JP2016023202A - Conductive polymer solution and conductive coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive polymer solution that can reduce problems caused by an amine compound and problems caused by water and that can impart an antistatic function to a silicone film and reduce silicone curing impediment, and a conductive coating formed by supplying the above solution on a substrate.SOLUTION: The conductive polymer solution is prepared by mixing: a conductive polymer compound (I) that comprises (a) a π-conjugate conductive polymer, (b) a polyanion introduced to dope the above (a) π-conjugate conductive polymer, and a reaction product of an anion other than the anion in the polyanion used for doping, with an organic compound containing an oxirane group and/or an oxetane group, and that can be dispersed in a solvent essentially comprising an organic solvent; an addition reaction-curable organopolysiloxane composition (II); and a conducting agent (III) that is liquid at 25°C and has a boiling point of 150 to 400°C, by 1 to 100% in terms of mass fraction with respect to the above addition reaction-curable organopolysiloxane composition. The conductive coating is formed by supplying the above solution on a substrate.SELECTED DRAWING: None

Description

  The present invention relates to a conductive polymer solution capable of forming a conductive silicone film, and a conductive coating film formed by supplying the solution onto a substrate.

  In general, a π-conjugated conductive polymer whose main chain is composed of a conjugated system containing π electrons is synthesized by an electrolytic polymerization method or a chemical oxidative polymerization method. In the electropolymerization method, a mixed solution of an electrolyte serving as a dopant and a precursor monomer for forming a π-conjugated conductive polymer is prepared, an electrode is placed in the solution, and a previously formed electrode material or the like is prepared. By immersing the support and applying a voltage between the electrodes, a π-conjugated conductive polymer is formed on the surface of the support in the form of a film. As described above, the electrolytic polymerization method is inferior in mass productivity because it requires an apparatus for electrolytic polymerization and batch production. On the other hand, in the chemical oxidative polymerization method, there is no restriction as described above, and an oxidant and an oxidation polymerization catalyst are added to the precursor monomer that forms the π-conjugated conductive polymer, and a large amount of π-conjugated conductive in solution. Can be produced.

  However, in the chemical oxidative polymerization method, the solubility in a solvent becomes poor with the growth of the conjugated system of the main chain constituting the π-conjugated conductive polymer, so the π-conjugated conductive polymer is insoluble in the solvent. Obtained as a solid powder. For this reason, it is difficult to form a π-conjugated conductive polymer film with a uniform thickness on various substrates such as plastics by a technique such as coating. For this reason, a method of introducing a functional group into a π-conjugated conductive polymer to make it soluble in a solvent, a method of dispersing a π-conjugated conductive polymer in a binder resin and making it soluble in a solvent, a π-conjugated system An attempt has been made to add an anionic group-containing polymer acid to a conductive polymer and solubilize it in a solvent.

  For example, in order to improve the solubility of π-conjugated conductive polymer in water, an oxidizing agent is used in the presence of polystyrene sulfonic acid as an anion group-containing polymer acid having a molecular weight of 2,000 to 500,000. A method for producing a poly (3,4-dialkoxythiophene) aqueous solution by chemical oxidative polymerization of 3,4-dialkoxythiophene is known (see, for example, Patent Document 1). Also known is a method of producing a π-conjugated conductive polymer colloid aqueous solution by chemical oxidative polymerization of a precursor monomer for forming a π-conjugated conductive polymer in the presence of polyacrylic acid ( For example, see Patent Document 2).

  Furthermore, a method for producing a conductive solution that is soluble or dispersed in an organic solvent and can be mixed with an organic resin has been proposed. As an example, an organic solvent solution of polyaniline and a method for producing the same are known (for example, see Patent Document 3). In addition, a solvent replacement method by phase inversion from an aqueous solution containing a polyanion and an intrinsic conductive polymer to an organic solvent is also known (see, for example, Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7). . In addition, a method of dissolving an intrinsic conductive polymer after lyophilization in an organic solvent is also known (see, for example, Patent Document 8). However, in these methods, there is a problem that mixing with other organic resins is difficult as in the case of polyaniline, and in addition, the solvent system is limited to a large amount of water. Even when the amount of water is small or substantially free of water, an amine compound is used as in the above-mentioned documents (see, for example, Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7). As a result, there is a problem that the color tone deteriorates with time when mixed with the resin, and the polyanion dope into the conductive polymer is gradually pulled out by the amine and the conductivity decreases with time. Furthermore, when a conductive polymer is mixed with an addition reaction curable silicone resin, there is a drawback that curing is inhibited by amines and the silicone resin is not sufficiently cured. On the other hand, when a conductive polymer is mixed with a condensation curable silicone resin, there is a drawback in that a phenomenon such as participation in the condensation of silanol or alkoxysilyl group by amine occurs and storage characteristics are deteriorated.

  Conventionally, in the silicone industry, there is a demand for imparting an antistatic function to a silicone composition having a high insulating property for a peeling application or an adhesive application. In order to meet this demand, conventionally, a method of adding carbon powder, metal powder, and ionic conductive material to a silicone composition has been attempted. However, in such a method, at present, many functions such as transparency, peeling performance, adhesion performance, and electrical conductivity humidity resistance of the silicone resin have not been satisfied. In addition, although the technique which mixes a conductive polymer with a silicone resin emulsion in the form of an emulsion is known (for example, refer patent document 9 and patent document 10), the product of this technique is an aqueous dispersion. For this reason, there is a limit to practicality and there are drawbacks such as corrosion of equipment due to water and insufficient adhesion.

