JP5581084B2 - Transparent conductor, method for manufacturing the same, and input device - Google Patents

Description

 The present invention relates to a transparent conductor that can be used for a transparent electrode and the like, a manufacturing method thereof, and an input device including the transparent conductor.

Electronic devices such as digital cameras, mobile phones, camcorders, PDAs (Personal Digital Assistants), and electronic papers are equipped with input devices, such as keyboards, input means such as JOG dials, and touch panels. Has been.
As a touch panel, a capacitance method and a resistance film method are generally widely used.
In the capacitive touch panel, a capacitance sheet is provided under the input operation surface, and the input position where the finger is touched is detected on the input operation surface, and the finger is touched and the finger is not touched. (Non-contact) is discriminated.
In the resistive touch panel, a resistance adjustment film is provided under the input operation surface. The input position on the input operation surface is detected by touching the finger, and the finger is touched and the finger is not touched (not touched). Contact).
Usually, a conductive film is used for the capacitance sheet and the resistance adjustment film. As the conductive film, transparent conductive oxide (TCO) films such as indium tin oxide (ITO), antimony tin oxide (ATO), and zinc oxide (ZnO) have been used in many cases.

  By the way, in the electrostatic capacitance sheet used for the capacitive touch panel, as shown in Table 1, a higher surface resistance is required than in other applications.

Therefore, when the TCO film is used for the capacitance sheet, the TCO film is made thin in order to increase the surface resistance. Even when the surface resistance of the ITO film is 20Ω, the thickness must be about 500 nm, and in order to be 350-400Ω, the thickness needs to be about 35-30 nm. Therefore, in order to obtain a surface resistance of 1000Ω or more, it must be further reduced, but in general, when the film is made thinner, uniformity, durability (water resistance, ethanol resistance, scratch resistance) and physical continuity are obtained. Tend to decrease.
ATO can obtain a higher surface resistance value with a film thickness thicker than that of ITO. For example, the surface resistance of an ATO film having a thickness of 25 to 30 nm is about 2000Ω. However, the ATO film has a problem that it is less transparent than the ITO film.
For these reasons, a conductive film excellent in durability (water resistance, ethanol resistance, scratch resistance), conductivity, and transparency has been demanded. Furthermore, the conductive film is required to have excellent adhesion to a transparent substrate such as glass or plastics.
In response to these requirements, Patent Document 1 proposes forming a conductive film using a conductive paint containing a π-conjugated conductive polymer and a water-soluble epoxy monomer.

JP 2005-146259 A

However, although the electrically conductive film described in Patent Document 1 is excellent in water resistance, ethanol resistance is not sufficient. Moreover, since the scratch resistance of the conductive film is low, the surface is scratched in the touch panel manufacturing process and the like, which has been a factor of greatly reducing the product rate.
The present invention has been made in view of the above problems, and provides a conductive film that is excellent in durability (water resistance, ethanol resistance, scratch resistance), conductivity, transparency, and adhesion to a transparent substrate. It is an object to provide a transparent conductor having the same and a method for producing the same. Moreover, it aims at providing the input device provided with such a transparent conductor.

The present invention has the following configuration.
[1] A transparent substrate, and a conductive film provided on at least one surface of the transparent substrate, wherein the conductive film is a fluorine-containing conductive polymer, a polyanion, and at least part of hydrogen atoms of the epoxy compound is fluorine. A transparent conductor comprising a cured product of a conductive composition containing a fluorine-containing epoxy compound represented by the following general formula substituted with an atom.
_{Gu- (OCH 2) p - {} X} - (CH 2 O) p -Gu
(Gu represents a glycidyl group. X is at least one of (CF ₂ ) _l and (CF ₂ —O—CF ₂ ) _m. P is 0 to 1, l is 1 to 8, m is 1 to 8. is there.)
[2] The transparent conductor according to [1], wherein the fluorine-containing epoxy compound is a linear compound having two epoxy groups and an ether bond.
[3] The transparent conductor according to [1] or [2], wherein the conductive composition contains one or both of an oxetane compound and an epoxy compound other than the fluorine-containing epoxy compound .
[4] A fluorine-containing epoxy compound represented by the following general formula in which at least one surface of the transparent substrate is substituted with a π-conjugated conductive polymer, a polyanion, and at least a part of hydrogen atoms of the epoxy compound are substituted with fluorine atoms; A method for producing a transparent conductor, wherein a conductive paint containing a solvent is applied and cured.
_{Gu- (OCH 2) p - {} X} - (CH 2 O) p -Gu
(Gu represents a glycidyl group. X is at least one of (CF ₂ ) _l and (CF ₂ —O—CF ₂ ) _m. P is 0 to 1, l is 1 to 8, m is 1 to 8. is there.)
[5] The method for producing a transparent conductor according to [4], wherein the fluorine-containing epoxy compound is a linear compound having two epoxy groups and an ether bond.
[6] The method for producing a transparent conductor according to [4] or [5], wherein the conductive paint contains one or both of an oxetane compound and an epoxy compound other than the fluorine-containing epoxy compound .
[7] An input device comprising the transparent conductor according to any one of [1] to [3].

The transparent conductor of the present invention has a conductive film that is excellent in durability (water resistance, ethanol resistance, scratch resistance), conductivity, transparency, and adhesion to a transparent substrate.
According to the method for producing a transparent conductor of the present invention, it is possible to produce a transparent conductor having a conductive film that is excellent in durability, conductivity, and transparency and excellent in adhesion to a transparent substrate.
The input device of the present invention has a conductive film that is excellent in durability, conductivity, and transparency, and also has excellent adhesion to a transparent substrate.

It is sectional drawing which shows an example of the input device of this invention.

"Transparent conductor"
The transparent conductor of the present invention has a transparent substrate and a conductive film provided on at least one surface of the transparent substrate.

<Transparent substrate>
Examples of the transparent substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, and cellulose acetate propionate. A film or sheet may be mentioned. Moreover, glass etc. can also be used.

<Conductive film>
The conductive film contains a π-conjugated conductive polymer, a polyanion, and a fluorine-containing epoxy compound as essential components, and from a cured product of a conductive composition containing a binder, a conductivity improver, an additive, and the like as optional components. Become.

(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. From the viewpoint of compatibility with a polar solvent and transparency, a polythiophene system is more preferable.

  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 can be obtained. However, in order to further increase the conductivity, an alkyl group, a carboxy group, a sulfo group, an alkoxy group, a hydroxy group, etc. A functional group may be introduced into the π-conjugated conductive polymer.
Among the π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is preferable from the viewpoint of conductivity, transparency, and heat resistance.

(Polyanion)
Examples of the polyanion include a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, and a substituted or unsubstituted polyester having an anionic group. Examples thereof include a polymer composed only of a structural unit, and a polymer composed of a structural unit having an anionic group and a structural unit not having an anionic group.
Note that the polyanion also functions as a dopant for the π-conjugated conductive polymer.

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 hydroxy group, an amino group, a carboxy group, a cyano group, a phenyl group, a phenol group, an ester group, and an alkoxy group. In view of solubility in a solvent, heat resistance and the like, an alkyl group, a hydroxy group, a phenol group, and an ester group are preferable.

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 hydroxy group include a hydroxy 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. Hydroxy 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, polyacrylonitrile, polyacrylate, polystyrene and the like.
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 carboxy 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 polyanion is coordinated to the π-conjugated conductive polymer. Therefore, the π-conjugated conductive polymer and the polyanion form a complex. The total content of the π-conjugated conductive polymer and the polyanion in the conductive polymer solution is preferably 0.05 to 5.0% by mass, and preferably 0.1 to 4.0% by mass. More preferred. When the total content of the π-conjugated conductive polymer and the polyanion is less than 0.05% by mass, sufficient conductivity may not be obtained. When the total content exceeds 5.0% by mass, a uniform conductive film is formed. It may not be obtained.

