CN106167662B

CN106167662B - Thermosetting antistatic coating agent, cured coating film thereof, and plastic film

Info

Publication number: CN106167662B
Application number: CN201610330792.8A
Authority: CN
Inventors: 伊藤良树; 东本徹
Original assignee: Arakawa Chemical Industries Ltd
Current assignee: Arakawa Chemical Industries Ltd
Priority date: 2015-05-18
Filing date: 2016-05-18
Publication date: 2020-07-10
Anticipated expiration: 2036-05-18
Also published as: KR20160135668A; CN106167662A; JP2016216714A; TWI692509B; KR102559995B1; TW201710413A; JP6631881B2

Abstract

The invention provides a novel thermosetting antistatic coating agent which can form a cured coating film on the surface of a plastic film, wherein the cured coating film can inhibit the surface resistivity from increasing even under high voltage and has little change with time, and a cured coating film and a plastic film thereof. The thermosetting antistatic coating agent contains a carboxylate anion group-containing acrylic copolymer (A), a curing agent (B), a pi-conjugated conductive polymer (C) and a conductive inorganic filler (D), wherein the component (D) contains at least one selected from the group consisting of a metal oxide conductive filler (D1) and a carbon conductive filler (D2), and when the component (D1) is used, the amount thereof is 5 to 30 parts by mass in terms of solid content relative to 100 parts by mass of the total of the components (A) and (B), and when the component (D2) is used, the amount thereof is 0.5 to 10 parts by mass in terms of solid content relative to 100 parts by mass of the total of the components (A) and (B).

Description

Thermosetting antistatic coating agent, cured coating film thereof, and plastic film

Technical Field

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

Background

Conventionally, plastic films are used in a wide variety of applications, and for example, films for carrier tapes or cover tapes used in processes such as semiconductor processing, release films, heat-seal films, plate-making films, packaging films, decorative films, protective films, and the like used in processes for manufacturing electronic components or ceramic capacitors are known.

Plastic films are also used as optical films, for example, as members of liquid crystal display devices, such as prism sheets, touch panels, liquid crystal backlights, and organic E L displays.

Plastic films are easily charged with static electricity when being wound or unwound or when being processed. Therefore, dust in the atmosphere adheres to the surface to cause physical defects (pinholes, etc.), or cause running defects in 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 operational errors of electric products.

Therefore, a means of kneading an antistatic agent into a plastic film or coating an antistatic coating agent on the surface is employed. As the latter, for example, an antistatic coating agent in which a pi-conjugated conductive polymer such as polythiophene or polypyrrole is combined with an organic binder resin is known (patent documents 1 and 2).

However, it is generally considered that a coating film made of such an antistatic coating agent tends to have a high surface resistivity at a high voltage. Therefore, a plastic film treated with a conventional antistatic coating agent may not be suitable as a member of a device or a member used under high voltage.

As a composition capable of suppressing an increase in the surface resistivity of a coating film even at a high voltage, a conductive composition in which an acetylene glycol surfactant is blended with a conductive polymer obtained by oxidative polymerization of 3, 4-dialkoxythiophene in the presence of a polyanion in an aqueous solvent is known (patent document 3). However, the surface resistivity of the coating film of the conductive composition may increase with time. Further, when a higher voltage is applied, the surface resistivity is also easily increased.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2009-256623

Patent document 2: japanese laid-open patent publication No. 2010-196022

Patent document 3: japanese patent laid-open publication No. 2014-040550

Disclosure of Invention

Problems to be solved by the invention

The main object of the present invention is to provide a novel thermosetting antistatic coating agent which can form a cured film on the surface of a plastic film, the surface resistivity of which is not likely to change over time, and which can suppress the increase in surface resistivity even when applied at a higher voltage.

Means for solving the problems

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

1. A heat-curable antistatic coating agent comprising an acrylic copolymer (A) containing a carboxylate anion group, a curing agent (B), a pi-conjugated conductive polymer (C) and a conductive inorganic filler (D),

(D) component (B) contains at least one selected from the group consisting of a metal oxide-based conductive filler (D1) and a carbon-based conductive filler (D2),

when the component (D1) is used, the amount thereof is 5 to 30 parts by mass (in terms of solid content) based on 100 parts by mass (in terms of solid content) of the total of the components (A) and (B),

when the component (D2) is used, the amount thereof is 0.5 to 10 parts by mass (in terms of solid content) per 100 parts by mass (in terms of solid content) of the total of the components (A) and (B).

