JP4611834B2 - Conductive polymer paint, conductive coating - Google Patents

Description

  The present invention relates to a polyfunctional acrylamide monomer used for paints, plate making materials, printing inks, adhesives, and the like, and a method for producing the same. Moreover, it is related with the conductive polymer coating material which can form a highly conductive coating film, and a highly conductive conductive coating film.

In general, acrylate oligomers and monomers are widely used in the fields of paints, plate making materials, printing inks, adhesives, etc., and are used in electronic materials such as hologram materials and printed wiring boards, and flat panel displays such as liquid crystal displays and plasma displays. It is also used in manufacturing. In flat panel display applications, in particular, polyfunctional acrylate oligomers and acrylate monomers are used in order to increase the crosslink density and increase the hardness after curing.
Examples of the polyfunctional acrylate oligomer include polyester acrylate having a polyester structure composed of polybasic acid / polyol, urethane acrylate obtained by adding hydroxyl-containing acrylate such as hydroxyethyl acrylate to terminal isocyanate oligomer composed of polyol and isocyanate compound, epoxy resin An epoxy acrylate to which acrylic acid is added is known (see Non-Patent Document 1).
Moreover, as an acrylate monomer, polyfunctional acrylate (for example, refer patent document 1, 2), monofunctional acrylate, etc. are known, for example.
Japanese Examined Patent Publication No. 48-011084 Japanese Patent Publication No. 60-051822 Naoyuki Seo, “Hardening Failure / Inhibition Factors in UV Curing and Countermeasures (Monomer / Oligomer, Initiator / Resin Selection and Compounding Technology)”, published by Technical Information Association, June 1, 2004, p. 50-55

In recent years, from the viewpoint of environmental problems, in paints, the use of water-insoluble solvents is refrained, and water-soluble solvents or water-water-soluble solvent mixtures (hereinafter referred to as water-soluble solvents) tend to be used. .
However, since polyester acrylate repeats the polyester structure, it is possible to design a material having a wide range of physical properties. However, when the solubility in water-soluble solvents is increased, the crosslinking density after curing is decreased.
In the urethane acrylate, when the solubility in water-soluble solvents is improved, the crosslinking density may be insufficient and the water resistance may be lowered.
Epoxy acrylate is excellent in curability because a hydroxyl group is formed in the vicinity of the acrylic group, but if the hydroxyl group is modified with a polybasic acid in order to increase hydrophilicity, the crosslinking density cannot be increased, and the hardness after crosslinking is reduced. It became insufficient.

A monofunctional acrylate is used as a reactive diluent because it has a low viscosity and a high dilution effect. However, a cured product of the monofunctional acrylate alone is soft and brittle because it does not form a three-dimensional crosslinked structure.
On the other hand, the polyfunctional acrylate cannot obtain a sufficient crosslinking density or has low solubility in water-soluble solvents. For example, phenyl glycidyl ether acrylate and hydroxyethyl acrylate phthalic acid adducts can give hydroxyl groups, carboxylic acid groups and the like to the polymer chain after the curing reaction, but a sufficient crosslinking density cannot be obtained. In addition, tricyclodecanediol diacrylate, ethylene oxide 4 mol-modified bisphenol A diacrylate, and the like have low solubility in water-soluble solvents.
That is, with conventional acrylate oligomers and monomers, it has been difficult to increase both the solubility in water-soluble solvents and the crosslink density after curing.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a polyfunctional acrylamide monomer capable of increasing the crosslinking density after curing, and a method for producing the same, in addition to high solubility in water-soluble solvents. And Moreover, it aims at providing the conductive polymer coating material which can form a conductive coating film with high crosslinking density, and a conductive coating film with high crosslinking density.

The conductive polymer paint of the present invention is a conductive polymer paint containing a polyfunctional acrylamide monomer, a π-conjugated conductive polymer, a polyanion, a binder resin, and a water-soluble solvent. In the presence of a strong acid catalyst and a polymerization inhibitor, N-alkoxyalkyl (meth) acrylamide or N-hydroxyalkyl (meth) acrylamide represented by the following general formula (II) and three or more hydroxyl groups, all hydroxyl groups Is a compound obtained by dehydration condensation or dealcoholization condensation in a reaction solvent with a primary polyhydric alcohol represented by the following general formula (III) in which is primary. In the following general formula (II), R ¹ represents a hydrogen atom or a methyl group, R ² represents a methylene group, an ethylene group, a propylene group, or a butylene group, and R ³ represents a hydrogen atom, a methyl group, an ethyl group, n -Represents one of a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. R ⁴ in the general formula (III) represents an organic group having at least one hydroxyl group.

In the conductive polymer paint of the present invention, the polyfunctional acrylamide monomer is preferably ditrimethylolpropane tetraacrylamide or dipentaerythritol hexamethacrylamide.
The conductive coating film of the present invention is formed by applying the above-described conductive polymer paint.

The polyfunctional acrylamide monomer of the present invention has high solubility in water-soluble solvents, and can increase the crosslinking density after curing, and can increase water resistance and solvent resistance.
According to the method for producing a polyfunctional acrylamide monomer of the present invention, it is possible to produce a polyfunctional acrylamide monomer that has high solubility in water-soluble solvents and can increase the crosslinking density after curing.
According to the conductive polymer paint of the present invention, a conductive coating film having a high crosslinking density can be formed.
The conductive coating film of the present invention has a high crosslinking density and is excellent in water resistance and solvent resistance.

<Polyfunctional acrylamide monomer and production method thereof>
The polyfunctional acrylamide monomer of the present invention is a compound having two or more chemical structures represented by the above general formula (I).
In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a methylene group, an ethylene group, a propylene group, or a butylene group.

  The polyfunctional acrylamide monomer includes N-alkoxymethyl (meth) acrylamide represented by the general formula (II) and a primary polyhydric alcohol represented by the general formula (III) in the presence of a strong acid catalyst and a polymerization inhibitor. Is obtained by dehydration condensation in a reaction solvent. The following reaction formula shows an example of a condensation reaction between N-alkoxymethyl (meth) acrylamide and a primary polyhydric alcohol. In the produced polyfunctional acrylamide monomer, the remaining hydroxyl group may further undergo a condensation reaction with N-alkoxymethyl (meth) acrylamide.

In the general formula (II), R ¹ represents a hydrogen atom or a methyl group, R ² represents a methylene group, an ethylene group, a propylene group, or a butylene group, and R ³ represents a hydrogen atom, a methyl group, an ethyl group, or a normal propyl group. , Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, or t-butyl group. In the general formula (III), R ⁴ represents an organic group having at least one hydroxyl group, and examples thereof include a monool group and a diol group.

