JP2016138169A - Antistatic resin composition and container and packaging material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic resin composition which has sufficient antistatic properties having persistence, hardly causes elution of ions when formed into a molding, and is suitable for housing and conveyance containers and a packaging material of electric and electronic components, and a container and a packaging material using the same.SOLUTION: The antistatic resin composition contains based on 100 pts.mass of a synthetic resin, 3-20 pts.mass of one or more polymer compounds (E) and 0.1-5 pts.mass of one or more salts (F) of alkali metal. The polymer compound (E) has such a structure that diol, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, a compound (B) having one or more groups represented by general formula (1) and hydroxyl groups at both terminals, and a polyhydric alcohol compound (D) having three or more hydroxyl groups are bonded to each other through an ester bond.SELECTED DRAWING: None

Description

  The present invention relates to an antistatic resin composition (hereinafter, also simply referred to as “resin composition”) and a container and a packaging material using the same, and in particular, has sufficient antistatic properties having durability, and The present invention relates to an antistatic resin composition suitable for storage / conveying containers and packaging materials for electrical and electronic parts, and containers and packaging materials using the same, in which almost no ions are eluted when formed into a molded body.

  Electrical and electronic equipment includes silicon wafers, hard disks, disk substrates, glass substrates, IC chips, semiconductors, optical storage disks, color filters, hard disk magnetic head elements, CCD elements, and other electrical and / or electronic components (hereinafter “ "Electrical and electronic parts"). In assembling these electric and electronic devices, there is a need to transport and transport the parts in order to use the parts on an assembly line, and a transport container for this purpose is used. Further, when storing and storing parts as intermediate products or products, storage containers and packaging materials are used.

  Conventionally, synthetic resins such as polyolefin resins and polystyrene resins, which are excellent in moldability and chemical resistance, are used for containers for transporting electric and electronic parts, containers for storing, and packaging materials for packaging electric and electronic parts. It is used.

  In such electric and electronic parts, the occurrence of static electricity causes a serious problem such as failure or attracting fine dust. Therefore, in order to prevent the generation of static electricity, an antistatic agent is added to the synthetic resin to impart antistatic properties. As these antistatic agents, use of a polymer type antistatic agent has been proposed in order to impart lasting antistatic properties (for example, Patent Documents 1 to 3).

JP 2012-62067 A JP-A-8-12755 JP 2001-278985 A

  These polymer-type antistatic agents often contain an electrolyte such as an alkali metal salt for the purpose of improving antistatic properties, and when used in a container / container for electrical and electronic parts, they elute from the molded product. Ions are a problem. On the other hand, when no electrolyte is contained, there is a problem that ion elution is small but sufficient antistatic performance cannot be obtained. Therefore, at present, there is a demand for a resin composition having a sufficient amount of ion elution while having sufficient antistatic properties that are durable.

  Accordingly, the object of the present invention is suitable for storage and transport containers and packaging materials for electrical and electronic parts that have sufficient antistatic properties that are durable and have almost no elution of ions when formed into molded bodies. An object is to provide an antistatic resin composition, and a container and a packaging material using the same.

  As a result of intensive studies to solve the above problems, the present inventors have used the antistatic polymer compound having a specific structure and an alkali metal salt in combination at a predetermined ratio. As a result, the present invention has been completed.

That is, the antistatic resin composition of the present invention comprises 3 to 20 parts by mass of one or more polymer compounds (E) and one or more salts of alkali metal (F) with respect to 100 parts by mass of the synthetic resin. An antistatic resin composition containing 0.1 to 5 parts by mass,
Compound (B) in which the polymer compound (E) has a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, one or more groups represented by the following general formula (1), and a hydroxyl group at both ends. And a polyhydric alcohol compound (D) having three or more hydroxyl groups are bonded to each other through an ester bond.

  In the antistatic resin composition of the present invention, the polymer compound (E) is a polyester (A) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, the compound (B), The polyhydric alcohol compound (D) preferably has a structure formed by bonding through an ester bond.

  In the antistatic resin composition of the present invention, the polymer compound (E) is composed of a block composed of the polyester (A) and a block composed of the compound (B) via an ester bond. It is preferable that the block polymer (C) having a carboxyl group at both ends which are alternately and repeatedly bonded and the polyhydric alcohol compound (D) have a structure formed by bonding via an ester bond.

  Furthermore, in the antistatic resin composition of this invention, it is preferable that the said polyester (A) which comprises the said high molecular compound (E) has a structure which has a carboxyl group in both terminal.

  Furthermore, in the antistatic resin composition of the present invention, in the polymer compound (E), the number average molecular weight of the block composed of the polyester (A) is 800 to 8,000 in terms of polystyrene, The number average molecular weight of the block composed of the compound (B) is 400 to 6,000 in terms of polystyrene, and the number average molecular weight of the block polymer (C) is 5,000 to 25,000 in terms of polystyrene. It is preferable that

  Furthermore, in the antistatic resin composition of the present invention, it is preferable that the compound (B) constituting the polymer compound (E) is polyethylene glycol, and the synthetic resin is a polyolefin resin and polystyrene. It is preferable that it is 1 or more types chosen from the group which consists of resin.

  The container and the packaging material of the present invention are formed by molding the antistatic resin composition of the present invention.

