CN106167662A - Thermohardening type antistatic coating agent and curing overlay film, plastic foil - Google Patents
Thermohardening type antistatic coating agent and curing overlay film, plastic foil Download PDFInfo
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- CN106167662A CN106167662A CN201610330792.8A CN201610330792A CN106167662A CN 106167662 A CN106167662 A CN 106167662A CN 201610330792 A CN201610330792 A CN 201610330792A CN 106167662 A CN106167662 A CN 106167662A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
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- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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Abstract
Also surface resistivity can be suppressed under high voltages to raise and the new thermohardening type antistatic coating agent of time dependent curing overlay film with low uncertainty and curing overlay film, plastic foil even if the present invention provides to be formed on the surface of plastic foil.This thermohardening type antistatic coating agent contains the acrylic copolymer (A) of group containing carboxylate anion, curing agent (B), pi-conjugated system electric conductive polymer (C) and Conductive inorganic filler (D), (D) composition comprises at least one in the group being made up of burning system electroconductive stuffing (D1) and carbon series conductive filler (D2), in the case of using (D1) composition, it is 5～30 mass parts with solid constituent its amount that converts relative to total 100 mass parts of (A) composition and (B) composition, in the case of using (D2) composition, it is 0.5～10 mass parts with solid constituent its amount that converts relative to total 100 mass parts of (A) composition and (B) composition.
Description
Technical field
The present invention relates to thermohardening type antistatic coating agent and curing overlay film thereof and the plastic foil possessing this curing overlay film.
Background technology
All the time; plastic foil is for extensive purposes, it is known that the carrier band using in the operations such as such as semiconductor machining with or the manufacturing process of the film of cover strip, electronic unit or ceramic capacitor in use mold release film, blanching film, plate-making film, film for packaging, decorating film, diaphragm etc..
Plastic foil also serves as blooming and is used, and for example, the component as the prismatic lens of liquid crystal indicator component, contact panel, LCD backlight, organic el display etc. uses.
Plastic foil easy static electrification when winding or uncoiling or when processing.Therefore, the dust in air is attached to surface and produces physical imperfection (pin hole etc.), or it is bad to produce traveling on machining production line.In addition, along with the miniaturization of various semiconductors and electronic equipment and highly integrated, electrostatic become cause electric product botch routines etc. problem the reason.
Therefore, have employed in plastic foil, knead antistatic agent or the means at surface coating antistatic coating agent.As the latter, it is known that for example in organic bond resin, combination has the antistatic coating agent (patent document the 1st, 2) of the pi-conjugated system such as polythiophene, polypyrrole electric conductive polymer.
But, the overlay film being made up of such antistatic coating agent is typically considered to surface resistivity under high voltages and easily raises.Therefore, the plastic foil after utilizing conventional antistatic coating agent to process is not suitable as equipment, the component of parts using under high voltages sometimes.
Even if the composition of the rising as the surface resistivity that also can suppress overlay film under high voltages, known making 3,4-dialkoxythiophene carries out being combined with in electroconductive polymer obtained from oxidation polymerization the conductive composition (patent document 3) of acetylenediol system surfactant in the presence of polyanion in water solvent.But, the surface resistivity of the overlay film of this conductive composition may through when raise.In the case of additionally, apply under higher voltage, surface resistivity also easily raises.
Prior art literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2009-256623 publication
Patent document 2: Japanese Unexamined Patent Publication 2010-196022 publication
Patent document 3: Japanese Unexamined Patent Publication 2014-040550 publication
Content of the invention
Invent problem to be solved
Even if the major subjects of the present invention is to provide the new thermohardening type antistatic coating agent changing and applying under higher voltage the curing overlay film that surface resistivity also can be suppressed to raise when can form surface resistivity not The book of Changes on the surface of plastic foil.
For solving the method for problem
That the present inventor furthers investigate it was found that utilize thermohardening type coating agent obtained from predetermined material combination, can solve the problem that the problems referred to above.That is, the present invention relates to following thermohardening type antistatic coating agent, its curing overlay film and the plastic foil possessing this curing overlay film.
1. a thermohardening type antistatic coating agent, it contains the acrylic copolymer (A) of group containing carboxylate anion, curing agent (B), pi-conjugated system electric conductive polymer (C) and Conductive inorganic filler (D)
(D) composition comprises at least one in the group being made up of burning system electroconductive stuffing (D1) and carbon series conductive filler (D2),
In the case of using (D1) composition, its amount is 5～30 mass parts (solid constituent conversions) relative to total 100 mass parts (solid constituent conversion) of (A) composition and (B) composition,
In the case of using (D2) composition, its amount is 0.5～10 mass parts (solid constituent conversion) relative to total 100 mass parts (solid constituent conversion) of (A) composition and (B) composition.
2. the thermohardening type antistatic coating agent as described in above-mentioned item 1, wherein, (A) composition is for by comprising α, the neutralization salt of the copolymer that the monomer group (α) of β unsaturated carboxylic acid class (a1) and (methyl) alkyl-acrylates (a2) is constituted.
3. the thermohardening type antistatic coating agent as described in above-mentioned item 1 or 2, wherein, the carboxylate anion group content (mol/g) of (A) composition is 0.0003～0.005.
4. the thermohardening type antistatic coating agent as according to any one of above-mentioned item 1～3, wherein, (B) composition is aziridine based compound.
5. the thermohardening type antistatic coating agent as according to any one of above-mentioned item 1～4, wherein, (A) composition is 5/5～9/1 with the solid constituent mass ratio [(A)/(B)] of (B) composition.
6. the thermohardening type antistatic coating agent as according to any one of above-mentioned item 1～5, wherein, (C) composition is polythiophene class.
7. the thermohardening type antistatic coating agent as according to any one of above-mentioned item 1～6, wherein, the content of (C) composition is calculated as 5～25 mass parts relative to total 100 mass parts of (A) composition and (B) composition with solid constituent conversion.
8. the thermohardening type antistatic coating agent as according to any one of above-mentioned item 1～7, wherein, (D1) composition is at least one in the group being made up of the tin oxide of Sb doped, the indium oxide of tin dope, the tin oxide of phosphorus doping, tin oxide, the zinc oxide of aluminium doping, the zinc oxide of gallium doping and zinc antimonates.
9. the thermohardening type antistatic coating agent as according to any one of above-mentioned item 1～8, wherein, (D2) composition is CNT.
