JP2016216714A - Thermosetting antistatic coating agent, cured coating, and plastic film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel thermosetting antistatic coating agent capable of suppressing raise of surface resistivity even under high voltage and forming a cured coating less in change with time on a surface of a plastic film.SOLUTION: There is provided a thermosetting antistatic coating agent containing a carboxylate anionic group-containing acryl copolymer (A), a curing agent (B), a π conjugation-based conductive polymer (C) and a conductive inorganic filler (D), where the (D) component contains at least one kind selected from a group consisting of a metal oxide-based conductive filler (D1) and a carbon-based conductive filler (D2), the amount of the (D1) component, if it is contained, is 5 to 30 pts.mass (in terms of solid component) based on total 100 pts.mass (in terms of solid component) of the (A) component and the (B) component and the amount of the (D2) component, if it is contained, is 0.5 to 10 pts.mass (in terms of solid component) based on total 100 pts.mass (in terms of solid component) of the (A) component and the (B) component.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting antistatic coating agent, a cured film thereof, and a plastic film provided with the cured film.

  Conventionally, plastic films have been used in a wide range of applications. For example, films for carrier tapes or cover tapes used in processes such as semiconductor processing, release films used in the manufacturing process of electronic components and ceramic capacitors, hot films Stamping films, plate-making films, packaging films, decorative films, protective films and the like are known.

  The plastic film is also used as an optical film. For example, the plastic film is used as a member such as a prism lens sheet of a liquid crystal display device member, a touch panel, a liquid crystal backlight, or an organic EL display.

  By the way, a plastic film is easily charged with static electricity during winding, rewinding or processing. For this reason, dust in the atmosphere adheres to the surface, resulting in physical defects (pinholes and the like), and poor running on the processing line. In addition, with the miniaturization and high integration of various semiconductors and electronic devices, the generation of static electricity causes problems such as malfunction of electrical products.

  Therefore, means for kneading an antistatic agent into a plastic film or coating an antistatic coating agent on the surface has been adopted. As the latter, for example, a combination of an organic binder resin and a π-conjugated conductive polymer such as polythiophene or polypyrrole is known (Patent Documents 1 and 2).

  However, a film made of such an antistatic coating agent is generally considered to have a high surface resistivity under a high voltage. For this reason, a plastic film treated with a conventional antistatic coating agent may be inappropriate as a member of equipment or parts used under high voltage.

  As a composition that suppresses the increase in surface resistivity of the film even under high voltage, 3,4-dialkoxythiophene is converted into an acetylene glycol-based conductive polymer obtained by oxidative polymerization in the presence of a polyanion in an aqueous solvent. A conductive composition containing a surfactant is known (Patent Document 3). However, there is a concern that the surface resistivity of the conductive composition film increases with time. Furthermore, the surface resistivity tends to increase even when a higher voltage is applied.

JP 2009-256623 A JP 2010-196022 A JP 2014-040550 A

  The present invention is a novel thermosetting antistatic coating capable of forming a cured film on the surface of a plastic film, in which the surface resistivity is less likely to change over time and can be suppressed even when applied at a higher voltage. The main issue is to provide the agent.

  As a result of intensive studies, the present inventor has found that the above problems can be solved by a thermosetting coating agent formed by combining predetermined raw materials. That is, the present invention relates to the following thermosetting antistatic coating agent, a cured film thereof, and a plastic film provided with the cured film.

1. A carboxylate anion group-containing acrylic copolymer (A), a curing agent (B), a π-conjugated conductive polymer (C), and a conductive inorganic filler (D);
The component (D) includes at least one selected from the group consisting of a metal oxide conductive filler (D1) and a carbon conductive filler (D2),
(D1) When using a component, the quantity is 5-30 mass parts (solid content conversion) with respect to a total of 100 mass parts (solid content conversion) of (A) component and (B) component,
(D2) When using a component, the quantity is 0.5-10 mass parts (solid content conversion) with respect to 100 mass parts (solid content conversion) of the sum total of (A) component and (B) component,
Thermosetting antistatic coating agent.

2. The component (A) is a neutralized salt of a copolymer consisting of a monomer group (α) containing α, β unsaturated carboxylic acids (a1) and (meth) acrylic acid alkyl esters (a2). Item 2. The thermosetting antistatic coating agent according to Item 1.

3. Item (A) The thermosetting antistatic coating agent according to Item 1 or 2, wherein the carboxylate anion group content (mol / g) of the component is 0.0003 to 0.005.

4). (B) The thermosetting antistatic coating agent according to any one of Items 1 to 3, wherein the component is an aziridine compound.

5. The thermosetting antistatic coating agent according to any one of Items 1 to 4, wherein the solid content mass ratio [(A) / (B)] of the component (A) to the component (B) is 5/5 to 9/1. .

6). (C) The thermosetting antistatic coating agent according to any one of Items 1 to 5, wherein the component is a polythiophene.

7). The thermosetting type according to any one of Items 1 to 6, wherein the content of the component (C) is 5 to 25 parts by mass in terms of solid content with respect to a total of 100 parts by mass of the component (A) and the component (B). Antistatic coating agent.

