JP2019131773A - Curable composition and antistatic silicone coating - Google Patents

Abstract

The present invention provides a curable composition capable of forming a silicone film having excellent antistatic properties and peelability.
The conductive polymer includes a conductive polymer and a curable organopolysiloxane, the conductive polymer having an aliphatic carbon-carbon double bond, and the aliphatic carbon-carbon double bond. A curable composition, wherein a polysiloxane having a SiH group is added to at least a part thereof.
[Selection figure] None

Description

  The present invention relates to a curable composition and an antistatic silicone film obtained by curing the curable composition.

As a method for imparting peelability to the surface of a substrate such as a plastic film or paper, a method of forming a release layer made of a silicone film is widely used. The release layer may require antistatic performance.
Among known antistatic agents, π-conjugated conductive polymers are preferable in that they do not have conductivity humidity dependency or bleed out. A π-conjugated conductive polymer is an insoluble and infusible substance. Generally, a polyanion is used as a dopant and a surfactant, and a complex containing a π-conjugated conductive polymer and a polyanion is dispersed in water. Used in state.

Since silicone has low hydrophilicity, it is difficult to solubilize with an aqueous dispersion of a complex of a π-conjugated conductive polymer and a polyanion. Therefore, a method using a non-aqueous conductive polymer dispersion instead of an aqueous dispersion has been proposed.
As a method for preparing a non-aqueous conductive polymer dispersion, for example, Patent Document 1 described below describes an organic solvent solution of polyaniline and a method for producing the same. Patent Documents 2 to 5 below describe solvent replacement methods by phase inversion from an aqueous solution containing a polyanion and a conductive polymer to an organic solvent. Patent Document 6 below also discloses a method of dissolving a lyophilized conductive polymer in an organic solvent.
With respect to the aqueous dispersion, Patent Documents 7 and 8 below propose techniques for mixing a conductive polymer into a silicone emulsion in the form of an emulsion. Since the composition obtained by this technique is an aqueous dispersion, it has limitations in practicality and has drawbacks such as corrosion of equipment due to water and insufficient adhesion.

International Publication No. 2005/052058 JP 2006-249303 A JP 2007-254730 A JP 2008-050661 A JP 2008-045116 A JP 2011-032382 A JP 2002-241613 A JP 2003-251756 A

However, what was obtained by mixing a silicone-based release agent (silicone solution) with the organic solvent solution described in Patent Document 1 is solubilized depending on the choice of the solvent. The system conductive polymer and the polyanion complex are separated, and the desired antistatic property and peelability cannot be obtained.
When the silicone release agent is simply mixed in the organic solvent dispersion described in Patent Documents 2 to 6, the silicone release agent and the complex of π-conjugated conductive polymer and polyanion are not soluble, It was difficult to obtain desired antistatic properties and peelability.
Moreover, since the method of patent documents 2-6 is a method using an amine compound, when a conductive polymer is mixed with addition curable silicone, the hardening inhibition by amine arises and the hardening of silicone is inadequate. There are also disadvantages. On the other hand, when a conductive polymer is mixed with the condensation curable silicone, there is a drawback that a phenomenon such as participation in condensation of silanol or alkoxysilyl group by an amine occurs and storage characteristics are deteriorated.

  An object of this invention is to provide the curable composition which can form the silicone film excellent in antistatic property and peelability, and the antistatic silicone film excellent in antistatic property and peelability.

The present invention has the following aspects.
[1] A conductive polymer and a curable organopolysiloxane,
The conductive polymer has an aliphatic carbon-carbon double bond, and a polysiloxane having a SiH group is added to at least a part of the aliphatic carbon-carbon double bond. A curable composition.
[2] The curable composition according to [1], wherein the curable organopolysiloxane is an addition-curable organopolysiloxane.
[3] The curable composition according to [1], wherein the curable organopolysiloxane is a condensation curable organopolysiloxane.
[4] The curable composition according to [1], wherein the curable organopolysiloxane is an ionizing radiation curable organopolysiloxane.
[5] The conductive polymer is a complex of a π-conjugated conductive polymer (a) and a solubilized polymer (b), and the solubilized polymer (b) includes an anion group and an electron withdrawing group. [1] to [1] to [3] having at least one of the above and an aliphatic carbon-carbon double bond, and a polysiloxane having a SiH group added to at least a part of the aliphatic carbon-carbon double bond. 4] The curable composition according to any of the above.
[6] The π-conjugated conductive polymer (a) is selected from the group consisting of polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, and polythiophene vinylenes. The curable composition according to [5], which is a polymer having at least a seed as a constituent unit.
[7] The curable composition according to [6], wherein the π-conjugated conductive polymer (a) is poly (3,4-ethylenedioxythiophene) or polypyrrole.
[8] The above-mentioned solubilized polymer (b) has an anion group, and the anion group is one or more selected from a sulfo group, a phosphate group, and a carboxy group. Any curable composition.
[9] The solubilized polymer (b) is selected from the group consisting of styrene sulfonic acid, vinyl sulfonic acid, acrylic acid alkylene sulfonic acid, and 2-acrylamido-2-methyl-1-propanesulfonic acid The curable composition according to any one of [5] to [8], having a monomer unit based on the above.
[10] The curable composition according to any one of [1] to [9], comprising one or more selected from the group consisting of allyl group-containing isocyanurates and derivatives thereof.
[11] The curable composition according to any one of [1] to [10], comprising an organic solvent (c).
[12] An antistatic silicone film comprising a cured product of the curable composition according to any one of [1] to [11].

The curable composition of the present invention can form a silicone film excellent in antistatic properties and releasability.
The antistatic silicone film of the present invention is excellent in antistatic properties and peelability.

≪Curable composition≫
The curable composition which concerns on embodiment of this invention contains a conductive polymer and curable organopolysiloxane. Moreover, the hardening component (a crosslinking agent, a catalyst, etc.) which contributes to hardening reaction other than curable organopolysiloxane is contained as needed.
The curable composition may be solid or liquid. When the curable composition is a liquid, it is preferable that the solid content in the curable composition is sufficiently dissolved or dispersed.
In this specification, solid content means the component (non-volatile component) except a solvent.
When the curable composition is a liquid, the curable composition preferably contains an organic solvent (c).
The curable composition can be produced by mixing a conductive polymer and a curable organopolysiloxane composition containing a curable organopolysiloxane.
The curable composition is preferably produced by mixing the conductive polymer composition (I) containing a conductive polymer and the curable organopolysiloxane composition (II).
The conductive polymer composition (I) may contain an organic solvent (c).
The curable organopolysiloxane composition (II) may contain an organic solvent (c).
The curing component may be contained in the curable organopolysiloxane composition (II), or may be added separately.

[Organic solvent (c)]
The organic solvent (c) preferably contains a water-insoluble organic solvent (c1) as a main component. An organic solvent (c2) other than the water-insoluble organic solvent may be included.
The water-insoluble organic solvent means an organic solvent having a solubility in 100 g of water at 20 ° C. of 2 g or less. The water-insoluble organic solvent is a low polarity organic solvent, and is excellent in solubility of a highly hydrophobic resin such as silicone.
On the other hand, a water-soluble organic solvent means an organic solvent having a solubility in 100 g of water at 20 ° C. of more than 2 g.
When the curable composition contains a medium (solvent or dispersion medium), it is preferable that water is not substantially contained. The content of the water-insoluble organic solvent (c1) is 10 to 100% by mass with respect to the total mass of the remaining medium excluding the solid content (nonvolatile components), and the remainder is the organic solvent (c2). Is preferred.

