JP5515338B2 - Antistatic coating agent and plastic film - Google Patents

Description

The present invention relates to a coating agent having an antistatic function and a plastic film to which the coating agent is applied.

Conventionally, plastic films such as polyester films have been used in a wide range of applications such as plate-making films, packaging films, optical component films, semiconductor processing tape films, hot stamping films, and plastic molded decorative films. By the way, plastic film is prone to static electricity during winding, rewinding, or processing, and dust in the air adheres to it, resulting in physical defects (pinholes, etc.) on the surface, and poor running on the processing line. May occur. Therefore, various means have been proposed for the purpose of suppressing the charging of the plastic film.

As such means, for example, a method in which an antistatic agent is previously kneaded into the film can be considered. However, in this method, problems have been pointed out that the antistatic agent bleeds out on the surface of the film, which causes tackiness (stickiness) on the film surface, or the antistatic agent drops off and the antistatic property decreases. .

Therefore, a method of applying a coating agent having an antistatic function to the surface of the film can be considered. In addition to the antistatic function, the antistatic coating agent is generally required to have various performances such as solvent resistance and blocking resistance of the coating and adhesion between the plastic substrate and the coating. For example, when the solvent resistance is inferior, the coating film may expand or fall off when the organic solvent comes into contact with the film processing line. Moreover, when blocking resistance is inadequate, there exist problems, such as big resistance producing at the time of unwinding a film, or a film being stripped off.

  As a known antistatic coating agent, for example, a coating agent using a quaternary ammonium salt type cationic polymer compound as a conductive polymer is known (see Patent Document 1), and is used for feeding and running a film. It is said that there will be less electrification. However, this type of antistatic coating agent is easily affected by humidity, and depending on the usage environment, it may not be able to fully exhibit the antistatic function.

  In order to avoid such problems, it is conceivable to use a π-conjugated conductive polymer that exhibits an antistatic function by electron transfer. For example, Patent Document 2 discloses a charge containing a π-conjugated conductive polymer such as poly (thiophene) or poly (pyrrole), and a nonionic acrylic copolymer synthesized from alkyl acrylate and acrylamide. An anti-coating agent is described (Patent Document 2), and is said to be excellent in antistatic properties, anti-blocking properties, adhesiveness to plastic films, and the like. However, there is a problem inferior in water resistance and solvent resistance.

Japanese Patent Laid-Open No. 10-315373 JP 2003-292655 A

An object of the present invention is to provide a novel antistatic coating agent that is excellent in antistatic properties, solvent resistance, and blocking resistance of a coating, and adhesion between the coating and a plastic substrate.

As a result of intensive studies, the present inventor has found that the above problems can be solved by the antistatic coating agent having the following constitution, and has completed the present invention.

That is, the present invention relates to a copolymer obtained by reacting an α, β unsaturated carboxylic acid (a1), a (meth) acrylic acid alkyl ester (a2) and, if necessary, other unsaturated monomers (a3). An acrylic resin (A) having a carboxylate anion group amount (mol / g) of 0.0003 to 0.005 , a polyfunctional aziridine compound (B ) obtained by neutralizing a polymer with a tertiary amine and / or ammonia. ), And a heteroatom-containing π-conjugated conductive polymer (C) composed of poly (aniline) s and / or poly (thiophenes) , and the number of moles of the carboxylate anion group of component (A) (mol) X and the number of moles (mol) of the aziridinyl group of component (B) where y is 0.001 to 10 in an amount such that x / y is 0.001 to 10 and component (B) It is related with the antistatic coating agent characterized by containing .

According to the antistatic coating agent of the present invention, a film having not only excellent antistatic properties but also excellent coating properties such as solvent resistance, blocking resistance and adhesion to a plastic film can be obtained. Therefore, the antistatic coating agent should be used in a wide range of applications such as plate-making films, packaging films, optical component films, display protective films, semiconductor processing tape films, hot stamping films, and plastic molded decorative films. Can do.

The antistatic coating agent of the present invention is referred to as a predetermined carboxylate anion group-containing acrylic resin (A) (hereinafter sometimes referred to as component (A)), a polyfunctional aziridine compound (B) or less, and component (B). And a predetermined heteroatom-containing π-conjugated conductive polymer (C) (hereinafter sometimes referred to as (C) component), and, if necessary, a curing catalyst (D) (hereinafter referred to as (D) component) In some cases).

As component (A), α, β unsaturated carboxylic acid (a1) (hereinafter referred to as component (a1)), (meth) acrylic acid alkyl ester (a2) (hereinafter referred to as component (a2)), and necessary Intramolecular, obtained by neutralizing a copolymer obtained by reacting an unsaturated monomer (a3) other than these (hereinafter referred to as component (a3)) with a tertiary amine and / or ammonia . Any acrylic resin having a carboxylate anion group (—COO ⁻ ) in the range of 0.0003 to 0.005 (mol / g) can be used, and various known ones can be used. In addition, the carboxylate anion group of (A) component originates in the carboxyl group which (a1) component has. “(Meth) acryl” means acryl or methacryl (hereinafter the same).

  As the component (a1), various known α, β unsaturated carboxylic acids such as α, β-unsaturated monocarboxylic acid, α, β-unsaturated dicarboxylic acid, α, β-unsaturated dicarboxylic acid and aliphatic Examples include monoesters with alcohols, half amides of α, β-unsaturated dicarboxylic acids, and neutralized products thereof. These can be used alone or in combination of two or more.

  Examples of the α, β-unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and isocrotonic acid. Examples of the α, β-unsaturated dicarboxylic acid include maleic acid, maleic anhydride, fumaric acid, and itaconic acid. Examples of the aliphatic alcohol forming the monoester of the α, β-unsaturated dicarboxylic acid include methanol, ethanol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, methyl cellosolve, and ethyl cellosolve. Can be mentioned. Examples of the half amide of the α, β-unsaturated dicarboxylic acid include itaconic acid monoanilide. These may be previously neutralized with a neutralizing agent described later. As the component (a1), α, β-unsaturated monocarboxylic acid, particularly acrylic acid and / or methacrylic acid is preferable.

As the component (a2), various known (meth) acrylic acid alkyl esters can be used without particular limitation. The shape of the alkyl group contained in the component (a2) is not particularly limited, and may be linear, branched or cyclic. Moreover, carbon number of this alkyl group is about 1-20 normally.

Examples of the linear alkyl group-containing (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, normal butyl (meth) acrylate, and (meth) acrylic. Examples include lauryl acid and stearyl (meth) acrylate. Examples of the branched alkyl group-containing (meth) acrylic acid alkyl ester include isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Examples of the cyclic alkyl group-containing (meth) acrylic acid alkyl ester include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, and isobornyl (meth) acrylate. These can be used alone or in combination of two or more.

  The component (a3) is not particularly limited as long as it is an unsaturated monomer other than the component (a1) and the component (a2) and can undergo a radical polymerization reaction with these. Can be used. Specifically, for example, (meth) acrylamides, hydroxyalkyl (meth) acrylates, styrenes, unsaturated sulfonic acids, aminoalkyl unsaturated monomers, polyoxyalkylene unsaturated monomers , Chlorosilane-based (meth) acrylates, (poly) siloxane mono (meth) acrylates, fluoroalkyl (mono) acrylates, and the like. These may be used alone or in combination of two or more. Can do.

