JP2016017115A - Curable static charge prevention fluorine-containing resin composition, and static charge prevention fluorine-containing resin coated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable static charge prevention fluorine-containing resin composition capable of forming a fluorine-containing resin reduced in a defect originated from an amine compound and a defect originated from water and excellent in transparency, peel strength, and electroconductivity, and a static charge prevention fluorine-containing resin coated film obtained by curing the same.SOLUTION: The present invention is related to a curable static charge prevention fluorine-containing resin composition including: a π-conjugated electroconductive polymer (a); a polyanion (b) doped to the π-conjugated electroconductive polymer (a); a reaction product (c) of an anion other than needed to dope in the polyanion (b) with an oxirane group- and/or an oxetane group-containing organic compound; an electroconductive polymer composition (I) dispersable in a solvent mainly composed of an organic solvent; and a curable fluorine-containing resin composition (II), and a static charge prevention fluorine-containing resin coated film obtained by curing the same.SELECTED DRAWING: None

Description

  The present invention relates to a curable antistatic fluorine-containing resin composition capable of forming a fluororesin film excellent in antistatic performance, and an antistatic fluorine-containing resin film obtained by curing the composition.

  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 solubilizing in a solvent, π An attempt has been made to add an anionic group-containing polymer acid to a conjugated 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).

  On the other hand, there is a demand for imparting an antistatic function to a fluorine-containing resin composition having high insulation. In order to meet this demand, a method of adding carbon powder, metal powder, and ionic conductive material to a fluorine-containing resin composition has been conventionally attempted.

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

  However, the conventional method has a problem that it is difficult to mix with other organic resins as in the case of polyaniline, and in addition, it is limited to a solvent system containing a large amount of water. Even if the amount of water is small or substantially free of water, if an amine compound is used, due to this, color tone deterioration with time when mixed with a resin, polyanion to the conductive polymer There is a possibility that the dope is gradually pulled out by the amine and the conductivity decreases with time. That is, the above-mentioned conventional conductive solution uses an amine compound, and when the conductive polymer is phase-inverted from an aqueous phase to an organic phase, it is difficult to overcome the above-mentioned drawbacks derived from the amine compound. In addition, when imparting conductivity to a resin using an isocyanate-based compound, there is a problem that the conductive polymer aggregates due to amine. Furthermore, the form of the water dispersion has the disadvantages that it is not practical and is easily corroded by water.

  In addition, the conventional method of adding carbon powder, metal powder, and ionic conductive material to the fluorine-containing resin composition satisfies many functions such as transparency of the fluorine-containing resin, peel strength, and electrical conductivity humidity dependency. The current situation has not led to this.

  The present invention has been made in order to solve the above-mentioned problems, and reduces fluorine-containing defects and water-derived defects, and is superior in transparency, peel strength, and conductivity. It is an object of the present invention to provide a curable antistatic fluorine-containing resin composition capable of forming a resin and an antistatic fluorine-containing resin film obtained by curing the resin composition.

  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. And the present invention was completed by imparting an excellent antistatic function to the fluororesin. Specific problem solving means are as follows.

  In order to achieve the above object, the curable antistatic fluorine-containing resin composition according to the embodiment of the present invention comprises (a) a π-conjugated conductive polymer and (b) the (a) π-conjugated conductive. A polyanion doped in a polymer; and (c) a reaction product of an anion other than that required for doping in the (b) polyanion and an oxirane group and / or oxetane group-containing organic compound, A conductive polymer composition (I) that is dispersible and soluble in the solvent, and a curable fluorine-containing resin composition (II).

  In the curable antistatic fluorine-containing resin composition according to another embodiment, (a) the π-conjugated conductive polymer is polypyrrole, polythiophene, polyacetylene, polyphenylene, polyphenylene vinylene, polyaniline, polyacene. , Polythiophene vinylenes, and at least one repeating unit selected from the group consisting of two or more copolymers thereof.

