JP2017128695A - Antistatic thermoplastic resin composition and molded body formed by molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic thermoplastic resin composition capable of providing a molded product which can keep excellent antistatic properties for a long period of time and has good thermal stability, and to provide a molded body formed by molding the same.SOLUTION: There is provided an antistatic thermoplastic resin composition which contains 2-40 pts.mass of a polymer compound (A) with respect to 60-98 pts.mass of a thermoplastic resin and 0.001-20 pts.mass of a phosphorus-based antioxidant (B) with respect to 100 pts.mass of the total amount of the thermoplastic resin and the polymer compound, where the polymer compound (A) has diol, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and one or more groups represented by the general formula (1), and a compound (C) having hydroxyl groups on both of terminal ends and a compound (D) having a reactive functional group are bonded to each other through an ester bond or the ester bond and an amide bond.SELECTED DRAWING: None

Description

  The present invention relates to an antistatic thermoplastic resin composition (hereinafter also simply referred to as “resin composition”) and a molded article formed by molding the same, and more particularly, excellent antistatic properties can be maintained over 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 formed by molding the same.

  Thermoplastic resins are widely used in various molded products such as automotive materials, household appliances, household goods, films, sheets, and structural parts, according to various advantages such as moldability, heat resistance, and low specific gravity. Yes.

  On the other hand, the thermoplastic resin has excellent electrical insulation, but has a problem that it is easily charged by friction or the like. When a molded product made of a thermoplastic resin is charged, static electricity may be generated or the appearance may be impaired by attracting surrounding dust. In addition, when the molded product is an electronic product, the circuit may not operate normally due to charging. In addition, there are problems caused by electric shock. Electric shock not only causes an electric shock to the human body from the thermoplastic resin and gives unpleasant feeling, but also may cause an explosion accident in the presence of flammable gas or dust.

  Nowadays, various methods have been proposed to prevent such an electrostatic failure, and a solution has been made by using an antistatic agent. Examples of such an antistatic agent include those used by spraying, dipping, coating, and the like on the resin molding surface, and kneading molds that are processed by being added to the polymer material as an additive. Most of those that are sprayed, dipped, or applied to the resin molding surface are water-soluble surfactants, 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 the antistatic agent and the resin are decomposed and colored to impair the appearance of the molded product when the compatibility with the resin and the heat resistance against the molding processing temperature are poor.

  From this point of view, an antistatic thermoplastic resin composition capable of exhibiting sustained antistatic properties and sufficient heat resistance has been demanded today. For example, Patent Document 1 proposes a fatty acid amide compound of aminoethylethanolamine. Patent Documents 2 and 3 propose polyether ester amides. In Patent Documents 4 to 6, various kneaded antistatic agents such as a block polymer having a structure in which an olefin block and a hydrophilic polymer block are repeatedly and alternately bonded are proposed. Among them, Patent Documents 5 and 6 propose an antistatic resin composition containing a polyether ester polymer type antistatic agent.

JP 2011-256293 A JP 58-118838 A JP-A-3-290464 JP 2001-278985 A International Publication WO2014 / 115745 International publication WO2014 / 148454

  However, an antistatic agent made of polyetheresteramide cannot obtain sufficient antistatic performance unless it is added in a large amount to the resin. Moreover, although the antistatic agent described in Patent Documents 1 to 4 has been shown for the effect of antistatic properties, the heat resistance of the resin molded body, particularly regarding the problem of coloring that occurs when the molded body is heated, Not considered. Further, there is a problem in that the coloring of the resin becomes stronger as the amount of the antistatic agent added increases, and further improvement is required. In Patent Documents 5 and 6, an antistatic resin composition containing a polyether ester polymer type antistatic agent is proposed. However, since it does not contain an aromatic dicarboxylic acid, the antistatic resin composition according to the present invention is used. The structure is different from that of 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 formed by molding the same. Is to provide.

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

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す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 is 2 to 40 parts by mass of the polymer compound (A) with respect to 60 to 98 parts by mass of the thermoplastic resin, and the thermoplastic resin and the polymer compound are In the antistatic thermoplastic resin composition containing 0.001 to 20 parts by mass of the phosphorus-based antioxidant (B) with respect to a total amount of 100 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 one or more groups represented by the above 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 bond. It has the structure formed by connecting via.

  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), and the compound ( D) is preferably 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) includes a block composed of the polyester (E) and a block composed of the compound (C), which are alternately bonded via ester bonds. The block polymer (G) having carboxyl groups at both ends thus formed and the compound (D) have a structure formed by bonding via an ester bond or via an ester bond and an amide bond. preferable.

  Furthermore, in the antistatic 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 number average molecular weight of the block composed of the polyester (E) is 800 to 8,000 in terms of polystyrene, and the number of blocks composed of the compound (C). The average molecular weight is preferably 400 to 6,000 in terms of polystyrene, and the number average molecular weight of the block polymer (G) is preferably 5,000 to 25,000 in terms of polystyrene.

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

  In the resin composition of the present invention, the compound (D) includes a polyvalent epoxy compound having two or more epoxy groups, a polyhydric alcohol compound having three or more hydroxyl groups, and two or more amino groups. It is preferably at least one selected from the group consisting of polyvalent amine compounds having

  Furthermore, it is preferable that the resin composition of this invention contains 0.01-5 mass parts of 1 or more types of alkali metal salt (F) further.

（式（２）中、Ｒ^１およびＲ^２は、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、または、炭素原子数７〜１２のアラルキル基等を表す。）、

（式（３）中、Ｒ^３およびＲ^４は、各々独立して、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基を表し、Ｒ^５およびＲ^６は、各々独立して、水素原子または炭素原子数１〜４のアルキル基を表し、ｋは、２〜４の整数を表し、ｋ＝２の場合、Ｌ１は、単結合、または、炭素原子数１〜８のアルカンジイル基を表し、ｋ＝３の場合、Ｌ１は、炭素原子数１〜８のアルカントリイル基を表し、ｋ＝４の場合、Ｌ^１は、アルカンテトライル基を表す。）、

（式（４）中、Ｒ^７およびＲ^８は、各々独立して、水素原子、炭素原子数１〜９のアルキル基、炭素原子数５〜８のシクロアルキル基、炭素原子数６〜１２のアルキルシクロアルキル基、炭素原子数７〜１２のアラルキル基、または、フェニル基を表し、Ｌ^２は単結合、硫黄原子、または炭素原子数１〜８のアルカンジイル基を表し、Ｒ^９は、ハロゲン原子、炭素原子数１〜２０のアルキル基、または炭素原子数６〜３０のアリール基を表す。）、

（式（５）中、Ｒ^１０は炭素原子数１〜２０のアルキル基を表し、Ｒ^１１は、水素原子、炭素原子数１〜２０のアルキル基、または無置換または炭素原子数１〜８のアルキル基で置換されたアリール基を表し、ａは、０＜ａ≦３の整数を表し、ｂは、ａ＋ｂ＝３の条件を満たす整数を表す。）、

（式（６）中、Ｒ^１２およびＲ^１３は、各々独立して、水素原子、炭素原子数１〜９のアルキル基、炭素原子数５〜８のシクロアルキル基、炭素原子数６〜１２のアルキルシクロアルキル基、炭素原子数７〜１２のアラルキル基またはフェニル基を表し、Ｌ^３は単結合、硫黄原子、または炭素原子数１〜８のアルカンジイル基を表し、Ｌ^４は、炭素原子数１〜８のアルキレン基を表す。）で表される化合物からなる群から選ばれる少なくとも一種であることが好ましい。 Furthermore, in the resin composition of the present invention, the phosphorus-based antioxidant (B) is represented by the following general formulas (2) to (6),

(In Formula (2), R ¹ and R ² represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or the like.) ,

(In Formula (3), R ³ and R ⁴ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ⁵ and R ⁶ are each independently And a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, k represents an integer of 2 to 4, and when k = 2, L1 is a single bond or a carbon atom having 1 to 8 carbon atoms. It represents an alkanediyl group, when the k = 3, L1 represents alkanetriyl group having 1 to 8 carbon atoms, in the case of k = 4, ^{L 1} represents a alkanetetrayl group.)

(In Formula (4), R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a 6 to 12 carbon atom. An alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group; L ² represents a single bond, a sulfur atom, or an alkanediyl group having 1 to 8 carbon atoms; and R ⁹ is a halogen atom. An atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

(In Formula (5), R ¹⁰ represents an alkyl group having 1 to 20 carbon atoms, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or unsubstituted or having 1 to 8 carbon atoms. An aryl group substituted with an alkyl group, a represents an integer of 0 <a ≦ 3, and b represents an integer satisfying the condition of a + b = 3).