10. a curing overlay film, which is the curing overlay film of thermohardening type antistatic coating agent according to any one of above-mentioned item 1～9.
11. 1 kinds of plastic foils, it possesses the curing overlay film described in above-mentioned item 10 at least one side.
Invention effect
Thermohardening type antistatic coating agent according to the present invention, even if the curing overlay film applying under high voltages also to suppress surface resistivity to raise can be formed on the surface of plastic foil.And then, curing overlay film displays that good static electricity resistance after being not only under the damp condition of about 50% and placing a couple of days under conditions of the very high humidity of about 90%.In addition, this curing overlay film is not only excellent with the adaptation of plastic foil, and curability, resistance to blocking, solvent resistance, the transparency are also good.
The plastic foil of the present invention has a curing overlay film with above-mentioned all characteristics in surface configuration, therefore, and the component such as the diaphragm of the goods such as precision equipment being suitable as under high voltage condition using, film carrier.
Detailed description of the invention
The Thermocurable antistatic coating agent (hereinafter referred to as coating agent) of the present invention is the composition of the acrylic copolymer (A) (hereinafter referred to as (A) composition) containing group containing carboxylate anion, curing agent (B) (hereinafter referred to as (B) composition) and pi-conjugated system electric conductive polymer (C) (hereinafter referred to as (C) composition) and predetermined Conductive inorganic filler (D) (hereinafter referred to as (D) composition).
As (A) composition, as long as there is carboxylate anion group (-COO in intramolecular-) acrylic copolymer then can use various known material without particular limitation.Specifically, preferably by comprising α, the neutralization salt of the copolymer that the monomer group (α) (hereinafter referred to as (α) composition) of β unsaturated carboxylic acid class (a1) (hereinafter referred to as (a1) composition) and (methyl) alkyl-acrylates (a2) (hereinafter referred to as (a2) composition) is constituted.
As (a1) composition, various known α, β unsaturated carboxylic acid class can be used without particular limitation.As concrete example, can enumerate: the α such as acrylic acid, methacrylic acid, crotonic acid and iso-crotonic acid, β unsaturated monocarboxylic and salt thereof；The α such as maleic acid, maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride, β unsaturated dicarboxylic and salt thereof；The half ester of the alcohol of this α, β unsaturated dicarboxylic and carbon number about 1～30 and salt thereof；The half amide of the amine of this α, β unsaturated dicarboxylic and carbon number about 1～30 and neutralization salt etc. thereof, can be applied in combination two or more.As above-mentioned alcohol, such as methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, methyl cellosolve and ethyl cellosolve etc. can be enumerated.As above-mentioned amine, such as methylamine, ethamine, propylamine, n-butylamine, n-hexylamine and n-octyl amine etc. can be enumerated.As the compound forming above-mentioned salt, it is possible to use nertralizer described later.As (a1) composition, from the viewpoint of the curability of the overlay film being made up of the coating agent of the present invention, preferably above-mentioned α, β unsaturated monocarboxylic, particularly preferred acrylic acid and/or methacrylic acid.
As (a2) composition, various known (methyl) alkyl acrylate can be used without particular limitation.This alkyl can be straight-chain, branched or ring-type.As (methyl) alkyl acrylate of straight-chain, such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) lauryl acrylate and (methyl) stearyl acrylate ester etc. can be enumerated.As (methyl) alkyl acrylate of branched, such as (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate and (methyl) 2-EHA etc. can be enumerated.As ring-type (methyl) alkyl acrylate, such as (methyl) cyclohexyl acrylate, (methyl) acrylic acid ring pentyl ester and (methyl) isobornyl acrylate etc. can be enumerated, can be applied in combination two or more.Wherein, from the curing overlay film of the present invention particularly with the adaptation of plastic foil from the viewpoint of, (methyl) alkyl acrylate of preferably above-mentioned straight-chain, the carbon number of particularly preferred alkyl is (methyl) alkyl acrylate of the straight-chain of about 1～20 (preferably about 1～8).
(α) composition can be containing the unsaturated monomer (hereinafter referred to as (a3) composition) beyond above-mentioned (a1) composition and (a2) composition.As (a3) composition, can enumerate for example: acrylamide, Methacrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-isopropyl (methyl) acrylamide, normal-butyl (methyl) acrylamide, the N-tert-butyl group (methyl) acrylamide, N-lauryl (methyl) acrylamide, N-cyclohexyl replaces alkyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diisopropyl (methyl) acrylamide, N, N-di-t-butyl (methyl) acrylamide, N, N-dilauryl (methyl) acrylamide, N, N-bis-t-octyl (methyl) acrylamide and N, the acrylic amides such as N-dicyclohexyl (methyl) acrylamide；(methyl) the hydroxyalkyl acrylates classes such as (methyl) acrylic acid 2-hydroxy methyl, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl, glycerine list (methyl) acrylate, glycerine two (methyl) acrylate, pentaerythrite list (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate；The phenylethylenes such as styrene, AMS, t-butyl styrene, dimethyl styrene, acetoxy-styrene, hydroxy styrenes, vinyltoluene and chlorovinyl toluene；The unsaturated sulfonic acid classes such as vinyl sulfonic acid, (methyl) allyl sulphonic acid, 2-acrylamide-2-methyl propane sulfonic, sulfonated phenylethylene；(methyl) acrylate, (methyl) acrylic-amino propyl ester, (methyl) acrylic-amino butyl ester, (methyl) acrylic acid N-methylamino ethyl ester, (methyl) acrylic acid N-methylamino propyl ester, (methyl) acrylic acid N-methylamino butyl ester, (methyl) acrylic acid N, N-dimethylamino ethyl ester, (methyl) acrylic acid N, N-dimethylamino propyl ester, (methyl) acrylic acid N, N-dimethylamino butyl ester, (methyl) acrylic acid N, N-diethylamino ethyl ester, (methyl) acrylic acid N, N-diethylamino propyl ester, (methyl) acrylic acid N, the aminoalkyl