JP2016145302A - Conductive polymer composition and release film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive polymer composition capable of forming a coating film having excellent release characteristics, high adhesion to a substrate, and high conductivity, and to provide a release film formed by applying the conductive polymer composition onto a substrate and curing it.SOLUTION: The present invention relates to: a conductive polymer composition containing a curable organopolysiloxane composition, a conductive polymer, a polyanion, and a silane compound represented by Formula (1); and a release film formed by applying the conductive polymer composition onto a substrate and curing it. (Rand Rare each independently a substituted/unsubstituted hydrocarbon group or alkoxy group, H, or a mercapto group; n is a positive integer of 1-4; when n is 2-4, a plurality of Rs may be the same or different; and when n is 1 or 2, a plurality of Rs may be the same or different.)SELECTED DRAWING: None

Description

  The present invention relates to a composition for a conductive polymer and a release film obtained by coating the composition on a substrate and curing it.

  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 the addition reaction curable silicone resin, there is a drawback that the curing inhibition by the amine occurs and the curing of the silicone resin is insufficient.

  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.

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

  In order to eliminate the drawbacks of the prior art, a method of mixing a conductive polymer and silicone can be considered. However, when a coating material simply formed by mixing a conductive polymer and silicone in an organic solvent is applied to a substrate, there is a problem that the adhesion of the coating material to the substrate is low and the conductivity is also low. For this reason, it is strongly desired to further improve the adhesion and conductivity to the substrate without deteriorating the peeling characteristics as an antistatic release coating.

  The present invention has been made to meet the above-mentioned demand, and is a conductive polymer composition capable of forming a coating film having excellent peeling characteristics, high adhesion to a substrate, and high conductivity, and a substrate thereof An object is to provide a release film which is coated and cured.

  In order to achieve the above object, the present inventors have completed the present invention by producing a paint using a conductive polymer composition containing a specific silane compound. Specific problem solving means are as follows.

One embodiment of the conductive polymer composition for achieving the above object includes a curable organopolysiloxane composition, a conductive polymer, a polyanion, and a silane compound represented by the following chemical formula (1): Is a conductive polymer composition.
In chemical formula (1), R ¹ and R ² may be the same or different, and both are groups that may contain a substituent. n: A positive integer of 1 to 4. When n = 2 to 4, the plurality of R ¹ may be the same or different, and when n = 1 or 2, the plurality of R ² may be the same or different.

In another embodiment of the conductive polymer composition, the silane compound is a compound represented by the following chemical formula (2).
In chemical formula (2), R ² and R ³ may be the same or different, and both are groups that may contain a substituent. n: A positive integer of 1 to 4. When n = 2 to 4, the plurality of R ³ may be the same or different, and when n = 1 or 2, the plurality of R ² may be the same or different.

In another embodiment of the conductive polymer composition, the silane compound may be a hydrocarbon group or alkoxy group, hydrogen or mercapto group in which at least one of R ¹ , R ² and R ³ may contain a substituent. The compound is

  In another embodiment of the conductive polymer composition, the conductive polymer is a π-conjugated conductive polymer and further contains an oxirane group and / or oxetane group-containing organic compound.

  Another embodiment of the conductive polymer composition further includes a reaction product of a polyanion and an organic compound containing an oxirane group and / or an oxetane group.

  In another embodiment of the conductive polymer composition, the π-conjugated conductive polymer is polyethylene dioxythiophene, and the polyanion is polystyrene sulfonic acid.

  In another embodiment of the conductive polymer composition, the silane compound is one or more selected from triacetoxymethylsilane, triacetoxyethylsilane, and vinyltriacetoxysilane.

  In another embodiment of the conductive polymer composition, the curable organopolysiloxane composition is an addition-reactive silicone composition.

  One embodiment of the release film is formed by applying one of the above-described conductive polymer compositions onto a substrate and curing it.

  According to the present invention, a conductive polymer composition capable of forming a coating film having excellent peeling properties, high adhesion to a substrate and high conductivity, and coating and curing on the substrate. A release film can be provided.

  Hereinafter, each embodiment of the conductive polymer composition and the release film according to the present invention will be described. In addition, this invention is not limited to each following embodiment, Moreover, the component in each embodiment is not necessarily an essential component for this invention.

<A Embodiment of Conductive Polymer Composition>
1. Conductive polymer composition

The conductive polymer composition according to the embodiment of the present invention includes a curable organopolysiloxane composition, a conductive polymer, a polyanion, and a silane compound represented by the following chemical formula (1). It is a conductive polymer composition. In the present application, the form of the conductive polymer composition is preferably interpreted in a broad sense so as to include a liquid or gel form having fluidity that can be applied as a paint on a substrate.
(In the chemical formula (1), R ¹ and R ² may be the same or different, and each may contain a substituent. N: a positive integer of 1 to 4. n = 2. In the case of ˜4, the plurality of R ¹ may be the same or different, and in the case of n = 1 or 2, the plurality of R ² may be the same or different.)

