KR20090104807A - Organic solvent dispersion of conductive polymer?dopant and composition containing the dispersion - Google Patents

Abstract

Disclosed is an organic solvent dispersion of a conductive polymer/dopant, which is obtained by dispersing a conductive polymer (A) and a dopant (B) in an organic solvent by using a dispersing agent composed of a hydroxylated acrylic polymer having a weight average molecular weight of 10,000-50,000 and a hydroxyl number of 160-230 mgKOH/g. The water content of this organic solvent dispersion is not more than 20% by weight. Also disclosed are a resin composition containing the organic solvent dispersion and a binder, and a coating composition containing such a resin composition.

Description

Organic solvent dispersion of conductive polymer / dopant and composition containing said dispersion {ORGANIC SOLVENT DISPERSION OF CONDUCTIVE POLYMER / DOPANT AND COMPOSITION CONTAINING THE DISPERSION}

The present invention relates to an organic solvent dispersion of a conductive polymer / dopant and a composition containing the organic solvent dispersion.

Since the conductive polymer having a π-conjugated structure exhibits good conductivity and stability, it is used as an industrial material such as various antistatic agents and electrode materials. High conductivity is imparted to this conjugated conductive polymer by adding a substance for expressing conductivity called a dopant. For example, poly (3,4-ethylenedioxythiophene) (hereinafter sometimes referred to as PEDOT) has recently been widely used mainly for antistatic agents. PEDOT polymerizes a monomeric 3,4-ethylenedioxythiophene in an aqueous phase in the presence of a polyanion such as polystyrenesulfonic acid (hereinafter sometimes referred to as PSS) as a dopant, using an oxidizing agent to form a water-soluble or water-dispersible poly ( It is obtained in the state of a complex of 3,4-ethylenedioxythiophene) / polyanion.

It is known that this PEDOT / PSS water dispersion can form a conductive coating film on a substrate by blending and applying it to an aqueous urethane resin and the like, and are used for transparent electrodes, antistatic applications, and the like. However, since PEDOT / PSS is in the form of an aqueous dispersion and contains a high proportion of PSS having an ionic structure, the following drawbacks and the versatility are poor.

A general organic solvent can be added in a small amount to the PEDOT / PSS water dispersion, but when a large amount is added, a phenomenon in which the conductive polymer is agglomerated without maintaining a stable dispersion state occurs.

Moreover, in order to obtain an electroconductive coating film, the method of mixing, disperse | distributing, and superposing | polymerizing is usually a binder polymer or the solution or dispersion liquid of the monomer used as this polymer, and a conductive polymer. In this case, the solution or dispersion of the polymer or monomer is often an organic solvent. The solution or dispersion of an organic solvent-based binder polymer or a monomer which becomes the polymer is because water is retained in the coating film and evaporates when the water dispersion of PEDOT / PSS is added, or because of compatibility with PSS and binder polymer. As a result, defects such as deterioration in transparency of the coating film and instability in the coated state may occur due to poor separation.

In addition, when applied to water-sensitive materials such as organic electroluminescence device, the defects caused by water derived from this water dispersion often occur, there was a limitation in the application.

Patent document 1 describes a method for eliminating all the disadvantages of the PEDOT / PSS water dispersion, and using a water-soluble organic solvent dispersion by substituting a part of the water dispersion solvent with an organic solvent that is easily mixed with water such as a lower alcohol. Doing. However, in general, the range of application is limited because the solubility of the binder polymer or its raw material monomer in alcohol is not sufficient. Moreover, since it is a water-based solvent system, when using the organic solvent type binder polymer or monomer together similarly to the case of using a water-only dispersion, defects, such as the fall of transparency of a coating film, may arise.

In addition, Patent Document 2 discloses a method of forming a dispersion of an organic solvent by adding an organic solvent having a property of azeotroping with water to a PEDOT / PSS aqueous dispersion and removing water by azeotropy. However, in this case, there is a limit in application because the type of organic solvent that can be applied is limited to amides, pyrrolidones and the like.

Patent Literature 2 also discloses a method of dispersing the PEDOT / PSS aqueous dispersion as a solid by heating or lyophilizing it as a solid and dispersing the pulverized product with an organic solvent. In this case, the particles dispersed in water tend to be firmly fixed to each other, are not easy to be disintegrated to the original particle size, and the energy necessary for dispersing is necessary because a dispersion by a bead mill or the like is required to form a dispersion. There was a problem that time was large.

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-532292

Patent Document 2: Japanese Patent Application Laid-Open No. 2004-514753

An object of the present invention is to provide an organic solvent dispersion of a conductive polymer / dopant having excellent dispersion stability.

This inventor earnestly researched in order to achieve the said subject. As a result, the present invention can be accomplished by deriving what can accomplish the above problem by dispersing the conductive polymer / dopant using a dispersant that is a specific hydroxyl group-containing acrylic polymer.

This invention provides the resin composition containing the following organic solvent dispersion of the conductive polymer / dopant, this organic solvent dispersion, and a binder, and the coating material composition containing the said resin composition.

1. The water obtained by dispersing the conductive polymer (A) and the dopant (B) in an organic solvent using a dispersant having a weight average molecular weight of 10,000 to 50,000 and a hydroxyl value containing a hydroxyl group of 160 to 230 mgKOH / g. An organic solvent dispersion of a conductive polymer / dopant having a content of 20% by weight or less.

2. The conductive polymer (A) is at least one member selected from the group consisting of polyaniline, polythiophene, polypyrrole, polyprene, polyphenylene, polyphenylenevinylene, polyacene and polythiophenevinylene. An organic solvent dispersion according to the above item 1.

3. The organic solvent dispersion according to item 1, wherein the dopant (B) is an anionic compound.

4. The organic solvent dispersion according to item 3, wherein the anionic group of the anionic compound is at least one member selected from the group consisting of a monosubstituted sulfuric acid ester group, a monosubstituted phosphate ester group, a phosphate group, a carboxyl group and a sulfone group.

5. The organic solvent dispersion according to item 1, wherein the conductive polymer (A) is poly (3,4-ethylenedioxythiophene) and the dopant (B) is polystyrenesulfonic acid.

6. Ring-opening ester of carboxyl group-containing vinyl monomer (c) in copolymer obtained by polymerizing monomer component containing epoxy group-containing (meth) acrylic monomer (a) and alkylene oxide structure-containing vinyl monomer (b) The organic-solvent dispersion as described in said claim | item 1 which is a hydroxyl-containing acrylic polymer (I) obtained by carrying out a reaction.

7. The hydroxyl group-containing acrylic polymer (I) contains the epoxy group-containing (meth) acrylic monomer (a) and the alkylene oxide structure-containing vinyl monomer (b) based on the total of the former 65 to 95% by weight and the latter 5 to 35 The organic solvent dispersion of Claim 6 which is a copolymer obtained by superposing | polymerizing in the ratio of weight%.

8. Alkylene oxide structure-containing vinyl monomer (b) is represented by general formula (1)

[Formula 1]

CH ₂ = CR ¹ COO (A _m O) _n R ² (1)

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrocarbon group and A represents a hydrocarbon group, respectively, m represents an integer of 1 to 3 and n represents an integer of 1 to 23, respectively) The organic-solvent dispersion of said claim | item 6 which is a monomer represented by.).

9. Said 1 whose dispersing agent is hydroxyl group containing acrylic polymer (II) obtained by superposing | polymerizing the monomer component containing a hydroxyl group containing (meth) acrylic monomer (e) and (meth) acrylic monomer (f) other than this monomer (e). The organic solvent dispersion of description.

10. Said dispersing agent is hydroxyl group containing acrylic polymer (III) obtained by ring-opening-esterifying a carboxyl group-containing vinyl monomer (c) to the polymer obtained by superposing | polymerizing the monomer component containing an epoxy-group-containing (meth) acrylic-type monomer (a). The organic solvent dispersion of Claim 1.

11. The organic solvent dispersion according to item 1, wherein the mixing ratio of the conductive polymer (A) and the dopant (B) is 200 to 3,000 parts by weight based on 100 parts by weight of the former.

12. The organic solvent dispersion according to the above item 1, further containing at least one compound (C) selected from the group consisting of amines and nonionic surfactants.

13. The organic solvent dispersion according to item 12, wherein the compound (C) is at least one member selected from the group consisting of alkylamines and polyalkylene oxide structure-containing amines.

14. The conductive polymer (A) is poly (3,4-ethylenedioxythiophene), the dopant (B) is polystyrenesulfonic acid, and the compound (C) is a polyalkylene oxide structure-containing alkylamine. Organic solvent dispersions.

15. A resin composition containing an organic solvent dispersion of the conductive polymer / dopant according to item 1 and a binder polymer other than the conductive polymer.

16. A coating material composition comprising the resin composition according to item 15 above.

17. The resin composition containing the polymerizable monomer used as the organic-solvent dispersion of the said conductive polymer / dopant of Claim 1, and a binder polymer.

18. A coating material composition comprising the resin composition according to item 17.

Conductive Polymer / Dopant  Organic solvent Dispersion

The organic solvent dispersion of the conductive polymer / dopant of the present invention is a conductive polymer (A) and a dopant (B) which are hydroxyl-containing acrylic polymers having a weight average molecular weight of about 10,000 to 50,000 and a hydroxyl value of about 160 to 230 mgKOH / g. It disperse | distributes in the organic solvent using the dispersing agent, and makes content of water into 20 weight% or less.

Conductive Polymer (A)

As a conductive polymer (A) used for this invention, if a main chain is an organic conductive polymer comprised by (pi) conjugated system, it will not specifically limit, A well-known thing can be used.

As (A) component, polyaniline, polythiophene, polypyrrole, polyprene, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polythiophene vinylene, etc. are mentioned, for example. have. These may be used independently and may be used in mixture of multiple. Moreover, although the polymer which is (A) component does not need substitution, sufficient electroconductivity and compatibility of binder resin can be acquired, but in order to raise electroconductivity, functional groups, such as an alkyl group, a carboxy group, a sulfone group, an alkoxy group, a hydroxyl group, and a cyano group, are contained in a polymer, It is preferable to introduce.

Specific examples of the component (A) include polypyrrole, poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), poly (3-butylpyrrole) and 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-dibutylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene ), Poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3-octyloxythiophene), Poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4- Dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihex) Siloxythiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyloxythiophene), poly (3,4-didecyloxythiophene), poly (3,4- Dodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), 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-carboxyethyl Thiophene), poly (3-methyl-4-carboxybutylthiophene), polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), poly (3-aniline Sulfonic acid), and the like. As the component (A), polythiophenes are preferable for reasons such as color.

As (A) component, a commercial item can be used as it is. Moreover, the (B) component complex of (A) component is easily acquired by chemical-oxidation-polymerizing the precursor monomer which forms (pi) conjugated system conductive polymer in a suitable solvent in presence of a suitable oxidizing agent, an oxidation catalyst, and (B) component mentioned later. can do.