(In Formula (6), R < ¹² > and R <^13> are respectively independently a hydrogen atom, a C1-C9 alkyl group, a C5-C8 cycloalkyl group, and a C6-C12 carbon atom. An alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, L ³ represents a single bond, a sulfur atom, or an alkanediyl group having 1 to 8 carbon atoms, and L ⁴ represents the number of carbon atoms. It is preferably at least one selected from the group consisting of compounds represented by 1-8 alkylene groups).

  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 characterized in that the resin composition of the present invention is molded.

  According to the present invention, an antistatic thermoplastic resin composition capable of maintaining excellent antistatic properties over a long period of time and providing a molded article having good thermal stability, and a molded body formed by molding the same 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）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 formed by molding the same will be described in detail. The resin composition of the present invention is 2 to 40 parts by mass of the polymer compound (A) with respect to 60 to 98 parts by mass of the thermoplastic resin, and 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound. It contains 0.001 to 20 parts by mass of a phosphorus-based antioxidant (B). In the resin composition of the present invention, the polymer compound (A) is a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, the following general formula (1),

The compound (C) having one or more groups represented by the above 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 bond. It has a structure formed by bonding via.

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 limited as long as it is a thermoplastic resin, but from the viewpoint of durability of antistatic performance and moldability, in particular, polyolefin resin, styrene resin, polyester resin. Polyether resins, polycarbonate resins, polyamide resins, and halogen-containing resins are preferred.

  Examples of polyolefin resins include polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, cross-linked polyethylene, ultrahigh 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 polymer such as pentene, block or random copolymer of ethylene-propylene, impact copolymer polypropylene, ethylene-methyl methacrylate Α-olefin copolymers such as rate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-vinyl acetate copolymers, polyfluoroolefins, and more Examples thereof include polyolefin-based thermoplastic elastomers, and two or more kinds of these copolymers may be used.

  Examples of the styrenic resin include vinyl group-containing aromatic hydrocarbons alone and vinyl group-containing aromatic hydrocarbons and other monomers (for example, maleic anhydride, phenylmaleimide, (meth) acrylic acid esters, Butadiene, (meth) acrylonitrile, etc.), for example, polystyrene (PS) resin, impact 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-ethylenepropylene rubber-styrene (AES) resin, styrene-butadiene-butylene-styrene (SBBS) resin, methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin, and butadiene or isoprene Styrene-ethylene-butylene-styrene (SEBS) resin, hydrogenated double bond, styrene-ethylene-propylene-styrene (SEPS) resin, styrene-ethylene-propylene (SEP) resin, styrene-ethylene-ethylene-propylene-styrene (SEEPS) A hydrogenated styrene elastomer resin such as a resin may be used.

  Examples of polyester resins include polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, and polycyclohexanedimethylene terephthalate; aromatic polyesters such as polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate; and polytetramethylene terephthalate. Linear polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, poly (2-oxetanone) and the like Examples include polyester.

  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 the polyamide-based resin include ε-caprolactam (nylon 6), undecane lactam (nylon 11), lauryl lactam (nylon 12), aminocaproic acid, enanthractam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9- Polymers such as aminononanoic acid, α-pyrrolidone, α-piperidone; diamines such as hexamethylenediamine, nonanediamine, nonanemethylenediamine, methylpentadiamine, undecanmethylenediamine, dodecanmethylenediamine, metaxylenediamine, adibic acid, sebacic acid , Terephthalic acid, isophthalic acid, dodecanedicarboxylic acid, copolymers obtained by copolymerizing carboxylic acid compounds such as dicarboxylic acids such as glutaric acid, or a mixture of these polymers or copolymers. That. Examples thereof include aramid resins such as Du Pont's trade name “Kevlar”, DuPont's trade name “Nomex”, Teijin's main trade name “Twaron”, and “Conex”.

  Examples of halogen-containing resins include polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-chloride. Vinylidene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexyl maleimide copolymer, etc. It is done.

  Further examples of thermoplastic resins include petroleum resin, coumarone resin, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyphenylene sulfide, polyurethane, fiber-based resin, polyimide resin. , Thermoplastic resins such as polysulfone and liquid crystal polymer, and blends thereof can be used.

  Thermoplastic resins are isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluorine rubber, silicone rubber, polyester elastomer, nitrile elastomer, nylon elastomer, vinyl chloride elastomer, It may be an elastomer such as a polyamide-based elastomer or a polyurethane-based elastomer, or may be used in combination.

  In the resin composition of this invention, these thermoplastic resins may be used independently and may use 2 or more types together. Moreover, it may be alloyed. These thermoplastic resins include molecular weight, degree of polymerization, density, softening point, proportion of insoluble matter in the solvent, degree of stereoregularity, presence or absence of catalyst residues, type and blending ratio of raw material monomers, polymerization catalyst Can be used regardless of the type (eg, Ziegler catalyst, metallocene catalyst, etc.).

Next, the polymer compound (A) will be described.
The polymer compound (A) is blended to impart 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 hydroxyl groups at both ends. The compound (C) having a reactive compound 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) includes a polyester (E) composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, a compound (C), and a compound (D). Preferably have a structure formed by bonding via an ester bond or via an ester bond and an amide bond, and a block formed from a polyester (E) and a block formed from a compound (C) Block polymer (G) having a carboxyl group at both ends formed by alternately and alternately bonding via an ester bond and compound (D) via an ester bond or via an ester bond and an amide bond It is also preferable to have a structure formed by bonding.

  Polyester (E) should just consist of diol, aliphatic dicarboxylic acid, and aromatic dicarboxylic acid, and the residue except the hydroxyl group of diol, and the residue except the carboxyl group of aliphatic dicarboxylic acid, A structure having a structure that bonds via an ester bond, and a structure in which a residue that excludes a hydroxyl group of a diol and a residue that excludes a carboxyl group of an aromatic dicarboxylic acid are bonded via 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 2-50.

  Examples of the diol that can be used in the resin composition of the present invention include aliphatic diols and aromatic group-containing diols. 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-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentane Diol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanedio 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-cyclohexanedimethanol and hydrogenated bisphenol A are preferable from the viewpoint of sustaining antistatic performance, and 1,4-cyclohexanedimethanol is more preferable.

  In addition, since it is preferable that aliphatic diol has hydrophobicity, polyethyleneglycol which has hydrophilic property among aliphatic diols is not preferable. However, this is not the case when used with other diols.

  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. Dimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, polyhydroxyethyl adduct of mononuclear dihydric phenol compounds such as 1,4-bis (2-hydroxyethoxy) benzene, resorcin, pyrocatechol Etc. 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.

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

  The aliphatic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Examples include sebacic acid, 1,10-decanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, maleic acid, and fumaric acid. Among these aliphatic dicarboxylic acids, aliphatic dicarboxylic acids having 4 to 16 carbon atoms are preferable, and aliphatic dicarboxylic acids having 6 to 12 carbon atoms are more preferable from the viewpoint of melting point and heat resistance.

  The aromatic dicarboxylic acid that can be used in the resin composition of the present invention may be an aromatic dicarboxylic acid derivative (eg, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.). Moreover, 2 or more types of mixtures may be sufficient as aromatic dicarboxylic acid and its derivative (s).

  The aromatic dicarboxylic acid is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms. For example, terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutar 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 etc. are mentioned.

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 hydrophilic compound, more preferably a polyether having a group represented by the above general formula (1), and particularly preferably polyethylene glycol represented by the following general formula (7).

上記一般式（７）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 (7), m represents an integer of 5 to 250. m is preferably 20 to 150 from the viewpoint of heat resistance and compatibility.

  As the compound (C), in addition to polyethylene glycol obtained by addition reaction of the group represented by the general formula (1), ethylene oxide and other alkylene oxides (for example, propylene oxide, 1,2-, 1, 4-, 2,3- or 1,3-butylene oxide and the like) and polyether obtained by addition reaction. This polyether may be either random or block.

  Further examples of the compound (C) include compounds having a structure in which ethylene oxide is added to an active hydrogen atom-containing compound, ethylene oxide and other alkylene oxides (for example, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and the like). 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 glycol, C2-C20 aliphatic glycol, C5-C12 alicyclic glycol, C8-C26 aromatic glycol, etc. can be used.

  Examples of the aliphatic glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-butanediol, Hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecane Examples include diol, 1,20-eicosanediol, diethylene glycol, triethylene glycol, and thiodiethylene glycol.

  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. Examples include -1,3-propanediol, triphenylethylene glycol, tetraphenylethylene glycol, and benzopinacol.

  As the dihydric phenol, phenol having 6 to 30 carbon atoms can be used, for example, catechol, resorcinol, 1,4-dihydroxybenzene, hydroquinone, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxydiphenylthioether, binaphthol. And these alkyls (having 1 to 10 carbon atoms) or halogen substituents.

