JPH01174555A - Production of aromatic polyester resin composition - Google Patents
Production of aromatic polyester resin compositionInfo
- Publication number
- JPH01174555A JPH01174555A JP33502587A JP33502587A JPH01174555A JP H01174555 A JPH01174555 A JP H01174555A JP 33502587 A JP33502587 A JP 33502587A JP 33502587 A JP33502587 A JP 33502587A JP H01174555 A JPH01174555 A JP H01174555A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyester
- acid
- weight
- epoxy compound
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 229920001225 polyester resin Polymers 0.000 title claims description 7
- 239000004645 polyester resin Substances 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920000728 polyester Polymers 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000004593 Epoxy Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000011256 inorganic filler Substances 0.000 claims abstract description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 16
- 229920001038 ethylene copolymer Polymers 0.000 claims description 27
- -1 polyethylene terephthalate Polymers 0.000 abstract description 34
- 229920001577 copolymer Polymers 0.000 abstract description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 14
- 239000003365 glass fiber Substances 0.000 abstract description 12
- 230000007062 hydrolysis Effects 0.000 abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 4
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 17
- 238000000034 method Methods 0.000 description 10
- 229920001707 polybutylene terephthalate Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- MLVSWIXRZNPEKF-UPHRSURJSA-N bis(oxiran-2-ylmethyl) (z)-but-2-enedioate Chemical compound C1OC1COC(=O)\C=C/C(=O)OCC1CO1 MLVSWIXRZNPEKF-UPHRSURJSA-N 0.000 description 2
- KIKYOFDZBWIHTF-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-3-ene-1,2-dicarboxylate Chemical compound C1CC=CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KIKYOFDZBWIHTF-UHFFFAOYSA-N 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- KBRJTGNCPIFGFI-AATRIKPKSA-N (e)-n,n,n',n'-tetramethylbut-2-enediamide Chemical compound CN(C)C(=O)\C=C\C(=O)N(C)C KBRJTGNCPIFGFI-AATRIKPKSA-N 0.000 description 1
- VPFXWMDVXYAJGV-SNAWJCMRSA-N (e)-n,n-dimethylbut-2-enamide Chemical compound C\C=C\C(=O)N(C)C VPFXWMDVXYAJGV-SNAWJCMRSA-N 0.000 description 1
- VYKKUIWIHXELAN-UHFFFAOYSA-N 1-N,1-N,2-N,2-N-tetramethylcyclohex-3-ene-1,2-dicarboxamide Chemical compound CN(C(C1C(C(=O)N(C)C)CCC=C1)=O)C VYKKUIWIHXELAN-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- JGBOVFKUKBGAJQ-UHFFFAOYSA-N 2-methylidenebutanediamide Chemical compound NC(=O)CC(=C)C(N)=O JGBOVFKUKBGAJQ-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- CCFNMXDJVOYPEY-UHFFFAOYSA-N 2-phenyl-3a,4,5,7a-tetrahydroisoindole-1,3-dione Chemical compound O=C1C2CCC=CC2C(=O)N1C1=CC=CC=C1 CCFNMXDJVOYPEY-UHFFFAOYSA-N 0.000 description 1
- JLLCBHHFPWVBQP-UHFFFAOYSA-N 3-methylidene-1-phenylpyrrolidine-2,5-dione Chemical compound O=C1C(=C)CC(=O)N1C1=CC=CC=C1 JLLCBHHFPWVBQP-UHFFFAOYSA-N 0.000 description 1
- FKAWETHEYBZGSR-UHFFFAOYSA-N 3-methylidenepyrrolidine-2,5-dione Chemical compound C=C1CC(=O)NC1=O FKAWETHEYBZGSR-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- CIFFBTOJCKSRJY-UHFFFAOYSA-N 3α,4,7,7α-tetrahydro-1h-isoindole-1,3(2h)-dione Chemical compound C1C=CCC2C(=O)NC(=O)C21 CIFFBTOJCKSRJY-UHFFFAOYSA-N 0.000 description 1