As a precursor monomer, if it has a (pi) conjugated system in a molecule | numerator, and a (pi) conjugated system is formed in the main chain, even if it polymerizes by the action of an appropriate oxidizing agent, a well-known thing can be used. Specifically, pyrrole and its derivatives, thiophene and its derivatives, aniline and its derivatives, etc. are mentioned, for example.

Specific examples of the precursor monomers include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, and 3,4 -Dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxypyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3- Hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-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-dibutyl tea Offen, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythione Offen, 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-ethylenedioxe Citiopen, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 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, 3-isobutylaniline, 2-aniline sulfonic acid, 3-aniline Sulfonic acid and the like.

It does not specifically limit as a solvent to be used, It is a solvent which can melt | dissolve or disperse the said precursor monomer, What is necessary is just a thing which can maintain the oxidizing power of an oxidizing agent and an oxidation catalyst. For example, water, N-methyl- 2-pyrrolidone, N, N- dimethylformamide, N, N- dimethylacetamide, dimethyl sulfoxide, hexamethylenephosphoryl triamide, acetonitrile, benzonitrile, etc. Polar solvents; Phenols such as cresol, phenol and xylenol; Alcohols such as methanol, ethanol, propanol 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; Chain ethers such as ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether and polypropylene glycol dialkyl ether; Heterocyclic compounds such as 3-methyl-2-oxazolidinone; Nitrile compounds, such as acetonitrile, glutarodinitrile, a methoxy acetonitrile, a propionitrile, a benzonitrile, etc. are mentioned. These solvents may be used alone, as a mixture of two or more kinds, or as a mixture with other organic solvents.

As an oxidizing agent and an oxidation catalyst, what is necessary is just to be able to acquire (pi) conjugated system conductive polymer by oxidizing the said precursor monomer, For example, peroxodisulfates, such as ammonium peroxo disulfide, sodium peroxodisulfate, and potassium peroxodisulfate; Transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride; Metal halogen compounds such as boron trifluoride and aluminum chloride; Metal oxides such as silver oxide and cesium oxide; Inorganic peroxides such as hydrogen peroxide and ozone; Organic peroxides such as benzoyl peroxide; Oxygen, and the like.

Dopant (B)

The component (B) used in the present invention is not particularly limited as long as it is an anionic compound. An anionic compound is a compound which has an anion group in which the chemical oxidation dope to (A) component can arise in a molecule | numerator.

As an anionic group which an anionic compound has, a sulfate ester group, a phosphate ester group, a phosphoric acid group, a carboxyl group, a sulfone group, etc. are preferable from a viewpoint of the ease of manufacture and stability. Among these anion groups, a sulfone group, a sulfate ester group and a carboxyl group are more preferable from the viewpoint of being excellent in the dope effect to (A) component.

Specific examples of the anionic compound include dodecylbenzenesulfonic acid, 10-camphorsulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- Heptadecafluoro-l-octanesulphonic acid, l, l, l-trifluoro-N-[(trifluoromethyl) sulfonyl] methanesulfonamide, 2-acrylamide-2-methylpropanesulfonic acid, p-toluene And anionic group-containing polymers such as sulfonic acid, 1,5-anthraquinonedisulfonic acid, 2,6-anthraquinonedisulfonic acid, anthraquinonesulfonic acid, 4-hydroxybenzenesulfonic acid, methylsulfonic acid and nitrobenzenesulfonic acid.

Examples of the anionic group-containing polymer include a polymer obtained by polymerizing an anion group into the polymer by polymerizing a polymer having no anion group with a sulfonating agent, or a polymer obtained by polymerizing an anionic group-containing polymerizable monomer. Can be.

Usually, since an anionic group containing polymer is easy to manufacture, it is preferable to polymerize and manufacture an anionic group containing polymerizable monomer.

As a method for producing an anionic group-containing polymer by polymerization of an anionic group-containing polymerizable monomer, for example, an anion group-containing polymerizable monomer in a solvent is subjected to oxidation polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst. The manufacturing method is mentioned. Specifically, a predetermined amount of anionic group-containing polymerizable monomer is dissolved in a solvent and 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 reaction for a predetermined time. The polymer obtained by this reaction is adjusted to a constant concentration by the solvent. In this manufacturing method, you may copolymerize the polymerizable monomer which does not have an anion group to an anion group containing polymerizable monomer. The oxidizing agent, oxidation catalyst, and solvent which are used at the time of superposition | polymerization of an anionic-group containing polymerizable monomer are the same as what is used when superposing | polymerizing the precursor monomer which forms (A) component.

The anionic group-containing polymerizable monomer is a monomer having an anionic group and a polymerizable functional group in a molecule, and specifically, vinylsulfonic acid and salts thereof, allylsulfonic acid and salts thereof, methacrylic sulfonic acid and salts thereof, styrenesulfonic acid salts and salts thereof, metalyloxy Benzenesulfonic acid and salts thereof, allyloxybenzenesulfonic acid and salts thereof, α-methylstyrenesulfonic acid and salts thereof, acrylamide-t-butylsulfonic acid and salts thereof, 2-acrylamide-2-methylpropanesulfonic acid salts and salts thereof, cyclobutyl Ren-3-sulfonic acid and salts thereof, isoprenesulfonic acid and salts thereof, 1,3-butadiene-1-sulfonic acid and salts thereof, 1-methyl-1,3-butadiene-2-sulfonic acid and salts thereof, 1-methyl-1 , 3-butadiene-4-sulfonic acid and salts thereof, ethyl sulphonic acid acrylate (CH ₂ = CH-COO- (CH ₂ ) ₂ -SO ₃ H) and salts thereof, propylsulfonic acid acrylate (CH ₂ = CH-COO- (CH ₂ ) ₃ -SO ₃ H) and salts thereof, 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-butylsulfonic acid (CH ₂ = CH-COO- (CH ₂ ) ₄ -SO ₃ H) and salts thereof, ethyl allyl sulfonic acid (CH ₂ = CHCH ₂ -COO-(CH ₂ ) ₂ -SO ₃ H) and salts thereof, allyl acid -t-butylsulfonic acid (CH ₂ = CHCH ₂ -COO-C (CH ₃ ) ₂ CH ₂ -SO ₃ H) and salts thereof, 4-pentenoic acid sulfonic acid (CH ₂ = CH (CH ₂ ) ₂ -COO- (CH ₂ ) ₂ -SO ₃ H) and salts thereof, 4 -Pentenoic acid 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-pentenoic acid -t-butylsulfonic acid (CH ₂ = CH (CH ₂ ) ₂ -COO-C (CH ₃ ) ₂ CH ₂ -SO ₃ H) and its salts, 4-pentene acid-phenylenediamine sulfonic acid _{(CH 2 = CH (CH 2} ) 2 -COO-C 6 H 4 -SO 3 H) and its salts, 4-pen tensan 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, methacrylate propylsulfonic acid (CH ₂ = C (CH ₃ ) -COO- (CH ₂ ) ₃ -SO ₃ H) and salts thereof, methacrylic acid -t-butylsulfonic acid (CH ₂ = C (CH ₃ ) -COO-C (CH ₃ ) ₂ CH ₂ -SO ₃ H) and its salts, methacrylic acid-n-butylsulfonic acid (CH ₂ = C (CH ₃ ) -COO- (CH _{2) 4} ) SO ₃ H) and salts thereof, phenylenesulfonic acid methacrylic acid (CH ₂ = C (CH ₃ ) -COO-C ₆ H ₄ -SO ₃ H) and salts thereof, naphthalenesulfonic acid methacrylic acid (CH ₂ = C (CH ₃ ) -COO-C ₁₀ H ₈ -SO ₃ H) and salts thereof. 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-ethyl styrene, p-butylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, (alpha) -methylstyrene, 2-vinyl naphthalene, 6-methyl- 2-vinyl naphthalene, 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, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, isooctyl acrylate, isononyl butyl acrylate, lauryl acrylate, allyl acrylate, stearyl acrylate, isobornyl acrylate, Cyclohexyl acrylate, benzyl acrylate, arc Ethyl carboxylate, phenoxy ethyl acrylate, hydroxyethyl acrylate, methoxy ethyl acrylate, ethoxy ethyl acrylate, methoxy butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate , I-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate , Methacrylic acid 2-hydroxyethyl, methacrylic acid 2-hydroxypropyl, acryloyl morpholine, vinylamine, N, N-dimethylvinylamine, N, N-diethylvinylamine, N, N-di Butylvinylamine, N, N-di-t-butylvinylamine, N, N-diphenylvinylamine, N-vinylcarbazole, vinyl alcohol, vinyl chloride, vinyl fluoride, methyl vinyl ether, ethyl vinyl ether, cycloprop Pen, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 2-methylcyclone Hexene, vinylphenol, 1,3-butadiene, 1-methyl-1,3-butadiene, 2-methyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene, 1,2-dimethyl-1 , 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, etc. are mentioned.

Although the polymerization degree of the anionic group containing polymer obtained in this way is not specifically limited, Usually, a monomeric unit is about 10-100,000, It is preferable to set it as about 50-10,000 for solvent solubility and electroconductivity.

As a specific example of an anionic group containing polymer, polystyrene sulfonic acid, polyisoprene sulfonic acid, ethyl sulfonic acid polyacrylate, and butyl sulfonic acid polyacrylate are preferable.

When the anionic compound obtained is an anionic salt, it is preferable to modify it with an anionic acid. As a method of changing with anionic acid, the ion exchange method using an ion exchange resin, a dialysis method, an ultrafiltration method, etc. are mentioned, Among these, an ultrafiltration method is preferable at the point which is easy to work.

As the combination of the component (A) and the component (B) used in the present invention, one selected from the group described above can be used, but the component (A) is poly (3,4-ethylene) for reasons of chemical stability, electrical conductivity and storage stability. Dioxythiophene), and (B) component is preferably polystyrenesulfonic acid. As described above, they may be synthesized by carrying out polymerization in the presence of an oxidizing agent in an aqueous solution or aqueous dispersion state in which the monomer and the dopant of the conductive polymer coexist, or a commercially available conductive polymer / dopant water dispersion may be used. Commercially available conductive polymer / dopant water dispersions include, for example, "Baytron P" (trade name HC STARK, PEDOT / PSS water dispersion), "Orgacon" (trade name, AGFA, PEDOT / PSS water dispersion), and the like. Can be.

Dispersant

In the present invention, the dispersant used to disperse the conductive polymer (A) and the dopant (B) in an organic solvent has a weight average molecular weight of about 10,000 to 50,000 and a hydroxyl value of about 160 to 230 mgKOH / g. Polymer.

