JP5919095B2 - Conductive polymer paint and conductive coating film - Google Patents

Description

  The present invention relates to a conductive polymer paint and a conductive coating film containing a π-conjugated conductive polymer.

A π-conjugated conductive polymer whose main chain is composed of a conjugated system containing π electrons can be synthesized by an electrolytic polymerization method and a chemical oxidative polymerization method.
In the electropolymerization method, a support such as a previously formed electrode material is immersed in a mixed solution of an electrolyte serving as a dopant and a precursor monomer that forms a π-conjugated conductive polymer, and the π-conjugated system is formed on the support. A conductive polymer is formed into a film. Therefore, it is difficult to manufacture in large quantities.
On the other hand, in the chemical oxidation polymerization method, there is no such limitation, an oxidizing agent and an oxidation polymerization catalyst are added to the precursor monomer of the π-conjugated conductive polymer, and a large amount of π-conjugated conductive polymer is added in the solution. Can be manufactured.
However, in the chemical oxidative polymerization method, as the conjugated system of the π-conjugated conductive polymer main chain grows, the solubility in a solvent becomes poor, so that an insoluble solid powder can be obtained. If it is insoluble, it becomes difficult to form a π-conjugated conductive polymer film uniformly on the support surface.

Therefore, a method of introducing a functional group into a π-conjugated conductive polymer and solubilizing, a method of dispersing and solubilizing in a binder, and a method of solubilizing by adding an anion group-containing polymer have been tried.
For example, in order to improve the dispersibility in water, using an oxidizing agent in the presence of polystyrene sulfonic acid, which is an anion group-containing polymer acid (polyanion) having a molecular weight in the range of 2,000 to 500,000, A method for producing a dispersion of poly (3,4-dialkoxythiophene) by chemical oxidative polymerization of 3,4-dialkoxythiophene has been proposed (see Patent Document 1). In addition, a method for producing a π-conjugated conductive polymer colloid dispersion by chemical oxidative polymerization in the presence of polyacrylic acid has been proposed (see Patent Document 2).

According to the methods described in Patent Documents 1 and 2, an aqueous dispersion containing a π-conjugated conductive polymer can be easily produced. However, the conductive coating film formed by applying the aqueous dispersion produced by these methods has a problem that the surface resistance rapidly increases when exposed to visible light or ultraviolet light.
Then, the method of suppressing the raise of the surface resistance of the electroconductive coating film formed from the aqueous dispersion solution containing (pi) conjugated system conductive polymer by adding polyphosphoric acid etc. is proposed (patent document 3). However, even the method described in Patent Document 3 cannot sufficiently suppress the increase in surface resistance after irradiation with ultraviolet light, and the addition of polyphosphoric acid causes a new problem that the stability of the aqueous dispersion decreases. Also occurred.

Japanese Patent No. 2636968 Japanese Patent Laid-Open No. 7-165892 JP-T-2006-505099

  The present invention has been made in view of the above-mentioned problems, and provides a conductive polymer paint in which the obtained conductive coating film has high light resistance and the surface resistance is hardly increased even when irradiated with ultraviolet light. Objective. It is another object of the present invention to provide a conductive coating film that has high light resistance and whose surface resistance hardly increases even when irradiated with ultraviolet light.

The present invention has the following aspects.
[1] π-conjugated conductive polymer, polyanion, compound represented by chemical formula (1) below, amine compound, acrylic compound, and dispersion medium, content A of compound represented by chemical formula (1) When the mass ratio (a / B) 5 to 35 der the total content B of π-conjugated conductive polymer and polyanion is, the acrylic compound, acrylate monomers, methacrylate monomers, acrylamide monomers, methacrylamide monomers Conductive polymer paint, characterized in that it is one or more selected from the group consisting of epoxy acrylate, urethane acrylate, polyester acrylate, and polyacryl acrylate .
(In the formula, R ¹ and R ² are each independently a hydrogen atom or an arbitrary substituent.)
[2] A conductive coating film formed by applying the conductive polymer paint according to [1].

The conductive coating obtained from the π-conjugated conductive polymer paint of the present invention has high light resistance, and the surface resistance is hardly increased even when irradiated with ultraviolet light. Further, the π-conjugated conductive polymer paint of the present invention is excellent in stability.
The conductive coating film of the present invention has high light resistance, and the surface resistance is hardly increased even when irradiated with ultraviolet light.

<Conductive polymer paint>
The conductive polymer paint of the present invention comprises a π-conjugated conductive polymer, a polyanion, a compound represented by the chemical formula (1) (hereinafter referred to as “compound 1”), an amine compound, an acrylic compound, and a dispersion medium. contains.