- 125000005828 4,4′-bicyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])(C([H])([H])C([H])([H])C1([H])[*:1])C1([H])C([H])([H])C([H])([H])C([H])([*:2])C([H])([H])C1([H])[H] 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- ZFDIRQKJPRINOQ-HWKANZROSA-N Ethyl crotonate Chemical compound CCOC(=O)\C=C\C ZFDIRQKJPRINOQ-HWKANZROSA-N 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- URRLLRVIUROMEQ-UHFFFAOYSA-N anthracene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC3=CC(C(=O)O)=CC=C3C=C21 URRLLRVIUROMEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- MLVSWIXRZNPEKF-OWOJBTEDSA-N bis(oxiran-2-ylmethyl) (e)-but-2-enedioate Chemical compound C1OC1COC(=O)/C=C/C(=O)OCC1CO1 MLVSWIXRZNPEKF-OWOJBTEDSA-N 0.000 description 1
- NRTSLUOVGBFANI-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 2-methylidenebutanedioate Chemical compound C1OC1COC(=O)C(=C)CC(=O)OCC1CO1 NRTSLUOVGBFANI-UHFFFAOYSA-N 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- ZXOATMQSUNJNNG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 ZXOATMQSUNJNNG-UHFFFAOYSA-N 0.000 description 1
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 1
- LSELIYBTFJVUSX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate Chemical compound C1=CC2CC1C(C(=O)OCC1OC1)C2C(=O)OCC1CO1 LSELIYBTFJVUSX-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- OBDHDEWJGUTWOK-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxamide Chemical compound NC(=O)C1CCC=CC1C(N)=O OBDHDEWJGUTWOK-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 1
- LLBFUTBRBOIQFH-UHFFFAOYSA-N dibutyl cyclohex-3-ene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1CCC=CC1C(=O)OCCCC LLBFUTBRBOIQFH-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 1
- XSBSXJAYEPDGSF-UHFFFAOYSA-N diethyl 3,5-dimethyl-1h-pyrrole-2,4-dicarboxylate Chemical compound CCOC(=O)C=1NC(C)=C(C(=O)OCC)C=1C XSBSXJAYEPDGSF-UHFFFAOYSA-N 0.000 description 1
- UXRMRBNLTQHPEU-UHFFFAOYSA-N diethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate Chemical compound C1C2C=CC1C(C(=O)OCC)C2C(=O)OCC UXRMRBNLTQHPEU-UHFFFAOYSA-N 0.000 description 1
- GDCXITNLGXJUPZ-UHFFFAOYSA-N diethyl cyclohex-3-ene-1,2-dicarboxylate Chemical compound CCOC(=O)C1CCC=CC1C(=O)OCC GDCXITNLGXJUPZ-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- HBBLLXJYSICJGE-UHFFFAOYSA-N n,n,n',n'-tetramethyl-2-methylidenebutanediamide Chemical compound CN(C)C(=O)CC(=C)C(=O)N(C)C HBBLLXJYSICJGE-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、耐衝撃性、引張り強さなどの機械的性質に優
れ、さらには極めて高い耐ヒートサイクル性、耐加水分
解性を有す、る芳香族ポリエステル樹脂組成物の製造方
法に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a material having excellent mechanical properties such as impact resistance and tensile strength, as well as extremely high heat cycle resistance and hydrolysis resistance. The present invention relates to a method for producing an aromatic polyester resin composition.
〈従来の技術〉
ポリブチレンテレフタレートやポリエチレンテレフタレ
ートに代表される芳香族ポリエステル樹脂は、耐溶剤性
などの化学的性質や物理的、機械的性質に優れ、さらに
はガラス繊維などの強化剤を用いることにより機械強度
、耐熱性が大きく向上することから、自動車部品、機械
機構部品、電気・電子機器部品等の幅広い分野に使用さ
れている。<Prior art> Aromatic polyester resins represented by polybutylene terephthalate and polyethylene terephthalate have excellent chemical properties such as solvent resistance, and physical and mechanical properties, and can also be used with reinforcing agents such as glass fiber. Because it greatly improves mechanical strength and heat resistance, it is used in a wide range of fields such as automobile parts, mechanical mechanism parts, and electrical and electronic equipment parts.
