JP2012097227A - Conductive polymer solution, conductive coating film, and input device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive polymer solution having excellent storage stability, capable of forming a conductive coated film which has a small contact resistance to a different conductor, and which is excellent in conductivity, durability, transparency and adhesiveness to a base material.SOLUTION: This conductive polymer solution includes a π-conjugated conductive polymer, a poly-anion, surface-modified carbon having an acid functional group on the surface of carbon, and a solvent, wherein the content of the surface-modified carbon is 0.01-10 mass% based on 100 mass% total of the π-conjugated conductive polymer and the poly-anion. Preferably, the acid functional group of the surface-modified carbon is a carboxy group and a hydroxy group, and a functional group equivalent is 0.1-10 μeq/mper carbon surface area.

Description

  The present invention relates to a conductive polymer solution for forming a conductive coating used for a transparent electrode or the like, a conductive coating that can be used for a transparent electrode of an input device, or the like, an input device such as a touch panel.

The touch panel is an input device installed on the image display device, and at least a portion overlapping the image display device is transparent.
As the touch panel, for example, a resistance film type touch panel is known. In a resistive touch panel, a fixed electrode sheet and a movable electrode sheet in which a transparent electrode is formed on one side of a transparent substrate are arranged so that the transparent electrodes face each other. As a transparent electrode of an electrode sheet, an indium-doped tin oxide film (hereinafter referred to as ITO film) has been widely used.
A sheet having an ITO film formed on one side of a transparent substrate (hereinafter referred to as an ITO film-forming sheet) is suitable as a fixed electrode sheet on the image display device side because of its low flexibility and easy fixing. However, since it has low bending resistance, when it is used as a movable electrode sheet on the input side of a touch panel, there is a problem that durability (water resistance, ethanol resistance, scratch resistance) when repeatedly flexed is low. Was.
Therefore, as an alternative to the ITO film forming sheet, as a movable electrode sheet on the input side of the touch panel, a flexible conductive film containing a π-conjugated conductive polymer is formed on one side of a transparent substrate. A sheet (hereinafter referred to as a conductive polymer film forming sheet) may be used.
However, when an ITO film forming sheet is used as the fixed electrode sheet on the image display device side and a conductive polymer film forming sheet is used as the movable electrode sheet on the input side of the touch panel, that is, when different conductors are connected to each other. The contact resistance is large, and problems such as a decrease in input sensitivity and a delay in coordinate input time may occur.

In order to solve the above problem, Patent Document 1 proposes adding metal ions to a conductive coating film containing a π-conjugated conductive polymer. However, in the electrode sheet described in Patent Document 1, the contact resistance to the ITO film has not been sufficiently reduced.
Patent Documents 2 and 3 disclose electrode sheets obtained by adding metal particles to a conductive coating film containing a π-conjugated conductive polymer. However, the electrode sheets described in Patent Documents 2 and 3 may have low transparency, and further, the contact resistance may be reduced unevenly. Therefore, when applied to a resistive touch panel, the visibility of the image on the image display device may be reduced when installed on the image display device, or the input sensitivity may be reduced and the coordinate input time may be delayed. was there.
Therefore, the electrode sheets described in Patent Documents 1 to 3 are not suitable for touch panels.
In order to solve these problems, Patent Document 4 proposes adding carbon black to a conductive coating film containing a π-conjugated conductive polymer.
When the coating film described in Patent Document 4 is used, an electrode sheet having excellent contact resistance and ethanol resistance can be obtained. However, in recent years, with higher functionality of touch panels and changes in usage environments, further excellent contact resistance, improved ethanol resistance, improved transparency, and improved adhesion to substrates have been demanded. In addition, the conductive polymer solution for forming the conductive coating described in Patent Document 4 has insufficient storage stability, and the voltage distribution linearity after the sliding writing durability test of the conductive coating is also present. It had the problem of being insufficient.

JP 2007-172984 A JP 2005-327910 A JP 2007-080541 A JP 2009-097873 A

  The present invention has been made in view of the above circumstances, has a low contact resistance to different conductors, can form a conductive coating film that is excellent in conductivity, durability, transparency, and adhesion to a substrate, and is preserved. It aims at providing the conductive polymer solution which is excellent in stability. An object of the present invention is to provide a conductive coating film that has a low contact resistance to a different conductor and is excellent in conductivity, durability, transparency, and adhesion to a substrate. It is another object of the present invention to provide an input device that is excellent in image visibility of an image display device when installed on the image display device, prevents malfunction, and has excellent durability.

[1] A π-conjugated conductive polymer, a polyanion, a surface-modified carbon having an acidic functional group on the surface of carbon, and a solvent, and the content of the surface-modified carbon is π-conjugated conductive A conductive polymer solution, characterized in that the content is 0.01 to 10% by mass relative to 100% by mass of the total of the polymer and the polyanion.
[2] The conductive functional group according to [1], wherein the acidic functional groups of the surface-modified carbon are a carboxy group and a hydroxy group, and the functional group equivalent is 0.1 to 10 μeq / m ² per carbon surface area. Polymer solution.
[3] The conductive polymer solution according to [1] or [2], which contains one or both of an oxetane compound and an epoxy compound.
[4] A conductive coating film formed by applying the conductive polymer solution according to any one of [1] to [3].
[5] An input device comprising the conductive coating film according to [4] as a transparent electrode.

