JP2017193646A - Thermoplastic resin composition and molded body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which can keep excellent antistatic properties for a long period of time and can achieve a molded body having good rigidity and impact resistance under low temperature environment, and to provide a molded body using the same.SOLUTION: A thermoplastic resin composition contains 2-50 pts.mass of a thermoplastic elastomer with respect to 50-98 pts.mass of a thermoplastic resin, and 2-40 pts.mass of a polymer compound (A) with respect to 100 pts.mass of the total amount of the thermoplastic resin and the thermoplastic elastomer, where the polymer compound (A) has a structure formed by bonding a compound (C) having diol, aliphatic dicarboxylic acid, aromatic dicarboxylic acid and one or more groups represented by general formula (1) and hydroxyl groups on both terminals and a compound (D) having a reactive functional group through an ester bond or an ester bond and an amide bond.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition (hereinafter, also simply referred to as “resin composition”) containing a thermoplastic resin, a thermoplastic elastomer, and an antistatic agent, and maintains excellent antistatic properties for a long period of time. The present invention relates to a thermoplastic resin composition capable of providing a molded article having both high impact properties and high rigidity, and a molded article using 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.

  Thermoplastic resins have low impact resistance under low-temperature environments. For applications such as automotive materials, shoe soles, and hoses that are used outdoors in winter or in cold regions, thermoplastic elastomers are used to improve impact resistance. It is carried out using together.

  On the other hand, thermoplastic resins and thermoplastic elastomers have excellent electrical insulation, but have a problem that they are easily charged by friction or the like. When a molded body made of a thermoplastic resin and a thermoplastic elastomer is charged, the appearance may be impaired by attracting surrounding dust. Moreover, when a molded object contacts an electronic product, an electronic circuit may not operate | move normally by charging, or it may be damaged. In addition, there are problems caused by electric shock. Electric shock not only causes an electric shock from the molded body to the human body 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 the antistatic agent include those used by spraying, dipping, coating, and the like on the surface of the resin molded body, and kneading molds which are added to the polymer material and processed. Most of the materials that are sprayed, dipped, or applied to the surface of the resin molded body are water-soluble surfactants, but there has been a problem that the antistatic effect is lost by wiping or washing. On the other hand, if the kneading mold has poor compatibility with the resin and heat resistance against the molding processing temperature, the antistatic agent and the resin are decomposed and colored, and the appearance of the molded article is impaired.

  From this point of view, there is a need today for an antistatic thermoplastic resin composition that has sufficient antistatic properties and can maintain it for a long period of time. For example, Patent Document 1 proposes a fatty acid amide compound of aminoethylethanolamine. Patent Documents 2 and 3 propose polyether ester amides. Further, Patent Documents 4 to 7 propose various kneading type antistatic agents such as a block polymer having a structure in which an olefin block and a hydrophilic polymer block are alternately and repeatedly bonded. Among them, Patent Documents 5 and 6 propose an antistatic resin composition containing a polyether ester polymer type antistatic agent.

Japanese Unexamined Patent Publication No. 2011-256293 JP 58-118838 A JP-A-3-290464 JP 2001-278985 A International Publication No. 2014/115745 International Publication No. 2014/148454 JP, 2006-023254, A

  However, polymer type antistatic agents such as polyether ester amide have long-lasting antistatic performance, but sufficient antistatic performance cannot be obtained unless a large amount is added to the resin. Further, there is a problem that the impact resistance is remarkably lowered under a low temperature environment. Further, in Patent Documents 1 to 7, although the effect of adding an antistatic agent to impart antistatic properties is shown, no consideration is given to the problem that impact resistance is lowered at low temperatures. In Patent Documents 5 and 6, antistatic resin compositions containing polyether ester polymer type antistatic agents are proposed, but these antistatic agents do not contain aromatic dicarboxylic acids. The structure is different from the polymer compound (A) used as an antistatic agent in the present invention. Patent Document 7 proposes a polyether ester polymer type antistatic agent having a structure overlapping that of the polymer compound (A) used as an antistatic agent in the present invention. An example is not shown. Furthermore, the specific effect when the polymer compound (A) is blended with the combination of the thermoplastic resin and the thermoplastic elastomer is not described in any document.

  Accordingly, an object of the present invention is to provide a thermoplastic resin composition that can maintain a superior antistatic property for a long period of time and can realize a molded article having excellent rigidity and impact resistance in a low-temperature environment, and a method using the same. The object is to provide a molded body.

  As a result of intensive studies, 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 have completed the present invention.

