TW201000544A - Antistatic coating agent - Google Patents

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 plastic film obtained by coating a f-package preventing coating agent and applying the coating agent. Hunger-recovery [prior art] Plastic film such as polyester film, it is easy to produce static snow when it is taken up or released or traveled. 4... Do not hold static electricity, causing dust in the atmosphere to adhere, :: Production line t produces poor travel and the like. Therefore, in order to suppress the occurrence of a method of pre-blending (mixing) a charge preventing agent in a film. However, in the original plastics of Zhou Shoushu _ + L before the film processing, when the antistatic agent is blended in advance, there is a charging inhibitor that oozes out to the surface of the film to cause adhesion or bleed. The prevention of the detachment of the agent causes the possibility of preventing the charging from being lowered. Therefore, it is considered that the method of coating a coating agent having a charging prevention function on the surface of the film to form a film is considered. In addition to the charging prevention function, the charging preventing coating agent is required to have solvent resistance or blocking resistance of the film, adhesion between the plastic substrate and the film, and the like. If the solvent resistance is poor, the coated film may swell or fall off when it contacts the organic solvent in the film processing line. Further, when the caking resistance is insufficient, there is a case where a large resistance is generated at the time of unwinding or the crucible is peeled off. For example, in the patent document, a fourth-stage ammonium salt type cationic polymer compound is used as a coating agent which is a conductive polymer. However, since the charging prevention coating core 201000544 is affected by the temperature, the charging prevention function cannot be sufficiently exhibited due to the use environment. Therefore, a 7-inch conjugated conductive polymer which exhibits a charge prevention function by electron transfer is considered. For example, Patent Document 2 discloses a charge-preventing coating agent using a 7-inch conjugated conductive polymer. In particular, it is proposed to prepare a poly(thiophene) in a copolymer such as an alkyl acrylate or an acrylamide. Waiting for the winner. However, since the solvent resistance of the coated film is insufficient, the properties of the film are not balanced. [Prior Art Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2003-292055 [Patent Document 2] [Problems to be Solved by the Invention] The present invention The main problem is to provide a novel charge-preventing coating agent which is excellent in charge prevention, solvent resistance, blocking resistance, and adhesion of a film to a plastic substrate. [Technical means for solving the problem] The inventors of the present invention can solve the above problems by repeating the results of intensive studies and electrically preventing the coating agent,

