of the bond, a compound in which a cyclic compound is bonded to one end of the bond, urea and urea derivatives in which the functional groups at both ends are hydrogen Etc.
Specific examples of the amide compound include acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-fluamide, formamide, N-methylformamide, propionamide , Propioluamide, butyramide, isobutylamide, methacrylamide, palmitoamide, stearylamide, oleamide, oxamide, glutaramide, adipamide, cinnamamide, glycolamide, lactamide, glyceramide, tartaramide, citrulamide, glyoxylamide, plubuamide, acetoacetamide, Dimethylacetamide, benzylamide, anthranilamide, ethylenediamine Laacetamide, diacetamide, triacetamide, dibenzamide, tribenzamide, rhodanine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea, 1,3-dimethylurea, 1,3-diethylurea and These derivatives are mentioned.

  Moreover, acrylamide can also be used as an amide compound. As acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethyl methacrylamide, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like can be mentioned.

  The molecular weight of the amide compound is preferably 46 to 10,000, more preferably 46 to 5,000, and particularly preferably 46 to 1,000.

-Imide compound As an amide compound, since electroconductivity becomes higher, the monomolecular compound (henceforth an imide compound) which has an imide bond is preferable. Examples of the imide compound include phthalimide and phthalimide derivatives, succinimide and succinimide derivatives, benzimide and benzimide derivatives, maleimide and maleimide derivatives, naphthalimide and naphthalimide derivatives from the skeleton.

Moreover, although an imide compound is classified into an aliphatic imide, an aromatic imide, etc. by the kind of functional group of both terminal, an aliphatic imide is preferable from a soluble viewpoint.
Furthermore, the aliphatic imide compound is classified into a saturated aliphatic imide compound having an unsaturated bond between carbons in the molecule and an unsaturated aliphatic imide compound having an unsaturated bond between carbons in the molecule.
The saturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and is a compound in which both R ¹ and R ² are saturated hydrocarbons. Specifically, cyclohexane-1,2-dicarboximide, allantoin, hydantoin, barbituric acid, alloxan, glutarimide, succinimide, 5-butylhydantoic acid, 5,5-dimethylhydantoin, 1-methylhydantoin, 1,5 , 5-trimethylhydantoin, 5-hydantoin acetic acid, N-hydroxy-5-norbornene-2,3-dicarboximide, glutarimide, semicarbazide, α, α-dimethyl-6-methylsuccinimide, bis [2- (succinimideoxy) Carbonyloxy) ethyl] sulfone, α-methyl-α-propylsuccinimide, cyclohexylimide and the like.
The unsaturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and one or both of R ¹ and R ² are one or more unsaturated bonds. Specific examples are 1,3-dipropylene urea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, 1,8-bis. Maleimide octane, N-carboxyheptylmaleimide and the like can be mentioned.

  The molecular weight of the imide compound is preferably 60 to 5,000, more preferably 70 to 1,000, and particularly preferably 80 to 500.

-Lactam compound A lactam compound is an intramolecular cyclic amide of aminocarboxylic acid, and a part of the ring is -CO-NR- (R is hydrogen or an arbitrary substituent). However, one or more carbon atoms in the ring may be replaced with an unsaturated or heteroatom.
Examples of the lactam compound include pentano-4-lactam, 4-pentanelactam-5-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidinone, hexano-6-lactam, 6-hexane lactam and the like.

-Compound having glycidyl group Examples of the compound having glycidyl group include ethyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl phenyl ether, bisphenol A, diglycidyl ether, acrylic Examples thereof include glycidyl compounds such as acid glycidyl ether and methacrylic acid glycidyl ether.

The content of the conductivity improver in the conductive polymer layer 13 is preferably 1 to 10,000 parts by mass with respect to 100 parts by mass in total of the π-conjugated conductive polymer and the dopant, and 50 to More preferably, it is 5,000 parts by mass.
If the content of the conductivity improver is less than the lower limit, the effect of the conductivity improver tends to be low and the conductivity tends to be low. If the content exceeds the upper limit, the π-conjugated conductive polymer concentration There is a tendency for the conductivity to decrease due to the decrease in.

[Other dopants]
The other dopant may be either a donor dopant or an acceptor dopant.

Donor-type dopants Examples of donor-type dopants include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, and dimethyl. And quaternary amine salt compounds such as diethylammonium.