JP-A-7-090060 Japanese Patent Laid-Open No. 7-165892 International Publication WO2005 / 052058 JP 2006-249303 A JP 2007-254730 A JP 2008-050661 A JP 2008-045116 A JP 2011-032382 A JP 2002-241613 A JP 2003-251756 A

  The conventional conductive solution described above cannot overcome the above-described drawbacks derived from amine compounds when an amine compound is used and the conductive polymer is phase-inverted from an aqueous phase to an organic phase. In addition, the form of the water dispersion has the disadvantages that it has low practicality and is easily corroded by water. There is a strong desire to overcome the disadvantages and to solve the problem of imparting an antistatic function to the silicone film and inhibiting silicone curing.

  The present invention provides a conductive polymer solution that can reduce problems derived from amine compounds and water, and can impart an antistatic function to the silicone film and reduce silicone curing inhibition, and the same on a substrate. An object is to provide a conductive coating film formed by supplying and forming.

  In order to achieve the above object, the present inventors have developed a completely new technology that enables phase inversion from an aqueous phase to an organic phase by using an oxirane or oxetane compound without using an amine compound. The present inventors have developed and produced a conductive polymer solution compatible with a conductive agent and a curable organopolysiloxane composition, and completed the present invention. Specific problem solving means are as follows.

  The conductive polymer solution for achieving the above object comprises (a) a π-conjugated conductive polymer, (b) the polyanion doped in the (a) π-conjugated conductive polymer, and (c) the above (B) A highly conductive material that is dispersible and soluble in a solvent mainly composed of an organic solvent, including a reaction product of an anion other than that required for doping in the polyanion and an organic compound containing an oxirane group and / or an oxetane group. Molecular composition (I), addition reaction curable organopolysiloxane composition (II), liquid at 25 ° C. and having a boiling point of 150 to 400 ° C., addition reaction curable organopolysiloxane composition And 1 to 100% of a conductive agent (III) by mass fraction.

  The conductive polymer solution according to another embodiment comprises: (a) a π-conjugated conductive polymer, polypyrrole, polythiophene, polyacetylene, polyphenylene, polyphenylene vinylene, polyaniline, polyacene, polythiophene vinylene. And at least one repeating unit selected from the group consisting of two or more copolymers among them.

  In the conductive polymer solution according to another embodiment, (a) the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene) or polypyrrole.

  In the conductive polymer solution according to another embodiment, (b) the polyanion is a mixture of one or more selected from a sulfonic acid group, a phosphoric acid group, and a carboxyl group.

  The conductive polymer solution according to another embodiment comprises (b) a polyanion, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyacrylic acid alkylene sulfonic acid, poly (2-acrylamido-2-methyl-1-propanesulfonic acid). ) Or one or more of them as a copolymerized constituent.

  The conductive coating film according to the embodiment of the present invention is formed by supplying any of the above conductive polymer solutions onto a substrate and curing the solution.

  ADVANTAGE OF THE INVENTION According to this invention, the conductive polymer solution which can reduce the problem derived from an amine compound, and the problem derived from water, and can provide the antistatic function to a silicone film | membrane and reduction of silicone hardening inhibition, and its base | substrate It is possible to provide a conductive coating film that is supplied and formed thereon.

  Hereinafter, each embodiment of the conductive polymer solution and the conductive coating film according to the present invention will be described.

<A Embodiment of Conductive Polymer Solution>
1. Conductive polymer composition The conductive polymer composition (I) contained in the conductive polymer solution according to the embodiment of the present invention comprises (a) a π-conjugated conductive polymer, (b) the above ( a) a reaction product of a polyanion doped in a π-conjugated conductive polymer, (c) an anion other than that required for doping in the (b) polyanion, and an organic compound containing an oxirane group and / or oxetane group And a composition that is dispersible and soluble in a solvent mainly composed of an organic solvent. The intrinsic conductive polymer having a polyanion as a dopant used in the present application is formed from fine particles having a particle size of approximately several tens of nanometers. Such fine particles are transparent in the visible light region due to the presence of a polyanion that also acts as a surfactant, and the fine particles appear to be dissolved in the solvent. Actually, the fine particles are dispersed in a solvent. In the present application, this state is referred to as a “dispersion-soluble” state. The solvent in this case is a solvent mainly composed of an organic solvent. Here, “mainly organic solvent” means that the organic solvent in the solvent exceeds 50%. In particular, the solvent is preferably in the range of organic solvent: water = 90: 10 to 100: 0 by weight ratio.

1.1 Manufacturing Method The conductive polymer composition can be manufactured by the following method as an example.
(1) Method for producing conductive polymer / polyanion complex aqueous dispersion from solution The conductive polymer / polyanion complex aqueous dispersion is an aqueous solution or aqueous dispersion in which a monomer for a conductive polymer and a dopant coexist. Polymerization is carried out in the presence of an oxidizing agent. However, not only polymerization from such a monomer but also a commercially available conductive polymer / dopant aqueous dispersion may be used. Examples of commercially available conductive polymer / dopant aqueous dispersions include Heraeus PEDOT / PSS aqueous dispersion (trade name: Clevios), Agfa PEDOT / PSS aqueous dispersion (trade name: Orgacon), and the like. be able to.

  The conductive polymer composition is prepared by adding an oxirane group or oxetane group-containing compound together with a solvent to the aqueous dispersion, reacting the anion with an oxirane group or oxetane group, and then concentrating, filtering, or separating the reaction solution. Obtained by drying. Thereafter, the obtained concentrate or solid is preferably dissolved or dispersed in a solvent mainly composed of an organic solvent and used in the form of a paint. Further, after adding the oxirane group or oxetane group-containing compound together with the solvent to the aqueous dispersion, an organic solvent insoluble in water is added during or after the reaction between the anion and the oxirane group or oxetane group. The conductive polymer composition is phase-inverted to an insoluble solvent phase, and if necessary, after steps such as dehydration, the conductive polymer composition is dissolved or dispersed in a solvent mainly composed of an organic solvent. May be.