また、最近になって特開昭５５−２１３０号公報、特開
昭６１−１６３９５６号公報などに開示されているエチ
レン系共重合体に不飽和力〃ボン酸誘導体をグラフト共
重合した変性エチレン系共重合体を芳香族ポリエステル
にブレンドする方法が開発され、芳香族ポリエステルの
欠点とされてきた耐衝撃性が改良され、その用途が大幅
にひろがりつつある。しかし、需要の多いガラス繊維に
代表される無機充填剤を含有する芳香族ポリエステルに
このような耐衝撃技術を適用しても、その耐衝撃性の改
良効果は小さなものであった。In addition, modified ethylene copolymers prepared by graft copolymerizing unsaturated carbonic acid derivatives onto ethylene copolymers have recently been disclosed in JP-A-55-2130 and JP-A-61-163956. A method of blending copolymers with aromatic polyesters has been developed, improving impact resistance, which has been considered a drawback of aromatic polyesters, and its uses are expanding significantly. However, even when such impact resistance technology was applied to aromatic polyesters containing inorganic fillers, such as glass fibers, which are in high demand, the effect of improving impact resistance was small.
そこで特開昭５６−１００８４５号公報に開示されるよ
うに、芳香族ポリエステルとガラス□繊維をあらかじめ
溶融混合した後、変性エチレン系共重合体を混合するこ
とにより、耐衝撃性の改良をはかるなどの試みがなされ
ていた。Therefore, as disclosed in JP-A-56-100845, impact resistance was improved by melt-mixing aromatic polyester and glass fibers in advance and then mixing modified ethylene copolymer. attempts were being made.
〈発明が解決しようとする問題点〉
しかしながら、これらの方法によっては押出機中でガラ
ス繊維が折れたり、芳香族ポリエステルが熱分解するた
めに得られた樹脂組成物の耐衝撃性はあまり改良されず
、また引張り強度などの機械物性が低くなったり、成形
品の耐加水分解性が悪くなったりするという問題があっ
た。<Problems to be Solved by the Invention> However, depending on these methods, the impact resistance of the resulting resin composition may not be improved much because the glass fibers may break in the extruder or the aromatic polyester may thermally decompose. Furthermore, there are problems in that mechanical properties such as tensile strength are lowered, and the hydrolysis resistance of molded products is deteriorated.
く問題点を解決するための手段〉
そこで本発明者らは、ガラス繊維に代表される無機充填
剤により強化した場合にも耐衝撃強さ、引張り強さなど
の機械的性質に優れ、良好な耐加水分解性を有する樹脂
組成物を得るために鋭意検討した結果、芳香族ポリエス
テル、エポキシ化合物および無機充填剤を溶融混合した
後に、不飽和カルボ、ン酸またはその誘導体をグラフト
共重合した変性エチレン系共重合体を溶融混合した場合
には、上記の目的が達成されるばかりでなく、驚くべき
ことに耐ヒートサイクル性にも優れた樹脂組成物が得ら
れることを発見し、本発明に到達した。Means for Solving the Problems> Therefore, the present inventors have developed a method that has excellent mechanical properties such as impact strength and tensile strength even when reinforced with an inorganic filler such as glass fiber, and has good properties. As a result of extensive research in order to obtain a resin composition with hydrolysis resistance, modified ethylene was obtained by melt-mixing an aromatic polyester, an epoxy compound, and an inorganic filler, and then graft copolymerizing an unsaturated carboxylic acid or a derivative thereof. The present inventors have discovered that when the above-mentioned copolymers are melt-blended, not only can the above objectives be achieved, but also a resin composition that surprisingly has excellent heat cycle resistance can be obtained, leading to the present invention. did.
すなわち本発明は、
（Ａ） 芳香族ポリエステル１００重量部に対して
ＣＢ） 無機充填剤１〜１２０重量部（Ｃ） エポ
キシ化合物０．０１〜１０重１部（Ｄ） エチレン系
共重合体に不飽和カルボン酸またはその誘導体０．０１
〜１０ｉｉｉｆｆ１％をグラフト共重合した変性エチレ
ン系共重合体１〜７０重量部からなる樹脂組成物を製造
する際、
（Ａ）、（Ｂ）および（Ｃ）を溶融混合した後、ＣＤ）
を溶融混合することを特徴とする芳香族ポリエステル樹
脂組成物の製造方法を提供するものである。That is, the present invention provides: (A) CB) 1 to 120 parts by weight of an inorganic filler based on 100 parts by weight of aromatic polyester (C) 0.01 to 10 parts by weight of an epoxy compound (D) Ingredients in the ethylene copolymer Saturated carboxylic acid or its derivative 0.01
When producing a resin composition consisting of 1 to 70 parts by weight of a modified ethylene copolymer graft-copolymerized with ~10iiiff1%, after melt-mixing (A), (B) and (C), CD)
The present invention provides a method for producing an aromatic polyester resin composition, which comprises melt-mixing the following.
