WO2019021944A1 - Composé macromoléculaire, composition contenant celui-ci, composition de résine contenant ceux-ci ainsi que corps moulé associé - Google Patents

Composé macromoléculaire, composition contenant celui-ci, composition de résine contenant ceux-ci ainsi que corps moulé associé 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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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention fournit un composé macromoléculaire qui permet de conférer de manière continue un excellent effet antistatique à une résine synthétique, une composition contenant ce composé macromoléculaire, et une composition de résine contenant ce composé macromoléculaire et cette composition ainsi qu'un corps moulé de cette composition. Plus précisément, l'invention concerne un composé macromoléculaire qui est obtenu par réaction : d'un polyester (a) obtenu par réaction d'un diol et d'un acide dicarboxylique aliphatique ainsi que d'un acide dicarboxylique aromatique ; d'un composé (b) qui possède un groupe hydroxyle à ses deux extrémités présentant au moins un groupe éthylèneoxy ; et d'un composé éther diglycidylique de polyalkylène glycol (D).
PCT/JP2018/027166 2017-07-24 2018-07-19 Composé macromoléculaire, composition contenant celui-ci, composition de résine contenant ceux-ci ainsi que corps moulé associé WO2019021944A1 (fr)

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JPWO2020202642A1 (fr) * 2019-03-29 2020-10-08
WO2020203618A1 (fr) * 2019-03-29 2020-10-08 株式会社Adeka Agent antistatique, composition d'agent antistatique le contenant, composition de résine antistatique le contenant, corps moulé et film associé

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JPS56109241A (en) * 1980-02-04 1981-08-29 Matsumoto Yushi Seiyaku Kk Water-absorbing macromolecular material
JPS62275153A (ja) * 1986-02-26 1987-11-30 Toyobo Co Ltd ポリエステル組成物
JPH02252753A (ja) * 1989-03-27 1990-10-11 Kanegafuchi Chem Ind Co Ltd ポリエステルエステルエラストマー組成物
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JPH07304844A (ja) * 1994-05-10 1995-11-21 Dainippon Ink & Chem Inc 変性ポリエステル樹脂の製造方法
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JPWO2020202642A1 (fr) * 2019-03-29 2020-10-08
WO2020203618A1 (fr) * 2019-03-29 2020-10-08 株式会社Adeka Agent antistatique, composition d'agent antistatique le contenant, composition de résine antistatique le contenant, corps moulé et film associé
CN113631622A (zh) * 2019-03-29 2021-11-09 株式会社Adeka 抗静电剂、包含其的抗静电剂组合物、包含这些的抗静电性树脂组合物及其成型体
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