(Fluorine-containing epoxy compound)
The fluorine-containing epoxy compound is a compound in which at least a part of hydrogen atoms of the epoxy compound is substituted with fluorine atoms.
As a fluorine-containing epoxy compound, the thing of the following general formula is mentioned, for example.
_{Gu- (OCH 2) p - {} X} - (CH 2 O) p -Gu
Here, Gu represents a glycidyl group. X is (CF ₂ ) ₁ and / or (CF ₂ —O—CF ₂ ) _m . P is 0 to 1, l is 1 to 8, and m is 1 to 8.

  Of fluorine-containing epoxy compounds, saturated epoxy compounds that do not contain unsaturated bonds (there are carbon-carbon double bonds and triple bonds) are preferable because they are excellent in compatibility with π-conjugated conductive polymers. Moreover, a linear saturated epoxy compound is preferable from the aspect of compatibility. Furthermore, from the viewpoint of compatibility, the saturated epoxy compound preferably has less than 16 carbon atoms, and more preferably has 12 or less carbon atoms.

Moreover, as a linear fluorine-containing epoxy compound, it is preferable to have two epoxy groups and an ether bond from the point which the storage stability of a coating material improves more.
Epoxy compounds having two epoxy groups and ether bonds are fluorinated triethylene glycol diepoxide (product name: C6GDEP) and fluorinated tetraethylene glycol diepoxide (product name: C8GDEP) from Exflow Corporation of the United States. 1H, 1H, 4H, 4H-perfluoro-1,4-butanediol diepoxide (product name: C4DEP), 1H, 1H, 5H, 5H-perfluoro-1,5-pentanediol diepoxide (product name: C5DEP), 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol diepoxide (product name: C6DEP), 1H, 1H, 8H, 8H-perfluoro-1,8-octanediol diepoxide (product) Name: C8DEP), 1H, 1H, 10H, 10H-perfluoro 1,10-decanediol diepoxide (product name: C10DEP) are commercially available.
In addition, as a fluorine-containing epoxy compound having no ether bond, 1,6-bis (2 ′, 3′-epoxypropyl) -perfluoro-n-hexane, 1,4-bis from Daikin Industries, Ltd. (2 ′, 3′-epoxypropyl) -perfluoro-n-butane, 1,2-bis (2 ′, 3′-epoxypropyl) -perfluoro-n-ethane is commercially available.
The said fluorine-containing epoxy compound may be used individually by 1 type, and may use 2 or more types together. Furthermore, you may use as a mixture of another epoxy resin or an acrylic resin as needed.

  The fluorine-containing epoxy compound is preferably 1 to 100% by mass, and more preferably 1 to 50% by mass with respect to 100% by mass of the total solid content of the π-conjugated conductive polymer and the polyanion. If the content of the fluorine-containing epoxy compound is less than 1% by mass, scratch resistance and ethanol resistance of the conductive coating film may be insufficient, and if it exceeds 100% by mass, π-conjugate in the conductive coating film The content of the system conductive polymer is decreased, and sufficient conductivity may not be obtained. Moreover, if it is 50 mass% or less, more sufficient electroconductivity can be obtained.

(Binder)
The binder is included for the purpose of improving durability and transparency and improving adhesion to the substrate. The binder may be a thermosetting resin or a thermoplastic resin.
For example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyimide, polyamideimide, polyamide 6, polyamide 6,6, polyamide 12, polyamide 11, etc., polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, polychlorinated Examples thereof include vinyl resins such as vinyl, epoxy resins, oxetane resins, xylene resins, aramid resins, polyimide silicones, polyurethanes, polyureas, melamine resins, phenol resins, polyethers, acrylic resins, and copolymers thereof.
Among the binders, an oxetane resin, an epoxy resin, and an acrylic resin are preferable because they are highly miscible with the fluorine-containing epoxy compound and have high adhesion to the substrate.

[Oxetane compounds]
Specific examples of the oxetane compound constituting the oxetane resin include, for example, xylylenebisoxetane, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, 4,4 ′-(3 -Ethyloxetane-3-ylmethyloxymethyl) biphenyl, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di {1-ethyl (3-oxetanyl)} methyl ether, 1 , 6-bis {(3-ethyl-3-oxetanyl) methoxy} hexane, 9,9-bis {2-methyl-4- [2- (3-oxetanyl)] butoxyphenyl} fluorene, 9,9-bis { Compounds having a bifunctional oxetane ring such as 4- {2- [2- (3-oxetanyl)] butoxy} ethoxyphenyl} fluorene, oxeta Polyfunctional oxetane compounds such as conjugated novolak resin, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-phenoxymethyloxetane, 3 Examples thereof include compounds having a monofunctional oxetane ring such as-(methacryloyloxymethyl) oxetane and 3- (methacryloyloxymethyl) -2-phenyloxetane.

  The content of the oxetane compound is preferably 1 to 200% by mass and more preferably 10 to 100% by mass with respect to 100% by mass of the total solid content of the π-conjugated conductive polymer and the polyanion. . When the content of the oxetane compound is less than 1% by mass, the water resistance of the conductive coating film may be insufficient. When it exceeds 200% by mass, the inclusion of the π-conjugated conductive polymer in the conductive coating film The amount is reduced, and sufficient conductivity may not be obtained.

[Epoxy compound]
Examples of the epoxy compound constituting the epoxy resin include water-soluble epoxy resins and epoxy emulsions. A water-soluble epoxy resin is preferable from the viewpoint of transparency. More preferably, it is a monomer. The water-soluble epoxy resin is a resin having an epoxy group and dissolving 1 g or more in 100 g of water at 25 ° C.
Specific examples of the water-soluble epoxy resin include, for example, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester, propylene glycol diglycidyl ether, Tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, fatty acid-modified epoxy, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol polyglycidyl ether , Ethylene oxide lauryl alcohol glycidyl ether, ethyl Emissions oxide phenol glycidyl ether, adipic acid glycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate.
Among water-soluble epoxy resins, those having two or more epoxy groups are preferable.

The epoxy emulsion is an emulsion containing an oil-soluble epoxy resin having two or more epoxy groups.
Examples of the epoxy resin include bifunctional glycidyl ether type epoxy resins such as biphenyl type, naphthalene type, fluorene type, polyalkylene glycol type and alkylene glycol type, phenol novolak type, orthocresol novolak type, DPP novolak type, 3 Multifunctional glycidyl ether type epoxy resin such as functional type, tris-hydroxyphenylmethane type, tetraphenylolethane type, tetraglycidyldiaminodiphenylmethane, triglycidyl isocyanurate, hydantoin type, TRAD-D type, aminophenol type, aniline Type, toluidine type glycidylamine type epoxy resin, alicyclic epoxy resin, urethane modified epoxy resin having urethane bond, polybutadiene or polyacrylonitrile Rubber-modified epoxy resin containing Tajien the like.

  The content of the epoxy compound is preferably 1 to 200% by mass and more preferably 10 to 100% by mass with respect to 100% by mass of the total solid content of the π-conjugated conductive polymer and the polyanion. . When the content of the epoxy compound is less than 1% by mass, the water resistance of the conductive coating film may be insufficient, and when it exceeds 200% by mass, the inclusion of the π-conjugated conductive polymer in the conductive coating film The amount is reduced, and sufficient conductivity may not be obtained.