(Π-conjugated conductive polymer)
The π-conjugated conductive polymer is an organic polymer whose main chain is composed of a π-conjugated system, for example, polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, Examples thereof include polythiophene vinylenes and copolymers thereof. Of these, polypyrroles, polythiophenes and polyanilines are preferred from the viewpoint of ease of polymerization and stability in air. Furthermore, polyophenes are preferable from the viewpoint of compatibility with a polar solvent and transparency.

  The π-conjugated conductive polymer may remain unsubstituted, but in order to obtain sufficient conductivity and compatibility with the binder resin, 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 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 the π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is preferable from the viewpoint of conductivity, transparency, and heat resistance.

(Polyanion)
A polyanion is a polymer having a structural unit having an anion 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.
The anion group of the polyanion may be any functional group that can undergo chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a sulfonic acid group, mono-substituted A sulfate group, a monosubstituted phosphate group, a phosphate group, a carboxyl 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 sulfonic acid group, a monosubstituted sulfate group, and a carboxyl group are more preferable.
Specific examples of polyanions include polystyrene sulfonic acid, polyvinyl 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.

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

By doping the π-conjugated conductive polymer with the polyanion, a complex of the π-conjugated conductive polymer and the polyanion is formed.
In the polyanion, all the anion groups are not doped into the π-conjugated conductive polymer and have an excess anion group. Since this surplus anion group is a hydrophilic group, it serves to solubilize the complex in water.

(Compound 1)
In compound 1, R ¹ and R ² are each independently a hydrogen atom or an arbitrary substituent.
Preferred R ¹ includes a hydrogen atom and an alkyl group, and preferred R ² includes an alkyl group and a 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione group. . A part of hydrogen of the alkyl group may be substituted with a part other than R ^{2 of the} compound 1.
Specific examples of the compound 1 is pentaerythritol tetrakis (3-mercapto butyrate) (hereinafter. Referred to as "Compound 1-a"), 1,3,5-tris (3-Merukaputobuchi Li Ruokishiechiru) -1,3 , 5-triazine-2,4,6 (1H, 3H, 5H) -trione (hereinafter referred to as “compound 1-b”), 1,4-bis (3-mercaptobutyryloxy) butane, β-mercapto Propionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopro Pionate, trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropyl Pionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), etc. Is mentioned.

  The mass ratio (A / B) of the content A of the compound represented by the chemical formula (1) and the total content B of the π-conjugated conductive polymer and the polyanion is 5 to 35 and 15 to 35. It is preferable. When (A / B) is less than the lower limit, the coating film formed from the conductive polymer paint has insufficient light resistance, and when it exceeds the upper limit, the conductivity is insufficient.

(Amine compound)
The amine compound can be coordinated or bonded to the anion group of the polyanion to improve the dispersibility of the complex of the π-conjugated conductive polymer and the polyanion in the organic solvent. Therefore, when an organic solvent is used as the dispersion medium, a composite organic solvent dispersion can be prepared.
The amine compound is not particularly limited as long as it is coordinated or bonded to the anion group of the polyanion. Here, “coordinating or bonding” is a bonding form in which the polyanion and the amine compound donate / accept electrons to each other, thereby shortening the intermolecular distance between them.
Examples of the amine compound include compounds having a nitrogen atom in the molecule. Specific examples include primary amines, secondary amines, tertiary amines, and aromatic amines.
Examples of the primary amine include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, undecylamine, dodecylamine, stearylamine and the like.
Examples of the secondary amine include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, didecylamine, diundecylamine, didodecylamine and the like.
Tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, tridecylamine, triundecylamine, tridodecylamine, imidazole, N- Methyl-imidazole, N-ethyl-imidazole, N-propyl-imidazole, N-butyl-imidazole, N-pentyl-imidazole, N-hexyl-imidazole, N-heptyl-imidazole, N-octyl-imidazole, N-decyl- Examples include imidazole, N-undecyl-imidazole, N-dodecyl-imidazole, and 2-heptadecylimidazole.

  The addition amount of the amine compound to the conductive polymer coating is preferably 0.1 to 50% by mass, more preferably 1 to 20% by mass when the conductive polymer coating is 100% by mass. preferable. If the addition amount of an amine compound is more than the said lower limit, the precipitation property of a conductive polymer will become high and a solid substance can be obtained reliably. However, even if the upper limit value is exceeded, the effect of improving the precipitation reaches a peak, which is useless.

(Acrylic compound )
When the conductive polymer paint contains an acrylic compound, a highly practical coating strength can be obtained.
As the acrylic compound , an active energy ray-curable acrylic compound is preferable. When the active energy ray-curable acrylic compound is contained, when the active energy ray is irradiated and cured, a part of the compound 1 reacts with the acrylic compound to improve the coating film strength.