As the water-insoluble organic solvent (c1), aromatic organic solvents such as benzene, toluene, xylene and ethylbenzene, aliphatic or alicyclic such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and decahydronaphthalene Hydrocarbon-based organic solvents; halogen-based organic solvents such as chloroform, dichloroethane, dichloromethane, trichloroethane, and trichloroethylene are listed. These may be used individually by 1 type and may use 2 or more types together.
The water-insoluble organic solvent (c1) is selected from the group consisting of benzene, toluene, xylene, ethylbenzene, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, decahydronaphthalene, chloroform, dichloroethane, dichloromethane, trichloroethane, and trichloroethylene. It is preferable that it is 1 or more types.

  The organic solvent (c2) is an organic solvent other than the water-insoluble organic solvent. For example, polar such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetonitrile, etc. Solvents; phenols such as cresol, phenol and xylenol; alcohols such as methanol, ethanol, propanol, butanol and ethylene glycol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate, propyl acetate and butyl acetate; ethylene carbonate Carbonate compounds such as propylene carbonate; ether compounds such as dioxane, diethyl ether and tetrahydrofuran; ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol Chain monoalkyl ethers, propylene glycol dialkyl ethers, polyethylene glycol dialkyl ethers, polypropylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates and other chain ethers; and 3-methyl-2-oxazolidinone One or more kinds selected from the group consisting of: a ring compound; a nitrile compound such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile;

<Conductive polymer (I)>
The conductive polymer composition (I) has an aliphatic carbon-carbon double bond, and is obtained by adding a polysiloxane having a SiH group to at least a part of the aliphatic carbon-carbon double bond. Contains functional polymers.
A conductive polymer is a reaction in which a polysiloxane having a SiH group is added to a conductive polymer precursor having a residue (functional group) containing an aliphatic carbon-carbon double bond (hydrosilylation reaction). It can be obtained as a product. The reaction product has a Si—C bond in which Si is added to a carbon atom derived from a carbon-carbon double bond.

[Conductive polymer]
A preferred embodiment of the conductive polymer is a complex of a π-conjugated conductive polymer (a) (hereinafter also referred to as conductive polymer (a)) and a solubilized polymer (b). The polymer (b) has at least one of an anionic group and an electron withdrawing group and has an aliphatic carbon-carbon double bond, and at least a part of the aliphatic carbon-carbon double bond contains a SiH group. It has a Si—C bond to which a polysiloxane having a hydrogen atom is added.
The solubilized polymer (b) has a double bond-containing polymer (b ′) in which an aliphatic carbon-carbon double bond is introduced into the solubilized polymer precursor (b ″), and an SiH group. Obtained as a reaction product with polysiloxane.

In the conductive polymer of this embodiment, a part of the anion group and electron withdrawing group in the solubilized polymer (b) is coordinated to the conductive polymer (a), and the conductive polymer (a) The solubilized polymer (b) forms a complex.
The conductive polymer of this embodiment is produced by reacting a precursor complex (D) containing a double bond-containing polymer (b ′) and a conductive polymer (a) with a polysiloxane having a SiH group. it can.
The composite of the conductive polymer (a) and the solubilized polymer (b) is a fine particle having a particle size of about several tens of nanometers, and the dispersion liquid in which the fine particle is dispersed in the medium is in the visible light region. It appears to be transparent and dissolved in the medium. Therefore, in the present invention, the dispersion liquid and the solution, and the dispersion medium and the solvent are not strictly distinguished.

[Π-Conjugated Conductive Polymer (a)]
The conductive polymer (a) can be used as long as it is an organic polymer whose main chain is composed of a π-conjugated system. For example, a homopolymer or a block copolymer having a structural unit based on one or more selected from the group consisting of polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, and polythiophene vinylenes. A polymer is mentioned. From the viewpoint of easy polymerization and stability in air, polypyrroles, polythiophenes and polyanilines are preferred.
The conductive polymer (a) can obtain sufficient conductivity even if it is not substituted, but may have a substituent. For example, a substituent such as an alkyl group, a carboxy group, a sulfo group, an alkoxy group, a hydroxy group, or a cyano group may be introduced in order to further increase the conductivity.

  Examples of polypyrroles include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), 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-carboxyl Pyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxy) Roll), poly (3-methyl-4-hexyloxy-pyrrole), poly (3-methyl-4-hexyloxy-pyrrole) and the like.

  Examples of polythiophenes include poly (thiophene), poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene) ), Poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), Poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene) ), Poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3- Toxithiophene), 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-diheptyloxythiophene), poly (3,4-dioctyloxy) Thiophene), poly (3,4-didecyloxythiophene), poly (3,4- Dodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butenedioxythiophene), poly (3-methyl-4-methoxy) Thiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly ( 3-methyl-4-carboxybutylthiophene) and the like.

Examples of polyanilines include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid) and the like.
Examples of polyacetylenes include trans-type polyacetylene and cis-type polyacetylene.
Examples of polyphenylenes include polyparaphenylene, polynaphthylene, polycarbazole, polyazulene, polypyrene, and the like.
Examples of polyphenylene vinylenes include polyparaphenylene vinylene and polythienylene vinylene.
These may be used individually by 1 type and may use 2 or more types together.

Among them, one selected from the group consisting of polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene), poly (3-methoxythiophene), and poly (3,4-ethylenedioxythiophene) Homopolymers or block copolymers having structural units based on the above are preferably used from the viewpoints of resistance and reactivity.
Polypyrrole and poly (3,4-ethylenedioxythiophene) are more preferable because they have higher conductivity and improved heat resistance.
Alkyl-substituted compounds such as poly (N-methylpyrrole) and poly (3-methylthiophene) are more preferable because they further improve solvent solubility and compatibility and dispersibility when a hydrophobic resin is added. Among alkyl groups, a methyl group is preferred because it hardly affects the conductivity.

[Solubilized polymer (b)]
The solubilized polymer (b) is a polymer compound that forms a complex with the conductive polymer (a) and improves the conductivity and water dispersibility of the conductive polymer (a). Specifically, it has at least one of an anionic group and an electron withdrawing group, has an aliphatic carbon-carbon double bond, and an SiH group is formed on at least a part of the aliphatic carbon-carbon double bond. It is a polymer compound added with polysiloxane.

[High molecular compound having an anionic group]
A polymer compound having an anion group (hereinafter referred to as “polyanion”) is a polymer compound having a plurality of anion groups in one molecule.
In the present invention, a polymer compound having both an anion group and an electron withdrawing group is included in the polyanion.

The polyanion can be produced by a known method. For example, it can be obtained by a method of polymerizing a monomer having an anionic group or a method of copolymerizing a monomer having an anionic group and a monomer having no anionic group. These monomers can be used alone or in combination of two or more.
It can also be obtained by obtaining a polymer having no anionic group and then sulfonating with a sulfonating agent such as sulfuric acid, fuming sulfuric acid, sulfamic acid and the like. Further, once a polymer having an anion group is obtained, the polyanion having a higher anion group content can be obtained by further sulfonation.

The monomer having an anionic group has a polymerizable functional group and an anionic group.
Examples of the anionic _{^{group, -O-SO 3 - X +}} , -SO 3 - X +, -COO - X +, -O-PO 4 - X +, -PO 4 - X + (X + is a hydrogen in each formula Represents an ion or an alkali metal ion). Among these, from the viewpoint of excellent doping effect of the conductive polymer (a), sulfuric acid ester group _{^{(-O-SO 3 - X +}} ), a sulfo group _(-SO ³ - ^X +), a carboxyl group (-COO ^- X ⁺⁾ are _{^{preferred, -SO 3 - X +, -COO}} - X + are more preferable.
The anionic groups are preferably arranged in the main chain of the polyanion adjacent to each other or at a predetermined interval.
As the monomer having an anion group, a known polyanion monomer doped with a conductive polymer to form a complex can be used.

