CN101538435A - Antistatic coating agent - Google Patents
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- CN101538435A CN101538435A CN200910126843A CN200910126843A CN101538435A CN 101538435 A CN101538435 A CN 101538435A CN 200910126843 A CN200910126843 A CN 200910126843A CN 200910126843 A CN200910126843 A CN 200910126843A CN 101538435 A CN101538435 A CN 101538435A
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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
- 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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- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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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
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides a novel coating agent with an excellent antistatic property, solvent resistance and adhesive resistance. The antistatic coating agent contains acroid resin (A) having carboxylate anion group, a polyfunctional aziridine compound (B) and a Pi conjugated conductive polymer (C) containing hetero atoms.
Description
Technical field
The present invention relates to a kind of antistatic coating agent and apply the plastics film that this antistatic coating agent obtains.
Background technology
Plastics films such as polyester film are easy to generate static when film spins or be mobile when reeling or recoil, can adhere to airborne dust or be moved bad in processing line.Therefore, produce, propose to have the method for in film, mixing static inhibitor in advance in order to suppress electrostatic.
But when mixing static inhibitor in the raw material plastics before carrying out processing film in advance, static inhibitor may ooze out and produces crease at film surface, or the static inhibitor that oozes out comes off and cause static resistance to descend.Therefore, consider to apply the method that the coating agent with anti-static function forms tunicle at film surface.
For antistatic coating agent, except anti-static function, also require tunicle to have adaptation of solvent resistance, anti-adhesive, plastic basis material and tunicle etc.If its poor solvent resistance, when then contacting with organic solvent in the processing film line, the coating tunicle can expand or come off.In addition, if its anti-adhesive is insufficient, then when recoiling film, produce big resistance sometimes, or tunicle peels off.
As antistatic coating agent, for example, in patent documentation 1, known have utilized the coating agent of quaternary ammonium salt cationic macromolecular compound as electroconductive polymer.But this antistatic coating agent is subjected to the influence of humidity easily, causes giving full play to anti-static function because of environment for use sometimes.Therefore, consider that it is electric conductive polymer that utilization is brought into play the pi-conjugated of anti-static function by electron migration.
As having utilized pi-conjugated is the antistatic coating agent of electric conductive polymer, and for example, in patent documentation 2, motion has poly-(thiophene) etc. is matched with the coating agent that the multipolymer of alkyl-acrylates or acrylic amide etc. forms particularly.But, insufficient the harmonious not enough of coating performance that wait of the solvent resistance of coating tunicle.
Patent documentation 1: Japanese kokai publication hei 10-315373 communique
Patent documentation 2: TOHKEMY 2003-292655 communique
Summary of the invention
Major subjects of the present invention is, a kind of excellent novel antistatic coating agents such as adaptation of static resistance, solvent resistance, anti-adhesive and tunicle and plastic basis material of tunicle are provided.
The inventor concentrates on studies repeatedly, found that, utilizes following antistatic coating agent can solve above-mentioned problem, has finished the present invention.
Promptly, the present invention relates to a kind of antistatic coating agent and apply the plastics film that this antistatic coating agent forms, described antistatic coating agent contains: contain acrylic resin (A), the polyfunctional aziridine compound (B) of carboxylate anion base and contain heteroatomic pi-conjugated be electric conductive polymer (C).
Utilize antistatic coating agent of the present invention, can obtain excellent antistatic property not only but also solvent resistance, anti-adhesive, with all excellent tunicle of the coating performances such as adaptation of plastics film.Thereby; this antistatic coating agent can be used for plate-making with film, packaging film, used for optical part film, indicating meter with protective film, semiconductor machining band with purposes widely such as film, hot stamping film, plastic shaping decorating film (carrying out moulding with base material integral body) for and film use surperficial with Dicoration base materials such as chromatic patterns.
Embodiment
Antistatic coating agent of the present invention contains: contain the carboxylate anion base acrylic resin (A) (below be sometimes referred to as (A) composition), polyfunctional aziridine compound (B) (below be sometimes referred to as (B) composition), contain heteroatomic pi-conjugated be electric conductive polymer (C) (below be sometimes referred to as (C) composition) and the curing catalysts (D) that adds as required (below be sometimes referred to as (D) composition).
As (A) composition, so long as intramolecularly has " COO
-" acrylic resin of carboxylate anion base of expression, just be not particularly limited, can use various known materials.
Particularly, can enumerate α, beta-unsaturated carboxylic acid (a1), (methyl) alkyl acrylate (a2) are (wherein, (methyl) alkyl acrylate is meant alkyl acrylate or alkyl methacrylate, and (methyl) in the following record also uses with the same meaning) and add the neutralized salt of above-mentioned (a1), (a2) unsaturated monomer (a3) in addition as required as the multipolymer of polymerization composition.Below, with each composition according to (a1) composition, (a2) composition and (a3) order of composition describe.Need to prove the carboxyl that above-mentioned carboxylate anion base has from (a1) composition.
As (a1) composition, can use various known α, beta-unsaturated carboxylic acid.For example, as α, β-unsaturated monocarboxylic acid class can enumerate (methyl) vinylformic acid, Ba Dousuan etc.; As α, β-unsaturated dicarboxylic acid class.Can enumerate toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid etc.In addition, also can enumerate: be called the α of methylene-succinic acid one anilide, the half amide of β-unsaturated dicarboxylic acid, α, an ester of β-unsaturated dicarboxylic acid and fatty alcohol or its corrective etc.As fatty alcohol, can enumerate: methyl alcohol, ethanol, propyl alcohol, butanols etc.As the neutralizing agent that is used to form each corrective, can utilize material described later.As (a1) composition, preferred α, β-unsaturated monocarboxylic acid, preferred especially (methyl) vinylformic acid.
As (a2) composition, can use various known (methyl) alkyl acrylate.In addition, the carbon number of alkyl is generally about 1～20, and the shape of alkyl can be straight chain shape, chain or ring-type.As the concrete example of (a2) composition, can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate base ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid ring pentyl ester, (methyl) isobornyl acrylate etc.