That is, the thermoplastic resin composition of the present invention contains 2 to 50 parts by mass of a thermoplastic elastomer with respect to 50 to 98 parts by mass of the thermoplastic resin, and the total amount of the thermoplastic resin and the thermoplastic elastomer is 100 parts by mass. In contrast, a thermoplastic resin composition containing 2 to 40 parts by mass of the polymer compound (A),
The polymer compound (A) is a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a compound (C) having one or more groups represented by the following general formula (1) and having hydroxyl groups at both ends; and The compound (D) having a reactive functional group has a structure formed by bonding 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, the compound (C), and the reactive functional group. It is preferable that the compound (D) having a bond has a structure formed by bonding 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) has 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 a carboxyl group at both ends and the compound (D) having the reactive functional group are bonded via an ester bond or an ester bond and an amide bond. It is preferable to have the following structure.

  Furthermore, in the resin composition of this invention, the number average molecular weight of the block comprised from the said polyester (E) is 800-8,000 in polystyrene conversion, and the number average of the block comprised from the said compound (C). The 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 polyester (E) preferably has a structure having carboxyl groups at both ends.

  Furthermore, in the resin composition of this invention, it is preferable that the compound (D) which has the said reactive functional group is a polyvalent epoxy compound which has a 2 or more epoxy group.

  Furthermore, in the resin composition of this invention, it is preferable that the said compound (C) is polyethyleneglycol.

  It is preferable that the resin composition of the present invention further contains 0.01 to 5 parts by mass of one or more alkali metal salts (F).

  Furthermore, in the resin composition of the present invention, it is preferable that the thermoplastic resin contains a polyolefin resin.

  Furthermore, in the resin composition of the present invention, the thermoplastic elastomer preferably contains a copolymer of ethylene and α-olefin or a copolymer of ethylene and vinyl ester.

  The molded product of the present invention is characterized by comprising the resin composition of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition which can maintain the outstanding antistatic property for a long period of time, and can implement | achieve the molded object with favorable rigidity and the impact resistance in a low-temperature environment, and a molded object using the same Can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
The thermoplastic resin composition of the present invention contains 2 to 50 parts by mass of a thermoplastic elastomer with respect to 50 to 98 parts by mass of the thermoplastic resin, and is high with respect to 100 parts by mass of the total amount of the thermoplastic resin and the thermoplastic elastomer. It contains 2 to 40 parts by mass of the molecular compound (A).

First, the thermoplastic resin used in the present invention will be described.
The resin that can be used in the thermoplastic resin composition of the present invention is not particularly limited as long as it is a thermoplastic resin, but a polyolefin resin is particularly preferable because the effects of the invention are remarkable.

  Polyolefin resins include polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, cross-linked polyethylene, ultra high molecular weight polyethylene, polypropylene, homopolypropylene, random copolymer polypropylene, block copolymer polypropylene, isotactic polypropylene, and Shinji. Tactic polypropylene, hemiisotactic polypropylene, polybutene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, etc. These α-olefin polymers may be used, and those containing two or more polyolefin resins may be used.

Next, the thermoplastic elastomer will be described.
The thermoplastic elastomer is not particularly limited as long as it is a known thermoplastic elastomer, but is preferably a copolymer of ethylene and another monomer because it is excellent in compatibility with the polyolefin resin.

  Other monomers include linear or branched α-olefins having 3 to 20 carbon atoms, aromatic vinyl compounds having 8 to 20 carbon atoms, other vinyl compounds, conjugated dienes, alkyl methacrylate esters, Examples include alkyl acrylates. These other monomers may be used alone or in combination of two or more.

  Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 3-methyl-1-butene, 3-ethyl-1-butene, 1-pentene, 3-methyl-1-pentene, 3 -Ethyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl -1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like, preferably propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene are exemplified.

  Examples of the aromatic vinyl compound having 8 to 20 carbon atoms include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, p- Examples thereof include tert-butyl styrene, chloromethyl styrene, vinyl toluene, and preferably mono- or polyalkyl styrene.

  Examples of other vinyl compounds include halogenated olefins, unsaturated amines, unsaturated carboxylic acids, vinyl esters, unsaturated epoxy compounds, and ethylenically unsaturated silane compounds.

  Here, the halogenated olefin represents one obtained by adding a halogen atom such as chlorine, bromine or iodine to the α-olefin.

  Examples of the unsaturated amine include allylamine, 5-hexeneamine, and 6-hepteneamine.

  Examples of the unsaturated carboxylic acid include propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid and 10-undecene. An acid etc. are mentioned, The thing substituted by the halogen atom may be sufficient.