  Here, as N-alkoxyalkyl (meth) acrylamide represented by the general formula (II), for example, N-methylol (meth) acrylamide, N- (methoxymethyl) (meth) acrylamide, N- (ethoxymethyl) ) (Meth) acrylamide, N- (n-propylmethyl) (meth) acrylamide, N- (isopropylmethyl) (meth) acrylamide, N- (n-butylmethyl) (meth) acrylamide, N- (isobutylmethyl) (meta ) Acrylamide, N- (sec-butylmethyl) (meth) acrylamide, N-ethylol (meth) acrylamide, N- (methoxyethyl) (meth) acrylamide, N- (ethoxyethyl) (meth) acrylamide, N- (n- Propylethyl) (meth) acrylamide, N- (isopropyl) Pyrethyl) (meth) acrylamide, N- (n-butylethyl) (meth) acrylamide, N- (isobutylethyl) (meth) acrylamide, N- (sec-butylethyl) (meth) acrylamide, N-propylol (meth) acrylamide N- (methoxypropyl) (meth) acrylamide, N- (ethoxypropyl) (meth) acrylamide, N- (n-propylpropyl) (meth) acrylamide, N- (isopropylpropyl) (meth) acrylamide, N- ( n-butylpropyl) (meth) acrylamide, N- (isobutylpropyl) (meth) acrylamide, N- (sec-butylpropyl) (meth) acrylamide, N-butyrol (meth) acrylamide, N- (methoxybutyl) (meta ) Acrylamide, N- (Ethoxybutyl) (meth) acrylamide, N- (n-propylbutyl) (meth) acrylamide, N- (isopropylbutyl) (meth) acrylamide, N- (n-butylbutyl) (meth) acrylamide, N- (isobutylbutyl) ) (Meth) acrylamide, N- (sec-butylbutyl) (meth) acrylamide and the like.

Examples of primary polyhydric alcohols include primary diols and triols, and primary polyhydric alcohols having 3 or more hydroxyl groups are preferred.
Examples of the primary polyhydric alcohol having 3 or more hydroxyl groups include, for example, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, trimethylolpropane and propylene oxide. A compound in which ethylene oxide is added to trimethylolpropane, a compound in which propylene oxide is added to pentaerythritol, a compound in which ethylene oxide is added to pentaerythritol, a compound in which propylene oxide is added to ditrimethylolpropane, ethylene oxide to ditrimethylolpropane A compound in which propylene oxide is added to dipentaerythritol, a compound in which dipentaerythritol is added, And compounds obtained by adding N'okishido the like. These may be used alone or in combination of two or more.

The strong acid catalyst is preferably at least one selected from sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, 1,6-naphthalenesulfonic acid, 2,5-naphthalenesulfonic acid, and ammonium chloride. Ammonium chloride is included in the strong acid catalyst because it decomposes due to heat in the condensation reaction system, and ammonia evaporates and becomes acidic with hydrochloric acid.
Among the above strong acid catalysts, p-toluenesulfonic acid is more preferable. p-Toluenesulfonic acid not only functions as a strong acid catalyst, but also functions as a dopant for the π-conjugated conductive polymer. Therefore, the conductivity can be increased by mixing p-toluenesulfonic acid together with the polyfunctional acrylamide monomer into an aqueous solution containing a π-conjugated conductive polymer.

 The addition amount of the strong acid catalyst is preferably 0.001 to 1 molar equivalent, more preferably 0.01 to 0.1 molar equivalent with respect to the amount of N-alkoxymethyl (meth) acrylamide. When the addition amount of the strong acid catalyst is less than 0.001 molar equivalent, the heating temperature must be increased when the reaction is promoted when the pH in the reaction solvent is 4 or more, and as a result, the vinyl group is cleaved. There is a fear. Moreover, when the addition amount of a strong acid catalyst exceeds 1 molar equivalent, there exists a possibility of causing the superposition | polymerization of a vinyl group.

The polymerization inhibitor is preferably at least one selected from hydroquinone monomethyl ether, hydroquinone, sodium nitrate, cuferon, and α-aminoacetic acid.
The addition amount of the polymerization inhibitor is preferably 1 ppm to 100%, more preferably 10 ppm to 10% with respect to the amount of N-alkoxymethyl (meth) acrylamide. When the addition amount of the polymerization inhibitor is less than 1 ppm, the vinyl group may be polymerized by heat during the condensation reaction, and when it exceeds 100%, the curing may be inhibited.

 The reaction solvent is preferably an inert solvent. For example, tetrahydrofuran (THF), ethyl acetate, butyl acetate, 1,3-dioxolane, 1,4-dioxane, methoxyethyl acetate, methyl isobutyl ketone, cellosolve acetate, acetonitrile, N One type or two or more types selected from -methyl-2-pyrrolidone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, and dimethyl sulfoxide can be used.

  In the condensation reaction, it is preferable to send dry nitrogen heated to room temperature or about 40 to 100 ° C. to discharge generated water and alcohol out of the system. Moreover, since a yield becomes high, it is preferable to add drying agents, such as a molecular sieve, in the reaction solvent.

 In the condensation reaction of the above formula (1), when the primary polyhydric alcohol has 3 or more hydroxyl groups, the amount of N-alkoxymethyl (meth) acrylamide added is that of the primary polyhydric alcohol having 3 or more hydroxyl groups. It is preferable that it is 0.1-10 mol equivalent with respect to a hydroxyl group, and it is more preferable that it is 0.5-3 mol equivalent. When the addition amount of N-alkoxymethyl (meth) acrylamide is less than 0.1 molar equivalent, substitution by condensation reaction is not performed, and an unreacted hydroxyl group remains, and sufficient hardness is obtained when cured. It may not be possible. In addition, a large amount of unreacted N-alkoxymethyl (meth) acrylamide, a condensation compound of N-alkoxymethyl (meth) acrylamides, and a bifunctional acrylamide monomer are produced. As a result, when the product obtained by the condensation reaction is cured without purification, the hardness may not be sufficiently increased because these inhibit crosslinking.

The product of the polyfunctional acrylamide monomer is preferably purified after the condensation reaction. Examples of the purification method include recrystallization, reprecipitation, column chromatography and the like. As the solvent for recrystallization and reprecipitation, a general organic solvent is used, and alcohols, ketones, acetates and the like are preferably used. As column chromatography, reverse layer chromatography or the like is preferably used.
For analysis of the product of the polyfunctional acrylamide monomer, gel permeation chromatography (GPC), liquid chromatography (LC), ¹ H-NMR, elemental analysis and the like are applied.

The polyfunctional acrylamide monomer has a chemical structure represented by the general formula (I) and has high hydrophilicity. Therefore, the polyfunctional acrylamide monomer has high solubility in water-soluble solvents and can be contained in water-based paints. For example, it can be contained in an aqueous conductive polymer coating containing a π-conjugated conductive polymer such as polypyrrole or polyethylenedioxythiophene (PEDOT). Moreover, since this polyfunctional acrylamide monomer can increase the crosslinking density after crosslinking, it is excellent in water resistance and solvent resistance after curing. That is, the polyfunctional acrylamide monomer has high solubility in water-soluble solvents and can increase the crosslinking density after curing.
Furthermore, since the polyfunctional acrylamide monomer has high solubility in an aqueous solvent, it can be developed with water, and the cured film can be easily patterned.

<Conductive polymer paint>
The conductive polymer paint of the present invention contains the polyfunctional acrylamide monomer, a π-conjugated conductive polymer, a polyanion, a binder resin, and a water-soluble solvent.

(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 thereof 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 and compatibility with the binder resin can be obtained, but in order to further improve conductivity and dispersibility or solubility in the binder resin. It is preferable to introduce a functional group such as an alkyl group, a carboxy group, a sulfo group, an alkoxy group, a hydroxy group, or a cyano 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), poly (thiophene), 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-di Butylthiophene), 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) And the like.

Among them, from one or two kinds 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.
In addition, alkyl-substituted compounds such as poly (N-methylpyrrole) and poly (3-methylthiophene) are more preferable because they improve solvent solubility, compatibility with a binder resin, and dispersibility. Among the alkyl groups, a methyl group is preferred because it does not adversely affect the conductivity. Furthermore, poly (3,4-ethylenedioxythiophene) doped with polystyrene sulfonic acid (abbreviated as PEDOT-PSS) is water-soluble, has relatively high thermal stability, and has a low degree of polymerization. This is preferable because it is advantageous in terms of stability of the conductive paint when mixed with the monomer.