  In the curable antistatic fluorine-containing resin composition according to another embodiment, (a) the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene) or polypyrrole.

  The curable antistatic fluorine-containing resin composition according to another embodiment is (b) one or more mixtures in which the polyanion is selected from a sulfonic acid group, a phosphoric acid group, and a carboxyl group.

  In the curable antistatic fluorine-containing resin composition according to another embodiment, (b) the polyanion is polystyrenesulfonic acid, polyvinylsulfonic acid, polyacrylic acid alkylenesulfonic acid, poly (2-acrylamido-2-methyl-1). -Propanesulfonic acid) or one or more of them as a copolymerization constituent.

  The curable antistatic fluorine-containing resin composition according to another embodiment contains a polyvalent isocyanate compound as a curing agent for the curable fluorine-containing resin composition (II).

  The curable antistatic fluorine-containing resin composition according to another embodiment further contains an organic solvent.

  In addition, the antistatic fluorine-containing resin film according to the embodiment of the present invention is formed by supplying any one of the above-described curable antistatic fluorine-containing resin compositions onto a substrate and curing it.

  According to the present invention, a curable antistatic fluorine-containing resin composition capable of reducing a defect derived from an amine compound and a defect derived from water, and capable of forming a fluorine-containing resin having superior transparency, peel strength, and conductivity as compared with the prior art. And an antistatic fluorine-containing resin film obtained by curing the product.

  Hereinafter, each embodiment of the curable antistatic fluorine-containing resin composition according to the present invention and the antistatic fluorine-containing resin film formed by curing the same will be described.

<A. Embodiment of curable antistatic fluorine-containing resin composition>
1. Conductive polymer composition
The conductive polymer composition (I) contained in the curable antistatic fluorine-containing resin composition according to the embodiment of the present invention includes (a) a π-conjugated conductive polymer, (b) the above (a) a polyanion doped with a π-conjugated conductive polymer, and (c) a reaction product of the anion in the polyanion (b) and an oxirane group and / or oxetane group-containing organic compound, and mainly an organic solvent A composition that is dispersible and soluble in a 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-solubilized” state. The solvent in this case is a solvent mainly composed of an organic solvent. The term “mainly organic solvent” as used in the present application 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 The conductive polymer composition (I) 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 conductive polymer composition (I) 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 the reaction solution. Obtained by filtration or 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 into an insoluble solvent phase (also referred to as an organic phase), and if necessary, after steps such as dehydration, the conductive polymer composition is placed in a solvent mainly composed of an organic solvent. It may be soluble in or dispersed in. Here, the “conductive polymer composition” or “conductive composition” includes (a) a π-conjugated conductive polymer, and (b) a polyanion doped in the (a) π-conjugated conductive polymer. And (c) an anion other than that required for doping in the polyanion and an organic compound containing an oxirane group and / or an oxetane group. Includes reaction products. In addition, the conductive polymer composition or the conductive composition includes both a form containing an organic solvent and a form not containing an organic solvent.

(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 (I). 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. As described above, in the method (2), since the freeze-dried conductive polymer composition solid is used as a raw material, the time for the concentration step can be shortened.

1.2 Raw material for conductive polymer composition (I) (a) π-conjugated conductive polymer π-conjugated conductive polymer may be an organic polymer whose main chain is composed of π-conjugated system. For example, it 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. The π-conjugated conductive polymer exhibits sufficiently high conductivity and compatibility with a binder even if it is not substituted. However, in order to further improve conductivity, dispersibility or solubility in the binder, an alkyl group A functional group such as an alkenyl group, a carboxyl group, a sulfo group (also referred to as a sulfonic acid group or a sulfone 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 in which an anion group-containing polymerizable monomer is polymerized in addition to a polymer in which an anion group is introduced into a polymer by sulfonation with a sulfonating agent using a sulfonating agent. Mention may be made of the polymers obtained. 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 reacting (a) the π-conjugated conductive polymer and (b) the polyanion with an oxirane group and / or oxetane group-containing organic compound.