[Acrylic compound]
Acrylic compounds constituting the acrylic resin include monofunctional acrylic compounds and polyfunctional acrylic compounds.
Monofunctional acrylic compounds include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethyl-α-hydroxymethyl acrylate, 2- Hydroxyethylacrylamide is mentioned.
The polymer of the (meth) acrylamide compound has good compatibility with the complex of the π-conjugated conductive polymer and the polyanion, and can further improve the conductivity.

The polyfunctional acrylic compound is an acrylic compound having two or more unsaturated double bonds. If a polyfunctional acrylic compound is contained, the film-forming property will improve at the time of coating film formation.
Specific examples of the polyfunctional acrylic compound include dipropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and dimethylol dicyclopentadi (meth) acrylate. , Polyethylene glycol (hereinafter referred to as PEG) 400 di (meth) acrylate, PEG300 di (meth) acrylate, PEG600 di (meth) acrylate, bifunctional acrylic compounds such as N, N′-methylenebisacrylamide, and trimethylol Propane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, glycerin propoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated glycerin triac Trifunctional acrylic compounds such as relate, pentaerythritol ethoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (penta) (meth) acrylate, dipentaerythritol mono A tetrafunctional or higher functional acrylic compound such as hydroxypenta (meth) acrylate, a pentafunctional or higher functional acrylic compound such as sorbitol pentaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol hexaacrylate, alkylene oxide modified hexaacrylate, caprolactone 6 or more functional acrylic compounds such as modified dipentaerythritol hexaacrylate, 2 or more functional A urethane acrylate.

Of the polyfunctional acrylic compounds, the polyfunctional acrylic monomer preferably has a molecular weight of 3000 or less. A polyfunctional acrylic monomer having a molecular weight exceeding 3000 has low solvent solubility. In addition, since the unsaturated double bond equivalent is reduced, it is difficult to crosslink the composite, and sufficient strength cannot be obtained after formation of the conductive film.
Of the polyfunctional acrylic compounds, the polyfunctional urethane acrylate preferably has a molecular weight of 1000 or less in terms of solvent solubility, wear resistance, and low shrinkage. In the polyfunctional urethane acrylate having a molecular weight exceeding 1000, the introduction rate of the urethane group formed by the isocyanate group and the polyol (hydroxyl group) decreases, and the solubility in the solvent tends to be low.

  In terms of further improving film formability, it is preferable to further contain one or both of a (meth) acrylamide compound and a polyfunctional acrylic compound.

  The content of the acrylic compound is preferably 0.05 to 50% by mass and more preferably 0.3 to 30% by mass with respect to 100% by mass in total of the π-conjugated conductive polymer and the polyanion. . If the content of the acrylic compound is 0.05% by mass or more, the film formability of the conductive film is sufficiently high, and if it is 50% by mass or less, a sufficient amount of π-conjugated conductive polymer is contained in the conductive film. Since it is contained, sufficient electrical conductivity is obtained.

  As said epoxy compound, oxetane compound, and an acrylic compound, the compound which does not contain a fluorine is preferable from the point of the storage stability of an electrically conductive coating material.

(Conductivity improver)
The conductivity improver is a component that improves the conductivity of the conductive film formed from the conductive polymer solution.
Specifically, the conductivity improver includes the acrylic compound, 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 It is at least one compound selected from the group consisting of a compound having one or more carboxy groups, a compound having an amide group, a compound having an imide group, a lactam compound, a compound having a glycidyl group, and a water-soluble organic solvent.

Nitrogen-containing aromatic cyclic compounds Examples of nitrogen-containing aromatic cyclic compounds include pyridines and derivatives thereof containing one nitrogen atom, imidazoles and derivatives thereof containing two nitrogen atoms, and pyrimidines. And derivatives thereof, pyrazines and derivatives thereof, triazines containing three nitrogen atoms, and derivatives thereof. From the viewpoint of solvent solubility and the like, pyridines and derivatives thereof, imidazoles and derivatives thereof, and pyrimidines and derivatives thereof are preferable.

  Specific examples of pyridines and derivatives thereof 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-pyridinecarboxaldehyde, 4-aminopyridine, 2,3-diaminopyridine, 2 , 6-diaminopyridine, 2,6-diamino-4-methylpyridine, 4-hydroxypyridine, 4-pyridinemethanol, 2,6-dihydroxypyridine, 2,6-pyridinedimethanol, methyl 6-hydroxynicotinate, 2 -Hydroxy-5-pyridinemethanol, ethyl 6-hydroxynicotinate, 4-pi Lysine methanol, 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, Examples include 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, and 3-pyridinesulfonic acid.

  Specific examples of imidazoles and derivatives thereof include imidazole, 2-methylimidazole, 2-propylimidazole, 2-undecylimidazole, 2-phenylimidazole, N-methylimidazole, N-vinylimidazole, and N-allylimidazole. 1- (2-hydroxyethyl) imidazole (N-hydroxyethylimidazole), 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 4,5-imidazoledicarbo Acid, dimethyl 4,5-imidazole dicarboxylate, benzimidazole, 2-aminobenzimidazole, 2-aminobenzimidazole-2-sulfonic acid, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole , 2- (2-pyridyl) benzimidazole and the like.

  Specific examples of pyrimidines and derivatives thereof 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, 2,4-pyrimidinediol, etc. Is mentioned.

  Specific examples of the pyrazines and derivatives thereof include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5-methylpyrazinecarboxylic acid, pyrazineamide, 5 -Methylpyrazine amide, 2-cyanopyrazine, aminopyrazine, 3-aminopyrazine-2-carboxylic acid, 2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, 2,3-diethylpyrazine and the like.

  Specific examples of triazines and derivatives thereof include 1,3,5-triazine, 2-amino-1,3,5-triazine, 3-amino-1,2,4-triazine, and 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′- Disodium disulphonate, 2-hydroxy-4,6-dichloro -1,3,5-triazine and the like.

  The content of the nitrogen-containing aromatic cyclic compound is preferably in the range of 0.1 to 100 mol, more preferably in the range of 0.5 to 30 mol, with respect to 1 mol of the anion group unit of the polyanion. A range of 1 to 10 mol is particularly preferable from the viewpoint of physical properties and conductivity of the solid electrolyte layer 14. When the content of the nitrogen-containing aromatic cyclic compound is less than 0.1 mol, the interaction between the nitrogen-containing aromatic cyclic compound, the polyanion and the conjugated conductive polymer tends to be weak, and the conductivity May be insufficient. In addition, when the nitrogen-containing aromatic cyclic compound exceeds 100 moles, the content of the conjugated conductive polymer decreases, and it is difficult to obtain sufficient conductivity, and the physical properties of the solid electrolyte layer 14 change. There are things to do.

-Compound having two or more hydroxy groups Examples of the compound having two or more hydroxy 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;
Polymeric alcohols such as 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.

  The content of the compound having two or more hydroxy groups is preferably in the range of 0.05 to 50 mol and more preferably in the range of 0.3 to 10 mol with respect to 1 mol of the anion group unit of the polyanion. More preferred. If the content of the compound having two or more hydroxy groups is less than 0.05 mol with respect to 1 mol of the anion group unit of the polyanion, conductivity and heat resistance may be insufficient. In addition, when the content of the compound having two or more hydroxy groups is more than 50 mol with respect to 1 mol of the anion group unit of the polyanion, the content of the π-conjugated conductive polymer in the solid electrolyte layer 14 is small. Thus, it is difficult to obtain sufficient conductivity, and the physical properties of the solid electrolyte layer 14 may change.