The conductive polymer solution of the present invention has a low contact resistance to a different conductor, can form a conductive coating film excellent in conductivity, durability, transparency, and adhesion to a substrate, and is excellent in storage stability.
The conductive coating film of the present invention has a small contact resistance to a different conductor and is excellent in conductivity, durability, transparency, and adhesion to a substrate.
The input device of the present invention has excellent image visibility of the image display device when installed on the image display device, prevents malfunction, and also has excellent durability.

It is sectional drawing which shows an example of the input device of this invention. It is sectional drawing which shows the electrode sheet by the side of an input person in the measuring method of contact resistance. It is sectional drawing which shows the electrode sheet by the side of the image display apparatus in the measuring method of contact resistance. It is a schematic diagram which shows the circuit in the measuring method of contact resistance. It is a figure which shows the measuring method of the linearity of voltage distribution. It is a graph which shows the voltage distribution in an example of a movable electrode sheet.

"Conductive polymer solution"
The conductive polymer solution of the present invention contains a π-conjugated conductive polymer, a polyanion, surface-modified carbon, and a solvent. Moreover, the conductive polymer solution of the present invention can contain a binder, a curing agent, a conductivity improver, and an additive as necessary.

(Π-conjugated conductive polymer)
The π-conjugated conductive polymer can be used as long as the main chain is an organic polymer having a π-conjugated system. Examples include polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of easy polymerization and stability in air, polypyrroles, polythiophenes and polyanilines are preferred.
Even if the π-conjugated conductive polymer remains unsubstituted, sufficient conductivity can be obtained. However, in order to further improve the conductivity, an alkyl group, a carboxy group, a sulfo group, an alkoxy group, a hydroxy group, a cyano group, It is preferable to introduce a functional group such as a group into the π-conjugated conductive polymer.

  Specific examples of such π-conjugated conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), and poly (3-n-propylpyrrole). ), Poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4 Dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), Poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly 3-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole), polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene) , Poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3 -Phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibuty) Ruthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyl) Oxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene), Poly (3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyl) Oxythiophene), poly (3,4-diheptyloxythiophene), poly (3 4-dioctyloxythiophene), poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylene) Dioxythiophene), poly (3,4-butenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene), polyaniline, poly (2-methylaniline), poly (3 -Isobutylaniline), poly (2-anilinesulfonic acid), poly (3-anilinesulfonic acid), etc. It is below.

  Among them, from one or two selected from polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene), poly (3-methoxythiophene), and poly (3,4-ethylenedioxythiophene) The (co) polymer is preferably used from the viewpoints of resistance and reactivity. Furthermore, polypyrrole and poly (3,4-ethylenedioxythiophene) are more preferable because they have higher conductivity and improved 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.

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 to the principal chain of a polyanion adjacently or at regular intervals.

  Among the polyanions, polyisoprenesulfonic acid, a copolymer containing polyisoprenesulfonic acid, a polysulfoethyl methacrylate, a copolymer containing polysulfoethyl methacrylate, poly (4 -Sulfobutyl methacrylate), copolymers containing poly (4-sulfobutyl methacrylate), polymethallyloxybenzenesulfonic acid, copolymers containing polymethallyloxybenzenesulfonic acid, polystyrenesulfonic acid, polystyrenesulfonic acid A copolymer or the like is preferred.

  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 polyanion 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 polyanion content is less than the lower limit, the doping effect on the π-conjugated conductive polymer tends to be weakened, and the conductivity may be insufficient. In addition, the dispersibility and solubility in the solvent are lowered, making it difficult to obtain a uniform dispersion. On the other hand, when the polyanion content exceeds the upper limit, the content of the π-conjugated conductive polymer decreases, and it is difficult to obtain sufficient conductivity.

(Surface modified carbon)
The surface-modified carbon has an acidic functional group on the surface of carbon. Examples of the acidic functional group include a carboxy group, a hydroxy group, a sulfo group, and a phospho group, and preferably has both a carboxy group and a hydroxy group.
A part or all of the acidic functional group may be neutralized with an inorganic compound of a basic compound. Examples of basic inorganic compounds include sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia. Moreover, it is preferable that pH is adjusted to 4-7 by neutralization.

When the acidic functional group has a carboxy group and a hydroxy group, the acidic functional group equivalent is preferably 0.1 to 10 μeq / m ² with respect to the carbon surface area. If the acidic functional group equivalent is greater than or equal to the lower limit, aggregation of the surface-modified carbon can be prevented, and if the acidic functional group equivalent is less than or equal to the upper limit, the contact resistance in different conductor contact can be sufficiently reduced.
Here, the acidic functional group equivalent is the sum of the carboxy group equivalent, the hydroxy group equivalent, and the carboxy group equivalent and hydroxy group equivalent neutralized and bound with a basic compound or sodium.
In addition, these functional group equivalents are measured by the following method.
“Carboxy group equivalent”: 2 to 5 g of surface-modified carbon is added to 0.976 mol / dm ^{3 of} an aqueous sodium bicarbonate solution of 0.576 ³ and shaken for 6 hours to react. Thereafter, carbon is filtered off from the obtained reaction solution. And neutralization titration is carried out using 0.05 mol / dm < ³ > sodium hydroxide aqueous solution until pH will be set to 7.0, and the amount of carboxy groups is quantified.
“Hydroxy group equivalent”: 2,2′-diphenyl-1-picrylhydrazide (DPPH) is dissolved in carbon tetrachloride to prepare a solution having a concentration of 50 mmol / dm ³ . 0.1-0.6g of surface modified carbon is added to this solution, and it stirs in a 60 degreeC thermostat for 6 hours. Thereafter, carbon is separated by filtration, and the amount of hydroxy groups contained in the filtrate is quantified using an ultraviolet absorptiometer.
"Carboxy group equivalent neutralized with base", "Hydroxy group equivalent neutralized with base": Treating surface-modified carbon with strong acid such as hydrochloric acid to remove anions ion-bonded to carboxy group and hydroxy group, Quantification is performed in the same manner as in the above-described method for measuring the amount of carboxy group and the amount of hydroxy group, with the end point where no anion is detected by ion chromatography.