  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 is dissolved 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 conductivity and mechanical properties of the conductive film formed.

  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 technologies and the present application is that 1) a reaction product obtained by reacting a polyanion which is a dopant and a dispersant for a conductive polymer and an oxirane group or oxetane group-containing compound is obtained. All moisture is 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.

  Unlike the components (a) to (c) described above, the organic solvent used in the solvent for dissolving or dispersing the conductive polymer composition (I) is different from the conductive polymer composition ( It may or may not be included in I). Examples of the organic solvent include polar solvents represented by N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylenephosphonium triamide, acetonitrile, benzonitrile and the like; Phenols typified by phenol, xylenol, etc .; alcohols typified by methanol, ethanol, propanol, butanol, etc .; ketones typified by acetone, methyl ethyl ketone, methyl isobutyl ketone, etc .; ethyl acetate, propyl acetate, butyl acetate Esters such as hexane, heptane, benzene, toluene, xylene, etc .; hydrocarbons such as formic acid, acetic acid, etc .; ethylene carbonate, propylene carbonate Carbonate compounds typified by: 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 .; 3- Preferred examples include heterocyclic compounds typified by 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.

(D) Others Examples of additives to the solvent in which the conductive polymer composition (I) is soluble or dispersed 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.

2. Curable fluorine-containing resin composition The conductive polymer composition (I) described above is mixed with the curable fluorine-containing resin composition (II) in order to obtain a fluorine-containing resin having antistatic performance. As the curable fluorine-containing resin composition in this embodiment, those exemplified below can be suitably used. The curable fluorine-containing resin composition refers to a monomer, dimer or higher polymer that becomes a fluorine-containing resin having a higher molecular weight when cured. The curable fluorine-containing resin in the present application (also simply referred to as a fluorine-containing resin) refers to a copolymer of a monomer having a fluorine atom and a monomer having a curable functional group. Hereinafter, the monomer used in the copolymer may be referred to as “copolymer unit”.

  As the monomer having a fluorine atom, a fluorine-containing monomer used as a fluororesin raw material can be mentioned without particular limitation. Specifically, tetrafluoroethylene (TFE), vinylidene fluoride (VdF), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), perfluoro (alkyl vinyl ether) (PAVE), a monomer in which a fluoroalkyl group and a polymerizable unsaturated group are linked by an ether bond or an ester bond. Among these, TFE, VdF, HFP, CTFE, and VF are preferable, and TFE and CTFE are more preferable. One of the above monomers can be used alone, or two or more can be used in combination.

  Examples of the monomer having a curable functional group include monomers having a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, a silyl group, a silanate group, and among them, a viewpoint having good curability. Therefore, a monomer having a hydroxyl group or a silyl group is preferable, and a monomer having a hydroxyl group is more preferable.

  Examples of the monomer having a hydroxyl group include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2. -Hydroxyl-containing vinyl ethers such as methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, and hydroxyl-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, etc. Can be mentioned.

  Further, if necessary, it may be copolymerized in combination with a monomer other than the above (hereinafter referred to as “other monomer”). Examples of other monomers include reactive silicone oils, alkyl vinyl ethers, alkyl allyl ethers, methacrylic acid esters and acrylic acid esters, carboxylic acid vinyl esters, and olefins. These other monomers may be used alone or in combination of two or more.

The reactive silicone oil is represented by the following formula (1) or (2).
^{_{R 1 - [Si (CH 3}} ) 2 -O] n -Si (CH 3) 2 -R 2 ··· (1)
(In Formula (1), R ¹ is an alkyl group having 1 to 6 carbon atoms, — (CH ₂ ) _r —OOC (CH ₃ ) C═CH ₂ or —CH═CH ₂ , and R ² is — (CH _{2) r} -OOC _(CH 3) a C = CH ₂ or -CH = CH ₂ .n is 1 to 420, r is 1-6.)