In the conductive polymer composition, the silane compound is preferably a compound represented by the following chemical formula (2).
(In the chemical formula (2), R ² and R ³ may be the same or different, and each may contain a substituent. N: a positive integer of 1 to 4. n = 2. In the case of ˜4, the plurality of R ³ may be the same or different, and in the case of n = 1 or 2, the plurality of R ² may be the same or different.)

The silane compound contained in the conductive polymer composition contains at least one of R ¹ , R ² and R ³ , preferably a hydrocarbon group or alkoxy group which may contain a substituent, hydrogen or a mercapto group To do.

1.1 Raw Material for Conductive Polymer Composition (1) Curable Organopolysiloxane Composition As the curable organopolysiloxane composition used in this embodiment, those exemplified below can be used. Among the following various curable organopolysiloxane compositions, an addition-curable organopolysiloxane composition is particularly preferable.

(Additionally curable organopolysiloxane composition)
The addition-curable organopolysiloxane composition includes, for example, a silicone rubber having a vinyl group at its end (such as raw rubber), a crosslinking agent having a Si—H group, and an addition reaction catalyst. The cross-linking agent is an organohydrogenpolysiloxane having a Si—H group, and either linear or branched 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. Examples of the addition-curable organopolysiloxane composition include an organopolysiloxane having at least two alkenyl groups in the molecule, an organopolysiloxane having at least three hydrosilyl groups in the molecule, mainly platinum, palladium, A hydrosilylation catalyst comprising a platinum group metal modification or complex such as rhodium is included. However, the curable organopolysiloxane composition including the addition curable organopolysiloxane composition may also refer to a composition that does not contain a catalyst.

(Condensation-curable organopolysiloxane composition)
The condensation-curable organopolysiloxane composition is mainly composed of any of the compounds described in Examples 1 to 3 below.
<Example 1>
A) Organopolysiloxane having at least two silanol groups in the molecule B) Organosilane or organopolysiloxane having at least three hydrolyzable groups in the molecule C) Condensation catalyst <Example 2>
A) Organopolysiloxane having at least two silanol groups in the molecule B) Organopolysiloxane having at least three hydrosilyl groups in the molecule C) Condensation catalyst <Example 3>
A) Organopolysiloxane having at least 3 hydrolyzable groups in the molecule B) Condensation catalyst

(Ionizing radiation curable organopolysiloxane composition)
The ionizing radiation-curable organopolysiloxane composition contains, for example, any of the compounds described in Examples 1 to 6 below, and is cured by ultraviolet rays using a photoinitiator or by electron beams.
<Example 1>
Acrylamide group-containing organopolysiloxane This organopolysiloxane is an organopolysiloxane containing an acrylamide functional group represented by the following chemical formula (3) in the molecule.

In the above chemical formula (3), R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ 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 chemical formula (4) in one molecule. is there.

In the above chemical formula (4), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ 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. The composition which consists of organopolysiloxane containing.
<Example 4>
Alkenyl group-containing organopolysiloxane This organopolysiloxane is an organopolysiloxane containing an alkenyl group (—C _n H _2n-1 (n is an integer of 2 or more)) in the molecule.
<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

  The curable organopolysiloxane composition is preferably 100 to 20000 mass% with respect to 100 mass% of the total amount of the conductive polymer (preferably a π-conjugated conductive polymer described later) and the polyanion, More preferably, it is contained in the range of 500 to 10000 mass%, more preferably 1000 to 10000 mass%.

(2) Conductive polymer The conductive polymer composition according to this embodiment preferably includes at least a π-conjugated conductive polymer as the conductive polymer. The conductive polymer composition includes a polyanion in addition to the conductive polymer. The conductive polymer composition preferably contains an oxirane group and / or oxetane group-containing organic compound, and more preferably contains a reaction product of a polyanion and an oxirane group and / or oxetane group-containing organic compound. When the oxirane group or the 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, such a conductive polymer can be solubilized or dispersed in an organic solvent at a high concentration. By doping the π-conjugated conductive polymer with the polyanion, a complex of the π-conjugated conductive polymer and the polyanion is formed. In the polyanion, all the anion groups are not doped into the π-conjugated conductive polymer and have an excess anion group. Since this surplus anion group is a hydrophilic group, it serves to solubilize the complex in water. In order to solubilize the complex in an organic solvent, it is necessary to exert some action on an anionic group as a hydrophilic group to lower its hydrophilicity. The oxirane group and / or oxetane group-containing organic compound contributes to lowering the hydrophilicity.

  The conductive polymer having a polyanion that can be used in the present application as a dopant is formed from fine particles having a particle size of approximately several tens of nanometers. Such fine particles are transparent in the visible light region due to the presence of a polyanion that also acts as a surfactant, and the fine particles appear to be dissolved in the solvent. Actually, the fine particles are dispersed in a solvent. In the present application, this state is referred to as a “dispersion-soluble” state. The solvent in this case is a solvent mainly composed of an organic solvent. Here, “mainly organic solvent” means that the organic solvent in the solvent exceeds 50%. In particular, the solvent is preferably in the range of organic solvent: water = 90: 10 to 100: 0 by weight ratio. Hereinafter, a π-conjugated conductive polymer that is a preferable conductive polymer will be described.