本発明で用いる芳香族ポリエステル（Ａ）とは、芳−香
環を重合体の連鎖単位に有するポリエステルで、芳香族
ジカルボン酸（あるいはそのエステル形成誘導体）とジ
オール（あるいはそのエステル形成誘導体）とを主成分
とする重縮合反応により得られる重合体ないし共重合体
である。The aromatic polyester (A) used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is composed of an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a polycondensation reaction in which the main component is a polycondensation reaction.
ここでいう芳香族ジカルボン酸としては、テレフタル酸
、イソフタル酸、オルトフタル酸、１．５−ナフタレン
ジカルボン酸、２．５−ナフタレンジカルボン酸、２．
６−ナフタレンジカルボン酸、２．２’−ビフェニルジ
カルボン酸、３．３′−ビフェニルジカルボン酸、４．
４’−ビフェニルジカルボン酸、４．４′−ジフェニル
エーテルジカルボン酸、４．４’−ジフェニルメタンシ
カルホン酸、４．４’−ジフェニルスルフォンジカルボ
ン酸、４．４’−ジフェニルイソプロピリデンジカルボ
ン酸、ｌ、２−ビス（フェノキシ）エタン−４，４′−
ジカルボン酸、２．５−アントラセンジカルボン酸、２
．６−アントラセンジカルボン酸、４．４’−ｐ−ター
フェニレンジカルボン酸、２．５−ピリジンジカルボン
酸などであり、テレフタル酸が好ましく使用できる。The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1.5-naphthalene dicarboxylic acid, 2.5-naphthalene dicarboxylic acid, 2.
6-naphthalenedicarboxylic acid, 2.2'-biphenyldicarboxylic acid, 3.3'-biphenyldicarboxylic acid, 4.
4'-biphenyl dicarboxylic acid, 4.4'-diphenyl ether dicarboxylic acid, 4.4'-diphenylmethane dicarboxylic acid, 4.4'-diphenylsulfone dicarboxylic acid, 4.4'-diphenylisopropylidene dicarboxylic acid, l, 2 -bis(phenoxy)ethane-4,4'-
Dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2
．． These include 6-anthracenedicarboxylic acid, 4,4'-p-terphenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, and terephthalic acid is preferably used.
これらの芳香族ジカルボン酸は２種以１を混合して使用
してもよい。なお、少量であればこれらの芳香族ジカル
ボン酸とともに、アジピン酸、アゼライン酸、ドデカン
ジオン酸、セバシン酸などの脂肪族ジカルボン酸、シク
ロヘキサンジカルボン酸なとの脂環族ジカルボン酸を一
種以上混合して使用することができる。These aromatic dicarboxylic acids may be used in combination of two or more. If the amount is small, one or more types of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be mixed with these aromatic dicarboxylic acids. can be used.
また、ジオール成分としては、エチレングリコール、プ
ロピレングリコール、ブチレングリコ−ＪＬ／、１ 、
５−ベンタンジオール、ヘキシレングリコール、ネオペ
ンチルグリコール、２−メチル−１，３−プロパンジオ
ール、ジエチレングリコール、トリエチレングリコール
などの脂肪族ジオール、１．４−シクロヘキサンジメタ
ツールなどの脂環族ジオールなどおよびそれらの混合物
などが挙げられる。なお少量であれば、分子量４００〜
６．０００の長鎖ジオール、すなわちポリエチレングリ
コール、ポリ−ｔ。In addition, as diol components, ethylene glycol, propylene glycol, butylene glycol-JL/, 1,
Aliphatic diols such as 5-bentanediol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, alicyclic diols such as 1,4-cyclohexane dimetatool, etc. and mixtures thereof. In addition, if the amount is small, the molecular weight is 400~
6.000 long chain diols, namely polyethylene glycol, poly-t.
３−プロピレングリコール、ポリテトラメチレンゲ、リ
コールなどを一種以上共重合せしめてもよい。One or more types of 3-propylene glycol, polytetramethylene glycol, recall, etc. may be copolymerized.