In the container and packaging material of the present invention, the amount of sodium ions and lithium ions eluted when immersed in 100 g of water at 40 ° C. for 2 hours is preferably 12 ppb or less per 1 cm ^{2 of} surface area.

  According to the present invention, there is sufficient antistatic property having durability, and there is almost no elution of ions when formed into a molded body, which is suitable for storage and transport containers and packaging materials for electrical and electronic parts. The resin composition and the container and packaging material using the same can be provided.

Hereinafter, the antistatic resin composition, container, and packaging material of the present invention will be described in detail.
First, the antistatic resin composition of the present invention will be described. The antistatic resin composition of the present invention comprises 3 to 20 parts by weight of one or more polymer compounds (E) and 100% by weight of one or more alkali metal salts (F). 1 to 5 parts by mass. In the resin composition of the present invention, the polymer compound (E) has a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and at least one group represented by the following general formula (1). The compound (B) having a hydroxyl group and the polyhydric alcohol compound (D) having three or more hydroxyl groups are bonded via an ester bond.

  Next, the synthetic resin used in the present invention will be described. In the resin composition of the present invention, the resin to be used is not particularly limited as long as it is a synthetic resin, but a thermoplastic resin is preferable, and a polyolefin resin and a polystyrene resin are particularly preferable.

  Examples of the polyolefin resin include low density polyethylene, linear low density polyethylene, high density polyethylene, homopolypropylene, random copolymer polypropylene, block copolymer polypropylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, Α-olefin polymers such as polybutene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene-propylene Block or random copolymer, impact copolymer polypropylene, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl Examples include α-olefin copolymers such as acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-vinyl acetate copolymers, and polyolefin-based thermoplastic elastomers, and these two or more types of copolymers may be used. . Two or more of these polyolefin resins may be used.

  Examples of polystyrene resins include vinyl group-containing aromatic hydrocarbons alone, and vinyl group-containing aromatic hydrocarbons and other monomers (for example, maleic anhydride, phenylmaleimide, (meth) acrylic acid esters, Butadiene, (meth) acrylonitrile, etc.), for example, polystyrene (PS) resin, impact polystyrene (HIPS), acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin , Methyl methacrylate-butadiene-styrene (MBS) resin, heat-resistant ABS resin, acrylonitrile-acrylate-styrene (AAS) resin, styrene-maleic anhydride (SMA) resin, methacrylate-styrene (MS) resin, styrene-isoprene-styrene (SIS) resin Thermoplastic resins such as acrylonitrile-ethylenepropylene rubber-styrene (AES) resin, styrene-butadiene-butylene-styrene (SBBS) resin, methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin, and butadiene or isoprene Styrene-ethylene-butylene-styrene (SEBS) resin, hydrogenated double bond, styrene-ethylene-propylene-styrene (SEPS) resin, styrene-ethylene-propylene (SEP) resin, styrene-ethylene-ethylene-propylene-styrene (SEEPS) A hydrogenated styrene-based elastomer resin such as a resin may be used, and two or more of these may be used.

  In the resin composition of the present invention, as synthetic resins other than polyolefin resins and polystyrene resins, for example, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber chloride, vinyl chloride- Vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride- Halogen-containing resins such as maleic acid ester copolymer and vinyl chloride-cyclohexyl maleimide copolymer; petroleum resin, coumarone resin, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; polyethylene Aromatic polyesters such as polyalkylene terephthalates such as phthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate, and linear polyesters such as polytetramethylene terephthalate; Degradable aliphatic polyesters such as rate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, poly (2-oxetanone); polyphenylene oxide, polycaprolactam and polyhexamethylene Polyamide such as adipamide, polycarbonate, polycarbonate / ABS resin, branched polycarbonate, polyaceta Le, polyphenylene sulfide, polyurethane, cellulose resins, polyimide resins, polysulfone, polyphenylene ether, polyether ketone, polyether ether ketone, a thermoplastic resin and blends thereof such as a liquid crystal polymer. Furthermore, isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluorine rubber, silicone rubber, polyester elastomer, nitrile elastomer, nylon elastomer, vinyl chloride elastomer, polyamide elastomer, An elastomer such as a polyurethane elastomer may be used.

  In the resin composition of this invention, these synthetic resins may be used independently and may use 2 or more types together. Moreover, it may be alloyed. These synthetic resins are composed of a molecular weight, a degree of polymerization, a density, a softening point, a ratio of insoluble matter in a solvent, a degree of stereoregularity, the presence or absence of a catalyst residue, the type and blending ratio of raw materials, and the polymerization catalyst. It can be used regardless of the type (for example, Ziegler catalyst, metallocene catalyst, etc.).

Next, the polymer compound (E) used in the present invention will be described. The polymer compound (E) is blended to impart antistatic properties to the resin composition of the present invention.
As described above, the polymer compound (E) used in the present invention has a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and at least one group represented by the following general formula (1). The compound (B) having a hydroxyl group and the polyhydric alcohol compound (D) having three or more hydroxyl groups are bonded via an ester bond.

  The polymer compound (E) includes a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and a compound (B) having one or more groups represented by the general formula (1) and having hydroxyl groups at both ends. It can be obtained by esterifying a polyhydric alcohol compound (D) having 3 or more hydroxyl groups.

First, the diol used in the present invention will be described.
Examples of the diol used in 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 antistatic properties and suppression of ion elution, and 1,4-cyclohexanedimethanol is more preferable.

