WO2019021944A1 - Polymer compound, composition including same, resin composition including these, and molded body thereof - Google Patents

Polymer compound, composition including same, resin composition including these, and molded body thereof Download PDF

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WO2019021944A1
WO2019021944A1 PCT/JP2018/027166 JP2018027166W WO2019021944A1 WO 2019021944 A1 WO2019021944 A1 WO 2019021944A1 JP 2018027166 W JP2018027166 W JP 2018027166W WO 2019021944 A1 WO2019021944 A1 WO 2019021944A1
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acid
compound
polymer compound
polyester
group
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PCT/JP2018/027166
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French (fr)
Japanese (ja)
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直樹 圓城
直人 上田
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株式会社Adeka
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/16—Anti-static materials

Definitions

  • the present invention relates to a polymer compound, a composition containing the same, a resin composition containing the same, and a molded article thereof, and in particular, it is possible to continuously impart an excellent antistatic effect to a synthetic resin.
  • the present invention relates to a polymer compound, a composition containing the same, a resin composition containing them, and a molded article thereof.
  • Thermoplastic resins are not only lightweight and easy to process, but also have excellent properties such as being able to design the base material according to the application, so they are important materials that can not be indispensable today is there.
  • thermoplastic resins are frequently used for components of electric products, etc. because they have excellent electrical insulation properties.
  • the thermoplastic resin has too high insulation, there is a problem that it is easily charged by friction or the like.
  • thermoplastic resin attracts dust and dirt around it, there arises a problem that the appearance of the resin molded product is impaired. Further, among electronic products, for example, in precision equipment such as a computer, the circuit may not be able to operate normally due to charging. In addition, there is also a problem with lightning. When a resin generates an electric shock to the human body, it not only makes the person feel uncomfortable, but it may also cause an explosion accident in the presence of combustible gas and dust.
  • the most common antistatic treatment method is to add an antistatic agent to the synthetic resin.
  • antistatic agents include a coating type that is applied to the surface of a resin molded product and a kneading type that is added when processing and molding a resin, but the coating type has poor sustainability.
  • there is a problem that the contact with the surface is contaminated because a large amount of organic matter is applied to the surface.
  • Patent Documents 1 and 2 propose polyetheresteramides for imparting antistatic properties to polyolefin resins.
  • Patent Document 3 proposes a block polymer having a structure in which a block of polyolefin and a block of hydrophilic polymer are repeatedly and alternately bonded.
  • Patent Document 4 proposes a polymeric antistatic agent having a block of polyester.
  • an object of the present invention is to provide a polymer compound capable of continuously imparting an excellent antistatic effect to a synthetic resin, a composition containing the same, a resin composition containing these, and a molded article thereof. It is to do.
  • the inventors of the present invention conducted intensive studies to solve the above problems, and as a result, a polymer compound having a predetermined structure can impart excellent antistatic performance to a thermoplastic resin. It has been found that the above problems can be solved, and the present invention has been completed.
  • the polymer compound of the present invention is a polyester (a) obtained by reacting a diol with an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and a compound having a hydroxyl group at both ends having one or more ethyleneoxy groups. It is characterized by being obtained by reacting (b) with a polyalkylene glycol diglycidyl ether compound (D).
  • the polyester has the block (A) of the polyester composed of the polyester (a) and the block (B) of the polyether composed of the compound (b), and the polyester An ester bond formed by the reaction of a hydroxyl group or carboxyl group at the end of (a), a hydroxyl group at the end of the compound (b), and an epoxy group of the polyalkylene glycol diglycidyl ether compound (D) Alternatively, it is preferable to have a structure formed by bonding via an ether bond.
  • the polyester block (A) and the polyether block (B) have carboxyl groups at both ends, which are alternately and repeatedly bonded via an ester bond.
  • the block polymer (C) and the polyalkylene glycol diglycidyl ether compound (D) are preferably bonded via an ester bond.
  • the polyalkylene glycol diglycidyl ether compound (D) is preferably polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether.
  • the epoxy equivalent of the polyalkylene glycol diglycidyl ether compound (D) is preferably 70 to 2,000.
  • the polyester (a) has a structure having a carboxyl group at both ends.
  • the compound (b) is preferably polyethylene glycol. Furthermore, in the polymer compound of the present invention, the number average molecular weight of the compound (b) is preferably 400 to 10,000. In the polymer compound of the present invention, the number average molecular weight of the block polymer (C) is preferably 5,000 to 30,000.
  • composition of the present invention is characterized in that the polymer compound of the present invention is further blended with one or more selected from the group consisting of salts of alkali metals and salts of Group 2 elements. It is.
  • the resin composition of the present invention is characterized in that the polymer compound of the present invention or the composition of the present invention is blended with a thermoplastic resin.
  • thermoplastic resin is preferably at least one selected from the group consisting of polyolefin resins, polystyrene resins, and copolymers thereof.
  • the molded article of the present invention is characterized by comprising the resin composition of the present invention.
  • a polymer compound capable of continuously imparting an excellent antistatic effect to a synthetic resin, a composition containing the same, a resin composition containing the same, and a molded article thereof.
  • the resin composition of the present invention is excellent in antistatic property and its persistence.
  • the molded article of the present invention has the advantage of being less likely to cause a drop in the commercial value due to surface contamination or dust adhesion due to static electricity.
  • the polymer compound of the present invention (hereinafter also referred to as “polymer compound (E)”) is a polyester (a) obtained by reacting a diol with an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and ethyleneoxy It is obtained by reacting a compound (b) having a hydroxyl group at both ends having one or more groups and a polyalkylene glycol diglycidyl ether compound (D).
  • the ethyleneoxy group is a group represented by the following general formula (1).
  • the polymer compound of the present invention comprises a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the compound (b), and the polyester (a) Through an ester bond or an ether bond formed by the reaction of a hydroxyl group or carboxyl group at the end of the group, a hydroxyl group at the end of the compound (b), and an epoxy group of the polyalkylene glycol diglycidyl ether compound (D) It is preferable to have a structure formed by bonding.
  • a block polymer (C) having a carboxyl group at both ends in which a polyester block (A) and a polyether block (B) are repeatedly and alternately bonded via an ester bond, and a polyalkylene glycol di It is preferable that the glycidyl ether compound (D) is bonded via an ester bond.
  • the polyester (a) can be obtained by subjecting a diol to an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid by an esterification reaction.
  • diol which is a component of polyester (a) will be described.
  • the diols used in the present invention include aliphatic diols and aromatic group-containing diols.
  • the diol may also be a mixture of two or more.
  • 1,2-ethanediol ethylene glycol
  • 1,2-propanediol propylene glycol
  • 1,3-propanediol 1,2-butanediol
  • 1,3-butanediol 2-methyl-1,3-propanediol
  • 1,4-butanediol 1,5-pentanediol
  • 2,2-diethyl- 1,3-propanediol 3-,3-dimethylolpentane
  • 2-n-butyl-2-ethyl-1,3propanediol 3-methyl-1,5-pentane Diol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1
  • 1,4-cyclohexanedimethanol and hydrogenated bisphenol A are preferable from the viewpoint of the antistatic property and the durability, and 1,4-cyclohexanedimethanol is more preferable.
  • 1,4-cyclohexanedimethanol is more preferable.
  • aliphatic diol since it is preferable that aliphatic diol has hydrophobicity from the point of antistatic property and its persistence, use of the polyethyleneglycol which has hydrophilicity is unpreferable.
  • aromatic group-containing diol for example, bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, ethylene oxide adduct of bisphenol A
  • examples thereof include propylene oxide adducts of bisphenol A, 1,4-bis (2-hydroxyethoxy) benzene, resorcin, polyhydroxyethyl adducts of mononuclear dihydric phenol compounds such as pyrocatechol, and the like.
  • diols having these aromatic groups ethylene oxide adduct of bisphenol A and 1,4-bis ( ⁇ -hydroxyethoxy) benzene are preferable.
  • the aromatic diol is preferably hydrophobic from the viewpoint of antistaticity and its durability.
  • the aliphatic dicarboxylic acid used in the present invention may be a derivative of 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 preferably includes aliphatic dicarboxylic acids having 2 to 20 carbon atoms, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Examples thereof include sebacic acid, 1,10-decanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, maleic acid, fumaric acid and the like.
  • dicarboxylic acids having 4 to 16 carbon atoms are preferable, and dicarboxylic acids having 6 to 12 carbon atoms are more preferable, from the viewpoint of the antistatic property and the durability.
  • the aromatic dicarboxylic acid used in the present invention may be a derivative of aromatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.).
  • the aromatic dicarboxylic acid and its derivative may be a mixture of two or more.
  • the aromatic dicarboxylic acid preferably includes an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, and ⁇ -phenyl glutar acid.
  • Acid, ⁇ -phenyl adipic acid, ⁇ -phenyl adipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalene dicarboxylic acid, sodium 3-sulfoisophthalic acid and 3-sulfoisophthalic acid Potassium and the like can be mentioned.
  • aromatic dicarboxylic acids terephthalic acid, isophthalic acid and phthalic acid (including phthalic anhydride) are preferable, and phthalic acid (including phthalic anhydride) is more preferable, from the viewpoint of the antistatic property and the durability.
  • the polyether block (B) is composed of a compound (b) having a hydroxyl group at both ends having one or more ethyleneoxy groups represented by the following general formula (1).
  • a compound having hydrophilicity is preferable, and an ethyleneoxy group represented by the general formula (1) are more preferred, and from the viewpoint of antistatic properties and durability, polyethylene glycol is even more preferred, and polyethylene glycol represented by the following general formula (2) is particularly preferred.
  • m represents a number of 5 to 250. m is preferably 20 to 200, and more preferably 40 to 180, in view of the antistatic property and its durability.
  • ethylene oxide and other alkylene oxides for example, propylene oxide, 1,2-, 1,4-, 2,3-, or
  • polyethylene glycol obtained by addition reaction of ethylene oxide The polyether which carried out the addition reaction with 1 or more types of 1, 3- butylene oxide etc. is mentioned, This polyether may be random and may be block or any.
  • Examples of the compound (b) further include a compound having a structure in which ethylene oxide is added to an active hydrogen atom-containing compound, ethylene oxide and other alkylene oxides (eg, propylene oxide, 1,2-, 1,4-, And compounds having a structure in which one or more of 2,3- or 1,3-butylene oxide etc. are added. 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.
  • glycol aliphatic glycols having 2 to 20 carbon atoms, alicyclic glycols having 5 to 12 carbon atoms, aromatic glycols having 8 to 26 carbon atoms, and the like can be used.
  • aliphatic glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol Hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecane Diol, 1, 20-eicosanediol, diethylene glycol, triethylene glycol, thiodiethylene glycol and the like.
  • alicyclic glycols examples include 1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1-methyl-3,4-cyclohexanediol And 2-hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol, 1,1'-dihydroxy-1,1'-dicyclohexyl and the like.
  • aromatic glycols examples include dihydroxymethylbenzene, 1,4-bis ( ⁇ -hydroxyethoxy) benzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, 2-benzyl And 1,3-propanediol, triphenyl ethylene glycol, tetraphenyl ethylene glycol, benzopinacol and the like.
  • phenol having 6 to 30 carbon atoms can be used.
  • primary monoamines examples include aliphatic primary monoamines having 1 to 20 carbon atoms, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, s-butylamine, isobutylamine, n- Amylamine, isoamylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-octadecylamine, n-icosylamine and the like.
  • aliphatic primary monoamines having 1 to 20 carbon atoms such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, s-butylamine, isobutylamine, n- Amylamine, isoamylamine, n-hexylamine, n-heptylamine, n-o
  • secondary diamines examples 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.
  • Aromatic secondary diamines of ⁇ 14 and secondary alkanoldiamines having 3 to 22 carbon atoms can be used.
  • aliphatic secondary diamines include N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine, N, N'-dibutylethylenediamine, N, N'-dimethylpropylenediamine, 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.
  • heterocyclic secondary diamines examples include piperazine, 1-aminopiperidine and the like.
  • alicyclic secondary diamines 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'- Dimethyl-1,3-cyclohexanediamine, N, N'-diethyl-1,3-cyclohexanediamine, N, N'-dibutyl-1,3-cyclohexanediamine and the like can be mentioned.
  • aromatic secondary diamines include N, N'-dimethyl-phenylenediamine, N, N'-dimethyl-xylylenediamine, N, N'-dimethyl-diphenylmethanediamine, N, N'-dimethyl-diphenyletherdiamine And N, N'-dimethyl-benzidine and N, N'-dimethyl-1,4-naphthalenediamine.
  • secondary alkanoldiamines include N-methyldiethanolamine, N-octyldiethanolamine, N-stearyldiethanolamine and N-methyldipropanolamine.
  • dicarboxylic acids having 2 to 20 carbon atoms can be used, and for example, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids can be used.
  • aliphatic dicarboxylic acids examples include oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid, ⁇ -methylglutaric acid, ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid and icosandioic acid.
  • aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, ⁇ -phenylglutaric acid, ⁇ -phenyladipic acid, ⁇ -phenyladipic acid, biphenyl-2 , 2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate and potassium 3-sulfoisophthalate.
  • 1,3-cyclopentane dicarboxylic acid for example, 1,3-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarbon
  • acids 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid and dicyclohexyl-4,4'-dicarboxylic acid.
  • active hydrogen atom-containing compounds may be used alone or in combination of two or more.
  • the polyalkylene glycol diglycidyl ether compound (D) which comprises a high molecular compound (E) is demonstrated.
  • the polyalkylene glycol diglycidyl ether compound (D) is a compound obtained by glycidyl etherifying hydroxyl groups at both ends of the polyalkylene glycol.
  • polyalkylene glycols examples include polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.
  • polyethylene glycol obtained by addition reaction of ethylene oxide polypropylene glycol obtained by addition reaction of propylene oxide, butylene oxide
  • polybutylene glycol obtained by addition reaction of two or more alkylene oxides eg, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide etc.
  • alkylene oxides eg, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide etc.
  • polyalkylene glycols obtained other than the addition reaction of alkylene oxide are also included.
  • the polyalkylene glycol may have one or more alkyleneoxy groups such as ethyleneoxy group, propyleneoxy group, butyleneoxy group etc. Those are included in the compound (D).
  • polyalkylene glycol diglycidyl ether compound (D) examples include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol Glycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutylene glycol diglycidyl ether, etc. may be mentioned. Two or more such polyalkylene glycol diglycidyl ether compounds (D) may be used. Among these, as the polyalkylene glycol diglycidyl ether compound (D), polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are preferable from the viewpoint of the antistatic property and the durability.
  • the epoxy equivalent of the polyalkylene glycol diglycidyl ether compound (D) is preferably 70 to 2,000, more preferably 140 to 1,000, and particularly preferably 180 to 600, from the viewpoint of the antistatic property and its durability. More preferable.
  • the polymer compound (E) is formed of a hydroxyl group or carboxyl group at the end of the polyester (a), a hydroxyl group at the end of the compound (b), and an epoxy group of the polyalkylene glycol diglycidyl ether compound (D) Structure in which the polyester block (A), the polyether block (B), and the polyalkylene glycol diglycidyl ether compound (D) in which the epoxy group is reacted are linked via an ester bond or an ether bond by the ester bond Have.
  • the polymer compound (E) is a block of a polyester (A) composed of a polyester (a) and a block of a polyether (B) composed of a compound (b) from the viewpoint of antistaticity and its durability.
  • Block polymer (C) having a carboxyl group at both ends formed by repeating and alternately bonding via an ester bond, and a polyalkylene glycol diglycidyl ether compound (D), and the carboxyl group of the block polymer (C) It is preferable to have a structure formed by bonding via an ester bond formed by the epoxy group of the polyalkylene glycol diglycidyl ether compound (D).
  • the polyester (a) constituting the block (A) of the polyester according to the present invention may be any one comprising a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and is preferably from the viewpoint of antistatic properties and its durability.
  • the polyester (a) is preferably one having a carboxyl group at both ends from the viewpoint of the antistatic property and its durability. Furthermore, the degree of polymerization of the polyester (a) is preferably in the range of 2 to 50 from the viewpoint of the antistatic property and its durability.
  • the polyester (a) having a carboxyl group 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 aliphatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.), and when the derivative is used to obtain polyester (a), Finally, both ends may be treated to form carboxyl groups, and in the state as such, the reaction may be advanced to obtain a block polymer (C) having a structure having carboxyl groups at both ends.
  • the aliphatic dicarboxylic acid and its derivative may be a mixture of two or more.
  • the aromatic dicarboxylic acid may be a derivative of aromatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.), and if derivative is used to obtain polyester, the final Both ends may be treated to form a carboxyl group, and in the state as it is, the reaction may proceed to the next reaction for obtaining a block polymer (C) having a structure having a carboxyl group at both ends.
  • the aromatic dicarboxylic acid and its derivative may be a mixture of two or more.
  • the ratio of the residue of the aliphatic dicarboxylic acid other than the carboxyl group in the polyester (a) to the residue other than the carboxyl group of the aromatic dicarboxylic acid is a molar ratio in terms of antistaticity and its durability. 90:10 to 99.9: 0.1 is preferable, and 93: 7 to 99.9: 0.1 is more preferable.
  • the polyester (a) having a carboxyl group at both ends can be obtained, for example, by subjecting the above-mentioned aliphatic dicarboxylic acid or its derivative and the above-mentioned aromatic dicarboxylic acid or its derivative to a polycondensation reaction with the above-mentioned diol.
  • the reaction ratio of aliphatic dicarboxylic acid or derivative thereof and aromatic dicarboxylic acid or derivative thereof with diol is such that aliphatic dicarboxylic acid or derivative thereof and aromatic dicarboxylic acid or derivative thereof are obtained such that both ends are carboxyl groups. It is preferable to use an excess, and it is preferable to use in a molar ratio of 1 molar excess to the diol.
  • the compounding ratio of the aliphatic dicarboxylic acid or derivative thereof to the aromatic dicarboxylic acid or derivative thereof during the polycondensation reaction is preferably 90:10 to 99.9: 0.1 in molar ratio, and 93: 7 to 99.9. 0.1 is more preferable.
  • a polyester composed of only diol and aliphatic dicarboxylic acid, or a polyester composed only of diol and aromatic dicarboxylic acid may be produced. They may be mixed in a), and they may be reacted with compound (b) to obtain block polymer (C).
  • a catalyst that promotes the esterification reaction may be used, and as the catalyst, conventionally known ones such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, zinc acetate and the like can be used.
  • a suitable polyester (a) consisting of 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 compound (b) to form a block polymer (C).
  • the carboxyl groups at both ends may be protected as long as they form a structure, may be protected, or may be in the form of a precursor.
  • an antioxidant such as a phenolic antioxidant may be added to the reaction system.
  • the compound (b) having an ethyleneoxy group and having a hydroxyl group at both ends may form an ester bond by reacting with the polyester (a) to form the structure of the block polymer (C), both
  • the terminal hydroxyl group may be protected, modified or in the form of a precursor.
  • the block polymer (C) having a structure having a carboxyl group at both ends comprises a block (A) composed of the above polyester (a) and a block (B) composed of the above compound (b) And has a structure in which these blocks are repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group. If an example of this block polymer (C) is given, what has a structure represented by following General formula (3) will be mentioned, for example.
  • (A) represents a block composed of a polyester (a) having a carboxyl group at the both ends, and (B) represents a compound (b) having a hydroxyl group at the both ends It represents a constructed block, and t is the number of repeating units, preferably 1 to 10 in terms of antistaticity and durability. t is more preferably a number of 1 to 7, and most preferably a number of 1 to 5.
  • part of the block composed of the polyester (a) is a block 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 by a block of polyester.
  • the block polymer (C) having a structure having a carboxyl group at both ends is obtained by subjecting the polyester (a) having a carboxyl group at both ends to a polycondensation reaction with the compound (b) having a hydroxyl group at both ends.
  • the structure is equivalent to one having a structure in which the polyester (a) and the compound (b) are repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group. It is not necessary to synthesize from the above-mentioned polyester (a) and the above-mentioned compound (b) as long as it has the
  • the reaction ratio of the polyester (a) to the compound (b) is adjusted such that the polyester (a) is X + 1 mol with respect to X mol of the compound (b), carboxyl groups at both ends are obtained.
  • the block polymer (C) having
  • the compound (b) may be added to the reaction system without isolating the polyester (a), and the reaction may be carried out as it is.
  • a catalyst that promotes the esterification reaction may be used, and as the catalyst, conventionally known ones such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, zinc acetate and the like can be used.
  • an antioxidant such as a phenolic antioxidant may be added to the 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, and these may be directly used as a compound (b) And the block polymer (C).
  • the block polymer (C) is composed of a polyester composed only of a diol and an aliphatic dicarboxylic acid, in addition to a block (A) composed of a polyester (a) and a block (B) composed of a compound (b) Or a block composed of a polyester composed only of a diol and an aromatic dicarboxylic acid may be included in the structure.
  • a block polymer (C) having a structure having a carboxyl group at both ends and a polyalkylene glycol glycidyl ether compound (D) are block polymers (C) It has a structure formed by bonding via an ester bond formed by the terminal carboxyl group and the epoxy group of the polyalkylene glycol glycidyl ether compound (D).
  • the polymer compound (E) may further contain an ester bond formed by the carboxyl group of the polyester (a) and the epoxy group of the polyalkylene glycol glycidyl ether compound (D).
  • the polymer compound (E) further includes an ether bond formed by the hydroxyl group of the polyester (a) or the hydroxyl group of the compound (b) and the epoxy group of the polyalkylene glycol glycidyl ether compound (D). May be included.
  • the carboxyl group of the block polymer (C) and the epoxy group of the polyalkylene glycol glycidyl ether compound (D) may be reacted.
  • the number of epoxy groups of the polyalkylene glycol glycidyl ether compound (D) is preferably 0.5 to 5 equivalents of the number of carboxyl groups of the block polymer (C) to be reacted, and more preferably 0.5 to 1.5 equivalents. .
  • the above reaction may be carried out in various solvents or in a molten state.
  • the amount of the polyalkylene glycol glycidyl ether compound (D) to be reacted is preferably 0.1 to 2.0 equivalents, and more preferably 0.2 to 1.5 equivalents of the number of carboxyl groups of the block polymer (C) to be reacted.
  • the polyalkylene glycol glycidyl ether compound (D) may be added to the reaction system without isolating the block polymer (C), and the reaction may be carried out as it is .
  • the carboxyl group of the unreacted polyester (A) used in excess when synthesizing the block polymer (C) reacts with a part of epoxy groups of the polyalkylene glycol glycidyl ether compound (D), It may form an ester bond.
  • a block polymer (C) having a structure having a carboxyl group at both ends and a polyalkylene glycol glycidyl ether compound (D) are formed by the respective carboxyl group and epoxy group It is not necessary to synthesize from the block polymer (C) and the polyalkylene glycol glycidyl ether compound (D), as long as it has a structure equivalent to one having a structure bonded via an ester bond.
  • the number average molecular weight of the block composed of the compound (b) having a hydroxyl group at both ends in the polymer compound (E) is calculated from the measured value of the hydroxyl value, and the antistatic property and its persistence From the point of view, it is preferably 400 to 10,000, more preferably 1,000 to 8,000, and still more preferably 2,000 to 8,000.
  • the number average molecular weight of the block composed of the polyester (a) in the polymer compound (E) is preferably 800 to 8,000 in terms of polystyrene in terms of antistatic property and its durability. More preferably, it is 1,000 to 6,000, and more preferably 2,000 to 4,000.
  • the number average molecular weight of the block composed of the block polymer (C) having a structure having a carboxyl group at both ends is preferably 5,000 to 30,000 in terms of polystyrene More preferably, it is 7,000 to 20,000, and more preferably 9,000 to 17,000.
  • the polymer compound (E) of the present invention is a compound (b) and / or a compound (b) after the polyester (a) is not isolated after obtaining the polyester (a) from a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid. Alternatively, it may be reacted with a polyalkylene glycol glycidyl ether compound (D).
  • the polymer compound (E) of the present invention further comprises one or more selected from the group consisting of salts of alkali metals and salts of Group 2 elements to provide excellent antistatic performance and durability. It becomes a composition which it has and is preferable.
  • Examples of the salts of alkali metals and salts of Group 2 elements include salts of organic acids or inorganic acids, and examples of alkali metals include lithium, sodium, potassium, cesium, rubidium and the like, and Group 2 elements
  • Examples of the organic acid include beryllium, magnesium, calcium, strontium, barium and the like, and examples of the organic acid include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid and lactic acid Aliphatic dicarboxylic acids having 1 to 12 carbon atoms such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid and adipic acid; and aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid and salicylic acid Charcoal such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenz
  • inorganic acids examples include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like. .
  • alkali metal salts are preferable, lithium, sodium and potassium are more preferable, and sodium is most preferable, from the viewpoint of the antistatic property and the durability, the safety to the living body and the environment.