The π-conjugated conductive polymer is a chemical oxidative polymerization of a precursor monomer that forms a π-conjugated conductive polymer in a solvent in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a solubilized polymer component described below. Can be manufactured easily.
[Precursor monomer]
The precursor monomer has a π-conjugated system in the molecule, and a π-conjugated system is formed in the main chain even when polymerized by the action of an appropriate oxidizing agent. Examples thereof include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.
Specific examples of the precursor monomer include pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3- Dodecylpyrrole, 3,4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole 3-hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3 -Methylthiophene, 3-ethylthiophene, -Propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3 -Iodothiophene, 3-cyanothiophene, 3-phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3- Hexyloxythiophene, 3-heptyloxythiophene, 3-octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene 3,4-dimethoxythiophene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxythiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butene Oxythiophene, 3-methyl-4-methoxythiophene, 3-methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4 -Carboxybutylthiophene, aniline, 2-methylaniline, Examples include 3-isobutylaniline, 2-aniline sulfonic acid, and 3-aniline sulfonic acid.

[solvent]
The solvent used in the production of the π-conjugated conductive polymer is not particularly limited, and is a solvent that can dissolve or disperse the precursor monomer, and can maintain the oxidizing power of the oxidizing agent and the oxidation catalyst. Specific examples thereof include water and water-soluble solvents.

[Oxidizing agent and oxidation catalyst]
Any oxidizing agent or oxidation catalyst may be used as long as it can oxidize the precursor monomer to obtain a π-conjugated conductive polymer. For example, ammonium peroxodisulfate, sodium peroxodisulfate, peroxodisulfide Peroxodisulfates such as potassium sulfate, transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate and cupric chloride, metal halides such as boron trifluoride and aluminum chloride, silver oxide Metal oxides such as cesium oxide, peroxides such as hydrogen peroxide and ozone, organic peroxides such as benzoyl peroxide, oxygen, and the like.

(Polyanion)
The polyanion is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a copolymer thereof. It consists of a structural unit having a group and a structural unit having no anionic group.
The anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.

 A polyalkylene is a polymer whose main chain is composed of repeating methylenes. Examples of the polyalkylene include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, poly3,3,3-trifluoropropylene, polyacrylonitrile, polyacrylate, polystyrene, and the like.

Polyalkenylene is a polymer composed of structural units containing one or more unsaturated bonds (vinyl groups) in the main chain. 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-butyl-2-pentenylene, 4-he Selected from sil-2-pentenylene, 4-cyano-2-pentenylene, 3-methyl-2-pentenylene, 4-ethyl-2-pentenylene, 3-phenyl-2-pentenylene, 4-hydroxy-2-pentenylene, hexenylene, etc. And a polymer containing one or more structural units.
Among these, substituted or unsubstituted butenylene is preferable because of the interaction between the unsaturated bond and the π-conjugated conductive polymer and the ease of synthesis using substituted or unsubstituted butadiene as a starting material.

Examples of polyimide include pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2,3,3-tetracarboxydiphenyl ether dianhydride, 2,2- [4,4 Examples include polyimides from anhydrides such as' -di (dicarboxyphenyloxy) phenyl] propane dianhydride and diamines such as oxydianine, paraphenylenediamine, metaphenylenediamine, and benzophenonediamine.
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, compatibility with a resin, and the like, an alkyl group, a hydroxy group, a phenol group, and an ester group are preferable.
Alkyl groups can increase solubility and dispersibility in polar or nonpolar solvents, compatibility and dispersibility in resins, and hydroxy groups form hydrogen bonds with other hydrogen atoms. This makes it easy to increase solubility in organic solvents, compatibility with resins, dispersibility, and adhesion. In addition, the cyano group and the hydroxyphenyl group can increase the compatibility and solubility in the polar resin, and can also increase the heat resistance.
Among the above substituents, an alkyl group, a hydroxy group, an ester group, and a cyano group are preferable.

Examples of the alkyl group include chain 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. . In consideration of solubility in an organic solvent, dispersibility in a resin, steric hindrance, and the like, an alkyl group having 1 to 12 carbon atoms is more preferable.
Examples of the hydroxy group include a hydroxy group directly bonded to the main chain of the polyanion or a hydroxy group bonded via another functional group. Examples of other functional groups include an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an amide group, and an imide group. The hydroxy group is substituted at the end or in these functional groups. Among these, a hydroxy group bonded to the terminal of an alkyl group having 1 to 6 carbon atoms bonded to the main chain is more preferable from the viewpoint of compatibility with a resin and solubility in an organic solvent.
Examples of the amino group include an amino group directly bonded to the main chain of the polyanion or an amino group bonded via another functional group. Examples of other functional groups include an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an amide group, and an imide group. The amino group is substituted at the end or in these functional groups.
Examples of the phenol group include a phenol group directly bonded to the main chain of the polyanion or a phenol group bonded via another functional group. Examples of other functional groups include an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an amide group, and an imide group. The phenol group is substituted at the end or in these functional groups.
Examples of the ester group include an alkyl ester group directly bonded to the main chain of the polyanion, an aromatic ester group, and an alkyl ester group or an aromatic ester group having another functional group interposed therebetween.
The cyano group includes a cyano group directly bonded to the main chain of the polyanion, a cyano group bonded to the terminal of the alkyl group having 1 to 7 carbon atoms bonded to the main chain of the polyanion, and 2 to 2 carbon atoms bonded to the main chain of the polyanion. And a cyano group bonded to the terminal of 7 alkenyl group.

 The anion group of the polyanion may be a functional group capable of undergoing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate group, A monosubstituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.

Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfonic acid, polyvinyl carboxylic acid. Examples include acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
Of these, polyacrylsulfonic acid and polymethacrylsulfonic acid are preferred. Polyacrylsulfonic acid and polymethacrylsulfonic acid are excellent in heat resistance and environmental resistance because thermal decomposition of the π-conjugated conductive polymer component is relaxed by absorbing thermal energy and decomposing by itself. Furthermore, since it has a sulfonic acid group, it is excellent in compatibility and dispersibility with a polyfunctional acrylamide monomer, and is excellent in compatibility and dispersibility of an ester group and a binder resin.

 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.

Examples of methods for producing polyanions include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, and anionic group-containing polymerization. And a method of production by polymerization of a functional monomer.
Examples of the method for producing an anion group-containing polymerizable monomer by polymerization include a method for producing an anion group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst. Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, kept at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, an anionic group-containing polymerizable monomer may be copolymerized with a polymerizable monomer having no anionic group.
The oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the π-conjugated conductive polymer.
When the obtained polymer is a polyanionic salt, it is preferably transformed into a polyanionic acid. Examples of the method for converting to an anionic acid include an ion exchange method using an ion exchange resin, a dialysis method, an ultrafiltration method, and the like. Among these, the ultrafiltration method is preferable from the viewpoint of easy work.