  In addition, since the aliphatic diol preferably has hydrophobicity, among the aliphatic diols, polyethylene glycol having hydrophilicity is not preferable. However, this is not the case when used with other diols.

  Examples of the aromatic group-containing diol include bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, ethylene oxide adduct of bisphenol A, Examples include propylene oxide adducts of bisphenol A, polyhydroxyethyl adducts of mononuclear dihydric phenol compounds such as 1,4-bis (2-hydroxyethoxy) benzene, resorcin, and pyrocatechol. Among these diols having an aromatic group, ethylene oxide adduct of bisphenol A and 1,4-bis (β-hydroxyethoxy) benzene are preferable.

Next, the aliphatic dicarboxylic acid used in the present invention will be described.
The aliphatic dicarboxylic acid used in the present invention may be a derivative of an aliphatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, 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, a dicarboxylic acid having 4 to 16 carbon atoms is preferable and a dicarboxylic acid having 6 to 12 carbon atoms is more preferable from the viewpoint of melting point and heat resistance.

Next, the aromatic dicarboxylic acid used in the present invention will be described.
The aromatic dicarboxylic acid used in the present invention may be a derivative of an aromatic dicarboxylic acid (for example, 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.

上記一般式（２）中、ｍは５〜２５０の数を表す。ｍは、耐熱性や相溶性の点から、好ましくは２０〜１５０である。 Next, the compound (B) having one or more groups represented by the above general formula (1) and having hydroxyl groups at both ends used in the present invention will be described.
As the compound (B) having at least one group represented by the general formula (1) and having hydroxyl groups at both ends, a hydrophilic compound is preferable, and a polysiloxane having a group represented by the general formula (1) is preferable. Ether is more preferable, and polyethylene glycol represented by the following general formula (2) is particularly preferable.

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

  As the compound (B), in addition to polyethylene glycol obtained by addition reaction of ethylene oxide, ethylene oxide and other alkylene oxides (for example, propylene oxide, 1,2-, 1,4-, 2,3- or And a polyether obtained by addition reaction of one or more of 1,3-butylene oxide and the like. The polyether may be random or block.

  Further examples of the compound (B) include compounds having a structure in which ethylene oxide is added to the 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.

  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 8 carbon atoms. -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 can be used singly or in a mixture of two or more.

Next, the polyhydric alcohol compound (D) having 3 or more hydroxyl groups used in the present invention will be described.
The polyhydric alcohol compound (D) used in the present invention 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 Trihydric alcohols such as 5-tris (2-hydroxyethyl) isocyanurate; pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4 5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, ditrimethylolpropane, sorbitan, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, Tetravalent alcohols such as N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine; pentavalent alcohols such as adonitol, arabitol, xylitol, triglycerin; dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, Hexavalent alcohols such as allose; Pentaerythritol, and the like. The molecular weight of the polyhydric alcohol compound is not particularly limited, and high molecular weight polyhydric alcohols such as polypentaerythritol and polyvinyl alcohol can be used, and synthetic polyhydric alcohols such as polyester polyols can also be used. Two or more kinds of such polyhydric alcohol compounds (D) may be used.

  The polymer compound (E) includes a polyester (A) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, the above compound (B), and the above from the viewpoint of antistatic properties and suppression of ion elution. The polyhydric alcohol compound (D) preferably has a structure formed by bonding through an ester bond.

  Furthermore, the polymer compound (E) includes a block composed of a polyester (A) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid and the above compound (B) from the viewpoint of antistatic properties and suppression of ion elution. ) And the polyhydric alcohol compound (D) are bonded to each other through an ester bond. It is preferable to have a structure formed by

  The polyester (A) according to the present invention is only required to be composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and preferably includes a residue excluding the hydroxyl group of the diol and a carboxyl group of the aliphatic dicarboxylic acid. The removed residue has a structure bonded via an ester bond, and the residue obtained by removing the hydroxyl group of the diol and the residue obtained by removing the carboxyl group of the aromatic dicarboxylic acid are linked via an ester bond. Structure.

  The polyester (A) preferably has a structure having carboxyl groups at both ends. Furthermore, the degree of polymerization of the polyester (A) is preferably in the range of 2-50.

  The polyester (A) having carboxyl groups at both ends can be obtained, for example, by subjecting the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid to a polycondensation reaction with the diol.

  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.). When the polyester (A) is obtained using the derivative, It is sufficient that the both ends are finally processed into carboxyl groups, and the reaction for proceeding to the next block polymer (C) having a structure having carboxyl groups at both ends may be carried out as it is. The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more.

  The aromatic dicarboxylic acid may be a derivative of an aromatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.). It is sufficient that the both ends are treated to form carboxyl groups, and the reaction for proceeding to the next block polymer (C) having a structure having carboxyl groups at both ends may be proceeded as it is. Moreover, 2 or more types of mixtures may be sufficient as aromatic dicarboxylic acid and its derivative (s).

  In the polyester (A), 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.

  The polyester (A) having carboxyl groups at both ends can be obtained, for example, by subjecting the aliphatic dicarboxylic acid or derivative thereof and the aromatic dicarboxylic acid or derivative thereof to a polycondensation reaction with the diol.

