JP2016023288A - Curable silicone composition and release sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating of a curable silicone composition containing a conductive polymer that can reduce problems relating to an amine compound and water.SOLUTION: A curable silicone composition is provided, which comprises: (I) a conductive polymer composition that contains (a) a π-conjugate conductive polymer, (b) a polyanion used for doping, and (c) a reaction product of an anion other than the anion used for doping, with and an organic compound containing an oxirane group and/or an oxetane group, and that can be dispersed in a solvent essentially comprising an organic solvent; and (II) an addition-curable organopolysiloxane composition containing (A) 100 parts by mass of an organopolysiloxane represented by formula (1) and having at least two alkenyl groups in one molecule, (B) an organohydrogenpolysiloxane represented by an average composition formula (8) and having at least two hydrogen atoms bonded to a silicon atom in one molecule, (C) a platinum-group metal catalyst in a catalytic amount, and (D) an optional amount of an organic solvent. A release sheet is provided, which includes a substrate and a coating obtained by applying and curing the above curable silicon composition on a film substrate.SELECTED DRAWING: None

Description

  The present invention relates to a curable silicone composition and a coating film formed by coating the same, and in particular, a curing capable of forming a siloxane film that is cured by a hydrosilylation reaction or the like and has excellent peeling performance and antistatic performance for adhesive substances. The present invention relates to a functional silicone composition and a release sheet comprising a substrate and a coating film obtained by curing the composition on the substrate.

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

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

  For example, in order to improve the solubility of π-conjugated conductive polymer in water, an oxidizing agent is used in the presence of polystyrene sulfonic acid as an anion group-containing polymer acid having a molecular weight of 2,000 to 500,000. A method for producing a poly (3,4-dialkoxythiophene) aqueous solution by chemical oxidative polymerization of 3,4-dialkoxythiophene is known (see, for example, Patent Document 1). Also known is a method of producing a π-conjugated conductive polymer colloid aqueous solution by chemical oxidative polymerization of a precursor monomer for forming a π-conjugated conductive polymer in the presence of polyacrylic acid ( For example, see Patent Document 2). Furthermore, a method for producing a conductive solution that is soluble or dispersed in an organic solvent and can be mixed with an organic resin has been proposed. As an example, an organic solvent solution of polyaniline and a method for producing the same are known (for example, see Patent Document 3). In addition, a solvent replacement method by phase inversion from an aqueous solution containing a polyanion and an intrinsic conductive polymer to an organic solvent is also known (see, for example, Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7). . In addition, a method of dissolving an intrinsic conductive polymer after lyophilization in an organic solvent is also known (see, for example, Patent Document 8).

  However, in these methods, there is a problem that mixing with other organic resins is difficult as in the case of polyaniline, and in addition, the solvent system is limited to a large amount of water. Even when the amount of water is small or substantially free of water, an amine compound is used as in the above-mentioned documents (see, for example, Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7). As a result, there is a problem that the color tone deteriorates with time when mixed with the resin, and the polyanion dope into the conductive polymer is gradually pulled out by the amine and the conductivity decreases with time. Furthermore, when a conductive polymer is mixed with an addition-curable silicone resin, there is a drawback that curing is inhibited by amines and the silicone resin is not sufficiently cured. On the other hand, when a conductive polymer is mixed with a condensation curable silicone resin, there is a drawback in that a phenomenon such as participation in the condensation of silanol or alkoxysilyl group by amine occurs and storage characteristics are deteriorated.

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

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

  However, the conventional conductive solution described above cannot overcome the above-described drawbacks derived from amine compounds when an amine compound is used and the conductive polymer is phase-inverted from an aqueous phase to an organic phase. In addition, the form of the water dispersion has the disadvantages that it has low practicality and is easily corroded by water.

  The present invention provides a curable silicone composition capable of reducing problems derived from amine compounds and water, and a release sheet comprising a substrate and a coating film formed by curing the composition thereon. For the purpose.

  In order to achieve the above object, the present inventors have developed a completely new technology that enables phase inversion from an aqueous phase to an organic phase by using an oxirane or oxetane compound without using an amine compound. Development has led to the completion of the present invention. Specific problem solving means are as follows.

（式中、Ｒ^１は独立にアルケニル基であり、Ｒ^２は独立に脂肪族不飽和結合を含有しない一価有機基であり、下記Ｘ^１〜Ｘ^３は独立に下記一般式（２）、（３）および（４）

下記Ｘ^４〜Ｘ^６は独立に下記一般式（５）、（６）および（７）

でそれぞれ示される基である。ａ３〜ａ６、ａ１２〜ａ１５、ａ２２〜ａ２５、ａ３２〜ａ３５、ａ４２、ａ４３、ａ５２、ａ５３、ａ６２およびａ６３はオルガノポリシロキサンの２５℃での粘度を０．０５Ｐａ・ｓから３０質量％トルエン希釈粘度で７０Ｐａ・ｓの範囲とする正数から選ばれ、ａ４〜ａ６、ａ１２〜ａ１５、ａ２２〜ａ２５、ａ３２〜ａ３５、ａ４２、ａ４３、ａ５２、ａ５３、ａ６２およびａ６３は０であってもよい。ａ１、ａ２、ａ１１、ａ２１、ａ３１、ａ４１、ａ５１およびａ６１はそれぞれ独立に０〜３の整数である。）
（Ｂ）１分子中にケイ素原子に結合した水素原子を少なくとも２個有し、下記平均組成式（８）で示されるオルガノハイドロジェンポリシロキサン：含有されるケイ素原子に結合した水素原子のモル数が、アルケニル基含有成分の総アルケニル基モル数の１〜２０倍に相当する量

（式中、Ｒ^２は脂肪族不飽和結合を含有しない一価有機基であり、ｂ１は０．１〜２、ｂ２は０．１〜３で、ｂ１＋ｂ２は１〜３の実数であり、１分子中に２個以上のＳｉＨ基を有し、２５℃の粘度が０．００５〜１０Ｐａ・ｓの範囲に入るように選ばれる。）
（Ｃ）触媒量の白金族金属系触媒
（Ｄ）任意量の有機溶剤
を含む。 The curable silicone composition for achieving the above object comprises (a) a π-conjugated conductive polymer, (b) the polyanion doped in the (a) π-conjugated conductive polymer, and (c) the above. (B) A highly conductive material that is dispersible and soluble in a solvent mainly composed of an organic solvent, including a reaction product of an anion other than that required for doping in the polyanion and an organic compound containing an oxirane group and / or an oxetane group. A molecular composition (I) and a curable organopolysiloxane composition (II) are included. Here, the curable organopolysiloxane composition (II) is an addition reaction curable composition. More specifically, the curable silicone composition is
I) a conductive polymer composition that includes the following (a), (b) and (c), and is dispersible and soluble in a solvent mainly composed of an organic solvent;
(A) a π-conjugated conductive polymer (b) a polyanion doped in the (a) π-conjugated conductive polymer (c) an anion other than that required for doping in the (b) polyanion, an oxirane group, and And / or reaction product II with an oxetane group-containing organic compound II) an addition-curable organopolysiloxane composition comprising the following (A), (B), (C) and (D):
(A) Organopolysiloxane represented by the following general formula (1) and having at least two alkenyl groups in one molecule: 100 parts by mass

(In the formula, R ¹ is independently an alkenyl group, R ² is a monovalent organic group that does not independently contain an aliphatic unsaturated bond, and the following X ^{1 to} X ³ are independently the following general formula (2), (3) and (4)

The following X ^{4 to} X ⁶ are independently the following general formulas (5), (6) and (7)

Are groups represented by a3-a6, a12-a15, a22-a25, a32-a35, a42, a43, a52, a53, a62 and a63 are the viscosity of the organopolysiloxane at 25 ° C. from 0.05 Pa · s to 30% by mass toluene diluted viscosity And a4 to a6, a12 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62 and a63 may be 0. a1, a2, a11, a21, a31, a41, a51 and a61 are each independently an integer of 0 to 3. )
(B) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule and represented by the following average composition formula (8): Number of moles of hydrogen atoms bonded to contained silicon atoms Is equivalent to 1 to 20 times the total number of moles of the alkenyl group-containing component

(In the formula, R ² is a monovalent organic group containing no aliphatic unsaturated bond, b 1 is 0.1 to 2, b 2 is 0.1 to 3, b 1 + b 2 is a real number 1 to 3, (It is selected so that the molecule has two or more SiH groups and the viscosity at 25 ° C. falls within the range of 0.005 to 10 Pa · s.)
(C) A catalytic amount of a platinum group metal catalyst (D) includes an arbitrary amount of an organic solvent.

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

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

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

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

（式中、Ｒ^２は上記と同じであり、Ｒ^５は独立に水素原子又は脂肪族不飽和結合を含有しない一価有機基であり、Ｒ^６およびＲ^７はＭｅ以外の脂肪族不飽和結合を含有しない一価有機基で示される基であり、ｂ１１およびｂ１２は０〜３の整数、ｂ１３は１以上の整数、ｂ２３は３以上の整数、ｂ１４〜ｂ１７、ｂ２４〜ｂ２７は０以上の整数であって、１分子中に２個以上のＳｉＨ基を有し、２５℃の粘度が０．００５〜１０Ｐａ・ｓの範囲に入るように選ばれる。） In the curable silicone composition according to another embodiment, the component (B) is an organohydrogenpolysiloxane represented by the following general formula (9) and / or the following general formula (10).

(Wherein R ² is the same as above, R ⁵ is independently a hydrogen atom or a monovalent organic group containing no aliphatic unsaturated bond, and R ⁶ and R ⁷ are aliphatic unsaturated bonds other than Me. B11 and b12 are integers of 0 to 3, b13 is an integer of 1 or more, b23 is an integer of 3 or more, b14 to b17, b24 to b27 are integers of 0 or more And having two or more SiH groups in one molecule and having a viscosity at 25 ° C. in the range of 0.005 to 10 Pa · s.)