R ² —Si [OSi (CH ₃ ) ₃ ] ₃ (2)
(In the formula (2), R ² has the same definition as above.)

  In addition, as the reactive silicone oil represented by the above formula (1) or (2), one end is methacryl-modified polydimethylsiloxane, one end is acryl-modified polydimethylsiloxane, and both ends are methacryl-modified. Polydimethylsiloxane and the like are preferred. These reactive silicone oils may be used alone or in combination of two or more.

Furthermore, the above-mentioned reactive silicone oil may be represented by the following formulas (3), (4), (5), (6).
_{CH 2 = C (CH 3)} -COO-C 3 H 6 - [Si (CH 3) 2 -O] m -Si (CH 3) 2 -R 3 ··· (3)
(In formula (3), R ³ represents an alkyl group having 1 to 6 carbon atoms. M represents an integer of 1 to 250.)

_{CH 2 = CH-COO-C} 3 H 6 - [Si (CH 3) 2 -O] p -Si (CH 3) 2 -R 4 ··· (4)
(In formula (4), R ⁴ represents an alkyl group having 1 to 6 carbon atoms. P represents an integer of 1 to 250.)

^{_{R 5 -C 3 H 6 - [}} Si (CH 3) 2 -O] q -C 3 H 6 -R 5 ··· (5)
(In formula (5), R ⁵ represents —OCOC (CH ₃ ) ═CH _2. Q represents an integer of 1 to 250.)

_{CH 2 = C (CH 3)} COO-C 3 H 6 Si [OSi (CH 3) 3] 3 ··· (6)

Specific examples of the alkyl vinyl ethers include ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, octadecyl vinyl ether, glycidyl vinyl ether,
Examples thereof include glycidyloxymethyl vinyl ether, glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxypentyl vinyl ether, glycidyloxycyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether.

  Specific examples of alkyl allyl ethers include ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, isobutyl allyl ether, n-propyl allyl ether, allyl glycidyl ether, 3-allyloxy-1,2 propanediol, glycerol monoallyl ether Etc.

  Specific examples of the acrylate esters include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, and the like.

  Specific examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxy methacrylate. And propyl.

  Specific examples of vinyl carboxylates include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexyl carboxylate, And vinyl benzoate and vinyl para-t-butylbenzoate.

  Examples of olefins include olefins having 2 to 20 carbon atoms, and specific examples include ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-heptene, 1-octene, 1-decene, and 1-tetradecene. 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene and the like.

  Examples of fluorine-containing resins include TFE / isobutylene / hydroxybutyl vinyl ether / other monomer copolymer, TFE / vinyl versatate / hydroxybutyl vinyl ether / other monomer copolymer, and CTFE / hydroxybutyl. Examples thereof include a vinyl ether / other monomer copolymer and a TFE / VdF / hydroxybutyl vinyl ether / other monomer copolymer. Commercially available products include the Zaffle GK series made by Daikin Industries, which contains TFE as a copolymer unit, the Lumiflon series made by Asahi Glass Co., which contains CTFE as a copolymer unit, the fluorinate series made by DIC, and the product made by Toa Gosei. Examples include the ZAFLON series and Cefral Coat series manufactured by Central Glass. In addition, as a commercial product of a curable fluorine-containing resin composition containing a reactive silicone as a copolymer unit, the F Clear series manufactured by Kanto Denka Kogyo Co., Ltd. may be mentioned.