2. The thermosetting antistatic coating agent according to item 1 above, wherein the component (A) is a neutralized salt of a copolymer comprising a monomer group (α) of α unsaturated carboxylic acids (a1) and alkyl (meth) acrylates (a 2).

3. The heat-curable antistatic coating agent according to item 1 or 2 above, wherein the content (mol/g) of the carboxylate anion group in the component (A) is 0.0003 to 0.005.

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

5. The thermosetting antistatic coating agent according to any one of the above 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. The heat-curable antistatic coating agent according to any one of the above items 1 to 5, wherein the component (C) is a polythiophene.

7. The heat-curable antistatic coating agent 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, based on 100 parts by mass of the total of the components (A) and (B).

8. The thermosetting antistatic coating agent according to any one of the above items 1 to 7, wherein 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, aluminum-doped zinc oxide, gallium-doped zinc oxide, and zinc antimonate.

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

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

11. A plastic film comprising the cured coating film according to item 10 above on at least one surface thereof.

Effects of the invention

According to the thermosetting antistatic coating agent of the present invention, a cured coating film capable of suppressing an increase in surface resistivity even when applied at a high voltage can be formed on the surface of a plastic film. Furthermore, the cured film exhibited good antistatic properties not only under 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 is excellent in adhesion to a plastic film and also in curability, blocking resistance, solvent resistance and transparency.

The plastic film of the present invention is provided with a cured coating film having the above-described properties on the surface thereof, and therefore, is suitable as a product used under high voltage conditions, for example, a member such as a protective film or a carrier film for precision equipment.

Detailed Description

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

The component (A) is not particularly limited as long as it has a carboxylate anion group (-COO) in the molecule^-) The acrylic copolymer (C) may be any of various known acrylic copolymers without particular limitation, and specifically, it is preferably composed of α -containing unsaturated carboxylic acidA neutralized salt of a copolymer composed of a monomer group (α) (hereinafter referred to as component (α)) of the type (a1) (hereinafter referred to as component (a 1)) and an alkyl (meth) acrylate (a2) (hereinafter referred to as component (a 2)).

Specific examples of the component (a1) include β, β unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and isocrotonic acid and salts thereof, α unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride and salts thereof, half esters of the α unsaturated dicarboxylic acid with an alcohol having 1 to 30 carbon atoms and salts thereof, half amides of the α unsaturated dicarboxylic acid with an amine having 1 to 30 carbon atoms and salts thereof neutralized with one another, and two or more of these compounds may be used in combination.

As the component (a2), various known alkyl (meth) acrylates can be used without particular limitation. The alkyl group may be linear, branched or cyclic. Examples of the linear alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. Examples of the branched alkyl (meth) acrylate include isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Examples of the cyclic alkyl (meth) acrylate include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, and isobornyl (meth) acrylate, and two or more kinds of the cyclic alkyl (meth) acrylates may be used in combination. Among these, the linear alkyl (meth) acrylate is preferable from the viewpoint of adhesion particularly to a plastic film of the cured coating film of the present invention, and the linear alkyl (meth) acrylate having an alkyl group with about 1 to 20 carbon atoms (preferably about 1 to 8 carbon atoms) is particularly preferable.

Examples of the component (α) may include unsaturated monomers other than the above-mentioned component (a1) and component (a2) (hereinafter referred to as component (a 3)), examples of the component (a3) include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-lauryl (meth) acrylamide, N-cyclohexyl substituted alkyl (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diisopropyl (meth) acrylamide, N-di-t-butyl (meth) acrylamide, N-dilauryl (meth) acrylamide, N-di-t-octyl (meth) acrylamide, N-dicyclohexyl (meth) acrylamide, acrylamides such as 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylamide, N-di-t-octyl (meth) acrylamide, N-dicyclohexyl (meth) acrylamide, N-allyl methacrylate, N-propyl (meth) acrylamide, N-ethyl methacrylate, N-butyl methacrylate, N-ethyl methacrylate, N-isopropyl methacrylate, N-butyl (meth) acrylamide, N-butyl methacrylate, N-isopropyl methacrylate, N-butyl methacrylate, N-ethyl methacrylate, N-butyl methacrylate, N-ethyl methacrylate, N-butyl methacrylate, N-ethyl methacrylate, N-butyl methacrylate, N-ethyl methacrylate, N-butyl methacrylate, N-ethyl methacrylate, N-butyl methacrylate, N-ethyl methacrylate, N-butyl methacrylate, N-ethyl methacrylate, N-butyl methacrylate, N-ethyl methacrylate, N-butyl methacrylate, N-ethyl methacrylate, N-butyl methacrylate, N-ethyl methacrylate, N-butyl methacrylate ethyl methacrylate, N-ethyl methacrylate.