system unsaturated monomer classes such as N-diethylamino butyl ester；The poly (oxyalkylene) base system unsaturated monomer classes such as polyoxy alkylidene (methyl) esters of acrylic acid, poly (oxyalkylene) base glycerol (methyl) esters of acrylic acid, polyoxy alkylidene monoalkyl (methyl) esters of acrylic acid, polyoxy alkylidene mono alkenyl (methyl) esters of acrylic acid, polyoxy alkylidene (methyl) allyl ether, poly (oxyalkylene) base glycerol (methyl) allyl ether；nullVinyldimethylchlorosilane、Vinyl methyl dichlorosilane、Vinyl trichlorosilane、Allyldimethylcholrosilane、Allyl methyl dichlorosilane、Allyltrichlorosilane、4-cyclobutenyl dimethylchlorosilane、4-butenylmethyl dichlorosilane、4-cyclobutenyl trichlorosilane、5-pentenyl dimethylchlorosilane、5-pentenyl dimethyl dichlorosilane (DMCS)、5-pentenyl trichlorosilane、3-methacryloxypropyl dimethylchlorosilane、3-methacryloyloxypropyl methyl dichlorosilane、3-methacryloxypropyl trichlorosilane、3-acryloxypropyl dimethylchlorosilane、3-acryloxypropyl dichlorosilane、3-acryloxypropyl trichlorosilane、4-methacryloxy butyldimethylchlorosilane、4-methacryloxy butyl methyl dichlorosilane、4-methacryloxy butyl trichlorosilane、4-acryloxy butyldimethylchlorosilane、Chlorosilane system (methyl) esters of acrylic acid of 4-acryloxy butyl methyl dichlorosilane etc.；Polysiloxanes list (methyl) esters of acrylic acids such as " サ イ ラ プ レ Application FM-0711 ", " サ イ ラ プ レ Application FM-0721 ", " サ イ ラ プ レ Application FM-0725 " etc. (being JNC Corporation to manufacture)；(methyl) acrylic acid 2,2,2-trifluoro ethyl ester, (methyl) acrylic acid 2,2,3,3-tetrafluoro propyl ester, (methyl) acrylic acid 2,2,2-tri-fluoro-1-trifluoro methyl esters, (methyl) acrylic acid 2,2,3,3-tetrafluoro propyl ester, (methyl) acrylic acid H, 1H, 5H-octafluoro pentyl ester, (methyl) acrylic acid 2,2,3,3,4,4,5,5-octafluoro pentyl ester, (methyl) acrylic acid 2,2,3,3,4,4,5,5,5-nine fluorine pentyl ester etc..Additionally, as commercially available product, (methyl) fluoroalkyl base esters etc. such as " PVC ス U ト 3F ", " PVC ス U ト 4F ", " PVC ス U ト 8F ", " PVC ス U ト 8FM ", " PVC ス U ト 13FM " etc. (being Osaka Organic Chemical Industry Co., Ltd. to manufacture) can be enumerated, can be applied in combination two or more.
(α) content of (a1) composition in composition, (a2) composition and (a3) composition is not particularly limited, and from the viewpoint of the curability of the coating agent of the present invention, is described generally below.
<in the case of not using (a3) composition>
(a1) composition: about 3 mass %～about 30 mass %, preferably from about 5 mass %～about 20 mass %
(a2) composition: 70 mass %～97 mass %, preferably from about 80 mass %～about 95 mass %
<in the case of using (a3) composition>
(a1) composition: about 3 mass %～about 30 mass %, preferably from about 5 mass %～about 20 mass %
(a2) composition: about 20 mass %～about 96 mass %, preferably from about 50 mass %～about 90 mass %
(a3) composition: about 1 mass %～about 50 mass %, preferably from about 5 mass %～about 30 mass %
(A) manufacture method of composition is not particularly limited, and can use various known method.Specifically, for example, it is possible to by obtaining the polymerisation that (a1) composition and (a2) composition and (a3) composition being added as needed on are carried out normally about 1 hour～about 20 hours in suitable reaction vessel at normally about 60 DEG C～about 180 DEG C.The reaction sequence of each composition is not particularly limited, can be for successively or together.
During reaction, it is possible to use various known initiators, chain-transferring agent and the solvent described later as reaction dissolvent.
As initiator, can enumerate for example: the inorganic peroxygen species such as hydrogen peroxide, ammonium persulfate and potassium peroxydisulfate；The organic peroxide classes such as peroxidized t-butyl perbenzoate, dicumyl peroxide and lauryl peroxide；2,2 '-azodiisobutyronitrile, 2, the azo compounds species etc. such as 2 '-azo-bis-iso-dimethyl, can be applied in combination two or more.Usage amount is not particularly limited, and total 100 mass parts being commonly angled relative to (a1) composition～(a3) composition is about 0.01 mass parts～about 10 mass parts.
Chain-transferring agent uses based on the purpose of the molecular weight regulating (A) composition.As concrete example, lauryl mercaptan, 2-mercaptobenzothiazole and bromine chloroform etc. can be enumerated, can be applied in combination two or more.Usage amount is not particularly limited, and total 100 mass parts being commonly angled relative to (a1) composition～(a3) composition is about 0.01 mass parts～about 5 mass parts.
In the case of (a1) composition all correctives or a part for corrective in the case of, obtained copolymer is (A) composition.In the case of (a1) composition all unneutralized things, obtain (A) composition by neutralizing obtained copolymer nertralizer (alkali composition).
As alkali composition, can enumerate for example: ammonia；The primary amine classes such as MMA, mono aminoethane, dibutyl amine and cyclohexylamine；The secondary amine class such as dimethylamine and diethylamine；The tertiary amines such as trimethylamine, triethylamine and tri-n-butylamine；Other amines such as aniline, arylamine and alkanolamine；The alkali metal compound such as NaOH and potassium hydroxide；The alkaline earth metal compound such as calcium hydroxide and magnesium hydroxide etc..Wherein, preferably easy from curing overlay film volatilization and be difficult to residual amine, more preferably tertiary amines and/or ammonia.The usage amount of alkali composition is not particularly limited, and the free carboxy being commonly angled relative in (a1) composition is about the scope of 50 moles of %～about 200 mole %.
(A) carboxylate anion group amount (mol/g) in composition is not particularly limited, and typically about 0.0003～about 0.005.By being set as more than 0.0003, the solvent resistance of the curability and curing overlay film with the coating agent of the present invention becomes good tendency, in addition, by being set as less than 0.005, the antistatic characteristic with curing overlay film becomes good tendency.Considering from this viewpoint, carboxylate anion group amount is preferably from about 0.001～about 0.003.It should be noted that " carboxylate anion group amount " refers to the molal quantity of the carboxylate anion group containing in (A) composition 1g (solid constituent conversion), which is calculated value.