As (a3) composition, be that above-mentioned (a1) composition reaches (a2) composition unsaturated monomer in addition, can use the material that can carry out Raolical polymerizable with these compositions.Particularly, can enumerate: chlorosilane system (methyl) esters of acrylic acid, (methyl) acrylic amide, (methyl) vinylformic acid hydroxyalkyl acrylate class, styrenic, unsaturated sulfonic acid class, aminoalkyl group are that unsaturated monomer class, polyalkylene glycol are unsaturated monomer class, (gathering) siloxanes one (methyl) esters of acrylic acid, (list) fluoroalkyl acrylate class etc.
As chlorosilane system (methyl) esters of acrylic acid, can enumerate: vinyl-dimethyl base chlorosilane, allyldimethylcholrosilane, 4-butenyl dimethylchlorosilane, 5-pentenyl dimethylchlorosilane, 3-methacryloxypropyl dimethylchlorosilane, 4-methacryloxy butyl dimethylchlorosilane etc.
As (methyl) acrylic amide, can enumerate: (methyl) acrylamide, N-methyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-lauryl (methyl) acrylamide, N-cyclohexyl substituted alkyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-di-isopropyl (methyl) acrylamide, N, N-dilauryl (methyl) acrylamide etc.
As (methyl) vinylformic acid hydroxyalkyl acrylate class, can enumerate: (methyl) vinylformic acid 2-hydroxyl methyl esters, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester etc.
As styrenic, can enumerate: vinylbenzene, alpha-methyl styrene, t-butyl styrene, dimethyl styrene, acetoxy-styrene, hydroxy styrenes, Vinyl toluene, chlorovinyl toluene etc.
As the unsaturated sulfonic acid class, can enumerate: vinyl sulfonic acid, (methyl) allyl sulphonic acid, 2-acrylamide-2-methyl propane sulfonic acid, sulfonated phenylethylene etc.
As aminoalkyl group is the unsaturated monomer class, can enumerate: (methyl) vinylformic acid ammonia ethyl ester, (methyl) vinylformic acid ammonia propyl ester, (methyl) vinylformic acid N-methyl ammonia ethyl ester, (methyl) vinylformic acid N-methyl ammonia butyl ester, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) vinylformic acid N, N-diethyl amino propyl ester etc.
As polyalkylene glycol is the unsaturated monomer class, can enumerate: glycol ether one (methyl) acrylate, triglycol one (methyl) acrylate, Tetraglycol 99 one (methyl) acrylate, dipropylene glycol one (methyl) acrylate, tripropylene glycol one (methyl) acrylate etc.
As (gathering) siloxanes list (methyl) esters of acrylic acid, can enumerate: " SILAPLANE FM-0711 ", " SILAPLANE FM-0721 ", " SILAPLANE FM-0725 " commercially available products such as (being Japanese Chisso Corp make).
As (list) fluoroalkyl acrylate class, can enumerate: (methyl) vinylformic acid-2,2,2-trifluoro ethyl ester, (methyl) vinylformic acid-2,2,2-three fluoro-1-trifluoro methyl esters, (methyl) vinylformic acid-2,2,3,3-tetrafluoro propyl ester, (methyl) vinylformic acid-H, 1H, 5H-octafluoro pentyl ester etc.In addition, as its commercially available product, can enumerate: " V-3F ", " V-3FM ", " V-4F ", " V-8F ", " V-8FM " (being Osaka, Japan organic chemistry Industrial Co., Ltd makes) etc.
As (a3) composition, consider especially preferably above-mentioned (gathering) siloxanes list (methyl) esters of acrylic acid and/or fluoroalkyl (list) esters of acrylic acid from the viewpoint of resulting tunicle being given anti-adhesive.
(a1) composition～(a3) usage quantity of each composition of composition is not particularly limited, with (a1) composition～when (a3) total amount of composition is set at 100 weight parts, (a1) composition is about 3～30 weight parts, (a2) composition is about 20～97 weight parts, (a3) composition is about 0～50 weight part.In addition, when using (a3) composition, (a1) composition is about 3～30 weight parts, (a2) composition is about 20～87 weight parts, (a3) composition is about 10～50 weight parts.
(A) composition can obtain by the following method, for example, makes that above-mentioned (a1) composition～(a3) composition carries out radical polymerization about 1～20 hour about 60～180 ℃, then, and with in the neutralizing agent and resulting multipolymer.In addition, when reaction, also can utilize reaction solvents such as radical polymerization initiator or chain-transfer agent, organic solvent or ion exchanged water.
As neutralizing agent, can enumerate: ammonia, primary amine～tertiary amines, alkali metal compound and alkaline earth metal compound etc.As primary amine, can enumerate: Monomethylamine, monoethylamine, monobutylamine (MBA), hexahydroaniline etc.; As secondary amine, can enumerate: dimethylamine, diethylamine etc.; As tertiary amine, can enumerate: Trimethylamine 99, triethylamine etc.As alkali metal compound, can enumerate: sodium hydroxide, potassium hydroxide etc.As alkaline earth metal compound, can enumerate magnesium hydroxide etc.In addition, can also use aniline, arylamine, hydramine etc.When using tertiary amines and/or ammonia as neutralizing agent, the solvent resistance of package stability (working life), tunicle is good, so preferred.The carboxyl that relative this free radical polyalcohol has, the usage ratio of preferred neutralizing agent is generally 80～300 moles of %.
As radical polymerization initiator, for example,, can enumerate hydrogen peroxide, ammonium persulphate, Potassium Persulphate etc. as the inorganic peroxide class; As the organo-peroxide class, can enumerate peroxidized t-butyl perbenzoate, dicumyl peroxide, lauroyl peroxide etc.; Also have as the azo-compound class, can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo-bis-iso-dimethyl etc.Total amount 100 weight parts of composition of (a1) composition～(a3) relatively, the consumption of radical polymerization initiator is generally about 0.01～10 weight part.
As chain-transfer agent, for example can enumerate: dodecyl mercaptans, 2-mercaptobenzothiazole, trichlorobromomethane etc.In addition, relative total amount 100 weight parts of composition of (a1) composition～(a3), its consumption is generally about 0.01～5 weight part.
As organic solvent, for example,, can enumerate methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, ethylene glycol, glycol ether, ethylene glycol monoethyl ether, ethylene glycol one n-propyl ether etc. as alcohols; As rudimentary ketone, can enumerate acetone, methyl ethyl ketone etc.; As aromatic hydrocarbon based, can enumerate toluene, benzene etc.; In addition, also can enumerate vinyl acetic monomer, chloroform, dimethyl formamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone etc.