具体的な芳香族ポリエステルとしては、ポリエチレンテ
レフタレート、ポリプロピレンテレフタレート、ポリブ
チ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、ポリエチレン−１，２−ビス
（フェノキシ）エタン−４，４′−ジカルボキシレート
などのほか、ポリエチレンイソフタレート／テレフタレ
ート、ポリブチレンテレフタレート／イソフタレート、
ポリブチレンテレフタレート／デカンジカルボキシレー
トなどの共重合ポリエステルが挙げられる。これらのう
ち機械的性質、成形性などのバランスのとれたポリブチ
レンテレフタレートおよびポリエチレンテレフタレート
が好ましく使用できる。Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, etc. In addition, polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate,
Examples include copolymerized polyesters such as polybutylene terephthalate/decanedicarboxylate. Among these, polybutylene terephthalate and polyethylene terephthalate, which have well-balanced mechanical properties and moldability, can be preferably used.
本発明において使用する芳香族ポリエステル＋！、０．
５％の０−クロルフェノール溶＋１１２５℃で測定した
相対粘度が１，１５〜２．Ｏｌ特にＬ３〜１８５のもの
が好ましい。Aromatic polyester used in the present invention +! ,0.
The relative viscosity measured at 5% 0-chlorophenol solution + 1125°C is 1.15-2. Ol especially those with L3 to 185 are preferred.
本発明で用いる無機充填剤（Ｂ）は、特に限定されるも
のではないが、好ましくは、強化熱可塑性樹脂に一般に
用いられているガラス繊維（シラン系カップリング剤等
で表面処理されているものを含む）、炭素繊維、金属繊
維、アスベスト、チタン酸カリウムウィスカ、ワラステ
ナイト、ガラスフレーク、ガラスピーズ、タルク、マイ
カ、クレー、炭酸カルシウム、硫酸バリウム、酸化チタ
ン、酸化アルミニウムなどが挙げられ、中でもチョツプ
ドストランドタイプのガラス繊維が最も好ましく用いら
れる。The inorganic filler (B) used in the present invention is not particularly limited, but preferably glass fibers commonly used in reinforced thermoplastic resins (surface-treated with a silane coupling agent, etc.) are used. carbon fiber, metal fiber, asbestos, potassium titanate whiskers, wollastenite, glass flakes, glass peas, talc, mica, clay, calcium carbonate, barium sulfate, titanium oxide, aluminum oxide, etc. Pudstrand type glass fibers are most preferably used.
無機充填剤の添加量は、芳香族ポリエステル１００重量
部に対して１〜１２０重量部が好ましい。１重量部未満
では芳香族ポリエステルの機械物性の改良効果が充分で
なく、また、１２０重量部を越えるとかえって機械物性
の低下を招き好ましくない。The amount of the inorganic filler added is preferably 1 to 120 parts by weight per 100 parts by weight of the aromatic polyester. If it is less than 1 part by weight, the effect of improving the mechanical properties of the aromatic polyester will not be sufficient, and if it exceeds 120 parts by weight, the mechanical properties will deteriorate, which is not preferable.
本発明で使用するエポキシ化合物（Ｃ）は、必ずしも限
定されるものではないが、ビスフェノール−Ａ−ジグリ
シジルエーテル、オルトフェニルフェニルグリシジルエ
ーテルなどのグリシジルエーテル類や、ヘキサヒドロフ
タル酸ジグリシジルエステル、テトラヒドロフタル酸ジ
グリシジルエステル、テレフタル酸ジグリシジルエステ
ル、イソフタル酸ジグリシジルエステルなどのグリシジ
ルエステル類などが挙げられるが、下記一般式（１）で
示される化合物が最も好ましい。The epoxy compound (C) used in the present invention is not necessarily limited to, but includes glycidyl ethers such as bisphenol-A-diglycidyl ether and orthophenylphenylglycidyl ether, hexahydrophthalic acid diglycidyl ester, and tetrahydrophthalic acid diglycidyl ether. Examples include glycidyl esters such as phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and isophthalic acid diglycidyl ester, but the compound represented by the following general formula (1) is most preferred.