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

  Examples of secondary diamines include aliphatic secondary diamines having 4 to 18 carbon atoms, heterocyclic secondary diamines having 4 to 13 carbon atoms, alicyclic secondary diamines having 6 to 14 carbon atoms, and the number of carbon atoms. 8-14 aromatic secondary diamines and secondary alkanol diamines 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 Etc.

  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, N, N′-dibutyl-1,2- Cyclobutanediamine, N, N'-dimethyl-1,4-cyclohexanediamine, N, N'-diethyl-1,4-cyclohexanediamine, N, N'-dibutyl-1,4-cyclohexanediamine, N, N'- Examples include dimethyl-1,3-cyclohexanediamine, N, N′-diethyl-1,3-cyclohexanediamine, and N, N′-dibutyl-1,3-cyclohexanediamine.

  Examples of the aromatic secondary diamine include N, N′-dimethyl-phenylenediamine, N, N′-dimethyl-xylylenediamine, N, N′-dimethyl-diphenylmethanediamine, and 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, and N-methyldipropanolamine.

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

  Examples of the aliphatic dicarboxylic acid include 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, undecanedioic acid, dodecanedioic acid, tridecanediic acid, tetradecanediic acid, hexadecanediic acid, octadecanediic acid and icosandiic acid.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, and biphenyl-2. 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. Examples include acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid and dicyclohexyl-4,4′-dicarboxylic acid.

  These active hydrogen atom-containing compounds may be used alone or in 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 may be any compound that 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) ) Can be bonded via an ester bond or an amide bond, or a block composed of polyester (E) and a block composed of compound (C) are repeatedly bonded alternately 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 in the both terminal which becomes through an ester bond or an amide bond. Such functional groups include epoxy groups, hydroxyl groups, amino groups, and the like.

  In the present invention, the compound (D) having a reactive functional group is preferably a polyhydric epoxy compound (D) -1 having two or more epoxy groups, a polyhydric alcohol compound (D)-having three or more hydroxyl groups. A polyvalent amine compound (D) -3 having two and 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 polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (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-hi Roxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, polyglycidyl ether compounds of polynuclear polyphenols 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, glu Phosphoric 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 diglycidylorthotoluidine; vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Epoxidized products of cyclic olefin compounds such as carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, 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. In addition, these polyvalent epoxy compounds can be obtained by using those internally crosslinked by terminal isocyanate prepolymers or polyvalent active hydrogen compounds (polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphate esters, etc.). The molecular weight may be used. Two or more kinds of such polyvalent epoxy 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, 2 -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-tri Trivalent alcohols such as (2-hydroxyethyl) isocyanurate; pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 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 ′, Tetravalent alcohols such as N′-tetrakis (2-hydroxyethyl) ethylenediamine; pentavalent alcohols such as adonitol, arabitol, xylitol, triglycerin; dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, allose Hexavalent alcohol; Data erythritol, and the like. Moreover, there is no restriction | limiting in particular in the molecular weight of a polyol compound, High molecular weight polyols, such as polypentaerythritol and polyvinyl alcohol, can also be used, Polyester polyol etc. can also be used. Two or more kinds of such 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 alkylene diamines such as diamine, heptamethylene diamine, octamethylene diamine, decamethylene diamine; aliphatic amines such as 2,2 ′, 2 ″ -triaminotriethylamine and bis (hexamethylene) triamine, diethylenetriamine A polyalkylene polyamine having 2 to 6 carbon atoms of an alkylene group such as 1,6,11-undecantriamine, 1,8-diamino-4-aminomethyloctane, 1,3,6- Alkanetriamines such as hexamethylenetriamine; melamine, piperazine; N- N-aminoalkylpiperazine having 2 to 6 carbon atoms in the alkylene group, such as minoethylpiperazine; heterocyclic polyamines such as heterocyclic polyamine described in JP-B No. 55-21044, isophoronediamine, bicycloheptane C4-C20 alicyclic polyamine such as triamine; carbon atoms such as phenyldiamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine, triphenylmethanetriamine Examples include aromatic polyamines of formula 6 to 20. Two or more kinds of such polyvalent amine compounds may be used.

Next, polyester (E) and block polymer (G) will be described.
As described above, in the resin composition of the present invention, from the viewpoint of antistatic performance, the polymer compound (A) is a polyester (E) composed of diol, aliphatic dicarboxylic acid and aromatic dicarboxylic acid, 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.

  Furthermore, 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 a compound (C). A block polymer (G) having a carboxyl group at both ends formed by repeating alternately and alternately bonded blocks via an ester bond and a compound (D) having a reactive functional group are bonded via an ester bond or It preferably has a structure formed by bonding via an ester bond and an amide bond.

  Polyester (E) can be obtained, for example, by subjecting an aliphatic dicarboxylic acid or derivative thereof, an aromatic dicarboxylic acid or 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, etc.). If obtained, both ends may be finally treated to carboxyl groups, and the reaction for obtaining the next block polymer (G) having a structure having carboxyl groups at both ends is left as it is. You may go on. The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more.

  As described above, the aromatic dicarboxylic acid may also be a derivative of an aromatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.). If obtained, both ends may be finally treated to carboxyl groups, and the reaction for obtaining the next block polymer (G) having a structure having carboxyl groups at both ends is left as it is. You may go on. Moreover, 2 or more types of mixtures may be sufficient as aromatic dicarboxylic acid and its derivative (s).

  In the polyester (E), the 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 is 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, the polyester (E) is preferably a polyester having carboxyl groups at both ends, and the reaction ratio between the aliphatic dicarboxylic acid or derivative thereof and the aromatic dicarboxylic acid or derivative thereof and the diol is In addition, it is preferable to use an aliphatic dicarboxylic acid or a derivative thereof and an aromatic dicarboxylic acid or a derivative thereof in excess so that both ends are carboxyl groups, and to use a molar excess of the diol with respect to the diol. Is preferred.

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

  Further, depending on the blending ratio and reaction conditions, there are cases where 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. They may be mixed in E), or they may be reacted as they are with the compound (C) to obtain the block polymer (G).

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

  As described above, aliphatic dicarboxylic acids and aromatic dicarboxylic acids can be obtained by using diols, carboxylic acid esters, carboxylic acid metal salts, carboxylic acid halides or the like instead of dicarboxylic acids. After the reaction, both ends may be treated to form a dicarboxylic acid, and the reaction may proceed to the next reaction for obtaining a block polymer (G) having a structure having a carboxyl group at both ends as it is.

  Moreover, polyester (E) which consists of diol, aliphatic dicarboxylic acid, and aromatic dicarboxylic acid will form an ester bond by reacting with a compound (C), and if the structure of a block polymer (G) is formed. Good. Moreover, there may be a carboxyl group at both ends of the polyester (E), and the carboxyl group may be protected, modified, or in the form of a precursor. Moreover, in order to suppress the oxidation of a product at the time of reaction, you may add antioxidants, such as a phenolic antioxidant, to a reaction system.

  Furthermore, the compound (C) may be any compound that 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 ends may be protected. It may be modified and may be in the form of a precursor.

Next, the block polymer (G) will be described.
The block polymer (G) having a carboxyl group at both ends according to the present invention has a block composed of a polyester (E) and a block composed of a compound (C). It has a structure formed by repeatedly and alternately bonding through ester bonds formed by carboxyl groups and hydroxyl groups. An example of such a block polymer (G) is, for example, one having a structure represented by the following general formula (8).

一般式（８）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 general formula (8), (E) represents a block composed of polyester (E) having carboxyl groups at both ends, and (C) was composed of compound (C) having hydroxyl groups at both ends. Represents a block, and t represents the number of repeating units, and preferably represents a number of 1 to 10. t is more preferably a number of 1 to 7, and most preferably a number of 1 to 5.

  A part of the block composed of the polyester (E) in the block polymer (G) is composed of a polyester composed only of a diol and an aliphatic dicarboxylic acid, or composed only of a diol and an aromatic dicarboxylic acid. It may be replaced with a block made of polyester.

  The block polymer (G) having a structure having carboxyl groups at both ends is obtained by polycondensation reaction between a polyester (E) having carboxyl groups at both ends and a compound (C) having hydroxyl groups at both ends. However, the polyester (E) and the compound (C) have a structure equivalent to that having a structure in which the polyester (E) and the compound (C) are alternately and repeatedly bonded via an ester bond formed by a carboxyl group and a hydroxyl group. If present, 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 carboxyl groups at both ends (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 and reacted as it is without isolating the polyester (E).

  For the polycondensation reaction, a catalyst that promotes the esterification reaction may be used. As the catalyst, conventionally known ones such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used. Moreover, in order to suppress the oxidation of a product at the time of reaction, you may add antioxidants, such as a phenolic antioxidant, to a reaction system.

  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 a block composed of a polyester (E) and a block composed of a compound (C), a block composed of a polyester composed only of a diol and an aliphatic dicarboxylic acid, A block composed of polyester composed only of aromatic dicarboxylic acid may be included in the structure.