Examples of acrylic compounds include bisphenol A / ethylene oxide-modified diacrylate, dipentaerythritol hexa (penta) acrylate, dipentaerythritol monohydroxypentaacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, glycerin propoxytriacrylate, 4- Hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate , Tripropylene glycol diacrylate, etc. Acrylates, 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, glycidyl methacrylate, 1,6 -Methacrylates such as hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, t-butyl methacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate, diacetone acrylamide, N, N-dimethylacrylic Amide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylformamide, N-methylacrylamide, N-isopropylacrylamide, Nt- Acrylic (methacrylic) amides such as butylacrylamide, N-phenylacrylamide, acryloylpiperidine, 2-hydroxyethylacrylamide, 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, etc. Vinyl ethers, vinyl butyrate, vinyl monochloroacetate, pivalin Examples thereof include monofunctional monomers and polyfunctional monomers of carboxylic acid vinyl esters such as vinyl acid.
Furthermore, polyfunctional acrylates such as epoxy acrylate, urethane acrylate, polyester acrylate, polyacryl acrylate, etc. synthesized by reacting acrylic monomers can be mentioned. These acrylic compounds may be used individually by 1 type, and may use 2 or more types together.

The content of the acrylic compound is preferably 1000 to 100000 parts by mass, more preferably 3000 to 50000 parts by mass with respect to 100 parts by mass of the composite. If an acrylic compound is more than the said lower limit, the intensity | strength of the electroconductive coating film obtained can fully be improved, and if it is below the said upper limit, sufficient electroconductivity can be ensured.

(Dispersion medium)
Examples of the dispersion medium include polar solvents such as water, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylene phosphortriamide, acetonitrile, benzonitrile, and cresol. Phenols such as phenol and xylenol, alcohols such as methanol, ethanol, propanol, isopropanol and butanol, ketones such as acetone and methyl ethyl ketone, hydrocarbons such as hexane, benzene and toluene, carboxylic acids such as formic acid and acetic acid, Carbonate compounds such as ethylene carbonate and propylene carbonate; ether compounds such as dioxane and diethyl ether; ethylene glycol dialkyl ether; propylene glycol dialkyl ether; Chain ethers such as lenglycol dialkyl ether and polypropylene glycol dialkyl ether, heterocyclic compounds such as 3-methyl-2-oxazolidinone, nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile, etc. Can be mentioned. These dispersion media may be used individually by 1 type, may be 2 or more types of mixtures, and are good also as a mixture with another organic solvent.

<Conductive coating film>
The conductive coating film of the present invention is a coating film formed by applying the conductive polymer paint.
The conductive coating film is usually formed by coating on a substrate. Here, the base material is not particularly limited as long as it is a resin base material. However, since the conductive coating film has transparency, the base material is also preferably transparent.
The material constituting the transparent substrate is polyethylene terephthalate (PET), polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propio And the like. Moreover, glass etc. can also be used.

As a method for applying the conductive polymer paint, 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 paint.
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 ultraviolet light 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 irradiation with ultraviolet light is preferably 100 mW / cm ² or more. If the illuminance is less than 100 mW / cm ² , the film may not be sufficiently crosslinked. 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). .

(Thickness of conductive coating)
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 0.001 μm or more, sufficient conductivity can be secured, and if it is 10 μm or less, sufficient flexibility can be secured.

(Function and effect)
As a result of investigation by the present inventors, the conductive coating film obtained from the conductive polymer paint of the present invention has high light resistance by containing the compound 1, and the surface resistance increases even when irradiated with ultraviolet light. I found it difficult to do.

(Production Example 1) Synthesis of polystyrene sulfonic acid 206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and while stirring at 80 ° C., 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water was dissolved. The solution was added dropwise for 20 minutes, and the solution was stirred for 12 hours.
To the obtained sodium styrenesulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, about 1000 ml of the polystyrenesulfonic acid-containing solution was removed by ultrafiltration, and 2000 ml of ion-exchanged water was added to the remaining liquid. About 2000 ml of solution was removed by ultrafiltration. The above ultrafiltration operation was repeated three times. Further, about 2000 ml of ion-exchanged water was added to the obtained filtrate, and about 2000 ml of the solution was removed by ultrafiltration. This ultrafiltration operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

Production Example 2 Synthesis of Aqueous Dispersion of Polystyrenesulfonic Acid Doped Poly (3,4-ethylenedioxythiophene) 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrenesulfonic acid in 2000 ml of ions The solution dissolved in the exchange 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 obtained reaction solution, and about 2000 ml of solution was removed by ultrafiltration. 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 resulting solution, about 2000 ml of solution is removed by ultrafiltration, and 2000 ml of ion-exchanged water is added to this solution. About 2000 ml of solution was removed by external filtration. This operation was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed by ultrafiltration. This operation was repeated 5 times to obtain an aqueous dispersion (PEDOT-PSS aqueous dispersion) of polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) having a concentration of 1.2% by mass.

