JP6418829B2 - Conductive polymer solution and conductive coating film - Google Patents

Description

  The present invention relates to a conductive polymer solution capable of forming an adhesive layer having conductivity, 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-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 demand to overcome such drawbacks and to impart conductivity to the silicone adhesive.

  The present invention relates to a conductive polymer solution capable of reducing problems derived from amine compounds and water, and capable of forming a conductive silicone adhesive layer, and a conductive coating film formed by supplying the same onto a substrate. The purpose is to provide.

  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 the silicone pressure-sensitive adhesive, and completed the present invention. Specific problem solving means are as follows.

  A conductive polymer solution for achieving the above object includes (a) a π-conjugated conductive polymer, (b) the polyanion doped in the (a) π-conjugated conductive polymer, and (c) the ( b) a reaction product of an anion other than that required for doping in the polyanion, an oxirane group and / or oxetane group-containing organic compound, (d) a silicone pressure-sensitive adhesive, and (e) an organic solvent.

  In the conductive polymer solution according to another embodiment, (d) a silicone pressure-sensitive adhesive is of an addition curing type.

  In the conductive polymer solution according to another embodiment, (d) the silicone adhesive is an electron beam curable type.

  The conductive polymer solution according to another embodiment comprises (a) a π-conjugated conductive polymer, polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes. And at least one repeating unit selected from the group consisting of two or more of these copolymers.

  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 1 type or more of them shall be included as a copolymerization structure.

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

  ADVANTAGE OF THE INVENTION According to this invention, the problem derived from an amine compound and the problem derived from water can be reduced, and the electroconductive polymer solution which can form the silicone adhesive layer which has electroconductivity, and the electroconductivity formed by supplying it on a base | substrate and forming A coating film can be provided.

  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 solution The conductive polymer solution according to the embodiment of the present invention includes (a) a π-conjugated conductive polymer, (b) the polyanion doped in the (a) π-conjugated conductive polymer, (C) (b) a 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, (d) a silicone adhesive, and (e) an organic solvent. including. 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 an organic solvent, but is not limited to only an organic solvent, and may contain a small amount of water as long as the organic solvent is mainly used. Here, “mainly organic solvent” means that the organic solvent in the solvent exceeds 50% by mass. In particular, the solvent is preferably in the range of organic solvent: water = 90: 10 to 100: 0 by weight ratio.

1.1 Production Method (a) A polyanion doped in a π-conjugated conductive polymer that constitutes a conductive polymer solution, (c) an anion other than that required for doping in the (b) polyanion, an oxirane group, and A pressure-sensitive adhesive-free composition containing a reaction product with an oxetane group-containing organic compound and not yet containing a silicone pressure-sensitive adhesive can be produced, for example, by the following method.
(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 pressure-sensitive adhesive-free composition is prepared by adding an oxirane group or oxetane group-containing compound together with a solvent to the aqueous dispersion, reacting an anion with an oxirane group or oxetane group, and then concentrating and filtering the reaction solution. Obtained separately or 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 adhesive-free composition is phase-inverted into an insoluble solvent phase, and after steps such as dehydration as necessary, the adhesive-free 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 an adhesive-free 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. Also, 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 adhesive-free composition is phase-inverted to the water-insoluble solvent phase, and if necessary After the steps such as dehydration, the pressure-sensitive adhesive-free composition may be dissolved or dispersed in a solvent mainly composed of an organic solvent. As described above, in the method (2), since the freeze-dried pressure-sensitive adhesive-free composition is used as a raw material, the time for the concentration step can be shortened.

1.2 Raw Material for Conductive Polymer Solution (a) π-Conjugated Conductive Polymer π-conjugated conductive polymer is not limited as long as the main chain is an organic polymer composed of π-conjugated system. Can be used. 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 adjusted 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. A compound having 10 or more carbon atoms is preferably used. 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.

  As described above, since the oxirane group or oxetane group is reacted with the anion group of the polyanion, the hydrophilicity of the polyanion is lost and the lipophilicity is exhibited. Therefore, (a) a reaction between a polyanion doped in a π-conjugated conductive polymer, (c) an anion other than that required for doping in the (b) polyanion, and an oxirane group and / or oxetane group-containing organic compound The composition containing the product can be solubilized or dispersed at a high concentration in an organic solvent.

(D) Silicone pressure-sensitive adhesive Silicone pressure-sensitive adhesives are classified into several types such as an addition reaction curable type, a peroxide curable type, and an electron beam curable type depending on the curing method.