8). Items (1) to (D1) above, wherein the component is at least one selected from the group consisting of antimony-doped tin oxide, tin-doped indium oxide, phosphorus-doped tin oxide, tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and zinc antimonate. 7. The thermosetting antistatic coating agent according to any one of 7;

9. (D2) The thermosetting antistatic coating agent according to any one of Items 1 to 8, wherein the component is a carbon nanotube.

10. 10. A cured film of the thermosetting antistatic coating agent according to any one of Items 1 to 9.

11. A plastic film comprising the cured film of item 10 on at least one side.

  According to the thermosetting antistatic coating agent of the present invention, it is possible to form a cured film capable of suppressing an increase in surface resistivity even when applied at a high voltage to the surface of a plastic film. Furthermore, the cured film exhibits good antistatic properties not only after being subjected to a humidity condition of about 50% but also after being left for several days under a very high humidity condition of about 90%. The cured film not only has excellent adhesion to a plastic film, but also has good curability, blocking resistance, solvent resistance, and transparency.

  Since the plastic film of the present invention is provided with a cured film having the above-mentioned properties on its surface, it is suitable as a product used under high voltage conditions, for example, a member such as a protective film or carrier film for precision equipment. .

  The thermosetting antistatic coating agent (hereinafter referred to as coating agent) of the present invention comprises a carboxylate anion group-containing acrylic copolymer (A) (hereinafter referred to as component (A)), a curing agent (B) (hereinafter referred to as component (B)). And a π-conjugated conductive polymer (C) (hereinafter referred to as component (C)) and a predetermined conductive inorganic filler (D) (hereinafter referred to as component (D)).

As the component (A), various known ones can be used without particular limitation as long as they are acrylic copolymers having a carboxylate anion group (—COO ⁻ ) in the molecule. Specifically, a monomer group including α, β unsaturated carboxylic acids (a1) (hereinafter referred to as component (a1)) and (meth) acrylic acid alkyl esters (a2) (hereinafter referred to as component (a2)) A neutralized salt of a copolymer comprising α) (hereinafter referred to as (α) component) is preferred.

  As the component (a1), various known α, β unsaturated carboxylic acids can be used without particular limitation. Specific examples include α, β unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and isocrotonic acid and salts thereof; α, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride. β-unsaturated dicarboxylic acids and salts thereof; half esters of the α and β-unsaturated dicarboxylic acids with alcohols having about 1 to 30 carbon atoms and salts thereof; α and β-unsaturated dicarboxylic acids with about 1 to 30 carbon atoms Examples thereof include half amides with amines and neutralized salts thereof, and two or more of them may be used in combination. Examples of the alcohol include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, methyl cellosolve, and ethyl cellosolve. Examples of the amine include methylamine, ethylamine, propylamine, n-butylamine, n-hexylamine, and n-octylamine. As the compound that forms the salt, a neutralizing agent described later can be used. As the component (a1), the α, β-unsaturated monocarboxylic acid, particularly acrylic acid and / or methacrylic acid, is preferable from the viewpoint of the curability of the film made of the coating agent of the present invention.

  As the component (a2), various known (meth) acrylic acid alkyl esters can be used without particular limitation. The alkyl group may be linear, branched or cyclic. Examples of the straight chain include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, lauryl (meth) acrylate and (meth). Examples include stearyl acrylate. Examples of branched ones include isobutyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Examples of the cyclic group include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, and isobornyl (meth) acrylate, and two or more kinds may be used in combination. Among these, from the viewpoint of adhesion of the cured film according to the present invention, particularly with a plastic film, the linear (meth) acrylic acid alkyl ester has an alkyl group with about 1 to 20 carbon atoms (preferably 1). About 8).