In the curable silicone composition according to another embodiment, the component (B) is an organohydrogenpolysiloxane mixture of (B1) / (B2) parts by mass = 1/9 to 9/1.
((B1) is the above general formula (9) and / or the above general formula (10), wherein R ² is a monovalent organic group other than aromatic and does not contain an aliphatic unsaturated bond, and R ⁵ is independently A monovalent organic group that does not contain a hydrogen atom or an aliphatic unsaturated bond other than aromatic, and R ⁶ and R ⁷ are monovalent organic groups that do not contain an aliphatic unsaturated bond other than aromatic except Me group (B2). Is the general formula (9) and / or the general formula (10), wherein at least one of R ² and R ^{5 to} R ⁷ is an aromatic monovalent organic group.

（式中、Ｒ^８は独立に水酸基、アルコキシ基、Ｒ^９は水酸基及びアルコキシ基を含有しない一価有機基、Ｒ^１０は水酸基及びアルコキシ基を含有しないＭｅ基以外の一価有機基、ｅ１およびｅ２は１〜３の整数、ｅ３〜ｅ５はオルガノポリシロキサンの２５℃での粘度を１Ｐａ・ｓから３０質量％トルエン希釈粘度で１００Ｐａ・ｓの範囲とする整数から選ばれる。）
を追加成分として含む。 The curable silicone composition concerning another embodiment is 0.1-30 mass parts of organopolysiloxane shown by following General formula (11) as (E) component

(Wherein R ⁸ is independently a hydroxyl group and an alkoxy group, R ⁹ is a monovalent organic group not containing a hydroxyl group and an alkoxy group, R ¹⁰ is a monovalent organic group other than a Me group not containing a hydroxyl group and an alkoxy group, e 1 and e2 is an integer of 1 to 3, and e3 to e5 are selected from integers that make the viscosity of the organopolysiloxane at 25 ° C. in the range of 1 Pa · s to 30 mass% toluene diluted viscosity 100 Pa · s.)
As an additional component.

The curable silicone composition according to another embodiment comprises 10 to 100 parts by mass (structure) of an organopolysiloxane having the following structure having at least two alkenyl groups as the component (F):
R ² _(3-f1) R ¹ _f1 —SiO _1/2 siloxane unit represented as M ^R1R2 ,
^Consisting of R ² SiO _3/2 siloxane units denoted as T ^R2 ,
A organopolysiloxane M ^R1R2 / ^{T R2} siloxane units molar ratio satisfies 0.2 to 0.8, a viscosity at 25 ° C. has a degree of polymerization in the range of 0.001Pa · s~1Pa · s, The molecular ends are mainly blocked with ^MR1R2 siloxane units, but some of the ends may be formed as silanol groups or alkoxy groups.
(In the formula, R ¹ is an alkenyl group, R ² is a monovalent organic group that does not independently contain an aliphatic unsaturated bond, and f 1 is each independently an integer of 1 to ^3. )
As an additional component.

（式中、Ｒ^１１はエポキシ基を持つ有機基、Ｒ^１２は炭素数１〜６アルキル基でエーテル結合を含んでもよく、一部は加水分解されて水酸基となっていてもよい、Ｒ^１３はエポキシ基を持たない有機基であってアルコキシ基を除く。ｇ１およびｇ２は整数で１≦ｇ１、１≦ｇ２、２≦ｇ１＋ｇ２≦４を満たし、ｇ３〜ｇ５は実数で０＜ｇ３、０＜ｇ４、０≦ｇ５、１＜ｇ３＋ｇ４＋ｇ５≦３を満たし、オルガノポリシロキサンの２５℃での粘度を０．００１Ｐａ・ｓ〜１Ｐａ・ｓの範囲とする正の数から選ばれる。）
を追加成分として含む。 The curable silicone composition according to another embodiment includes an organosilane represented by the following general formula (12) having at least an epoxy group and an alkoxysilyl group per molecule as component (G) and / or the following general formula (13). 0.1-10 parts by mass of the partially hydrolyzed co-condensed siloxane represented by

(Wherein, R ¹¹ is an organic group having an epoxy group, R ¹² may be made may contain an ether bond-C6 alkyl group having a carbon part is hydrolyzed to a hydroxyl group, R ¹³ is An organic group having no epoxy group, excluding an alkoxy group, g1 and g2 are integers satisfying 1 ≦ g1, 1 ≦ g2, 2 ≦ g1 + g2 ≦ 4, and g3 to g5 are real numbers 0 <g3, 0 <g4 And 0 ≦ g5, 1 <g3 + g4 + g5 ≦ 3, and the viscosity of the organopolysiloxane at 25 ° C. is selected from positive numbers in the range of 0.001 Pa · s to 1 Pa · s.)
As an additional component.

（式中、Ｒ^１およびＲ^２は上記と同じ有機基、ｈ１は０〜３の整数から選ばれる。）
を追加成分として含む。 The curable silicone composition according to another embodiment includes, as component (H), a siloxane unit of the following general formula (14) / a siloxane unit molar ratio of the following general formula (15) = 2/8 to 8/2. 1 to 100 parts by mass of MQ resin

(In the formula, R ¹ and R ² are the same organic groups as described above, and h1 is selected from integers of 0 to ^3. )
As an additional component.

  Moreover, the peeling sheet concerning one Embodiment is provided with the coating film obtained by apply | coating a base material and one of the said curable silicone compositions on it, and making it harden | cure.

  According to the present invention, there is provided a curable silicone composition capable of reducing problems derived from amine compounds and water, and a release sheet comprising a substrate and a coating film formed by curing the composition thereon. Can be provided.

  Next, each embodiment of the curable silicone composition and release sheet of the present invention will be described.

1. Curable Silicone Composition A curable silicone composition according to an embodiment of the present invention includes a conductive polymer composition (I) that is dispersible and soluble in a solvent mainly composed of an organic solvent, and a predetermined addition reaction curable type. And an organopolysiloxane composition (II). The conductive polymer composition (I) comprises (a) a π-conjugated conductive polymer, (b) the polyanion doped in the (a) π-conjugated conductive polymer, and (c) the (b) polyanion. It includes a reaction product of an anion other than that required for the dope and an organic compound containing an oxirane group and / or an oxetane group. The predetermined addition reaction curable organopolysiloxane composition (II) includes the following (A), (B), (C) and (D). Here, the total of the component (a), the component (b) and the component (c) is preferably 0.1 to 100 parts by mass with respect to the total of 100 parts by mass of the component (A) and the component (B). Preferably it is 0.5-50 mass parts, More preferably, it is 2-30 mass parts.

（式中、Ｒ^１は独立にアルケニル基であり、Ｒ^２は独立に脂肪族不飽和結合を含有しない一価有機基であり、下記Ｘ^１〜Ｘ^３は独立に下記一般式（２）、（３）および（４）

下記Ｘ^４〜Ｘ^６は独立に下記一般式（５）、（６）および（７）

でそれぞれ示される基である。ａ３〜ａ６、ａ１２〜ａ１５、ａ２２〜ａ２５、ａ３２〜ａ３５、ａ４２、ａ４３、ａ５２、ａ５３、ａ６２およびａ６３はオルガノポリシロキサンの２５℃での粘度を０．０５Ｐａ・ｓから３０質量％トルエン希釈粘度で７０Ｐａ・ｓの範囲とする正数から選ばれ、ａ４〜ａ６、ａ１２〜ａ１５、ａ２２〜ａ２５、ａ３２〜ａ３５、ａ４２、ａ４３、ａ５２、ａ５３、ａ６２およびａ６３は０であってもよい。ａ１、ａ２、ａ１１、ａ２１、ａ３１、ａ４１、ａ５１およびａ６１はそれぞれ独立に０〜３の整数である。） (A) Organopolysiloxane represented by the following general formula (1) and having at least two alkenyl groups in one molecule: 100 parts by mass

(In the formula, R ¹ is independently an alkenyl group, R ² is a monovalent organic group that does not independently contain an aliphatic unsaturated bond, and the following X ^{1 to} X ³ are independently the following general formula (2), (3) and (4)

The following X ^{4 to} X ⁶ are independently the following general formulas (5), (6) and (7)

Are groups represented by a3-a6, a12-a15, a22-a25, a32-a35, a42, a43, a52, a53, a62 and a63 are the viscosity of the organopolysiloxane at 25 ° C. from 0.05 Pa · s to 30% by mass toluene diluted viscosity And a4 to a6, a12 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62 and a63 may be 0. a1, a2, a11, a21, a31, a41, a51 and a61 are each independently an integer of 0 to 3. )

（式中、Ｒ^２は脂肪族不飽和結合を含有しない一価有機基であり、ｂ１は０．１〜２、ｂ２は０．１〜３で、ｂ１＋ｂ２は１〜３の実数であり、１分子中に２個以上のＳｉＨ基を有し、２５℃の粘度が０．００５〜１０Ｐａ・ｓの範囲に入るように選ばれる。） (B) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule and represented by the following average composition formula (8): Number of moles of hydrogen atoms bonded to contained silicon atoms Is equivalent to 1 to 20 times the total number of moles of the alkenyl group-containing component

(In the formula, R ² is a monovalent organic group containing no aliphatic unsaturated bond, b 1 is 0.1 to 2, b 2 is 0.1 to 3, b 1 + b 2 is a real number 1 to 3, (It is selected so that the molecule has two or more SiH groups and the viscosity at 25 ° C. falls within the range of 0.005 to 10 Pa · s.)