(C); and a plastic film of the acrylic resin (A), a polyfunctional anthracene ring, and a hetero atom-containing π-based conductive polymer, which are coated with the charge-preventing coating agent. [Efficacy] According to the present invention, the lightning protection u, the enamel film, the ... thunder ... electric anti-breaking agent 'can obtain a kind of film' no /, antimony prevention is superior to wt and solvent resistance, anti-knot Blockiness, as well as adhesion to plastic film, etc. [.$ 扪 扪 性能 performance is also excellent. In this way, the charge-preventing coating agent can be used for a film for a film, a film for packaging, a film for a photonic device, a film for a film for a display, a film for a conductor for processing a conductive tape, a film for hot stamping, and a 朔踉+ <; and a wide range of applications such as plastic molding film (integrated with the substrate, used for the film used in the surface of the substrate). [Embodiment] The charge-preventing coating agent of the present invention contains an acid-based anion-based acrylic resin (hereinafter referred to as a "ruthenium" component), and a polyfunctional anthracene-cyclopropane compound (Β). (hereinafter, there is a case called a (Β) component), and a π-conjugated conductive polymer (c) containing a hetero atom (hereinafter, referred to as a component (c)); and, if necessary, a hardening Catalyst (hereinafter, there is a case called a component (D)). The (A) component is not particularly limited as long as it is an acrylic resin having a slow-acid anion group represented by a group in the molecule, and various known materials can be used. Specifically, α,/5-unsaturated carboxylic acid (ai), (mercapto) propylene is used. (A 2 ) (also, (meth)acrylic acid burning means Acrylic acid entangled or alkyl methacrylate, and the (meth) described below is also used in the same sense as 201000544); and if necessary, other unsaturated monomers (a3) are polymerized. A neutralizing salt of the copolymer of the ingredients. Hereinafter, each component will be referred to as (al) component, (a2) component, and (a3) component in order. Further, the buffer acid anion group is derived from a carboxyl group of the component (a1). As the (al) component ', various well-known α β _ unsaturated carboxylic acids can be used. For example, 〇:, _ unsaturated monocarboxylic acids, (meth)acrylic acid, crotonic acid, etc.; and, α, point-unsaturated dicarboxylic acids, ^ maleic acid, maleic acid Diacid anhydride, fumaric acid, itaconic acid, and the like. Further, 'may be mentioned: a semi-amine of an alpha, a-unsaturated dicarboxylic acid called ikonic acid anilide, or a monoester of an alpha, point-unsaturated dicarboxylic acid and an aliphatic alcohol or Among them, things and so on. Examples of the aliphatic alcohol include methanol, ethanol, propanol, butanol and the like. The neutralizing agent for forming each component can be used as described later. As the (al) component, an α-unsaturated monocarboxylic acid is preferred, and (meth)acrylic acid is particularly preferred. As the component (a2), various well-known alkyl (meth) acrylates can be used. Further, the carbon number of the alkyl group is usually about 1 to 2 Å, and the shape of the alkyl group may be linear, branched or cyclic. Specific examples of the component (a2) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and (fluorenyl). Lauryl acrylate, (meth) acrylate stearate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (mercapto) acrylate Cyclohexyl ester, cyclopentyl (meth)acrylate, isodecyl (meth)acrylate, and the like. The component (a3) is a non-saturated 6 201000544 and a monomer other than the (al) component and the (a2) component, and can be radically polymerized with the components. Specific examples thereof include chlorodecane-based (meth) acrylates, (fluorenyl) acrylamides, (mercapto) acrylic ketones, styrenes, unsaturated acides, and amine alkyls. Unsaturated monomers, polyalkylene glycol-based unsaturated monomers, (poly)oxyalkylene mono(meth)acrylates, (mono)fluoroalkyl acrylates, and the like. Examples of the gas decane-based (meth) acrylates include vinyl dimethyl lactate, propyl dimethyl chlorite, and 4-butylutyl dimethyl chlorsulfide, 5 - pentyldifluorenyl sulphate, 3-methylpropenyloxypropyl dimethyl chlorodecane, 4-methylpropenyloxy butyl decyl chlorodecane, and the like. (Mercapto) acrylamides can be exemplified by (meth) acrylamide, N-methyl (mercapto) acrylamide, N-isopropyl (decyl) acrylamide, lauryl ( Methyl) acrylamide, N-cyclohexyl substituted (meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diisopropyl(methyl) propylene oxime Amine, N, N-monolaurin (mercapto) acrylamide and the like. (Mercapto) hydroxyalkyl acrylates are exemplified by 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (methyl) 2-hydroxybutyl acrylate and the like. Examples of the styrene include α-methylstyrene, tert-butylstyrene, dimethylstyrene, ethoxylated styrene, hydroxystyrene, vinyltoluene, and vinylidene. Examples of the unsaturated sulfonic acid include vinylsulfonic acid, (mercapto)propenylsulfonic acid, 2-propenylamine-2-methylpropanesulfonic acid, and sulfonated styrene. Examples of the amine alkyl group-unsaturated monomer include (meth)acrylic acid amine group 7 201000544 ethyl ester, (meth)acrylic acid aminopropyl ester, and (mercapto)acrylic acid N-decylaminoethyl ester. N-decylaminobutyl (meth)acrylate, N,N-didecylaminoethyl (meth)acrylate, ruthenium (meth)acrylate, fluorenyl-didecylaminopropyl (fluorenyl) hydrazide acrylate, hydrazine-diethylaminopropyl propyl g. Examples of the poly(alkylene terephthalate) unsaturated monomer include diethylene glycol mono(meth)acrylic acid, diethylene glycol (mercapto)acrylic acid, and tetraethylene glycol (methyl)propyl. Diluted acid ester, dipropylene glycol mono(meth)acrylate, tris-propionyl diacetate (meth)acrylic acid S. (poly) oxime mono(meth) acrylates, such as "Silapiane FM-0711", "Silaplane FM-0721", "Silaplane fm-0725" (any one is CHISSO) And other commercial products. (Single) fluoroalkyl acrylates are exemplified by 2,2,2-trifluoroethyl (meth)acrylate and 2,2,2-trifluoro-i-trifluorodecyl (meth)acrylate. Mercapto) 2,2,3,3-tetrafluoropropyl acrylate, H, m, 5H octafluoropentyl (meth)acrylate, and the like. In addition, such commercial products include: r V_3F", "V_3FM", "V-4F", "V_8F", and "V_8FM" (all are all made by Osaka Organic Chemical Industry Co., Ltd.). . From the viewpoint of imparting blocking resistance to the obtained film, the (a3) component is particularly preferably a poly(a) siloxane mono(meth) acrylate and/or a (mono) fluoroalkyl acrylate. The amount of each component of the component (a) to the component (a3) is not particularly limited, and when the total amount of the component (a) to the component (a3) is 1 part by weight, the component (a) is 3 to 30 parts by weight. The component (a2) is about 2 to 97 parts by weight, and the component (4) is about 0 to 50 parts by weight. When the component (9) is used, the component of the component (8) is 3 to 30 parts by weight (a2). The component is about 2 to 87 parts by weight, and the component 3) is about 〇5 to 5 parts by weight. The component (A) can be, for example, the component (a) to (a3) is usually 6 〇. 18 (free radical polymerization is carried out for about 1 to 2 hours, and then obtained by neutralizing the obtained copolymer with a neutralizing agent. Further, in the reaction, "capable of using a radical polymerization initiator or a chain transfer agent, Organic solvent: or a reaction solvent such as an ion-exchanger for water. The neutralizing agent can be exemplified by ammonia, a third-grade amine, a metal-based compound, and a soil-based metal compound. Output: monomethylamine: monoethylamine, monobutylamine, cyclohexylamine, etc., and 'secondary amines', which may be monomethylamine, diethylamine, etc. Further, examples of the third-order amines include a base metal compound such as trimethylamine or =amine, and examples thereof include sodium hydroxide and potassium oxychloride. The alkaline earth metal compound may, for example, be magnesium hydroxide. Use aniline, arylamine, alkanol, etc. ., , ^ ^ ^ When using a grade 3 amine and / or ^ as a neutralizer 'because of storage stability (lifetime (state)) or solvent resistance Goodness is preferred. The thiol-neutralizers which are present in relation to the radical polymer are usually used in a ratio of 8 〇 to 3 〇〇 mol %. = radical polymerization initiators are, for example, inorganic Oxides can be exemplified by the succinct + ^ ^ " potassium, and organic peroxides, sm. v pores - isopropyl, oxidized laurel, and azo compounds, 2, 2 , gas double isobutyronitrile, dioxane 2,2 _ azobisisobutyrate, etc. Human 呻1Λλ 4 relative to (al) component ~ (a3) component. Leaf 100 parts by weight, free radical polymerization ~1〇 (4) The amount is usually _ 9 201000544 bond transfer agent, which may be thiazole, bromotrichloromethane, etc. Decyl-alkyl mercaptan, 2-decylthiobenzene total _ weight , A:, with respect to the (Al) component ~⑷) facing the component, and by using an organic solvent is generally ηΛι Sword parts by weight or so catching rabbits. Examples of the alcohol, isopropyl alcohol, and butyl alcohol include methanol, ethanol, n-propyl, ethyl propyl ether, etc., fork, you, one, ethylene glycol monomethyl ether, ethylene glycol one person 'low grade steel Examples of the class I φ aromatic cigarettes include toluene monoketone, methyl ethyl ketone, etc., and esters, gas imitations, - A, and a succinct one, etc., and others may be exemplified by ethyl acetate-f-methylformamidine. Amines, etc. The carboxylic acid in the component (A) is usually 〇._~0·005 left/anionic group (mole/g), which is more than 0.0003, and the film is shot....〇〇1~〇.003 is preferred. . By the following, the w job becomes good. Further, by 0.005 or less, it is possible to easily maintain the balance between the electric radiation prevention and the solvent resistance of the irrigated pancreas. Further, the amount of the carboxylate anion group, ^ , -^ , " is a value calculated from the carboxylic acid contained in the (A) component which is not volatile. The molar number of the anion group of the citric acid wind, and the glass blocking temperature of the component (4) is usually 2G to 15Gt, and the 卩7()~15 generation is preferable from the viewpoint of the blocking resistance obtained from the dish. . In addition, the number average molecular weight (polystyrene equivalent value obtained by a gel permeation chromatograph) is usually 2000 to i 〇〇〇〇 n α υυυ in terms of workability at the time of production and ease of handling, and the like. Left and right, 25000~1〇〇〇〇〇 is preferred. Specific examples of the (Β) component include a cyclopropane derivative having at least a cyclopropane group in the molecule having the following structure. Such a system can be manufactured, for example, by the method described in, for example, U.S. Patent No. 4,382,135, Japanese Patent Application Laid-Open No. Hei No. 2003-104970, and the like, 10 201000544 [Chemical Formula 3]