The anionic group-containing polymerizable monomer is one in which a part of the monomer is substituted with a mono-substituted sulfate group, a carboxy group, a sulfo group, etc., for example, a substituted or unsubstituted ethylene sulfonic acid compound, a substituted or unsubstituted Styrene sulfonic acid compound, substituted or unsubstituted acrylate sulfonic acid compound, substituted or unsubstituted methacrylate sulfonic acid compound, substituted or unsubstituted acrylamide sulfonic acid compound, substituted or unsubstituted cyclovinylene sulfonic acid compound, substituted or unsubstituted And a substituted or unsubstituted vinyl aromatic sulfonic acid compound.
Specifically, vinyl sulfonic acid and salts thereof, allyl sulfonic acid and salts thereof, methallyl sulfonic acid and salts thereof, styrene sulfonic acid, methallyloxybenzene sulfonic acid and salts thereof, allyloxybenzene sulfonic acid and salts thereof, α-methylstyrenesulfonic acid and its salts, acrylamide-t-butylsulfonic acid and its salts, 2-acrylamido-2-methylpropanesulfonic acid and its salts, cyclobutene-3-sulfonic acid and its salts, isoprenesulfonic acid and its Salts, 1,3-butadiene-1-sulfonic acid and its salts, 1-methyl-1,3-butadiene-2-sulfonic acid and its salts, 1-methyl-1,3-butadiene-4-sulfonic acid and its salts, ethyl acrylate sulfonic acid _{(CH 2 CH-COO- (CH} 2 ₂ -SO ₃ H) and its salts, acrylic acid propyl sulfonic acid _{(CH 2 CH-COO- (CH} 2) 3 -SO 3 H) and its salts, acrylic acid -t- butyl sulfonic acid _(CH 2 _{CH-COO -C (CH 3) 2 CH 2} -SO 3 H) and its salts, acrylic acid -n- butyl sulfonic acid _{(CH 2 CH-COO- (CH} 2) 4 -SO 3 H) and salts thereof, ethyl allyl acid sulfonic acid _{(CH 2 CHCH 2 -COO- (CH} 2) 2 -SO 3 H) and its salts, allyl acid -t- butyl sulfonic acid _{(CH 2 CHCH 2 -COO-C} (CH 3) 2 CH 2 -SO ₃ H) and salts thereof, 4-pentenoic acid ethylsulfonic acid (CH ₂ CH (CH ₂ ) ₂ —COO— (CH ₂ ) ₂ —SO ₃ H) and salts thereof, 4-pentenoic acid propyl sulfonic acid (CH ₂ CH (CH ₂ ) ₂ —COO— (CH ₂ ) ₃ -SO ₃ H) and salts thereof, 4-pentenoic acid-n-butylsulfonic acid (CH ₂ CH (CH ₂ ) ₂ —COO— (CH ₂ ) ₄ —SO ₃ H) and salts thereof, 4-pentene Acid-t-butyl sulfonic acid (CH ₂ CH (CH ₂ ) ₂ —COO—C (CH ₃ ) ₂ CH ₂ —SO ₃ H) and its salts, 4-pentenoic acid phenylene sulfonic acid (CH ₂ CH (CH _{2 2} ) -COO—C ₆ H ₄ —SO ₃ H) and salts thereof, 4-pentenoic acid naphthalenesulfonic acid (CH ₂ CH (CH ₂ ) ₂ —COO—C ₁₀ H ₈ —SO ₃ H) and salts thereof, Ethyl methacrylate sulfonic acid (CH ₂ C (CH ₃ ) —COO— (CH ₂ ) ₂ —SO ₃ H) and salts thereof, propyl methacrylate methacrylate (CH ₂ C (CH ₃ ) —COO— (CH ₂ ) ₃ -SO ₃ H) and its salts, methacrylic acid-t-butylsulfate Acid _{(CH 2 C (CH 3)} -COO-C (CH 3) 2 CH 2 -SO 3 H) and its salts, methacrylic acid -n- butyl sulfonic acid _{(CH 2 C (CH 3)} -COO- ( CH ₂ ) ₄ —SO ₃ H) and salts thereof, phenylene sulfonic acid methacrylate (CH ₂ C (CH ₃ ) —COO—C ₆ H ₄ —SO ₃ H) and salts thereof, naphthalene sulfonic acid methacrylate (CH ₂₎ C (CH ₃ ) —COO—C ₁₀ H ₈ —SO ₃ H) and salts thereof, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamide— Examples include 2-methylpropanecarboxylic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. Moreover, the copolymer containing 2 or more types of these may be sufficient.

Examples of the polymerizable monomer having no anionic group include ethylene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, styrene, p-methylstyrene, p. -Ethylstyrene, p-butylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, α-methylstyrene, 2-vinylnaphthalene, 6-methyl-2-vinylnaphthalene, 1-vinylimidazole, vinylpyridine, Vinyl acetate, acrylaldehyde, acrylonitrile, N-vinyl-2-pyrrolidone, N-vinylacetamide, N-vinylformamide, N-vinylimidazole, acrylamide, N, N-dimethylacrylamide, acrylic acid, methyl acrylate, Ethyl acrylate, propyl acrylate, acrylic acid -Butyl, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, isononyl butyl acrylate, lauryl acrylate, allyl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, benzyl acrylate, ethyl acrylate Carbitol, phenoxyethyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, methoxybutyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacryl T-butyl acid, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, methacrylic acid Benzyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acryloylmorpholine, vinylamine, N, N-dimethylvinylamine, N, N-diethylvinylamine, N, N-dibutylvinylamine, N, N-di -T-butylvinylamine, N, N-diphenylvinylamine, N-vinylcarbazole, vinyl alcohol, vinyl chloride, vinyl fluoride, methyl vinyl ether, ethyl vinyl ether, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 2-methylcyclohexene, vinylphenol, 1,3-butadiene, 1-methyl-1,3-butadiene, 2-methyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene, 1,2- Dimethyl , 3-butadiene, 1,3-dimethyl-1,3-butadiene, 1-octyl-1,3-butadiene, 2-octyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 2-phenyl -1,3-butadiene, 1-hydroxy-1,3-butadiene, 2-hydroxy-1,3-butadiene and the like.
By copolymerizing these polymerizable monomers having no anionic group, solvent solubility and compatibility with the binder resin can be controlled.

A polymer having an electron withdrawing group may be mixed with the polyanion. Examples of the electron-withdrawing group of the polymer having an electron-withdrawing group include a polymer having as a structural unit a compound having at least one selected from a cyano group, a nitro group, a formyl group, a carbonyl group, and an acetyl group. Among these, a cyano group is preferable because it has high polarity and can solubilize a π-conjugated conductive polymer. Moreover, since compatibility with a binder resin and dispersibility can be made higher, it is preferable.
Specific examples of the polymer having an electron-withdrawing group include polyacrylonitrile, polymethacrylonitrile, acrylonitrile-styrene resin, acrylonitrile-butadiene resin, acrylonitrile-butadiene-styrene resin, and cyanoethylated hydroxyl group or amino group-containing resin. Examples thereof include resins (for example, cyanoethyl cellulose), polyvinyl pyrrolidone, alkylated polyvinyl pyrrolidone, and nitrocellulose.

 The polyanion may contain a synthetic rubber for improving impact resistance, an anti-aging agent, an antioxidant, and an ultraviolet absorber for improving environmental resistance. However, amine compound antioxidants may interfere with the action of the oxidizer used when polymerizing the above conductive polymer, so the antioxidant may be phenolic or mixed after polymerization. It is necessary to take measures such as

(Dopant)
In order to improve the electrical conductivity (conductivity) of the π-conjugated conductive polymer, other dopants may be added in addition to the polyanion. Other dopants may be donor or acceptor as long as the π-conjugated conductive polymer can be oxidized and reduced.

[Donor dopant]
Examples of the donor dopant include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, dimethyldiethylammonium, and the like. A quaternary amine compound etc. are mentioned.

