JP6652842B2 - Antistatic thermoplastic resin composition and molded article obtained by molding the same - Google Patents

Description

  The present invention relates to an antistatic thermoplastic resin composition (hereinafter, also simply referred to as “resin composition”) and a molded article obtained by molding the same. More specifically, the present invention can maintain excellent antistatic properties for a long period of time, The present invention relates to an antistatic thermoplastic resin composition capable of providing a molded article having good stability, and a molded article obtained by molding the same.

  Thermoplastic resins are widely used in various molded articles such as automotive materials, home appliances, household goods, films, sheets and structural parts, depending on various advantages such as moldability, heat resistance, and low specific gravity. I have.

  On the other hand, thermoplastic resins have excellent electrical insulation properties, but have a problem that they are easily charged by friction or the like. When a molded article made of a thermoplastic resin is charged, static electricity may be generated, or dust may be attracted to the surroundings, and the appearance may be impaired. When the molded product is an electronic product, the circuit may not be able to operate normally due to charging. In addition, there is the problem of electric shock. The electric shock not only gives an electric shock to the human body from the thermoplastic resin and gives an unpleasant feeling, but also may cause an explosion accident where there is a combustible gas or dust.

  Today, various methods have been proposed to prevent such electrostatic damage, and solutions have been achieved by using antistatic agents. Examples of such an antistatic agent include those used by spraying, dipping, coating, and the like on a resin molding surface, and kneading molds that are processed by adding an additive to a polymer material. What is sprayed, immersed, or applied to the resin molding surface is mostly a water-soluble surfactant, and there is a problem that the antistatic effect is lost by wiping or washing. On the other hand, the kneading mold has a problem that if the compatibility with the resin or the heat resistance against the molding processing temperature is poor, the antistatic agent and the resin are decomposed and colored, thereby impairing the appearance of the molded article.

  From such a viewpoint, there is a demand for an antistatic thermoplastic resin composition that can exhibit a sustained antistatic property and sufficient heat resistance. For example, Patent Document 1 proposes a fatty acid amide compound of aminoethylethanolamine. Patent Literatures 2 and 3 propose polyetheresteramides. Patent Documents 4 to 6 propose various kneading-type antistatic agents such as a block polymer having a structure in which olefin blocks and hydrophilic polymer blocks are repeatedly and alternately bonded. Among them, Patent Documents 5 and 6 propose an antistatic resin composition containing a polyetherester polymer antistatic agent.

JP 2011-256293 A JP-A-58-11838 JP-A-3-29064 JP 2001-278985 A International Publication WO2014 / 115745 International Publication WO2014 / 148454

  However, unless the antistatic agent composed of polyetheresteramide is added in a large amount to the resin, sufficient antistatic performance cannot be obtained. In addition, although the antistatic agents described in Patent Documents 1 to 4 have been shown to have an antistatic effect, they do not relate to the heat resistance of the resin molded product, and particularly to the problem of coloring that occurs when the molded product is heated. Not considered. Further, there is a problem that the coloring of the resin becomes strong when the amount of the antistatic agent added increases, and further improvement is required. In Patent Documents 5 and 6, antistatic resin compositions containing a polyetherester polymer antistatic agent are proposed. However, since they do not contain an aromatic dicarboxylic acid, the present invention provides an antistatic resin composition. The structure is different from the polymer compound (A) used as the agent.

  Accordingly, an object of the present invention is to provide an antistatic thermoplastic resin composition capable of maintaining excellent antistatic properties for a long period of time and providing a molded article having good thermal stability, and a molded article obtained by molding the same. Is to provide.

  The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by using a polymer compound having a predetermined structure as an antistatic agent, and have completed the present invention. Was.

で表される基を一つ以上有し、両末端に水酸基を有する化合物（Ｃ）、および、反応性官能基を有する化合物（Ｄ）が、エステル結合を介して、または、エステル結合およびアミド結合を介して結合してなる構造を有し、
前記アミン系酸化防止剤が、ヒドロキシルアミン化合物であることを特徴とするものである。 That is, the antistatic thermoplastic resin composition of the present invention comprises 2 to 40 parts by mass of the polymer compound (A) based on 60 to 98 parts by mass of the thermoplastic resin. In an antistatic thermoplastic resin composition containing 0.001 to 20 parts by mass of an amine antioxidant (B) with respect to 100 parts by mass in total,
The polymer compound (A) is a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, the following general formula (1),

The compound (C) having at least one group represented by the formula (I) and having a hydroxyl group at both terminals and the compound (D) having a reactive functional group are formed through an ester bond or an ester bond and an amide bond. Having a structure that is bonded through
The amine-based antioxidant is a hydroxylamine compound.

  Further, in the resin composition of the present invention, the polymer compound (A) includes a polyester (E) composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid; the compound (C); It is preferable that the compound (D) is bonded through an ester bond or through an ester bond and an amide bond.

  Further, in the resin composition of the present invention, in the polymer compound (A), the block composed of the polyester (E) and the block composed of the compound (C) are repeatedly and alternately bonded via an ester bond. Has a structure in which the block polymer (G) having carboxyl groups at both ends and the compound (D) are bonded via an ester bond or via an ester bond and an amide bond. preferable.

  Still further, in the antistatic resin composition of the present invention, the block composed of the polyester (E) has a number average molecular weight of 800 to 8,000 in terms of polystyrene, and is composed of the compound (C). The number average molecular weight of the block is preferably from 400 to 6,000 in terms of polystyrene, and the number average molecular weight of the block polymer (G) is preferably from 5,000 to 25,000 in terms of polystyrene.

  In the resin composition of the present invention, the polyester (E) preferably has a structure having carboxyl groups at both ends.

  Furthermore, in the resin composition of the present invention, the compound (D) is a polyhydric epoxy compound (D) having two or more epoxy groups, and a polyhydric alcohol compound (D) having three or more hydroxyl groups. -2 and at least one selected from the group consisting of polyamine compounds (D) -3 having two or more amino groups.

  In the resin composition of the present invention, the compound (C) is preferably polyethylene glycol.

  Further, the resin composition of the present invention preferably further contains 0.01 to 5 parts by mass of one or more alkali metal salts (F).

  Furthermore, in the resin composition of the present invention, the thermoplastic resin is a group consisting of a polyolefin resin, a styrene resin, a polyester resin, a polyether resin, a polycarbonate resin, a polyamide resin, and a halogen-containing resin. It is preferably at least one selected from

  The molded article of the present invention is obtained by molding the resin composition of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the antistatic thermoplastic resin composition which can maintain the excellent antistatic property for a long period of time and can provide the molded article with favorable heat stability, and the molded object formed by shape | molding it are provided. can do.

で表される基を一つ以上有し、両末端に水酸基を有する化合物（Ｃ）、および、反応性官能基を有する化合物（Ｄ）とが、エステル結合を介して、または、エステル結合およびアミド結合を介して結合してなる構造を有している。 Hereinafter, the antistatic thermoplastic resin composition of the present invention and a molded article obtained by molding the same will be described in detail. The resin composition of the present invention contains 2 to 40 parts by mass of the polymer compound (A) based on 60 to 98 parts by mass of the thermoplastic resin, and 100 parts by mass of the total of the thermoplastic resin and the polymer compound. It contains 0.001 to 20 parts by mass of an amine antioxidant (B). In the resin composition of the present invention, the polymer compound (A) includes a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a compound represented by the following general formula (1),

The compound (C) having one or more groups represented by the following formulas and having a hydroxyl group at both ends and the compound (D) having a reactive functional group are bonded via an ester bond or an ester bond and an amide It has a structure that is connected via a bond.

First, the thermoplastic resin used in the resin composition of the present invention will be described.
The resin that can be used in the resin composition of the present invention is not particularly limited as long as it is a thermoplastic resin.From the viewpoint of durability and moldability of antistatic performance, particularly, polyolefin-based resins, styrene-based resins, and polyester-based resins , Polyether resins, polycarbonate resins, polyamide resins, and halogen-containing resins are preferred.

  Examples of the polyolefin resin include polyethylene, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, cross-linked polyethylene, ultra-high-molecular-weight polyethylene, polypropylene, homopolypropylene, random copolymer polypropylene, block copolymer polypropylene, and isotactic polypropylene. , Syndiotactic polypropylene, hemiisotactic polypropylene, polybutene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1- Α-olefin polymers such as pentene, ethylene-propylene block or random copolymers, impact copolymer polypropylene, ethylene-methyl methacrylate Rate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, α-olefin copolymer such as ethylene-vinyl acetate copolymer, polyfluoroolefin, and more. Polyolefin-based thermoplastic elastomers may be mentioned, and copolymers of two or more of these may be used.

  Examples of the styrene resin include, for example, a vinyl group-containing aromatic hydrocarbon alone, and a vinyl group-containing aromatic hydrocarbon, and another monomer (for example, maleic anhydride, phenylmaleimide, (meth) acrylate, Butadiene, (meth) acrylonitrile, etc.), for example, polystyrene (PS) resin, impact-resistant polystyrene (HIPS), acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin , Methyl methacrylate-butadiene-styrene (MBS) resin, heat-resistant ABS resin, acrylonitrile-acrylate-styrene (AAS) resin, styrene-maleic anhydride (SMA) resin, methacrylate-styrene (MS) resin, styrene-isoprene-styrene (SIS) Resin, a Thermoplastic resins such as rilonitrile-ethylene propylene rubber-styrene (AES) resin, styrene-butadiene-butylene-styrene (SBBS) resin, and methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin, and those butadiene or isoprene. Styrene-ethylene-butylene-styrene (SEBS) resin with hydrogenated double bond, styrene-ethylene-propylene-styrene (SEPS) resin, styrene-ethylene-propylene (SEP) resin, styrene-ethylene-ethylene-propylene-styrene (SEEPS) resin and the like.

  Polyester resins include, for example, polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, and polycyclohexane dimethylene terephthalate; aromatic polyesters such as polyalkylene naphthalate such as polyethylene naphthalate and polybutylene naphthalate; polytetramethylene terephthalate Linear polyester such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, poly (2-oxetanone) and the like. Polyester and the like.