Examples of (meth) acrylamides include N-substituted monoalkyl (meth) acrylamides and N-substituted dialkyl (meth) acrylamides in addition to acrylamide and / or methacrylamide. Examples of the N-substituted monoalkyl (meth) acrylamides include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-tertiary. Examples include butyl (meth) acrylamide, N-lauryl (meth) acrylamide, and N-cyclohexyl substituted alkyl (meth) acrylamide. Examples of the N-substituted dialkyl (meth) acrylamides include N, N-dimethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-ditertiary butyl (meth) acrylamide, and N, N. -Dilauryl (meth) acrylamide, N, N-di-octyl octyl (meth) acrylamide, N, N-dicyclohexyl (meth) acrylamide, etc. are mentioned.

  Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Glycerin mono (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate and the like.

Examples of styrenes include styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, hydroxystyrene, vinyltoluene, chlorovinyltoluene and the like.

Examples of the unsaturated sulfonic acids include vinyl sulfonic acid, (meth) allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and sulfonated styrene.

As aminoalkyl unsaturated monomers, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, (meth) N-methylaminopropyl acrylate, N-methylaminobutyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, (meth) acrylic acid Examples thereof include N, N-dimethylaminobutyl, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, and N, N-diethylaminobutyl (meth) acrylate.

Examples of polyoxyalkylene unsaturated monomers include polyoxyalkylene (meth) acrylic acid esters, polyoxyalkylene glycerin (meth) acrylic acid esters, polyoxyalkylene monoalkyl (meth) acrylic acid esters, poly Examples thereof include oxyalkylene monoalkenyl (meth) acrylic acid esters, polyoxyalkylene (meth) allyl ether, polyoxyalkylene glycerin (meth) allyl ether, and the like.

  Examples of chlorosilane (meth) acrylates include vinyldimethylchlorosilane, vinylmethyldichlorosilane, vinyltrichlorosilane, allyldimethylchlorosilane, allylmethyldichlorosilane, allyltrichlorosilane, 4-butenyldimethylchlorosilane, 4-butenylmethyldichlorosilane. 4-butenyltrichlorosilane, 5-pentenyldimethylchlorosilane, 5-pentenylmethyldichlorosilane, 5-pentenyltrichlorosilane, 3-methacryloxypropyldimethylchlorosilane, 3-methacryloxypropylmethyldichlorosilane, 3-methacryloxypropyltri Chlorosilane, 3-acryloxypropyldimethylchlorosilane, 3-acryloxypropylmethyldichlorosilane, 3-acryloxypropylto Chlorosilanes, 4-methacryloxy-butyldimethylchlorosilane, 4-methacryloxy butyl methyl dichlorosilane, 4-methacryloxy butyl trichlorosilane, 4-acryloxy-butyldimethylchlorosilane, 4-acryloxy-butyl methyl dichlorosilane, and the like.

Examples of (poly) siloxane mono (meth) acrylates include “Silaplane FM-0711”, “Silaplane FM-0721”, “Silaplane FM-0725” and the like (all manufactured by Chisso Corporation). Is mentioned.

Fluoroalkyl (mono) acrylates include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl ( (Meth) acrylate, 2,2,2-trifluoro-1-trifluoromethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, H, 1H, 5H-octafluoropentyl (meth) ) Acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5,5,5-nonafluoropentyl (meth) ) Crate and the like. Moreover, as a commercial item, "V-3F", "V-3FM", "V-4F", "V-8F", "V-8FM" etc. (all are Osaka Organic Chemical Industries Ltd. make) etc. Can be mentioned.

As the component (a3), the (poly) siloxane mono (meth) acrylates and / or fluoroalkyl (mono) acrylates are particularly preferable from the viewpoint of blocking resistance of the coating.

The used weight of each of the components (a1) to (a3) is such that the component (a1) is about 3 to 30% by weight, the component (a2) is about 20 to 97% by weight, and the component (a3) is 0 to 50% by weight. % (However, the total weight of all components does not exceed 100% by weight). When the (poly) siloxane mono (meth) acrylates and / or fluoroalkyl (mono) acrylates are used as the component (a3), the component (a1) is about 3 to 30% by weight, and the component (a2) Is about 20 to 87% by weight, and the component (a3) is about 10 to 50% by weight (however, the total weight of all the components does not exceed 100% by weight).

  The manufacturing method of (A) component is not specifically limited, Various well-known methods are employable. Specifically, for example, a method of subjecting the components (a1) to (a3) to a radical polymerization reaction usually at about 60 to 180 ° C. for about 1 to 20 hours can be mentioned. The reaction order of the components (a1) to (a3) is not particularly limited, and may be sequential or collectively.

  In addition, when all of the (a1) component is a neutralized product, the obtained radical polymer is directly used as the (A) component. On the other hand, when part of the component (a1) is a neutralized product, or when all of the component (a1) is an unneutralized product, radical polymerization that reacts the components (a1) to (a3) The component (A) is obtained by further neutralizing the product with a neutralizing agent.

Examples of the neutralizing agent include ammonia, primary to tertiary amines, alkali metal compounds and alkaline earth metal compounds, and these can be used alone or in combination of two or more. .

In the present invention, the use of a tertiary amine such as trimethylamine or triethylamine and / or ammonia as a neutralizing agent improves the solvent resistance of the coating. It is preferable to use this neutralizing agent normally in the ratio of 80-300 mol% with respect to the carboxyl group which the said radical polymer has.

  In the radical polymerization reaction, various known radical polymerization initiators such as inorganic peroxides, organic peroxides, and azo compounds can be used without particular limitation. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

Examples of the inorganic peroxides include hydrogen peroxide, ammonium persulfate, and potassium persulfate. Examples of the organic peroxides include t-butyl peroxybenzoate, dicumyl peroxide, lauryl peroxide and the like. Examples of the azo compounds include 2,2'-azobisisobutyronitrile and dimethyl-2,2'-azobisisobutyrate. Moreover, the usage-amount is about 0.01-10 weight part normally with respect to a total of 100 weight part of (a1) component-(a3) component.

Various known chain transfer agents can be used without particular limitation for the purpose of adjusting the molecular weight of the radical polymer. Specific examples include dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and the like. These may be used alone or in combination of two or more. Moreover, the usage-amount is about 0.01-5 weight part normally with respect to a total of 100 weight part of (a1) component-(a3) component.

In the radical polymerization reaction, various known reaction solvents can be used without particular limitation. Examples of the reaction solvent include organic solvents and water, and examples of the organic solvent include alcohols, lower ketones, aromatic hydrocarbons, ethyl acetate, chloroform, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and the like. Examples of water include ion exchange water. These can be used alone or in combination of two or more.

Examples of the alcohols include methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, butyl alcohol, ethylene glycol, diethylene glycol, ethylene glycol monoethyl ether, and ethylene glycol mono n-propyl ether. Examples of the lower ketones include acetone and methyl ethyl ketone. Examples of the aromatic hydrocarbons include toluene, benzene and the like.