  (C) A catalytic amount of a platinum group metal catalyst

  (D) Arbitrary amount of organic solvent

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

The said conductive polymer composition can be manufactured with 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 water dispersions include Heraeus PEDOT / PSS water dispersion (trade name: Clevios, Agfa PEDOT / PSS water dispersion (trade name: Orgacon), etc. Can do.

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

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

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

  Preferred examples of the π-conjugated conductive polymer include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), and poly (3-n-propylpyrrole). ), Poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4 Dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), Poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly ( -Hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole), polythiophene, 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-promothiophene), poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3- Phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutyl) Thiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxy) Thiophene), 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-dihexyloxy) Thiophene), poly (3,4-diheptyloxythiophene), poly (3,4 -Dioctyloxythiophene), poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedi) Oxythiophene), poly (3,4-butenedioxythiophene), 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), poly (3-anilinesulfonic acid), etc. It is.

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

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

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

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

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

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

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

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

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

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

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

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

  The amount of the oxirane group and / or oxetane group-containing organic compound is preferably 0.1 with respect to 1 molar equivalent of the anion group or electron withdrawing group in the polyanion that does not contribute to the doping of the π-conjugated conductive polymer. It is -50 molar equivalent, More preferably, it is 1.0-30.0 molar equivalent. When the amount of the oxirane group and / or oxetane group-containing organic compound is 0.1 mole equivalent or more, the oxirane group and / or oxetane group-containing organic compound may be modified to such an extent that the anion group of the polyanion dissolves in the solvent. I can do it. On the other hand, when the amount of the oxirane group and / or oxetane group-containing organic compound is 50 mole equivalents or less, the excess oxirane group and / or oxetane group-containing organic compound is hardly precipitated in the conductive polymer solution. It is easy to prevent a decrease in the conductivity and mechanical properties of the conductive coating film.

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

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

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

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

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

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

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

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

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

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

  The content of the conductivity improver is preferably 10 to 10,000 parts by mass and more preferably 30 to 5,000 parts by mass with respect to 100 parts by mass of the conductive component. When the content of the conductivity improver is at least the lower limit, the antistatic property can be further improved. On the other hand, if it is below the said upper limit, peelability can be improved more.

1.2 Addition reaction curable silicone composition (II)
The addition reaction curable silicone composition is a silicone composition containing the following components (A) to (D), preferably at least one of components (E) to (H). It cures.

（式中、Ｒ^１は独立にアルケニル基であり、Ｒ^２は独立に脂肪族不飽和結合を含有しない一価有機基であり、下記Ｘ^１〜Ｘ^３は独立に下記一般式（２）、（３）および（４）

下記Ｘ^４〜Ｘ^６は独立に下記一般式（５）、（６）および（７）

でそれぞれ示される基である。ａ３〜ａ６、ａ１２〜ａ１５、ａ２２〜ａ２５、ａ３２〜ａ３５、ａ４２、ａ４３、ａ５２、ａ５３、ａ６２およびａ６３はオルガノポリシロキサンの２５℃での粘度を０．０５Ｐａ・ｓから３０質量％トルエン希釈粘度で７０Ｐａ・ｓの範囲とする正数から選ばれ、ａ４〜ａ６、ａ１２〜ａ１５、ａ２２〜ａ２５、ａ３２〜ａ３５、ａ４２、ａ４３、ａ５２、ａ５３、ａ６２およびａ６３は０であってもよい。ａ１、ａ２、ａ１１、ａ２１、ａ３１、ａ４１、ａ５１およびａ６１はそれぞれ独立に０〜３の整数である。） Component (A) The organopolysiloxane of component (A) has a structure represented by the following general formula (1) and has at least two alkenyl groups in one molecule.

(In the formula, R ¹ is independently an alkenyl group, R ² is a monovalent organic group that does not independently contain an aliphatic unsaturated bond, and the following X ^{1 to} X ³ are independently the following general formula (2), (3) and (4)

The following X ^{4 to} X ⁶ are independently the following general formulas (5), (6) and (7)

Are groups represented by a3-a6, a12-a15, a22-a25, a32-a35, a42, a43, a52, a53, a62 and a63 are the viscosity of the organopolysiloxane at 25 ° C. from 0.05 Pa · s to 30% by mass toluene diluted viscosity And a4 to a6, a12 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62 and a63 may be 0. a1, a2, a11, a21, a31, a41, a51 and a61 are each independently an integer of 0 to 3. )

In the above formula (1), R ¹ is preferably the same or different alkenyl group having 2 to 10 carbon atoms such as vinyl group, allyl group and propenyl group, and R ² is the same or different methyl group, ethyl group. Group, propyl group, alkyl group such as butyl group, cycloalkyl group such as cyclohexyl group, aryl group such as phenyl group and tolyl group, or a part or all of hydrogen atoms bonded to carbon atoms of these groups is fluorine, An aliphatic unsaturated bond having preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as a chloromethyl group, trifluoropropyl group, or cyanoethyl group substituted with a halogen atom such as chlorine or bromine, a cyano group, or the like An organic group such as an unsubstituted or substituted monovalent hydrocarbon group that does not contain. It is industrially preferable that R ¹ is a vinyl group, and R ² is preferably 80 mol% or more in terms of production and characteristics in terms of a methyl group and a phenyl group. More preferably, the phenyl group in R ² is 40 mol% or less.

  There are two or more alkenyl groups in one molecule of the organopolysiloxane of the component (A), and if it is less than two, there is a high possibility that uncrosslinked molecules remain after curing, and the curing property is lowered, which is not desirable. Desirably, the alkenyl group content per 100 g of organopolysiloxane is 0.001 to 0.5 mol, and more desirably 0.002 to 0.45 mol. If this content is less than 0.001 mol, the curability may be lowered, and if it exceeds 0.5 mol, the pot life may be shortened and handling may be difficult.

  In the above formulas (1) to (7), a1 to a63 are positive numbers that satisfy the viscosity described later, but the number of alkenyl groups in one molecule [a1 + a2 + a4 + a5 × {a11 + a13 + a14 × (a41 + a43) + a15 × (A51 + a53 + 61 + a63)} + a6 × {a21 + a23 + a31 + a32 + (a24 + a34) × (a41 + a43) + (a25 + a35) × (a51 + a53 + a61 + a63)}] is preferably selected in the range of 2 to 300, particularly 3 to 280.

  The viscosity of the organopolysiloxane (A) at 25 ° C. is in the range of 0.05 Pa · s to 70 Pa · s with 30% by mass toluene dilution viscosity, preferably 0.1 Pa · s to 30% by mass toluene dilution viscosity. In the range of 60 Pa · s or less. When the viscosity is 0.05 Pa · s or more, the releasability is sufficient, and when the viscosity is 30% by mass toluene dilution and 70 Pa · s or less, the workability is improved. Here, the viscosity can be measured by a rotational viscometer.

  In the formulas (1) to (7), as a5 to a14, the degree of polymerization [2 + a3 + a4 + a5 × {2 + a12 + a13 + a14 × (2 + a42 + a43) + a15 × (3 + a52 + a53 +) + a6 × {3 + a22 + a23 + a32 + 34 + 34 + 34 + 34 + 34 + 34 + × (3 + a52 + a53 + a62 + a63)}] is preferably selected to be in the range of 50 to 20,000, particularly 55 to 19,000.

  Although the main skeleton structure of the organopolysiloxane of component (A) is a straight chain, in the formula (1), those containing a branched chain structure as shown in the case where a5 and / or a6 is not 0 can also be used. Specific examples of the component (A) include the following formulas (16) to (23).

Component (B) The organohydrogenpolysiloxane used as the component (B) is an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule. Preferably, having 3 or more hydrogen atoms is advantageous for curability of the composition.

（式中、Ｒ^２は脂肪族不飽和結合を含有しない一価有機基であり、ｂ１は０．１〜２、好ましくは０．２〜１．５、ｂ２は０．１〜３、好ましくは０．２〜２で、ｂ１＋ｂ２は１〜３、好ましくは１．５〜２．８の実数であり、１分子中に２個以上のＳｉＨ基を有し、２５℃の粘度が０．００５〜１０Ｐａ・ｓ、好ましくは０．０１〜１０Ｐａ・ｓの範囲に入るように選ばれる。） The organohydrogenpolysiloxane as the component (B) is preferably represented by the following average composition formula (8).

(Wherein R ² is a monovalent organic group not containing an aliphatic unsaturated bond, b1 is 0.1 to 2, preferably 0.2 to 1.5, and b2 is 0.1 to 3, preferably 0.2 to 2, b1 + b2 is a real number of 1 to 3, preferably 1.5 to 2.8, has 2 or more SiH groups in one molecule, and has a viscosity at 25 ° C. of 0.005 to 0.005. 10 Pa · s, preferably 0.01 to 10 Pa · s.

  Specific examples include organohydrogenpolysiloxanes. More specifically, a polymer of methylhydrogenpolysiloxane; a copolymer of methylhydrogenpolysiloxane and dimethylpolysiloxane; and methylhydrogenpolysiloxane Copolymer of methylphenylpolysiloxane; copolymer of methylhydrogenpolysiloxane and dimethylpolysiloxane and methylphenylpolysiloxane; copolymer of methylhydrogenpolysiloxane and dimethylpolysiloxane and diphenylpolysiloxane Can be mentioned.

（式中、Ｒ^２は上記と同じであり、Ｒ^５は独立に水素原子又は脂肪族不飽和結合を含有しない一価有機基であり、Ｒ^６およびＲ^７はＭｅ以外の脂肪族不飽和結合を含有しない一価有機基で示される基であり、ｂ１１およびｂ１２は０〜３の整数、ｂ１３は１以上の整数、ｂ２３は３以上の整数、ｂ１４〜ｂ１７、ｂ２４〜ｂ２７は０以上の整数であって、１分子中に２個以上のＳｉＨ基を有し、２５℃の粘度が０．００５〜１０Ｐａ・ｓの範囲に入るように選ばれる。） In addition, the molecular structure of component (B) may be any of linear, branched or cyclic, and may be a combination of these, or a mixture of them may be used. The component (B) is more preferably a linear or cyclic organohydrogenpolysiloxane represented by the following general formula (9) and / or (10), wherein the linear structure and the cyclic structure are contained in one molecule. May be an organohydrogenpolysiloxane that is simultaneously contained.

