JP5046478B2 - Antistatic agent for thermoplastic polymer, antistatic method for thermoplastic polymer molding, and antistatic thermoplastic polymer molding - Google Patents

Description

  The present invention relates to an antistatic agent for thermoplastic polymers, an antistatic method for thermoplastic polymer moldings, and an antistatic thermoplastic polymer molding. Various thermoplastic polymers are widely used as thermoplastic polymer moldings such as films, sheets, containers, and casings. However, it is known that such a thermoplastic polymer molded body may cause various electrostatic disturbances during its production and processing steps and during its use. In the production or processing of a thermoplastic polymer molded body, it is required to use an antistatic agent that can sufficiently prevent such electrostatic damage. On the other hand, in recent years, from the viewpoint of avoiding environmental pollution and at the same time reducing manufacturing and processing costs, recycle wastes and used thermoplastic polymer moldings produced in the manufacturing and processing steps of thermoplastic polymer moldings. However, for this purpose, it is required that the antistatic agent used in the production or processing of the thermoplastic polymer molded body as described above does not cause a problem in such reuse. . The present invention relates to an antistatic agent for thermoplastic polymers that meets the above requirements, an antistatic method for a thermoplastic polymer molding using the same, and an antistatic thermoplastic polymer molding using the same.

  Conventionally, a wide variety of ionic polymer compounds are generally used as antistatic agents for thermoplastic polymers. However, ionic polymer compounds that have been conventionally used as an antistatic agent for thermoplastic polymers are generally poor in heat resistance. As a result, the thermoplastic polymer molded article has a sufficiently durable charge. 2) When it is used in the production or processing of thermoplastic polymer moldings, it is colored when it is remelted to produce scraps or used thermoplastic polymer moldings. 3) There is a problem that the applicability to the thermoplastic polymer molding is inferior.

As an antistatic agent for thermoplastic polymers that improves the above problems, polycation polymers having a plurality of nitrogen atoms in the molecule have been proposed (see, for example, Patent Documents 1 to 4). However, although the polycation polymer conventionally proposed as an antistatic agent for thermoplastic polymers has a correspondingly improved heat resistance, it can impart an appropriate antistatic property to a thermoplastic polymer molded article. Reuse is restricted as described above 2) Applicability is inferior as above 3) Easy transfer from the coated surface of a thermoplastic polymer molding using the same 4) Using it When the thermoplastic polymer molded body is a film, a sheet or the like, they are likely to block each other, and when the thermoplastic polymer molded body using the thermoplastic polymer molded body is a container or a casing, they are tacky. There is a problem in some way, such as (stickiness).
JP-A-1-146931 JP-A-1-174538 JP-A-8-281891 JP-A-9-31224

  The problem to be solved by the present invention is that the thermoplastic polymer molding can be provided with sufficiently durable antistatic properties, and at the same time, reusability of the thermoplastic polymer molding, etc., to the thermoplastic polymer molding. High thermoplastic properties with desirable properties such as coating properties, non-transferability from thermoplastic polymer moldings, blocking resistance between thermoplastic polymer moldings and non-tacking properties of thermoplastic polymer moldings The object is to provide an antistatic agent for molecules, an antistatic method for a thermoplastic polymer molded article using the same, and an antistatic thermoplastic polymer molded article using the same.

  Therefore, as a result of researches to solve the above problems, the present inventor, as an antistatic agent for thermoplastic polymers, is a structural unit formed from a specific monomer having a quaternary ammonium base in the molecule. It has been found that it is preferable to use a vinyl copolymer having a predetermined number average molecular weight and having a predetermined ratio of a structural unit formed from a specific crosslinkable monomer.

  That is, the present invention relates to an antistatic agent for thermoplastic polymers, comprising one or more selected from the following vinyl copolymer M and the following vinyl copolymer N.

  Vinyl copolymer M: The structural unit A formed from 80 to 99 mol% of the monomer represented by the following chemical formula 1 in the molecule and the structural unit B formed from the following crosslinkable monomer 1 to 1 A vinyl copolymer having a number average molecular weight of 7000 to 100,000 having 20 mol% (100 mol% in total)

  Vinyl copolymer N: 80 to 98 mol% of the structural unit A formed from the monomer represented by the following chemical formula 1 in the molecule, 1 to 1 of the structural unit B formed from the following crosslinkable monomer 1 to 19 mol% (total 100) of 19 mol% and the structural unit C formed from the monomer represented by the following chemical formula 1 or the following other monomer copolymerizable with the following crosslinkable monomer: Mol%) vinyl copolymer having a number average molecular weight of 7000 to 100,000

Crosslinkable monomer: one selected from a crosslinkable monomer represented by the following chemical formula 2, a crosslinkable monomer represented by the following chemical formula 3 and a crosslinkable monomer represented by the following chemical formula 4 Two or more

In Chemical Formulas 1 to 4,
R ¹ , R ⁵ , R ⁷ , R ⁸ , R ⁹ : hydrogen atom or methyl group R ² , R ³ , R ⁴ : hydrogen atom, methyl group or hydroxyalkyl group having 2 or 3 carbon atoms in the alkyl group (provided that And at least two of R ^{2 to} R ⁴ are a methyl group or a hydroxyalkyl group having 2 or 3 carbon atoms in an alkyl group)
R ⁶ : hydrogen atom or alkyl group having 1 to 6 carbon atoms B: ethylene group or trimethylene group X ⁻ : nitrate ion group or methylsulfonate ion group Y ¹ : organic having 3 to 10 carbon atoms having hydrogen atom or epoxy group Group Y ² : an organic group having 3 to 10 carbon atoms having a hydrogen atom or an epoxy group

  Other monomers: ester of aliphatic alcohol having 1 to 4 carbon atoms and (meth) acrylic acid, N-alkyl (meth) acrylamide substituted with alkyl group having 1 to 4 carbon atoms, carbon number Selected from N, N-dialkyl (meth) acrylamides substituted with 1 to 4 alkyl groups and (di) esters of unsaturated dibasic acids having 4 or 5 carbon atoms and glycols having 2 to 8 carbon atoms One or more

The present invention is also characterized in that the above-mentioned antistatic agent for thermoplastic polymers according to the present invention is adhered in a ratio of 0.01 to 1 g per 1 m ² of the surface of the thermoplastic polymer molded body. The present invention relates to an antistatic method for a plastic polymer molded body.

Further, the present invention is characterized in that the above-mentioned antistatic agent for thermoplastic polymer according to the present invention is adhered in a ratio of 0.01 to 1 g per 1 m ² of the surface of the thermoplastic polymer molded body. The present invention relates to a preventive thermoplastic polymer molding.

  First, the antistatic agent for thermoplastic polymers according to the present invention (hereinafter simply referred to as the antistatic agent of the present invention) will be described. The vinyl copolymer used as the antistatic agent of the present invention includes a vinyl copolymer comprising a structural unit A formed from the monomer represented by Chemical Formula 1 and a structural unit B formed from a crosslinkable monomer. M, a structural unit A formed from a monomer represented by Chemical Formula 1, a structural unit B formed from a crosslinkable monomer, and a monomer or a crosslinkable monomer represented by Chemical Formula 1 can be copolymerized A vinyl copolymer N composed of a structural unit C formed from another monomer (hereinafter simply referred to as another monomer), one selected from the above vinyl copolymer M and vinyl copolymer N, or Two or more are included.