(D1) Addition reaction curable type The addition curable type silicone pressure sensitive adhesive includes, for example, a silicone rubber having a vinyl group at its terminal (raw rubber, etc.), a silicone resin, a crosslinking agent having a Si-H group, a reaction inhibitor, And an addition reaction catalyst. Since the silicone rubber itself has poor adhesiveness, the addition-curable silicone adhesive is formed by mixing a silicone resin as a tackifier. The silicone resin preferably has an M unit (a unit in which one O and three methyl groups are bonded to Si) in order to bond a Q unit (a unit in which four Os are bonded to Si) and stop the terminal reaction. ). The cross-linking agent is an organohydrogenpolysiloxane having a Si—H group, and either linear or branched can be used. The reaction control agent is a component for preventing thickening and gelation of the pressure-sensitive adhesive before curing, such as 3-methyl-1-butyn-3-ol and 3-methyl-1-pentyne-3-ol. 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5 -Dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1, 3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and the like can be used. Examples of the addition reaction catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and an olefin compound, and a reaction product of chloroplatinic acid and a 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.

As an example, the addition-curable silicone pressure-sensitive adhesive is mainly composed of the following compounds.
a) Organopolysiloxane having at least two alkenyl groups in the molecule b) Silicone resin having a trimethylsilyl group at the end c) Organopolysiloxane having at least three hydrosilyl groups in the molecule d) Mainly platinum, palladium, rhodium Hydrosilylation catalyst comprising platinum group metal modification or complex such as

(D2) Peroxide-curing type The peroxide-curing type silicone pressure-sensitive adhesive contains, for example, a polydialkylsiloxane typified by polydimethylsiloxane, a silicone resin, and an organic peroxide typified by benzoyl peroxide. . The same type of silicone resin as that contained in the addition reaction curable silicone pressure-sensitive adhesive can be used. Examples of the organic peroxide include dibenzoyl peroxide, 4,4′-dimethyldibenzoyl peroxide, 3,3′-dimethyldibenzoyl peroxide, 2,2′-dimethyldibenzoyl peroxide, and 2,2 ′. , 4,4′-tetrachlorodibenzoyl peroxide, cumyl peroxide, and the like.

(D3) Electron beam curable type The electron beam curable silicone pressure-sensitive adhesive contains, for example, the same type of silicone resin as described above and a polymerization initiator in addition to any of the compounds described in Examples 1 to 6 below. Is cured by.
<Example 1>
Acrylamide group-containing organopolysiloxane This organopolysiloxane is an organopolysiloxane containing an acrylamide functional group represented by the following general formula (I) in the molecule.

In the general formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ is a divalent hydrocarbon group. .

<Example 2>
Organopolysiloxane having at least two mercaptoalkyl groups in one molecule This organopolysiloxane is an organopolysiloxane having at least two mercaptoalkyl functional groups represented by the following general formula (II) in one molecule. is there.

In the general formula (II), R ¹ is a hydrogen atom or a methyl group, and R ² is a divalent hydrocarbon group.

<Example 3>
A composition comprising an organopolysiloxane having at least two alkenyl groups in one molecule. This organopolysiloxane has at least two alkenyl groups (-C _n H _2n-1 (n is 2 or more) in one molecule. A composition comprising an organopolysiloxane.
<Example 4>
Alkenyl group-containing organopolysiloxane The organopolysiloxane alkenyl groups in the molecule _{(-C n H 2n-1 (} n is a number of 2 or more.)) Is an organopolysiloxane containing.
<Example 5>
Acrylic or Methacrylic Group-Containing Organopolysiloxane This organopolysiloxane is an organopolysiloxane containing an acrylic group (CH ₂ CHCO—) or a methacryl group (CH ₂ C (CH ₃ ) CO—) in the molecule.
<Example 6>
a) Organopolysiloxane having at least two alkenyl groups in one molecule b) Organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule

(E) Organic solvent Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylenephosphonium triamide, acetonitrile, benzonitrile and the like. Polar solvents; phenols typified by cresol, phenol, xylenol, etc .; alcohols typified by methanol, ethanol, propanol, butanol, etc .; ketones typified by acetone, methyl ethyl ketone, methyl isobutyl ketone, etc .; ethyl acetate, acetic acid Esters represented by propyl, butyl acetate, etc .; Hydrocarbons represented by hexane, heptane, benzene, toluene, xylene, etc .; Carboxylic acids represented by formic acid, acetic acid, etc .; Ethylene carbonate, propylene carbonate Carbonate compounds typified by carbonates; ether compounds typified by dioxane, diethyl ether, etc .; chain ethers typified by ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc. Preferred examples include heterocyclic compounds typified by 3-methyl-2-oxazolidinone and the like; nitrile compounds typified by acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile and the like. 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.