(Wherein R ² is the same as above, R ⁵ is independently a hydrogen atom or a monovalent organic group containing no aliphatic unsaturated bond, and R ⁶ and R ⁷ are aliphatic unsaturated bonds other than Me. B11 and b12 are integers of 0 to 3, b13 is an integer of 1 or more, b23 is an integer of 3 or more, b14 to b17, b24 to b27 are integers of 0 or more And having two or more SiH groups in one molecule and having a viscosity at 25 ° C. in the range of 0.005 to 10 Pa · s.)

  Since the cross-linked state of the cured film can be different for linear, branched, and cyclic, the peeling characteristics can be controlled by properly using it. The straight chain is effective in reducing the peel strength of the cured film, but the branched is more effective in improving the curing property of the composition in that many terminal SiH functional groups advantageous for the curing reaction can be introduced.

Examples of branched organohydrogenpolysiloxanes include monofunctional HR ² ₂ SiO _1/2 siloxane units (hereinafter referred to as ^MH units) and / or R ² ₃ SiO _1/2 siloxane units (hereinafter referred to as M And a siloxane composed of tetrafunctional SiO _4/2 siloxane units (hereinafter referred to as Q units). R ² is preferably a methyl group or a phenyl group industrially.

  The substituents contained in one molecule of the component (B) may be different from each other, but it is economical that the methyl group is desirably 50 mol% or more, more preferably 80 mol% or more of the total substituents. Is advantageous. In the release film, there are many uses that require higher transparency of the cured film and adhesion to the substrate. In that case, the substituent of the component (B) is bulky with more carbon atoms than the methyl group. By changing to a substituent or an aromatic substituent, an effect of promoting wetting or interaction with the film substrate surface can be obtained.

In the general formula (9) and / or the general formula (10), the component (B) having no aromatic substituent is the component (B1). In the general formula (9), R ² is an aromatic not containing an aliphatic unsaturated bond. R ⁵ is independently a hydrogen atom or a monovalent organic group containing no aliphatic unsaturated bond other than aromatic, R ⁶ and R ⁷ are aliphatic unsaturated other than aromatic except Me group This corresponds to a monovalent organic group containing no bond.

In the general formula (9) and / or the general formula (10), the component (B) having an aromatic substituent is the component (B2). In the formula, at least one of R ² and R ^{5 to} R ⁷ is Aromatic monovalent organic groups are equivalent.

  If the method of using the component (B1) and the component (B2) in combination, it becomes easy to balance other characteristics such as the peel strength of the cured film, and the (B1) / (B2) mass part ratio = 1/9 to 9/1. It is preferable to use a mixture of

The substituent R ⁶ of the component (B) is preferably an alkyl group, to obtain the effect of changing the performance of the cured film by a substituent of varying carbon number. However, if the carbon number becomes too large, the curability tends to decrease on the contrary, and therefore the carbon number is selected from 4 or less, but an ethyl group and a propyl group are industrially preferable. An ethyl group having 2 carbon atoms is a desirable choice for obtaining releasability.

Examples of the organohydrogenpolysiloxane in which a linear structure and a cyclic structure are simultaneously contained in one molecule include, for example, the organohydrogenpolysiloxane represented by the above formula (9) and the above formula (10). The organohydrogenpolysiloxane is crosslinked between one of the molecular chain terminal SiH groups of the formula (9) and one of the SiH groups of the formula (10), and the Si atoms are divalent organic groups (—CH ₂ — Examples thereof include organohydrogenpolysiloxanes having two structures of a linear structure and a cyclic structure bonded via a CH ₂ — or the like) or an oxygen atom (—O—).

  In the organohydrogenpolysiloxane of component (B), the number of hydrogen atoms bonded to silicon atoms in one molecule is 2 or more, preferably 3 to 1,000. If it is less than 2, the curability is insufficient. Desirably, the SiH group content per 100 g of organohydrogenpolysiloxane is 0.2 to 1.7 mol, and more desirably 0.3 to 1.7 mol. If the content is too small, the curability may be insufficient, and if the content is too large, the storage stability may decrease.

  The viscosity of the organohydrogenpolysiloxane (B) at 25 ° C. is preferably in the range of 0.005 to 10 Pa · s, more preferably in the range of 0.005 to 5 Pa · s. If the viscosity is too small, the curability may be insufficient, and if it is too high, the storage stability may be insufficient.

  The blending amount of the organohydrogenpolysiloxane of the component (B) is the total number of alkenyl group-containing components such as the component (A) in which the number of moles of hydrogen atoms bonded to silicon atoms (hereinafter referred to as SiH groups) is Is an amount corresponding to 1 to 20 times the number of moles of the alkenyl group. (B) When the number of moles of SiH groups contained in the amount of component is less than the lower limit of the total number of moles of alkenyl groups contained in component (A), etc. However, there is no significant increase in effect, which causes a change over time and is also economically disadvantageous. As a compounding quantity with the organohydrogenpolysiloxane of a general (B) component, it is the range of 0.1-30 mass parts with respect to 100 mass parts of (A) component organopolysiloxane.

Component (C) The platinum group metal catalyst (addition reaction catalyst) as the component (C) is used to promote a crosslinking reaction between the component (A) and the component (B) and form a cured film. Examples of such an addition reaction catalyst include platinum black, chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-alcohol coordination compound, platinum-vinyl group-containing siloxane coordination compound, rhodium, rhodium-olefin complex, and the like. Is mentioned.

  The addition reaction catalyst forms a cured film that is sufficient to be blended in an amount of 5 to 1,000 ppm (mass ratio) as the amount of platinum or the amount of rhodium with respect to the total mass of the components (A) and (B). Although preferable above, it can be appropriately increased or decreased depending on the reactivity of the components or the desired curing rate.

(D) Component The organic solvent as (D) component is mix | blended as needed for the purpose of the improvement of coating bath stability, the coating property with respect to various base materials, and adjustment of a coating amount and a viscosity. In particular, the silicone composition for a release film is advantageous because it provides a desired effect. For example, an organic solvent that can uniformly dissolve the composition, such as toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, and hexane, can be used.

  The component (D) is an optional component that does not necessarily exist. When the danger or reduction in safety due to an organic solvent is not preferable, the curability for solventless release paper or release film is not blended. It can also be used as a silicone composition.

  (D) Although the usage-amount in mix | blending a component can be determined arbitrarily, it is 10-100,000 mass parts with respect to 100 mass parts of said (A) component, Especially the range of 10-10,000 mass parts. Is preferred. When the blending amount is 100,000 parts by mass or less, the coating amount is easily controlled. When the blending amount is 10 parts by mass or more, the solvent blending effect, coating property and pot life are easily improved.

  The addition reaction curable silicone composition used in the present invention can be easily produced by uniformly mixing the components (A), (B), (C) and (D). In order to ensure a safe pot life, the component (B) or the component (C) is preferably added and mixed immediately before coating. Moreover, when using an organic solvent, it is advantageous to mix (B) component and / or (C) component, after melt | dissolving (A) component uniformly in (D) component.

  In the addition reaction curable silicone composition used in the present invention, the following components (E) to (H) can be used as optional additional components as long as the effects of the present invention are not reduced.

（式中、Ｒ^８は独立に水酸基、アルコキシ基、Ｒ^９は水酸基及びアルコキシ基を含有しない一価有機基、Ｒ^１０は水酸基及びアルコキシ基を含有しないＭｅ基以外の一価有機基、ｅ１およびｅ２は１〜３の整数、ｅ３〜ｅ５はオルガノポリシロキサンの２５℃での粘度を１Ｐａ・ｓから３０質量％トルエン希釈粘度で１００Ｐａ・ｓの範囲とする整数から選ばれる。） (E) Component As the component (E), an organopolysiloxane represented by the following general formula (11) can be given.

(Wherein R ⁸ is independently a hydroxyl group and an alkoxy group, R ⁹ is a monovalent organic group not containing a hydroxyl group and an alkoxy group, R ¹⁰ is a monovalent organic group other than a Me group not containing a hydroxyl group and an alkoxy group, e 1 and e2 is an integer of 1 to 3, and e3 to e5 are selected from integers that make the viscosity of the organopolysiloxane at 25 ° C. in the range of 1 Pa · s to 30 mass% toluene diluted viscosity 100 Pa · s.)

  Siloxanes that are linear polymers and do not have functional groups in their side chains are effective for imparting slipperiness to the cured film, and lightening the peel force without reducing the residual adhesive force. Can also be expected. The release film also exhibits the effect of preventing the cured film from falling off due to the effect of sliding. (E) The suitable compounding quantity of a component is 0.1-30 mass parts with respect to 100 mass parts of (A) component. Addition of 0.1 parts by mass or more facilitates obtaining a slip imparting effect, and addition of 30 parts by mass or less facilitates maintaining a high residual adhesive force.