  The reaction ratio of the aliphatic dicarboxylic acid or derivative thereof and the aromatic dicarboxylic acid or derivative thereof to the diol is such that the aliphatic dicarboxylic acid or derivative thereof and the aromatic dicarboxylic acid or derivative thereof are adjusted so that both ends are carboxyl groups. It is preferable to use in excess, and it is preferable to use 1 molar excess with respect to diol by molar ratio.

  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 A), or they may be directly reacted with the component (B) to obtain the block polymer (C).

  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.

  In addition, aliphatic dicarboxylic acids and aromatic dicarboxylic acids can be obtained by reacting them with a diol when a derivative such as a carboxylic acid ester, a carboxylic acid metal salt, or a carboxylic acid halide is used instead of the dicarboxylic acid. The terminal may be treated to form a dicarboxylic acid, or the reaction may proceed to the next reaction for obtaining a block polymer (C) having a structure having a carboxyl group at both ends.

  A suitable polyester (A) comprising a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid and having carboxyl groups at both ends forms an ester bond by reacting with the component (B), and the structure of the block polymer (C) And the carboxyl groups at both ends 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 (B) having hydroxyl groups at both ends only needs to form an ester bond by reacting with the component (A) to form the structure of the block polymer (C), and the hydroxyl groups at both ends are protected. It may be modified, modified, or in the form of a precursor.

上記一般式（３）中、（Ａ）は、上記両末端にカルボキシル基を有するポリエステル（Ａ）から構成されたブロックを表し、（Ｂ）は、上記両末端に水酸基を有する化合物（Ｂ）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。 The block polymer (C) having a structure having a carboxyl group at both ends according to the present invention has a block composed of the polyester (A) and a block composed of the compound (B). The block has a structure in which the block is repeatedly and alternately bonded through an ester bond formed by a carboxyl group and a hydroxyl group. An example of such a block polymer (C) is, for example, one having a structure represented by the following general formula (3).

In the general formula (3), (A) represents a block composed of the polyester (A) having carboxyl groups at both ends, and (B) is from the compound (B) having hydroxyl groups at both ends. Represents a configured block, and t is 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 (A) in the block polymer (C) 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 (C) having a structure having carboxyl groups at both ends is a polycondensation reaction between the polyester (A) having carboxyl groups at both ends and the compound (B) having hydroxyl groups at both ends. The structure equivalent to that having a structure in which the polyester (A) and the compound (B) are repeatedly bonded alternately via an ester bond formed by a carboxyl group and a hydroxyl group. It is not always necessary to synthesize from the polyester (A) and the compound (B).

  If the reaction ratio of the polyester (A) to the compound (B) is adjusted so that the polyester (A) is X + 1 mol with respect to X mol of the compound (B), carboxyl groups are present at both ends. A block polymer (C) having the following can be preferably obtained.

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

  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 (A) 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 (C).

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

  The polymer compound (E) according to the present invention is preferably a block polymer (C) having a structure having carboxyl groups at both ends and a polyhydric alcohol compound (D) having three or more hydroxyl groups. It has a structure formed by bonding via an ester bond formed by the terminal carboxyl group of the polymer (C) and the hydroxyl group of the polyhydric alcohol compound (D). The polymer compound (E) may further contain an ester bond formed by the carboxyl group of the polyester (A) and the hydroxyl group of the polyhydric alcohol compound (D).

  In order to obtain the polymer compound (E), the carboxyl group of the block polymer (C) may be reacted with the hydroxyl group of the polyhydric alcohol compound (D). The number of hydroxyl groups of the polyhydric alcohol compound to be reacted is preferably 0.5 to 5.0 equivalents, more preferably 0.5 to 2.0 equivalents, of the number of carboxyl groups of the block polymer (C) to be reacted. Moreover, the said reaction may be performed in various solvents and may be performed in a molten state.

  The polyhydric alcohol compound (D) having 3 or more hydroxyl groups to be reacted is preferably 0.1 to 2.0 equivalents, preferably 0.2 to 1.5 equivalents, of the number of carboxyl groups of the block polymer (C) to be reacted. Is more preferable.

  In the reaction, after completion of the synthesis reaction of the block polymer (C), the polyhydric alcohol compound (D) may be added to the reaction system and reacted as it is without isolating the block polymer (C). In that case, the carboxyl group of the unreacted polyester (A) used excessively when the block polymer (C) is synthesized reacts with a part of the hydroxyl groups of the polyhydric alcohol compound (D) to form an ester bond. It may be formed.

  A preferred polymer compound (E) of the present invention comprises a block polymer (C) having a structure having carboxyl groups at both ends and a polyhydric alcohol compound (D) having three or more hydroxyl groups, each having a carboxyl group and a hydroxyl group. It is not always necessary to synthesize from the block polymer (C) and the polyhydric alcohol compound (D) as long as it has a structure equivalent to that having a structure bonded through an ester bond formed by .

  In the present invention, the number average molecular weight of the block composed of the polyester (A) in the polymer compound (E) is preferably 800 to 8,000, more preferably 1,000 to 6,000 in terms of polystyrene. More preferably, it is 2,000 to 4,000. The number average molecular weight of the block composed of the compound (B) having hydroxyl groups at both ends in the polymer compound (E) is preferably 400 to 6,000, more preferably 1,000 in terms of polystyrene. 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 (C) having a structure having carboxyl groups at both ends in the polymer compound (E) 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 addition, the polymer compound (E) of the present invention is obtained by obtaining the polyester (A) from a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and then isolating the polyester (A) without isolating the polyester (A). Or you may make it react with a polyhydric alcohol compound (D).