The amount of carboxylate anion group (mol / g) of the component (A) thus obtained is about 0.0003 to 0.005, preferably 0.001 to 0.003. When it is 0.0003 or more, the solvent resistance of the coating tends to be good, and when it is 0.005 or less, it becomes easy to maintain the balance between the antistatic property and the solvent resistance of the coating. The “carboxylate anion group amount” refers to the number of moles of carboxylate anion group contained in 1 g of component (A) (in terms of solid content), and is a calculated value.

  For example, from the viewpoint of blocking resistance of the coating, the glass transition temperature is usually 20 to 150 ° C, preferably 70 to 150 ° C. In addition, for example, from the viewpoint of workability at the time of production and ease of handling, the number average molecular weight (polystyrene conversion value by gel permeation chromatography) is about 2000 to 100,000, preferably 25,000 to 100,000.

Specific examples of the component (B) include aziridin derivatives having at least three aziridinyl groups having the following structure in the molecule. As such a thing, what is manufactured by the method described in US Patent 4382135, Unexamined-Japanese-Patent No. 2003-104970 etc., for example can be used. In addition, even if it replaces with (B) component and uses another polyfunctional compound, for example, a polyfunctional oxazoline compound, a polyfunctional epoxy compound independently, the film | membrane excellent in sclerosis | hardenability and solvent resistance cannot be obtained.

(In the formula, R ¹ and R ² represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and both may be the same or different.)

  As the component (B), a trifunctional aziridine compound and / or a tetrafunctional aziridine compound is particularly preferable in consideration of the solvent resistance of the coating.

  As the trifunctional aziridine compound, those represented by the following general formula (1) are preferable in view of availability.

(In the formula (1), X represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylol group having 1 to 3 carbon atoms. Further, ^{R 1} and ^{R 2} are hydrogen or alkyl having 1 to 6 carbon atoms And both may be the same or different, and R ³ represents hydrogen or a methyl group.)

  Among the compounds represented by the general formula (1), those in which X is hydrogen include, for example, glycerol-tris (1-aziridinylpropionate), glycerol-tris [2-methyl- (1-aziridinyl). )] Propionate, glycerol-tris [2-ethyl- (1-aziridinyl)] propionate, glycerol-tris [2-butyl- (1-aziridinyl)] propionate), glycerol-tris [2-propyl -(1-aziridinyl)] propionate, glycerol-tris [2-pentyl- (1-aziridinyl)] propionate, glycerol-tris [2-hexyl- (1-aziridinyl)] propionate, glycerol-tris [2,3-dimethyl- (1-aziridinyl)] propionate, glycerol-tris [2 3-diethyl- (1-aziridinyl)] propionate, glycerol-tris [2,3-dibutyl- (1-aziridinyl)] propionate), glycerol-tris [2,3-dipropyl- (1-aziridinyl) Propionate, glycerol-tris [2,3-dipentyl- (1-aziridinyl)] propionate, glycerol-tris [2,3-dihexyl- (1-aziridinyl)] propionate, and the like. Taking glycerol-tris (1-aziridinylpropionate) as an example, the following structure can be shown.

  Examples of the alkyl group having X of about 1 to 6 carbon atoms (preferably 2 to 3) include trimethylolpropane-tris (1-aziridinylpropionate), trimethylolpropane-tris [2- Methyl- (1-aziridinyl)] propionate, trimethylolpropane-tris [2-ethyl- (1-aziridinyl)] propionate, trimethylolpropane-tris [2-butyl- (1-aziridinyl)] propionate G), trimethylolpropane-tris [2-propyl- (1-aziridinyl)] propionate, trimethylolpropane-tris [2-pentyl- (1-aziridinyl)] propionate, trimethylolpropane-tris [2 -Hexyl- (1-aziridinyl)] propionate, trimethylolpropanate [2,3-dimethyl- (1-aziridinyl)] propionate, trimethylolpropane-tris [2,3-diethyl- (1-aziridinyl)] propionate, trimethylolpropane-tris [2,3- Dibutyl- (1-aziridinyl)] propionate), trimethylolpropane-tris [2,3-dipropyl- (1-aziridinyl)] propionate, trimethylolpropane-tris [2,3-dipentyl- (1- Aziridinyl)] propionate, trimethylolpropane-tris [2,3-dihexyl- (1-aziridinyl)] propionate, and the like. Taking trimethylolpropane-tris (1-aziridinylpropionate) as an example, the following structure can be shown.

  In addition, X is an alkylol group having 1 to 3 carbon atoms, such as tetramethylolmethane-tris (1-aziridinylpropionate), tetramethylolmethane-tris [2-methyl- (1-aziridinyl) ] Propionate, tetramethylolmethane-tris [2-ethyl- (1-aziridinyl)] propionate, tetramethylolmethane-tris [2-butyl- (1-aziridinyl)] propionate), tetramethylolmethane- Tris [2-propyl- (1-aziridinyl)] propionate, tetramethylolmethane-tris [2-pentyl- (1-aziridinyl)] propionate, tetramethylolmethane-tris [2-hexyl- (1-aziridinyl) )] Propionate, tetramethylolmethane-tris [2,3-dimethyl] -(1-aziridinyl)] propionate, tetramethylolmethane-tris [2,3-diethyl- (1-aziridinyl)] propionate, tetramethylolmethane-tris [2,3-dibutyl- (1-aziridinyl) Propionate), tetramethylolmethane-tris [2,3-dipropyl- (1-aziridinyl)] propionate, tetramethylolmethane-tris [2,3-dipentyl- (1-aziridinyl)] propionate, And tetramethylolmethane-tris [2,3-dihexyl- (1-aziridinyl)] propionate. Taking tetramethylolmethane-tris (1-aziridinylpropionate) as an example, the following structure can be shown.

  As the tetrafunctional aziridine compound, specifically, those represented by the following general formula (2) are suitable.

(In formula (2), R ¹ and R ² may be the same or different and each represents hydrogen or an alkyl group having 1 to 6 carbon atoms. R ³ represents hydrogen or a methyl group.)

Specific examples of the compound represented by the formula (2) include pentaerythritol-tetra (1-aziridinylpropionate), pentaerythritol-tetra [2-methyl- (1-aziridinyl)] propione- Pentaerythritol-tetra [2-ethyl- (1-aziridinyl)] propionate, pentaerythritol-tetra [2-butyl- (1-aziridinyl)] propionate), pentaerythritol-tetra [2-propyl- (1-aziridinyl)] propionate, pentaerythritol-tetra [2-pentyl- (1-aziridinyl)] propionate, pentaerythritol-tetra [2-hexyl- (1-aziridinyl)] propionate, pentaerythritol -Tetra [2,3-dimethyl- (1-aziridinini )] Propionate, pentaerythritol-tetra [2,3-diethyl- (1-aziridinyl)] propionate, pentaerythritol-tetra [2,3-dibutyl- (1-aziridinyl)] propionate), penta Erythritol-tetra [2,3-dipropyl- (1-aziridinyl)] propionate, pentaerythritol-tetra [2,3-dipentyl- (1-aziridinyl)] propionate, pentaerythritol-tetra [2,3- And dihexyl- (1-aziridinyl)] propionate. Of these, when pentaerythritol-tetra (1-aziridinylpropionate) is taken as an example, the following structure can be shown.