  • salts of acetic acid, salts of perchloric acid, salts of p-toluenesulfonic acid and salts of dodecylbenzenesulfonic acid are preferable, and salts of dodecylbenzenesulfonic acid are more preferable.
  • salts of alkali metals and salts of group 2 elements include, for example, lithium acetate, sodium acetate, potassium acetate, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium phosphate, sodium phosphate , Potassium phosphate, lithium sulfate, sodium sulfate, magnesium sulfate, calcium sulfate, lithium perchlorate, sodium perchlorate, potassium perchlorate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, p-toluenesulfone Acid potassium, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate and the like.
  • lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, and dodecylbenzenesulfonic acid are preferred from the viewpoints of antistatic properties and their durability, and safety to the living body and the environment.
  • Sodium and the like, most preferred is sodium dodecylbenzene sulfonate.
  • One or more selected from the group consisting of a salt of an alkali metal and a salt of a group 2 element may be added to the polymer compound (E) of the present invention, or together with the polymer compound (E), a thermoplastic resin You may mix and use for.
  • the amount of one or more selected from the group consisting of a salt of an alkali metal and a salt of a group 2 element is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the polymer compound (E), The amount is more preferably 0.1 to 15 parts by mass, and most preferably 3.0 to 12 parts by mass.
  • these optional components may be mixed, and various mixers can be used for mixing. It may be heated at the time of mixing. Examples of mixers that can be used include tumbler mixers, Henschel mixers, ribbon blenders, V-type mixers, W-type mixers, super mixers, Nauta mixers, and the like.
  • mixers that can be used include tumbler mixers, Henschel mixers, ribbon blenders, V-type mixers, W-type mixers, super mixers, Nauta mixers, and the like.
  • one or more selected from the group consisting of a salt of an alkali metal and a salt of a group 2 element may be added to the reaction system.
  • the compound (E) of the present invention may be blended with a surfactant and used as a composition having antistatic properties.
  • a surfactant nonionic, anionic, cationic or amphoteric surfactants can be used.
  • Polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts as nonionic surfactants; fatty acid esters of polyethylene oxide, glycerin
  • polyvalent alcohol type nonionic surfactants such as fatty acid esters of pentaerythritol, fatty acid esters of sorbite or sorbitan, alkyl ethers of polyhydric alcohols, aliphatic amides of alkanolamines, etc.
  • anionic surfactants For example, carboxylates such as alkali metal salts of higher fatty acids; sul
  • Amphoteric surfactants include amino acid type amphoteric surfactants such as higher alkyl amino propionates, and betaine type amphoteric surfactants such as higher alkyl dimethyl betaines and higher alkyl dihydroxyethyl betaines, etc. These may be used alone or in combination. Two or more can be used in combination.
  • anionic surfactants are preferred, and in particular, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates and paraffin sulfonates are preferred.
  • the surfactant may be blended in the polymer compound (E), or may be blended in the thermoplastic resin together with the polymer compound (E).
  • the compounding amount of the surfactant is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and most preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer compound (E). preferable.
  • the polymer compound (E) of the present invention may be used as a composition having an antistatic property by blending a polymer type antistatic agent.
  • a polymer type antistatic agent for example, polymer type antistatic agents such as known polyether ester amide can be used, and as the known polyether ester amide, for example, JP-A 7-10989 Mention may be made of the polyetheresteramides which consist of polyoxyalkylene adducts of bisphenol A as described.
  • block polymers in which the bonding units of the polyolefin block and the hydrophilic polymer block have a repeating structure of 2 to 50 can be used, and for example, block polymers described in US Pat. No. 6,552,131 can be mentioned.
  • the polymer type antistatic agent may be blended with the polymer compound (E) of the present invention, or may be blended with a polymer compound (E) and used in a thermoplastic resin.
  • the amount of the polymer type antistatic agent is preferably 0 to 50 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the polymer compound (E).
  • the polymer compound (E) of the present invention may be blended with an ionic liquid and used as a composition having antistatic properties.
  • the ionic liquid it has a melting point below room temperature, and at least one of the cations or anions constituting the ionic liquid is an organic ion, and the initial conductivity is 1 to 200 ms / cm, preferably 10 to 200 ms. It is a room temperature molten salt which is / cm, for example, the room temperature molten salt described in WO 95/15572.
  • a cation which comprises an ionic liquid the cation chosen from the group which consists of amidinium, pyridinium, pyrazolium, and guanidinium cation is mentioned.
  • amidinium cation the following may be mentioned.
  • Imidazolinium cation those having 5 to 15 carbon atoms, and examples thereof include 1,2,3,4-tetramethylimidazolinium, 1,3-dimethylimidazolinium;
  • Imidazolium cation examples thereof include those having 5 to 15 carbon atoms, such as 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium;
  • Tetrahydropyrimidinium cation those having 6 to 15 carbon atoms, and examples thereof include 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetra Methyl-1,4,5,6-tetrahydropyrimidinium;
  • Dihydropyrimidinium cation examples thereof include those having 6 to 20 carbon atoms, and examples thereof include 1,3-dimethyl-1,4-dihydropyrimidinium and 1,3-dimethyl-1,6-dihydropyrimidi. , 8-methyl-1,8-diazabicyclo [5,4,0] -7,9-undecadienium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,10-un Decadienium.
  • pyridinium cations include those having 6 to 20 carbon atoms, such as 3-methyl-1-propylpyridinium and 1-butyl-3,4-dimethylpyridinium.
  • the pyrazolium cation includes those having 5 to 15 carbon atoms, and examples thereof include 1,2-dimethyl pyrazolium and 1-n-butyl-2-methyl pyrazolium.
  • Guanidinium cation having an imidazolinium skeleton those having 8 to 15 carbon atoms, and examples thereof include 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3. , 4-trimethylimidazolinium;
  • Guanidinium cation having an imidazolium skeleton those having 8 to 15 carbon atoms, and examples thereof include 2-dimethylamino-1,3,4-trimethylimidazolium and 2-diethylamino-1,3,4. -Trimethylimidazolium;
  • Guanidinium cation having a tetrahydropyrimidinium skeleton those having 10 to 20 carbon atoms, and examples thereof include 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydrofuran Pyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium;
  • Guanidinium cation having a dihydropyrimidinium skeleton those having 10 to 20 carbon atoms, and examples thereof include 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 cations may be used alone or in combination of two or more.
  • an amidinium cation is preferable from the viewpoint of antistatic properties, more preferably an imidazolium cation, and particularly preferably a 1-ethyl-3-methylimidazolium cation.
  • Examples of the organic acid or inorganic acid constituting the anion in the ionic liquid include the following.
  • As an organic acid for example, carboxylic acid, sulfuric acid ester, sulfonic acid and phosphoric acid ester;
  • As an inorganic acid for example, super strong acid (eg, borofluoric acid, tetraboronic acid, perchloric acid, phosphorus hexafluoride) Acids, hexafluoroantimonic acid and hexaarsenic acid), phosphoric acid and boric acid.
  • the organic acid and the inorganic acid may be used alone or in combination of two or more.
  • organic acids and inorganic acids preferred from the viewpoint of the antistatic property of the ionic liquid is a conjugate of a super strong acid whose Hammett acidity function (-H 0 ) of the anion constituting the ionic liquid is 12 to 100.
  • Bases acids which form anions other than the conjugate bases of super strong acids, and mixtures thereof.
  • halogen eg, fluorine, chlorine and bromine
  • alkyl C 1-12 carbon atoms
  • benzenesulfonic acid eg, p-toluenesulfonic acid and dodecylbenzenesulfonic acid
  • fluoroalkanesulfonic acid eg, undecafluoropentanesulfonic acid
  • super acids include those derived from protic acids and combinations of protic acids and Lewis acids, and mixtures thereof.
  • borofluoric acid trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imidic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferable from the viewpoint of easiness of synthesis.
  • Protic acids used in combination with Lewis acids include, for example, hydrogen halide (eg, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethane Sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof can be mentioned.
  • hydrogen fluoride is preferred from the viewpoint of the initial conductivity of the ionic liquid.
  • Lewis acid for example, boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride and mixtures thereof can be mentioned.
  • boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of the ionic liquid.
  • the combination of a protonic acid and a Lewis acid is optional, but as a superstrong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, hexafluorinated acid And tantalum sulfonic acid, boron tetrafluoride, phosphoric acid hexafluoride, boron trichloride chloroborate, arsenic hexafluoride hexafluoride, and mixtures thereof.
  • tetrafluoroboric acid hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, hexafluorinated acid And tantalum sulfonic acid, boron tetrafluoride, phosphoric acid hexafluoride, boron trichloride chlor
  • super-acid conjugate bases (super-strong acids consisting of protic acids and super-strong acids consisting of a combination of protic acids and Lewis acids) from the viewpoint of the antistatic properties of ionic liquids, more preferred Is a conjugate base of a super strong acid consisting of a protic acid and a super strong acid consisting of a protic acid and a boron trifluoride and / or a phosphorus pentafluoride.
  • an ionic liquid having an amidinium cation is preferable from the viewpoint of antistaticity, an ionic liquid having a 1-ethyl-3-methylimidazolium cation is more preferable, and an ionic liquid having a 1-ethyl-3-methylimidazolium cation is particularly preferable.
  • 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide is particularly preferable.
  • the blending amount of the ionic liquid is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and most preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer compound (E). preferable.
  • the polymer compound (E) of the present invention may be blended with a compatibilizer to form a composition having antistatic properties.
  • a compatibilizer By blending the compatibilizer, the compatibility of the polymer compound (E) with other components and the thermoplastic resin can be improved.
  • a compatibilizer modified vinyl polymers 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, for example, Examples thereof include polymers described in JP-A-3-258850, modified vinyl polymers having a sulfonyl group described in JP-A-6-345927, and block polymers having a polyolefin portion and an aromatic vinyl polymer portion.
  • the compatibilizer may be blended with the polymer compound (E) of the present invention, or may be blended with the polymer compound (E) in a thermoplastic resin.
  • the amount of the compatibilizing agent is preferably 0.1 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer compound (E).
  • composition of the present invention other components may be blended as optional components in addition to the polymer compound (E) and the components listed above, as long as the effects of the present invention are not impaired.
  • these other components may be directly blended into the composition, or a resin composition having antistatic properties by blending the polymer compound (E) or the composition of the present invention into a synthetic resin such as a thermoplastic resin. When used as, it may be blended with a synthetic resin.
  • thermoplastic resins include polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, crosslinked polyethylene, ultrahigh molecular weight polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene and the like
  • Polyolefin resins such as ⁇ -olefin polymers or ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-propylene copolymers and copolymers thereof; polyvinyl chloride, polyvinylidene chloride, chlorine Polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride, vinyl chlor
  • Polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonates, polycarbonates / ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, fibrous resin, polyimide resin
  • Polysulfone, polyphenylene ether, polyether ketone, polyether ether ketone include thermoplastic resins and blends thereof such as a liquid crystal polymer.
  • thermoplastic resin is isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, olefin elastomer, styrene elastomer, polyester elastomer, nitrile elastomer, nylon It may be an elastomer such as a system elastomer, a vinyl chloride elastomer, a polyamide elastomer, or a polyurethane elastomer. In the present invention, these thermoplastic resins may be used alone or in combination of two or more. The thermoplastic resin may be alloyed.
  • thermoplastic resins have a molecular weight, polymerization degree, density, softening point, ratio of insoluble matter to solvent, degree of stereoregularity, presence or absence of catalyst residue, kind and blending ratio of raw material monomers, kind of polymerization catalyst It can be used regardless of (eg, Ziegler catalyst, metallocene catalyst, etc.) and the like.
  • thermoplastic resins at least one selected from the group consisting of polyolefin resins, polystyrene resins and copolymers thereof is preferable from the viewpoint of antistatic properties.
  • the mass ratio of the thermoplastic resin to the polymer compound (E) or the composition in the resin composition of the present invention is preferably in the range of 99/1 to 40/60.
  • the method of blending the polymer compound (E) into the thermoplastic resin is not particularly limited, and any commonly used method can be used, for example, roll kneading, bumper kneading, extruder, kneader, etc. It may be mixed, kneaded and blended.
  • the polymer compound (E) may be added to the thermoplastic resin as it is, but may be added after the carrier is impregnated, if necessary. 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 and then impregnated into the carrier, and then the solvent may be removed.
  • a filler known as a filler of a synthetic resin or a filler, or a flame retardant or a light stabilizer which is solid at normal temperature can be used.
  • a filler of a synthetic resin or a filler or a flame retardant or a light stabilizer which is solid at normal temperature
  • calcium silicate powder, silica powder, talc powder, alumina powder examples thereof include titanium oxide powder, those obtained by chemically modifying the surface of these carriers, and solid substances among the flame retardants and antioxidants listed below.
  • these carriers those in which the surface of the carrier is chemically modified are preferable, and those in which the surface of the silica powder is chemically modified are more preferable.
  • the carrier preferably has an average particle diameter of 0.1 to 100 ⁇ m, and more preferably 0.5 to 50 ⁇ m.
  • thermoplastic resin of a high molecular compound (E), a high molecular compound (E), while kneading a block polymer (C) and a polyalkylene glycol diglycidyl ether compound (D) simultaneously with a thermoplastic resin May be synthesized and compounded, and at the same time, one or more selected from the group consisting of salts of alkali metals and salts of Group 2 elements may be simultaneously kneaded, or at the time of molding such as injection molding, etc.
  • the polymer compound (E) and the thermoplastic resin may be mixed to obtain a molded product, and at that time, it may be further selected from the group consisting of alkali metal salts and salts of Group 2 elements.
  • More than one species may be blended, and further, a masterbatch of the polymer compound (E) and the thermoplastic resin may be prepared in advance, and this masterbatch may be blended. It may be blended at least one selected from the group consisting of salts of alkali metals salts and a Group 2 element.
  • various additives such as phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet light absorbers, hindered amine light stabilizers and the like are further added as necessary.
  • the resin composition of the present invention can be stabilized.
  • antioxidants such as these antioxidants may be blended into the composition of the present invention before blending into the synthetic resin. Furthermore, you may mix
  • phenolic antioxidants examples include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4) -Hydroxybenzyl) phosphonate, 1,6-hexamethylene bis [(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-di-tert-butylphenol), 2,2'-ethylidenebis (4-sec-but
  • Examples of the above-mentioned 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-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butyl
  • thioether-based antioxidants examples include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra ( ⁇ -alkylthiopropionic acid). Esters are mentioned.
  • 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 thermoplastic resin.
  • UV absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone).
  • 2-hydroxybenzophenones such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chloro Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-third) Octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2 2- (2) -methylenebis (4-tert-octyl-6- (benzotriazolyl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl) benzotriazole, etc.
  • hindered amine light stabilizers examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,3, 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- Butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, bis (2, , 6,6-Tetramethyl-4-piperidyl), di (tride
  • 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 (stearoamide), ethylene bis (12-hydroxy stearoamide) and stearic acid amide.
  • fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate
  • fatty acid amides such as ethylene bis (stearoamide), ethylene bis (12-hydroxy stearoamide) and stearic acid amide.
  • the compound is mentioned and these neutralizing agents may be mixed and used.
  • the resin composition of the present invention may further contain, as other additives, metal salts of aromatic carboxylic acids, metal salts of alicyclic alkyl carboxylic acids, and p-numbers as long as the effects of the present invention are not impaired.
  • Nucleating agents such as aluminum tributylbenzoate, metal salts of aromatic phosphates, dibenzylidene sorbitols, metal soaps, hydrotalcites, triazine ring-containing compounds, metal hydroxides, phosphoric acid ester flame retardants, condensed phosphorus Acid ester flame retardants, phosphate flame retardants, inorganic phosphorus flame retardants, (poly) phosphate flame retardants, halogen flame retardants, silicon flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardants Fuel aids, other organic fire retardant aids, fillers, pigments, lubricants, foaming agents, etc. may be added.
  • triazine ring-containing compounds examples include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene Examples thereof include dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, and 1,3-hexylene dimelamine.
  • metal hydroxide examples 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.
  • phosphate ester flame retardant examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, tris dichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, Trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, tris isopropyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t-butyl phenyl phosphate) Phenyl) phosphate, isopropylphenyl diphenyl phosphate, bis-
  • condensed phosphoric acid ester flame retardant examples 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 retardants include ammonium salts and amine salts of (poly) phosphoric acids such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melamine pyrophosphate and piperazine pyrophosphate. .
  • inorganic flame retardant aids include, for example, inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, montmorillonite, and surface-treated products thereof.
  • inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, montmorillonite, and surface-treated products thereof.
  • 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
  • Talsite Various commercial products such as Kyowa Chemical Industry Co., Ltd. can be used.
  • organic type flame retardant auxiliary agent pentaerythritol is mentioned, for example.
  • the resin composition of the present invention may, if necessary, be an additive generally used for a synthetic resin, as long as the effects of the present invention are not impaired, such as a crosslinking agent, an antifogging agent, an antiplateout agent, Surface treatment agents, plasticizers, lubricants, flame retardants, fluorescent agents, fungicides, bactericides, foaming agents, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, etc. It can mix
  • the additive to be added to the resin composition of the present invention may be added directly to the thermoplastic resin, or added to the thermoplastic resin after being added to the polymer compound (E) or the composition of the present invention It is also good.
  • a resin molded product having antistatic properties By molding the resin composition of the present invention, a resin molded product having antistatic properties can be obtained.
  • the molding method is not particularly limited, and extrusion, calendering, injection molding, rolling, compression molding, blow molding, rotational molding, etc. may be mentioned, resin plate, sheet, film, bottle, fiber, profiled article Molded articles of various shapes such as can be manufactured.
  • the molded object obtained by the resin composition of this invention is excellent in antistatic performance and its sustainability.
  • the resin composition of the present invention and a molded article using the same are used in electric / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, fiber, clothing, medical, coal, petroleum, rubber, leather, automobile, precision equipment, wood It can be used in a wide range of industrial fields such as construction materials, civil engineering, furniture, printing and musical instruments.
  • the resin composition of the present invention and the molded article thereof can be used in printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers), Calculators, electronic organizers, cards, holders, stationery, office work, office automation equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, household appliances such as irons, TVs, VTRs, video cameras, radio cassette players , Tape recorder, mini disc, CD player, speaker, AV equipment such as liquid crystal display, connector, relay, capacitor, switch, printed circuit board, coil bobbin, semiconductor sealing material, LED sealing material, electric wire, cable, transformer, deflection yoke , Electric and electronic parts such as distribution boards and watches, and communication devices, interior and exterior materials for automobiles, plate making Film, adhesive film, bottles, food containers, food packaging films, pharmaceutical and pharmaceutical wrap film, product packaging film, agricultural film, agricultural sheeting, used in applications such as
  • the resin composition of the present invention and the molded article thereof can be used in a seat (filler, outer fabric, etc.), a belt, a ceiling, a convertible top, an armrest, a door trim, a rear package tray, a carpet, a mat, a sun visor, a foil cover, a mattress cover , Air bag, insulation material, hanging hand, hanging band, electric wire coating material, electric insulation material, paint, coating material, covering material, flooring material, floor material, corner wall, carpet, wallpaper, wall covering material, exterior material, interior material , roofing materials, decking materials, wall materials, pillars, floorboards, materials for fences, frameworks and moldings, windows and door profiles, shingles, crosses, terraces, balconies, soundproofing boards, insulation boards, window materials, etc.
  • the polymer compound (E) used in the present invention was produced according to the following production examples. Moreover, in the following production example, the number average molecular weight of the compound (b) was measured by the following ⁇ molecular weight measuring method 1>, and the number average molecular weights other than the compound (b) were measured by the following ⁇ molecular weight measuring method 2> .
  • ⁇ Molecular weight measurement method 1> The hydroxyl value was measured by the following hydroxyl value measurement method, and the number average molecular weight (hereinafter also referred to as "Mn") was determined by the following equation. Number average molecular weight (56110 ⁇ 2) / hydroxyl value ⁇ hydroxyl value measurement method>
  • Reagent A acetylating agent
  • Triethyl phosphate 1560 mL (2) 193 mL of acetic anhydride (3)
  • the above reagents are mixed in the order of (1) ⁇ (2) ⁇ (3).
  • ⁇ Reagent B Pyridine and pure water are mixed in a volume ratio of 3: 1.
  • ⁇ Reagent C Add 2-3 drops of phenolphthalein solution to 500 mL of isopropyl alcohol, and neutralize with 1N aqueous KOH solution.
  • Mn number average molecular weight
  • Polyethylene glycol diglycidyl ether (epoxy equivalent 268 g / eq) 1 as polyalkylene glycol diglycidyl ether compound (D) -1 was added to 100 g of block polymer (C) -1 having a structure having a carboxyl group at both ends obtained. .5g was charged and polymerized under reduced pressure at 240 ° C for 3 hours to obtain 102g of a polymer compound (E) -1.
  • Production Example 3 100 g of a block polymer (C)-having a structure having a carboxyl group at both ends obtained in the same manner as in Production Example 1 and polyethylene glycol diglycidyl ether (epoxy) as polyalkylene glycol diglycidyl ether compound (D) -3 An amount of 1.6 g equivalent to 277 g / eq) was charged, and polymerization was carried out at 240 ° C. for 3 hours under reduced pressure to obtain 102 g of a polymer compound (E) -3.
  • Production Example 5 Polypropylene glycol diglycidyl ether (polyalkylene glycol diglycidyl ether compound (D) -5) was added to 100 g of block polymer (C) -1 having a structure having a carboxyl group at both ends obtained in the same manner as in Production Example 1 1.7 g of epoxy equivalent 300 g / eq) was charged, and polymerization was carried out under reduced pressure at 240 ° C. for 3 hours to obtain 103 g of a polymer compound (E) -5.
  • Polypropylene glycol diglycidyl ether (polyalkylene glycol diglycidyl ether compound (D) -6) was added to 100 g of block polymer (C) -1 having a structure having a carboxyl group at both ends obtained in the same manner as in Production Example 1 1.8 g of epoxy equivalent weight 315 g / eq) was charged and polymerized under reduced pressure at 240 ° C. for 3 hours to obtain 103 g of a polymer compound (E) -6.
  • Production Example 7 Polypropylene glycol diglycidyl ether (polyalkylene glycol diglycidyl ether compound (D) -7) was added to 100 g of block polymer (C) -1 having a structure having a carboxyl group at both ends obtained in the same manner as in Production Example 1 2.4 g of epoxy equivalent weight 417 g / eq) was charged and polymerized under reduced pressure at 240 ° C. for 3 hours to obtain 103 g of a polymer compound (E) -7.
  • Comparative Production Example 1 In 100 g of block polymer (C) -1 obtained in the same manner as in Production Example 1, 1.0 g of bisphenol F diglycidyl ether (epoxy equivalent 170 g / eq) was charged and polymerized under reduced pressure at 240 ° C. for 3 hours. Thus, 102 g of Comparative Polymer Compound 1 was obtained.
  • Comparative Production Example 2 In 100 g of block polymer (C) -1 obtained in the same manner as in Production Example 1, 1.5 g of bisphenol A diglycidyl ether (epoxy equivalent 250 g / eq) was charged and polymerized under reduced pressure at 240 ° C. for 3 hours. Thus, 102 g of Comparative Polymer Compound 2 was obtained.
  • Examples 1 to 10 Comparative Examples 1 to 4
  • Test pieces were obtained using the resin compositions of Examples and Comparative Examples blended based on the compounding amounts described in Tables 1 to 3 below, according to the test piece preparation conditions shown below.
  • the surface resistivity (SR value) was measured according to the following using the obtained test piece, and the antistatic property and its durability were evaluated.
  • ⁇ Homopolypropylene resin composition test piece preparation conditions Resin compositions blended based on the compounding amounts shown in Tables 1 to 3 below were produced using Ikegai Co., Ltd. twin screw extruder (containing PCM 30, 60 mesh) under conditions of 230 ° C. and 6 kg / hour. Granulated to obtain pellets. The obtained pellets are molded using a horizontal injection molding machine (NEX 80: manufactured by Nissei Resin Industry Co., Ltd.) under processing conditions of a resin temperature of 230 ° C. and a mold temperature of 40 ° C., test pieces (100 mm ⁇ 100 mm ⁇ 3 mm) I got
  • SR value ⁇ Method of measuring surface resistivity (SR value)>
  • the obtained test piece is stored under the conditions of temperature 25 ° C. and humidity 50% RH, and after storage for 1 day and 30 days of molding processing, under the same atmosphere, R8340 resistance meter made by Advantest Corp.
  • the surface resistivity ( ⁇ / ⁇ ) was measured under the conditions of an applied voltage of 100 V and an application time of 1 minute. The measurement was carried out at five points per five test pieces, and the average value was determined.
  • NaDBS sodium dodecylbenzene sulfonate.