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

< case where component (a3) was not used >

(a1) The components: about 3 to about 30% by mass, preferably about 5 to about 20% by mass

(a2) The components: 70 to 97% by mass, preferably about 80 to 95% by mass

< case of Using component (a3) >

(a2) The components: about 20 to about 96% by mass, preferably about 50 to about 90% by mass

(a3) The components: about 1 to about 50% by mass, preferably about 5 to about 30% by mass

(A) The method for producing the component (a) is not particularly limited, and various known methods can be used. Specifically, for example, the polymerization reaction can be carried out by polymerizing the component (a1), the component (a2) and, if necessary, the component (a3) in an appropriate reaction vessel at usually about 60 to about 180 ℃ for usually about 1 to about 20 hours. The reaction sequence of the components is not particularly limited, and may be sequential or simultaneous.

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

Examples of initiators include: inorganic peroxides such as hydrogen peroxide, ammonium persulfate, and potassium persulfate; organic peroxides such as t-butyl peroxybenzoate, dicumyl peroxide and lauryl peroxide; azo compounds such as 2,2 '-azobisisobutyronitrile and dimethyl 2, 2' -azobisisobutyrate, and two or more of these compounds may be used in combination. The amount used is not particularly limited, and is usually about 0.01 to about 10 parts by mass per 100 parts by mass of the total of components (a1) to (a 3).

The chain transfer agent is used for the purpose of adjusting the molecular weight of the component (a). Specific examples thereof include dodecylmercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and the like, and two or more of them may be used in combination. The amount used is not particularly limited, and is usually about 0.01 to about 5 parts by mass per 100 parts by mass of the total of components (a1) to (a 3).

When the component (a1) is a neutralized product in its entirety 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 obtained copolymer is neutralized with a neutralizing agent (alkali component) to obtain the component (a).

Examples of the alkali 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, aromatic amines and alkanolamines; alkali metal compounds such as sodium hydroxide and potassium hydroxide; and alkaline earth metal compounds such as calcium hydroxide and magnesium hydroxide. Among these, amines which are easily volatilized from the cured coating and hardly remain are preferable, and tertiary amines and/or ammonia are more preferable. The amount of the base component used is not particularly limited, and is usually in the range of about 50 to about 200 mol% relative to the free carboxyl groups in the component (a 1).

(A) The amount (mol/g) of the carboxylate anion group in the component (A) is not particularly limited, but is usually about 0.0003 to about 0.005. By setting the amount 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 the amount to 0.005 or less, the antistatic properties of the cured film tend to be good. From this viewpoint, the amount of the carboxylate anion group is preferably from about 0.001 to about 0.003. The "amount of carboxylate anion groups" means the number of moles of carboxylate anion groups contained in 1g (in terms of solid content) of the component (a), and is a calculated value.

Other physical properties of the component (A) include a glass transition temperature and a number average molecular weight (polystyrene equivalent value obtained by gel permeation chromatography). The glass transition temperature and the number average molecular weight may be set within ranges from the viewpoint of adhesion of the cured coating, curability, blocking resistance, and the like, and the former is usually from about 20 ℃ to about 150 ℃, preferably from about 70 ℃ to about 150 ℃, and the latter is usually from about 2000 to about 150000, preferably from about 10000 to about 100000.

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

Oxazoline compounds, metal chelate compounds, and the like.

Examples of the aziridine compound include diphenylmethane-4, 4' -bis (1-aziridinecarboxamide), trimethylolpropane tri- β aziridinylpropionate, tetramethylolmethane tri- β aziridinylpropionate, toluene-2, 4-bis (1-aziridinecarboxamide), triethylenemelamine, bis-isophthaloyl-1- (2-methylaziridine), tris-1- (2-methylaziridine) phosphine, and trimethylolpropane tri- β (2-methylaziridine) propionate, and commercially available products include CROSS L INKERC L-427 (manufactured by CROSS CORPOR Co., Ltd.), ケミタイト PZ-33, and DZ-22E (manufactured by Nippon catalyst Co., Ltd.), and two or more thereof may be used in combination.