  Examples of the polyether resin include polyacetal, polyphenylene ether, polyether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone, polyether sulfone, and polyether imide.

  Examples of the polycarbonate-based resin include polycarbonate, polycarbonate / ABS resin, and branched polycarbonate.

  Examples of polyamide resins include ε-caprolactam (nylon 6), undecane lactam (nylon 11), lauryl lactam (nylon 12), aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9- Polymers such as aminononanoic acid, α-pyrrolidone, α-piperidone; diamines such as hexamethylenediamine, nonanediamine, nonanemethylenediamine, methylpentadiamine, undecanemethylenediamine, dodecanemethylenediamine, and metaxylenediamine; adibic acid and sebacic acid A copolymer obtained by copolymerizing a carboxylic acid compound such as terephthalic acid, isophthalic acid, dodecanedicarboxylic acid, or dicarboxylic acid such as glutaric acid, or a mixture of these polymers or copolymers. That. Aramid resins such as "Kevlar" (trade name, manufactured by DuPont), "Nomex" (trade name, manufactured by DuPont), "Twaron" (trade name), and "CONEX" (trade name) manufactured by Teijin Limited.

  Examples of the halogen-containing resin include polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chloride rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-chloride. Vinylidene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-cyclohexylmaleimide copolymer, and the like. Can be

  Further examples of the thermoplastic resin, for example, petroleum resin, cumarone resin, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyphenylene sulfide, polyurethane, cellulose resin, polyimide resin , Polysulfone, thermoplastic resins such as liquid crystal polymers, and blends thereof.

  Further, thermoplastic resins are isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluoro rubber, silicone rubber, polyester elastomer, nitrile elastomer, nylon elastomer, vinyl chloride elastomer, Elastomers such as polyamide-based elastomers and polyurethane-based elastomers may be used, or may be used in combination.

  In the resin composition of the present invention, these thermoplastic resins may be used alone or in combination of two or more. Further, it may be alloyed. These thermoplastic resins have a molecular weight, a degree of polymerization, a density, a softening point, a proportion of an insoluble portion in a solvent, a degree of stereoregularity, the presence or absence of a catalyst residue, a kind and a mixing ratio of a monomer as a raw material, a polymerization catalyst, (Eg, Ziegler catalyst, metallocene catalyst, etc.).

Next, the polymer compound (A) will be described.
The polymer compound (A) is blended for imparting antistatic properties to the resin composition. The polymer compound (A) used in the present invention has a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and one or more groups represented by the following general formula (1), and has a hydroxyl group at both terminals. The compound (C) has a structure in which the compound (C) and the compound (D) having a reactive functional group are bonded via an ester bond or via an ester bond and an amide bond.

  In the resin composition of the present invention, the polymer compound (A) comprises a polyester (E) composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, a compound (C), and a reactive functional group. The compound (D) preferably has a structure in which the compound (D) is bonded through an ester bond or through an ester bond and an amide bond, and further has a block composed of the polyester (E) and a compound (C). ), A block polymer (G) having carboxyl groups at both ends and a compound (D) having a reactive functional group, which is formed by alternately bonding the blocks constituted by ester bonds, via an ester bond. It is also preferable to have a structure formed by bonding through an ester bond and an amide bond.

  The polyester (E) may be composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and a residue obtained by removing a hydroxyl group of a diol and a residue obtained by removing a carboxyl group of an aliphatic dicarboxylic acid, Having a structure in which the residue excluding the hydroxyl group of the diol and the residue in which the carboxyl group of the aromatic dicarboxylic acid is removed through an ester bond have a structure in which the residue is removed through an ester bond. Is preferred.

  In the resin composition of the present invention, the polyester (E) preferably has a structure having carboxyl groups at both ends, and the degree of polymerization of the polyester (E) is preferably in the range of 2 to 50.

  Examples of the diol that can be used in the resin composition of the present invention include an aliphatic diol and an aromatic group-containing diol. The diol may be a mixture of two or more. Examples of the aliphatic diol include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, and 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-pentane Diol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol 1,2-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, polyethylene glycol and the like. Among these aliphatic diols, 1,4-cyclohexane dimethanol and hydrogenated bisphenol A are preferable from the viewpoint of durability of antistatic performance, and 1,4-cyclohexane dimethanol is more preferable.

  In addition, since the aliphatic diol preferably has hydrophobicity, polyethylene glycol having hydrophilicity is not preferred among the aliphatic diols. However, when it is used together with other diols, it is not limited.

  Examples of the aromatic group-containing diol that can be used in the resin composition of the present invention include bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, and 1,4-benzene. Polyhydroxyethyl adducts of mononuclear dihydric phenol compounds such as dimethanol, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, 1,4-bis (2-hydroxyethoxy) benzene, resorcinol and pyrocatechol And the like. Among these diols having an aromatic group, an ethylene oxide adduct of bisphenol A and 1,4-bis (β-hydroxyethoxy) benzene are preferable from the viewpoint of durability of antistatic performance.

  Aliphatic dicarboxylic acids that can be used in the resin composition of the present invention may be derivatives of aliphatic dicarboxylic acids (eg, acid anhydrides, alkyl esters, alkali metal salts, acid halides, etc.). The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more.

  As the aliphatic dicarboxylic acid, preferably an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Sebacic acid, 1,10-decanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, maleic acid, fumaric acid and the like can be mentioned. Among these aliphatic dicarboxylic acids, from the viewpoint of melting point and heat resistance, aliphatic dicarboxylic acids having 4 to 16 carbon atoms are preferable, and aliphatic dicarboxylic acids having 6 to 12 carbon atoms are more preferable.

  The aromatic dicarboxylic acid that can be used in the resin composition of the present invention may be a derivative of an aromatic dicarboxylic acid (eg, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.). Further, the aromatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

  Preferred aromatic dicarboxylic acids include aromatic dicarboxylic acids having 8 to 20 carbon atoms, such as terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, and β-phenylglutaric acid. Acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate and 3-sulfoisophthalic acid Potassium and the like.

Next, the compound (C) having one or more groups represented by the general formula (1) and having hydroxyl groups at both ends will be described.
The compound (C) is preferably a compound having hydrophilicity, more preferably a polyether having a group represented by the above general formula (1), and particularly preferably a polyethylene glycol represented by the following general formula (2).

一般式（２）中、ｍは５〜２５０の整数を表す。ｍは、耐熱性や相溶性の点から、好ましくは２０〜１５０である。

In the general formula (2), m represents an integer of 5 to 250. m is preferably from 20 to 150 from the viewpoint of heat resistance and compatibility.

  As the compound (C), in addition to polyethylene glycol obtained by subjecting the group represented by the general formula (1) to an addition reaction, ethylene oxide and another alkylene oxide (for example, propylene oxide, 1,2-, 1, 4-, 2,3- or 1,3-butylene oxide). The polyether may be random or block.

  Further examples of compound (C) include compounds having a structure in which ethylene oxide is added to a compound containing an active hydrogen atom, and ethylene oxide and other alkylene oxides (for example, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide). These may be either random addition or block addition.

  Examples of the active hydrogen atom-containing compound include glycol, dihydric phenol, primary monoamine, secondary diamine, and dicarboxylic acid.

  As the glycol, an aliphatic glycol having 2 to 20 carbon atoms, an alicyclic glycol having 5 to 12 carbon atoms and an aromatic glycol having 8 to 26 carbon atoms can be used.

  As the aliphatic glycol, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3- Hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecane Diol, 1,20-eicosanediol, diethylene glycol, triethylene glycol, thiodiethylene glycol and the like.

  Examples of the alicyclic glycol include 1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 1-methyl-3,4-cyclohexanediol. , 2-hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol, 1,1'-dihydroxy-1,1'-dicyclohexyl, and the like.

  Examples of the aromatic glycol include dihydroxymethylbenzene, 1,4-bis (β-hydroxyethoxy) benzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, and 2-benzyl -1,3-propanediol, triphenylethylene glycol, tetraphenylethylene glycol, benzopinacol and the like.

  As the dihydric phenol, phenols having 6 to 30 carbon atoms can be used. For example, catechol, resorcinol, 1,4-dihydroxybenzene, hydroquinone, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenylether, dihydroxydiphenylthioether, binaphthol And alkyl (1 to 10 carbon atoms) or halogen-substituted products thereof.

  Examples of the primary monoamine include an aliphatic primary monoamine having 1 to 20 carbon atoms, and examples thereof include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, s-butylamine, isobutylamine, and n-butylamine. Examples include amylamine, isoamylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-octadecylamine, and n-icosylamine.

  As the secondary diamine, an aliphatic secondary diamine having 4 to 18 carbon atoms, a heterocyclic secondary diamine having 4 to 13 carbon atoms, an alicyclic secondary diamine having 6 to 14 carbon atoms, An aromatic secondary diamine having 8 to 14 carbon atoms and a secondary alkanol diamine having 3 to 22 carbon atoms can be used.

  Examples of the aliphatic secondary diamine include N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-dibutylethylenediamine, N, N′-dimethylpropylenediamine, and N, N′-diethylpropylene. Diamine, N, N'-dibutylpropylenediamine, N, N'-dimethyltetramethylenediamine, N, N'-diethyltetramethylenediamine, N, N'-dibutyltetramethylenediamine, N, N'-dimethylhexamethylenediamine N, N'-diethylhexamethylenediamine, N, N'-dibutylhexamethylenediamine, N, N'-dimethyldecamethylenediamine, N, N'-diethyldecamethylenediamine and N, N'-dibutyldecamethylenediamine And the like.

  Examples of the heterocyclic secondary diamine include piperazine and 1-aminopiperidine.

  Examples of the alicyclic secondary diamine include N, N′-dimethyl-1,2-cyclobutanediamine, N, N′-diethyl-1,2-cyclobutanediamine, and N, N′-dibutyl-1,2-diamine. Cyclobutanediamine, N, N'-dimethyl-1,4-cyclohexanediamine, N, N'-diethyl-1,4-cyclohexanediamine, N, N'-dibutyl-1,4-cyclohexanediamine, N, N'- Dimethyl-1,3-cyclohexanediamine, N, N'-diethyl-1,3-cyclohexanediamine, N, N'-dibutyl-1,3-cyclohexanediamine, and the like.