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Abstract

Provided are a polymer compound, a composition including the same, a resin composition including these, and a molded body thereof that can sustainably impart a superior antistatic effect to a synthetic resin. This polymer compound is obtained by reacting a polyester (a) that is obtained by reacting a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, a compound (b) that has one or more ethyleneoxy groups and has a hydroxyl group at both ends, and a polyalkylene glycol diglycidyl ether compound (D).

Description

高分子化合物、これを含む組成物、これらを含む樹脂組成物、およびその成形体Polymer compound, composition containing the same, resin composition containing them, and molded article thereof
　本発明は、高分子化合物、これを含む組成物、これらを含む樹脂組成物、およびその成形体に関し、詳しくは、合成樹脂に対して、優れた帯電防止効果を持続的に付与することができる高分子化合物、これを含む組成物、これらを含む樹脂組成物、およびその成形体に関する。 The present invention relates to a polymer compound, a composition containing the same, a resin composition containing the same, and a molded article thereof, and in particular, it is possible to continuously impart an excellent antistatic effect to a synthetic resin. The present invention relates to a polymer compound, a composition containing the same, a resin composition containing them, and a molded article thereof.
　熱可塑性樹脂は、軽量で加工が容易であるのみならず、用途に応じて基材を設計することができる等の優れた特性を有しているため、現代では欠かすことのできない重要な素材である。また、熱可塑性樹脂は電気絶縁性に優れるという特性を有するため、電気製品のコンポーネント等に頻繁に利用されている。しかしながら、熱可塑性樹脂はあまりにも絶縁性が高いため、摩擦等により帯電しやすいという問題がある。 Thermoplastic resins are not only lightweight and easy to process, but also have excellent properties such as being able to design the base material according to the application, so they are important materials that can not be indispensable today is there. In addition, thermoplastic resins are frequently used for components of electric products, etc. because they have excellent electrical insulation properties. However, since the thermoplastic resin has too high insulation, there is a problem that it is easily charged by friction or the like.
　帯電した熱可塑性樹脂は周囲の埃や塵を引き付けるため、樹脂成形品の外観を損ねるという問題が生ずる。また、電子製品の中でも、例えば、コンピューター等の精密機器は、帯電により回路が正常に作動することができなくなる場合がある。さらに、電撃による問題も存在する。樹脂から人体に対して電撃が発生すると、人に不快感を与えるだけでなく、可燃性気体や粉塵のあるところでは、爆発事故を誘引する可能性もある。 Since the charged thermoplastic resin attracts dust and dirt around it, there arises a problem that the appearance of the resin molded product is impaired. Further, among electronic products, for example, in precision equipment such as a computer, the circuit may not be able to operate normally due to charging. In addition, there is also a problem with lightning. When a resin generates an electric shock to the human body, it not only makes the person feel uncomfortable, but it may also cause an explosion accident in the presence of combustible gas and dust.
　このような問題を解消するために、従来から、合成樹脂に対して帯電を防止する処理がなされている。最も一般的な帯電防止処理方法は、合成樹脂に帯電防止剤を加える方法である。このような帯電防止剤には、樹脂成形体表面に塗布する塗布型のものと、樹脂を加工成形する際に添加する練り込み型のものとがあるが、塗布型のものは持続性に劣ることに加え、表面に大量の有機物が塗布されるために、その表面に触れたものが汚染されるという問題があった。 In order to solve such a problem, conventionally, a process for preventing charging of a synthetic resin has been performed. The most common antistatic treatment method is to add an antistatic agent to the synthetic resin. Such antistatic agents include a coating type that is applied to the surface of a resin molded product and a kneading type that is added when processing and molding a resin, but the coating type has poor sustainability. In addition to that, there is a problem that the contact with the surface is contaminated because a large amount of organic matter is applied to the surface.
　かかる観点から、従来、主として練り込み型の帯電防止剤が検討されており、例えば、特許文献１、２では、ポリオレフィン系樹脂への帯電防止性付与のためにポリエーテルエステルアミドが提案されている。また、特許文献３では、ポリオレフィンのブロックと親水性ポリマーのブロックとが、繰り返し交互に結合した構造を有するブロックポリマーが提案されている。さらに、特許文献４では、ポリエステルのブロックを有する高分子型帯電防止剤が提案されている。 From this point of view, conventionally, kneading-type antistatic agents have been mainly studied. For example, Patent Documents 1 and 2 propose polyetheresteramides for imparting antistatic properties to polyolefin resins. . Further, Patent Document 3 proposes a block polymer having a structure in which a block of polyolefin and a block of hydrophilic polymer are repeatedly and alternately bonded. Further, Patent Document 4 proposes a polymeric antistatic agent having a block of polyester.
特開昭５８－１１８８３８号公報Japanese Patent Application Laid-Open No. 58-118838 特開平３－２９０４６４号公報Unexamined-Japanese-Patent No. 3-290464 特開２００１－２７８９８５号公報JP 2001-278985 A 特開２０１６－２３２５４号公報JP, 2016-23254, A
　しかしながら、これら従来の帯電防止剤は、帯電防止性能において、必ずしも充分とはいえず、さらなる改良が望まれているのが現状である。 However, these conventional antistatic agents are not always sufficient in antistatic performance, and further improvement is desired at present.
　そこで、本発明の目的は、合成樹脂に対して、優れた帯電防止効果を持続的に付与することができる高分子化合物、これを含む組成物、これらを含む樹脂組成物およびその成形体を提供することにある。 Therefore, an object of the present invention is to provide a polymer compound capable of continuously imparting an excellent antistatic effect to a synthetic resin, a composition containing the same, a resin composition containing these, and a molded article thereof. It is to do.
　本発明者等は、上記課題を解消するために鋭意検討した結果、所定の構造を有する高分子化合物が熱可塑性樹脂に対して優れた帯電防止性能を付与することができ、これを用いることで、上記課題を解消することができることを見出し、本発明を完成するに至った。 The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, a polymer compound having a predetermined structure can impart excellent antistatic performance to a thermoplastic resin. It has been found that the above problems can be solved, and the present invention has been completed.
　すなわち、本発明の高分子化合物は、ジオールと、脂肪族ジカルボン酸および芳香族ジカルボン酸と、が反応して得られるポリエステル（ａ）と、エチレンオキシ基を１以上有する両末端に水酸基を有する化合物（ｂ）と、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）と、が反応して得られることを特徴とするものである。 That is, the polymer compound of the present invention is a polyester (a) obtained by reacting a diol with an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and a compound having a hydroxyl group at both ends having one or more ethyleneoxy groups. It is characterized by being obtained by reacting (b) with a polyalkylene glycol diglycidyl ether compound (D).
　本発明の高分子化合物においては、前記ポリエステル（ａ）から構成されるポリエステルのブロック（Ａ）と、前記化合物（ｂ）から構成されるポリエーテルのブロック（Ｂ）と、を有し、前記ポリエステル（ａ）の末端に有する水酸基またはカルボキシル基と、前記化合物（ｂ）の末端に有する水酸基と、前記ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）のエポキシ基と、の反応により形成された、エステル結合またはエーテル結合を介して結合してなる構造を有することが好ましい。また、本発明の高分子化合物においては、前記ポリエステルのブロック（Ａ）と、前記ポリエーテルのブロック（Ｂ）と、がエステル結合を介して繰り返し交互に結合してなる両末端にカルボキシル基を有するブロックポリマー（Ｃ）と、前記ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）と、がエステル結合を介して結合してなることが好ましい。さらに、本発明の高分子化合物においては、前記ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）が、ポリエチレングリコールジグリシジルエーテル、またはポリプロピレングリコールジグリシジルエーテルであることが好ましい。さらにまた、本発明の高分子化合物においては、前記ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）のエポキシ当量が、７０～２，０００であることが好ましい。また、本発明の高分子化合物においては、前記ポリエステル（ａ）が、両末端にカルボキシル基を有する構造であることが好ましい。さらに、本発明の高分子化合物においては、前記化合物（ｂ）が、ポリエチレングリコールであることが好ましい。さらにまた、本発明の高分子化合物においては、前記化合物（ｂ）の数平均分子量が、４００～１０，０００であることが好ましい。また、本発明の高分子化合物においては、前記ブロックポリマー（Ｃ）の数平均分子量が、５，０００～３０，０００であることが好ましい。 In the polymer compound of the present invention, the polyester has the block (A) of the polyester composed of the polyester (a) and the block (B) of the polyether composed of the compound (b), and the polyester An ester bond formed by the reaction of a hydroxyl group or carboxyl group at the end of (a), a hydroxyl group at the end of the compound (b), and an epoxy group of the polyalkylene glycol diglycidyl ether compound (D) Alternatively, it is preferable to have a structure formed by bonding via an ether bond. In addition, in the polymer compound of the present invention, the polyester block (A) and the polyether block (B) have carboxyl groups at both ends, which are alternately and repeatedly bonded via an ester bond. The block polymer (C) and the polyalkylene glycol diglycidyl ether compound (D) are preferably bonded via an ester bond. Furthermore, in the polymer compound of the present invention, the polyalkylene glycol diglycidyl ether compound (D) is preferably polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether. Furthermore, in the polymer compound of the present invention, the epoxy equivalent of the polyalkylene glycol diglycidyl ether compound (D) is preferably 70 to 2,000. Moreover, in the polymer compound of the present invention, it is preferable that the polyester (a) has a structure having a carboxyl group at both ends. Furthermore, in the polymer compound of the present invention, the compound (b) is preferably polyethylene glycol. Furthermore, in the polymer compound of the present invention, the number average molecular weight of the compound (b) is preferably 400 to 10,000. In the polymer compound of the present invention, the number average molecular weight of the block polymer (C) is preferably 5,000 to 30,000.
　本発明の組成物は、本発明の高分子化合物に対し、さらに、アルカリ金属の塩および第２族元素の塩からなる群から選択される１種以上が配合されてなることを特徴とするものである。 The composition of the present invention is characterized in that the polymer compound of the present invention is further blended with one or more selected from the group consisting of salts of alkali metals and salts of Group 2 elements. It is.
　本発明の樹脂組成物は、熱可塑性樹脂に対し、本発明の高分子化合物または本発明の組成物が配合されてなることを特徴とするものである。 The resin composition of the present invention is characterized in that the polymer compound of the present invention or the composition of the present invention is blended with a thermoplastic resin.
　本発明の樹脂組成物においては、前記熱可塑性樹脂は、ポリオレフィン系樹脂、ポリスチレン系樹脂およびそれらの共重合体からなる群から選ばれる１種以上であることが好ましい。 In the resin composition of the present invention, the thermoplastic resin is preferably at least one selected from the group consisting of polyolefin resins, polystyrene resins, and copolymers thereof.
　本発明の成形体は、本発明の樹脂組成物からなることを特徴とするものである。 The molded article of the present invention is characterized by comprising the resin composition of the present invention.
　本発明によれば、合成樹脂に対して、優れた帯電防止効果を持続的に付与することができる高分子化合物、これを含む組成物、これらを含む樹脂組成物およびその成形体を提供することができる。そのため、本発明の樹脂組成物は、帯電防止性とその持続性に優れている。また、本発明の成形体は、静電気による表面の汚染や埃の付着による商品価値の下落を生じにくいという利点を有している。 According to the present invention, there are provided a polymer compound capable of continuously imparting an excellent antistatic effect to a synthetic resin, a composition containing the same, a resin composition containing the same, and a molded article thereof. Can. Therefore, the resin composition of the present invention is excellent in antistatic property and its persistence. In addition, the molded article of the present invention has the advantage of being less likely to cause a drop in the commercial value due to surface contamination or dust adhesion due to static electricity.
　以下、本発明の実施形態について詳細に説明する。本発明の高分子化合物（以下、「高分子化合物（Ｅ）」とも称す）は、ジオールと、脂肪族ジカルボン酸および芳香族ジカルボン酸と、が反応して得られるポリエステル（ａ）と、エチレンオキシ基を１以上有する両末端に水酸基を有する化合物（ｂ）と、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）と、が反応して得られる。ここで、エチレンオキシ基とは、下記一般式（１）で示される基である。
Figure JPOXMLDOC01-appb-I000001
Hereinafter, embodiments of the present invention will be described in detail. The polymer compound of the present invention (hereinafter also referred to as “polymer compound (E)”) is a polyester (a) obtained by reacting a diol with an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and ethyleneoxy It is obtained by reacting a compound (b) having a hydroxyl group at both ends having one or more groups and a polyalkylene glycol diglycidyl ether compound (D). Here, the ethyleneoxy group is a group represented by the following general formula (1).
Figure JPOXMLDOC01-appb-I000001
　本発明の高分子化合物においては、ポリエステル（ａ）から構成されるポリエステルのブロック（Ａ）と、化合物（ｂ）から構成されるポリエーテルのブロック（Ｂ）と、を有し、ポリエステル（ａ）の末端に有する水酸基またはカルボキシル基と、化合物（ｂ）の末端に有する水酸基と、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）のエポキシ基と、の反応により形成された、エステル結合またはエーテル結合を介して結合してなる構造を有することが好ましい。特に、ポリエステルのブロック（Ａ）と、ポリエーテルのブロック（Ｂ）と、がエステル結合を介して繰り返し交互に結合してなる両末端にカルボキシル基を有するブロックポリマー（Ｃ）と、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）と、がエステル結合を介して結合してなることが好ましい。なお、ポリエステル（ａ）はジオールと、脂肪族ジカルボン酸および芳香族ジカルボン酸と、をエステル化反応させれば得ることができる。 The polymer compound of the present invention comprises a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the compound (b), and the polyester (a) Through an ester bond or an ether bond formed by the reaction of a hydroxyl group or carboxyl group at the end of the group, a hydroxyl group at the end of the compound (b), and an epoxy group of the polyalkylene glycol diglycidyl ether compound (D) It is preferable to have a structure formed by bonding. In particular, a block polymer (C) having a carboxyl group at both ends, in which a polyester block (A) and a polyether block (B) are repeatedly and alternately bonded via an ester bond, and a polyalkylene glycol di It is preferable that the glycidyl ether compound (D) is bonded via an ester bond. The polyester (a) can be obtained by subjecting a diol to an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid by an esterification reaction.
　まず、ポリエステル（ａ）の構成成分であるジオールについて説明する。本発明で用いられるジオールとしては、脂肪族ジオール、芳香族基含有ジオールが挙げられる。また、ジオールは、２種以上の混合物でもよい。 First, diol which is a component of polyester (a) will be described. The diols used in the present invention include aliphatic diols and aromatic group-containing diols. The diol may also be a mixture of two or more.
　脂肪族ジオールとしては、例えば、１，２－エタンジオール（エチレングリコール）、１，２－プロパンジオール（プロピレングリコール）、１，３－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、２－メチル－１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、２，２－ジメチル－１，３－プロパンジオール（ネオペンチルグリコール）、２，２－ジエチル－１，３－プロパンジオール（３，３－ジメチロールペンタン）、２－ｎ－ブチル－２－エチル－１，３プロパンジオール（３，３－ジメチロールヘプタン）、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、２－エチル－１，３－ヘキサンジオール、２－メチル－１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、１，１２－オクタデカンジオール、１，４－シクロヘキサンジメタノール、水添ビスフェノールＡ、１，２－、１，３－または１，４－シクロヘキサンジオール、シクロドデカンジオール、ダイマージオール、水添ダイマージオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール等が挙げられる。これら脂肪族ジオールの中でも、１，４－シクロヘキサンジメタノール、水添ビスフェノールＡが、帯電防止性とその持続性の点から好ましく、１，４－シクロヘキサンジメタノールがより好ましい。なお、脂肪族ジオールは、帯電防止性とその持続性の点から、疎水性を有することが好ましいので、親水性を有するポリエチレングリコールの使用は好ましくない。 As aliphatic diol, for example, 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, 1,3-butanediol , 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl- 1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentane Diol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediyl , 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1, Examples thereof include 2-, 1,3- or 1,4-cyclohexanediol, cyclododecanediol, dimerdiol, hydrogenated dimerdiol, diethylene glycol, dipropylene glycol, triethylene glycol and the like. Among these aliphatic diols, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A are preferable from the viewpoint of the antistatic property and the durability, and 1,4-cyclohexanedimethanol is more preferable. In addition, since it is preferable that aliphatic diol has hydrophobicity from the point of antistatic property and its persistence, use of the polyethyleneglycol which has hydrophilicity is unpreferable.
　芳香族基含有ジオールとしては、例えば、ビスフェノールＡ、１，２－ヒドロキシベンゼン、１，３－ヒドロキシベンゼン、１，４－ヒドロキシベンゼン、１，４－ベンゼンジメタノール、ビスフェノールＡのエチレンオキサイド付加物、ビスフェノールＡのプロピレンオキサイド付加物、１，４－ビス（２－ヒドロキシエトキシ）ベンゼン、レゾルシン、ピロカテコール等の単核２価フェノール化合物のポリヒドロキシエチル付加物等が挙げられる。これら芳香族基を有するジオールの中でも、ビスフェノールＡのエチレンオキサイド付加物、１，４－ビス（β－ヒドロキシエトキシ）ベンゼンが好ましい。芳香族ジオールは、帯電防止性とその持続性の点から、疎水性を有することが好ましい。 As the aromatic group-containing diol, for example, bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, ethylene oxide adduct of bisphenol A, Examples thereof include propylene oxide adducts of bisphenol A, 1,4-bis (2-hydroxyethoxy) benzene, resorcin, polyhydroxyethyl adducts of mononuclear dihydric phenol compounds such as pyrocatechol, and the like. Among the diols having these aromatic groups, ethylene oxide adduct of bisphenol A and 1,4-bis (β-hydroxyethoxy) benzene are preferable. The aromatic diol is preferably hydrophobic from the viewpoint of antistaticity and its durability.
　次に、ポリエステル（ａ）の構成成分であるジカルボン酸について説明する。本発明で用いられる脂肪族ジカルボン酸は、脂肪族ジカルボン酸の誘導体（例えば、酸無水物、アルキルエステル、アルカリ金属塩、酸ハライド等）であってもよい。脂肪族ジカルボン酸およびその誘導体は、２種以上の混合物でもよい。 Next, the dicarboxylic acid which is a component of polyester (a) is demonstrated. The aliphatic dicarboxylic acid used in the present invention may be a derivative of 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.
　脂肪族ジカルボン酸としては、好ましくは炭素原子数２～２０の脂肪族ジカルボン酸が挙げられ、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、１，１０－デカンジカルボン酸、１，４－シクロヘキサンジカルボン酸、ダイマー酸、マレイン酸、フマル酸等が挙げられる。これら脂肪族ジカルボン酸の中でも、帯電防止性とその持続性の点から、炭素原子数４～１６のジカルボン酸が好ましく、炭素原子数６～１２のジカルボン酸がより好ましい。 The aliphatic dicarboxylic acid preferably includes aliphatic dicarboxylic acids having 2 to 20 carbon atoms, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Examples thereof include sebacic acid, 1,10-decanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, maleic acid, fumaric acid and the like. Among these aliphatic dicarboxylic acids, dicarboxylic acids having 4 to 16 carbon atoms are preferable, and dicarboxylic acids having 6 to 12 carbon atoms are more preferable, from the viewpoint of the antistatic property and the durability.
　本発明で用いられる芳香族ジカルボン酸は、芳香族ジカルボン酸の誘導体（例えば、酸無水物、アルキルエステル、アルカリ金属塩、酸ハライド等）であってもよい。また、芳香族ジカルボン酸およびその誘導体は、２種以上の混合物でもよい。 The aromatic dicarboxylic acid used in the present invention may be a derivative of aromatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.). The aromatic dicarboxylic acid and its derivative may be a mixture of two or more.
　芳香族ジカルボン酸としては、好ましくは炭素原子数８～２０の芳香族ジカルボン酸が挙げられ、例えば、テレフタル酸、イソフタル酸、フタル酸、フェニルマロン酸、ホモフタル酸、フェニルコハク酸、β－フェニルグルタル酸、α－フェニルアジピン酸、β－フェニルアジピン酸、ビフェニル－２，２’－ジカルボン酸、ビフェニル－４，４’－ジカルボン酸、ナフタレンジカルボン酸、３－スルホイソフタル酸ナトリウムおよび３－スルホイソフタル酸カリウム等が挙げられる。これら芳香族ジカルボン酸の中でも、帯電防止性とその持続性の点から、テレフタル酸、イソフタル酸、フタル酸（無水フタル酸を含む）が好ましく、フタル酸（無水フタル酸を含む）がより好ましい。 The aromatic dicarboxylic acid preferably includes an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, and β-phenyl glutar acid. Acid, α-phenyl adipic acid, β-phenyl adipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalene dicarboxylic acid, sodium 3-sulfoisophthalic acid and 3-sulfoisophthalic acid Potassium and the like can be mentioned. Among these aromatic dicarboxylic acids, terephthalic acid, isophthalic acid and phthalic acid (including phthalic anhydride) are preferable, and phthalic acid (including phthalic anhydride) is more preferable, from the viewpoint of the antistatic property and the durability.
　次に、高分子化合物（Ｅ）のポリエーテルのブロック（Ｂ）について説明する。ポリエーテルのブロック（Ｂ）は、下記一般式（１）で示されるエチレンオキシ基を１以上有する両末端に水酸基を有する化合物（ｂ）から構成される。 Next, the block (B) of the polyether of the polymer compound (E) will be described. The polyether block (B) is composed of a compound (b) having a hydroxyl group at both ends having one or more ethyleneoxy groups represented by the following general formula (1).
Figure JPOXMLDOC01-appb-I000002
　上記一般式（１）で示されるエチレンオキシ基を１以上有し両末端に水酸基を有する化合物（ｂ）としては、親水性を有する化合物が好ましく、上記一般式（１）で示されるエチレンオキシ基を有するポリエーテルがより好ましく、帯電防止性とその持続性の点から、ポリエチレングリコールがさらにより好ましく、下記一般式（２）で表されるポリエチレングリコールが特に好ましい。
Figure JPOXMLDOC01-appb-I000002
As the compound (b) having one or more ethyleneoxy groups represented by the general formula (1) and having a hydroxyl group at both ends, a compound having hydrophilicity is preferable, and an ethyleneoxy group represented by the general formula (1) Are more preferred, and from the viewpoint of antistatic properties and durability, polyethylene glycol is even more preferred, and polyethylene glycol represented by the following general formula (2) is particularly preferred.
Figure JPOXMLDOC01-appb-I000003
　上記一般式（２）中、ｍは５～２５０の数を表す。ｍは、帯電防止性とその持続性の点から、２０～２００が好ましく、４０～１８０がより好ましい。
Figure JPOXMLDOC01-appb-I000003
In the above general formula (2), m represents a number of 5 to 250. m is preferably 20 to 200, and more preferably 40 to 180, in view of the antistatic property and its durability.
　化合物（ｂ）としては、エチレンオキサイドを付加反応させて得られるポリエチレングリコール以外に、エチレンオキサイドと、他のアルキレンオキサイド（例えば、プロピレンオキサイド、１，２－、１，４－、２，３－または１，３－ブチレンオキサイド等）の１種以上とを付加反応させたポリエーテルが挙げられ、このポリエーテルはランダムでもブロックでもいずれでもよい。 As the compound (b), ethylene oxide and other alkylene oxides (for example, propylene oxide, 1,2-, 1,4-, 2,3-, or) besides polyethylene glycol obtained by addition reaction of ethylene oxide The polyether which carried out the addition reaction with 1 or more types of 1, 3- butylene oxide etc. is mentioned, This polyether may be random and may be block or any.
　化合物（ｂ）の例をさらに挙げると、活性水素原子含有化合物にエチレンオキサイドが付加した構造の化合物や、エチレンオキサイドおよび他のアルキレンオキサイド（例えば、プロピレンオキサイド、１，２－、１，４－、２，３－または１，３－ブチレンオキサイド等）の１種以上が付加した構造の化合物が挙げられる。これらはランダム付加およびブロック付加のいずれでもよい。 Examples of the compound (b) further include a compound having a structure in which ethylene oxide is added to an active hydrogen atom-containing compound, ethylene oxide and other alkylene oxides (eg, propylene oxide, 1,2-, 1,4-, And compounds having a structure in which one or more of 2,3- or 1,3-butylene oxide etc. are added. These may be either random addition or block addition.
　活性水素原子含有化合物としては、グリコール、２価フェノール、１級モノアミン、２級ジアミンおよびジカルボン酸等が挙げられる。 Examples of the active hydrogen atom-containing compound include glycol, dihydric phenol, primary monoamine, secondary diamine and dicarboxylic acid.
　グリコールとしては、炭素原子数２～２０の脂肪族グリコール、炭素原子数５～１２の脂環式グリコールおよび炭素原子数８～２６の芳香族グリコール等が使用できる。 As the glycol, aliphatic glycols having 2 to 20 carbon atoms, alicyclic glycols having 5 to 12 carbon atoms, aromatic glycols having 8 to 26 carbon atoms, and the like can be used.