（ただし、式中Ａｒは炭素数６〜２０の芳香族基または
脂環基を、ｎは０または１〜２ｏの整数を示す。）
Ａｒの具体例としては、１．４−フェニレン、１．３−
フェニレン、１．２−フェニレン、２−メチル−１，４
−フェニレン、４．４′−ビフェニレン、３．３′−ビ
フェニレン、２．２′−ビフェニレン、３，４′−ビフ
ェニレン、１．４−ナフチレン、１．５−ナフチレン、
２．６−ナフチレン、２．７−ナフチレン、ｌ、４−シ
クロヘキシレン、１．３−シクロヘキシレン、ｌ、２−
シクロヘキシレン、４ 、４’−ビシクロヘキシレン、
２，６−ゾカヒドロナフチレンなどが好ましく挙げられ
、なかでも１．４−フェニレン、ｌ、３−フェニレンお
よび２．６−ナフチレンが特に好ましい。(However, in the formula, Ar represents an aromatic group or alicyclic group having 6 to 20 carbon atoms, and n represents an integer of 0 or 1 to 2o.) Specific examples of Ar include 1.4-phenylene, 1. 3-
Phenylene, 1,2-phenylene, 2-methyl-1,4
-phenylene, 4.4'-biphenylene, 3.3'-biphenylene, 2.2'-biphenylene, 3,4'-biphenylene, 1.4-naphthylene, 1.5-naphthylene,
2.6-naphthylene, 2.7-naphthylene, l,4-cyclohexylene, 1.3-cyclohexylene, l,2-
Cyclohexylene, 4,4'-bicyclohexylene,
Preferable examples include 2,6-zocahydronaphthylene, among which 1,4-phenylene, 1,3-phenylene and 2,6-naphthylene are particularly preferable.
（１）式の化合物の重合度ｎの値は、Ｏまたは１〜２０
の整数であり、０または１〜１０の整数が好ましく、ま
た、各種の重合度を有する化合物の混合物であってもよ
い。The value of the degree of polymerization n of the compound of formula (1) is O or 1 to 20
, preferably an integer of 0 or 1 to 10, and may be a mixture of compounds having various degrees of polymerization.
特に好ましいのは平均重合ＮＯ〜２の範囲にあり、重量
平均分子ｆｆｉ （Ｍｗ）と、数平均分子機（Ｍｎ）（
７）比Ｍ ｗ ／ Ｍ ｎが１．０〜３．０ （７）範
囲にあるものである。（１）式で示されるエポキシ化合
物の製造方法は特に限定されるものではないが、例えば
、ヒドロキシカルボン酸と、エヒハロヒトリントを４級
アンモニウム塩、３級アミン、３級ホスフィンなどの触
媒存在下、４０〜１５０℃で反応させて、ハロヒドリン
エステルエーテル化を行い、次いでアルカリ金属塩を添
加して脱ハロゲン化水素して製造する方法が挙げられる
。重合度の高いものについては、さらに、ヒドロキシカ
ルボン酸を触媒の存在下比率を変え反応させることによ
り得る、ことができる。Particularly preferred is the average polymerization NO in the range of ~2, weight average molecular ffi (Mw) and number average molecular machine (Mn) (
7) The ratio Mw/Mn is in the range of 1.0 to 3.0 (7). The method for producing the epoxy compound represented by the formula (1) is not particularly limited, but for example, a hydroxycarboxylic acid and an epoxy compound in the presence of a catalyst such as a quaternary ammonium salt, a tertiary amine, or a tertiary phosphine can be used. Below, there is a method in which the reaction is carried out at 40 to 150°C to perform halohydrin ester etherification, and then an alkali metal salt is added to perform dehydrohalogenation. A product with a high degree of polymerization can be further obtained by reacting a hydroxycarboxylic acid in the presence of a catalyst while changing the ratio.
本発明におけるエポキシ化合物の添加量は、ポリエステ
ル１００重量部に対して０．０１〜ｌＯ重量部、好まし
くは０．０５〜５重量部、より好ましくは０．２〜３重
量部が望ましい。添加量が０．０１重量部未満の場合は
、芳香族ポリエステルの耐加水分解性改良効果が充分で
なく、−方ｌＯ重量部を越える場合には、芳香族ポリエ
ステル樹脂の機械物性を損ねるためいずれも好ましくな
い。The amount of the epoxy compound added in the present invention is desirably 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.2 to 3 parts by weight per 100 parts by weight of polyester. If the amount added is less than 0.01 parts by weight, the effect of improving the hydrolysis resistance of the aromatic polyester will not be sufficient, and if it exceeds 10 parts by weight, the mechanical properties of the aromatic polyester resin will be impaired. I also don't like it.