  In the vinyl copolymer M, the structural unit A is formed from a monomer represented by Chemical Formula 1. In the monomer represented by Chemical Formula 1, B in Chemical Formula 1 is an ethylene group or a trimethylene group.

In the monomer represented by Chemical Formula 1, R ^{1 in} Chemical Formula ¹ is a hydrogen atom or a methyl group, and R ² , R ³ , and R ⁴ in Chemical Formula 1 are carbon atoms of a hydrogen atom, a methyl group, or an alkyl group. It is a hydroxyalkyl group having 2 or 3 numbers, and at least two of R ^{2 to} R ⁴ are methyl groups or alkyl groups having 2 or 3 carbon atoms in the alkyl group. That is, when R ² is a hydrogen atom, R ³ and R ⁴ are a methyl group or a hydroxyalkyl group having 2 or 3 carbon atoms in the alkyl group. Similarly, when R ³ is a hydrogen atom, R ² and R ⁴ Is a hydroxyalkyl group having 2 or 3 carbon atoms in the methyl group or alkyl group. Similarly, when R ⁴ is a hydrogen atom, R ² and R ³ are those in which the methyl group or alkyl group has 2 or 3 carbon atoms. A hydroxyalkyl group;

In the monomer represented by the addition of 1, in Formula 1 X ^- is a nitrate group or a methyl sulfonate ion group, preferably a methyl sulfonate ion group.

  Specific examples of the monomer represented by Chemical Formula 1 described above include acryloyloxyethyltrimethylammonium methylsulfonate, acryloyloxypropyl 2-hydroxyethyldimethylammonium nitrate, acryloyloxypropyltrimethylammonium nitrate, and the like.

  In the vinyl copolymer M, the structural unit B is formed from a crosslinkable monomer. The crosslinkable monomer may be one or more selected from a crosslinkable monomer represented by Chemical Formula 2, a crosslinkable monomer represented by Chemical Formula 3, and a crosslinkable monomer represented by Chemical Formula 4. However, as the crosslinkable monomer, one represented by Chemical Formula 2 is preferable.

In the crosslinkable monomer represented by Chemical Formula 2, R ^{5 in} Chemical Formula 2 is a hydrogen atom or a methyl group, and R ^{6 in} Chemical Formula 2 is 1) a hydrogen atom, 2) a methyl group, an ethyl group, or a propyl group. , An isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group and the like, and R ⁶ is preferably a hydrogen atom or a methyl group.

  Specific examples of the crosslinkable monomer represented by Chemical Formula 2 described above include N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide, N- Tertiary butyloxymethyl acrylamide, N-hexyloxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl methacrylamide, N-butoxymethyl methacrylamide, N-tertiary butyloxymethyl methacrylamide, N-hexyloxymethyl Although methacrylamide etc. are mentioned, N-methylol acrylamide, N-methoxymethyl acrylamide, N-butoxymethyl acrylamide etc. are especially preferable.

In the crosslinkable monomer represented by Chemical Formula 3, R ⁷ and R ^{8 in} Chemical Formula 3 are a hydrogen atom or a methyl group, and Y ^{1 in} Chemical Formula 3 is 1) a hydrogen atom, or 2) a glycidyl group, 2, An organic group having 3 to 10 carbon atoms having an epoxy group such as a 3-epoxybutyl group, a 2,3-epoxy-2-methylpropyl group, and a 2- (3,4-epoxycyclohexyl) ethyl group, but a glycidyl group An organic group having 3 or 4 carbon atoms having an epoxy group such as 2,3-epoxybutyl group or 2,3-epoxy-2-methylpropyl group is preferable, and a glycidyl group is more preferable.

  Specific examples of the crosslinkable monomer represented by Chemical Formula 3 described above include acrylic acid, methacrylic acid, crotonic acid, glycidyl acrylate, glycidyl methacrylate, 2,3-epoxybutyl acrylate, 2,3-epoxybutyl methacrylate, 2,3-epoxy-2-methylpropyl acrylate, 2,3-epoxy-2-methylpropyl methacrylate, glycidyl crotonate and the like can be mentioned, among which acrylic acid and glycidyl methacrylate are preferable.

In the crosslinkable monomer represented by Chemical formula 4, R ^{9 in} Chemical formula 4 is a hydrogen atom or a methyl group, and Y ^{2 in} Chemical formula 4 is 1) a hydrogen atom, or 2) a glycidyl group, 2,3- An organic group having 3 to 10 carbon atoms having an epoxy group such as an epoxybutyl group, a 2,3-epoxy-2-methylpropyl group, and a 2- (3,4-epoxycyclohexyl) ethyl group. Among these, Y ² is preferably an organic group having 3 or 4 carbon atoms having an epoxy group, and more preferably a glycidyl group.

  Specific examples of the crosslinkable monomer represented by Chemical Formula 4 described above include allyl alcohol, allyl glycidyl ether, allyl = 2,3-epoxybutyl ether, allyl = 2,3-epoxybutyl ether, allyl = 2,3- Examples include epoxy-2-methylpropyl ether, methallyl glycidyl ether, methallyl = 2,3-epoxybutyl ether, methallyl = 2,3-epoxybutyl ether, methallyl = 2,3-epoxy-2-methylpropyl ether, Of these, allyl alcohol and allyl glycidyl ether are preferable.

  The vinyl copolymer M used as the antistatic agent of the present invention is obtained by radical copolymerization of the monomer represented by Chemical Formula 1 described above and a crosslinkable monomer. The radical copolymerization itself can be carried out by a known method, usually in an aqueous solution using water or a mixed solvent of water and a water-soluble organic solvent. For example, after dissolving a vinyl monomer represented by Chemical Formula 1 and a crosslinkable monomer in water and preparing an aqueous solution containing these monomers in a total amount of 10 to 45% by weight, Then, a radical initiator is added thereto, and a radical polymerization reaction is performed at 50 to 80 ° C. for 4 to 8 hours. The radical initiator to be used is not particularly limited as long as it decomposes at a polymerization reaction temperature and generates radicals, but a water-soluble radical initiator is preferably used. Examples of the water-soluble radical initiator include potassium persulfate, ammonium persulfate, hydrogen peroxide, 2,2-azobis (2-amidinopropane) dihydrochloride, and the like. These can also be used as a redox initiator in combination with a reducing substance such as sulfite or L-ascorbic acid, or an amine.

  The vinyl copolymer M is obtained by the radical copolymerization described above, but the structural unit A formed from the monomer represented by Chemical Formula 1 in the molecule is 80 to 99 mol%, preferably 88 to 98 mol%. And 1 to 20 mol%, preferably 2 to 12 mol% (100 mol% in total) of the structural unit B formed from the crosslinkable monomer. The number average molecular weight of the vinyl copolymer M is 7,000 to 100,000. When the number average molecular weight is less than 7000, the antistatic property imparted to the thermoplastic polymer molded article becomes insufficient. Conversely, when the number average molecular weight exceeds 100,000, the thermoplastic polymer molded article is uniformly coated. Becomes difficult.