  Preferable examples of the monomer containing a sulfo group include styrene sulfonic acid, vinyl sulfonic acid, acrylic acid alkylene sulfonic acid, 2-acrylamido-2-methyl-1-propane sulfonic acid and the like. These monomers may be used alone or in combination of two or more, and may be used in the form of a salt neutralized with a base such as ammonia, triethylamine or sodium hydroxide.

  Examples of the monomer containing a phosphoric acid group include 3-chloro-2-acid phosphoxypropyl (meth) acrylate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, and mono (2-hydroxyethyl acrylate). Acid phosphate, mono (2-hydroxyethyl methacrylate) acid phosphate, mono (2-hydroxypropyl acrylate) acid phosphate, mono (2-hydroxypropyl methacrylate) acid phosphate, mono (3-hydroxypropyl acrylate) acid phosphate, mono (3 -Hydroxypropyl methacrylate) acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate Such as over doors and the like. These monomers may be used alone or in combination of two or more, and may be used in the form of a salt neutralized with a base.

  Examples of the monomer containing a carboxy group include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; ethylenically unsaturated polyvalent carboxylic acids such as maleic acid, fumaric acid, and itaconic acid; Examples thereof include acid anhydrides thereof; partially esterified products of ethylenically unsaturated polyvalent carboxylic acids such as methyl maleate and methyl itaconate; and the like. These monomers may be used alone or in combination of two or more, and may be used in the form of a salt neutralized with a base.

  A known compound can be appropriately used as the other monomer that does not contain an anion group and can be copolymerized with a monomer having an anion group. For example, the monomer as described in the paragraph [0038] of international publication 2014/1225827 is mentioned.

Among the polyanions, a homopolymer or a copolymer having a monomer unit based on a monomer containing a sulfo group is preferable.
Specifically, a monomer unit based on at least one selected from the group consisting of styrene sulfonic acid, vinyl sulfonic acid, acrylic acrylate alkylene sulfonic acid, and 2-acrylamido-2-methyl-1-propane sulfonic acid. A homopolymer or copolymer having a monomer unit based on styrene sulfonic acid is more preferable, and a polystyrene sulfonic acid is particularly preferable.

The polyanion may have a substituent. As the substituent, an alkyl group, a hydroxy group, an amino group, a carboxy group, a cyano group, a phenyl group, a phenol group, an ester group, an alkoxyl group and the like are preferable. In view of solubility in a solvent, heat resistance, compatibility with a resin, and the like, an alkyl group, a hydroxy group, a phenol group, and an ester group are more preferable.
Alkyl groups can increase solubility and dispersibility in polar or nonpolar solvents, compatibility and dispersibility in resins, and hydroxy groups form hydrogen bonds with other hydrogen atoms. This makes it easy to increase solubility in organic solvents, compatibility with resins, dispersibility, and adhesion. In addition, the cyano group and the hydroxyphenyl group can increase the compatibility and solubility in the polar resin, and can also increase the heat resistance.
Among the above substituents, an alkyl group, a hydroxy group, an ester group, and a cyano group are preferable.

[Polymer compound having an electron withdrawing group]
The polymer compound having an electron withdrawing group is a homopolymer or copolymer having a monomer unit based on a monomer having an electron withdrawing group. The electron withdrawing group preferably has at least one selected from a cyano group, a nitro group, a formyl group, a carbonyl group, and an acetyl group. In particular, the cyano group is preferable because it has high polarity and can further improve the solvent solubility of the conductive polymer (a). Moreover, it is preferable at the point which can make compatibility and dispersibility with binder resin higher.
Specific examples of the polymer compound having an electron-withdrawing group include polyacrylonitrile, polymethacrylonitrile, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, hydroxy group or amino group. Examples thereof include resins obtained by cyanoethylating a group-containing resin (for example, cyanoethyl cellulose), polyvinyl pyrrolidone, alkylated polyvinyl pyrrolidone, and nitrocellulose.

  The molecular weight of the solubilized polymer (b) is preferably 20,000 to 1,000,000 in the state before the aliphatic carbon-carbon double bond is introduced (solubilized polymer precursor (b ″)). When the amount is not less than the above lower limit value, the effect of solubilizing the conductive polymer (a) can be sufficiently obtained, and when it is not more than the upper limit value, excellent conductivity can be easily obtained.

The total content of anionic groups and electron withdrawing groups in the solubilized polymer (b) is such that the total of anionic groups and electron withdrawing groups in the solubilized polymer precursor (b ″) is the conductive polymer (a ) Monomer unit is preferably in the range of 0.1 to 20 mol, more preferably in the range of 1 to 12 mol. When it is at least the lower limit of the above range, the effect of solubilizing the conductive polymer (a) can be sufficiently obtained. On the other hand, when the content is not more than the upper limit of the above range, the relative content of the conductive polymer (a) can be sufficiently secured, and excellent conductivity can be easily obtained.
Here, the monomer unit of the conductive polymer (a) means a repeating unit that forms a constituent unit of the conductive polymer (a). For example, when the conductive polymer (a) is a polymer composed of structural units based on “poly (3,4-ethylenedioxythiophene)”, 1 mol of the monomer unit of the conductive polymer (a) Is 1 mole of units based on “3,4-ethylenedioxythiophene”.

[Introduction of aliphatic carbon-carbon double bond]
An aliphatic carbon-carbon double bond is introduced into the solubilized polymer (b).
The aliphatic carbon-carbon double bond is preferably at least one selected from the group consisting of a vinyl group, a vinylidene group and a vinylene group from the viewpoint of reactivity with the SiH group.

  For example, copolymerizing a monomer containing an aliphatic carbon-carbon double bond and a monomer having an anionic group, or a monomer having an anionic group and a monomer having an electron withdrawing group Thus, a double bond-containing polymer (b ′) in which an aliphatic carbon-carbon double bond is introduced into the solubilized polymer precursor (b ″) can be obtained.

As a method for introducing an aliphatic carbon-carbon double bond into the solubilized polymer precursor (b ″), an oxirane group is added to the anion group of the solubilized polymer precursor (b ″). And an aliphatic carbon-carbon double bond and at least one of the compounds having an oxetane group and an aliphatic carbon-carbon double bond (hereinafter referred to as an “oxirane group having a double bond (oxetane group)”. ) Is also referred to as a containing compound).
The oxirane group and / or oxetane group is subjected to ring-opening addition to the anion group of the solubilized polymer precursor (b ″).
The oxirane group (oxetane group) -containing compound having a double bond may be a compound having an aliphatic carbon-carbon double bond and an oxirane group or oxetane group in one molecule. Having one oxirane group or oxetane group in one molecule is preferable from the viewpoint of easily reducing aggregation and gelation.
The molecular weight of the oxirane group (oxetane group) -containing compound having a double bond is preferably 50 to 2,000, more preferably 70 to 300, from the viewpoint of excellent dispersibility improvement effect in an organic solvent.

Examples of the oxirane group-containing compound having a double bond include allyl glycidyl ether, glycidyl methacrylate, 1,2-epoxy-1-methyl-4-isopropenylcyclohexane, 1,2-epoxycyclohexene, 1,2-epoxy- 4-vinylcyclohexane, 2,3-epoxy-5-vinylnorbornane, 2,6-dimethyl-2,3-epoxy-7-octene, a compound represented by the following formula (4) (k is an integer of 2 to 12) ) And the like.
Among these, the compound represented by the following formula (4) is preferable. Specific examples include 1,2-epoxy-3-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene and the like.