  The polymer compound (A) according to the present invention is an ester formed from a carboxyl group at the end of a block polymer (G) having a structure having a carboxyl group at both ends and a compound (D) having a reactive functional group Those having a structure through a bond or through an ester bond and an amide bond are preferred. Such a polymer compound (A) further includes an ester bond formed through an ester bond formed by the carboxyl group of the polyester (E) and the reactive functional group of the compound (D) having a reactive functional group. And a structure formed through an amide bond may be included.

  In order to obtain such a polymer compound (A), the carboxyl group of the block polymer (G), the epoxy group of the polyvalent epoxy compound (D) -1 of the compound (D), the polyhydric alcohol compound (D) -2 And the amino group of the polyvalent amine compound (D) -3 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 is the number of carboxyl groups in the block polymer (G) to be reacted. 0.5 to 5 equivalents are preferable, and 0.5 to 1.5 equivalents are more preferable.

  The polyvalent epoxy 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. 5 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 of the polyhydric alcohol compound (D) -2 is the carboxyl group of the block polymer (G) to be reacted. 0.5 to 5 equivalents, and 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, 0.2 to 1.5 The equivalent is more preferable.

  When the compound (D) is a polyvalent amine compound (D) -3 having two or more amino groups, the number of amino groups of the polyvalent amine compound is the number of carboxyl groups of the block polymer (G) to be reacted. 0.5 to 5 equivalents are preferable, and 0.5 to 1.5 equivalents are more preferable.

  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. 5 equivalents are more preferred.

  In the reaction, after completion of the synthesis reaction of the block polymer (G), the compound (D) may be added and reacted as it is without isolating the block polymer (G). In that case, the carboxyl group of the unreacted polyester (E) used excessively when synthesizing the block polymer (G) reacts with some 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 a carboxyl group at both ends and the compound (D) are bonded via an ester bond or via an ester bond and an amide bond. As long as it has a structure equivalent to that having a bonded structure, it is not necessarily limited to the block polymer (G) and the compound (D).

  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 800 to 8,000, more preferably 1,000 in terms of polystyrene. 6,000 to 6,000, more preferably 2,000 to 4,000. Moreover, the number average molecular weight of the block comprised from the compound (C) which has a hydroxyl group in both ends in a high molecular compound (A) becomes like this. Preferably it is 400-6,000 in polystyrene conversion, More preferably, it is 1,000. It is -5,000, More preferably, it is 2,000-4,000.

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

  In the polymer compound (A) according to the present invention, after obtaining the polyester (E) from the diol, the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid, the above compound (C) and It may also be reacted with compound (D).

  When the polymer compound (A) is blended in the thermoplastic resin, 2 to 40 parts by mass of the polymer compound (A) is charged with respect to 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). From the viewpoint of prevention, 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. If the amount exceeds 40 parts by mass, the physical properties of the molded product may be adversely affected.

Next, the phosphorus antioxidant (B) will be described.
The phosphorus antioxidant is not particularly limited as long as it is a known compound, and can be added to the thermoplastic resin together with the polymer compound (A), but can impart excellent heat resistance. It is preferable to use phosphorus antioxidants represented by the following general formulas (2) to (6).

ここで、式（２）中、Ｒ^１およびＲ^２は、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、または、炭素原子数７〜１２のアラルキル基を表す。

Here, in Formula (2), R ¹ and R ² represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

ここで、式（３）中、Ｒ^３およびＲ^４は、各々独立して、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基を表し、Ｒ^５およびＲ^６は、各々独立して、水素原子または炭素原子数１〜４のアルキル基を表し、ｋは、２〜４の整数を表し、ｋ＝２の場合、Ｌ^１は、単結合、または、炭素原子数１〜８のアルカンジイル基を表し、ｋ＝３の場合、Ｌ^１は、炭素原子数１〜８のアルカントリイル基を表し、ｋ＝４の場合、Ｌ^１は、アルカンテトライル基を表す。

Here, in formula (3), R ³ and R ⁴ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ⁵ and R ⁶ are Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, k represents an integer of 2 to 4, and when k = 2, L ¹ represents a single bond or 1 carbon atom. Represents an alkanediyl group of ˜8, and when k = 3, L ¹ represents an alkanetriyl group having 1 to 8 carbon atoms, and when k = 4, L ¹ represents an alkanetetrayl group.

ここで、式（４）中、Ｒ^７およびＲ^８は、各々独立して、水素原子、炭素原子数１〜９のアルキル基、炭素原子数５〜８のシクロアルキル基、炭素原子数６〜１２のアルキルシクロアルキル基、炭素原子数７〜１２のアラルキル基、または、フェニル基を表し、Ｌ^２は単結合、硫黄原子、または炭素原子数１〜８のアルカンジイル基を表し、Ｒ^９は、ハロゲン原子、炭素原子数１〜２０のアルキル基、または炭素原子数６〜３０のアリール基を表す。

Here, in formula (4), R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 to 6 carbon atoms. 12 represents an alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, L ² represents a single bond, a sulfur atom, or an alkanediyl group having 1 to 8 carbon atoms, and R ⁹ represents , A halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

式（５）中、Ｒ^１０は炭素原子数１〜２０のアルキル基を表し、Ｒ^１１は、水素原子、炭素原子数１〜２０のアルキル基、または無置換または炭素原子数１〜８のアルキル基で置換されたアリール基を表し、ａは、０＜ａ≦３の整数を表し、ｂは、ａ＋ｂ＝３の条件を満たす整数を表す。

In Formula (5), R ¹⁰ represents an alkyl group having 1 to 20 carbon atoms, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or unsubstituted or alkyl having 1 to 8 carbon atoms. Represents an aryl group substituted with a group, a represents an integer of 0 <a ≦ 3, and b represents an integer satisfying the condition of a + b = 3.

式（６）中、Ｒ^１２およびＲ^１３は、各々独立して、水素原子、炭素原子数１〜９のアルキル基、炭素原子数５〜８のシクロアルキル基、炭素原子数６〜１２のアルキルシクロアルキル基、炭素原子数７〜１２のアラルキル基またはフェニル基を表し、Ｌ^３は単結合、硫黄原子、または炭素原子数１〜８のアルカンジイル基を表し、Ｌ^４は、炭素原子数１〜８のアルキレン基を表す。

In formula (6), R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl having 6 to 12 carbon atoms. A cycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, L ³ represents a single bond, a sulfur atom, or an alkanediyl group having 1 to 8 carbon atoms, and L ⁴ has 1 carbon atom. Represents an alkylene group of ˜8.

In general formula (2), examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, Pentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, etc. Can be mentioned.

In the general formula (2), the aryl group having 6 to 30 carbon atoms represented by R ¹ and R ² includes phenyl, 2,4-dimethylphenyl, 2,4-di-tert-butylphenyl, 2, Examples include 6-di-tert-butyl-4-methylphenyl, methylphenyl, ethylphenyl, 2,4-dicumylphenyl, nonylphenyl, and the like.

In the general formula (2), examples of the aralkyl group having 7 to 12 carbon atoms represented by R ¹ and R ² include benzyl.

  Examples of the phosphorus-based antioxidant represented by the general formula (2) include bis (decyl) pentaerythritol diphosphite, bis (diisodecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, Bis (tridecyl) pentaerythritol diphosphite, bis (stearyl) pentaerythritol diphosphite, trilaurylthiophosphite heptakis (dipropylene glycol) triphosphitebis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, Scan (2,4-dicumylphenyl) pentaerythritol diphosphite poly (dipropylene glycol) phenyl phosphite, and the like.

In the general formula (3), the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 30 carbon atoms represented by R ³ and R ⁴ include R ¹ and R in the general formula (2). ² represents the same thing.

In the general formula (3), examples of the alkanediyl group having 1 to 8 carbon atoms represented by L ¹ include ethylene, propylene, butylene, isobutylene, heptylene, octylene, and the like. Examples of the alkanetriyl group having 8 include ethanetriyl, butanetriyl, heptanetriyl, cyclohexanetriyl, octanetriyl and the like. Examples of the alkanetetrayl group having 1 to 8 carbon atoms include methanetetrayl and ethanetetrayl. Yl, propanetetrayl, butanetetrayl, heptanetetrayl, octanetetrayl and the like.

In general formula (3), examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁵ and R ⁶ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like. Is mentioned. In general formula (3), there are a plurality of R ⁵ and R ⁶ , but each may be the same or different.

  Examples of the phosphorus-based antioxidant represented by the general formula (3) include tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl). -5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-di-tert- Butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4′-biphenylidenephosphonite, tetra (C12-C15 alkyl) -4,4'-isopropylidene diphenyl diphosphite, alkyl (C 0) bisphenol A phosphite, 4,4'-butylidene - bis (3-methyl -6-tert-butylphenyl ditridecyl) phosphite, and the like.