  Examples of vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl pentanoate, vinyl decanoate, vinyl undecylate, vinyl laurate, vinyl myristate, pentadecylic acid. Examples thereof include aliphatic vinyl esters such as vinyl, vinyl palmitate, vinyl stearate, vinyl versatate (a carboxylic acid mixture having 9 to 11 carbon atoms), and aromatic vinyl esters such as vinyl benzoate. Preferable vinyl esters include vinyl esters having 3 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and more preferably vinyl acetate.

  Examples of the unsaturated epoxy compound include 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene, 7-epoxy-1-heptene, 8-epoxy-1-octene, 9 -Epoxy-1-nonene, 10-epoxy-1-decene, 11-epoxy-1-undecene and the like.

  Examples of ethylenically unsaturated silane compounds include vinyltriethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-methacryloxy. And propyltrimethoxysilane.

  Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, 2, Examples include 4-hexadiene and 1,3-octadiene.

  Examples of the methacrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and n-pentyl (meth) acrylate. , Isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-methylpentyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, n- Examples include dodecyl (meth) acrylate and n-octadecyl (meth) acrylate.

  As alkyl acrylates, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (n-propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate, 3-methoxypropyl acrylate, 3-ethoxypropyl acrylate , 2- (n-propoxy) propyl acrylate, 2- (n-butoxy) propyl acrylate, and the like.

  In the thermoplastic resin composition of the present invention, the thermoplastic elastomer may be one obtained by copolymerizing these monomers alone with ethylene, or by combining two or more monomers together with ethylene. It may be polymerized.

  In the resin composition of the present invention, specific examples of the thermoplastic elastomer include block or random copolymers such as ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, and ethylene-methyl methacrylate. Copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, styrene-ethylene-butylene copolymer, styrene-ethylene-butylene-styrene copolymer, ethylene- A vinyl acetate copolymer etc. are mentioned.

  Examples of the thermoplastic elastomer other than the combination of ethylene and other monomers include thermoplastic polyesters and thermoplastic polyurethanes.

  In the present invention, an ethylene-α-olefin copolymer is preferable because of excellent compatibility with the olefin resin. Also preferred are copolymers of ethylene and vinyl esters.

  In the resin composition of the present invention, these thermoplastic resins and thermoplastic elastomers may be used alone or in combination of two or more. Moreover, it may be alloyed. These thermoplastic resins and thermoplastic elastomers are composed of molecular weight, degree of polymerization, density, softening point, proportion of insoluble matter in solvent, degree of stereoregularity, presence / absence of catalyst residues, types and blends of raw monomers. It can be used regardless of the ratio, the type of polymerization catalyst (for example, Ziegler catalyst, metallocene catalyst, etc.).

  In the present invention, the ratio of the thermoplastic resin and the thermoplastic elastomer is mass ratio, and the ratio of thermoplastic resin / thermoplastic elastomer is 98/2 to 50/50, preferably 95/5 to 55/45. Range. When the thermoplastic resin is more than 98 parts by mass, the impact strength under a low temperature environment may be insufficient, and when it is less than 50 parts by mass, the rigidity may be insufficient.

Next, the polymer compound (A) will be described.
In the present invention, the polymer compound (A) is blended for imparting antistatic properties to the resin composition. The polymer compound (A) is a compound (C) having a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, one or more groups represented by the following general formula (1), and hydroxyl groups at both ends. 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.

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

  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.

  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 (2).

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

In general formula (2), 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 binds to a carboxyl group via an ester bond, or any compound that can be bonded via an amide bond. Polyester (E) and 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 alternately bonded via an ester bond. What is necessary is just to be able to couple | bond with the block polymer (G) which has a carboxyl group at the terminal through an ester bond or 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.

  In the present invention, the compound (D) having a reactive functional group is particularly preferably a polyvalent epoxy compound (D) -1.

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 properties, the polymer compound (A) is a polyester (E) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and the above compound It is preferable that (C) and the compound (D) having the 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) includes a block composed of a polyester (E) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and the above compound (C). A block polymer (G) having a carboxyl group at both ends, in which the constituted block is repeatedly and alternately bonded via an ester bond, and the compound (D) having the reactive functional group are bonded via an ester bond. Alternatively, 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 a derivative thereof, an aromatic dicarboxylic acid or a derivative thereof, and the 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 of the aliphatic dicarboxylic acid or derivative thereof and the aromatic dicarboxylic acid or derivative thereof to the diol is: 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. preferable.

  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.

  In addition, the polyester (E) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid may form an ester bond by reacting with the compound (C) to form the structure of the block polymer (G). That's fine. 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.