Examples of the carbodiimide-based compound include poly (4,4 '-diphenylmethane carbodiimide), poly (3, 3' -dimethyl-4, 4 '-biphenylmethane carbodiimide), poly (tolylcarbodiimide), poly (p-phenylene carbodiimide), poly (m-phenylene carbodiimide), poly (3, 3' -dimethyl-4, 4 '-diphenylmethane carbodiimide), poly (naphthylene carbodiimide), poly (1, 6-hexamethylene carbodiimide), poly (1, 4-tetramethylene carbodiimide), poly (1, 3-cyclohexylene carbodiimide), poly (1, 4-cyclohexylene carbodiimide), poly (1,3, 5-triethylenecarbodiimide), poly (4, 4' -methylenedicyclohexylcarbodiimide), Examples of commercially available products include poly (1, 3-diisopropylphenylene carbodiimide), poly (1-methyl-3, 5-diisopropylphenylene carbodiimide), and poly (isopropylphenylene carbodiimide), and カルボジライト V-02 and カルボジライト V-04 (manufactured by Nisshinbo Co., Ltd.) may be used in combination of two or more.

Examples of the melamine-based compound include methylated melamine compounds and butylated melamine compounds, and commercially available products include ニカラック MW-30M (manufactured by Sanko Co., Ltd.) and サイメル 303L F (manufactured by オルネクスジャパン Co., Ltd.), and two or more of them can be used in combination.

Examples of the isocyanate-based 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; examples of commercially available aromatic polyisocyanates such as 2, 4-xylylene diisocyanate, 4' -diphenylmethane diisocyanate and xylylene diisocyanate include アクアネート 100 (manufactured by Tosoh Corp.) and デュラネート WB40-100 (manufactured by Asahi Kasei Co., Ltd.), and two or more of them can be used in combination.

Examples of the epoxy compound include aliphatic epoxy compounds such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, and bisphenol a-or bisphenol F-type epoxy compounds, and examples of commercially available epoxy compounds include デナコール EX-614 (manufactured by ナガセケムテックス corporation) and jER YX8034 (manufactured by mitsubishi chemical corporation), and two or more of them can be used in combination.

As

As the oxazoline-based compound, for example, 2-isopropenyl-2-

Oxazoline, 2-vinyl-2-

Oxazoline and 2-vinyl-4-methyl-2-

Polyaddition type of oxazoline or the like

As commercially available oxazoline compounds, エポクロス WS-300, WS-500 and WS-700 (manufactured by Nippon catalyst Co., Ltd.) can be exemplified, and two or more kinds thereof can be used in combination.

Specific examples of the metal chelate compound include aluminum compounds such as diisopropoxyaluminum monooleate acetoacetic acid ester, monoisopropoxyaluminum bisoleate acetoacetic acid ester, monoisopropoxyaluminum monooleate monoethyl acetoacetic acid ester, diisopropoxyaluminum monolauryl acetoacetate ester, diisopropoxyaluminum monostearyl acetoacetate ester, monoisopropoxyaluminum mono-N-lauroyl- β aluminum oxide monolauryl acetoacetate ester, aluminum triacetylacetone, aluminum monoacetylacetonate bis (isobutyl acetoacetate) chelate ester, aluminum monoacetylacetonate bis (2-ethylhexyl acetoacetate) chelate ester, aluminum monoacetylacetonate bis (dodecyl acetoacetate) chelate ester and aluminum monoacetylacetonate bis (oleic acetoacetate) chelate ester, diisopropoxybis (acetylacetonato) titanium, titanium acetylacetonate, dioctyloxybis (octylglycolate) titanium, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (tetraethoxysilane) titanium, titanium triethanolate, zirconium lactate and zirconium acetate, and the commercially available titanium chelate compounds such as titanium マツモトファインケミカル -acetate-zirconium acetate chelate ester, zirconium acetate-acetate chelate ester, zirconium acetate-zirconium acetate chelate ester, zirconium acetate-zirconium acetate-zirconium-acetate-zirconium-acetate-and the like, and the commercially available compounds are.

Among these components (B), from the viewpoint of being easily reacted with the carboxylate anion group contained in component (A), it is preferably selected from the group consisting of aziridine-based compounds, carbodiimide compounds, epoxy-based compounds, and mixtures thereof,

Among them, aziridine compounds are preferred from the viewpoint of curability of the coating film.