(A) amount (mol/g) of the carboxylate anion base in the composition is generally about 0.0003～0.005, is preferably 0.001～0.003.By being more than 0.0003, can make the solvent resistance of tunicle good.In addition, by being below 0.005, keep the equilibrium of the static resistance and the solvent resistance of tunicle easily.Here, " amount of carboxylate anion base " is meant the mole number of the carboxylate anion base that comprises among the nonvolatile component 1g of (A) composition, is calculated value.
In addition, consider that from the viewpoint of the anti-adhesive of the tunicle guaranteeing to obtain (A) second-order transition temperature of composition is generally 20～150 ℃, is preferably 70～150 ℃.In addition, the workability when making or easily viewpoint such as the property handled consider that (A) number-average molecular weight of composition (utilizing the polystyrene conversion value of gel permeation chromatography) is generally about 2000～100000, is preferably 25000～100000.
As (B) composition, specifically can enumerate the aziridine derivative that intramolecularly has the '-aziridino of at least 3 following structures.As such aziridine derivative, for example, the aziridine derivative that can use the method for records such as No. 4382135, United States Patent (USP) for example, TOHKEMY 2003-104970 number to make.
[changing 3]
(in the formula, R
1And R
2The alkyl of expression hydrogen or carbon number 1～6, both can be identical, also can be different.)
As (B) composition, consider from the viewpoint of the solvent resistance of guaranteeing tunicle etc., preferred especially 3 officials can aziridine cpd and/or 4 officials can aziridine cpd.
As 3 officials energy aziridine cpd, as the material that obtains easily, 3 officials of preferred following general formula (1) expression can aziridine cpd.
[changing 4]
In the formula (1), X represents that hydrogen, carbon number are that 1～6 alkyl or carbon number are 1～3 alkyl alcohol radical.In addition, R
1And R
2Expression hydrogen or carbon number are 1～6 alkyl, and both can be identical, also can be different.In addition, R
3Expression hydrogen or methyl.
In the compound of general formula (1) expression, as X is the compound of hydrogen, for example can enumerate: glycerine-three (1-'-aziridino propionic ester), glycerine-three [2-methyl-(1-'-aziridino)] propionic ester, glycerine-three [2-propyl group-(1-'-aziridino)] propionic ester, glycerine-three [2-hexyl-(1-'-aziridino)] propionic ester, glycerine-three [2,3-dimethyl-(1-'-aziridino)] propionic ester, glycerine-three [2,3-dihexyl-(1-'-aziridino)] propionic ester etc.
In the compound of general formula (1) expression, as X is the compound of the alkyl of carbon number about 1～6 (being preferably 2～3), for example can enumerate: TriMethylolPropane(TMP)-three (1-'-aziridino propionic ester), TriMethylolPropane(TMP)-three [2-methyl-(1-'-aziridino)] propionic ester, TriMethylolPropane(TMP)-three [2-propyl group-(1-'-aziridino)] propionic ester, TriMethylolPropane(TMP)-three [2-hexyl-(1-'-aziridino)] propionic ester, TriMethylolPropane(TMP)-three [2,3-dimethyl-(1-'-aziridino)] propionic ester, TriMethylolPropane(TMP)-three [2,3-dihexyl-(1-'-aziridino)] propionic ester etc.
In the compound of general formula (1) expression, as X is the compound of the alkyl alcohol radical of carbon number 1～3, for example can enumerate: tetramethylol methane-three (1-'-aziridino propionic ester), tetramethylol methane-three [2-methyl-(1-'-aziridino)] propionic ester, tetramethylol methane-three [2-propyl group-(1-'-aziridino)] propionic ester, tetramethylol methane-three [2-hexyl-(1-'-aziridino)] propionic ester, tetramethylol methane-three [2,3-dimethyl-(1-'-aziridino)] propionic ester, tetramethylol methane-three [2,3-dihexyl-(1-'-aziridino)] propionic ester etc.
As 4 officials energy aziridine cpd, 4 officials of preference such as following general formula (2) expression can aziridine cpd.In addition, can utilize four '-aziridino m-xylene diamines, four '-aziridino methyl p-Xylol diamines etc.
[changing 8]
(in the formula (2), R
1And R
2Can be identical or different, the alkyl of expression hydrogen or carbon number 1～6.In addition, R
3Expression hydrogen or methyl.)
In the compound of general formula (2) expression, for example can enumerate: tetramethylolmethane-four (1-'-aziridino propionic ester), tetramethylolmethane-four [2-methyl-(1-'-aziridino)] propionic ester, tetramethylolmethane-four [2-hexyl-(1-'-aziridino)] propionic ester, tetramethylolmethane-four [2,3-diethyl-(1-'-aziridino)] propionic ester, tetramethylolmethane-four [2,3-dihexyl-(1-'-aziridino)] propionic ester etc.
In addition, as (B) composition, 6 officials that can comprise 2 officials energy aziridine cpd or above-mentioned TOHKEMY 2003-104970 number record as required can aziridine cpd.As 2 officials energy aziridine cpd, can enumerate neopentyl glycol two (β-'-aziridino propionic ester) etc.
Also can use the simple function aziridines when using (B) composition here.For example can enumerate: aziridine, 2-methylaziridine, 2-ethyl aziridine, 2,2-dimethyl aziridine, 2,3-dimethyl aziridine, 2-phenyl aziridine etc.
Here, consider that (B) amount of the '-aziridino of composition (mol/g) is generally about 0.001～0.02, is preferably 0.003～0.01 scope from the viewpoint of the solvent resistance of guaranteeing tunicle etc.Here, " amount of '-aziridino " is meant the mole number of the '-aziridino that comprises in 1g (B) composition, is calculated value.
(A) composition in the antistatic coating agent of the present invention and (B) content of composition be not particularly limited, but with the mole number of the carboxylate anion base unit weight of (A) composition be set at x, when the mole number of the aziridine base unit weight of (B) composition is set at y, x/y is generally about 0.1～10, be preferably 0.03～5 scope.So long as this numerical range just can obtain the tunicle that the adaptation of solvent resistance, anti-adhesive, relative plastics film, the particularly adaptation of relative pet film are all given full play to.