As said dispersing agent, a carboxyl group-containing vinyl monomer (c) is ring-opened in the copolymer obtained by superposing | polymerizing the monomer component containing an epoxy group containing (meth) acrylic-type monomer (a) and an alkylene oxide structure containing vinylic monomer (B). -Polymerizing a monomer component comprising a hydroxyl group-containing acrylic polymer (I), a hydroxyl group-containing (meth) acrylic monomer (e) and a (meth) acrylic monomer (f) other than the monomer (e) obtained by esterification reaction. A hydroxyl group containing acrylic polymer obtained by ring-opening-esterifying-reacting a carboxyl group-containing vinyl monomer (c) to the polymer obtained by superposing | polymerizing the monomer component containing the hydroxyl group containing acrylic polymer (II) obtained and the epoxy group containing (meth) acrylic-type monomer (a) ( III) or the like is preferable.

Hydroxyl-containing acrylic polymer (I)

The acrylic polymer (I) is a carboxyl group-containing vinyl monomer (c) in a copolymer obtained by polymerizing a monomer component containing an epoxy group-containing (meth) acrylic monomer (a) and an alkylene oxide structure-containing vinyl monomer (b). It is obtained by ring-opening esterification reaction. The ring-opening esterification reaction is a reaction in which an epoxy group contained in a copolymer of monomers (a) and (b) reacts with a carboxyl group included in monomer (c) to ring-open an epoxy group and simultaneously produce an ester bond and a hydroxyl group. By this ring-opening esterification reaction, monomer (c) is added to the copolymer of monomer (a) and monomer (b) by ester bond.

As an epoxy group containing (meth) acrylic-type monomer (a), if it is a compound which has an epoxy group and a (meth) acryl group in a molecule | numerator, it will not specifically limit, A well-known thing can be employ | adopted.

Specifically, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, etc. are mentioned, for example. You may use these individually or in mixture of 2 or more types.

As an alkylene oxide structure containing vinylic monomer (b), if it is a vinylic monomer which has an alkylene oxide structure in a molecule | numerator, it will not specifically limit, A well-known thing can be employ | adopted. Specifically, for example, general formula (1):

[Formula 1]

CH ₂ = CR ¹ COO (A _m O) _n R ² (1)

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrocarbon group and A represents a hydrocarbon group, respectively, m represents an integer of 1 to 3 and n represents an integer of 1 to 23, respectively) The monomer represented by.) Can be used. As a compound represented by General formula (1), a methoxy polyethyleneglycol mono (meth) acrylate, a methoxy polypropylene glycol mono (meth) acrylate, etc. are mentioned, for example. You may use these individually or in mixture of 2 or more types.

Moreover, as monomer components other than a monomer (a) and a monomer (b), the well-known vinyl compound which can copolymerize with a monomer (a) and / or a monomer (b) can be used together without having a functional group which has reactivity with an epoxy group. have. As such a monomer, For example, (meth) acrylic acid ester, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and ethylhexyl (meth) acrylate; Aromatic vinyl compounds such as styrene and α-methylstyrene; Vinyl acetate, (meth) acrylonitrile, etc. are mentioned. You may use these individually or in mixture of 2 or more types.

The use ratio of the epoxy group-containing (meth) acrylic monomer (a) and the alkylene oxide structure-containing vinyl monomer (b) is preferably in the ratio of 65 to 95% by weight of the former and 5 to 35% by weight of the latter based on the sum of both. Do. Moreover, when using monomers other than a monomer (a) and a monomer (b) as a monomer component, it is preferable to use the usage-amount normally in 20 weight% or less in a monomer component.

The polymerization of the monomer component including the epoxy group-containing (meth) acrylic monomer (a) and the alkylene oxide structure-containing vinyl monomer (B) is not particularly limited, and may be performed by a known method. Specifically, for example, it can be carried out by bulk polymerization, solution polymerization, emulsion polymerization and the like. Usually, what is necessary is just to superpose | polymerize, for example in presence of a well-known polymerization initiator. In addition, when performing the said polymerization, you may use a well-known chain transfer agent etc. as needed. The copolymer thus obtained usually has a weight average molecular weight (polystyrene equivalent value according to the gel permeation chromatography method) of about 5,000 to 30,000 and an epoxy equivalent of about 140 to 290 g / eq.

As a carboxyl group-containing vinylic monomer (c), if it is a vinylic monomer which has a carboxyl group, it will not specifically limit, A well-known thing can be used. Specifically, (meth) acrylic acid, (meth) acrylic acid dimer, etc. are mentioned, for example. The reaction between the copolymer and the monomer (c) may be carried out according to a known method. Usually, both reactive components are mixed and, if necessary, heated to about 80 to 120 ° C. using a solvent that does not react with both components. good. The monomer (c) to be used is usually added at least equimolar to the epoxy group contained in the copolymer, and may be reacted so that the hydroxyl value of the dispersant obtained is about 160 to 230 mgKOH / g. When the usage-amount of monomer (c) becomes less than equimolar with respect to an epoxy group, it may gelatinize at reaction, and also there exists a tendency for stability after reaction to worsen.

The hydroxyl group-containing acrylic polymer (I) thus obtained as the dispersant usually has a hydroxyl value of about 160 to 230 mgKOH / g and a weight average molecular weight (polystyrene equivalent value according to gel permeation chromatography (GPC)) of 10,000 to It is preferable to set it to about 50,000.

By setting the hydroxyl value in the corresponding range, the storage stability of the dispersion selected using this dispersant becomes good, and the synthesis of the dispersant is preferred, which is preferable. Moreover, since the wear resistance after active energy ray irradiation improves and the synthesis | combination of a dispersing agent becomes easy by making a weight average molecular weight into the said range, it is preferable.

The hydroxyl group-containing acrylic polymer (I) more preferably has a hydroxyl value of about 160 to 230 mgKOH / g and a weight average molecular weight (polystyrene equivalent value according to gel permeation chromatography (GPC)) of about 12,000 to 30,000.

The hydroxyl group-containing acrylic polymer (I) has a curing reactivity because it produces an acrylate group that gives crosslinking reactivity with the hydroxyl group in the acrylic polymer. The organic solvent dispersion of the conductive polymer / dopant using such a reactive dispersant is a composition to which a polymerizable monomer is further added, and forms a coating layer which gives conductivity, high hardness and transparency to the substrate by coating and curing various substrates. can do.

Hydroxyl-containing acrylic polymer (II)

The hydroxyl group-containing acrylic polymer (II) is obtained by polymerizing a monomer component containing a hydroxyl group-containing (meth) acrylic monomer (e) and a (meth) acrylic monomer (f) other than the monomer (e).

The hydroxyl group-containing acrylic polymer (II) preferably has a hydroxyl value in the range of about 160 to 230 mgKOH / g, and more preferably in the range of about 170 to 210 mgKOH / g. When the hydroxyl value is less than 160 mgKOH / g, it is difficult to make sufficient dispersion stability of the conductive polymer / dopant, and when the hydroxyl value exceeds 230 mgKOH / g, it is difficult to secure sufficient conductivity.

As a hydroxyl group containing (meth) acrylic-type monomer (e), glycol esters, such as 2-hydroxy (meth) acrylate and 4-hydroxybutyl (meth) acrylate, etc. are mentioned, for example. Moreover, as monomer (f), For example, (meth) acrylic acid ester, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and ethylhexyl (meth) acrylate; Aromatic vinyl compounds such as styrene and α-methylstyrene; Vinyl acetate, (meth) acrylonitrile, etc. are mentioned.

Although the usage-amount of monomer (e) and monomer (f) may be suitably determined by the kind of monomer (e) and monomer (f) so that a hydroxyl value may be in the range of about 160-230 mgKOH / g, Usually, an acrylic polymer ( It is preferable to use about 30-70 weight% of former and about 70-30 weight% of the latter based on the sum total of both monomers of monomer (e) and monomer (f) among the monomer components of II).

Although acrylic polymer (II) can be manufactured by superposing | polymerizing monomer (e) and monomer (f), it does not specifically limit as a polymerization method, It is good to carry out by a well-known method. Specifically, for example, it can be carried out by bulk polymerization, solution polymerization, emulsion polymerization and the like. Usually, what is necessary is just to superpose | polymerize, for example in presence of a well-known polymerization initiator. In addition, when performing the said polymerization, you may use a well-known chain transfer agent etc. as needed.

It is preferable to make the weight average molecular weight (polystyrene conversion value according to the gel permeation chromatography method) about 10,000-50,000, and, as for the acryl-type polymer (II) obtained in this way, it is more preferable to set it as about 12,000-30,000. When the weight average molecular weight is less than 10,000, the wear resistance of the conductive cured film obtained is insufficient, and when it exceeds 50,000, synthesis may be difficult.

Since hydroxyl-containing acrylic polymer (II) has a hydroxyl group in the said acrylic polymer, it is hardening reactivity. The organic solvent dispersion of the conductive polymer / dopant using such a reactive dispersant is a composition in which a binder polymer is further added as necessary. The organic solvent dispersion may be applied to various substrates and then subjected to reaction curing to impart conductivity, high hardness and transparency to the substrate. The coating layer can be formed.

Hydroxyl-containing acrylic polymer (III)

A hydroxyl group containing acrylic polymer (III) is obtained by ring-opening-esterifying-reacting a carboxyl group-containing vinyl monomer (c) with the polymer obtained by superposing | polymerizing the monomer component containing an epoxy group containing (meth) acrylic-type monomer (a).

The hydroxyl group-containing acrylic polymer (III) preferably has a hydroxyl value in the range of about 160 to 230 mgKOH / g, and more preferably in the range of about 170 to 210 mgKOH / g. When the hydroxyl value is less than 160 mgKOH / g, it is difficult to make sufficient dispersion stability of the conductive polymer / dopant, and when the hydroxyl value exceeds 230 mgKOH / g, it is difficult to secure sufficient conductivity.

A hydroxyl group containing acrylic polymer (III) is a carboxyl group-containing vinyl type in the copolymer obtained by superposing | polymerizing the monomer component containing two types of monomers of an epoxy group containing (meth) acrylic-type monomer (a) and other (meth) acrylic-type monomer (g). It is obtained by ring-opening esterification reaction of monomer (c).

The epoxy group-containing (meth) acrylic monomer (a) is the same as that used for the hydroxyl group-containing acrylic polymer (I).

As a (meth) acrylic-type monomer (g) other than a monomer (a), it is a monomer which does not contain an epoxy group in a molecule | numerator, and contains a (meth) acryl group, does not have a functional group which has reactivity with the epoxy group of the monomer (a), and has a monomer ( It will not specifically limit, if it is copolymerizable with a). Specifically, For example, (meth) acrylic acid ester, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and ethylhexyl (meth) acrylate; Aromatic vinyl compounds such as styrene and α-methylstyrene; Vinyl acetate, (meth) acrylonitrile, etc. are mentioned. Moreover, when using the monomer which has an epoxy group reactivity as monomer (g), it may react with an epoxy group and may generate high viscosity and gelation.

When copolymerizing a monomer (g), it is preferable to use monomer (g) at 50 weight% or less among all the monomer components used for the copolymer obtained normally, and it is more preferable to use at 20 weight% or less.