In the general formula (4), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl group having 6 to 12 carbon atoms. Represents an aralkyl group or a phenyl group having 7 to 12 carbon atoms. Specific examples of R ⁷ and R ⁸ include, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl group, t-pentyl group, 2-ethylhexyl. Group, cyclohexyl group, phenyl group, benzyl group and the like. In the resin composition of the present invention, an alkyl group having a tertiary carbon such as tert-butyl or tert-amyl group is preferable because the effect of stabilizing the resin is high.

In General Formula (4), R ⁹ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Specific examples of R ⁹ include halogen atoms such as chlorine and fluorine atoms; alkyls such as octyl, 2-ethylhexyl and n-octyl; 3- (3-methyl-4-hydroxy-5-tert-butylphenyl) And propyl.

In the general formula (4), examples of the alkanediyl group having 1 to 8 carbon atoms represented by L ² include ethanediyl, n-propipandiyl, n-butanediyl, isobutanediyl, n-pentanediyl, isopentanediyl, and n-octane. Examples include diyl and isooctanediyl. In the present invention, L ² is preferably a single bond or ethylidene.

  Examples of the compound represented by the general formula (4) include 2,2′-methylenebis-4,6-di-tert-butylphenyl-2-butylphosphite, 2,2′-methylenebis-4,6- Di-tert-butylphenyl-2-ethylhexyl phosphite, 2,2′-methylenebis-4,6-di-tert-butylphenyl-2-decyl phosphite, 2,2′-methylenebis-4,6-di- tert-butylphenyl-2-dodecyl phosphite, 2,2'-methylenebis-4,6-di-tert-butylphenyl-2-octadecyl phosphite, 2,2'-ethylenebis (4,6-di-tert -Butylphenyl) fluorophosphite, 6-ethylhexyl-2,4,8,10-tetra-tert-butyldibenzo [d. f] [1,3,2] dioxaphosphine, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert -Butyldibenzo [d. f] [1, 3, 2] dioxaphosphine (Sumilizer-GP) and the like.

R ¹⁰ in the general formula (5) represents an alkyl group having 1 to 20 carbon atoms, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or unsubstituted or unsubstituted 1 to 8 carbon atoms. Represents an aryl group substituted with an alkyl group. Specific examples of R ¹⁰ include methyl, ethyl, ethylhexyl, decyl, iso-decyl, isooctyl, lauryl, tridecyl and the like. Alternatively, the alkyl group —CH ₂ — may be used as a high molecular weight phosphorus antioxidant in which ether, ethylene glycol, or propylene glycol is replaced.

R ¹¹ in the general formula (5) is a phenyl group, 2,4-di-tert-butyl group, 2,4-di-tert-butyl-6-methylphenyl in addition to the alkyl group described in R ^10. Aryl groups such as

  Examples of the compound represented by the general formula (5) include triethyl phosphite, tris (2-ethylhexyl) phosphite, tri (decyl) phosphite, triisodecyl phosphite, triisooctyl phosphite, and trilauryl phosphite. Phyto, tris (tridecyl) phosphite, tristearyl phosphite, tris (dipropylene glycol) phosphite, trioleyl phosphite, trisnonyl phenyl phosphite, dioleyl hydrogen phosphite, diisooctyl phenyl phosphite, di ( Decyl) monophenyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, diphenyl octyl phosphite, dipheny Isooctyl phosphite, diphenyl decyl phosphite, diphenyl tridecyl phosphite, diisooctyl phosphite, bis (tridecyl) phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, etc. Is mentioned.

In general formula (6), R ¹² and R ¹³ represent the same as those exemplified for R ⁷ and R ⁸ in general formula (4), and L ³ in general formula (6) represents the general formula (4) represents the same as L ^{2 in FIG} .

Examples of the alkylene group having 1 to 8 carbon atoms represented by L ⁴ in the general formula (6) include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, and octylene.

  Examples of the compound represented by the general formula (6) include tris [2-[(2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphos. Fepin-6-yl) oxy] ethyl] amine and the like.

  In addition to the compounds exemplified in the general formulas (2) to (6), other phosphorus antioxidants usable in the present invention include tris (2,4-di-tert-butylphenyl) phosphite and tetraphenyl. Dipropyl glycol diphosphite, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, tetrakis (2,4-di-tert-butylphenyl) Biphenylene diphosphonite, hydrogenated bisphenol-A-pentaerythritol phosphite polymer (Johoku Chemical Industry Co., Ltd. trade name JPH-3800), 2-hydroxyethyl methacrylate acid phosphate (Johoku Chemical Co., Ltd. trade name "JPA-514") , Stenbisphenol-A phosphite polymer (Johoku Chemical Co., Ltd.) Company product name HBP), stearyl acid phosphate zinc salt (Johoku Chemical Industry Co., Ltd. trade name JP-518Zn), and the like.

  The blending amount of the phosphorus-based antioxidant (B) may be appropriately determined in consideration of desired heat resistance, but is 0.001 with respect to 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). Mass parts to 20 parts by mass are preferable, 0.01 to 5 parts by mass are preferable, and 0.03 to 2 parts by mass are more preferable. If the amount of the phosphorus 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.

  The resin composition of the present invention preferably further contains one or more alkali metal salts (F) from the viewpoint of improving the antistatic property, its sustainability, and 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 acid, acetic acid, propionic acid, butyric acid, lactic acid, pentanoic acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid C 1-18 aliphatic monocarboxylic acids such as stearic acid, 12-hydroxystearic acid; C 1-12 carbon atoms such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid Aliphatic dicarboxylic acids; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; carbon atoms such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethanesulfonic acid 1 -20 sulfonic acids and the like. Examples of inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like. Among these, lithium, sodium, and potassium are more preferable from the viewpoint of antistatic properties, and lithium and sodium are most preferable. From the standpoint of sustaining antistatic performance, acetic acid salts, perchloric acid salts, p-toluenesulfonic acid salts, and dodecylbenzenesulfonic acid salts 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. Among these, preferred are lithium acetate, potassium acetate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, lithium chloride and the like.

  The blending amount of the alkali metal salt (F) is 0.01 to 5.0 parts by mass, and 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin from the viewpoint of antistatic properties. Preferably, 0.3-2.0 mass parts is more preferable. If the amount of the alkali metal salt (F) is less than 0.01 parts by mass, the effect of adding the alkali metal salt (F) may not be sufficient. 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 Group 2 element salts include organic acid or inorganic acid salts. Examples of Group 2 elements include beryllium, magnesium, calcium, strontium, barium, and the like. Examples of organic acids include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, etc. Aliphatic dicarboxylic acid having 1 to 12 carbon atoms; aromatic carboxylic acid such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethane Examples thereof include sulfonic acids having 1 to 20 carbon atoms such as sulfonic acids. Examples of inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like.

  The resin composition of the present invention may contain a surfactant as long as the effects of the present invention are not impaired. As the surfactant, nonionic, anionic, cationic or amphoteric surfactants 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; polyethylene oxide, fatty acid esters of glycerin And polyvalent alcohol type nonionic surfactants such as fatty acid esters of pentaerythritol, fatty acid esters of sorbit or sorbitan, alkyl ethers of polyhydric alcohols, aliphatic amides of alkanolamines, and the like.

  Examples of the anionic surfactant include carboxylates such as alkali metal salts of higher fatty acids; sulfates such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfonates, alkyl sulfonates, Examples thereof include sulfonates such as paraffin sulfonates; phosphate esters such as higher alcohol phosphates.

  Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts.

  Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, betaine-type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkyldihydroxyethylbetaines, and these are used alone or Two or more types can be used in combination.

  0.1-5 mass parts is preferable with respect to 100 mass parts of total amounts of a thermoplastic resin and a high molecular compound (A), and, as for the compounding quantity in the case of mix | blending surfactant, 0.5-2 mass parts is. More preferred.

  Furthermore, you may mix | blend a polymeric antistatic agent with the resin composition of this invention in the range which does not impair the effect of this invention. As the polymer antistatic agent, for example, a polymer type antistatic agent such as a known polyether ester amide can be used, and examples of the known polyether ester amide include those described in JP-A-7-10989. And polyether ester amides comprising the polyoxyalkylene adducts of bisphenol A described. Moreover, the block polymer which has a repeating structure whose coupling unit of a polyolefin block and a hydrophilic polymer block is 2-50 can be used, For example, the block polymer of US Patent 6552131 can be mentioned.

  The blending amount in the case of blending the polymer antistatic agent is preferably 0.1 to 10 parts by weight, and 0.5 to 5 parts per 100 parts by weight of the total amount of the thermoplastic resin and the polymer compound (A). Part by mass is more preferable.