[Acceptor dopant]
As the acceptor dopant, for example, a halogen compound, Lewis acid, proton acid, organic cyano compound, organometallic compound, fullerene, hydrogenated fullerene, hydroxylated fullerene, carboxylated fullerene, sulfonated fullerene, or the like can be used.
Furthermore, examples of the halogen compound include chlorine (Cl ₂ ), bromine (Br ₂ ), iodine (I ₂ ), iodine chloride (ICl), iodine bromide (IBr), and iodine fluoride (IF). .
Examples of the Lewis acid include PF ₅ , AsF ₅ , SbF ₅ , BF ₅ , BCl ₅ , BBr ₅ , SO _{3 and the} like.
As the organic cyano compound, a compound containing two or more cyano groups in a conjugated bond can be used. Examples include tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, dichlorodicyanobenzoquinone (DDQ), tetracyanoquinodimethane, and tetracyanoazanaphthalene.

  Examples of the protonic acid include inorganic acids and organic acids. Furthermore, examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, borohydrofluoric acid, hydrofluoric acid, and perchloric acid. Examples of organic acids include organic carboxylic acids, phenols, and organic sulfonic acids.

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

As the organic sulfonic acid, aliphatic, aromatic, cycloaliphatic or the like containing one or more sulfo groups, or a polymer containing sulfo groups can be used.
As one containing one sulfo group, for example, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1 -Nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, 1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid, 2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfone Acid, trifluoroethanesulfonic acid, colistin methanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 2-amino-5-naphthol- 7-sulfonic acid, 3-aminopropanesulfone N-cyclohexyl-3-aminopropanesulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hex Tylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, 2, 4-dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid 4-amino-2-chlorotoluene-5-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-amino-5-methoxy-2-methylbenzenesulfonic acid, 2-amino-5-methyl Benzene-1-sulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4 -Acetamide-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, 4 -Amino-1-naphthalenesulfonic acid, 8-chloronaphthalene-1- Examples include sulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, anthraquinone sulfonic acid, and pyrene sulfonic acid. These metal salts can also be used.

  Examples of those containing two or more sulfo groups include ethanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, decanedisulfonic acid, o-benzenedisulfonic acid, m-benzenedisulfonic acid, p-benzenedisulfonic acid, and toluenedisulfonic acid. Xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, dimethylbenzene disulfonic acid, diethylbenzene disulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 3,4-dihydroxy-1,3 Benzene disulfonic acid, naphthalene disulfonic acid, methyl naphthalene disulfonic acid, ethyl naphthalene disulfonic acid, pentadecyl naphthalene disulfonic acid, 3-amino-5-hydroxy-2,7-naphthalene disulfonic acid, 1- Cetamide-8-hydroxy-3,6-naphthalenedisulfonic acid, 2-amino-1,4-benzenedisulfonic acid, 1-amino-3,8-naphthalenedisulfonic acid, 3-amino-1,5-naphthalenedisulfonic acid, 8-Amino-1-naphthol-3,6-disulfonic acid, 4-amino-5-naphthol-2,7-disulfonic acid, 4-acetamido-4'-isothio-cyanotostilbene-2,2'-disulfonic acid 4-acetamido-4′-isothiocyanatostilbene-2,2′-disulfonic acid, 4-acetamido-4′-maleimidylstilbene-2,2′-disulfonic acid, naphthalenetrisulfonic acid, dinaphthylmethanedisulfone An acid, anthraquinone disulfonic acid, anthracene sulfonic acid, etc. are mentioned. These metal salts can also be used.

  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 0.1 mol, the doping effect on the π-conjugated conductive polymer tends to be weak, and the conductivity may be insufficient. In addition, the dispersibility and solubility in the solvent are reduced, making it difficult to obtain a uniform dispersion. On the other hand, when the polyanion content is more than 10 mol, the content ratio of the π-conjugated conductive polymer decreases, and it is difficult to obtain sufficient conductivity.

[Binder resin]
The binder resin is compatible or mixed with π-conjugated conductive polymer and polyfunctional acrylamide monomer, and also has high scratch resistance and surface hardness of conductive coating film formed from conductive polymer paint. And any material that can improve the adhesion to the substrate. For example, it may be a thermoplastic resin, a thermosetting resin, or a photosensitive vinyl group-containing compound. Good.
Specifically, examples of the thermoplastic resin include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyimides such as polyimide and polyamideimide; polyamides such as polyamide 6, polyamide 6,6, polyamide 12, and polyamide 11; Fluorine resins such as polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, and polychlorotrifluoroethylene; Vinyl resins such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, and polyvinyl chloride; Epoxy resin; Oxetane resin; Xylene resin; Aramid resin; Polyimide silicone; Polyurethane; Polyurea; Melamine resin; ; It includes acrylic resins and the like copolymers of these.
These binder resins may be dissolved in an organic solvent, may be provided with a functional group such as a sulfo group or a carboxy group, may be formed into an aqueous solution, or may be dispersed in water such as emulsification.
Further, the binder resin can be used by adding a curing agent such as a cross-linking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity adjusting agent, and the like as necessary.

 Among the binder resins, one or more of polyurethane, polyester, acrylic resin, polyamide, polyimide, epoxy resin, and polyimide silicone are preferable because they can be easily mixed. Acrylic resins are suitable for applications such as optical filters because of their high hardness and excellent transparency.

The thermosetting resin preferably includes a liquid polymer that is cured by thermal energy. Here, examples of the liquid polymer that is cured by thermal energy include a reactive polymer and a self-crosslinking polymer.
A reactive polymer is a polymer in which a monomer having a substituent is polymerized, and examples of the substituent include a hydroxy group, a carboxy group, an acid anhydride, an oxetane group, a glycidyl group, and an amino group. Specific monomers include polyfunctional alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol, and glycerin, malonic acid, succinic acid, glutamic acid, pimelic acid, ascorbic acid, phthalic acid, acetylsalicylic acid, adipic acid, and isophthalic acid. Acid anhydrides such as acid, benzoic acid, carboxylic acid compounds such as m-toluic acid, maleic anhydride, phthalic anhydride, dodecyl succinic anhydride, dichloromaleic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, pimelic anhydride , Oxetane compounds such as 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-methyl-3-hydroxymethyloxetane, azidomethylmethyloxetane, bisphenol A diglycidyl ether, bisphenol F diglycidyl Ether, phenol novolac polyglycidyl ether, N, N-diglycidyl-p-aminophenol glycidyl ether, tetrabromobisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether (ie 2,2-bis (4-glycidyloxycyclohexyl) ) Glycidyl ether compounds such as propane), N, N-diglycidylaniline, tetraglycidyldiaminodiphenylmethane, N, N, N, N-tetraglycidyl-m-xylylenediamine, triglycidyl isocyanurate, N, N-diglycidyl- Glycidylamine compounds such as 5,5-dialkylhydantoin, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, N-aminoethylpiperazine, benzyldimethyl Ruamine, tris (dimethylaminomethyl) phenol, DHP30-tri (2-ethylhexoate), metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide, boron trifluoride, monoethylamine, methanediamine, xylenediamine, ethyl Among the amine compounds such as methylimidazole, among the compounds containing two or more oxirane rings in one molecule, glycidyl compounds by epichlorohydrin of bisphenol A, or the like can be mentioned.

In the reactive polymer, at least a bifunctional or higher functional crosslinking agent is used. Examples of the crosslinking agent include melamine resin, epoxy resin, metal oxide and the like. Examples of the metal oxide include basic metal compounds Al (OH) ₃ , Al (OOC · CH ₃ ) ₂ (OOCH), Al (OOC · CH ₃ ) ₂ , ZrO (OCH ₃ ), Mg (OOC · CH _3). ), Ca (OH) ₂ , Ba (OH) _{3 and the} like can be used as appropriate.