  The component (α) may include an unsaturated monomer (hereinafter referred to as the component (a3)) other than the component (a1) and the component (a2). Examples of the component (a3) include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, and Nt-. Butyl (meth) acrylamide, N-lauryl (meth) acrylamide, N-cyclohexyl substituted alkyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-dit Acrylamides such as butyl (meth) acrylamide, N, N-dilauryl (meth) acrylamide, N, N-di-t-octyl (meth) acrylamide, and N, N-dicyclohexyl (meth) acrylamide; (meth) acrylic acid 2-hydroxymethyl, ( 2) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol mono (meth) acrylate , Hydroxyalkyl (meth) acrylates such as pentaerythritol di (meth) acrylate and pentaerythritol tri (meth) acrylate; styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, hydroxystyrene, vinyltoluene And styrenes such as chlorovinyltoluene; unsaturated sulfonic acids such as vinylsulfonic acid, (meth) allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and sulfonated styrene; Aminoethyl methacrylate, aminopropyl (meth) acrylate, aminobutyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N-methylaminopropyl (meth) acrylate, (meth) acrylic acid N-methylaminobutyl, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, (meth) acrylic acid Aminoalkyl unsaturated monomers such as N, N-diethylaminoethyl, N, N-diethylaminopropyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate; polyoxyalkylene (meth) acrylic acid Esters, polyoxyalkylene glycerin (meth) acrylic acid esters, polio Polyoxyalkylene-based polymers such as cycloalkylene monoalkyl (meth) acrylic acid esters, polyoxyalkylene monoalkenyl (meth) acrylic acid esters, polyoxyalkylene (meth) allyl ether, polyoxyalkylene glycerol (meth) allyl ether Saturated monomers: vinyldimethylchlorosilane, vinylmethyldichlorosilane, vinyltrichlorosilane, allyldimethylchlorosilane, allylmethyldichlorosilane, allyltrichlorosilane, 4-butenyldimethylchlorosilane, 4-butenylmethyldichlorosilane, 4-butyl Tenenyltrichlorosilane, 5-pentenyldimethylchlorosilane, 5-pentenylmethyldichlorosilane, 5-pentenyltrichlorosilane, 3-methacryloxypropyldimethylchlorosilane 3-methacryloxypropylmethyldichlorosilane, 3-methacryloxypropyltrichlorosilane, 3-acryloxypropyldimethylchlorosilane, 3-acryloxypropylmethyldichlorosilane, 3-acryloxypropyltrichlorosilane, 4-methacryloxybutyldimethylchlorosilane, Chlorosilane (meth) acrylates such as 4-methacryloxybutylmethyldichlorosilane, 4-methacryloxybutyltrichlorosilane, 4-acryloxybutyldimethylchlorosilane, 4-acryloxybutylmethyldichlorosilane; “Silaplane FM-0711” Polysiloxane mono (meth) acrylates such as “Silaplane FM-0721”, “Silaplane FM-0725” (all manufactured by JNC Corporation); 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,2- Trifluoro-1-trifluoromethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, H, 1H, 5H-octafluoropentyl (meth) acrylate, 2,2,3,3 4,4,5,5-octafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5,5,5-nonafluoropentyl (meth) acrylate and the like. In addition, as commercially available products, fluoroalkyl (meta) such as “Biscoat 3F”, “Biscoat 4F”, “Biscoat 8F”, “Biscoat 8FM”, “Biscoat 13FM” (all manufactured by Osaka Organic Chemical Industries, Ltd.) Examples thereof include acrylates, and two or more kinds may be used in combination.

  The contents of the component (a1), component (a2) and component (a3) in the component (α) are not particularly limited, but are usually as follows from the viewpoint of curability of the coating agent according to the present invention.

<When (a3) component is not used>
(A1) component: about 3 to 30% by mass, preferably about 5 to 20% by mass (a2) component: 70 to 97% by mass, preferably about 80 to 95% by mass

<When (a3) component is used>
(A1) component: about 3 to 30% by mass, preferably about 5 to 20% by mass (a2) component: about 20 to 96% by mass, preferably about 50 to 90% by mass (a3) component: 1 to 50% by mass Degree, preferably about 5 to 30% by mass

  The manufacturing method of (A) component is not specifically limited, Various well-known methods are employable. Specifically, for example, the components (a1) and (a2) and, if necessary, the component (a3) are polymerized in an appropriate reaction vessel, usually at about 60 to 180 ° C., usually for about 1 to 20 hours. It is obtained by reacting. The reaction order of each component is not particularly limited, and may be sequential or batch.

  In the reaction, various known initiators, chain transfer agents, and solvents described below can be used as reaction solvents.

  Examples of the initiator include inorganic peroxides such as hydrogen peroxide, ammonium persulfate and potassium persulfate; organic peroxides such as t-butyl peroxybenzoate, dicumyl peroxide and lauryl peroxide; Examples include azo compounds such as 2′-azobisisobutyronitrile and dimethyl-2,2′-azobisisobutyrate, and two or more of them may be used in combination. Although the usage-amount is not specifically limited, Usually, it is about 0.01-10 mass parts with respect to a total of 100 mass parts of (a1) component-(a3) component.

  The chain transfer agent is used for the purpose of adjusting the molecular weight of the component (A). Specific examples include dodecyl mercaptan, 2-mercaptobenzothiazole and bromotrichloromethane, and two or more of them may be used in combination. Although the usage-amount is not specifically limited, Usually, it is about 0.01-5 mass parts with respect to a total of 100 mass parts of (a1) component-(a3) component.

  When all of the component (a1) is a neutralized product or a part thereof is a neutralized product, the obtained copolymer is the component (A). When all of the component (a1) is an unneutralized product, the component (A) can be obtained by neutralizing the obtained copolymer with a neutralizing agent (base component).

  Examples of the base component include ammonia; primary amines such as monomethylamine, monoethylamine, monobutylamine and cyclohexylamine; secondary amines such as dimethylamine and diethylamine; tertiary amines such as trimethylamine, triethylamine and tributylamine; Other amines such as aniline, arylamine and alkanolamine; alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide and magnesium hydroxide. Among these, amines which are easily volatilized from the cured film and hardly remain are preferable, and tertiary amines and / or ammonia are more preferable. Although the usage-amount of a base component is not specifically limited, Usually, it is the range used as about 50-200 mol% with respect to the free carboxyl group in (a1) component.

  The amount (mol / g) of the carboxylate anion group in the component (A) is not particularly limited, but is usually about 0.0003 to 0.005. By setting it to 0.0003 or more, the curability of the coating agent of the present invention and the solvent resistance of the cured film tend to be good, and by setting it to 0.005 or less, the antistatic property of the cured film. Tend to be good. From this viewpoint, the amount of carboxylate anion group is preferably about 0.001 to 0.003. “Carboxylate anion group amount” refers to the number of moles of carboxylate anion group contained in 1 g of component (A) (in terms of solid content), and is a calculated value.

