Antistatic resin composition and molded body and film thereof

Abstract

To provide an antistatic resin composition which has sufficient antistatic properties having durability and provides a molded body having excellent transparency and to provide a molded body and a film thereof.SOLUTION: There is provided an antistatic resin composition which comprises 1 to 50 pts.mass of the following (X) component and 0.01 to 10.0 pts.mass of the following (Y) component based on 100 pts.mass of a modified polyethylene-based resin. Component (X): an antistatic agent containing one or more polymer compounds (E) obtained by reacting a diol (a1), a dicarboxylic acid (a2), a polyether (b) having hydroxyl groups at both ends and an epoxy compound (D) having two or more epoxy groups, wherein the polyether (b) having hydroxyl groups at both ends is a polyethylene glycol (b1) and a polytetramethylene glycol (b2) and the ratio of the polytetramethylene glycol (b2) is 10 to 80 mol% based on the total molar amount of the polyethylene glycol (b1) and the polytetramethylene glycol (b2). Component (Y): one or more selected from the group consisting of an alkali metal salt (F) and an ionic liquid (G).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an antistatic resin composition (hereinafter also simply referred to as "resin composition"), a molded article and a film thereof, and more particularly to an antistatic resin composition suitable for a molded article and a film having excellent, long-lasting antistatic properties, and a molded article and a film thereof. [Background technology]

[0002] Synthetic resins are an indispensable material in modern times because they are lightweight, easy to process, and have other excellent properties, such as the ability to design substrates according to the application. Furthermore, because synthetic resins have excellent electrical insulating properties, they are frequently used in components of electrical products. However, because synthetic resins have such high insulating properties, they are prone to becoming electrically charged due to friction, etc.

[0003] Electrostatically charged synthetic resins attract surrounding dust and dirt, causing problems such as marring the appearance of resin molded products. Furthermore, in electronic products, for example, in precision equipment such as computers, electrostatic charging can cause circuits to malfunction. Furthermore, problems arise from electric shock. Electric shocks to the human body from resins not only cause discomfort, but can also lead to explosions in areas where flammable gases or dust are present. Furthermore, in the synthetic resin films and packaging films used in the manufacturing process of electrical and electronic equipment and electrical and electronic components, static electricity can attract fine dust particles, causing electric shocks and causing malfunctions in the components and equipment, creating major problems.

[0004] Among synthetic resins, modified polyethylene resins such as ethylene-vinyl acetate copolymers have a lower melting point and higher flexibility than polyethylene, making them widely used in films and sealants. They are particularly used in dicing tapes used in the dicing process of semiconductor, electronic, and optical component manufacturing. These dicing tapes must be antistatic. Furthermore, they must be highly transparent when laser light is irradiated through the dicing tape film, such as for identifying characters through the tape or for laser dicing. Furthermore, modified polyethylene resins such as ethylene-vinyl acetate copolymers are used in containers for transporting and storing electronic components, and packaging materials for electrical and electronic components. These containers and packaging materials also require antistatic properties.

[0005] To solve these problems, synthetic resins have been conventionally treated to prevent static buildup. The most common antistatic treatment method is to add an antistatic agent to the synthetic resin. Such antistatic agents include coating-type agents that are applied to the surface of a resin molded product, and kneading-type agents that are added when the resin is processed and molded. However, coating-type antistatic agents have problems in that they are less durable and that a large amount of organic matter is applied to the surface, which can contaminate anything that comes into contact with the surface.

[0006] From this perspective, polymeric antistatic agents that are mainly kneaded into synthetic resins have been studied, and for example, Patent Document 1 proposes polyether ester amide for imparting antistatic properties to polyolefin resins. Also, Patent Document 2 proposes a block polymer having a structure in which polyolefin blocks and hydrophilic polymer blocks are repeatedly and alternately bonded. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 3-290464 [Patent Document 2] Japanese Patent Application Laid-Open No. 2001-278985 Summary of the Invention [Problem to be solved by the invention]

[0008] However, conventional polymer-type antistatic agents have not provided sufficient antistatic properties and their durability. Furthermore, when conventional polymer-type antistatic agents are used, there is a problem that sufficient transparency cannot be obtained. Therefore, there is currently a demand for resin compositions that have sufficient and durable antistatic properties and produce molded articles with excellent transparency. Therefore, an object of the present invention is to provide an antistatic resin composition which has sufficient long-lasting antistatic properties and produces molded articles with excellent transparency, and a molded article and film thereof. [Means for solving the problem]

[0009] As a result of extensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using, in a predetermined ratio, one or more antistatic polymeric compounds having a specific structure and one or more compounds selected from the group consisting of alkali metal salts and ionic liquids, and have thus completed the present invention.

[0010] That is, the antistatic resin composition of the present invention is an antistatic resin composition containing 1 to 50 parts by mass of the following component (X) and 0.01 to 10.0 parts by mass of the following component (Y) per 100 parts by mass of a modified polyethylene resin: Component (X): An antistatic agent containing one or more polymeric compounds (E) obtained by reacting a diol (a1), a dicarboxylic acid (a2), a polyether (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups, wherein the polyether (b) having hydroxyl groups at both ends is polyethylene glycol (b1) and polytetramethylene glycol (b2), and the proportion of polytetramethylene glycol (b2) is 10 to 80 mol % relative to the total number of moles of the polyethylene glycol (b1) and the polytetramethylene glycol (b2). Component (Y): one or more selected from the group consisting of alkali metal salts (F) and ionic liquids (G).

[0011] In the antistatic resin composition of the present invention, the polymer compound (E) is preferably obtained by reacting a polyester (a) obtained by reacting a diol (a1) with a dicarboxylic acid (a2), a polyether (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups.

[0012] In addition, in the antistatic resin composition of the present invention, it is preferable that the polymer compound (E) has a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the polyether (b), and has a structure in which the blocks are bonded via an ester bond or an ether bond formed by a reaction between a hydroxyl group or a carboxyl group at the end of the polyester (a), a hydroxyl group at the end of the polyether (b), and an epoxy group of the epoxy compound (D) or a hydroxyl group formed by a reaction of an epoxy group.

[0013] Furthermore, in the antistatic resin composition of the present invention, it is preferable that the polymer compound (E) has a structure in which the block polymer (C) having carboxyl groups at both ends and formed by repeatedly and alternately bonding the polyester block (A) and the polyether block (B) via ester bonds is bonded to the epoxy compound (D) via an ester bond.

[0014] In the antistatic resin composition of the present invention, the epoxy compound (D) of the polymer compound (E) is preferably polypropylene glycol diglycidyl ether. The molded article of the present invention is characterized by being obtained by molding the antistatic resin composition. The molded article of the present invention is preferably a film. The film of the present invention is preferably a substrate film for a dicing tape. The molded article of the present invention is also suitable as a packaging material for electronic parts. The molded article of the present invention is also suitable as a container for electronic parts. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide an antistatic resin composition having sufficient, long-lasting antistatic properties and excellent transparency when molded, and a molded article and film thereof. The molded article and film of the present invention have excellent, long-lasting antistatic properties and also excellent transparency. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, embodiments of the present invention will be described in detail. First, the antistatic resin composition of the present invention will be described. The resin composition of the present invention contains 1 to 50 parts by mass of the following component (X) and 0.01 to 10.0 parts by mass of the following component (Y) per 100 parts by mass of a modified polyethylene resin. Component (X): An antistatic agent containing one or more polymeric compounds (E) obtained by reacting a diol (a1), a dicarboxylic acid (a2), a polyether (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups, wherein the polyether (b) having hydroxyl groups at both ends is polyethylene glycol (b1) and polytetramethylene glycol (b2), and the proportion of polytetramethylene glycol (b2) is 10 to 80 mol % relative to the total number of moles of the polyethylene glycol (b1) and the polytetramethylene glycol (b2). Component (Y): one or more selected from the group consisting of alkali metal salts (F) and ionic liquids (G).

[0017] First, the modified polyethylene resin used in the present invention will be described. Examples of modified polyethylene resins include ethylene-vinyl acetate copolymer (EVA resin), ethylene-methacrylic acid copolymer (EMAA resin), ethylene-methyl methacrylate copolymer (EMMA resin), ethylene-acrylic acid copolymer (EAA resin), ethylene-ethyl acrylate copolymer (EEA resin), ethylene-methyl acrylate copolymer (EMA resin), and ionomer resins obtained by crosslinking these copolymers with metal ions such as zinc ions. Copolymers of two or more of these may also be used. Two or more of these modified polyethylene resins may also be used. The modified polyethylene resin may be a copolymer with a resin other than the modified polyethylene resin. The modified polyethylene resin may also be used in combination with a resin other than the modified polyethylene resin.

[0018] Next, the component (X) used in the present invention will be described. The component (X) of the present invention is an antistatic agent containing one or more polymeric compounds (E) obtained by reacting a diol (a1), a dicarboxylic acid (a2), a polyether (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups, wherein the polyether (b) having hydroxyl groups at both ends is polyethylene glycol (b1) and polytetramethylene glycol (b2), and the proportion of polytetramethylene glycol (b2) is 10 to 80 mol % based on the total number of moles of the polyethylene glycol (b1) and the polytetramethylene glycol (b2).

[0019] In terms of the antistatic property and its durability, and the transparency of the molded product, the polymer compound (E) related to this antistatic agent is preferably a polymer compound obtained by reacting a polyester (a) obtained by reacting a diol (a1) with a dicarboxylic acid (a2), a polyether (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups.

[0020] Furthermore, in terms of antistatic properties and their durability, and the transparency of molded articles, the polymer compound (E) preferably has a structure in which a polyester block (A) composed of a polyester (a) and a polyether block (B) composed of a polyether (b) having hydroxyl groups at both ends are bonded via an ester bond or an ether bond formed by the reaction of a hydroxyl or carboxyl group at the end of the polyester (a), a hydroxyl group at the end of the polyether (b), and an epoxy group of an epoxy compound (D) having two or more epoxy groups, or a hydroxyl group formed by the reaction of an epoxy group. Here, the hydroxyl group formed by the reaction of an epoxy group refers to a hydroxyl group formed by the ring-opening reaction of an epoxy group of the epoxy compound (D) with a hydroxyl or carboxyl group.

[0021] The polyester block (A) of the polymer compound (E) is composed of a polyester (a) obtained by reacting a diol (a1) with a dicarboxylic acid (a2). The polyester (a) can be obtained by esterifying the diol (a1) with the dicarboxylic acid (a2).

[0022] The diol (a1) used in the polymer compound (E) according to the present invention includes an aliphatic diol and an aromatic group-containing diol, and the diol (a1) may be a mixture of two or more kinds.

[0023] Examples of aliphatic diols include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3propanediol (3,3-dimethylolheptane), 3-methyl 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,2-, 1,3-, or 1,4-cyclohexanediol, cyclododecanediol, dimer diol, hydrogenated dimer diol, diethylene glycol, dipropylene glycol, triethylene glycol, etc. Among these aliphatic diols, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A are preferred in terms of antistatic properties and their durability, and transparency of molded articles, and 1,4-cyclohexanedimethanol is more preferred. It is preferable that the aliphatic diol has hydrophobic properties in terms of antistatic properties and their durability, and transparency of the molded product, and therefore, the use of hydrophilic polyethylene glycol is not preferable.