(2) Production Method from Lyophilized Conductive Polymer / Polyanion Complex Solid Material A conductive composition in a polyanion state doped with a π-conjugated system conductive polymer that has already been solid, and water and / or After adding an appropriate amount of a solvent in which the oxirane group or oxetane group-containing compound is dissolved, the anion is reacted with the oxirane group or oxetane group. Thereafter, the reaction solution is concentrated, filtered or dried to obtain a conductive polymer composition. Thereafter, the obtained concentrate or solid is preferably dissolved or dispersed in a solvent mainly composed of an organic solvent and used in the form of a paint. In the above production, after reacting an anion with an oxirane group or oxetane group, an organic solvent insoluble in water is added, and the conductive polymer composition is phase-inverted into a water-insoluble solvent phase. After the steps such as dehydration, the conductive polymer composition may be dissolved or dispersed in a solvent mainly composed of an organic solvent. Thus, in the method (2), since the freeze-dried conductive composition is used as a raw material, the time for the concentration step can be shortened.

1.2 Raw Material for Conductive Polymer Composition (a) π Conjugated Conductive Polymer Any π conjugated conductive polymer can be used as long as the main chain is an organic polymer composed of π conjugated system. Can be used without any limitation. For example, polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers of two or more thereof can be preferably exemplified. In view of ease of polymerization and stability in air, polypyrroles, polythiophenes or polyanilines can be particularly preferably used. In the present invention, the π-conjugated conductive polymer exhibits sufficiently high conductivity and compatibility with the binder even if it is not substituted, but in order to further improve conductivity, dispersibility or solubility in the binder. A functional group such as an alkyl group, an alkenyl group, a carboxyl group, a sulfo group, an alkoxyl group, a hydroxyl group, or a cyano group may be introduced.

  Preferred examples of the π-conjugated conductive polymer include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), and poly (3-n-propylpyrrole). ), Poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4 Dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), Poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly ( -Hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole), polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butyl Thiophene), 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-dihexyloxythiophene), poly (3,4-diheptyl) Oxythiophene), poly (3,4-dioctyloxythiophene), poly (3,4- Decyloxythiophene), poly (3,4-didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butenedioxy) Thiophene), poly (3-methyl-4-methoxythiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3 -Methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene), polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), And poly (3-aniline sulfonic acid).

  In the example of the π-conjugated conductive polymer, considering resistance value or reactivity, polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methoxythiophene), poly (3,4-ethylenediene) A copolymer composed of one or more selected from oxythiophene) can be used particularly preferably. In terms of high conductivity and high heat resistance, polypyrrole and poly (3,4-ethylenedioxythiophene) can be preferably used. In addition, alkyl-substituted compounds such as poly (N-methylpyrrole) and poly (3-methylthiophene) are soluble in solvents mainly composed of organic solvents, compatible and dispersible when a hydrophobic resin is added. In order to improve this, it can use more suitably. Among alkyl groups, a methyl group is more preferable because it hardly affects the conductivity.

(B) Polyanion The polyanion can be used without particular limitation as long as it is an anionic compound. An anionic compound is a compound having in the molecule an anionic group capable of causing chemical oxidation doping to the (a) π-conjugated conductive polymer. As the anion group, a sulfate ester group, a phosphate ester group, a phosphate group, a carboxyl group, a sulfone group, and the like are preferable from the viewpoint of ease of production and high stability. Among these anionic groups, (a) a sulfone group, a sulfate ester group, and a carboxyl group are more preferable because of its excellent doping effect on the π-conjugated conductive polymer.

  Examples of the polyanion include a polymer obtained by polymerizing an anion group-containing polymerizable monomer in addition to a polymer in which an anion group is introduced into a polymer by sulfonating a polymer having no anion group with a sulfonating agent. Can do. Usually, the polyanion is preferably obtained by polymerizing an anion group-containing polymerizable monomer from the viewpoint of ease of production. Examples of the production method include a method obtained by subjecting an anionic group-containing polymerizable monomer to oxidative polymerization or radical polymerization in a solvent in the presence of an oxidizing agent and / or a polymerization catalyst. More specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent and maintained at a constant temperature, and a predetermined amount of an oxidizing agent and / or a polymerization catalyst is previously dissolved in the solvent. The solution was added and allowed to react for a predetermined time. The polymer obtained by the reaction is prepared to a certain concentration by a catalyst. In this production method, a polymerizable monomer having no anionic group can be copolymerized with the anionic group-containing polymerizable monomer. The oxidizing agent and / or oxidation catalyst and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer (a) forming the π-conjugated conductive polymer. .