In the formula Y, R1 and R2 represent hydrogen or an alkyl group having 1 to 6 carbon atoms, which may be the same or different. From the viewpoint of ensuring the solvent resistance of the film, the component (B) is particularly preferably a trifunctional oxime propane compound and/or a tetrafunctional fluorene cyclopropane compound. From the viewpoint of easy availability, the trifunctional D-cyclopropane compound is preferably represented by the following formula U), [Chemical Formula 4]

X R1

R2 CH green c(=0)_〇_CH+H2—〇—fH2 R1 °)~C(R3)HCH2—u’

(1) In the formula (1), X represents an alkanol group having 1 to 3 atomic number of hydrogen and a broken atom number. Further, 1 is extinguished, and ^^ R and R are hydrogen or a carbon atom, and the substituents may be the same or different. Also, hydrogen or methyl. Among the compounds represented by the formula (1), those in which hydrazine is nitrogen include, for example, 11 201000544 ginseng (i-indolecyclopropane propionate), glycerol ginseng [2_mercapto-(1_cyclopropane) Base)] propionate, glycerol [2-propyl-(1-cyclopropyl)]propionate, glycerol [2_hexyl-(1-cyclopropyl)]propionate, glycerol [2, 3-dimethyl-(1-cyclopropane)]propenyl fecS曰, glycerol gin[2,3-hexyl-(1-cyclopropanyl)]propionic acid g. Among the compounds represented by the formula (1), X is an alkyl group having a carbon number of from about 66 to about 6, preferably from 2 to 3, and is exemplified by trimethylolpropane-parameter (1_吖cyclopropane). Hospital based propionic acid vinegar), trimethoprimin-parameter [2_methyl servant. Anthracycline propionate), trimethylolpropane, ginseng [2_propyl_(1_吖cyclopropanepropionate 酉曰), dimethylolpropane _ gin [2_ hexyl _ (1 - anthracene-propanyl)]propionate), trimethylolpropane-parade [2,3-dimethyl-servo-π-cyclopropanyl)]propionic acid (bristle), two methyl propane-parameters [2, 3_dihexyl-(1_d丫cyclopropane-based propionic acid, etc. Among the compounds represented by the formula (1), X is a hospital alcohol group having a carbon number of 3, and tetrahydroxymethyl decane-parameter (1_D丫cyclopropane-propionic acid vinegar), tetras-decyl decane-parade [2_methyl (dipenocyclopropanepropionate), tetramethylolpropane-sodium [2-propyl-(1_σ丫 ring) Propionate)] propionate ]], 目 methyl propyl ketone - ginseng [2_ hexyl _ (1 "anthracycline)] propionic acid (five), tons of mercaptopropene - ginseng [2,3- Dimethyl _(dioxacyclopropane)] propionic acid vinegar), (d) methyl propyl ketone - ginseng [2,3-dihexyl _(1 - anthranilyl)] propionate), etc.丫 丙 丙 化合物 化合物 , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,