[0024] Examples of aromatic group-containing diols include bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, 1,4-bis(2-hydroxyethoxy)benzene, resorcinol, and polyhydroxyethyl adducts of mononuclear dihydric phenol compounds such as pyrocatechol. Among these diols having an aromatic group, ethylene oxide adducts of bisphenol A and 1,4-bis(β-hydroxyethoxy)benzene are preferred. It is preferable that the aromatic diol be hydrophobic in terms of antistatic properties and their durability, and transparency of molded articles. Among these diols, 1,4-cyclohexanedimethanol is particularly preferred in terms of antistatic properties and their durability, and transparency of the molded product.

[0025] The dicarboxylic acid (a2) used in the polymer compound (E) according to the present invention includes an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and the dicarboxylic acid (a2) may be a mixture of two or more kinds.

[0026] The aliphatic dicarboxylic acid used in the polymer compound (E) according to the present invention may be a derivative of an aliphatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.) The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more kinds. The aliphatic dicarboxylic acid preferably includes an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, such as oxalic acid, malonic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid, 3-methylglutaric acid, ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid (1,10-decanedicarboxylic acid), tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanediic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, 1,1-cyclohexanediacetic acid, dimer acid, maleic acid, and fumaric acid. Among these aliphatic dicarboxylic acids, dicarboxylic acids having 4 to 12 carbon atoms are more preferred, and adipic acid is even more preferred, from the viewpoints of antistatic properties and their durability, and transparency of molded articles.

[0027] The aromatic dicarboxylic acid used in the polymer compound (E) according to the present invention may be a derivative of the aromatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.) The aromatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

[0028] The aromatic dicarboxylic acid is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms, such as terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate, potassium 3-sulfoisophthalate, etc. Among these aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, and phthalic acid (including phthalic anhydride) are preferred, and phthalic acid (including phthalic anhydride) is more preferred, from the viewpoints of antistatic properties and their durability, and transparency of molded articles.

[0029] As the dicarboxylic acid (a2), it is preferable to use both an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid in combination, and it is particularly preferable to use adipic acid as the aliphatic dicarboxylic acid and phthalic acid (including phthalic anhydride) as the aromatic dicarboxylic acid in combination.

[0030] Next, the polyether (b) having hydroxyl groups at both ends and the polyether block (B) of the polymer compound (E) will be described. The polyether block (B) is composed of the polyether (b) having hydroxyl groups at both ends, and the polyether (b) having hydroxyl groups at both ends is polyethylene glycol (b1) and polytetramethylene glycol (b2), with the proportion of polytetramethylene glycol (b2) being 10 to 80 mol % relative to the total number of moles of the polyethylene glycol (b1) and polytetramethylene glycol (b2).

[0031] The number average molecular weight of the polyethylene glycol (b1) is calculated from the measured hydroxyl value, and from the viewpoints of antistatic property and its durability, and transparency of the molded product, it is preferably 400 to 8,000, more preferably 1,000 to 6,000, even more preferably 1,500 to 5,000, and still more preferably 1,800 to 4,000. The method for measuring the hydroxyl value and the method for calculating the number average molecular weight from the hydroxyl value are described below.

[0032] <Method of calculating number average molecular weight from hydroxyl value> The hydroxyl value was measured by the hydroxyl value measurement method described below, and the number average molecular weight (hereinafter also referred to as "Mn") was determined by the following formula. Number average molecular weight = (56110 x 2) / hydroxyl value

[0033] <Hydroxyl value measurement method> Reagent A (acetylating agent) (1) Triethyl phosphate 1560mL (2) Acetic anhydride 193 mL (3) Perchloric acid (60%) 16g The above reagents are mixed in the order of (1) → (2) → (3). Reagent B Pyridine and pure water are mixed in a volume ratio of 3:1. Reagent C Add 2 to 3 drops of phenolphthalein solution to 500 mL of isopropyl alcohol and neutralize with 1N KOH aqueous solution.

[0034] First, weigh 2 g of sample into a 200 mL Erlenmeyer flask, add 10 mL of xylene, and heat to dissolve. Add 15 mL of reagent A, add a stopper, and shake vigorously. Add 20 mL of reagent B, add a stopper, and shake vigorously. Add 50 mL of reagent C. Titrate with 1N KOH aqueous solution and calculate using the formula below. Hydroxyl value [mgKOH / g] = 56.11 × f × (TB) / S f: Factor of 1N-KOH solution B: Blank test titration volume [mL] T: Test titer [mL] S: Sample amount [g]

[0035] The number average molecular weight of the polytetramethylene glycol (b2) is calculated from the measured hydroxyl value, and from the viewpoints of antistatic properties and their durability, and transparency of the molded product, it is preferably 400 to 8,000, more preferably 1,000 to 6,000, even more preferably 1,500 to 5,000, and even more preferably 1,800 to 4,000.

[0036] The method for measuring the hydroxyl value of polytetramethylene glycol (b2) and the method for calculating the number average molecular weight from the hydroxyl value are the same as the method for measuring the hydroxyl value of polyethylene glycol (a1) and the method for calculating the number average molecular weight from the hydroxyl value.

[0037] The ratio of polyethylene glycol (b1) and polytetramethylene glycol (b2) in the polyether (b) having hydroxyl groups at both ends is 10 to 80 mol % of polytetramethylene glycol (b2) relative to the total number of moles of polyethylene glycol (b1) and polytetramethylene glycol (b2), and from the viewpoints of antistatic properties and their durability and transparency of molded articles, the ratio is preferably 15 to 70 mol %, more preferably 18 to 55 mol %, and even more preferably 20 to 50 mol %.

[0038] Next, the epoxy compound (D) having two or more epoxy groups that constitutes the polymer compound (E) will be described. The epoxy compound (D) used in the antistatic agent of the present invention is not particularly limited as long as it has two or more epoxy groups, and examples thereof include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(ortho-cresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis(ortho-cresol), tetrabromobisphenol, and the like. Polyglyceryl esters of polynuclear polyhydric phenol compounds such as phenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, and terpene phenols. ether compounds; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct, and dicyclopentadiene dimethanol; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic, or alicyclic polybasic acids, such as azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and endomethylenetetrahydrophthalic acid, and glycidyl methacrylate; epoxy compounds having a glycidylamino group, such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, and diglycidyl orthotoluidine;Examples of epoxy compounds include epoxidized cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers; heterocyclic compounds such as triglycidyl isocyanurate; and epoxidized soybean oil. These epoxy compounds may be internally crosslinked with a terminal isocyanate prepolymer or may be polymerized using a polyvalent active hydrogen compound (such as a polyphenol, polyamine, carbonyl group-containing compound, or polyphosphate ester). Two or more types of epoxy compounds (D) may be used.

[0039] From the viewpoints of antistatic properties and their durability, and the transparency of molded articles, the epoxy compound (D) is preferably polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, bisphenol F diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, or hexanediol diglycidyl ether, more preferably polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, bisphenol F diglycidyl ether, or hydrogenated bisphenol A diglycidyl ether, and even more preferably polypropylene glycol diglycidyl ether. From the viewpoints of antistatic properties and their durability, and the transparency of molded articles, the polypropylene glycol diglycidyl ether is particularly preferably polypropylene glycol diglycidyl ether represented by the following general formula (1):

[0040] [ka]

[0041] In general formula (1), n represents a number of 1 to 30. n is preferably 2 to 25, more preferably 3 to 15, from the viewpoints of antistatic properties and their durability, and transparency of molded articles. The number average molecular weight of the polypropylene glycol diglycidyl ether is preferably from 200 to 2,000, more preferably from 250 to 1,500, and even more preferably from 300 to 1,000, from the viewpoints of antistatic property and its durability, and transparency of the molded product.

[0042] As the polypropylene glycol diglycidyl ether, commercially available products on the market may be used, and examples of commercially available products include ADEKA GLYCIROL (registered trademark) ED-506 manufactured by ADEKA CORPORATION, and DENACOL (registered trademark) EX-920 and DENACOL (registered trademark) EX-931 manufactured by Nagase ChemteX Corporation.

[0043] The epoxy equivalent of the epoxy compound (D) is preferably from 70 to 2000, more preferably from 100 to 1000, particularly more preferably from 150 to 600, from the viewpoints of antistatic property and its durability, and transparency of the molded product.

[0044] In view of the antistatic properties and their durability, and the transparency of molded articles, the preferred polymer compound (E) of the present invention is one obtained by reacting a polyester (a) obtained by reacting a diol (a1) with a dicarboxylic acid (a2), with a polyether (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups. The polymer compound (E) has a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the polyether (b), and has a structure in which the hydroxyl or carboxyl groups at the ends of the polyester (a) are bonded via ester bonds or ether bonds formed by the reaction of the hydroxyl groups at the ends of the polyether (b) with the epoxy groups of an epoxy compound having two or more epoxy groups, or with hydroxyl groups formed by the reaction of these epoxy groups. Furthermore, from the viewpoints of antistatic properties and their durability, and transparency of molded articles, the polymer compound (E) preferably has a structure in which a block polymer (C) having carboxyl groups at both ends, which is formed by repeatedly and alternately bonding polyester blocks (A) composed of polyester (a) and polyether blocks (B) composed of polyether (b) via ester bonds, is bonded to an epoxy compound (D) via an ester bond formed between the carboxyl group of the block polymer (C) and the epoxy group of the epoxy compound (D).Furthermore, it is also preferable that the polymer compound (E) has a structure in which a hydroxyl group formed by ring-opening of the epoxy group in a reaction with the carboxyl group is bonded to the block polymer (C) via an ester bond formed by a reaction with the carboxyl group.

[0045] The polyester (a) constituting the block of the polyester (A) according to the present invention may be composed of a diol (a1) and a dicarboxylic acid (a2), and from the viewpoints of antistatic properties and their durability and the transparency of molded articles, preferably has a structure in which the residue obtained by removing the hydroxyl group from the diol (a1) and the residue obtained by removing the carboxyl group from the dicarboxylic acid (a2) are bonded via an ester bond. From the viewpoints of antistatic properties and their durability and the transparency of molded articles, the polyester (a) constituting the block (A) of the polyester according to the present invention is more preferably composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, and from the viewpoints of antistatic properties and their durability and the transparency of molded articles, preferably has a structure in which the residue obtained by removing the hydroxyl group from the diol and the residue obtained by removing the carboxyl group from the aliphatic dicarboxylic acid are bonded via an ester bond, and the residue obtained by removing the hydroxyl group from the diol and the residue obtained by removing the carboxyl group from the aromatic dicarboxylic acid are bonded via an ester bond.

[0046] In addition, the polyester (a) preferably has a structure having carboxyl groups at both ends from the viewpoints of antistatic property and its durability, and transparency of the molded product. Furthermore, the degree of polymerization of the polyester (a) is preferably in the range of 2 to 50 from the viewpoints of antistatic property and its durability, and transparency of the molded product.

[0047] The polyester (a) having carboxyl groups at both ends can be obtained, for example, by esterifying the diol (a1) with the dicarboxylic acid (a2) (preferably an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid).