Here, also can be among the present invention also with the linking agent beyond a spot of (B) composition, for example: Duo Guan Neng oxazoline compound, multi-functional epoxy compound, multifunctional carbodiimide compound, consider that from the solidified nature of the coating tunicle guaranteeing to obtain or the viewpoint of solvent resistance these linking agents can not use with independent form.
As (C) composition, can utilize various known contain heteroatomic pi-conjugated be electric conductive polymer.In addition, (C) composition is the state that has mixed with various doping agents among the present invention.In addition, " heteroatoms " is meant hydrogen and carbon atom (for example nitrogen-atoms or sulphur atom etc.) in addition.In addition, " contain heteroatomic pi-conjugated be electric conductive polymer " be meant that intramolecularly has the organic high molecular compound that this heteroatoms and molecular backbone chain form pi-conjugated structure.In addition, (C) composition uses with the form that nonvolatile component concentration is generally the aqueous solution about 0.1～10 weight % usually.
As contain heteroatomic pi-conjugated be the concrete example of electric conductive polymer, for example, contain heteroatomic heterocyclic pi-conjugated to be electric conductive polymer, can to enumerate as having: poly-(thiophene) class, poly-(the inferior ethene of thiophene) class, poly-(pyrroles) class, poly-(furans) class etc.As having the pi-conjugated of heteroatomic aromatic nucleus is electric conductive polymer, can enumerate poly-(aniline) class etc.
In heterocycle or aromatic nucleus, alkyl, alkoxyl group, alkylenedioxy group can be combined into dendroid or ring-type.As alkyl, can enumerate: methyl, ethyl, propyl group, butyl, hexyl, octyl group, decyl, dodecyl, octadecyl etc.As alkoxyl group, can enumerate: methoxyl group, oxyethyl group, butoxy, hexyloxy, the last of the ten Heavenly stems oxygen base, octadecane oxygen base etc.As alkylenedioxy group, can enumerate: ethylidene dioxy base, propylidene dioxy base, butylidene dioxy base etc.
As poly-(thiophene) class, can enumerate: poly-(thiophene), poly-(3 methyl thiophene), poly-(3-butyl thiophene), poly-(3-decylthiophene), poly-(3, the 4-thioxene), poly-(3,4-dibutyl thiophene), poly-(3-methoxythiophene), poly-(3-butoxy thiophene), poly-(3-hexyloxy thiophene), poly-(3-oxygen in heptan base thiophene), poly-(3-octyloxy thiophene), poly-(3, the 4-dimethoxy-thiophene), poly-(3,4-diethoxy thiophene), poly-(3,4-ethylidene dioxy base thiophene), poly-(3,4-propylidene dioxy base thiophene), poly-(3,4-butylidene dioxy base thiophene) etc.
As poly-(the inferior ethene of thiophene) class, can enumerate: poly-(the inferior ethene of thiophene), poly-(the inferior ethene of 3 methyl thiophene), poly-(the inferior ethene of 3-butyl thiophene), poly-(3, the inferior ethene of 4-thioxene), poly-(3, the inferior ethene of 4-dibutyl thiophene), poly-(the inferior ethene of 3-methoxythiophene), poly-(the inferior ethene of 3-butoxy thiophene), poly-(the inferior ethene of 3-hexyloxy thiophene), poly-(the inferior ethene of 3-octyloxy thiophene), poly-(3, the inferior ethene of 4-dimethoxy-thiophene), poly-(3, the inferior ethene of 4-ethylidene dioxy base thiophene), poly-(3, the inferior ethene of 4-propylidene dioxy base thiophene), poly-(3, the inferior ethene of 4-butylidene dioxy base thiophene) etc.
As poly-(pyrroles) class, can enumerate: poly-(pyrroles), poly-(3-methylpyrrole), poly-(3-butyl pyrroles), poly-(3-decyl pyrroles), poly-(3, the 4-dimethyl pyrrole), poly-(3,4-dibutyl pyrroles), poly-(3-methoxyl group pyrroles), poly-(3-butoxy pyrroles), poly-(3,4-dimethoxy pyrroles), poly-(3,4-diethoxy pyrroles), poly-(3,4-ethylidene dioxy base pyrroles), poly-(3,4-propylidene dioxy base pyrroles), poly-(3,4-butylidene dioxy base pyrroles) etc.
As poly-(furans) class, can enumerate: poly-(furans), poly-(3-methyl furan), poly-(3-butyl furans), poly-(3-decyl furans), poly-(3, the 4-dimethyl furan), poly-(3,4-dibutyl furans), poly-(3-methoxyl group furans), poly-(3-butoxy furans), poly-(3-hexyloxy furans), poly-(3,4-dimethoxy furans), poly-(3,4-diethoxy furans), poly-(3,4-ethylidene dioxy base furans), poly-(3,4-propylidene dioxy base furans), poly-(3,4-butylidene dioxy base furans) etc.
As poly-(aniline) class, can enumerate: poly-(aniline), poly-(2-aminotoluene), poly-(3-isobutyl-aniline), poly-(2-aniline sulfonic acid), poly-(3-aniline sulfonic acid) etc.
As doping agent, can enumerate: Lewis acid, protonic acid, electrolytic anion, anionic property polymkeric substance.
As Lewis acid, for example can enumerate: PF
5, AsF
5, SbF
5Deng; As protonic acid, can enumerate: HF, HCl, H
2SO
4Deng; As electrolytic anion, can enumerate: Cl
-, Br
-, sulfonate anion etc.In addition, as the anionic property polymkeric substance, can enumerate: polystyrolsulfon acid (PSS), polyvinylsulfonic acid, polyene propyl sulfonic acid, polyacrylic acid ethylsulfonic acid, polyacrylic acid butyl sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyene propyl group carboxylic acid, polypropylene-base carboxylic acid, polymethyl yl carboxylic acid and these lewis acidic salts thereof etc.
As (C) composition, consider preferred poly-(thiophene) class and/or poly-(aniline) class, especially preferably poly-(thiophene) class from the viewpoint of the static resistance of tunicle.In addition, as poly-(thiophene) class, the aspect that is easy to get calmly considers, preferably with the PSS alkylenedioxy group poly-(thiophene) that forms (particularly 3,4-ethylidene dioxy base thiophene (PEDOT)) that mixes.