N-C H 2C (R 3)H -C (=0 〇 〇 -c

—〇(=0)—C(R3)HCH2

—C(=〇)—C(R3)HCH2

C H 2—〇 - C (=〇 )—c (R 3)H c H

(In the formula (2), R1 and R2 may be the same or different, and the gas or the alkyl group having 1 to 6 carbon atoms may be recorded. Further, R3 means hydrogen or a fluorenyl group. The compound represented by the formula (2) includes, for example, neodymidine tetracyl (1 - anthracycline propionate vinegar), neopentyl alcohol tetrakis [2_methyl servone fluorenyl propyl propyl group]] Propionic acid vinegar), neopentyl alcohol tetrakis[2-hexyl-(1decylpropanyl)]propionic acid vinegar, neopentyl alcohol tetrakis[2,3·diethyl-(anthracene propyl) Propionic acid from the purpose), pentaerythritol tetra [2'3-hexyl-(1_0丫% propyl propyl)] propionic acid cool) and the like. Further, the (Β) component may contain a bifunctional anthracene cyclopropane compound as necessary, or a 6-functional anthracene cyclopropane compound described in Japanese Laid-Open Patent Publication No. 2003_丨〇497. The bifunctional oxime cyclopropane compound may, for example, be: tetracyclopropane m-xylylenediamine, tetra-β-cyclopropanylmethyl-p-xylene di-p-pentalol (β-α-cyclopropanepropionic acid) Stuffed, etc. Further, a monofunctional anthracycline may be used together with the (Β) component. There may be mentioned, for example, anthracycline and 2-methyl.丫 ring propylene appearance, 2_ethyl (tetra) propyl sulphur, :: methyl propyl propyl ketone, an anthracycline, 2 phenyl oxime ring and 'from the viewpoint of ensuring the solvent property of the film, (Β) The composition of the ring 13 ring 13 201000544 propylene base amount (mole / gram), usually about 0.001 ~ 0. 02 or so, preferably in the range of 0.003 ~ (10). In addition, the amount of the propylene group is the number of moles of the π丫cyclopropanone contained in 77 gram of (Β), and is a calculated value. 2 The θ content of the (Α) component and the (Β) component in the charge inhibitor of the present invention is particularly limited, and the carboxylate anion amount (mol) of the (Α) component is X X and (B) When the amount of the indole cyclopropane group (mol/gram) of the component is y, the 'x'y is usually (m~10 or so, preferably in the range of 〇3 to 3). A film which exhibits a good balance between solvent resistance, agglomeration, adhesion to a plastic film, and particularly adhesion to a poly(10) acid ethylene glycol film. Further, in the present invention, a small amount may be used in combination (B) The cross-linking agent other than the component, for example, the ss-oxazoline compound 'polyfunctional epoxy compound, polyfunctional carbon=diimine compound', from the viewpoint of ensuring the curability of the obtained coating film or the benzoic agent property, It is not possible to use it as a monomer. (6) It is possible to use various well-known heteropoly-containing conjugated conductive polymers. Further, right too. In addition, in the present invention, the component (C) is doped with various dopants. In addition, "hetero atom" means an atom other than hydrogen and carbon (for example, a nitrogen atom). Sulfur atom, etc.) J, "The 7-doped conjugated ruthenium-containing conductive polymer containing a hetero atom means that the hetero-atoms are present in the molecule & /, and the molecular main chain constitutes an organic high score of a 7-inch conjugated structure, Knife compound. Further, the component (C) is used as an aqueous solution having a non-volatile moisture content of usually about 01 to 10% by weight. As a hetero atom containing 7 Γ, a total of erbium and 1 blunt V electrical polymerization Specific examples of the material may be a conjugated conductive poly bovine, for example, a 7Γ 14 201000544 compound having a hetero atomic jujube, which may be a polyfluorene group such as I? The general-purpose polymer may, for example, be a poly-'a π-co-electrical conduction t (the present amine) having an aromatic ring. A heterocyclic ring or a aryl group, a hydrazone, a hydrazine 3 is an alkyl group, an alkoxy group, an alkylene dioxy bond: a: or a ring. Examples of the alkyl group include a mercapto group, an ethyl group, a propyl group, a butyl group, a base group, a twelve-yard base, and an eighteen-yard base. Alkoxy, hydrazine, ethoxy, butoxy, hexyloxy, decyloxy, decyloxy. Examples of the alkylene oxides include an ethylenedioxy group, a propanedioxy group, and a dibutyloxy group. Poly (. phenophene) class can be exemplified by poly(s), poly(3-methylthiophene), poly(3-butylthiophene), poly(3·decylthiophene), poly(3,4) _ dimethyl porphin), poly(, butyl thiophene), poly (3 methoxy thiophene), poly (3-butoxy thiophene)