[0048] The aliphatic dicarboxylic acid may be a derivative of an aliphatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.), and when a derivative is used to obtain polyester (a), both ends may be finally treated to form carboxyl groups, and the polyester may be directly subjected to the next reaction to obtain block polymer (C) having a structure having carboxyl groups at both ends. Furthermore, the aliphatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

[0049] The aromatic dicarboxylic acid may be a derivative of an aromatic dicarboxylic acid (e.g., an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.), and when a polyester is obtained using a derivative, both ends may be finally treated to form carboxyl groups, and the polyester may proceed directly to the next reaction for obtaining a block polymer (C) having a structure with carboxyl groups at both ends. The aromatic dicarboxylic acid and its derivative may also be a mixture of two or more kinds.

[0050] When an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid are used, the molar ratio of the residue of the aliphatic dicarboxylic acid excluding the carboxyl group to the residue of the aromatic dicarboxylic acid excluding the carboxyl group in the polyester (a) is preferably 90:10 to 99.9:0.1, more preferably 93:7 to 99.9:0.1, from the viewpoints of antistatic property and its durability, and transparency of the molded product.

[0051] The polyester (a) having carboxyl groups at both ends can be obtained, for example, by esterifying the above-mentioned dicarboxylic acid or its derivative (preferably the above-mentioned aliphatic dicarboxylic acid or its derivative, and the above-mentioned aromatic dicarboxylic acid or its derivative) with the above-mentioned diol.

[0052] Regarding the reaction ratio of dicarboxylic acid or derivative thereof (preferably, aliphatic dicarboxylic acid or derivative thereof, and aromatic dicarboxylic acid or derivative thereof) to diol, it is preferable to use an excess of dicarboxylic acid or derivative thereof (preferably, aliphatic dicarboxylic acid or derivative thereof, and aromatic dicarboxylic acid or derivative thereof) so that both ends have carboxyl groups, and it is preferable to use it in a molar excess of 1 mole relative to the diol.

[0053] The molar ratio of the aliphatic dicarboxylic acid or its derivative to the aromatic dicarboxylic acid or its derivative during the esterification reaction is preferably 90:10 to 99.9:0.1, more preferably 93:7 to 99.9:0.1.

[0054] Depending on the blending ratio and reaction conditions, a polyester composed only of a diol and an aliphatic dicarboxylic acid or a polyester composed only of a diol and an aromatic dicarboxylic acid may be produced. In the present invention, however, such a polyester may be mixed into the polyester (a), and the polyester may be reacted with the compound (b) as is to obtain the block polymer (C).

[0055] The esterification reaction may be carried out in the presence of a catalyst for accelerating the reaction. Examples of the catalyst that can be used include conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate.

[0056] Furthermore, when a derivative of a dicarboxylic acid (preferably an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid), such as a carboxylic acid ester, a carboxylic acid metal salt, or a carboxylic acid halide, is used instead of the dicarboxylic acid, the dicarboxylic acid may be reacted with a diol and then treated at both ends to form a dicarboxylic acid, or the resulting product may be directly subjected to the next reaction for obtaining a block polymer (C) having a structure having carboxyl groups at both ends.

[0057] A suitable polyester (a) consisting of a diol and a dicarboxylic acid (preferably an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid) and having carboxyl groups at both ends may be any polyester that can form an ester bond by reacting with a polyether (b) to form a block polymer (C) structure, and the carboxyl groups at both ends may be protected, modified, or in the form of a precursor. An antioxidant such as a phenolic antioxidant may be added to the reaction system to suppress oxidation of the product during the reaction.

[0058] The polyether (b) having hydroxyl groups at both ends preferably reacts with the polyester (a) to form an ester bond or an ether bond, preferably an ester bond, to form the structure of the block polymer (C), and the hydroxyl groups at both ends may be protected or modified, or may be in the form of a precursor.

[0059] The block polymer (C) having a structure having carboxyl groups at both ends of the polymer compound (E) according to the present invention has a structure in which a block (A) composed of the polyester (a) and a block (B) composed of the polyether (b) are repeatedly and alternately bonded via ester bonds formed between carboxyl groups and hydroxyl groups. An example of such a block polymer (C) is one having a structure represented by the following general formula (2):

[0060] [ka]

[0061] In general formula (2), (A) represents a block composed of the polyester (a) having carboxyl groups at both ends, (B) represents a block composed of the polyether (b) having hydroxyl groups at both ends, and t represents the number of repeating units, which is preferably a number from 1 to 10 from the viewpoints of antistatic properties and their durability, and transparency of molded articles. t is more preferably a number from 1 to 7, and most preferably a number from 1 to 5. The block polymer (C) having a structure with carboxyl groups at both ends can be obtained by polycondensation reaction of a polyester (a) having carboxyl groups at both ends and a polyether (b) having hydroxyl groups at both ends. However, it is not necessarily required to synthesize the block polymer (C) from the polyester (a) and the polyether (b) as long as the block polymer (C) has a structure equivalent to a structure in which the polyester (a) and the polyether (b) are repeatedly and alternately bonded via ester bonds formed by carboxyl groups and hydroxyl groups.

[0062] The reaction ratio of the polyester (a) to the polyether (b) is adjusted so that X moles of the polyether (b) and X+1 moles of the polyester (a) are used, whereby a block polymer (C) having carboxyl groups at both ends can be preferably obtained.

[0063] In the reaction, after completion of the synthesis reaction of the polyester (a), the polyester (a) may be added to the reaction system and reacted as is without isolating the polyester (a).

[0064] A catalyst for promoting the esterification reaction may be used in the polycondensation reaction, and examples of the catalyst that can be used include conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, zinc acetate, etc. Furthermore, in order to suppress oxidation of the product during the reaction, an antioxidant such as a phenolic antioxidant may be added to the reaction system.

[0065] From the viewpoints of antistatic properties and their durability, and the transparency of molded articles, the polymer compound (E) according to the present invention preferably has a structure in which a block polymer (C) having a structure with carboxyl groups at both ends and an epoxy compound (D) having two or more epoxy groups are bonded via an ester bond. The ester bond may be either an ester bond formed by the reaction of the terminal carboxyl group of the block polymer (C) with the epoxy group of the epoxy compound (D), or an ester bond formed by the reaction of a hydroxyl group formed by this reaction (the reaction of a carboxyl group with an epoxy group) with a carboxyl group. The presence of both ester bonds is preferred from the viewpoints of antistatic properties and their durability, and the transparency of molded articles.

[0066] Furthermore, the polymer compound (E) may further contain an ester bond formed between a carboxyl group of the polyester (a) and an epoxy group of the epoxy compound (D).

[0067] Furthermore, the polymer compound (E) may contain an ester bond formed by a carboxyl group of the polyester (a) and a hydroxyl group formed by reaction of an epoxy group of the epoxy compound.

[0068] Furthermore, the polymer compound (E) may further contain an ether bond formed by a hydroxyl group of the polyester (a) or a hydroxyl group of the polyether (b) and an epoxy group of the epoxy compound (D).

[0069] To obtain a preferred polymer compound (E), the block polymer (C) and the epoxy compound (D) may be reacted. That is, the carboxyl groups of the block polymer (C) may be reacted with the epoxy groups of the epoxy compound (D). More preferably, the hydroxyl groups formed from the reacted epoxy groups may be reacted with the carboxyl groups. The number of epoxy groups in the epoxy compound (D) is preferably 0.5 to 5 equivalents, more preferably 0.5 to 1.5 equivalents, of the number of carboxyl groups in the block polymer (C) to be reacted. The reaction may be carried out in various solvents or in a molten state.

[0070] The amount of the epoxy compound (D) having two or more epoxy groups to be reacted is preferably 0.1 to 2.0 equivalents, more preferably 0.2 to 1.5 equivalents, relative to the number of carboxyl groups in the block polymer (C) to be reacted.

[0071] In the reaction, after completion of the synthesis reaction of the block polymer (C), the epoxy compound (D) may be added to the reaction system and reacted as is without isolating the block polymer (C). In this case, carboxyl groups of the unreacted polyester (a) used in excess when synthesizing the block polymer (C) may react with some of the epoxy groups of the epoxy compound (D) to form ester bonds.

[0072] A preferred polymer compound (E) according to the present invention does not necessarily have to be synthesized from the block polymer (C) and the epoxy compound (D) as long as it has a structure equivalent to that in which a block polymer (C) having a structure with carboxyl groups at both ends and an epoxy compound (D) having two or more epoxy groups are bonded via ester bonds formed between the respective carboxyl groups and the epoxy groups. The ester bond formed between a carboxyl group and an epoxy group here also includes an ester bond formed between a carboxyl group and a hydroxyl group formed from the epoxy group by reacting with the carboxyl group.

[0073] Furthermore, the polymer compound (E) according to the present invention may be prepared by obtaining polyester (a) from diol (a1) and dicarboxylic acid (a2), and then reacting the polyester (a) with polyether (b) and / or epoxy compound (D) without isolating the polyester (a).

[0074] In the polymer compound (E) of the present invention, the number average molecular weight of the polyester (a) constituting the block (A) composed of the polyester (a) is preferably 1,000 to 10,000, more preferably 1,500 to 8,000, and even more preferably 2,500 to 7,500, in terms of polystyrene, from the viewpoints of antistatic property and its durability, and transparency of the molded product. If the number average molecular weight is less than 1,000, storage stability may be poor, while if it exceeds 10,000, the reaction to obtain the polymer compound (E) may take a long time, which may be economical, or the obtained polymer compound may become discolored due to the long reaction time.

[0075] The method for measuring the number average molecular weight in terms of polystyrene is preferably gel permeation chromatography (GPC), and the measurement method is shown below. <Method for measuring number average molecular weight in polystyrene equivalent> The number average molecular weight (hereinafter also referred to as "Mn") was measured by gel permeation chromatography (GPC) under the following conditions: Equipment: GPC equipment manufactured by JASCO Corporation Solvent: Chloroform Reference material: Polystyrene Detector: Differential refractometer (RI detector) Column stationary phase: Showa Denko Shodex LF-804 Column temperature: 40℃ Sample concentration: 1mg / 1mL Flow rate: 0.8mL / min. Injection volume: 100μL

[0076] Furthermore, in the polymer compound (E), the block polymer (C) having a structure with carboxyl groups at both ends preferably has a number-average molecular weight of 5,000 to 50,000, more preferably 10,000 to 45,000, in terms of polystyrene equivalent, from the viewpoints of antistatic properties and their durability, and transparency of molded articles. If the number-average molecular weight is less than 5,000, storage stability may be poor, while if it exceeds 50,000, the reaction to obtain the polymer compound (E) may take a long time, which may be uneconomical, or the resulting polymer compound may become discolored due to the long reaction time. The method for measuring the number-average molecular weight in terms of polystyrene equivalent is preferably gel permeation chromatography (GPC), and the measurement method is as described above.

[0077] In the antistatic resin composition of the present invention, the content of the component (X) is 1 to 50 parts by mass relative to 100 parts by mass of the modified polyethylene resin. From the viewpoints of antistatic properties and their durability, and transparency of the molded product, the content is preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass.

[0078] Next, the component (Y) of the present invention will be described. The component (Y) of the present invention is at least one selected from the group consisting of an alkali metal salt (F) and an ionic liquid (G).