Here, the PEDOT that forms with the PSS doping can obtain by the following method, for example, at aqueous phase, in the presence of as the PSS of doping agent, make as monomeric PEDOT polymerization with oxygenant, can obtain polystyrolsulfon acid and 3 thus, the aqueous solution of the complex compound (PEDOT/PSS) of 4-ethylidene dioxy base thiophene.As the aqueous solution of (PEDOT/PSS), can utilize for example Baytron P commercially available products such as (manufacturings of Starck company).
Here, in the present invention, also can and use (C) composition electric conductive polymer in addition, for example: poly-(inferior ethene) class, poly-(phenylene) class, poly-(the inferior ethene of phenylene) class, many (acene) class etc. are non-to contain heteroatomic electric conductive polymer, but consider that from the viewpoint of static resistance or color the electric conductive polymer beyond these (C) compositions can not use separately.
(C) composition in the antistatic coating agent of the present invention is not particularly limited in the content that nonvolatile component converts, consider from isostatic viewpoints such as the static resistance of the tunicle that obtains, solvent resistance, anti-adhesives, (A) composition and (B) total amount 100 weight parts that convert in nonvolatile component of composition relatively are generally about 0.1～30 weight part, the scope of preferred 0.5～30 weight part.
As (D) composition, can enumerate various known curing catalysts, for example: acid catalyst, acid-producing agent.As acid catalyst, can enumerate: tosic acid, hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, hydrofluoric acid, fluosulfonic acid, sulfuric acid, phosphoric acid etc.In addition, as acid-producing agent, can enumerate: diaryl group iodized salt, triarylsulfonium salt, Er Fang Ji phosphonium salt etc.Wherein, consider preferred acid catalyzer, particularly tosic acid from the easy to handle viewpoint.
(D) composition in the antistatic coating agent of the present invention is not particularly limited in the consumption that nonvolatile component converts, consider from the viewpoint of the solvent resistance of the tunicle that obtains, anti-adhesive etc., (A) composition and (B) total amount 100 weight parts that convert in nonvolatile component of composition relatively are generally about 0～10 weight part, the scope of preferred 0.1～5 weight part.
Here, when using above-mentioned acid catalyst,, also can in antistatic coating agent of the present invention, add above-mentioned tertiary amines in addition in order to improve package stability (working life) as (D) composition.
In antistatic coating agent of the present invention, can use above-mentioned organic solvent or water as required as diluting solvent.As organic solvent, consider from the viewpoint of package stability, the alcohols of preferred carbon number about 1～4, for example: methyl alcohol, ethanol, n-propyl alcohol, Virahol etc.The consumption of diluting solvent is generally: make the nonvolatile component concentration of antistatic coating agent of the present invention be generally scope about 0.1～30 weight part %.
Here, in antistatic coating agent of the present invention, in addition, can cooperate suitable various known additive, for example: defoamer, slipproofing agent, sanitas, rust-preventive agent, pH regulator agent, antioxidant, pigment, dyestuff, lubricant etc.
The method that antistatic coating agent of the present invention is coated on the base material is not particularly limited, and can use various known means.Specifically can enumerate: print roll coating, contrary print roll coating, notch board coating, scraper coating, scraper coating etc.In addition, the coating amount on base material is not particularly limited, and generally, counts 0.01～10g/m with nonvolatile component
2In addition,, not only can apply by single face base material, and can the two sides coating.
As above-mentioned base material; can enumerate the film that is formed by for example plastics such as polycarbonate, polymethylmethacrylate, polystyrene, polyethylene terephthalate, polyimide, polyolefine, nylon, Resins, epoxy, melamine resin, tri acetyl cellulose resin, ABS resin, AS resin, norbornene resin, these base materials can carry out surface treatments such as corona discharge as required.In addition, for this plastics film,, the layer that utilizes antistatic coating agent of the present invention coating agent in addition to form can be set on its single face or two sides.
Embodiment
Below, utilize Production Example, embodiment and comparative example to illustrate in greater detail the present invention, but the present invention is not limited to these embodiment.In addition, " % " among the embodiment, " part " are benchmark with the weight part.In addition, second-order transition temperature is a value of utilizing differential scanning calorimeter to measure.In addition, number-average molecular weight is to utilize the value of gel permeation chromatography.
Differential scanning calorimeter ... name of product " DSC6200 ", Seiko Electronics Co., Ltd makes
Gel permeation chromatography ... name of product " HLC-8220GPC ", TOSOH Co., Ltd makes
Production Example 1
In the four-hole boiling flask that has nitrogen ingress pipe, thermometer, reflux exchanger and whipping appts, drop into 144 parts of 16 parts in vinylformic acid and methyl methacrylates, further add 320 parts of Virahols, make monomer solution.Then in monomer solution, add 2,3.2 parts of 2 '-Diisopropyl azodicarboxylates.Then, make reaction system be warming up to 80 ℃, carried out Raolical polymerizable 8 hours.Then, in reaction system, add 300 parts of 22.4 parts of triethylamines and ion exchanged waters, fully stir, be cooled to normal temperature.Thus, obtain the solution that nonvolatile component is (A-1) composition of 20%.Here, (A-1) the carboxylate anion base unit weight of composition is that 0.00139mol/g, second-order transition temperature are that 100 ℃, number-average molecular weight are 30000.
Production Example 2～9
Make the composition of the consumption of employed monomeric kind and amount, polymerization starter and neutralizing agent solution as shown in table 1, in addition, all the other and Production Example 1 are operated equally, obtain each solution of composition of (A-2) composition～(A-9).Its rerum natura is shown in table 2.
Table 1
In the table 1, AA is meant vinylformic acid, and MAA is meant methacrylic acid, and MMA is meant methyl methacrylate, SMA is meant the methacrylic acid stearyl, FM0721 is meant (gathering) siloxanes one (methyl) acrylate (molecular-weight average is 5000 for name of product " SILAPLANE ", the manufacturing of Japanese Chisso Corp), V-8FM is meant that (Osaka Organic Chemical Industry Co., Ltd. makes methacrylic acid octafluoro pentyl ester, molecular weight is 254), AIBN is meant Diisopropyl azodicarboxylate, TEA is meant triethylamine.
Table 2
In the table 2, CAV is meant the carboxylate anion base unit weight, and Tg is meant second-order transition temperature, and Mn is meant number-average molecular weight.