  Examples of other tetrafunctional aziridine compounds include tetraaziridinyl metaxylenediamine, tetraaziridinylmethylparaxylenediamine, and tetramethylpropanetetraaziridinylpropionate.

  In addition, as the component (B), for example, a bifunctional aziridine compound or a hexafunctional aziridine compound can be used in combination as necessary other than those described above.

  Examples of the bifunctional aziridine compound include neopentyl glycol di (β-aziridinylpropionate), 4,4′-isopropylidenediphenoldi (β-aziridinylpropionate), 4,4′- Examples include methylenediphenoldi (β-aziridinylpropionate) and 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane. Examples of the hexafunctional aziridine compound include compounds described in JP-A-2003-104970.

  Various known monofunctional aziridines can also be used together with the component (B). Specifically, for example, aziridine, 2-methylaziridine, 2-ethylaziridine, 2,2-dimethylaziridine, 2,3-dimethylaziridine, 2-phenylaziridine and the like can be used. Or in combination of two or more.

  The amount (mol / g) of the aziridinyl group of the component (B) is usually about 0.001 to 0.02, preferably about 0.002 in consideration of adhesion of the coating to a plastic film (particularly, polyethylene terephthalate film). It is the range which becomes 003-0.01. The “aziridinyl group amount” means the number of moles of the aziridinyl group contained in 1 g of the component (B), and is a calculated value.

The content of the component (A) and the component (B) in the antistatic coating agent of the present invention is such that the mole number (mol) of the carboxylate anion group of the component (A) is x, and the mole of the aziridinyl group of the component (B). When the number (mol) is y, x / y is usually in the range of about 0.01 to 10, preferably about 0.03 to 5. By being in this numerical range, the solvent resistance, blocking resistance, and plastic film (particularly polyethylene terephthalate film) adhesion of the coating film can be easily balanced.

The π-conjugated conductive polymer having a hetero atom as the component (C), from the viewpoint of antistatic properties of the coating, using a poly (aniline) s and / or poly (thiophene) s. The poly (aniline) is a π-conjugated conductive polymer having an aromatic ring, and the poly (thiophene) is a π-conjugated conductive polymer having a heterocycle having a hetero atom. In the present invention, the component (C) is in a state doped with various dopants. The “heteroatom” refers to an atom other than hydrogen and carbon (for example, a nitrogen atom or a sulfur atom). The “heteroatom-containing π-conjugated conductive polymer” refers to an organic polymer compound having a heteroatom in the molecule and a molecular main chain having a π-conjugated structure. The component (C) is usually used as an aqueous solution having a nonvolatile content concentration of usually about 0.1 to 10% by weight.

In addition, specific examples of the hetero atom-containing π-conjugated conductive polymer other than the component (C) include, for example , poly (thiophene vinylene) s, (Pyrrole), poly (furan) and the like .

  In addition, an alkyl group, an alkoxy group, or an alkylenedioxy group may be bonded to the heterocyclic ring or the aromatic ring in a branched or cyclic manner. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, a decyloxy group, and an octadecyloxy group. Examples of the alkyleneoxy group include an ethylenedioxy group, a propyleneoxy group, and a butenedioxy group.

Examples of the poly (thiophene) include poly (thiophene), poly (alkylthiophene), poly (monoalkoxythiophene), poly (dialkoxythiophene), poly (alkylenedioxythiophene) and the like. It is done.

Examples of the poly (alkylthiophene) s include poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene), Poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3,4-dimethylthiophene), And poly (3,4-dibutylthiophene). The poly (monoalkoxythiophene) s include poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3- Heptyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene) and the like. The poly (dialkoxythiophene) s include poly (3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), and poly (3,4). -Dibutoxythiophene), poly (3,4-dihexyloxythiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyloxythiophene), poly (3,4-didecyloxythiophene) ), Poly (3,4-didodecyloxythiophene) and the like. Examples of the poly (alkylenedioxythiophene) s include poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), and poly (3,4-butenedioxythiophene). Is mentioned.

Examples of the poly (thiophene vinylene) s include poly (thiophene vinylene), poly (alkylthiophene vinylenes), poly (monoalkoxythiophene vinylenes), poly (dialkoxythiophene vinylenes), and poly (alkylenedioxythiophenes). Vinylene) and the like.

Examples of the (alkyl polythiophene vinylene) include poly (3-methylthiophenvinylene), poly (3-ethylthiophenvinylene), poly (3-propylthiophenvinylene), poly (3-butylthiophenvinylene), poly (3- Hexylthiophene vinylene), poly (3-heptylthiophene vinylene), poly (3-octylthiophene vinylene), poly (3-decylthiophene vinylene), poly (3-dodecylthiophene vinylene), poly (3-octadecylthiophene vinylene), Poly (3,4-dimethylthiophene vinylene), poly (3,4-dibutylthiophene vinylene) and the like can be mentioned. Examples of the poly (monoalkoxythiophene vinylene) include poly (3-methoxythiophene vinylene), poly (3-ethoxythiophene vinylene), poly (3-butoxythiophene vinylene), and poly (3-hexyloxythiophene vinylene). , Poly (3-heptyloxythiophene vinylene), poly (3-octyloxythiophene vinylene), poly (3-decyloxythiophene vinylene), poly (3-dodecyloxythiophene vinylene), poly (3-octadecyloxythiophene vinylene) Etc. Examples of the poly (dialkoxythiophene vinylene) include poly (3,4-dimethoxythiophene vinylene), poly (3,4-diethoxythiophene vinylene), poly (3,4-dipropoxythiophene vinylene), poly (3,4-dibutoxythiophene vinylene), poly (3,4-dihexyloxythiophene vinylene), poly (3,4-diheptyloxythiophene vinylene), poly (3,4-dioctyloxythiophene vinylene), poly ( 3,4-didecyloxythiophene vinylene), poly (3,4-didodecyloxythiophene vinylene) and the like. Examples of the poly (alkylenedioxythiophene vinylene) s include poly (3,4-ethylenedioxythiophene vinylene), poly (3,4-propylenedioxythiophene vinylene), and poly (3,4-butenedioxy). Thiophene vinylene) and the like.

Examples of the poly (pyrrole) include poly (pyrrole), poly (alkylpyrrole), poly (monoalkoxypyrrole), poly (dialkoxypyrrole), poly (alkylenedioxypyrrole) and the like. It is done.

Examples of the poly (alkylpyrrole) include poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-propylpyrrole), poly (3-butylpyrrole), poly (3-hexylpyrrole), Poly (3-heptylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3-octadecylpyrrole), poly (3,4-dimethylpyrrole), And poly (3,4-dibutylpyrrole). Examples of the poly (monoalkoxypyrrole) include poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), and poly (3- Heptyloxypyrrole), poly (3-octyloxypyrrole), poly (3-decyloxypyrrole), poly (3-dodecyloxypyrrole), poly (3-octadecyloxypyrrole) and the like. Examples of the poly (dialkoxypyrrole) include poly (3,4-dimethoxypyrrole), poly (3,4-diethoxypyrrole), poly (3,4-dipropoxypyrrole), and poly (3,4). -Dibutoxypyrrole), poly (3,4-dihexyloxypyrrole), poly (3,4-diheptyloxypyrrole), poly (3,4-dioctyloxypyrrole), poly (3,4-didecyloxypyrrole) ), Poly (3,4-didodecyloxypyrrole) and the like. Examples of the poly (alkylenedioxypyrrole) include poly (3,4-ethylenedioxypyrrole), poly (3,4-propylenedioxypyrrole), and poly (3,4-butenedioxypyrrole). Is mentioned.