  The compounding amount of the polymer compound (E) is 3 to 20 parts by mass with respect to 100 parts by mass of the synthetic resin, and is preferably 5 to 18 parts by mass from the viewpoint of antistatic properties and suppression of ion elution. -15 mass parts is more preferable. If the blending amount is less than 3 parts by mass, sufficient antistatic properties cannot be obtained, and if it exceeds 20 parts by mass, the mechanical properties of the resin may be adversely affected.

  Next, the alkali metal salt (F) used in the present invention will be described. The alkali metal salt (F) is blended to impart antistatic properties to the resin composition of the present invention.

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 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. 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 include, for example, lithium acetate, sodium acetate, potassium acetate, lithium chloride, sodium chloride, potassium chloride, lithium phosphate, sodium phosphate, potassium phosphate, lithium sulfate, sodium sulfate, perchlorine. Lithium acid, sodium perchlorate, potassium perchlorate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, dodecylbenzenesulfonic acid Potassium etc. are mentioned. Among these, lithium acetate, potassium acetate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, lithium chloride and the like are preferable.

  The blending amount of the alkali metal salt (F) is 0.1 to 5 parts by mass and 0.3 to 2 parts by mass with respect to 100 parts by mass of the synthetic resin from the viewpoint of antistatic properties and suppression of ion elution. Is preferable, and 0.4-1 mass part is more preferable. When the amount of the alkali metal salt is less than 0.1 parts by mass, the antistatic property is not sufficient, and when it exceeds 5 parts by mass, the ion elution amount increases.

  The resin composition of the present invention may further contain a group 2 element salt within a range not impairing the effects of the present invention. However, care must be taken because the salts of Group 2 elements also contaminate electrical and electronic components due to the elution of ions.

  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 synthetic resins, and, as for the compounding quantity in the case of mix | blending surfactant, 0.5-2 mass parts is more preferable.

  Furthermore, the resin composition of the present invention may contain a polymer type antistatic agent. 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.

  0.1-10 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending a polymer type antistatic agent, 0.5-5 mass parts 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, at least one of cations or anions constituting the ionic liquid is an organic ion, and an initial conductivity of 1 to 200 ms / cm, preferably 10 to 200 ms. A room temperature molten salt that is / 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. Among these, 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 conjugate base of a super strong acid in which the Hammett acidity function (-H0) 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.

  0.01-5 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending an ionic liquid, 0.1-3 mass parts is more preferable.

  Furthermore, the resin composition of the present invention may contain a compatibilizing agent as long as the effects of the present invention are not impaired. 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. .

  0.01-5 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending a compatibilizing agent, 0.1-3 mass parts is more preferable.

  In addition, the resin composition of the present invention includes phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet absorbers, hindered amines, as necessary, as long as the effects of the present invention are not impaired. Various additives such as a light stabilizer can be further added, whereby the resin composition of the present invention can be stabilized.

  Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) Nol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tertiary) Butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4- Hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5- Ditertiarybutyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] methane, thiodiethyleneglycol Bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], bis [3 3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methyl) Benzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2- {(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] And ndecane and triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]. The amount of these phenolic antioxidants added is preferably 0.001 to 10 parts by mass and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin.

  Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl]. Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1 , 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6- Tributylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4 6-ditert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl) oxy] ethyl) amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, and the like. The addition amount of these phosphorus antioxidants is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin.

  Examples of the thioether antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (β-alkylthiopropionic acid). Examples include esters. The addition amount of these thioether-based antioxidants is preferably 0.001 to 10 parts by mass and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert. Octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2, 2- (2 such as' -methylenebis (4-tert-octyl-6- (benzotriazolyl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl) benzotriazole '-Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl- Benzoates such as 3,5-ditert-butyl-4-hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy- Substituted oxanilides such as 4′-dodecyl oxanilide; ethyl-α-cyano-β, β-diphenylacrylate And cyanoacrylates such as methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4 -Di-tert-butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) And triaryltriazines such as -4,6-bis (2,4-ditert-butylphenyl) -s-triazine. The addition amount of these ultraviolet absorbers is preferably 0.001 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the synthetic resin.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2 6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (Tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditertiary 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. The amount of these hindered amine light stabilizers added is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the synthetic resin.

  Furthermore, it is preferable to add a known neutralizing agent in order to neutralize the residual catalyst in the synthetic resin such as polyolefin resin as required. Examples of the neutralizing agent include fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, or fatty acid amides such as ethylene bis (stearamide), ethylene bis (12-hydroxystearamide), and stearic acid amide. Compounds, and these neutralizing agents may be used in combination.

  Furthermore, the resin composition of the present invention may further include an aromatic carboxylic acid metal salt, an alicyclic alkyl carboxylic acid metal salt, an aluminum p-tert-butylbenzoate, an aromatic phosphate metal salt as necessary. Nucleating agents such as dibenzylidene sorbitol, metal soap, hydrotalcite, triazine ring-containing compound, metal hydroxide, phosphate ester flame retardant, condensed phosphate ester flame retardant, phosphate flame retardant, inorganic phosphorus Flame retardants, (poly) phosphate flame retardants, halogen flame retardants, silicon flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardant aids, other organic flame retardant aids, Fillers, pigments, lubricants, foaming agents and the like may be added.