(F) component As (F) component, the component which improves base-material adhesiveness can be mix | blended. Component (F) is an organopolysiloxane having at least two alkenyl groups,
R ² _(3-f1) R ¹ _f1 —SiO _1/2 siloxane unit represented as M ^R1R2 ,
^Consisting of R ² SiO _3/2 siloxane units denoted as T ^R2 ,
A organopolysiloxane M ^R1R2 / ^{T R2} siloxane units molar ratio satisfies 0.2 to 0.8, a viscosity at 25 ° C. has a degree of polymerization in the range of 0.001Pa · s~1Pa · s, The molecular ends are mainly blocked with ^MR1R2 siloxane units, but some of the ends may be formed as silanol groups or alkoxy groups.
(In the formula, R ¹ is an alkenyl group, R ² is a monovalent organic group that does not independently contain an aliphatic unsaturated bond, and f 1 is each independently an integer of 1 to ^3. )

The (F) component organopolysiloxane preferably has a viscosity at 25 ° C. in the range of 0.001 Pa · s to 1 Pa · s. Although it is desirable that the ^{MR 1R2} siloxane unit is bonded to the molecular terminal, it may be partially formed as a silanol group or an alkoxy group.

The component (F) may contain D siloxane units and Q siloxane units as long as they do not impair the effects of the component. However, particularly when a release film requires stronger adhesion, M ^R1R2 / T ^R2 does not contain them. Siloxane having a siloxane unit molar ratio of 0.3 to 0.7 is desirable. Industrially, R ¹ is preferably a Vi group, and R ² is preferably a Me group or a Ph group.

  The blending amount of the component (F) is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the component (A). Easy to lower. By adding the component (B) such that the ratio of the number of moles of hydrogen atoms bonded to the silicon atoms contained in the component (B) to the number of moles of the alkenyl group contained in the component (F) is 1 or more, This is desirable because it can prevent a decrease in cure properties.

（式中、Ｒ^１１はエポキシ基を持つ有機基、Ｒ^１２は炭素数１〜６アルキル基でエーテル結合を含んでもよく、一部は加水分解されて水酸基となっていてもよい、Ｒ^１３はエポキシ基を持たない有機基であってアルコキシ基を除く。ｇ１およびｇ２は整数で１≦ｇ１、１≦ｇ２、２≦ｇ１＋ｇ２≦４を満たし、ｇ３〜ｇ５は実数で０＜ｇ３、０＜ｇ４、０≦ｇ５、１＜ｇ３＋ｇ４＋ｇ５≦３を満たし、オルガノポリシロキサンの２５℃での粘度を０．００１Ｐａ・ｓ〜１Ｐａ・ｓの範囲とする正の数から選ばれる。） Component (G) The component (G) is a component that improves the adhesion of the substrate, and an organosilane of the following general formula (12) having at least an epoxy group and an alkoxysilyl group in one molecule and of the following composition formula (13) Partially hydrolyzed co-condensed siloxane.

(Wherein, R ¹¹ is an organic group having an epoxy group, R ¹² may be made may contain an ether bond-C6 alkyl group having a carbon part is hydrolyzed to a hydroxyl group, R ¹³ is An organic group having no epoxy group, excluding an alkoxy group, g1 and g2 are integers satisfying 1 ≦ g1, 1 ≦ g2, 2 ≦ g1 + g2 ≦ 4, and g3 to g5 are real numbers 0 <g3, 0 <g4 And 0 ≦ g5, 1 <g3 + g4 + g5 ≦ 3, and the viscosity of the organopolysiloxane at 25 ° C. is selected from positive numbers in the range of 0.001 Pa · s to 1 Pa · s.)

Examples of the epoxy group include 3-glycidoxyalkyl, 2- (3,4-epoxycyclohexyl) alkyl group, and examples of the alkoxy group (OR ¹² ) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. .

  The partially hydrolyzed condensate can be obtained by adding water to the silane of formula (12), reacting in the presence of a catalyst, and removing the produced alcohol by distillation. Moreover, a partial hydrolysis cocondensate can also be obtained by mixing and reacting the silane of formula (13) and other alkoxysilanes.

  The desirable blending amount of the component (G) is 0.1 to 10 parts by mass, and an adhesion improvement effect is easily obtained by addition of 0.1 part by mass or more, and the residual adhesive strength is kept high by addition of 10 parts by mass or less. It's easy to do. In order to bring out the effect of improving the adhesion of the component (G), a catalytic amount of an acid, an alkali or a metal compound can be added. These are for activating the functional group of the component (G), but need to be added within a range that does not affect the curing property, pot life, and storage stability of the composition.

（式中、Ｒ^１およびＲ^２は上記と同じ有機基、ｈ１は０〜３の整数から選ばれる。） (H) Component As the (H) component, MQ resin having the following general formula (14) siloxane unit / the following general formula (15) siloxane unit molar ratio = 2/8 to 8/2 is raised.

(Wherein R ¹ and R ² are the same organic groups as described above, and h1 is selected from integers of 0 to 3)

The component (H) is used as a peeling force control agent. (H) As for the compounding quantity of a component, 1-100 mass parts is preferable with respect to 100 mass parts of (A) component. Addition of 1 part by mass or more facilitates enhancing the peeling effect, and addition of 100 parts by mass or less facilitates maintaining high curability. By adding the component (B) so that the ratio of the number of moles of hydrogen atoms bonded to the silicon atoms contained in the component (B) to the number of moles of alkenyl groups in the blended component (H) is 1 or more, This is desirable because it can prevent a decrease in cure properties. The molar ratio of the above formula (14) siloxane unit / the above formula (15) siloxane unit is more preferably 2/8 to 8/2, and more preferably 3/7 to 7/3. The component (H) may contain D siloxane units and T siloxane units as long as the effect is not impaired. As specific examples, (ViMe ₂ SiO _1/2 ) ₅ (Me ₃ SiO _1/2 ) ₄₅ (SiO _4/2 ) ₅₀ , (ViMe ₂ SiO _1/2 ) ₆ (Me ₃ SiO _1/2 ) ₅₄ ( Examples include Me ₂ SiO _2/2 ) ₅ (SiO _4/2 ) ₆₀ and (Me ₃ SiO _1/2 ) ₅₀ (MeSiO _3/2 ) ₃ (SiO _4/2 ) ₄₀ .

  In the addition reaction curable silicone composition used in the present invention, a surfactant may be added as another optional component (component I). The surfactant is expected to have an effect of improving the compatibility with the conductive agent component that can be one of the components of the conductive polymer composition (I). The transparency and smoothness of the cured film can be improved by compatibilizing the hydrophobic silicone component and the hydrophilic conductive agent component with a surfactant to improve leveling. As the surfactant, a nonionic surfactant having little influence on the addition reaction is preferable. As for the compounding quantity of surfactant, 0.1 mass part or more is preferable with respect to 100 mass parts of (A) component. Increasing the compounding amount of the surfactant may reduce the curing property of the composition, and therefore it is desirable to suppress it to 5 parts by mass or less with respect to 100 parts by mass of the component (A). Specific examples of the component (I) include polyoxyethylene lauryl ether and polyoxyethylene polyoxypropylene stearyl ether.

  In addition, an organic resin may be contained. The organic resin is a component blended for the purpose of treatment bath stability, improvement of coating properties for various substrates, improvement of film formation, adjustment of peeling characteristics, adjustment of coating amount and viscosity, such as polyvinyl alcohol. , Poly (meth) acrylate, polyester, cellulose, derivatives thereof, and the like can be used, and it is preferably contained in the range of 2 to 400 parts by mass with respect to 100 parts by mass of the peelable component. However, when there is a risk of adversely affecting the peeling characteristics and the antistatic characteristics, it is not necessary to add an organic resin. Specific examples of the derivative include those obtained by etherifying a part of the hydroxy group of cellulose with an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and an ethyl group is particularly preferable.

2. Release sheet One embodiment of the release sheet of the present invention includes a base material and a coating film obtained by applying and curing any of the curable silicone compositions described above on the base material. Antistatic release paper or release film as a more specific form of release sheet is a base material made of plastic film or paper and antistatic release as a coating film formed on at least one surface of the base material. And an agent layer. The antistatic release agent layer is a curable silicone composition (antistatic release paper or release film silicone composition) comprising a conductive polymer composition (I) and an addition reaction curable silicone composition (II). (Also referred to as an object). The layer can be used by directly mixing an addition reaction curable silicone composition and a conductive polymer composition solubilized and dispersed in a solvent mainly composed of an organic solvent. You may do it.

  As thickness of a peeling sheet, 2-500 micrometers is preferable and 10-100 micrometers is more preferable. As thickness of the peeling sheet of another aspect, 10 micrometers-1000 micrometers are preferable, and 50 micrometers-300 micrometers are more preferable. Here, the thickness of the release sheet can be measured by a known thickness measuring instrument (thickness gauge) such as a dial gauge or an ultrasonic thickness gauge. In the release sheet, the thickness of the coating film (release agent layer) is preferably 0.1 to 5.0 μm, and more preferably 0.1 to 2.0 μm. Here, the thickness of the release agent layer can be measured by a fluorescent X measuring device.

  Examples of the resin material constituting the plastic film as an example of the substrate include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacryl, polycarbonate, and polyvinylidene fluoride. , Polyarylate, styrene-based elastomer, polyester-based elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, and cellulose acetate propionate. Among these resin materials, polyethylene terephthalate is preferable in terms of transparency, flexibility, antifouling property, strength, and the like. As paper which is another example of the substrate, fine paper, kraft paper, coated paper, and the like can be used.

  The method for producing a release sheet includes, for example, a step of applying the curable silicone composition to at least one surface of a plastic film, and a step of drying the applied product to form a coating film.

As a coating method, for example, a method using a coating machine such as a bar coater, a gravure coater, an air knife coater, a roll coater, or a wire bar is applied. Although there is no restriction | limiting in particular as an application quantity, Usually, the range of 0.1-5.0 g / m < ² > is preferable as solid content. Examples of the drying method include a method of removing volatile components and solvent components by heating. Specifically, a hot air dryer, IR dryer, etc. are mentioned. Or you may leave as it is at normal temperature. As temperature at the time of drying, 50-200 degreeC is preferable and 70-180 degreeC is more preferable. The time for drying is preferably 1 to 120 seconds, more preferably 5 to 90 seconds. As another aspect, as temperature at the time of drying, 80-200 degreeC is preferable and 100-150 degreeC is more preferable. The time for drying is preferably 0.5 to 10 minutes, and more preferably 0.5 to 2 minutes.