Examples of the poly (furan) include poly (furan), poly (alkylfuran), poly (monoalkoxyfuran), poly (dialkoxyfuran), poly (alkylenedioxyfuran) and the like. It is done.

Examples of the poly (alkyl furan) include poly (3-methyl furan), poly (3-ethyl furan), poly (3-propyl furan), poly (3-butyl furan), poly (3-hexyl furan), Poly (3-heptylfuran), poly (3-octylfuran), poly (3-decylfuran), poly (3-dodecylfuran), poly (3-octadecylfuran), poly (3,4-dimethylfuran), poly (3,4-dibutylfuran) and the like. Examples of the poly (monoalkoxyfuran) include poly (3-methoxyfuran), poly (3-ethoxyfuran), poly (3-butoxyfuran), poly (3-hexyloxyfuran), poly (3- Heptyloxyfuran), poly (3-octyloxyfuran), poly (3-decyloxyfuran), poly (3-dodecyloxyfuran), poly (3-octadecyloxyfuran) and the like. Examples of the poly (dialkoxyfuran) include poly (3,4-dimethoxyfuran), poly (3,4-diethoxyfuran), poly (3,4-dipropoxyfuran), and poly (3,4). -Dibutoxyfuran), poly (3,4-dihexyloxyfuran), poly (3,4-diheptyloxyfuran), poly (3,4-dioctyloxyfuran), poly (3,4-didecyloxyfuran) ), Poly (3,4-didodecyloxyfuran) and the like. Examples of the poly (alkylenedioxyfuran) include poly (3,4-ethylenedioxyfuran), poly (3,4-propylenedioxyfuran), poly (3,4-butenedioxyfuran), and the like. Is mentioned.

  Examples of the poly (aniline) include poly (aniline), poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid) and the like. Can be mentioned.

Examples of the dopant include Lewis acids (PF ₅ , AsF ₅ , SbF ₅ etc.), proton acids (HF, HCl, H ₂ SO ₄ etc.), electrolyte anions (Cl ⁻ , Br ⁻ , sulfoanions etc.), anionic properties Examples thereof include polymers.

Examples of the anionic polymer include polystyrene sulfonic acid (PSS), polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, and poly-2-acrylamido-2-methyl. Propanesulfonic acid, polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, and polyisoprene carboxylic acid , Polyacrylic acid, and at least one selected from the group consisting of salts thereof.

  Component (C) is usually used as an aqueous solution. The solid content concentration is usually about 0.1 to 10% by weight.

Among the components (C) , poly (thiophene) s include alkylenedioxypoly (thiophene) doped with PSS (especially 3,4-ethylenedioxythiophene (PEDOT)) in consideration of availability. Is preferred.

  In addition, PEDOT doped with PSS is, for example, by polymerizing 3,4-ethylenedioxythiophene (EDOT), which is a monomer, in the aqueous phase using an oxidizing agent in the presence of PSS as a dopant, It can be obtained as an aqueous solution of a complex of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (PEDOT / PSS).

  As such an aqueous solution of PEDOT / PSS, for example, a commercially available product such as Baytron P (manufactured by Starck) can be used.

As long as the intended effect of the present invention is not impaired, non-heteroatom-based conductive polymer, for example, poly (acetylene) s, poly (phenylene) s, poly (phenylene vinylenes), poly (acene) ) Can also be used in combination. However, these cannot be used alone from the viewpoint of antistatic properties and color tone.

The content of the component (C) (in terms of solid content) in the antistatic coating agent of the present invention is not particularly limited, but from the viewpoint of the balance of antistatic properties, solvent resistance, blocking resistance, etc. of the film, (A) It is usually in the range of about 0.1 to 30 parts by weight, preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the total of component and component (B).

As the component (D), various known curing catalysts such as an acid catalyst and an acid generator can be used without particular limitation. Examples of the acid catalyst include p-toluenesulfonic acid, hydrochloric acid, bromic acid, iodic acid, fluorine acid, fluorosulfonic acid, sulfuric acid, and phosphoric acid. Examples of the acid generator include diaryl iodonium salts, triaryl sulfonium salts, diaryl phosphonium salts and the like. These may be used alone or in combinations of two or more. In these, since it is easy to handle, an acid catalyst is preferable, especially para-toluenesulfonic acid.

Although content of (D) component in the antistatic coating agent of this invention is not specifically limited, From viewpoints, such as a solvent resistance of a film and blocking resistance, (A) component (solid content conversion) and (B) component It is the range which becomes about 0-10 weight part normally with respect to a total of 100 weight part, Preferably it is 0.1-5 weight part.

When the acid catalyst , particularly paratoluenesulfonic acid, is used as the component (D), the antistatic coating agent of the present invention contains the tertiary amine for the purpose of improving storage stability (pot life). Can be added separately.

Moreover, the said organic solvent and water can be used for the antistatic coating agent of this invention as a dilution solvent as needed. As the organic solvent, alcohols having about 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol and the like are preferable from the viewpoint of storage stability (pot life). Moreover, ion-exchange water is preferable as water. The amount of the diluting solvent used is usually in the range where the solid content concentration of the antistatic coating agent of the present invention is usually about 0.1 to 30 parts by weight.

In addition, the antistatic coating agent of the present invention includes various other known additives as appropriate, such as antifoaming agents, antiskid agents, antiseptics, rust inhibitors, pH adjusters, antioxidants, pigments, and dyes. A lubricant or the like can be blended.

The plastic film of the present invention is formed by applying the antistatic coating agent of the present invention. The coating method is not particularly limited, and is based on various known means. Specific examples include a roll coater, a reverse roll coater, a gravure coater, a knife coater, and a bar coater. Moreover, the coating amount to a base material is not specifically limited, Usually, it is about 0.01-10 g / m < ² > as dry solid content. Further, the substrate may be coated not only on one side but also on both sides.

Examples of the base material include polycarbonate, polymethyl methacrylate, polystyrene, polyethylene terephthalate (PET), polyimide, polyolefin, nylon, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, and the like. Examples thereof include films made of plastic, and these may be subjected to surface treatment (corona discharge or the like) as necessary. Moreover, the said plastic film may be provided with the layer by coating other than the antistatic coating agent of this invention in the single side | surface or both surfaces.

  Hereinafter, the present invention will be described in more detail through production examples, examples, and comparative examples, but the present invention is not limited to these examples. In the examples, “%” and “parts” are based on parts by weight. The glass transition temperature is a value measured with a differential scanning calorimeter (product name “DSC6200”, manufactured by Seiko Instruments Inc.). The number average molecular weight is a value measured by gel permeation chromatography (product name “HLC-8220GPC”, manufactured by Tosoh Corporation).