As other physical property of (A) composition, glass transition temperature, number-average molecular weight (the polystyrene conversion value being obtained by gel permeation chromatography) can be enumerated.Glass transition temperature, number-average molecular weight all consider setting range from viewpoints such as the adaptation of curing overlay film, curability, resistance to blockings, the former is typically about 20 DEG C～about 150 DEG C, it is preferably from about 70 DEG C～about 150 DEG C, additionally, the latter is typically about 2000～about 150000, preferably from about 10000～about 100000.
As (B) composition, as long as making coating overlay film fully solidify, then can use various known composition without particular limitation.Specifically, can enumerate for example aziridine based compound, carbodiimide compound, melamine based compound, isocyanates based compound, epoxy compound,Oxazoline based compound, metallo-chelate based compound etc..
As aziridine based compound, such as diphenyl methane-4 can be enumerated, 4 '-bis-(1-aziridine carboxylic acid amides), trimethylolpropane tris-β '-aziridino propionic ester, tetramethylol methane three-β '-aziridino propionic ester, Toluene-2,4-diisocyanate, 4-is double (1-aziridine carboxylic acid amides), triethylenemelanin, double isophthalic diformyl-1-(2-methylaziridine), three-1-(2-methylaziridine) phosphine and trimethylolpropane tris-β (2-methylaziridine) propionic ester etc., as commercially available product, CROSSLINKER CL-427 (manufacture of mutual Yao Gong Co., Ltd.) can be illustrated, ケ ミ タ イ ト PZ-33 and DZ-22E (catalyst Co., Ltd. of Japan manufactures) etc., can be applied in combination two or more.
nullAs carbodiimide based compound，For example poly-(4 can be enumerated,4 '-diphenyl methane carbodiimide)、Poly-(3,3 '-dimethyl-4,4 '-diphenyl methanes carbodiimide)、Poly-(tolyl carbodiimide)、Poly-(to phenylene carbodiimide)、Poly-(metaphenylene carbodiimide)、Poly-(3,3 '-dimethyl-4,4 '-diphenyl methane carbodiimide)、Poly-(naphthylene carbodiimide)、Poly-(1,6-hexa-methylene carbodiimide)、Poly-(1,4-tetramethylene carbodiimide)、Poly-(1,3-cyclohexylidene carbodiimide)、Poly-(1,4-cyclohexylidene carbodiimide)、Poly-(1,3,5-triethyl group phenylene carbodiimide)、Poly-(4,4 '-methylene bis cyclohexyl carbodiimide)、Poly-(1,3-diisopropyl phenylene carbodiimide)、Poly-(1-methyl-3,5-diisopropyl phenylene carbodiimide) and poly-(isopropyl phenylene carbodiimide) etc.，As commercially available product，カ Le ボ ジ ラ イ ト V-02 and カ Le ボ ジ ラ イ ト V-04 (manufacture of Nisshinbo KCC) etc. can be illustrated，Can be applied in combination two or more.
As melamine based compound, such as methylated melamine compound and butylated melamines compound etc. can be enumerated, as commercially available product, ニ カ ラ ッ Network MW-30M (Sanwa Co., Ltd. chemistry manufacture) and サ イ メ Le 303LF (オ Le ネ Network ス ジ ャ パ Application Co., Ltd. manufacture) etc. can be illustrated, can be applied in combination two or more.
As isocyanates based compound, the such as lower aliphatic polyisocyanates such as ethylidene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate can be enumerated；The alicyclic polyisocyanates of cyclopentylene diisocyanate, cyclohexylene diisocyanate and IPDI etc.；2,4-tolylene diisocyanate, 4, the aromatic polyisocyanate such as 4 '-methyl diphenylene diisocyanate and eylylene diisocyanate etc., as commercially available product, ア Network ア ネ ト 100 (TOSOH Co., Ltd's manufacture) and デ ュ ラ ネ ト WB40-100 (Asahi Chemical Corp's manufacture) etc. can be illustrated, can be applied in combination two or more.
As epoxy compound, such as ethylene glycol diglycidylether can be enumerated, propylene glycol diglycidylether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, trimethylolethane trimethacrylate glycidol ether, D-sorbite polyglycidyl ether, the aliphatic polyepoxide such as pentaerythrite polyglycidyl ether, bisphenol-A or the epoxide etc. of bisphenol-f type, as commercially available product, デ Na U Le EX-614 (Na ガ セ ケ system テ ッ Network ス Co., Ltd. manufacture) can be illustrated, jER YX8034 (Mitsubishi chemical Co., Ltd's manufacture) etc., can be applied in combination two or more.
AsOxazoline based compound, can enumerate such as 2-isopropenyl-2-Oxazoline, 2-vinyl-2-Oxazoline and 2-vinyl-4-methyl-2-The polyaddition type such as oxazolineIsoxazoline compounds etc., as commercially available product, can illustrate エ Port Network ロ ス WS-300, WS-500 and WS-700 (catalyst Co., Ltd. of Japan manufactures) etc., can be applied in combination two or more.
As metallo-chelate based compound, the compound for example containing aluminium, zirconium, titanium, zinc, iron, tin etc. as metallic element can be enumerated.Specifically, such as diisopropoxy aluminium list oleic acid base acetoacetic ester can be enumerated, the double oleic acid base acetoacetic ester of single aluminum isopropoxide, single aluminum isopropoxide monoleate list ethyl acetoacetic ester, diisopropoxy aluminium list lauryl acetoacetate, diisopropoxy aluminium list stearyl acetoacetic ester, diisopropoxy aluminium list iso stearyl acetoacetic ester, single aluminum isopropoxide list-N-lauroyl-β aluminum oxide list lauryl acetoacetate, praseodynium aluminium, double (isobutyl acetoacetate) chelate of single acetyl acetone aluminium, double (2-ethylhexyl acetoacetate) chelate of single acetyl acetone aluminium, the aluminum chelate compounds such as double (dodecyl acetoacetic ester) chelate of single acetyl acetone aluminium and double (the oleic acid base acetoacetic ester) chelates of single acetyl acetone aluminium；The titanium chelate compounds such as double (acetylacetone,2,4-pentanedione) titanium of diisopropoxy, four titanium acetylacetones, double (octene ethyl glycolate) titanium of two octyloxies, double (ethyl acetoacetic ester) titanium of diisopropoxy, double (triethanolamine compound) titanium of diisopropoxy, lactic acid titanium ammonium salt and lactic acid titanium；Double (ethyl acetoacetic ester) zirconium of four acetylacetone,2,4-pentanedione zirconiums, three butoxy single acetyl acetone zirconiums, only son's epoxide acetylacetone,2,4-pentanedione, the double zirconium chelate compound etc. such as (ethyl acetoacetic ester) zirconium and four acetylacetone,2,4-pentanedione zirconiums of dibutoxy, as commercially available product, オ Le ガ チ ッ Network ス TC-100 and TC-300 (マ Star モ ト Off ァ イ Application ケ ミ カ Le Co., Ltd. manufacture) etc. can be illustrated, can be applied in combination two or more.