  The compound (C) may be any compound as long as it reacts with the polyester (E) to form an ester bond to form the structure of the block polymer (G), and the hydroxyl groups at both ends may be protected. It may also 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 (3).

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

In general formula (3), (E) represents a block composed of a polyester (E) having carboxyl groups at both ends, and (C) was composed of a 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. The polyester (E) and the compound (C) having a structure equivalent to that having a structure in which the polyester (E) and the compound (C) are alternately and repeatedly bonded through an ester bond formed by a carboxyl group and a hydroxyl group. If so, it is not always necessary to synthesize from the polyester (E) and the compound (C).

  The reaction ratio between 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 with respect to X mol. A block polymer (G) having the following 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) is a block composed of a polyester composed only of a diol and an aliphatic dicarboxylic acid in addition to a block composed of a polyester (E) and the above compound (C), or a diol And 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. The polymer compound (A) is further produced 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, or an ester. A structure formed via a bond and 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 of the compound (D), the hydroxyl group of the polyhydric alcohol compound, or the amino of the polyvalent amine compound What is necessary is just to react with group.

  When the compound (D) is a polyvalent epoxy compound (D) -1 having two or more epoxy groups, the number of epoxy groups in the polyvalent epoxy compound (D) -1 is the number of the block polymer (G) to be reacted. 0.5-5 equivalent of the number of carboxyl groups is preferable, and 0.5-1.5 equivalent is 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 in the polyvalent amine compound (D) -3 depends on the block polymer (G) to be reacted. 0.5-5 equivalent of the number of carboxyl groups is preferable, and 0.5-1.5 equivalent is 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 to the reaction system 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. Alternatively, 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) have an ester bond or an ester bond and an amide bond. As long as it has a structure equivalent to that having a structure bonded thereto, 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 high molecular compound (A) is blended in the thermoplastic resin, the high molecular compound (A) is 2 to 40 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin and the thermoplastic elastomer. From the viewpoint of the effect on the prevention and the physical properties of the resin, 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.

  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 viewpoint of antistatic properties, 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) in the resin composition of the present invention is 0 with respect to 100 parts by mass of the total amount of the thermoplastic resin, the thermoplastic elastomer and the polymer compound (A) from the viewpoint of antistatic properties. 0.01 to 5.0 parts by mass, preferably 0.1 to 3.0 parts by mass, and more preferably 0.3 to 2.0 parts by mass. 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.

  Moreover, you may mix | blend surfactant with the resin composition of this invention in the range which does not impair the effect of this invention. 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, a thermoplastic elastomer, and a high molecular compound (A), and the compounding quantity in the case of mix | blending surfactant is 0.5- 2 parts by mass is more preferable.

  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 type antistatic agent is 2 to 40 parts by mass with respect to the polymer compound (A) with respect to 100 parts by mass of the total amount of the thermoplastic resin and the thermoplastic elastomer. It is preferable that 2 to 30 parts 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.

  The cation may be used alone or in combination of two or more. 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 the above organic acids and inorganic acids, from the viewpoint of antistatic properties of the ionic liquid, a super strong acid conjugate base in which the Hammett acidity function (-Ho) of the anion constituting the ionic liquid is 12 to 100 is preferable. , Acids that form anions other than the 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 thermoplastic resin, the thermoplastic elastomer and the polymer compound (A). Is more preferable.

  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 compatibilizing agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin, the thermoplastic elastomer and the polymer compound (A). 3 parts by mass is more preferred.

  In addition, the resin composition of the present invention may optionally contain known resin additives (for example, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, and the like, as long as the effects of the present invention are not impaired). Antioxidants, ultraviolet absorbers, hindered amine compounds, nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, metal soaps, hydrotalcites, pigments, dyes, and the like). The known resin additive may be mixed with the polymer compound (A) and then added to the resin component, or may be separately added to the resin component and molded.

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), 3,5-di Polymer of ester of tert-butyl-4-hydroxy-benzenepropanoic acid and C13-15 alkyl, 2,5-di-tert-amylhydroquinone, hindered phenol (trade name AO.OH.98 manufactured by Adeka Palmalol) ), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2-tert-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 (3H) -ben Reaction product of furanone 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-hydroxyphenyl) propionate, Distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-di-tert-butyl-4- Roxybenzylthioacetate, 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- ( ', 5'-di-tert-butyl-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-hydroxy Phenyl) propionic acid amide, palmityl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid , Myristyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, etc. And 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives.
The blending amount in the case of blending the phenolic antioxidant is preferably 0.001 to 20 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin, the thermoplastic elastomer and the polymer compound (A). 01-5 mass parts is more preferable.