  The release paper or release film, which is a form of release sheet, is provided with a release agent layer containing the antistatic release paper and the silicone composition for release film, and thus has excellent antistatic properties and release properties, and has a transparent appearance. It becomes a high quality thing. Therefore, it is preferable to use the release paper or release film as an adhesive sheet for optical or electronic / electrical components.

  Examples and Comparative Examples are shown below, but the present invention is not limited to the following Examples. In the following examples, “part” means “part by mass”, and “%” means “% by mass”. The stated viscosity values are those measured with a rotational viscometer at 25 ° C.

<Production Examples 1 to 8 of an organic solvent in which PEDOT-PSS is dispersed>
(Production Example 1) Production of polystyrene sulfonic acid 206 g of sodium styrene sulfonate was dissolved in 1,000 ml of ion-exchanged water and stirred at 80 ° C., and 1.14 g of excessively dissolved in 10 ml of water in advance. The ammonium sulfate oxidant solution was added dropwise for 20 minutes and the solution was stirred for 12 hours. To the obtained sodium styrenesulfonate-containing solution, 1,000 ml of sulfuric acid diluted to 10% by mass was added, and 1,000 ml of the polystyrenesulfonic acid-containing solution was removed using an ultrafiltration method. 2,000 ml of ion exchanged water was added and about 2,000 ml of solution was removed using ultrafiltration. The above ultrafiltration operation was repeated three times.

  Further, about 2,000 ml of ion-exchanged water was added to the obtained filtrate, and about 2,000 ml of the 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, It 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 2,000 ml of ion-exchanged water. The solution was mixed at 20 ° C. While maintaining the mixed solution obtained at 20 ° C. with stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion exchange water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added. The reaction was stirred for 3 hours. 2,000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2,000 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 2,000 ml of ion-exchanged water are added to the resulting solution, and about 2,000 ml of solution is removed using an ultrafiltration method. 2,000 ml of ion exchanged water was added and about 2,000 ml of solution was removed using ultrafiltration. This operation was repeated three times. Furthermore, 2,000 ml of ion-exchanged water was added to the obtained solution, and about 2,000 ml of the solution was removed using an ultrafiltration method. This operation was repeated 5 times to obtain an aqueous solution of about 1.2% by mass of blue PEDOT-PSS.

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

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

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

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

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

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

<Preparation Examples 1-8 of Addition Reaction Curing Type Silicone Composition>
(Preparation Example 1)
As component (A), a 30% by mass toluene solution having a viscosity at 25 ° C. of 20 Pa · s and both ends of the molecular chain are represented by (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 0.7 mol% of a methylvinylsiloxane unit blocked with a vinylsilyl group and having a main skeleton excluding the terminal represented by (CH ₃ ) (CH ₂ ═CH) SiO _2/2 and (CH ₃ ) ₂ SiO _{2 /} 100 parts by mass of organopolysiloxane A-1 (vinyl group content = 0.01 mol / 100 g) in which the dimethylsiloxane unit represented by ₂ is composed of 99.3 mol%,
As a component (D), 237 parts by mass of a 1/1 mixed solvent of toluene and 2-butanone was placed in a flask and dissolved by stirring at 20 to 40 ° C.
In the obtained solution, as the component (B), both ends of the molecular chain are blocked with a trimethylsilyl group represented by (CH ₃ ) ₃ SiO _1/2 and methyl hydro hydride represented by (CH ₃ ) HSiO _2/2. 2 parts by mass of linear organohydrogenpolysiloxane B-1 (SiH content = 1.5 mol / 100 g) containing 95 mol% of disiloxane units and having a viscosity at 25 ° C. of 0.03 Pa · s ( The number of moles of hydrogen atoms directly connected to silicon atoms is equivalent to 3 times the unsaturated group contained in component (A)).
As a bath life extending agent, 1 part by mass of 3-methyl-1-butyn-3-ol was blended and stirred and mixed at 20 to 40 ° C. for 1 hour.

(Preparation Example 2)
As component (A), a 30% by weight toluene solution having a viscosity at 25 ° C. of 10 Pa · s and a molecular chain terminal represented by (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 2.8 mol% of a methylvinylsiloxane unit blocked with a silyl group and having a main skeleton excluding the terminal represented by (CH ₃ ) (CH ₂ ═CH) SiO _2/2 and (CH ₃ ) ₂ SiO _2/2 The organopolysiloxane A-2 (vinyl group-containing) is composed of 96.9 mol% of the dimethylsiloxane unit represented by the formula ( ₁ ) and 0.1 mol% of the methylsiloxane unit represented by (CH ₃ ) SiO _3/2. Amount = 0.04 mol / 100 g) 100 parts by mass,
As component (D), 246 parts by mass of toluene and 2-butanone 1/1 mixed solvent were placed in a flask and dissolved by stirring at 20 to 40 ° C.
In the obtained solution, as component (B), 4 parts by mass of linear organohydrogenpolysiloxane B-1 (SiH content = 1.5 mol / 100 g) and (CH ₃ ) HSiO _2/2 2 masses of cyclic organohydrogenpolysiloxane B-2 (SiH content = 1.7 mol / 100 g) consisting of 100 mol% of methylhydrogensiloxane units and having a viscosity at 25 ° C. of 0.005 Pa · s. Part (corresponding to 2.4 times the number of moles of hydrogen atoms directly bonded to silicon atoms relative to the unsaturated group contained in component (A)),
As a bath life extending agent, 1 part by mass of 3-methyl-1-butyn-3-ol was blended and stirred and mixed at 20 to 40 ° C. for 1 hour.

(Preparation Example 3)
As the component (A), 100 parts by mass of the organopolysiloxane A-1 of Example 1 (vinyl group content = 0.01 mol / 100 g),
As a component (D), 238 parts by mass of toluene and 2-butanone 1/1 mixed solvent were placed in a flask and dissolved by stirring at 20 to 40 ° C.
In the resulting solution, 1.5 parts by mass of linear organohydrogenpolysiloxane B-1 (SiH content = 1.5 mol / 100 g) as the component (B) and both ends of the molecular chain are (CH ₃ ) 60 mol% of methylhydrogensiloxane units represented by (CH ₃ ) HSiO _2/2 blocked with a dimethylhydrogensilyl group represented by ₂ HSiO _1/2 , (CH ₃ ) ₃ SiO _1/2 20 mol% of dimethylsiloxane units represented by the formula, 20 mol% of diphenylsiloxane units represented by (C ₆ H ₅ ) ₂ SiO _2/2 , and a viscosity at 25 ° C. of 0.5 Pa · s. 1 part by mass of chain organohydrogenpolysiloxane B-3 (SiH content = 0.68 mol / 100 g) (the number of moles of hydrogen atoms directly bonded to silicon atoms included the component (A)) Equivalent to 3 times the unsaturated groups),
As a bath life extending agent, 1 part by mass of 3-methyl-1-butyn-3-ol was blended and stirred and mixed at 20 to 40 ° C. for 1 hour.

(Preparation Example 4)
As an additional component (E) in Preparation Example 1, the viscosity of a 30% by weight toluene solution at 25 ° C. is 40 Pa · s, both ends of the molecular chain are blocked with dimethylhydroxylsilyl groups, and the main component excluding the ends is excluded. The skeleton contains 1 part by mass of organopolysiloxane E (hydroxyl group content = 0.0002 mol / 100 g) composed of 100 mol% of dimethylsiloxane units,
As the component (B), 2 parts by mass of a linear organohydrogenpolysiloxane B-1 (SiH content = 1.5 mol / 100 g) (the number of moles of hydrogen atoms directly connected to silicon atoms is (A), ( E) equivalent to 3 times the unsaturated group contained in the component)
As the component (D), a composition was prepared in the same manner except that 239 parts by mass of toluene and 2-butanone 1/1 mixed solvent were blended.

(Preparation Example 5)
As the component (A), a 30% by mass toluene solution has a viscosity at 25 ° C. of 15 Pa · s, and both ends of the molecular chain are represented by (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 The main skeleton that is blocked with a vinylsilyl group and excluding the terminal is 1.5 mol% of a methylvinylsiloxane unit represented by (CH ₃ ) (CH ₂ ═CH) SiO _2/2 and (CH ₃ ) ₂ SiO _{2 /} 100 parts by mass of organopolysiloxane A-3 (vinyl group content = 0.02 mol / 100 g) in which the dimethylsiloxane unit represented by ₂ is composed of 98.5 mol%,
(F) Component has a viscosity at 25 ° C. of 0.03 Pa · s and the end of the molecular chain is blocked with a dimethylvinylsilyl group, (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 unit 20 parts by mass of 50 mol%, organopolysiloxane F (vinyl group content = 0.6 mol / 100 g) composed of 50 mol% of CH ₃ SiO _3/2 units,
As a component (D), 312 parts by mass of toluene and 2-butanone 1/1 mixed solvent was placed in a flask and dissolved by stirring at 20 to 40 ° C.
In the obtained solution, as component (B), 14 parts by mass of linear organohydrogenpolysiloxane B-1 (SiH content = 1.5 mol / 100 g) (number of moles of hydrogen atoms directly bonded to silicon atoms) Is equivalent to 1.5 times the unsaturated group contained in the components (A) and (G)),
As a bath life extending agent, 1 part by mass of 3-methyl-1-butyn-3-ol was blended and stirred and mixed at 20 to 40 ° C. for 1 hour.