  On the other hand, in the vinyl copolymer N, the structural unit A and the structural unit B are the same as those described above for the vinyl copolymer M. The structural unit C is formed from other monomers. Such other monomers include esters of aliphatic alcohols having 1 to 4 carbon atoms and (meth) acrylic acid, N-alkyl (meth) acrylamides substituted with alkyl groups having 1 to 4 carbon atoms, (Di) ester of N, N-dialkyl (meth) acrylamide substituted with alkyl group having 1 to 4 carbon atoms and unsaturated dibasic acid having 4 or 5 carbon atoms and glycol having 2 to 8 carbon atoms One or two or more selected from may be mentioned.

  The vinyl copolymer N is obtained by radical copolymerization of the monomer represented by Chemical Formula 1 described above, a crosslinkable monomer, and another monomer. Such radical copolymerization is the same as described above for the vinyl copolymer M.

  The vinyl copolymer N is composed of 80 to 98 mol%, preferably 86 to 96 mol%, of a structural unit A formed from a monomer represented by Chemical Formula 1 in the molecule, and a crosslinkable monomer. 1 to 19 mol% of unit B, preferably 2 to 12 mol%, and 1 to 19 mol%, preferably 2 to 12 mol% (total of 100 mol%) of structural unit C formed from other monomers Shall. The number average molecular weight of the vinyl copolymer N is 7,000 to 100,000. When the number average molecular weight is less than 7000, the antistatic property imparted to the thermoplastic polymer molded article becomes insufficient. Conversely, when the number average molecular weight exceeds 100,000, the thermoplastic polymer molded article is uniformly coated. Becomes difficult.

Next, the antistatic method for the thermoplastic polymer molded body according to the present invention (hereinafter simply referred to as the antistatic method of the present invention) will be described. The antistatic method of the present invention is a method in which the above-described antistatic agent of the present invention is adhered so as to have a ratio of 0.01 to 1 g per 1 m ² of the surface of the thermoplastic polymer molded body. Here, per 1 m ² of the surface means per 1 m ^{2 of} one surface or outer surface. Usually, when the thermoplastic polymer molding is a flat one such as a film or sheet, it is per 1 m ^{2 on} one surface, and the thermoplastic polymer molding is a three-dimensional one such as a container or housing. In some cases, this is per 1 m ² of the outer surface.

In the antistatic method of the present invention, the form of the antistatic agent of the present invention to be used is not particularly limited, but the antistatic agent of the present invention contains water as a main solvent, and if necessary, methyl alcohol, ethyl alcohol, isopropyl alcohol, An aqueous liquid is preferred using a solvent containing a lower alcohol such as butyl alcohol, ethylene glycol or diethylene glycol, a ketone such as acetone or methyl isobutyl ketone, or an ether such as butyl cellosolve, methyl cellosolve or tetrahydrofuran. Also when using this aqueous liquid, it adheres so that it may become a ratio of 0.01-1g as antistatic agent of this invention per 1 m < ² > of the surface of a thermoplastic polymer molded object. Adhesion is mainly related to the shape of the thermoplastic polymer molded body, known as roll coating, gravure coating, air knife coating, bar coating, kiss coating, spray coating, dip coating, etc. Can be applied.

In the antistatic method of the present invention, the antistatic agent of the present invention is applied to a thermoplastic polymer molded body, but as a result, it may be applied to a thermoplastic polymer molded body. For example, it may be applied to an unstretched film or a uniaxially stretched film made of a thermoplastic polymer material that is subjected to a stretching process and then commercialized, or a container made of a thermoplastic polymer material that has been commercialized. It may be applied to a case or a case. Even when applied to an unstretched film or a uniaxially stretched film made of a thermoplastic polymer material that is subsequently subjected to a stretching process to produce a product, the application amount of the antistatic agent of the present invention becomes a product after the stretching process. The ratio is 0.01 to 1 g per 1 m ^{2 of the} thermoplastic polymer film, that is, the thermoplastic polymer molded body. In application, a binder resin, a surfactant, an antioxidant, an ultraviolet absorber, a lubricant, a crosslinking agent, and the like can be used in combination as long as the effects of the present invention are not impaired.

  The antistatic method of the present invention can be applied to thermoplastic polymer moldings of various shapes produced from various thermoplastic polymer materials. Such thermoplastic polymer materials include: 1) polyester polymer materials such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, polyethylene naphthalate, 2) polycarbonate polymer materials, 3) polystyrene, acrylonitrile-styrene copolymer Polystyrene polymer materials such as polymers, acrylonitrile-butadiene-styrene copolymers (hereinafter simply referred to as ABS), 4) polyacrylic polymer materials such as polymethyl methacrylate (hereinafter simply referred to as PMMA), 5) polyvinyl chloride, Polyvinyl polymer materials such as polyvinyl acetate, 6) Polyolefin polymer materials such as polyethylene and polypropylene (hereinafter simply referred to as PP), 7) Nylon 6, Nylon 11, Nylon 12, Nylon 6, 6, Nylon 6 10, polyamide of 1,3-bis (aminomethyl) cyclohexane and aliphatic dicarboxylic acid, polyamide of aliphatic diamine and 1,4-cyclohexanedicarboxylic acid, poly-p-phenylene terephthalamide, poly-m-phenylene iso Examples thereof include polyamide polymer materials such as phthalamide, 8) polymer blends of two or more thermoplastic polymer materials selected from the above 1) to 7), and thermoplastic polymer materials such as polymer alloys. Among these, the antistatic agent of the present invention is one or more selected from polycarbonate polymer materials, polystyrene polymer materials, polyacrylic polymer materials, polyvinyl polymer materials, and polyolefin polymer materials. The effect is high when applied to a thermoplastic polymer molded body produced from the above thermoplastic polymer material. When applying the antistatic agent of the present invention, the thermoplastic polymer material as described above includes inorganic fillers such as titanium oxide, talc, aluminum oxide, calcium carbonate, and silicone, a crosslinked polystyrene resin, a crosslinked acrylic resin, a urea resin, Even if it contains organic fillers such as melamine resin and silicone resin, antioxidants, ultraviolet absorbers, fluorescent brighteners, lubricants, flame retardants, etc., there is no problem.

Finally, the antistatic thermoplastic polymer molded product according to the present invention (hereinafter simply referred to as the antistatic molded product of the present invention) will be described. The antistatic molded article of the present invention is formed by adhering the above-described antistatic agent of the present invention at a ratio of 0.01 to 1 g per 1 m ² of the surface of the thermoplastic polymer molded article. In the antistatic molded article of the present invention, a thermoplastic polymer molded article, the meaning per 1 m ^{2 of} the surface thereof, a thermoplastic polymer material used for producing the thermoplastic polymer molded article, and particularly preferred thermoplastic polymers. The materials and the like are the same as described above for the antistatic method of the present invention.

  According to the antistatic agent of the present invention, sufficient antistatic properties can be imparted to the thermoplastic polymer molded body, and at the same time, the reusability of the thermoplastic polymer molded body, etc., and the thermoplastic polymer molded body There are effects such as excellent coating properties, non-transferability from the thermoplastic polymer molding, blocking resistance between the thermoplastic polymer moldings, and non-tackiness of the thermoplastic polymer molding.