  Other physical properties of the component (A) include glass transition temperature and number average molecular weight (polystyrene conversion value by gel permeation chromatography). In any case, the range may be set in terms of adhesion, curability, blocking resistance, etc. of the cured film. The former is usually about 20 to 150 ° C., preferably about 70 to 150 ° C., and the latter is usually It is about 2000 to 150,000, preferably about 10,000 to 100,000.

  As the component (B), various known materials can be used without particular limitation as long as the coating film is sufficiently cured. Specific examples include aziridine compounds, carbodiimide compounds, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, metal chelate compounds, and the like.

  Examples of the aziridine compound include diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane tri-βaziridinylpropionate, tetramethylolmethanetri-βaziridinylpropionate. , Toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, bisisophthaloyl-1- (2-methylaziridine), tris-1- (2-methylaziridine) phosphine and trimethylolpropane Tri-β (2-methylaziridine) propionate and the like are listed, and commercially available products include CROSSLINKER CL-427 (manufactured by Mutual Yakuhin Co., Ltd.), Chemite PZ-33 and DZ-22E (manufactured by Nippon Shokubai Co., Ltd.) Etc., and two or more of them may be used in combination.

  Examples of the carbodiimide compound include poly (4,4′-diphenylmethanecarbodiimide), poly (3,3′-dimethyl-4,4′-biphenylmethanecarbodiimide), poly (tolylcarbodiimide), and poly (p-phenylenecarbodiimide). ), Poly (m-phenylenecarbodiimide), poly (3,3′-dimethyl-4,4′-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (1,6-hexamethylenecarbodiimide), poly (1, 4-tetramethylenecarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (1,3,5-triethylphenylenecarbodiimide), poly (4,4′-methylene Biscyclohexylcarbodi ), Poly (1,3-diisopropylphenylenecarbodiimide), poly (1-methyl-3,5-diisopropylphenylenecarbodiimide), poly (isopropylphenylenecarbodiimide) and the like, and commercially available products include carbodilite V-02 and Carbodilite V-04 (manufactured by Nisshinbo Chemical Co., Ltd.) can be exemplified, and two or more kinds may be used in combination.

  Examples of the melamine compounds include methylated melamine compounds and butylated melamine compounds, and commercially available products include Nicalak MW-30M (manufactured by Sanwa Chemical Co., Ltd.) and Cymel 303LF (Ornex Japan Co., Ltd.). Etc.), and two or more of them may be used in combination.

  Examples of the isocyanate compound include lower aliphatic polyisocyanates such as ethylene diisocyanate, butylene diisocyanate and hexamethylene diisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; 2,4-tolylene diisocyanate Examples include isocyanates, aromatic polyisocyanates such as 4,4′-diphenylmethane diisocyanate and xylylene diisocyanate, and commercially available products include Aquanate 100 (manufactured by Tosoh Corporation) and Duranate WB40-100 (Asahi Kasei Chemicals Corporation). Etc.), and two or more of them may be used in combination.

  Examples of the epoxy compound include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, and sorbitol polyglycidyl ether. And aliphatic polyepoxy compounds such as pentaerythritol polyglycidyl ether, bisphenol A or bisphenol F type epoxy compounds, and the like, and commercially available products include Denacol EX-614 (manufactured by Nagase ChemteX Corporation), jER YX8034 ( Mitsubishi Chemical Co., Ltd.) can be exemplified, and two or more kinds may be used in combination.

  Examples of the oxazoline compound include addition-polymerizable oxazoline compounds such as 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, and 2-vinyl-4-methyl-2-oxazoline. Examples include Epocross WS-300, WS-500 and WS-700 (manufactured by Nippon Shokubai Co., Ltd.), and two or more of them may be used in combination.

  Examples of the metal chelate compound include those containing aluminum, zirconium, titanium, zinc, iron, tin or the like as a metal element. Specifically, for example, diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, diisopropoxy aluminum Monostearyl acetoacetate, diisopropoxyaluminum monoisostearyl acetoacetate, monoisopropoxyaluminum mono-N-lauroyl-β-alanate monolauryl acetoacetate, aluminum trisacetylacetonate, monoacetylacetonate aluminum bis (isobutylacetoacetate) Chelate, monoacetylacetonate aluminum bis (2-ethylhexyl) Cetoacetate) chelates, monoacetylacetonate aluminum bis (dodecyl acetoacetate) chelates, and monoacetylacetonate aluminum bis (oleyl acetoacetate) chelates and other aluminum chelate compounds; titanium diisopropoxy bis (acetylacetonate), titanium tetra Titanium chelates such as acetylacetonate, titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), titanium diisopropoxybis (triethanolaminate), titanium lactate ammonium salt and titanium lactate Compound: zirconium tetraacetylacetonate, zirconium tributoxy monoacetylacetonate, zirconium monobutoxyacetylacetate Examples include zirconium chelate compounds such as tonate bis (ethyl acetoacetate), zirconium dibutoxy bis (ethyl acetoacetate), and zirconium tetraacetylacetonate, and commercially available products such as ORGATIX TC-100 and TC-300 (Matsumoto Fine Chemical Co., Ltd.) )) And the like, and two or more of them may be used in combination.