Production Example 3 Preparation of Conductive Polymer Paint 1000 g of PEDOT-PSS dispersion was freeze-dried to obtain 12 g of PEDOT-PSS powder. To 12.0 g of the obtained PEDOT-PSS powder, 2882 g of isopropanol and 106 g of trioctylamine were added and stirred to obtain an isopropanol dispersion of PEDOT-PSS having a concentration of 0.4 mass%.

Example 1
To 75 g of the PEDOT-PSS dispersion obtained in Production Example 3, 10 g of pentaerythritol triacrylate, 15 g of diacetone alcohol, 0.2 g of Ciba Japan Irgacure 127 and 1.5 g of compound 1-a are added. And stirred to obtain a conductive polymer paint.
Then, the conductive polymer paint was applied onto a PET film using a # 16 bar coater, dried to form a conductive coating film, and the surface resistance value of the coating film was measured. Moreover, after irradiating the conductive coating film with ultraviolet light for 48 hours by carbon arc, the surface resistance value was measured.
The surface resistance value (Ω / □) of the conductive coating film was measured using Hiresta (Mitsubishi Chemical). The measurement results are shown in Table 1.

(Example 2)
A conductive coating film was formed in the same manner as in Example 1 except that the amount of Compound 1-a added in Example 1 was changed to 5 g, and the surface resistance value before and after ultraviolet light irradiation was measured. The measurement results are shown in Table 1.

(Example 3)
A conductive coating film was formed in the same manner as in Example 1 except that the amount of compound 1-a added in Example 1 was 10 g, and the surface resistance values before and after ultraviolet light irradiation were measured. The measurement results are shown in Table 1.

Example 4
A conductive coating film was formed in the same manner as in Example 1 except that 3 g of Compound 1-b was added instead of Compound 1-a in Example 1. The surface resistance value after irradiation was measured. The measurement results are shown in Table 1.

(Comparative Example 1)
A conductive coating film was formed in the same manner as in Example 1 except that the amount of compound 1-a added in Example 1 was 1 g, and the surface resistance values before and after ultraviolet light irradiation were measured. The measurement results are shown in Table 1.

(Comparative Example 2)
A conductive coating film was formed in the same manner as in Example 1 except that the amount of compound 1-a added in Example 1 was 15 g, and the surface resistance values before and after ultraviolet light irradiation were measured. The measurement results are shown in Table 1.

(Comparative Example 3)
A conductive coating film was formed in the same manner as in Example 1 except that 5 g of dodecanethiol was added instead of Compound 1-a in Example 1, and the surface resistance values before and after ultraviolet light irradiation were measured. . The measurement results are shown in Table 1.

The conductive coatings of Examples 1 to 4 in which the mass ratio between the content of Compound 1 and the total content of the π-conjugated conductive polymer and the polyanion was within the scope of the present invention were the surface resistance before ultraviolet irradiation. And the increase in surface resistance after irradiation with ultraviolet light was suppressed.
On the other hand, the conductive coating film of Comparative Example 1 in which the mass ratio between the content of Compound 1 and the total content of the π-conjugated conductive polymer and the polyanion was smaller than within the scope of the present invention is The increase in the surface resistance of was not suppressed.
The conductive coating film of Comparative Example 2 in which the mass ratio of the content of Compound 1 to the total content of the π-conjugated conductive polymer and the polyanion was larger than the range of the present invention had a large surface resistance before ultraviolet irradiation. It was. That is, the conductivity was insufficient. In Comparative Example 2, since the surface resistance before ultraviolet irradiation was large, the surface resistance after ultraviolet irradiation was not measured.
In addition, the conductive coating film of Comparative Example 3 containing a π-conjugated conductive polymer and a polyanion but containing dodecanethiol instead of Compound 1 had a large increase in surface resistance after irradiation with ultraviolet light. This indicates that a thiol compound having a general structure does not have an effect of suppressing an increase in surface resistance due to ultraviolet light irradiation.

Claims (2)

a π-conjugated conductive polymer, a polyanion, a compound represented by the following chemical formula (1), an amine compound, an acrylic compound, and a dispersion medium;
And the content A of the compound represented by Formula (1), the total content B and the mass ratio of the π-conjugated conductive polymer and polyanion (A / B) is Ri 5-35 der,
The conductive polymer paint , wherein the acrylic compound is at least one selected from the group consisting of acrylate monomer, methacrylate monomer, acrylamide monomer, methacrylamide monomer, epoxy acrylate, urethane acrylate, polyester acrylate, and polyacryl acrylate .

(In the formula, R ¹ and R ² are each independently a hydrogen atom or an arbitrary substituent.)   A conductive coating film formed by applying the conductive polymer paint according to claim 1.