　脂肪族グリコールとしては、例えば、エチレングリコール、１，２－プロピレングリコール、１，３－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，３－ヘキサンジオール、１，４－ヘキサンジオール、１，６－ヘキサンジオール、２，５－ヘキサンジオール、１，２－オクタンジオール、１，８－オクタンジオール、１，１０－デカンジオール、１，１８－オクタデカンジオール、１，２０－エイコサンジオール、ジエチレングリコール、トリエチレングリコールおよびチオジエチレングリコール等が挙げられる。 Examples of aliphatic glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol Hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecane Diol, 1, 20-eicosanediol, diethylene glycol, triethylene glycol, thiodiethylene glycol and the like.
　脂環式グリコールとしては、例えば、１－ヒドロキシメチル－１－シクロブタノール、１，２－シクロヘキサンジオール、１，３－シクロヘキサンジオール、１，４－シクロヘキサンジオール、１－メチル－３，４－シクロヘキサンジオール、２－ヒドロキシメチルシクロヘキサノール、４－ヒドロキシメチルシクロヘキサノール、１，４－シクロヘキサンジメタノールおよび１，１’－ジヒドロキシ－１，１’－ジシクロヘキシル等が挙げられる。 Examples of alicyclic glycols include 1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1-methyl-3,4-cyclohexanediol And 2-hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol, 1,1'-dihydroxy-1,1'-dicyclohexyl and the like.
　芳香族グリコールとしては、例えば、ジヒドロキシメチルベンゼン、１，４－ビス（β－ヒドロキシエトキシ）ベンゼン、２－フェニル－１，３－プロパンジオール、２－フェニル－１，４－ブタンジオール、２－ベンジル－１，３－プロパンジオール、トリフェニルエチレングリコール、テトラフェニルエチレングリコールおよびベンゾピナコール等が挙げられる。 Examples of aromatic glycols include dihydroxymethylbenzene, 1,4-bis (β-hydroxyethoxy) benzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, 2-benzyl And 1,3-propanediol, triphenyl ethylene glycol, tetraphenyl ethylene glycol, benzopinacol and the like.
　２価フェノールとしては、炭素原子数６～３０のフェノールが使用でき、例えば、カテコール、レゾルシノール、１，４－ジヒドロキシベンゼン、ハイドロキノン、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ジヒドロキシジフェニルエーテル、ジヒドロキシジフェニルチオエーテル、ビナフトールおよびこれらのアルキル（炭素原子数１～１０）またはハロゲン置換体等が挙げられる。 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, dihydroxydiphenyl thioether, binaphthol And their alkyl (1 to 10 carbon atoms) or halogen substituents.
　１級モノアミンとしては、炭素原子数１～２０の脂肪族１級モノアミンが挙げられ、例えば、メチルアミン、エチルアミン、ｎ－プロピルアミン、イソプロピルアミン、ｎ－ブチルアミン、ｓ－ブチルアミン、イソブチルアミン、ｎ－アミルアミン、イソアミルアミン、ｎ－ヘキシルアミン、ｎ－ヘプチルアミン、ｎ－オクチルアミン、ｎ－デシルアミン、ｎ－オクタデシルアミンおよびｎ－イコシルアミン等が挙げられる。 Examples of primary monoamines include aliphatic primary monoamines having 1 to 20 carbon atoms, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, s-butylamine, isobutylamine, n- Amylamine, isoamylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-octadecylamine, n-icosylamine and the like.
　２級ジアミンとしては、炭素原子数４～１８の脂肪族２級ジアミン、炭素原子数４～１３の複素環式２級ジアミン、炭素原子数６～１４の脂環式２級ジアミン、炭素数８～１４の芳香族２級ジアミンおよび炭素原子数３～２２の２級アルカノールジアミン等が使用できる。 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 8 carbon atoms. Aromatic secondary diamines of ̃14 and secondary alkanoldiamines having 3 to 22 carbon atoms can be used.
　脂肪族２級ジアミンとしては、例えば、Ｎ，Ｎ’－ジメチルエチレンジアミン、Ｎ，Ｎ’－ジエチルエチレンジアミン、Ｎ，Ｎ’－ジブチルエチレンジアミン、Ｎ，Ｎ’－ジメチルプロピレンジアミン、Ｎ，Ｎ’－ジエチルプロピレンジアミン、Ｎ，Ｎ’－ジブチルプロピレンジアミン、Ｎ，Ｎ’－ジメチルテトラメチレンジアミン、Ｎ，Ｎ’－ジエチルテトラメチレンジアミン、Ｎ，Ｎ’－ジブチルテトラメチレンジアミン、Ｎ，Ｎ’－ジメチルヘキサメチレンジアミン、Ｎ，Ｎ’－ジエチルヘキサメチレンジアミン、Ｎ，Ｎ’－ジブチルヘキサメチレンジアミン、Ｎ，Ｎ’－ジメチルデカメチレンジアミン、Ｎ，Ｎ’－ジエチルデカメチレンジアミンおよびＮ，Ｎ’－ジブチルデカメチレンジアミン等が挙げられる。 Examples of aliphatic secondary diamines include N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine, N, N'-dibutylethylenediamine, N, N'-dimethylpropylenediamine, 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.
　複素環式２級ジアミンとしては、例えば、ピペラジン、１－アミノピペリジン等が挙げられる。 Examples of heterocyclic secondary diamines include piperazine, 1-aminopiperidine and the like.
　脂環式２級ジアミンとしては、例えば、Ｎ，Ｎ’－ジメチル－１，２－シクロブタンジアミン、Ｎ，Ｎ’－ジエチル－１，２－シクロブタンジアミン、Ｎ，Ｎ’－ジブチル－１，２－シクロブタンジアミン、Ｎ，Ｎ’－ジメチル－１，４－シクロヘキサンジアミン、Ｎ，Ｎ’－ジエチル－１，４－シクロヘキサンジアミン、Ｎ，Ｎ’－ジブチル－１，４－シクロヘキサンジアミン、Ｎ，Ｎ’－ジメチル－１，３－シクロヘキサンジアミン、Ｎ，Ｎ’－ジエチル－１，３－シクロヘキサンジアミン、Ｎ，Ｎ’－ジブチル－１，３－シクロヘキサンジアミン等が挙げられる。 Examples of alicyclic secondary diamines 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'- Dimethyl-1,3-cyclohexanediamine, N, N'-diethyl-1,3-cyclohexanediamine, N, N'-dibutyl-1,3-cyclohexanediamine and the like can be mentioned.
　芳香族２級ジアミンとしては、例えば、Ｎ，Ｎ’－ジメチル－フェニレンジアミン、Ｎ，Ｎ’－ジメチル－キシリレンジアミン、Ｎ，Ｎ’－ジメチル－ジフェニルメタンジアミン、Ｎ，Ｎ’－ジメチル－ジフェニルエーテルジアミン、Ｎ，Ｎ’－ジメチル－ベンジジンおよびＮ，Ｎ’－ジメチル－１，４－ナフタレンジアミン等が挙げられる。 Examples of aromatic secondary diamines include N, N'-dimethyl-phenylenediamine, N, N'-dimethyl-xylylenediamine, N, N'-dimethyl-diphenylmethanediamine, N, N'-dimethyl-diphenyletherdiamine And N, N'-dimethyl-benzidine and N, N'-dimethyl-1,4-naphthalenediamine.
　２級アルカノールジアミンとしては、例えば、Ｎ－メチルジエタノールアミン、Ｎ－オクチルジエタノールアミン、Ｎ－ステアリルジエタノールアミンおよびＮ－メチルジプロパノールアミン等が挙げられる。 Examples of secondary alkanoldiamines include N-methyldiethanolamine, N-octyldiethanolamine, N-stearyldiethanolamine and N-methyldipropanolamine.
　ジカルボン酸としては、炭素数２～２０のジカルボン酸が使用でき、例えば、脂肪族ジカルボン酸、芳香族ジカルボン酸および脂環式ジカルボン酸等が用いられる。 As the dicarboxylic acid, dicarboxylic acids having 2 to 20 carbon atoms can be used, and for example, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids can be used.
　脂肪族ジカルボン酸としては、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、メチルコハク酸、ジメチルマロン酸、β－メチルグルタル酸、エチルコハク酸、イソプロピルマロン酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカンジ酸、ドデカンジ酸、トリデカンジ酸、テトラデカンジ酸、ヘキサデカンジ酸、オクタデカンジ酸およびイコサンジ酸が挙げられる。 Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid, β-methylglutaric acid, ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid and icosandioic acid.
　芳香族ジカルボン酸としては、例えば、テレフタル酸、イソフタル酸、フタル酸、フェニルマロン酸、ホモフタル酸、フェニルコハク酸、β－フェニルグルタル酸、α－フェニルアジピン酸、β－フェニルアジピン酸、ビフェニル－２，２’－ジカルボン酸、ビフェニル－４，４’－ジカルボン酸、ナフタレンジカルボン酸、３－スルホイソフタル酸ナトリウムおよび３－スルホイソフタル酸カリウム等が挙げられる。 Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2 , 2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate and potassium 3-sulfoisophthalate.
　脂環式ジカルボン酸としては、例えば、１，３－シクロペンタンジカルボン酸、１，２－シクロペンタンジカルボン酸、１，４－シクロヘキサンジカルボン酸、１，２－シクロヘキサンジカルボン酸、１，３－シクロヘキサンジカルボン酸、１，４－シクロヘキサンジ酢酸、１，３－シクロヘキサンジ酢酸、１，２－シクロヘキサンジ酢酸およびジシクロヘキシル－４、４’－ジカルボン酸等が挙げられる。 As an alicyclic dicarboxylic acid, for example, 1,3-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarbon Examples thereof include acids, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid and dicyclohexyl-4,4'-dicarboxylic acid.
　これらの活性水素原子含有化合物は、１種でも２種以上の混合物でも使用することができる。 These active hydrogen atom-containing compounds may be used alone or in combination of two or more.
　次に、高分子化合物（Ｅ）を構成するポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）について説明する。ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）は、ポリアルキレングリコールの両末端の水酸基をグリシジルエーテル化した化合物である。 Next, the polyalkylene glycol diglycidyl ether compound (D) which comprises a high molecular compound (E) is demonstrated. The polyalkylene glycol diglycidyl ether compound (D) is a compound obtained by glycidyl etherifying hydroxyl groups at both ends of the polyalkylene glycol.
　ここでポリアルキレングリコールとは、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール等が挙げられ、例えば、エチレンオキサイドを付加反応させて得られるポリエチレングリコール、プロピレンオキサイドを付加反応させて得られるポリプロピレングリコール、ブチレンオキサイドを付加反応させて得られるポリブチレングリコール以外に、２種以上のアルキレンオキサイド（例えば、エチレンオキサイド、プロピレンオキサイド、１，２－、１，４－、２，３－または１，３－ブチレンオキサイド等）を付加反応させたものも含まれる（これらはランダムでもブロックでもいずれでもよい。）。また、アルキレンオキサイドの付加反応以外で得られるポリアルキレングリコールも含まれる。 Examples of polyalkylene glycols include polyethylene glycol, polypropylene glycol, polybutylene glycol, etc. For example, polyethylene glycol obtained by addition reaction of ethylene oxide, polypropylene glycol obtained by addition reaction of propylene oxide, butylene oxide In addition to polybutylene glycol obtained by addition reaction of two or more alkylene oxides (eg, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide etc.) And those obtained by the addition reaction of these are also included (these may be either random or block). In addition, polyalkylene glycols obtained other than the addition reaction of alkylene oxide are also included.
　また、本発明においては、ポリアルキレングリコールは、エチレンオキシ基、プロピレンオキシ基、ブチレンオキシ基等のアルキレンオキシ基を一つ以上有していればよく、これらの両末端の水酸基をグリシジルエーテル化したものは化合物（Ｄ）に含まれる。 In the present invention, the polyalkylene glycol may have one or more alkyleneoxy groups such as ethyleneoxy group, propyleneoxy group, butyleneoxy group etc. Those are included in the compound (D).
　ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）を具体的に挙げると、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ジプロピレングリコールグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ポリブチレングリコールジグリシジルエーテル等が挙げられる。かかるポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）は、２種以上を使用してもよい。これらの中でも、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）は、帯電防止性とその持続性の点から、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテルが好ましい。 Specific examples of the polyalkylene glycol diglycidyl ether compound (D) include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol Glycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutylene glycol diglycidyl ether, etc. may be mentioned. Two or more such polyalkylene glycol diglycidyl ether compounds (D) may be used. Among these, as the polyalkylene glycol diglycidyl ether compound (D), polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are preferable from the viewpoint of the antistatic property and the durability.
　また、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）のエポキシ当量は、帯電防止性とその持続性の点から、７０～２，０００が好ましく、１４０～１，０００がより好ましく、１８０～６００が特により好ましい。 Further, the epoxy equivalent of the polyalkylene glycol diglycidyl ether compound (D) is preferably 70 to 2,000, more preferably 140 to 1,000, and particularly preferably 180 to 600, from the viewpoint of the antistatic property and its durability. More preferable.
　高分子化合物（Ｅ）は、ポリエステル（ａ）の末端に有する水酸基またはカルボキシル基と、化合物（ｂ）の末端に有する水酸基と、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）のエポキシ基とにより形成されたエステル結合により、ポリエステルのブロック（Ａ）、ポリエーテルのブロック（Ｂ）、エポキシ基が反応したポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）が、エステル結合またはエーテル結合を介して結合してなる構造を有する。 The polymer compound (E) is formed of a hydroxyl group or carboxyl group at the end of the polyester (a), a hydroxyl group at the end of the compound (b), and an epoxy group of the polyalkylene glycol diglycidyl ether compound (D) Structure in which the polyester block (A), the polyether block (B), and the polyalkylene glycol diglycidyl ether compound (D) in which the epoxy group is reacted are linked via an ester bond or an ether bond by the ester bond Have.
　さらに、高分子化合物（Ｅ）は、帯電防止性とその持続性の点から、ポリエステル（ａ）から構成されるポリエステルのブロック（Ａ）および化合物（ｂ）から構成されるポリエーテルのブロック（Ｂ）がエステル結合を介して繰り返し交互に結合してなる両末端にカルボキシル基を有するブロックポリマー（Ｃ）と、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）とが、ブロックポリマー（Ｃ）のカルボキシル基とポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）のエポキシ基により形成されたエステル結合を介して結合してなる構造を有することが好ましい。 Further, the polymer compound (E) is a block of a polyester (A) composed of a polyester (a) and a block of a polyether (B) composed of a compound (b) from the viewpoint of antistaticity and its durability. Block polymer (C) having a carboxyl group at both ends formed by repeating and alternately bonding via an ester bond, and a polyalkylene glycol diglycidyl ether compound (D), and the carboxyl group of the block polymer (C) It is preferable to have a structure formed by bonding via an ester bond formed by the epoxy group of the polyalkylene glycol diglycidyl ether compound (D).
　本発明に係るポリエステルのブロック（Ａ）を構成するポリエステル（ａ）は、ジオール、脂肪族ジカルボン酸および芳香族ジカルボン酸からなるものであればよく、帯電防止性とその持続性の点から、好ましくは、ジオールの水酸基を除いた残基と、脂肪族ジカルボン酸のカルボキシル基を除いた残基とが、エステル結合を介して結合する構造を有し、かつ、ジオールの水酸基を除いた残基と、芳香族ジカルボン酸のカルボキシル基を除いた残基とが、エステル結合を介して結合する構造を有する。 The polyester (a) constituting the block (A) of the polyester according to the present invention may be any one comprising a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and is preferably from the viewpoint of antistatic properties and its durability. Has a structure in which a residue other than the hydroxyl group of the diol and a residue other than the carboxyl group of the aliphatic dicarboxylic acid are linked via an ester bond, and a residue other than the hydroxyl group of the diol And the residue except the carboxyl group of aromatic dicarboxylic acid has a structure couple | bonded via an ester bond.
　また、ポリエステル（ａ）は、帯電防止性とその持続性の点から両末端にカルボキシル基を有する構造のものが好ましい。さらに、ポリエステル（ａ）の重合度は、帯電防止性とその持続性の点から好適には２～５０の範囲である。 The polyester (a) is preferably one having a carboxyl group at both ends from the viewpoint of the antistatic property and its durability. Furthermore, the degree of polymerization of the polyester (a) is preferably in the range of 2 to 50 from the viewpoint of the antistatic property and its durability.
　両末端にカルボキシル基を有するポリエステル（ａ）は、例えば、上記脂肪族ジカルボン酸および上記芳香族ジカルボン酸と、上記ジオールとを重縮合反応させることにより得ることができる。 The polyester (a) having a carboxyl group 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.
　脂肪族ジカルボン酸は、脂肪族ジカルボン酸の誘導体（例えば、酸無水物、アルキルエステル、アルカリ金属塩、酸ハライド等）であってもよく、誘導体を使用してポリエステル（ａ）を得た場合は、最終的に両末端を処理してカルボキシル基にすればよく、そのままの状態で、次の、両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）を得るための反応に進んでもよい。また、脂肪族ジカルボン酸およびその誘導体は、２種以上の混合物であってもよい。 The aliphatic dicarboxylic acid may be a derivative of aliphatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.), and when the derivative is used to obtain polyester (a), Finally, both ends may be treated to form carboxyl groups, and in the state as such, the reaction may be advanced to obtain a block polymer (C) having a structure having carboxyl groups at both ends. The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more.
　芳香族ジカルボン酸は、芳香族ジカルボン酸の誘導体（例えば、酸無水物、アルキルエステル、アルカリ金属塩、酸ハライド等）であってもよく、誘導体を使用してポリエステルを得た場合は、最終的に両末端を処理してカルボキシル基にすればよく、そのままの状態で、次の、両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）を得るための反応に進んでもよい。また、芳香族ジカルボン酸およびその誘導体は、２種以上の混合物であってもよい。 The aromatic dicarboxylic acid may be a derivative of aromatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.), and if derivative is used to obtain polyester, the final Both ends may be treated to form a carboxyl group, and in the state as it is, the reaction may proceed to the next reaction for obtaining a block polymer (C) having a structure having a carboxyl group at both ends. Also, the aromatic dicarboxylic acid and its derivative may be a mixture of two or more.
　ポリエステル（ａ）中の、脂肪族ジカルボン酸のカルボキシル基を除いた残基と、芳香族ジカルボン酸のカルボキシル基を除いた残基との比は、帯電防止性とその持続性の点からモル比で９０：１０～９９．９：０．１が好ましく、９３：７～９９．９：０．１がより好ましい。 The ratio of the residue of the aliphatic dicarboxylic acid other than the carboxyl group in the polyester (a) to the residue other than the carboxyl group of the aromatic dicarboxylic acid is a molar ratio in terms of antistaticity and its durability. 90:10 to 99.9: 0.1 is preferable, and 93: 7 to 99.9: 0.1 is more preferable.
　両末端にカルボキシル基を有するポリエステル（ａ）は、例えば、上記脂肪族ジカルボン酸またはその誘導体および上記芳香族ジカルボン酸またはその誘導体と、上記ジオールとを重縮合反応させることにより得ることができる。 The polyester (a) having a carboxyl group at both ends can be obtained, for example, by subjecting the above-mentioned aliphatic dicarboxylic acid or its derivative and the above-mentioned aromatic dicarboxylic acid or its derivative to a polycondensation reaction with the above-mentioned diol.
　脂肪族ジカルボン酸またはその誘導体および芳香族ジカルボン酸またはその誘導体と、ジオールとの反応比は、両末端がカルボキシル基となるように、脂肪族ジカルボン酸またはその誘導体および芳香族ジカルボン酸またはその誘導体を過剰に使用することが好ましく、モル比で、ジオールに対して１モル過剰に使用することが好ましい。 The reaction ratio of aliphatic dicarboxylic acid or derivative thereof and aromatic dicarboxylic acid or derivative thereof with diol is such that aliphatic dicarboxylic acid or derivative thereof and aromatic dicarboxylic acid or derivative thereof are obtained such that both ends are carboxyl groups. It is preferable to use an excess, and it is preferable to use in a molar ratio of 1 molar excess to the diol.
　重縮合反応時の脂肪族ジカルボン酸またはその誘導体と芳香族ジカルボン酸またはその誘導体との配合比は、モル比で９０：１０～９９．９：０．１が好ましく、９３：７～９９．９：０．１がより好ましい。 The compounding ratio of the aliphatic dicarboxylic acid or derivative thereof to the aromatic dicarboxylic acid or derivative thereof during the polycondensation reaction is preferably 90:10 to 99.9: 0.1 in molar ratio, and 93: 7 to 99.9. 0.1 is more preferable.
　また、配合比や反応条件によっては、ジオールおよび脂肪族ジカルボン酸のみから構成されるポリエステルや、ジオールおよび芳香族ジカルボン酸からのみ構成されるポリエステルが生成する場合もあるが、本発明では、ポリエステル（ａ）に、それらが混入していてもよく、そのままそれらを化合物（ｂ）と反応させて、ブロックポリマー（Ｃ）を得てもよい。 Also, depending on the compounding ratio and reaction conditions, a polyester composed of only diol and aliphatic dicarboxylic acid, or a polyester composed only of diol and aromatic dicarboxylic acid may be produced. They may be mixed in a), and they may be reacted with compound (b) to obtain block polymer (C).
　重縮合反応には、エステル化反応を促進する触媒を使用してもよく、触媒としては、ジブチル錫オキサイド、テトラアルキルチタネート、酢酸ジルコニウム、酢酸亜鉛等、従来公知のものが使用できる。 For the polycondensation reaction, a catalyst that promotes the esterification reaction may be used, and as the catalyst, conventionally known ones such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, zinc acetate and the like can be used.
　また、脂肪族ジカルボン酸および芳香族ジカルボン酸は、ジカルボン酸の代わりに、カルボン酸エステル、カルボン酸金属塩、カルボン酸ハライド等の誘導体を使用した場合には、それらとジオールとの反応後に、両末端を処理してジカルボン酸としてもよく、そのままの状態で、次の、両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）を得るための反応に進んでもよい。 In addition, when aliphatic dicarboxylic acid and aromatic dicarboxylic acid are used in place of dicarboxylic acid, when a derivative such as carboxylic acid ester, carboxylic acid metal salt or carboxylic acid halide is used, both are reacted with the diol after reaction. The ends may be treated as dicarboxylic acids, and in the state as such, the reaction may proceed to the next reaction for obtaining a block polymer (C) having a structure having carboxyl groups at both ends.
　ジオールと、脂肪族ジカルボン酸および芳香族ジカルボン酸からなり両末端にカルボキシル基を有する好適なポリエステル（ａ）は、化合物（ｂ）と反応することでエステル結合を形成し、ブロックポリマー（Ｃ）の構造を形成するものであればよく、両末端のカルボキシル基は、保護されていてもよく、修飾されていてもよく、また、前駆体の形であってもよい。また、反応時に生成物の酸化を抑えるために、反応系にフェノール系酸化防止剤等の酸化防止剤を添加してもよい。 A suitable polyester (a) consisting of 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 compound (b) to form a block polymer (C). The carboxyl groups at both ends may be protected as long as they form a structure, may be protected, or may be in the form of a precursor. Moreover, in order to suppress the oxidation of a product at the time of reaction, an antioxidant such as a phenolic antioxidant may be added to the reaction system.
　エチレンオキシ基を有し両末端に水酸基を有する化合物（ｂ）は、ポリエステル（ａ）と反応することでエステル結合を形成し、ブロックポリマー（Ｃ）の構造を形成するものであればよく、両末端の水酸基は、保護されていてもよく、修飾されていてもよく、また、前駆体の形であってもよい。 The compound (b) having an ethyleneoxy group and having a hydroxyl group at both ends may form an ester bond by reacting with the polyester (a) to form the structure of the block polymer (C), both The terminal hydroxyl group may be protected, modified or in the form of a precursor.
　本発明に係る両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）は、上記ポリエステル（ａ）から構成されたブロック（Ａ）と、上記化合物（ｂ）から構成されたブロック（Ｂ）とを有し、これらのブロックが、カルボキシル基と水酸基とにより形成されたエステル結合を介して繰り返し交互に結合してなる構造を有する。かかるブロックポリマー（Ｃ）の一例を挙げると、例えば、下記一般式（３）で表される構造を有するものが挙げられる。 The block polymer (C) having a structure having a carboxyl group at both ends according to the present invention comprises a block (A) composed of the above polyester (a) and a block (B) composed of the above compound (b) And has a structure in which these blocks are repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group. If an example of this block polymer (C) is given, what has a structure represented by following General formula (3) will be mentioned, for example.
Figure JPOXMLDOC01-appb-I000004
　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、帯電防止性とその持続性の点から好ましくは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。
Figure JPOXMLDOC01-appb-I000004
In the above general formula (3), (A) represents a block composed of a polyester (a) having a carboxyl group at the both ends, and (B) represents a compound (b) having a hydroxyl group at the both ends It represents a constructed block, and t is the number of repeating units, preferably 1 to 10 in terms of antistaticity and durability. t is more preferably a number of 1 to 7, and most preferably a number of 1 to 5.