As embodiment of the antistatic agent of this invention, what consists of one or two or more chosen from the following vinyl copolymer MP and the following vinyl copolymer NP is mentioned.
Vinyl copolymer M-P: in the molecule, X in Chemical Formula 1 ^- is a nitrate group or a methyl sulfonate ion groups, monomer B is represented by Formula 1 when it is an ethylene group or a trimethylene group A vinyl having a number average molecular weight of 7000 to 100,000 having a structural unit of 80 to 99 mol% and a structural unit of 1 to 20 mol% (100 mol% in total) formed from a crosslinkable monomer represented by Chemical Formula 2 copolymer vinyl copolymer N-P: in the molecule, X in Chemical Formula 1 ^- is the nitrate ion group or a methyl sulfonate ion group, represented by Formula 1 where B is an ethylene group or a trimethylene group 80 to 98 mol% of the structural unit formed from the monomer, 1 to 19 mol% of the structural unit formed from the crosslinkable monomer represented by Chemical Formula 2 and the following other monomers were formed. 1-19 mol% of structural unit Vinyl copolymer having a number average molecular weight of 7000 to 100,000 having a total number of 100 mol%) Other monomer: ester of aliphatic alcohol having 1 to 4 carbon atoms and (meth) acrylic acid, having 1 to 4 carbon atoms N-alkyl (meth) acrylamide substituted with an alkyl group, N, N-dialkyl (meth) acrylamide substituted with an alkyl group having 1 to 4 carbon atoms, and an unsaturated dibasic acid having 4 or 5 carbon atoms; One or more selected from (di) esters with glycols having 2 to 8 carbon atoms

Further, as an embodiment of the antistatic method and antistatic molded article of the present invention, the antistatic agent of the present invention corresponding to the above embodiment is an aqueous liquid, and the aqueous liquid is made from the following thermoplastic polymer material. Examples of the antistatic agent of the present invention per 1 m ² of the surface of the produced thermoplastic polymer molded body include a method of adhering to a ratio of 0.01 to 1 g, and a method obtained by this method.
Thermoplastic polymer material: one or two selected from polyester polymer material, polycarbonate polymer material, polystyrene polymer material, polyacrylic polymer material, polyvinyl polymer material and polyolefin polymer material more than

  Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by weight” and “%” means “% by weight”.

Test Category 1 (Synthesis of vinyl copolymer as antistatic agent)
Example 1 {Synthesis of vinyl copolymer (M-1)}
340 g of water was charged into a reaction vessel, and the inside of the reaction vessel was purged with nitrogen to 80 ° C. with stirring. Then, 287.3 g (1.14 mol) of acryloyloxyethyldimethylammonium methylsulfonate, N-methylolacrylamide 12 A vinyl monomer aqueous solution composed of 0.7 g (0.13 mol) and 300 g of water and 30 g of 5% ammonium persulfate aqueous solution were dropped simultaneously over 2 hours to carry out radical polymerization reaction. Subsequently, 30 g of a 5% aqueous solution of ammonium persulfate was added over 1 hour, and then the radical polymerization reaction was continued for 6 hours while maintaining the reaction temperature at 80 ° C. to obtain a reaction product. As a result of purifying and analyzing a part of the reaction product, R ^{1 in} Chemical Formula ¹ is a hydrogen atom, R ² is a methyl, R ³ is a methyl group, R ⁴ is a methyl group, B is an ethylene group, and X ⁻ is a methyl sulfone. In the case where it is an acid ion group, the structural unit formed from the monomer (E-1) represented by Chemical Formula 1 is 90 mol%, R ^{5 in} Chemical Formula 2 is a hydrogen atom, and R ⁶ is a hydrogen atom. This was a vinyl copolymer (M-1) having a number average molecular weight of 30,000 having 10 mol% (total of 100 mol%) of a structural unit formed from the monomer (F-1) represented by Chemical Formula 2. This was designated as an antistatic agent (M-1) of the present invention.

Examples or Reference Examples 2 to 23 and Comparative Examples 1 to 6 {vinyl copolymers (M-2) to (M-11), (N-1) to (N-12) and (R-1) to Synthesis of (R-6)}
In the same manner as the vinyl copolymer (M-1) of Example 1, the vinyl copolymers (M-2) to (M-11) of Examples or Reference Examples 2 to 11, and the Examples or Reference Examples 12 to 23 vinyl copolymers (N-1) to (N-12) and vinyl copolymers (R-1) to (R-6) of Comparative Examples 1 to 6 were synthesized. These are the antistatic agents (M-2) to (M-11), (N-1) to (N-12) or comparative antistatic agents (R-1) to (R-) of the present invention or reference, respectively. 6). These contents including the vinyl copolymer (M-1) are summarized in Table 1.

In Table 1,
Percentage: Unit is mol%
Monomers (E-1) to (E-10): Monomers represented by Chemical Formula 1 whose contents are collectively shown in Table 2 below. Monomers (F-1) to (F-6): Monomers represented by Chemical Formula 2 whose contents are summarized in Table 3 Monomers (G-1) to (G-6): Monomers represented by Chemical Formula 3 whose contents are summarized in Table 4 below. Monomers (H-1) to (H-5): Monomers represented by chemical formula 4 whose contents are collectively shown in Table 5 below: K-1: butyl acrylate K-2: N-ethyl Acrylamide K-3: N, N-dimethylacrylamide K-4: Diethyl maleate K-5: Acrylamide K-6: Vinyl acetate K-7: Sodium styrene sulfonate K-8: Dipolyethylene glycol maleate (polyethylene glycol moiety) Average molecular weight of 200)

In Table 2,
L-1: 2-hydroxyethyl group L-2: 3-hydroxypropyl group B-1: ethylene group B-2: trimethylene group B-3: tetramethylene group B-4: hexamethylene group X-1: methylsulfone Acid ion group X-2: Ethylsulfonic acid ion group X-3: Nitrate ion group

In Table 4,
Y-1: Residue obtained by removing one hydroxyl group from polyoxyethylene diol having a polyoxyethylene group composed of three oxyethylene units in the molecule Y-2: Ten oxypropylene units in the molecule Residue obtained by removing one hydroxyl group from a polyoxypropylene diol having a polyoxypropylene group constituted

In Table 5,
Y-3: a residue obtained by removing one hydroxyl group from a polyoxyethylene diol having a polyoxyethylene group composed of two oxyethylene units in the molecule Y-4: five oxyethylene units in the molecule and Residue obtained by removing one hydroxyl group from a polyoxyethylene polyoxypropylene diol having a polyoxyethylene polyoxypropylene group composed of five oxypropylene units

Test Category 2 (Application of antistatic agent to polyethylene terephthalate film and its evaluation)
-Application of antistatic agent to polyethylene terephthalate film Polyethylene terephthalate having an intrinsic viscosity of 0.65 was melt extruded at 280 to 300 ° C and cooled with a cooling roll at 15 ° C to obtain an unstretched film. This unstretched film was uniaxially stretched 3.5 times in the longitudinal direction between a pair of 85 ° C. rolls having different peripheral speeds to obtain a uniaxially stretched film. Next, the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 is diluted with water to form a 5% aqueous liquid, and this 5% aqueous liquid is further stretched into a uniaxially stretched film to obtain a product. It was applied by kiss coating method so that a coating amount according to the surface 1 m ² per table 6 biaxially oriented film, and dried with hot air at 70 ° C., was uniaxially stretched coated polyester film. Finally, the uniaxially stretched coated polyester film was stretched 3.5 times in the transverse direction at 98 ° C. with a tenter and heat-set at 200 to 210 ° C. to obtain a biaxially stretched coated polyester film having a thickness of 100 μm as a product. . The following evaluation was performed about the obtained uniaxially stretched or biaxially stretched coated polyester film. The results are summarized in Table 6.