[0079] The alkali metal salt (F) will be described below. Examples of the alkali metal salt (F) include salts of organic or inorganic acids. Examples of alkali metals include lithium, sodium, potassium, cesium, and rubidium. Examples of organic acids include aliphatic monocarboxylic acids having 1 to 18 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; aliphatic dicarboxylic acids having 1 to 12 carbon atoms, such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, and adipic acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; and sulfonic acids having 1 to 20 carbon atoms, such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethanesulfonic acid. Examples of inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, and perchloric acid. Among these, in terms of antistatic properties and their durability, transparency of the molded article, and safety to living organisms and the environment, lithium, sodium, and potassium salts are preferred, and sodium is more preferred. Furthermore, in terms of antistatic properties and their durability, and transparency of the molded article, acetic acid salts, perchloric acid salts, p-toluenesulfonic acid salts, and dodecylbenzenesulfonic acid salts are preferred, and dodecylbenzenesulfonic acid salts are more preferred. Two or more types of alkali metal salts may be used.

[0080] Specific examples of the alkali metal salt (F) include lithium acetate, sodium acetate, potassium acetate, lithium chloride, sodium chloride, potassium chloride, lithium phosphate, sodium phosphate, potassium phosphate, lithium sulfate, sodium sulfate, lithium perchlorate, sodium perchlorate, potassium perchlorate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, etc. Among these, in terms of antistatic properties and their sustainability, transparency of molded articles, and safety to living bodies and the environment, preferred are lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, etc., and most preferred is sodium dodecylbenzenesulfonate.

[0081] Next, the ionic liquid (G) will be described. Examples of ionic liquids include room-temperature molten salts having a melting point of 100°C or less, at least one of the cations or anions constituting the ionic liquid being an organic ion, and an initial conductivity of 1 to 200 ms / cm, preferably 10 to 200 ms / cm, such as those described in WO 95 / 15572.

[0082] Examples of cations constituting the ionic liquid include cations selected from the group consisting of amidinium, pyridinium, pyrazolium, and guanidinium cations. Among these, examples of amidinium cations include the following: (1) Imidazolinium cation Examples include those having 5 to 15 carbon atoms, such as 1,2,3,4-tetramethylimidazolinium and 1,3-dimethylimidazolinium; (2) Imidazolium cation Examples include those having 5 to 15 carbon atoms, such as 1,3-dimethylimidazolium and 1-ethyl-3-methylimidazolium; (3) Tetrahydropyrimidinium cation Examples include those having 6 to 15 carbon atoms, such as 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium and 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium; (4) Dihydropyrimidinium cation Examples include those having 6 to 20 carbon atoms, such as 1,3-dimethyl-1,4-dihydropyrimidinium, 1,3-dimethyl-1,6-dihydropyrimidinium, 8-methyl-1,8-diazabicyclo[5,4,0]-7,9-undecadienium, and 8-methyl-1,8-diazabicyclo[5,4,0]-7,10-undecadienium. Examples of the pyridinium cation include those having 6 to 20 carbon atoms, such as 3-methyl-1-propylpyridinium and 1-butyl-3,4-dimethylpyridinium. Examples of the pyrazolium cation include those having 5 to 15 carbon atoms, such as 1,2-dimethylpyrazolium and 1-n-butyl-2-methylpyrazolium.

[0083] Examples of guanidinium cations include the following: (1) Guanidinium cation with an imidazolinium skeleton Examples include those having 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolinium and 2-diethylamino-1,3,4-trimethylimidazolinium; (2) Guanidinium cation with an imidazolium skeleton Examples include those having 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolium and 2-diethylamino-1,3,4-trimethylimidazolium; (3) Guanidinium cation with a tetrahydropyrimidinium skeleton Examples include those having 10 to 20 carbon atoms, such as 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium and 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium; (4) Guanidinium cation with a dihydropyrimidinium skeleton Examples include those having 10 to 20 carbon atoms, such as 2-dimethylamino-1,3,4-trimethyl-1,4-dihydropyrimidinium, 2-dimethylamino-1,3,4-trimethyl-1,6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4-dihydropyrimidinium, and 2-diethylamino-1,3-dimethyl-4-ethyl-1,6-dihydropyrimidinium.

[0084] The above cations may be used alone or in combination of two or more. Among these, from the viewpoints of antistatic properties and their durability, and transparency of molded articles, the amidinium cation is preferred, the imidazolium cation is more preferred, and the 1-ethyl-3-methylimidazolium cation is particularly preferred.

[0085] In ionic liquids, examples of organic or inorganic acids that constitute the anions include the following. Examples of organic acids include carboxylic acids, sulfates, sulfonic acids, and phosphates; examples of inorganic acids include superacids (e.g., fluoroboric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, and hexafluoroarsenic acid), phosphoric acid, and boric acid. The above organic acids and inorganic acids may be used alone or in combination of two or more.

[0086] Of the above organic acids and inorganic acids, preferred from the viewpoints of the antistatic properties and their durability of the ionic liquid and the transparency of the molded product are acids that form conjugate bases of super strong acids, anions other than the conjugate bases of super strong acids, and mixtures thereof, in which the Hammett acidity function (-H0) of the anions constituting the ionic liquid is 12 to 100.

[0087] Examples of anions other than the conjugate base of a superacid include halogen (e.g., fluorine, chlorine, and bromine) ions, alkyl (having 1 to 12 carbon atoms) benzenesulfonate (e.g., p-toluenesulfonate and dodecylbenzenesulfonate) ions, and poly(n=1 to 25) fluoroalkanesulfonate (e.g., undecafluoropentanesulfonate) ions.

[0088] Examples of superacids include protonic acids, those derived from a combination of a protonic acid and a Lewis acid, and mixtures thereof. Examples of superacids include bis(trifluoromethylsulfonyl)imide acid, bis(pentafluoroethylsulfonyl)imide acid, tris(trifluoromethylsulfonyl)methane, perchloric acid, fluorosulfonic acid, alkane (having 1 to 30 carbon atoms) sulfonic acids (e.g., methanesulfonic acid, dodecanesulfonic acid, etc.), poly(n=1 to 30)fluoroalkane (having 1 to 30 carbon atoms) sulfonic acids (e.g., trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, and tridecafluorohexanesulfonic acid), fluoroboric acid, and tetrafluoroboric acid. Of these, preferred from the viewpoint of ease of synthesis are borofluoroacid, trifluoromethanesulfonic acid, bis(trifluoromethanesulfonyl)imide acid, and bis(pentafluoroethylsulfonyl)imide acid. Examples of protonic acids that can be used in combination with Lewis acids include hydrogen halides (e.g., hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, and mixtures thereof. Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of the ionic liquid.

[0089] Examples of Lewis acids include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof. Among these, boron trifluoride and phosphorus pentafluoride are preferred from the viewpoint of the initial conductivity of the ionic liquid.

[0090] The protonic acid and Lewis acid may be combined in any desired manner, and examples of super strong acids formed by such combinations include tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, hexafluorotantalum sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chlorotrifluoroboric acid, hexafluoroarsenic acid, and mixtures thereof.

[0091] Of the above anions, from the viewpoint of the antistatic properties of the ionic liquid and their durability, conjugate bases of super strong acids (super strong acids composed of protonic acids and super strong acids composed of a combination of a protonic acid and a Lewis acid) are preferred, and even more preferred are super strong acids composed of protonic acids and conjugate bases of super strong acids composed of a protonic acid and boron trifluoride and / or phosphorus pentafluoride.

[0092] Among ionic liquids, from the viewpoints of antistatic properties and their durability, and transparency of molded articles, preferred are ionic liquids having an amidinium cation, more preferred are ionic liquids having a 1-ethyl-3-methylimidazolium cation, and particularly preferred is 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide. In the component (Y) of the present invention, the alkali metal salt (F) and the ionic liquid (G) may be used in combination.

[0093] In the antistatic resin composition of the present invention, the content of the component (Y) is 0.01 to 10.0 parts by mass relative to 100 parts by mass of the modified polyethylene resin, and from the viewpoints of antistatic properties and their durability and transparency of molded articles, it is preferably 0.5 to 5.0 parts by mass, more preferably 0.8 to 3.0 parts by mass. When the component (Y) is blended with the modified polyethylene resin, it may be blended directly, or the component (Y) may be added to the reaction system during the synthesis reaction of the polymer compound (E), which is the component (X), and then blended.

[0094] The resin composition of the present invention preferably contains a compatibilizer from the viewpoints of antistatic properties and their durability, and transparency of the molded product. Examples of the compatibilizer include one or more acid anhydride-modified polyolefins. Acid anhydride-modified polyolefins are polymers in which an acid anhydride such as maleic anhydride is grafted onto a polyolefin.

[0095] The polyolefin portion of the acid anhydride-modified polyolefin may be a polymer or copolymer of ethylene, propylene, α-olefin, or diene. Examples of α-olefins include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, and 1-dodecene. Examples of dienes include butadiene, isoprene, cyclopentadiene, and 1,11-dodecadiene. Other copolymerization components may also be included. Specific examples include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / propylene / diene terpolymer, ethylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, and mixtures thereof. Among these, from the viewpoints of antistatic properties and their durability, and transparency of molded articles, polymers or copolymers of ethylene, propylene, α-olefins having 4 to 12 carbon atoms, butadiene, and isoprene are preferred, polymers or copolymers of ethylene, propylene, α-olefins having 4 to 8 carbon atoms, and butadiene are more preferred, and polymers or copolymers of ethylene, propylene, and butadiene are even more preferred.

[0096] Examples of the acid anhydride include maleic anhydride and itaconic anhydride, with maleic anhydride being preferred from the viewpoints of antistatic properties and their durability, and transparency of the molded product. The acid anhydride-modified polyolefin is preferably a maleic anhydride-modified polyolefin, more preferably a maleic anhydride-modified polypropylene, from the viewpoints of antistatic property and its durability, and transparency of the molded product. The acid anhydride-modified polyolefin is obtained by a conventionally known method by subjecting a polyolefin to a grafting reaction with an acid anhydride such as maleic anhydride, and various commercially available products may be used.

[0097] In the antistatic resin composition of the present invention, the content of the compatibilizer is preferably 0.01 to 30.0 parts by mass, more preferably 0.1 to 20.0 parts by mass, and even more preferably 0.5 to 15.0 parts by mass, relative to 100 parts by mass of the modified polyethylene resin, from the viewpoints of antistatic property and its durability, and transparency of the molded product.

[0098] The resin composition of the present invention may further contain a salt of a Group 2 element within a range that does not impair the effects of the present invention. Salts of Group 2 elements include salts of organic or inorganic acids, and examples of Group 2 elements include beryllium, magnesium, calcium, strontium, and barium. Examples of organic acids include aliphatic monocarboxylic acids having 1 to 18 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; aliphatic dicarboxylic acids having 1 to 12 carbon atoms, such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, and adipic acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; and sulfonic acids having 1 to 20 carbon atoms, such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethanesulfonic acid. Examples of inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, and perchloric acid.

[0099] The resin composition of the present invention may contain a surfactant within a range that does not impair the effects of the present invention. As the surfactant, a nonionic, anionic, cationic or amphoteric surfactant can be used.

[0100] Examples of nonionic surfactants include polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; and polyhydric alcohol-type nonionic surfactants such as polyethylene oxide, fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and fatty amides of alkanolamines.

[0101] Examples of anionic surfactants include carboxylates such as alkali metal salts of higher fatty acids; sulfates such as higher alcohol sulfates and higher alkyl ether sulfates; sulfonates such as alkylbenzene sulfonates, alkyl sulfonates and paraffin sulfonates; and phosphates such as higher alcohol phosphates.