Examples of the oxetane group-containing compound having a double bond include oxetane-2-ylmethanol allyl ether and oxetane-2-ylmethanol vinyl ether.
The said oxirane group containing compound may be 1 type, and may use 2 or more types together. The said oxetane group containing compound may be 1 type, and may use 2 or more types together. You may use together 1 or more types of the said oxirane group containing compound, and 1 or more types of the said oxetane group containing compound.

The amount used for the reaction is that the total of the oxirane group having a double bond and the oxetane group-containing compound is 1.0 to 200 times by mass with respect to the solubilized polymer precursor (b ″). Is preferable, and 5.0 to 100 times is more preferable.
The total equivalent ratio of the oxirane group and the oxetane group in the added compound is preferably 0.05 to 20 times the equivalent of the anion group in the solubilized polymer precursor (b ″). 0.1 to 10 times is more preferable.
When the amount of use or addition amount of the oxirane group (oxetane group) -containing compound having a double bond is not less than the lower limit of the above range, the effect of improving dispersibility in an organic solvent is excellent, and if it is not more than the upper limit, An oxirane group (oxetane group) -containing compound having a double bond is easily removed.

  Further, when the oxirane group (oxetane group) -containing compound having a double bond is reacted with the solubilized polymer precursor (b ″), the oxirane group and / or oxetane group-containing compound having a long-chain alkyl group is reacted. One or more kinds may be reacted. By further introducing a long-chain alkyl group, the hydrophobicity of the conductive polymer can be further increased, and the affinity with a low-polar organic solvent can be further increased. The long chain alkyl group preferably has 4 to 30 carbon atoms, and more preferably 6 to 18 carbon atoms.

  Examples of the oxirane group-containing compound having a long-chain alkyl group include C12 and C13 mixed higher alcohol glycidyl ethers (mixtures of alcohols having 12 and 13 carbon atoms), 1,2-epoxyoctane, 1,2- Examples thereof include epoxydecane, 2-ethylhexyl glycidyl ether, glycidyl stearate and the like.

The amount of the oxirane group and / or oxetane group-containing compound having a long-chain alkyl group to be reacted with the solubilized polymer precursor (b ″) is based on the mass of the solubilized polymer precursor (b ″). The ratio is preferably 1.0 to 200 times, and more preferably 5.0 to 100 times.
When it is at least the lower limit of the above range, the effect of improving dispersibility in an organic solvent is further improved, and when it is at most the upper limit, the oxirane group-containing compound having an excessive long-chain alkyl group can be easily removed.
The amount of the oxirane group (oxetane group) -containing compound having a double bond and the oxirane group and / or oxetane group-containing compound having a long chain alkyl group is 100 masses of the oxirane group (oxetane group) -containing compound having a double bond. The oxirane group and / or oxetane group-containing compound having a long-chain alkyl group is preferably 1.0 to 10000 parts by mass, more preferably 5.0 to 2000 parts by mass with respect to parts.
When it is at least the lower limit of the above range, the effect of improving the dispersibility of the long-chain alkyl group in an organic solvent is excellent, and when it is at most the upper limit, a double bond that reacts with the polysiloxane having SiH groups can be secured.
In addition, an oxirane group (oxetane group) -containing compound having a double bond and an oxirane group and / or oxetane having a long-chain alkyl group with respect to the equivalent of the anion group in the solubilized polymer precursor (b ″) The total equivalent ratio of the oxirane group and the oxetane group in the group-containing compound is preferably 0.05 to 20 times, and more preferably 0.1 to 10 times.

[Polysiloxane having SiH groups]
In the solubilized polymer (b), at least a part of the aliphatic carbon-carbon double bond forms a Si—C bond by an addition reaction (hydrosilylation reaction) of a polysiloxane having a SiH group.
As the polysiloxane having a SiH group, a compound represented by the following general formula (1) is preferable.

In the general formula (1), R ^{1 to} R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a group represented by the following general formula (2).
In General Formula (2), R ^{11 to} R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ¹⁷ is a hydrogen atom or an optionally substituted carbon number. They are a C1-C20 alkyl group, the C6-C20 aromatic hydrocarbon group which may have a substituent, or the C1-C20 alkoxy group which may have a substituent. p and r are each independently 0 or an integer of 1 or more.
In the general formula (1), R and R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom having 6 to 6 carbon atoms. 20 aromatic hydrocarbon group, or an optionally substituted alkoxy group having 1 to 20 carbon atoms, wherein a silicon atom to which R and R ⁶ are bonded forms -Si-O-Si- A ring represented by the following general formula (3) may be formed. m is an integer of 1 or more, and n is 0 or an integer of 1 or more.

The alkyl group as R or R ⁶ may be linear, branched or cyclic, and is preferably linear. Carbon number is 1-20, and 1-6 are preferable. Examples of the substituent of the alkyl group include an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, a fluorine atom, and a chlorine atom.
The aromatic hydrocarbon group as R or R ⁶ has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Examples of the substituent of the aromatic hydrocarbon group include an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, a fluorine atom, and a chlorine atom.
The alkoxy group as R or R ⁶ may be linear, branched or cyclic, and is preferably linear. Carbon number is 1-20, and 1-6 are preferable. Examples of the substituent of the alkyl group include an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, a fluorine atom, and a chlorine atom.
R is particularly preferably a hydrogen atom, a methyl group or a phenyl group.
R ⁶ is particularly preferably a hydrogen atom, a methyl group, or a phenyl group.

A preferred embodiment of R ^{17 is the same as} the preferred embodiment of R ⁶ . R ^{11 to} R ¹⁶ are each independently preferably a hydrogen atom, a methyl group or a phenyl group.
When only R < ¹² > is a hydrogen atom among R < ¹¹ > -R < ¹⁶ > and p is an integer greater than or equal to 2, several R < ¹¹ > may mutually be same or different.
It may be p = 0 and r = 0. When only R ¹² is a hydrogen atom among R ^{11 to} R ¹⁶ and p is 1 or more, r / (r + p) is preferably 0.01 to 0.95, more preferably 0.05 to 0.80. .

R ^{1 to} R ⁵ are preferably each independently a methyl group or a phenyl group.
When m is an integer of 2 or more, the plurality of R ¹ may be the same as or different from each other.
n / (n + m) is preferably 0.01 to 0.95, and more preferably 0.05 to 0.80.

The molecular weight of the polysiloxane having a SiH group is preferably 200 to 100,000, and more preferably 200 to 10,000. When the molecular weight is at least the lower limit of the above range, the effect of improving the dispersibility of the polysiloxane in the organic solvent is excellent, and when the molecular weight is not more than the upper limit, the viscosity of the conductive polymer composition can be prevented from excessively increasing.
When n is 1 or more, the order of bonding of the unit represented by-(SiHR ¹ )-and the unit represented by-(SiR ² R ³ )-is not limited. When at least one of m or n is 2 or more, it may be a random bond or a block bond.
When n is an integer of 2 or more, the plurality of R ² may be the same as or different from each other, and the plurality of R ³ may be the same as or different from each other.
The amount of the polysiloxane having SiH groups used for the addition reaction is the double bond-containing polymer (b) in which an aliphatic carbon-carbon double bond is introduced into the solubilized polymer precursor (b ″). 0.1-10 mass parts is preferable with respect to 1 mass part of precursor complex (D) containing ') and the conductive polymer (a), and 0.2-5.0 mass parts is more preferable. When the amount of the polysiloxane having a SiH group is not less than the lower limit of the above range, the dispersibility in an organic solvent tends to be good. If it is less than or equal to the upper limit value, residual unreacted polysiloxane tends to decrease.

The conductive polymer composition (I) may contain an organic solvent (c) in addition to the solid content.
The organic solvent (c) in the conductive polymer composition (I) preferably contains a water-insoluble organic solvent (c1). The content of the water-insoluble organic solvent (c1) with respect to the total mass of the organic solvent (c) in the conductive polymer composition (I) is preferably 10 to 100% by mass, and more preferably 20 to 100% by mass. preferable.