・ Evaluation of antistatic property Condition 1
The uniaxially stretched coated polyester film was conditioned at 20 ° C. under conditions of 50% relative humidity for 24 hours, and then surface resistivity (Ω) was measured under the same conditions using a surface resistance value measuring device (trade name, manufactured by Sicid Electric Co., Ltd.). It was measured using Megaresta HT-301) and evaluated according to the following criteria.
Evaluation criteria A: Surface specific resistance is less than 1 × 10 ¹⁰ Ω ○: Surface specific resistance is 1 × 10 ¹⁰ Ω or more and less than 1 × 10 ¹¹ Ω Δ: Surface specific resistance is 1 × 10 ¹¹ Ω or more and less than 1 × 10 ¹² Ω ×: Surface specific resistance is 1 × 10 ¹² Ω or more

Condition 2
The biaxially stretched coated polyester film was evaluated in the same manner as in Condition 1.

Condition 3
The biaxially stretched coated polyester film is conditioned at 20 ° C. under a relative humidity of 30% for 24 hours, and the surface specific resistance (Ω) is measured under the same conditions by using a surface resistance value measuring device (commercially available from Cishido Electric Co., Ltd.). No. Megaresta HT-301) was measured and evaluated according to the following criteria.
Evaluation criteria A: Surface specific resistance is less than 1 × 10 ¹¹ Ω ○: Surface specific resistance is 1 × 10 ¹¹ Ω or more and less than 1 × 10 ¹² Ω Δ: Surface specific resistance is 1 × 10 ¹² Ω or more and less than 1 × 10 ¹³ Ω ×: Surface specific resistance is 1 × 10 ¹³ Ω or more

Evaluation of reusability The above-mentioned biaxially stretched coated polyester film was pulverized and melted at about 300 ° C. with an extruder to form chips. A melt film was formed using this chip to produce a recycled film. Separately, a recycled film was produced using a biaxially stretched coated polyester film coated with only water as a blank. The reusability was evaluated according to the following criteria from the degree of coloring of both recycled films.
Evaluation criteria ◎: Equivalent to blank and almost uncolored ○: Slightly colored compared to blank, but no problem in reuse △: Clearly colored compared to blank , There are restrictions on reuse ×: Remarkably colored compared to blank, and cannot be reused

-Evaluation of applicability The surface of the biaxially stretched coated polyester film was observed with the naked eye and evaluated according to the following criteria.
Evaluation Criteria A: Uniform coating film without omission of coating O: Almost no coating omission but almost uniform coating film Δ: There is some coating omission, but almost uniform coating as a whole It is a film. X: There are many coating omissions and it is an uneven coating film

Evaluation of non-transferability A sample piece cut into a 20 cm × 20 cm square from the uniaxially stretched coated polyester film and a non-coated uniaxially stretched polyester film were stacked on the coating surface, and a load of 1 kg / m ² was applied evenly. After conditioning for 60 hours at 20 ° C. under a relative humidity of 50%, the surface resistivity (Ω) of the coating surface of the sample piece was measured under the same conditions by using a surface resistance measuring device (trade name Megaresta HT- manufactured by Sicid Electric Co., Ltd.). 301) and evaluated according to the following criteria.
Evaluation criteria A: Surface specific resistance is less than 1 × 10 ¹⁰ Ω ○: Surface specific resistance is 1 × 10 ¹⁰ Ω or more and less than 1 × 10 ¹¹ Ω Δ: Surface specific resistance is 1 × 10 ¹¹ Ω or more and less than 1 × 10 ¹² Ω ×: Surface specific resistance is 1 × 10 ¹² Ω or more

· A uniaxially stretched polyester film of a uniaxial oriented coating polyester film blocking resistance evaluation the not specimen and the coating process was cut into a square of 20 cm × 20 cm overlap with the coating surface, toward uniform load 1 kg / m ^2, After holding at 50 ° C. for 24 hours, the film was cut to a width of 10 mm, the peel strength between the sample piece and the uncoated film was measured, and the blocking resistance was evaluated according to the following criteria.
Evaluation criteria A: Peeling force less than 5 gf / 10 mm O: Peeling force 5 gf / 10 mm or more, less than 8 gf / 10 mm Δ: Peeling force 8 gf / 10 mm or more, less than 15 gf / 10 mm ×: Peeling force 15 gf / 10 mm or more

In Table 6,
Ratio:% by weight in antistatic agent (hereinafter the same)
Application amount: Adhesion amount (g) as an antistatic agent per 1 m ^{2 of a} biaxially stretched film as a product (hereinafter the same)
R-7: a polycation polymer having a number average molecular weight of 32,000 having m pyrrolidinium rings represented by the following chemical formula 5 in the molecule (the same applies hereinafter)
R-8: a polycation polymer having a number average molecular weight of 23,000 having n pyrrolidinium rings represented by the following chemical formula 6 in the molecule (hereinafter the same)

Test category 3 (Application of antistatic agent to polycarbonate sheet and its evaluation)
-Application of antistatic agent to polycarbonate sheet Polycarbonate is put into a twin screw extruder, melted and kneaded at 280 ° C, cast onto a 30 ° C cooling roll by the T-die method, and a polycarbonate sheet with a thickness of 1 mm is obtained. Produced. Next, the vinyl copolymer synthesized in Test Category 1 (antistatic agent) is diluted with water to form a 5% aqueous liquid, and this 5% aqueous liquid is shown in Table 7 per 1 m ² of the surface of the polycarbonate sheet. Was applied by a kiss coating method so as to be a coating amount of 1, and dried with hot air at 150 ° C. for 1 minute to obtain an antistatic treated polycarbonate sheet. The following evaluation was performed on this antistatic treated polycarbonate sheet. The results are summarized in Table 7.

・ Evaluation of antistatic property Condition 1
The antistatic polycarbonate sheet was conditioned at 20 ° C. under a relative humidity of 50% for 24 hours, and the surface specific resistance (Ω) was measured under the same conditions using a surface resistance value measuring device (manufactured by Cishido Electric Co., Ltd.). It measured using the brand name Megaresta HT-301) and evaluated on the following reference | standard.
Evaluation criteria A: Surface specific resistance is less than 1 × 10 ⁹ Ω ○: Surface specific resistance is 1 × 10 ⁹ Ω or more and less than 1 × 10 ¹⁰ Ω Δ: Surface specific resistance is 1 × 10 ¹⁰ Ω or more and less than 1 × 10 ¹¹ Ω ×: Surface resistivity is 1 × 10 ¹¹ Ω or more

Condition 2
The antistatic polycarbonate sheet was conditioned at 20 ° C. under a relative humidity of 40% for 24 hours, and the surface specific resistance (Ω) was measured under the same conditions by using a surface resistance measuring device (manufactured by Cishido Electric Co., Ltd.). It measured using the brand name Megaresta HT-301) and evaluated on the following reference | standard.
Evaluation criteria A: Surface specific resistance is less than 2 × 10 ⁹ Ω ○: Surface specific resistance is 2 × 10 ⁹ Ω or more and less than 2 × 10 ¹⁰ Ω Δ: Surface specific resistance is 2 × 10 ¹⁰ Ω or more and less than 2 × 10 ¹¹ Ω ×: Surface specific resistance is 2 × 10 ¹¹ Ω or more