  The surface-modified carbon preferably has an average particle size measured by observation with an electron microscope of 0.001 to 10 μm, and more preferably 0.01 to 0.5 μm. If the average particle diameter of the surface-modified carbon is equal to or greater than the lower limit, the contact resistance in the different conductor contact can be sufficiently reduced, and if the average particle diameter is equal to or smaller than the upper limit, the weight in the surface-modified state is reduced. It becomes small and becomes difficult to settle in a conductive polymer solution.

Examples of commercially available surface-modified carbon include the following carbon black.
That is, Mitsubishi Chemical Corporation, # 2700, # 2650, # 2400, # 2350, # 1000, MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, German Degussa, Color Black FW200, FW2, FW2V, FW285, FW1, FW18, S170, S160, Special Black 6, 5, 4, 4A, Printex U, V, 140U, 140V, CAB-O-JET 200, 300 manufactured by Cabot Corporation, Tokai Carbon Co., Ltd., Talker Black # 3855, 3845, 3800, Aqua-Black001, 120, 162, 164 and the like.
Among these, Aqua-Black001, 120, 162, and 164 are preferable because they have appropriate amounts of carboxy group and hydroxy group. Carbon black having a carboxy group and a hydroxy group on the surface is superior in dispersibility between carbon black particles in water, and has higher long-term storage stability.

The surface-modified carbon is produced by stirring and mixing carbon and an oxidizing agent such as nitric acid, sulfuric acid, chlorate, persulfate, perborate, percarbonate in an aqueous solution. The temperature during stirring is preferably about room temperature to 90 ° C. If it is the said temperature range, an acidic functional group equivalent can be easily made into 0.1-10microeq / m < ² >.

  The content of the surface-modified carbon is 0.01 to 10% by mass and 1.0 to 8.0% by mass with respect to 100% by mass in total of the π-conjugated conductive polymer and the polyanion. Is preferred. If the content of the surface-modified carbon is less than the lower limit value, the contact resistance in the different conductor contact may not be sufficiently lowered and may cause malfunction, and if the content exceeds the upper limit value, the conductive polymer solution In some cases, the transparency of the conductive coating film formed from the material may be lowered.

  The above surface-modified carbon has a specified amount of acidic functional groups, so that the dispersibility in the conductive polymer solution is excellent regardless of the liquidity of the conductive polymer solution. Is easy.

(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, polyamides such as polyamide 12 and polyamide 11, polyvinyl resins such as polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride, epoxy resins, oxetane resins, xylene resins, aramid resins, polyimide silicones, polyurethanes, polyureas, melamine resins , Phenol resins, polyethers, acrylic resins and copolymers thereof.
Among binders, oxetane resins, epoxy resins, and acrylic resins are preferable because of their 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 the lower limit, the water resistance of the conductive coating film may be insufficient. When the content exceeds the upper limit, the content 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 the lower limit value, the water resistance of the conductive coating film may be insufficient. When the upper limit value is exceeded, 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. Further, since the unsaturated double bond equivalent is reduced, it is difficult to crosslink the composite, and sufficient strength cannot be obtained after the formation of the conductive coating 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 not less than the lower limit, the film formability of the conductive coating is sufficiently high, and if it is not more than the upper limit, the π-conjugated conductive polymer is present in the conductive coating. Since a sufficient amount is contained, sufficient conductivity can be obtained.

  As the epoxy compound, oxetane compound and acrylic compound, a compound containing no fluorine is preferable from the viewpoint of storage stability of the conductive polymer solution.

(Curing agent)
When the conductive polymer solution contains an oxetane compound or an epoxy compound as a binder, it is preferable to contain a curing agent for oxetane / epoxy because the water resistance and strength of the resulting conductive coating film are higher. .
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 the oxetane compound and the epoxy compound are rapidly and sufficiently cured, the conductive polymer solution preferably 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 equal to or higher than the lower limit value, the oxetane compound and the epoxy compound can be sufficiently cured, and if the total content is equal to or lower than the upper limit value, the conductivity formed from the conductive polymer solution. Binder characteristics can be sufficiently exhibited in the coating film.

[Polymerization of acrylic compounds]
When the conductive polymer solution contains an acrylic compound as a binder, radical polymerization, thermal polymerization, photoradical polymerization, cationic polymerization, and plasma polymerization can be applied for 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.