π-Conjugated Conductive Polymer As the π-conjugated conductive polymer, any organic polymer having a main chain composed of a π-conjugated system can be used without any limitation. For example, polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers of two or more thereof can be preferably exemplified. In view of ease of polymerization and stability in air, polypyrroles, polythiophenes or polyanilines can be particularly preferably used. 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 carboxy 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.

(3) Polyanion Next, the polyanion that forms a complex with the π-conjugated conductive polymer will be described.

  The polyanion can be used without particular limitation as long as it is an anionic compound. An anionic compound is a compound having an anionic group capable of causing chemical oxidation doping to a π-conjugated conductive polymer in the molecule. As the anionic group, a phosphate group, a carboxy group, a sulfo group, and the like are preferable from the viewpoint of ease of production and high stability. Of these anionic groups, a sulfo group or a carboxy group is more preferred 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 the polymer by sulfonating a polymer having no anion group with a sulfonating agent. Can be mentioned. 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 that forms 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 a polyanion, those selected from each of those groups can be used. From the viewpoint of chemical stability, conductivity, storage stability, availability, and the like, A combination of poly (3,4-ethylenedioxythiophene), which is an example of a conjugated conductive polymer, and polystyrene sulfonic acid, which is an example of a polyanion, 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. A commercially available aqueous dispersion of a conductive polymer / dopant complex may also be used.

  The content of the polyanion is preferably in the range of 50 to 500% by mass, more preferably in the range of 100 to 300% by mass with respect to 100% by mass of the π-conjugated conductive polymer. By setting the polyanion content to 50% by mass 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 500% by mass or less, the content ratio of the π-conjugated conductive polymer can be relatively increased, and higher conductivity can be exhibited.

(4) Oxirane Group and / or Oxetane Group-Containing Organic Compound Next, the oxirane group and / or oxetane group-containing organic compound that can be suitably contained in the conductive polymer composition will be described.

  The oxirane group and / or oxetane group-containing organic compound is preferably coordinated or bonded to the anion group or electron withdrawing group of the polyanion. In addition, 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 suitable total mass of the oxirane group and / or oxetane group-containing organic compound is in the range of 50 to 200% with respect to 100% of the total mass of the π-conjugated conductive polymer and the polyanion.

  The oxirane group and / or oxetane group-containing organic compound may be a compound having any molecular structure as long as it has an oxirane group or oxetane group in the molecule. However, a compound having a large number of carbons is effective for solubilization in an organic solvent having a low polarity. In particular, those having 10 or more carbon atoms are preferable for solubilization in organic solvents having low polarity. In addition, when water is frequently used during the production process, it is preferable to avoid using a compound containing an alkoxysilyl group having a functional group that reacts with hydrolysis or water as much as possible. On the other hand, in the case of a production method via lyophilization, an alkoxysilyl group-containing compound may also be used because it is dispersed or soluble in a solvent while maintaining its characteristics.

  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, 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.

(5) Silane Compound In the silane compound represented by the above chemical formula (1) and further the chemical formula (2), R ¹ , R ² and R ³ are hydrogen or any other group. Examples of the optional group include alkyl groups such as methyl group, ethyl group, isopropyl group, vinyl group and allyl group, aryl groups such as phenyl group and naphthyl group, benzyl group, acyl group, epoxy group and mercapto group. Can be mentioned. Specific silane compounds include triacetoxymethylsilane, triacetoxyethylsilane, dimethyldiacetoxysilane, diethyldiacetoxysilane, methyltriisopropenoxysilane, vinyltriacetoxysilane, tetraacetoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, methylvinylacetoxysilane, ethylvinylacetoxysilane, butylvinylacetoxysilane, di-tert-butoxydiacetoxysilane, 3-methacryloxypropyltriacetoxysilane, allyltrimethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropi Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-phenylamino Propyltrimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxysilane, diisobutyl Dimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane Cyclohexylmethyl dimethoxysilane, n- octyltriethoxysilane, n- decyl trimethoxysilane, and the like phenyltrimethoxysilane.

In particular, since conductivity can be further increased, it is preferable that at least one of R ¹ and R ^{2 in} the chemical formula (1) is an acyl group. From the viewpoint of availability, triacetoxymethylsilane, triacetoxyethylsilane, or vinyltriacetoxysilane is more preferable as the silane compound. The blending amount of the silane compound is 50% by mass to 300% by mass with respect to 100% by mass of the total amount of the π-conjugated conductive polymer and the polyanion in consideration of the balance between adhesion, curability, and peeling force increase. preferable.

(6) Others In addition to the components (1) to (5) described above, the conductive polymer composition according to this embodiment can also include, for example, the following components.