Production Example 1
A four-necked flask equipped with a nitrogen gas inlet tube, a thermometer, a reflux condenser and a stirring device was charged with 16 parts of acrylic acid and 144 parts of methyl methacrylate, and 320 parts of isopropyl alcohol was further added to form a monomer solution. . Next, 3.2 parts of 2,2′-azobisisobutyronitrile was added to the monomer solution as a polymerization initiator. Next, the reaction system was set to 80 ° C., and a radical polymerization reaction was performed for 8 hours. Next, 22.4 parts of triethylamine and 300 parts of ion-exchanged water were added to the reaction system, stirred well, and cooled to room temperature. Thus, a solution of the component (A-1) having a solid content of 20% was obtained. In addition, the carboxylate anion group amount of the component (A-1) was 0.00139 mol / g, the glass transition temperature was 100 ° C., and the number average molecular weight was 30000.

Production Example 2
A four-necked flask similar to Production Example 1 was charged with 19 parts of methacrylic acid and 141 parts of methyl methacrylate, and 320 parts of isopropyl alcohol was further added to obtain a monomer solution. Next, azobisisobutyronitrile 3.2 was added to the monomer solution as a polymerization initiator. Subsequently, after raising the temperature of the reaction system to 80 ° C., a radical polymerization reaction was performed for 8 hours. Thereafter, 22.4 parts of triethylamine and 300 parts of ion-exchanged water were added to the reaction system, stirred well, and cooled to room temperature. Thus, a solution of component (A-2) having a solid content of about 20% was obtained. In addition, the carboxylate anion group amount of the component (A-2) was 0.00138 mol / g, the glass transition temperature was 110 ° C., and the number average molecular weight was 30000.

Production Example 3
A four-necked flask similar to Production Example 1 was charged with 24 parts of acrylic acid and 136 parts of methyl methacrylate, and 320 parts of isopropyl alcohol was further added to obtain a monomer solution. Next, 3.2 parts of azobisisobutyronitrile as a polymerization initiator was added to the monomer solution. Subsequently, after raising the temperature of the reaction system to 80 ° C., a radical polymerization reaction was performed for 8 hours. Thereafter, 33.7 parts of triethylamine and 285 parts of ion-exchanged water were added to the reaction system, stirred well, and cooled to room temperature. Thus, a solution of the component (A-3) having a solid content of about 20% was obtained. In addition, the carboxylate anion group amount of the component (A-3) was 0.00208 mol / g, the glass transition temperature was 95 ° C., and the number average molecular weight was 30000.

Production Example 4
In a four-necked flask similar to Production Example 1, 16 parts of acrylic acid, 96 parts of methyl methacrylate, and 48 parts of stearyl methacrylate were added, and 320 parts of isopropyl alcohol was further added to obtain a monomer solution. Next, 3.2 parts of azobisisobutyronitrile as a polymerization initiator was added to the monomer solution. Next, the temperature of the reaction system was raised to 80 ° C. and held for 8 hours to perform radical polymerization reaction. Thereafter, 22.4 parts of triethylamine and 300 parts of ion-exchanged water were added to the reaction system, stirred well, and cooled to room temperature. Thus, a solution of component (A-4) having a solid content of about 20% was obtained. In addition, the carboxylate anion group amount of the component (A-4) was 0.00139 mol / g, the glass transition temperature was 67 ° C., and the number average molecular weight was 30000.

Production Example 5
In a four-necked flask similar to Production Example 1, 16 parts of acrylic acid, 136 parts of methyl methacrylate, and polysiloxane monomethacrylate (product name “Silaplane FM-0721”, manufactured by Chisso Corporation, average molecular weight 5000) 8 Then, 320 parts of isopropyl alcohol was added to obtain a monomer solution. Next, 3.2 parts of azobisisobutyronitrile as a polymerization initiator was added to the monomer solution. Subsequently, after raising the temperature of the reaction system to 80 ° C., a radical polymerization reaction was performed for 8 hours. Thereafter, 22.4 parts of triethylamine and 300 parts of ion-exchanged water were added to the reaction system, stirred well, and cooled to room temperature. Thus, a solution of component (A-5) having a solid content of about 20% was obtained. In addition, the carboxylate anion group amount of the component (A-5) was 0.00139 mol / g, the glass transition temperature was 95 ° C., and the number average molecular weight was 30000.

Production Example 6
In a four-necked flask similar to Production Example 1, 16 parts of acrylic acid, 136 parts of methyl methacrylate, and octafluoropentyl methacrylate (product name “V-8FM”, manufactured by Osaka Organic Chemical Industry Co., Ltd., molecular weight 254) 8 parts were charged, and 320 parts of isopropyl alcohol was further added to obtain a monomer solution. Next, 3.2 parts of azobisisobutyronitrile as a polymerization initiator was added to the monomer solution. Next, the temperature of the reaction system was raised to 80 ° C. and held for 8 hours to perform radical polymerization reaction. Thereafter, 22.4 parts of triethylamine and 300 parts of ion-exchanged water were added to the reaction system, stirred well, and cooled to room temperature. Thus, a solution of component (A-6) having a solid content of about 20% was obtained. In addition, the carboxylate anion group amount of the component (A-6) was 0.00139 mol / g, the glass transition temperature was 100 ° C., and the number average molecular weight was 30000.

Production Example 7
A four-necked flask similar to Production Example 1 was charged with 16 parts of acrylic acid and 144 parts of methyl methacrylate, and 320 parts of isopropyl alcohol was further added to obtain a monomer solution. Next, 2.4 parts of azobisisobutyronitrile as a polymerization initiator was added to the monomer solution. Next, the temperature of the reaction system was raised to 80 ° C. and held for 8 hours to perform radical polymerization reaction. Thereafter, 22.4 parts of triethylamine and 300 parts of ion-exchanged water were added to the reaction system, stirred well, and cooled to room temperature. Thus, a solution of component (A-7) having a solid content of about 21% was obtained. In addition, the carboxylate anion group amount of the component (A-7) was 0.00139 mol / g, the glass transition temperature was 100 ° C., and the number average molecular weight was 50000.

Production Example 8
A four-necked flask similar to Production Example 1 was charged with 1.6 parts of acrylic acid and 158.4 parts of methyl methacrylate, and 320 parts of isopropyl alcohol was further added to form a monomer solution. Next, 3.2 parts of azobisisobutyronitrile as a polymerization initiator was added to the monomer solution. Next, the temperature of the reaction system was raised to 80 ° C. and held for 8 hours to perform radical polymerization reaction. Thereafter, 2.2 parts of triethylamine and 320 parts of ion-exchanged water were added to the reaction system, stirred well, and cooled to room temperature. Thus, a solution of component (A-8) having a solid content of about 20% was obtained. In addition, the carboxylate anion group amount of the component (A-8) was 0.00014 mol / g, the glass transition temperature was 105 ° C., and the number average molecular weight was 30000.