The anionic group-containing polymerizable monomer is a monomer having a functional group capable of polymerizing with an anionic group in the molecule. Specifically, vinylsulfonic acid and its salts, allylsulfonic acid and its salts, methallylsulfonic acid and its Salts, styrenesulfonic acid and its salts, methallyloxybenzenesulfonic acid and its salts, allyloxybenzenesulfonic acid and its salts, α-methylstyrenesulfonic acid and its salts, acrylamide-t-butylsulfonic acid and its salts, 2 Acrylamide-2-methylpropanesulfonic acid and its salts, cyclobutene-3-sulfonic acid and its salts, isoprenesulfonic acid and its salts, 1,3-butadiene-1-sulfonic acid and its salts, 1-methyl-1, 3-butadiene-2-sulfonic acid and its salts, 1-methyl 1,3-butadiene-4-sulfonic acid and salts thereof, ethyl acrylate sulfonic acid _{(CH 2 CH-COO- (CH} 2) 2 -SO 3 H) and its salts, acrylic acid propyl sulfonic acid _(CH 2 CH- COO— (CH ₂ ) ₃ —SO ₃ H) and salts thereof, acrylic acid-t-butylsulfonic acid (CH ₂ CH—COO—C (CH ₃ ) ₂ CH ₂ —SO ₃ H) and salts thereof, acrylic acid -n- butyl sulfonic acid _{(CH 2 CH-COO- (CH} 2) 4 -SO 3 H) and its salts, allyl ethyl sulfonic acid _{(CH 2 CHCH 2 -COO- (CH} 2) 2 -SO 3 H) and its salts, allyl acid -t- butyl sulfonic acid _{(CH 2 CHCH 2 -COO-C} (CH 3) 2 CH 2 -SO 3 H) and salts thereof, 4-pentenoic acid ethyl Sulfonic acid _{(CH 2 CH (CH 2)} 2 -COO- (CH 2) 2 -SO 3 H) and salts thereof, 4-pentenoic acid propyl sulfonic acid _{(CH 2 CH (CH 2)} 2 -COO- (CH 2 ) ₃ -SO ₃ H) and salts thereof, 4-pentenoic acid-n-butylsulfonic acid (CH ₂ CH (CH ₂ ) ₂ —COO— (CH ₂ ) ₄ —SO ₃ H) and salts thereof, 4-pentene acid -t- butyl sulfonic acid _{(CH 2 CH (CH 2)} 2 -COO-C (CH 3) 2 CH 2 -SO 3 H) and salts thereof, 4-pentenoic acid phenylene sulfonic acid _{(CH 2} CH _(CH 2 ) _2- COO—C ₆ H ₄ —SO ₃ H) and salts thereof, 4-pentenoic acid naphthalenesulfonic acid (CH ₂ CH (CH ₂ ) ₂ —COO—C ₁₀ H ₈ —SO ₃ H) and salts thereof, Me Methacrylic acid ethyl sulfonic acid _{(CH 2 C (CH 3)} -COO- (CH 2) 2 -SO 3 H) and salts thereof, propyl methacrylate sulfonic acid _{(CH 2 C (CH 3)} -COO- (CH 2) ₃ -SO ₃ H) and its salts, methacrylic acid -t- butyl sulfonic acid _{(CH 2 C (CH 3)} -COO-C (CH 3) 2 CH 2 -SO 3 H) and its salts, methacrylic acid -n - butyl sulfonic acid _{(CH 2 C (CH 3)} -COO- (CH 2) 4 -SO 3 H) and its salts, methacrylic acid phenylene sulfonic acid _{(CH 2 C (CH 3)} -COO-C 6 H 4 - SO ₃ H) and its salts, methacrylic acid naphthalenesulfonic acid (CH ₂ C (CH ₃ ) —COO—C ₁₀ H ₈ —SO ₃ H) and its salts, and the like. Moreover, the copolymer containing 2 or more types of these may be sufficient.

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

  The degree of polymerization of the polyanion thus obtained is not particularly limited, but is usually from about 10 to 100,000 monomer units, and from the viewpoint of improving solvent solubilization, dispersibility, and conductivity. More preferably, it is about 10,000.

  Specific examples of the polyanion include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly (2-acrylamido-2-methyl-1-propanesulfonic acid). Can be preferably mentioned.

  When the obtained anionic compound is an anionic salt, it is preferable to change it to an anionic acid. Examples of the method for converting to an anionic acid include an ion exchange method using an ion exchange resin, a dialysis method, and an ultrafiltration method. Among these methods, the ultrafiltration method is preferable from the viewpoint of workability. However, when it is necessary to reduce the metal ion concentration, an ion exchange method is used.

  As a combination of (a) π-conjugated conductive polymer and (b) polyanion, those selected from each group of (a) and (b) can be used, but chemical stability, conductivity, storage From the viewpoint of stability, availability, etc., (a) poly (3,4-ethylenedioxythiophene) which is an example of a π-conjugated conductive polymer, and (b) polystyrene sulfonic acid which is an example of a polyanion The combination of is preferable. As described above, poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid are in the presence of an oxidizing agent in the state of an aqueous solution or aqueous dispersion in which a monomer for a conductive polymer and a dopant coexist. Polymerization may be performed for synthesis. Further, a commercially available conductive polymer / dopant aqueous dispersion may be used.

  The content of the polyanion is preferably in the range of 0.1 to 10 mol, more preferably in the range of 1 to 7 mol, with respect to 1 mol of the π-conjugated conductive polymer. By setting the polyanion content to 0.1 mol or more, the doping effect on the π-conjugated conductive polymer can be enhanced, and the conductivity can be enhanced. In addition, the solubility in a solvent becomes high, and it becomes easy to obtain a solution of a conductive polymer in a uniformly dispersed form. On the other hand, when the polyanion content is 10 mol or less, the content ratio of the π-conjugated conductive polymer can be relatively increased, and higher conductivity can be exhibited.

(C) Reaction product of an anion other than that required for doping in the polyanion and an oxirane group and / or oxetane group-containing organic compound Anion other than that required for doping in the polyanion, and an oxirane group and / or oxetane group A reaction product with an organic compound can be obtained by adding an oxirane group and / or oxetane group-containing organic compound to the aforementioned (a) π-conjugated conductive polymer and (b) polyanion for reaction.