  Furthermore, 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 are those having a melting point of room temperature or lower and at least one of 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 following are mentioned as an amidinium cation.
(1) Imidazolinium cation Examples include those having 5 to 15 carbon atoms, such as 1,2,3,4-tetramethylimidazolinium and 1,3-dimethylimidazolinium;
(2) Imidazolium cation Examples include those having 5 to 15 carbon atoms, such as 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium;
(3) Tetrahydropyrimidinium cation One having 6 to 15 carbon atoms is exemplified, for example, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetra Methyl-1,4,5,6-tetrahydropyrimidinium;
(4) Dihydropyrimidinium cation A thing with 6-20 carbon atoms is mentioned, for example, 1,3-dimethyl-1,4-dihydropyrimidinium, 1,3-dimethyl-1,6-dihydropyrimidi Ni, 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.

The following are mentioned as a guanidinium cation.
(1) Guanidinium cation having an imidazolinium skeleton One having 8 to 15 carbon atoms is exemplified, for example, 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3 , 4-trimethylimidazolinium;
(2) Guanidinium cation having an imidazolium skeleton, those having 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4 -Trimethylimidazolium;
(3) A 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, such as 2-dimethylamino-1,3,4-trimethyl-1,4-dihydropyrimidinium, 2-dimethylamino-1,3,4-trimethyl-1,6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4-dihydropyrimidinium, 2-diethylamino-1 , 3-Dimethyl-4-ethyl-1,6-dihydropyrimidinium.

  A cation may be used individually by 1 type, or may use 2 or more types together. Among these, from the viewpoint of antistatic properties, an amidinium cation is preferable, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

  In the ionic liquid, examples of the organic acid or inorganic acid constituting the anion include the following. Examples of the organic acid include carboxylic acid, sulfuric acid ester, sulfonic acid and phosphoric acid ester; examples of the inorganic acid include super strong acid (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, phosphorus hexafluoride). Acid, hexafluoroantimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid. The organic acid and inorganic acid may be used singly or in combination of two or more.

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

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

  Examples of super strong acids include those derived from proton acids, combinations of proton acids and Lewis acids, and mixtures thereof. Examples of the protonic acid as the super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane ( 1 to 30 carbon atoms) sulfonic acid (for example, methanesulfonic acid, dodecanesulfonic acid, etc.), poly (n = 1 to 30) fluoroalkane (1 to 30 carbon atoms) sulfonic acid (for example, trifluoromethanesulfonic acid, Pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboric acid. Of these, borofluoric acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imidic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferable from the viewpoint of ease of synthesis.

  Examples of the protonic acid used in combination with the Lewis acid include hydrogen halide (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, and trifluoromethane. Examples include sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, and mixtures thereof. Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of the ionic liquid.

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

  The combination of the protonic acid and the Lewis acid is arbitrary, but examples of the super strong acid composed of these combinations include tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, hexafluoride. Tantalum sulfonate, tetrafluoroboronic acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride and mixtures thereof.

  Of the above anions, preferred from the viewpoint of antistatic properties of the ionic liquid is a conjugate base of a super strong acid (a super strong acid comprising a proton acid and a super strong acid comprising a combination of a proton acid and a Lewis acid), and more preferred. Is a conjugate base of a super strong acid composed of a proton acid and a super strong acid composed of a proton acid and boron trifluoride and / or phosphorus pentafluoride.

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

  The blending amount in the case of blending the ionic liquid is preferably 0.01 to 5 parts by mass, and 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.

  Furthermore, the resin composition of the present invention may be blended with a compatibilizer, if necessary, within a range not impairing the effects of the present invention. By mix | blending a compatibilizing agent, the compatibility with an antistatic component, another component, and a 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. And the polymer described in JP-A-258850, the modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, or the block polymer having a polyolefin portion and an aromatic vinyl polymer portion. .

  The blending amount in the case of blending the compatibilizer is preferably 0.01 to 5 parts by mass, and 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.

  In addition, the resin composition of the present invention may optionally be a known resin additive (for example, a phenolic antioxidant, a thioether antioxidant, an ultraviolet absorber, a hindered amine compound, a A nucleating agent, a flame retardant, a flame retardant aid, a lubricant, a filler, hydrotalcites, an antistatic agent different from the polymer compound (A) according to the present invention, a pigment, a dye, or the like) may be contained. In addition, known resin additives may be added to the thermoplastic resin after being mixed with the polymer compound (A) and the phosphorus-based antioxidant (B), or separately added to the thermoplastic resin for molding. You may do.

  Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 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, Polymer of 5-di-tert-butyl-4-hydroxy-benzenepropanoic acid and C13-15 alkyl, 2,5-di-tert-amylhydroquinone, hindered phenol (trade name AO. Manufactured by Adeka Palmalol). 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] -dioxaphosphobin, 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- Til-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) butyric 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, 1 , 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) propionic acid amide, palmityl-3- (3,5-di-tert-butyl-4-hydroxyphene) Nyl) propionic acid amide, myristyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Examples include 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as propionic acid amide. 0.001-20 mass parts is preferable with respect to 100 mass parts of total amounts of a thermoplastic resin and a high molecular compound (A), and, as for the compounding quantity in the case of mix | blending a phenolic antioxidant, 0.01-5 masses is preferable. Part is more preferred.

  Examples of the thioether-based antioxidant include tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl. ) Sulfide, ditridecyl-3,3′-thiodipropionate, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate Lauryl / stearyl thiodipropionate, 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-thiobis (6-tert-butyl-p-cresol), distearyl-di Sulfide is mentioned. 0.001-20 mass parts is preferable with respect to 100 mass parts of total amounts of a thermoplastic resin and a high molecular compound (A), and the compounding quantity in the case of mix | blending a thioether type | system | group antioxidant is 0.01-5 masses. Part is more preferred.

  Examples of amine-based antioxidants include dioctylmethylamine oxide, trioctylamine oxide, didecylmethylamine oxide, tridecylamine oxide, di (hydrogenated C12-14 alkyl) methylamine oxide, and 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 tri (C20-22) alkyl) Amine oxide compounds such as amine oxide, N, N-dibenzylhydroxylamine, phenylnaphthylamine, 4,4′-dimethoxydiphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, 4-isopropoxydiphenylamine N, N-diarylhydroxylamine, N, N-alkylarylhydroxylamine, N, N-dicycloalkylhydroxylamine, diethylhydroxylamine, dioctylhydroxylamine, didodecylhydroxylamine, dioctadecylhydroxylamine, N-dialkylhydroxylamine is mentioned. In the present invention, N, N-diarylhydroxylamine and N, N-dialkylhydroxylamine compounds are preferred, more preferably N, N-dialkylhydroxylamine compounds having an alkyl group of 6 to 30 carbon atoms, particularly Dioctadecylhydroxylamine is preferred.

  The compounding amount of the amine-based antioxidant may be appropriately determined in consideration of desired heat resistance, but is 0.001 part by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin and the polymer compound (A). To 20 parts by mass, preferably 0.01 to 5 parts by mass, and more preferably 0.03 to 2 parts by mass. If the compounding amount of the amine-based 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.

  As other antioxidants, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, 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 Nitron compounds such as heptadecyl nitrone and 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, 5, 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. 0.001-20 mass parts is preferable with respect to 100 mass parts of total amounts of a thermoplastic resin and a high molecular compound (A), and, as for the compounding quantity in the case of mix | blending another antioxidant, 0.01-5 mass parts Is more preferable.

  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 -[2-hydroxy-3- ert-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, 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, 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-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts; Alternatively, metal chelates, particularly nickel, chromium salts, chelates, and the like can be given. 0.001-10 mass parts is preferable with respect to 100 mass parts of total amounts of a thermoplastic resin and a high molecular compound (A), and the compounding quantity in the case of mix | blending a ultraviolet absorber is 0.01-0.5 mass. Part is more preferred.

  Examples of the hindered amine compound include 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-piperyl) L) -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} decanedionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate, TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals. 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of a thermoplastic resin and a high molecular compound (A), and the compounding quantity in the case of mix | blending a hindered amine compound is 0.05-0.5 mass part. Is more preferable.