　ブロックポリマー（Ｃ）中の、ポリエステル（ａ）から構成されたブロックの一部は、ジオールおよび脂肪族ジカルボン酸のみから構成されたポリエステルからなるブロック、または、ジオールおよび芳香族ジカルボン酸のみから構成されたポリエステルからなるブロックに置き換えられていてもよい。 In the block polymer (C), part of the block composed of the polyester (a) is a block 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 by a block of polyester.
　両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）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）と、上記両末端に水酸基を有する化合物（ｂ）とを、重縮合反応させることによって得ることができるが、上記ポリエステル（ａ）と上記化合物（ｂ）とが、カルボキシル基と水酸基とにより形成されたエステル結合を介して繰り返し交互に結合してなる構造を有するものと同等の構造を有するものであれば、必ずしも上記ポリエステル（ａ）と上記化合物（ｂ）とから合成する必要はない。 The block polymer (C) having a structure having a carboxyl group at both ends is obtained by subjecting the polyester (a) having a carboxyl group at both ends to a polycondensation reaction with the compound (b) having a hydroxyl group at both ends. However, the structure is equivalent to one having a structure in which the polyester (a) and the compound (b) are repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group. It is not necessary to synthesize from the above-mentioned polyester (a) and the above-mentioned compound (b) as long as it has the
　上記ポリエステル（ａ）と上記化合物（ｂ）との反応比は、上記化合物（ｂ）がＸモルに対して、上記ポリエステル（ａ）がＸ＋１モルとなるように調整すれば、両末端にカルボキシル基を有するブロックポリマー（Ｃ）を好ましく得ることができる。 When the reaction ratio of the polyester (a) to the compound (b) is adjusted such that the polyester (a) is X + 1 mol with respect to X mol of the compound (b), carboxyl groups at both ends are obtained. Preferably, the block polymer (C) having
　反応に際しては、上記ポリエステル（ａ）の合成反応の完結後に、上記ポリエステル（ａ）を単離せずに、上記化合物（ｂ）を反応系に加えて、そのまま反応させてもよい。 In the reaction, after completion of the synthesis reaction of the polyester (a), the compound (b) may be added to the reaction system without isolating the polyester (a), and the reaction may be carried out as it is.
　重縮合反応には、エステル化反応を促進する触媒を使用してもよく、触媒としては、ジブチル錫オキサイド、テトラアルキルチタネート、酢酸ジルコニウム、酢酸亜鉛等、従来公知のものが使用できる。また、反応時に生成物の酸化を抑えるために、反応系にフェノール系酸化防止剤等の酸化防止剤を添加してもよい。 For the polycondensation reaction, a catalyst that promotes the esterification reaction may be used, and as the catalyst, conventionally known ones such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, zinc acetate and the like can be used. Moreover, in order to suppress the oxidation of a product at the time of reaction, an antioxidant such as a phenolic antioxidant may be added to the reaction system.
　また、ポリエステル（ａ）には、ジオールおよび脂肪族ジカルボン酸のみから構成されるポリエステルや、ジオールおよび芳香族ジカルボン酸からのみ構成されるポリエステルが混入していてもよく、それらをそのまま化合物（ｂ）と反応させ、ブロックポリマー（Ｃ）を得てもよい。 Further, 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, and these may be directly used as a compound (b) And the block polymer (C).
　ブロックポリマー（Ｃ）は、ポリエステル（ａ）から構成されるブロック（Ａ）と化合物（ｂ）から構成されるブロック（Ｂ）以外に、ジオールと脂肪族ジカルボン酸のみから構成されるポリエステルから構成されるブロックや、ジオールと芳香族ジカルボン酸からのみ構成されるポリエステルから構成されるブロックが構造中に含まれていてもよい。 The block polymer (C) is composed of a polyester composed only of a diol and an aliphatic dicarboxylic acid, in addition to a block (A) composed of a polyester (a) and a block (B) composed of a compound (b) Or a block composed of a polyester composed only of a diol and an aromatic dicarboxylic acid may be included in the structure.
　本発明に係る高分子化合物（Ｅ）は、好ましくは、両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）と、ポリアルキレングリコールグリシジルエーテル化合物（Ｄ）とが、ブロックポリマー（Ｃ）の末端のカルボキシル基とポリアルキレングリコールグリシジルエーテル化合物（Ｄ）のエポキシ基とにより形成されたエステル結合を介して結合してなる構造を有する。また、かかる高分子化合物（Ｅ）は、さらに、上記ポリエステル（ａ）のカルボキシル基と上記ポリアルキレングリコールグリシジルエーテル化合物（Ｄ）のエポキシ基とにより形成されたエステル結合を含んでいてもよい。また、かかる高分子化合物（Ｅ）は、さらに、上記ポリエステル（ａ）の水酸基または上記化合物（ｂ）の水酸基と、上記ポリアルキレングリコールグリシジルエーテル化合物（Ｄ）のエポキシ基とにより形成されたエーテル結合を含んでいてもよい。 In the polymer compound (E) according to the present invention, preferably, a block polymer (C) having a structure having a carboxyl group at both ends and a polyalkylene glycol glycidyl ether compound (D) are block polymers (C) It has a structure formed by bonding via an ester bond formed by the terminal carboxyl group and the epoxy group of the polyalkylene glycol glycidyl ether compound (D). The polymer compound (E) may further contain an ester bond formed by the carboxyl group of the polyester (a) and the epoxy group of the polyalkylene glycol glycidyl ether compound (D). Further, the polymer compound (E) further includes an ether bond formed by the hydroxyl group of the polyester (a) or the hydroxyl group of the compound (b) and the epoxy group of the polyalkylene glycol glycidyl ether compound (D). May be included.
　高分子化合物（Ｅ）を得るためには、上記ブロックポリマー（Ｃ）のカルボキシル基と、上記ポリアルキレングリコールグリシジルエーテル化合物（Ｄ）のエポキシ基とを反応させればよい。ポリアルキレングリコールグリシジルエーテル化合物（Ｄ）のエポキシ基の数は、反応させるブロックポリマー（Ｃ）のカルボキシル基の数の、０．５～５当量が好ましく、０．５～１．５当量がより好ましい。また、上記反応は、各種溶媒中で行ってもよく、溶融状態で行ってもよい。 In order to obtain the polymer compound (E), the carboxyl group of the block polymer (C) and the epoxy group of the polyalkylene glycol glycidyl ether compound (D) may be reacted. The number of epoxy groups of the polyalkylene glycol glycidyl ether compound (D) is preferably 0.5 to 5 equivalents of the number of carboxyl groups of the block polymer (C) to be reacted, and more preferably 0.5 to 1.5 equivalents. . The above reaction may be carried out in various solvents or in a molten state.
　反応させるポリアルキレングリコールグリシジルエーテル化合物（Ｄ）は、反応させるブロックポリマー（Ｃ）のカルボキシル基の数の、０．１～２．０当量が好ましく、０．２～１．５当量がより好ましい。 The amount of the polyalkylene glycol glycidyl ether compound (D) to be reacted is preferably 0.1 to 2.0 equivalents, and more preferably 0.2 to 1.5 equivalents of the number of carboxyl groups of the block polymer (C) to be reacted.
　反応に際しては、上記ブロックポリマー（Ｃ）の合成反応の完結後に、ブロックポリマー（Ｃ）を単離せずに、反応系にポリアルキレングリコールグリシジルエーテル化合物（Ｄ）を加えて、そのまま反応させてもよい。その場合、ブロックポリマー（Ｃ）を合成するときに過剰に使用した未反応のポリエステル（Ａ）のカルボキシル基と、ポリアルキレングリコールグリシジルエーテル化合物（Ｄ）の一部のエポキシ基とが反応して、エステル結合を形成してもよい。 In the reaction, after completion of the synthesis reaction of the block polymer (C), the polyalkylene glycol glycidyl ether compound (D) may be added to the reaction system without isolating the block polymer (C), and the reaction may be carried out as it is . In that case, the carboxyl group of the unreacted polyester (A) used in excess when synthesizing the block polymer (C) reacts with a part of epoxy groups of the polyalkylene glycol glycidyl ether compound (D), It may form an ester bond.
　本発明の好ましい高分子化合物（Ｅ）は、両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）とポリアルキレングリコールグリシジルエーテル化合物（Ｄ）とが、それぞれのカルボキシル基とエポキシ基とにより形成されたエステル結合を介して結合した構造を有するものと同等の構造を有するものであれば、必ずしも上記ブロックポリマー（Ｃ）と上記ポリアルキレングリコールグリシジルエーテル化合物（Ｄ）とから合成する必要はない。 In the preferred polymer compound (E) of the present invention, a block polymer (C) having a structure having a carboxyl group at both ends and a polyalkylene glycol glycidyl ether compound (D) are formed by the respective carboxyl group and epoxy group It is not necessary to synthesize from the block polymer (C) and the polyalkylene glycol glycidyl ether compound (D), as long as it has a structure equivalent to one having a structure bonded via an ester bond.
　本発明において、高分子化合物（Ｅ）における、両末端に水酸基を有する化合物（ｂ）から構成されるブロックの数平均分子量は、水酸基価の測定値から算出し、帯電防止性とその持続性の点から好ましくは４００～１０，０００であり、より好ましくは１，０００～８，０００であり、さらに好ましくは２，０００～８，０００である。 In the present invention, the number average molecular weight of the block composed of the compound (b) having a hydroxyl group at both ends in the polymer compound (E) is calculated from the measured value of the hydroxyl value, and the antistatic property and its persistence From the point of view, it is preferably 400 to 10,000, more preferably 1,000 to 8,000, and still more preferably 2,000 to 8,000.
　また、本発明において、高分子化合物（Ｅ）における、ポリエステル（ａ）から構成されるブロックの数平均分子量は、帯電防止性とその持続性の点から好ましくはポリスチレン換算で８００～８，０００であり、より好ましくは１，０００～６，０００であり、さらに好ましくは２，０００～４，０００である。 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 in terms of polystyrene in terms of antistatic property and its durability. More preferably, it is 1,000 to 6,000, and more preferably 2,000 to 4,000.
　さらに、高分子化合物（Ｅ）における、両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）から構成されるブロックの数平均分子量は、好ましくはポリスチレン換算で５，０００～３０，０００であり、より好ましくは７，０００～２０，０００であり、より好ましくは９，０００～１７，０００である。 Furthermore, in the polymer compound (E), the number average molecular weight of the block composed of the block polymer (C) having a structure having a carboxyl group at both ends is preferably 5,000 to 30,000 in terms of polystyrene More preferably, it is 7,000 to 20,000, and more preferably 9,000 to 17,000.
　また、本発明の高分子化合物（Ｅ）は、ジオール、脂肪族ジカルボン酸および芳香族ジカルボン酸からポリエステル（ａ）を得たのち、ポリエステル（ａ）を単離せずに、化合物（ｂ）および／またはポリアルキレングリコールグリシジルエーテル化合物（Ｄ）と反応させてもよい。 In addition, the polymer compound (E) of the present invention is a compound (b) and / or a compound (b) after the polyester (a) is not isolated after obtaining the polyester (a) from a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid. Alternatively, it may be reacted with a polyalkylene glycol glycidyl ether compound (D).
　本発明の高分子化合物（Ｅ）は、さらに、アルカリ金属の塩および第２族元素の塩からなる群から選択される１種以上を配合することにより、優れた帯電防止性能とその持続性を有する組成物となり好ましい。 The polymer compound (E) of the present invention further comprises one or more selected from the group consisting of salts of alkali metals and salts of Group 2 elements to provide excellent antistatic performance and durability. It becomes a composition which it has and is preferable.
　アルカリ金属の塩および第２族元素の塩としては、有機酸または無機酸の塩が挙げられ、アルカリ金属の例としては、リチウム、ナトリウム、カリウム、セシウム、ルビジウム等が挙げられ、第２族元素の例としては、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム等が挙げられ、有機酸の例としては、ギ酸、酢酸、プロピオン酸、酪酸、乳酸等の炭素原子数１～１８の脂肪族モノカルボン酸；シュウ酸、マロン酸、コハク酸、フマル酸、マレイン酸、アジピン酸等の炭素原子数１～１２の脂肪族ジカルボン酸；安息香酸、フタル酸、イソフタル酸、テレフタル酸、サリチル酸等の芳香族カルボン酸；メタンスルホン酸、ｐ－トルエンスルホン酸、ドデシルベンゼンスルホン酸、トリフルオロメタンスルホン酸等の炭素原子数１～２０のスルホン酸等が挙げられ、無機酸の例としては、塩酸、臭化水素酸、硫酸、亜硫酸、リン酸、亜リン酸、ポリリン酸、硝酸、過塩素酸等が挙げられる。中でも、帯電防止性とその持続性、生体や環境に対する安全性の点から、アルカリ金属の塩が好ましく、リチウム、ナトリウム、カリウムがより好ましく、ナトリウムが最も好ましい。また、帯電防止性とその持続性の点から、酢酸の塩、過塩素酸の塩、ｐ－トルエンスルホン酸の塩、ドデシルベンゼンスルホン酸の塩が好ましく、ドデシルベンゼンスルホン酸の塩がより好ましい。 Examples of the salts of alkali metals and salts of Group 2 elements include salts of organic acids or inorganic acids, and examples of alkali metals include lithium, sodium, potassium, cesium, rubidium and the like, and Group 2 elements Examples of the organic acid include beryllium, magnesium, calcium, strontium, barium and the like, and examples of the organic acid include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid and lactic acid Aliphatic dicarboxylic acids having 1 to 12 carbon atoms such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid and adipic acid; and aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid and salicylic acid Charcoal such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, etc. 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 them, alkali metal salts are preferable, lithium, sodium and potassium are more preferable, and sodium is most preferable, from the viewpoint of the antistatic property and the durability, the safety to the living body and the environment. Further, from the viewpoint of the antistatic property and its durability, salts of acetic acid, salts of perchloric acid, salts of p-toluenesulfonic acid and salts of dodecylbenzenesulfonic acid are preferable, and salts of dodecylbenzenesulfonic acid are more preferable.
　アルカリ金属の塩および第２族元素の塩の具体例としては、例えば、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、塩化リチウム、塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化カルシウム、リン酸リチウム、リン酸ナトリウム、リン酸カリウム、硫酸リチウム、硫酸ナトリウム、硫酸マグネシウム、硫酸カルシウム、過塩素酸リチウム、過塩素酸ナトリウム、過塩素酸カリウム、ｐ－トルエンスルホン酸リチウム、ｐ－トルエンスルホン酸ナトリウム、ｐ－トルエンスルホン酸カリウム、ドデシルベンゼンスルホン酸リチウム、ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸カリウム等が挙げられる。これらの中で帯電防止性とその持続性、生体や環境に対する安全性の点から、好ましいのは、ｐ－トルエンスルホン酸リチウム、ｐ－トルエンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸リチウム、ドデシルベンゼンスルホン酸ナトリウム等であり、最も好ましいのはドデシルベンゼンスルホン酸ナトリウムである。 Specific examples of the salts of alkali metals and salts of group 2 elements include, for example, lithium acetate, sodium acetate, potassium acetate, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium phosphate, sodium phosphate , Potassium phosphate, lithium sulfate, sodium sulfate, magnesium sulfate, calcium sulfate, lithium perchlorate, sodium perchlorate, potassium perchlorate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, p-toluenesulfone Acid potassium, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate and the like. Among them, lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, and dodecylbenzenesulfonic acid are preferred from the viewpoints of antistatic properties and their durability, and safety to the living body and the environment. Sodium and the like, most preferred is sodium dodecylbenzene sulfonate.
　アルカリ金属の塩および第２族元素の塩からなる群から選択される１種以上は、本発明の高分子化合物（Ｅ）に配合してもよいし、高分子化合物（Ｅ）とともに熱可塑性樹脂に配合して使用してもよい。アルカリ金属の塩および第２族元素の塩からなる群から選択される１種以上の配合量は、高分子化合物（Ｅ）の１００質量部に対して、０．０１～２０質量部が好ましく、０．１～１５質量部がより好ましく、３．０～１２質量部が最も好ましい。 One or more selected from the group consisting of a salt of an alkali metal and a salt of a group 2 element may be added to the polymer compound (E) of the present invention, or together with the polymer compound (E), a thermoplastic resin You may mix and use for. The amount of one or more selected from the group consisting of a salt of an alkali metal and a salt of a group 2 element is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the polymer compound (E), The amount is more preferably 0.1 to 15 parts by mass, and most preferably 3.0 to 12 parts by mass.
　本発明の組成物を得るためには、必須成分の高分子化合物（Ｅ）および、アルカリ金属の塩および第２族元素の塩からなる群から選択される１種以上を、必要に応じて他の任意成分を混合すればよく、混合には各種混合機を用いることができる。混合時には加熱してもよい。使用できる混合機の例を挙げると、タンブラーミキサー、ヘンシェルミキサー、リボンブレンダー、Ｖ型混合機、Ｗ型混合機、スーパーミキサー、ナウターミキサー等が挙げられる。また、高分子化合物（Ｅ）の合成反応中に、反応系にアルカリ金属の塩および第２族元素の塩からなる群から選択される１種以上を添加したものでもよい。 In order to obtain the composition of the present invention, at least one member selected from the group consisting of the polymer compound (E) as an essential component, a salt of an alkali metal and a salt of a group 2 element, as needed, and others These optional components may be mixed, and various mixers can be used for mixing. It may be heated at the time of mixing. Examples of mixers that can be used include tumbler mixers, Henschel mixers, ribbon blenders, V-type mixers, W-type mixers, super mixers, Nauta mixers, and the like. Further, during the synthesis reaction of the polymer compound (E), one or more selected from the group consisting of a salt of an alkali metal and a salt of a group 2 element may be added to the reaction system.
　また、本発明の化合物（Ｅ）は、界面活性剤を配合して、帯電防止性を有する組成物として使用してもよい。界面活性剤としては、非イオン性、アニオン性、カチオン性または両性の界面活性剤を使用することができる。非イオン性界面活性剤としては、高級アルコールエチレンオキシド付加物、脂肪酸エチレンオキシド付加物、高級アルキルアミンエチレンオキシド付加物、ポリプロピレングリコールエチレンオキシド付加物等のポリエチレングリコール型非イオン界面活性剤；ポリエチレンオキシド、グリセリンの脂肪酸エステル、ペンタエリスリットの脂肪酸エステル、ソルビット若しくはソルビタンの脂肪酸エステル、多価アルコールのアルキルエーテル、アルカノールアミンの脂肪族アミド等の多価アルコール型非イオン界面活性剤等が挙げられ、アニオン性界面活性剤としては、例えば、高級脂肪酸のアルカリ金属塩等のカルボン酸塩；高級アルコール硫酸エステル塩、高級アルキルエーテル硫酸エステル塩等の硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルスルホン酸塩、パラフィンスルホン酸塩等のスルホン酸塩；高級アルコールリン酸エステル塩等のリン酸エステル塩等が挙げられ、カチオン性界面活性剤としては、アルキルトリメチルアンモニウム塩等の第４級アンモニウム塩等が挙げられる。両性界面活性剤としては、高級アルキルアミノプロピオン酸塩等のアミノ酸型両性界面活性剤、高級アルキルジメチルベタイン、高級アルキルジヒドロキシエチルベタイン等のベタイン型両性界面活性剤等が挙げられ、これらは単独でまたは２種以上組み合わせて使用することができる。本発明においては、上記界面活性剤の中でも、アニオン性界面活性剤が好ましく、特に、アルキルベンゼンスルホン酸塩、アルキルスルホン酸塩、パラフィンスルホン酸塩等のスルホン酸塩が好ましい。 In addition, the compound (E) of the present invention may be blended with a surfactant and used as a composition having antistatic properties. As the surfactant, nonionic, anionic, cationic or amphoteric surfactants can be used. Polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts as nonionic surfactants; fatty acid esters of polyethylene oxide, glycerin And polyvalent alcohol type nonionic surfactants such as fatty acid esters of pentaerythritol, fatty acid esters of sorbite or sorbitan, alkyl ethers of polyhydric alcohols, aliphatic amides of alkanolamines, etc., and as anionic surfactants For example, carboxylates such as alkali metal salts of higher fatty acids; sulfates such as higher alcohol sulfates, higher alkyl ether sulfates, alkyl benzenes Sulfonic acid salts such as fluoro acid salts, alkyl sulfonic acid salts and paraffin sulfonic acid salts; phosphoric acid ester salts such as higher alcohol phosphoric acid ester salts and the like, and as cationic surfactants, alkyl trimethyl ammonium salts etc. Examples include quaternary ammonium salts and the like. Amphoteric surfactants include amino acid type amphoteric surfactants such as higher alkyl amino propionates, and betaine type amphoteric surfactants such as higher alkyl dimethyl betaines and higher alkyl dihydroxyethyl betaines, etc. These may be used alone or in combination. Two or more can be used in combination. In the present invention, among the above surfactants, anionic surfactants are preferred, and in particular, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates and paraffin sulfonates are preferred.
　界面活性剤は、高分子化合物（Ｅ）に配合してもよく、高分子化合物（Ｅ）とともに熱可塑性樹脂に配合して使用してもよい。界面活性剤の配合量は、高分子化合物（Ｅ）の１００質量部に対して、０．０１～２０質量部が好ましく、０．１～１５質量部がより好ましく、１～１０質量部が最も好ましい。 The surfactant may be blended in the polymer compound (E), or may be blended in the thermoplastic resin together with the polymer compound (E). The compounding amount of the surfactant is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and most preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer compound (E). preferable.
　さらに、本発明の高分子化合物（Ｅ）は、高分子型帯電防止剤を配合して、帯電防止性を有する組成物として使用してもよい。高分子帯電防止剤としては、例えば、公知のポリエーテルエステルアミド等の高分子型帯電防止剤を使用することができ、公知のポリエーテルエステルアミドとしては、例えば、特開平７－１０９８９号公報に記載のビスフェノールＡのポリオキシアルキレン付加物からなるポリエーテルエステルアミドが挙げられる。また、ポリオレフィンブロックと親水性ポリマーブロックとの結合単位が２～５０の繰り返し構造を有するブロックポリマーを使用することができ、例えば、米国特許第６５５２１３１号明細書記載のブロックポリマーを挙げることができる。 Furthermore, the polymer compound (E) of the present invention may be used as a composition having an antistatic property by blending a polymer type antistatic agent. As the polymer antistatic agent, for example, polymer type antistatic agents such as known polyether ester amide can be used, and as the known polyether ester amide, for example, JP-A 7-10989 Mention may be made of the polyetheresteramides which consist of polyoxyalkylene adducts of bisphenol A as described. In addition, block polymers in which the bonding units of the polyolefin block and the hydrophilic polymer block have a repeating structure of 2 to 50 can be used, and for example, block polymers described in US Pat. No. 6,552,131 can be mentioned.
　高分子型帯電防止剤は、本発明の高分子化合物（Ｅ）に配合してもよく、高分子化合物（Ｅ）とともに、熱可塑性樹脂に配合して使用してもよい。高分子型帯電防止剤の配合量は、高分子化合物（Ｅ）の１００質量部に対して、０～５０質量部が好ましく、５～２０質量部がより好ましい。 The polymer type antistatic agent may be blended with the polymer compound (E) of the present invention, or may be blended with a polymer compound (E) and used in a thermoplastic resin. The amount of the polymer type antistatic agent is preferably 0 to 50 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the polymer compound (E).
　さらにまた、本発明の高分子化合物（Ｅ）は、イオン性液体を配合して、帯電防止性を有する組成物として使用してもよい。イオン性液体の例としては、室温以下の融点を有し、イオン性液体を構成するカチオンまたはアニオンのうち少なくとも一つが有機物イオンであり、初期電導度が１～２００ｍｓ／ｃｍ、好ましくは１０～２００ｍｓ／ｃｍである常温溶融塩であって、例えば、国際公開第９５／１５５７２号に記載の常温溶融塩が挙げられる。 Furthermore, the polymer compound (E) of the present invention may be blended with an ionic liquid and used as a composition having antistatic properties. As an example of the ionic liquid, it has a melting point below room temperature, and at least one of the cations or anions constituting the ionic liquid is an organic ion, and the initial conductivity is 1 to 200 ms / cm, preferably 10 to 200 ms. It is a room temperature molten salt which is / cm, for example, the room temperature molten salt described in WO 95/15572.
　イオン性液体を構成するカチオンとしては、アミジニウム、ピリジニウム、ピラゾリウムおよびグアニジニウムカチオンからなる群から選ばれるカチオンが挙げられる。 As a cation which comprises an ionic liquid, the cation chosen from the group which consists of amidinium, pyridinium, pyrazolium, and guanidinium cation is mentioned.
　このうち、アミジニウムカチオンとしては、下記のものが挙げられる。 Among these, as the amidinium cation, the following may be mentioned.