  The oxirane group and / or oxetane group-containing organic compound is not particularly limited as long as it is coordinated or bonded to the anion group or electron withdrawing group of the polyanion. It is more preferable to use a compound containing one or less oxirane group or oxetane group in one molecule because aggregation and gelation can be reduced. The molecular weight of the oxirane group and / or oxetane group-containing organic compound is preferably in the range of 50 to 2,000 in view of easy solubility in an organic solvent.

  The amount of the oxirane group and / or oxetane group-containing organic compound is preferably 0.1 to 50 by weight with respect to the anion group or electron withdrawing group in the polyanion of the π-conjugated conductive polymer, and more Preferably it is 1.0-30.0. When the amount of the oxirane group and / or oxetane group-containing organic compound is 0.1 or more in the above weight ratio, the oxirane group and / or oxetane group-containing organic compound is modified so that the anion group of the polyanion dissolves in the solvent. I can do it. On the other hand, if the amount of the oxirane group and / or oxetane group-containing organic compound is 50 or less in the above weight ratio, the excess oxirane group and / or oxetane group-containing organic compound is difficult to precipitate in the conductive polymer solution. It is easy to prevent a decrease in the electrical conductivity and mechanical properties of the resulting conductive coating film.

  The oxirane group and / or oxetane group-containing organic compound may be a compound having any molecular structure as long as it has an oxirane group or oxetane group in the molecule. However, a compound having a large number of carbons is effective for solubilization in an organic solvent having a low polarity. In particular, those having 10 or more carbon atoms are preferable for solubilization in organic solvents having low polarity. In addition, when water is frequently used during the production process, it is preferable to avoid using a compound containing an alkoxysilyl group having a functional group that reacts with hydrolysis or water as much as possible. On the other hand, in the case of a production method via lyophilization, an alkoxysilyl group-containing compound may also be used because it is dispersed or soluble in a solvent while maintaining its characteristics. Conventionally, a compound having an oxirane group or an oxetane group as a conductivity improver or a crosslinking agent is added to a conductive polymer aqueous solution. The difference between these known techniques and the present application is that 1) a reaction product obtained by reacting a polyanion which is a dopant / dispersant of a conductive polymer and an oxirane group or oxetane group-containing compound is obtained. Is being removed or reduced. By achieving the requirements 1) and 2), it is possible to achieve the effect that solubilization in an organic solvent is achieved in a state of low moisture, and mixing with an organic resin is possible.

  Examples of organic compounds containing oxirane groups and / or oxetane groups will be given below.

(Oxirane group-containing compound)
Monofunctional oxirane group-containing compounds include propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monooxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2-epoxy octadecane, 1,2-epoxyhexadecane, ethyl glycidyl ether Glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeicosane, 2- (chloromethyl) -1,2-epoxypropane, glycidol, epichlorohydrin, epibromohydrin, butyl glycidyl ether 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2- (chloromethyl) -1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2-epoxy-1H, 1H, 2H, 2H , 3H, 3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclododecane, 1-methyl-1,2-epoxy Cyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H, 1H, 2H, 2H, 3H, 3H-heptadecafluorobutane, 3, 4-epoxytetrahydrofuran, glycidyl stearate , 3-glycidyloxypropyltrimethoxysilane, epoxysuccinic acid, glycidylphenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, benzylglycidyl ether, diethoxy (3-glycidyloxypropyl) methylsilane, 3- [ 2- (Perfluorohexyl) ethoxy] -1,2-epoxypropane, 1,1,1,3,5,5,5-heptamethyl-3- (3-glycidyloxypropyl) trisiloxane, 9,10-epoxy -1,5-cyclododecadiene, glycidyl 4-tert-butylbenzoate, 2,2-bis (4-glycidyloxyphenyl) propane, 2-tert-butyl-2- [2- (4-chlorophenyl)] ethyl Oxirane, styrene oxide, glycidyl Tyl ether, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α, 6α-epoxide, stilbene oxide, glycidyl p-toluenesulfonate, 3-methyl-3-phenylglycyl Ethyl sidate, N-propyl-N- (2,3-epoxypropyl) perfluoro-n-octylsulfonamide, (2S, 3S) -1,2-epoxy-3- (tert-butoxycarbonylamino) -4- Phenylbutane, 3-nitrobenzenesulfonic acid (R) -glycidyl, 3-nitrobenzenesulfonic acid-glycidyl, parthenolide, N-glycidylphthalimide, endrin, dieldrin, 4-glycidyloxycarbazole, 7,7-dimethyloctanoic acid [oxirani Methyl] etc. can be exemplified.

  Polyfunctional oxirane group-containing compounds include 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, 4-butanediol diglycidyl ether, 1,2: 3,4-diepoxybutane, 1,2-cyclohexane Diglycidyl dicarboxylate, triglycidyl isocyanurate triglycidyl neopentyl glycol diglycidyl ether, 1,2: 3,4-diepoxybutane, polyethylene glycol # 200 diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether Ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-he Sanji ol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether and the like can be exemplified.

(Oxetane group-containing compound)
Monofunctional oxetane group-containing compounds include 3-ethyl-3-hydroxymethyloxetane (= oxetane alcohol), 2-ethylhexyloxetane, (3-ethyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) A methacrylate etc. can be illustrated.

  Examples of the polyfunctional oxetane group-containing compound include xylylene bisoxetane, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, 1,4-benzenedicarboxylic acid, bis {[3- And ethyl-3-oxetanyl] methyl} ester.

  In the conductive polymer composition as described above, since the oxirane group or oxetane group is reacted with the anion group of the polyanion, the hydrophilic property of the polyanion is lost and the lipophilicity is exhibited. Therefore, this conductive polymer composition can be solubilized or dispersed in an organic solvent at a high concentration.