  Examples of the nucleating agent include sodium-2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, lithium-2,2′-methylenebis (4,6-di-tert-butylphenyl). Phosphate, aluminum hydroxybis [2,2′methylenebis (4,6-di-tert-butylphenyl) phosphate], sodium benzoate, 4-tert-butylaluminum benzoate, sodium adipate and disodium bicyclo [2. 2.1] Metal salt of carboxylic acid 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 Examples include amide compounds such as -benzenetricarboxamide, N, N'-dicyclohexylnaphthalenedicarboxamide, and 1,3,5-tri (dimethylisopropoylamino) benzene. 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of a thermoplastic resin and a high molecular compound (A), and the compounding quantity in the case of mix | blending a nucleating agent is 0.005-0.5 mass. Part is 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), (1-methylethylidene) -4,1-phenylenetetraphenyl diphosphate, 1,3-phenylenetetrakis (2,6-dimethylphenyl) phosphate, trade name ADEKA STAB FP-500 manufactured by ADEKA Corporation, trade name ADEKA STAB FP-600 manufactured by ADEKA Corporation, stock Company ADEKA product name Adeka Stub FP-800 aromatic phosphate ester, phenylphosphonic acid divinyl, phenylphosphonic acid diallyl, phenylphosphonic acid (1-butenyl) phosphonic acid ester, di Phosphinic acid esters such as phenyl phenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, bis (2-allylphenoxy) phosphazene, dicresyl phosphazene, etc. Phosphazene compounds, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing flame retardants such as phosphorus-containing vinylbenzyl compounds and red phosphorus, Metal hydroxide such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylene bis 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, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, Examples thereof include pentabromobenzyl acrylate and brominated flame retardants such as brominated styrene. These flame retardants are preferably used in combination with anti-drip agents such as fluororesins and flame retardant aids such as polyols and hydrotalcites. 1-50 mass parts is preferable with respect to 100 mass parts of total amounts of a thermoplastic resin and a high molecular compound (A), and, as for the compounding quantity in the case of mix | blending a flame retardant, 10-30 mass parts is more preferable.

  The lubricant is added for the purpose of imparting lubricity to the surface of the molded body and enhancing the damage prevention effect. Examples of the lubricant include 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, Examples include sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearic acid amide, oleic acid amide, ethylene bis stearic acid amide and the like. These may be used alone or in combination of two or more. The blending amount when the lubricant is blended is preferably 0.01 to 2 parts by weight, and 0.03 to 0.5 parts by weight with respect to 100 parts by weight 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 whisker, wollastonite, fibrous magnesium oxysulfate, etc., and appropriately select and use the particle diameter (in the fibrous form, the fiber diameter, fiber length, and aspect ratio) Can do. Moreover, what was surface-treated as needed can be used for a filler. 0.01-80 mass parts is preferable with respect to 100 mass parts of total amounts of a thermoplastic resin and a high molecular compound (A), and, as for the compounding quantity in the case of mix | blending a filler, 1-50 mass parts is more preferable.

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

ここで、一般式（９）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（１０）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。 Hydrotalcite is a complex salt compound consisting of magnesium, aluminum, hydroxyl group, carbonate group and any crystal water known as a natural product or synthetic product. Examples include those substituted with metals and those obtained by substituting hydroxyl groups and carbonate groups with other anionic groups. Specifically, for example, the metal of hydrotalcite represented by the following general formula (9) is replaced with an alkali metal. The thing which was done is mentioned. In addition, as the Al—Li hydrotalcites, compounds represented by the following general formula (10) can also be used.

Here, in the general formula (9), 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 general formula (10), A ^q- represents a q-valent anion, and p represents 0 or a positive number. Further, the carbonate anion in the hydrotalcite may be partially substituted with another anion.

  Hydrotalcite may be obtained by dehydrating crystallization water, higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal such as alkali metal dodecylbenzenesulfonate. It may be coated with a salt, higher fatty acid amide, higher fatty acid ester or wax.

  Hydrotalcites may be natural products or synthetic products. As synthesis methods, Japanese Patent Publication No. Sho 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, Japanese Patent Publication No. 61-174270, Japanese Patent Publication No. Hei 5- The publicly known method described in 179052 gazette etc. is mentioned. Hydrotalcites can be used without being limited by their crystal structure, crystal particles, and the like. 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of a thermoplastic resin and a high molecular compound (A), and the compounding quantity in the case of mix | blending hydrotalcite is 0.05-3 mass parts. More preferred.

  A commercially available pigment can also be used as the pigment. 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 dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And dyes such as cyanine dyes, and a plurality of these may be used in combination.

  The method for producing the resin composition of the present invention is not particularly limited, and the thermoplastic resin may be a polymer compound (A), a phosphorus-based antioxidant (B), an alkali metal salt (F), if necessary, and other optional components. What is necessary is just to mix | blend a component and the arbitrary methods normally used can be used for the method. For example, they may be mixed and kneaded by roll kneading, bumper kneading, an extruder, a kneader or the like.

  Moreover, although a high molecular compound (A) may be added as it is, you may add after impregnating a support | carrier as needed. In order to impregnate the carrier, it may be heated and mixed as it is, or if necessary, it may be diluted with an organic solvent, impregnated into the carrier, and then the solvent is removed. As such a carrier, those known as fillers and fillers for thermoplastic resins, or flame retardants and light stabilizers that are solid at room temperature can be used. For example, calcium silicate powder, silica powder, talc powder, alumina Examples thereof include powders, titanium oxide powders, those obtained by chemically modifying the surface of these carriers, and solids among the flame retardants and antioxidants listed below. Among these carriers, those obtained by chemically modifying the surface of the carrier are preferred, and those obtained by chemically modifying the surface of the silica powder are more preferred. These carriers preferably have an average particle size of 0.1 to 100 μm, and more preferably 0.5 to 50 μm.

  Further, as a method of blending the polymer compound (A) into the thermoplastic resin component, the block polymer (G), the polymer compound (A) and the phosphorus antioxidant (B) may be blended together. Well, you may mix separately. The polymer compound (A) is prepared by synthesizing the polymer compound (A) while kneading the block polymer (G) and the compound (D) having a reactive functional group into the thermoplastic resin component. At that time, the alkali metal salt (F) may be kneaded at the same time, and the polymer compound (A), the alkali metal salt (F) and the thermoplastic resin component may be mixed at the time of molding such as injection molding. You may mix | blend by the method of obtaining a molded article, and also manufacture the master batch of phosphorus antioxidant (B) and / or alkali metal salt (F), and a thermoplastic resin beforehand, and this master. Batches may be blended.

  Furthermore, the polymer compound (A) and the alkali metal salt (F) may be mixed in advance and then blended into the thermoplastic resin, and synthesized by adding the alkali metal salt (F) during the reaction. You may mix | blend a high molecular compound (A) with a thermoplastic resin.

Next, the molded product 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, such as resin plates, sheets, films, bottles, fibers, and irregular shaped products. Various shaped articles can be produced.

  Usually, when an antistatic agent is blended, the physical properties are often lowered, but the molded article of the present invention is excellent in excellent antistatic properties and heat resistance, and has few physical properties. In particular, it has antistatic resistance against wiping of the surface of the molded body.

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

  More specifically, the resin composition of the present invention and the molded product thereof are 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), Calculator, electronic notebook, card, holder, office supplies such as stationery, OA equipment, washing machine, refrigerator, vacuum cleaner, microwave oven, lighting equipment, game machine, iron, kotatsu and other household appliances, TV, VTR, video camera, radio cassette , AV equipment such as tape recorders, mini-discs, CD players, speakers, liquid crystal displays, connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor sealing materials, LED sealing materials, electric wires, cables, transformers, deflection yokes , Electrical and electronic parts such as distribution boards and watches, and communication equipment, automotive interior and exterior materials, 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 the molded product thereof are a seat (filling, outer material, etc.), belt, ceiling, compatible top, armrest, door trim, rear package tray, carpet, mat, sun visor, foil cover, mattress cover. , Airbags, insulation materials, suspension hands, suspension straps, wire coating materials, electrical insulation materials, paints, coating materials, upholstery materials, flooring materials, corner walls, carpets, wallpaper, wall covering materials, exterior materials, interior materials , Roofing materials, deck materials, wall materials, pillar materials, floorboards, fence materials, frames and repetitive shapes, window and door shapes, slabs, plaids, terraces, balconies, soundproofing plates, heat insulating plates, window materials, etc. Automobiles, vehicles, ships, aircraft, buildings, housing and construction materials and civil engineering materials, clothing, curtains, sheets, non-woven fabrics, plywood, synthetic fiber boards, 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 specifically described with reference to examples.
The polymer compound (A) was produced according to the following Production Examples 1 to 3. 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 measurement conditions for Mn are as follows.
Apparatus: GPC apparatus manufactured by JASCO Corporation Solvent: Tetrahydrofuran Reference material: Polystyrene Detector: Differential refractometer (RI detector)
Column stationary phase: Shodex KF-804L manufactured by Showa Denko KK
Column temperature: 40 ° C
Sample concentration: 1 mg / 1 mL
Flow rate: 0.8mL / 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 (4.84 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), 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 added, and the temperature was gradually raised from 160 ° C. to 210 ° C. while polymerizing at normal pressure for 5 hours and then 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 has one or more groups represented by the general formula (1), and has a number average molecular weight of 4,000 as a compound (C) having hydroxyl groups at both ends. Charge 300 g of polyethylene glycol (C) -1, 0.5 g of antioxidant (ADK STAB AO-60) and 0.8 g of zirconium octylate, and polymerize at 210 ° C. for 7 hours under reduced pressure. The block polymer (G) -1 having The acid value of this block polymer (G) -1 was 9, and the number average molecular weight Mn was 12,000 in terms of polystyrene.