(F) Others Examples of additives to the conductive polymer solution include those that improve conductivity.
(Conductivity improver)
Examples of conductivity improvers include glycidyl compounds, polar solvents, polyhydric aliphatic alcohols, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxy groups, compounds having two or more carboxy groups, one Examples thereof include compounds having the above hydroxy group and one or more carboxy groups, and lactam compounds. Among these, those that hardly inhibit the curing of the peelable component are preferable. If it is difficult to inhibit curing of the peelable component, it is possible to prevent the release agent from being transferred to the pressure-sensitive adhesive layer after the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is superimposed on the release agent layer obtained from the antistatic release agent. it can. Examples of the conductivity improver that does not easily inhibit the peelable component include a glycidyl compound, a polar solvent, and a polyhydric aliphatic alcohol. Further, the conductivity improver is preferably liquid at 25 ° C. If it is liquid, the transparency of the release agent layer formed from the antistatic release agent can be improved, and transfer of foreign matter to the pressure-sensitive adhesive layer bonded to the release agent layer can be prevented.

  Specific examples of glycidyl compounds include ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl phenyl ether, bisphenol A diglycidyl ether, glycidyl methacrylate, glycidyl methacrylate Examples include ether. Specific examples of the polar solvent include N-methylformamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methyl-2-pyrrolidone, N-methyl Acetamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylene phosphortriamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, milk Methyl, ethyl lactate, propyl and the like. Examples of the polyhydric aliphatic alcohol include ethylene glycol, diethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, diglycerin, isoprene glycol, butanediol, 1,5-pentanediol, 1, Examples include 6-hexanediol, 1,9-nonanediol, neopentyl glycol, trimethylol ethane, trimethylol propane, thiodiethanol, and dipropylene glycol.

  The content of the conductivity improver is preferably 10 to 10000 parts by mass and more preferably 30 to 5000 parts by mass with respect to 100 parts by mass of the conductive component. When the content of the conductivity improver is at least the lower limit, the antistatic property can be further improved. On the other hand, if it is below the said upper limit, peelability can be improved more.

<Embodiment of B conductive coating film>
The conductive coating film according to the embodiment of the present invention is a film formed by supplying the conductive polymer solution onto a substrate. The conductive polymer solution is supplied onto a substrate represented by, for example, paper, plastic, iron, ceramics, and glass. Supply methods include brush and bar coater coating methods, dipping method in which the substrate is immersed in a conductive polymer solution, spin coating method in which the conductive polymer solution is dropped onto the substrate and the substrate is rotated to spread the solution, etc. Various methods can be exemplified. Examples of the method for curing the conductive polymer solution on the substrate include a method of removing a solvent such as an organic solvent by heating, a method of curing by irradiating light such as ultraviolet rays or an electron beam, and the like.

  As described above, the conductive coating film according to this embodiment includes reaction products 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. It is dispersible and soluble in solvents mainly composed of organic solvents. The conductive polymer solution that forms the conductive coating film is a solvent-substituted method by reaction with a polyanion residue in a conductive polymer aqueous dispersion using a conventionally known amine compound and phase transfer catalyst. In addition to being excellent in storage stability and electrical resistance stability, it can also be applied to fields where amines and the like are obstacles. By including a silicone adhesive in the conductive polymer solution, a conductive silicone adhesive can be obtained.

  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 206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water was stirred at 80 ° C. The solution was added dropwise for 20 minutes, and the solution was stirred for 12 hours. To the obtained sodium styrenesulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, about 1000 ml of the polystyrenesulfonic acid-containing solution was removed using an ultrafiltration method, and 2000 ml of ion-exchanged water was added to the remaining liquid. And about 2000 ml 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.