-Compound having two or more carboxy groups Examples of the compound having two or more carboxy groups include 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 carboxy group is bonded to an aromatic ring, such as carboxylic dianhydride, naphthalene dicarboxylic acid, trimellitic acid, pyromellitic acid; diglycolic acid, oxydibutyric acid Thiodiacetic acid (thiodiacetic acid), thiodibutyric acid, iminodiacetic acid, iminobutyric acid and the like.

  The compound having two or more carboxy groups is preferably in the range of 0.1 to 30 mol, more preferably in the range of 0.3 to 10 mol, relative to 1 mol of the anion group unit of the polyanion. When the content of the compound having two or more carboxy groups is less than 0.1 mol relative to 1 mol of the anion group unit of the polyanion, conductivity and heat resistance may be insufficient. In addition, when the content of the compound having two or more carboxy groups is more than 30 mol with respect to 1 mol of the anion group unit of the polyanion, the content of the π-conjugated conductive polymer in the solid electrolyte layer 14 is decreased. However, it is difficult to obtain sufficient conductivity, and the physical properties of the solid electrolyte layer 14 may change.

-A compound having one or more hydroxy groups and one or more carboxy groups As a compound having one or more hydroxy groups and one or more carboxy groups, tartaric acid, glyceric acid, dimethylolbutanoic acid, dimethylolpropanoic acid , D-glucaric acid, glutaconic acid and the like.

  The content of the compound having one or more hydroxy groups and one or more carboxy groups is preferably 1 to 5,000 parts by mass with respect to 100 parts by mass in total of the polyanion and the π-conjugated conductive polymer. 50 to 500 parts by mass is more preferable. When the content of the compound having one or more hydroxy groups and one or more carboxy groups is less than 1 part by mass, conductivity and heat resistance may be insufficient. In addition, when the content of the compound having one or more hydroxy groups and one or more carboxy groups exceeds 5,000 parts by mass, the content of the π-conjugated conductive polymer in the solid electrolyte layer 14 decreases. Again, it is difficult to obtain sufficient conductivity.

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 amide compounds 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, pyruvamide, acetoacetamide, dimethyl Acetamide, 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, Examples thereof include N-diethyl methacrylamide, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like.

  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.

  The content of the amide compound is preferably 1 to 5,000 parts by mass and more preferably 50 to 500 parts by mass with respect to 100 parts by mass in total of the polyanion and the π-conjugated conductive polymer. When the content of the amide compound is less than 1 part by mass, conductivity and heat resistance may be insufficient. Moreover, when the content of the amide compound is more than 5,000 parts by mass, the content of the π-conjugated conductive polymer in the solid electrolyte layer 14 is decreased, and it is difficult to obtain sufficient conductivity.

-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, semicarbazide, α, α-dimethyl-6-methylsuccinimide, bis [2- (succinimidooxycarbonyloxy) 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.

  The content of the imide compound is preferably 10 to 10,000 parts by mass, more preferably 50 to 5,000 parts by mass with respect to 100 parts by mass in total of the π-conjugated conductive polymer and the polyanion. . If the addition amount of the amide compound and the imide compound is less than the lower limit, the effect of the addition of the amide compound and the imide compound is lowered, which is not preferable. Moreover, when the said upper limit is exceeded, since the electroconductive fall resulting from the fall of (pi) conjugated system conductive polymer concentration will occur, it is unpreferable.

-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.

  The content of the lactam compound is preferably 10 to 10,000 parts by mass, and more preferably 50 to 5000 parts by mass with respect to 100 parts by mass in total of the π-conjugated conductive polymer and the polyanion. If the amount of the lactam compound added is less than the lower limit, the effect of the addition of the lactam compound is reduced, which is not preferable. Moreover, when the said upper limit is exceeded, since the electroconductive fall resulting from the fall of (pi) conjugated system conductive polymer concentration will occur, it is unpreferable.

-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 compound having a glycidyl group is preferably 10 to 10,000 parts by mass, and more preferably 50 to 5000 parts by mass with respect to 100 parts by mass in total of the π-conjugated conductive polymer and the polyanion. When the amount of the compound having a glycidyl group is less than the lower limit, the effect of adding the compound having a glycidyl group is undesirably reduced. Moreover, when the said upper limit is exceeded, since the electroconductive fall resulting from the fall of (pi) conjugated system conductive polymer concentration will occur, it is unpreferable.

Water-soluble organic solvent Examples of the water-soluble organic solvent include N-methyl-2pyrrolidone, N-methylacetamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylene phosphortriamide, N -Polar solvents such as vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, phenols such as cresol, phenol, xylenol, ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4 butylene glycol , D-glucose, D-glucitol, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentylglycol, and other polyhydric aliphatic alcohols Carbonate compounds such as ethylene carbonate and propylene carbonate, ether compounds such as dioxane and diethyl ether, chain ethers such as dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether and polypropylene glycol dialkyl ether, 3-methyl-2- Examples include heterocyclic compounds such as oxazolidinone, and nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, and benzonitrile. These solvents may be used alone or as a mixture of two or more.

(Additive)
The conductive composition may contain an additive as necessary. The additive is not particularly limited as long as it can be mixed with a π-conjugated conductive polymer and a polyanion. For example, an inorganic conductive agent, an antifoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber, or the like is used. it can.
Examples of the inorganic conductive agent include metal ions (formed by dissolving a metal salt in water), conductive carbon, and the like.
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.

(Thickness of conductive film)
The thickness of the conductive film is preferably 0.001 to 10 μm, and more preferably 0.01 to 1 μm. If the thickness of the conductive film is 0.001 μm or more, sufficient conductivity can be secured, and if it is 10 μm or less, sufficient flexibility can be secured.

(Surface resistance value of conductive film)
The surface resistance value of the conductive film can be appropriately selected according to the purpose, and is, for example, 5,000Ω or less, preferably 2,500Ω or less, and more preferably 500Ω or less.

<Method for producing transparent conductor>
The method for producing a transparent conductor of the present invention is a method in which a conductive paint is applied to at least one surface of a transparent substrate and cured. Here, the conductive paint contains a π-conjugated conductive polymer, a polyanion, a fluorine-containing epoxy compound, and a solvent as essential components, and a binder, a curing agent, a conductivity improver, and an additive as optional components. To do.

When the conductive coating contains an oxetane compound or an epoxy compound as a binder, the water resistance and strength of the obtained conductive film are further increased, and therefore it is preferable to contain a curing agent for oxetane / epoxy.
Examples of the curing agent include amine curing agents, acid or acid anhydride curing agents, basic active hydrogen compounds, imidazoles, polymercaptan curing agents, and isocyanate curing agents.
Examples of amine curing agents include aliphatic polyamines such as ethylenediamine, diethylenetriamine and triethylenetetramine, aliphatic polyamines such as isophoronediamine and 1,3-bisaminomethylcyclohexane, aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone, It is obtained by reacting secondary amines such as chain diamine, tetramethylguanidine, triethanol, amine, piperidine, pyridine, benzyldimethylamine or tertiary amines, dimer acid and polyamines such as diethylenetriamine and triethylenetetramine. And polyamidoamine.
Examples of acid or acid anhydride curing agents include polycarboxylic acids such as adipic acid, azelaic acid, trimellitic acid, pyromellitic acid, decanedicarboxylic acid, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, Aromatic anhydrides such as 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, cyclic aliphatic acid anhydrides such as maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Examples thereof include aliphatic acid anhydrides such as polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, dodecenyl succinic anhydride, poly (ethyl) octadecanedioic acid) anhydride, and the like.
Examples of the active hydrogen compound include organic acid dihydrazide.
Examples of imidazole include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptanedecylimidazole, and the like.
Examples of the polymercaptan curing agent include esters of thioglycolic acid such as pentaerythritol tetrathioglycolate and dipentaerythritol hexathioglycolate.
Examples of the isocyanate curing agent include isocyanate compounds such as hexamethylene diisocyanate and xylene diisocyanate, and blocked isocyanate compounds obtained by reacting an isocyanate group with phenol, alcohol, caprolactone, and the like.