Poly(3 hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxyphene), poly(3,4-dimethoxy porphin), poly(3,4) _Diethoxy group), poly(3,4-extended ethylenedioxy porphin), poly(3,4_extension@dioxy phenanthrene), poly-μ-butyl-oxy porphin) Wait. Examples of poly(thiophene vinyl)s include poly(thiophene vinyl), poly(methyl stopper vinyl), poly(3-butylthiophene vinyl), poly(3,4-methyl) Α Α 乙烯基 vinyl), poly (3,4-dibutyl n-phene thiophene), poly(3-methoxythiophene extended vinyl), poly(3-butoxythiophene extended vinyl) Poly(3-hexyloxythiophenevinyl), poly(3-octyloxythiophenevinyl), poly(3,4-dimethoxythiophenevinyl), poly(3,4_) Dioxythiophene-extended vinyl), poly(3,4-extended propylenedioxythiophene-extended vinylpoly(3,4-butenedioxythiophene-extended vinyl), etc. 15 201000544 Poly (better) Classes, which can be exemplified by polypyrrole), poly(3-mercaptopyrrolidine), poly(3_butylene ratio fq@-1 quinonepyrrole), poly(3,4-di-T-pyrrole), poly (3,4-butyl oxime), poly ί&quot; 1 field A- 承1·3' methoxypyrrole), poly(3-butoxypyrrole), poly-indenylpyrrolidine, Poly(3,4-diethoxypyrrole), poly(3,4-extended ethylene-oxyl n ratio), life gate / ^ A (,4_extension Port pyrrole), poly (butene-3,4-dioxo-yl ° pyrrole) and the like. Poly (°fu) class can be exemplified by poly(furan), poly(3-methylfuran), polyfluorene (3 butyl phoran), poly(3~mercaptofuran), poly(3,4- Dimercaptofuran), poly(,l-butylfuran), poly(3-methoxyfuran), poly(3·butoxyfuran) poly(3-hexyloxyfuran), poly(3, 4-dimethoxyfuran), poly(3,4-oxyfungan), poly(3,4-exetylenedioxyfuran), poly(3,4-propanedioxyfon), Poly (3,4-butadiene dioxyl. Fu) and the like. Examples of the poly(aniline) include poly(aniline), poly(2-mercaptoaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly(3-anilinesulfonic acid). )Wait. The dopant is exemplified by a Lewis acid, a protic acid, an electrolyte anion, an anionic polymer, and the like. The Lewis acid can be exemplified by, for example, PF5, AsF5, SbF5, etc.; protonic acid, rebel Φ. υϋ + itj. HF, HC1, H2S〇4, etc.; electrolyte anion, 可 • Plant 1 - τ&gt; - . Br, sulfoanion, and the like. Further, examples of the anionic polymer include, for example, polystyrenesulfonic acid (PSS), polyvinyl s s &amp; polydip sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulphate, Names are vinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polypropylene fee tempering acid and poly(methacrylic acid) carboxylic acid, and salts thereof. From the viewpoint of the charge prevention property of the beak, the component (C) is preferably at least one selected from the group consisting of poly(thiophene), poly(aniline), and poly(pyrrole). The class of (thiophene) is particularly preferred. Further, considering the ease of obtaining, the poly(thia:) group is a peroxydioxypoly group obtained by blending PSS (porphyrin (4) is not a 3,4_ethylenedioxythiophene (ΡΕΕ&gt;0Τ) ) is better. Also, 'external-based dioxypoly(P) blended using PSS is carried out by using an oxidizing agent by using a monomer, that is, PED〇T, in an aqueous phase and in the presence of a PSS as a dopant. Polymerization, a complex of polystyrene and acid, and a solution of p-ethylenedioxy porphin (pED〇T/p aqueous solution) can be obtained. An aqueous solution of coffee (10) PSS can be used, for example, Baym&gt;np (made by Starek Corporation). In the present invention, the conductive polymer other than the component (c) may be used in combination with, for example, a polyether, a polyphenylene, or a polyphenylene. The conductive polymer of the hetero atom is not used alone from the viewpoint of the charge prevention property or the color tone. The conversion of the component (6) in the charge-preventing coating material of the present invention is not particularly limited. From the viewpoint of obtaining a balance between the charge prevention property, the solvent resistance, and the blocking resistance of the film, the total amount of the nonvolatile matter of the component (4) and the component (8) is 1 part by weight 'usually 〇1 to Μ by weight. ... _ 5 ~ 3 〇 part of the weight is better. () into the knife V to give a variety of well-known A hardening catalyst, such as an acid catalyst or an acid generator Q, can be exemplified by p-toluenesulfonic acid, hydrochloric acid, H gas acid, gas naphthenic acid, acid, etc. Further, an acid generator, It can be exemplified by: Erfangqi _., Tu Babian 1 wind, diaryl sulfonium salt, diaryl sulfonium salt, etc. Among them, the treatment of macro total, secret a __ easy to produce and 5 's liter catalyst P-toluenesulfonic acid is particularly preferred. 17 201000544 The amount of the non-volatile content of the component (9) in the charge-preventing coating material of the present invention is not particularly limited, and the solvent resistance of the obtained film is limited. Or the viewpoint of blocking resistance, etc., relative to the total non-volatile content of the (A) component and the (B) component, 1 〇〇 by weight, and the hanging weight is 0 to 1 〇 by weight, 〇·1~ The range of 5 parts by weight is preferable. Further, the '(9) component is used for the purpose of improving the storage property (p〇t life) by contacting (4) (4), and may also be in the charge prevention agent of the present invention. In addition, the above-mentioned third-stage amines are added. In the charging prevention of the present invention, it is necessary to use the above-mentioned organic agents or water as a diluent solvent. ^ ^ The viewpoint of storing the enthalpy is that the organic roller is preferably an alcohol having a carbon number of about 1 to 4, such as methanol, ethanol or n-propanol. The solvent is diluted to prevent the coating agent from being dissolved. Volatile Concentration. South* is the right-hand range of the present invention. The W-degree is usually ~3Q% by weight. The left-hand week is in the seed: the anti-static coating agent of the crucible, and can also be used to mix various other autos. Suitable solvents, such as anti-rust rust, dH 1 ^ anti-(7) agent, preservative, anti-rust pH adjuster, antioxidant, and the like, the charging, the hydrazine, the monthly agent, etc. of the present invention. The method of owing you to the substrate is not mentioned: roll coater, reverse roll, body, bar coater, etc. Further, the coating squeegee coater of the base material is not volatile; % Q() 1 t is particularly limited, and generally "is 〇·〇!~10 g/m2 left, not only: leather-faced The substrate may be coated on both sides. The substrate may be referred to as a substrate: for example, 1 methyl methacrylate 18 201000544 ester, polystyrene, polyethylene terephthalate, polyimide, polyolefin, resistance, % A film made of a plastic such as an oxygen resin, a melamine resin, a triethylene sulfonated cellulose resin, an ABS resin, an AS resin, or a decylene-based resin may be subjected to surface treatment such as corona discharge as necessary. The plastic film may be provided with a layer of a coating agent other than the charge preventing coating agent of the present invention on one or both sides. [Examples] Hereinafter, the present invention will be described in more detail by way of production examples, examples and comparative examples. However, the present invention is not limited to the examples. Further, in the examples, "〇" and "parts" are based on parts by weight. Further, the glass transition temperature is a value measured by a differential scanning calorimeter. Further, the number average molecular weight is a value measured by a gel permeation chromatograph. The differential scanning calorimeter··.product name r DSC6200”, manufactured by Seiko Instruments Co., Ltd. (gel permeation chromatograph..