  As the aromatic secondary diamine, for example, N, N′-dimethyl-phenylenediamine, N, N′-dimethyl-xylylenediamine, N, N′-dimethyl-diphenylmethanediamine, N, N′-dimethyl-diphenyletherdiamine , N, N'-dimethyl-benzidine and N, N'-dimethyl-1,4-naphthalenediamine.

  Examples of the secondary alkanoldiamine include N-methyldiethanolamine, N-octyldiethanolamine, N-stearyldiethanolamine, N-methyldipropanolamine, and the like.

  As the dicarboxylic acid, a dicarboxylic acid having 2 to 20 carbon atoms can be used, and for example, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid and the like are used.

  As the aliphatic dicarboxylic acid, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, methyl succinic acid, dimethyl malonic acid, β-methyl glutaric acid, ethyl succinic acid, isopropyl malonic acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecandioic acid, tetradecandioic acid, hexadecandioic acid, octadecandioic acid and icosandioic acid.

  As the aromatic dicarboxylic acid, for example, 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 and potassium 3-sulfoisophthalate.

  Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid Acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, dicyclohexyl-4,4′-dicarboxylic acid and the like.

  These active hydrogen atom-containing compounds can be used alone or as a mixture of two or more.

Next, the compound (D) having a reactive functional group will be described.
In the present invention, the compound (D) having a reactive functional group is not particularly limited as long as it can be bonded to a carboxyl group via an ester bond or can be bonded via an amide bond. The polyester (E) and the compound (C) ) And a block composed of an ester bond or an amide bond, or a block composed of polyester (E) and a block composed of compound (C) are repeatedly and alternately coupled via an ester bond. What is necessary is just to be able to couple | bond with the block polymer (G) which has a carboxyl group at both ends by an ester bond or an amide bond. Examples of such a functional group include an epoxy group, a hydroxyl group, and an amino group.

  In the present invention, the compound (D) having a reactive functional group is preferably a polyvalent epoxy compound (D) -1 having two or more epoxy groups, a polyhydric alcohol compound (D)-having three or more hydroxyl groups. The polyvalent amine compound (D) -3 having two or two or more amino groups is preferably used because of good reaction.

  The polyvalent epoxy compound (D) -1 is not particularly limited as long as it is a compound having two or more epoxy groups, and examples thereof include mononuclear polyphenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds: dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3 -Bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra ( 4-H Roxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, polyglycidyl ether compounds of polynuclear polyphenol compounds such as terpene phenol; ethylene Polyglycidyl ethers of polyols such as glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, Fumaric acid, itaconic acid, succinic acid, glue Lulic acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as endomethylenetetrahydrophthalic acid and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N- Epoxy compounds having a glycidylamino group such as methyl-N-glycidylamino) phenyl) methane and diglycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Epoxides of cyclic olefin compounds such as carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene; Examples include epoxidized conjugated diene polymers such as epoxidized styrene-butadiene copolymer, heterocyclic compounds such as triglycidyl isocyanurate, and epoxidized soybean oil. These polyepoxy compounds can be prepared by internally cross-linking with a prepolymer of terminal isocyanate or using a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). It may have a reduced molecular weight. Two or more polyepoxy compounds may be used.

  The polyhydric alcohol compound (D) -2 is not particularly limited as long as it has three or more hydroxyl groups. For example, glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, -Methyl-1,2,3-propanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,3,5-pentanetriol, 2,3,4-pentanetriol, 2- Methyl-2,3,4-butanetriol, trimethylolethane, 2,3,4-hexanetriol, 2-ethyl-1,2,3-butanetriol, trimethylolpropane, 4-propyl-3,4,5 -Heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, triethanolamine, triisopropanolamine, 1,3,5-triol Trihydric alcohols such as (2-hydroxyethyl) isocyanurate; pentaerythritol, 1,2,3,4-pentane tetrol, 2,3,4,5-hexane tetrol, 1,2,4,5-pen Tantetrol, 1,3,4,5-hexanetetrol, diglycerin, ditrimethylolpropane, sorbitan, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, Quaternary alcohols such as N'-tetrakis (2-hydroxyethyl) ethylenediamine; pentavalent alcohols such as adonitol, arabitol, xylitol, triglycerin; dipentaerythritol, sorbitol, mannitol, iditol, inositol, darcitol, talose, allose, etc. Hexahydric alcohol; furthermore, tripe Data erythritol, and the like. The molecular weight of the polyol compound is not particularly limited, and high molecular weight polyols such as polypentaerythritol and polyvinyl alcohol can be used, and polyester polyols can also be used. Two or more polyhydric alcohol compounds may be used.

  The polyvalent amine compound (D) -3 is not particularly limited as long as it has two or more primary amino groups and / or secondary amino groups. For example, ethylenediamine, trimethylenediamine, hexamethylene C2-C12 alkylenediamines such as diamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine; aliphatic amines such as 2,2 ', 2 "-triaminotriethylamine and bis (hexamethylene) triamine; diethylenetriamine A polyalkylene polyamine having 2 to 6 carbon atoms in the alkylene group and a degree of polymerization of 2 to 5; 1,6,11-undecanetriamine, 1,8-diamino-4-aminomethyloctane, 1,3,6- Alkanetriamines such as hexamethylenetriamine; melamine, piperazine; N-aminoalkylpiperazines having 2 to 6 carbon atoms in the alkylene group, such as minoethylpiperazine; heterocyclic polyamines such as heterocyclic polyamines described in JP-B-55-21044; dicyclohexylmethanediamine, isophoronediamine, bicycloheptane Alicyclic polyamines having 4 to 20 carbon atoms such as triamine; carbon atoms such as phenyldiamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine and triphenylmethanetriamine Examples thereof include aromatic polyamines of the formulas 6 to 20. Such polyamine compounds may be used in combination of two or more.

Next, the polyester (E) and the block polymer (G) will be described.
As described above, in the resin composition of the present invention, from the viewpoint of antistatic properties, the polymer compound (A) comprises a polyester (E) comprising a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and a compound ( It is preferable that C) and the compound (D) having a reactive functional group have a structure formed by bonding via an ester bond or via an ester bond and an amide bond.

  Further, from the viewpoint of antistatic properties, the polymer compound (A) is composed of a block composed of a polyester (E) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and composed of a compound (C). The block polymer (G) having carboxyl groups at both ends formed by repeating the blocks repeatedly and alternately via an ester bond, and the compound (D) having a reactive functional group are bonded via an ester bond, or It is preferred to have a structure formed by bonding through an ester bond and an amide bond.

  The polyester (E) can be obtained, for example, by subjecting an aliphatic dicarboxylic acid or a derivative thereof, an aromatic dicarboxylic acid or a derivative thereof, and a diol to a polycondensation reaction.

  As described above, 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, or the like). When it is obtained, both ends may be finally treated to form a carboxyl group. In the state as it is, a subsequent reaction for obtaining a block polymer (G) having a structure having a carboxyl group at both ends is carried out. You may proceed. Further, the aliphatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

  As described above, the aromatic dicarboxylic acid may be a derivative of the aromatic dicarboxylic acid (eg, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, or the like). When it is obtained, both ends may be finally treated to form a carboxyl group. In the state as it is, a subsequent reaction for obtaining a block polymer (G) having a structure having a carboxyl group at both ends is carried out. You may proceed. Further, the aromatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

  In the polyester (E), the molar ratio of the residue excluding the carboxyl group of the aliphatic dicarboxylic acid to the residue excluding the carboxyl group of the aromatic dicarboxylic acid was 90:10 to 99.9: 0. 1 is preferable, and 93: 7 to 99.9: 0.1 is more preferable.

  In the resin composition of the present invention, as the polyester (E), a polyester having a carboxyl group at both terminals is preferable, and the reaction ratio between an aliphatic dicarboxylic acid or a derivative thereof and an aromatic dicarboxylic acid or a derivative thereof and a diol is as follows. It is preferable to use an excess of an aliphatic dicarboxylic acid or a derivative thereof and an aromatic dicarboxylic acid or a derivative thereof such that both terminals are carboxyl groups. Is preferred.

  The mixing ratio of the aliphatic dicarboxylic acid or its derivative to the aromatic dicarboxylic acid or its derivative during the polycondensation reaction is preferably 90:10 to 99.9: 0.1, and 93: 7 to 99.9 in molar ratio. : 0.1 is more preferable.

  Further, depending on the mixing ratio and the 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. E) may be mixed with them, or they may be reacted with the compound (C) to obtain a block polymer (G).

  In the polycondensation reaction, a catalyst that promotes the esterification reaction may be used. As the catalyst, conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used.

  Note that, as described above, when aliphatic dicarboxylic acid and aromatic dicarboxylic acid are used instead of dicarboxylic acid, when a derivative such as a carboxylic acid ester, a carboxylic acid metal salt, or a carboxylic acid halide is used, the derivative of the diol with the diol is used. After the reaction, both ends may be treated to give a dicarboxylic acid, or the reaction may proceed as it is to obtain a block polymer (G) having a structure having a carboxyl group at both ends.

  Further, the polyester (E) comprising a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid may form an ester bond by reacting with the compound (C) and form a structure of the block polymer (G). Good. Further, the carboxyl group may be present at both ends of the polyester (E), and the carboxyl group may be protected, modified, or in the form of a precursor. Further, an antioxidant such as a phenolic antioxidant may be added to the reaction system in order to suppress oxidation of the product during the reaction.

  Further, the compound (C) may be any as long as it reacts with the polyester (E) to form an ester bond and form the structure of the block polymer (G), and the hydroxyl groups at both terminals may be protected, It may be modified or in precursor form.

Next, the block polymer (G) will be described.
The block polymer (G) having a structure having carboxyl groups at both ends according to the present invention has a block composed of a polyester (E) and a block composed of a compound (C), and these blocks are: It has a structure that is repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group. As an example of such a block polymer (G), for example, a polymer having a structure represented by the following general formula (3) may be mentioned.