Condition 3
The antistatic polycarbonate sheet was conditioned at 20 ° C. under a relative humidity of 30% for 24 hours, and the surface specific resistance (Ω) was measured under the same conditions using a surface resistance value measuring device (manufactured by Sicid Electric Co., Ltd.). It measured using the brand name Megaresta HT-301) and evaluated on the following reference | standard.
Evaluation criteria A: Surface specific resistance is less than 1 × 10 ¹⁰ Ω ○: Surface specific resistance is 1 × 10 ¹⁰ Ω or more and less than 1 × 10 ¹¹ Ω Δ: Surface specific resistance is 1 × 10 ¹¹ Ω or more and less than 1 × 10 ¹² Ω ×: Surface specific resistance is 1 × 10 ¹² Ω or more

Evaluation of reusability The above-mentioned antistatic-treated polycarbonate sheet was pulverized and melted at about 280 ° C. with an extruder to form chips. This chip was used to melt and form a recycled sheet. Separately, a recycled sheet was produced using a polycarbonate sheet coated with only water as a blank. The reusability was evaluated in the same manner as the reusability of Test Category 2 from the degree of coloring of both recycled sheets.

-Evaluation of applicability The surface of the above-mentioned polycarbonate sheet subjected to antistatic treatment was observed with the naked eye and evaluated in the same manner as the applicability of test category 2.

・ Evaluation of non-transferability A sample piece cut into a 20 cm × 20 cm square from the above-mentioned antistatic-treated polycarbonate sheet and an untreated polycarbonate sheet not subjected to antistatic treatment are stacked on the surface to which the antistatic agent is applied, and the load is applied. Applying 1kg / m ² evenly, adjusting the humidity for 20 hours at 20 ° C under the condition of 50% relative humidity, and then measuring the surface specific resistance (Ω) of the antistatic agent application surface of the sample piece under the same conditions It measured using the apparatus (Brand name Megaresta HT-301 by Sisid Electric Co., Ltd.), and evaluated according to the following criteria.
Evaluation criteria A: Surface specific resistance is less than 1 × 10 ⁹ Ω ○: Surface specific resistance is 1 × 10 ⁹ Ω or more and less than 1 × 10 ¹⁰ Ω Δ: Surface specific resistance is 1 × 10 ¹⁰ Ω or more and less than 1 × 10 ¹¹ Ω ×: Surface resistivity is 1 × 10 ¹¹ Ω or more

Evaluation of blocking resistance A sample piece cut into a 20 cm × 20 cm square from the above-mentioned antistatic-treated polycarbonate sheet and an untreated polycarbonate sheet not subjected to antistatic treatment were stacked on the coating surface, and the load was 1 kg / m ^2. After holding at 50 ° C. for 24 hours, the sheet is cut to a width of 10 mm, the peel strength between the sample piece and the untreated polycarbonate sheet not subjected to antistatic treatment is measured, and the blocking resistance is tested. Evaluation was made in the same manner as the blocking resistance of No. 2.

Test Category 4 (Application of antistatic agent to ABS sheet and its evaluation)
-Application of antistatic agent to ABS sheet ABS is put into a twin screw extruder, melt kneaded at 220 ° C, cast on a cooling roll at 30 ° C by T-die method, and a 1 mm thick ABS sheet is obtained. Produced. Next, the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 is diluted with water to form a 5% aqueous liquid. This 5% aqueous liquid is listed in Table 8 per 1 m ² of the surface of the ABS sheet. Was applied by a kiss coating method so as to be an application amount of 1, and dried with hot air of 150 ° C. for 1 minute to obtain an antistatic treated ABS sheet. The following evaluation was performed on the antistatic treated ABS sheet. The results are summarized in Table 8.

-Evaluation of antistatic property The antistatic property of the antistatic treated ABS sheet was evaluated in the same manner as the antistatic property of Test Category 3.

Evaluation of reusability The antistatic ABS sheet was crushed and melted at about 220 ° C. with an extruder to form a chip. This chip was used to melt and form a recycled ABS sheet. Separately, a recycled ABS sheet was produced using an ABS resin sheet coated only with water as a blank. The reusability was evaluated in the same manner as the reusability of Test Category 2 from the degree of coloring of both recycled ABS sheets.

-Evaluation of applicability The surface of the antistatic treated ABS sheet was observed with the naked eye and evaluated in the same manner as the applicability of test category 2.

-Evaluation of non-transferability The non-transferability of the antistatic treated ABS sheet was evaluated in the same manner as the non-transferability of Test Category 3.

-Evaluation of blocking resistance The blocking resistance of the antistatic treated ABS sheet was evaluated in the same manner as the blocking resistance of Test Category 3.

Test Category 5 (Application of antistatic agent to PMMA sheet and its evaluation)
-Application of antistatic agent to PMMA sheet PMMA is put into a twin screw extruder, melted and kneaded at 230 ° C, cast on a cooling roll at 30 ° C by the T-die method, and a 1 mm thick PMMA sheet is obtained. Produced. Next, the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 was diluted with water to form a 5% aqueous liquid, and this 5% aqueous liquid was listed in Table 9 per 1 m ² of the surface of the PMMA sheet. The PMMA sheet was coated by the kiss coating method so as to have a coating amount and dried with hot air at 150 ° C. for 1 minute to obtain an antistatic treatment PMMA sheet. The following evaluation was performed on this antistatic PMMA sheet. The results are summarized in Table 9.

Evaluation of antistatic property The antistatic property of the antistatic treated PMMA sheet was evaluated in the same manner as the antistatic property of Test Category 3.

Evaluation of reusability The antistatic PMMA sheet was crushed and melted at about 230 ° C. with an extruder to form a chip. Using this chip, melt film formation was performed to produce a recycled PMMA sheet. Separately, a regenerated PMMA sheet was produced using a PMMA sheet coated only with water as a blank. The reusability was evaluated in the same manner as the reusability of Test Category 2 from the degree of coloring of both recycled PMMA sheets.

-Evaluation of applicability The surface of the antistatic treated PMMA sheet was observed with the naked eye and evaluated in the same manner as the applicability of test category 2.

-Evaluation of non-transferability The non-transferability of the antistatic PMMA sheet was evaluated in the same manner as the non-transferability of Test Category 3.

-Evaluation of blocking resistance The blocking resistance of the antistatic PMMA sheet was evaluated in the same manner as the blocking resistance of Test Section 3.

Test Category 6 (Application of antistatic agent to polyvinyl chloride sheet and its evaluation)
Application of antistatic agent to polyvinyl chloride sheet After adding 40 parts of di-2-ethylhexyl phthalate as a plasticizer to a mixer per 100 parts of polyvinyl chloride, 2 parts of barium stearate and stearic acid as stabilizers 1 part of zinc was added and mixed. The mixture was melt-kneaded by a twin screw extruder to produce a polyvinyl chloride sheet having a thickness of 2 mm by the T-die method. Next, the vinyl copolymer synthesized in Test Category 1 (antistatic agent) was diluted with water to form a 5% aqueous liquid, and this 5% aqueous liquid was listed in Table 10 per 1 m ^{2 of the} polyvinyl chloride sheet. The coating amount was applied by a kiss coating method and dried with hot air at 100 ° C. for 1 minute to obtain an antistatic treated polyvinyl chloride sheet. The following evaluation was performed on this antistatic treated polyvinyl chloride sheet. The results are summarized in Table 10.