Production Example 9
A four-necked flask similar to Production Example 1 was charged with 72 parts of acrylic acid and 88 parts of methyl methacrylate, and 320 parts of isopropyl alcohol was further added to obtain a monomer solution. Next, 3.2 parts of azobisisobutyronitrile as a polymerization initiator was added to the monomer solution. Next, the temperature of the reaction system was raised to 80 ° C. and held for 8 hours to perform radical polymerization reaction. Thereafter, 101 parts of triethylamine and 220 parts of ion-exchanged water were added to the reaction system, stirred well, and cooled to room temperature. Thus, a solution of component (A-9) having a solid content of about 20% was obtained. In addition, the carboxylate anion group amount of the component (A-9) was 0.00625 mol / g, the glass transition temperature was 95 ° C., and the number average molecular weight was 30000.

In Table 1, AA is acrylic acid, MAA is methacrylic acid, MMA is methyl methacrylate, SMA is stearyl methacrylate, FM0721 is (poly) siloxane mono (meth) acrylate (product name “Silaplane”, manufactured by Chisso Corporation) , Average molecular weight 5000), V-8FM means octafluoropentyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., molecular weight 254), AIBN means azobisisobutyronitrile, and TEA means triethylamine.

  In Table 2, CAV means the amount of carboxylate anion group, Tg means glass transition temperature, and Mn means number average molecular weight.

As component (A), a commercially available carboxylate anion group-containing acrylic resin (product name “ARUFON UC3000”, manufactured by Toagosei Co., Ltd., carboxylate anion group amount 0.00132 mol / g, glass transition temperature 65 ° C., number average molecular weight 10,000) ) 10.6 parts (solid content concentration 98%), 4 parts tetramethylolmethane-tris (1-aziridinylpropionate) (TMMTAP; aziridinyl group amount 0.00702 mol / g) as component (B) As the component (C), 23 parts of poly (3,4-ethylenedioxythiophene) (PEDOT / PSS) (product name “Baytron P”, Starck) doped with polystyrene (solid content concentration 1.2%) ), 2 parts triethylamine, 57 parts ion-exchanged water, 50 parts isopropyl alcohol, Mix well to prepare an antistatic coating agent.

52.8 parts of the solution of component (A-1) obtained in Production Example 1, 4 parts of TMMTAP, 23 parts of PEDOT / PSS, 0.8 parts of triethylamine, 36 parts of ion-exchanged water, and 30 parts of isopropyl alcohol Part of the mixture was mixed well to prepare an antistatic coating agent.

  An antistatic coating agent was prepared in the same manner as in Example 2, except that the solution of the component (A-1) was replaced with the solution of the component (A-2).

  An antistatic coating agent was prepared in the same manner as in Example 2, except that the solution of the component (A-1) was replaced with the solution of the component (A-3).

An antistatic coating agent was prepared in the same manner as in Example 2, except that the solution of component (A-1) was replaced with the solution of component (A-4).

An antistatic coating agent was prepared in the same manner as in Example 2, except that the solution of component (A-1) was replaced with the solution of component (A-5).

An antistatic coating agent was prepared in the same manner as in Example 2, except that the solution of component (A-1) was replaced with the solution of component (A-6).

An antistatic coating agent was prepared in the same manner as in Example 2, except that the solution of component (A-1) was replaced with the solution of component (A-7).

Reference example 1
An antistatic coating agent was prepared in the same manner as in Example 2, except that the solution of component (A-1) was replaced with the solution of component (A-8).

Reference example 2
An antistatic coating agent was prepared in the same manner as in Example 2, except that the solution of component (A-1) was replaced with the solution of component (A-9).

Example 9
An antistatic coating agent was prepared in the same manner as in Example 2, except that TMMTAP was replaced with trimethylolpropane-tris (1-aziridinylpropionate) (TMPTAP; aziridinyl group amount 0.00705 mol / g). did.

Example 10
10.6 parts “ARUFON UC3000”, 4 parts TMMTAP, 23 parts PEDOT / PSS, 2 parts triethylamine, 57 parts ion-exchanged water, 50 parts isopropyl alcohol, and paratoluenesulfonic acid (PTS) 0.2 part was mixed well to prepare an antistatic coating agent.

Example 11
26.4 parts of the component (A-1) solution 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 isopropyl alcohol Was mixed well with 0.1 part of PTS to prepare an antistatic coating agent.

Example 12
An antistatic coating agent was prepared in the same manner as in Example 13, except that the solution of component (A-1) was replaced with the solution of component (A-2).

Example 13
An antistatic coating agent was prepared in the same manner as in Example 13 except that the solution of the component (A-1) was replaced with the solution of the component (A-3).

Example 14
An antistatic coating agent was prepared in the same manner as in Example 13, except that the solution of component (A-1) was replaced with the solution of component (A-4).

Example 15
An antistatic coating agent was prepared in the same manner as in Example 13, except that the solution of component (A-1) was replaced with the solution of component (A-5).

Example 16
An antistatic coating agent was prepared in the same manner as in Example 13, except that the solution of component (A-1) was replaced with the solution of component (A-6).

Example 17
An antistatic coating agent was prepared in the same manner as in Example 13, except that the solution of component (A-1) was replaced with the solution of component (A-7).

Reference example 3
An antistatic coating agent was prepared in the same manner as in Example 13 except that the solution of component (A-1) was replaced with the solution of component (A-8).

Reference example 4
An antistatic coating agent was prepared in the same manner as in Example 13 except that the solution of component (A-1) was replaced with the solution of component (A-9).

Example 18
26.4 parts of the solution of component (A-1) obtained in Production Example 1, 5 parts of TMMTAP, 11.5 parts of PEDOT / PSS, 0.4 parts of triethylamine, 24 parts of ion-exchanged water, isopropyl alcohol Was mixed well with 0.1 part of PTS to prepare an antistatic coating agent.

Example 19
An antistatic coating agent was prepared in the same manner as in Example 22 except that TMMTAP was changed to 0.15 part, ion-exchanged water to 15 parts, and isopropyl alcohol to 2 parts.

Example 20
An antistatic coating agent was prepared in the same manner as in Example 13, except that PEDOT / PSS was changed to polyaniline (product name “ORMECON D1031W”, manufactured by Nissan Chemical Industries, Ltd., aqueous solution having a solid content concentration of 2%). .

Example 21
An antistatic coating agent was prepared in the same manner as in Example 15 except that PEDOT / PSS was changed to polyaniline.

Reference example 5
An antistatic coating agent was prepared in the same manner as in Reference Example 3 except that PEDOT / PSS was changed to polyaniline.

Reference example 6
An antistatic coating agent was prepared in the same manner as in Reference Example 4 except that PEDOT / PSS was changed to polyaniline.

Comparative Example 1
An antistatic coating agent was prepared in the same manner as in Example 1 except that the component (B) was not used.

Comparative Example 2
An antistatic coating agent was prepared in the same manner as in Example 2 except that the component (B) was not used.

Comparative Example 3
An antistatic coating agent was prepared in the same manner as in Example 3 except that the component (B) was not used.

Comparative Example 4
An antistatic coating agent was prepared in the same manner as in Example 4 except that the component (B) was not used.

Comparative Example 5
An antistatic coating agent was prepared in the same manner as in Example 5 except that the component (B) was not used.

Comparative Example 6
An antistatic coating agent was prepared in the same manner as in Example 6 except that the component (B) was not used.

Comparative Example 7
An antistatic coating agent was prepared in the same manner as in Example 7 except that the component (B) was not used.