(6.1) Organic solvent The organic solvent is a component that can be contained in the conductive polymer composition according to this embodiment. Examples of the organic solvent used as a solvent for solubilizing or dispersing the conductive polymer composition include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylenephosphonium tri Polar solvents represented by amide, acetonitrile, benzonitrile, etc .; phenols represented by cresol, phenol, xylenol, etc .; alcohols represented by methanol, ethanol, propanol, butanol, etc .; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones typified by; esters represented by ethyl acetate, propyl acetate, butyl acetate, etc .; hydrocarbons typified by hexane, heptane, benzene, toluene, xylene, etc .; carbo typified by formic acid, acetic acid, etc. Acids; carbonate compounds typified by ethylene carbonate, propylene carbonate, etc .; ether compounds typified by dioxane, diethyl ether, etc .; typified by ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc. Preferred examples include heterocyclic ethers represented by 3-methyl-2-oxazolidinone, etc .; nitrile compounds represented by acetonitrile, glutarodinitrile, 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. When a conductive polymer composition is used to form a coating film, the conductive polymer composition is dispersed and solubilized in an organic solvent to produce a paint, which is applied to a substrate and then a part of the organic solvent or Remove everything. Accordingly, an organic solvent having a low boiling point is preferably selected. Thereby, the drying time at the time of coating film formation can be shortened, and the productivity of a coating film can be improved.

(6.2) Conductivity improver From the following compounds (6.2.1) to (6.2.7) in order to further improve the conductivity of the coating film during the production of the conductive polymer composition. It is preferable to add one or more selected conductivity improvers.
(6.2.1) Nitrogen-containing aromatic cyclic compound (6.2.2) Compound having two or more hydroxy groups (6.2.3) Compound having two or more carboxy groups (6. 2.4) A compound having one or more hydroxy groups and one or more carboxy groups (6.2.5) A compound having amide groups (6.2.6) A compound having imide groups (6.2.7) ) Lactam compounds

(6.2.1) Nitrogen-containing aromatic cyclic compound The nitrogen-containing aromatic cyclic compound preferably contains pyridines containing one nitrogen atom and derivatives thereof, and two nitrogen atoms. Examples include imidazoles and derivatives thereof, pyrimidines and derivatives thereof, pyrazines and derivatives thereof, triazines containing three nitrogen atoms, and derivatives thereof. From the viewpoint of solvent solubility and the like, pyridines and derivatives thereof, imidazoles and derivatives thereof, and pyrimidines and derivatives thereof are preferable.

  Specific examples of pyridines and derivatives thereof include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, N-vinylpyridine, 2,4-dimethylpyridine, 2,4 , 6-trimethylpyridine, 3-cyano-5-methylpyridine, 2-pyridinecarboxylic acid, 6-methyl-2-pyridinecarboxylic acid, 4-pyridinecarboxaldehyde, 4-aminopyridine, 2,3-diaminopyridine, 2 , 6-diaminopyridine, 2,6-diamino-4-methylpyridine, 4-hydroxypyridine, 4-pyridinemethanol, 2,6-dihydroxypyridine, 2,6-pyridinedimethanol, methyl 6-hydroxynicotinate, 2 -Hydroxy-5-pyridinemethanol, ethyl 6-hydroxynicotinate, 4- Pyridinemethanol, 4-pyridineethanol, 2-phenylpyridine, 3-methylquinoline, 3-ethylquinoline, quinolinol, 2,3-cyclopentenopyridine, 2,3-cyclohexanopyridine, 1,2-di (4- Pyridyl) ethane, 1,2-di (4-pyridyl) propane, 2-pyridinecarboxaldehyde, 2-pyridinecarboxylic acid, 2-pyridinecarbonitrile, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, Examples include 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, and 3-pyridinesulfonic acid.

  Specific examples of imidazoles and derivatives thereof include imidazole, 2-methylimidazole, 2-propylimidazole, 2-undecylimidazole, 2-phenylimidazole, N-methylimidazole, N-vinylimidazole, and N-allylimidazole. 1- (2-hydroxyethyl) imidazole (N-hydroxyethylimidazole), 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 4,5-imidazole dical Acid, dimethyl 4,5-imidazole dicarboxylate, benzimidazole, 2-aminobenzimidazole, 2-aminobenzimidazole-2-sulfonic acid, 2-amino-1-methylbenzimidazole, 2-hydroxybens Examples include imidazole and 2- (2-pyridyl) benzimidazole.

  Specific examples of pyrimidines and derivatives thereof include 2-amino-4-chloro-6-methylpyrimidine, 2-amino-6-chloro-4-methoxypyrimidine, 2-amino-4,6-dichloropyrimidine, 2-amino-4,6-dihydroxypyrimidine, 2-amino-4,6-dimethylpyrimidine, 2-amino-4,6-dimethoxypyrimidine, 2-aminopyrimidine, 2-amino-4-methylpyrimidine, 4,6 -Dihydroxypyrimidine, 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,4,6-triaminopyrimidine, 2,4-dimethoxypyrimidine, 2,4,5-trihydroxypyrimidine, 2,4-pyrimidinediol, etc. Is mentioned.