ａ＝１．７、ｂ＝１、平均重合度３、２５℃での粘度０．１Ｐａ・ｓのエポキシ基を持ったシロキサンオリゴマーＧを３質量部、
（Ｂ）成分として、直鎖状オルガノハイドロジェンポリシロキサンＢ−１（ＳｉＨ含有量＝１．５モル／１００ｇ）を４質量部（ケイ素原子に直結した水素原子のモル数が（Ａ）成分の含有する不飽和基に対し３倍に相当）、
バスライフ延長剤として、３−メチル−１−ブチン−３−オールを１質量部配合し、２０〜４０℃で１時間撹拌混合した。 (Preparation Example 6)
As the component (A), a 30% by mass toluene solution has a viscosity at 25 ° C. of 15 Pa · s, and both ends of the molecular chain are represented by (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 The main skeleton that is blocked with a vinylsilyl group and excluding the terminal is 1.5 mol% of a methylvinylsiloxane unit represented by (CH ₃ ) (CH ₂ ═CH) SiO _2/2 and (CH ₃ ) ₂ SiO _{2 /} 100 parts by mass of organopolysiloxane A-3 (vinyl group content = 0.02 mol / 100 g) in which the dimethylsiloxane unit represented by ₂ is composed of 98.5 mol%,
As a component (D), 249 parts by mass of toluene and 2-butanone 1/1 mixed solvent were placed in a flask and dissolved by stirring at 20 to 40 ° C.
As component (G),
Represented by the composition formula (CH ₃ O—) _a R ^Ep _b SiO _{(4-ab) / 2} ,
R ^Ep is represented by the following formula (24),

3 parts by mass of siloxane oligomer G having an epoxy group with a = 1.7, b = 1, average polymerization degree 3, viscosity of 0.1 Pa · s at 25 ° C.
As component (B), 4 parts by mass of linear organohydrogenpolysiloxane B-1 (SiH content = 1.5 mol / 100 g) (the number of moles of hydrogen atoms directly bonded to silicon atoms is the component (A)) Equivalent to 3 times the unsaturated group contained)
As a bath life extending agent, 1 part by mass of 3-methyl-1-butyn-3-ol was blended and stirred and mixed at 20 to 40 ° C. for 1 hour.

(Preparation Example 7)
As the component (A), a 30% by mass toluene solution has a viscosity at 25 ° C. of 15 Pa · s, and both ends of the molecular chain are represented by (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 The main skeleton that is blocked with a vinylsilyl group and excluding the terminal is composed of 4 mol% of a methylvinylsiloxane unit represented by (CH ₃ ) (CH ₂ ═CH) SiO _2/2 and (CH ₃ ) ₂ SiO _2/2 . dimethylsiloxane units 91 _mole% represented, _{(C 6} H 5) ₂ organopolysiloxane diphenylsiloxane units represented by _{SiO 2/2} is composed of 5 mole% A-4 (a vinyl group content = 0.04 mol / 100 g) 100 parts by mass,
As a component (D), 298 parts by mass of toluene and 2-butanone 1/1 mixed solvent were placed in a flask and dissolved by stirring at 20 to 40 ° C.
As component (H), (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 unit 5 mol%, (CH ₃ ) ₃ SiO _1/2 unit 45 mol%, SiO _4/2 unit 50 mol% 20 parts by mass of an organopolysiloxane I having an average degree of polymerization of 100 (vinyl group content 0.07 mol / 100 g),
As the component (B), only 8 parts by mass of the linear organohydrogenpolysiloxane B-1 (SiH content = 1.5 mol / 100 g) (the number of hydrogen atoms directly bonded to the silicon atom is (A), (H) 2.2 times the unsaturated group contained in the component)
As a bath life extending agent, 1 part by mass of 3-methyl-1-butyn-3-ol was blended and stirred and mixed at 20 to 40 ° C. for 1 hour.

(Preparation Example 8)
In Preparation Example 1, as an additional component (I), 1 part by mass of a polyoxyethylene alkyl ether type nonionic surfactant was added,
As the component (D), a composition was prepared in the same manner except that 239 parts by mass of toluene and 2-butanone 1/1 mixed solvent were blended.

  Table 1 shows the constituent components of Adjustment Examples 1 to 8. Here, “-” in the table means that it is not blended. The same applies to the following tables.

Example 1
I) 2000 parts by mass of PEDOT-PSS solution obtained in Production Example 3 as a conductive polymer composition,
II) Composition of Preparation Example 1 as an addition reaction curable silicone composition 100 parts by weight as an active ingredient,
As a catalyst for component C), a platinum-vinylsiloxane complex was added in an amount corresponding to 0.07 parts by mass of platinum to prepare a coating composition.
The paint was applied onto a PET film using a # 5 bar coater and dried at 120 ° C. for 1 minute to form a film. Thus, a release sheet was completed.

(Example 2)
II) As an addition reaction curable silicone composition, instead of Preparation Example 1, a coating composition was prepared under the same conditions as in Example 1 except that the equivalent amount of the composition of Preparation Example 2 was added as an active ingredient. The prepared release sheet was prepared.

(Example 3)
II) As an addition reaction curable silicone composition, instead of Preparation Example 1, a coating composition was prepared under the same conditions as in Example 1 except that the equivalent amount of the composition of Preparation Example 3 was added as an active ingredient. The prepared release sheet was prepared.

Example 4
II) As an addition reaction curable silicone composition, instead of Preparation Example 1, a coating composition was prepared under the same conditions as in Example 1 except that the equivalent amount of the composition of Preparation Example 4 was added as an active ingredient. The prepared release sheet was prepared.

(Example 5)
II) As an addition reaction curable silicone composition, instead of Preparation Example 1, a coating composition was prepared under the same conditions as in Example 1 except that the equivalent amount of the composition of Preparation Example 5 was added as an active ingredient. The prepared release sheet was prepared.

(Example 6)
II) As an addition reaction curable silicone composition, instead of Preparation Example 1, a coating composition was prepared under the same conditions as in Example 1, except that an equivalent amount of the composition of Preparation Example 6 was added as an active ingredient. The prepared release sheet was prepared.

(Example 7)
II) As an addition reaction curable silicone composition, instead of Preparation Example 1, a coating composition was prepared under the same conditions as in Example 1, except that an equivalent amount of the composition of Preparation Example 7 was added as an active ingredient. The prepared release sheet was prepared.

(Example 8)
II) As an addition reaction curable silicone composition, instead of Preparation Example 1, a coating composition was prepared under the same conditions as in Example 1 except that the equivalent amount of the composition of Preparation Example 8 was added as an active ingredient. The prepared release sheet was prepared.

Example 9
I) A coating composition was prepared under the same conditions as in Example 6 except that Production Example 4 was used instead of Production Example 3 as the conductive polymer composition, and a release sheet was completed.

(Example 10)
I) A coating composition was prepared under the same conditions as in Example 6 except that Production Example 5 was used instead of Production Example 3 as the conductive polymer composition, and a release sheet was completed.

(Example 11)
I) A coating composition was prepared under the same conditions as in Example 6 except that Production Example 6 was used instead of Production Example 3 as the conductive polymer composition, and a release sheet was completed.

(Example 12)
I) A coating composition was prepared under the same conditions as in Example 6 except that Production Example 7 was used instead of Production Example 3 as the conductive polymer composition, and a release sheet was completed.

(Example 13)
I) A coating composition was prepared under the same conditions as in Example 6 except that Production Example 8 was used instead of Production Example 3 as the conductive polymer composition, and a release sheet was completed.

(Example 14)
I) PEDOT-PSS solution obtained in Production Example 3 as a conductive polymer composition 50 parts by mass,
II) 100 parts by mass of the composition of Preparation Example 1 as an active ingredient as an addition reaction curable silicone composition;
As a catalyst for component C), a platinum-vinylsiloxane complex is added in an amount corresponding to 0.07 parts by mass of platinum,
As a solvent for component D), 1,750 parts by mass of methyl ethyl ketone was mixed to prepare a coating composition. The paint was applied onto a PET film using a # 5 bar coater and dried at 120 ° C. for 1 minute to form a film. Thus, a release sheet was completed.

(Example 15)
I) 10,000 parts by mass of a PEDOT-PSS solution obtained in Production Example 3 as a conductive polymer composition,
II) 100 parts by mass of the composition of Preparation Example 1 as an active ingredient as an addition-curable silicone composition;
As a catalyst for component C), a platinum-vinylsiloxane complex was added in an amount corresponding to 0.07 parts by mass of platinum to prepare a coating composition.
The paint was applied onto a PET film using a # 14 bar coater and dried at 120 ° C. for 1 minute to form a film. Thus, a release sheet was completed.

(Comparative Example 1)
In Example 1, except that the PEDOT-PSS solution obtained in Production Example 3 was changed to the PEDOT-PSS solution obtained in Production Example 2, a paint was produced in the same manner as in Example 1, but PEDOT- PSS aggregation and separation occurred and could not be dispersed in silicone.

(Comparative Example 2)
In Example 1, I) The conductive polymer composition was omitted, and 1,795 parts by mass of methyl ethyl ketone was added as a solvent for the component (D) to prepare a coating composition.
The paint was applied onto a PET film using a # 5 bar coater and dried at 120 ° C. for 1 minute to form a film. Thus, a release sheet was completed.

<Evaluation>
The evaluation results by the following methods are shown in Tables 2 to 4.