  Among these (B) components, it is selected from the group consisting of an aziridine compound, a carbodiimide compound, an epoxy compound, an oxazoline compound, and a metal chelate compound because it easily reacts with the carboxylate anion group contained in the component (A). Among these, at least one kind is preferable, and among them, an aziridine compound is preferable from the viewpoint of curability of the film.

  Although the usage-amount of (B) component is not specifically limited, Solid content mass ratio [(A) / of (A) component and (B) component from points, such as adhesiveness of a cured film, sclerosis | hardenability, and solvent resistance. (B)] is usually in the range of about 5/5 to 9/1, preferably about 6/4 to 8/2.

  The component (C) is essential for the cured film of the present invention to exhibit excellent antistatic properties, and various known π-conjugated conductive polymers can be used without particular limitation. Specific examples include at least one selected from the group consisting of polythiophenes, polyanilines, polythiophene vinylenes, polypyrroles, polyfurans, and the like. Among these, polythiophenes are preferable from the viewpoint of antistatic properties and transparency of the cured film.

  Examples of polythiophenes include polythiophene, poly (alkylthiophene) s, poly (monoalkoxythiophene) s, poly (dialkoxythiophene) s, poly (alkylenedioxythiophene) s, and the like. Among these, in particular, alkylenedioxypoly (thiophene) doped with polystyrene sulfonic acid (PSS) is particularly a complex of poly3,4-ethylenedioxythiophene (PEDOT) and PSS (hereinafter also referred to as PEDOT / PSS). ) Is preferred. PEDOT / PSS is obtained, for example, by polymerizing 3,4-ethylenedioxythiophene (EDOT), which is a monomer, in an aqueous phase using an oxidizing agent in the presence of polystyrene sulfonic acid (PSS) as a dopant. It is done. Examples of commercially available products include Clevios P (manufactured by Heraeus Co., Ltd.) and Orgacon ICP1010 (manufactured by Nippon Agfa Materials Co., Ltd.), and two or more of them may be used in combination.

  Examples of polyanilines include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid). You may do it.

  Although content of (C) component in the coating agent of this invention is not specifically limited, From points, such as an antistatic characteristic and transparency of a cured film, with respect to a total of 100 mass parts of (A) component and (B) component. It is usually about 5 to 25 parts by mass, preferably about 10 to 15 parts by mass in terms of solid content.

  The component (D) is a component that imparts excellent antistatic properties to the coating agent of the present invention even under a high voltage by combining the component (C).

  The component (D) is a metal oxide-based conductive filler (D1) (hereinafter referred to as (D1) component) and / or a carbon-based conductive filler (D2) (hereinafter referred to as (D2) component).

  As the component (D1), various known materials can be used without particular limitation as long as they are conductive metal oxide fillers. Specifically, for example, antimony-doped tin oxide (ATO), fluorine-doped tin oxide, phosphorus-doped tin oxide (PTO), aluminum-doped tin oxide, niobium-doped tin oxide, tantalum-doped tin oxide, tungsten-doped tin oxide, indium-doped tin oxide , Tin oxide, tin doped indium oxide (ITO), fluorine doped indium oxide, cadmium doped indium oxide, indium doped zinc oxide, fluorine doped zinc oxide, aluminum doped zinc oxide, gallium doped zinc oxide, magnesium doped zinc oxide, silicon doped zinc oxide , Tin-doped zinc oxide, boron-doped zinc oxide, zinc oxide, zinc antimonate (AZO), niobium-doped titanium oxide, and the like, and two or more of them may be used in combination. Among these, at least one selected from the group consisting of antimony-doped tin oxide, tin-doped indium oxide, phosphorus-doped tin oxide, tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, zinc antimonate, and the like is preferable and applied at a high voltage. However, antimony-doped tin oxide, tin-doped indium oxide, phosphorus-doped tin oxide, tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and zinc antimonate are particularly preferable from the viewpoint of suppressing an increase in surface resistivity.

  The shape of the component (D1) is not particularly limited, and examples thereof include powder, aqueous sol, and organic solvent sol. Examples of the powdered (D1) component include those in which inorganic particles such as titanium oxide are coated with the (D1) component.

  As a commercial item of (D1) component, for example, T-1, S-2000, S-1, SP-2, E-ITO, TDL-1, TDL-SA, SPDL and SDL (above, Mitsubishi Materials Corporation )), Celnax CX-Z330H, CX-Z610-F2, CX-Z410K, CX-S301H, CX-S204IP and CX-S501M (above, manufactured by Nissan Chemical Industries, Ltd.), Pazette CK and Pazette GK-40 (Huxuitec Co., Ltd.) and the like may be used, and two or more may be used in combination.

  In the coating agent of this invention, when (D1) component is used, the content is about 5-30 mass parts (solid content) with respect to a total of 100 mass parts (solid content conversion) of (A) component and (B) component. Minute conversion). When the surface resistivity is less than 5 parts by mass, the surface resistivity of the cured film according to the present invention tends to increase greatly when applied at a high voltage. Moreover, when it exceeds 30 mass parts, it exists in the tendency for the transparency of a cured film to fall. From this viewpoint, the content of the component (D1) is preferably about 7 to 25 parts by mass (in terms of solid content).