Embodiment 1
Will be as the commercially available acrylic resin that the contains the carboxylate anion base (name of product " ARUFON UC3000 " of (A) composition, Toagosei Co., Ltd makes, the carboxylate anion base unit weight is 0.00132mol/g, second-order transition temperature is 65 ℃, number-average molecular weight is 10000) 10.6 parts (nonvolatile component concentration is 98%), (TMMTAP) 4 parts of tetramethylol methanes-three (1-'-aziridino propionic ester) (the aziridine base unit weight is 0.00702mol/g) as (B) composition, as (C) composition with polystyrene mix form poly-(3,4-ethylidene dioxy base thiophene) (PEDOT/PSS) (name of product " BaytronP ", the manufacturing of Starck company) 23 parts (nonvolatile component concentration is 1.2%), 2 parts of triethylamines, 57 parts of ion exchanged waters, 50 parts of thorough mixing of Virahol are made antistatic coating agent.
Embodiment 2
30 parts of thorough mixing of 36 parts of 0.8 part of 23 parts of 4 parts of 52.8 parts of solution, TMMTAP, PEDOT/PSS, triethylamine, ion exchanged waters, Virahol of (A-1) composition that Production Example 1 is obtained are made antistatic coating agent.
Embodiment 3～10
In embodiment 2, the solution of (A-1) composition is replaced as the solution of composition of the solution of (A-2) composition～(A-9), in addition, operate equally, make antistatic coating agent.
Embodiment 11
In embodiment 2, TMMTAP is replaced as TriMethylolPropane(TMP)-three (1-'-aziridino propionic ester) (TMPTAP; The amount of '-aziridino is 0.00705mol/g), in addition, operate equally, make antistatic coating agent.
＜embodiment: (D) composition also uses 〉
Embodiment 12
With " ARUFON UC3000 " 10.6 parts, 23 parts of 4 parts of TMMTAP, PEDOT/PSS, 2 parts of triethylamines, 57 parts of ion exchanged waters, 50 parts of Virahols and 0.2 part of thorough mixing of tosic acid (PTS), make antistatic coating agent.
Embodiment 13
15 parts of 18 parts of 0.4 part of 11.5 parts of 2 parts of 26.4 parts of solution, TMMTAP, PEDOT/PSS, triethylamine, ion exchanged waters, Virahols and 0.1 part of thorough mixing of PTS of (A-1) composition that Production Example 1 is obtained are made antistatic coating agent.
Embodiment 14～21
In embodiment 13, the solution of (A-1) composition is replaced as the solution of composition of the solution of (A-2) composition～(A-9), in addition, operate equally, make antistatic coating agent.
＜embodiment: (B) change of composition consumption 〉
Embodiment 22
25 parts of 24 parts of 0.4 part of 11.5 parts of 5 parts of 26.4 parts of solution, TMMTAP, PEDOT/PSS, triethylamine, ion exchanged waters, Virahols and 0.1 part of thorough mixing of PTS of (A-1) composition that Production Example 1 is obtained are made antistatic coating agent.
Embodiment 23
In embodiment 22, TMMTAP is changed to 0.15 part, ion exchanged water is changed to 15 parts, Virahol is changed to 2 parts, in addition, operate equally, make antistatic coating agent.
Embodiment 24
In embodiment 13, PEDOT/PSS is changed to polyaniline (nonvolatile component concentration is 2% the aqueous solution for name of product " ORMECOND1031W ", Nissan Chemical Ind Ltd's manufacturing), in addition, operate equally, make antistatic coating agent.
Embodiment 25～27
In embodiment 15,20,21, PEDOT/PSS is changed to polyaniline, in addition, operate equally, make antistatic coating agent.
＜comparative example: do not have (B) composition 〉
Comparative example 1～10
Do not use (B) composition, in addition, operate equally, make antistatic coating agent with embodiment 1～10.
＜comparative example: do not have (C) composition 〉
Comparative example 11～20
Do not use (C) composition, in addition, operate equally, make antistatic coating agent with embodiment 1～10.
＜comparative example: the use of the linking agent different〉with (B) composition
Comparative example 21
In embodiment 2, using carbodiimide is that (" CARBODILITE (Japan: V-02 カ Le ボ ジ ラ イ ト), Misshin Spinning Co., Ltd's manufacturing) replaces TMMTAP4 part for 10 parts to name of product to solidifying agent, in addition; operate equally, makes antistatic coating agent.
Comparative example 22
In embodiment 2, Shi Yong oxazoline is that (" EPOCROS (Japanese: WS-500 エ Port Network ロ ス), Nippon Shokubai Co., Ltd's manufacturing) replaces 4 parts of TMMTAP for 10 parts to name of product to solidifying agent, in addition, operates equally, makes antistatic coating agent.
Comparative example 23
In embodiment 2, using epoxy is that (" EPOLIGHT (Japanese: 40E エ Port ラ イ ト), Kyoeisha Chemical Co., Ltd.'s manufacturing) replaces 4 parts of TMMTAP to name of product to solidifying agent, in addition, operates equally, makes antistatic coating agent.
[the test making of film]
Use metering bar coater No.10, the coating agent of embodiment 1 is coated on the PET film, make this coating film in drying machine with the wind, under 140 ℃, 1 minute condition, carry out drying, make to test and use film.
[mensuration of surface resistivity]
Use determination of resistivity machine (ProductName " the inferior electric wave of ULTRA MEGOHMME TER SM-8210, SME-8311 ” ， East Industrial Co., Ltd makes), and the test surface resistivity of the applicator surface of film of measuring embodiment 1 (Ω/).Test for other embodiment, comparative example is measured too with film.Surface resistivity is more little, and the expression antistatic property is good more.
[solvent resistance test]
With impregnation the test of absorbent cotton rod friction embodiment 1 of acetone with the applicator surface of film, the friction number of times when disappearing according to filming is estimated the solvent resistance of tunicle.Number of times is many more, and the solvent resistance of expression tunicle is excellent more.
[anti-adhesive test]
Prepare the test film of 2 embodiment 1, with the applicator surface of a slice film wherein and another sheet film uncoated overlapping, at 4kg/cm
2Load-carrying under, placed 24 hours at 80 ℃.Then, the degree of easily tearing when tearing film is in order to the anti-adhesive of standard evaluation down.Here, when numerical value is linked with "～" (for example 4～5), be expressed as the evaluation between the standard separately.
5 ... a little imperceptible resistance.
4 ... almost imperceptible resistance.
3 ... feel resistance slightly.