-Acceptor dopant As an acceptor dopant, a halogen compound, a Lewis acid, a proton acid, an organic cyano compound, an organometallic compound etc. can be used, for example.
Furthermore, examples of the halogen compound include chlorine (Cl ₂ ), bromine (Br ₂ ), iodine (I ₂ ), iodine chloride (ICl), iodine bromide (IBr), and iodine fluoride (IF). .
As the organic cyano compound, a compound containing two or more cyano groups in a conjugated bond can be used. For example, tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, tetracyanoquinodimethane, tetracyanoazanaphthalene, and the like can be given.

[Other resin components]
In order to ensure sufficient film formability and film strength of the conductive polymer layer 13, it is preferable to contain other resin components.
The other resin component is not particularly limited as long as it is compatible or mixed and dispersible with the π-conjugated conductive polymer and the polyanion, and may be a thermosetting resin or a thermoplastic resin. . For example, polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyimides such as polyimide and polyamideimide, polyamides such as polyamide 6, polyamide 6,6, polyamide 12 and polyamide 11, polyvinylidene fluoride, polyvinyl fluoride, poly Fluorine resin such as tetrafluoroethylene, ethylenetetrafluoroethylene copolymer, polychlorotrifluoroethylene, polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, vinyl resin such as polyvinyl chloride, epoxy resin, xylene resin, aramid resin, Examples include polyurethane, polyurea, melamine resin, phenolic resin, polyether, acrylic resin, and copolymers thereof.

  When the other resin component is contained, the content of the other resin component in the conductive polymer layer 13 is preferably 0.1 to 98% by mass, and more preferably 1 to 90% by mass. If the content of the other resin component is 1% by mass or more, the film formability and film strength can be further increased, and if it is 90% by mass or less, the decrease in conductivity can be prevented.

[Additive]
The additive is not particularly limited as long as it can be mixed with the π-conjugated conductive polymer, and for example, a surfactant, an antifoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber and the like can be used.
Surfactants include anionic surfactants such as carboxylates, sulfonates, sulfates and phosphates; cationic surfactants such as amine salts and quaternary ammonium salts; carboxybetaines and aminocarboxylics Examples include amphoteric surfactants such as acid salts and imidazolium betaines; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, ethylene glycol fatty acid esters, and polyoxyethylene fatty acid amides.
Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone resin.
Examples of the coupling agent include silane coupling agents having a vinyl group, an amino group, an epoxy group, and the like.
Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, saccharides, vitamins and the like.
Examples of UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, and benzoate UV absorbers. Is mentioned.
It is preferable to use an antioxidant and an ultraviolet absorber in combination.

  When the additive is contained, the content of the additive in the conductive polymer layer 13 is preferably 0.1 to 90% by mass, and more preferably 0.5 to 80% by mass. When the content of the additive is 0.1% by mass or more, the effect of the additive can be sufficiently exerted, and when it is 90% by mass or less, a decrease in conductivity can be prevented.

In the conductive polymer layer 13 of the conductive laminate 10 described above, the acid dopant is low because the acid dopant is neutralized. Therefore, since the deterioration of the metal electrode layer 12 can be prevented, the conductive laminate 10 is excellent in conductivity. In addition, the conductive laminate 10 including the transparent base material 11, the metal-based electrode layer 12, and the conductive polymer layer 13 described above is transparent.
In addition, since the conductive laminate 10 is formed by laminating the metal electrode layer 12 and the conductive polymer layer 13, the conductivity lowers when the metal electrode layer 12 is cracked, and the metal electrode layer 12. And the color tone change due to the metal-based electrode layer 12 is suppressed.
Such a conductive laminate 10 can be suitably used for a coordinate input device such as a touch panel, an image display device such as an inorganic electroluminescence display and electronic paper, a dye-sensitized solar cell, and the like.

"Method for producing conductive laminate"
One embodiment of the method for producing a conductive laminate of the present invention will be described.
The method for producing a conductive laminate according to this embodiment includes a step of forming a metal electrode layer 12 on one side of the transparent substrate 11 (hereinafter referred to as a first step) and a surface of the metal electrode layer 12. And a step of forming a conductive polymer layer 13 by applying a conductive polymer solution (hereinafter referred to as a second step).

<First step>
Examples of the method for forming the metal electrode layer 12 on the transparent substrate 11 in the first step include an electron beam evaporation method, a sputtering method, a plasma CVD method, and the like.

<Second step>
The conductive polymer solution used in the second step is a solution obtained by neutralizing a conductive polymer mixed solution containing a π-conjugated conductive polymer, an acid dopant and water as essential components. is there. The conductive polymer solution may contain a conductivity improver, other dopants, other resin components, additives, and the like as optional components.