  As the component (D2), various known materials can be used without particular limitation as long as they are carbon-based conductive fillers. Specifically, for example, carbon black such as carbon nanotube, carbon nanowire, acetylene black and furnace black, graphite, activated carbon and the like may be used, and two or more kinds may be used in combination. Among these, carbon nanotubes are particularly preferable from the viewpoint of suppressing an increase in surface resistivity even when applied under a high voltage. Examples of carbon nanotubes include single-walled carbon nanotubes, multi-walled carbon nanotubes, and coiled carbon nanotubes. Carbon nanotubes can be obtained by, for example, catalytic reduction of carbon dioxide, arc discharge method, laser evaporation method, CVD method, vapor phase growth method and the like. The carbon nanotubes may be pulverized by a ball mill, a vibration mill or the like, or may be cut short by chemical or physical treatment.

  The shape of the component (D2) is not particularly limited, and examples thereof include powders, aqueous sols, and organic solvent sols.

  As a commercial item of (D2) component, UW-153, UW-253 (above, Ube Industries, Ltd. product), CARBOBYK-9810 (Bic Chemie Japan Co., Ltd. product) etc. are mentioned, for example. May be used in combination.

  In the coating agent of this invention, when (D2) component is used, the content is about 0.5-10 mass parts (solid content conversion) with respect to a total of 100 mass parts of (A) component and (B) component. It is. When the amount is less than 0.5 parts by mass, the surface resistivity of the cured film according to the present invention tends to greatly increase under a high voltage. Moreover, when it exceeds 10 mass parts, it exists in the tendency for the transparency of a cured film to fall. From this viewpoint, the content of the component (D2) is preferably about 0.8 to 5 parts by mass (in terms of solid content).

  The coating agent of the present invention may contain a solvent. Examples of the solvent include an organic solvent and water. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, diethylene glycol, ethylene glycol monoethyl ether, and ethylene glycol mono n-propyl ether; acetone And ketones such as methyl ethyl ketone; aromatic hydrocarbons such as toluene, xylene, and benzene; and other examples include ethyl acetate, chloroform, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. good. Examples of the water include ion exchange water. Among these, alcohols having about 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol and isopropyl alcohol are preferable from the viewpoint of storage stability of the coating agent of the present invention. Moreover, ion-exchange water is preferable as water.

  Although content of the solvent in the coating agent of this invention is not specifically limited, Usually, what is necessary is just the range from which solid content concentration of this coating agent will be about 0.1-30 mass%.

  The coating agent of the present invention includes additives such as an antifoaming agent, an antiskid agent, an antiseptic agent, a rust inhibitor, a pH adjuster, an antioxidant, a pigment, a dye, a lubricant, a leveling agent, a conductivity improver, and a curing catalyst. May be included.

  Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, and perfluoropolydimethylsiloxane, and two or more kinds may be used in combination. Although the usage-amount of this leveling agent is not specifically limited, It is less than 10 mass parts with respect to 100 mass parts (solid content conversion) of the sum total of (A) component and (B) component.

  Examples of the conductivity improver include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, and glycerin. Dimethyl sulfoxide, N-methylpyrrolidone, N-methylformamide, N-dimethylformamide, isophorone, propylene carbonate, cyclohexanone and the like, and two or more of them may be used in combination. Although the usage-amount of this electroconductivity improver is not specifically limited, It is less than 300 mass parts with respect to a total of 100 mass parts (solid content conversion) of (A) component and (B) component.

  Examples of curing catalysts include acid catalysts such as paratoluenesulfonic acid, hydrochloric acid, sulfuric acid, and phosphoric acid; acid generators such as diaryliodonium salts, triarylsulfonium salts, and diarylphosphonium salts. You may do it. Although the usage-amount of this curing catalyst is not specifically limited, It is less than 3 mass parts with respect to a total of 100 mass parts (solid content conversion) of (A) component and (B) component.

  The coating agent of the present invention can be obtained by stirring and mixing the component (A), the component (B), the component (C) and the component (D) and, if necessary, the solvent and the additive.

  The cured film of the present invention can be obtained by applying the coating agent of the present invention to a plastic film and thermally curing it.

  Examples of the plastic film include polycarbonate film, polymethyl methacrylate film, polystyrene film, polyethylene terephthalate film, polyimide film, polyolefin film, nylon film, epoxy resin film, melamine resin film, triacetyl cellulose resin film, ABS resin film, AS Examples thereof include a resin film and a norbornene resin film. These may be subjected to surface treatment (corona discharge or the like) as necessary. Moreover, the said plastic film may be provided with various functional layers on one side or both sides.

  The coating method is not particularly limited, and various known means can be used. Examples thereof include roll coating, reverse roll coating, gravure coating, knife coating, bar coating, and dip coating.

  After coating the coating agent of the present invention on the substrate surface, it is preferable to perform a drying treatment from the viewpoint of blocking resistance of the cured film. Although a drying temperature is not specifically limited, Usually, about 60-150 degreeC, Preferably it is about 80-120 degreeC. The drying time is not particularly limited, but is usually about 10 to 120 seconds.