Examples of phosphorus antioxidants include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, diphenyl Tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis (Tridecyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecyl phosphite, dinonylphenyl bi (Nonylphenyl) phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyldipropylene glycol diphosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris ( 2,4-di-tert-butyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl ] Phosphite, tri (decyl) phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite, a mixture of distearyl pentaerythritol and calcium stearate, alkyl (C 0) Bisphenol A phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) ) Pentaerythritol diphosphite, tetraphenyl-tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidenedipheno Rudiphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4- Hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, (1-methyl-1-propenyl-3-ylidene) tris (1,1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecyl phosphite, 2,2'-methylenebis (4 , 6-Di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebi (4,6-di-tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphite, 4,4′-butylidenebis (3-methyl -6-tert-butylphenylditridecyl) phosphite, tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine) -6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphisspiro [5,5] undecane, 2, 4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4′-isopropylidenediphenol C1 Include the -15 alcohol phosphite.
The blending amount when the phosphorus antioxidant is blended is preferably 0.001 to 20 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin, the thermoplastic elastomer and the polymer compound (A). 01-5 mass parts is more preferable.

Examples of the thioether-based antioxidant include 3,3′-thiodipropionic acid, alkyl (C12-14) thiopropionic acid, di (lauryl) -3,3′-thiodipropionate, di (tridecyl)- 3,3′-thiodipropionate, di (myristyl) -3,3′-thiodipropionate, di (stearyl) -3,3′-thiodipropionate, di (octadecyl) -3,3′- Thiodipropionate, lauryl stearyl thiodipropionate, tetrakis [methylene-3- (dodecylthio) propionate] methane, thiobis (2-tert-butyl-5-methyl-4,1-phenylene) bis (3- (dodecylthio) Propionate), 2,2'-thiodiethylenebis (3-aminobutenoate), 4,6-bis (octylthiomethyl) -o-alkyl Resole, 2,2′-thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,2′-thiobis (6-tert-butyl-p-cresol), 2-ethylhexyl- (3,5-di-tert-butyl-4-hydroxybenzyl) thioacetate, 4,4′-thiobis (6- tert-butyl-3-methylphenol), 4,4′-thiobis (4-methyl-6-tert-butylphenol), 4,4 ′-[thiobis (methylene)] bis (2-tert-butyl-6-methyl) -1-hydroxybenzyl), bis (4,6-di-tert-butylphenol-2-yl) sulfide, tridecyl-3,5-di-tert-butyl 4-hydroxybenzylthioacetate, 1,4-bis (octylthiomethyl) -6-methylphenol, 2,4-bis (dodecylthiomethyl) -6-methylphenol, distearyl-disulfide, bis (methyl -4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl) sulfide and the like.
The amount of the thioether-based antioxidant to be blended is preferably 0.001 to 20 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin, the thermoplastic elastomer and the polymer compound (A). 01-5 mass parts is more preferable.

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- ((15-hydroxy-3,6,9,13-tetraoxapentadecyl) oxy) phenyl) benzofuran compounds such as benzofuran-2 (3H) one, dioctylmethylamineoxy , Trioctylamine oxide, didecylmethylamine oxide, tridecylamine oxide, di (hydrogenated C12-14 alkyl) methylamine oxide, tri (hydrogenated C12-14 alkyl) amine oxide, di (hydrogenated C16-18 alkyl) ) Amine oxide compounds such as methylamine oxide, tri (hydrogenated C16-18 alkyl) amine oxide, di (C20-22) alkylmethylamine oxide and tri (C20-22) alkyl) amine oxide, N, N-dibenzyl N, N-diarylhydroxylamine such as hydroxylamine, phenylnaphthylamine, 4,4′-dimethoxydiphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, 4-isopropoxydiphenylamine, N, N-alkyl Aryl Hydroxylamine, N, N-di-cycloalkyl hydroxylamine, diethylhydroxylamine, dioctylhydroxylamine, didodecyl hydroxylamine, amine compounds such as dioctadecyl hydroxylamine and the like.
0.001-20 mass parts is preferable with respect to 100 mass parts of total amounts of a thermoplastic resin, a thermoplastic elastomer, and a high molecular compound (A), when the other antioxidant is mix | blended, 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-) -Tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 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-te rt-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; Nilsalicylate, 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'-dodecyloxy Substituted oxanilides such as zanilide; 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, a thermoplastic elastomer, and a high molecular compound (A), and the compounding quantity in the case of mix | blending a ultraviolet absorber is 0.01- 0.5 parts by mass is more preferable.