The polymerization method of the monomer component containing the monomer (a) or the monomer (a) and the monomer (g) is not particularly limited and may be carried out by a known method. Specifically, for example, it can be carried out by bulk polymerization, solution polymerization, emulsion polymerization and the like. Usually, what is necessary is just to superpose | polymerize, for example in presence of a well-known polymerization initiator. In addition, when performing the said superposition | polymerization, you may use a well-known chain transfer agent etc. as needed. The carboxyl group-containing (meth) acrylic monomer (c) subjected to ring-opening esterification reaction to the obtained polymer is the same as that used in the hydroxyl group-containing acrylic polymer (I). The ring-opening esterification reaction is also the same as the reaction in the synthesis of the hydroxyl group-containing acrylic polymer (I).

It is preferable to make the weight average molecular weight (polystyrene conversion value according to the gel permeation chromatography method) about 10,000-50,000, and, as for the acryl-type polymer (III) obtained in this way, it is more preferable to set it as about 12,000-30,000. If the weight average molecular weight is less than 10,000, the wear resistance after the active energy ray irradiation becomes insufficient, and if it exceeds 50,000, synthesis may be difficult.

The hydroxyl group-containing acrylic polymer (III) has curing reactivity because it generates an acrylate group that gives crosslinking reactivity to hydroxyl groups in the acrylic polymer. The organic solvent dispersion of the conductive polymer / dopant using such a reactive dispersant is a composition to which a polymerizable monomer is further added, and a coating layer which gives conductivity, high hardness and transparency to the substrate by coating and curing various substrates and then reacting and curing the substrate. Can be formed.

Conductive Polymer / Dopant  Organic solvent Dispersion  pharmacy

The organic solvent dispersion of the conductive polymer / dopant of the present invention usually contains a conductive polymer (A), a dopant (B) and a hydroxyl group-containing acrylic compound having a weight average molecular weight of about 10,000 to 50,000 and a hydroxyl value of about 160 to 230 mgKOH / g. The dispersing agent which is a polymer can be easily prepared by mixing in an organic solvent, stirring. As a stirring means, simple means, such as a shaker and an emulsion dispersion machine, can be employ | adopted.

The conductive polymer (A) and the dopant (B) are often used in an aqueous dispersion state. In this case, the whole becomes a gel state by stirring and mixing a conductive polymer (A) and a dopant (B) for about 10 to 30 minutes in an organic solvent normally. This was filtered under reduced pressure, and an organic solvent was added to the residue. The process of stirring, mixing, vacuum filtration, and adding an organic solvent is further suitably repeated as needed, and after making content of water into 20 weight% or less, the dispersing agent of this invention, and also adding compound (C) as needed, The dispersion of the invention can be prepared.

Examples of the organic solvent for dispersing the conductive polymer (A) and the dopant (B) include alcohols, ketones, ethers, amides, sulfoxides, sulfones, esters, nitriles, and the like. Examples of the alcohols include monoalcohols such as methanol, ethanol, propanol, isopropanol and butanol, dialcohols such as ethylene glycol, propylene glycol and polypropylene glycol, and polyhydric alcohols such as glycerin and pentaerythritol. As ketones, acetone, methyl ethyl ketone, etc. are mentioned, for example. As the ethers, ethers such as diethyl ether, ethyl isopropyl ether, dioxane, tetrahydrofuran, polyethylene glycol dialkyl ethers and polypropylene glycol dialkyl ethers can be used. Examples of the amides include dimethylformamide, N-methylpyrrolidone, and the like. Dimethyl sulfoxide etc. are mentioned as sulfoxides. Examples of the sulfones include sulfolane. Examples of the esters include methyl acetate and ethyl acetate. Examples of the nitriles include acetonitrile and propionitrile. These may be used independently, or may mix and use plurality. Among them, alcohols, in particular ethanol, isopropanol, ethylene glycol, methyl ethyl ketone and methyl isobutyl ketone are preferred for reasons of handling and dispersion stability.

As a mixing ratio of a conductive polymer (A) and a dopant (B), it is preferable that the latter is about 200-3,000 weight part with respect to 100 weight part of electrons, and it is more preferable that it is about 250-2,000 weight part. If the dopant (B) is too small than 200 parts by weight, the conductivity is less likely to be expressed. On the other hand, if the dopant (B) is too large, the compatibility with the binder component tends to be lowered.

Moreover, it is preferable that it is about 15-500 weight part with respect to a total of 100 weight part of conductive polymer (A) and a dopant (B), and, as for the usage-amount of a dispersing agent, it is more preferable that it is about 30-250 weight part. When the dispersant is too small than 15 parts by weight, the stability of the dispersion is lowered. On the other hand, when the dispersant is excessively more than 500 parts by weight, the surface resistance of the cured coating film tends to increase.

The organic solvent dispersion of the conductive polymer / dopant of the present invention needs to adjust the water content to 20% by weight or less. When the content of water exceeds 20% by weight, aggregation is likely to occur when mixed with the binder component and the dispersibility is impaired. It is preferable that content of water is 5 weight% or less.

In addition to the conductive polymer (A) and the dopant (B), the organic solvent dispersion of the conductive polymer / dopant of the present invention may contain at least one compound (C) selected from the group consisting of amines and nonionic surfactants, if necessary. It can be contained further. As content of a compound (C), it is preferable to set it as about 10-200 weight part with respect to a total of 100 weight part of a conductive polymer (A) and a dopant (B) normally, and it is more preferable that it is 50-150 weight part. If it is less than 10 parts by weight, the stability of the dispersion decreases, and if it exceeds 200 parts by weight, the surface resistance of the resulting cured coating film tends to increase.

As a compound (C), if it is an amine and / or nonionic surfactant, it will not specifically limit, A well-known thing can be used.

As amines, if it is a compound which has at least 1 amino group in a molecule | numerator, it will not specifically limit, A well-known thing can be used. As amines, it is a general formula (2), for example.

[Formula 2]

R ³ _n NH _{3 — n} (2)

(Wherein R ³ is an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, a phenyl group or benzyl group which may have a substituent, or a group-X-R ⁴ (X is an alkylene oxide group which may have a branched structure, ⁴ represents an alkyl group or a hydrogen atom, respectively.) N represents an integer of 1 to 3). Specifically, ammonia; Methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine Alkylamines such as tricyclohexylamine; Aromatic amines such as aniline and benzylamine; Amines having a polyalkylene oxide structure such as polyoxyethylene oleyl amine, polyoxyethylene stearyl amine and polyoxyethylene lauryl amine. Oxygen amines, such as morpholine, pyridine, etc. other than these can also be used as an amine. As amines, amines having alkylamines and polyalkylene oxide structures are preferred for reasons of dispersion stability, and polyoxyethylene alkylamines are more preferable.

It does not specifically limit as a nonionic surfactant, A well-known thing can be used. Specifically, polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitan fatty acid ester, etc. are mentioned, for example.

The organic solvent dispersion of the conductive polymer / dopant of the present invention thus obtained can be used as a coating material in the field of electronic devices, for example, by using a resin composition in combination with a binder polymer other than the conductive polymer. The composition is, for example, by dissolving a polymer other than the conductive polymer in an organic solvent having the same or compatible solvent as the dispersing solvent, adding the conductive polymer / dopant organic solvent dispersion, and performing dispersion treatment as necessary. It can be prepared by adding an antifoaming agent, a leveling agent and the like. As a polymer used, if it is a polymer normally used for a coating material, it will not specifically limit, A well-known thing can be used. Specifically, various resins, such as an acrylic resin, a polyurethane resin, a polyester resin, and an epoxy resin, are mentioned. The composition thus obtained is applied onto a substrate and then subjected to a drying treatment to form a polymer film in which the conductive polymer is dispersed.

Furthermore, by using together the conductive polymer / dopant organic solvent dispersion of this invention and the polymerizable monomer which can become a binder polymer, it can be used as a coating material in the field of electronic devices etc., for example. It will not specifically limit, if it is a monomer which can be radically polymerized as a polymerizable monomer, A well-known thing can be used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-butyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid hydroxypropyl, (meth) acrylate acrylic acid Dill, N- (meth) acryloyloxysuccinimide, ethylene glycol-di- (meth) acrylic acid ester, tribromophenyl (meth) acrylate, glycosyloxyethyl 2- (meth) acrylate, 2-methacryl Polymerizable carboxylic acid esters such as oxyethylphosphorylcholine; (Meth) acrylamide, N, N-dimethylacrylamide, N-isopropyl (meth) acrylamide, Nvinylformamide, 3-acrylamide phenylboronic acid, N-acryloyl-N 'biotinyl-3 Unsaturated carboxylic acid amides such as 6-dioxaoctane-1,9-diamine and N- (meth) acryloylmorpholine; Polymerizable unsaturated nitriles such as (meth) acrylonitrile; Vinyl halides such as vinyl chloride, vinylidene chloride and vinyl bromide; Conjugated dienes such as butadiene and isoprene; Macromonomers such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; Polymerizable unsaturated aromatics such as styrene, chlorstyrene, α-methylstyrene, divinylbenzene and vinyltoluene; Polymerizable unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, maleic acid, and phthalic acid; Polymerizable unsaturated sulfonic acids such as styrenesulfonic acid and sodium styrenesulfonic acid; (Meth) acrolein, vinyl acetate, vinylpyridine, N-vinylpyrrolidone, etc. are mentioned.

The coating material is, for example, mixed with a polymerizable monomer and an organic solvent having the same or compatible as the dispersing solvent, the dispersion of the conductive polymer / dopant organic solvent dispersion of the present invention to perform the dispersion treatment In addition, it is obtained by adding an antifoamer, a leveling agent, etc. as needed. This coating material can be polymerized by heat or an active energy ray (ultraviolet ray, electron beam, etc.) etc. in presence of a polymerization initiator as needed, and the film | membrane in which the conductive polymer was disperse | distributed in the polymer produced as a result is obtained.

In addition, the conductive polymer / dopant organic solvent dispersion of the present invention is added to the powder or solution of the polymer which can be a matrix of the molded product, and the organic solvent is volatilized, whereby the conductive polymer is dispersed and mixed in the polymer powder surface or polymer liquid. It may also be prepared. The polymer used as a matrix may be thermoplastic or thermosetting, and in the case of a thermoplastic polymer, a nucleating agent, a mold release agent, etc. may be added as needed, and in the case of a thermosetting polymer, a hardening | curing agent, a hardening adjuvant, etc. may be added as needed. By performing injection molding, extrusion molding, blow molding, and the like on the thermoplastic resin composition, a sheet, a film, and the like of a polymer in which the conductive polymer is dispersed are obtained. Further, by performing compression molding, transfer molding, or the like with respect to the thermosetting resin composition, sheets, plates, and the like of the polymer in which the conductive polymer is dispersed are obtained.

Effects of the Invention

According to the organic solvent dispersion of the conductive polymer / dopant of the present invention, the following remarkable effects are obtained.