·product name “HLC-8220GPC”, TOSOH (share) system (manufacturing example 1) a four-neck flask of a nitrogen gas introduction tube, a thermometer, a reflux condenser, and a stirring device, adding 16 parts of acrylic acid and hydrazine 44 parts of methyl methacrylate, and adding 320 parts of isopropyl alcohol as a monomer solution. Then adding in a monomer solution 3.2 parts of 2,2'-azobisisobutyronitrile. Then the reaction system was 8 (Γ(:, and subjected to radical polymerization for 8 hours. Then, 22.4 parts of diethylamine and 300 parts of ion exchange were added to the reaction system). The water was stirred well and cooled to a temperature of 201,000 544. This was carried out to obtain a solution of the component (A-1) having a nonvolatile content of 20 ° C. Further, the anion amount of the carboxylate anion of the component (A-1) was 0.00139. Mohr/g, the glass transition temperature was 10 ° C, and the number average molecular weight was 30,000. (Production Examples 2 to 9) In addition to the type and amount of the monomer used, the amount of the polymerization initiator used, and the neutralizer solution The composition is as shown in Table 1, and is similar to the manufacturing example 1. Each of the solutions of the components (A-2) to (A-9) was obtained. The physical properties are shown in Table 2. [Table 1] (al) component (a2) component (a3) component AIBN neutralizing agent seed species Partial portion TEA (parts) Water (parts) Manufacturing Example 1 (A-1) AA 16 MMA 144 - 3.2 22.4 300 Manufacturing Example 2 (A-2) MAA 19 MMA 144 - 3.2 22.4 300 Manufacturing Example 3 (A- 3) AA 24 MMA 136 - 3.2 33.7 285 Manufacturing Example 4 (A-4) AA 16 MMA SMA 96 48 - 3.2 22.4 300 Manufacturing Example 5 (A-5) AA 16 MMA 136 FM072I 8 3.2 22.4 300 Manufacturing Example 6 (A -6) AA 16 MMA 136 V-8FM 8 3.2 22.4 300 Manufacturing Example 7 (A-7) AA 16 MMA 144 - 2.4 22.4 300 Manufacturing Example 8 (A-8) AA 1.6 MMA 158.4 - 3.2 2.2 320 Manufacturing Example 9 ( A-9) AA 72 MMA 88 - 3.2 101 220 In Table 1, AA means acrylic acid, MAA methacrylic acid, MMA methyl methacrylate, SMA thioglycolyl stearate, FM702 1 series ( Poly) siloxane mono(meth) acrylate (product name "Silaplane", manufactured by CHISSO (stock), average molecular weight 5000), V-8FM octafluoropentyl methacrylate (Osaka Organic Chemical Industry Co., Ltd.) System, molecular weight 254), AIB azo Double isobutyronitrile, TEA triethylamine. 20 201000544 [Table 2] CAV Tg Μη Manufacturing Example 1 (A-1) 0.00139 100 30000 Manufacturing Example 2 (A-2) 0.00138 110 30000 Manufacturing Example 3 (A-3) 0.00208 95 30000 Manufacturing Example 4 (A-4) 0.00139 67 30000 Manufacturing Example 5 (A-5) 0.00139 95 30000 Manufacturing Example 6 (A-6) 0.00139 100 30000 Manufacturing Example 7 (A-7) 0.00139 100 30000 Manufacturing Example 8 (A-8) 0.00014 105 30000 Manufacturing Example 9 (A-9) 0.00625 95 30000 In Table 2, CAV represents the carboxylate anion group amount, Tg represents the glass transition temperature, and Μη represents the number average molecular weight. (Example 1) 10.6 parts (nonvolatile content: 98%) of a commercially available carboxylate anion group-containing acrylic resin (product name "ARUFON UC3000", manufactured by Toagosei Co., Ltd.) 0.00132 mol/g, glass transition temperature of 65 ° C, number average molecular weight of 10,000) as (Α) component, 4 parts (anthracycline base amount of 0.007 mol/g) tetrahydroindenyl methane (1- Indole cyclopropanepropionate as a component (B), 23 parts (nonvolatile concentration 1.2%), poly(3,4-ethylenedioxythiophene (PEDOT/PSS) blended with polystyrene (product name "Baytron P", manufactured by Starck) as a component (C), two parts of triethylamine, 57 parts of 'ion-exchanged water, and 50 parts of isopropyl alcohol, and sufficiently mixed to prepare a charge-preventing coating agent. (Example 2 52.8 parts of the solution of the component (A-1) obtained in Production Example 1, 4 parts of 21 201000544 ΤΜΜΤΑΡ, 23 parts of PEDOT/PSS, 0.8 parts of triethylamine, 36 parts of ion-exchanged water, and 30 parts of isopropyl alcohol, fully The charge-preventing coating agent was prepared by mixing. (Examples 3 to 10) In the case of Example 2, the solution of the component (A-1) was replaced with The charge-preventing coating agent was prepared in the same manner as the solution of the component (A-2) to the solution of the component (A-9). (Example 11) In the second embodiment, the component (B) was replaced with a tris-hydroxyl group. The charge-preventing coating agent was prepared in the same manner except for the propane ginseng (1-indolyl propane-propionate) (TMPTAP). [Example: Combination of the components (D) &gt; (Example 12) 10.6 parts "ARUFON UC3000", 4 parts of TPMTAP, 23 parts of PEDOT/PSS, 57 parts of ion-exchanged water, 50 parts of isopropyl alcohol, and 0.2 parts of p-toluenesulfonic acid (PTS) are mixed thoroughly to prepare a charge-preventing coating agent. Example 13) 26.4 parts of the solution of the component (A-1) obtained in Production Example 1, 2 parts of TMMTAP, 11.5 parts of PEDOT/PSS, 0.4 parts of triethylamine, 18 parts of ion-exchanged water, and 15 parts of isopropyl alcohol and 0.1 part of PTS was mixed sufficiently to prepare a charge-preventing coating agent. (Example 1 4 to 2 1) For Example 12, except that the solution of the component (A-1) was substituted with 22 201000544 (A-2). The charge-preventing coating agent was prepared in the same manner as the solution of the solution ~(A-9) component. <Example: (B) Change in usage> 26.4 parts of the solution of the component (A-1) obtained in Production Example 1, 5 parts of TMMTAP, 1 1.5 parts of PEDOT/PSS, 0.4 parts of triethylamine, 24 parts of ion-exchanged water, and 25 parts Isopropanol and 0.1 part of PTS were thoroughly mixed to prepare a charge-preventing coating agent. (Example 23) In the same manner as in Example 22 except that 0.15 parts of TMMTAP, 15 parts of ion-exchanged water, and 2 parts of isopropyl alcohol were changed, the charge-preventing coating material was prepared in the same manner. (Example 24) In the same manner as in Example 13, except that PEDOT/PSS was changed to polyaniline (product name "ORMECON D1031W", manufactured by Seiko Chemical Industry Co., Ltd., and an aqueous solution having a nonvolatile concentration of 2%). It is prepared to modulate the charging prevention coating agent. (Examples 25 to 27) In Examples 15, 20, and 21, the charge-preventing coating agent was prepared in the same manner except that PEDOT/PSS was changed to polyaniline. <Comparative Example: None (B) Component> (Comparative Examples 1 to 10) A charge-preventing coating agent was prepared in the same manner as in Examples 1 to 10 except that the component (B) was not used. <Comparative Example: None (c) component> (Comparative Examples 11 to 20) A charge-preventing coating agent was prepared in the same manner as in the example columns 1 to 1 except that the component (C) was not used. <Comparative Example: Using a Crosslinking Agent Different from Component (B)&gt; (Comparative Example 21) 10 parts of carbonization was carried out for Example 2 except that (product name CARBODILITE V-02, TMMTAP, and Example 1 to electric prevention The coating agent was prepared in the same manner as the four parts in the same manner as in the case of the diimide-based hardening agent (Comparative Example). (Comparative Example 22) For Example 2, except that 10 parts of 4