  Specific examples of pyrazines and derivatives thereof include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5-methylpyrazinecarboxylic acid, pyrazineamide, 5 -Methylpyrazine amide, 2-cyanopyrazine, aminopyrazine, 3-aminopyrazine-2-carboxylic acid, 2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, 2,3-diethylpyrazine and the like.

  Specific examples of triazines and derivatives thereof include 1,3,5-triazine, 2-amino-1,3,5-triazine, 3-amino-1,2,4-triazine, and 2,4-diamino. -6-phenyl-1,3,5-triazine, 2,4,6-triamino-1,3,5-triazine, 2,4,6-tris (trifluoromethyl) -1,3,5-triazine, 2,4,6-tri-2-pyridine-1,3,5-triazine, 3- (2-pyridine) -5,6-bis (4-phenylsulfonic acid) -1,2,4-triazine disodium 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine, 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine-ρ, ρ′- Disodium disulphonate, 2-hydroxy-4,6-dichloro And ro-1,3,5-triazine.

(6.2.2) Compound having two or more hydroxy groups Examples of the compound having two or more hydroxy groups include propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, di Glycerin, D-glucose, D-glucitol, isoprene glycol, dimethylolpropionic acid, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentylglycol, trimethylolethane, 1, polyhydric aliphatic alcohols such as trimethylolpropane, pentaerythritol, dipentaerythritol, thiodiethanol, glucose, tartaric acid, D-glucaric acid and glutaconic acid; polymeric alcohols such as cellulose, polysaccharide and sugar alcohol; Dihydroxy , 1,3-dihydroxybenzene, 2,3-dihydroxy-1-pentadecylbenzene, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,4-dihydroxybenzophenone, 2,6-dihydroxybenzophenone, 3, , 4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 2,4′-dihydroxydiphenylsulfone, 2,2 ′, 5,5′-tetrahydroxydiphenylsulfone, 3,3 ′, 5,5′-tetramethyl- 4,4′-dihydroxydiphenylsulfone, hydroxyquinonecarboxylic acid and salts thereof, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3 , 5-Dihydroxybenzoic acid 1,4-hydroquinonesulfonic acid and its salts, 4,5-hydroxybenzene-1,3-disulfonic acid and its salts, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2 , 7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene-2,6-dicarboxylic acid, 1,6-dihydroxynaphthalene-2,5-dicarboxylic acid, 1,5-dihydroxynaphthoic acid, 1 , 4-Dihydroxy-2-naphthoic acid phenyl ester, 4,5-dihydroxynaphthalene-2,7-disulfonic acid and its salts, 1,8-dihydroxy-3,6-naphthalenedisulfonic acid and its salts, 6,7- Dihydroxy-2-naphthalenesulfonic acid and its salts, 1, 2,3-trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene, 5-methyl-1,2,3-trihydroxybenzene, 5-ethyl-1,2,3-trihydroxybenzene, 5 -Propyl-1,2,3-trihydroxybenzene, trihydroxybenzoic acid, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzaldehyde, trihydroxyanthraquinone, 2,4,6-trihydroxybenzene, tetrahydroxy-p- Examples include benzoquinone, tetrahydroxyanthraquinone, aromatic compounds such as methyl garlic acid (methyl gallate) and ethyl garlic acid (ethyl gallate), and potassium hydroquinone sulfonate.

(6.2.3) Compound having two or more carboxy groups As a compound having two or more carboxy groups, maleic acid, fumaric acid, itaconic acid, citraconic acid, malonic acid, 1,4-butanedicarboxylic acid Aliphatic carboxylic acid compounds such as succinic acid, tartaric acid, adipic acid, D-glucaric acid, glutaconic acid, citric acid; phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride, 5-sulfoisophthalic acid, 5-hydroxy Aromatic properties such as isophthalic acid, methyltetrahydrophthalic anhydride, 4,4'-oxydiphthalic acid, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid Aromatic carboxylic acid having at least one carboxy group bonded to the ring Compounds; diglycolic acid, oxy two acid, thiodiacetic acid (thiodiacetic acid), thiodiacetic acid, iminodiacetic acid, etc. imino acid are exemplified.

(6.2.4) Compound having one or more hydroxy groups and one or more carboxy groups Examples of the compound having one or more hydroxy groups and one or more carboxy groups include tartaric acid, glyceric acid, and dimethylolbutane. Examples include acid, dimethylolpropanoic acid, D-glucaric acid, and glutaconic acid.