(1) In the dispersion of the present invention, organic solvent dispersions of conductive polymers / dopants having excellent storage stability by using a specific dispersant do not require complicated dispersion treatment operations such as bead mills, and only perform simple dispersion treatment. Can be obtained.

(2) Since the conductive polymer / dopant organic solvent dispersion of the present invention has good solubility in many kinds of polymers, it is possible to prepare a composition containing a polymer other than the conductive polymer, and to provide conductivity and transparency. Can be used for purposes.

(3) The organic solvent dispersion of the conductive polymer / dopant using the hydroxyl group-containing acrylic polymer (I) as a dispersant has excellent coating properties and paint stability, and the surface of various substrates has conductivity, transparency, appearance of the coated surface after curing, and the like. In addition to being excellent, an antistatic cured film can be formed. In addition, the dispersion does not cause deterioration or bleed out of cured film properties such as conductivity and transparency. Therefore, the cured film obtained using this dispersion can be used suitably as a conductive sheet, an antistatic sheet, a touch panel, a carrier of a semiconductor element, etc.

(4) A resin composition containing an organic solvent dispersion of a conductive polymer / dopant and a polymerizable monomer using a hydroxyl group-containing acrylic polymer (II) or (III) as a dispersant is a coating material capable of forming a transparent and cured conductive cured film. As an excellent thing.

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples. However, the present invention is not limited by these examples. In addition, in each case, "part" and "%" are all a basis of weight unless there is particular notice.

In each example, the hydroxyl value and the weight average molecular weight were measured by the following method, respectively.

Hydroxyl value: It measured based on JISK1557.

Weight average molecular weight: measured by gel permeation chromatography. "HLC-8020" (brand name, product made by TOSOH Corporation) is used as a measuring instrument, and "G5000HXL", "G4000HXL", "G3000HXL", and "G2000HXL" (all brand names, TOSOH Corporation make) are used as a column. It was.

Conductive Polymer / Dopant  Hydroxyl group-containing acrylic as dispersant for dispersing organic solvent Polymer (I)  About aspect that we used Production Example , Example  And Comparative example

Conductive Polymer / Dopant  Preparation of Dispersant for Dispersing Organic Solvents

Production Example  One

200 parts of glycidyl methacrylate (hereinafter referred to as GMA), 50 parts of methoxypolyethylene glycol monomethacrylate, lauryl mercaptan 1.3 in a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube. Parts, 1,000 parts of butyl acetate and 7.5 parts of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, and then the temperature in the system reached about 85 ° C. over about 1 hour under a nitrogen stream. It heated up and warmed for 1 hour. Subsequently, the mixed liquid was taken under nitrogen stream for about 2 hours from a dropping funnel in which a mixed liquid consisting of 600 parts of GMA, 150 parts of methoxy polyethylene glycol monomethacrylate, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was injected. After dripping inside and keeping at the same temperature for 3 hours, 10 parts of AIBNs were injected | poured and it was kept for 1 hour. Then, it heated up at 120 degreeC and kept warm for 2 hours. After cooling to 60 ° C, the nitrogen inlet tube was replaced with an air inlet tube, 406 parts of acrylic acid (hereinafter referred to as AA), 1.8 parts of metoquinone and 4.8 parts of triphenylphosphine were mixed and mixed, followed by 110 under air bubbling. It heated up to ° C. After keeping at the same temperature for 8 hours, 1.3 parts of metoquinone was injected and cooled, and ethyl acetate was added so as to have a nonvolatile content of 60% to obtain a solution of the dispersant (i) for the present invention. Dispersing agent (i) was hydroxyl value 224 mgKOH / g, weight average molecular weight 17,000 (styrene conversion value by the gel permeation chromatography (GPC) method).

Production Example  2

175 parts of glycidyl methacrylate (hereinafter referred to as GMA), 62.5 parts of methyl methacrylate (hereinafter referred to as MMA) and methoxy to a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube. 12.5 parts of polyethylene glycol monomethacrylate, 1.3 parts of lauryl mercaptan, 1,000 parts of butyl acetate, and 7.5 parts of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, followed by about 1 part under nitrogen stream. It heated up until the system became about 85 degreeC over time, and it warmed for 1 hour. Then, the mixed liquid was dripped under nitrogen stream from the dropping funnel which injected the mixed liquid which consists of 525 parts of GMA, 187.5 parts of MMA, 37.5 parts of methoxy polyethyleneglycol monomethacrylate, 3.7 parts of lauryl mercaptan, and 22.5 parts of AIBN beforehand by mixing with nitrogen stream. It took time, it dripped in the system, and insulated at the same temperature for 3 hours, 10 parts of AIBNs were injected, and it was kept for 1 hour. Then, it heated up at 120 degreeC and kept warm for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, 355.4 parts of acrylic acid (hereinafter referred to as AA), 1.8 parts of metoquinone and 4.8 parts of triphenylphosphine were mixed and mixed, followed by air bubbling. It heated up to ° C. After keeping at the same temperature for 8 hours, 1.3 parts of metoquinone was injected and cooled, and ethyl acetate was added so as to have a nonvolatile content of 60% to obtain a solution of the dispersant (ii) for the present invention. Dispersant (ii) was hydroxyl value 204 mgKOH / g, weight average molecular weight 17,800 (styrene conversion value by GPC method).

Production Example  3

162.5 parts of glycidyl methacrylate (hereinafter referred to as GMA), 87.5 parts of methoxypolyethylene glycol monomethacrylate, and lauryl mercaptan in a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube. Part, 1,000 parts of butyl acetate and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, and the temperature was raised to about 85 ° C. over about 1 hour under a stream of nitrogen. It kept warm for 1 hour. Subsequently, the mixture was taken under a stream of nitrogen for about 2 hours from a dropping funnel in which a mixture of 487.5 parts of GMA, 262.5 parts of methoxypolyethylene glycol monomethacrylate, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was injected. After dripping inside and keeping at the same temperature for 3 hours, 10 parts of AIBNs were injected | poured and it was kept for 1 hour. Then, it heated up at 120 degreeC and kept warm for 2 hours. After cooling to 60 ° C, the nitrogen inlet tube was replaced with an air inlet tube, 330 parts of acrylic acid (hereinafter referred to as AA), 1.8 parts of metoquinone and 4.8 parts of triphenylphosphine were mixed and mixed, followed by air bubbling. It heated up to ° C. After keeping at the same temperature for 8 hours, 1.3 parts of metoquinone was injected and cooled, and ethyl acetate was added so as to have a nonvolatile content of 60% to obtain a solution of the dispersant for the present invention. The dispersant had a hydroxyl value of 193 mgKOH / g and a weight average molecular weight of 18,000 (styrene conversion value according to the GPC method).

Production Example  4

200 parts of glycidyl methacrylate (hereinafter referred to as GMA), 50 parts of methoxypolyethylene glycol monomethacrylate, lauryl mercaptan 1.3 in a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube. Part, 1,000 parts of butyl acetate and 3.7 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, and the temperature was raised to about 75 ° C. over about 1 hour under a stream of nitrogen. It kept warm for 1 hour. Subsequently, the mixed liquid was taken under nitrogen stream for about 2 hours from a dropping funnel in which a mixed liquid consisting of 600 parts of GMA, 150 parts of methoxy polyethylene glycol monomethacrylate, 3.7 parts of lauryl mercaptan and 11.3 parts of AIBN was injected. After dripping inside and keeping at the same temperature for 5 hours, 10 parts of AIBNs were injected | poured, and it was kept for 1 hour. Then, it heated up at 120 degreeC and kept warm for 2 hours. After cooling to 60 ° C, the nitrogen inlet tube was replaced with an air inlet tube, 406 parts of acrylic acid (hereinafter referred to as AA), 1.8 parts of metoquinone and 4.8 parts of triphenylphosphine were mixed and mixed, followed by 110 under air bubbling. It heated up to ° C. After keeping at the same temperature for 8 hours, 1.3 parts of metoquinone was injected and cooled, and ethyl acetate was added so that a nonvolatile content might be 60%, and the solution of the dispersing agent for this invention was obtained. The dispersant was a hydroxyl value of 224 mgKOH / g and a weight average molecular weight of 43,000 (styrene equivalent value according to the GPC method).

Production Example  5

162.5 parts of glycidyl methacrylate (hereinafter referred to as GMA), 87.5 parts of polypropylene glycol monomethacrylate, and 1.3 parts of lauryl mercaptan in a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube. , 1,000 parts of butyl acetate and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, and the temperature was raised to about 85 ° C. over 1 hour under a nitrogen stream, followed by 1 Warmed for time. Subsequently, the mixture was taken under a nitrogen stream for about 2 hours from a dropping funnel in which a mixed solution consisting of 487.5 parts of GMA, 262.5 parts of polypropylene glycol monomethacrylate, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was injected, and then the mixed solution was consumed in the system. After dripping and keeping warm at the same temperature for 3 hours, 10 parts of AIBN were injected and kept warm for 1 hour. Then, it heated up at 120 degreeC and kept warm for 2 hours. After cooling to 60 ° C, the nitrogen inlet tube was replaced with an air inlet tube, 330 parts of acrylic acid (hereinafter referred to as AA), 1.8 parts of metoquinone and 4.8 parts of triphenylphosphine were mixed and mixed, followed by air bubbling. It heated up to ° C. After keeping at the same temperature for 8 hours, 1.3 parts of metoquinone was injected and cooled, and ethyl acetate was added so as to have a nonvolatile content of 60% to obtain a solution of the dispersant (v) for the present invention. Dispersing agent (v) was hydroxyl value 193 mgKOH / g, weight average molecular weight 17,300 (styrene conversion value by GPC method).

Production Example  6

200 parts of methylmethacrylic acid (hereinafter referred to as MMA), 50 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA) to a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube; After 1.3 parts of lauryl mercaptan, 1,000 parts of butyl acetate and 7.5 parts of 2,2′-azobisisobutyronitrile were injected, the temperature was raised to about 100 ° C. over about 1 hour under a nitrogen stream. It kept warm for 1 hour. Subsequently, from the dropping funnel in which the mixed liquid consisting of 600 parts of MMA, 150 parts of HEMA, 3.7 parts of lauryl mercaptan, and 22.5 parts of AIBN was inject | poured, the mixed liquid was dripped in a system under nitrogen stream for about 2 hours, and the same temperature was carried out for 3 hours. After keeping warm, 10 parts of AIBN were injected and kept warm for 1 hour. Thereafter, the mixture was warmed to 120 ° C, kept warm for 2 hours, 1.3 parts of metoquinone was injected and cooled, and ethyl acetate was added so as to have a nonvolatile content of 60% to obtain a solution of a comparative dispersant. The dispersant was a hydroxyl value of 86 mgKOH / g and a weight average molecular weight of 9,000 (styrene equivalent value according to GPC).