(solvent)
The solvent is preferably mainly composed of water from the viewpoint of dispersibility of the surface-modified carbon, and water, particularly deionized water is more preferable from the viewpoint of safety at low cost.
A water-soluble organic solvent can also be used as the solvent. Examples of water-soluble organic solvents include water-soluble alcohols such as methanol, ethanol, 1-propanol and 2-propanol, glycols such as ethylene glycol, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol, polyethylene glycol and propylene glycol. Glycerol, polyglycerol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polyhydric alcohols such as 2,3-butanediol, water-soluble ketones such as acetone, Water-soluble fatty acids such as formic acid, acetic acid, propionic acid and butyric acid, water-soluble nitrogen compounds such as N, N-dimethylformamide and N-methylpyrrolidone, and water-soluble sulfur compounds such as dimethyl sulfoxide And the like.

  40-99 mass% is preferable and, as for content of the solvent in a conductive polymer solution, 50-98 mass% is more preferable. If the content of the solvent is not less than the lower limit, the dispersibility of the surface-modified carbon and the solubility of the binder will be higher, and the stability of the resulting conductive polymer solution will be improved. For example, the dispersibility of the π-conjugated conductive polymer becomes higher.

(Conductivity improver)
The conductivity improver is a component that improves the conductivity of a conductive coating film formed from a conductive polymer solution.
Specifically, the conductivity improver includes the acrylic compound, a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxy groups, a compound having two or more carboxy groups, one or more hydroxy 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 moles is particularly preferable from the viewpoints of physical properties and conductivity of the conductive coating film. When the content of the nitrogen-containing aromatic cyclic compound is less than the lower limit, the interaction between the nitrogen-containing aromatic cyclic compound, the polyanion and the conjugated conductive polymer tends to be weak, and the conductivity is low. There may be a shortage. In addition, if the nitrogen-containing aromatic cyclic compound exceeds the upper limit, the content of the conjugated conductive polymer is decreased, it is difficult to obtain sufficient conductivity, and the physical properties of the conductive coating film are reduced. May change.

-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. When the content of the compound having two or more hydroxy groups is less than the lower limit mole relative to 1 mole 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 larger than the upper limit with respect to 1 mol of the anion group unit of the polyanion, the content of the π-conjugated conductive polymer in the conductive coating film is increased. As a result, it is difficult to obtain sufficient conductivity, and the physical properties of the conductive coating 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 the lower limit mole relative to 1 mole of anion group unit of the polyanion, the conductivity and heat resistance may be insufficient. In addition, when the content of the compound having two or more carboxy groups is larger than the upper limit with respect to 1 mol of the anion group unit of the polyanion, the content of the π-conjugated conductive polymer in the conductive coating film is small. Therefore, it is difficult to obtain sufficient conductivity, and the physical properties of the conductive coating film 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 the lower limit value, 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 the upper limit, the content of the π-conjugated conductive polymer in the conductive coating film decreases, 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 the lower limit, the conductivity and heat resistance may be insufficient. On the other hand, when the content of the amide compound exceeds the upper limit, the content of the π-conjugated conductive polymer in the conductive coating film decreases, 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 polymer solution 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.

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

  Since the surface-modified carbon contained in the conductive polymer solution has an acidic functional group, the dispersibility of the surface-modified carbon can be increased, so that the surface-modified carbon hardly aggregates. Therefore, in addition to excellent storage stability, the surface-modified carbon is uniformly dispersed in the conductive coating film formed from the conductive polymer solution. Therefore, the conductive coating film has low contact resistance with respect to a different conductor, and is excellent in conductivity, durability, transparency, and adhesion to a substrate.

"Conductive coating"
The conductive coating film of the present invention is a coating film formed by applying the conductive polymer solution.
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 thickness of the conductive coating film is preferably 0.001 to 10 μm, and more preferably 0.01 to 1 μm. If the thickness of the conductive coating film is not less than the lower limit value, sufficient conductivity can be ensured, and if the thickness is not more than the upper limit value, sufficient flexibility can be ensured.

  The surface resistance value of the conductive coating can be appropriately selected depending on the purpose, and is, for example, 5,000Ω or less, preferably 2,500Ω or less, and more preferably 500Ω or less. .

  The conductive coating film 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 conductive coating film 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 conductive coating film 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 coating film 12 formed on the surface of a transparent substrate 11, and a movable electrode sheet 10 disposed on the input side and a surface of the transparent substrate 21. The ITO film 22 is formed, and the fixed electrode sheet 20 disposed on the image display device side is provided so that the conductive coating film 12 and the ITO 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, since the transparent base material 11 of the movable electrode sheet 10 is flexible, a plastic film is preferable, and the transparent base material 21 of the fixed electrode sheet 20 is easily fixed, and thus a glass plate is used. Those are preferred.