2 ... feel big resistance.
1 ... feel sizable resistance.
[PET film fitness test]
After the test of embodiment 1 attaches sealing tape and makes its abundant crimping with the applicator surface of film, it is torn with sudden force, in order to the residual amount of filming of standard visual assessment down.
Zero ... residual filming more than 70%.
△ ... residual filming of 40% above less than 70%.
* ... only residual filming of less than 40%.
For the coating agent of other embodiment, comparative example, also make the test film according to same program, implement same test.
Table 3
| (A) | (B) | x/y | (C) | (D) | Surface resistivity | Solvent resistance | Anti-adhesive | The PET adaptation | |
| Embodiment 1 | ARUFON | TMMTAP | 0.5 | PEDOT/PSS | - | 10 8 | 25 | 4 | ○ |
| Embodiment 2 | (A-1) | TMMTAP | 0.5 | PEDOT/PSS | - | 10 8 | 40 | 4～5 | ○ |
| Embodiment 3 | (A-2) | TMMTAP | 0.5 | PEDOT/PSS | - | 10 8 | 40 | 4～5 | ○ |
| Embodiment 4 | (A-3) | TMMTAP | 0.8 | PEDOT/PSS | - | 10 8 | 60 | 4～5 | ○ |
| Embodiment 5 | (A-4) | TMMTAP | 0.5 | PEDOT/PSS | - | 10 8 | 40 | 4 | ○ |
| Embodiment 6 | (A-5) | TMMTAP | 0.5 | PEDOT/PSS | - | 10 8 | 45 | 5 | ○ |
| Embodiment 7 | (A-6) | TMMTAP | 0.5 | PEDOT/PSS | - | 10 8 | 45 | 5 | ○ |
| Embodiment 8 | (A-7) | TMMTAP | 0.5 | PEDOT/PSS | - | 10 8 | 45 | 4～5 | ○ |
| Embodiment 9 | (A-8) | TMMTAP | 0.05 | PEDOT/PSS | - | 10 8 | 20 | 4 | ○ |
| Embodiment 10 | (A-9) | TMMTAP | 2.3 | PEDOT/PSS | - | 10 9 | ＞100 | 4～5 | ○ |
| Embodiment 11 | (A-1) | TMMTAP | 0.5 | PEDOT/PSS | - | 10 8 | 40 | 4～5 | ○ |
| Embodiment 12 | ARUFON | TMMTAP | 0.5 | PEDOT/PSS | PTS | 10 8 | ＞100 | 4～5 | ○ |
| Embodiment 13 | (A-1) | TMMTAP | 0.5 | PEDOT/PSS | PTS | 10 8 | ＞100 | 5 | ○ |
| Embodiment 14 | (A-2) | TMMTAP | 0.5 | PEDOT/PSS | PTS | 10 8 | ＞100 | 5 | ○ |
| Embodiment 15 | (A-3) | TMMTAP | 0.8 | PEDOT/PSS | PTS | 10 8 | ＞100 | 5 | ○ |
| Embodiment 16 | (A-4) | TMMTAP | 0.5 | PEDOT/PSS | PTS | 10 8 | ＞100 | 4～5 | ○ |
| Embodiment 17 | (A-5) | TMMTAP | 0.5 | PEDOT/PSS | PTS | 10 8 | ＞100 | 5 | ○ |
| Embodiment 18 | (A-6) | TMMTAP | 0.5 | PEDOT/PSS | PTS | 10 8 | ＞100 | 5 | ○ |
| Embodiment 19 | (A-7) | TMMTAP | 0.5 | PEDOT/PSS | PTS | 10 8 | ＞100 | 5 | ○ |
| Embodiment 20 | (A-8) | TMMTAP | 0.05 | PEDOT/PSS | PTS | 10 8 | ＞100 | 4～5 | ○ |
| Embodiment 21 | (A-9) | TMMTAP | 2.3 | PEDOT/PSS | PTS | 10 9 | ＞100 | 4～5 | ○ |
| Embodiment 22 | (A-1) | TMMTAP | 0.2 | PEDOT/PSS | PTS | 10 9 | ＞100 | 5 | ○ |
| Embodiment 23 | (A-1) | TMMTAP | 7 | PEDOT/PSS | PTS | 10 8 | 20 | 3～4 | △ |
| Embodiment 24 | (A-1) | TMMTAP | 0.5 | Polyaniline | PTS | 10 9 | ＞100 | 4～5 | ○ |
| Embodiment 25 | (A-3) | TMMTAP | 0.8 | Polyaniline | PTS | 10 9 | ＞100 | 4～5 | ○ |
| Embodiment 26 | (A-8) | TMMTAP | 0.05 | Polyaniline | PTS | 10 9 | ＞100 | 4 | ○ |
| Embodiment 27 | (A9) | TMMTAP | 2.3 | Polyaniline | PTS | 10 10 | ＞100 | 4～5 | ○ |
In the table 3, x/y is the value (following same) that obtains divided by the mole number (mol) of the '-aziridino in (B) composition with the mole number (mol) of the carboxylate anion base unit weight in (A) composition.