(Comparative Example 23)

Porphyrin hardener (products 4 parts TMMTAP

The product name Epolite is used to modulate the electrification to prevent the coating agent. In the same manner as in the case of using a 1 part of oxygen-based hardener (product name Epolite segment) instead of 4 parts of TMMTAP, the same [[Production of test film]] The coating agent of Example 1 was applied to a bar coater No. 10, 201000544 PET film. The test film was dried in a downwind dryer under the conditions of 14 〇t, i minutes to produce a test film. [Measurement of surface resistance value] A ring electrode (product name "URTRameg〇hmmeter SM-8210, SME-8311", manufactured by Toa Dentsu Kogyo Co., Ltd.) was used, in accordance with JIS-K-6911K, and a voltage of 5 〇〇V was applied. In the case, the surface resistance value (〇/mouth) of the coated surface of the test film of Example 1 was measured. The test films of the other examples and comparative examples were also measured in the same manner. The lower the surface resistance value, the better the charging prevention performance. [Solvent resistance test] The coated surface of the test film of Example 摩擦 was rubbed with a cotton swab impregnated with acetone, and the solvent resistance of the film was evaluated in accordance with the number of times when the coating film disappeared. The more the number of times, the more excellent the solvent resistance of the film. [Agglomeration resistance test] Two sheets of the test film of Example 1 were prepared, and the coated surface was overlapped with the other non-coated surface, and under the weight of 4 kg/cm 2 'at 80T: placed for 24 hours . In the case of the base, A (10) evaluated the blocking resistance based on the ease of peeling when the film was peeled off. Λ * For "玍 and ' with ~, continuous value (for example, 4~5), means that it is evaluated between the respective ~ 甘合目I. 5· · · No feeling of resistance at all 4 · · · Almost no resistance 25 201000544 3 · · · Feeling a little resistance 2 · · · Feeling a big resistance 1··· Feeling a very large resistance [PET film adhesion test] Adhesive tape and implemented in accordance with the following basis The coated surface of the test film of Example 1 was sufficiently pressure-bonded, and then strongly pulled and peeled off to visually evaluate the amount of the residual coating film. 〇· · · 70% or more of the coating film remained. △ ·· 40% or more and less than 70% of the coating film remaining X · · Less than 40% of the coating film remains. The same test was carried out in the same manner as in the test thin samples of the other examples and comparative examples. .

26 201000544 [Table 3] (A) (B) x/y (C) (D) Surface resistance value Solvent resistance Blocking PET Adhesion Example 1 ARUFON TMMTAP 0.5 PEDOT/PSS - 108 25 4 0 Example 2 (A-1) TMMTAP 0.5 PEDOT/PSS 108 40 4~5 0 Example 3 (A-2) TMMTAP 0.5 PEDOT/PSS - 10s 40 4~5 0 Example 4 (A-3) TMMTAP 0.8 PEDOT/PSS - 108 60 4~5 0 Example 5 (A-4) TMMTAP 0.5 PEDOT/PSS - 108 40 4 0 Example 6 (A-5) TMMTAP 0.5 PEDOT/PSS - ΙΟ8 45 5 0 Example 7 (A-6 ) TMMTAP 0.5 PEDOT/PSS - ΙΟ8 45 5 0 Example 8 (A-7) TMMTAP 0.5 PEDOT/PSS - ΙΟ8 45 4~5 0 Example 9 (A-8) TMMTAP 0.05 PEDOT/PSS - ΙΟ8 20 4 0 Implementation Example 10 (A-9) TMMTAP 2.3 PEDOT/PSS - ΙΟ9 &gt; 100 4~5 〇 Example 11 (A-1) TMMTAP 0.5 PEDOT/PSS - ΙΟ8 40 4~5 0 Example 12 ARUFON TMMTAP 0.5 PEDOT/PSS PTS ΙΟ8 &gt;100 4~5 0 Embodiment 13 (A-1) TMMTAP 0.5 PEDOT/PSS PTS ΙΟ8 &gt; 100 5 0 Embodiment 14 (A-2) TMMTAP 0.5 PEDOT/PSS PTS ΙΟ8 &gt;100 5 0 Implementation Example 15 (A-3) TMMTAP 0.8 PEDOT/PSS PTS ΙΟ8 &gt; 100 5 0 Example 16 (A-4) TMMTAP 0.5 PEDOT/PSS PTS ΙΟ8 &gt;100 4~5 0 Embodiment 17 (A-5) TMMTAP 0.5 PEDOT/PSS PTS ΙΟ8 &gt; 100 5 〇 Example 18 (A-6) TMMTAP 0.5 PEDOT/PSS PTS ΙΟ8 &gt;100 5 0 Example 19 (A-7) TMMTAP 0.5 PEDOT/PSS PTS ΙΟ8 &gt; 100 5 0 Example 20 (A-8) TMMTAP 0.05 PEDOT/PSS PTS ΙΟ8 &gt; 100 4~5 0 Example 21 (A- 9) TMMTAP 2.3 PEDOT/PSS PTS ΙΟ9 &gt;100 4~5 0 Example 22 (A-1) TMMTAP 0.2 PEDOT/PSS PTS ΙΟ9 &gt;100 5 0 Example 23 (A-1) TMMTAP 7 PEDOT/PSS PTS ΙΟ8 20 3~4 Δ Example 24 (A-1) TMMTAP 0.5 Polyaniline PTS ΙΟ9 &gt; 100 4~5 0 Example 25 (A-3) TMMTAP 0.8 Polystyrene PTS ΙΟ9 &gt; 100 4~5 0 Implementation Example 26 (A-8) TMMTAP 0.05 Polyaniline PTS 10s &gt; 100 4 0 Example 27 (A-9) TMMTAP 2.3 Polyaniline PTS ΙΟ10 &gt; 100 4~5 0 In Table 3, x/y system (A) The amount of the carboxylate anion group (mol/g) in the component was divided by the amount of the indole cyclopropyl group (mol/gram) in the component (B) (hereinafter, the same). 27 201000544 [Table 4]