 Self-crosslinking polymers are those that self-crosslink between functional groups by heating, and examples include those containing a glycidyl group and a carboxy group, and those containing both an N-methylol and a carboxy group.

Examples of the photosensitive vinyl group-containing compound include (meth) acrylic acid ester monomers, (meth) acrylamide monomers, allyl monomers, vinyl ester monomers, vinyl ether monomers, styrene monomers, or vinyl groups. A compound having two or more.
Furthermore, as (meth) acrylic acid ester monomers, for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, tetra Of ethylene oxide adducts of decaethylene glycol di (meth) acrylate, nonapropylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, glycerin di (meth) acrylate, polyols and the like and 1,3-propanediol di (meth) acrylate.
Examples of (meth) acrylamide compounds include methylenebis (meth) acrylamide, ethylenediamine, diaminopropane, diaminobutane, pentamethylenediamine, bis (2-aminopropyl) amine, diethylenetriaminediamine, phenylenediamine, and diaminebenzoic acid. And poly (meth) acrylamide derived from
Examples of allylic monomers include diallyl phthalate and diallyl malonate.
Examples of vinyl ester monomers include divinyl succinate and divinyl adipate.
Examples of vinyl ether monomers include ethylene glycol divinyl ether and 1,3,5-tri-β-vinyloxyethoxybenzene.
Examples of the styrene monomer include divinylbenzene and p-allylstyrene.

Examples of the compound having two or more vinyl groups include compounds having an acrylate or methacrylate group at the terminal and / or side chain of the oligomer, or esters or amides of the compound.
Specific examples include esters of unsaturated carboxylic acids and polyhydric alcohols, and amides of unsaturated carboxylic acids and polyvalent amine compounds.
In addition, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxy group, an amino group, a mercapto group, and the like, and a monofunctional or polyfunctional isocyanate, epoxy, or And a dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid.
In addition, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol Can be mentioned.
Furthermore, there is a substitution reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a detachable substituent such as a halogen group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine, or thiol. Can be mentioned.

Examples of the unsaturated carboxylic acid that is a raw material for forming the compound having two or more vinyl groups include maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride.
Examples of the polyhydric alcohols include ethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, pentaerythritol, glycerin, trimethylolpropane and the like.
Examples of isocyanates include hexamethylene diisocyanate, methylene diphenylene diisocyanate, xylene diisocyanate, 1,4-naphthalene diisocyanate, and phenylene diisocyanate.
Examples of the compound having a carboxy group include vinyl benzoate, crotonic acid, cinnamic acid, and acrylic acid dimer.
Examples of the compound having an epoxy group include diglycidyl phthalate, propylene glycol diglycidyl ether, vinylcyclohexene diepoxide, epoxidized phenol resin, and epoxidized polybutadiene.
Examples of compounds capable of forming an oligomer having an allyl group include triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, triallyl trimellitate, triallyl citrate and the like.

Examples of the photosensitive vinyl group-containing compound include a photosensitive liquid polymer that is cured by light energy. Examples of the photosensitive liquid polymer include oligomers or prepolymers such as polyester, epoxy resin, oxetane resin, polyacryl, polyurethane, polyimide, polyamide, polyamideimide, and polyimide silicone.
Examples of the monomer unit constituting the photosensitive liquid polymer include bisphenol A / ethylene oxide modified diacrylate, dipentaerythritol hexa (penta) acrylate, dipentaerythritol monohydroxypentaacrylate, dipropylene glycol diacrylate, Methylolpropane triacrylate, glycerin propoxytriacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate Acrylate, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate, tripropyl Acrylates such as ethylene glycol diacrylate, tetraethylene glycol dimethacrylate, alkyl methacrylate, allyl methacrylate, 1,3-butylene glycol dimethacrylate, n-butyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, diethylene glycol dimethacrylate, 2-ethylhexyl methacrylate, Methacrylates such as glycidyl methacrylate, 1,6-hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, t-butyl methacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate, Allyl glycidyl A , Butyl glycidyl ether, higher alcohol glycidyl ether, 1,6-hexanediol glycidyl ether, phenyl glycidyl ether, glycidyl ethers such as stearyl glycidyl ether, diacetone acrylamide, N, N-dimethylacrylamide, dimethylaminopropyl acrylamide, dimethyl Aminopropylmethacrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylformamide, N-methylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide, N-phenylacrylamide, Acrylic (methacrylic) amides such as acryloylpiperidine and 2-hydroxyethylacrylamide; Monofunctional monomers of 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, isobutyl vinyl ether, vinyl ethers such as triethylene glycol vinyl ether, carboxylic acid vinyl esters such as vinyl butyrate, vinyl monochloroacetate and vinyl pivalate, and A polyfunctional monomer is mentioned.

In addition, as the photosensitive vinyl group-containing compound, at least two ethylenically unsaturated compounds obtained by reacting a polyol compound having at least two hydroxyl groups and a polyisocyanate compound having at least two or more isocyanate groups. The polyfunctional urethane compound which has group is mentioned.
Further, the conductive polymer paint may further contain a known negative or positive photosensitive oligomer other than the photosensitive vinyl group-containing compound.

The photosensitive vinyl group-containing compound is cured by a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthones and the like. Furthermore, n-butylamine, triethylamine, tri-n-butylphosphine, or the like can be mixed as a photosensitizer.
Examples of the cationic polymerization initiator include aryldiazonium salts, diarylhalonium salts, triphenylsulfonium salts, silanol / aluminum chelates, α-sulfonyloxyketones, and the like.

(Water-soluble solvent)
Examples of the water-soluble solvent include polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylene phosphortriamide, acetonitrile, and benzonitrile. Phenols such as cresol, phenol and xylenol, alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, carboxylic acids such as formic acid and acetic acid, carbonate compounds such as ethylene carbonate and propylene carbonate, dioxane , Ether compounds such as diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene group Chain ethers call dialkyl ether, 3-methyl-2-oxazolidinone heterocyclic compounds such as, acetonitrile, glutarodinitrile, methoxy acetonitrile, propionitrile, nitrile compounds such as benzonitrile and the like. These solvents may be used alone or as a mixture of two or more.
A water-insoluble solvent or water may be added to the water-soluble solvent.

  In this conductive polymer paint, it is preferable that 0.1 to 100 mole equivalent of polyfunctional acrylamide monomer is contained with respect to the π-conjugated conductive polymer. When the polyfunctional acrylamide monomer exceeds 100 molar equivalents with respect to the π-conjugated conductive polymer, the conductivity tends to be low. In addition, when the polyfunctional acrylamide monomer is less than 0.1 molar equivalent, the water resistance, solvent resistance, thermal stability, film formability, abrasion resistance, and substrate adhesion tend to be low.

The binder resin is preferably contained in the conductive polymer paint in an amount of 0.1 to 100 molar equivalents, more preferably 2 to 50 molar equivalents, relative to the polyfunctional acrylamide monomer.
Moreover, it is preferable that 0.1-100 mol equivalence of binder resin is contained with respect to (pi) conjugated system conductive polymer.

Since the conductive polymer paint described above contains the polyfunctional acrylamide monomer, the crosslink density after curing is high.
Moreover, although the said conductive polymer coating material contains a water-soluble solvent, the said polyfunctional acrylamide monomer has high solubility to water-soluble solvents, and is melt | dissolving uniformly.