[0102] Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine, and these can be used alone or in combination of two or more.

[0103] When a surfactant is added, the amount added is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass, per 100 parts by mass of the modified polyethylene resin.

[0104] Furthermore, the resin composition of the present invention may contain a polymeric antistatic agent. Examples of the polymeric antistatic agent include known polymeric antistatic agents such as polyetheresteramides. Examples of known polyetheresteramides include the polyetheresteramides formed from polyoxyalkylene adducts of bisphenol A described in JP-A-7-10989. Also usable are block polymers having a repeating structure with 2 to 50 bond units between a polyolefin block and a hydrophilic polymer block, such as the block polymers described in U.S. Pat. No. 6,552,131.

[0105] When a polymeric antistatic agent is added, the amount added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the modified polyethylene resin.

[0106] The resin composition of the present invention may contain other thermoplastic resins in addition to the modified polyethylene resins described above, provided that the effects of the present invention are not impaired. Examples of other thermoplastic resins include polyolefin resins such as α-olefin polymers such as polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, cross-linked polyethylene, ultra-high molecular weight polyethylene, polybutene-1, poly-3-methylpentene, and poly-4-methylpentene, and ethylene-propylene copolymers, and copolymers thereof; halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, and vinyl chloride-cyclohexylmaleimide copolymer; petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and / or α-methylstyrene and other monomers; copolymers with monomers (e.g., maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) (e.g., AS resin, ABS (acrylonitrile butadiene styrene copolymer) resin, ACS resin, SBS resin, MBS resin, heat-resistant ABS resin, etc.); polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; aromatic polyesters such as polyalkylene terephthalates (e.g., polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate), polyalkylene naphthalates (e.g., polyethylene naphthalate, polybutylene naphthalate), and linear polyesters such as polytetramethylene terephthalate; degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, poly(2-oxetanone);Examples of suitable thermoplastic resins include polyamides such as polyphenylene oxide, polycaprolactam, and polyhexamethylene adipamide, polycarbonate, polycarbonate / ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, cellulose resin, polyimide resin, polysulfone, polyphenylene ether, polyether ketone, polyether ether ketone, and liquid crystal polymer, as well as blends thereof. Examples of suitable thermoplastic resins include isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, and silicone rubber. Examples of suitable thermoplastic elastomers include olefin-based elastomers, styrene-based elastomers, polyester-based elastomers, nitrile-based elastomers, nylon-based elastomers, vinyl chloride-based elastomers, polyamide-based elastomers, and polyurethane-based elastomers. These thermoplastic resins may be used alone or in combination. The thermoplastic resin may also be alloyed.

[0107] Furthermore, various additives such as a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, a hindered amine-based light stabilizer, and an ultraviolet absorber can be further added to the resin composition of the present invention within a range that does not impair the effects of the present invention, thereby stabilizing the resin composition of the present invention.

[0108] Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butyl- Ethylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, diethyl)-2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)methylpropionate]methane, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] ], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid] glycol ester, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl] terephthalate, 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], etc. The amount of these phenolic antioxidants added is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the modified polyethylene resin. Examples of phosphorus-based antioxidants include trisnonylphenyl phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, bis(2,4-ditert-butylphenyl)pentaerythritol diphosphite, bis(2,6-ditert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tritert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetra(tridecyl)isopropylidenediphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidenebis(2- tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite, 2 Examples of suitable phosphorus-based antioxidants include 2,2'-methylenebis(4,6-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, and phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol. The amount of these phosphorus-based antioxidants added is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the modified polyethylene resin.

[0109] Examples of thioether-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra(β-alkylthiopropionic acid) esters. The amount of these thioether-based antioxidants added is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the modified polyethylene resin.

[0110] Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2 ,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzoate) dibenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4 -piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,Examples of the hindered amine compounds include 6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl)aminoundecane. The amount of these hindered amine light stabilizers added is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, per 100 parts by mass of the modified polyethylene resin.

[0111] Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5'- 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), and 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole; phenyl Benzoates such as ricinate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β,β-diphenylacrylate, methyl and triaryltriazines such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine. The amount of these ultraviolet absorbers added is preferably 0.001 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass, per 100 parts by mass of the modified polyethylene resin.

[0112] Furthermore, if necessary, a known neutralizing agent may be added to neutralize residual catalyst in the modified polyethylene resin or polyolefin resin. Examples of the neutralizing agent include fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, and fatty acid amide compounds such as ethylene bis(stearamide), ethylene bis(12-hydroxystearamide), and stearic acid amide. These neutralizing agents may be used in combination.

[0113] Furthermore, the resin composition of the present invention may further contain, as necessary, metal salts of carboxylic acids such as sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, lithium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, aluminum hydroxybis[2,2'methylenebis(4,6-di-tert-butylphenyl)phosphate], sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate, and disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzyl)propanol; Nucleating agents such as aromatic carboxylic acid metal salts, alicyclic alkyl carboxylic acid metal salts, aluminum p-tert-butylbenzoate, aromatic phosphate ester metal salts, dibenzylidene sorbitols, and the like may also be blended.

[0114] Furthermore, if necessary, metal soap, hydrotalcite, a triazine ring-containing compound, a metal hydroxide, a phosphate ester-based flame retardant, a condensed phosphate ester-based flame retardant, a phosphate-based flame retardant, an inorganic phosphorus-based flame retardant, a (poly)phosphate-based flame retardant, a halogen-based flame retardant, a silicon-based flame retardant, antimony oxide such as antimony trioxide, an inorganic flame retardant auxiliary, an organic flame retardant auxiliary, an anti-drip agent, a filler, a pigment, a lubricant, a foaming agent, and the like may be added to the resin composition of the present invention.

[0115] Examples of the triazine ring-containing compound include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornenediguanamine, methylenediguanamine, ethylenedimelamine, trimethylenedimelamine, tetramethylenedimelamine, hexamethylenedimelamine, and 1,3-hexylenedimelamine.

[0116] Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and Kismer 5A (magnesium hydroxide, manufactured by Kyowa Chemical Industry Co., Ltd.).

[0117] Examples of the phosphate ester-based flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis-(t-butylphenyl)phenyl phosphate, tris-(t-butylphenyl)phosphate, isopropylphenyl diphenyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, and tris-(isopropylphenyl)phosphate.

[0118] Examples of the condensed phosphate ester flame retardant include 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(dixylenyl phosphate), bisphenol A bis(diphenyl phosphate), and the like.

[0119] Examples of the (poly)phosphate-based flame retardant include ammonium salts and amine salts of (poly)phosphoric acid, such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melamine pyrophosphate, and piperazine pyrophosphate.

[0120] Examples of inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, and montmorillonite, and surface-treated products thereof, and various commercially available products can be used, such as TIPAQUE R-680 (titanium oxide: manufactured by Ishihara Sangyo Kaisha), Kyowamag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), and Alkamiser 4 (zinc-modified hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.). Examples of organic flame retardant aids include pentaerythritol.

[0121] Furthermore, the resin composition of the present invention may contain additives that are typically used in modified polyethylene resins, such as crosslinking agents, anti-fogging agents, anti-plate-out agents, surface treatment agents, plasticizers, lubricants, flame retardants, fluorescent agents, anti-fungal agents, bactericides, foaming agents, metal deactivators, release agents, pigments, processing aids, antioxidants, and light stabilizers, as needed, within limits that do not impair the effects of the present invention.

[0122] The method for producing the resin composition of the present invention is not particularly limited, and it is sufficient to blend one or more polymeric compounds (E) as component (X), one or more alkali metal salts (F) and ionic liquids (G) as component (Y), and other optional components with a modified polyethylene resin, and any commonly used method can be used for this purpose, such as dry blending using a blender or Henschel mixer, or melt blending using an extruder, Banbury mixer, kneader, or the like.

[0123] The polymer compound (E), component (X), may be added directly or, if necessary, after impregnation into a carrier. Impregnation into the carrier can be achieved by heating and mixing the polymer compound directly, or by diluting the polymer compound with an organic solvent, if necessary, before impregnating the carrier, and then removing the solvent. Examples of such carriers include synthetic resin fillers and bulking agents, as well as flame retardants and light stabilizers that are solid at room temperature. Examples include calcium silicate powder, silica powder, talc powder, alumina powder, titanium oxide powder, or carriers whose surfaces have been chemically modified, and solid flame retardants and antioxidants listed above. Among these carriers, carriers whose surfaces have been chemically modified are preferred, and silica powder whose surfaces have been chemically modified is more preferred. These carriers preferably have an average particle size of 0.1 to 100 μm, more preferably 0.5 to 50 μm.

[0124] Furthermore, as a method for blending the polymer compound (E), which is component (X), into the modified polyethylene-based resin, the polymer compound (E) may be synthesized and blended while kneading the block polymer (C) and the epoxy compound (D) having two or more epoxy groups into the resin component, and at the same time, one or more compounds selected from the group consisting of the alkali metal salt (F) and the ionic liquid (G), which are component (Y), may be blended in at the same time. Alternatively, the blending may be performed by a method in which the polymer compound (E), one or more compounds selected from the group consisting of the alkali metal salt (F) and the ionic liquid (G), and the resin component are mixed during molding such as injection molding to obtain a molded product. Furthermore, a masterbatch of the polymer compound (E), one or more compounds selected from the group consisting of the alkali metal salt (F) and the ionic liquid (G), and the modified polyethylene-based resin may be prepared in advance, and this masterbatch may be blended. Furthermore, the polymer compound (E) and one or more selected from the group consisting of the alkali metal salt (F) and the ionic liquid (G) may be mixed in advance and then blended into the modified polyethylene resin, or the polymer compound (E) synthesized by adding one or more selected from the group consisting of the alkali metal salt (F) and the ionic liquid (G) during the synthesis reaction may be blended into the modified polyethylene resin.

[0125] Next, the molded article and film of the present invention will be described. The molded article and film of the present invention are obtained by molding the antistatic resin composition of the present invention. By molding the resin composition of the present invention, a resin molded article having antistatic properties can be obtained. The molding method is not particularly limited, and examples include extrusion, calendaring, injection molding, rolling, compression molding, blow molding, and rotational molding, and molded articles of various shapes such as resin plates, sheets, films, bottles, fibers, and irregularly shaped articles can be produced. The molded article obtained from the resin composition of the present invention has excellent antistatic properties and their durability, as well as transparency.

[0126] Among the molded articles obtainable from the resin composition of the present invention, films and sheets are preferred because they have excellent antistatic properties, their durability, and transparency, and are less likely to generate static electricity, and are suitable for backgrinding tapes, expansion tapes, and dicing tapes, and are particularly suitable as substrates for dicing tapes, particularly for dicing tapes for laser dicing, which require high transparency.

[0127] Furthermore, molded articles obtained from the resin composition of the present invention are suitable for packaging materials and containers for electronic components and electronic materials. Packaging materials and containers obtained from the resin composition of the present invention are suitable for storage containers, transport containers, and packaging materials for electronic components and electronic materials. Examples include transport containers, storage containers, trays, cases, packaging materials, and carrier tapes and cover tapes for packaging electronic components for various parts and products such as silicon wafers, hard disks, disk substrates, glass substrates, IC chips, semiconductors, optical storage disks, color filters, hard disk magnetic head elements, and CCD elements.