(6.2.5) Amide Compound A compound having an amide group is a monomolecular compound having an amide bond represented by —CO—NH— (the CO moiety is a double bond) in the molecule. That is, as the amide compound, for example, a compound having functional groups at both ends of the bond, a compound in which a cyclic compound is bonded to one end of the bond, urea and a urea derivative in which the functional groups at both ends are hydrogen Etc. Specific examples of amide compounds include acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-fluamide, formamide, N-methylformamide, propionamide , Propioluamide, butyramide, isobutylamide, methacrylamide, palmitoamide, stearylamide, oleamide, oxamide, glutaramide, adipamide, cinnamamide, glycolamide, lactamide, glyceramide, tartaramide, citrulamide, glyoxylamide, pyruvamide, acetoacetamide, dimethyl Acetamide, benzylamide, anthranilamide, ethylenediamine Laacetamide, diacetamide, triacetamide, dibenzamide, tribenzamide, rhodanine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea, 1,3-dimethylurea, 1,3-diethylurea and These derivatives are mentioned.

  Moreover, acrylamide can also be used as an amide compound. As acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, Examples thereof include N-diethyl methacrylamide, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like. The molecular weight of the amide compound is preferably 46 to 10,000, more preferably 46 to 5,000, and particularly preferably 46 to 1,000.

(6.2.6) Imide compound Examples of the imide compound include phthalimide and phthalimide derivatives, succinimide and succinimide derivatives, benzimide and benzimide derivatives, maleimide and maleimide derivatives, naphthalimide and naphthalimide derivatives based on the skeleton.

Moreover, although an imide compound is classified into an aliphatic imide, an aromatic imide, etc. according to the kind of functional group of both terminal, an aliphatic imide is preferable from a soluble viewpoint. Furthermore, the aliphatic imide compound is classified into a saturated aliphatic imide compound having an unsaturated bond between carbons in the molecule and an unsaturated aliphatic imide compound having an unsaturated bond between carbons in the molecule. The saturated aliphatic imide compound is a compound represented by R ¹⁰ —CO—NH—CO—R ¹¹ , and is a compound in which both R ¹⁰ and R ¹¹ are saturated hydrocarbons. Specifically, cyclohexane-1,2-dicarboximide, allantoin, hydantoin, barbituric acid, alloxan, glutarimide, succinimide, 5-butylhydantoic acid, 5,5-dimethylhydantoin, 1-methylhydantoin, 1,5 , 5-trimethylhydantoin, 5-hydantoin acetic acid, N-hydroxy-5-norbornene-2,3-dicarboximide, semicarbazide, α, α-dimethyl-6-methylsuccinimide, bis [2- (succinimidooxycarbonyloxy) Ethyl] sulfone, α-methyl-α-propylsuccinimide, cyclohexylimide and the like. The unsaturated aliphatic imide compound is a compound represented by R ¹⁰ —CO—NH—CO—R ¹¹ , and one or both of R ¹⁰ and R ¹¹ are one or more unsaturated bonds. Specific examples thereof include 1,3-dipropylene urea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, 1,8 -Bismaleimide octane, N-carboxyheptylmaleimide and the like.

  The molecular weight of the imide compound is preferably 60 to 5,000, more preferably 70 to 1,000, and particularly preferably 80 to 500.

(6.2.7) Lactam Compound A lactam compound is an intramolecular cyclic amide of an aminocarboxylic acid, and a part of the ring is —CO—NR ¹² — (R ¹² is hydrogen or an arbitrary substituent). It is. However, one or more carbon atoms in the ring may be replaced with an unsaturated or heteroatom. Examples of the lactam compound include pentano-4-lactam, 4-pentanelactam-5-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidinone, hexano-6-lactam, 6-hexane lactam and the like.

  The content of the conductivity improver is preferably 10 to 10,000% by mass and more preferably 30 to 5000% by mass with respect to 100% by mass of the total amount of the π-conjugated conductive polymer and the polyanion. When the content of the conductivity improver is not less than the lower limit and not more than the upper limit, the antistatic property can be further improved.

1.2 Manufacturing Method The conductive polymer composition according to this embodiment includes a curable organopolysiloxane composition, a conductive polymer, and a silane compound represented by the chemical formula (1) or the chemical formula (2). Can be mixed. In the production, it is preferable to previously mix an organic solvent with at least one of the curable organopolysiloxane composition and the silane compound.

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

  The conductive polymer is prepared by adding an oxirane group or oxetane group-containing compound together with a solvent to the aqueous dispersion, preferably reacting an anion with an oxirane group or oxetane group, and then concentrating, filtering, or separating the reaction solution. Obtained by drying. Thereafter, the obtained concentrate or solid is preferably placed in a solvent mainly composed of a curable organopolysiloxane composition and an organic solvent containing a silane compound represented by chemical formula (1) or chemical formula (2). Dissolve or disperse and use in the form of paint. Further, after adding the oxirane group or oxetane group-containing compound together with the solvent to the aqueous dispersion, preferably adding an organic solvent insoluble in water during or after the reaction between the anion and the oxirane group or oxetane group. The curable organopolysiloxane composition and the silane represented by the chemical formula (1) or the chemical formula (2) are obtained by phase-transferring the conductive polymer to a water-insoluble solvent phase and, if necessary, passing through steps such as dehydration. The conductive polymer may be dissolved or dispersed in a solvent mainly composed of an organic solvent containing a compound.