In these (B) compositions, from easily with the carboxylate anion radical reaction that contains (A) composition from the viewpoint of, be preferably selected from by aziridine based compound, carbodiimide compound, epoxy compound,At least one in the group of oxazoline based compound and metallo-chelate based compound composition, wherein, from the viewpoint of the curability of overlay film, preferably aziridine based compound.
(B) usage amount of composition is not particularly limited, consider from viewpoints such as the adaptation of curing overlay film, curability and solvent resistances, (A) composition and the solid constituent mass ratio [(A)/(B)] of (B) composition are usually about 5/5～9/1, the scope of preferably about 6/4～8/2.
(C) composition is to make the curing overlay film of the present invention play excellent antistatic characteristic and required, can use various known pi-conjugated systems electric conductive polymer without particular limitation.Specifically, at least one in the group being selected from being made up of polythiophene class, polyaniline compound, the sub-vinyl of polythiophene, multi-metal polypyrrole and poly-furans etc. can be enumerated.Wherein, from the viewpoint of the antistatic characteristic of curing overlay film and the transparency etc., preferably polythiophene class.
As polythiophene class, polythiophene, poly-(alkylthrophene) class, poly-(monoalkoxy thiophene) class, poly-(dialkoxythiophene) class and poly-(alkylenedioxythiophene) class etc. can be enumerated.Wherein, particularly preferably utilize alkylenedioxy group poly-(thiophene) obtained from polystyrolsulfon acid (PSS) doping, particularly preferably poly-3,4-ethene-dioxythiophene (PEDOT) and the complex compound (hereinafter also referred to PEDOT/PSS) of PSS.PEDOT/PSS is for example by obtaining using oxidant to carry out polymerization as the 3,4-ethene-dioxythiophene (EDOT) of monomer in the presence of as polystyrolsulfon acid (PSS) of adulterant in aqueous phase.As commercially available product, such as Clevios P (ヘ レ ウ ス Co., Ltd. manufacture), Orgacon ICP1010 (Japan ア グ Off ア マ テ リ ア Le ズ Co., Ltd. manufacture) etc. can be enumerated, can be applied in combination two or more.
As polyaniline compound, polyaniline, poly-(2-aminotoluene), poly-(3-isobutyl-aniline), poly-(2-anilinesulfonic acid) and poly-(3-anilinesulfonic acid) etc. can be enumerated, can be applied in combination two or more.
The content of (C) composition in the coating agent of the present invention is not particularly limited, from the viewpoint of the antistatic characteristic of curing overlay film and the transparency etc., it is typically about 5 mass parts～about 25 mass parts, preferably from about 10 mass parts～about 15 mass parts relative to total 100 mass parts of (A) composition and (B) composition in terms of solid constituent conversion.
(D) composition is by above-mentioned (C) even if the coating agent to the present invention for the combination of composition gives the composition of antistatic characteristic also excellent under high voltages.
(D) composition is burning system electroconductive stuffing (D1) (hereinafter referred to as (D1) composition) and/or carbon series conductive filler (D2) (hereinafter referred to as (D2) composition).
As (D1) composition, as long as the metal oxide filler with electric conductivity then can use various known material without particular limitation.Specifically, the tin oxide (ATO) of such as Sb doped can be enumerated, the tin oxide of Fluorin doped, the tin oxide (PTO) of phosphorus doping, the tin oxide of aluminium doping, the tin oxide of niobium doping, the tin oxide of tantalum doping, the tin oxide of witch culture, the tin oxide of indium doping, tin oxide, the indium oxide (ITO) of tin dope, the indium oxide of Fluorin doped, the indium oxide of cadmium doping, the zinc oxide of indium doping, the zinc oxide of Fluorin doped, the zinc oxide of aluminium doping, the zinc oxide of gallium doping, the zinc oxide of mg-doped, the zinc oxide of silicon doping, the zinc oxide of tin dope, boron doped zinc oxide, zinc oxide, zinc antimonates (AZO) and the titanium oxide etc. of niobium doping, can be applied in combination two or more.Wherein, the particularly preferably at least one in the group being made up of the tin oxide of Sb doped, the indium oxide of tin dope, the tin oxide of phosphorus doping, tin oxide, the zinc oxide of aluminium doping, the zinc oxide of gallium doping and zinc antimonates etc., even if from the viewpoint of applying under high voltages also to suppress surface resistivity to raise, the tin oxide of particularly preferred Sb doped, the indium oxide of tin dope, the tin oxide of phosphorus doping, tin oxide, the zinc oxide of aluminium doping, the zinc oxide of gallium doping and zinc antimonates.
(D1) shape of composition is not particularly limited, and can enumerate powder, aqueous sol and organic solvent colloidal sol etc..As (D1) composition of powder, can enumerate for example by material obtained from the inorganic particulates such as titanium oxide (D1) composition cladding.
Commercially available product as (D1) composition, such as T-1, S-2000, S-1, SP-2, E-ITO, TDL-1, TDL-SA, SPDL and SDL (above manufacture for Mitsubishi Materials Corp), セ Le Na ッ Network ス CX-Z330H, CX-Z610-F2, CX-Z410K, CX-S301H, CX-S204IP and CX-S501M (above manufacture for Nissan Chemical Ind Ltd), パ ゼ ッ ト CK and パ ゼ ッ ト GK-40 (be above Ha Network ス イ テ ッ Network Co., Ltd. manufacture) etc. can be enumerated, can be applied in combination two or more.
In the coating agent of the present invention, in the case of using (D1) composition, its content is about 5 mass parts～about 30 mass parts (solid constituent conversion) relative to total 100 mass parts (solid constituent conversion) of (A) composition and (B) composition.During less than 5 mass parts, there is the tendency significantly raising when applying under high voltages in the surface resistivity of the curing overlay film of the present invention.In addition, during more than 30 mass parts, there is the tendency reducing in the transparency of curing overlay film.Considering from this viewpoint, the content of (D1) composition is preferably from about 7 mass parts～about 25 mass parts (solid constituent conversion).