本発明で用いる変性エチレン系共重合体（Ｄ）ハ、エチ
レン系共重合体に不飽和カルボン酸またはその誘導体０
．０１〜１０重量％をグラフト共重合して得られるもの
である。Modified ethylene copolymer (D) used in the present invention C. There is no unsaturated carboxylic acid or derivative thereof in the ethylene copolymer.
．． It is obtained by graft copolymerizing 01 to 10% by weight.
幹ポリマーとして用いるエチレン系共重合体トシては、
ガラス転移温度が３０℃以下であれば特に限定されるも
のでないが、好ましくは、エチレンとプロピレン、ブテ
ン−１，ペンテン−１１４−メチルペンテン−１などの
α−オレフィンとの共重合体、α−オレフィンとさらに
１．４−へキサジエン、エチリデンノルボーネン、クシ
５クロペンタジエンなどの非共役ジエンを含有する共重
合体、エチルアクリレート、ブチルアクリレート、メチ
ルメタクリレートなどのアルキルアクリレートまたはア
ルキルメタクリレートとの共重合体、酢酸ビニルとの共
重合体、さらにはスチレン−イソプレン−スチレン共重
合体や、スチレン−ブタジェン−スチレン共重合体など
に含まれる脂肪族二重結合の一部またはすべてを水素添
加した重合体などであって、具体的には、エチレン／プ
ロピレン共重合体、エチレン／ブテン−１共重合体、エ
チレン／ペンテン−１共重合体、エチレン／４−メチＪ
ｌ／ ヘ：／ ｆ ：／ −１共Ｍ 合体、エチレン／
プロピレン／エチリデンノルボーネン共重合体、エチレ
ン／プロピレン／ジシクロペンタジェン共重合体、エチ
レン／ブテン−１／工チリデンノルボーネン共重合体、
エチレン／エチルアクリレート共重合体、エチレン／ブ
チルアクリレート共重合体、エチレン／メチルメタクリ
レート共重合体、水添スチレン−イソプレン−スチレン
三元ブロック共重合体、水添スチレン−ブタジェン−ス
チレンブロック共重合体などが挙げられる。The ethylene copolymer used as the backbone polymer is
Although not particularly limited as long as the glass transition temperature is 30°C or lower, copolymers of ethylene and α-olefins such as propylene, butene-1, pentene-114-methylpentene-1, α- Copolymers containing olefins and further non-conjugated dienes such as 1,4-hexadiene, ethylidenenorbornene, and cyclopentadiene, and copolymers with alkyl acrylates or alkyl methacrylates such as ethyl acrylate, butyl acrylate, and methyl methacrylate. , copolymers with vinyl acetate, and polymers in which part or all of the aliphatic double bonds contained in styrene-isoprene-styrene copolymers, styrene-butadiene-styrene copolymers, etc. are hydrogenated, etc. Specifically, ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/pentene-1 copolymer, ethylene/4-methylene
l/ F:/ f:/ -1 coM combination, ethylene/
Propylene/ethylidene norbornene copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/butene-1/engineered ethylene norbornene copolymer,
Ethylene/ethyl acrylate copolymer, ethylene/butyl acrylate copolymer, ethylene/methyl methacrylate copolymer, hydrogenated styrene-isoprene-styrene triblock copolymer, hydrogenated styrene-butadiene-styrene block copolymer, etc. can be mentioned.
また用いる幹ポリマーは、ガラス転移温度が３０℃以下
、好ましくは０℃以下、より好ましくは一２０℃以下で
あることが望ましい。さらに１９０℃で測定したメルト
フローレ−１−（ＭＦＲ）が０．０５〜１５０（単位ｆ
ｒ／１０分）のものが好ましい。Further, it is desirable that the backbone polymer used has a glass transition temperature of 30°C or lower, preferably 0°C or lower, and more preferably -20°C or lower. Furthermore, the melt flow rate 1- (MFR) measured at 190°C is 0.05 to 150 (unit f
r/10 minutes) is preferred.
特に好ましい幹ポリマーの例としては、エチレン／プロ
ピレン共重合体およびエチレン／エチルアクリレート共
重合体が挙げられる。Examples of particularly preferred backbone polymers include ethylene/propylene copolymers and ethylene/ethyl acrylate copolymers.