(A) (B) x/y (C) (D) Surface Resistance Value Solvent Resistance Adhesion PET Adhesion Comparative Example 1 ARUFON - - PEDOT/PSS - 107 1 1~2 X Comparative Example 2 (A-1 ) - - PEDOT/PSS - 107 2 1~2 X Comparative Example 3 (A-2) - - PEDOT/PSS 107 2 1~2 X Comparative Example 4 (A-3) - - PEDOT/PSS - ΙΟ7 2 1~ 2 X Comparative Example 5 (A-4) - - PEDOT/PSS - ΙΟ7 2 1~2 X Comparative Example 6 (A-5) - - PEDOT/PSS - ΙΟ7 2 2 X Comparative Example 7 (A-6) - - PEDOT/PSS - ΙΟ7 2 2 X Comparative Example 8 (A-7) - - PEDOT/PSS - ΙΟ7 2 2 X Comparative Example 9 (A-8) - - PEDOT/PSS - ΙΟ7 2 1~2 X Comparative Example 10 ( A-9) - - PEDOT/PSS - ΙΟ8 2 1~2 X Comparative Example 11 ARUFON TMMTAP 0.5 - - &gt;1014 20 4 〇Comparative Example 12 (Α·1) TMMTAP 0.5 - - &gt;1014 35 4~5 0 Comparative Example 13 (A-2) TMMTAP 0.5 &gt; 1014 35 4 to 5 0 Comparative Example 14 (A-3) TMMTAP 0.8 - - &gt; 1014 60 4 to 5 0 Comparative Example 15 (A-4) TMMTAP 0.5 - - &gt;1014 40 4 0 Comparative Example 16 (A-5) TMMTAP 0.5 - - &gt; 1014 40 5 0 Comparative Example 17 (A-6) TMMTAP 0.5 - - &gt; 1014 40 5 0 Comparative Example 18 (A-7) TMMTAP 0.5 - - &gt;1014 40 4~5 0 Comparative Example 19 (A-8) TMMTAP 0.05 - - &gt;10 丨4 10 4 0 Comparative Example 20 (A-9) TMMTAP 0.23 - &gt;10Η &gt;100 4~5 0 Comparative Example 21 (A-1) V-02 - PEDOT/PSS - ΙΟ8 2 2 X Comparative Example 22 (A-1) WS-500 - PEDOT/PSS - ΙΟ8 2 2 X Comparative Example 23 (A-1) 40E - PEDOT/PSS - 10s 1 1 X [Simplified Schematic] [Main Components Explanation of symbols] No 28

Claims (1)

201000544 VII. Patent application scope: 1. An electric anti-coating agent containing: an acrylic acid resin (A) containing a carboxylate anion group, a polyfunctional anthracene cyclopropane compound, and a hetero atom containing 7 Γ A total of conductive polymer (C). 2. The charge-preventing coating agent according to item 1 of the patent application, wherein (A) a / knife ' is a Q:, a point-unsaturated carboxylic acid (al) and an alkyl (meth)acrylate (a2) And a copolymer salt formed by reacting an unsaturated monomer other than those necessary. 3. The charge-preventing coating agent according to claim 2, wherein the (al) component is methacrylic acid and/or acrylic acid. 4. The charge-preventing coating agent according to claim 2, wherein (a3) is a knife-forming (poly) decane mono(indenyl) acrylate, and/or (mono) fluoroalkyl acrylate class. 5. The charge-preventing coating agent according to item 1 of the Shenjing patent scope, wherein the amount of the anion base (mol/g) of the knife is G.GGG3~0.005. As claimed in the patent | The charged anti-coating agent described in item i, wherein the component (4) has a glass transition temperature of 20 to 1501. For example, the charge-preventing coating agent described in the item i of the patent scope, wherein the component (8) has a number average molecular weight of 2 GGG to 1_00. And the anti-static coating agent mentioned in the first paragraph of the patent application, wherein (B), :, B, b, 丫, 衣, propyl, and/or 4-functional 丫 丫 嫁 29 29 2010 2010 2010 2010 2010 2010 2010 2010 2010 /y is the amount of the indole cyclopropane group (mol/g) of 0·1 to 1 0, and the amount (a) and the component (B) are contained. 10. The flat electricity prevention coating agent (C) as described in the first paragraph of the patent application scope is the (poly) porphin and/or (poly) styrene. 11. If the scope of the patent application contains a hardening catalyst (D). 12. If the scope of application (D) of the patent application is p-phenylene*xanthate. (1) The charge-preventing coating agent according to the item 1 of the present invention, wherein the material of the present invention is in accordance with any one of the claims 1 to 12, which is coated as described in any one of the claims. It is composed of a charge preventing agent. 30 201000544 IV. Designation of representative drawings: (1) The representative representative of the case is: None (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: »*»&gt;