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, a thermoplastic elastomer, and a high molecular compound (A), and the compounding quantity in the case of mix | blending a hindered amine compound is 0.005-0. More preferably, 5 parts by mass.

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-butyl aluminum benzoate, sodium adipate and disodium bicyclo [2 2.1] Carboxylic acid metal salts such as heptane-2,3-dicarboxylate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, bis (p-ethylbenzylidene) Sorbitol and bis (dimethylbenzene Polyol derivatives such as silylidene) 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, a thermoplastic elastomer, and a high molecular compound (A), and, as for the compounding quantity in the case of mix | blending a nucleating agent, 0.005- 0.5 parts by mass is more preferable.

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.
The blending amount in the case of blending the flame retardant is preferably 1 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin, the thermoplastic elastomer and the polymer compound (A). 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 in the case of blending the lubricant is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin, the thermoplastic elastomer and the polymer compound (A). 5 parts by mass is more preferable.

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. , Silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate, and the like, and the particle diameter (in the fibrous form, the fiber diameter, fiber length, and aspect ratio) can be appropriately selected and used. . Moreover, what was surface-treated as needed can be used for a filler.
The blending amount when the filler is blended is preferably 0.01 to 80 parts by weight, and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the thermoplastic resin, thermoplastic elastomer and polymer compound (A). 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.
0.001-10 mass parts is preferable with respect to 100 mass parts of total amounts of a thermoplastic resin, a thermoplastic elastomer, and a high molecular compound (A), and, as for the compounding quantity in the case of mix | blending metal soap, 0.01-5 masses. Part is more preferred.

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

ここで、一般式（５）中、Ａ^ｑ−は、ｑ価のアニオンを表し、ｐは０または正の数を表す。また、ハイドロタルサイト類における炭酸アニオンは、一部を他のアニオンで置換したものでもよい。 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 metal, hydroxyl groups, and carbonate groups substituted with other anionic groups. Specifically, for example, the hydrotalcite metal represented by the following general formula (4) 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 (5) can also be used.

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

Here, in the general formula (5), A ^q− represents a q-valent anion, and p represents 0 or a positive number. Further, the carbonate anion in the 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, a thermoplastic elastomer, and a high molecular compound (A), and the compounding quantity in the case of mix | blending hydrotalcite is 0.05- 3 parts by mass is 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 production method of the resin composition of the present invention is not particularly limited as long as the polymer compound (A), if necessary, an alkali metal salt (F) and other optional components are blended with the thermoplastic resin and the thermoplastic elastomer. In general, any commonly used method can be used. 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 blending method of the polymer compound (A) to the thermoplastic resin and the thermoplastic elastomer, the block polymer (G) and the polymer compound (A) may be blended together or blended separately. May be.

  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, or the polymer compound (A), the alkali metal salt (F) and the resin component are mixed at the time of molding such as injection molding. In addition, a master batch of the polymer compound (A) and / or alkali metal salt (F) and a thermoplastic resin is produced in advance, and this master batch is blended. May be.

  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, rigidity and low temperature impact 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 has excellent antistatic properties, rigidity and low-temperature impact resistance, and little physical property degradation. In particular, it is excellent in maintaining 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.

Hereinafter, the present invention will be specifically described with reference to examples.
The polymer compound (A) was produced according to the following production example. 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 may be abbreviated as “Mn”) was measured by a gel permeation chromatography (GPC) method under the following measurement conditions.
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: 0.8 mL / min.
Injection volume: 100 μL

[Production Example 1] (Production of polymer compound (A) -1)
In a separable flask, 656 g (4.55 mol) of 1,4-cyclohexanedimethanol as a diol, 708 g (4.85 mol) of adipic acid as an aliphatic dicarboxylic acid, and phthalic anhydride as an aromatic dicarboxylic acid 0.7 g (4.73 × 10 ⁻³ mol), antioxidant (tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane; trade name of ADEKA Corporation "Adeka Stub AO-60") was charged in an amount of 0.7 g, 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. Got. 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 is used as a compound (C) having one or more groups represented by the general formula (1) and having hydroxyl groups at both ends, and having a number average molecular weight of 4,000. 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. A block polymer (G) -1 having a structure having a group was obtained. The acid value of the block polymer (G) -1 having a structure having a carboxyl group at both ends was 9, and the number average molecular weight Mn was 12,000 in terms of polystyrene.