Production Example  7

62.5 parts of glycidyl methacrylate (hereinafter referred to as GMA), 87.5 parts of methyl methacrylate (hereinafter referred to as MMA) and butyl acryl in a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube. 100 parts of the rate (hereinafter referred to as BA), 1.3 parts of lauryl mercaptan, 1,000 parts of butyl acetate, and 7.5 parts of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, followed by a nitrogen stream. It heated up until the in-system temperature became about 60 degreeC over about 1 hour, and it warmed for 1 hour. Thereafter, from the dropping funnel in which the mixed liquid consisting of 187.5 parts of GMA, 262.5 parts of MMA, 300 parts of BA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was injected, the mixed solution was dripped in the system under nitrogen stream for about 2 hours. After keeping at the same temperature for 7 hours, 10 parts of AIBN was injected and kept for 1 hour. Then, it heated up at 120 degreeC and kept warm for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, 127 parts of acrylic acid (hereinafter referred to as AA), 1.5 parts of methoquinone and 1.9 parts of triphenylphosphine were mixed and mixed, followed by air bubbling. It heated up to ° C. After keeping at the same temperature for 8 hours, 1.3 parts of metoquinone was injected and cooled, and ethyl acetate was added so as to have a nonvolatile content of 60% to obtain a solution of a comparative dispersant. The dispersant had a hydroxyl value of 127 mgKOH / g and a weight average molecular weight of 46,000 (styrene equivalent value according to the GPC method).

Conductive Polymer / Dopant  Organic solvent Dispersion  pharmacy

Example  One

An organic solvent dispersion was prepared using AGFA's "Orgacon" (trade name, PEDOT / PSS weight ratio of 1: 2.5), which is a commercially available PEDOT / PSS water dispersion, as an aqueous dispersion of a conductive polymer / dopant.

100 g of "Orgacon" (1.2% solids) was removed from the flask, and 100 g of ethanol was added and 0.5 ml of 10% hydrochloric acid was added while stirring. Then, it stirred for 1 hour after continuing stirring for 30 minutes. After the obtained gel-like material was filtered under reduced pressure using a glass filter, 200 g of ethanol was added and the pressure-reduced filter was repeated eight times. The solids were taken out of the glass filter in a state where the solids were not completely dry, and the solids weight was calculated from the heating weight reduction to obtain 15 g of a wet blue solid having a 7.8% solids. 45 g of ethanol was added to a beaker and 0.4 g of an amine alkylene oxide adduct (trade name "Ethomeen C / 15", manufactured by LION AKZO) was added, and then 15 g of the wet blue solid was added thereto, followed by an emulsifying disperser (trade name: TK HOMO DISPER, specialty). 10 minutes treatment at 4,000 rpm using a vaporization industry) to obtain a PEDOT / PSS ethanol dispersion (solid content concentration 2%, water content 5% by weight).

20 parts of the PEDOT / PSS ethanol dispersion thus obtained, 66 parts of the dispersant (i) obtained in Preparation Example 1 (60% solids concentration) and 14 parts of ethanol were stirred in a glass bottle, uniformly dispersed, and dispersed in a conductive polymer / dopant An organic solvent dispersion was obtained.

Example  2 to 5

A conductive polymer / dopant organic solvent dispersion was obtained in the same manner as in Example 1 except that the dispersant (i) used in Example 1 was changed to the dispersant shown in Table 1.

Comparative example  1 and 2

A conductive polymer / dopant organic solvent dispersion was obtained in the same manner except that the dispersant (i) used in Example 1 was changed as shown in Table 1.

Comparative example  3

In Example 1, except using 40 parts of polyfunctional polyester acrylate (brand name "ARONIX M-400", Dong-A Synthetic Co., Ltd. product, 100% of solid content concentration) which is a polymerizable monomer, without using a dispersing agent (i). In the same manner to obtain a conductive polymer / dopant organic solvent dispersion.

Comparative example  4

In Example 1, the polyfunctional urethane acrylate (brand name "UA-306H", Kyoe Chemical Co., Ltd. make, 100% of solid content concentration) which is a polymerizable monomer is used without using a dispersing agent (i). Conductive polymer / dopant organic solvent dispersions were obtained in the same manner except that parts were used.

Example  6

20 parts of PEDOT / PSS ethanol dispersion (solid content concentration 2%) prepared from the poly (3, 4- ethylene dioxythiophene) / polystyrene sulfonic acid water dispersion (brand name "Orgacon", AGFA company make), the dispersing agent obtained by the manufacture example 1 ( i) (60% of solid content concentration) 7 parts, polyfunctional polyester acrylate which is a polymerizable monomer (brand name "ARONIX M-400", Dong-A Synthetic Co., Ltd., dipentaerythritol hexaacrylate, solid content concentration 100%) 35 parts and 38 parts of ethanol were put in a glass bottle, stirred and uniformly dispersed to obtain an organic solvent dispersion of a conductive polymer / dopant.

Example  7

Polyfunctional urethane acrylate (brand name "UA-306H") which is a polymerizable monomer using the polyfunctional polyester acrylate (brand name "ARONIX M-400", Dong-A Synthetic Co., Ltd. product, solid content concentration 100%) used in Example 6 , Kyosei Chemical Co., Ltd., solid content concentration 100%), except that the conductive polymer / dopant organic solvent dispersion was obtained in the same manner.

Example  8 to 11

A conductive polymer / dopant organic solvent dispersion was obtained in the same manner as in Example 6 except that the dispersant (i) used in Example 6 was changed to the dispersant shown in Table 1.

The dispersion stability of the conductive polymer / dopant organic solvent dispersions obtained in Examples 1 to 11 and Comparative Examples 1 to 4 was investigated by the following test method.

Dispersion stability: After leaving each electroconductive polymer / dopant organic solvent dispersion for 1 month at room temperature, particle | grain aggregation and sedimentation were visually confirmed and it was good that it did not change.

The test results of dispersion stability are shown in Table 1 below.

Dispersion Dispersant / Polymerizable Monomer Usage (part) Ethanol amount (part) stability Example 1 Production Example 1 / 66 / 14 Good Example 2 Production Example 2 /- 66 / 14 Good Example 3 Production Example 3 / 66 / 14 Good Example 4 Production Example 4 / 66 / 14 Good Example 5 Production Example 5 / 66 / 14 Good Example 6 Preparation Example 1 / Polyester acrylate 7/35 38 Good Example 7 Preparation Example 1 / Polyurethane acrylate 7/35 38 Good Example 8 Preparation Example 2 / Polyester acrylate 7/35 38 Good Example 9 Preparation Example 3 / Polyester acrylate 7/35 38 Good Example 10 Production Example 4 / Polyester acrylate 7/35 38 Good Example 11 Production Example 5 / Polyester acrylate 7/35 38 Good Comparative Example 1 Production Example 6 / 66 / 14 Cohesion Comparative Example 2 Production Example 7 / 66 / 14 Cohesion Comparative Example 3 -/ Polyester acrylate ― / 40 40 Cohesion  Comparative Example 4 -/ Polyurethane acrylate ― / 40 40 Cohesion

Example  12 to 21 and Comparative example  5 to 6

Each of the conductive polymer / dopant organic solvent dispersions obtained in Examples 1 to 6, Examples 8 to 11, Comparative Examples 1 and 2, and 1-hydroxycyclohexyl-phenylketone as a photopolymerization initiator (hereinafter referred to as HCPK). The performance was evaluated by the following test method about the surface resistance value and transparency of the cured coating film obtained by hardening | curing the active-energy-ray-curable coating material composition which mix | blended 2 parts of brand name "Irgacure184" and the product made by Chiba Japan.

(1) surface resistance

The active energy ray-curable coating composition using the dispersion described in Table 2 was applied on a polyethylene terephthalate (PET) film with a # 12 bar coater (calculated value: film thickness of 4.8 μm), dried at 80 ° C. for 2 minutes, and under air. Using a high pressure mercury lamp, it was made to pass through so that an irradiation amount of 500 mJ / cm 2 was cured. The surface resistance value of this cured coating film part was measured at the temperature of 25 degreeC using the ultra insulation resistance / microammeter (made by ADVANTEST Corporation). The unit of surface resistance value is ohms / square (omega / square).

(2) transparency of cured film

The total light transmittance and the haze value of the cured coating film portion were measured based on the PET film using a color haze meter (manufactured by Murakami Color Technology Research Institute).

Table 2 shows the results of each performance evaluation.

Dispersion Surface resistance Total light transmittance Haze Example 12 Example 1 5.1 × 10 ¹⁵ 87.2% 0.2 Example 13 Example 2 7.8 × 10 ¹⁵ 87.0% 0.2 Example 14 Example 3 5.1 × 10 ¹⁴ 87.1% 0.3 Example 15 Example 4 3.6 × 10 ¹⁵ 87.0% 0.2 Example 16 Example 5 6.9 × 10 ¹⁴ 86.9% 0.2 Example 17 Example 6 5.4 × 10 ¹⁰ 86.8% 0.2 Example 18 Example 8 8.0 × 10 ¹⁰ 87.3% 0.2 Example 19 Example 9 6.2 × 10 ⁹ 87.2% 0.2 Example 20 Example 10 2.7 × 10 ¹⁰ 87.1% 0.3 Example 21 Example 11 9.9 × 10 ⁹ 87.0% 0.2 Comparative Example 5 Comparative Example 1 1.2 × 10 ¹⁴ 86.5% 0.3 Comparative Example 6 Comparative Example 2 4.3 × 10 ¹⁵ 87.0% 0.3

Conductive Polymer / Dopant  Regarding an embodiment using hydroxyl group-containing acrylic polymer (II) or (III) as a dispersant for dispersing an organic solvent Production Example , Example  And Comparative example

Conductive Polymer / Dopant  Preparation of Dispersant for Dispersing Organic Solvents

Production Example  8

175 parts of glycidyl methacrylate (hereinafter referred to as GMA), 75 parts of methyl methacrylate (hereinafter referred to as MMA) and lauryl in a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube. After 1.3 parts of mercaptan, 1,000 parts of methyl isobutyl ketone and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, the temperature in the system was about 85 over an hour under a stream of nitrogen. It heated up until it became C and kept warm for 1 hour. Subsequently, from the dropping funnel in which the mixed liquid consisting of 525 parts of GMA, 225 parts of MMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was injected, the mixture was dropped into the system under nitrogen stream for about 2 hours, and then the same temperature for 3 hours. After keeping warm, 10 parts of AIBN were injected and kept warm for 1 hour. Then, it heated up at 130 degreeC and kept warm for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, 355 parts of acrylic acid (hereinafter referred to as AA), 1.8 parts of metoquinone and 4.8 parts of triphenylphosphine were mixed and mixed, followed by air bubbling. It heated up to ° C. After keeping at the same temperature for 8 hours, 1.3 parts of metoquinone was injected and cooled, and methyl isobutyl ketone was added so as to have a nonvolatile content of 60% to obtain a solution of the dispersant for the present invention. The dispersing agent was 204 mgKOH / g of hydroxyl value, and the weight average molecular weight (styrene conversion value by GPC method) 17,600.