(B) The amount of the component (B) is not particularly limited, but the solid content mass ratio [ (a)/(B) ] of the component (a) to the component (B) is usually about 5/5 to 9/1, preferably about 6/4 to 8/2, from the viewpoint of adhesion, curability, solvent resistance and the like of the cured coating film.

(C) The component (b) is necessary for the cured film of the present invention to exhibit excellent antistatic properties, and various known pi-conjugated conductive polymers can be used without particular limitation. Specifically, for example, at least one selected from the group consisting of polythiophenes, polyanilines, polythiophenevinylenes, polypyrroles, polyfuranes, and the like can be cited. Among them, polythiophenes are preferable from the viewpoint of antistatic properties, transparency, and the like of the cured film.

Examples of the polythiophene include polythiophene, poly (alkylthiophene), poly (monoalkoxythiophene), poly (dialkoxythiophene), and poly (alkylenedioxythiophene). Among them, alkylenedioxy poly (thiophene) doped with polystyrene sulfonic acid (PSS) is particularly preferable, and a complex of poly (3, 4-ethylenedioxythiophene) (PEDOT) and PSS (hereinafter also referred to as PEDOT/PSS) is particularly preferable. PEDOT/PSS is obtained, for example, by polymerizing 3, 4-Ethylenedioxythiophene (EDOT) as a monomer in an aqueous phase in the presence of polystyrene sulfonic acid (PSS) as a dopant using an oxidizing agent. Examples of commercially available products include Clevios P (manufactured by ヘレウス), Orgacon ICP1010 (manufactured by アグフアマテリアルズ, japan), and two or more thereof may be used in combination.

The polyaniline includes polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), and poly (3-anilinesulfonic acid), and two or more kinds of polyaniline may be used in combination.

The content of the component (C) in the coating agent of the present invention is not particularly limited, and is usually about 5 to about 25 parts by mass, preferably about 10 to about 15 parts by mass in terms of solid content, relative to 100 parts by mass of the total of the component (a) and the component (B), from the viewpoints of antistatic properties, transparency, and the like of a cured film.

(D) Component (C) is a component which imparts excellent antistatic properties to the coating agent of the present invention even at high voltage.

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

As the component (D1), various known materials can be used without particular limitation as long as they are metal oxide fillers having conductivity. 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-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 Antimonate (AZO), niobium-doped titanium oxide, and the like can be used in combination of two or more. Among them, at least one selected from the group consisting of antimony-doped tin oxide, tin-doped indium oxide, phosphorus-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, zinc antimonate, and the like is particularly preferable, and antimony-doped tin oxide, tin-doped indium oxide, phosphorus-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and zinc antimonate are particularly preferable from the viewpoint that an increase in surface resistivity can be suppressed even when applied under a high voltage.

(D1) The shape of the component is not particularly limited, and examples thereof include a powder, an aqueous sol, and an organic solvent sol. The powdery component (D1) includes, for example, inorganic particles such as titanium oxide coated with the component (D1).

Examples of the commercially available products of component (D1) include T-1, S-2000, S-1, SP-2, E-ITO, TD L-1, TD L-SA, SPD L and SD L (manufactured by Mitsubishi corporation), セルナックス CX-Z330H, CX-Z610-F2, CX-Z410K, CX-S301H, CX-S204IP and CX-S501M (manufactured by Nissan chemical industries, Ltd.), パゼット CK and パゼット GK-40 (manufactured by ハクスイテック corporation), and two or more of them may be used in combination.

When the component (D1) is used in the coating agent of the present invention, the content thereof is about 5 parts by mass to about 30 parts by mass (in terms of solid content) based on 100 parts by mass (in terms of solid content) of the total of the component (a) and the component (B). When the amount is less than 5 parts by mass, the surface resistivity of the cured coating film of the present invention tends to be greatly increased when applied at a high voltage. When the amount is more than 30 parts by mass, the transparency of the cured film tends to be lowered. From this viewpoint, the content of the component (D1) is preferably about 7 parts by mass to about 25 parts by mass (in terms of solid content).

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

(D2) The shape of the component is not particularly limited, and examples thereof include a powder, an aqueous sol, and an organic solvent sol.

Examples of commercially available products of component (D2) include UW-153, UW-253 (manufactured by Utsu Kaishu Co., Ltd.), CARBOBYK-9810 (manufactured by ビックケミー and ジャパン Co., Ltd.), and two or more thereof may be used in combination.