Comparative Example 8
An antistatic coating agent was prepared in the same manner as in Example 8 except that the component (B) was not used.

Comparative Example 9
An antistatic coating agent was prepared in the same manner as in Example 9 except that the component (B) was not used.

Comparative Example 10
An antistatic coating agent was prepared in the same manner as in Example 10 except that the component (B) was not used.

Comparative Example 11
A coating agent was prepared in the same manner as in Example 1 except that the component (C) was not used.

Comparative Example 12
A coating agent was prepared in the same manner as in Example 2 except that the component (C) was not used.

Comparative Example 13
A coating agent was prepared in the same manner as in Example 3 except that the component (C) was not used.

Comparative Example 14
A coating agent was prepared in the same manner as in Example 4 except that the component (C) was not used.

Comparative Example 15
A coating agent was prepared in the same manner as in Example 5 except that the component (C) was not used.

Comparative Example 16
A coating agent was prepared in the same manner as in Example 6 except that the component (C) was not used.

Comparative Example 17
A coating agent was prepared in the same manner as in Example 7 except that the component (C) was not used.

Comparative Example 18
A coating agent was prepared in the same manner as in Example 8 except that the component (C) was not used.

Comparative Example 19
A coating agent was prepared in the same manner as in Example 9 except that the component (C) was not used.

Comparative Example 20
A coating agent was prepared in the same manner as in Example 10 except that the component (C) was not used.

Comparative Example 21
An antistatic coating agent was prepared in the same manner as in Example 2, except that 10 parts of carbodiimide-based curing agent (product name “Carbodilite V-02”, manufactured by Nisshinbo Co., Ltd.) was used instead of 4 parts of TMMTAP.

Comparative Example 22
An antistatic coating agent was prepared in the same manner as in Example 2, except that 10 parts of an oxazoline-based curing agent (product name Epocross WS-500, manufactured by Nippon Shokubai Co., Ltd.) was used instead of 4 parts of TMMTAP.

Comparative Example 23
An antistatic coating agent was prepared in the same manner as in Example 2, except that an epoxy-based curing agent (product name “Epolite 40E”, manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of 4 parts of TMMTAP.

[Creation of test film]
Bar coater No. 10 was used to apply the coating agent of Example 1 onto a PET film, and the coated film was dried in a normal air dryer (140 ° C., 1 minute) to prepare a test film. In the same manner also coatings of Examples 2 to 2 1 and Reference Examples 1 to 6 and Comparative Examples 1 to 23, to prepare a test film.

[Measurement of surface resistivity]
The surface resistivity (Ω / □) for the coated surface of the test film according to Example 1 was measured using a resistivity measuring device (product name “ULTRA MEGOHMMETER SM-8210, SME-883”, manufactured by Toa Denpa Kogyo Co., Ltd.). It measured using. Moreover, it measured similarly about the film for a test concerning another Example and a comparative example. The smaller the surface resistance value, the better the antistatic performance. The results are shown in Tables 3 and 4.

[Solvent resistance test]
The coated surface of the test film according to Example 1 was rubbed with a cotton swab impregnated with acetone, and the solvent resistance of the coating film was evaluated by the number of times when the coating film disappeared. It means that it is excellent in the solvent resistance of a film, so that there are many times. Moreover, it evaluated similarly about the film for a test concerning another Example and a comparative example. The results are shown in Tables 3 and 4.

[Blocking resistance test]
Two test films according to Example 1 were prepared, and one coated surface and the other non-coated surface were overlapped and allowed to stand at 80 ° C. for 24 hours under a load of 4 kg / cm ² . Next, based on the ease of peeling when the film was peeled off, blocking resistance was evaluated according to the following criteria. In addition, when a numerical value is connected by "-" (for example, 4-5), it means that it is evaluation between each reference | standard. Moreover, it evaluated similarly about the film for a test concerning another Example and a comparative example. The results are shown in Tables 3 and 4.
5 ... I don't feel any resistance.
4 ... Little resistance is felt.
3 ... I feel a little resistance.
2 ... I feel a great resistance.
1 ... I feel a lot of resistance.

[PET film adhesion test]
After sticking the adhesive tape on the coated surface of the test film according to Example 1 and pressing it well, it was peeled off vigorously, and the amount of the remaining coating film was visually evaluated according to the following criteria. Moreover, it evaluated similarly about the film for a test concerning another Example and a comparative example. The results are shown in Tables 3 and 4.
○: 70% or more of the coating film remained.
Δ: 40% or more and less than 70% of the coating film remained.
X: The remaining coating film was less than 40%.

    In Table 3, x / y is a value obtained by dividing the number of moles (mol) of the carboxylate anion group in the component (A) by the number of moles (mol) of the aziridinyl group in the component (B) (hereinafter, The same).

Claims (14)

A copolymer obtained by reacting an α, β-unsaturated carboxylic acid (a1), a (meth) acrylic acid alkyl ester (a2), and, if necessary, an unsaturated monomer (a3) other than these is used as the third copolymer. An acrylic resin (A) having a carboxylate anion group amount (mol / g) of 0.0003 to 0.005, which is neutralized with a secondary amine and / or ammonia ;
Polyfunctional aziridine compound (B),
And a heteroatom-containing π-conjugated conductive polymer (C) comprising poly (aniline) and / or poly (thiophene) ,
And when x is the number of moles (mol) of the carboxylate anion group of the component (A) and y is the number of moles (mol) of the aziridinyl group of the component (B), x / y is 0.001 to 10 The component (A) and the component (B) are contained in an amount of
Antistatic coating agent. The antistatic coating agent according to claim 1 , wherein the component (a1) is methacrylic acid and / or acrylic acid. The antistatic coating agent according to claim 1 or 2 , wherein the component (a3) is (poly) siloxane mono (meth) acrylates and / or fluoroalkyl (mono) acrylates. (A) Antistatic coating agent in any one of Claims 1-3 whose glass transition temperature of a component is 20-150 degreeC. (A) The number average molecular weight of the component is 2,000 to 100,000, any of the antistatic coating agent according to claim 1-4. Component (B) is a trifunctional aziridine compound and / or tetrafunctional aziridine compounds, any of the antistatic coating agent according to claim 1-5. (C) Content of a component (solid content conversion) is 0.1-30 weight part with respect to a total of 100 weight part of (A) component and (B) component, In any one of Claims 1-6 Antistatic coating agent. Further comprising a curing catalyst (D), any of the antistatic coating agent according to claim 1-7. (D) Antistatic coating agent of Claim 8 whose component is para-toluenesulfonic acid. The antistatic coating agent of Claim 8 or 9 whose usage-amount of (D) component is 0-10 weight part with respect to a total of 100 weight part of (A) component (solid content conversion) and (B) component. The antistatic coating agent according to claim 9 or 10, wherein a tertiary amine is separately added when paratoluenesulfonic acid is used as the component (D). Furthermore, the antistatic coating agent in any one of Claims 1-11 containing C1-C4 alcohol and water as a dilution solvent. The antistatic coating agent of Claim 12 which uses a dilution solvent in the range used as solid content concentration of 0.1-30 weight part. Plastic film antistatic coating agent, which are coated as claimed in any one of claims 1 to 13.