[0128] Further examples of preferred molded articles obtained from the resin composition of the present invention include sealant materials, heat sealing materials, sealant films, laminate films, packaging films, packaging materials, protective films for electric and electronic components, sealing films for electric and electronic components, agricultural materials, etc. [Example]

[0129] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. Polymer compound (E), which is component (X) of the present invention, was produced according to the following production examples. In the following production examples, the number average molecular weight of polyether (b) was calculated by the following "Method for calculating number average molecular weight from hydroxyl value," and the number average molecular weights of polyester (a) and block polymer (C) were calculated by the following "Method for measuring number average molecular weight in polystyrene equivalent." The molecular weight of polypropylene glycol diglycidyl ether was calculated from the epoxy equivalent.

[0130] <Method of calculating number average molecular weight from hydroxyl value> The hydroxyl value was measured by the hydroxyl value measurement method described below, and the number average molecular weight (hereinafter also referred to as "Mn") was determined by the following formula. Number average molecular weight = (56110 x 2) / hydroxyl value

[0131] <Hydroxyl value measurement method> Reagent A (acetylating agent) (1) Triethyl phosphate 1560mL (2) Acetic anhydride 193 mL (3) Perchloric acid (60%) 16g The above reagents are mixed in the order of (1) → (2) → (3). Reagent B Pyridine and pure water are mixed in a volume ratio of 3:1. Reagent C Add 2 to 3 drops of phenolphthalein solution to 500 mL of isopropyl alcohol and neutralize with 1N KOH aqueous solution.

[0132] First, weigh 2 g of sample into a 200 mL Erlenmeyer flask, add 10 mL of triethyl phosphate, and heat to dissolve. Add 15 mL of reagent A, add a stopper, and shake vigorously. Add 20 mL of reagent B, add a stopper, and shake vigorously. Add 50 mL of reagent C. Titrate with 1N KOH aqueous solution and calculate using the formula below.

[0133] Hydroxyl value [mgKOH / g] = 56.11 × f × (TB) / S f: Factor of 1N-KOH solution B: Blank test titration volume [mL] T: Test titer [mL] S: Sample amount [g]

[0134] <Method for measuring number average molecular weight in polystyrene equivalent> The number average molecular weight (hereinafter also referred to as "Mn") was measured by gel permeation chromatography (GPC) under the following conditions: Equipment: GPC equipment manufactured by JASCO Corporation Solvent: Chloroform Reference material: Polystyrene Detector: Differential refractometer (RI detector) Column stationary phase: Shodex LF-804 manufactured by Showa Denko K.K. Column temperature: 40℃ Sample concentration: 1mg / 1mL Flow rate: 0.8mL / min. Injection volume: 100μL

[0135] [Production Example 1] A separable flask was charged with 111 g of 1,4-cyclohexanedimethanol, 122 g of adipic acid, 0.1 g of phthalic anhydride, and 0.4 g of an antioxidant (tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, ADK STAB AO-60, manufactured by ADEKA Corporation). The temperature was gradually increased from 170°C to 215°C while polymerization was carried out at normal pressure for 4 hours, and then at 215°C under reduced pressure for 3 hours to obtain polyester (a)-1. The number average molecular weight Mn of the resulting polyester (a)-1 was 2931.

[0136] Next, 205 g of the resulting polyester (a)-1, 144 g of polyethylene glycol having a number average molecular weight of 3650 as compound (b1)-1 of polyether (b) having hydroxyl groups at both ends, 40 g of polytetramethylene glycol having a number average molecular weight of 3042 as compound (b2)-1 (the proportion of polytetramethylene glycol (b2) was 25 mol% based on the total moles of polyethylene glycol and polytetramethylene glycol), 0.4 g of antioxidant (ADK STAB AO-60), and 3.4 g of zirconium octylate were charged and polymerized under reduced pressure for 7 hours while gradually increasing the temperature from 215 °C to 240 °C to obtain block polymer (C)-1 having a structure with carboxyl groups at both ends. The number average molecular weight Mn of this block polymer (C)-1 having a structure with carboxyl groups at both ends was 22,109.

[0137] To 392 g of the obtained block polymer (C)-1 having a structure with carboxyl groups at both ends, 4.0 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-1 was added, and the mixture was polymerized at 240°C for 3 hours under reduced pressure, yielding 396 g of polymer compound (E)-1.

[0138] [Production Example 2] 207 g of polyester (a)-1 obtained in the same manner as in Production Example 1, 153 g of polyethylene glycol having a number average molecular weight of 3650 as compound (b1)-1 of polyether (b) having hydroxyl groups at both ends, 32 g of polytetramethylene glycol having a number average molecular weight of 3042 as compound (b2)-1 (the proportion of polytetramethylene glycol (b2) was 20 mol% based on the total moles of polyethylene glycol and polytetramethylene glycol), 0.4 g of antioxidant (ADK STAB AO-60), and 3.4 g of zirconium octylate were charged and polymerized under reduced pressure for 7 hours while gradually increasing the temperature from 215°C to 240°C to obtain block polymer (C)-2 having a structure with carboxyl groups at both ends. The number average molecular weight Mn of this block polymer (C)-2 having a structure with carboxyl groups at both ends was 22,302.

[0139] To 429 g of the obtained block polymer (C)-2 having a structure with carboxyl groups at both ends, 3.9 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-1 was added, and the mixture was polymerized at 240°C for 3 hours under reduced pressure, yielding 434 g of polymer compound (E)-2.

[0140] [Production Example 3] 196 g of polyester (a)-1 obtained in the same manner as in Production Example 1, 96 g of polyethylene glycol having a number average molecular weight of 3650 as compound (b1)-1 of polyether (b) having hydroxyl groups at both ends, 80 g of polytetramethylene glycol having a number average molecular weight of 3042 as compound (b2)-1 (the proportion of polytetramethylene glycol (b2) was 50 mol% based on the total moles of polyethylene glycol and polytetramethylene glycol), 0.4 g of antioxidant (ADK STAB AO-60), and 3.3 g of zirconium octylate were charged and polymerized under reduced pressure for 7 hours while gradually increasing the temperature from 215°C to 240°C to obtain block polymer (C)-3 having a structure with carboxyl groups at both ends. The number average molecular weight Mn of this block polymer (C)-3 having a structure with carboxyl groups at both ends was 21134.

[0141] To 376 g of the obtained block polymer (C)-3 having a structure with carboxyl groups at both ends, 4.0 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-1 was added, and the mixture was polymerized at 240°C for 3 hours under reduced pressure to obtain 380 g of polymer compound (E)-3.

[0142] [Production Example 4] 209 g of polyester (a)-1 obtained in the same manner as in Production Example 1, 163 g of polyethylene glycol having a number average molecular weight of 3650 as compound (b1)-1 of polyether (b) having hydroxyl groups at both ends, 24 g of polytetramethylene glycol having a number average molecular weight of 3042 as compound (b2)-1 (the proportion of polytetramethylene glycol (b2) was 15 mol% based on the total moles of polyethylene glycol and polytetramethylene glycol), 0.4 g of antioxidant (ADK STAB AO-60), and 3.5 g of zirconium octylate were charged and polymerized under reduced pressure for 7 hours while gradually increasing the temperature from 215°C to 240°C to obtain block polymer (C)-4 having a structure with carboxyl groups at both ends. The number average molecular weight Mn of this block polymer (C)-4 having a structure with carboxyl groups at both ends was 22,485.

[0143] To 396 g of the obtained block polymer (C)-4 having a structure with carboxyl groups at both ends, 4.0 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-1 was added, and the mixture was polymerized at 240°C for 3 hours under reduced pressure to obtain 400 g of polymer compound (E)-4.

[0144] [Production Example 5] 189 g of polyester (a)-1 obtained in the same manner as in Production Example 1, 57 g of polyethylene glycol having a number average molecular weight of 3650 as compound (b1)-1 of polyether (b) having hydroxyl groups at both ends, 112 g of polytetramethylene glycol having a number average molecular weight of 3042 as compound (b2)-1 (the proportion of polytetramethylene glycol (b2) was 70 mol% based on the total moles of polyethylene glycol and polytetramethylene glycol), 0.4 g of antioxidant (ADK STAB AO-60), and 3.2 g of zirconium octylate were charged and polymerized under reduced pressure for 7 hours while gradually increasing the temperature from 215°C to 240°C to obtain block polymer (C)-5 having a structure with carboxyl groups at both ends. The number average molecular weight Mn of this block polymer (C)-5 having a structure with carboxyl groups at both ends was 20,372.

[0145] To 396 g of the obtained block polymer (C)-5 having a structure with carboxyl groups at both ends, 4.0 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-1 was added, and the mixture was polymerized at 240°C for 3 hours under reduced pressure to obtain 400 g of polymer compound (E)-5.

[0146] [Production Example 6] 202 g of polyester (a)-1 obtained in the same manner as in Production Example 1, 135 g of polyethylene glycol having a number average molecular weight of 2000 as compound (b1)-2 of polyether (b) having hydroxyl groups at both ends, 45 g of polytetramethylene glycol having a number average molecular weight of 2000 as compound (b2)-2 (the proportion of polytetramethylene glycol (b2) was 25 mol% based on the total moles of polyethylene glycol and polytetramethylene glycol), 0.4 g of antioxidant (ADK STAB AO-60), and 3.2 g of zirconium octylate were charged and polymerized under reduced pressure for 7 hours while gradually increasing the temperature from 215°C to 240°C to obtain block polymer (C)-6 having a structure with carboxyl groups at both ends. The number average molecular weight Mn of this block polymer (C)-6 having a structure with carboxyl groups at both ends was 12631.

[0147] To 397 g of the obtained block polymer (C)-6 having a structure with carboxyl groups at both ends, 6.3 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-1 was added, and the mixture was polymerized at 240°C for 3 hours under reduced pressure, yielding 405 g of polymer compound (E)-6.

[0148] [Production Example 7] 200 g of polyester (a)-1 obtained in the same manner as in Production Example 1, 135 g of polyethylene glycol having a number average molecular weight of 4000 as compound (b1)-3 of polyether (b) having hydroxyl groups at both ends, 45 g of polytetramethylene glycol having a number average molecular weight of 4000 as compound (b2)-3 (the proportion of polytetramethylene glycol (b2) was 25 mol% based on the total moles of polyethylene glycol and polytetramethylene glycol), 0.4 g of antioxidant (ADK STAB AO-60), and 3.2 g of zirconium octylate were charged and polymerized under reduced pressure for 7 hours while gradually increasing the temperature from 215 °C to 240 °C to obtain block polymer (C)-7 having a structure with carboxyl groups at both ends. The number average molecular weight Mn of this block polymer (C)-7 having a structure with carboxyl groups at both ends was 25,243.

[0149] To 398 g of the resulting block polymer (C)-7 having a structure with carboxyl groups at both ends, 3.2 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-1 was added, and the mixture was polymerized at 240°C for 3 hours under reduced pressure, yielding 402 g of polymer compound (E)-7.

[0150] [Production Example 8] A separable flask was charged with 97 g of 1,4-cyclohexanedimethanol, 112 g of adipic acid, 0.1 g of phthalic anhydride, and 0.4 g of an antioxidant (tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, ADK STAB AO-60, manufactured by ADEKA Corporation). The mixture was gradually heated from 170°C to 215°C while undergoing polymerization at normal pressure for 4 hours, and then at 215°C under reduced pressure for 3 hours to obtain polyester (a)-2. The number average molecular weight Mn of the resulting polyester (a)-2 was 2053.