Moreover, since an oxetane compound and an epoxy compound are hardened rapidly and fully, it is preferable that a conductive paint contains a cation generating compound.
The cation generating compound is a compound that generates a Lewis acid. Here, specific examples of the cation generating compound include a photo cation initiator and a thermal cation initiator. The photo cation initiator and the thermal cation initiator may be used in combination.

Examples of the photocation initiator include diazonium salts of Lewis acids, iodonium salts of Lewis acids, sulfonium salts of Lewis acids, and the like. In these, the cation part is aromatic diazonium, aromatic iodonium, aromatic sulfonium, etc., and the anion part is (boron tetrafluoride (BF ₄ ⁻ ), phosphorus hexafluoride (PF ₆ ⁻ ), hexafluoride. An onium salt composed of antimony (SbF ₆ ⁻ ), [BX ₄ ] ⁻ (wherein X is a phenyl group substituted with at least two fluorine or trifluoromethyl groups) and the like.
Specific examples include phenyldiazonium salt of boron tetrafluoride, diphenyliodonium salt of phosphorus hexafluoride, diphenyliodonium salt of antimony hexafluoride, tri-4-methylphenylsulfonium salt of arsenic hexafluoride, tetrafluoro Antimony tri-4-methylphenylsulfonium salt, tetrakis (pentafluorophenyl) boron diphenyliodonium salt, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridinium salt, phosphorus hexafluoride allene-iron complex It is done.
As a commercial product of a photocationic initiator, CD-1012 (manufactured by Sartomer). PCI-019, PCI-021 (Nippon Kayaku Co., Ltd.), Optomer SP-150, Optomer SP-170 (ADEKA), UVI-6990 (Dow Chemical), CPI-100P, CPI100A (San Apro) , TEPBI-S (manufactured by Nippon Shokubai Co., Ltd.), WPI031, WPI-054, WPI-113, WPI-116, WPI-170 (manufactured by Wako Pure Chemical Industries, Ltd.), Irgacure 250 (manufactured by Ciba Specialty Chemical Company), etc. Can be mentioned.

Thermal cationic initiators include cationic or protonic acid catalysts such as aromatic onium salts, triflate salts, boron trifluoride ether complex compounds and boron trifluoride. Of these, aromatic onium salts are preferred. Some aromatic onium salts generate cationic species by heat, and can also be used as a thermal cationic polymerization initiator. For example, aromatic sulfonium salts such as Sun-Aid SI-60L, SI-80L, SI-100L, SI-110L, SI-180L available from Sanshin Chemical Co., Ltd. can be mentioned.
Examples of thermal cation initiators other than those manufactured by Sanshin Chemical Co., Ltd. include Adeka Opton CP-66, CP-77 (manufactured by ADEKA), CI-2920, CI2921, CI2946, CI-2638, CI-2624, CI-2064 ( Nippon Soda Co., Ltd.), FC-520 (manufactured by 3M), and the like.
The said cation generating compound may be used individually by 1 type, and may use 2 or more types together.

  The total content of the curing agent and the cation generator is preferably 0.1 to 100% by mass, more preferably 1 to 80% by mass when the oxetane compound or the epoxy compound is 100% by mass. . If the total content of the curing agent and the cation generator is 0.1% by mass or more, the oxetane compound or the epoxy compound can be sufficiently cured, and if it is 100% by mass or less, the conductive film formed from the conductive paint. Can sufficiently exhibit the characteristics of the binder.

When the conductive paint contains an acrylic compound as a binder, a radical polymerization method, a thermal polymerization method, a photo radical polymerization method, a cationic polymerization method, and a plasma polymerization method can be applied to the polymerization of the acrylic compound.
In the radical polymerization method, polymerization is performed using, for example, an azo compound such as azobisisobutyronitrile, a peroxide such as benzoyl peroxide, diacyl peroxides, peroxyesters, and hydroperoxides as a polymerization initiator.
In the photo radical polymerization method, polymerization is performed using a carbonyl compound, a sulfur compound, an organic peroxide, an azo compound, or the like as a polymerization initiator. Specifically, benzophenone, Michler's ketone, xanthone, thioxanthone, 2-ethylanthraquinone, acetophenone, trichloroacetophenone, 2-hydroxy-2-methyl-propiophenone, 1-hydroxycyclohexyl phenyl ketone, benzoin ether, 2,2-di Ethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, benzyl, methylbenzoylformate, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 2,4,6-trimethylbenzoyldiphenyl Examples include phosphine oxide, tetramethylthiuram, dithiocarbamate, benzoyl peroxide, N-laurylpyridium azide, and polymethylphenylsilane. Furthermore, n-butylamine, triethylamine, tri-n-butylphosphine, or the like can be mixed as a photosensitizer for photo radical polymerization.
In the cationic polymerization method, aryldiazonium salts, diarylhalonium salts, triphenylsulfonium salts, silanol / aluminum chelates, α-sulfonyloxy ketones, and the like can be used as the cationic polymerization initiator.
In plasma polymerization, plasma is irradiated for a short time, receives energy from electron bombardment of the plasma, performs fragmentation and rearrangement, and then generates a polymer by recombination of radicals.

The solvent is not particularly limited, but an aqueous solvent is preferable because it easily dissolves the polyanion.
Examples of the aqueous solvent include solvents having a solubility parameter of 10 or more, for example, water, alcohols such as methanol, ethanol and isopropyl alcohol, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol and propylene glycol. Glycerin, polyglycerin, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol and other polyhydric alcohols, N-methylpyrrolidone, dimethylacetamide, dimethyl Examples include amides such as formamide. These solvents may be used alone or in combination of two or more.

  The content of the solvent in the conductive paint is preferably 40 to 99% by mass, and more preferably 50 to 98% by mass in order to sufficiently dissolve the fluorine-containing epoxy compound and the binder. When the content of the solvent is less than 40% by mass, the solubility of the fluorine-containing saturated epoxy compound and the binder may be hindered, and the stability of the obtained conductive paint may be insufficient. If it exceeds, the dispersibility of the π-conjugated conductive polymer may be insufficient.

  The conductive paint can be prepared, for example, by chemically oxidatively polymerizing a precursor monomer of a π-conjugated conductive polymer in an aqueous solution of polyanion and then adding a solvent and a fluorine-containing epoxy compound. After chemical oxidative polymerization, water may be removed.

As a method for applying the conductive polymer solution, for example, bar coating, comma coating, reverse coating, lip coating, spray coating, flexographic printing, gravure printing, and the like are applied. It is preferable to perform a curing treatment after the application of the conductive polymer solution. As the curing method, heating or light irradiation is applied. As a heating method, for example, a normal method such as hot air heating or infrared heating can be employed. Moreover, when hardening by light irradiation, the method of irradiating an ultraviolet-ray from light sources, such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, can be employ | adopted, for example.
The illuminance upon UV irradiation is preferably 100 mW / cm ² or more. Since the reducing agent may inhibit the polymerization of the acrylic compound, if the illuminance is less than 100 mW / cm ² , it does not sufficiently crosslink, and the sliding resistance (durability) of the conductive coating tends to decrease. is there. In addition, the illumination intensity in this invention is the value measured using Topcon Co., Ltd. UVR-T1 (Industrial UV checker, light receiver; UD-T36, measurement wavelength range; 300-390 nm, peak sensitivity wavelength; about 355 nm). .
The transparent conductor of this invention can be obtained with the above methods.