-Evaluation of antistatic property The antistatic property of the antistatic treated polyvinyl chloride sheet was evaluated in the same manner as the antistatic property of Test Category 3.

Evaluation of reusability The antistatic treated polyvinyl chloride sheet was pulverized and melted at about 180 ° C. with an extruder to form chips. Using this chip, a melt film was formed to produce a recycled polyvinyl chloride sheet. Separately, a recycled polyvinyl chloride sheet was produced using a polyvinyl chloride sheet coated only with water as a blank. The reusability was evaluated in the same manner as in Test Category 2 from the degree of coloring of both recycled polyvinyl chloride sheets.

-Evaluation of applicability The surface of the antistatic treated polyvinyl chloride sheet was observed with the naked eye and evaluated in the same manner as the applicability of test category 2.

-Evaluation of non-transferability The non-transferability of the antistatic treated polyvinyl chloride sheet was evaluated in the same manner as the non-transferability of Test Category 3.

-Evaluation of blocking resistance The blocking resistance of the antistatic treated polyvinyl chloride sheet was evaluated in the same manner as the blocking resistance of Test Section 3.

Test category 7 (Application of antistatic agent to PP sheet and its evaluation)
-Application of antistatic agent to PP sheet Polypropylene is put into a twin screw extruder, melted and kneaded at 250 ° C, cast onto a 30 ° C cooling roll by the T-die method, and a 1 mm thick PP sheet is obtained. Produced. Next, the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 was diluted with water to form a 5% aqueous liquid, and this 5% aqueous liquid was listed in Table 11 per 1 m ^{2 of the} PP sheet surface. It was applied by a kiss coating method so as to have a coating amount and dried with hot air at 100 ° C. for 1 minute to obtain an antistatic treated PP sheet. The following evaluation was performed on this antistatic treated PP sheet. The results are summarized in Table 11.

Evaluation of antistatic property The antistatic property of the antistatic treated PP sheet was evaluated in the same manner as the antistatic property of Test Category 3.

Evaluation of reusability The antistatic treated PP sheet was pulverized and melted at about 230 ° C. with an extruder to form a chip. This chip was used to melt and form a recycled PP sheet. Separately, a recycled PP sheet was produced using a PP sheet coated only with water as a blank. The reusability was evaluated in the same manner as the reusability in Test Category 2 from the degree of coloring of both recycled PP sheets.

-Evaluation of applicability The surface of the antistatic treated PP sheet was observed with the naked eye and evaluated in the same manner as the applicability of Test Category 2.

-Evaluation of non-transferability The non-transferability of the antistatic treated PP sheet was evaluated in the same manner as the non-transferability of Test Category 3.

-Evaluation of blocking resistance The blocking resistance of the antistatic treated PP sheet was evaluated in the same manner as the blocking resistance of Test Category 3.

Test Category 8 (Application of antistatic agent to polyethylene terephthalate molding and its evaluation)
-Application | coating of the antistatic agent to a polyethylene terephthalate molded object Polyethylene terephthalate was injection-molded at 290-300 degreeC, and produced the polyethylene terephthalate molded object of length 15cm x width 2cm x thickness 4mm. Next, a vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 was diluted with water to form a 5% aqueous liquid, and this 5% aqueous liquid is shown in Table 12 per 1 m ² of the surface of the polyethylene terephthalate molded body. It was applied by a spray method so as to have the stated application amount, and dried with hot air at 150 ° C. for 1 minute to obtain an antistatic-treated polyethylene terephthalate molded body. The following evaluation was performed on this antistatic-treated polyethylene terephthalate molded body. The results are summarized in Table 12.

・ Evaluation of antistatic property Condition 1
The above-mentioned antistatic-treated polyethylene terephthalate molded body was conditioned at 20 ° C. under a condition of 50% relative humidity for 24 hours, and then the surface resistivity (Ω) was measured under the same conditions using a surface resistance value measuring device (Cishid Electric) It was measured using a product name “Megaresta HT-301” manufactured by the same company, and was evaluated according to the same standard as the condition 1 of the antistatic property of Test Category 2.

Condition 2
The above-mentioned antistatic-treated polyethylene terephthalate molded body was conditioned at 20 ° C. under a relative humidity of 40% for 24 hours, and then the surface resistivity (Ω) was measured under the same conditions using a surface resistance value measuring device (Cishid Electric) It was measured using a product name “Megaresta HT-301” manufactured by the same company, and was evaluated according to the same standard as the condition 1 of the antistatic property of Test Category 2.

Condition 3
The above-mentioned antistatic-treated polyethylene terephthalate molded body was conditioned at 20 ° C. under a relative humidity of 30% for 24 hours, and then the surface resistivity (Ω) was measured under the same conditions by a surface resistance value measuring device (Cishid Electric) It was measured using a product name “Megaresta HT-301” manufactured by the same company, and evaluated according to the same standard as the condition 3 of the antistatic property of Test Category 2.

Evaluation of reusability The antistatic-treated polyethylene terephthalate molded body was pulverized and melted at about 300 ° C. with an extruder to form a chip. This chip was used to melt and form a recycled polyethylene terephthalate sheet. Separately, a recycled polyethylene terephthalate sheet was produced using a polyethylene terephthalate molded body coated only with water as a blank. The reusability was evaluated in the same manner as the reusability in Test Category 2 from the degree of coloring of both recycled polyethylene terephthalate sheets.

-Evaluation of applicability The surface of the antistatic-treated polyethylene terephthalate molded body was observed with the naked eye and evaluated according to the following criteria.
Evaluation criteria ◎: There is no cissing and it is a uniform coating film ○: There is very little cissing, but it is almost uniform coating film △: There is some cissing, but the coating film is almost uniform as a whole ×: There are many repellent and non-uniform coating films

Evaluation of non-transferability The antistatic-treated polyethylene terephthalate molded body and the untreated polyethylene terephthalate molded body not subjected to antistatic treatment are stacked on the surface to which the antistatic agent is applied, and a load of 1 kg / m ² is applied evenly. The surface resistivity of the surface coated with the antistatic agent of the polyethylene terephthalate molded body that was antistatic treated under the same conditions for 60 hours at 20 ° C and 50% relative humidity was measured. The measurement was performed using an apparatus (trade name Megaresta HT-301, manufactured by Sicid Electric Co., Ltd.), and the same evaluation as the non-transferability of Test Category 2 was performed.

-Evaluation of non-tack property The non-tack property of the antistatic-treated polyethylene terephthalate molding was evaluated according to the following criteria.
Evaluation criteria ◎: No stickiness and good surface ○: Slightly sticky, usable level △: Some stickiness, limited use ×: Clear stickiness, I can not use it

Test category 9 (Application of antistatic agent to polycarbonate molding and its evaluation)
-Application | coating of the antistatic agent to a polycarbonate molded object Polycarbonate was injection-molded at 290-300 degreeC, and produced the polycarbonate molded object of length 15cm x width 2cm x thickness 4mm. Next, the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 is diluted with water to form a 5% aqueous liquid. This 5% aqueous liquid is listed in Table 13 per 1 m ² of the surface of the polycarbonate molded body. Was applied by a spray method so as to be a coating amount of 1, and dried with hot air at 150 ° C. for 1 minute to obtain an antistatic-treated polycarbonate molded body. The following evaluation was performed on the polycarbonate molded body subjected to the antistatic treatment. The results are summarized in Table 13.