  As the neutralization treatment for neutralizing the conductive polymer mixed solution, for example, a treatment for adding a neutralizing agent, a treatment for esterifying the acid group of the dopant, a treatment for amidating the acid group of the dopant, or the like is applied. Can do. Among these, a treatment for adding a neutralizing agent is preferable because neutralization can be easily performed.

As the neutralizing agent used in the treatment for adding the neutralizing agent, known inorganic alkali compounds and organic alkali compounds can be used. Examples of the inorganic alkali compound include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia and the like.
Examples of the organic alkali compound include aliphatic amines, aromatic amines, quaternary amines, nitrogen-containing compounds other than amines, metal alkoxides, and dimethyl sulfoxide. Among these, one or two or more selected from the group consisting of aliphatic amines, aromatic amines, and quaternary amines are preferable because of higher conductivity.

Examples of the aliphatic amine include ethylamine, propylamine, butylamine, hexylamine, octylamine, stearylamine, diethylamine, dipropylamine, dibutylamine, dioctylamine, methylethylamine, triethylamine, tripropylamine, and tributylamine. It is done.
Examples of the aromatic amine include aniline, benzylamine, pyrrole, pyridine and derivatives thereof, imidazole and derivatives thereof, pyrimidine and derivatives thereof, pyrazine and derivatives thereof, triazine and derivatives thereof, and the like. Of these, pyridine and derivatives thereof, imidazole and derivatives thereof, pyrimidine and derivatives thereof, pyrazine and derivatives thereof, triazine and derivatives thereof also function as conductivity improvers.
Examples of the quaternary amine include tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, and tetraoctylammonium hydroxide.
Examples of nitrogen-containing compounds other than amines include N-methyl-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylene phosphortriamide, N-vinylpyrrolidone, N-vinylformamide, and N-vinyl. Examples include acetamide.
Examples of the metal alkoxide include sodium alkoxide such as sodium methoxide and sodium ethoxide, potassium alkoxide, calcium alkoxide and the like.

  Although the addition time at the time of adding a neutralizing agent is not restrict | limited, it is preferable to add a neutralizing agent last among all the components which comprise a conductive polymer solution at the point which can neutralize with high precision. In terms of simplifying the addition operation, it is preferable to add the neutralizing agent and other components simultaneously.

  It is more preferable that the pH (measured at 25 ° C.) of the conductive polymer solution is 4 to 10 and 5 to 9 by the neutralization treatment. If the pH is less than 4, the acidity is too strong, and the deterioration of the metal electrode layer 12 may not be prevented. If it exceeds 10, the formation of the coating becomes difficult or the coating is formed. However, the electrical conductivity may decrease.

  The solid content concentration of the conductive polymer solution is preferably 0.1 to 80% by mass, and more preferably 1 to 50% by mass. If the solid content concentration is 0.1% by mass or more, a uniform conductive polymer layer can be easily formed, and if it is 80% by mass or less, a sufficient coating thickness can be ensured by a single application. .

  Examples of the method for applying the conductive polymer solution include a screen printing method, a flow coating method, a gravure coating method, a comma coating method, and a spin coating method.

  In the manufacturing method described above, since the conductive polymer layer 13 is formed by applying the neutralized conductive polymer solution on the metal electrode layer 12, the acidity of the conductive polymer layer 13 is increased. Can be lowered. Therefore, according to this manufacturing method, it is possible to prevent the conductive polymer layer 13 from deteriorating the metal electrode layer 12 and to manufacture the conductive laminate 10 having high conductivity.

  Note that the present invention is not limited to the above-described embodiments. For example, in the embodiment described above, the metal electrode layer is formed only on one side of the transparent substrate, but the metal electrode layer may be formed on both surfaces of the transparent substrate.

Examples of the present invention will be specifically described below, but the present invention is not limited to the examples.
(Production Example 1) Preparation of polystyrene sulfonic acid 206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water was stirred at 80 ° C. The solution was added dropwise for 20 minutes, and the solution was stirred for 2 hours.
1000 ml and 10,000 ml of ion-exchanged water diluted with 10% by mass of sulfuric acid diluted to 10% by mass were added to the sodium styrenesulfonate-containing solution thus obtained, and about 10,000 ml of the polystyrenesulfonic acid-containing solution was removed using an ultrafiltration method. Then, 10,000 ml of ion-exchanged water was added to the remaining liquid, and about 10,000 ml of solution was removed using an ultrafiltration method. The above ultrafiltration operation was repeated three times.
Furthermore, about 10,000 ml of ion-exchanged water was added to the obtained filtrate, and about 10,000 ml of solution was removed using an ultrafiltration method. This ultrafiltration operation was repeated three times.
The ultrafiltration conditions were as follows (the same applies to other examples).
Molecular weight cut off of ultrafiltration membrane: 30K
Cross flow type Supply liquid flow rate: 3000 ml / min Membrane partial pressure: 0.12 Pa
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