  Examples of the organic solvent used as a solvent for solubilizing or dispersing the conductive polymer composition include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylenephosphonium tri Polar solvents represented by amide, acetonitrile, benzonitrile, etc .; phenols represented by cresol, phenol, xylenol, etc .; alcohols represented by methanol, ethanol, propanol, butanol, etc .; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones typified by; esters represented by ethyl acetate, propyl acetate, butyl acetate, etc .; hydrocarbons typified by hexane, heptane, benzene, toluene, xylene, etc .; categorized by formic acid, acetic acid, etc. Boric acid; carbonate compounds represented by ethylene carbonate, propylene carbonate, etc .; ether compounds represented by dioxane, diethyl ether, etc .; represented by ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc. Preferred examples of the chain ethers: heterocyclic compounds represented by 3-methyl-2-oxazolidinone, etc .; nitrile compounds represented by acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, etc. it can. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, alcohols, ketones, ethers, esters, and hydrocarbons can be more suitably used from the viewpoint of easy mixing with various organic substances.

2. Addition reaction curable organopolysiloxane composition An addition reaction curable organopolysiloxane composition includes, for example, a silicone rubber having a vinyl group at its terminal (such as raw rubber), a crosslinking agent having a Si-H group, and an addition reaction catalyst. including. The cross-linking agent is an organohydrogenpolysiloxane having a Si—H group, and either linear or branched can be used. As addition reaction catalysts, chloroplatinic acid, alcohol solution of chloroplatinic acid, reaction product of chloroplatinic acid and alcohol, reaction product of chloroplatinic acid and olefin compound, reaction product of chloroplatinic acid and vinyl group-containing siloxane Platinum-based catalysts such as platinum-olefin complexes and platinum-vinyl group-containing siloxane complexes, and platinum group metal catalysts such as rhodium complexes and ruthenium complexes. Moreover, what melt | dissolved and disperse | distributed these things to solvents, such as isopropanol and toluene, silicone oil, etc. can be used. Examples of addition reaction curable organopolysiloxane compositions include: a) an organopolysiloxane having at least two alkenyl groups in the molecule; b) an organopolysiloxane having at least three hydrosilyl groups in the molecule; c) A hydrosilylation catalyst mainly composed of a platinum group metal modification or complex such as platinum, palladium, or rhodium is included. In addition to the addition reaction curable organopolysiloxane composition, a condensation curable or electron beam curable organopolysiloxane composition may be used.

3. Conductive agent The conductive agent contained in the conductive polymer solution according to the embodiment of the present invention is liquid at 25 ° C. (normal temperature) and has a boiling point (under atmospheric pressure) of 150 to 400 ° C. When the boiling point of the conductive agent is 150 ° C. or higher, methylethylketone and toluene are volatilized first in the drying process, and a highly effective solvent for the conductive polymer is volatilized last, resulting in excellent resistance. It is effective in that it expresses. On the other hand, when the boiling point of the conductive agent is 400 ° C. or lower, there is an effect in that the influence on the curing to the silicone is small during the drying step. Therefore, the boiling point of the conductive agent is 150 ° C. or higher and 400 ° C. or lower. Is preferred. The conductive agent is preferably contained in a mass fraction of 1 to 100%, more preferably 30 to 100%, based on the above addition reaction curable organopolysiloxane composition. Examples of the conductive agent (also referred to as a high conductive agent) include a polar solvent and a polyhydric aliphatic alcohol. Since the conductive agent used here is liquid at 25 ° C., the transparency of the coating film formed from the conductive polymer solution can be further improved, and the adhesive layer bonded to the coating film can be improved. The transfer of foreign matter can be effectively prevented.

  Preferable examples of the conductive agent include hydroxyethyl acrylate (boiling point: 210 ° C.), hydroxyethyl acrylamide (boiling point: 370 ° C.), dimethyl sulfoxide (boiling point: 189 ° C.), ethyl lactate (boiling point: 155 ° C.), propyl lactate (Boiling point: 168 ° C), propylene glycol (boiling point: 188 ° C), glycerin (boiling point: 290 ° C), dipropylene glycol (boiling point: 231 ° C), formamide (boiling point: 210 ° C), N, N dimethylformamide (boiling point: 153 ° C), N-methylacrylamide (boiling point: 172 ° C), N-methylmethacrylamide (boiling point: 240 ° C), N, N-dimethylacrylamide (boiling point: 190 ° C), N, N-dimethylmethacrylamide (boiling point: 195 ° C.), 2-hydroxymethylacrylamide (boiling) Point: 277 ° C., ethylene glycol (boiling point: 197 ° C.), 1,3 butylene glycol (boiling point: 208 ° C.), isoprene glycol (boiling point: 203 ° C.), 1,5-pentanediol (boiling point: 242 ° C.), thio Diethanol (boiling point: 285 ° C), glycidyl phenyl ether (boiling point: 245 ° C), glycidyl acrylate (boiling point: 170 ° C), glycidyl methacrylate (boiling point: 189 ° C), bisphenol A (boiling point: 220 ° C), etc. Can do.

<Embodiment of B conductive coating film>
The conductive coating film according to the embodiment of the present invention is formed by supplying the conductive polymer solution as a coating material onto a substrate. The paint is supplied on a substrate represented by paper, plastic, iron, ceramics, and glass. Examples of the supply method include various methods such as a coating method using a brush or a bar coater, a dipping method in which the substrate is immersed in the paint, and a spin coating method in which the paint is dropped on the substrate to rotate the substrate to spread the paint. it can. Examples of the method for curing the paint on the substrate include a method of removing the organic solvent by heating or standing at room temperature.