(Conductive coating)
The conductive coating film of the present invention is formed by applying the conductive polymer paint.
Examples of the method for applying the conductive polymer coating include immersion, comma coating, spray coating, roll coating, and gravure printing.
After application, the solvent may be removed by heating, or may be cured by heat or light. As a heating method in the case of heating, for example, a normal method such as hot air heating or infrared heating can be adopted. In addition, as a light irradiation method when forming a coating film by photocuring, for example, a method of irradiating ultraviolet rays from a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be adopted. .
Since the thus formed conductive coating film has a high crosslinking density, it can be suitably used for an antistatic film, an optical filter, an optical information recording medium, a resistive film of a touch panel, and the like.

Example 1
In 800 ml of dehydrated THF, 250 g (1 mol) of ditrimethylolpropane, 444 g (4.4 mol) of N-methylolacrylamide and 0.3 g (0.002 mol) of hydroquinone monomethyl ether are placed in a four-necked separable flask and stirred. Dissolved. After the separable flask was placed in an oil bath, the temperature of the oil bath was set to 50 ° C. Next, 0.3 g (0.0016 mol) of p-toluenesulfonic acid was added to the separable flask, and the mixture was stirred for 1 hour under a nitrogen stream, and then neutralized with 10% aqueous ammonia to react. finished. Next, the solvent was removed by evaporation and vacuum drying, and the paste-like reaction product thus obtained was recrystallized to obtain ditrimethylolpropanetetraacrylamide as a white powder crystal.

LC body is Waters 2690, detector is Waters 996PDA detector, column is Symmetry C-18, column temperature is 40 ° C, eluent is methanol and water gradient, eluent flow rate is 1.0ml; sample injection The volume was 10 μl.
The progress of the reaction was confirmed by liquid chromatography (LC). The LC chart shows unreacted ditrimethylolpropane, N-methylolacrylamide, a dimer of N-methylolacrylamides, N-methylolacrylamide substituted with ditrimethylolpropane, and 2, 3, and 4 similarly. Was detected.
When 10 mg of the crystal obtained in Example 1 was dissolved in 10 ml of methanol and LC was measured, a single peak was observed at a retention time of 18.9 minutes.

¹ H-NMR of the crystal obtained in Example 1 was measured.
¹ H-NMR (500 MHz, acetone-D6) δ:
0.67 (t, 6H, ditrimethylolpropane CH ₃ -);
1.29 (q, 4H, ditrimethylolpropane —CH ₂ —)
3.25 (s, 12H, ditrimethylolpropane C—CH ₂ —O—);
4.77 (d, 8H, N-methylolacrylamide O—CH ₂ —NH—);
5.64 (t, 4H, N-methylolacrylamide C—CH═C);
6.25-6.29 (d, 8H, N- methylolacrylamide C = _CH 2);
8.03 (br s, 4H, -NH-)
From this result, it was confirmed that ditrimethylolpropane tetraacrylamide was produced.

(Example 2)
In a mixed solution of 800 ml of DMF and dehydrated THF in a mass ratio of 50:50, 254 g (1 mol) of dipentaerythritol, 691 g (4.4 mol) of N- (n-butoxymethyl) methacrylamide, 0.14 g (0. 002 mol) sodium nitrate was placed in a four-necked separable flask and stirred to dissolve. After the separable flask was placed in an oil bath, the temperature of the oil bath was set to 50 ° C. Next, 0.3 g (0.0016 mol) of p-toluenesulfonic acid was added to the separable flask, stirred for 1.5 hours under a nitrogen stream, and then neutralized with ammonia water diluted to 10%. The reaction was terminated. Subsequently, the obtained product was recrystallized to obtain dipentaerythritol hexamethacrylamide as a white powder crystal.

As in Example 1, the progress of the reaction was confirmed by LC. The LC chart includes unreacted dipentaerythritol, N- (n-butoxymethyl) methacrylamide, a dimer of N- (n-butoxymethyl) methacrylamide, and N- (n-butoxymethyl) methacrylamide. One substituted with ditrimethylolpropane, and similarly 2, 3, 4, 5, 6 substituted, were detected.
When the crystal obtained in Example 2 was treated in the same manner as in Example 1 and LC was measured, a single peak was observed at a retention time of 17.3 minutes.

Further, ¹ H-NMR was measured.
¹ H-NMR (500 MHz, acetone-D6) δ:
2.27 (s, 18H, N- ( n- butoxymethyl) methacrylamide = _C-CH 3);
3.25 (s, 16H, dipentaerythritol C—CH ₂ —O);
4.77 (d, 12H, N- (n-butoxymethyl) methacrylamide O—CH ₂ —NH—);
6.23 (d, 12H, N- ( n- butoxymethyl) methacrylamide C = _CH 2);
8.03 (brs, 6H, -NH-)
From this result, it was confirmed that dipentaerythritol hexamethacrylamide was produced.

(Comparative Example 1)
A product was obtained in the same manner as in Example 1 except that 176 g (1 mol) of sorbitol was used instead of ditrimethylolpropane.
The progress of the reaction was observed by LC, but a 1 to 6-substituted condensation reaction product with sorbitol (six hydroxyl groups) was not detected. That is, in Comparative Example 1, it is considered that the reaction between sorbitol and N-methylolacrylamide did not proceed and the polyfunctional acrylamide monomer was not formed.

(Comparative Example 2)
Example 2 was the same as Example 2 except that sodium nitrate was not added and no substitute was added. 0.5 hours after starting the reaction, the inside of the flask was in a gel state. That is, in Comparative Example 2, since the polymerization inhibitor was not added, it is considered that the polymerization between N- (n-butoxymethyl) acrylamides was accelerated by heat and became a gel state having a crosslinked structure.

(Comparative Example 3)
In Example 1, the reaction was performed in the same manner as in Example 1 except that 0.16 g (0.0016 mol) of phosphoric acid was used instead of p-toluenesulfonic acid.
Although the progress of the reaction was observed by LC, the raw material could be detected, but the condensation product of ditrimethylolpropane and N-methylolacrylamide was not detected. That is, in Comparative Example 3, it was considered that the condensation reaction did not proceed because a phosphoric acid catalyst that was not a strong acid catalyst was used.

(Preparation Example 1) Preparation of Polyethylenedioxythiophene and Polystyrenesulfonic Acid Conductive Polymer Solution 1 185 g (1 mol) of sodium styrenesulfonate was dissolved in 1000 ml of ion-exchanged water, and the mixture was stirred at 80 ° C. and 10 ml in advance. 1.14 g (0.005 mol) of an ammonium persulfate (ammonium peroxodisulfate) oxidizer solution dissolved in water was added dropwise over 20 minutes, and then stirred for 12 hours.
1000 ml of sulfuric acid diluted to 10% by mass was added to the resulting solution, about 1000 ml solution was removed using an ultrafiltration method, 2000 ml of ion-exchanged water was added thereto, and about 100 ml was added using an ultrafiltration method. 2000 ml of solution was removed. This ultrafiltration operation was repeated three times. And the water in the obtained solution was removed under reduced pressure, and colorless solid content was obtained.
Subsequently, 14.2 g (0.1 mol) of ethylenedioxythiophene and 18.5 g (0.15 ol) of polystyrene sulfonic acid dissolved in 2000 ml of ion-exchanged water were mixed.
While maintaining this mixed liquid at 20 ° C., stirring was performed to prepare 8.0 g (0.02 mol) of ferric sulfate oxidation catalyst solution of 29.64 g (0.13 mol) of ammonium persulfate dissolved in 200 ml of ion exchange water. Slowly added and stirred for 5 hours to react.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solution was removed using an ultrafiltration method. This operation was repeated three times.
Then, 2000 ml of ion-exchanged water is added to the obtained solution, about 2000 ml of the solution is removed using an ultrafiltration method, and about 1.5% by mass of a blue polystyrene sulfonic acid doped poly (ethylenedioxythiophene) solution is added. Obtained. This was designated as Conductive Polymer Solution 1.