  The plastic film of the present invention is an article provided with the cured film according to the present invention on at least one side. Although the thickness of a cured film is not specifically limited, Usually, it is about 0.01-2 micrometers. The thickness of the plastic film is not particularly limited, but is usually about 25 to 125 μm.

  Hereinafter, the present invention will be described in detail through examples and comparative examples. However, the technical scope of the present invention is not limited by them. “Parts” and “%” in the examples are based on mass unless otherwise specified.

  In each production example, the glass transition temperature is a value measured by a differential scanning calorimeter (product name “DSC6200”, manufactured by Seiko Instruments Inc.). The number average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (product name “HLC-8220GPC”, manufactured by Tosoh Corporation).

<Manufacture of (A) component>
Production Example 1
A four-necked flask equipped with a nitrogen gas inlet tube, a thermometer, a reflux condenser and a stirrer is charged with 16 parts of acrylic acid and 144 parts of methyl methacrylate, and 446 parts of isopropyl alcohol are further added to prepare a monomer solution. did. Next, 3.2 parts of 2,2′-azobisisobutyronitrile was added to the monomer solution as a polymerization initiator. Next, the reaction system was set to 80 ° C., and a radical polymerization reaction was performed for 8 hours. Next, 22.4 parts of triethylamine and 1000 parts of ion-exchanged water are added to the reaction system, and the mixture is stirred well and cooled to room temperature, whereby a solution of a carboxylate anion group-containing acrylic copolymer (A-1) component having a solid content of 10% is obtained. Got. The amount of carboxylate anion group of the component (A-1) was 0.00139 mol / g, the glass transition temperature was 100 ° C., and the number average molecular weight was 30000.

Production Example 2
A four-necked flask similar to Production Example 1 was charged with 24 parts of acrylic acid and 136 parts of methyl methacrylate, and 435 parts of isopropyl alcohol was further added to form a monomer solution. Next, 3.2 parts of azobisisobutyronitrile as a polymerization initiator was added to the monomer solution. Subsequently, after raising the temperature of the reaction system to 80 ° C., a radical polymerization reaction was performed for 8 hours. Thereafter, 33.7 parts of triethylamine and 1000 parts of ion-exchanged water were added to the reaction system, and the mixture was stirred well and cooled to room temperature, so that the carboxylate anion group-containing acrylic copolymer (A-2) component having a solid content of 10% was obtained. A solution was obtained. In addition, the carboxylate anion group amount of the component (A-2) was 0.00208 mol / g, the glass transition temperature was 95 ° C., and the number average molecular weight was 30000.

Comparative production example 1
In Production Example 1, without using triethylamine after the polymerization reaction, only 1000 parts of isopropyl alcohol was added to the reaction system, stirred well, and cooled to room temperature, whereby a carboxyl group-containing acrylic copolymer (E-1 having a solid content of 10%) ) Was obtained. Component (E-1): carboxylate anion group amount: 0 mol / g, glass transition temperature: 100 ° C., number average molecular weight: 30000

Example 1
As component (A), 700 parts of component (A-1) (solid content conversion: 70 parts), and as component (B), trimethylolpropane-tris (1-aziridinylpropionate) (trade name “Chemite PZ -33 ", Nippon Shokubai Co., Ltd.) 30 parts, (C) Component PEDOT / PSS aqueous solution (trade name" Orgacon ICP1010 ", Nihon Agfa Materials Co., Ltd., solid content 1.2%) 1000 parts ( (Solid content 12 parts), antimony-doped tin oxide (trade name “TDL-1”, manufactured by Mitsubishi Materials Corporation, solid content 17%) 60 parts (solid content 10 parts), triethylamine 3.0% as component (D) Parts, 1 part of BYK-333 (polyether-modified polydimethylsiloxane, manufactured by Big Chemie Japan Co., Ltd.) as a leveling agent, 1 part of paratoluenesulfonic acid as a catalyst, 6900 parts of ion exchange water and 3500 parts of isopropyl alcohol were mixed at room temperature for 10 minutes to prepare a coating agent having a solid content of 1.0%.

Examples 2-16, Comparative Examples 1-17
A coating agent was prepared in the same manner as in Example 1, except that the type or amount used was as shown in Table 1.

[Preparation of test film]
Bar coater No. 3, the coating agent of Example 1 was coated on a PET film, and the coated film was dried in a smooth air dryer (100 ° C., 1 minute) to prepare a test film. Test films were prepared in the same manner for the coating agents of Examples 2 to 16 and Comparative Examples 1 to 17.

[Measurement of surface resistivity]
In the coated surface of the test film according to Example 1, in accordance with JIS K6911, using a Hirestar UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation under an applied voltage of 100 V and 1000 V, a temperature of 23 ° C., and a humidity of 50%. The surface resistivity (Ω / □) was measured. Moreover, the film for a test concerning Examples 2-17 and Comparative Examples 1-17 was measured similarly. The smaller the surface resistivity value, the better the antistatic performance. The results are shown in Table 1 (the same applies hereinafter).

[Surface resistivity after wet heat]
The test film according to Example 1 was allowed to stand for 4 days in an environment of a temperature of 40 ° C. and a humidity of 90%. The film for a test concerning Examples 2-16 and comparative examples 1-17 was measured similarly. The smaller the surface resistivity value, the better the antistatic performance.