When the component (D2) is used in the coating agent of the present invention, the content thereof is about 0.5 to about 10 parts by mass (in terms of solid content) per 100 parts by mass of the total of the components (a) and (B). When the amount is less than 0.5 parts by mass, the surface resistivity of the cured coating film of the present invention tends to be greatly increased when applied at a high voltage. When the amount is more than 10 parts by mass, the transparency of the cured film tends to be lowered. From this viewpoint, the content of the component (D2) is preferably about 0.8 to about 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 methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, diethylene glycol, ethylene glycol monoethyl ether, and ethylene glycol mono-n-propyl ether; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene, xylene, and benzene; and ethyl acetate, chloroform, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and the like, and two or more of them may be used in combination. Examples of the water include ion-exchanged water. Among them, alcohols having about 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, and isopropanol, are preferable from the viewpoint of storage stability of the coating agent of the present invention. Further, ion-exchanged water is preferable as the water.

The content of the solvent in the coating agent of the present invention is not particularly limited, and may be generally in the range of about 0.1 to about 30% by mass in terms of the solid content concentration of the coating agent.

The coating agent of the present invention may contain additives such as a defoaming agent, an anti-slip agent, an antiseptic agent, a rust preventive agent, a pH adjuster, an antioxidant, a pigment, a dye, a lubricant, a leveling agent, a conductivity improver, and a curing catalyst.

Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, and perfluoropolydimethylsiloxane, and two or more of these may be used in combination. The amount of the leveling agent to be used is not particularly limited, and is less than 10 parts by mass per 100 parts by mass (in terms of solid content) of the total of the component (a) and the component (B).

Examples of the conductivity improver include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, cyclohexanediol, cyclohexanedimethanol, glycerol, dimethyl sulfoxide, N-methylpyrrolidone, N-methylformamide, N-dimethylformamide, isophorone, propylene carbonate, and cyclohexanone, and two or more of these may be used in combination. The amount of the conductivity improver used is not particularly limited, and is less than 300 parts by mass per 100 parts by mass (in terms of solid content) of the total of the components (a) and (B).

Examples of the curing catalyst include acid catalysts such as p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, and phosphoric acid; diaryl iodides

Salts, triarylsulfonium salts, diaryl groups

And acid generators such as salts, and two or more of them may be used in combination. The amount of the curing catalyst used is not particularly limited, and is 3 parts by mass based on 100 parts by mass (in terms of solid content) of the total of the components (a) and (B).

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 additives at room temperature.

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

Examples of the plastic film include a polycarbonate film, a polymethyl methacrylate film, a polystyrene film, a polyethylene terephthalate film, a polyimide film, a polyolefin film, a nylon film, an epoxy resin film, a melamine resin film, a triacetyl cellulose resin film, an ABS resin film, an AS resin film, and a norbornene resin film. These films may be surface-treated (corona discharge or the like) as necessary. In addition, the plastic film may be provided with various functional layers on one or both surfaces thereof.

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

After the coating agent of the present invention is applied to the surface of the substrate, it is preferable to perform a drying treatment from the viewpoint of blocking resistance of the cured film. The drying temperature is not particularly limited, and is usually from about 60 ℃ to about 150 ℃, preferably from about 80 ℃ to about 120 ℃. The drying time is also not particularly limited, and is usually about 10 seconds to about 120 seconds.

The plastic film of the present invention is an article having the cured coating film of the present invention on at least one surface thereof. The thickness of the cured coating is not particularly limited, but is usually about 0.01 μm to about 2 μm. The thickness of the plastic film is also not particularly limited, and is usually about 25 μm to about 125 μm.

[ examples ]

The present invention will be specifically described below with reference to examples and comparative examples. However, it is needless to say that the technical scope of the present invention is not limited to these examples. In the examples, "parts" and "%" are given by mass unless otherwise specified.

In each production example, the glass transition temperature is a value measured by a differential scanning calorimeter (product name "DSC 6200", manufactured by セイコーインスツルメンツ Co., Ltd.) and the number average molecular weight is a polystyrene equivalent value measured by a coacervation permeation chromatograph (product name "H L C-8220 GPC", manufactured by Tosoh corporation).