  Examples of the triazine ring-containing compound include melamine, ammelin, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene Dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimelamine and the like can be mentioned.

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

  Examples of the phosphate ester flame retardant include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, Trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t-butyl Phenyl) phosphate, isopropylphenyldiphenylphosphate, bis- (i Propyl phenyl) diphenyl phosphate, tris - (isopropylphenyl) phosphate, and the like.

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

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

  Examples of other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, montmorillonite, and surface-treated products thereof. For example, TIPAQUE R-680 ( Titanium oxide: manufactured by Ishihara Sangyo Co., Ltd.), Kyowa Mag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), Alkamizer 4 (zinc modified hydro Various commercial products such as talcite (manufactured by Kyowa Chemical Industry Co., Ltd.) can be used. Examples of other organic flame retardant aids include pentaerythritol.

  Further, the resin composition of the present invention contains additives that are usually used in synthetic resins as necessary, for example, crosslinking agents, antifogging agents, plate-out preventing agents, surface treatment agents, plasticizers, lubricants, flame retardants. , Fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, etc., as long as the effects of the present invention are not impaired. be able to.

  The method for producing the resin composition of the present invention is not particularly limited, and the polymer compound (E), the alkali metal salt (F), and other optional components may be added to the synthetic resin, and the method is usually used. Any method that has been described 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 the high molecular compound (E) may be added as it is, it may be added after impregnating the carrier as required. 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 of synthetic 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 powder In addition, titanium oxide powder, those obtained by chemically modifying the surface of these carriers, solid ones among the flame retardants and antioxidants listed below, and the like can be mentioned. Among these carriers, those obtained by chemically modifying the surface of the carrier are preferred, and those obtained by chemically modifying the surface of the silica powder are more preferred. These carriers preferably have an average particle size of 0.1 to 100 μm, and more preferably 0.5 to 50 μm.

Further, as a method of blending the polymer compound (E) into the resin component, the polymer compound (E) is synthesized while kneading the block polymer (C) and the polyhydric alcohol compound (D) into the resin component. The alkali metal salt (F) may be kneaded at the same time, and the polymer compound (E), the alkali metal salt (F), and the resin component may be mixed at the time of molding such as injection molding. You may mix | blend by the method of mixing and obtaining a molded article, Furthermore, the masterbatch of an alkali metal salt (F) and a synthetic resin may be manufactured previously, and this masterbatch may be mix | blended.
Furthermore, the polymer compound (E) and the alkali metal salt (F) may be mixed in advance and then blended into the synthetic resin, or synthesized by adding the alkali metal salt (F) during the reaction. The polymer compound (E) may be blended with a synthetic resin.

  Next, the container and packaging material of this invention are demonstrated.

  The container and the packaging material of the present invention are formed by molding the antistatic resin composition of the present invention. By molding the resin composition of the present invention, a resin molded body having antistatic properties can be obtained. The molding method is not particularly limited, and examples thereof include extrusion processing, calendar processing, injection molding, roll, compression molding, blow molding, rotational molding, and the like. Resin plate, sheet, film, bottle, fiber, irregular shape product Various shaped products such as these can be manufactured. The molded product obtained from the resin composition of the present invention is excellent in antistatic performance and its sustainability. It also has resistance to wiping.

Moreover, the molded object obtained by the resin composition of this invention has almost no elution of ion, and can prevent the contamination by ion. In particular, in the molded article of the present invention, the amount of sodium ions and lithium ions eluted when immersed in 100 g of water at 40 ° C. for 2 hours is preferably 12 ppb or less per 1 cm ² of surface area of the molded article. It is more preferable.

  Containers and packaging materials obtained from the resin composition of the present invention are suitable for storage containers, transport containers, and packaging materials for electrical and electronic parts. For example, silicon wafers, hard disks, disk substrates, glass substrates, IC chips, semiconductors, optical storage disks, color filters, hard disk magnetic head elements, CCD elements, etc., various parts and product transport containers, storage containers, trays, cases, Examples include packaging materials.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to these. In the following examples and comparative examples, “%” and “ppb” are based on mass unless otherwise specified.

  According to the following Production Examples 1 to 3, the polymer compound (E) used in the present invention was produced. Moreover, in the following manufacture examples 1-3, the number average molecular weight was measured with the following molecular weight measuring method.

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

[Production Example 1]
In a separable flask, 544 g of 1,4-cyclohexanedimethanol, 582 g (3.98 mol) of adipic acid, 0.7 g (0.01 mol) of phthalic anhydride, an antioxidant (tetrakis [3- (3 , 5-ditertiarybutyl-4-hydroxyphenyl) propionyloxymethyl] methane, Adeka Stub AO-60 manufactured by ADEKA), and gradually heated from 160 ° C. to 210 ° C. at normal pressure. Polymerization was carried out for 4 hours and then at 210 ° C. under reduced pressure for 3 hours to obtain polyester (A) -1. Polyester (A) -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 polyester (A) -1 obtained, 300 g of polyethylene glycol having a number average molecular weight of 4,000 as the compound (B) -1 having hydroxyl groups at both ends, and an antioxidant (ADK STAB AO-60) were added. 0.5 g and 0.8 g of zirconium octylate were charged and polymerized under reduced pressure at 210 ° C. for 7 hours to obtain a block polymer (C) -1 having a structure having carboxyl groups at both ends. The acid value of the block polymer (C) -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.