[transparency]
The haze value of the test film was measured according to JIS-K-7136 using a haze meter “HM-150” (Murakami Color Research Laboratory). The difference from the haze value of the PET film alone is ΔHz, and the smaller the value, the better the transparency.

[Curing property]
The test film was rubbed with a cotton swab dipped in methyl ethyl ketone, and the number of times (reciprocation) until the substrate was exposed was measured.
◎: The substrate is not exposed even after rubbing 100 times or more ○: The substrate is exposed when rubbing 60 to 100 times Δ: The substrate is exposed when rubbing 20 to 59 times ×: Rubbing 1 to 19 times The substrate is exposed

[Adhesion]
After sticking the adhesive tape on the test film and pressing it well, it was peeled off vigorously, and the amount of the remaining coating film was visually evaluated according to the following criteria.
A ... 100% coating film remained. A ... 70% or more and less than 100% coating film remained. A ... 40% or more and less than 70% coating film remained.
X: Less than 40% of the coating film remained.

* The amount of each component used is indicated in terms of solid content.

[Component (B)]
(B-1) Trimethylolpropane-tris (1-aziridinylpropionate) (trade name “Chemite PZ-33”, manufactured by Nippon Shokubai Co., Ltd.)
(B-2) Tetramethylolmethane-tris (1-aziridinylpropionate) (trade name “CLOSLINKER CL427”, manufactured by Mutual Yakuhin Co., Ltd.)
(B-3) Carbodiimide type curing agent (trade name “Carbodilite V-02”, manufactured by Nisshinbo Industries, Inc.)
[Component (C)]
(C-1) PEDOT / PSS (trade name “Orgacon ICP1010”, manufactured by Japan Agfa Materials Co., Ltd., solid content 1.2%)
[(D1) component]
(D1-1) Antimony-doped tin oxide (trade name “TDL-1”, manufactured by Mitsubishi Materials Corporation, solid content 17%)
(D1-2) Tin-doped indium oxide (trade name “Prototype ITO aqueous dispersion”, manufactured by Mitsubishi Materials Corporation, solid content 20%)
(D1-3) Phosphorus-doped tin oxide (trade name “CELNAX CX-S301H”, manufactured by Nissan Chemical Industries, Ltd., solid content 30%)
(D1-4) Zinc antimonate (trade name “CELNAX CX-Z330H”, manufactured by Nissan Chemical Industries, Ltd., solid content 30%)
[(D2) component]
(D2) Carbon nanotube (trade name “UW-153”, manufactured by Ube Industries, Ltd., solid content 2.5%)
[Other conductive components]
(F-1) Lithium trifluoromethanesulfonate (trade name “EF-15”, manufactured by Mitsubishi Materials Corporation)
(F-2) Lithium bis (trifluoromethanesulfonyl) imide (trade name “EF-N115”, manufactured by Mitsubishi Materials Corporation)
(G-1) Acetylene glycol surfactant (trade name “Surfinol 485”, manufactured by Nissin Chemical Industry Co., Ltd.)

Claims (11)

A carboxylate anion group-containing acrylic copolymer (A), a curing agent (B), a π-conjugated conductive polymer (C), and a conductive inorganic filler (D);
The component (D) includes at least one selected from the group consisting of a metal oxide conductive filler (D1) and a carbon conductive filler (D2),
(D1) When using a component, the quantity is 5-30 mass parts (solid content conversion) with respect to a total of 100 mass parts (solid content conversion) of (A) component and (B) component,
(D2) When using a component, the quantity is 0.5-10 mass parts (solid content conversion) with respect to 100 mass parts (solid content conversion) of the sum total of (A) component and (B) component,
Thermosetting antistatic coating agent. The component (A) is a neutralized salt of a copolymer consisting of a monomer group (α) containing α, β unsaturated carboxylic acids (a1) and (meth) acrylic acid alkyl esters (a2). Item 2. The thermosetting antistatic coating agent according to Item 1. The thermosetting antistatic coating agent according to claim 1 or 2, wherein the component (A) has a carboxylate anion group content (mol / g) of 0.0003 to 0.005. The thermosetting antistatic coating agent according to any one of claims 1 to 3, wherein the component (B) is an aziridine compound. The thermosetting antistatic coating agent according to any one of claims 1 to 4, wherein the solid content mass ratio [(A) / (B)] of the component (A) and the component (B) is 5/5 to 9/1. . The thermosetting antistatic coating agent according to any one of claims 1 to 5, wherein the component (C) is a polythiophene. The thermosetting type according to any one of claims 1 to 6, wherein the content of the component (C) is 5 to 25 parts by mass in terms of solid content with respect to a total of 100 parts by mass of the component (A) and the component (B). Antistatic coating agent. The component (D1) is at least one selected from the group consisting of antimony-doped tin oxide, tin-doped indium oxide, phosphorus-doped tin oxide, tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and zinc antimonate. 7. The thermosetting antistatic coating agent according to any one of 7; (D2) The thermosetting antistatic coating agent according to any one of claims 1 to 8, wherein the component is a carbon nanotube. A cured film of the thermosetting antistatic coating agent according to claim 1. A plastic film comprising the cured film of claim 10 on at least one side.