In the transparent conductive film of the present invention, ethanol resistance was remarkably improved by the addition of the fluorine-containing epoxy compound. When the ethanol resistance is high, the dirt can be easily removed by washing with ethanol when the dirt on the conductive film is wiped during the manufacturing process. In addition, the addition of the fluorine-containing epoxy compound improves the surface slipperiness, so that the scratch resistance of the conductive film is increased. When the scratch resistance is high, it is possible to prevent a serious defect that damages the uniformity of the resistance value by scratching the surface of the conductive film by handling in the process, and the product rate is improved. Furthermore, even if the conductive film contains a fluorine-containing epoxy compound, water resistance, conductivity, transparency, and adhesion to a transparent substrate are not impaired.
The transparent conductor of the present invention can be used as a transparent electrode of a display device. Examples of the display device include an electroluminescence display and a liquid crystal display.

"Input device"
The input device of the present invention comprises the transparent conductor of the present invention as a transparent electrode. Among the input devices, the resistive touch panel is preferable because the effects of the present invention are particularly exhibited.
Hereinafter, an example of a resistive film type touch panel provided with the transparent conductor of the present invention as a transparent electrode will be described.
As shown in FIG. 1, the resistive touch panel of this example has a conductive film 12 formed on the surface of the transparent substrate 11, a movable electrode sheet 10 disposed on the input side, and a conductive film 22 on the surface of the transparent substrate 21. The fixed electrode sheet 20 formed and disposed on the image display device side is provided so that the conductive film 12 and the conductive film 22 face each other. A transparent dot spacer 24 is disposed between the movable electrode sheet 10 and the fixed electrode sheet 20 to form a gap.

  Examples of the transparent substrates 11 and 21 of the movable electrode sheet 10 or the fixed electrode sheet 20 include a single layer or two or more layers of plastic films, glass plates, and laminates of films and glass plates. However, the transparent substrate 11 of the movable electrode sheet 10 is preferably a plastic film because of its flexibility, and the transparent substrate 21 of the fixed electrode sheet 20 is preferably a glass plate because it is easy to fix. preferable.

  The thickness of the transparent substrate 11 of the movable electrode sheet 10 is preferably 100 to 250 μm. If the thickness of the transparent substrate 11 is 100 μm or more, sufficient strength can be secured, and if it is 250 μm or less, sufficient flexibility can be secured. The thickness of the conductive film 12 of the movable electrode sheet 10 is preferably 50 to 700 μm. If the thickness of the transparent substrate 11 is 50 μm or more, sufficient conductivity can be secured, and if it is 700 μm or less, sufficient flexibility and transparency can be secured. The thickness of the transparent substrate 21 of the fixed electrode sheet 20 is preferably 0.8 to 2.5 mm. If the thickness of the transparent substrate 11 is 0.8 mm or more, sufficient strength can be ensured, and if it is 2.5 mm or less, the thickness can be reduced and space saving can be realized. The thickness of the conductive film 22 of the fixed electrode sheet 20 is preferably 0.01 to 1.0 μm. If the thickness of the conductive film 22 is 0.01 μm or more, sufficient conductivity can be ensured, and if the thickness is 1.0 μm or less, the conductive film 22 can be made thin and space saving can be realized. It is preferable that the space | interval at the time of the non-pressing of the movable electrode sheet 10 and the fixed electrode sheet 20 is 20-100 micrometers. If the distance between the movable electrode sheet 10 and the fixed electrode sheet 20 when not pressed is 20 μm or more, the movable electrode sheet 10 and the fixed electrode sheet 20 can be reliably prevented from contacting each other when not pressed, and the distance is 100 μm or less. If it exists, the movable electrode sheet 10 and the fixed electrode sheet 20 can be reliably brought into contact at the time of pressing. In order to achieve the spacing, the size of the dot spacers 24 may be selected as appropriate.

  In this resistive touch panel, when the movable electrode sheet 10 is pushed by a finger or a stylus, the conductive film 12 of the movable electrode sheet 10 and the conductive film 22 of the fixed electrode sheet 20 are brought into contact with each other to conduct electricity. The voltage is taken in and the position is detected.

  The input device may be a capacitive touch panel. As a capacitive touch panel using the conductive film, for example, a pair of transparent electrodes made of the conductive film is provided on both surfaces of a transparent substrate, and a low-voltage electric field is formed on the entire transparent electrode and touched with a finger. One that detects changes in surface charge and detects the position can be mentioned.

  Such an input device is provided in, for example, an electronic notebook, a personal digital assistant (PDA), a mobile phone, a PHS, an automatic teller machine (ATM), a vending machine, a point-of-sale information management (POS) register, and the like. .

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 were added to 2000 ml of ion-exchanged water. The solution dissolved in 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 an about 1.5% by mass blue polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS) aqueous solution.

Example 1
To 100 g of the PEDOT-PSS aqueous solution obtained in Production Example 2, 0.015 g (1% by mass) of a fluorine-containing saturated epoxy compound containing an ether bond (product name: C6GDEP manufactured by Exflow Co., Ltd.) was added, and ultrasonic vibration was added. PEDOT-PSS aqueous solution containing a saturated epoxy compound containing an ether bond was prepared by stirring using a machine (Alex Corporation High Power Ultrasonic Cleaning Machine Neonenik).
Separately, 3 g of diglycerin polyglycidyl ether (SR-DGE manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), 0.03 g of sun aid SI-110L (manufactured by Sanshin Chemical Co., Ltd.), 3.3 g of dimethyl sulfoxide, and 133 g of ethanol are mixed and stirred did. A PEDOT-PSS aqueous solution containing a saturated epoxy compound containing an ether bond was added to the solution thus obtained, and the mixture was stirred with an ultrasonic vibrator to obtain a conductive paint A.
Conductive paint A is applied to a polyethylene terephthalate film (A4300 manufactured by Toyobo Co., Ltd., thickness: 188 μm) with a bar coater and dried by infrared heating at 120 ° C. for 2 minutes to form a conductive coating film. Got.
The surface resistance, total light transmittance and haze, water resistance, ethanol resistance, scratch resistance, and adhesion of the coating film of the obtained transparent conductor were measured by the following methods. The results are shown in Table 2.

[Surface resistance]
Measurement was performed according to JIS K 7194 using a Loresta MCP-T600 manufactured by Mitsubishi Chemical Corporation. The measurement results are shown in Table 1.

[Total light transmittance and haze]
The total light transmittance and haze were measured according to JIS K7136 using a Nippon Denshoku Industries Co., Ltd. haze meter measuring device (NDH5000). The measurement results are shown in Table 2.