(Preparation Example 2) Preparation of Conductive Polymer Solution 2 of Polypyrrole and Polystyrene Sulfonate 2 Dissolve 185 g (1 mol) of sodium styrene sulfonate in 1000 ml of ion exchange water and stir at 80 ° C. in 10 ml of water in advance. Dissolved 1.14 g (0.005 mol) of ammonium persulfate oxidizing solution was added dropwise for 20 minutes, and then stirred for 12 hours.
1000 ml of sulfuric acid diluted to 10% by mass was added to the resulting solution, about 1000 ml of solution was removed using ultrafiltration, 2000 ml of ion-exchanged water was added thereto, and ultrafiltration was used. About 2000 ml of solution was removed. This ultrafiltration operation was repeated three times. And the water in the obtained solution was removed under reduced pressure, and colorless solid content was obtained.
Subsequently, 6.6 g (0.1 mol) of pyrrole and 18.5 g (0.15 mol) of polystyrene sulfonic acid dissolved in 2000 ml of ion exchange water were mixed.
While maintaining this mixed liquid at 20 ° C., stirring was performed to prepare 8.0 g (0.02 mol) of ferric sulfate oxidation catalyst solution of 29.64 g (0.13 mol) of ammonium persulfate dissolved in 200 ml of ion exchange water. Slowly added and allowed to react with stirring for 2 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, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed using an ultrafiltration method. This operation was repeated 5 times to obtain about 1.5% by mass of a blue polystyrene sulfonic acid doped polypyrrole solution. This was designated as Conductive Polymer Solution 2.

(Example 3)
A solution prepared by dissolving 100 g of ditrimethylolpropane tetraacrylamide obtained in Example 1 in 500 ml of a mixed solvent (mass ratio of ethanol and methyl ethyl ketone is 1: 1), and 500 g of conductive high-conductivity obtained in Preparation Example 1. The molecular solution 1 was mixed, and 3 g of photopolymerization initiator Irgacure 754 was added to prepare a conductive polymer paint.
The conductive polymer paint was applied to a primer-treated polyethylene terephthalate film (thickness: 100 μm) with a wire coater # 16. And after drying for 2 minutes in 80 degreeC oven, UV irradiation was performed at 300 mJ / cm < ² >, the coating material was hardened, and the electrically conductive coating film was formed.
The obtained conductive coating film was subjected to surface resistance and scratch resistance test, water resistance test, MEK resistance test, total light transmittance measurement, and haze measurement.

The surface resistance was measured with a diamond instrument made of Loresta (probe: ASP).
In the scratch resistance test, # 0000 steel wool was reciprocated 20 times while applying a load of 500 g / cm ² on the conductive coating, and the number of scratches formed thereby was measured.
In the water resistance test, absorbent cotton wetted with water was reciprocated 200 times on the conductive coating film while applying a load of 250 g / cm ² , and the change in resistance value caused thereby was measured.
In the MEK resistance test, absorbent cotton moistened with MEK was reciprocated 200 times on a conductive coating film while applying a load of 250 g / cm ² , and a change in resistance value caused thereby was measured.
The total light transmittance was measured based on JIS Z 8701.
The haze was measured based on JIS K 6714.
The measurement results are shown in Table 1.

Example 4
A solution obtained by dissolving 100 g of dipentaerythritol hexamethacrylamide obtained in Example 2 in 500 ml of a mixed solvent (mass ratio of ethanol and methyl ethyl ketone is 1: 1), and 500 g of conductivity obtained in Preparation Example 2. Polymer solution 2 was mixed, and 3 g of photopolymerization initiator Irgacure 754 was added to prepare a conductive polymer paint. Thereafter, a conductive coating film was formed in the same manner as in Example 3 using this conductive polymer paint.
And like Example 3, about the obtained electroconductive coating film, the surface resistance and the abrasion resistance test, the water resistance test, the MEK resistance test, the total light transmittance measurement, and the haze measurement were performed. The measurement results are shown in Table 1.

(Comparative Example 4)
A conductive coating film was formed in the same manner as in Example 3 except that the product obtained in Comparative Example 1 was used instead of the product in Example 1 (ditrimethylolpropanetetraacrylamide).
And like Example 3, about the obtained electroconductive coating film, the surface resistance and the abrasion resistance test, the water resistance test, the MEK resistance test, the total light transmittance measurement, and the haze measurement were performed. The measurement results are shown in Table 1.

(Comparative Example 5)
A conductive coating film was formed in the same manner as in Example 4 except that the product obtained in Comparative Example 2 was used instead of the product in Example 2 (dipentaerythritol hexamethacrylamide).
And like Example 3, about the obtained electroconductive coating film, the surface resistance and the abrasion resistance test, the water resistance test, the MEK resistance test, the total light transmittance measurement, and the haze measurement were performed. The measurement results are shown in Table 1.

(Comparative Example 6)
A conductive coating film was formed in the same manner as in Example 3 except that the product obtained in Comparative Example 3 was used instead of the product in Example 1 (ditrimethylolpropanetetraacrylamide).
And like Example 3, about the obtained electroconductive coating film, the surface resistance and the abrasion resistance test, the water resistance test, the MEK resistance test, the total light transmittance measurement, and the haze measurement were performed. The measurement results are shown in Table 1.

The conductive polymer paints of Examples 3 and 4 containing the polyfunctional acrylamide monomer of the present invention were excellent in paint stability and dispersibility. In addition, the conductive coating film formed from this conductive polymer paint was excellent in total light transmittance and haze, and also excellent in scratch resistance, water resistance and MEK resistance.
The conductive polymer paints of Comparative Examples 1 to 3 that did not contain the polyfunctional acrylamide monomer of the present invention had low scratch resistance, water resistance, and MEK resistance.

Claims (3)

A conductive polymer paint containing a polyfunctional acrylamide monomer, a π-conjugated conductive polymer, a polyanion, a binder resin, and a water-soluble solvent,
The polyfunctional acrylamide monomer contains N-alkoxyalkyl (meth) acrylamide or N-hydroxyalkyl (meth) acrylamide represented by the following general formula (II) and three or more hydroxyl groups in the presence of a strong acid catalyst and a polymerization inhibitor. And a compound obtained by dehydration condensation or dealcoholization condensation in a reaction solvent with a primary polyhydric alcohol represented by the following general formula (III) in which all hydroxyl groups are primary: Conductive polymer paint.

(R ¹ in the general formula (II) represents a hydrogen atom or a methyl group, R ² represents a methylene group, an ethylene group, a propylene group, or a butylene group, and R ³ represents a hydrogen atom, a methyl group, an ethyl group, or n-propyl. And any one of a group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group, R ⁴ in the general formula (III) represents an organic group having at least one hydroxyl group.) The conductive polymer paint according to claim 1, wherein the polyfunctional acrylamide monomer is ditrimethylolpropane tetraacrylamide or dipentaerythritol hexamethacrylamide. A conductive coating film formed by applying the conductive polymer paint according to claim 1 .