<Method for producing conductive polymer composition>
The conductive polymer of this aspect produces a precursor complex (D) containing a conductive polymer (a) and a double bond-containing polymer (b ′), and the precursor complex (D) It can be produced by adding a polysiloxane having SiH groups.
In the precursor complex (D), part of the anion group and electron withdrawing group in the double bond-containing polymer (b ′) is coordinated to the conductive polymer (a).

The precursor complex (D) can be produced by the following method.
Hereinafter, for example, the complex of (a) and (b) is also referred to as “(a)-(b) complex”.
(1) A production method from an aqueous dispersion (or an aqueous solution) in which a conductive polymer (a) -solubilized polymer precursor (b ″) complex is dispersed.
The aqueous dispersion in which the conductive polymer (a) -solubilized polymer precursor (b ″) complex is dispersed contains the monomer (a ′) constituting the conductive polymer (a) It is obtained by polymerizing the monomer (a ′) in the presence of an oxidizing agent in an aqueous solution or aqueous dispersion containing the solubilized polymer precursor (b ″).
A commercially available aqueous dispersion of a conductive polymer (a) -solubilized polymer precursor (b ″) complex may be used. Examples of commercially available products include PEDOT-PSS complex aqueous dispersion (trade name: Clevios) manufactured by Heraeus, PEDOT-PSS composite aqueous dispersion (trade name: Orgacon) manufactured by Agfa.

As a method for obtaining the precursor complex (D), for example, an oxirane group (oxetane group) -containing compound having a double bond is added to the aqueous dispersion together with a solvent, and a solubilized polymer precursor (b ″) is obtained. An anoxirane group and / or an oxetane group having a double bond is subjected to a ring-opening addition reaction with the anion group. At this time, an oxirane group and / or an oxetane group may be further subjected to ring-opening addition to the hydroxy group generated by ring-opening addition.
The reaction solution obtained by the above reaction is concentrated, filtered or dried to obtain a concentrate or a solid precursor complex (D). Thereafter, the obtained concentrate or solid is preferably dissolved or dispersed in the organic solvent (c) to obtain a dispersion of the precursor complex (D).

(2) A method for producing a freeze-dried conductive polymer (a) -solubilized polymer precursor (b ″) complex from a solid.
After adding an appropriate amount of one or both of a solvent in which an oxirane group (oxetane group) -containing compound having a double bond is dissolved, and one or both of water to the solid matter, the anionic group of the solubilized polymer precursor (b ″) An oxirane group and / or oxetane group having a double bond is subjected to a ring-opening addition reaction. By this reaction, a precursor complex (D) is generated.
Thereafter, a dispersion of the precursor composite (D) is obtained in the same manner as in the method (1).

The addition reaction of the polysiloxane having a SiH group to the precursor composite (D) can be performed by a hydrosilylation reaction using a known catalyst such as platinum. The hydrosilylation reaction is preferably performed in a solvent.
By adding polysiloxane having SiH groups in the dispersion of the precursor composite (D), a conductive polymer composition containing a conductive polymer in an organic solvent can be obtained. Furthermore, in order to maintain the dispersibility of the conductive polymer in the organic solvent and to obtain high conductivity, it may be treated with a homogenizer or a high-pressure homogenizer, or another organic solvent may be added.

According to said manufacturing method, the conductive polymer which becomes hydrophobic by introduce | transducing a polysiloxane structure into a precursor complex (D), and can disperse | distribute also to a water-insoluble organic solvent (low polarity organic solvent). It becomes. Therefore, a conductive polymer composition in which a conductive polymer is dispersed in a solvent containing a water-insoluble organic solvent as a main solvent component can be obtained. Such a conductive polymer composition can be used by blending with a resin that is generally soluble only in a low-polar solvent such as a silicone resin.
In particular, when an oxirane group-containing organic compound and / or an oxetane group-containing organic compound is used as a compound for introducing an aliphatic carbon-carbon double bond, a conductive polymer (a) -solubilized polymer precursor ( b ″) The effect of increasing the hydrophobicity of the complex by introducing an oxirane group and / or oxetane group into the complex, and further introducing a polysiloxane structure into the aliphatic carbon-carbon double bond Thus, both of the effects of increasing hydrophobicity can be obtained, and the dispersibility of the conductive polymer in the water-insoluble organic solvent (low polarity organic solvent) can be sufficiently improved.
In particular, as a conductive polymer (a) -solubilized polymer precursor (b ″) complex, a complex of polystyrene sulfonic acid and poly (3,4-ethylenedioxythiophene) (hereinafter referred to as “PEDOT- Use of "PSS".) Is preferable in that the composition has high thermal stability and high transparency after coating film formation.

<Curable organopolysiloxane composition (II)>
The curable organopolysiloxane composition (II) is a curable organopolysiloxane having a siloxane bond as a main skeleton and having an organic group bonded to a silicon atom and having a functional group contributing to a curing reaction. Containing.
The curable organopolysiloxane composition (II) is preferably a liquid composition containing an organic solvent (c).
The organic solvent (c) in the curable organopolysiloxane composition (II) preferably contains the water-insoluble organic solvent (c1). 10-100 mass% is preferable and, as for the ratio of the water-insoluble organic solvent (c1) among the organic solvents contained in curable organopolysiloxane composition (II), 20-100 mass% is more preferable.
The curable organopolysiloxane composition (II) may further contain a curing component (crosslinking agent, catalyst, initiator, etc.) as necessary.

As the curable organopolysiloxane and the curable component that contributes to the curable organopolysiloxane, those known as materials for the silicone film can be used. For example, addition curable organopolysiloxane, condensation curable organopolysiloxane, or ionizing radiation curable organopolysiloxane can be used.
The molecular weight of the curable organopolysiloxane is preferably 500 to 1,000,000, more preferably 1,000 to 500,000.
Below, the example of the combination of curable organopolysiloxane and a hardening component is given.

(II-1) Addition-Curable Organopolysiloxane Composition The solid content of the addition-curable organopolysiloxane composition is mainly composed of a combination of the following compounds.
a) an organopolysiloxane having at least two alkenyl groups in the molecule;
b) an organopolysiloxane having at least three hydrosilyl groups in the molecule, and c) an addition reaction catalyst (hydrosilylation catalyst) mainly composed of a platinum group metal modification or complex such as platinum, palladium, rhodium and the like.

(II-2) Condensation-curable organopolysiloxane composition The solid content of the condensation-curable organopolysiloxane composition is mainly composed of a combination of any of the compounds of Examples 1 to 3 below.
[Example 1]
a) an organopolysiloxane having at least two silanol groups in the molecule;
b) an organosilane or organopolysiloxane having at least 3 hydrolyzable groups in the molecule, and c) a condensation catalyst.
[Example 2]
a) an organopolysiloxane having at least two silanol groups in the molecule;
b) an organopolysiloxane having at least 3 hydrosilyl groups in the molecule, and c) a condensation catalyst.
[Example 3]
a) an organopolysiloxane having at least 3 hydrolyzable groups in the molecule, and b) a condensation catalyst.