[0151] Next, 185 g of the resulting polyester (a)-2, 185 g of polyethylene glycol having a number-average molecular weight of 3650 as compound (b1)-1 of polyether (b) having hydroxyl groups at both ends, 51 g of polytetramethylene glycol having a number-average molecular weight of 3042 as compound (b2)-1 (the proportion of polytetramethylene glycol (b2) was 25 mol% based on the total moles of polyethylene glycol and polytetramethylene glycol), 0.4 g of antioxidant (ADK STAB AO-60), and 3.7 g of zirconium octylate were charged and polymerized under reduced pressure for 7 hours while gradually increasing the temperature from 215 °C to 240 °C to obtain block polymer (C)-8 having a structure with carboxyl groups at both ends. The number-average molecular weight Mn of this block polymer (C)-8 having a structure with carboxyl groups at both ends was 18,600.

[0152] To 461 g of the obtained block polymer (C)-8 having a structure with carboxyl groups at both ends, 5.0 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-1 was added, and the mixture was polymerized at 240°C for 3 hours under reduced pressure, yielding 467 g of polymer compound (E)-8.

[0153] [Production Example 9] A separable flask was charged with 135 g of 1,4-cyclohexanedimethanol, 143 g of adipic acid, 1.5 g of phthalic anhydride, and 0.4 g of an antioxidant (tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, ADK STAB AO-60, manufactured by ADEKA Corporation). The mixture was gradually heated from 170°C to 215°C while undergoing polymerization at normal pressure for 4 hours, and then at 215°C under reduced pressure for 3 hours to obtain polyester (a)-3. The number average molecular weight Mn of the resulting polyester (a)-3 was 5347.

[0154] Next, 244 g of the resulting polyester (a)-3, 94 g of polyethylene glycol having a number average molecular weight of 3650 as compound (b1)-1 of polyether (b) having hydroxyl groups at both ends, 26 g of polytetramethylene glycol having a number average molecular weight of 3042 as compound (b2)-1 (the proportion of polytetramethylene glycol (b2) was 25 mol% based on the total moles of polyethylene glycol and polytetramethylene glycol), 0.4 g of antioxidant (ADK STAB AO-60), and 3.1 g of zirconium octylate were charged and polymerized under reduced pressure for 7 hours while gradually increasing the temperature from 215 °C to 240 °C to obtain block polymer (C)-9 having a structure with carboxyl groups at both ends. The number average molecular weight Mn of this block polymer (C)-9 having a structure with carboxyl groups at both ends was 31,773.

[0155] To 401 g of the obtained block polymer (C)-9 having a structure with carboxyl groups at both ends, 2.6 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-1 was added, and the mixture was polymerized at 240°C for 3 hours under reduced pressure to obtain 404 g of polymer compound (E)-9.

[0156] [Production Example 10] 401 g of block polymer (C)-1 having a structure with carboxyl groups at both ends, obtained in the same manner as in Production Example 1, was charged with 1.7 g of polypropylene glycol diglycidyl ether (number average molecular weight: 304, epoxy equivalent: 200 g / eq) as epoxy compound (D)-2, and the mixture was polymerized at 240°C for 3 hours under reduced pressure, yielding 403 g of polymer compound (E)-10.

[0157] [Production Example 11] 391 g of block polymer (C)-1 having a structure with carboxyl groups at both ends, obtained in the same manner as in Production Example 1, was charged with 2.4 g of polypropylene glycol diglycidyl ether (number average molecular weight: 769, epoxy equivalent: 471 g / eq) as epoxy compound (D)-3, and the mixture was polymerized at 240°C for 3 hours under reduced pressure, yielding 394 g of polymer compound (E)-11.

[0158] [Production Example 12] 391 g of block polymer (C)-1 having a structure with carboxyl groups at both ends, obtained in the same manner as in Production Example 1, was charged with 2.1 g of bisphenol F diglycidyl ether (epoxy equivalent: 170 g / eq) as epoxy compound (D)-4, and the mixture was polymerized at 240°C for 3 hours under reduced pressure, yielding 394 g of polymer compound (E)-12.

[0159] [Production Example 13] A separable flask was charged with 124 g of hydrogenated bisphenol A, 84 g of adipic acid, 0.1 g of phthalic anhydride, and 0.4 g of an antioxidant (tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, ADK STAB AO-60, manufactured by ADEKA Corporation). The temperature was gradually increased from 170°C to 215°C while polymerization was carried out at normal pressure for 4 hours, and then at 215°C under reduced pressure for 3 hours to obtain polyester (a)-4. The number average molecular weight Mn of the resulting polyester (a)-4 was 2922.

[0160] Next, 190 g of the resulting polyester (a)-4, 133 g of polyethylene glycol having a number-average molecular weight of 3650 as compound (b1)-1 of polyether (b) having hydroxyl groups at both ends, 37 g of polytetramethylene glycol having a number-average molecular weight of 3042 as compound (b2)-1 (the proportion of polytetramethylene glycol (b2) was 25 mol% based on the total moles of polyethylene glycol and polytetramethylene glycol), 0.4 g of antioxidant (ADK STAB AO-60), and 3.1 g of zirconium octylate were charged and polymerized under reduced pressure for 7 hours while gradually increasing the temperature from 215 °C to 240 °C to obtain block polymer (C)-10 having a structure with carboxyl groups at both ends. The number-average molecular weight Mn of this block polymer (C)-10 having a structure with carboxyl groups at both ends was 21,500.

[0161] To 391 g of the resulting block polymer (C)-10 having a structure with carboxyl groups at both ends, 3.7 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-1 was added, and the mixture was polymerized at 240°C for 3 hours under reduced pressure, yielding 396 g of polymer compound (E)-13.

[0162] [Production Example 14] A separable flask was charged with 111 g of 1,4-cyclohexanedimethanol, 122 g of adipic acid, and 0.4 g of an antioxidant (tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, ADK STAB AO-60, manufactured by ADEKA Corporation). The mixture was gradually heated from 170°C to 215°C while undergoing polymerization at normal pressure for 4 hours, and then at 215°C under reduced pressure for 3 hours to obtain polyester (a)-5. The number average molecular weight Mn of the resulting polyester (a)-5 was 2931.

[0163] Next, 206 g of the resulting polyester (a)-5, 144 g of polyethylene glycol having a number average molecular weight of 3650 as compound (b1)-1 of polyether (b) having hydroxyl groups at both ends, 40 g of polytetramethylene glycol having a number average molecular weight of 3042 as compound (b2)-1 (the proportion of polytetramethylene glycol (b2) was 25 mol% based on the total moles of polyethylene glycol and polytetramethylene glycol), 0.4 g of antioxidant (ADK STAB AO-60), and 3.3 g of zirconium octylate were charged and polymerized under reduced pressure for 7 hours while gradually increasing the temperature from 215 °C to 240 °C to obtain block polymer (C)-11 having a structure with carboxyl groups at both ends. The number average molecular weight Mn of this block polymer (C)-11 having a structure with carboxyl groups at both ends was 22,109.

[0164] To 392 g of the resulting block polymer (C)-11 having a structure with carboxyl groups at both ends, 4.4 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-1 was added, and the mixture was polymerized at 240°C for 3 hours under reduced pressure, yielding 396 g of polymer compound (E)-14.

[0165] [Production Example 15] A separable flask was charged with 111 g of 1,4-cyclohexanedimethanol, 123 g of adipic acid, 0.1 g of phthalic anhydride, 0.4 g of an antioxidant (tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, ADK STAB AO-60, manufactured by ADEKA Corporation), 144 g of polyethylene glycol having a number average molecular weight of 3650 as compound (b1)-1 of polyether (b) having hydroxyl groups at both ends, and 40 g of polytetramethylene glycol having a number average molecular weight of 3042 as compound (b2)-1 (the proportion of polytetramethylene glycol (b2) was 25 mol % based on the total number of moles of polyethylene glycol and polytetramethylene glycol), and the mixture was polymerized at normal pressure for 4 hours while gradually increasing the temperature from 170°C to 215°C. 3.5 g of zirconium octylate was added, and polymerization was carried out under reduced pressure for 7 hours while gradually increasing the temperature from 215° C. to 240° C. to obtain a polymer. The number average molecular weight Mn of the obtained polymer was 22,109.

[0166] To 392 g of the obtained polymer, 4.0 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-1 was added, and the mixture was polymerized at 240°C for 3 hours under reduced pressure to obtain 396 g of polymer compound (E)-15.

[0167] [Examples 1 to 25, Comparative Examples 1 to 14] Test films were obtained according to the test film preparation method described below, using each resin composition blended in the amounts (parts by mass) shown in Tables 1 to 8 below. The surface resistivity (SR value) of the obtained test films was measured according to the measurement method described below, and antistatic properties and their durability were evaluated. Furthermore, the haze value was measured and evaluated according to the measurement method described below. The results are also shown in Tables 1 to 8. Furthermore, measurements and evaluations were performed in the same manner as in the examples, using comparative antistatic agent-1 in the amounts shown in Tables 1 to 8. The results are also shown in Tables 1 to 8.

[0168] <Method for producing ethylene-vinyl acetate copolymer (EVA) resin composition test film> Each resin composition was melt-extruded at 150°C using an extrusion molding machine equipped with a T-die manufactured by Toyo Seiki Seisakusho, Ltd., and quenched with a cooling roll at 40°C to obtain a test film (5 cm x 12 cm x 50 μm).

[0169] <Method for preparing ethylene-methyl methacrylate copolymer (EMMA) resin composition test film> Each resin composition was melt-extruded at 180°C using an extrusion molding machine equipped with a T-die manufactured by Toyo Seiki Seisakusho Co., Ltd., and quenched with a cooling roll at 40°C to obtain a test film (5 cm x 12 cm x 50 μm).

[0170] <Method for preparing ethylene-ethyl acrylate copolymer (EEA) resin composition test film> Each resin composition was melt-extruded at 180°C using an extrusion molding machine equipped with a T-die manufactured by Toyo Seiki Seisakusho Co., Ltd., and quenched with a cooling roll at 40°C to obtain a test film (5 cm x 12 cm x 50 μm).

[0171] <Method for preparing ethylene-methyl acrylate copolymer (EMA) resin composition test film> Each resin composition was melt-extruded at 180°C using an extrusion molding machine equipped with a T-die manufactured by Toyo Seiki Seisakusho Co., Ltd., and quenched with a cooling roll at 40°C to obtain a test film (5 cm x 12 cm x 50 μm).

[0172] <Method for producing ionomer resin composition test film> Each resin composition was melt-extruded at 180°C using an extrusion molding machine equipped with a T-die manufactured by Toyo Seiki Seisakusho Co., Ltd., and quenched with a cooling roll at 40°C to obtain a test film (5 cm x 12 cm x 50 μm).

[0173] <Surface resistivity (SR value) measurement method> The obtained test films were stored immediately after molding under the conditions of a temperature of 25°C and a humidity of 50%RH. After 1 day and 30 days of storage after molding, the surface resistivity (Ω / □) was measured under the same atmosphere using a Hirester-UX Hirester (MCP-HT800) resistivity meter manufactured by Mitsubishi Chemical Analytech Co., Ltd. under the conditions of an applied voltage of 100V and an applied time of 1 minute. The measurement was performed at 5 points per test film for 5 test films, and the average value was obtained.