  Into 300 g of the obtained block polymer (C) -1 having a structure having a carboxyl group at both ends, 1.7 g of pentaerythritol as a polyhydric alcohol compound (D) -1 was charged, and 240 ° C. for 5 hours under reduced pressure. Polymerization was performed to obtain a polymer compound (E) -1 used in the present invention.

[Production Example 2]
In a separable flask, 370 g of 1,4-bis (β-hydroxyethoxy) benzene, 289 g (1.98 mol) of adipic acid, 9 g (0.04 mol) of 2,6-naphthalenedicarboxylic acid, both ends As the compound (B) -1 having a hydroxyl group, 300 g of polyethylene glycol having a number average molecular weight of 4,000 and 0.8 g of an antioxidant (ADK STAB AO-60) are charged, and the temperature is gradually increased from 180 ° C. to 220 ° C. Polymerized with pressure for 5 hours. Thereafter, 0.8 g of tetraisopropoxy titanate was charged and polymerized at 220 ° C. under reduced pressure for 6 hours to obtain a block polymer (C) -2 having a structure having carboxyl groups at both ends. The acid value of the block polymer (C) -2 having a structure having a carboxyl group at both ends was 9, and the number average molecular weight Mn was 11,800 in terms of polystyrene.

  Into 300 g of the obtained block polymer (C) -2 having a structure having a carboxyl group at both ends, 1.1 g of polypentaerythritol (hydroxyl value 13) was charged as a polyhydric alcohol compound (D) -2, at 240 ° C. Polymerization was performed under reduced pressure for 2 hours to obtain a polymer compound (E) -2 used in the present invention.

[Production Example 3]
In a separable flask, 591 g of ethylene oxide adduct of bisphenol A, 235 g (1.16 mol) of sebacic acid, 8 g (0.05 mol) of isophthalic acid, 0.5 g of antioxidant (ADK STAB AO-60) The polymerization was conducted at normal pressure for 4 hours while gradually heating from 160 ° 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 (A) -3. Polyester (A) -3 had an acid value of 56 and a number average molecular weight Mn of 2,300 in terms of polystyrene.

  Next, 300 g of the obtained polyester (A) -3, 200 g of polyethylene glycol having a number average molecular weight of 2,000 as a compound (B) -2 having hydroxyl groups at both ends, and an antioxidant (ADK STAB AO-60) are used. 0.5 g and 0.5 g of zirconium acetate were charged and polymerized under reduced pressure at 220 ° C. for 8 hours to obtain a block polymer (C) -3 having a structure having carboxyl groups at both ends. The acid value of the block polymer (C) -3 having a structure having a carboxyl group at both ends was 11, and the number average molecular weight Mn was 10,500 in terms of polystyrene.

  300 g of the resulting block polymer (C) -3 having a structure having a carboxyl group at both ends was charged with 3.0 g of trimethylolpropane and 3.9 g of zirconium acetate as the polyhydric alcohol compound (D) -3, 240 Polymerization was performed under reduced pressure at 4 ° C. for 4 hours to obtain a polymer compound (E) -3 used in the present invention.

[Examples 1-18, Comparative Examples 1-23]
Using the resin composition blended based on the blending amount (parts by mass) described in Tables 1 to 3 below, test pieces were obtained according to the test piece preparation conditions shown below. Using the obtained test piece, a surface resistivity (SR value) measurement, a water wiping resistance evaluation test, and a water resistance evaluation test were performed according to the following. Moreover, the ion amount elution test was done on the following conditions using the obtained test piece. Similarly, a resin composition of a comparative example was prepared by using the formulations shown in Tables 4 to 7 below, and test pieces were prepared and evaluated.

<Test specimen preparation conditions>
The resin composition blended based on the blending amounts shown in the following tables is granulated under the conditions of 230 ° C. and 6 kg / hour using a twin screw extruder (PCM30, 60 mesh) made by Ikegai Co., Ltd. And pellets were obtained. The obtained pellets are molded using a horizontal injection molding machine (NEX80: manufactured by Nissei Plastic Industry Co., Ltd.) under processing conditions of a resin temperature of 230 ° C. and a mold temperature of 40 ° C. to 50 ° C. for surface resistivity measurement. A test piece (100 mm × 100 mm × 3 mm) and an ion amount elution test test piece (80 mm × 10 mm × 4 mm, surface area 23.2 cm ² ) were obtained.

<Method for measuring surface resistivity (SR value)>
The obtained test piece (100 mm × 100 mm × 3 mm) was stored immediately after molding under conditions of temperature 25 ° C., humidity 60% RH and 20% RH, and after storage for 1 day and 30 days of molding, the same Under the atmosphere, the surface resistivity (Ω / □) was measured using an R8340 resistance meter manufactured by Advantest Corporation under the conditions of an applied voltage of 100 V and an applied time of 1 minute. The measurement was performed for 5 points and the average value was obtained.

<Water wiping resistance evaluation test>
The surface of the obtained specimen for measuring surface resistivity (100 mm × 100 mm × 3 mm) was wiped 50 times with a running water cloth and then stored for 2 hours under conditions of a temperature of 25 ° C. and a humidity of 60%. Under the atmosphere, the surface resistivity (Ω / □) was measured using an R8340 resistance meter manufactured by Advantest Corporation under the conditions of an applied voltage of 100 V and an applied time of 1 minute. The measurement was performed at 5 points, and the average value was obtained.