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 equal to or greater than the lower limit value, sufficient strength can be ensured, and if the thickness is equal to or less than the upper limit value, sufficient flexibility can be ensured.
The thickness of the conductive coating film 12 of the movable electrode sheet 10 is preferably 50 to 700 μm. If the thickness of the transparent substrate 11 is not less than the lower limit value, sufficient conductivity can be secured, and if the thickness is not more than the upper limit value, 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 equal to or greater than the lower limit value, sufficient strength can be ensured, and if the thickness is equal to or smaller than the upper limit value, the thickness can be reduced and space saving can be realized.
The thickness of the ITO film 22 of the fixed electrode sheet 20 is preferably 0.01 to 1.0 μm. If the thickness of the ITO film 22 is equal to or greater than the lower limit value, sufficient conductivity can be secured, and if the thickness is equal to or smaller than the upper limit value, the thickness can be reduced 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 interval when the movable electrode sheet 10 and the fixed electrode sheet 20 are not pressed is equal to or greater than the lower limit value, the movable electrode sheet 10 and the fixed electrode sheet 20 can be reliably prevented from contacting when not pressed. If it is below an upper limit, 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 pressed with a finger or a stylus, the conductive coating film 12 of the movable electrode sheet 10 and the same conductive coating film 22 of the fixed electrode sheet 20 are brought into contact with each other to conduct. The position is detected by taking in the voltage at that time.

  The input device may be a capacitive touch panel. As the capacitive touch panel using the conductive coating film, for example, a pair of transparent electrodes made of the conductive coating film is provided on both surfaces of the transparent substrate, and a low-voltage electric field is formed on the entire transparent electrode, Examples include detecting the position by touching with a finger to detect changes in surface charge.

Since the input device of the present invention is excellent in the transparency of the conductive coating film, it is excellent in the image visibility of the image display device when installed on the image display device. In addition, since the contact resistance is small, malfunction is prevented. And since durability of an electroconductive coating film is high, durability of an input device is also excellent.
The input device of the present invention 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 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 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, 0.096 g of # 2350 (manufactured by Mitsubishi Chemical Corporation, carboxy group equivalent 1.5 μeq / m ² , hydroxy group equivalent 0.2 μeq / m ² , average particle diameter 15 nm) 8 mass%) was added, and the mixture was stirred using an ultrasonic vibrator (High Power Ultrasonic Cleaning Machine Neonenik manufactured by Alex Corporation) to prepare a PEDOT-PSS aqueous solution containing # 2350.
Separately, 3 g of polyglycerin polyglycidyl ether (SR-4GLS 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 # 2350 was added to the solution thus obtained, and the mixture was stirred with an ultrasonic vibrator to obtain a conductive polymer solution A.
The conductive polymer solution A was 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 130 ° C. for 2 minutes to form a conductive coating film.
The surface resistance, total light transmittance and haze of the conductive coating film, contact resistance, scratch resistance, water resistance, ethanol resistance, adhesion, linearity of voltage distribution, and storage stability of the solution were measured by the following methods. . The results are shown in Table 1.

[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.

[Contact resistance]
The obtained conductive sheet was cut into 40 mm × 50 mm, and a conductive paste (FA-401CA manufactured by Fujikura Kasei Co., Ltd.) was screen printed on the edge of the cut sheet on the inorganic conductive layer 12b and dried. Electrode wirings 13a and 13b were formed to obtain a movable electrode sheet 10 (see FIG. 2) on the input side.
Further, a glass plate 21 (surface resistance: 300Ω) provided with an ITO film 22 and cut to 40 mm × 50 mm was prepared. A conductive paste (XA436 manufactured by Fujikura Kasei Co., Ltd.) was screen-printed on the edge of the prepared glass plate 21 on the ITO film 22 in the longitudinal direction and dried to form electrode wirings 23a and 23b. Subsequently, a dot spacer paste (SN-8400C manufactured by Fujikura Kasei Co., Ltd.) was screen-printed on the ITO film 22, dried, and irradiated with ultraviolet rays to form dot spacers 24. Next, a resist paste (SN-8800G manufactured by Fujikura Kasei Co., Ltd.) was screen-printed on the electrode wirings 23a and 23b, dried, and irradiated with UV to form the insulating layer 25. Further, an adhesive (XB-114 manufactured by Fujikura Kasei Co., Ltd.) was screen-printed on the insulating layer 25 and dried to form an adhesive layer 26 for bonding to the movable electrode sheet 10. Thereby, the fixed electrode sheet 20 (refer FIG. 3) for image display apparatuses was obtained.
Next, as shown in FIG. 4, the movable electrode sheet 10 and the fixed electrode sheet 20 are arranged so that the inorganic conductive layer 12 b and the ITO film 22 face each other, and are bonded together by an adhesive layer 26 to be a resistive film type touch panel module. Was made. In addition, one electrode wiring 23 a of the fixed electrode sheet 20 and the precision power source 31 are connected to a pull-up resistor (82.3 kΩ) 32 and a pull-up resistor 32 in parallel with a voltage measurement tester 33 for the pull-up resistor 32. Electrically connected. The precision power supply 31 and one electrode wiring 13a of the movable electrode sheet 10 were electrically connected. In addition, the other electrode wiring 13b of the movable electrode sheet 10 and the other electrode wiring 23b of the fixed electrode sheet 20 were electrically connected via a voltage measurement tester 34 of a resistive film type touch panel module. Thereby, an electrical circuit for contact resistance measurement was obtained.
The contact resistance was measured as follows. With a polyacetal stylus 35 with a tip of 0.8R, the movable electrode sheet 10 is pressed with a load of 250 g, and the voltage of the pull-up resistor and the voltage of the resistive touch panel module when a voltage of 5 V is applied by the precision power supply 31 are measured. And contact resistance was measured from these measurement results.
Specifically, the current value flowing through the pull-up resistor 32 is calculated from Ohm's law using the measured voltage value, and the calculated current value and the voltage value of the resistive touch panel module are substituted into the following equation. Contact resistance was determined.
Contact resistance (Ω) = [(resistance film type touch panel module voltage (V)) / (pull-up resistance voltage (V))] × pull-up resistance (Ω)