  The above-mentioned fluorine-containing resin is preferably dissolved in an organic solvent or the like, and then used in the state of a solution containing a curable fluorine-containing resin composition. Specific examples of the organic solvent include ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, alcohol solvents such as ethanol and isopropyl alcohol, and aromatic solvents such as benzene, toluene and xylene. Solvents, aliphatic saturated hydrocarbon solvents such as hexane, isohexane, heptane, octane and isooctane, aliphatic solvents such as cyclohexane, methylcyclohexane and dimethylcyclohexane, chlorinated solvents such as trichloroethylene, chloroform and m-xylene hexachloride, Ether solvents such as acetone, diethyl ether, diisopropyl ether and tetrahydrofuran; fluorine solvents such as methyl perfluorobutyl ether and ethyl perfluorobutyl ether; Disiloxane, silicone solvents such as hexamethylcyclotrisiloxane and heptamethyltrisiloxane and the like. Among them, one or a combination of two or more of ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, and xylene isopropyl alcohol is preferable from the viewpoint of solubility of the fluorine-containing resin.

  The hydroxyl value of the fluorine-containing resin having a hydroxyl group is preferably 5 to 200 mgKOH / g, and more preferably 30 to 180 mgKOH / g. This is because when the hydroxyl value is 5 mgKOH / g or more, the curing reactivity is excellent, and when it is 200 mgKOH / g or less, the solubility in an organic solvent is excellent.

3. Other (curing agent)
The curing agent can be appropriately selected and added according to the functional group of the fluorine-containing resin. For example, when a fluorine-containing resin having a hydroxyl group is used, a polyvalent isocyanate compound, a melamine curing agent, a urea resin curing agent, a silicate compound, an isocyanate group-containing silane compound, a polybasic acid curing agent, or the like can be used. Among these, a polyvalent isocyanate compound is preferable in that the physical property balance of the cured film is excellent.

  Examples of the polyvalent isocyanate compound include polyisocyanates such as aromatic, aliphatic and alicyclic diisocyanates, and isocyanurate type polyisocyanates, burette type isocyanates derived from these polyisocyanates alone or as a mixture. These diisocyanates and ethylene glycol, polyether polyols (polyethylene glycol, polypropylene glycol, etc.), caprolactone polyols, polycarbonate polyols, low molecular weight polyester resins having functional groups that react with isocyanate groups (including oil-modified types) and acrylics Random type adducts such as copolymers, 2-hydroxypropyl (meth) acrylate and hexamethylene diisocyanate molar adducts, isocyanate ethyl (meta And a copolymer having an isocyanate group obtained a vinyl monomer as an essential component having an isocyanate group and a copolymerizable unsaturated group such as acrylate and the like. Furthermore, the blocked polyisocyanate which stabilized the isocyanate group with the blocking agent with respect to these polyisocyanate compounds can also be mentioned. From the viewpoint of curing reactivity, those having at least two, more preferably 2-3 isocyanate groups and / or blocked isocyanate groups in one molecule of the polyvalent isocyanate compound are preferable. Specifically, adducts obtained by the reaction of bifunctional or higher polyols and the like with the polyisocyanates, diisocyanate derivatives such as isocyanurates, burettes of the isocyanates, allophanates, and uretidinediones are preferred. As commercial products, the Duranate series manufactured by Asahi Kasei Chemicals Corporation, the Sumijour series and the Dismodule series manufactured by Sumika Bayer Urethane are listed. The above polyisocyanate compounds may be used alone or in combination of two or more.

  The addition amount of the polyvalent isocyanate compound is such that the ratio (NCO / OH) to the number of moles of isocyanate groups (NCO) in the polyvalent isocyanate compound and the number of moles of hydroxyl groups in the fluorine-containing resin is 0.5 to 2.0. It is preferable to adjust to. A more preferable ratio is 0.7 to 1.3. When the ratio is 0.5 or more, the curability of the film and the adhesion between the film and the substrate can be improved. Moreover, when the said ratio is 2.0 or less, the transparency of a film | membrane is securable.

(Curing accelerator)
Curing accelerators include potassium acetate, 2-ethylhexane potassium, calcium acetate, lead octylate, dibutyltin dilaurate, tin octylate, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2-ethylhexanoate, octylic acid Zinc, zinc neodecanoate, phosphine, phospholine and the like can be used, and any one of them can be used alone or in combination of two or more. The addition amount of the curing accelerator is preferably 0.0001 to 0.01 parts by mass, and more preferably 0.0002 to 0.005 parts by mass with respect to 100 parts by mass of the curable fluorine-containing resin.