[Sliding test (Evaluation of water resistance and ethanol resistance)]
In order to measure the coating film strength of the conductive film, Kimwipe (manufactured by Nippon Paper Crecia Co., Ltd.) moistened with water or ethanol was rubbed 50 times with a load of 100 gf / cm ² , and then the peeling of the conductive film was visually observed. Evaluation was made based on the following evaluation criteria. Moreover, surface resistance and contact resistance were measured. The results are shown in Table 2.
◎: No peeling, ○: Slight peeling, △: Partial peeling, ×: Complete peeling

[Evaluation of scratch resistance]
In order to measure the coating film strength of the conductive film, Kim Wipe (manufactured by Nippon Paper Crecia Co., Ltd.) applied a load of 100 gf / cm ² and rubbed it 50 times to conduct a scratch test. Evaluation was performed based on the evaluation criteria. Moreover, surface resistance and contact resistance were measured. The results are shown in Table 2. These results are indicators of the film strength of the conductive film.
◎: No scratch, ○: Several scratches, △: Several tens of scratches, ×: Numerous scratches

[Evaluation of adhesion]
The surface of the formed conductive film was made to reach a transparent substrate (polyethylene terephthalate or glass), and a grid-like cut was made with a cutter knife. The cellophane tape was adhered to the cut conductive film, and then peeled off. The peeling state of the electrically conductive film in that case was observed visually, and evaluated based on the following evaluation criteria. The results are shown in Table 2.
◎: No peeling, ○: Slight peeling, △: Partial peeling, ×: Complete peeling

(Example 2)
The addition amount of a saturated epoxy compound containing a fluorine-containing ether bond (manufactured by Exflow, product name C6GDEP) was changed to 0.075 g (5% by mass), and diglycerin polyglycidyl ether (SR-DGE made by Sakamoto Yakuhin Kogyo Co., Ltd.) ) Was changed to 2.625 g, and the conductive paint B was obtained in the same manner as in Example 1 except that the addition amount of Sun-Aid SI-110L (manufactured by Sanshin Chemical Co., Ltd.) was changed to 0.02625 g. . A conductive coating film was formed in the same manner as in Example 1 except that the conductive paint B was used instead of the conductive paint A, and the transparent conductor was evaluated. The evaluation results are shown in Table 2.

Example 3
The addition amount of a saturated epoxy compound containing a fluorine-containing ether bond (manufactured by Exflow, product name C6GDEP) was changed to 0.225 g (15% by mass), and diglycerin polyglycidyl ether (SR-DGE manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) ) Was changed to 2.25 g, and the conductive paint C was produced in the same manner as in Example 1 except that the addition amount of Sun-Aid SI-110L (manufactured by Sanshin Chemical Co., Ltd.) was changed to 0.0225 g. . And the conductive coating film was formed similarly to Example 1 except having used the conductive paint C instead of the conductive paint A, and the transparent conductor was evaluated. The evaluation results are shown in Table 2.

Example 4
0.015 g (1% by mass) of a saturated epoxy compound containing a fluorine-containing ether bond (product name: C6GDEP manufactured by Exflow Co., Ltd.) and an epoxy compound (product name: E-7432 manufactured by Daikin Co., Ltd.) in which hydrocarbons are not etherified 1,6-bis (2 ′, 3′-epoxypropyl) -perfluoro-n-hexane) was changed to 0.45 g (30% by mass), and diglycerin polyglycidyl ether (SR-DGE manufactured by Sakamoto Pharmaceutical Co., Ltd.) Was changed to 1.875 g, and the conductive paint D was obtained in the same manner as in Example 1 except that the amount of Sun-Aid SI-110L (manufactured by Sanshin Chemical Co., Ltd.) was changed to 0.01875 g. And the conductive coating film was formed similarly to Example 1 except having used the conductive coating material D instead of the conductive coating material A, and the transparent conductor was evaluated.

(Example 5)
0.015 g (1% by mass) of a saturated epoxy compound containing a fluorine-containing ether bond (product name: C6GDEP, manufactured by Exflow), an epoxy compound (C5DEP, 1H, 1H, manufactured by Exflow), which is not etherified with hydrocarbons 5H, 5H-perfluoro-1,5-pentanediol diepoxide) was changed to 0.675 g (45 parts by mass), and 1.5 g of diglycerin polyglycidyl ether (SR-DGE manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was added. The conductive paint E was obtained in the same manner as in Example 1 except that the addition amount of Sun-Aid SI-110L (manufactured by Sanshin Chemical Co., Ltd.) was changed to 0.015 g. A conductive coating film was formed in the same manner as in Example 1 except that the conductive paint E was used instead of the conductive paint A, and the transparent conductor was evaluated. The evaluation results are shown in Table 2.

(Example 6)
The addition amount of a saturated epoxy compound containing a fluorine-containing ether bond (Xflow, product name C6GDEP) was changed to 0.9 g (60% by mass), and diglycerin polyglycidyl ether (Sakamoto Yakuhin Kogyo SR-DGE) ) 3 g was changed to 1.125 g of 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (OXT221 manufactured by Toagosei Co., Ltd.) and Sun-Aid SI-110L (manufactured by Sanshin Chemical Co., Ltd.) ) Was changed to 0.01125 g, and a conductive coating material F was obtained in the same manner as in Example 1. And the conductive coating film was formed similarly to Example 1 except having used the conductive coating material F instead of the conductive coating material A, and the transparent conductor was evaluated. The evaluation results are shown in Table 2.

(Example 7)
To 100 g of the PEDOT-PSS aqueous solution obtained in Production Example 2, 1.125 g (75% by mass) of a fluorine-containing saturated epoxy compound containing an ether bond (product name: C6GDEP manufactured by Exflow Co., Ltd.) was added, and ultrasonic vibration was added. PEDOT-PSS aqueous solution containing a saturated epoxy compound containing an ether bond was prepared by stirring using a machine (Alex Corporation High Power Ultrasonic Cleaning Machine Neonenik).
Apart from this, 0.75 g of pentaerythritol triacrylate, 0.0075 g of Irgacure 184 (manufactured by Ciba Specialty Chemicals), 3.3 g of 2-hydroxyethyl (meth) acrylate, 2,3,3 ′, 4,4 '5'-Hexahydroxybenzophenone 0.45 g and ethanol 133 g were mixed and stirred. A PEDOT-PSS aqueous solution containing a saturated epoxy compound containing an ether bond was added to the solution thus obtained, and the mixture was stirred with an ultrasonic vibrator to obtain a conductive paint G.
The conductive paint G was applied to a polyethylene terephthalate film (Toyobo A4300, thickness: 188 μm) with a bar coater, and dried by infrared irradiation at 100 ° C. for 2 minutes. Thereafter, ultraviolet rays (high pressure mercury lamp 120W, 360 mJ / cm ² , 178 mW / cm ² ) were irradiated and cured to form a conductive coating film, thereby obtaining a transparent conductor. The obtained transparent conductor was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 8)
The addition amount of a saturated epoxy compound containing a fluorine-containing ether bond (manufactured by Exflow, product name C6GDEP) was changed to 1.35 g (90% by mass), and diglycerin polyglycidyl ether (SR-DGE manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) ) 3 g was changed to 0.375 g polyglycerin polyglycidyl ether (Sakamoto Yakuhin Kogyo Co., Ltd. SR-4GLS), and the addition amount of Sun-Aid SI-110L (Sanshin Chemical Co., Ltd.) was changed to 0.00375 g. Conductive paint H was obtained in the same manner as Example 1. And the conductive coating film was formed similarly to Example 1 except having used the conductive paint H instead of the conductive paint A, and the transparent conductor was evaluated. The evaluation results are shown in Table 2.