(II-3) Ionizing radiation curable organopolysiloxane composition The solid content of the ionizing radiation curable organopolysiloxane composition includes any of the compounds of Examples 1 to 6 below, and ultraviolet rays using a photoinitiator. Or cured by an electron beam.
[Example 1]
Acrylamide-containing organopolysiloxanes: in the ^{_{molecule, CH 2 = C (R 21}} ) -C (= O) -N (R 22) -R 23 - ( ^{wherein, R 21} is a hydrogen atom or a methyl ^{group, R 22} Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ²³ is a divalent hydrocarbon group having 2 to 8 carbon atoms).
[Example 2]
Two or more mercaptoalkyl group-containing organopolysiloxanes: CH ₂ ═C (R ³¹ ) —S—R ³² — (wherein R ³¹ is a hydrogen atom or a methyl group, and R ³² has 2 carbon atoms). Organopolysiloxane containing at least two mercaptoalkyl functional groups represented by ˜8 divalent hydrocarbon groups).
[Example 3]
Two or more alkenyl group-containing organopolysiloxane: An organopolysiloxane containing at least two alkenyl groups (-C _n H _2n-1 (n is a number of 2 or more)) in one molecule.
[Example 4]
Alkenyl group-containing organopolysiloxane: alkenyl groups in one molecule _{(. -C n H 2n-1} (n is a number of 2 or more)), organopolysiloxane having one.
[Example 5]
Acrylic group or methacryl group-containing organopolysiloxane: 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) an organopolysiloxane having at least two alkenyl groups in one molecule, and b) an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule.

It is preferable that the curable composition further contains at least one selected from the group consisting of allyl group-containing isocyanurates and derivatives thereof as a curing component. An allyl group-containing isocyanurate is a compound having a triazine ring in one molecule and at least one allyl group.
Allyl group-containing isocyanurates and derivatives thereof contribute to the curability of addition-type silicones. Specific examples include triallyl isocyanurate, diallylmethyl isocyanurate, LDAIC, and DD-1 (all manufactured by Shikoku Kasei Kogyo Co., Ltd.), and triallyl isocyanurate is preferred in terms of reactivity.
When the curable composition contains an allyl group-containing isocyanurate or a derivative thereof, the content is preferably 0.1 to 20% by mass, and preferably 1 to 10% by mass with respect to the total mass of the curable organopolysiloxane. More preferred.

In addition to the conductive polymer, curable organopolysiloxane, organic solvent (c), and curing component, the curable composition further contains one or more known additives within a range not impairing the effects of the present invention. May be included.
Examples of additives include antioxidants, ozone aging inhibitors, UV absorbers, heat and light stabilizers, water resistance agents, antiseptic / antibacterial agents, insecticides, plasticizers, dispersants, polymerization inhibitors, antifoaming agents Agents, surfactants, antifoaming agents, flame retardants, pigments, dyes.
The total content of additives is preferably 10 parts by mass or less and more preferably 1 part by mass or less with respect to 100 parts by mass in total of the conductive polymer and the curable organopolysiloxane.

In the curable composition, the mass of the conductive polymer is preferably 1 to 500 parts by mass, more preferably 5 to 100 parts by mass, and 10 to 50 parts by mass with respect to 100 parts by mass of the total mass of the curable organopolysiloxane. Is more preferable.
When the ratio of the mass of the conductive polymer is not less than the lower limit of the above range, the cured product of the curable composition has sufficiently high conductivity and good antistatic properties can be obtained. When it is at least the upper limit of the above range, a uniform coating film is easily obtained when the curable composition is applied.

≪Antistatic silicone film≫
The antistatic silicone film according to the embodiment of the present invention is a film made of a cured product of the above-described curable composition.
The antistatic silicone film is formed by supplying a coating material containing a solvent to a substrate, removing the solvent, and curing reaction.
When the curable composition is a liquid, it is used as it is as a paint or diluted with a solvent to prepare a paint.
When the curable composition is solid, a coating material is prepared from a solution in which the curable composition is soluble or dispersed in a solvent mainly containing an organic solvent.
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.
The method of curing the paint on the substrate depends on the type of curable organopolysiloxane, heat curing, curing by reacting with moisture in the air at room temperature, light such as ultraviolet rays and electron beams (ionizing radiation) Known methods such as a method of irradiating and curing can be used.

By curing the curable composition according to the embodiment of the present invention, a silicone film excellent in antistatic performance can be obtained.
Moreover, it is possible to uniformly mix the conductive polymer and the curable organopolysiloxane using an organic solvent as a medium without using an amine compound as described in Patent Documents 4 to 8. Good curability of the functional organopolysiloxane can be obtained, and an antistatic silicone film excellent in antistatic properties and peelability can be obtained.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

<Production example>
(Production Example 1) ... Production of polystyrene sulfonic acid (solubilized polymer precursor (b '')) 206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water and stirred at 80 ° C. 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water 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 14.0 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 maintaining the mixed solution thus obtained at 20 ° C. and stirring, 29.6 g of ammonium persulfate dissolved in 200 ml of ion exchange water and 2.8 g of ferric sulfate oxidation catalyst solution were slowly added. , Reacted for 8 hours with stirring.
The anionic group in polystyrene sulfonic acid was 2 mol with respect to 1 mol of the monomer unit of 3,4-ethylenedioxythiophene used in the reaction in this example.
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 of Precursor Composite (D)>
(Production Example 3)
100 g of the aqueous solution of PEDOT-PSS obtained in Production Example 2, 100 g of methanol, and 25 g of 1,2-epoxy-5-hexene (molecular weight 98.15) are mixed, and the mixture is heated to 60 ° C. using a stirrer. And stirred for 4 hours. The precipitated solid was collected by filtration, and 150 g of methyl ethyl ketone was added to the obtained solid and dispersed under high pressure to obtain a 0.5 mass% dispersion of the precursor complex (D).
In this example, the mass of 1,2-epoxy-5-hexene used is about 29 times the mass of polystyrene sulfonic acid in PEDOT-PSS.
Further, when the amount of 1,2-epoxy-5-hexene added is estimated from the weight of the recovered precursor complex (D), it is added to the equivalent of the anion group in the polystyrene sulfonic acid constituting PEDOT-PSS. The equivalent of the oxirane group in 1,2-epoxy-5-hexene was about 0.8 times.

(Production Example 4)
0.5% by mass of the same conditions as in Production Example 3 except that 1,2-epoxy-5-hexene of Production Example 3 was changed to 1,2-epoxy-9-decene (molecular weight: 154.25). A dispersion of the precursor composite (D) was obtained.
In this example, the mass of 1,2-epoxy-9-decene used is about 29 times the mass of polystyrene sulfonic acid in PEDOT-PSS.
Moreover, when the addition amount of 1,2-epoxy-9-decene is estimated from the weight of the recovered precursor complex (D), the addition amount is equivalent to the equivalent of the anion group in the polystyrene sulfonic acid constituting PEDOT-PSS. The equivalent of the oxirane group in 1,2-epoxy-9-decene was about 0.7 times.

(Production Example 5)
Same as Production Example 3, except that 25 g of 1,2-epoxy-5-hexene of Production Example 3 was changed to 25 g of C12, C13 mixed higher alcohol glycidyl ether and 5 g of 1,2-epoxy-9-decene. Under the conditions, a dispersion of 0.5% by mass of the precursor composite (D) was obtained.
In this example, the mass of 1,2-epoxy-9-decene used is about 5.8 times the mass of polystyrene sulfonic acid in PEDOT-PSS.
Further, when the total addition amount of 1,2-epoxy-9-decene and C12, C13 mixed higher alcohol glycidyl ether is estimated from the weight of the recovered precursor complex, anions in polystyrene sulfonic acid constituting PEDOT-PSS The equivalent of the oxirane group in the total of 1,2-epoxy-9-decene added and C12, C13 mixed higher alcohol glycidyl ether was about 1.0 times the equivalent of the group.