  As described above, the conductive polymer composition constituting the conductive polymer solution according to this embodiment includes an anion other than that required for doping in the polyanion, and an oxirane group and / or oxetane group-containing organic compound. Therefore, it is dispersible and soluble in various organic solvents. In addition, the conductive polymer composition is soluble in various organic resins or organic resin composition solutions. Compared to the method of solvent substitution by reaction with a polyanion residue in a conductive polymer aqueous dispersion using a conventionally known amine compound and a phase transfer catalyst, the conductive polymer composition has storage stability, It is excellent in stability of electric resistance value, and can be applied to fields where amines are obstructed. By mixing such a conductive polymer composition, an addition reaction curable organopolysiloxane composition, and a predetermined conductive agent, it is possible to stably disperse and / or disperse in an organic solvent. A solubilized conductive polymer solution having excellent conductivity can be obtained. When the solution is supplied as a coating material onto a substrate and dried, a conductive coating film that is difficult to peel off, excellent in transparency, and also excellent in antistatic properties can be formed.

  Next, production examples and examples of the present invention will be described. However, the present invention is not limited to the following examples.

<Production example>
(Production Example 1) Production of polystyrene sulfonic acid 1.14 g of ammonium persulfate dissolved in 10 ml of water in advance while dissolving 206 g of sodium styrene sulfonate in 1000 ml of ion-exchanged water and stirring at 80 ° C. The oxidant solution was added dropwise for 20 minutes and the solution was stirred for 12 hours. To the obtained sodium styrenesulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, and 1000 ml of the polystyrenesulfonic acid-containing solution was removed using an ultrafiltration method, and 2000 ml of ion-exchanged water was used as the remaining liquid. And about 2000 ml of solution was removed using ultrafiltration. The above ultrafiltration operation was repeated three times. Further, about 2000 ml of ion-exchanged water was added to the obtained filtrate, and about 2000 ml of solution was removed using an ultrafiltration method. This ultrafiltration operation was repeated three times. Water in the obtained solution was removed under reduced pressure to obtain a colorless solid. As a result of measuring the weight average molecular weight of the obtained polystyrene sulfonic acid using Showa Denko pullulan as a standard substance using a HPLC (high performance liquid chromatography) system using a GPC (gel filtration chromatography) column, the molecular weight was 300,000. Met.

Production Example 2 Production of PEDOT-PSS aqueous solution 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 were dissolved in 2000 ml of ion-exchanged water. The solution was mixed at 20 ° C. While stirring the mixed solution obtained at 20 ° C., 29.64 g of ammonium persulfate dissolved in 200 ml of ion exchange water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added. The reaction was stirred for 3 hours. 2000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2000 ml of solution was removed using an ultrafiltration method. This operation was repeated three times. Next, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water are added to the resulting solution, and about 2000 ml of solution is removed using an ultrafiltration method. And about 2000 ml of solution was removed using ultrafiltration. This operation was repeated three times. Furthermore, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed using an ultrafiltration method. This operation was repeated 5 times to obtain an aqueous solution of about 1.2% by mass of blue PEDOT-PSS.

(Production Example 3) ... Production of organic solvent in which PEDOT-PSS was dispersed 150 g of methanol and 7.06 g of C10 and C12 mixed higher alcohol glycidyl ether (Epolite manufactured by Kyoeisha Chemical Co., Ltd.) were mixed. Next, 50 g of the PEDOT-PSS aqueous solution obtained in Production Example 2 was mixed and stirred at room temperature to obtain an amber-colored precipitate. The precipitate was collected by filtration, dispersed in methyl ethyl ketone, and a dispersion of PEDOT-PSS (concentration of about 0.5% by mass) dispersed in methyl ethyl ketone was obtained.

<Examples and Comparative Examples>
Table 1 shows conditions for various examples and comparative examples described below.
Example 1
4.5 g of the solution obtained in Production Example 3 and 1.5 g of KS-3703T (manufactured by Shin-Etsu Chemical Co., Ltd., addition reaction curable silicone release agent 30% active ingredient) (including 0.45 g of silicone oil, remaining) 1.05 g is toluene), 76.4955 g of methyl ethyl ketone (also referred to as MEK), 7.5 g of toluene, and 0.03 g of CAT-PL-50T (Shin-Etsu Chemical Co., Ltd., platinum catalyst) are added to make it conductive. As an agent, 0.0045 g of dimethyl sulfoxide (boiling point: 189 ° C.) was added and prepared. The prepared solution was transferred to a bar coater no. The film was coated on a PET film at 08 (Matsuo Sangyo Co., Ltd., coated film thickness 18.32 μm) and dried at 150 ° C. for 1 minute.

(Example 2)
A conductive polymer solution and a coating film were prepared under the same conditions as in Example 1 except that the amount of dimethyl sulfoxide was changed to 0.045 g and the amount of methyl ethyl ketone was changed to 76.455 g.

(Example 3)
A conductive polymer solution and a coating film were produced under the same conditions as in Example 1 except that the amount of dimethyl sulfoxide was changed to 0.135 g and the amount of methyl ethyl ketone was changed to 76.365 g.

Example 4
A conductive polymer solution and a coating film were prepared under the same conditions as in Example 1 except that the amount of dimethyl sulfoxide was changed to 0.225 g and the amount of methyl ethyl ketone was changed to 76.245 g.

(Example 5)
A conductive polymer solution and a coating film were produced under the same conditions as in Example 1 except that the amount of dimethyl sulfoxide was changed to 0.45 g and the amount of methyl ethyl ketone was changed to 76.05 g.