< production of component (A) >

Production example 1

16 parts of acrylic acid and 144 parts of methyl methacrylate were put into a four-necked flask equipped with a nitrogen inlet, a thermometer, a reflux condenser and a stirrer, and 446 parts of isopropyl alcohol was further added to prepare a monomer solution. Then, 3.2 parts of 2, 2' -azobisisobutyronitrile was added as a polymerization initiator to the monomer solution. Subsequently, the reaction system was brought to 80 ℃ to carry out radical polymerization for 8 hours. Next, 22.4 parts of triethylamine and 1000 parts of ion-exchanged water were added to the reaction system, and the mixture was sufficiently stirred and cooled to room temperature, thereby obtaining a solution of the component (a-1) of the carboxylate anion group-containing acrylic copolymer having a solid content of 10%. The amount of the carboxylate anion group in the component (A-1) was 0.00139mol/g, the glass transition temperature was 100 ℃ and the number average molecular weight was 30000.

Production example 2

24 parts of acrylic acid and 136 parts of methyl methacrylate were put into the same four-necked flask as in production example 1, and 435 parts of isopropyl alcohol was further added to prepare a monomer solution. Subsequently, 3.2 parts of azobisisobutyronitrile was added as a polymerization initiator to the monomer solution. Then, the reaction system was heated to 80 ℃ and then subjected to radical polymerization for 8 hours. Then, 33.7 parts of triethylamine and 1000 parts of ion-exchanged water were added to the reaction system, and the mixture was sufficiently stirred and cooled to room temperature, thereby obtaining a solution of the component (a-2) of the carboxylate anion group-containing acrylic copolymer having a solid content of 10%. The amount of the carboxylate anion group in the component (A-2) was 0.00208mol/g, the glass transition temperature was 95 ℃ and the number average molecular weight was 30000.

Comparative production example 1

In production example 1, 1000 parts of isopropyl alcohol alone was added to the reaction system without using triethylamine after the polymerization reaction, and the mixture was sufficiently stirred and cooled to room temperature to obtain a solution of the carboxyl group-containing acrylic copolymer (E-1) having a solid content of 10%. The amount of the carboxylate anion group in the component (E-1) was 0mol/g, the glass transition temperature was 100 ℃ and the number average molecular weight was 30000.

Example 1

700 parts (in terms of solid content: 70 parts) of (A-1) component (A), 30 parts of trimethylolpropane-tris (1-aziridinylpropionate) (trade name: ケミタイト PZ-33 ", manufactured by Nippon catalyst Co., Ltd.) as (B), 1000 parts of PEDOT/PSS aqueous solution (trade name" Orgacon ICP1010 ", manufactured by Nippon アグフアマテリアルズ Co., Ltd., solid content 1.2%) (solid content 12 parts) as (C), 60 parts of antimony-doped tin oxide (trade name" TD L-1 ", manufactured by Mitsubishi corporation, solid content 17%) (solid content 10 parts), 3.0 parts of triethylamine, 1 part of BYK-333 (polyether-modified polydimethylsiloxane, manufactured by ビックケミージャパン Co., Ltd.) as a leveling agent, 1 part of p-toluenesulfonic acid as a catalyst, 6900 parts of ion-exchanged 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 to 16 and comparative examples 1 to 17

Coating agents were prepared by the same method as in example 1, except for changing the kinds and the amounts shown in table 1.

[ production of test film ]

The coating agent of example 1 was applied to a PET film by using a bar coater No.3, and the coated film was dried in a down-wind dryer (100 ℃ C., 1 minute) to prepare a film for test. Test films were also prepared from the coating agents of examples 2 to 16 and comparative examples 1 to 17.

[ measurement of surface resistivity ]

The surface resistivity (Ω/□) of the coated surface of the test film of example 1 was measured at 23 ℃ and 50% humidity under applied voltages of 100V and 1000V, respectively, using ハイレスター UP MCP-HT450 manufactured by Mitsubishi chemical corporation in accordance with JIS K6911. The test films of examples 2 to 16 and comparative examples 1 to 17 were also measured in the same manner. The smaller the surface resistivity, the better the antistatic property. The results are shown in Table 1 (the same applies below).

[ surface resistivity after moist Heat ]

The test film of example 1 was left to stand at 40 ℃ and 90% humidity for 4 days, and then the surface resistivity was measured by the same method as described above. The test films of examples 2 to 16 and comparative examples 1 to 17 were also measured in the same manner. The smaller the surface resistivity, the better the antistatic property.

[ transparency ]

The haze value of the film for test was measured in accordance with JIS-K-7136 using a haze meter "HM-150" (color technical research institute on village). The difference from the haze value of only the PET film is Δ Hz, and the smaller the value, the better the transparency.

[ curability ]

The test film was wiped with a cotton swab immersed in methyl ethyl ketone, and the number of times until the substrate was exposed (reciprocation) was measured.