As (D2) composition, as long as the electroconductive stuffing of carbon system, then various known material can be used without particular limitation.Specifically, such as carbon black, graphite and the activated carbons etc. such as CNT, carbon nano wire, acetylene black and furnace black can be enumerated, can be applied in combination two or more.Wherein, even if from the viewpoint of applying under high voltages also to suppress surface resistivity to raise, particularly preferred CNT.As CNT, single-layer carbon nano-tube, multilayer carbon nanotube, spiral carbon nano pipe etc. can be enumerated.CNT is for example obtained by the contact reduction of carbon dioxide, arc discharge method, laser evaporization method, CVD, vapor growth method etc..In addition, CNT can be the CNT after being pulverized by ball mill, vibrating mill etc., it is also possible to be the CNT after utilizing chemical treatment or physical treatment to prescind.
(D2) shape of composition is not particularly limited, and can enumerate powder, aqueous sol and organic solvent colloidal sol etc..
Commercially available product as (D2) composition, such as UW-153, UW-253 (above manufacture for Ube Industries, Ltd), CARBOBYK-9810 (PVC ッ Network ケ ミ ジ ャ パ Application Co., Ltd. manufacture) etc. can be enumerated, can be applied in combination two or more.
In the coating agent of the present invention, in the case of using (D2) composition, its content is about 0.5 mass parts～about 10 mass parts (solid constituent conversion) relative to total 100 mass parts of (A) composition and (B) composition.During less than 0.5 mass parts, there is the tendency significantly raising when applying under high voltages in the surface resistivity of the curing overlay film of the present invention.In addition, during more than 10 mass parts, there is the tendency reducing in the transparency of curing overlay film.Considering from this viewpoint, the content of (D2) composition is preferably from about 0.8 mass parts～about 5 mass parts (solid constituent conversion).
The coating agent of the present invention can contain solvent.As solvent, such as organic solvent, water can be enumerated.As organic solvent, can enumerate for example: the alcohols such as methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, ethylene glycol, diethylene glycol, ethylene glycol monoethyl ether and ethylene glycol propyl ether；The ketone such as acetone and MEK；Toluene, dimethylbenzene and benzene etc. are aromatic hydrocarbon；And ethyl acetate, chloroform, dimethylformamide, dimethyl sulfoxide, 1-METHYLPYRROLIDONE etc., can be applied in combination two or more.As above-mentioned water, ion exchange water etc. can be enumerated.Wherein, from the viewpoint of the storage stability of the coating agent of the present invention, preferably carbon number is alcohols, such as methyl alcohol, ethanol, normal propyl alcohol and the isopropanol etc. of about 1～4.In addition, as water, preferred ion exchanged water.
The content of the solvent in the coating agent of the present invention is not particularly limited, and usually makes the solid component concentration of this coating agent reach the scope of about 0.1 mass %～about 30 mass %.
The coating agent of the present invention can improve the additive such as agent, curing catalysts containing defoamer, antilubricant, preservative, antirust agent, pH adjusting agent, antioxidant, pigment, dyestuff, lubricant, levelling agent, electric conductivity.
As levelling agent, for example polyether-modified dimethyl silicone polymer, polyester modification dimethyl silicone polymer, perfluor dimethyl silicone polymer etc. can be enumerated, can be applied in combination two or more.The usage amount of this levelling agent is not particularly limited, and is less than 10 mass parts relative to total 100 mass parts (solid constituent conversion) of (A) composition and (B) composition.
Improve agent as electric conductivity, can enumerate for example ethylene glycol, diethylene glycol, propane diols, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexylene glycol, cyclohexanediol, cyclohexanedimethanol, glycerine, dimethyl sulfoxide, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, dinethylformamide, isophorone, propene carbonate, cyclohexanone etc., can be applied in combination two or more.The usage amount that this electric conductivity improves agent is not particularly limited, and is less than 300 mass parts relative to total 100 mass parts (solid constituent conversion) of (A) composition and (B) composition.
As curing catalysts, the such as acid catalysts such as p-methyl benzenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid can be enumerated；Diaryl iodoniumSalt, triarylsulfonium salt, diarylThe acid producing agents etc. such as salt, can be applied in combination two or more.The usage amount of this curing catalysts is not particularly limited, relative to total 100 mass parts (solid constituent conversion) of (A) composition and (B) composition for 3 mass parts.
The coating agent of the present invention can be by being at room temperature stirred mixing and obtaining (A) composition, (B) composition, (C) composition and (D) composition and the solvent being added as needed on, above-mentioned additive.
The curing overlay film of the present invention by being coated to the coating agent of the present invention on plastic foil and can make its heat cure obtain.
As plastic foil, such as polycarbonate membrane, polymethyl methacrylate film, polystyrene film, polyethylene terephthalate film, polyimide film, polyolefin film, nylon membrane, epoxy resin film, melmac film, triacetyl cellulose resin film, ABS resin film, AS resin film and norbornene resin film etc. can be enumerated.These films can carry out surface treatment (corona discharge etc.) as required.In addition, this plastic foil can be provided with various functional layer in its one or two sides.
Coating method is not particularly limited, it is possible to use various known means.For example, it is possible to enumerate roller coat, reversion roller coat, intaglio plate coating, scraper for coating, rod painting, dip-coating etc..
It after applying the coating agent of the present invention on substrate surface, from the viewpoint of the resistance to blocking of curing overlay film, is preferable to carry out being dried process.Baking temperature is not particularly limited, typically about 60 DEG C～about 150 DEG C, preferably from about 80 DEG C～about 120 DEG C.In addition, drying time is also not particularly limited, typically about 10 seconds～about 120 seconds.
The plastic foil of the present invention is the article of the curing overlay film possessing the present invention at least one side.The thickness of curing overlay film is not particularly limited, typically about 0.01 μm～about 2 μm.The thickness of plastic foil is also not particularly limited, typically about 25 μm～about 125 μm.
[embodiment]
Hereinafter, by embodiment and comparative example, the present invention is specifically illustrated.But, the technical scope of the present invention is not limited by these examples, and this is self-evident." part " and " % " in embodiment is quality criteria at the situation table being not particularly illustrated.