Production Example  9

156.3 parts of glycidyl methacrylate (hereinafter referred to as GMA), 93.8 parts of methyl methacrylate (hereinafter referred to as MMA) and lauryl in a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube. After 1.3 parts of mercaptan, 1,000 parts of methyl isobutyl ketone and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, the temperature in the system was about 85 over an hour under a stream of nitrogen. It heated up until it became C and kept warm for 1 hour. Thereafter, from the dropping funnel in which the mixed solution consisting of 468.8 parts of GMA, 281.3 parts of MMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was injected, the mixture was dropped in the system under nitrogen stream for about 2 hours, and then the same temperature for 3 hours. After keeping warm, 10 parts of AIBN were injected and kept warm for 1 hour. Then, it heated up at 130 degreeC and kept warm for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, 317 parts of acrylic acid (hereinafter referred to as AA), 1.8 parts of metoquinone and 4.8 parts of triphenylphosphine were mixed and mixed, followed by air bubbling. It heated up to ° C. After keeping at the same temperature for 8 hours, 1.3 parts of metoquinone was injected and cooled, and methyl isobutyl ketone was added so as to have a nonvolatile content of 60% to obtain a solution of the dispersant for the present invention. The dispersing agent was 187 mgKOH / g of hydroxyl value, and the weight average molecular weight (styrene conversion value by GPC method) was 16,500.

Production Example  10

100 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), 150 parts of methyl methacrylate (hereinafter referred to as MMA) to a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube; 1.3 parts of lauryl mercaptan, 1,000 parts of methyl isobutyl ketone, 500 parts of propylene glycol monomethyl ether, and 7.5 parts of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, followed by It heated up until the in-system temperature became about 85 degreeC over 1 hour, and it warmed for 1 hour. Subsequently, from the dropping funnel in which the mixed liquid consisting of HEMA 300 parts, 450 parts of MMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was injected, the mixed solution was added dropwise into the system under nitrogen stream for about 2 hours, and then After warming to temperature, 10 parts of AIBN were injected and kept warm for 1 hour. Then, it heated up at 130 degreeC and kept warm for 2 hours. After cooling to 60 ° C, 1.3 parts of metoquinone was injected and cooled, and methyl isobutyl ketone was added so that the nonvolatile content was 40% to obtain a solution of the dispersant for the present invention. The dispersing agent was 168 mgKOH / g of hydroxyl value, and the weight average molecular weight (styrene conversion value by GPC method) 13,250.

Production Example  11

175 parts of glycidyl methacrylate (hereinafter referred to as GMA), 75 parts of methyl methacrylate (hereinafter referred to as MMA) and lauryl in a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube. When 1.3 parts of mercaptan, 1,000 parts of butyl acetate, and 3.7 parts of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, the system became about 70 ° C. over about 1 hour under a stream of nitrogen. It heated up to and warmed for 1 hour. Then, the mixed liquid was dripped under nitrogen stream from the dropping funnel which injected the mixed liquid which consists of 525 parts of GMA, 225 parts of MMA, 37.5 parts of methoxy polyethyleneglycol monomethacrylate, 3.7 parts of lauryl mercaptans, and 11.2 parts of AIBN beforehand by the nitrogen stream. It took time, it dripped in the system, and insulated at the same temperature for 6 hours, and 10 parts of AIBNs were injected and it was kept for 1 hour. Then, it heated up at 120 degreeC and kept warm for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, 355.4 parts of acrylic acid (hereinafter referred to as AA), 1.8 parts of metoquinone and 4.8 parts of triphenylphosphine were mixed and mixed, followed by air bubbling. It heated up to ° C. After warming at the same temperature for 8 hours, 1.3 parts of metoquinone was injected and cooled, and ethyl acetate was added so that a non-volatile content might be 60%, and the solution of the dispersing agent (Xi) for this invention was obtained. The dispersant (XI) had a hydroxyl value of 204 mg KOH / g and a weight average molecular weight of 43,500 (styrene equivalent value according to the GPC method).

Production Example  12

175 parts of glycidyl methacrylate (hereinafter referred to as GMA), 75 parts of isobornyl methacrylate (hereinafter referred to as IBXMA) in a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube; After 1.3 parts of lauryl mercaptan, 1,000 parts of butyl acetate and 7.5 parts of 2,2-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, the system became about 85 ° C. over about 1 hour under a stream of nitrogen. It heated up until and warmed for 1 hour. Subsequently, from the dropping funnel in which the mixed liquid consisting of 525 parts of GMA, 225 parts of IBXMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was injected, the mixture was dropped into the system under nitrogen stream for about 2 hours, and then the same temperature for 3 hours. After keeping warm, 10 parts of AIBN were injected and kept warm for 1 hour. Then, it heated up at 120 degreeC and kept warm for 2 hours. After cooling to 60 ° C, the nitrogen inlet tube was replaced with an air inlet tube, 330 parts of acrylic acid (hereinafter referred to as AA), 1.8 parts of metoquinone and 4.8 parts of triphenylphosphine were mixed and mixed, followed by air bubbling. It heated up to ° C. After keeping at the same temperature for 8 hours, 1.3 parts of metoquinone was injected and cooled, and ethyl acetate was added so as to have a nonvolatile content of 60% to obtain a solution of the dispersant (Xii) for the present invention. The dispersing agent (XII) was hydroxyl value 204 mgKOH / g, weight average molecular weight 16,300 (styrene conversion value by the gel permeation chromatography (GPC) method).

Production Example  13

50 parts of glycidyl methacrylate (hereinafter referred to as GMA), 200 parts of methyl methacrylate (hereinafter referred to as MMA) and lauryl in a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube. After 1.3 parts of mercaptan, 1,000 parts of methyl isobutyl ketone and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, the temperature in the system was about 85 over an hour under a stream of nitrogen. It heated up until it became C and kept warm for 1 hour. Then, from the dropping funnel in which the mixed liquid which consisted of 150 parts of GMA, 600 parts of MMA, 3.7 parts of lauryl mercaptan, and 22.5 parts of AIBN was previously dripped under the nitrogen stream, the mixed solution was dripped in the system for 3 hours and the same temperature for 3 hours. After keeping warm, 10 parts of AIBN were injected and kept warm for 1 hour. Then, it heated up at 130 degreeC and kept warm for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, 102 parts of acrylic acid (hereinafter referred to as AA), 1.8 parts of metoquinone and 4.8 parts of triphenylphosphine were mixed and mixed, followed by air bubbling. It heated up to ° C. After keeping at the same temperature for 8 hours, 1.3 parts of metoquinone was injected and cooled, and methyl isobutyl ketone was added so as to have a nonvolatile content of 60% to obtain a solution of a comparative dispersant. The dispersant had a hydroxyl value of 71.7 mgKOH / g and a weight average molecular weight (styrene conversion value according to the GPC method) of 15,300.

Production Example  14

250 parts of glycidyl methacrylate (hereinafter referred to as GMA), 1.3 parts of lauryl mercaptan, 1,000 parts of methyl isobutyl ketone and 2, in a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube; After injecting 7.5 parts of 2'-azobisisobutyronitrile (hereinafter referred to as AIBN), the mixture was heated to a temperature of about 90 DEG C over about 1 hour under nitrogen stream and kept warm for 1 hour. Then, from the dropping funnel in which the mixed liquid which consisted of 750 parts of GMA, 3.7 parts of lauryl mercaptan, and 22.5 parts of AIBN was previously dripped under nitrogen stream, the mixed liquid was dripped in the system, and it was kept at the same temperature for 3 hours, 10 parts of AIBN were injected and kept warm for 1 hour. Then, it heated up at 130 degreeC and kept warm for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, 507 parts of acrylic acid (hereinafter referred to as AA), 2.3 parts of metoquinone and 6.0 parts of triphenylphosphine were mixed and mixed, followed by air bubbling. It heated up to ° C. After keeping at the same temperature for 8 hours, 1.6 parts of metoquinone was injected and cooled, and methyl isobutyl ketone was added so as to have a nonvolatile content of 60% to obtain a solution of a comparative dispersant. The dispersant had a hydroxyl value of 262 mg KOH / g and a weight average molecular weight (styrene equivalent value according to the GPC method) of 22,000.

Production Example  15

75 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), 175 parts of methyl methacrylate (hereinafter referred to as MMA) to a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube; After 1.3 parts of lauryl mercaptan, 1500 parts of methyl isobutyl ketone and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, the temperature in the system was decreased over about 1 hour under a stream of nitrogen. It heated up until it became about 85 degreeC, and warmed for 1 hour. Subsequently, from the dropping funnel in which the mixed solution consisting of 225 parts of HEMA, 525 parts of MMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was injected, the mixture was dropped into the system under nitrogen stream for about 2 hours, and then the same temperature for 3 hours. After keeping warm, 10 parts of AIBN were injected and kept warm for 1 hour. Then, it heated up at 130 degreeC and kept warm for 2 hours. After cooling to 60 ° C., 1.3 parts of methoquinone was injected and cooled, and methyl isobutyl ketone was added so as to have a nonvolatile content of 40% to obtain a solution of a dispersant for comparison. The dispersant was a hydroxyl value of 127 mgKOH / g and a weight average molecular weight of 13,250 (styrene equivalent value according to the GPC method).

Production Example  16

175 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), 75 parts of methyl methacrylate (hereinafter referred to as MMA) to a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube; 1.3 parts of lauryl mercaptan, 1,000 parts of methyl isobutyl ketone, 500 parts of propylene glycol monomethyl ether, and 7.5 parts of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) were injected, followed by It heated up until the in-system temperature became about 85 degreeC over 1 hour, and it warmed for 1 hour. Subsequently, from the dropping funnel in which the mixed solution consisting of 525 parts of HEMA, 225 parts of MMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was injected, the mixture was dropped into the system under nitrogen stream for about 2 hours, and then the same temperature for 3 hours. After keeping warm, 10 parts of AIBN were injected and kept warm for 1 hour. Then, it heated up at 130 degreeC and kept warm for 2 hours. After cooling to 60 ° C., 1.3 parts of methoquinone was injected and cooled, and methyl isobutyl ketone was added so as to have a nonvolatile content of 40% to obtain a solution of a dispersant for comparison. The dispersant was a hydroxyl value of 297 mgKOH / g and a weight average molecular weight (styrene conversion value according to the GPC method) of 14,600.

Table 3 shows the monomer composition, hydroxyl value and weight average molecular weight of each dispersant obtained in Production Examples 8-16.