<B Embodiment of Antistatic Fluorine-Containing Resin Film>
An antistatic fluorine-containing resin film according to an embodiment of the present invention is formed on a substrate in the form of a paint in which the above-described curable antistatic fluorine-containing resin composition is soluble or dispersed in a solvent mainly composed of an organic solvent. It is a film formed by supplying and curing. The paint is supplied on a substrate represented by paper, plastic, iron, ceramics, and glass. Examples of supply methods include gravure coaters, roll coaters, curtain flow coaters, spin coaters, bar coaters, reverse coaters, kiss coaters, phantom coaters, rod coaters, air doctor coaters, knife coaters, blade coaters, cast coaters, screen coaters. Coating method using a coater such as air spray, airless spray, spraying method using a sprayer such as rotor dampening, dipping method such as dipping, etc., dripping paint onto the substrate and rotating the substrate to spread the paint Various methods such as a spin coating method and a brush method of spreading a paint with a brush can be applied. Examples of the method for curing the paint on the substrate include a method for removing the organic solvent by heating and a method for curing by irradiating light such as ultraviolet rays or an electron beam.

  The thickness of the film is preferably in the range of 100 nm to 1000 nm. This is because when a film in this range is formed, both the film performance and cost are excellent. (A) a π-conjugated conductive polymer, (b) a polyanion, (c) a conductive product comprising 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 The content of the polymer composition is preferably 0.05 to 20.0% by mass, more preferably 0.5 to 15.0% by mass when the weight of the entire coating is 100% by mass. preferable. This is because when the content of the conductive polymer composition is 0.05% by mass or more, sufficient conductivity can be ensured. Further, when the content of the conductive polymer composition is 20.0% by mass or less, it is easy to form a film that makes the conductivity more uniform depending on the location.

  The conductive polymer composition constituting the curable antistatic fluorine-containing resin composition according to this embodiment comprises an anion other than that required for doping in the polyanion, and an oxirane group and / or oxetane group-containing organic compound. Since it contains a reaction product, it is dispersed and soluble in various organic solvents. Moreover, the above-mentioned 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. A curable antistatic fluorine-containing resin composition stably dispersed and / or solubilized in a solvent mainly composed of an organic solvent by mixing such a conductive polymer composition with a curable fluorine-containing resin composition. You can get things. When the curable antistatic fluorine-containing resin composition (including organic solvents as the main solvent) is supplied onto the substrate as a coating and cured, it is difficult to peel off, has excellent transparency, and has antistatic performance. Excellent fluororesin film 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 obtained 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 were mixed. Next, 50 g of the aqueous solution of PEDOT-PSS obtained in Production Example 2 was mixed in the solution at room temperature, followed by stirring to obtain an amber-colored precipitate. The precipitate was collected by filtration and dispersed in methyl ethyl ketone to obtain a dispersion of PEDOT-PSS (concentration: about 0.5% by mass) dispersed in methyl ethyl ketone.

(Production Example 4) ... Production of organic solvent in which PEDOT-PSS is dispersed Methyl ethyl ketone was produced under the same conditions as in Production Example 3 except that C10 and C12 mixed higher alcohol glycidyl ether of Production Example 3 was changed to 12.5 g. A dispersion of PEDOT-PSS dispersed (concentration: about 0.5% by mass) was obtained.

(Production Example 5) ... Production of organic solvent in which PEDOT-PSS was dispersed Same as Production Example 3 except that C10 and C12 mixed higher alcohol glycidyl ether of Production Example 3 was changed to C12 and C13 mixed higher alcohol glycidyl ether. Under the conditions, a dispersion of PEDOT-PSS dispersed in methyl ethyl ketone (concentration: about 0.5% by mass) was obtained.