（１）イミダゾリニウムカチオン
　炭素原子数５～１５のものが挙げられ、例えば、１，２，３，４－テトラメチルイミダゾリニウム、１，３－ジメチルイミダゾリニウム； (1) Imidazolinium cation: those having 5 to 15 carbon atoms, and examples thereof include 1,2,3,4-tetramethylimidazolinium, 1,3-dimethylimidazolinium;
（２）イミダゾリウムカチオン
　炭素原子数５～１５のものが挙げられ、例えば、１，３－ジメチルイミダゾリウム、１－エチル－３－メチルイミダゾリウム； (2) Imidazolium cation Examples thereof include those having 5 to 15 carbon atoms, such as 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium;
（３）テトラヒドロピリミジニウムカチオン
　炭素原子数６～１５のものが挙げられ、例えば、１，３－ジメチル－１，４，５，６－テトラヒドロピリミジニウム、１，２，３，４－テトラメチル－１，４，５，６－テトラヒドロピリミジニウム； (3) Tetrahydropyrimidinium cation: those having 6 to 15 carbon atoms, and examples thereof include 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetra Methyl-1,4,5,6-tetrahydropyrimidinium;
（４）ジヒドロピリミジニウムカチオン
　炭素原子数６～２０のものが挙げられ、例えば、１，３－ジメチル－１，４－ジヒドロピリミジニウム、１，３－ジメチル－１，６－ジヒドロピリミジニウム、８－メチル－１，８－ジアザビシクロ［５，４，０］－７，９－ウンデカジエニウム、８－メチル－１，８－ジアザビシクロ［５，４，０］－７，１０－ウンデカジエニウム。 (4) Dihydropyrimidinium cation Examples thereof include those having 6 to 20 carbon atoms, and examples thereof include 1,3-dimethyl-1,4-dihydropyrimidinium and 1,3-dimethyl-1,6-dihydropyrimidi. , 8-methyl-1,8-diazabicyclo [5,4,0] -7,9-undecadienium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,10-un Decadienium.
　ピリジニウムカチオンとしては、炭素原子数６～２０のものが挙げられ、例えば、３－メチル－１－プロピルピリジニウム、１－ブチル－３，４－ジメチルピリジニウムが挙げられる。 Examples of pyridinium cations include those having 6 to 20 carbon atoms, such as 3-methyl-1-propylpyridinium and 1-butyl-3,4-dimethylpyridinium.
　ピラゾリウムカチオンとしては、炭素原子数５～１５のものが挙げられ、例えば、１、２－ジメチルピラゾリウム、１－ｎ－ブチル－２－メチルピラゾリウムが挙げられる。 The pyrazolium cation includes those having 5 to 15 carbon atoms, and examples thereof include 1,2-dimethyl pyrazolium and 1-n-butyl-2-methyl pyrazolium.
　グアニジニウムカチオンとしては、下記のものが挙げられる。
（１）イミダゾリニウム骨格を有するグアニジニウムカチオン
　炭素原子数８～１５のものが挙げられ、例えば、２－ジメチルアミノ－１，３，４－トリメチルイミダゾリニウム、２－ジエチルアミノ－１，３，４－トリメチルイミダゾリニウム； The following are mentioned as guanidinium cation.
(1) Guanidinium cation having an imidazolinium skeleton: those having 8 to 15 carbon atoms, and examples thereof include 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3. , 4-trimethylimidazolinium;
（２）イミダゾリウム骨格を有するグアニジニウムカチオン
　炭素原子数８～１５のものが挙げられ、例えば、２－ジメチルアミノ－１，３，４－トリメチルイミダゾリウム、２－ジエチルアミノ－１，３，４－トリメチルイミダゾリウム； (2) Guanidinium cation having an imidazolium skeleton: those having 8 to 15 carbon atoms, and examples thereof include 2-dimethylamino-1,3,4-trimethylimidazolium and 2-diethylamino-1,3,4. -Trimethylimidazolium;
（３）テトラヒドロピリミジニウム骨格を有するグアニジニウムカチオン
　炭素原子数１０～２０のものが挙げられ、例えば、２－ジメチルアミノ－１，３，４－トリメチル－１，４，５，６－テトラヒドロピリミジニウム、２－ジエチルアミノ－１，３－ジメチル－４－エチル－１，４，５，６－テトラヒドロピリミジニウム； (3) Guanidinium cation having a tetrahydropyrimidinium skeleton: those having 10 to 20 carbon atoms, and examples thereof include 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydrofuran Pyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium;
（４）ジヒドロピリミジニウム骨格を有するグアニジニウムカチオン
　炭素原子数１０～２０のものが挙げられ、例えば、２－ジメチルアミノ－１，３，４－トリメチル－１，４－ジヒドロピリミジニウム、２－ジメチルアミノ－１，３，４－トリメチル－１，６－ジヒドロピリミジニウム、２－ジエチルアミノ－１，３－ジメチル－４－エチル－１，４－ジヒドロピリミジニウム、２－ジエチルアミノ－１，３－ジメチル－４－エチル－１，６－ジヒドロピリミジニウム。 (4) Guanidinium cation having a dihydropyrimidinium skeleton: those having 10 to 20 carbon atoms, and examples thereof include 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.
　上記カチオンは１種を単独で用いても、また、２種以上を併用しても、いずれでもよい。これらのうち、帯電防止性の観点から好ましくはアミジニウムカチオン、より好ましくはイミダゾリウムカチオン、特に好ましくは１－エチル－３－メチルイミダゾリウムカチオンである。 The cations may be used alone or in combination of two or more. Among these, an amidinium cation is preferable from the viewpoint of antistatic properties, more preferably an imidazolium cation, and particularly preferably a 1-ethyl-3-methylimidazolium cation.
　イオン性液体において、アニオンを構成する有機酸または無機酸としては、下記のものが挙げられる。有機酸としては、例えば、カルボン酸、硫酸エステル、スルホン酸およびリン酸エステル；無機酸としては、例えば、超強酸（例えば、ホウフッ素酸、四フッ化ホウ素酸、過塩素酸、六フッ化リン酸、六フッ化アンチモン酸および六フッ化ヒ素酸）、リン酸およびホウ酸が挙げられる。上記有機酸および無機酸は、１種を単独で用いても、また、２種以上を併用しても、いずれでもよい。 Examples of the organic acid or inorganic acid constituting the anion in the ionic liquid include the following. As an organic acid, for example, carboxylic acid, sulfuric acid ester, sulfonic acid and phosphoric acid ester; As an inorganic acid, for example, super strong acid (eg, borofluoric acid, tetraboronic acid, perchloric acid, phosphorus hexafluoride) Acids, hexafluoroantimonic acid and hexaarsenic acid), phosphoric acid and boric acid. The organic acid and the inorganic acid may be used alone or in combination of two or more.
　上記有機酸および無機酸のうち、イオン性液体の帯電防止性の観点から好ましいのは、イオン性液体を構成するアニオンのＨａｍｍｅｔｔ酸度関数（－Ｈ０）が１２～１００である、超強酸の共役塩基、超強酸の共役塩基以外のアニオンを形成する酸およびこれらの混合物である。 Among the above organic acids and inorganic acids, preferred from the viewpoint of the antistatic property of the ionic liquid is a conjugate of a super strong acid whose Hammett acidity function (-H 0 ) of the anion constituting the ionic liquid is 12 to 100. Bases, acids which form anions other than the conjugate bases of super strong acids, and mixtures thereof.
　超強酸の共役塩基以外のアニオンとしては、例えば、ハロゲン（例えば、フッ素、塩素および臭素）イオン、アルキル（炭素原子数１～１２）ベンゼンスルホン酸（例えば、ｐ－トルエンスルホン酸およびドデシルベンゼンスルホン酸）イオンおよびポリ（ｎ＝１～２５）フルオロアルカンスルホン酸（例えば、ウンデカフルオロペンタンスルホン酸）イオンが挙げられる。 As anions other than conjugated bases of super strong acids, for example, halogen (eg, fluorine, chlorine and bromine) ion, alkyl (C 1-12 carbon atoms) benzenesulfonic acid (eg, p-toluenesulfonic acid and dodecylbenzenesulfonic acid) And ions of poly (n = 1 to 25) fluoroalkanesulfonic acid (eg, undecafluoropentanesulfonic acid).
　また、超強酸としては、プロトン酸およびプロトン酸とルイス酸との組み合わせから誘導されるもの、およびこれらの混合物が挙げられる。超強酸としてのプロトン酸としては、例えば、ビス（トリフルオロメチルスルホニル）イミド酸、ビス（ペンタフルオロエチルスルホニル）イミド酸、トリス（トリフルオロメチルスルホニル）メタン、過塩素酸、フルオロスルホン酸、アルカン（炭素原子数１～３０）スルホン酸（例えば、メタンスルホン酸、ドデカンスルホン酸等）、ポリ（ｎ＝１～３０）フルオロアルカン（炭素原子数１～３０）スルホン酸（例えば、トリフルオロメタンスルホン酸、ペンタフルオロエタンスルホン酸、ヘプタフルオロプロパンスルホン酸、ノナフルオロブタンスルホン酸、ウンデカフルオロペンタンスルホン酸およびトリデカフルオロヘキサンスルホン酸）、ホウフッ素酸および四フッ化ホウ素酸が挙げられる。これらのうち、合成の容易さの観点から好ましいのはホウフッ素酸、トリフルオロメタンスルホン酸、ビス（トリフルオロメタンスルホニル）イミド酸およびビス（ペンタフルオロエチルスルホニル）イミド酸である。 Also, super acids include those derived from protic acids and combinations of protic acids and Lewis acids, and mixtures thereof. Examples of protonic acids as super strong acids include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkanes (for example, C 1-30 C sulfonic acid (eg, methanesulfonic acid, dodecanesulfonic acid, etc.), poly (n = 1-30) fluoroalkane (C 1-30 carbon atoms) sulfonic acid (eg, trifluoromethanesulfonic acid, Pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboronic acid can be mentioned. Among these, borofluoric acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imidic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferable from the viewpoint of easiness of synthesis.
　ルイス酸と組合せて用いられるプロトン酸としては、例えば、ハロゲン化水素（例えば、フッ化水素、塩化水素、臭化水素およびヨウ化水素）、過塩素酸、フルオロスルホン酸、メタンスルホン酸、トリフルオロメタンスルホン酸、ペンタフルオロエタンスルホン酸、ノナフルオロブタンスルホン酸、ウンデカフルオロペンタンスルホン酸、トリデカフルオロヘキサンスルホン酸およびこれらの混合物が挙げられる。これらのうち、イオン性液体の初期電導度の観点から好ましいのはフッ化水素である。 Protic acids used in combination with Lewis acids include, for example, hydrogen halide (eg, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethane Sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof can be mentioned. Among these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of the ionic liquid.
　ルイス酸としては、例えば、三フッ化ホウ素、五フッ化リン、五フッ化アンチモン、五フッ化ヒ素、五フッ化タンタルおよびこれらの混合物が挙げられる。これらのうちでも、イオン性液体の初期電導度の観点から好ましいのは三フッ化ホウ素および五フッ化リンである。 As the Lewis acid, for example, boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride and mixtures thereof can be mentioned. Among these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of the ionic liquid.
　プロトン酸とルイス酸との組み合わせは任意であるが、これらの組み合わせからなる超強酸としては、例えば、テトラフルオロホウ酸、ヘキサフルオロリン酸、六フッ化タンタル酸、六フッ化アンチモン酸、六フッ化タンタルスルホン酸、四フッ化ホウ素酸、六フッ化リン酸、塩化三フッ化ホウ素酸、六フッ化ヒ素酸およびこれらの混合物が挙げられる。 The combination of a protonic acid and a Lewis acid is optional, but as a superstrong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, hexafluorinated acid And tantalum sulfonic acid, boron tetrafluoride, phosphoric acid hexafluoride, boron trichloride chloroborate, arsenic hexafluoride hexafluoride, and mixtures thereof.
　上記のアニオンのうち、イオン性液体の帯電防止性の観点から好ましいのは超強酸の共役塩基（プロトン酸からなる超強酸およびプロトン酸とルイス酸との組合せからなる超強酸）であり、さらに好ましいのはプロトン酸からなる超強酸およびプロトン酸と、三フッ化ホウ素および／または五フッ化リンとからなる超強酸の共役塩基である。 Among the above-mentioned anions, preferred are super-acid conjugate bases (super-strong acids consisting of protic acids and super-strong acids consisting of a combination of protic acids and Lewis acids) from the viewpoint of the antistatic properties of ionic liquids, more preferred Is a conjugate base of a super strong acid consisting of a protic acid and a super strong acid consisting of a protic acid and a boron trifluoride and / or a phosphorus pentafluoride.
　イオン性液体のうち、帯電防止性の観点から好ましいのは、アミジニウムカチオンを有するイオン性液体、より好ましいのは１－エチル－３－メチルイミダゾリウムカチオンを有するイオン性液体、特に好ましいのは１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミドである。 Among the ionic liquids, an ionic liquid having an amidinium cation is preferable from the viewpoint of antistaticity, an ionic liquid having a 1-ethyl-3-methylimidazolium cation is more preferable, and an ionic liquid having a 1-ethyl-3-methylimidazolium cation is particularly preferable. 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide.
　イオン性液体の配合量は、高分子化合物（Ｅ）の１００質量部に対して、０．０１～２０質量部が好ましく、０．１～１５質量部がより好ましく、１～１０質量部が最も好ましい。 The blending amount of the ionic liquid is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and most preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer compound (E). preferable.
　さらにまた、本発明の高分子化合物（Ｅ）は、相溶化剤を配合して、帯電防止性を有する組成物としてもよい。相溶化剤を配合することで、高分子化合物（Ｅ）と他成分や熱可塑性樹脂との相溶性を向上させることができる。かかる相溶化剤としては、カルボキシル基、エポキシ基、アミノ基、ヒドロキシル基およびポリオキシアルキレン基からなる群から選ばれる少なくとも１種の官能基（極性基）を有する変性ビニル重合体、例えば、特開平３－２５８８５０号公報に記載の重合体や、特開平６－３４５９２７号公報に記載のスルホニル基を有する変性ビニル重合体、あるいはポリオレフィン部分と芳香族ビニル重合体部分とを有するブロック重合体等が挙げられる。 Furthermore, the polymer compound (E) of the present invention may be blended with a compatibilizer to form a composition having antistatic properties. By blending the compatibilizer, the compatibility of the polymer compound (E) with other components and the thermoplastic resin can be improved. As such a compatibilizer, modified vinyl polymers 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, for example, Examples thereof include polymers described in JP-A-3-258850, modified vinyl polymers having a sulfonyl group described in JP-A-6-345927, and block polymers having a polyolefin portion and an aromatic vinyl polymer portion. Be
　相溶化剤は、本発明の高分子化合物（Ｅ）に配合してもよく、高分子化合物（Ｅ）とともに熱可塑性樹脂に配合して使用してもよい。相溶化剤の配合量は、高分子化合物（Ｅ）の１００質量部に対して、０．１～１５質量部が好ましく、１～１０質量部がより好ましい。 The compatibilizer may be blended with the polymer compound (E) of the present invention, or may be blended with the polymer compound (E) in a thermoplastic resin. The amount of the compatibilizing agent is preferably 0.1 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer compound (E).
　本発明の組成物には、本発明の効果を損なわない範囲で、高分子化合物（Ｅ）と上記で挙げた成分以外にも、任意の成分として他の成分を配合してもよい。これら他の成分は、組成物に直接配合してもよいし、高分子化合物（Ｅ）や本発明の組成物を熱可塑性樹脂等の合成樹脂に配合して、帯電防止性を有する樹脂組成物として使用する場合に、合成樹脂に配合してもよい。 In the composition of the present invention, other components may be blended as optional components in addition to the polymer compound (E) and the components listed above, as long as the effects of the present invention are not impaired. These other components may be directly blended into the composition, or a resin composition having antistatic properties by blending the polymer compound (E) or the composition of the present invention into a synthetic resin such as a thermoplastic resin. When used as, it may be blended with a synthetic resin.
　本発明の高分子化合物（Ｅ）および組成物は、特に好ましくは、熱可塑性樹脂に配合して、帯電防止性を有する樹脂組成物として使用できる。熱可塑性樹脂の例としては、ポリプロピレン、高密度ポリエチレン、低密度ポリエチレン、直鎖低密度ポリエチレン、架橋ポリエチレン、超高分子量ポリエチレン、ポリブテン－１、ポリ－３－メチルペンテン、ポリ－４－メチルペンテン等のα－オレフィン重合体またはエチレン－酢酸ビニル共重合体、エチレン－エチルアクリレート共重合体、エチレン－プロピレン共重合体等のポリオレフィン系樹脂およびこれらの共重合体；ポリ塩化ビニル、ポリ塩化ビニリデン、塩素化ポリエチレン、塩素化ポリプロピレン、ポリフッ化ビニリデン、塩化ゴム、塩化ビニル－酢酸ビニル共重合体、塩化ビニル－エチレン共重合体、塩化ビニル－塩化ビニリデン共重合体、塩化ビニル－塩化ビニリデン－酢酸ビニル三元共重合体、塩化ビニル－アクリル酸エステル共重合体、塩化ビニル－マレイン酸エステル共重合体、塩化ビニル－シクロヘキシルマレイミド共重合体等の含ハロゲン樹脂；石油樹脂、クマロン樹脂、ポリスチレン、ポリ酢酸ビニル、アクリル樹脂、スチレンおよび／またはα－メチルスチレンと他の単量体（例えば、無水マレイン酸、フェニルマレイミド、メタクリル酸メチル、ブタジエン、アクリロニトリル等）との共重合体（例えば、ＡＳ樹脂、ＡＢＳ（アクリロニトリルブタジエンスチレン共重合体）樹脂、ＡＣＳ樹脂、ＳＢＳ樹脂、ＭＢＳ樹脂、耐熱ＡＢＳ樹脂等）；ポリメチルメタクリレート、ポリビニルアルコール、ポリビニルホルマール、ポリビニルブチラール；ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリシクロヘキサンジメチレンテレフタレート等のポリアルキレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート等のポリアルキレンナフタレート等の芳香族ポリエステルおよびポリテトラメチレンテレフタレート等の直鎖ポリエステル；ポリヒドロキシブチレート、ポリカプロラクトン、ポリブチレンサクシネート、ポリエチレンサクシネート、ポリ乳酸、ポリリンゴ酸、ポリグリコール酸、ポリジオキサン、ポリ（２－オキセタノン）等の分解性脂肪族ポリエステル；ポリフェニレンオキサイド、ポリカプロラクタムおよびポリヘキサメチレンアジパミド等のポリアミド、ポリカーボネート、ポリカーボネート／ＡＢＳ樹脂、分岐ポリカーボネート、ポリアセタール、ポリフェニレンサルファイド、ポリウレタン、繊維素系樹脂、ポリイミド樹脂、ポリサルフォン、ポリフェニレンエーテル、ポリエーテルケトン、ポリエーテルエーテルケトン、液晶ポリマー等の熱可塑性樹脂およびこれらのブレンド物を挙げることができる。また、熱可塑性樹脂は、イソプレンゴム、ブタジエンゴム、アクリロニトリル－ブタジエン共重合ゴム、スチレン－ブタジエン共重合ゴム、フッ素ゴム、シリコーンゴム、オレフィン系エラストマー、スチレン系エラストマー、ポリエステル系エラストマー、ニトリル系エラストマー、ナイロン系エラストマー、塩化ビニル系エラストマー、ポリアミド系エラストマー、ポリウレタン系エラストマー等のエラストマーであってもよい。本発明において、これらの熱可塑性樹脂は、単独で使用してもよく、２種以上を併せて使用してもよい。また、熱可塑性樹脂はアロイ化されていてもよい。 The polymer compound (E) and the composition of the present invention can particularly preferably be blended with a thermoplastic resin and used as a resin composition having antistatic properties. Examples of thermoplastic resins include polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, crosslinked polyethylene, ultrahigh molecular weight polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene and the like Polyolefin resins such as α-olefin polymers or ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-propylene copolymers and copolymers thereof; polyvinyl chloride, polyvinylidene chloride, chlorine Polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary Copolymer, vinyl chloride-acrylic Halogen-containing resins such as acid ester copolymer, vinyl chloride-maleate ester copolymer, vinyl chloride-cyclohexyl maleimide copolymer; petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and / or α -A copolymer of methylstyrene and another monomer (eg, maleic anhydride, phenyl maleimide, methyl methacrylate, butadiene, acrylonitrile etc.) (eg AS resin, ABS (acrylonitrile butadiene styrene copolymer) resin, ACS resin, SBS resin, MBS resin, heat-resistant ABS resin, etc.); polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate Aromatic polyesters such as polyalkylene terephthalates such as phthalates, polyethylene naphthalates, polyalkylene naphthalates such as polybutylene naphthalates, and linear polyesters such as polytetramethylene terephthalates; polyhydroxybutyrates, polycaprolactones, polybutylene succinates, Degradable aliphatic polyesters such as polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, poly (2-oxetanone), etc. Polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonates, polycarbonates / ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, fibrous resin, polyimide resin Can polysulfone, polyphenylene ether, polyether ketone, polyether ether ketone, include thermoplastic resins and blends thereof such as a liquid crystal polymer. Further, the thermoplastic resin is isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, olefin elastomer, styrene elastomer, polyester elastomer, nitrile elastomer, nylon It may be an elastomer such as a system elastomer, a vinyl chloride elastomer, a polyamide elastomer, or a polyurethane elastomer. In the present invention, these thermoplastic resins may be used alone or in combination of two or more. The thermoplastic resin may be alloyed.
　これらの熱可塑性樹脂は、分子量、重合度、密度、軟化点、溶媒への不溶分の割合、立体規則性の程度、触媒残渣の有無、原料となるモノマーの種類や配合比率、重合触媒の種類（例えば、チーグラー触媒、メタロセン触媒等）等に関わらず使用することができる。これらの熱可塑性樹脂の中でも、帯電防止性の点から、ポリオレフィン系樹脂、ポリスチレン系樹脂およびそれらの共重合体からなる群から選ばれる１種以上が好ましい。 These thermoplastic resins have a molecular weight, polymerization degree, density, softening point, ratio of insoluble matter to solvent, degree of stereoregularity, presence or absence of catalyst residue, kind and blending ratio of raw material monomers, kind of polymerization catalyst It can be used regardless of (eg, Ziegler catalyst, metallocene catalyst, etc.) and the like. Among these thermoplastic resins, at least one selected from the group consisting of polyolefin resins, polystyrene resins and copolymers thereof is preferable from the viewpoint of antistatic properties.
　本発明の樹脂組成物中の、熱可塑性樹脂と、高分子化合物（Ｅ）または組成物との質量比は、９９／１～４０／６０の範囲が好ましい。 The mass ratio of the thermoplastic resin to the polymer compound (E) or the composition in the resin composition of the present invention is preferably in the range of 99/1 to 40/60.
　高分子化合物（Ｅ）の熱可塑性樹脂への配合方法は特に限定されず、通常使用されている任意の方法を用いることができ、例えば、ロール混練り、バンパー混練り、押し出し機、ニーダー等により混合、練り込みして配合すればよい。また、高分子化合物（Ｅ）は、そのまま熱可塑性樹脂に添加してもよいが、必要に応じて、担体に含浸させてから添加してもよい。担体に含浸させるには、そのまま加熱混合してもよいし、必要に応じて、有機溶媒で希釈してから担体に含浸させ、その後に溶媒を除去する方法でもよい。こうした担体としては、合成樹脂のフィラーや充填剤として知られているもの、または、常温で固体の難燃剤や光安定剤が使用でき、例えば、ケイ酸カルシウム粉末、シリカ粉末、タルク粉末、アルミナ粉末、酸化チタン粉末、または、これら担体の表面を化学修飾したもの、下記に挙げる難燃剤や酸化防止剤の中で固体のもの等が挙げられる。これらの担体の中でも担体の表面を化学修飾したものが好ましく、シリカ粉末の表面を化学修飾したものがより好ましい。これらの担体は、平均粒径が０．１～１００μｍのものが好ましく、０．５～５０μｍのものがより好ましい。 The method of blending the polymer compound (E) into the thermoplastic resin is not particularly limited, and any commonly used method can be used, for example, roll kneading, bumper kneading, extruder, kneader, etc. It may be mixed, kneaded and blended. The polymer compound (E) may be added to the thermoplastic resin as it is, but may be added after the carrier is impregnated, if necessary. 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 and then impregnated into the carrier, and then the solvent may be removed. As such a carrier, a filler known as a filler of a synthetic resin or a filler, or a flame retardant or a light stabilizer which is solid at normal temperature can be used. For example, calcium silicate powder, silica powder, talc powder, alumina powder Examples thereof include titanium oxide powder, those obtained by chemically modifying the surface of these carriers, and solid substances among the flame retardants and antioxidants listed below. Among these carriers, those in which the surface of the carrier is chemically modified are preferable, and those in which the surface of the silica powder is chemically modified are more preferable. The carrier preferably has an average particle diameter of 0.1 to 100 μm, and more preferably 0.5 to 50 μm.