(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 an appropriate amount of a solvent capable of dissolving the oxirane group or oxetane group-containing compound is added, preferably the anion is reacted with the oxirane group or oxetane group. Thereafter, the reaction solution is concentrated, filtered or dried. Thereafter, the obtained concentrate or solid is preferably placed in a solvent mainly composed of a curable organopolysiloxane composition and an organic solvent containing a silane compound represented by chemical formula (1) or chemical formula (2). Dissolve or disperse and use in the form of paint. In the above production, after reacting an anion with an oxirane group or oxetane group, an insoluble organic solvent is added to the water, and the conductive polymer is phase-inverted to the water-insoluble solvent phase, and dehydration is performed as necessary. The conductive polymer is soluble in a solvent mainly composed of a curable organopolysiloxane composition and an organic solvent containing a silane compound represented by the chemical formula (1) or the chemical formula (2). Alternatively, it may be dispersed. In the method (2), since the freeze-dried conductive composition is used as a raw material, the time for the concentration step can be shortened.

<Embodiment of B release film>
The release film according to the embodiment of the present invention is obtained by applying the above-described conductive polymer composition onto a substrate and curing it. The release film is a laminate of a coating film formed of a conductive polymer composition and a substrate. A third layer may be interposed between the coating film and the substrate. If the conductive polymer composition is solid, dissolve or disperse it in a solvent mainly composed of an organic solvent, and prepare a paint for preparing a release film, including a curable organopolysiloxane composition. To do. Further, when the conductive polymer composition is already a solution in a state of being soluble or dispersed in a solvent mainly composed of an organic solvent, it is diluted as it is or with an organic solvent, and a curable organopolysiloxane composition is added thereto. Prepare paints for producing release films including products. The paint is supplied on a substrate represented by paper, plastic, iron, ceramics, and glass. Examples of the supply method include various methods such as a coating method using a brush or a bar coater, a dipping method in which the substrate is immersed in the paint, and a spin coating method in which the paint is dropped on the substrate to rotate the substrate to spread the paint. it can. Examples of the method for curing the paint on the substrate include a method for removing the organic solvent by heating and a method for curing by irradiating light such as ultraviolet rays or an electron beam.

  The decrease in adhesion when the conductive polymer is mixed with the curable organopolysiloxane composition is because the silicone component and the conductive polymer that does not contribute to the reaction are present, thereby inhibiting the curing of the silicone component. If the bonding force between the silicone component and the conductive polymer is weak, it will adversely affect the decrease in the strength of the silicone film and the adhesion between the silicone and the substrate during coating formation. In the conductive polymer composition according to the present embodiment, the silane compound is reacted and bonded between the curable organopolysiloxane composition and the conductive polymer, so that the curable organopolysiloxane composition-conductive It is considered that the strength between the adhesive polymers is improved, and as a result, the adhesion is improved. In particular, when the conductive polymer contains a polyanion and an organic compound containing an oxirane group and / or an oxetane group, these compounds and the silane compound are likely to react with each other, so the effect is considered to be even more remarkable. . Further, the silane compound is preferably a silane compound having an acetoxy group, and acetic acid generated from the silane compound at the time of reaction makes the conductive polymer highly conductive, whereby the conductivity can be further improved.

  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 a HPLC (high performance liquid chromatography) system using a GPC (gel filtration chromatography) column and pullulan manufactured by Showa Denko KK as a standard substance, the molecular weight Was 300,000.

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

(Production Example 3)
100 g of methanol and 25 g of C12 and C13 mixed higher alcohol glycidyl ether (Kyoeisha Chemical Epolite 1230) were mixed. Next, 100 g of the aqueous solution of PEDOT-PSS obtained in Production Example 2 was added to the mixed solution, 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 a methyl ethyl ketone solution in which about 0.5% by mass of PEDOT-PSS was dispersed.

<Example>
Example 1
8.9955 g of the solution produced in Production Example 3, 0.0045 g of triacetoxymethylsilane, 58.5 g of methyl ethyl ketone, 21 g of toluene, and KS-3703T (addition-curable silicone: manufactured by Shin-Etsu Chemical Co., Ltd.) 1.5 g And CAT-PL-50T (platinum catalyst: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.03 g were mixed to prepare a solution.
(Example 2)
A solution was produced under the same conditions as in Example 1 except that the solution produced in Production Example 3 was changed to 8.991 g and triacetoxymethylsilane was changed to 0.009 g.
(Example 3)
A solution was produced under the same conditions as in Example 1 except that the solution produced in Production Example 3 was changed to 8.9775 g and triacetoxymethylsilane was changed to 0.0225 g.
Example 4
A solution was produced under the same conditions as in Example 1 except that the solution produced in Production Example 3 was changed to 8.9775 g and triacetoxymethylsilane was changed to 0.045 g.
(Example 5)
A solution was produced under the same conditions as in Example 1 except that the solution produced in Production Example 3 was changed to 8.91 g and triacetoxymethylsilane was changed to 0.09 g.
(Example 6)
A solution was produced under the same conditions as in Example 1 except that the solution produced in Production Example 3 was changed to 8.865 g and triacetoxymethylsilane was changed to 0.135 g.
(Example 7)
A solution was produced under the same conditions as in Example 1 except that the solution produced in Production Example 3 was changed to 8.865 g, and 0.045 g of methyltriisopropenoxysilane was used instead of triacetoxymethylsilane.
(Example 8)
A solution was prepared under the same conditions as in Example 1, except that the solution produced in Production Example 3 was changed to 8.865 g and 0.045 g of vinyltriacetoxysilane was used instead of triacetoxymethylsilane.
Example 9
A solution was prepared under the same conditions as in Example 8, except that the solution produced in Production Example 3 was changed to 8.865 g and vinyltriacetoxysilane was changed to 0.045 g of 3-glycidoxypropyltrimethoxysilane.