(Production Example 6) ... Production of organic solvent in which PEDOT-PSS was dispersed Except for changing the C12 and C13 mixed higher alcohol glycidyl ether of Production Example 5 to 12.5 g, to methyl ethyl ketone under the same conditions as Production Example 5 A dispersion of PEDOT-PSS dispersed (concentration: about 0.5% by mass) was obtained.

(Production Example 7) ... Production of organic solvent in which PEDOT-PSS was dispersed Same as Production Example 3 except that C10 and C12 mixed higher alcohol glycidyl ether of Production Example 3 was changed to C12 and C14 mixed higher alcohol glycidyl ether. Under the conditions, a dispersion of PEDOT-PSS dispersed in methyl ethyl ketone (concentration: about 0.5% by mass) was obtained.

(Production Example 8) ... Production of organic solvent in which PEDOT-PSS was dispersed Except for changing the C12 and C14 mixed higher alcohol glycidyl ether of Production Example 7 to 12.5 g, to methyl ethyl ketone under the same conditions as Production Example 7 A dispersion of PEDOT-PSS dispersed (concentration: about 0.5% by mass) was obtained.

<Manufacture of curable antistatic fluorine-containing resin composition>
Example 1
With respect to 800 parts by mass of “PEDOT-PSS dispersion dispersed in methyl ethyl ketone” (concentration: about 0.5% by mass) obtained in Production Example 3, the following curing agent 10.13 parts by mass and the following curing A curable antistatic fluorine-containing resin composition was prepared by adding 100 parts by mass of a curable fluorine-containing resin.
[Curing agent]
Product name: Duranate 24A-100 (hexamethylene diisocyanate type biuret type)
Manufacturer: Asahi Kasei Chemicals Corporation Solid content: 100% by mass
NCO content: 23.5% by mass
[Curable fluorinated resin]
Product name: F-clear KD (fluorine-containing copolymer containing reactive silicone as a copolymer unit, 62% by mass of butyl acetate and 8% by mass of methyl ethyl ketone)
Manufacturer: Kanto Denka Kogyo Co., Ltd. Solid concentration: 30% by mass
Hydroxyl value: 106 mgKOH / g

(Example 2)
Under the same conditions as in Example 1, except that the “PEDOT-PSS dispersion dispersed in methyl ethyl ketone” (concentration: about 0.5 mass%) used in Example 1 was changed to that obtained in Production Example 4. A conductive polymer solution was prepared.

(Example 3)
Under the same conditions as in Example 1, except that the “PEDOT-PSS dispersion in methyl ethyl ketone (concentration: about 0.5 mass%)” used in Example 1 was changed to that obtained in Production Example 5. A conductive polymer solution was prepared.

Example 4
Under the same conditions as in Example 1 except that the “PEDOT-PSS dispersion in methyl ethyl ketone (concentration: about 0.5 mass%)” used in Example 1 was changed to that obtained in Production Example 6. A conductive polymer solution was prepared.

(Example 5)
Under the same conditions as in Example 1, except that the “dispersion of PEDOT-PSS dispersed in methyl ethyl ketone (concentration: about 0.5 mass%)” used in Example 1 was changed to that obtained in Production Example 7. A conductive polymer solution was prepared.

(Example 6)
The same conditions as in Example 1 were used except that the “PEDOT-PSS dispersion in methyl ethyl ketone (concentration: about 0.5 mass%)” used in Example 1 was changed to that obtained in Production Example 8. A conductive polymer solution was prepared.

(Comparative Example 1)
The same conditions as in Example 1 were used except that the “PEDOT-PSS dispersion dispersed in methyl ethyl ketone (concentration: about 0.5 mass%)” used in Example 1 was changed to that obtained in Production Example 2. A conductive polymer solution was prepared. However, aggregation and separation of PEDOT-PSS occurred, and only a very poorly dispersed solution was obtained. For this reason, it was impossible to form a film described later.