Monomer Composition of Acrylic Polymer of Dispersant Hydroxyl value (mgKOH / g) Jungnang Average Molecular Weight Preparation Example 8 GMA / MMA = 70/30 204 17,600 Preparation Example 9 GMA / MMA = 62.5 / 37.5 187 16,500 Preparation Example 10 HEMA / MMA = 40/60 168 10,600 Preparation Example 11 GMA / MMA = 70/30 204 43,500 Preparation Example 12 GMA / IBXMA = 70/30 204 16,300 Preparation Example 13 GMA / MMA = 20/80 71.7 15,300 Preparation Example 14 GMA / MMA = 100/0 262 22,000 Preparation Example 15 HEMA / MMA = 30/70 127 13,250 Preparation Example 16 HEMA / MMA = 70/30 297 14,600

Conductive Polymer / Dopant  Organic solvent Dispersion  pharmacy

Example  22

The organic solvent dispersion was manufactured using AGFA "Orgacon" (brand name) which is a commercial PEDOT / PSS water dispersion as a water dispersion of a conductive polymer / dopant. 100 g of "Orgacon" (1.2% solids) was added to the flask, and 100 g of ethanol was added thereto and 0.5 ml of 10% hydrochloric acid was added while stirring. Thereafter, stirring was continued for 30 minutes and left for 1 hour. After the obtained gel-like material was filtered under reduced pressure using a glass filter, 200 g of ethanol was added and the pressure-reduced vacuum was repeated eight times. Solid content was taken out from the glass filter in the state which does not dry completely, and solid weight was computed from heating weight reduction, and 15 g of wet blue solids with 7.8% of solid content were obtained. 45 g of ethanol was added to a beaker and 0.4 g of an amine alkylene oxide adduct (trade name "Ethomeen C / 15", manufactured by LION AKZO) was added, and then 15 g of the wet blue solid was added to the emulsified disperser (trade name "TKHOMO DISPER", special Vaporization industry) was used for 10 minutes at a rotational speed of 4,000 rpm to obtain a PEDOT / PSS ethanol dispersion having a solid content concentration of 2% and a water content of 20% or less.

2 parts of the PEDOT / PSS ethanol dispersion, 66 parts of the dispersant (solid content concentration 60%) obtained in Preparation Example 8 and 14 parts of ethanol were stirred in a glass bottle, and uniformly dispersed to disperse the conductive polymer / dopant organic solvent. Sieve was obtained.

Comparative example  7 and Comparative example  8

A conductive polymer / dopant organic solvent dispersion was obtained in the same manner as in Example 22 except that the dispersant used in Example 22 was changed to the dispersant shown in Table 4.

Example  23

10 parts of the PEDOT / PSS ethanol dispersion described in Example 22, 50 parts of the dispersant (solid content concentration 40%) obtained in Preparation Example 9 and 40 parts of ethanol were placed in a glass bottle to obtain a conductive polymer / dopant organic solvent dispersion. It was.

Example  24 to 26

A conductive polymer / dopant organic solvent dispersion was obtained in the same manner as in Example 22 except that the dispersant used in Example 22 was changed to the dispersant shown in Table 4.

Comparative example  9 and Comparative example  10

A conductive polymer / dopant organic solvent dispersion was obtained in the same manner as in Example 22 except that the dispersant used in Example 22 was changed to the dispersant shown in Table 4.

Comparative example  11

20 parts of PEDOT / PSS ethanol dispersion of Example 22, the polyfunctional polyester acrylate which is a polymerizable monomer (brand name "ARONIX M-400", the Dong-A Synthetic Co., Ltd. product, dipentaerythritol hexaacrylate, solid content concentration 100 %) And 40 parts of ethanol were put in a glass bottle to obtain a conductive polymer / dopant organic solvent dispersion.

The dispersion stability of each conductive polymer / dopant organic solvent dispersion obtained in Examples 22 to 26 and Comparative Examples 7 to 11 was investigated by the following test method.

Dispersion stability: After leaving each electroconductive polymer / dopant organic solvent dispersion at 50 degreeC, particle | grain aggregation and sedimentation were visually confirmed and it judged by the following criteria.

(Double-circle): Aggregation and sedimentation were not recognized over 5 days.

(Circle): Aggregation and sedimentation were not recognized for 3 days.

(Triangle | delta): Aggregation and sedimentation were recognized on the 3rd day.

X: Aggregation and sedimentation were recognized within 1 day.

Table 4 shows the test results of dispersion stability.

 Dispersion Type of dispersant used Used organic solvent Stability of the dispersion Kinds Usage (part) Kinds Usage (part) Example 22 Preparation Example 8 66 ethanol 14 ○ Example 23 Preparation Example 9 66 ethanol 14 ○ Example 24 Preparation Example 10 50 ethanol 40 ○ Example 25 Preparation Example 11 66 ethanol 14 ◎ Example 26 Preparation Example 12 66 ethanol 14 ○ Comparative Example 7 Preparation Example 7 66 ethanol 14 × Comparative Example 8 Preparation Example 8 66 ethanol 14 ◎ Comparative Example 9 Preparation Example 9 50 ethanol 40 △ Comparative Example 10 Preparation Example 10 50 ethanol 40 ◎ Comparative Example 11 Multifunctional polyester acrylate which is a polymerizable monomer 40 ethanol 40 ×

Example  26-29, Comparative example  12 and Comparative example  13

Each conductive polymer / dopant organic solvent dispersion obtained in Examples 22, 23, 25, 26, Comparative Example 8 and Comparative Example 11, 1-hydroxy-cyclohexyl-phenylketone as a photopolymerization initiator (hereinafter referred to as HCPK, The performance was evaluated by the following test method about the surface resistance value, pencil hardness, and transparency of the cured coating film obtained by hardening | curing the active energy ray hardening-type coating material composition which mix | blended two parts of brand name "Irgacure184" and Chiba Specialty Chemical Co., Ltd.).

(1) surface resistance

The active energy ray-curable coating composition using the dispersion described in Table 4 was applied on a polyethylene terephthalate (PET) film with a # 12 bar coater (calculated value: film thickness of 4.8 µm), dried at 80 ° C for 2 minutes, and under air. using a high pressure mercury lamp to cure by passing so that the irradiation dose of 500mJ / cm ^2㎠. The surface resistance value of this hardened coating film part was measured at the temperature of 25 degreeC using the ultra insulation resistance / microammeter (made by ADVANTEST Corporation). The unit of surface resistance value is ohms / square (omega / square).

(2) pencil hardness

The cured coating film portion was evaluated by a pencil scraping test with a load of 500 g according to JIS K 5400.

(3) transparency of the cured film

The total light transmittance and the haze value of the cured coating film portion were measured based on the PET film using a color haze meter (manufactured by Murakami Color Technology Research Institute).

Table 5 shows the results of each performance evaluation.

 Dispersion Evaluation of Curing Film Performance Surface Resistance (Ω / □) Hardness Total light transmittance (%) Haze value Example 22 3.3 × 10 ¹⁴ 2H 88 0.2 Example 23 5.4 × 10 ¹² H 88.3 0.3 Example 25 6.3 × 10 ¹⁴ 2H 88.2 0.2 Example 26 9.6 × 10 ¹³ 2H 87.9 0.3 Comparative Example 8 3.0 × 10 ¹⁷ ＜ 2H 87.6 0.1 Comparative Example 11 3.0 × 10 ¹⁰ 3H 87.2 0.4

Claims (18)

The content of water obtained by dispersing the conductive polymer (A) and the dopant (B) in an organic solvent using a dispersant which is a hydroxyl group-containing acrylic polymer having a weight average molecular weight of 10,000 to 50,000 and a hydroxyl value of 160 to 230 mgKOH / g is 20. An organic solvent dispersion of conductive polymers / dopants of up to weight%. The method of claim 1, The conductive polymer (A) is at least one member selected from the group consisting of polyaniline, polythiophene, polypyrrole, polyprene, polyphenylene, polyphenylenevinylene, polyacene and polythiophenevinylene Organic solvent dispersions. The method of claim 1, Dopant (B) is an anionic compound Organic solvent dispersions. The method of claim 3, The anionic group of the anionic compound is at least one member selected from the group consisting of monosubstituted sulfuric acid ester group, monosubstituted phosphate ester group, phosphoric acid group, carboxyl group and sulfone group Organic solvent dispersions. The method of claim 1, The conductive polymer (A) is poly (3,4-ethylenedioxythiophene) and the dopant (B) is polystyrenesulfonic acid Organic solvent dispersions. The method of claim 1, Ring-opening esterification reaction of carboxyl group-containing vinyl monomer (c) to the copolymer obtained by superposing | polymerizing the monomer component containing an epoxy-group-containing (meth) acrylic-type monomer (a) and an alkylene oxide structure containing vinyl-type monomer (b) Hydroxyl group-containing acrylic polymer (I) Organic solvent dispersions. The method of claim 6, The hydroxyl group-containing acrylic polymer (I) is an epoxy group-containing (meth) acrylic monomer (a) and an alkylene oxide structure-containing vinyl monomer (b) based on the sum of both the former 65 to 95% by weight and the latter 5 to 35% by weight. It is a copolymer obtained by superposing | polymerizing in the ratio of Organic solvent dispersions. The method of claim 6, Alkylene oxide structure-containing vinyl monomer (b) is represented by general formula (1) [Formula 1] CH ₂ = CR ¹ COO (A _m O) _n R ² (1) (Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrocarbon group and A represents a hydrocarbon group, respectively, m represents an integer of 1 to 3 and n represents an integer of 1 to 23, respectively) Is a monomer represented by Organic solvent dispersions. The method of claim 1, The dispersant is a hydroxyl group-containing acrylic polymer (II) obtained by polymerizing a monomer component containing a hydroxyl group-containing (meth) acrylic monomer (e) and a (meth) acrylic monomer (f) other than the monomer (e). Organic solvent dispersions. The method of claim 1, The dispersant is a hydroxyl group-containing acrylic polymer (III) obtained by ring-opening esterification of a carboxyl group-containing vinyl monomer (c) to a polymer obtained by polymerizing a monomer component containing an epoxy group-containing (meth) acrylic monomer (a). Organic solvent dispersions. The method of claim 1, The mixing ratio of the conductive polymer (A) and the dopant (B) is 200 to 3,000 parts by weight based on 100 parts by weight of the former. Organic solvent dispersions. The method of claim 1, Further containing at least one compound (C) selected from the group consisting of amines and nonionic surfactants Organic solvent dispersions. The method of claim 12, Compound (C) is at least 1 sort (s) chosen from the group which consists of alkylamines and polyalkylene oxide structure containing amines. Organic solvent dispersions. The method of claim 13, The conductive polymer (A) is poly (3,4-ethylenedioxythiophene), the dopant (B) is polystyrenesulfonic acid, and the compound (C) is a polyalkylene oxide structure-containing alkylamines. Organic solvent dispersions. The resin composition containing the organic-solvent dispersion of the conductive polymer / dopant of Claim 1, and binder polymers other than the said conductive polymer. Coating material composition containing the resin composition of Claim 15. The resin composition containing the polymerizable monomer used as the organic solvent dispersion of the electrically conductive polymer / dopant of Claim 1, and a binder polymer. Coating material composition containing the resin composition of Claim 17.