一般式（３）中、（Ｅ）は、両末端にカルボキシル基を有するポリエステル（Ｅ）から構成されたブロックを表し、（Ｃ）は、両末端に水酸基を有する化合物（Ｃ）から構成されたブロックを表し、ｔは繰り返し単位の繰り返しの数であり、好ましくは１〜１０の数を表す。ｔは、より好ましくは１〜７の数であり、最も好ましくは１〜５の数である。

In the general formula (3), (E) represents a block composed of a polyester (E) having a carboxyl group at both ends, and (C) is composed of a compound (C) having a hydroxyl group at both ends. Represents a block, and t is the number of repetitions of the repeating unit, and preferably represents a number of 1 to 10. t is more preferably a number from 1 to 7, and most preferably a number from 1 to 5.

  Part of the block composed of polyester (E) in the block polymer (G) is composed of a block composed of polyester composed only of diol and aliphatic dicarboxylic acid, or composed of only diol and aromatic dicarboxylic acid. May be replaced by a block made of polyester.

  The block polymer (G) having a structure having carboxyl groups at both ends is obtained by subjecting a polyester (E) having carboxyl groups at both ends and a compound (C) having hydroxyl groups at both ends to a polycondensation reaction. A polyester (E) and a compound (C) having a structure equivalent to a structure in which a polyester (E) and a compound (C) are repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group. If so, it is not always necessary to synthesize from the polyester (E) and the compound (C).

  If the reaction ratio of the polyester (E) and the compound (C) is adjusted so that the compound (C) is X mol and the polyester (E) is X + 1 mol, the block polymer having a carboxyl group at both terminals is obtained. (G) can be preferably obtained.

  In the reaction, after completion of the synthesis reaction of the polyester (E), the compound (C) may be added to the reaction system without isolating the polyester (E), and the reaction may be performed as it is.

  In the polycondensation reaction, a catalyst that promotes the esterification reaction may be used. As the catalyst, conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used. Further, an antioxidant such as a phenolic antioxidant may be added to the reaction system in order to suppress oxidation of the product during the reaction.

  The polyester (E) may be mixed with 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. To obtain a block polymer (G).

  The block polymer (G) includes, in addition to the block composed of the polyester (E) and the block composed of the compound (C), a block composed of a polyester composed only of a diol and an aliphatic dicarboxylic acid, or a diol. A block composed of a polyester composed only of an aromatic dicarboxylic acid may be included in the structure.

  The polymer compound (A) according to the present invention is an ester formed by a terminal carboxyl group of a block polymer (G) having a structure having carboxyl groups at both ends and a compound (D) having a reactive functional group. Those having a structure formed through a bond or an ester bond and an amide bond are preferable. The polymer compound (A) further comprises an ester bond formed by a carboxyl group of the polyester (E) and a reactive functional group of the compound (D) having a reactive functional group, or And a structure formed via an amide bond.

  In order to obtain the polymer compound (A), the carboxyl group of the block polymer (G), the epoxy group of the polyhydric epoxy compound of the compound (D), the hydroxyl group of the polyhydric alcohol compound, or the amino group of the polyhydric amine compound And may be reacted.

  When the compound (D) is a polyvalent epoxy compound (D) -1 having two or more epoxy groups, the number of epoxy groups in the polyvalent epoxy compound (D) -1 depends on the number of the block polymer (G) to be reacted. The number of carboxyl groups is preferably 0.5 to 5 equivalents, more preferably 0.5 to 1.5 equivalents.

  The polyepoxy compound (D) -1 having two or more epoxy groups to be reacted is preferably 0.1 to 2.0 equivalents of the carboxyl group of the block polymer (G) to be reacted, and 0.2 to 1. Five equivalents are more preferred.

  When the compound (D) is a polyhydric alcohol compound (D) -2 having three or more hydroxyl groups, the number of hydroxyl groups in the polyhydric alcohol compound (D) -2 depends on the number of carboxyl groups in the block polymer (G) to be reacted. Is preferably 0.5 to 5 equivalents, more preferably 0.5 to 1.5 equivalents.

  The polyhydric alcohol compound (D) -2 having three or more hydroxyl groups to be reacted is preferably 0.1 to 2.0 equivalents of the carboxyl group of the block polymer (G) to be reacted, and 0.2 to 1.5 equivalents. Equivalents are more preferred.

  When the compound (D) is a polyamine compound (D) -3 having two or more amino groups, the number of amino groups of the polyamine compound (D) -3 depends on the number of the block polymer (G) to be reacted. The number of carboxyl groups is preferably 0.5 to 5 equivalents, more preferably 0.5 to 1.5 equivalents.

  The polyvalent amine compound (D) -3 having two or more amino groups to be reacted is preferably 0.1 to 2.0 equivalents of the carboxyl group of the block polymer (G) to be reacted, and 0.2 to 1. Five equivalents are more preferred.

  In the reaction, after completion of the synthesis reaction of the block polymer (G), the compound (D) may be added without isolating the block polymer (G), and the reaction may be performed as it is. In that case, the carboxyl group of the unreacted polyester (E) used excessively when synthesizing the block polymer (G) reacts with some of the reactive functional groups of the compound (D) to form an ester bond and An amide bond may be formed.

  In the preferred polymer compound (A) of the present invention, the block polymer (G) having a structure having carboxyl groups at both ends and the compound (D) are formed through an ester bond or through an ester bond and an amide bond. The structure is not necessarily limited to the block polymer (G) and the compound (D) as long as the structure has the same structure as the structure having the bonded structure.

  In the resin composition of the present invention, the number average molecular weight of the block composed of the polyester (E) in the polymer compound (A) is preferably from 800 to 8,000 in terms of polystyrene, more preferably 1,000. 6,000, more preferably 2,000-4,000. The number average molecular weight of the block composed of the compound (C) having a hydroxyl group at both ends in the polymer compound (A) is preferably 400 to 6,000 in terms of polystyrene, and more preferably 1,000. 5,000, more preferably 2,000-4,000.

  Further, the number average molecular weight of the block composed of the block polymer (G) having a structure having carboxyl groups at both ends in the polymer compound (A) is preferably 5,000 to 25,000 in terms of polystyrene. , More preferably from 7,000 to 17,000, and more preferably from 9,000 to 13,000.

  In the polymer compound (A) according to the present invention, after obtaining a polyester (E) from a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, the compound (C) and the polyester (E) are isolated without isolating the polyester (E). And / or may be reacted with compound (D).

  When the polymer compound (A) is blended with the thermoplastic resin, the polymer compound (A) is used in an amount of 2 to 40 parts by mass, based on 100 parts by mass of the total of the thermoplastic resin and the polymer compound (A). From the viewpoint of prevention and the effect on the resin physical properties, 5 to 20 parts by mass is preferable, and 7 to 15 parts by mass is more preferable. If the amount is less than 2 parts by mass, sufficient antistatic properties may not be obtained, and if it exceeds 40 parts by mass, the physical properties of the molded article may be adversely affected.

Next, the amine-based antioxidant (B) will be described.
The amine antioxidant (B) is not particularly limited as long as it has an amine structure and imparts heat resistance to the thermoplastic resin, and can be added to the thermoplastic resin together with the polymer compound (A). it can.

  Specific examples of the amine-based antioxidant (B) include, for example, dioctylmethylamine oxide, trioctylamine oxide, didecylmethylamine oxide, tridecylamine oxide, di (hydrogenated C12-14 alkyl) methylamine Oxide, tri (hydrogenated C12-14 alkyl) amine oxide, di (hydrogenated C16-18 alkyl) methylamine oxide, tri (hydrogenated C16-18 alkyl) amine oxide, di (C20-22) alkylmethylamine oxide and Amine oxide compounds such as tri (C20-22) alkyl) amine oxide, N, N-dibenzylhydroxylamine, phenylnaphthylamine, 4,4′-dimethoxydiphenylamine, 4,4′-bis (α, α-dimethylbenzyl) Diphenylamine, 4-isopro N, N-diarylhydroxylamine such as oxydiphenylamine, N, N-alkylarylhydroxylamine, N, N-dicycloalkylhydroxylamine, diethylhydroxylamine, dioctylhydroxylamine, didodecylhydroxylamine, dioctadecylhydroxylamine and the like N, N-dialkylhydroxylamine. In the present invention, N, N-diarylhydroxylamine and N, N-dialkylhydroxylamine compounds are preferred, and more preferably N, N-dialkylhydroxylamine compounds having an alkyl group of 6 to 30 carbon atoms, particularly , Dioctadecylhydroxylamine is preferred.

  The amount of the amine-based antioxidant (B) may be appropriately determined in consideration of the desired heat resistance. It is 001 to 20 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.03 to 2 parts by mass. If the amount of the amine antioxidant is less than 0.001 part by mass, the effect of improving heat resistance may not be obtained, and if it exceeds 20 parts by mass, the physical properties of the resin may be adversely affected.

  It is preferable that the resin composition of the present invention further contains one or more alkali metal salts (F) from the viewpoint of improving the antistatic property, its durability, and the crystallinity.

  Examples of the alkali metal salt (F) include salts of organic acids or inorganic acids. Examples of the alkali metal include lithium, sodium, potassium, cesium, rubidium and the like. Examples of organic acids include formic, acetic, propionic, butyric, lactic, pentanoic, caproic, heptanoic, caprylic, pelargonic, capric, lauric, myristic, pentadecyl, palmitic, margaric , Stearic acid, aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as 12-hydroxystearic acid; having 1 to 12 carbon atoms such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid and adipic acid; Aliphatic dicarboxylic acid; aromatic carboxylic acid such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; and 1 carbon atom such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethanesulfonic acid To 20 sulfonic acids. Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like. Among them, lithium, sodium and potassium are more preferable, and lithium and sodium are most preferable from the viewpoint of antistatic property. In addition, from the viewpoint of antistatic properties, salts of acetic acid, salts of perchloric acid, salts of p-toluenesulfonic acid, and salts of dodecylbenzenesulfonic acid are preferred.