　高分子化合物（Ｅ）の熱可塑性樹脂への配合方法としては、ブロックポリマー（Ｃ）と、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）とを熱可塑性樹脂と同時に練り込みながら高分子化合物（Ｅ）を合成して配合してもよく、そのときにさらにアルカリ金属の塩および第２族元素の塩からなる群から選択される１種以上を同時に練り込んでもよく、また、射出成形等の成形時に高分子化合物（Ｅ）と熱可塑性樹脂とを混合して成形品を得る方法で配合してもよく、そのときにさらにアルカリ金属の塩および第２族元素の塩からなる群から選択される１種以上を配合してもよく、さらに、あらかじめ高分子化合物（Ｅ）と熱可塑性樹脂とのマスターバッチを製造しておき、このマスターバッチを配合してもよく、そのときにアルカリ金属の塩および第２族元素の塩からなる群から選択される１種以上を配合してもよい。 As a compounding method to a thermoplastic resin of a high molecular compound (E), a high molecular compound (E), while kneading a block polymer (C) and a polyalkylene glycol diglycidyl ether compound (D) simultaneously with a thermoplastic resin May be synthesized and compounded, and at the same time, one or more selected from the group consisting of salts of alkali metals and salts of Group 2 elements may be simultaneously kneaded, or at the time of molding such as injection molding, etc. The polymer compound (E) and the thermoplastic resin may be mixed to obtain a molded product, and at that time, it may be further selected from the group consisting of alkali metal salts and salts of Group 2 elements. More than one species may be blended, and further, a masterbatch of the polymer compound (E) and the thermoplastic resin may be prepared in advance, and this masterbatch may be blended. It may be blended at least one selected from the group consisting of salts of alkali metals salts and a Group 2 element.
　本発明の樹脂組成物には、必要に応じて、フェノール系酸化防止剤、リン系酸化防止剤、チオエーテル系酸化防止剤、紫外線吸収剤、ヒンダードアミン系光安定剤等の各種添加剤をさらに添加することができ、これにより、本発明の樹脂組成物を安定化させることができる。 To the resin composition of the present invention, various additives such as phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet light absorbers, hindered amine light stabilizers and the like are further added as necessary. Thus, the resin composition of the present invention can be stabilized.
　これら酸化防止剤等の各種添加剤は、合成樹脂に配合するまえに、本発明の組成物中に配合しておいてもよい。さらには高分子化合物（Ｅ）の製造時に配合しておいてもよい。特に酸化防止剤は、高分子化合物（Ｅ）の製造時に配合することで、製造中の高分子化合物（Ｅ）の酸化劣化も防ぐことができるので好ましい。 Various additives such as these antioxidants may be blended into the composition of the present invention before blending into the synthetic resin. Furthermore, you may mix | blend at the time of manufacture of a high molecular compound (E). In particular, the antioxidant is preferable at the time of the production of the polymer compound (E) because it can prevent the oxidative degradation of the polymer compound (E) during the production.
　上記フェノール系酸化防止剤としては、例えば、２，６－ジ第三ブチル－ｐ－クレゾール、２，６－ジフェニル－４－オクタデシロキシフェノール、ジステアリル（３，５－ジ第三ブチル－４－ヒドロキシベンジル）ホスホネート、１，６－ヘキサメチレンビス〔（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオン酸アミド〕、４，４’－チオビス（６－第三ブチル－ｍ－クレゾール）、２，２’－メチレンビス（４－メチル－６－第三ブチルフェノール）、２，２’－メチレンビス（４－エチル－６－第三ブチルフェノール）、４，４’－ブチリデンビス（６－第三ブチル－ｍ－クレゾール）、２，２’－エチリデンビス（４，６―ジ第三ブチルフェノール）、２，２’－エチリデンビス（４－第二ブチル－６－第三ブチルフェノール）、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－第三ブチルフェニル）ブタン、１，３，５－トリス（２，６－ジメチル－３－ヒドロキシ－４－第三ブチルベンジル）イソシアヌレート、１，３，５－トリス（３，５－ジ第三ブチル－４－ヒドロキシベンジル）イソシアヌレート、１，３，５－トリス（３，５－ジ第三ブチル－４－ヒドロキシベンジル）－２，４，６－トリメチルベンゼン、２－第三ブチル－４－メチル－６－（２－アクリロイルオキシ－３－第三ブチル－５－メチルベンジル）フェノール、ステアリル（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオネート、テトラキス〔３－（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオン酸メチル〕メタン、チオジエチレングリコールビス〔（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオネート〕、１，６－ヘキサメチレンビス〔（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオネート〕、ビス〔３，３－ビス（４－ヒドロキシ－３－第三ブチルフェニル）ブチリックアシッド〕グリコールエステル、ビス〔２－第三ブチル－４－メチル－６－（２－ヒドロキシ－３－第三ブチル－５－メチルベンジル）フェニル〕テレフタレート、１，３，５－トリス〔（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオニルオキシエチル〕イソシアヌレート、３，９－ビス〔１，１－ジメチル－２－｛（３－第三ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ｝エチル〕－２，４，８，１０－テトラオキサスピロ〔５，５〕ウンデカン、トリエチレングリコールビス〔（３－第三ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート〕等が挙げられる。これらのフェノール系酸化防止剤の添加量は、熱可塑性樹脂１００質量部に対して、０．００１～１０質量部であることが好ましく、０．０５～５質量部であることがより好ましい。 Examples of the above-mentioned phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4) -Hydroxybenzyl) phosphonate, 1,6-hexamethylene bis [(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-di-tert-butylphenol), 2,2'-ethylidenebis (4-sec-butyl-6-tert-butyl) 1) 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- Di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol Bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [3, 3-Bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-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] Undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like can be mentioned. The addition amount of these phenolic 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 thermoplastic resin.
　上記リン系酸化防止剤としては、例えば、トリスノニルフェニルホスファイト、トリス〔２－第三ブチル－４－（３－第三ブチル－４－ヒドロキシ－５－メチルフェニルチオ）－５－メチルフェニル〕ホスファイト、トリデシルホスファイト、オクチルジフェニルホスファイト、ジ（デシル）モノフェニルホスファイト、ジ（トリデシル）ペンタエリスリトールジホスファイト、ジ（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４－ジ第三ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６－ジ第三ブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４，６－トリ第三ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４－ジクミルフェニル）ペンタエリスリトールジホスファイト、テトラ（トリデシル）イソプロピリデンジフェノールジホスファイト、テトラ（トリデシル）－４，４’－ｎ－ブチリデンビス（２－第三ブチル－５－メチルフェノール）ジホスファイト、ヘキサ（トリデシル）－１，１，３－トリス（２－メチル－４－ヒドロキシ－５－第三ブチルフェニル）ブタントリホスファイト、テトラキス（２，４－ジ第三ブチルフェニル）ビフェニレンジホスホナイト、９，１０－ジハイドロ－９－オキサ－１０－ホスファフェナンスレン－１０－オキサイド、２，２’－メチレンビス（４，６－第三ブチルフェニル）－２－エチルヘキシルホスファイト、２，２’－メチレンビス（４，６－第三ブチルフェニル）－オクタデシルホスファイト、２，２’－エチリデンビス（４，６－ジ第三ブチルフェニル）フルオロホスファイト、トリス（２－〔（２，４，８，１０－テトラキス第三ブチルジベンゾ〔ｄ，ｆ〕〔１，３，２〕ジオキサホスフェピン－６－イル）オキシ〕エチル）アミン、２－エチル－２－ブチルプロピレングリコールと２，４，６－トリ第三ブチルフェノールのホスファイト等が挙げられる。これらのリン系酸化防止剤の添加量は、熱可塑性樹脂１００質量部に対して０．００１～１０質量部であることが好ましく、０．０５～５質量部であることがより好ましい。 Examples of the above-mentioned 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-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol di- Phosphite, bis (2,4-dicumylphenyl) ester Taerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)- 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-di-tert-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- Tert-butylphenyl) -octadecyl phosphite, 2,2'-ethylidene bis ( , 6-di-tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyl dibenzo [d, f] [1,3,2] dioxaphosphepin- 6-yl) oxy] ethyl) amine, and phosphites of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol. The addition amount of these phosphorus-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 thermoplastic resin.
　上記チオエーテル系酸化防止剤としては、例えば、チオジプロピオン酸ジラウリル、チオジプロピオン酸ジミリスチル、チオジプロピオン酸ジステアリル等のジアルキルチオジプロピオネート類、および、ペンタエリスリトールテトラ（β－アルキルチオプロピオン酸）エステル類が挙げられる。これらのチオエーテル系酸化防止剤の添加量は、熱可塑性樹脂１００質量部に対して、０．００１～１０質量部であることが好ましく、０．０５～５質量部であることがより好ましい。 Examples of the above-mentioned thioether-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkylthiopropionic acid). Esters are mentioned. 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 thermoplastic resin.
　上記紫外線吸収剤としては、例えば、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－オクトキシベンゾフェノン、５，５’－メチレンビス（２－ヒドロキシ－４－メトキシベンゾフェノン）等の２－ヒドロキシベンゾフェノン類；２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ第三ブチルフェニル）－５－クロロベンゾトリアゾ－ル、２－（２’－ヒドロキシ－３’－第三ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾ－ル、２－（２’－ヒドロキシ－５’－第三オクチルフェニル）ベンゾトリアゾ－ル、２－（２’－ヒドロキシ－３’，５’－ジクミルフェニル）ベンゾトリアゾ－ル、２，２’－メチレンビス（４－第三オクチル－６－（ベンゾトリアゾリル）フェノール）、２－（２’－ヒドロキシ－３’－第三ブチル－５’－カルボキシフェニル）ベンゾトリアゾール等の２－（２’－ヒドロキシフェニル）ベンゾトリアゾール類；フェニルサリシレート、レゾルシノールモノベンゾエート、２，４－ジ第三ブチルフェニル－３，５－ジ第三ブチル－４－ヒドロキシベンゾエート、２，４－ジ第三アミルフェニル－３，５－ジ第三ブチル－４－ヒドロキシベンゾエート、ヘキサデシル－３，５－ジ第三ブチル－４－ヒドロキシベンゾエート等のベンゾエート類；２－エチル－２’－エトキシオキザニリド、２－エトキシ－４’－ドデシルオキザニリド等の置換オキザニリド類；エチル－α－シアノ－β、β－ジフェニルアクリレート、メチル－２－シアノ－３－メチル－３－（ｐ－メトキシフェニル）アクリレート等のシアノアクリレート類；２－（２－ヒドロキシ－４－オクトキシフェニル）－４，６－ビス（２，４－ジ第三ブチルフェニル）－ｓ－トリアジン、２－（２－ヒドロキシ－４－メトキシフェニル）－４，６－ジフェニル－ｓ－トリアジン、２－（２－ヒドロキシ－４－プロポキシ－５－メチルフェニル）－４，６－ビス（２，４－ジ第三ブチルフェニル）－ｓ－トリアジン等のトリアリールトリアジン類が挙げられる。これらの紫外線吸収剤の添加量は、熱可塑性樹脂１００質量部に対して、０．００１～３０質量部であることが好ましく、０．０５～１０質量部であることがより好ましい。 Examples of the UV absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone). And the like) 2-hydroxybenzophenones such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chloro Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-third) Octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2 2- (2) -methylenebis (4-tert-octyl-6- (benzotriazolyl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl) benzotriazole, etc. 2'-hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl Benzoates such as -3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxy oxanilide, 2-ethoxy Substituted oxanilides such as -4'-dodecyl oxanilide; ethyl-α-cyano-β, β-diphenylacryi 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-methyl) And triaryl triazines such as phenyl) -4,6-bis (2,4-di-tert-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 thermoplastic resin.
　上記ヒンダードアミン系光安定剤としては、例えば、２，２，６，６－テトラメチル－４－ピペリジルステアレート、１，２，２，６，６－ペンタメチル－４－ピペリジルステアレート、２，２，６，６－テトラメチル－４－ピペリジルベンゾエート、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セバケート、ビス（１－オクトキシ－２，２，６，６－テトラメチル－４－ピペリジル）セバケート、テトラキス（２，２，６，６－テトラメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６－ペンタメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（２，２，６，６－テトラメチル－４－ピペリジル）・ジ（トリデシル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）・ジ（トリデシル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（１，２，２，４，４－ペンタメチル－４－ピペリジル）－２－ブチル－２－（３，５－ジ第三ブチル－４－ヒドロキシベンジル）マロネート、１－（２－ヒドロキシエチル）－２，２，６，６－テトラメチル－４－ピペリジノ－ル／コハク酸ジエチル重縮合物、１，６－ビス（２，２，６，６－テトラメチル－４－ピペリジルアミノ）ヘキサン／２，４－ジクロロ－６－モルホリノ－ｓ－トリアジン重縮合物、１，６－ビス（２，２，６，６－テトラメチル－４－ピペリジルアミノ）ヘキサン／２，４－ジクロロ－６－第三オクチルアミノ－ｓ－トリアジン重縮合物、１，５，８，１２－テトラキス〔２，４－ビス（Ｎ－ブチル－Ｎ－（２，２，６，６－テトラメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕－１，５，８，１２－テトラアザドデカン、１，５，８，１２－テトラキス〔２，４－ビス（Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕－１，５，８－１２－テトラアザドデカン、１，６，１１－トリス〔２，４－ビス（Ｎ－ブチル－Ｎ－（２，２，６，６－テトラメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕アミノウンデカン、１，６，１１－トリス〔２，４－ビス（Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕アミノウンデカン等のヒンダードアミン化合物が挙げられる。これらのヒンダードアミン系光安定剤の添加量は、熱可塑性樹脂１００質量部に対して０．００１～３０質量部であることが好ましく、０．０５～１０質量部であることがより好ましい。 Examples of the above hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,3, 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- Butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, bis (2, , 6,6-Tetramethyl-4-piperidyl), di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl). Di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di (di) Tributyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2 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-Piperidylami ) Hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,2) 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, Hindered amine compounds such as 2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane can be mentioned. The addition amount of these hindered amine light stabilizers 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 thermoplastic resin.
　また、熱可塑性樹脂としてポリオレフィン系樹脂を使用する場合は、本発明の効果を損なわない範囲で、必要に応じてさらに、ポリオレフィン樹脂中の残渣触媒を中和するために、公知の中和剤を添加することが好ましい。中和剤としては、例えば、ステアリン酸カルシウム、ステアリン酸リチウム、ステアリン酸ナトリウム等の脂肪酸金属塩、または、エチレンビス（ステアロアミド）、エチレンビス（１２－ヒドロキシステアロアミド）、ステアリン酸アミド等の脂肪酸アミド化合物が挙げられ、これら中和剤は混合して用いてもよい。 Moreover, when using polyolefin resin as a thermoplastic resin, in order to neutralize the residual catalyst in polyolefin resin further as needed in the range which does not impair the effect of the present invention, It is preferable to add. 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 (stearoamide), ethylene bis (12-hydroxy stearoamide) and stearic acid amide. The compound is mentioned and these neutralizing agents may be mixed and used.
　本発明の樹脂組成物には、その他の添加剤として、必要に応じてさらに、本発明の効果を損なわない範囲で、芳香族カルボン酸金属塩、脂環式アルキルカルボン酸金属塩、ｐ－第三ブチル安息香酸アルミニウム、芳香族リン酸エステル金属塩、ジベンジリデンソルビトール類等の造核剤、金属石鹸、ハイドロタルサイト、トリアジン環含有化合物、金属水酸化物、リン酸エステル系難燃剤、縮合リン酸エステル系難燃剤、ホスフェート系難燃剤、無機リン系難燃剤、（ポリ）リン酸塩系難燃剤、ハロゲン系難燃剤、シリコン系難燃剤、三酸化アンチモン等の酸化アンチモン、その他の無機系難燃助剤、その他の有機系難燃助剤、充填剤、顔料、滑剤、発泡剤等を添加してもよい。 The resin composition of the present invention may further contain, as other additives, metal salts of aromatic carboxylic acids, metal salts of alicyclic alkyl carboxylic acids, and p-numbers as long as the effects of the present invention are not impaired. Nucleating agents such as aluminum tributylbenzoate, metal salts of aromatic phosphates, dibenzylidene sorbitols, metal soaps, hydrotalcites, triazine ring-containing compounds, metal hydroxides, phosphoric acid ester flame retardants, condensed phosphorus Acid ester flame retardants, phosphate flame retardants, inorganic phosphorus flame retardants, (poly) phosphate flame retardants, halogen flame retardants, silicon flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardants Fuel aids, other organic fire retardant aids, fillers, pigments, lubricants, foaming agents, etc. may be added.
　上記トリアジン環含有化合物としては、例えば、メラミン、アンメリン、ベンズグアナミン、アセトグアナミン、フタロジグアナミン、メラミンシアヌレート、ピロリン酸メラミン、ブチレンジグアナミン、ノルボルネンジグアナミン、メチレンジグアナミン、エチレンジメラミン、トリメチレンジメラミン、テトラメチレンジメラミン、ヘキサメチレンジメラミン、１，３－ヘキシレンジメラミン等が挙げられる。 Examples of the triazine ring-containing compounds include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene Examples thereof include dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, and 1,3-hexylene dimelamine.
　上記金属水酸化物としては、例えば、水酸化マグネシウム、水酸化アルミニウム、水酸化カルシウム、水酸化バリウム、水酸化亜鉛、キスマー５Ａ（水酸化マグネシウム：協和化学工業（株）製）等が挙げられる。 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.
　上記リン酸エステル系難燃剤としては、例えば、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリブトキシエチルホスフェート、トリスクロロエチルホスフェート、トリスジクロロプロピルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、クレジルジフェニルホスフェート、トリキシレニルホスフェート、オクチルジフェニルホスフェート、キシレニルジフェニルホスフェート、トリスイソプロピルフェニルホスフェート、２－エチルヘキシルジフェニルホスフェート、ｔ－ブチルフェニルジフェニルホスフェート、ビス－（ｔ－ブチルフェニル）フェニルホスフェート、トリス－（ｔ－ブチルフェニル）ホスフェート、イソプロピルフェニルジフェニルホスフェート、ビス－（イソプロピルフェニル）ジフェニルホスフェート、トリス－（イソプロピルフェニル）ホスフェート等が挙げられる。 Examples of the phosphate ester flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, tris dichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, Trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, tris isopropyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t-butyl phenyl phosphate) Phenyl) phosphate, isopropylphenyl diphenyl phosphate, bis- ( Isopropyl phenyl) diphenyl phosphate, tris - (isopropylphenyl) phosphate, and the like.
　上記縮合リン酸エステル系難燃剤の例としては、１，３－フェニレンビス（ジフェニルホスフェート）、１，３－フェニレンビス（ジキシレニルホスフェート）、ビスフェノールＡビス（ジフェニルホスフェート）等が挙げられる。 Examples of the condensed phosphoric acid ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate) and the like.
　上記（ポリ）リン酸塩系難燃剤の例としては、ポリリン酸アンモニウム、ポリリン酸メラミン、ポリリン酸ピペラジン、ピロリン酸メラミン、ピロリン酸ピペラジン等の（ポリ）リン酸のアンモニウム塩やアミン塩が挙げられる。 Examples of the (poly) phosphate flame retardants include ammonium salts and amine salts of (poly) phosphoric acids such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melamine pyrophosphate and piperazine pyrophosphate. .
　その他の無機系難燃助剤としては、例えば、酸化チタン、酸化アルミニウム、酸化マグネシウム、ハイドロタルサイト、タルク、モンモリロナイト等の無機化合物、およびその表面処理品が挙げられ、例えば、ＴＩＰＡＱＵＥ　Ｒ－６８０（酸化チタン：石原産業（株）製）、キョーワマグ１５０（酸化マグネシウム：協和化学工業（株）製）、ＤＨＴ－４Ａ（ハイドロタルサイト：協和化学工業（株）製）、アルカマイザー４（亜鉛変性ハイドロタルサイト：協和化学工業（株）製）等の種々の市販品を用いることができる。また、その他の有機系難燃助剤としては、例えば、ペンタエリスリトールが挙げられる。 Other inorganic flame retardant aids include, for example, 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) Talsite: Various commercial products such as Kyowa Chemical Industry Co., Ltd. can be used. Moreover, as another organic type flame retardant auxiliary agent, pentaerythritol is mentioned, for example.
　その他、本発明の樹脂組成物には、本発明の効果を損なわない範囲で、必要に応じて、通常合成樹脂に使用される添加剤、例えば、架橋剤、防曇剤、プレートアウト防止剤、表面処理剤、可塑剤、滑剤、難燃剤、蛍光剤、防黴剤、殺菌剤、発泡剤、金属不活性剤、離型剤、顔料、加工助剤、酸化防止剤、光安定剤等を、本発明の効果を損なわない範囲で配合することができる。 In addition, the resin composition of the present invention may, if necessary, be an additive generally used for a synthetic resin, as long as the effects of the present invention are not impaired, such as a crosslinking agent, an antifogging agent, an antiplateout agent, Surface treatment agents, plasticizers, lubricants, flame retardants, fluorescent agents, fungicides, bactericides, foaming agents, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, etc. It can mix | blend in the range which does not impair the effect of this invention.
　本発明の樹脂組成物に配合される添加剤は、熱可塑性樹脂に直接添加してもよく、本発明の高分子化合物（Ｅ）または組成物に配合してから、熱可塑性樹脂に添加してもよい。 The additive to be added to the resin composition of the present invention may be added directly to the thermoplastic resin, or added to the thermoplastic resin after being added to the polymer compound (E) or the composition of the present invention It is also good.
　本発明の樹脂組成物を成形することにより、帯電防止性を有する樹脂成形体を得ることができる。成形方法としては、特に限定されるものではなく、押出加工、カレンダー加工、射出成形、ロール、圧縮成形、ブロー成形、回転成形等が挙げられ、樹脂板、シート、フィルム、ボトル、繊維、異形品等の種々の形状の成形品が製造できる。 By molding the resin composition of the present invention, a resin molded product having antistatic properties can be obtained. The molding method is not particularly limited, and extrusion, calendering, injection molding, rolling, compression molding, blow molding, rotational molding, etc. may be mentioned, resin plate, sheet, film, bottle, fiber, profiled article Molded articles of various shapes such as can be manufactured.
　本発明の樹脂組成物により得られる成形体は、帯電防止性能およびその持続性に優れるものである。 The molded object obtained by the resin composition of this invention is excellent in antistatic performance and its sustainability.
　本発明の樹脂組成物およびこれを用いた成形体は、電気・電子・通信、農林水産、鉱業、建設、食品、繊維、衣類、医療、石炭、石油、ゴム、皮革、自動車、精密機器、木材、建材、土木、家具、印刷、楽器等の幅広い産業分野に使用できる。 The resin composition of the present invention and a molded article using the same are used in electric / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, fiber, clothing, medical, coal, petroleum, rubber, leather, automobile, precision equipment, wood It can be used in a wide range of industrial fields such as construction materials, civil engineering, furniture, printing and musical instruments.
　より具体的には、本発明の樹脂組成物およびその成形体は、プリンター、パソコン、ワープロ、キーボード、ＰＤＡ（小型情報端末機）、電話機、複写機、ファクシミリ、ＥＣＲ（電子式金銭登録機）、電卓、電子手帳、カード、ホルダー、文具等の事務、ＯＡ機器、洗濯機、冷蔵庫、掃除機、電子レンジ、照明器具、ゲーム機、アイロン、コタツ等の家電機器、ＴＶ、ＶＴＲ、ビデオカメラ、ラジカセ、テープレコーダー、ミニディスク、ＣＤプレーヤー、スピーカー、液晶ディスプレー等のＡＶ機器、コネクター、リレー、コンデンサー、スイッチ、プリント基板、コイルボビン、半導体封止材料、ＬＥＤ封止材料、電線、ケーブル、トランス、偏向ヨーク、分電盤、時計等の電気・電子部品および通信機器、自動車用内外装材、製版用フィルム、粘着フィルム、ボトル、食品用容器、食品包装用フィルム、製薬・医薬用ラップフィルム、製品包装フィルム、農業用フィルム、農業用シート、温室用フィルム等の用途に用いられる。 More specifically, the resin composition of the present invention and the molded article thereof can be used in printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers), Calculators, electronic organizers, cards, holders, stationery, office work, office automation equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, household appliances such as irons, TVs, VTRs, video cameras, radio cassette players , Tape recorder, mini disc, CD player, speaker, AV equipment such as liquid crystal display, connector, relay, capacitor, switch, printed circuit board, coil bobbin, semiconductor sealing material, LED sealing material, electric wire, cable, transformer, deflection yoke , Electric and electronic parts such as distribution boards and watches, and communication devices, interior and exterior materials for automobiles, plate making Film, adhesive film, bottles, food containers, food packaging films, pharmaceutical and pharmaceutical wrap film, product packaging film, agricultural film, agricultural sheeting, used in applications such as greenhouse films.