In each Production Example, glass transition temperature be utilize differential scanning calorimeter (ProductName " DSC6200 ", セ イ U イ Application ス ツルメン Star Co., Ltd. manufactures) be measured obtained from value.Number-average molecular weight is polystyrene conversion value obtained from utilization cohesion permeation chromatograph (ProductName " HLC-8220GPC ", TOSOH Co., Ltd manufactures) is measured.
<manufacture of (A) composition>
Production Example 1
Put into 16 parts of acrylic acid and methyl methacrylate 144 parts in the four-hole boiling flask possessing nitrogen ingress pipe, thermometer, reflux condenser and agitating device, add isopropanol 446 parts further, prepare monomer solution.Then, in this monomer solution, add 2 as polymerization initiator, 2 '-azodiisobutyronitrile 3.2 parts.Then, make reaction system reach 80 DEG C, carry out the Raolical polymerizable of 8 hours.Then, reaction system adds triethylamine 22.4 parts, ion exchange water 1000 parts, be sufficiently stirred for, be cooled to normal temperature, thus obtain the solution of acrylic copolymer (A-1) composition of the group containing carboxylate anion that solid constituent is 10%.(A-1) the carboxylate anion group amount of composition be 0.00139mol/g, glass transition temperature be 100 DEG C, number-average molecular weight be 30000.
Production Example 2
Put into 24 parts of acrylic acid and methyl methacrylate 136 parts in the four-hole boiling flask as Production Example 1, add isopropanol 435 parts further, make monomer solution.Then, in this monomer solution, add the azodiisobutyronitrile 3.2 parts as polymerization initiator.Then, from reaction system being warming up in the of 80 DEG C, the Raolical polymerizable of 8 hours is carried out.Then, reaction system adds triethylamine 33.7 parts, ion exchange water 1000 parts, be sufficiently stirred for, be cooled to normal temperature, thus obtain the solution of acrylic copolymer (A-2) composition of the group containing carboxylate anion that solid constituent is 10%.It should be noted that the carboxylate anion group amount of (A-2) composition is 0.00208mol/g, glass transition temperature is 95 DEG C, number-average molecular weight is 30000.
Relatively Production Example 1
In Production Example 1, do not use triethylamine after polymerization, in reaction system, only add isopropanol 1000 parts, be sufficiently stirred for, be cooled to normal temperature, thus obtain the solution of the acrylic copolymer (E-1) containing carboxyl that solid constituent is 10%.(E-1) the carboxylate anion group amount of composition be 0mol/g, glass transition temperature be 100 DEG C, number-average molecular weight be 30000.
Embodiment 1
nullWill be as (A-1) composition 700 parts (solid constituent converts: 70 parts) of (A) composition、Trimethylolpropane-three (1-'-aziridino propionic ester) (trade name " ケ ミ タ イ ト PZ-33 " as (B) composition，Catalyst Co., Ltd. of Japan manufactures) 30 parts、The PEDOT/PSS aqueous solution (trade name " Orgacon ICP1010 " as (C) composition，Japan ア グ Off ア マ テ リ ア Le ズ Co., Ltd. manufactures，Solid constituent 1.2%) 1000 parts (solid constituent 12 parts)、Tin oxide (trade name " TDL-1 " as the Sb doped of (D) composition，Mitsubishi Materials Corp manufactures，Solid constituent 17%) 60 parts (solid constituent 10 parts)、Triethylamine 3.0 parts、BYK-333 (polyether-modified dimethyl silicone polymer as levelling agent，PVC ッ Network ケ ミ ジ ャ パ Application Co., Ltd. manufactures) 1 part、P-methyl benzenesulfonic acid 1 part as catalyst、Ion exchange water 6900 parts and isopropanol 3500 parts at room temperature mix 10 minutes，Prepare the coating agent of solid constituent 1.0%.
Embodiment 2～16, comparative example 1～17
Change into the species shown in table 1 or usage amount, prepare coating agent respectively by method similarly to Example 1.
[making of test film]
Use bar coater No.3, be coated to the coating agent of embodiment 1 on PET film, make this coated film be dried (100 DEG C, 1 minute) in drying machine with the wind, make test film.For the coating agent of embodiment 2～16 and comparative example 1～17, make test film similarly.
[mensuration of surface resistivity]
Applicator surface at the test film of embodiment 1, according to JIS K6911, use the Ha イ レ ス タ UP MCP-HT450 that Mitsubishi Chemical Ind manufactures, under applying voltage 100V and 1000V, measure the surface resistivity (Ω/) in the environment of temperature 23 DEG C, humidity 50% respectively.In addition, the test film of embodiment 2～16 and comparative example 1～17 is measured similarly.Surface resistivity is less, represents that antistatic performance is better.Show the result in (lower same) in table 1.
[surface resistivity after damp and hot]
After the test film of embodiment 1 is placed 4 days in the environment of temperature 40 DEG C, humidity 90%, measure surface resistivity by above-mentioned same method.The test film of embodiment 2～16 and comparative example 1～17 is measured similarly.Surface resistivity is less, represents that antistatic performance is better.
[transparent]
Use haze meter " HM-150 " (color technical research institute in village), carry out the haze value of determination test film according to JIS-K-7136.The difference of the haze value with only PET film is set to Hz, and numerical value is less, then it represents that the transparency is better.
[curability]
By test film with impregnated in swab stick wiping in MEK, to exposing until base material till number of times (back and forth) be measured.
◎: even if wiping more than 100 times, base material does not also expose
Zero: during wiping 60～100 times, base material exposes
During △: wiping 20～59 times, base material exposes
×: during wiping 1～19 time, base material exposes
[adaptation]
Paste adhesive tape on test film so that it is after fully crimping, exerted oneself to peel off, carry out visual valuation based on the amount of the film to residual for the following benchmark.
◎ ... remain 100% film
Zero ... residual more than 70% and the film less than 100%
△ ... residual more than 40% and the film less than 70%.
× ... the film less than 40% for the residual.