[Appearance of coating composition]
The appearance of the compositions prepared in Examples and Comparative Examples was visually observed.
[Curing property]
The obtained release agent was applied to 100 μm thick PE laminated paper with a # 14 bar coater and heated in a 120 ° C. hot air dryer for 1 minute to form a release agent layer. The release agent layer was rubbed 10 times with a finger, and then the presence or absence of cloudiness and dropping off was visually observed and evaluated according to the following criteria.
A: Cloudy and omission were not seen.
B: Cloudy or falling off was observed.
[Adhesion]
The obtained release agent was applied to a PET film having a thickness of 38 μm with a # 5 bar coater or # 14 bar coater and heated in a 120 ° C. hot air dryer for 1 minute to form a release agent layer at 25 ° C. And 50% RH for one week or 60 ° C. and 90% RH for one week. After the release layer was rubbed 10 times with a finger, the presence or absence of cloudiness and dropping off was visually observed and evaluated according to the following criteria.
A: Clouding and dropping off were not observed even after one week at 60 ° C. and 90% RH.
B: Clouding and dropping off were observed after one week at 60 ° C. and 90% RH, but at 25 ° C. and 50% RH.
There was no clouding or shedding in one week.
C: Clouding or dropping off was observed at 25 ° C. and 50% RH for one week.
[Appearance of film]
The obtained release agent was applied to a PET film having a thickness of 38 μm with a # 5 bar coater or # 14 bar coater and heated in a 120 ° C. hot air dryer for 1 minute to form a release agent layer. Observed.
A: Transparent release agent layer without cloudiness B: Release agent layer with cloudiness [peeling force]
A release agent layer is formed in the same manner as in the above sclerosis evaluation, and a 50 mm wide polyester adhesive tape (No. 31B, product name manufactured by Nitto Denko Corporation) is placed on the surface of the release agent layer. Then, a load of 1976 Pa was put on and heat-treated at 70 ° C. for 20 hours, and a polyester adhesive tape was bonded to the release agent layer. 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 peeling force was measured.
[Residual adhesion rate]
Similarly to the measurement of the peeling force, a polyester adhesive tape was bonded to the release agent layer. Thereafter, the polyester adhesive tape was peeled off from the release agent layer, and the polyester adhesive tape was attached to a stainless steel plate. Subsequently, the polyester adhesive tape was peeled from the stainless steel plate using a tensile tester, and the peeling force X was measured.
Moreover, the peeling force Y measured by sticking a polyester adhesive tape to a polytetrafluoroethylene plate instead of the release agent layer and treating the same was measured.
And the residual adhesive rate was calculated | required from the formula of (peeling force X / peeling force Y) x100 (%).
The higher the residual adhesive rate, the better the release property of the release agent layer, and the lowering of 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. The unit “Ω / □” is the same as “Ω / sq.”. In the table, “x” indicates that the surface resistivity exceeded 1 × 10 ¹⁵ and could not be measured high.

Claims (12)

I) a conductive polymer composition that includes the following (a), (b) and (c), and is dispersible and soluble in a solvent mainly composed of an organic solvent;
(A) a π-conjugated conductive polymer (b) a polyanion doped in the (a) π-conjugated conductive polymer (c) an anion other than that required for doping in the (b) polyanion, an oxirane group, and And / or reaction product II with an oxetane group-containing organic compound II) an addition-curable organopolysiloxane composition comprising the following (A), (B), (C) and (D):
(A) Organopolysiloxane represented by the following general formula (1) and having at least two alkenyl groups in one molecule: 100 parts by mass

(In the formula, R ¹ is independently an alkenyl group, R ² is a monovalent organic group that does not independently contain an aliphatic unsaturated bond, and the following X ^{1 to} X ³ are independently the following general formula (2), (3) and (4)

The following X ^{4 to} X ⁶ are independently the following general formulas (5), (6) and (7)

Are groups represented by a3 to a6, a12 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62 and a63 are the viscosity of the organopolysiloxane at 25 ° C. from 0.05 Pa · s to 30% by weight toluene diluted viscosity And a4 to a6, a12 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62 and a63 may be 0. a1, a2, a11, a21, a31, a41, a51 and a61 are each independently an integer of 0 to 3. )
(B) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule and represented by the following average composition formula (8): Number of moles of hydrogen atoms bonded to contained silicon atoms Is equivalent to 1 to 20 times the total number of moles of the alkenyl group-containing component

(In the formula, R ² is a monovalent organic group containing no aliphatic unsaturated bond, b 1 is 0.1 to 2, b 2 is 0.1 to 3, b 1 + b 2 is a real number 1 to 3, (It is selected so that the molecule has two or more SiH groups and the viscosity at 25 ° C. falls within the range of 0.005 to 10 Pa · s.)
(C) A curable silicone composition containing a catalytic amount of a platinum group metal catalyst (D) and an arbitrary amount of an organic solvent.   The (a) π-conjugated conductive polymer is a polypyrrole, polythiophene, polyacetylene, polyphenylene, polyphenylene vinylene, polyaniline, polyacene, polythiophene vinylene, or a copolymer of two or more thereof The curable silicone composition according to claim 1, comprising at least one repeating unit selected from the group consisting of:   The curable silicone composition according to claim 1, wherein the (a) π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene) or polypyrrole.   The curability according to any one of claims 1 to 3, wherein the (b) polyanion is one or a mixture selected from a sulfonic acid group, a phosphoric acid group and a carboxyl group. Silicone composition.   The (b) polyanion is polystyrene sulfonic acid, polyvinyl sulfonic acid, polyacrylic acid alkylene sulfonic acid, poly (2-acrylamido-2-methyl-1-propanesulfonic acid) or one or more of them as a copolymerization constituent. It contains, The curable silicone composition of any one of Claims 1-4 characterized by the above-mentioned. The curable silicone composition according to claim 1, wherein the component (B) is an organohydrogenpolysiloxane represented by the following general formula (9) and / or the following general formula (10).

(Wherein R ² is the same as above, R ⁵ is independently a hydrogen atom or a monovalent organic group containing no aliphatic unsaturated bond, and R ⁶ and R ⁷ are aliphatic unsaturated bonds other than Me. B11 and b12 are integers of 0 to 3, b13 is an integer of 1 or more, b23 is an integer of 3 or more, b14 to b17, b24 to b27 are integers of 0 or more And having two or more SiH groups in one molecule and having a viscosity at 25 ° C. in the range of 0.005 to 10 Pa · s.) The curable silicone composition according to claim 1, wherein the component (B) is an organohydrogenpolysiloxane mixture having a (B1) / (B2) mass part ratio of 1/9 to 9/1. object.
((B1) is the above general formula (9) and / or the above general formula (10), wherein R ² is a monovalent organic group other than aromatic and does not contain an aliphatic unsaturated bond, and R ⁵ is independently A monovalent organic group that does not contain a hydrogen atom or an aliphatic unsaturated bond other than aromatic, and R ⁶ and R ⁷ are monovalent organic groups that do not contain an aliphatic unsaturated bond other than aromatic except Me group (B2). Is the general formula (9) and / or the general formula (10), wherein at least one of R ² and R ^{5 to} R ⁷ is an aromatic monovalent organic group. (E) 0.1-30 mass parts of organopolysiloxane shown by the following general formula (11) as a component

(Wherein R ⁸ is independently a hydroxyl group and an alkoxy group, R ⁹ is a monovalent organic group not containing a hydroxyl group and an alkoxy group, R ¹⁰ is a monovalent organic group other than a Me group not containing a hydroxyl group and an alkoxy group, e 1 and e2 is an integer of 1 to 3, and e3 to e5 are selected from integers that make the viscosity of the organopolysiloxane at 25 ° C. in the range of 1 Pa · s to 30 mass% toluene diluted viscosity 100 Pa · s.)
The curable silicone composition according to any one of claims 1 to 7, comprising: as an additional component. (F) 10-100 parts by mass (structure) of organopolysiloxane having the following structure having at least two alkenyl groups as component
R ² _(3-f1) R ¹ _f1 —SiO _1/2 siloxane unit represented as M ^R1R2 ,
^Consisting of R ² SiO _3/2 siloxane units denoted as T ^R2 ,
A organopolysiloxane M ^R1R2 / ^{T R2} siloxane units molar ratio satisfies 0.2 to 0.8, a viscosity at 25 ° C. has a degree of polymerization in the range of 0.001Pa · s~1Pa · s, The molecular ends are mainly blocked with ^MR1R2 siloxane units, but some of the ends may be formed as silanol groups or alkoxy groups.
(In the formula, R ¹ is an alkenyl group, R ² is a monovalent organic group that does not independently contain an aliphatic unsaturated bond, and f 1 is each independently an integer of 1 to ^3. )
The curable silicone composition according to any one of claims 1 to 8, which comprises an additional component. As component (G), an organosilane represented by the following general formula (12) having at least an epoxy group and an alkoxysilyl group in one molecule and / or a partially hydrolyzed cocondensed siloxane 0.1 represented by the following general formula (13) -10 parts by mass

(Wherein, R ¹¹ is an organic group having an epoxy group, R ¹² may be made may contain an ether bond-C6 alkyl group having a carbon part is hydrolyzed to a hydroxyl group, R ¹³ is An organic group having no epoxy group, excluding an alkoxy group, g1 and g2 are integers satisfying 1 ≦ g1, 1 ≦ g2, 2 ≦ g1 + g2 ≦ 4, and g3 to g5 are real numbers 0 <g3, 0 <g4 And 0 ≦ g5, 1 <g3 + g4 + g5 ≦ 3, and the viscosity of the organopolysiloxane at 25 ° C. is selected from positive numbers in the range of 0.001 Pa · s to 1 Pa · s.)
The curable silicone composition according to any one of claims 1 to 9, comprising As component (H), 1 to 100 parts by mass of MQ resin comprising a siloxane unit of the following general formula (14) / a siloxane unit molar ratio of the following general formula (15) = 2/8 to 8/2

(Wherein R ¹ and R ² are the same organic groups as described above, and h1 is selected from integers of 0 to 3)
The curable silicone composition according to any one of claims 1 to 10, comprising: as an additional component.   A release sheet comprising: the curable silicone composition according to any one of claims 1 to 11; and a coating film obtained by applying the curable silicone composition to a substrate and curing the composition.