(Example 6)
Conductive polymer under the same conditions as in Example 1 except that glycerol (boiling point: 290 ° C.) was used instead of dimethyl sulfoxide, the amount of glycerol was changed to 0.225 g, and the amount of methyl ethyl ketone was changed to 76.245 g. Production of the solution and preparation of the coating film were performed.

(Example 7)
A conductive polymer solution and a coating film were produced under the same conditions as in Example 6 except that propylene glycol (boiling point: 188 ° C.) was used instead of glycerin.

(Example 8)
A conductive polymer solution and a coating film were prepared under the same conditions as in Example 6 except that ethyl lactate (boiling point: 155 ° C.) was used instead of glycerin.

Example 9
A conductive polymer solution was produced and a coating film was produced under the same conditions as in Example 6 except that hydroxyethyl acrylate (boiling point: 210 ° C.) was used instead of glycerin.

(Example 10)
A conductive polymer solution and a coating film were prepared under the same conditions as in Example 6 except that hydroxyethylacrylamide (boiling point: 370 ° C.) was used instead of glycerin.

(Comparative Example 1)
A conductive polymer solution and a coating film were prepared under the same conditions as in Example 1 except that the conductive agent was not added and the amount of methyl ethyl ketone was changed to 76.5 g.

(Comparative Example 2)
A conductive polymer solution and a coating film were produced under the same conditions as in Example 1 except that the amount of dimethyl sulfoxide was changed to 0.00225 g.

(Comparative Example 3)
A conductive polymer solution and a coating film were prepared under the same conditions as in Example 1 except that the amount of dimethyl sulfoxide was changed to 4.5 g and the amount of methyl ethyl ketone was changed to 72 g.

(Comparative Example 4)
A conductive polymer solution and a coating film were produced under the same conditions as in Example 4 except that ethyl glycidyl ether (boiling point: 128 ° C.) was used instead of dimethyl sulfoxide.

(Comparative Example 5)
4.5 g of the solution obtained in Production Example 3 and 1.5 g of KS-3703T (manufactured by Shin-Etsu Chemical Co., Ltd., addition reaction curable silicone release agent 30% active ingredient) (including 0.45 g of silicone oil, remaining) 1.05 g is toluene), 76.48875 g of methyl ethyl ketone, 7.5 g of toluene, and 0.03 g of CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd., platinum catalyst) are added, and garlic acid ( 0.01125 g of powder) was added at 25 ° C. to prepare. The prepared solution was transferred to a bar coater no. The film was coated on a PET film at 08 (Matsuo Sangyo Co., Ltd., coated film thickness 18.32 μm) and dried at 150 ° C. for 1 minute.

<Evaluation method of coating film>
The surface resistance value of the obtained coating film, the curability when the coating film was rubbed with a finger, and the surface state of the film film surface were visually confirmed. The case where the film surface was able to be formed was rated as ◯, while the film surface of the film coating film could not be formed uniformly and the opaque surface was marked as x. The surface resistance value was measured at an applied voltage of 10 V using a high resistance ohmmeter Hiresta. Various properties are shown in Table 2.

<Evaluation results>
The coating films obtained in Examples 1 to 5 to which dimethyl sulfoxide was added had a very clean film surface and good curability, and the surface resistance value also decreased as the amount of conductive agent added increased. However, the coating film obtained in Comparative Example 2 in which the amount added was less than 1% had almost the same surface resistivity as Comparative Example 1 in which no conductive agent was added. Moreover, although the coating film obtained by the comparative example 3 which made the addition amount of the electrically conductive agent 1000% had a low surface resistance value, the film surface was rough and film forming property was bad. The coating film obtained in Comparative Example 4 using a low boiling point conductive agent did not have a decreased surface resistance value. When the powdered garlic acid of Comparative Example 5 was used, the conductive agent remained on the film surface at the time of drying, which caused deterioration of the curability of the silicone.

  The present invention can be effectively used for, for example, release paper, antistatic film, conductive paint, touch screen, organic EL, conductive polymer fiber, and the like.

Claims (6)

(A) a π-conjugated conductive polymer;
(B) (a) a polyanion doped in the π-conjugated conductive polymer;
(C) (b) a reaction product of an anion other than that required for doping in the polyanion and an organic compound containing an oxirane group and / or an oxetane group,
A conductive polymer composition (I) that is dispersible and soluble in a solvent mainly composed of an organic solvent,
Addition reaction curable organopolysiloxane composition (II);
A conductive agent (III) that is liquid at 25 ° C. and has a boiling point of 150 to 400 ° C., and 1 to 100% by mass fraction with respect to the addition reaction curable organopolysiloxane composition;
Conductive polymer solution made by mixing   The (a) π-conjugated conductive polymer is a polypyrrole, polythiophene, polyacetylene, polyphenylene, polyphenylene vinylene, polyaniline, polyacene, polythiophene vinylene, or a copolymer of two or more thereof The conductive polymer solution according to claim 1, comprising at least one repeating unit selected from the group consisting of:   The conductive polymer solution according to claim 2, wherein the (a) π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene) or polypyrrole.   The said (b) polyanion is 1 type, or the mixture of 1 or more selected from a sulfonic acid group, a phosphoric acid group, and a carboxyl group, The any one of Claims 1-3 characterized by the above-mentioned. Conductive polymer solution.   The (b) polyanion is polystyrene sulfonic acid, polyvinyl sulfonic acid, polyacrylic acid alkylene sulfonic acid, poly (2-acrylamido-2-methyl-1-propanesulfonic acid) or one or more of them as a copolymerization constituent. The conductive polymer solution according to any one of claims 1 to 4, wherein the conductive polymer solution is contained.   A conductive coating film formed by supplying the conductive polymer solution according to any one of claims 1 to 5 onto a substrate.