<Manufacture of film>
The solution of the curable antistatic fluorine-containing resin composition prepared in each of the above Examples and Comparative Examples was applied to a # 4 bar coater on a biaxially stretched PET film (product name: E5100, manufactured by Toyobo Co., Ltd.) having a thickness of 100 microns. , Dried at 120 ° C. for 1 minute, and aged at 80 ° C. for 24 hours to form a film.

<Evaluation method of film>
(1) Peel strength A 2.5 cm × 15 cm polyester adhesive tape (product name: Nitto No. 31B, manufactured by Nitto Denko Corporation) is placed on each film, and then crimped with a 2 kg roller on the adhesive tape. A polyester adhesive tape was bonded to the film. Then, it was left to stand at room temperature for 20 hours, and the test piece was completed. Next, the polyester adhesive tape was peeled from the film at an angle of 180 degrees using a tensile tester (peeling speed: 0.3 m / min), and the peel strength was measured. The smaller the peel strength, the easier the adhesive tape can be peeled after the adhesive tape is bonded to the film.
(2) Surface resistivity It measured on conditions of probe MCP-HTP12 and the applied voltage of 10V using Hiresta MCP-HT450 (product name) by Mitsubishi Chemical Analytech.
(3) Transmittance The transmittance of the film used for measuring the surface resistance value was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku).
(4) Appearance The film was visually observed and evaluated as “◯” when there was no aggregate or foreign matter on the film, and “X” when there was an aggregate or foreign matter.

<Evaluation results>
Table 1 shows the evaluation of the solutions obtained in each Example and Comparative Example and the film formed using the solution. When measurement is not possible, it is indicated by “-” in the table.

  As is clear from Table 1, the water-insoluble reaction product (precipitate) obtained in Production Example 3 was dissolved in methyl ethyl ketone. Moreover, when about 1 mass% PEDOT-PSS dispersion liquid which melt | dissolved this sediment in methyl ethyl ketone was diluted with double volume distilled water and measured with simple pH meter AS212 (made by Horiba, Ltd.), pH = It was 6.8. On the other hand, when 1.2 times by mass of distilled water was added to the 1.2 mass% PEDOT-PSS dispersion obtained in Production Example 2 and the same measurement was performed, the pH was 2.1. From this, it is considered that the precipitate is a product obtained by reacting at least a polyanion and an epoxy compound. The water-insoluble reactant (precipitate) obtained in Production Examples 4 to 8 was also the same as the sediment obtained in Production Example 3. Moreover, the film | membrane obtained in Examples 1-6 showed high electroconductivity, and was excellent also in the peeling strength after 20-hour progress at room temperature. On the other hand, in Comparative Example 1, PEDOT-PSS aggregated and separated, and could not be dispersed into the curable fluorine-containing resin, and could not be used for evaluation of the film.

  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 (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,
A conductive polymer composition (I) that is dispersible and soluble in a solvent mainly composed of an organic solvent,
A curable fluorine-containing resin composition (II);
A curable antistatic fluorine-containing resin composition.   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 curable antistatic fluorine-containing resin composition according to claim 1, which has at least one repeating unit selected from the group consisting of:   The curable antistatic fluorine-containing resin composition according to claim 2, wherein the (a) π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene) or polypyrrole.   The curable antistatic fluorine according to any one of claims 1 to 3, wherein the (b) polyanion is one or a mixture selected from a sulfonic acid group, a phosphoric acid group and a carboxyl group. Containing resin composition.   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 curable antistatic fluorine-containing resin composition according to any one of claims 1 to 4, which is contained.   The curable antistatic fluorine-containing resin composition according to any one of claims 1 to 5, comprising a polyvalent isocyanate compound as a curing agent for the curable fluorine-containing resin composition (II).   The curable antistatic fluorine-containing resin composition according to any one of claims 1 to 6, further comprising an organic solvent.   An antistatic fluorine-containing resin film obtained by supplying the curable antistatic fluorine-containing resin composition according to any one of claims 1 to 7 onto a substrate and curing it.