(Production Example 2) Preparation of Polystyrenesulfonic Acid Doped Poly (3,4-ethylenedioxythiophene) Aqueous Solution 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrenesulfonic acid obtained in Production Example 1 A solution dissolved in 2000 ml of ion-exchanged water was mixed at 20 ° C.
While maintaining the mixed solution thus obtained at 20 ° C. and stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion exchange water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added, The reaction was stirred for 3 hours.
2000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2000 ml of solution was removed using an ultrafiltration method. This operation was repeated three times.
Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water are added to the treatment liquid that has been subjected to the filtration treatment, and about 2000 ml of the treatment liquid is removed using an ultrafiltration method. Ion exchange water was added and about 2000 ml of liquid was removed using ultrafiltration. This operation was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the obtained treatment liquid, and about 2000 ml of the treatment liquid was removed using an ultrafiltration method. This operation was repeated 5 times to obtain about 1.5% by mass of blue polystyrenesulfonic acid doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS) as a conductive polymer mixture.

(Example 1)
To 100 g of the aqueous PEDOT-PSS solution obtained in Production Example 2, 1.2 g (2 molar equivalents relative to polystyrene sulfonic acid) of imidazole and 3.7 g (5 molar equivalents relative to polystyrene sulfonic acid) of N-hydroxyethyl Acrylamide, 0.1 g of Irgacure 1173 (manufactured by Ciba Specialty Chemicals) and 50 g of ethanol were added and mixed uniformly to obtain a conductive polymer solution. The pH of this conductive polymer solution was measured with a pH meter D-52 manufactured by Horiba, Ltd. The results are shown in Table 1.
The conductive polymer solution was made from an ITO vapor-deposited glass in which a metal electrode layer made of ITO was formed on a glass transparent substrate (manufactured by Sanyo Vacuum Industries, Ltd., surface resistance 250Ω, total light transmittance 88%, haze 1 8%) was applied with a flow coater, heated and dried in an oven at 100 ° C. for 2 minutes, and then irradiated with ultraviolet rays (high pressure mercury lamp 100 W, 200 mJ / cm ² ).
The obtained conductive laminate was evaluated by the following evaluation methods. The results are shown in Table 1.

・ Surface resistivity (conductivity)
The surface resistivity of the conductive laminate was measured with a Loresta (Mitsubishi Chemical).
-Evaluation of total light transmittance The total light transmittance was measured based on JISK7361-1.
-Evaluation of haze Haze was measured based on JISK7136.

(Production Example 2)
To 100 g of the PEDOT-PSS aqueous solution obtained in Production Example 2, 1.7 g (2 molar equivalents relative to polystyrene sulfonic acid) of vinylimidazole and 1.5 g (2 molar equivalents relative to polystyrene sulfonic acid) of glycidyl methacrylate. Ether, 2.9 g (3 molar equivalents relative to polystyrene sulfonic acid) acryloylformoline, 2.3 g (2 molar equivalents relative to polystyrene sulfonic acid) thiodipropionic acid, and 0.1 g Irgacure 1173 (Ciba Specialty Chemicals) and 50 g of ethanol were added and mixed uniformly to obtain a conductive polymer solution. The pH of this conductive polymer solution was measured in the same manner as in Example 1. Moreover, it carried out similarly to Example 1, and manufactured and evaluated the electrically conductive laminated body. The evaluation results are shown in Table 1.

(Example 3)
To 100 g of the PEDOT-PSS aqueous solution obtained in Production Example 2, 0.9 g (1.1 molar equivalents relative to polystyrene sulfonic acid) of triethylamine and 3.0 g of an acrylic copolymer (butyl acrylate: hydroxy methacrylate) Ethyl: styrene = 62: 10: 28 (mass ratio)), 4.6 g (4 molar equivalents relative to polystyrene sulfonic acid) of thiodipropionic acid and 50 g of ethanol were added and mixed uniformly. A conductive polymer solution was obtained. The pH of this conductive polymer solution was measured in the same manner as in Example 1. Moreover, it carried out similarly to Example 1, and manufactured and evaluated the electrically conductive laminated body. The evaluation results are shown in Table 1.