<Production of Conductive Polymer Composition (I)>
(Production Example 6)
100 g of toluene was added to 100 g of the dispersion liquid of the precursor complex (D) obtained in Production Example 3, and about 100 g of the solvent was distilled off with a rotary evaporator. 100 g of toluene was added again, and about 100 g of the solvent was distilled off using a rotary evaporator. The toluene solution thus obtained was transferred to a three-necked flask, a stirrer, a thermometer and a reflux condenser were attached, and 1.0 g of HMS-H271 (trade name, manufactured by Gelest, methylhydrosiloxane-dimethylsiloxane copolymer, hydrogen terminal) was added. In addition, the temperature was raised to 80 ° C. under a nitrogen stream, and 0.1 mL of CAT-PL-50T (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., platinum catalyst) was added and heated for 3 hours. The mixture was treated with a high-pressure homogenizer (Nano Veita manufactured by Yoshida Kikai Kogyo Co., Ltd.) and diluted 2-fold with methyl ethyl ketone to obtain 200 g of a conductive polymer composition.
The total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer composition obtained in this example was 0.75% by mass, and toluene with respect to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of polysiloxane having a SiH group in this example is 2 with respect to 1 part by mass of the precursor composite (D) (the total of the conductive polymer (a) and the double bond-containing polymer (b ′)). 0.0 part by mass.

(Production Example 7)
Production Example 6 except that the dispersion of the precursor composite (D) obtained in Production Example 3 was replaced with the dispersion of the precursor composite (D) obtained in Production Example 4 and HMS-H271 was changed to 0.5 g. The same operation was performed to obtain a conductive polymer composition.
The total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer composition obtained in this example is 0.5% by mass, and toluene with respect to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of polysiloxane having a SiH group in this example is 1 with respect to 1 part by mass of the precursor composite (D) (the total of the conductive polymer (a) and the double bond-containing polymer (b ′)). 0.0 part by mass.

(Production Example 8)
Instead of the dispersion of the precursor complex (D) obtained in Production Example 3 with the dispersion of the precursor complex (D) obtained in Production Example 5, 1.0 g of HMS-H271 was replaced with HMS-151 (trade name, A conductive polymer composition was obtained by performing the same operation as in Production Example 6 except that 0.5 g of Gelest, methylhydrosiloxane-dimethylsiloxane copolymer, trimethylsiloxy terminal, molecular weight 1900-2000) was used. .
The total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer composition obtained in this example is 0.5% by mass, and toluene with respect to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of polysiloxane having a SiH group in this example is 1 with respect to 1 part by mass of the precursor composite (D) (the total of the conductive polymer (a) and the double bond-containing polymer (b ′)). 0.0 part by mass.

(Production Example 9)
The dispersion of the precursor composite (D) obtained in Production Example 3 was replaced with the dispersion of the precursor composite (D) obtained in Production Example 5, and 1.0 g of HMS-H271 was replaced with HMS-082 (trade name, A conductive polymer composition was obtained in the same manner as in Production Example 6, except that 0.5 g of Gelest, methylhydrosiloxane-dimethylsiloxane copolymer, trimethylsiloxy terminal, molecular weight 5500-6500) was used. .
The total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer composition obtained in this example is 0.5% by mass, and toluene with respect to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of polysiloxane having a SiH group in this example is 1 with respect to 1 part by mass of the precursor composite (D) (the total of the conductive polymer (a) and the double bond-containing polymer (b ′)). 0.0 part by mass.

<Evaluation method of antistatic silicone film>
(Peel strength)
A 2.5 cm × 15 cm polyester adhesive tape (product name: Nitto No. 31B, manufactured by Nitto Denko Corporation) is placed on the surface of the film, and then pressure-bonded using a 2 kg roller on the adhesive tape, and a release agent. A polyester adhesive tape was bonded to the layer. Then, it was left to stand at room temperature for 20 hours or heat-treated at 85 ° C. for 20 hours to prepare a test piece. Then, using a tensile tester, the polyester adhesive tape was peeled from the release agent layer at an angle of 180 ° (peeling speed 0.3 m / min), and the peel strength was measured. The smaller the peel strength, the easier it is to peel the pressure-sensitive adhesive sheet after the pressure-sensitive adhesive sheet is bonded to the release agent layer (that is, light peeling).

(Residual adhesion rate)
Similarly to the measurement of the peel strength, a polyester adhesive tape was bonded to the release agent layer. After leaving at room temperature for 20 hours or heat treatment at 85 ° C. for 20 hours, the polyester adhesive tape was peeled from the release agent layer. Furthermore, the polyester adhesive tape was pressure-bonded to an untreated PET film (trade name: Lumirror, manufactured by Toray Industries, Inc.) using a 2 kg roller. Subsequently, the polyester adhesive tape was peeled from the PET film (peeling speed 0.3 m / min) in the same manner as the peel test using a tensile tester, and the peel strength X was measured. In addition, a polyester adhesive tape not bonded to the release agent layer is pressure-bonded to an untreated PET film using a 2 kg roller, the polyester adhesive tape is peeled from the PET film using a tensile tester, and the peel strength Y is measured. did. After the measurement, the residual adhesion rate was determined from the formula of peel strength X / peel strength Y × 100 (%). The higher the residual adhesive rate, the less the silicone of the release agent layer moves to the pressure-sensitive adhesive tape, indicating that the decrease in the adhesive strength of the polyester pressure-sensitive adhesive tape due to bonding to the release agent layer is suppressed.

(Surface resistivity)
Measured with a probe MCP-HTP12 and an applied voltage of 10 V using a Hiresta MCP-HT450 manufactured by Mitsubishi Chemical Corporation. Note that “OVER” in the table means that the surface resistivity is too high to be measured.

<Manufacture of antistatic silicone film>
Tables 1 and 2 show the composition of main components of the paint used in each example, and Tables 3 to 5 show the evaluation results of the films.
Example 1
Addition-curable silicone (KS-3703 (product name), manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 30% by mass, toluene solution) as a curable organopolysiloxane to 40 g of the conductive polymer composition obtained in Production Example 6. 5 g and 60 g of hexane were added, and 0.1 g of a platinum catalyst (CAT-PL-50T (product name), manufactured by Shin-Etsu Chemical Co., Ltd.) was added to prepare a paint (curable composition).
In the coating material of this example, the mass of the conductive polymer is 20 parts by mass with respect to the total mass of 100 parts by mass of the curable organopolysiloxane.
The obtained coating material was applied to a PET film having a thickness of 38 μm by a bar coater (No. 12) and heated in a hot air dryer at 120 ° C. for 1 minute to form a film. About the obtained membrane | film | coat, peeling strength, a residual adhesive rate, and surface resistivity were evaluated by said method.

(Example 2)
In Example 1, except that the amount of the conductive polymer composition was changed to 60 g, a coating material was produced under the same conditions as in Example 1 to form a film.
In the coating material of this example, the total mass of the conductive polymer (a) and the solubilized polymer (b) is 30 parts by mass with respect to 100 parts by mass of the total mass of the curable organopolysiloxane.

Example 3
In Example 1, except that the amount of the conductive polymer composition was changed to 80 g, a coating material was produced under the same conditions as in Example 1 to form a film.
In the coating material of this example, the total mass of the conductive polymer (a) and the solubilized polymer (b) is 40 parts by mass with respect to 100 parts by mass of the total mass of the curable organopolysiloxane.

Example 4
A coating material was formed under the same conditions as in Example 1 except that the conductive polymer composition obtained in Production Example 6 was replaced with the conductive polymer composition obtained in Production Example 7.
In the paint of this example, the total mass of the conductive polymer (a) and the solubilized polymer (b) is 20 parts by mass with respect to 100 parts by mass of the total mass of the curable organopolysiloxane.

(Example 5)
A coating material was formed under the same conditions as in Example 1 except that the conductive polymer composition obtained in Production Example 6 was replaced with the conductive polymer composition obtained in Production Example 8.
In the paint of this example, the total mass of the conductive polymer (a) and the solubilized polymer (b) is 20 parts by mass with respect to 100 parts by mass of the total mass of the curable organopolysiloxane.