<Comparative example>
(Comparative Example 1)
9 g of the solution produced in Production Example 3, 58.5 g of methyl ethyl ketone, 21 g of toluene, KS-3703T (addition curable silicone: manufactured by Shin-Etsu Chemical Co., Ltd.), and CAT-PL-50T (platinum catalyst: Shin-Etsu Chemical Co., Ltd.) To make a solution.

  Table 1 shows the composition of the solutions prepared under the conditions of the examples and comparative examples. The unit of the numerical value of each component in Table 1 is gram.

<Production and evaluation method of release film>
The various solutions shown in Table 1 were applied to an untreated film with a # 8 bar coater (solution coating amount: 18.32 μm) and dried at 150 ° C. for 1 minute. The curability was evaluated as “X” when cloudy by rubbing with a finger 10 times, “Δ” when cloudy, and “◯” when cloudy. The peeling force was measured by placing the prepared film in a bag for 20 hours and storing it in a 25 mm wide Nitto No. 31B (manufactured by Nitto Denko Corporation) was bonded and allowed to stand for 20 hours, and then measured with a tensile tester Autograph AGS-X (manufactured by Shimadzu Corporation) at a tensile speed of 300 mm / min. Adhesiveness was evaluated by leaving it in a bag for 20 hours after coating, rubbing it 10 times with a load of 50 gf / cm ² applied with gauze, and measuring the peeling force. At that time, the rub-off value was calculated from the following equation as the increase value of the peeling force.

(Formula): Love-off value = peeling force when rubbing at 50 gf / cm ² ÷ peeling force at a non-rubbed part

<Result>
Table 2 shows the evaluation results.

  When the conductive polymer of Comparative Example 1 is added to the solution, as is apparent from the numerical value of the rub-off value, the adhesion and curability are greatly reduced. However, as is clear from the results of the respective examples, it was found that adhesion and curability were improved by adding triacetoxymethylsilane or vinylacetoxysilane. In addition, it was found that when triacetoxymethylsilane or vinylacetoxysilane was added, the surface resistance value decreased and a film with excellent performance could be produced.

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

Claims (9)

A curable organopolysiloxane composition;
A conductive polymer;
A polyanion,
A silane compound represented by the following chemical formula (1);
A conductive polymer composition comprising:
(In the chemical formula (1), R ¹ and R ² may be the same or different, and each may contain a substituent. N: a positive integer of 1 to 4. n = 2. In the case of ˜4, the plurality of R ¹ may be the same or different, and in the case of n = 1 or 2, the plurality of R ² may be the same or different.) The conductive polymer composition according to claim 1, wherein the silane compound is a compound represented by the following chemical formula (2).
(In the chemical formula (2), R ² and R ³ may be the same or different, and each may contain a substituent. N: a positive integer of 1 to 4. n = 2. In the case of ˜4, the plurality of R ³ may be the same or different, and in the case of n = 1 or 2, the plurality of R ² may be the same or different.) The silane compound is a compound in which at least one of R ¹ , R ² and R ^{3 is} a hydrocarbon group or an alkoxy group which may contain a substituent, hydrogen or a mercapto group. The conductive polymer composition described in 1. The conductive polymer is a π-conjugated conductive polymer,
Furthermore, the electroconductive polymer composition of any one of Claims 1-3 containing an oxirane group and / or oxetane group containing organic compound.   The conductive polymer composition according to claim 4, comprising a reaction product of the polyanion and the organic compound containing the oxirane group and / or oxetane group. The π-conjugated conductive polymer is polyethylene dioxythiophene,
The conductive polymer composition according to claim 4 or 5, wherein the polyanion is polystyrene sulfonic acid.   The conductive polymer according to any one of Claims 1 to 6, wherein the silane compound is one or more selected from triacetoxymethylsilane, triacetoxyethylsilane, and vinyltriacetoxysilane. Composition.   The conductive polymer composition according to any one of claims 1 to 7, wherein the curable organopolysiloxane composition is an addition reaction type silicone composition.   A release film obtained by coating the conductive polymer composition according to any one of claims 1 to 8 on a substrate and curing it.