[Evaluation of scratch resistance]
In order to measure the film strength of the conductive coating film, after performing a scratch test by rubbing 50 times with Kimwipe (manufactured by Nippon Paper Crecia Co., Ltd.) under a load of 100 gf / cm ² , Visual evaluation was performed based on the following evaluation criteria. The results are shown in Table 1. These results are indicators of the film strength of the conductive coating film.
◎: No scratch, ○: Several scratches, △: Several tens of scratches, ×: Numerous scratches

[Sliding test (Evaluation of water resistance and ethanol resistance)]
In order to measure the coating strength of the conductive coating film, a 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 conductive coating film The peeling was visually evaluated based on the following evaluation criteria. Moreover, surface resistance and contact resistance were measured. The results are shown in Table 1.
◎: No peeling, ○: Slight peeling, △: Partial peeling, ×: Complete peeling

[Evaluation of adhesion]
A grid-like cut was made with a cutter knife so that the surface of the formed conductive coating film reached a transparent substrate (polyethylene terephthalate or glass). The cellophane tape was adhered to the conductive coating film with the cuts, and then peeled off. The peeling state of the conductive coating film at that time was visually observed and evaluated based on the following evaluation criteria. The results are shown in Table 1.
◎: No peeling, ○: Slight peeling, △: Partial peeling, ×: Complete peeling

[Linearity of voltage distribution]
Using a sliding writing durability tester manufactured by Touch Panel Laboratories, the tip of a polyacetal pen having a pen tip having a diameter of 0.8 mm was slid 300,000 times with a load of 450 g on the surface of the movable electrode sheet of the touch panel.
The linearity of the voltage distribution before and after the sliding was measured as follows. The results are shown in Table 1. The smaller the change in voltage distribution linearity before and after sliding, the better the durability.
Voltage distribution linearity As shown in FIG. 5, in the movable electrode sheet, a constant voltage is applied to one electrode wiring and the other electrode wiring, and an arbitrary interval from one electrode wiring to the other electrode wiring The voltage was measured at
Theoretically, the voltage distribution is a straight line, but the actual product shows a deviation from the theoretical line (see FIG. 6). The voltage at the measurement start point a is Ea, the voltage at the measurement end point b is Eb, the distance from the measurement start point a to the measurement end point b is Y, the distance from the measurement start point a to the measurement point x is X, and the applied voltage is Assuming Eab, the actually measured voltage at the measurement point x is Ex, and the theoretical voltage at the measurement point x is Ex ′, the linearity is expressed by the following equation.
Linearity (%) = {(Ex′−Ex) / (Eb−Ea)} × 100 (%)
However, Ex ′ = Eab × (X / Y) + Ea

[Storage stability of conductive polymer solution]
The conductive polymer solution was placed in a 100 ml glass sample bottle, and 80 ml of the solution was allowed to stand at 40 ° C. for 3 days to evaluate the stability of the solution. The solution after standing for 3 days was visually observed, and “◯” indicates that no carbon was precipitated, and “X” indicates that a large amount of carbon was precipitated. The results are shown in Table 1.

(Example 2)
# 2350 (Mitsubishi Chemical Corporation, carboxy group equivalent 1.5 μeq / m ² , hydroxy group equivalent 0.2 μeq / m ² , average particle diameter 15 nm) 0.096 g (8% by mass) MA230 (Mitsubishi Chemical Corporation, carboxy A group equivalent of 6.6 μeq / m ² , a hydroxy group equivalent of 0.2 μeq / m ² and an average particle diameter of 30 nm was changed to 0.084 g (7% by mass), and polyglycerin polyglycidyl ether (SR-4GLS manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) ) Was changed to 2.532 g, and the conductive polymer solution B was prepared 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 0.02532 g. Prepared. Then, a conductive coating film was formed and evaluated in the same manner as in Example 1 except that the conductive polymer solution B was used instead of the conductive polymer solution A. The evaluation results are shown in Table 1.

(Example 3)
# 2350 (Mitsubishi Chemical Corp.) 0.096 g (8% by mass) MA8 (Mitsubishi Chemical Co., carboxy group equivalent 3.8 μeq / m ² , hydroxy group equivalent 0.2 μeq / m ² , average particle size 24 nm) The amount of polyglycerin polyglycidyl ether (SR-4GLS manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was changed to 2.132 g, and Sun Aid SI-110L (manufactured by Sanshin Chemical Co., Ltd.) A conductive polymer solution C was prepared in the same manner as in Example 1 except that the addition amount was changed to 0.02132 g. Then, a conductive coating film was formed and evaluated in the same manner as in Example 1 except that the conductive polymer solution C was used instead of the conductive polymer solution A. The evaluation results are shown in Table 1.