  Specific examples of the alkali metal salt (F) include, for example, lithium acetate, sodium acetate, potassium acetate, lithium butyrate, sodium butyrate, potassium butyrate, lithium laurate, sodium laurate, potassium laurate, lithium myristate, myristic acid Sodium, potassium myristate, lithium palmitate, sodium palmitate, potassium palmitate, lithium stearate, sodium stearate, potassium stearate, lithium 12-hydroxystearate, sodium 12-hydroxystearate, potassium 12-hydroxystearate , Lithium chloride, sodium chloride, potassium chloride, lithium phosphate, sodium phosphate, potassium phosphate, lithium sulfate, sodium sulfate, lithium perchlorate, perchloric acid Thorium, potassium perchlorate, lithium p- toluenesulfonic acid, sodium p- toluenesulfonic acid, potassium p- toluenesulfonic acid, lithium dodecylbenzenesulfonate, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate and the like. Of these, lithium acetate, potassium acetate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, lithium chloride and the like are preferred.

  The blending amount of the alkali metal salt (F) is 0.01 to 5.0 parts by mass based on 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A) from the viewpoint of antistatic properties. 0.1 to 3.0 parts by mass is preferable, and 0.3 to 2.0 parts by mass is more preferable. If the amount of the alkali metal salt (F) is less than 0.01 part by mass, the effect of adding the alkali metal salt (F) may not be sufficient. If the amount exceeds 5.0 parts by mass, the physical properties of the resin are adversely affected. There may be.

  The resin composition of the present invention may further contain a salt of a Group 2 element as long as the effects of the present invention are not impaired.

  Examples of the salt of the Group 2 element include salts of an organic acid or an inorganic acid, and examples of the Group 2 element include beryllium, magnesium, calcium, strontium, barium, and the like. Examples of the organic acid include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, and the like. Aliphatic carboxylic acids having 1 to 12 carbon atoms; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethane Examples thereof include sulfonic acids having 1 to 20 carbon atoms such as sulfonic acids. Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like.

  Further, a surfactant may be added to the resin composition of the present invention as long as the effects of the present invention are not impaired. As the surfactant, a nonionic, anionic, cationic or amphoteric surfactant can be used.

  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; fatty acid esters of polyethylene oxide and glycerin And fatty acid esters of pentaerythritol, fatty acid esters of sorbit or sorbitan, alkyl ethers of polyhydric alcohols, and polyhydric alcohol-type nonionic surfactants such as aliphatic amides of alkanolamines.

  Examples of the anionic surfactant include a carboxylate such as an alkali metal salt of a higher fatty acid; a sulfate such as a higher alcohol sulfate or a higher alkyl ether sulfate; an alkylbenzene sulfonate; an alkyl sulfonate; Sulfonates such as paraffin sulfonates; phosphate esters such as higher alcohol phosphates; and the like.

  Examples of the cationic surfactant include a quaternary ammonium salt such as an alkyltrimethylammonium salt.

  Examples of the amphoteric surfactant include an amino acid-type amphoteric surfactant such as a higher alkylaminopropionate, a betaine-type amphoteric surfactant such as a higher alkyldimethylbetaine and a higher alkyldihydroxyethylbetaine, and the like. Two or more kinds can be used in combination.

  The amount of the surfactant is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). More preferred.

  Further, a polymer type antistatic agent may be added to the resin composition of the present invention as long as the effects of the present invention are not impaired. As the polymer antistatic agent, for example, a polymer type antistatic agent such as a known polyetheresteramide can be used, and as the known polyetheresteramide, for example, JP-A-7-10989 And polyetheresteramides comprising the above-mentioned bisphenol A polyoxyalkylene adducts. Further, a block polymer having a repeating structure in which a bonding unit between a polyolefin block and a hydrophilic polymer block has 2 to 50 can be used, and examples thereof include a block polymer described in US Pat. No. 6,552,131.

  When the polymer type antistatic agent is compounded, the compounding amount is preferably 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). Parts by mass are more preferred.

  Further, the resin composition of the present invention may contain an ionic liquid as long as the effects of the present invention are not impaired. Examples of the ionic liquid have a melting point below room temperature, at least one of the cations or anions constituting the ionic liquid is an organic ion, and the initial conductivity is preferably 1 to 200 ms / cm, more preferably A room-temperature molten salt of 10 to 200 ms / cm, for example, a room-temperature molten salt described in International Publication No. 95/15572.

  Examples of the cation constituting the ionic liquid include a cation selected from the group consisting of amidinium, pyridinium, pyrazolium and guanidinium cations.

The amidinium cations include the following.
(1) imidazolinium cations having 5 to 15 carbon atoms, for example, 1,2,3,4-tetramethylimidazolinium, 1,3-dimethylimidazolinium;
(2) imidazolium cations having 5 to 15 carbon atoms, for example, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium;
(3) Tetrahydropyrimidinium cation The one having 6 to 15 carbon atoms, for example, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetra Methyl-1,4,5,6-tetrahydropyrimidinium;
(4) Dihydropyrimidinium cation Examples thereof include those having 6 to 20 carbon atoms, such as 1,3-dimethyl-1,4-dihydropyrimidinium and 1,3-dimethyl-1,6-dihydropyrimidi. , 8-Methyl-1,8-diazabicyclo [5,4,0] -7,9-undecadienium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,10-un Decadienium.

  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.

Examples of the guanidinium cation include the following.
(1) Guanidinium cation having an imidazolinium skeleton having 8 to 15 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3 , 4-trimethylimidazolinium;
(2) Guanidinium cation having an imidazolium skeleton having 8 to 15 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4 -Trimethylimidazolium;
(3) Guanidinium cation having a tetrahydropyrimidinium skeleton having 10 to 20 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydro Pyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium;
(4) A guanidinium cation having a dihydropyrimidinium skeleton having 10 to 20 carbon atoms, for example, 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, 2-diethylamino-1 , 3-Dimethyl-4-ethyl-1,6-dihydropyrimidinium.

  One kind of cation may be used alone, or two or more kinds may be used in combination. Among these, an amidinium cation, more preferably an imidazolium cation, and particularly preferably a 1-ethyl-3-methylimidazolium cation from the viewpoint of antistatic properties.

  In the ionic liquid, examples of the organic acid or inorganic acid constituting the anion include the following. Organic acids include, for example, carboxylic acids, sulfates, sulfonic acids and phosphates; inorganic acids include, for example, superacids (eg, borofluoric acid, tetrafluoroboric acid, perchloric acid, phosphorus hexafluoride) Acids, antimony hexafluoride and arsenate hexafluoride), phosphoric acid and boric acid. The above organic acids and inorganic acids may be used alone or in combination of two or more.

  Among organic acids and inorganic acids, preferred from the viewpoint of the antistatic property of the ionic liquid are conjugate bases of super strong acids in which the Hammett acidity function (-Ho) of the anion constituting the ionic liquid is 12 to 100, Acids that form anions other than the conjugate base of superacids and mixtures thereof.

  Examples of anions other than the conjugate base of the super strong acid include halogen (eg, fluorine, chlorine and bromine) ions, alkyl (C 1 to C 12) benzenesulfonic acid (eg, p-toluenesulfonic acid and dodecylbenzenesulfonic acid) ) Ions and poly (n = 1-25) fluoroalkanesulfonic acid (e.g., undecafluoropentanesulfonic acid) ions.

  In addition, examples of the super strong acid include those derived from a protic acid and a combination of a protic acid and a Lewis acid, and a mixture thereof. Examples of the protic acid as a super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, and alkane ( C1-30 sulfonic acid (e.g., methanesulfonic acid, dodecanesulfonic acid, etc.), poly (n = 1-30) fluoroalkane (C1-30) sulfonic acid (e.g., trifluoromethanesulfonic acid, Pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and boron tetrafluoride. Of these, preferred from the viewpoint of ease of synthesis are borofluoric acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imidic acid, and bis (pentafluoroethylsulfonyl) imidic acid.

  Protic acids used in combination with Lewis acids include, for example, hydrogen halides (eg, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethane Sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof. Among these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of the ionic liquid.

  Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and a mixture thereof. Among these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of the ionic liquid.

  The combination of a protonic acid and a Lewis acid is optional, but examples of the super strong acid comprising these combinations include tetrafluoroboric acid, hexafluorophosphoric acid, tantalum hexafluoride, antimony hexafluoride, and hexafluoro acid. Tantalum sulfonic acid, boron tetrafluoride, hexafluorophosphoric acid, boron trifluoride, arsenic hexafluoride, and mixtures thereof.

  Among the above anions, preferred from the viewpoint of the antistatic property of the ionic liquid are conjugate bases of a superacid (a superacid composed of a protic acid and a superacid composed of a combination of a proton acid and a Lewis acid), and more preferred. Is a conjugate base of a super-strong acid consisting of a protic acid and a pro-acid and a super-strong acid consisting of boron trifluoride and / or phosphorus pentafluoride.

  Among the ionic liquids, preferred from the viewpoint of antistatic properties are ionic liquids having an amidinium cation, more preferred are ionic liquids having a 1-ethyl-3-methylimidazolium cation, and particularly preferred are 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide.

  When the ionic liquid is compounded, the compounding amount is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the thermoplastic resin and the polymer compound (A).

  Furthermore, the resin composition of the present invention may optionally contain a compatibilizer as long as the effects of the present invention are not impaired. By blending the compatibilizer, the compatibility between the antistatic component and other components or the resin component can be improved. Examples of the compatibilizer include a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and a polyoxyalkylene group. -258850, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, or a block polymer having a polyolefin portion and an aromatic vinyl polymer portion. .

  When the compatibilizer is compounded, the compounding amount is preferably 0.01 to 5 parts by mass, and preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). More preferred.

  Further, the resin composition of the present invention may optionally contain a known resin additive (for example, a phenolic antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, Antioxidants, ultraviolet absorbers, hindered amine compounds, nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, antistatic agents different from the polymer compound (A) according to the present invention, Pigments, dyes, etc.). The known resin additives may be mixed with the polymer compound (A) and the amine-based antioxidant (B) and then added to the thermoplastic resin, or separately added to the thermoplastic resin and molded. May be used.

  Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, and 2,2′-methylenebis (4 -Ethyl-6-tert-butylphenol), 2,2'-thiobis- (6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2′-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, 2,2'-oxamido-bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2-ethylhexyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2,2'-ethylenebis (4,6-di-tert-butylphenol), 3, Ester of 5-di-tert-butyl-4-hydroxy-benzenepropanoic acid and C13-15 alkyl, 2,5-di-tert-amylhydroquinone, and a polymer of hindered phenol (trade name AO. OH.98), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2-te t-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) Ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert- Butylbenz [d, f] [1,3,2] -dioxaphosphine, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [monoethyl (3 5-di-tert-butyl-4-hydroxybenzyl) phosphonate] calcium salt, 5,7-bis (1,1-dimethylethyl) -3-hydroxy-2 Reaction product of (3H) -benzofuranone and o-xylene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol , DL-a-tocophenol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3,3-bis- (4′-hydroxy-3′-tert-butyl-) Phenyl) butanoic acid] glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-tert- Tyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [ 3,3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, 4,4′-butylidenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (6 -Tert-butyl-3-methylphenol), 2,2'-ethylidenebis (4,6-di-tert- Butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert) -Butyl-5-methylbenzyl) phenyl] terephthalate, 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) -2,4,6-trimethylbenzene, , 3,5-Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [Methylene-3- (3 ', 5'-tert-tributyl-4'-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl) -5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8, 10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], stearyl-3- (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionamide, palmityl-3- (3,5-di-tert-butyl-4-hydroxyphene) Nyl) propionamide, myristyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, lauryl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as propionamide. When the phenolic antioxidant is compounded, the amount is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). More preferred.

  Examples of the phosphorus-based antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctyl phenyl phosphite, diphenyl Tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithio phosphite, bis (Tridecyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecylphosphite, dinonylphenylbi (Nonylphenyl) phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyldipropylene glycol diphosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris ( 2,4-di-tert-butyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl Phosphite, tri (decyl) phosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, distearylpentaerythritol diphosphite, a mixture of distearylpentaerythritol and calcium stearate, alkyl (C 0) bisphenol A phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) ) Pentaerythritol diphosphite, tetraphenyl-tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidene diphenol Rudiphosphite, 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) butanetriphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, (1-methyl-1-propenyl-3-ylidene) tris (1,1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecylphosphite, 2,2′-methylenebis (4 , 6-di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methyl Bis (4,6-di-tert-butylphenyl) -octadecylphosphite, 2,2′-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphite, 4,4′-butylidenebis (3- Methyl-6-tert-butylphenylditridecyl) phosphite, tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphospho Pin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphesspiro [5,5] undecane, , 4,6-Tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4'-isopropylidene dipheno Le C12-15 alcohols phosphite, and the like. When the phosphorus-based antioxidant is compounded, the compounding amount is preferably 0.001 to 20 parts by mass, and 0.01 to 5 parts by mass, based on 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). Parts are more preferred.

  Examples of the thioether-based antioxidant include 3,3′-thiodipropionic acid, alkyl (C12-14) thiopropionic acid, di (lauryl) -3,3′-thiodipropionate, and di (tridecyl)- 3,3'-thiodipropionate, di (myristyl) -3,3'-thiodipropionate, di (stearyl) -3,3'-thiodipropionate, di (octadecyl) -3,3'- Thiodipropionate, laurylstearylthiodipropionate, tetrakis [methylene-3- (dodecylthio) propionate] methane, thiobis (2-tert-butyl-5-methyl-4,1-phenylene) bis (3- (dodecylthio) Propionate), 2,2'-thiodiethylenebis (3-aminobutenoate), 4,6-bis (octylthiomethyl -O-cresol, 2,2'-thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2'-thiobis (4-methyl-6-tert- Butylphenol), 2,2'-thiobis (6-tert-butyl-p-cresol), 2-ethylhexyl- (3,5-di-tert-butyl-4-hydroxybenzyl) thioacetate, 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (4-methyl-6-tert-butylphenol), 4,4 ′-[thiobis (methylene)] bis (2-tert-butyl- 6-methyl-1-hydroxybenzyl), bis (4,6-di-tert-butylphenol-2-yl) sulfide, tridecyl-3,5 Di-tert-butyl-4-hydroxybenzylthioacetate, 1,4-bis (octylthiomethyl) -6-methylphenol, 2,4-bis (dodecylthiomethyl) -6-methylphenol, distearyl-disulfide And bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl) sulfide and the like. When the thioether-based antioxidant is compounded, the compounding amount is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). Parts are more preferred.

  Other antioxidants include N-benzyl-α-phenyl nitrone, N-ethyl-α-methyl nitrone, N-octyl-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α -Tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α Nitrone compounds such as -heptadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, 3-arylbenzofuran-2 (3H) -one, 3- (alkoxyphenyl) benzofuran-2-one, 3- (acyloxyphenyl) benzofuran -2 (3H) -one, 5,7-di-tert-butyl- 3- (3,4-dimethylphenyl) -benzofuran-2 (3H) -one, 5,7-di-tert-butyl-3- (4-hydroxyphenyl) -benzofuran-2 (3H) -one, 7-di-tert-butyl-3- {4- (2-hydroxyethoxy) phenyl} -benzofuran-2 (3H) -one, 6- (2- (4- (5,7-di-tert-2- Oxo-2,3-dihydrobenzofuran-3-yl) phenoxy) ethoxy) -6-oxohexyl-6-((6-hydroxyhexanoyl) oxy) hexanoate, 5-di-tert-butyl-3- (4- And benzofuran compounds such as ((15-hydroxy-3,6,9,13-tetraoxapentadecyl) oxy) phenyl) benzofuran-2 (3H) one. The amount of the other antioxidant is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). Is more preferred.

  Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) ) Benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 -Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert- Octyl-6-benzotriazolylphenol), 2- (2-hydroxy Polyethylene glycol ester of 3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy- 3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [ 2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, -[2-hydroxy-3- tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2- Hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [ 2- (2-hydroxy) such as 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole and 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole Phenyl) benzotriazoles; Phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate , Dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl-4) Benzoates such as -hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate and behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2 '-Ethoxyoxanilide, 2-ethoxy-4'-dodecy Substituted oxanilides such as oxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts; Alternatively, metal chelates, particularly salts of nickel and chromium, chelates and the like can be mentioned. The compounding amount when the ultraviolet absorber is compounded is preferably 0.001 to 10 parts by mass, and 0.01 to 0.5 part by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). Parts are more preferred.

  As the hindered amine compound, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6- Tetramethyl-4-piperidylbenzoate, bis (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) Ru) -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-hydroxybenzyl) 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- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane , Bis {4- (1-octyloxy-2,2,6,6- Tetramethyl) piperidyl} decandionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate, TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals, and the like. When the hindered amine compound is compounded, the amount is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 part by mass, based on 100 parts by mass of the total of the thermoplastic resin and the polymer compound (A). Is more preferred.

  Examples of the nucleating agent include sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate and 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] Carboxylic acid metal salts such as heptane-2,3-dicarboxylate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol , And bis (dimethyl Polyol derivatives such as benzylidene) sorbitol, N, N ', N "-tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N', N" -tricyclohexyl-1,3,5 Amide compounds such as -benzenetricarboxamide, N, N'-dicyclohexylnaphthalenedicarboxamide, and 1,3,5-tri (dimethylisopropoylamino) benzene. The compounding amount when the nucleating agent is compounded is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass, based on 100 parts by mass of the total of the thermoplastic resin and the polymer compound (A). Parts are more preferred.

  Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis (diphenyl phosphate), and (1-methylethylidene). -4,1-phenylenetetraphenyldiphosphate, 1,3-phenylenetetrakis (2,6-dimethylphenyl) phosphate, trade name ADK STAB FP-500 manufactured by ADEKA Corporation, trade name ADK STAB FP-600 manufactured by ADEKA Corporation, stock Aromatic phosphate esters such as ADEKA STAB FP-800 (trade name, manufactured by ADEKA Corporation), phosphonate esters such as divinyl phenylphosphonate, diallyl phenylphosphonate, and phenylphosphonic acid (1-butenyl); Phosphinic esters such as phenyl phenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, bis (2-allylphenoxy) phosphazene and dicresylphosphazene; Phosphazene compounds, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus, Metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolak type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis Pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene Ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, Pentabromobenzyl acrylate and brominated flame retardants such as brominated styrene can be mentioned. These flame retardants are preferably used in combination with an anti-drip agent such as a fluororesin and a flame retardant aid such as a polyol and hydrotalcite. The amount of the flame retardant to be blended is preferably 1 to 50 parts by mass, more preferably 10 to 30 parts by mass, based on 100 parts by mass of the total of the thermoplastic resin and the polymer compound (A).

  The lubricant is added for the purpose of imparting lubricity to the surface of the molded article and enhancing the effect of preventing damage. As the lubricant, for example, unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, stearic acid monoglyceride, sorbitan monopalmititate, Sorbitan monostearate, mannitol, stearic acid, hardened castor oil, stearin sun amide, oleic amide, ethylene bisstearic amide and the like can be mentioned. These may be used alone or in combination of two or more. The amount of the lubricant is preferably 0.01 to 2 parts by mass, more preferably 0.03 to 0.5 part by mass, per 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). More preferred.

  Examples of the filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, and dolomite. , Mica, silica, alumina, potassium titanate whiskers, walsteinite, fibrous magnesium oxysulfate, etc., and appropriately selecting and using the particle diameter (in the case of fibrous form, the fiber diameter, fiber length and aspect ratio). Can be. In addition, a filler that has been subjected to a surface treatment as necessary can be used. When the filler is compounded, the amount is preferably 0.01 to 80 parts by mass, more preferably 1 to 50 parts by mass, based on 100 parts by mass of the total of the thermoplastic resin and the polymer compound (A).