Example 4
Example 3 except that 1.5 g (1.1 molar equivalents relative to polystyrene sulfonic acid) of tetraethylammonium hydroxide was added to the PEDOT-PSS aqueous solution obtained in Production Example 2 instead of 0.9 g of triethylamine. In the same manner, a conductive polymer solution was obtained. The pH of this conductive polymer solution was measured in the same manner as in Example 1. Moreover, it carried out similarly to Example 1, and manufactured and evaluated the electrically conductive laminated body. The evaluation results are shown in Table 1.

(Comparative Example 1)
A conductive polymer solution was obtained in the same manner as in Example 1 except that the amount of imidazole added was 12 g (20 molar equivalents relative to polystyrene sulfonic acid). The pH of this conductive polymer solution was measured in the same manner as in Example 1.
Since this conductive polymer solution had poor dispersion and was difficult to apply, it could not be evaluated as a conductive laminate.

(Comparative Example 2)
A conductive polymer solution was obtained in the same manner as in Example 2 except that vinylimidazole was not added. The pH of this conductive polymer solution was measured in the same manner as in Example 1. Moreover, it carried out similarly to Example 1, and manufactured and evaluated the electrically conductive laminated body. The evaluation results are shown in Table 1.

(Comparative Example 3)
A conductive polymer solution was obtained in the same manner as in Example 3 except that the amount of triethylamine added was 8 g (10 molar equivalents relative to polystyrene sulfonic acid). The pH of this conductive polymer solution was measured in the same manner as in Example 1.
Since this conductive polymer solution had poor dispersion and was difficult to apply, it could not be evaluated as a conductive laminate.

(Comparative Example 4)
A conductive polymer solution was obtained in the same manner as in Example 4 except that tetraethylammonium hydroxide was not added. The pH of this conductive polymer solution was measured in the same manner as in Example 1. Moreover, it carried out similarly to Example 1, and manufactured and evaluated the electrically conductive laminated body. The evaluation results are shown in Table 1.

The conductive laminates of Examples 1 to 4 obtained using a conductive polymer solution that was neutralized and had a pH in the range of 4 to 10 were excellent in conductivity.
On the other hand, although the neutralization process was performed, in Comparative Examples 1 and 3 using the conductive polymer solution whose pH exceeded 10, it was difficult to produce the conductive laminate.
In Comparative Examples 2 and 4 using the conductive polymer solution that was not neutralized and had a pH of less than 4, the conductivity of the conductive laminate was low because the metal-based electrode layer was deteriorated. .

(Example 5)
A conductive polymer solution similar to that in Example 1 was placed on an ITO-deposited polyethylene terephthalate (PET) film (manufactured by Sanyo Vacuum Industry Co., Ltd., surface resistance 30Ω, total light transmittance 86%). This was coated with a 12 bar coater, heated and dried in an oven at 100 ° C. for 2 minutes, and then irradiated with ultraviolet rays (high pressure mercury lamp 100 W, 200 mJ / cm ² ).
About the obtained electroconductive laminate, the flexibility was evaluated by measuring the surface resistance after repeating the operation of wrapping around an iron rod having a diameter of 7 mm 20 times so that the conductive surface was on the outside. The results are shown in Table 2. An ITO-deposited polyethylene terephthalate film was used as a comparative control.

  The conductive laminate of Example 5 had almost no change in surface resistance even after being bent, and was excellent in flexibility. On the other hand, when the ITO-deposited polyethylene terephthalate film was bent, the surface resistance increased and the conductivity was impaired.

It is sectional drawing which shows one embodiment of the electroconductive laminated body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Conductive laminated body 11 Transparent base material 12 Metal-type electrode layer 13 Conductive polymer layer

Claims (5)

A transparent substrate, a metal electrode layer formed on at least one surface of the transparent substrate, and a conductive polymer layer formed on the surface of the metal electrode layer,
The conductive polymer layer is formed from a conductive polymer solution having a pH of 4 to 10 obtained by neutralizing a conductive polymer mixed solution containing a π-conjugated conductive polymer, an acid dopant and water. A conductive laminate, characterized by being a layer.   The conductive laminate according to claim 1, wherein the dopant is a polyanion. A step of forming a metal electrode layer on a transparent substrate, and a step of forming a conductive polymer layer by applying a conductive polymer solution on the metal electrode layer,
As the conductive polymer solution, a pH 4 to 10 solution obtained by neutralizing a conductive polymer mixed solution containing a π-conjugated conductive polymer, an acid dopant and water is used. A method for producing a conductive laminate.   4. The conductive material according to claim 3, wherein the neutralizing treatment is a treatment of adding one or more neutralizing agents selected from the group consisting of aliphatic amines, aromatic amines, and quaternary amines. Laminate.   The method for producing a conductive laminate according to claim 3 or 4, wherein the dopant is a polyanion.

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