[0174] <Measurement of Haze value> The Haze value of the test film was measured in accordance with ISO14782. The smaller the Haze value, the better the transparency.

[0175]

Table 1

[0176] *1: EVA: (Ethylene-vinyl acetate copolymer, melt flow rate = 5.7 g / 10 min, containing 28% by mass of vinyl acetate, manufactured by Toray Industries, Inc., trade name Ultrason 751) *2: NaDBS: Sodium dodecylbenzenesulfonate *3: C2mimDBS: 1-Ethyl-3-methylimidazolium dodecylbenzenesulfonate *4: (b2) / [(b1)+(b2)]: The ratio of polytetramethylene glycol to the total molar number of polyethylene glycol (b1) and polytetramethylene glycol (b2). Mol%. *5: Comparative antistatic agent-1: Polyether ester amide-based antistatic agent, manufactured by BASF, trade name Irgastat P-16

[0177]

Table 2

[0178] *1:EVA: (ethylene-vinyl acetate copolymer, melt flow rate = 5.7 g / 10 min, vinyl acetate content 28% by mass, manufactured by Tosoh Corporation, product name Ultrathene 751) *2: NaDBS: Sodium dodecylbenzenesulfonate *3: C2mimDBS: 1-ethyl-3-methylimidazolium dodecylbenzenesulfonate *4: (b2) / [(b1)+(b2)]: The ratio of polytetramethylene glycol to the total number of moles of polyethylene glycol (b1) and polytetramethylene glycol (b2). Molar %. *5: Comparative antistatic agent-1: Polyether ester amide antistatic agent, manufactured by BASF, product name Irgastat P-16

[0179] [Table 3]

[0180] *1:EVA: (ethylene-vinyl acetate copolymer, melt flow rate = 5.7 g / 10 min, vinyl acetate content 28% by mass, manufactured by Tosoh Corporation, product name Ultrathene 751) *2: NaDBS: Sodium dodecylbenzenesulfonate *3: C2mimDBS: 1-ethyl-3-methylimidazolium dodecylbenzenesulfonate *4: (b2) / [(b1)+(b2)]: The ratio of polytetramethylene glycol to the total number of moles of polyethylene glycol (b1) and polytetramethylene glycol (b2). Molar %. *5: Comparative antistatic agent-1: Polyether ester amide antistatic agent, manufactured by BASF, product name Irgastat P-16

[0181] [Table 4]

[0182] *1:EVA: (ethylene-vinyl acetate copolymer, melt flow rate = 5.7 g / 10 min, vinyl acetate content 28% by mass, manufactured by Tosoh Corporation, product name Ultrathene 751) *2: NaDBS: Sodium dodecylbenzenesulfonate *3: C2mimDBS: 1-ethyl-3-methylimidazolium dodecylbenzenesulfonate *4: (b2) / [(b1)+(b2)]: The ratio of polytetramethylene glycol to the total number of moles of polyethylene glycol (b1) and polytetramethylene glycol (b2). Molar %. *5: Comparative antistatic agent-1: Polyether ester amide antistatic agent, manufactured by BASF, product name Irgastat P-16

[0183] [Table 5]

[0184] *1:EVA: (ethylene-vinyl acetate copolymer, melt flow rate = 5.7 g / 10 min, vinyl acetate content 28% by mass, manufactured by Tosoh Corporation, product name Ultrathene 751) *2: NaDBS: Sodium dodecylbenzenesulfonate *3: C2mimDBS: 1-ethyl-3-methylimidazolium dodecylbenzenesulfonate *4: (b2) / [(b1)+(b2)]: The ratio of polytetramethylene glycol to the total number of moles of polyethylene glycol (b1) and polytetramethylene glycol (b2). Molar %. *5: Comparative antistatic agent-1: Polyether ester amide antistatic agent, manufactured by BASF, product name Irgastat P-16

[0185] [Table 6]

[0186] *6: EMMA: Ethylene-methyl methacrylate copolymer, manufactured by Sumitomo Chemical Co., Ltd., product name Acryft WK402 (melt flow rate = 20 g / 10 min, contains 25% by mass of methyl methacrylate) *7: EEA: Ethylene-ethyl acrylate copolymer: ENEOS NUC Corporation, product name NUC6570 (melt flow rate = 20 g / 10 min, contains 25% ethyl acrylate by mass) *8: EMA: Ethylene-methyl acrylate copolymer: manufactured by Japan Polyethylene Co., Ltd., product name: Rexpearl EMA EB440H (melt flow rate = 20 g / 10 min, contains 20% methyl acrylate by mass) *9: Ionomer resin: Mitsui Dow Polychemicals Co., Ltd., product name: Himilan 1855 (melt flow rate = 1.0 g / 10 min, ion type Zn) *10: Ionomer resin: Mitsui Dow Polychemicals Co., Ltd., product name: Himilan 1707 (melt flow rate = 0.9 g / 10 min, ion type Na) *2: NaDBS: Sodium dodecylbenzenesulfonate *4: (b2) / [(b1)+(b2)]: The ratio of polytetramethylene glycol to the total number of moles of polyethylene glycol (b1) and polytetramethylene glycol (b2). Molar %. *5: Comparative antistatic agent-1: Polyether ester amide antistatic agent, manufactured by BASF, product name Irgastat P-16

[0187] [Table 7]

[0188] *6: EMMA: Ethylene-methyl methacrylate copolymer, manufactured by Sumitomo Chemical Co., Ltd., product name Acryft WK402 (melt flow rate = 20 g / 10 min, contains 25% by mass of methyl methacrylate) *7: EEA: Ethylene-ethyl acrylate copolymer: ENEOS NUC Corporation, product name NUC6570 (melt flow rate = 20 g / 10 min, contains 25% ethyl acrylate by mass) *8: EMA: Ethylene-methyl acrylate copolymer: manufactured by Japan Polyethylene Co., Ltd., product name: Rexpearl EMA EB440H (melt flow rate = 20 g / 10 min, contains 20% methyl acrylate by mass) *9: Ionomer resin: Mitsui Dow Polychemicals Co., Ltd., product name: Himilan 1855 (melt flow rate = 1.0 g / 10 min, ion type Zn) *10: Ionomer resin: Mitsui Dow Polychemicals Co., Ltd., product name: Himilan 1707 (melt flow rate = 0.9 g / 10 min, ion type Na) *2: NaDBS: Sodium dodecylbenzenesulfonate *4: (b2) / [(b1)+(b2)]: The ratio of polytetramethylene glycol to the total number of moles of polyethylene glycol (b1) and polytetramethylene glycol (b2). Molar %. *5: Comparative antistatic agent-1: Polyether ester amide antistatic agent, manufactured by BASF, product name Irgastat P-16

[0189] [Table 8]

[0190] *6: EMMA: Ethylene-methyl methacrylate copolymer, manufactured by Sumitomo Chemical Co., Ltd., product name Acryft WK402 (melt flow rate = 20 g / 10 min, contains 25% by mass of methyl methacrylate) *7: EEA: Ethylene-ethyl acrylate copolymer: ENEOS NUC Corporation, product name NUC6570 (melt flow rate = 20 g / 10 min, contains 25% ethyl acrylate by mass) *8: EMA: Ethylene-methyl acrylate copolymer: manufactured by Japan Polyethylene Co., Ltd., product name: Rexpearl EMA EB440H (melt flow rate = 20 g / 10 min, contains 20% methyl acrylate by mass) *9: Ionomer resin: Mitsui Dow Polychemicals Co., Ltd., product name: Himilan 1855 (melt flow rate = 1.0 g / 10 min, ion type Zn) *10: Ionomer resin: Mitsui Dow Polychemicals Co., Ltd., product name: Himilan 1707 (melt flow rate = 0.9 g / 10 min, ion type Na) *2: NaDBS: Sodium dodecylbenzenesulfonate *4: (b2) / [(b1)+(b2)]: The ratio of polytetramethylene glycol to the total number of moles of polyethylene glycol (b1) and polytetramethylene glycol (b2). Molar %. *5: Comparative antistatic agent-1: Polyether ester amide antistatic agent, manufactured by BASF, product name Irgastat P-16

[0191] From the above, it can be seen that the antistatic resin composition of the present invention has sufficient antistatic properties with long-lasting properties and has excellent transparency when formed into a molded article. Therefore, the antistatic resin composition of the present invention is suitable for the base film of a dicing tape. Furthermore, the antistatic resin composition of the present invention is suitable for packaging materials and containers for electronic components.

Claims

1. An antistatic resin composition comprising, per 100 parts by mass of a modified polyethylene resin, 1 to 50 parts by mass of the following component (X) and 0.01 to 10.0 parts by mass of the following component (Y): Component (X): An antistatic agent containing one or more polymeric compounds (E) obtained by reacting a diol (a1), a dicarboxylic acid (a2), a polyether (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups, wherein the polyether (b) having hydroxyl groups at both ends is polyethylene glycol (b1) and polytetramethylene glycol (b2), and the proportion of polytetramethylene glycol (b2) is 10 to 80 mol % based on the total number of moles of the polyethylene glycol (b1) and the polytetramethylene glycol (b2). Component (Y): one or more members selected from the group consisting of alkali metal salts (F) and ionic liquids (G).

2. 2. The antistatic resin composition according to claim 1, wherein the polymer compound (E) is obtained by reacting a polyester (a) obtained by reacting a diol (a1) with a dicarboxylic acid (a2), a polyether (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups.

3. 3. The antistatic resin composition according to claim 2, wherein the polymer compound (E) has a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the polyether (b), and has a structure in which the blocks are bonded via an ester bond or an ether bond formed by a reaction between a hydroxyl group or a carboxyl group at an end of the polyester (a), a hydroxyl group at an end of the polyether (b), and an epoxy group of the epoxy compound (D) or a hydroxyl group formed by a reaction of an epoxy group.

4. 4. The antistatic resin composition according to claim 3, wherein the polymer compound (E) has a structure in which the epoxy compound (D) is bonded to a block polymer (C) via an ester bond, the block polymer (C) having carboxyl groups at both ends and formed by repeatedly and alternately bonding the polyester block (A) and the polyether block (B) via ester bonds.

5. 2. The antistatic resin composition according to claim 1, wherein the epoxy compound (D) of the polymer compound (E) is polypropylene glycol diglycidyl ether.

6. 3. The antistatic resin composition according to claim 2, wherein the epoxy compound (D) of the polymer compound (E) is polypropylene glycol diglycidyl ether.

7. 4. The antistatic resin composition according to claim 3, wherein the epoxy compound (D) of the polymer compound (E) is polypropylene glycol diglycidyl ether.

8. 5. The antistatic resin composition according to claim 4, wherein the epoxy compound (D) of the polymer compound (E) is polypropylene glycol diglycidyl ether.

9. A molded article obtained by molding the antistatic resin composition according to any one of claims 1 to 8.

10. The molded article according to claim 9, which is a film.

11. The molded article according to claim 10, wherein the film is a substrate film for a dicing tape.

12. The molded article according to claim 9, which is a packaging material for electronic components.

13. The molded article according to claim 9, which is a container for an electronic component.

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