(Production Example 2) Production of aqueous solution of PEDOT-PSS 14.2 g of 3,4-ethylenedioxythiophene and a solution of 36.7 g of polystyrene sulfonic acid dissolved in 2000 ml of ion-exchanged water were mixed at 20 ° C. . While maintaining the mixed solution thus obtained at 20 ° C. and stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion exchange water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added, The reaction was stirred for 3 hours. 2000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2000 ml of solution was removed using an ultrafiltration method. This operation was repeated three times. Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water are added to the resulting solution, and about 2000 ml of solution is removed using an ultrafiltration method, and 2000 ml of ion-exchanged water is added thereto. About 2000 ml of liquid was removed using an ultrafiltration method. 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 12.5 g of C12 and C13 mixed higher alcohol glycidyl ether were mixed. Next, 50 g of the aqueous solution of PEDOT-PSS obtained in Production Example 2 was mixed and stirred at room temperature to obtain an amber-colored precipitate. This precipitate was collected by filtration and dispersed in methyl ethyl ketone to obtain PEDOT-PSS (adhesive - free composition) dispersed in about 0.5% by mass of methyl ethyl ketone.

<Manufacture of conductive coating film>
Example 1
10 g of X-40-3229 (Shin-Etsu Chemical Co., Ltd. silicone adhesive) , 20 g of the adhesive-free composition obtained in Production Example 3, and 0.05 g of CAT-PL-50T (curing catalyst) were mixed. A conductive polymer solution was prepared and applied onto a PET film using a # 2 bar coater. The obtained coating film was dried at 130 ° C. for 2 minutes, and then the surface resistance value was measured. Next, after pasting the coating film with another PET film, it was allowed to stand at room temperature for 20 hours, cut into a width of 25 mm, peeled 180 ° at a speed of 0.3 m / min, and the peel strength was measured.

(Comparative Example 1)
In Example 2, the measurement was performed in the same manner except that the conductive polymer solution obtained in Production Example 3 was replaced with methyl ethyl ketone.
(Comparative Example 2)
In Example 7, the measurement was performed in the same manner except that the conductive polymer solution obtained in Production Example 3 was replaced with methyl ethyl ketone.
(Comparative Example 3)
In Example 9, the measurement was performed in the same manner except that the conductive polymer solution obtained in Production Example 3 was changed to methyl ethyl ketone.

<Evaluation method of coating film>
(Surface resistivity)
Measured with a probe MCP-HTP12 and an applied voltage of 10 V using a Hiresta MCP-HT450 manufactured by Mitsubishi Chemical Corporation.
(Peel strength)
The obtained paint (also referred to as an adhesive) was applied to a PET film having a thickness of 38 μm with a bar coater and heated in a hot air drier at 130 ° C. for 2 minutes to form an adhesive layer. Next, a 2.5 cm × 15 cm polyester film (trade name: Lumirror T-60, manufactured by Toray Industries, Inc.) is placed on the surface of the adhesive layer, and then crimped using a 2 kg roller on the adhesive tape, A polyester film was bonded to the adhesive layer. Then, it was left to stand at room temperature for 20 hours to produce a test piece. Then, using a tensile tester, the polyester film was peeled from the adhesive layer at an angle of 180 degrees (peeling speed 0.3 m / min), and the adhesive strength was measured.

<Evaluation results>
Table 1 shows the evaluation results of various examples and various comparative examples. In the table, “OVER” means the measurement upper limit value or more.

  As described above, the coating films of Comparative Examples 1 to 3 to which the conductive polymer solution of Production Example 3 was not added had low conductivity and did not have high antistatic performance. On the other hand, the coating films of Examples 1 to 9 to which the conductive polymer solution of Production Example 3 was added were excellent in conductivity and had a high antistatic function. Moreover, when Example 2 and Comparative Example 1, Example 7 and Comparative Example 2, and Example 9 and Comparative Example 3 were compared, respectively, the difference in the remarkable adhesive force by adding a conductive polymer was not seen.

  The present invention can be effectively used for, for example, industrial tapes, protective films, release papers, adhesive layers, antistatic films, conductive paints, touch screens, organic EL, conductive polymer fibers, and the like.

Claims (8)

(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,
(D) a silicone adhesive;
(E) an organic solvent;
A conductive polymer solution.   The conductive polymer solution according to claim 1, wherein the (d) silicone adhesive is of an addition curing type.   The conductive polymer solution according to claim 1, wherein the (d) silicone pressure-sensitive adhesive is of an electron beam curable type.   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 4. 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 4, wherein the (a) π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene) or polypyrrole.   The said (b) polyanion is 1 or more types of mixtures selected from a sulfonic acid group, a phosphoric acid group, and a carboxyl group, The any one of Claims 1-5 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 claim 1, wherein the conductive polymer solution is contained.   The electroconductive coating film formed by supplying the electroconductive polymer solution of any one of Claims 1-7 on a base | substrate, and making it harden | cure.