  360 g of the obtained block polymer (G) -1 having a structure having a carboxyl group at both ends is charged with 6 g of bisphenol F diglycidyl ether (D) -1 as a compound (D) having a reactive functional group, Polymerization was performed 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, and the mixture was subjected to reduced pressure at 240 ° C. 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.

[Examples 1-20, Comparative Examples 1-16]
Using the polymer compounds (A) -1 to (A) to 3 obtained by the above production method, test pieces were prepared by the following method and evaluated.

<Test specimen preparation conditions>
The resin composition blended based on the blending amounts shown in Tables 1 to 5 below is 230 ° C., 9 kg / hour using a twin screw extruder (product name: PCM 30, 60 mesh screen) manufactured by Ikegai Co., Ltd. The pellets were obtained by granulation under the following conditions. 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 200 ° C. and a mold temperature of 40 ° C., and a test piece for measuring surface resistivity ( 100 mm × 100 mm × 3 mm), and test pieces for measuring the flexural modulus and Charpy impact strength (80 mm × 10 mm × 4 mm) were prepared. Using these test pieces, the surface resistivity (Ω / □), flexural modulus (MPa), and Charpy impact strength (kJ / m ² ) were measured according to the following conditions.

<Surface specific resistance measurement method>
The obtained test piece (100 mm × 100 mm × 3 mm) was placed in a constant temperature and humidity chamber adjusted to 25 ° C. and a humidity of 60% RH immediately after molding, and 25 days after molding, 1 day and 30 days later. The surface specific resistance value (Ω / □) was measured under the conditions of an applied voltage of 500 V and an applied time of 1 minute using an R8340 resistance meter manufactured by Advantest Co., Ltd. in an atmosphere of ° C and humidity of 60% RH. In addition, the same as described above is applied to the test piece that was left in a constant temperature and humidity chamber adjusted to 25 ° C. and a humidity of 60% after wiping the surface of the test piece 30 days after molding 50 times with running water waste. The surface resistivity (Ω / □) was measured under the conditions. The measurement was performed at 5 points, and the average value was obtained. These test results are shown in the following Tables 1 to 5, respectively.

<Bending modulus evaluation method>
Immediately after molding the obtained test piece (80 mm × 10 mm × 4 mm), it was left in a thermostatic bath at 23 ° C. for 7 days, a bending test was performed in accordance with ISO178, and a flexural modulus (MPa) was measured. . In addition, when the test piece was too soft to be measured, it was expressed as “ND”. These test results are shown in the following Tables 1 to 5, respectively.

<Charpy impact strength evaluation method>
The obtained test piece (80 mm × 10 mm × 4 mm) was molded and immediately left in a constant temperature and humidity chamber of 23 ° C. and humidity 60% RH for 7 days, and the test piece was notched. The test piece with the notch is further left in a thermostatic chamber at −30 ° C. for 5 days, and then the test piece is taken out from the thermostatic chamber, and immediately, Charpy impact is applied in accordance with ISO179-1. The strength (kJ / m ² ) was measured. These test results are shown in Tables 1 to 5 below.

＊１：熱可塑性樹脂１；インパクトコポリマーポリプロピレン、メルトフローレート（ＩＳＯ１１３３ ２３０℃×２．１６ｋｇ）＝３０ｇ／１０ｍｉｎ
＊２：熱可塑性エラストマー１；エチレン−オクテン共重合体、メルトフローレート（ＩＳＯ１１３３ １９０℃×２．１６ｋｇ）＝１ｇ／１０ｍｉｎ
＊３：ＮａＤＢＳ；ドデシルベンゼンスルホン酸ナトリウム
＊４：ＬｉＯＴｓ；ｐ−トルエンスルホン酸リチウム

* 1: Thermoplastic resin 1; impact copolymer polypropylene, melt flow rate (ISO 1133 230 ° C. × 2.16 kg) = 30 g / 10 min
* 2: Thermoplastic elastomer 1; ethylene-octene copolymer, melt flow rate (ISO 1133 190 ° C. × 2.16 kg) = 1 g / 10 min
* 3: NaDBS; sodium dodecylbenzenesulfonate * 4: LiOTs; lithium p-toluenesulfonate

＊５：熱可塑性エラストマー２；エチレン−ブテン共重合体、メルトフローレート（ＩＳＯ１１３３ １９０℃×２．１６ｋｇ）＝０．５ｇ／１０ｍｉｎ

* 5: Thermoplastic elastomer 2; ethylene-butene copolymer, melt flow rate (ISO 1133 190 ° C. × 2.16 kg) = 0.5 g / 10 min