-Evaluation of antistatic property The antistatic property of the polycarbonate molded article subjected to the antistatic treatment was evaluated in the same manner as the antistatic property of the test section 8.

Evaluation of reusability The above-mentioned antistatic-treated polycarbonate molded body was pulverized and melted at about 280 ° C. with an extruder to form a chip. This chip was used to melt and form a recycled polycarbonate sheet. Separately, a recycled polycarbonate sheet was produced using a polycarbonate molded body coated only with water as a blank. The reusability was evaluated in the same manner as the reusability of Test Category 2 from the degree of coloring of both recycled polycarbonate sheets.

-Evaluation of applicability The surface of the polycarbonate molded body subjected to the antistatic treatment was observed with the naked eye and evaluated in the same manner as in Test Category 8.

-Evaluation of non-transferability The non-transferability of the antistatic treated polycarbonate molded article was evaluated in the same manner as the non-transferability of Test Category 8.

-Evaluation of non-tack property The non-tack property of the above-mentioned polycarbonate molded article subjected to antistatic treatment was evaluated in the same manner as the non-tack property of Test Category 8.

Test category 10 (Application of antistatic agent to ABS molded body and its evaluation)
Application of antistatic agent to ABS molded body ABS was injection molded at about 220 ° C. to prepare an ABS molded body of 15 cm long × 2 cm wide × 4 mm thick. Next, the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 was diluted with water to form a 5% aqueous liquid, and this 5% aqueous liquid was listed in Table 14 per 1 m ² of the surface of the ABS molded body. It was coated by a spray method so as to have a coating amount and dried with hot air at 100 ° C. for 1 minute to obtain an ABS molded body subjected to antistatic treatment. The antistatic-treated ABS molded body was evaluated as follows. The results are summarized in Table 14.

-Evaluation of antistatic property The antistatic property of the antistatic treated ABS molded body was evaluated in the same manner as the antistatic property of Test Category 8.

Evaluation of reusability The antistatic-treated ABS molded body was pulverized and melted at about 230 ° C. with an extruder to form a chip. This chip was used to melt and form a recycled ABS sheet. Separately, as a blank, a recycled ABS sheet was produced using an ABS molded body to which only water was applied. The reusability was evaluated in the same manner as the reusability of Test Category 2 from the degree of coloring of both recycled ABS sheets.

-Evaluation of applicability The surface of the antistatic treated ABS molded body was observed with the naked eye and evaluated in the same manner as in Test Category 8.

-Evaluation of non-transferability The non-transferability of the antistatic-treated ABS molded body was evaluated in the same manner as the non-transferability of Test Category 8.

-Evaluation of non-tack property The non-tack property of the anti-static-treated ABS molded body was evaluated in the same manner as the non-tack property of Test Category 8.

Claims (7)

An antistatic agent for a thermoplastic polymer, comprising one or more selected from the following vinyl copolymer M and the following vinyl copolymer N.
Vinyl copolymer M: The structural unit A formed from 80 to 99 mol% of the monomer represented by the following chemical formula 1 in the molecule and the structural unit B formed from the following crosslinkable monomer 1 to 1 Vinyl copolymer having a number average molecular weight of 7000 to 100,000 having 20 mol% (total of 100 mol%) Vinyl copolymer N: 80 to 80 of structural units A formed from monomers represented by the following chemical formula 1 in the molecule 98 mol%, 1 to 19 mol% of the structural unit B formed from the following crosslinkable monomer, and the monomer represented by the following chemical formula 1 or the following crosslinkable monomer can be copolymerized : Vinyl copolymer having a number average molecular weight of 7000 to 100,000 having 1 to 19 mol% (100 mol% in total) of structural units C formed from other monomers Crosslinkable monomer: Crosslink represented by the following chemical formula 2 Monomer, crosslinkable monomer represented by the following chemical formula 3 One or more selected from the crosslinkable monomer represented by the fine following Formula 4

{In Chemical Formulas 1 through 4,
R ¹ , R ⁵ , R ⁷ , R ⁸ , R ⁹ : hydrogen atom or methyl group R ² , R ³ , R ⁴ : hydrogen atom, methyl group or hydroxyalkyl group having 2 or 3 carbon atoms in the alkyl group (provided that And at least two of R ^{2 to} R ⁴ are a methyl group or a hydroxyalkyl group having 2 or 3 carbon atoms in an alkyl group)
R ^6: a hydrogen atom or an alkyl group having 1 to 6 carbon atoms B: an ethylene group or trimethylene group X ^-: nitrate group or a methyl sulfonate ion group Y ^1: 3 to 10 carbon atoms having hydrogen atoms Komata epoxy group Organic group Y ² : a hydrogen atom or an organic group having 3 to 10 carbon atoms having an epoxy group}
Other monomers: ester of aliphatic alcohol having 1 to 4 carbon atoms and (meth) acrylic acid, N-alkyl (meth) acrylamide substituted with alkyl group having 1 to 4 carbon atoms, carbon number Selected from N, N-dialkyl (meth) acrylamides substituted with 1 to 4 alkyl groups and (di) esters of unsaturated dibasic acids having 4 or 5 carbon atoms and glycols having 2 to 8 carbon atoms One or more The thermoplastic polymer antistatic agent according to claim 1 Symbol placement, thermoplastic polymer molding, characterized in that adhering to the ratio of the surface 1 m ² per 0.01 to 1 g of the thermoplastic polymer molded article Body antistatic method. The antistatic agent for thermoplastic polymers is an aqueous liquid, and the aqueous liquid is made of the following thermoplastic polymer material, and the antistatic agent for thermoplastic polymer per 1 m ² of the surface of a thermoplastic polymer molded body. The method for preventing static charge of a thermoplastic polymer molded article according to claim 2 , wherein the thermoplastic polymer molded article is adhered to a ratio of 0.01 to 1 g.
Thermoplastic polymer material: one or two selected from polyester polymer material, polycarbonate polymer material, polystyrene polymer material, polyacrylic polymer material, polyvinyl polymer material and polyolefin polymer material more than The method for preventing static charge of a thermoplastic polymer molded article according to claim 2 or 3 , wherein the thermoplastic polymer molded article is a thermoplastic polymer film or sheet. 1 Symbol placing thermoplastic polymer antistatic agent claims, thermoplastic polymer mold surface 1 m ² per 0.01 to 1 g antistatic thermoplastic, characterized by comprising attached in a proportion of Polymer molded body. The antistatic thermoplastic polymer molded article according to claim 5 , wherein the thermoplastic polymer molded article is produced from the following thermoplastic polymer material.
Thermoplastic polymer material: one or two selected from polyester polymer material, polycarbonate polymer material, polystyrene polymer material, polyacrylic polymer material, polyvinyl polymer material and polyolefin polymer material more than The antistatic thermoplastic polymer molded article according to claim 5 or 6 , wherein the thermoplastic polymer molded article is a thermoplastic polymer film or sheet.