(Example 6)
Addition-curing silicone (KS-847H (product name), manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration 30% by mass, toluene solution) as a curable organopolysiloxane to 60 g of the conductive polymer composition obtained in Production Example 9 ) 5 g and 60 g of hexane were added, and 0.1 g of the same platinum catalyst (CAT-PL-50T (product name)) as in Example 1 was added to prepare a paint and form a film.
In the paint of this example, the total mass of the conductive polymer (a) and the solubilized polymer (b) is 20 parts by mass with respect to 100 parts by mass of the total mass of the curable organopolysiloxane.

(Example 7)
5 g of the same addition-curable silicone (KS-3703 (product name)) as in Example 1, 60 g of hexane, and 0.15 g of triallyl isocyanurate were added to 60 g of the conductive polymer composition obtained in Production Example 6. 0.1 g of the same platinum catalyst (CAT-PL-50T (product name)) as in Example 1 was added to prepare a paint, and a film was formed.

(Comparative Example 1)
In Example 1, except that the conductive polymer composition obtained in Production Example 6 was changed to the aqueous solution of PEDOT-PSS obtained in Production Example 2, a paint was produced in the same manner as in Example 1. However, PEDOT-PSS aggregated and separated, and could not be used to form a film.

(Comparative Example 2)
In Example 1, the same procedure as in Example 1 was followed, except that the conductive polymer composition obtained in Production Example 6 was changed to the dispersion of the precursor composite (D) obtained in Production Example 4. Although a paint was produced, PEDOT-PSS aggregated and could not be used for forming a film.

(Comparative Example 3)
In Example 1, except that the conductive polymer composition obtained in Production Example 6 was changed to a mixture of 30 g of toluene and 30 g of methyl ethyl ketone, a paint was produced under the same conditions as in Example 1 to form a film.

(Example 8)
60 g of the conductive polymer composition obtained in Production Example 6 was added to 1 g of solvent-free UV curable silicone (X-62-7205 (product name) manufactured by Shin-Etsu Chemical Co., Ltd.) as a curable organopolysiloxane, 60 g of hexane, 7 g of acetone alcohol was added, and 0.15 g of photoinitiator (Darocur 1173 (product name), manufactured by Ciba Specialty Chemicals, solid content 5 mass%) was added to prepare a coating material. This paint was applied to a PET film with No. The film was applied using a 12 bar coater and irradiated with a mercury lamp at 800 mJ / cm ² in a nitrogen atmosphere. About the obtained membrane | film | coat, peeling strength, a residual adhesive rate, and surface resistivity were evaluated by said method. The results are shown in Table 2.

(Comparative Example 4)
In Example 8, the same procedure as in Example 8 was followed, except that the conductive polymer composition obtained in Production Example 6 was changed to a mixture of 30 g of PEDOT-PSS aqueous solution obtained in Production Example 2 and 30 g of water. However, PEDOT-PSS aggregated and separated, and could not be used for forming a coating.

Example 9
60 g of the conductive polymer composition obtained in Production Example 6 was added to a condensation curable silicone solution (KS-723B (product name) manufactured by Shin-Etsu Chemical Co., Ltd., solid content 30% by mass, toluene solution as a curable organopolysiloxane. 4 g and 60 g of hexane were added, and 0.04 g of a condensation catalyst (CAT-PS-8S (product name), manufactured by Shin-Etsu Chemical Co., Ltd.) was added to prepare a paint. This paint was applied to a PET film with No. The coating was performed using a 12 bar coater and dried at 120 ° C. for 1 minute to form a film. About the obtained membrane | film | coat, peeling strength, a residual adhesive rate, and surface resistivity were evaluated by said method. The results are shown in Table 3.

(Comparative Example 5)
In Example 9, except that the conductive polymer composition obtained in Production Example 6 was changed to a mixture of 30 g of PEDOT-PSS aqueous solution obtained in Production Example 2 and 30 g of water, the same as in Example 9. Although a coating material was produced, aggregation and separation of PEDOT-PSS occurred, and the coating material could not be used.

<Evaluation results>
The films obtained in Examples 1 to 9 have low surface resistivity, high conductivity, and excellent antistatic properties. Further, the peel strength after 20 hours at room temperature or 85 ° C. was small and good peelability was exhibited, and the residual adhesion rate was also good.
In Comparative Examples 1, 4, and 5, when the PEDOT-PSS solution before the introduction of the aliphatic carbon-carbon double bond and the curable silicone solution were mixed, aggregation and separation occurred, resulting in uniform A paint was not obtained.
In Comparative Example 2, after introducing an aliphatic carbon-carbon double bond into PEDOT-PSS, a dispersion of the precursor composite (D) before reacting with a polysiloxane having a SiH group, a curable silicone solution, When these were mixed, agglomeration and separation occurred, and a uniform paint could not be obtained.
Since the coating material of Comparative Example 3 did not contain PEDOT-PSS, which is a conductive component, the surface resistivity was too high to be measured.
The reason why such an effect is obtained is considered as follows.
The precursor composites (D) obtained in Production Examples 3 to 5 are obtained by ring-opening a polyanion with an oxirane group-containing compound having an aliphatic carbon-carbon double bond. Therefore, it is considered that the precursor complex (D) contains a large number of aliphatic carbon-carbon double bonds.
In Examples 1 to 9, the SiH group in the polysiloxane having SiH groups undergoes an addition reaction with the aliphatic carbon-carbon double bond to form a complex containing a polysiloxane structure, and thus more hydrophobic. It is considered that a uniform coating was obtained when mixed with a silicone solution.

  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 (12)

Comprising a conductive polymer and a curable organopolysiloxane;
The conductive polymer has an aliphatic carbon-carbon double bond, and a polysiloxane having a SiH group is added to at least a part of the aliphatic carbon-carbon double bond. A curable composition.   The curable composition according to claim 1, wherein the curable organopolysiloxane is an addition-curable organopolysiloxane.   The curable composition according to claim 1, wherein the curable organopolysiloxane is a condensation curable organopolysiloxane.   The curable composition according to claim 1, wherein the curable organopolysiloxane is an ionizing radiation curable organopolysiloxane.   The conductive polymer is a complex of a π-conjugated conductive polymer (a) and a solubilized polymer (b), and the solubilized polymer (b) is at least one of an anion group and an electron withdrawing group. And an aliphatic carbon-carbon double bond, and a polysiloxane having a SiH group is added to at least a part of the aliphatic carbon-carbon double bond. The curable composition according to item 1.   The π-conjugated conductive polymer (a) is at least one selected from the group consisting of polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, and polythiophene vinylenes. The curable composition of Claim 5 which is a polymer which has as a structural unit.   The curable composition according to claim 6, wherein the π-conjugated conductive polymer (a) is poly (3,4-ethylenedioxythiophene) or polypyrrole.   The solubilized polymer (b) has an anion group, and the anion group is at least one selected from a sulfo group, a phosphate group, and a carboxy group. The curable composition as described.   The solubilized polymer (b) is based on one or more selected from the group consisting of styrene sulfonic acid, vinyl sulfonic acid, acrylic acid alkylene sulfonic acid, and 2-acrylamido-2-methyl-1-propanesulfonic acid. The curable composition of any one of Claims 5-8 which has a monomer unit.   The curable composition of any one of Claims 1-9 containing 1 or more types chosen from the group which consists of an allyl group containing isocyanurate and its derivative (s).   The curable composition of any one of Claims 1-10 containing an organic solvent (c).   The antistatic silicone film which consists of hardened | cured material of the curable composition of any one of Claims 1-11.