<Water resistance evaluation test>
It was immersed in 25 degreeC distilled water for 12 hours so that the surface of the obtained surface resistivity test piece (100 mm x 100 mm x 3 mm) might be immersed completely. Thereafter, the test piece was dried with hot air (50 ° C.) for 3 hours and then stored for 12 hours under conditions of a temperature of 25 ° C. and a humidity of 60% RH. Thereafter, in the same atmosphere, the surface specific resistance value (Ω / □) was measured using an R8340 resistance meter manufactured by Advantest Corporation under the conditions of an applied voltage of 100 V and an applied time of 1 minute. The measurement was performed at 5 points, and the average value was obtained.

<Ion content elution test>
One test piece (80 mm × 10 mm × 4 mm, surface area 23.2 cm ² ) obtained in 100 g of 40 ° C. water was placed and immersed for 2 hours. After immersion, the test piece was taken out and the amount of the eluted alkali metal was analyzed using an ICP emission spectroscopic analyzer (SPS3500 manufactured by SII Nanotechnology Inc.). The value below the detection limit (less than 5 ppb) is expressed as nd.
Moreover, from the obtained elution amount, the elution amount per 1 cm ² of the surface area of the test piece was obtained by calculation.

＊１：ホモポリプロピレン、日本ポリプロ株式会社製、商品名 Ｈ−７００（メルトフローレート＝１０ｇ／１０ｍｉｎ）
＊２：ドデシルベンゼンスルホン酸ナトリウム
＊３：塩化ナトリウム
＊４：ｐ−トルエンスルホン酸リチウム

* 1: Homopolypropylene, manufactured by Nippon Polypro Co., Ltd., trade name H-700 (melt flow rate = 10 g / 10 min)
* 2: Sodium dodecylbenzenesulfonate * 3: Sodium chloride * 4: Lithium p-toluenesulfonate

＊５：耐衝撃性ポリスチレン、東洋スチレン株式会社製、商品名 Ｅ６４０Ｎ（メルトフローレート＝２．７ｇ／１０ｍｉｎ）

* 5: Impact-resistant polystyrene, manufactured by Toyo Styrene Co., Ltd., trade name E640N (melt flow rate = 2.7 g / 10 min)

＊６：ＡＢＳ樹脂、テクノポリマー株式会社製、商品名 ＡＢＳ１１０（メルトフローレート＝２３ｇ／１０ｍｉｎ）

* 6: ABS resin, manufactured by Techno Polymer Co., Ltd., trade name ABS110 (melt flow rate = 23 g / 10 min)

From the above, it can be seen that the resin composition of the present invention has sufficient antistatic properties with durability, and almost no ions are eluted when formed into a molded body. Therefore, the resin composition of the present invention is suitable for a container for storing and transporting electric and electronic parts and a packaging material.

Claims (11)

Antistatic agent containing 3 to 20 parts by mass of one or more polymer compounds (E) and 0.1 to 5 parts by mass of one or more alkali metal salts (F) with respect to 100 parts by mass of the synthetic resin A functional resin composition comprising:
Compound (B) in which the polymer compound (E) has a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, one or more groups represented by the following general formula (1), and a hydroxyl group at both ends. And a polyhydric alcohol compound (D) having 3 or more hydroxyl groups bonded to each other through an ester bond.

  The polymer compound (E) is an ester bond between a polyester (A) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, the compound (B), and the polyhydric alcohol compound (D). The antistatic resin composition according to claim 1, which has a structure formed by bonding via a resin.   The polymer compound (E) has a carboxyl group at both ends formed by alternately and alternately connecting a block composed of the polyester (A) and a block composed of the compound (B) via an ester bond. The antistatic resin composition according to claim 2, wherein the block polymer (C) and the polyhydric alcohol compound (D) have a structure formed by bonding via an ester bond.   The antistatic resin composition according to claim 2 or 3, wherein the polyester (A) constituting the polymer compound (E) has a structure having carboxyl groups at both ends.   In the polymer compound (E), the number average molecular weight of the block composed of the polyester (A) is 800 to 8,000 in terms of polystyrene, and the number average molecular weight of the block composed of the compound (B) is The antistatic resin composition according to claim 3 or 4, wherein the block polymer (C) has a number average molecular weight of 400 to 6,000 in terms of polystyrene, and 5,000 to 25,000 in terms of polystyrene. .   The said compound (B) which comprises the said high molecular compound (E) is polyethyleneglycol, The antistatic resin composition as described in any one of Claims 1-5.   The antistatic resin composition according to any one of claims 1 to 6, wherein the synthetic resin is at least one selected from the group consisting of polyolefin resins and polystyrene resins.   A container, wherein the antistatic resin composition according to any one of claims 1 to 7 is molded. The container according to claim 8, wherein an elution amount of sodium ions and lithium ions when immersed in 100 g of water at 40 ° C for 2 hours is 12 ppb or less per 1 cm ^{2 of} surface area.   A packaging material, wherein the antistatic resin composition according to any one of claims 1 to 7 is molded. The packaging material according to claim 10, wherein the elution amount of sodium ions and lithium ions when immersed in 100 g of water at 40 ° C for 2 hours is 12 ppb or less per 1 cm ^{2 of} surface area.