Example 4
# 2350 (Mitsubishi Chemical Co., Ltd.) 0.096 g (8% by mass) MA100 (Mitsubishi Chemical Co., carboxy group equivalent 9.6 μeq / m ² , hydroxy group equivalent 0.2 μeq / m ² , average particle size 24 nm) The amount of polyglycerin polyglycidyl ether (SR-4GLS manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was changed to 2.935 g, and Sun Aid SI-110L (manufactured by Sanshin Chemical Co., Ltd.) A conductive polymer solution D was prepared in the same manner as in Example 1 except that the addition amount was changed to 0.2935 g. Then, a conductive coating film was formed and evaluated in the same manner as in Example 1 except that the conductive polymer solution D was used instead of the conductive polymer solution A. The evaluation results are shown in Table 1.

(Example 5)
# 2350 (Mitsubishi Chemical Corp.) 0.096 g (8% by mass) MA220 (Mitsubishi Chemical Co., Ltd., carboxy group equivalent 4.3 μeq / m ² , hydroxy group equivalent 0.2 μeq / m ² , average particle size 55 nm) The amount was changed to 0.048 g (4% by mass), and 3 g of polyglycerin polyglycidyl ether (SR-4GLS manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was replaced with 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl } Oxetane (OXT221 manufactured by Toagosei Co., Ltd.) was changed to 1.125 g, and the conductivity was increased 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 0.01125 g. A molecular solution E was prepared. Then, a conductive coating film was formed and evaluated in the same manner as in Example 1 except that the conductive polymer solution E was used instead of the conductive polymer solution A. The evaluation results are shown in Table 1.

(Example 6)
To 100 g of the PEDOT-PSS aqueous solution obtained in Production Example 2, Aqua-Black 162 (manufactured by Tokai Carbon Co., Ltd., carboxy group equivalent 4.8 μeq / m ² , hydroxy group equivalent 0.2 μeq / m ² , average particle diameter 200 nm, solid content concentration) 1875% (19.2% by mass) was added to 0.1875 g (3% by mass) and stirred using an ultrasonic vibrator (High Power Ultrasonic Cleaning Machine Neonenik manufactured by Alex Corporation). Aqua-Black 162 (Tokai Carbon) PEDOT-PSS aqueous solution containing the product was prepared.
Apart from this, 0.52 g of pentaerythritol triacrylate, 0.0052 g of Irgacure 184 (manufactured by Ciba Specialty Chemicals), 3.3 g of 2-hydroxyethyl (meth) acrylate, 2,3,3 ′, 4,4 ', 5'-Hexahydroxybenzophenone 0.36g and ethanol 133g were mixed and stirred. A PEDOT-PSS aqueous solution containing the Aqua-Black 162 was added to the solution thus obtained, and the mixture was stirred with an ultrasonic vibrator to obtain a conductive polymer solution F.
The conductive polymer solution F was applied to a polyethylene terephthalate film (A4300 manufactured by Toyobo Co., Ltd., thickness: 188 μm) 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 ) and cured to form a conductive coating film. The conductive film was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 7)
# 2350 (manufactured by Mitsubishi Chemical Corporation) 0.096 g (8% by mass) was added to # 25 (manufactured by Mitsubishi Chemical Corporation, carboxy group equivalent 7.8 μeq / m ² , hydroxy group equivalent 0.2 μeq / m ² , average particle diameter 25 nm) ) Changed to 0.024 g (2% by mass), changed the amount of polyglycerin polyglycidyl ether (SR-4GLS made by Sakamoto Yakuhin Kogyo Co., Ltd.) to 2.25 g, and Sun Aid SI-110L (made by Sanshin Chemical Co., Ltd.) A conductive polymer solution G was prepared in the same manner as in Example 1 except that the amount of was changed to 0.0225 g. Then, a conductive coating film was formed and evaluated in the same manner as in Example 1 except that the conductive polymer solution G was used instead of the conductive polymer solution A. The evaluation results are shown in Table 1.

(Example 8)
# 2350 (Mitsubishi Chemical Co., Ltd.) 0.096 g (8% by mass) was added to # 5 (Mitsubishi Chemical Co., carboxy group equivalent 3.7 μeq / m ² , hydroxy group equivalent 0.2 μeq / m ² , average particle size 76 nm). ) 0.018 g (1.5% by mass), polyglycerin polyglycidyl ether (SR-4GLS manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was added to 2.58 g, and Sun Aid SI-110L (Sanshin Chemical Co., Ltd.) The conductive polymer solution H was prepared in the same manner as in Example 1 except that the amount of addition was changed to 0.0258 g. Then, a conductive coating film was formed and evaluated in the same manner as in Example 1 except that the conductive polymer solution H was used instead of the conductive polymer solution A. The evaluation results are shown in Table 1.

Example 9
# 2350 (Mitsubishi Chemical Co., Ltd.) 0.096 g (8% by mass) was replaced with # 10 (Mitsubishi Chemical Co., Ltd., carboxy group equivalent 3.3 μeq / m ² , hydroxy group equivalent 0.2 μeq / m ² , average particle size 75 nm. ) Changed to 0.012 g (1% by mass), 3 g of polyglycerin polyglycidyl ether (SR-4GLS made by Sakamoto Yakuhin Kogyo Co., Ltd.) into 2.63 g diglycerin polyglycidyl ether (SR-DGE made by Sakamoto Yakuhin Kogyo Co., Ltd.) A conductive polymer solution I was prepared 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 0.0263 g. Then, a conductive coating film was formed and evaluated in the same manner as in Example 1 except that the conductive polymer solution I was used instead of the conductive polymer solution A. The evaluation results are shown in Table 1.