  6 g of bisphenol F diglycidyl ether (D) -1 as a compound (D) having a reactive functional group of a polyvalent epoxy compound is added to 360 g of the obtained block polymer (G) -1 having a carboxyl group at both ends. The resultant was polymerized under reduced pressure at 240 ° C. 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, aromatic dicarboxylic acid As an example, 8 g (0.05 mol) of isophthalic acid and 0.5 g of an antioxidant (ADK STAB AO-60) were charged, and polymerization was performed at normal pressure for 5 hours while gradually raising the temperature from 180 ° C to 220 ° C. Thereafter, 0.5 g of tetraisopropoxy titanate was charged and polymerized at 220 ° C. under reduced pressure for 5 hours to obtain 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.

  As a compound (C) having 300 g of the obtained polyester (E) -2, one or more groups represented by the general formula (1) and having hydroxyl groups at both ends, a polyethylene glycol having a number average molecular weight of 4,000 ( A block polymer having 150 g of C) -1, 0.5 g of antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate, polymerized at 220 ° C. for 7 hours under reduced pressure, and having carboxyl at both ends (G) -2 was obtained. This block polymer (G) -2 had an acid value of 11, and a number average molecular weight Mn of 12,300 in terms of polystyrene.

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

[Production Example 3] (Production of polymer compound (A) -3)
In a separable flask, 591 g of an 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 the compound (C) having one or more groups 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 performed at normal pressure for 5 hours while gradually raising the temperature from 180 ° C to 220 ° C. Thereafter, 0.6 g of tetraisopropoxy titanate 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. This block polymer (G) -3 had an acid value of 10, and a number average molecular weight Mn of 10,100 in terms of polystyrene.

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

  Using the polymer compounds (A) -1 to (A) -3 obtained by the above production method, test pieces were prepared by the following method and evaluated.

<Test specimen preparation conditions>
Resin blended based on 0.1 parts by mass of phenolic antioxidant (trade name “Adeka Stub AO-60” manufactured by ADEKA Corporation), 0.05 mass of calcium stearate, and the blending amounts shown in Tables 1 to 6 below The composition was granulated using a twin screw extruder (product name: PCM 30, 60 mesh screen) manufactured by Ikegai Co., Ltd. under conditions of 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 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 made. Using these test pieces, the surface resistivity was measured and the thermal stability was evaluated according to the following conditions.

In Tables 1 to 6, polypropylene, styrene resin, compound No. 1-No. 4. The following compounds were used as comparative compounds and alkali metal salts (F) -1 and (F) -2.
Polypropylene: Homopolypropylene (melt flow rate (ISO 1133 230 ° C. × 2.16 kg) = 8 g / 10 min)
Styrene resin: Impact-resistant polystyrene (melt flow rate = 2.7 g / 10 min), trade name “E640N” manufactured by Toyo Styrene Co., Ltd.
Compound No. 1: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite compound No. 1 2: Tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite compound no. 3: 2,2′-methylenebis-4,6-di-tert-butylphenyl-2-ethylhexyl phosphite Compound No. 3 4: Tris (2,4-di-tert-butylphenyl) phosphite Comparative compound 1: Polyether ester amide type antistatic agent Product name “Irgastat-P18” manufactured by BASF
Comparative compound 2: polyether ester amide type antistatic agent, trade name “Irgastat-P20” manufactured by BASF
Alkali metal salt (F) -1: Dodecylbenzenesulfonic acid alkali metal salt (F) -2: p-toluenesulfonic acid lithium

<Method for measuring surface resistivity (SR value)>
The obtained test piece (100 mm × 100 mm × 3 mm) was placed in an oven at 100 ° C. and left after standing for 24 hours and 1000 hours, and stored for one day under the conditions of 25 ° C. and humidity 60% RH. Using a R8340 resistance meter manufactured by Advantest Corporation, the surface resistivity (Ω / □) was measured under the conditions of an applied voltage of 500 V and an applied time of 1 minute. The measurement was performed for 5 points, and the average value was obtained. These results are shown in Tables 1 to 6 below.

<Thermal stability evaluation method>
YI (Yellowness Index) was measured for the obtained test piece (100 mm × 100 mm × 3 mm) using a spectrocolorimeter 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 1000 hours, the test piece was taken out of the oven, YI was measured, and the difference (ΔYI) from YI of the test piece before being put in the oven was calculated. These test results are shown in Tables 1 to 6 below. In addition, ΔYI indicates that the smaller the color, the less discoloration and the better the thermal stability.

  From the comparison result between Comparative Example 6 and Example 8, the comparison result between Comparative Example 7 and Example 9, and the comparison result between Comparative Example 13 and Example 15, the polymer compound (A) according to the present invention and When different polyether ester amide type antistatic agents are used, the resin is often colored even if a phosphorus antioxidant is blended. In addition, the effect of antistatic properties is insufficient.

  On the other hand, it was confirmed that the antistatic thermoplastic resin composition of the present invention can maintain excellent antistatic properties and is superior in heat resistance as compared with polyether ester amide type antistatic agents. Further, from Example 15, it was confirmed that the desired effect of the present invention was obtained also for the styrene resin.

Claims (11)

The polymer compound (A) is 2 to 40 parts by mass with respect to 60 to 98 parts by mass of the thermoplastic resin, and the phosphorus-based antioxidant (100 parts by mass with respect to the total amount of the thermoplastic resin and the polymer compound). B) In the 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 one or more groups represented by the above 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 bond. An antistatic thermoplastic resin composition having a structure formed by bonding via   The polymer (A) is a polyester (E) composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, the compound (C), and the compound (D) via an ester bond. Or an antistatic thermoplastic resin composition according to claim 1, which is bonded via an ester bond and an amide bond.   The polymer compound (A) has a carboxyl group at both ends formed by alternately and alternately connecting a block composed of the polyester (E) and a block composed of the compound (C) via an ester bond. The antistatic thermoplastic resin composition according to claim 2, wherein the block polymer (G) and the compound (D) have a structure formed by bonding via an ester bond or via an ester bond and an amide bond. object.   The antistatic thermoplastic resin composition according to claim 2 or 3, wherein the polyester (E) has a structure having carboxyl groups at both ends.   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 3 or 4, wherein the block polymer (G) has a number average molecular weight of 5,000 to 25,000 in terms of polystyrene.   The said compound (C) is polyethyleneglycol, The antistatic thermoplastic resin composition as described in any one of Claims 1-5.   The compound (D) is selected from the group consisting of a polyvalent epoxy compound having two or more epoxy groups, a polyhydric alcohol compound having three or more hydroxyl groups, and a polyvalent amine compound having two or more amino groups. The antistatic thermoplastic resin composition according to claim 1, which is at least one kind.   Furthermore, the antistatic thermoplastic resin composition as described in any one of Claims 1-7 containing 0.01-5 mass parts of 1 or more types of alkali metal salt (F). The phosphorus-based antioxidant (B) is represented by the following general formulas (2) to (6),

(In Formula (2), R ¹ and R ² represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or the like.) ,

(In Formula (3), R ³ and R ⁴ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ⁵ and R ⁶ are each independently And a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, k represents an integer of 2 to 4, and when k = 2, L1 is a single bond or a carbon atom having 1 to 8 carbon atoms. It represents an alkanediyl group, when the k = 3, L1 represents alkanetriyl group having 1 to 8 carbon atoms, in the case of k = 4, ^{L 1} represents a alkanetetrayl group.)

(In Formula (4), R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a 6 to 12 carbon atom. An alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group; L ² represents a single bond, a sulfur atom, or an alkanediyl group having 1 to 8 carbon atoms; and R ⁹ is a halogen atom. An atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

(In Formula (5), R ¹⁰ represents an alkyl group having 1 to 20 carbon atoms, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or unsubstituted or having 1 to 8 carbon atoms. An aryl group substituted with an alkyl group, a represents an integer of 0 <a ≦ 3, and b represents an integer satisfying the condition of a + b = 3).

(In Formula (6), R < ¹² > and R <^13> are respectively independently a hydrogen atom, a C1-C9 alkyl group, a C5-C8 cycloalkyl group, and a C6-C12 carbon atom. An alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, L ³ represents a single bond, a sulfur atom, or an alkanediyl group having 1 to 8 carbon atoms, and L ⁴ represents the number of carbon atoms. The antistatic thermoplastic resin composition according to any one of claims 1 to 8, which is at least one selected from the group consisting of compounds represented by 1 to 8).   The thermoplastic resin 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 resins. The antistatic thermoplastic resin composition as described in any one of the above.   A molded article, wherein the antistatic thermoplastic resin composition according to any one of claims 1 to 10 is molded.