Example 9
The addition amount of a saturated epoxy compound containing a fluorine-containing ether bond (product name: C6GDEP manufactured by Exflow) was changed to 1.5 g (100% by mass), and diglycerin polyglycidyl ether (SR-DGE manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) ) 3 g was changed to 0.015 g of sorbitol-based polyglycidyl ether (Sakamoto Yakuhin Kogyo Co., Ltd. SR-SEP), and the addition amount of Sun-Aid SI-110L (Sanshin Chemical Co., Ltd.) was changed to 0.00015 g. Conductive paint I was obtained in the same manner as Example 1. And the conductive coating film was formed similarly to Example 1 except having used the conductive paint I instead of the conductive paint A, and the transparent conductor was evaluated. The evaluation results are shown in Table 2.

(Example 10)
Conductive paint A is applied to glass (thickness: 0.8 mm × 210 mm × 150 mm) with a bar coater, dried by infrared heating at 120 ° C. for 30 minutes to form a conductive coating, and a transparent conductor Got. And the surface resistance of the coating film, the total light transmittance and haze, water resistance, ethanol resistance, scratch resistance, and adhesion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 11)
Conductive paint B is applied to glass (thickness: 0.8 mm × 210 mm × 150 mm) with a bar coater, dried by infrared heating at 120 ° C. for 30 minutes to form a conductive coating, and a transparent conductor Got. And the surface resistance of the coating film, the total light transmittance and haze, water resistance, ethanol resistance, scratch resistance, and adhesion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 12)
Conductive paint C is applied to glass (thickness: 0.8 mm × 210 mm × 150 mm) with a bar coater, dried by infrared heating at 120 ° C. for 30 minutes to form a conductive coating, and a transparent conductor Got. And the surface resistance of the coating film, the total light transmittance and haze, water resistance, ethanol resistance, scratch resistance, and adhesion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 13)
Conductive paint D is applied to glass (thickness: 0.8 mm × 210 mm × 150 mm) with a bar coater, dried by infrared heating at 120 ° C. for 30 minutes to form a conductive coating, and a transparent conductor Got. And the surface resistance of the coating film, the total light transmittance and haze, water resistance, ethanol resistance, scratch resistance, and adhesion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 14)
Conductive paint E is applied to glass (thickness: 0.8 mm x 210 mm x 150 mm) with a bar coater, dried by infrared heating at 120 ° C for 30 minutes to form a conductive coating film, and transparent conductor Got. And the surface resistance of the coating film, the total light transmittance and haze, water resistance, ethanol resistance, scratch resistance, and adhesion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 15)
Conductive paint F is applied to glass (thickness: 0.8 mm × 210 mm × 150 mm) with a bar coater, dried by infrared heating at 120 ° C. for 30 minutes to form a conductive coating, and a transparent conductor Got. And the surface resistance of the coating film, the total light transmittance and haze, water resistance, ethanol resistance, scratch resistance, and adhesion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 16)
The conductive paint G was applied to glass (thickness: 0.8 mm × 210 mm × 150 mm) with a bar coater, dried at 100 ° C. for 2 minutes by infrared irradiation, and then irradiated with ultraviolet rays (high pressure mercury lamp 120 W, 360 mJ / cm ² , 178 mW / cm ² ) irradiation and curing to form a conductive coating film to obtain a transparent conductor. And the surface resistance of the coating film, the total light transmittance and haze, water resistance, ethanol resistance, scratch resistance, and adhesion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 17)
Conductive paint H is applied to glass (thickness: 0.8 mm × 210 mm × 150 mm) with a bar coater, dried by infrared heating at 120 ° C. for 30 minutes to form a conductive coating, and a transparent conductor Got. And the surface resistance of the coating film, the total light transmittance and haze, water resistance, ethanol resistance, scratch resistance, and adhesion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 18)
Conductive paint I is applied to glass (thickness: 0.8 mm x 210 mm x 150 mm) with a bar coater, dried by infrared heating at 120 ° C for 30 minutes to form a conductive coating, and a transparent conductor Got. And the surface resistance of the coating film, the total light transmittance and haze, water resistance, ethanol resistance, scratch resistance, and adhesion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Comparative Example 1)
A conductive paint J was obtained in the same manner as in Example 1 except that a saturated epoxy compound containing fluorine (product name: C6GDEP manufactured by Exflow Co., Ltd.) was not added. Then, a conductive coating film was formed in the same manner as in Example 1 except that the conductive paint J was used instead of the conductive paint A, and the transparent conductor was evaluated. The evaluation results are shown in Table 2.

(Comparative Example 2)
Conductive paint J is applied to glass (thickness: 0.8 mm × 210 mm × 150 mm) with a bar coater, dried by infrared heating at 120 ° C. for 30 minutes to form a conductive coating film, and transparent conductor Got. And the surface resistance of the coating film, the total light transmittance and haze, water resistance, ethanol resistance, scratch resistance, and adhesion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

The transparent conductors of Examples 1 to 9 obtained by applying a conductive paint containing a fluorine-containing epoxy compound to a polyethylene terephthalate film with a bar coater have surface resistance, transparency (total light transmittance and haze), and water resistance. It was excellent in all of ethanol resistance, adhesion, and scratch resistance.
The transparent conductors of Examples 10 to 18 obtained by applying a conductive paint containing a fluorine-containing epoxy compound to glass with a bar coater also have surface resistance, transparency (total light transmittance and haze), water resistance, It was excellent in all of ethanol property, adhesion, and scratch resistance.
On the other hand, in Comparative Examples 1 and 2 using a conductive paint not containing a fluorine-containing epoxy compound, the surface resistance, transparency (total light transmittance, haze), and water resistance were good results, Ethanol resistance, scratch resistance and adhesion were low.

10 movable electrode sheet 11 transparent substrate 12 conductive film 20 fixed electrode sheet 21 transparent substrate 22 conductive film 24 dot spacer

Claims (7)

A transparent substrate and a conductive film provided on at least one surface of the transparent substrate, wherein the conductive film is substituted with fluorine atoms at least part of hydrogen atoms of a π-conjugated conductive polymer, a polyanion, and an epoxy compound. A transparent conductor comprising a cured product of a conductive composition containing a fluorine-containing epoxy compound represented by the following general formula:
_{Gu- (OCH 2) p - {} X} - (CH 2 O) p -Gu
(Gu represents a glycidyl group. X is at least one of (CF ₂ ) _l and (CF ₂ —O—CF ₂ ) _m. P is 0 to 1, l is 1 to 8, m is 1 to 8. is there.)   The transparent conductor according to claim 1, wherein the fluorine-containing epoxy compound is a linear compound having two epoxy groups and an ether bond. The transparent conductor according to claim 1 or 2, wherein the conductive composition contains one or both of an oxetane compound and an epoxy compound other than the fluorine-containing epoxy compound . On at least one surface of the transparent substrate, a π-conjugated conductive polymer, a polyanion, a fluorine-containing epoxy compound represented by the following general formula in which at least a part of hydrogen atoms of the epoxy compound are substituted with fluorine atoms, a solvent, The manufacturing method of the transparent conductor characterized by apply | coating the conductive coating material containing this, and hardening.
_{Gu- (OCH 2) p - {} X} - (CH 2 O) p -Gu
(Gu represents a glycidyl group. X is at least one of (CF ₂ ) _l and (CF ₂ —O—CF ₂ ) _m. P is 0 to 1, l is 1 to 8, m is 1 to 8. is there.)   The method for producing a transparent conductor according to claim 4, wherein a linear compound having two epoxy groups and having an ether bond is used as the fluorine-containing epoxy compound. The method for producing a transparent conductor according to claim 4 or 5, wherein the conductive paint contains one or both of an oxetane compound and an epoxy compound other than the fluorine-containing epoxy compound . Input device, characterized in that it comprises a transparent conductor according to claim 1.

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