(Example 10)
# 2350 (Mitsubishi Chemical Co., Ltd.) 0.096 g (8% by mass), # 850 (Mitsubishi Chemical Co., Ltd., carboxy group equivalent 10.6 μeq / m ² , hydroxy group 0.3 μeq / m ² , average particle diameter 17 nm) A conductive polymer solution N was prepared in the same manner as in Example 1 except that the amount was changed to 0.036 g (3% by mass). Then, a conductive coating film was formed and evaluated in the same manner as in Example 1 except that the conductive polymer solution N was used instead of the conductive polymer solution A. The evaluation results are shown in Table 1.

(Comparative Example 1)
# 2350 (Mitsubishi Chemical Co., Ltd.) 0.096 g (8% by mass) is 0.06 g (5% by mass) of E300J (made by Lion, no acidic functional group, average particle size 25 nm), which is carbon whose surface has not been modified. %), A conductive polymer solution J was prepared in the same manner as in Example 1. Then, a conductive coating film was formed and evaluated in the same manner as in Example 1 except that the conductive polymer solution J was used instead of the conductive polymer solution A. The evaluation results are shown in Table 1.

(Comparative Example 2)
A conductive polymer solution K was prepared in the same manner as in Comparative Example 1 except that the amount of E300J was changed to 0.24 g (20% by mass). Then, a conductive coating film was formed and evaluated in the same manner as in Example 1 except that the conductive polymer solution K was used instead of the conductive polymer solution A. The evaluation results are shown in Table 1.

(Comparative Example 3)
# 3350 (manufactured by Mitsubishi Chemical Corporation) 0.096 g (8% by mass) is 0.00012 g of carbon # 3955 (manufactured by Tokai Carbon Co., Ltd., no acidic functional group, average particle size 21 nm) A conductive polymer solution L was prepared in the same manner as in Example 1 except that the content was changed to 0.0001% by mass). Then, a conductive coating film was formed and evaluated in the same manner as in Example 1 except that the conductive polymer solution L was used instead of the conductive polymer solution A. The evaluation results are shown in Table 1.

(Comparative Example 4)
A conductive polymer solution M was prepared in the same manner as in Example 1 except that the amount of # 3955 was changed to 0.144 g (12% by mass). Then, a conductive coating film was formed and evaluated in the same manner as in Example 1 except that the conductive polymer solution M was used instead of the conductive polymer solution A. The evaluation results are shown in Table 1.

In Examples 1 to 10 in which the surface-modified carbon is contained in the range of 0.01 to 10% by mass with respect to 100% by mass in total of the π-conjugated conductive polymer and the polyanion, the surface resistance, the total light transmittance, and the haze It was excellent in contact resistance, scratch resistance, water resistance, ethanol resistance, adhesion and storage stability of the solution. Further, in Examples 1 to 9 in which the acidic functional group functional group equivalent was 0.1 to 10 μeq / m ² per carbon surface area, the voltage distribution linearity was excellent.

In Comparative Example 1 containing 5% by mass of unmodified carbon on the surface with respect to 100% by mass of the total of the π-conjugated conductive polymer and the polyanion, the storage stability of the solution was insufficient.
In Comparative Example 2 containing 20% by mass of the surface unmodified carbon with respect to the total of 100% by mass of the π-conjugated conductive polymer and the polyanion, the total light transmittance, haze, scratch resistance, ethanol resistance, and adhesion In addition, the storage stability of the solution was insufficient.
In Comparative Example 3 containing 0.0001% by mass of unmodified carbon on the surface with respect to a total of 100% by mass of the π-conjugated conductive polymer and the polyanion, the contact resistance and voltage distribution linearity are insufficient and the solution The storage stability of was insufficient.
In Comparative Example 4 containing 12% by mass of surface unmodified carbon with respect to a total of 100% by mass of the π-conjugated conductive polymer and the polyanion, total light transmittance and haze, scratch resistance, ethanol resistance, adhesion In addition, the storage stability of the solution was insufficient.

DESCRIPTION OF SYMBOLS 10 Movable electrode sheet 11 Transparent base material 12a Organic conductive layer 12b Inorganic conductive layer 13a, 13b Electrode wiring 20 Fixed electrode sheet 21 Transparent base material 22 ITO film 23a, 23b Electrode wiring 24 Dot spacer

Claims (5)

  A π-conjugated conductive polymer, a polyanion, a surface-modified carbon having an acidic functional group on the surface of the carbon, and a solvent, and the content of the surface-modified carbon is π-conjugated conductive polymer A conductive polymer solution, characterized in that the content is 0.01 to 10% by mass with respect to 100% by mass in total of polyanions. ^2. The conductive polymer according to claim 1, wherein the acidic functional group of the surface-modified carbon is a carboxy group and a hydroxy group, and the functional group equivalent is 0.1 to 10 μeq / m ² per carbon surface area. solution.   The conductive polymer solution according to claim 1 or 2, which contains one or both of an oxetane compound and an epoxy compound.   A conductive coating film formed by applying the conductive polymer solution according to claim 1.   An input device comprising the conductive coating film according to claim 4 as a transparent electrode.

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