Table 4
| (A) | (B) | x/y | (C) | (D) | Surface resistivity | Solvent resistance | Anti-adhesive | The PET adaptation | |
| Comparative example 1 | ARUFON | - | - | PEDOT/PSS | - | 10 7 | 1 | 1～2 | × |
| Comparative example 2 | (A-1) | - | - | PEDOT/PSS | - | 10 7 | 2 | 1～2 | × |
| Comparative example 3 | (A-2) | - | - | PEDOT/PSS | - | 10 7 | 2 | 1～2 | × |
| Comparative example 4 | (A-3) | - | - | PEDOT/PSS | - | 10 7 | 2 | 1～2 | × |
| Comparative example 5 | (A-4) | - | - | PEDOT/PSS | - | 10 7 | 2 | 1～2 | × |
| Comparative example 6 | (A-5) | - | - | PEDOT/PSS | - | 10 7 | 2 | 2 | × |
| Comparative example 7 | (A-6) | - | - | PEDOT/PSS | - | 10 7 | 2 | 2 | × |
| Comparative example 8 | (A-7) | - | - | PEDOT/PSS | - | 10 7 | 2 | 2 | × |
| Comparative example 9 | (A-8) | - | - | PEDOT/PSS | - | 10 7 | 2 | 1～2 | × |
| Comparative example 10 | (A-9) | - | - | PEDOT/PSS | - | 10 8 | 2 | 1～2 | × |
| Comparative example 11 | ARUFON | TMMTAP | 0.5 | - | - | ＞10 14 | 20 | 4 | ○ |
| Comparative example 12 | (A-1) | TMMTAP | 0.5 | - | - | ＞10 14 | 35 | 4～5 | ○ |
| Comparative example 13 | (A-2) | TMMTAP | 0.5 | - | - | ＞10 14 | 35 | 4～5 | ○ |
| Comparative example 14 | (A-3) | TMMTAP | 0.8 | - | - | ＞10 14 | 60 | 4～5 | ○ |
| Comparative example 15 | (A-4) | TMMTAP | 0.5 | - | - | ＞10 14 | 40 | 4 | ○ |
| Comparative example 16 | (A-5) | TMMTAP | 0.5 | - | - | ＞10 14 | 40 | 5 | ○ |
| Comparative example 17 | (A-6) | TMMTAP | 0.5 | - | - | ＞10 14 | 40 | 5 | ○ |
| Comparative example 18 | (A-7) | TMMTAP | 0.5 | - | - | ＞10 14 | 40 | 4～5 | ○ |
| Comparative example 19 | (A-8) | TMMTAP | 0.05 | - | - | ＞10 14 | 10 | 4 | ○ |
| Comparative example 20 | (A-9) | TMMTAP | 2.3 | - | - | ＞10 14 | ＞100 | 4～5 | ○ |
| Comparative example 21 | (A-1) | V-02 | - | PEDOT/PSS | - | 10 8 | 2 | 2 | × |
| Comparative example 22 | (A-1) | WS-500 | - | PEDOT/PSS | - | 10 8 | 2 | 2 | × |
| Comparative example 23 | (A-1) | 40E | - | PEDOT/PSS | - | 10 8 | 1 | 1 | × |
Claims (13)
1. antistatic coating agent, it contains:
The acrylic resin (A) that contains the carboxylate anion base;
Polyfunctional aziridine compound (B); And
Contain heteroatomic pi-conjugated be electric conductive polymer (C).
2. antistatic coating agent as claimed in claim 1, wherein,
Described (A) composition is to make α, and described (a1), (a2) unsaturated monomer (a3) in addition of beta-unsaturated carboxylic acid (a1), (methyl) alkyl acrylate (a2) and adding as required react and the copolymer salt of formation.
3. antistatic coating agent as claimed in claim 2, wherein,
Described (a1) composition is methacrylic acid and/or vinylformic acid.
4. antistatic coating agent as claimed in claim 2, wherein,
Described (a3) composition is (gathering) siloxanes list (methyl) esters of acrylic acid and/or (list) fluoroalkyl acrylate class.
5. antistatic coating agent as claimed in claim 1, wherein,
The amount of the carboxylate anion base of described (A) composition is 0.0003mol/g～0.005mol/g.
6. antistatic coating agent as claimed in claim 1, wherein,
The second-order transition temperature of described (A) composition is 20～150 ℃.
7. antistatic coating agent as claimed in claim 1, wherein,
The number-average molecular weight of described (A) composition is 2000～100000.
8. antistatic coating agent as claimed in claim 1, wherein,
Described (B) composition is that 3 officials can aziridine cpd and/or 4 officials energy aziridine cpd.
9. antistatic coating agent as claimed in claim 1, wherein,
With the mole number (mol) of the carboxylate anion base of (A) composition be set at x, with the mole number (mol) of the '-aziridino of (B) composition when being set at y, be that 0.1～10 amount contains described (A) composition and (B) composition with x/y.
10. antistatic coating agent as claimed in claim 1, wherein,
Described (C) composition is (gathering) phenyl amines and/or (gathering) thiophene-based.
11. antistatic coating agent as claimed in claim 1, wherein,
Also contain curing catalysts (D).
12. antistatic coating agent as claimed in claim 1, wherein,
Described (D) composition is a tosic acid.
13. a plastics film,
It forms by each described antistatic coating agent in the coating claim 1～12.
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| CN102167942A (en) * | 2010-02-26 | 2011-08-31 | 荒川化学工业株式会社 | Primer for plastic with inorganic film, plastic with inorganic film, decorative film for inner mold forming and decorative film for insert part forming |
| CN102167942B (en) * | 2010-02-26 | 2016-02-24 | 荒川化学工业株式会社 | For the silane coupling agent with inorganic thin film plastics, band inorganic thin film plastics, mould internal shaping decorating film and insert part forming decorating film |
| CN103305108A (en) * | 2012-03-16 | 2013-09-18 | 中国科学院理化技术研究所 | Waterborne antistatic coating and preparation method thereof |
| CN103305108B (en) * | 2012-03-16 | 2015-11-04 | 中国科学院理化技术研究所 | A kind of aqueous antistatic coating and preparation method thereof |
| CN104312354A (en) * | 2014-10-08 | 2015-01-28 | 安徽真信涂料有限公司 | Antistatic coating |
| CN106167662A (en) * | 2015-05-18 | 2016-11-30 | 荒川化学工业株式会社 | Thermohardening type antistatic coating agent and curing overlay film, plastic foil |
| TWI692509B (en) * | 2015-05-18 | 2020-05-01 | 日商荒川化學工業股份有限公司 | Thermosetting antistatic coating agent, its hardened film, plastic film |
| CN106167662B (en) * | 2015-05-18 | 2020-07-10 | 荒川化学工业株式会社 | Thermosetting antistatic coating agent, cured coating film thereof, and plastic film |
| 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 |
| CN106675463A (en) * | 2016-12-27 | 2017-05-17 | 合肥乐凯科技产业有限公司 | Adhesive for polarizer protecting film and polarizer protecting film using adhesive |
| CN111655800A (en) * | 2018-01-29 | 2020-09-11 | 东丽先端素材株式会社 | Antistatic coating solution composition and antistatic polyester film using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5515338B2 (en) | 2014-06-11 |
| JP2009256623A (en) | 2009-11-05 |
| KR20090101091A (en) | 2009-09-24 |
| KR101560401B1 (en) | 2015-10-14 |
| TWI462962B (en) | 2014-12-01 |
| TW201000544A (en) | 2010-01-01 |
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Application publication date: 20090923 |