  As the metal soap, salts of metals such as magnesium, calcium, aluminum and zinc and saturated or unsaturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and oleic acid are used. The amount of the metal soap is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the total of the thermoplastic resin and the polymer compound (A). More preferred.

ここで、一般式（４）中、ｘ１およびｘ２はそれぞれ下記式、
０≦ｘ２／ｘ１＜１０，２≦ｘ１＋ｘ２≦２０
で表される条件を満たす数を表し、ｐは０または正の数を表す。

ここで、一般式（５）中、Ａ^ｑ−は、ｑ価のアニオンを表し、ｐは０または正の数を表す。また、ハイドロタルサイト類における炭酸アニオンは、一部を他のアニオンで置換したものでもよい。 Hydrotalcites are known as natural or synthetic products of magnesium, aluminum, a complex salt compound consisting of a hydroxyl group, a carbonate group and any crystal water, and a part of magnesium or aluminum is converted to another metal such as alkali metal or zinc. Examples thereof include those substituted with a metal and those in which a hydroxyl group or a carbonate group is substituted with another anion group. Specifically, for example, a metal of hydrotalcite represented by the following general formula (4) is substituted with an alkali metal. What was done. Further, as the Al—Li-based hydrotalcites, a compound represented by the following general formula (5) can also be used.

Here, in the general formula (4), x1 and x2 are respectively the following formulas:
0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 ≦ 20
And p represents 0 or a positive number.

Here, in the general formula (5), A ^q- represents a q-valent anion, and p represents 0 or a positive number. Further, the carbonate anion in the hydrotalcites may be one in which a part is substituted with another anion.

  Hydrotalcites may be obtained by dehydrating water of crystallization, and may be higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, or organic metal sulfonates such as alkali metal dodecylbenzenesulfonate. It may be coated with a salt, a higher fatty acid amide, a higher fatty acid ester or a wax.

  The hydrotalcites may be natural products or synthetic products. Examples of the synthesis method include JP-B-46-2280, JP-B-50-30039, JP-B-51-29129, JP-B-3-36839, JP-A-61-174270, and JP-A-5-218270. A known method described in, for example, Japanese Patent Publication No. 179052 or the like can be used. In addition, hydrotalcites can be used without being limited by their crystal structure, crystal particles, and the like. When the hydrotalcites are compounded, the amount is preferably 0.001 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). More preferred.

  As the pigment, a commercially available pigment can also be used. For example, Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112 , 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224 , 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71 Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 1 0, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

  As the dye, azo dye, anthraquinone dye, indigoid dye, triarylmethane dye, xanthene dye, alizarin dye, acridine dye, stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamine dye, oxazine dye, phthalocyanine dye And a dye such as a cyanine dye. These may be used as a mixture of two or more.

  The method for producing the resin composition of the present invention is not particularly limited, and the thermoplastic resin is added to the polymer compound (A), the amine-based antioxidant (B), and if necessary, the alkali metal salt (F) and other optional components. The components may be blended, and any method commonly used can be used. For example, they may be mixed by kneading with a roll, kneading with a bumper, an extruder, a kneader, or the like, and mixing.

  The polymer compound (A) may be added as it is, or, if necessary, after impregnating the carrier. In order to impregnate the carrier, the mixture may be heated and mixed as it is, or if necessary, may be diluted with an organic solvent, then impregnated into the carrier, and then the solvent may be removed. As such carriers, those known as fillers and fillers of thermoplastic resins, or flame retardants and light stabilizers which are solid at ordinary temperature can be used, for example, calcium silicate powder, silica powder, talc powder, alumina Powders, titanium oxide powders, those obtained by chemically modifying the surface of these carriers, and solid materials among the following flame retardants and antioxidants are exemplified. Among these carriers, those obtained by chemically modifying the surface of the carrier are preferable, and those obtained by chemically modifying the surface of the silica powder are more preferable. These carriers preferably have an average particle size of 0.1 to 100 μm, more preferably 0.5 to 50 μm.

  Further, as a method of blending the polymer compound (A) with the thermoplastic resin component, the block polymer (G), the polymer compound (A) and the amine-based antioxidant (B) may be blended together. Well, they may be blended separately.

  The polymer compound (A) is prepared by kneading the block polymer (G) and the compound (D) having a reactive functional group into the thermoplastic resin component while synthesizing the polymer compound (A). At this time, the alkali metal salt (F) may be kneaded at the same time, or the polymer compound (A), the alkali metal salt (F) and the resin component may be mixed at the time of molding such as injection molding to form a molded product. And a masterbatch of an amine-based antioxidant (B) and / or an alkali metal salt (F) and a thermoplastic resin is manufactured in advance. You may mix.

  Furthermore, the polymer compound (A) and the alkali metal salt (F) may be mixed in advance and then mixed with the thermoplastic resin, and synthesized by adding the alkali metal salt (F) during the reaction. The polymer compound (A) may be blended with the thermoplastic resin.

Next, the molded article of the present invention will be described.
The molded article of the present invention is obtained by molding the resin composition of the present invention. By molding the resin composition of the present invention, a molded article having excellent antistatic properties and high heat resistance can be produced. The molding method is not particularly limited, and examples include extrusion, calendering, injection molding, roll, compression molding, blow molding, rotational molding, and the like. Resin plates, sheets, films, bottles, fibers, deformed products, and the like Moldings of various shapes can be manufactured.

  Usually, when an antistatic agent is blended, the physical properties often decrease, but the molded article of the present invention has excellent antistatic properties and excellent heat resistance, and has little decrease in physical properties. In particular, it has resistance to antistatic properties against wiping the surface of the molded product.

  The resin composition of the present invention and a molded article thereof are used for electric / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical care, coal, petroleum, rubber, leather, automobile, precision equipment, wood, building materials, It can be used in a wide range of industrial fields such as civil engineering, furniture, printing, musical instruments, etc.

  More specifically, the resin composition of the present invention and a molded article thereof include a printer, a personal computer, a word processor, a keyboard, a PDA (small information terminal), a telephone, a copying machine, a facsimile, an ECR (electronic cash register), Office work such as calculators, electronic notebooks, cards, holders, stationery, etc., OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, kotatsu and other home appliances, TVs, VTRs, video cameras, radio and cassette players , Tape recorders, mini discs, CD players, speakers, liquid crystal displays, and other AV equipment, connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor sealing materials, LED sealing materials, electric wires, cables, transformers, deflection yokes , Distribution boards, electric and electronic parts such as watches, communication equipment, interior and exterior materials for automobiles, plate making Irumu, adhesive film, bottles, food containers, food packaging films, pharmaceutical and pharmaceutical wrap film, product packaging film, agricultural film, agricultural sheeting, used in applications such as greenhouse films.

  Further, the resin composition of the present invention and a molded article thereof are provided with a seat (filling, dress material, etc.), a belt, a ceiling covering, a compatible top, an armrest, a door trim, a rear package tray, a carpet, a mat, a sun visor, a foil cover, and a mattress cover. , Airbags, insulating materials, hanging hands, hanging straps, wire covering materials, electrical insulating materials, paints, coating materials, overlay materials, floor materials, corner walls, carpets, wallpapers, wall covering materials, exterior materials, interior materials , Roof materials, deck materials, wall materials, pillar materials, floorboards, fence materials, framing and profiles, window and door profiles, shingles, paneling, terraces, balconies, soundproofing boards, heat insulating boards, window materials, etc. Automobiles, vehicles, ships, aircraft, buildings, houses and construction materials and civil engineering materials, clothing, curtains, sheets, nonwovens, plywood, plywood, carpets, doormats, sheets, buckets, hoses, containers , It is possible to use glasses, bags, cases, goggles, skis, rackets, tents, household goods of musical instruments, etc., in various applications such as sporting goods.

Hereinafter, the present invention will be described specifically with reference to Examples.
The polymer compound (A) was produced according to the following production examples. In the following Production Examples, the number average molecular weight was measured by the following method.

(Molecular weight measurement)
The number average molecular weight (hereinafter, referred to as “Mn”) was measured by a gel permeation chromatography (GPC) method. The measuring conditions of Mn are as follows.
Apparatus: GPC apparatus manufactured by JASCO Corporation Solvent: tetrahydrofuran Reference substance: polystyrene Detector: Differential refractometer (RI detector)
Column stationary phase: Showex KF-804L manufactured by Showa Denko KK
Column temperature: 40 ° C
Sample concentration: 1mg / 1mL
Flow rate: 0.8 mL / min.
Injection volume: 100 μL

[Production Example 1] (Production of polymer compound (A) -1)
In a separable flask, 656 g (4.55 mol) of 1,4-cyclohexanedimethanol as a diol, 708 g (4.85 mol) of adipic acid as an aliphatic dicarboxylic acid, and phthalic anhydride as an aromatic dicarboxylic acid 0.7 g (4.73 × 10 ⁻³ mol) of an antioxidant (tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane; trade name of ADEKA Corporation) 0.7 g of “ADK STAB AO-60”) was charged and polymerized at normal pressure for 5 hours while gradually raising the temperature from 160 ° C. to 210 ° C., and then polymerized at 210 ° C. under reduced pressure for 3 hours to obtain polyester (E) -1. Obtained. Polyester (E) -1 had an acid value of 28 and a number average molecular weight Mn of 5,400 in terms of polystyrene.

  Next, 600 g of the obtained polyester (E) -1 was used as a compound (C) having at least one group represented by the general formula (1) and having hydroxyl groups at both ends, and having a number average molecular weight of 4,000. 300 g of polyethylene glycol (C) -1, 0.5 g of an antioxidant (Adecastab AO-60) and 0.8 g of zirconium octylate were charged, and polymerized at 210 ° C. for 7 hours under reduced pressure to obtain carboxyl groups at both ends. A block polymer (G) -1 having the following formula was obtained. The acid value of the block polymer (G) -1 was 9, and the number average molecular weight Mn was 12,000 in terms of polystyrene.

  To 360 g of the obtained block polymer (G) -1 having a carboxyl group at both ends, 6 g of bisphenol F diglycidyl ether (D) -1 as a compound (D) having a reactive functional group was charged, and heated at 240 ° C. Polymerization was performed under reduced pressure for 3 hours to obtain a polymer compound (A) -1.