[(B) composition]
(B-1) trimethylolpropane-three (1-'-aziridino propionic ester) (trade name " ケ ミ タ イ ト PZ-33 ", catalyst Co., Ltd. of Japan manufactures)
(B-2) tetramethylol methane-three (1-'-aziridino propionic ester) (trade name " CLOSSLINKER CL427 ", mutual Yao Gong Co., Ltd. manufactures)
(B-3) carbodiimide system curing agent (trade name " カ Le ボ ジ ラ イ ト V-02 ", Misshin Spinning Co., Ltd manufactures)
[(C) composition]
(C-1) PEDOT/PSS (trade name " Orgacon ICP1010 ", Japan ア グ Off ア マ テ リ ア Le ズ Co., Ltd. manufactures, solid constituent 1.2%)
[(D1) composition]
(D1-1) tin oxide (trade name " TDL-1 ", Mitsubishi Materials Corp manufactures, solid constituent 17%) of Sb doped
(D1-2) indium oxide (trade name " makees ITO aqueous dispersions ", and Mitsubishi Materials Corp manufactures, solid constituent 20%) of tin dope
(D1-3) tin oxide (trade name " セ Le Na ッ Network ス CX-S301H ", Nissan Chemical Ind Ltd manufactures, solid constituent 30%) of phosphorus doping
(D1-4) zinc antimonates (trade name " セ Le Na ッ Network ス CX-Z330H ", Nissan Chemical Ind Ltd manufactures, solid constituent 30%)
[(D2) composition]
(D2) CNT (trade name " UW-153 ", Ube Industries, Ltd manufactures, solid constituent 2.5%)
[other conductive component]
(F-1) trifluoromethayl sulfonic acid lithium (trade name " EF-15 ", Mitsubishi Materials Corp manufactures)
(F-2) double (trifyl) imide lis (trade name " EF-N115 ", Mitsubishi Materials Corp manufactures)
(G-1) acetylenediol system surfactant (trade name " サ Off ィ ノ Le 485 ", Nishin Chemical Industry Co. Lt manufactures).
Claims (11)
1. a thermohardening type antistatic coating agent, it contains third of group containing carboxylate anion
Olefin(e) acid analog copolymer (A), curing agent (B), pi-conjugated system electric conductive polymer (C) and Conductive inorganic
Filler (D),
(D) composition comprises selected from by burning system electroconductive stuffing (D1) and carbon series conductive
At least one in the group that filler (D2) forms,
In the case of using (D1) composition, its amount becomes relative to (A) in terms of solid constituent conversion
Total 100 mass parts with (B) composition is divided to be calculated as 5～30 mass parts with solid constituent conversion,
In the case of using (D2) composition, its amount becomes relative to (A) in terms of solid constituent conversion
Total 100 mass parts with (B) composition is divided to be calculated as 0.5～10 mass parts with solid constituent conversion.
2. thermohardening type antistatic coating agent as claimed in claim 1, wherein, (A) composition is
By comprising α, the monomer group (α) of β unsaturated carboxylic acid class (a1) and (methyl) alkyl-acrylates (a2)
The neutralization salt of the copolymer constituting.
3. thermohardening type antistatic coating agent as claimed in claim 1 or 2, wherein, (A)
The carboxylate anion group content of composition is 0.0003～0.005mol/g.
4. the thermohardening type antistatic coating agent as according to any one of claims 1 to 3, its
In, (B) composition is aziridine based compound.
5. the thermohardening type antistatic coating agent as according to any one of Claims 1 to 4, its
In, (A) composition is 5/5～9/1 with solid constituent mass ratio (A)/(B) of (B) composition.
6. the thermohardening type antistatic coating agent as according to any one of Claims 1 to 5, its
In, (C) composition is polythiophene class.
7. the thermohardening type antistatic coating agent as according to any one of claim 1～6, its
In, the content of (C) composition relative to total 100 mass parts of (A) composition and (B) composition with solid
Composition conversion is calculated as 5～25 mass parts.
8. the thermohardening type antistatic coating agent as according to any one of claim 1～7, its
In, (D1) composition is for selected from by the tin oxide of Sb doped, the indium oxide of tin dope, the oxygen of phosphorus doping
Change the group of tin, tin oxide, the zinc oxide of aluminium doping, the zinc oxide of gallium doping and zinc antimonates composition
In at least one.
9. the thermohardening type antistatic coating agent as according to any one of claim 1～8, its
In, (D2) composition is CNT.
10. a curing overlay film, which is the thermohardening type according to any one of claim 1～9
The curing overlay film of antistatic coating agent.
11. 1 kinds of plastic foils, its solidification possessing at least one side described in claim 10 is covered
Film.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219659A (en) * | 2016-12-09 | 2018-06-29 | 三星Sdi株式会社 | For the composition, polarizer and optical display of electrostatic dissipation coating |
| CN110491547A (en) * | 2019-08-22 | 2019-11-22 | 朱萍 | A kind of conductive material and its preparation process |
| CN114196316A (en) * | 2020-09-02 | 2022-03-18 | 荒川化学工业株式会社 | Active energy ray-curable resin composition, cured film, and film |
| CN115073129A (en) * | 2022-06-17 | 2022-09-20 | 广东盈浩工艺制品有限公司 | Anti-static ceramic and preparation method thereof |
Families Citing this family (4)
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| JP7412087B2 (en) | 2018-04-20 | 2024-01-12 | ナガセケムテックス株式会社 | coating composition |
| KR20200015881A (en) * | 2018-08-03 | 2020-02-13 | 아라까와 가가꾸 고교 가부시끼가이샤 | Water-based antistatic releasing coating composition and antistatic releasing film |
| JP2022170032A (en) | 2021-04-28 | 2022-11-10 | 藤森工業株式会社 | Surface protective film and optical component |
| JP2023001742A (en) * | 2021-06-21 | 2023-01-06 | 日東電工株式会社 | Pressure-sensitive adhesive sheet for semiconductor element processing |
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| CN110491547A (en) * | 2019-08-22 | 2019-11-22 | 朱萍 | A kind of conductive material and its preparation process |
| CN110491547B (en) * | 2019-08-22 | 2023-01-17 | 朱萍 | Conductive material and preparation process thereof |
| CN114196316A (en) * | 2020-09-02 | 2022-03-18 | 荒川化学工业株式会社 | Active energy ray-curable resin composition, cured film, and film |
| CN115073129A (en) * | 2022-06-17 | 2022-09-20 | 广东盈浩工艺制品有限公司 | Anti-static ceramic and preparation method thereof |
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| CN106167662B (en) | 2020-07-10 |
| JP2016216714A (en) | 2016-12-22 |
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| JP6631881B2 (en) | 2020-01-15 |
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| TWI692509B (en) | 2020-05-01 |
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