＊６：熱可塑性樹脂２；高密度ポリエチレン、メルトフローレート（ＩＳＯ１１３３ １９０℃×２．１６ｋｇ）＝７ｇ／１０ｍｉｎ
＊７：熱可塑性エラストマー３；エチレン−酢酸ビニル共重合体、メルトフローレート（ＩＳＯ１１３３ １９０℃×２．１６ｋｇ）＝２ｇ／１０ｍｉｎ

* 6: Thermoplastic resin 2; high density polyethylene, melt flow rate (ISO 1133 190 ° C. × 2.16 kg) = 7 g / 10 min
* 7: Thermoplastic elastomer 3; ethylene-vinyl acetate copolymer, melt flow rate (ISO 1133 190 ° C. × 2.16 kg) = 2 g / 10 min

＊８：比較帯電防止剤１；グリセリンモノステアレート
＊９：比較帯電防止剤２；ポリエーテルエステルアミド系帯電防止剤、Ａｒｋｅｍａ社製、商品名「ペバックスＭＶ１０７４」
＊１０：比較帯電防止剤３；ポリエーテルエステルアミド系帯電防止剤、ＢＡＳＦ社製、商品名「イルガスタットＰ１８」

* 8: Comparative antistatic agent 1; Glycerin monostearate * 9: Comparative antistatic agent 2; Polyetheresteramide antistatic agent, manufactured by Arkema, trade name “Pebax MV1074”
* 10: Comparative antistatic agent 3; polyether ester amide type antistatic agent, manufactured by BASF, trade name “Irgastat P18”

  From the comparative example 4 and the comparative example 5, when the antistatic agent different from this invention was used, the antistatic property was impaired by water wiping. Further, from Comparative Examples 11 to 13, when the thermoplastic elastomer was not used, the rigidity was excellent, but the impact resistance strength in a low temperature environment was extremely low. Furthermore, from Comparative Examples 14 to 16, when a thermoplastic resin was not used, the impact resistance strength under a low temperature environment was excellent, but the rigidity was not satisfactory. Furthermore, according to the comparison results of Example 2 and Comparative Example 6, and Example 2 and Comparative Example 7, the molded body using the polymer type antistatic agent different from the present invention has insufficient antistatic properties. In addition, the rigidity and impact strength under a low temperature environment were not satisfactory.

On the other hand, it was confirmed that the molded article of the present invention was excellent in all of antistatic properties, rigidity, and impact resistance in a low temperature environment. Therefore, the thermoplastic resin composition of the present invention is preferably used for applications that require rigidity and impact resistance strength in a low-temperature environment, such as automotive interior / exterior materials and electrical equipment exterior materials. it can.

Claims (12)

2-50 mass parts of thermoplastic elastomer is contained with respect to 50-98 mass parts of thermoplastic resins, and polymer compound (A) 2-40 with respect to 100 mass parts of total amounts of the thermoplastic resin and the thermoplastic elastomer. A thermoplastic resin composition containing parts by mass,
The polymer compound (A) is a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a compound (C) having one or more groups represented by the following general formula (1) and having hydroxyl groups at both ends; and A thermoplastic resin composition having a structure in which a compound (D) having a reactive functional group is bonded via an ester bond or via an ester bond and an amide bond.

  The polymer (A) is a polyester (E) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, the compound (C), and a compound (D) having the reactive functional group. The thermoplastic resin composition according to claim 1, which has a structure formed by bonding via an ester bond or 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 heat according to claim 2, wherein the block polymer (G) and the compound (D) having a reactive functional group have a structure formed by bonding via an ester bond or an ester bond and an amide bond. Plastic resin composition.   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 thermoplastic resin composition according to claim 3, wherein the block polymer (G) has a number average molecular weight of 5,000 to 25,000 in terms of polystyrene.   The thermoplastic resin composition according to any one of claims 2 to 4, wherein the polyester (E) has a structure having carboxyl groups at both ends.   The thermoplastic resin composition according to any one of claims 1 to 5, wherein the compound (D) having a reactive functional group is a polyvalent epoxy compound having two or more epoxy groups.   The said compound (C) is polyethyleneglycol, The thermoplastic resin composition as described in any one of Claims 1-6.   Furthermore, the 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 salts (F).   The thermoplastic resin composition according to any one of claims 1 to 8, wherein the thermoplastic resin contains a polyolefin-based resin.   The thermoplastic resin composition according to any one of claims 1 to 9, wherein the thermoplastic elastomer contains a copolymer of ethylene and an α-olefin.   The thermoplastic resin composition according to any one of claims 1 to 9, wherein the thermoplastic elastomer contains a copolymer of ethylene and vinyl ester. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 11.