[Production Example 2] (Production of polymer compound (A) -2)
In a separable flask, 370 g (1.87 mol) of 1,4-bis (β-hydroxyethoxy) benzene as a diol, 289 g (1.98 mol) of adipic acid as an aliphatic dicarboxylic acid, and aromatic dicarboxylic acid Then, 8 g (0.05 mol) of isophthalic acid and 0.5 g of an antioxidant (ADEKA STAB AO-60) were charged, and polymerized at normal pressure for 5 hours while gradually raising the temperature from 180 ° C. to 220 ° C. Thereafter, 0.5 g of tetraisopropoxytitanate was charged and polymerized at 220 ° C. under reduced pressure for 5 hours to obtain a polyester (E) -2. Polyester (E) -2 had an acid value of 56 and a number average molecular weight Mn of 4,900 in terms of polystyrene.

  300 g of the obtained polyester (E) -2 was used as a compound (C) having at least one group represented by the general formula (1) and having hydroxyl groups at both ends, as polyethylene glycol having a number average molecular weight of 4,000 ( C) -1 150 g, an antioxidant (Adecastab AO-60) 0.5 g, and zirconium acetate 0.5 g were charged, and polymerized at 220 ° C. for 7 hours under reduced pressure to obtain a block polymer having carboxyls at both ends. (G) -2 was obtained. The acid value of this block polymer (G) -2 was 11, and the number average molecular weight Mn was 12,300 in terms of polystyrene.

  To 300 g of the obtained block polymer (G) -2, 11 g of dicyclopentadienemethanol diglycidyl ether was charged as a compound (D) having a reactive functional group of a polyvalent epoxy compound, and the mixture was heated at 240 ° C. for 4 hours under reduced pressure. To obtain a polymer compound (A) -2.

[Production Example 3] (Production of polymer compound (A) -3)
In a separable flask, 591 g of ethylene oxide adduct of bisphenol A as a diol, 235 g (1.16 mol) of sebacic acid as an aliphatic dicarboxylic acid, and 8 g (0.05 mol of isophthalic acid as an aromatic dicarboxylic acid) ), 300 g of polyethylene glycol (C) -2 having a number average molecular weight of 2,000 as a compound (C) having at least one group represented by the general formula (1) and having hydroxyl groups at both ends, an antioxidant 0.8 g of (ADK STAB AO-60) was charged, and polymerization was carried out at normal pressure for 5 hours while gradually raising the temperature from 180 ° C to 220 ° C. Thereafter, 0.6 g of tetraisopropoxytitanate was charged and polymerized at 220 ° C. under reduced pressure for 7 hours to obtain a block polymer (G) -3 having carboxyl at both ends. The acid value of the block polymer (G) -3 was 10, and the number average molecular weight Mn was 10,100 in terms of polystyrene.

  300 g of the obtained block polymer (G) -3 was charged with 7 g of epoxidized soybean oil (D) -3 and 0.5 g of zirconium acetate as a compound (D) having a reactive functional group of a polyvalent epoxy compound. Polymerization was performed at 240 ° C. for 5 hours under reduced pressure to obtain a polymer compound (A) -3.

[Examples 1 to 17, Comparative Examples 1 to 16]
Using the polymer compounds (A) -1 to (A) -3 obtained by the above-mentioned production method, test pieces were prepared by the following method and evaluated.

<Test specimen preparation conditions>
0.1 parts by mass of a phenolic antioxidant (trade name “ADEKA STAB AO-60” manufactured by ADEKA Corporation), 0.1 parts by mass of a phosphorus antioxidant (trade name “ADEKA STAB 2112” manufactured by ADEKA CORPORATION), calcium stearate Using a twin-screw extruder (product name: PCM30, 60 mesh screen) manufactured by Ikegai Co., Ltd., a resin composition blended based on 0.05 mass and the compounding amount shown in Tables 1 to 5 below. At 230 ° C. and 9 kg / hour to obtain pellets. The obtained pellets were molded using a horizontal injection molding machine (product name: NEX80) manufactured by Nissei Plastic Industry Co., Ltd. under the processing conditions of a resin temperature of 230 ° C. and a mold temperature of 50 ° C., and a test piece (100 mm × 100 mm × 3 mm) Was prepared. Using these test pieces, the measurement of the surface resistivity and the thermal stability were evaluated under the following conditions.

In addition, the following compounds were used for polypropylene, styrene resin, compound 1, and alkali metal salts (F) -1 and (F) -2 in Tables 1 to 5.
Thermoplastic resin 1 (polypropylene): homopolypropylene (melt flow rate (ISO1133 230 ° C x 2.16 kg) = 8 g / 10 min)
Thermoplastic resin 2 (polyethylene): high-density polyethylene (melt flow rate = 7 g / 10 min) "Novatech HD HJ560" manufactured by Nippon Polyethylene Corporation
Thermoplastic resin 3 (styrene-based resin): Impact-resistant polystyrene (melt flow rate = 2.7 g / 10 min) “E640N” manufactured by Toyo Styrene Co., Ltd.
Compound 1: N, N-distearylhydroxylamine Comparative compound 1: Polyetheresteramide type antistatic agent, trade name “IRGASTAT P-18” manufactured by BASF
Comparative Compound 2: Polyetheresteramide-type antistatic agent, trade name “Irgastat P-20” manufactured by BASF
Alkali metal salt (F) -1: Sodium dodecylbenzenesulfonate Alkali metal salt (F) -2: Lithium p-toluenesulfonate

<Method of measuring surface resistivity (SR value)>
The obtained test piece (100 mm × 100 mm × 3 mm) was allowed to stand in an oven at 100 ° C. immediately after the forming process, and at 24 ° C. and 1000 hours after the forming process, at 25 ° C. and a humidity of 60% RH. For 1 day, and under the same atmosphere, the surface specific resistance (Ω / □) was measured using an R8340 ohmmeter manufactured by Advantest Co. under the conditions of an applied voltage of 500 V and an applied time of 1 minute. The measurement was performed for five points, and the average value was obtained. The results are shown in Tables 1 to 5 below.

<Thermal stability evaluation method>
YI (Yellowness Index) of the obtained test piece (100 mm × 100 mm × 3 mm) was measured using a spectrophotometer SC-P manufactured by Suga Test Co., Ltd. Next, the test piece was placed in an oven at 100 ° C. and allowed to stand. After a lapse of 1000 hours, the test piece was taken out of the oven, YI was measured, and the difference (ΔYI) from the YI of the test piece before being put in the oven was calculated. These test results are shown in Tables 1 to 5 below. It should be noted that ΔYI indicates that the smaller the value, the smaller the discoloration and the better the thermal stability.

  According to the comparison results of Comparative Example 6 and Example 5, and Comparative Example 16 and Examples 15 to 17, when a compound different from the polymer compound (A) of the present invention was used, an amine-based antioxidant was compounded. However, the resin is often colored. Further, the effect of the antistatic property is insufficient.

  On the other hand, it was confirmed that the antistatic thermoplastic resin composition of the present invention was able to maintain excellent antistatic properties and was superior in heat resistance as compared with the polyetheresteramide type antistatic agent. Furthermore, from the comparison between Example 2 and Example 5, when the alkali metal salt (F) was added to the antistatic thermoplastic resin composition of the present invention, the antistatic property was further improved. Furthermore, Examples 15 to 17 confirmed that the desired effect was obtained for styrene resins.

Claims (10)

The polymer compound (A) is used in an amount of 2 to 40 parts by mass with respect to 60 to 98 parts by mass of the thermoplastic resin, and an amine antioxidant (based on 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound). B) In an antistatic thermoplastic resin composition containing 0.001 to 20 parts by mass,
The polymer compound (A) is a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, the following general formula (1),

The compound (C) having at least one group represented by the formula (I) and having a hydroxyl group at both terminals and the compound (D) having a reactive functional group are formed through an ester bond or an ester bond and an amide bond. It has a formed by bonding structure via,
The antistatic thermoplastic resin composition, wherein the amine-based antioxidant is a hydroxylamine compound . The polyester (E) in which the polymer compound (A) is composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, the compound (C), and the compound (D) are linked via an ester bond. The antistatic thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is bonded via an ester bond or an amide bond. The polymer compound (A) has carboxyl groups at both ends where a block composed of the polyester (E) and a block composed of the compound (C) are alternately bonded via an ester bond. The antistatic thermoplastic resin composition according to claim 2 , having a structure in which the block polymer (G) and the compound (D) are bonded via an ester bond or via an ester bond and an amide bond. object. The number average molecular weight of the block composed of the polyester (E) is 800 to 8,000 in terms of polystyrene, and the number average molecular weight of the block composed of the compound (C) is 400 to 6,000 in terms of polystyrene. The antistatic thermoplastic resin composition according to claim 2 or 3 , wherein the number average molecular weight of the block polymer (G) is 5,000 to 25,000 in terms of polystyrene. The antistatic thermoplastic resin composition according to any one of claims 2 to 4 , wherein the polyester (E) has a structure having carboxyl groups at both ends. The compound (D) comprises a polyhydric epoxy compound (D) -1 having two or more epoxy groups, a polyhydric alcohol compound (D) -2 having three or more hydroxyl groups, and two or more amino groups. The antistatic thermoplastic resin composition according to any one of claims 1 to 5 , which is at least one selected from the group consisting of polyamine compounds (D) -3. The antistatic thermoplastic resin composition according to any one of claims 1 to 6 , wherein the compound (C) is polyethylene glycol. The antistatic thermoplastic resin composition according to any one of claims 1 to 7 , further comprising 0.01 to 5 parts by mass of at least one alkali metal salt (F). The thermoplastic resin is, according to claim 8 is at least one selected from the group consisting of polyolefin resins, styrene resins, polyester resins, polyether resins, polycarbonate resins, polyamide resins, and halogen-containing resin The antistatic thermoplastic resin composition according to any one of the above. A molded article obtained by molding the antistatic thermoplastic resin composition according to any one of claims 1 to 9 .