◎ even if the paper is wiped for more than 100 times, the substrate is not exposed

○ exposing the substrate after wiping for 60-100 times

△ exposing the substrate after wiping for 20-59 times

× exposing the substrate after 1-19 times of wiping

[ Adhesivity ]

After a pressure-sensitive adhesive tape was adhered to the test film and sufficiently pressed, the tape was peeled off by force, and the amount of the remaining coating film was visually evaluated based on the following criteria.

◎ … residual 100% coating film

○ … coating film with residual 70% or more and less than 100%

△ …, 40% or more and less than 70% of the coating film remained.

× … less than 40% of the film remained.

[ (B) component ]

(B-1) trimethylolpropane-tris (1-aziridinylpropionate) (trade name "ケミタイト PZ-33", manufactured by Nippon catalyst Co., Ltd.)

(B-2) Tetrakishydroxymethylmethane-tris (1-aziridinylpropionate) (trade name "C L OSS L INKER C L427", manufactured by CRYPTOKIDA)

(B-3) carbodiimide curing agent (trade name: カルボジライト V-02, manufactured by Nisshin textile Co., Ltd.)

[ (C) ingredient ]

(C-1) PEDOT/PSS (trade name "Orgacon ICP 1010", manufactured by Nippon アグフアマテリアルズ Co., Ltd., solid content 1.2%)

[ (D1) ingredient ]

(D1-1) antimony-doped tin oxide (trade name "TD L-1", manufactured by Mitsubishi synthetic materials corporation, solid content 17%)

(D1-2) tin-doped indium oxide (trade name "ITO aqueous dispersion", manufactured by Mitsubishi integrated materials K.K., solid content 20%)

(D1-3) phosphorus-doped tin oxide (trade name: セルナックス CX-S301H, manufactured by Nissan chemical industries, Ltd., solid content: 30%)

(D1-4) Zinc antimonate (trade name: セルナックス CX-Z330H, manufactured by Nissan chemical industries Co., Ltd., solid content: 30%)

[ (D2) ingredient ]

(D2) Carbon nanotubes (trade name "UW-153", manufactured by Udo Kyoho Co., Ltd., solid content: 2.5%)

[ other conductive Components ]

(F-1) lithium trifluoromethanesulfonate (trade name "EF-15", manufactured by Mitsubishi Integrated materials Co., Ltd.)

(F-2) lithium bis (trifluoromethanesulfonyl) imide (trade name "EF-N115", manufactured by Mitsubishi integrated materials Co., Ltd.)

(G-1) acetylene glycol surfactant (trade name: サーフィノール 485, manufactured by Nissin chemical industries Co., Ltd.)

Claims

(D1) the component is at least one selected from the group consisting of antimony-doped tin oxide, tin-doped indium oxide, phosphorus-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide and zinc antimonate,

(D2) the components are carbon nano-tubes, and the carbon nano-tubes,

when the component (D1) is used, the amount thereof is 5 to 30 parts by mass in terms of solid content per 100 parts by mass of the total of the components (A) and (B) in terms of solid content,

when the component (D2) is used, the amount thereof is 0.5 to 10 parts by mass in terms of solid content, relative to 100 parts by mass of the total of the component (A) and the component (B) in terms of solid content.

2. The thermosetting antistatic coating agent according to claim 1, wherein the component (A) is a neutralized salt of a copolymer comprising a monomer group (α) of α unsaturated carboxylic acids (a1) and alkyl (meth) acrylates (a 2).

3. The heat-curable antistatic coating agent according to claim 1 or 2, wherein the content of carboxylate anion groups of component (A) is 0.0003 to 0.005 mol/g.

4. The heat-curable antistatic coating agent according to claim 1 or 2, wherein the component (B) is an aziridine-based compound.

5. The thermosetting antistatic coating agent according to claim 1 or 2, wherein the solid content mass ratio (A)/(B) of the component (A) to the component (B) is 5/5 to 9/1.

6. The heat-curable antistatic coating agent according to claim 1 or 2, wherein the component (C) is a polythiophene.

7. The heat-curable antistatic coating agent according to claim 1 or 2, wherein the content of the component (C) is 5 to 25 parts by mass in terms of solid content, based on 100 parts by mass of the total of the components (A) and (B).

8. A cured coating film of the thermosetting antistatic coating agent according to any one of claims 1 to 7.

9. A plastic film comprising the cured coating film according to claim 8 on at least one surface thereof.