　さらに、本発明の樹脂組成物およびその成形体は、座席（詰物、表地等）、ベルト、天井張り、コンパーチブルトップ、アームレスト、ドアトリム、リアパッケージトレイ、カーペット、マット、サンバイザー、ホイルカバー、マットレスカバー、エアバック、絶縁材、吊り手、吊り手帯、電線被覆材、電気絶縁材、塗料、コーティング材、上張り材、床材、隅壁、カーペット、壁紙、壁装材、外装材、内装材、屋根材、デッキ材、壁材、柱材、敷板、塀の材料、骨組および繰形、窓およびドア形材、こけら板、羽目、テラス、バルコニー、防音板、断熱板、窓材等の自動車、車両、船舶、航空機、建物、住宅および建築用材料や土木材料、衣料、カーテン、シーツ、不織布、合板、合繊板、絨毯、玄関マット、シート、バケツ、ホース、容器、眼鏡、鞄、ケース、ゴーグル、スキー板、ラケット、テント、楽器等の生活用品、スポーツ用品等の各種用途に使用することができる。 Furthermore, the resin composition of the present invention and the molded article thereof can be used in a seat (filler, outer fabric, etc.), a belt, a ceiling, a convertible top, an armrest, a door trim, a rear package tray, a carpet, a mat, a sun visor, a foil cover, a mattress cover , Air bag, insulation material, hanging hand, hanging band, electric wire coating material, electric insulation material, paint, coating material, covering material, flooring material, floor material, corner wall, carpet, wallpaper, wall covering material, exterior material, interior material , Roofing materials, decking materials, wall materials, pillars, floorboards, materials for fences, frameworks and moldings, windows and door profiles, shingles, crosses, terraces, balconies, soundproofing boards, insulation boards, window materials, etc. Materials and civil engineering materials for automobiles, vehicles, ships, aircraft, buildings, houses and buildings, clothing, curtains, sheets, nonwoven fabrics, plywood, synthetic fiber boards, carpets, entrance mats, sheets, buckets, hoses, Vessel, glasses, bags, cases, goggles, skis, it is possible to use racket, tents, household goods of musical instruments, etc., in various applications such as sporting goods.
　以下、本発明を、実施例を用いてさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited thereto.
　下記の製造例に従い、本発明で用いられる高分子化合物（Ｅ）を製造した。また、下記の製造例において、化合物（ｂ）の数平均分子量は、下記＜分子量測定方法１＞で測定し、化合物（ｂ）以外の数平均分子量は、下記＜分子量測定方法２＞で測定した。 The polymer compound (E) used in the present invention was produced according to the following production examples. Moreover, in the following production example, the number average molecular weight of the compound (b) was measured by the following <molecular weight measuring method 1>, and the number average molecular weights other than the compound (b) were measured by the following <molecular weight measuring method 2> .
＜分子量測定方法１＞
　下記水酸基価測定方法で水酸基価を測定し、下記式で数平均分子量（以下「Ｍｎ」とも称する）を決定した。
　数平均分子量＝（５６１１０×２）／水酸基価
＜水酸基価測定法＞
・試薬Ａ（アセチル化剤）
（１）トリエチルホスフェート　１５６０ｍＬ
（２）無水酢酸　１９３ｍＬ
（３）過塩素酸（６０％）　１６ｇ
上記試薬を（１）→（２）→（３）の順に混合する。
・試薬Ｂ
ピリジンと純水を体積比率で３：１に混合する。
・試薬Ｃ
５００ｍＬのイソプロピルアルコールにフェノールフタレイン液を２～３滴加え、１Ｎ－ＫＯＨ水溶液で中性にする。 <Molecular weight measurement method 1>
The hydroxyl value was measured by the following hydroxyl value measurement method, and the number average molecular weight (hereinafter also referred to as "Mn") was determined by the following equation.
Number average molecular weight = (56110 × 2) / hydroxyl value <hydroxyl value measurement method>
Reagent A (acetylating agent)
(1) Triethyl phosphate 1560 mL
(2) 193 mL of acetic anhydride
(3) Perchloric acid (60%) 16 g
The above reagents are mixed in the order of (1) → (2) → (3).
・ Reagent B
Pyridine and pure water are mixed in a volume ratio of 3: 1.
・ Reagent C
Add 2-3 drops of phenolphthalein solution to 500 mL of isopropyl alcohol, and neutralize with 1N aqueous KOH solution.
　まず、２００ｍＬ三角フラスコにサンプルを２ｇ量りとり、キシレン１０ｍＬを加え、加熱溶解させる。試薬Ａ１５ｍＬを加え、共栓をして激しく振盪する。試薬Ｂ２０ｍＬを加え、共栓をして激しく振盪する。試薬Ｃ５０ｍＬを加える。１Ｎ－ＫＯＨ水溶液で滴定し、下式で計算する。 First, 2 g of a sample is weighed into a 200 mL Erlenmeyer flask, and 10 mL of xylene is added and dissolved by heating. Add 15 mL of Reagent A, stopper and shake vigorously. Add 20 mL of Reagent B, stopper and shake vigorously. Add 50 mL of reagent C. Titrate with 1 N KOH aqueous solution and calculate according to the following formula.
水酸基価［ｍｇＫＯＨ／ｇ］＝５６．１１×ｆ×（Ｔ－Ｂ）／Ｓ
ｆ：１Ｎ－ＫＯＨ水溶液のｆａｃｔｏｒ
Ｂ：空試験滴定量［ｍＬ］
Ｔ：本試験滴定量［ｍＬ］
Ｓ：サンプル量［ｇ］ Hydroxyl value [mg KOH / g] = 56. 11 x f x (T-B) / S
f: factor of 1 N KOH solution
B: Blank test titer [mL]
T: main test titer [mL]
S: Sample amount [g]
＜分子量測定方法２＞
　数平均分子量（以下、「Ｍｎ」とも称する）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によって測定した。Ｍｎの測定条件は以下の通りである。 <Molecular weight measurement method 2>
The number average molecular weight (hereinafter also referred to as “Mn”) was measured by gel permeation chromatography (GPC). The measurement conditions of Mn are as follows.
装置　　　　　　　　：日本分光（株）製，ＧＰＣ装置
溶媒　　　　　　　　：テトラヒドロフラン
基準物質　　　　　　：ポリスチレン
検出器　　　　　　　：示差屈折計（ＲＩ検出器）
カラム固定相　　　　：昭和電工（株）製，Ｓｈｏｄｅｘ　ＫＦ－８０４Ｌ
カラム温度　　　　　：４０℃
サンプル濃度　　　　：１ｍｇ／１ｍＬ
流量　　　　　　　　：０．８ｍＬ／ｍｉｎ．
注入量　　　　　　　：１００μＬ Device: JASCO Ltd. product, GPC device Solvent: Tetrahydrofuran standard substance: 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
〔製造例１〕
　セパラブルフラスコに、１，４－シクロヘキサンジメタノールを３３ｇ、アジピン酸を３６ｇ、無水フタル酸を０．０４ｇ、酸化防止剤（テトラキス［３－（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオニルオキシメチル］メタン、アデカスタブＡＯ－６０（株）ＡＤＥＫＡ製）を０．２ｇ仕込み、１６０℃から２１０℃まで徐々に昇温しながら常圧で４時間、その後２１０℃、減圧下で３時間重合して、ポリエステル（ａ）－１を得た。 Production Example 1
In a separable flask, 33 g of 1,4-cyclohexanedimethanol, 36 g of adipic acid, 0.04 g of phthalic anhydride, and an antioxidant (tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl)] 0.2g of propionyl oxymethyl] methane, Adekastab AO-60 (manufactured by ADEKA), charged, gradually raising temperature from 160 ° C to 210 ° C for 4 hours at normal pressure, then at 210 ° C, reduced pressure for 3 hours It polymerized and obtained polyester (a) -1.
　次に、得られたポリエステル（ａ）－１を６１ｇ、両末端に水酸基を有する化合物（ｂ）－１として数平均分子量３１００、エチレンオキシ基の繰り返し単位の数＝７０のポリエチレングリコールを３１ｇ、酸化防止剤（アデカスタブＡＯ－６０）を０．２ｇ、オクチル酸ジルコニウムを０．４ｇ仕込み、２１０℃で７時間、減圧下で重合して、両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）－１を１００ｇ得た。この両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）－１の酸価は１１、数平均分子量Ｍｎはポリスチレン換算で１６，０００あった。 Next, 61 g of the obtained polyester (a) -1, 31 g of polyethylene glycol having a number average molecular weight of 3100 and the number of repeating units of ethyleneoxy group = 70 as the compound (b) -1 having a hydroxyl group at both ends 0.2 g of inhibitor (ADEKA STAB AO-60) and 0.4 g of zirconium octylate are charged and polymerized under reduced pressure at 210 ° C. for 7 hours to obtain a block polymer (C) having a structure having carboxyl groups at both ends 100 g of -1 was obtained. The acid value of the block polymer (C) -1 having a structure having a carboxyl group at both ends is 11, and the number average molecular weight Mn is 16,000 in terms of polystyrene.
　得られた両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）－１の１００ｇに、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）－１としてポリエチレングリコールジグリシジルエーテル（エポキシ当量２６８ｇ／ｅｑ）１．５ｇを仕込み、２４０℃で３時間、減圧下で重合して、高分子化合物（Ｅ）－１を１０２ｇ得た。 Polyethylene glycol diglycidyl ether (epoxy equivalent 268 g / eq) 1 as polyalkylene glycol diglycidyl ether compound (D) -1 was added to 100 g of block polymer (C) -1 having a structure having a carboxyl group at both ends obtained. .5g was charged and polymerized under reduced pressure at 240 ° C for 3 hours to obtain 102g of a polymer compound (E) -1.
〔製造例２〕
　製造例１と同様にして得られた両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）－１の１００ｇに、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）－２としてポリエチレングリコールジグリシジルエーテル（エポキシ当量１９１ｇ／ｅｑ）１．１ｇを仕込み、２４０℃で３時間、減圧下で重合して、高分子化合物（Ｅ）－２を１０２ｇ得た。 Production Example 2
In 100 g of block polymer (C) -1 having a structure having a carboxyl group at both ends obtained in the same manner as in Production Example 1, polyethylene glycol diglycidyl ether (polyalkylene glycol diglycidyl ether compound (D) -2) 1.1 g of epoxy equivalent weight was charged and polymerized under reduced pressure at 240 ° C. for 3 hours to obtain 102 g of a polymer compound (E) -2.
〔製造例３〕
　製造例１と同様にして得られた両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）－の１００ｇに、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）－３としてポリエチレングリコールジグリシジルエーテル（エポキシ当量２７７ｇ／ｅｑ）１．６ｇを仕込み、２４０℃で３時間、減圧下で重合して、高分子化合物（Ｅ）－３を１０２ｇ得た。 Production Example 3
100 g of a block polymer (C)-having a structure having a carboxyl group at both ends obtained in the same manner as in Production Example 1 and polyethylene glycol diglycidyl ether (epoxy) as polyalkylene glycol diglycidyl ether compound (D) -3 An amount of 1.6 g equivalent to 277 g / eq) was charged, and polymerization was carried out at 240 ° C. for 3 hours under reduced pressure to obtain 102 g of a polymer compound (E) -3.
〔製造例４〕
　製造例１と同様にして得られた両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）－１の１００ｇに、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）－４としてジエチレングリコールジグリシジルエーテル（エポキシ当量１５２ｇ／ｅｑ）０．９ｇを仕込み、２４０℃で３時間、減圧下で重合して、高分子化合物（Ｅ）－４を１０２ｇ得た。 Production Example 4
In 100 g of block polymer (C) -1 having a structure having a carboxyl group at both ends obtained in the same manner as in Production Example 1, diethylene glycol diglycidyl ether (epoxy) as polyalkylene glycol diglycidyl ether compound (D) -4 0.9 g of an equivalent of 152 g / eq) was charged, and polymerization was performed under reduced pressure at 240 ° C. for 3 hours to obtain 102 g of a polymer compound (E) -4.
〔製造例５〕
　製造例１と同様にして得られた両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）－１の１００ｇに、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）－５としてポリプロピレングリコールジグリシジルエーテル（エポキシ当量３００ｇ／ｅｑ）１．７ｇを仕込み、２４０℃で３時間、減圧下で重合して、高分子化合物（Ｅ）－５を１０３ｇ得た。 Production Example 5
Polypropylene glycol diglycidyl ether (polyalkylene glycol diglycidyl ether compound (D) -5) was added to 100 g of block polymer (C) -1 having a structure having a carboxyl group at both ends obtained in the same manner as in Production Example 1 1.7 g of epoxy equivalent 300 g / eq) was charged, and polymerization was carried out under reduced pressure at 240 ° C. for 3 hours to obtain 103 g of a polymer compound (E) -5.
〔製造例６〕
　製造例１と同様にして得られた両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）－１の１００ｇに、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）－６としてポリプロピレングリコールジグリシジルエーテル（エポキシ当量３１５ｇ／ｅｑ）１．８ｇを仕込み、２４０℃で３時間、減圧下で重合して、高分子化合物（Ｅ）－６を１０３ｇ得た。 Production Example 6
Polypropylene glycol diglycidyl ether (polyalkylene glycol diglycidyl ether compound (D) -6) was added to 100 g of block polymer (C) -1 having a structure having a carboxyl group at both ends obtained in the same manner as in Production Example 1 1.8 g of epoxy equivalent weight 315 g / eq) was charged and polymerized under reduced pressure at 240 ° C. for 3 hours to obtain 103 g of a polymer compound (E) -6.
〔製造例７〕
　製造例１と同様にして得られた両末端にカルボキシル基を有する構造を有するブロックポリマー（Ｃ）－１の１００ｇに、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）－７としてポリプロピレングリコールジグリシジルエーテル（エポキシ当量４１７ｇ／ｅｑ）２．４ｇを仕込み、２４０℃で３時間、減圧下で重合して、高分子化合物（Ｅ）－７を１０３ｇ得た。 Production Example 7
Polypropylene glycol diglycidyl ether (polyalkylene glycol diglycidyl ether compound (D) -7) was added to 100 g of block polymer (C) -1 having a structure having a carboxyl group at both ends obtained in the same manner as in Production Example 1 2.4 g of epoxy equivalent weight 417 g / eq) was charged and polymerized under reduced pressure at 240 ° C. for 3 hours to obtain 103 g of a polymer compound (E) -7.
〔比較製造例１〕
　製造例１と同様にして得られたブロックポリマー（Ｃ）－１の１００ｇに、ビスフェノールＦジグリシジルエーテル（エポキシ当量１７０ｇ／ｅｑ）１．０ｇを仕込み、２４０℃で３時間、減圧下で重合して、比較高分子化合物－１を１０２ｇ得た。 Comparative Production Example 1
In 100 g of block polymer (C) -1 obtained in the same manner as in Production Example 1, 1.0 g of bisphenol F diglycidyl ether (epoxy equivalent 170 g / eq) was charged and polymerized under reduced pressure at 240 ° C. for 3 hours. Thus, 102 g of Comparative Polymer Compound 1 was obtained.
〔比較製造例２〕
　製造例１と同様にして得られたブロックポリマー（Ｃ）－１の１００ｇに、ビスフェノールＡジグリシジルエーテル（エポキシ当量２５０ｇ／ｅｑ）１．５ｇを仕込み、２４０℃で３時間、減圧下で重合して、比較高分子化合物－２を１０２ｇ得た。 Comparative Production Example 2
In 100 g of block polymer (C) -1 obtained in the same manner as in Production Example 1, 1.5 g of bisphenol A diglycidyl ether (epoxy equivalent 250 g / eq) was charged and polymerized under reduced pressure at 240 ° C. for 3 hours. Thus, 102 g of Comparative Polymer Compound 2 was obtained.
〔実施例１～１０、比較例１～４〕
　下記の表１～３に記載した配合量に基づいてブレンドした各実施例および各比較例の樹脂組成物を用いて、下記に示す試験片作製条件に従い、試験片を得た。得られた試験片を用いて、下記に従い、表面抵抗率（ＳＲ値）の測定を行い、帯電防止性とその持続性の評価を行った。 [Examples 1 to 10, Comparative Examples 1 to 4]
Test pieces were obtained using the resin compositions of Examples and Comparative Examples blended based on the compounding amounts described in Tables 1 to 3 below, according to the test piece preparation conditions shown below. The surface resistivity (SR value) was measured according to the following using the obtained test piece, and the antistatic property and its durability were evaluated.
＜ホモポリプロピレン樹脂組成物試験片作製条件＞
　下記の表１～３中に示す配合量に基づいてブレンドした樹脂組成物を、（株）池貝製２軸押出機（ＰＣＭ３０，６０ｍｅｓｈ入り）を用いて、２３０℃、６ｋｇ／時間の条件で造粒し、ペレットを得た。得られたペレットを、横型射出成形機（ＮＥＸ８０：日精樹脂工業（株）製）を用い、樹脂温度２３０℃、金型温度４０℃の加工条件で成形し、試験片（１００ｍｍ×１００ｍｍ×３ｍｍ）を得た。 <Homopolypropylene resin composition test piece preparation conditions>
Resin compositions blended based on the compounding amounts shown in Tables 1 to 3 below were produced using Ikegai Co., Ltd. twin screw extruder (containing PCM 30, 60 mesh) under conditions of 230 ° C. and 6 kg / hour. Granulated to obtain pellets. The obtained pellets are molded using a horizontal injection molding machine (NEX 80: manufactured by Nissei Resin Industry Co., Ltd.) under processing conditions of a resin temperature of 230 ° C. and a mold temperature of 40 ° C., test pieces (100 mm × 100 mm × 3 mm) I got
＜表面抵抗率（ＳＲ値）測定方法＞
　得られた試験片を、成形加工後直ちに、温度２５℃、湿度５０％ＲＨの条件下に保存し、成形加工の１日および３０日保存後に、同雰囲気下で、アドバンテスト社製のＲ８３４０抵抗計を用いて、印加電圧１００Ｖ、印加時間１分の条件で、表面抵抗率（Ω／□）を測定した。測定は５枚の試験片で１枚あたり５点について行い、その平均値を求めた。  <Method of measuring surface resistivity (SR value)>
Immediately after molding, the obtained test piece is stored under the conditions of temperature 25 ° C. and humidity 50% RH, and after storage for 1 day and 30 days of molding processing, under the same atmosphere, R8340 resistance meter made by Advantest Corp. The surface resistivity (Ω / □) was measured under the conditions of an applied voltage of 100 V and an application time of 1 minute. The measurement was carried out at five points per five test pieces, and the average value was determined.
Figure JPOXMLDOC01-appb-T000005
 ＊１：ＮａＤＢＳはドデシルベンゼンスルホン酸ナトリウムを表す。
＊２：ｈＰＰはホモポリプロピレン（メルトフローレート＝８）を表す。
Figure JPOXMLDOC01-appb-T000005
 * 1: NaDBS represents sodium dodecylbenzene sulfonate.
* 2: hPP represents homopolypropylene (melt flow rate = 8).
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表１～３中に示す結果から、本発明によれば、優れた帯電防止効果とその持続性を有した高分子化合物が得られることが明らかである。 From the results shown in Tables 1 to 3, it is clear that according to the present invention, a polymer compound having an excellent antistatic effect and its durability can be obtained.

Claims (15)

  1. 　ジオールと、脂肪族ジカルボン酸および芳香族ジカルボン酸と、が反応して得られるポリエステル（ａ）と、エチレンオキシ基を１以上有する両末端に水酸基を有する化合物（ｂ）と、ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）と、が反応して得られることを特徴とする高分子化合物。 A polyester (a) obtained by reacting a diol with an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, a compound (b) having hydroxyl groups at both ends having one or more ethyleneoxy groups, and polyalkylene glycol diglycidyl A polymer compound characterized by being obtained by reacting an ether compound (D).
  2. 　前記ポリエステル（ａ）から構成されるポリエステルのブロック（Ａ）と、前記化合物（ｂ）から構成されるポリエーテルのブロック（Ｂ）と、を有し、前記ポリエステル（ａ）の末端に有する水酸基またはカルボキシル基と、前記化合物（ｂ）の末端に有する水酸基と、前記ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）のエポキシ基と、の反応により形成された、エステル結合またはエーテル結合を介して結合してなる構造を有する請求項１記載の高分子化合物。 A hydroxyl group or a hydroxyl group at an end of the polyester (a), comprising a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the compound (b) Combined via an ester bond or an ether bond formed by the reaction of a carboxyl group, a hydroxyl group at the end of the compound (b) and an epoxy group of the polyalkylene glycol diglycidyl ether compound (D) The polymer compound according to claim 1 having the following structure.
  3. 　前記ポリエステルのブロック（Ａ）と、前記ポリエーテルのブロック（Ｂ）と、がエステル結合を介して繰り返し交互に結合してなる両末端にカルボキシル基を有するブロックポリマー（Ｃ）と、前記ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）と、がエステル結合を介して結合してなる構造を有する請求項２記載の高分子化合物。 A block polymer (C) having a carboxyl group at both ends formed by repeating alternately and alternately the block (A) of the polyester and the block (B) of the polyether via an ester bond, and the polyalkylene glycol The polymer compound according to claim 2, having a structure in which the diglycidyl ether compound (D) is bonded via an ester bond.
  4. 　前記ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）が、ポリエチレングリコールジグリシジルエーテルである請求項１～３のうちいずれか一項記載の高分子化合物。 The polymer compound according to any one of claims 1 to 3, wherein the polyalkylene glycol diglycidyl ether compound (D) is polyethylene glycol diglycidyl ether.
  5. 　前記ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）が、ポリプロピレングリコールジグリシジルエーテルである請求項１～３のうちいずれか一項記載の高分子化合物。 The polymer compound according to any one of claims 1 to 3, wherein the polyalkylene glycol diglycidyl ether compound (D) is polypropylene glycol diglycidyl ether.
  6. 　前記ポリアルキレングリコールジグリシジルエーテル化合物（Ｄ）のエポキシ当量が、７０～２，０００である請求項１～５のうちいずれか一項記載の高分子化合物。 The polymer compound according to any one of claims 1 to 5, wherein the epoxy equivalent of the polyalkylene glycol diglycidyl ether compound (D) is 70 to 2,000.
  7. 　前記ポリエステル（ａ）が、両末端にカルボキシル基を有する構造である請求項１～６のうちいずれか一項記載の高分子化合物。 The polymer compound according to any one of claims 1 to 6, wherein the polyester (a) has a structure having a carboxyl group at both ends.
  8. 　前記化合物（ｂ）が、ポリエチレングリコールである請求項１～７のうちいずれか一項記載の高分子化合物。 The polymer compound according to any one of claims 1 to 7, wherein the compound (b) is polyethylene glycol.
  9. 　前記化合物（ｂ）の数平均分子量が、４００～１０，０００である請求項１～８のうちいずれか一項記載の高分子化合物。 The polymer compound according to any one of claims 1 to 8, wherein the number average molecular weight of the compound (b) is 400 to 10,000.
  10. 　前記ブロックポリマー（Ｃ）の数平均分子量が、５，０００～３０，０００である請求項３～９のうちいずれか一項記載の高分子化合物。 The polymer compound according to any one of claims 3 to 9, wherein the number average molecular weight of the block polymer (C) is 5,000 to 30,000.
  11. 　請求項１～１０のうちいずれか一項記載の高分子化合物に対し、さらに、アルカリ金属の塩および第２族元素の塩からなる群から選択される１種以上が配合されてなることを特徴とする組成物。 11. The polymer compound according to any one of claims 1 to 10, further comprising one or more selected from the group consisting of a salt of an alkali metal and a salt of a group 2 element. And a composition.
  12. 　熱可塑性樹脂に対し、請求項１～１０のうちいずれか一項記載の高分子化合物が配合されてなることを特徴とする樹脂組成物。 A resin composition comprising the polymer compound according to any one of claims 1 to 10 blended with a thermoplastic resin.
  13. 　熱可塑性樹脂に対し、請求項１１記載の組成物が配合されてなることを特徴とする樹脂組成物。 A resin composition comprising the composition according to claim 11 blended with a thermoplastic resin.
  14. 　前記熱可塑性樹脂が、ポリオレフィン系樹脂、ポリスチレン系樹脂およびそれらの共重合体からなる群から選ばれる１種以上である請求項１２または１３記載の樹脂組成物。 The resin composition according to claim 12 or 13, wherein the thermoplastic resin is one or more selected from the group consisting of polyolefin resins, polystyrene resins and copolymers thereof.
  15. 　請求項１２～１４のうちいずれか一項記載の樹脂組成物からなることを特徴とする成形体。 A molded article comprising the resin composition according to any one of claims 12 to 14.
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