マタ、上記エチレン系共重合体昏こグラフト共重合する
不飽和カルボン酸とは、アクリル酸、メタクリル酸、ク
ロトン酸、マレイン酸、フマール酸、イタコン酸、５−
ノルボーネン−２゜３−ジカルボン酸、テトラヒドロフ
タル酸、ダイマー酸などが例として挙げられ、その誘導
体としては上記の酸の無水物、エステル、アミド、イミ
ド、塩などが挙げられる。具体的には、無水マレイン酸
、無水イタコン酸、無水−５−ノルボーネン−２，３−
ジカルボン酸、テトラヒドロフタル酸無水物、アクリル
酸エチル、アクリル酸ブチル、アクリル酸グリシジル、
メタクリル酸メチル、メタクリル酸エチル、メタクリル
酸グリシジル、クロトン酸エチル、クロトン酸ブチル、
クロトン酸グリシジル、マレイン酸ジエチル、マレイン
酸ジブチル１．マレイン酸ジグリシジル、フマール酸ジ
エチル、フマール酸ジブチル、フマール酸ジグリシジル
、イタコン酸ジエチル、イタコン酸ジブチル、イタコン
酸ジグリシジル、５−ノルボーネン−２，３−ジカルボ
ン酸ジエチル、５−ノルボーネン−２゜３−ジカルボン
酸ジブチル、５−ノルボーネン−２，３−ジカルボン酸
ジグリシジル、テトラヒドロフタル酸ジエチル、テトラ
ヒドロフタル酸ジブチル、テトラヒドロフタル酸ジグリ
シジル、ダイマー酸ジエチル、ダイマー酸ジブチル、ダ
イマー酸ジグリシジル、アクリルアミド、メタクリルア
ミド、クロトンアミド、マレインアミド、ツマ−ルアミ
ド、イタコンアミド、５−ノルボーネン−２，３−カル
ボンアミド、テトラヒドロフタルアミド、ダイマーアミ
ド Ｎ。The unsaturated carboxylic acids to be copolymerized with the above-mentioned ethylene copolymer include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 5-
Examples include norbornene-2-3-dicarboxylic acid, tetrahydrophthalic acid, dimer acid, etc., and derivatives thereof include anhydrides, esters, amides, imides, salts, etc. of the above acids. Specifically, maleic anhydride, itaconic anhydride, 5-norbornene anhydride-2,3-
dicarboxylic acid, tetrahydrophthalic anhydride, ethyl acrylate, butyl acrylate, glycidyl acrylate,
Methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, ethyl crotonate, butyl crotonate,
Glycidyl crotonate, diethyl maleate, dibutyl maleate 1. diglycidyl maleate, diethyl fumarate, dibutyl fumarate, diglycidyl fumarate, diethyl itaconate, dibutyl itaconate, diglycidyl itaconate, diethyl 5-norbornene-2,3-dicarboxylate, 5-norbornene-2゜3-dicarboxylic acid Dibutyl, diglycidyl 5-norbornene-2,3-dicarboxylate, diethyl tetrahydrophthalate, dibutyl tetrahydrophthalate, diglycidyl tetrahydrophthalate, diethyl dimerate, dibutyl dimerate, diglycidyl dimerate, acrylamide, methacrylamide, crotonamide, malein amide, tumeramide, itaconamide, 5-norbornene-2,3-carbonamide, tetrahydrophthalamide, dimeramide N.
Ｎ−ジメチルアクリルアミド、Ｎ、Ｎ−ジメチルメタク
リルアミド、Ｎ、Ｎ−ジメチルクロトンアミド、Ｎ、Ｎ
、Ｎ’、Ｎ’−テトラメチルマレインアミド、Ｎ、Ｎ、
Ｎ’、Ｎ’−テトラメチルツマ−ルアミド、Ｎ 、 Ｎ
、 Ｎ’ 、 Ｎ’−テトラメチルイタコンアミド、
Ｎ、Ｎ、Ｎ’、Ｎ’−テトラメチル−５−ノルボーネン
−２，３−カルボンアミド、Ｎ、Ｎ、Ｎ’、Ｎ’−テト
ラメチルテトラヒドロフタルアミド、Ｎ、Ｎ、Ｎ’、Ｎ
’−テトラメチルダイマーアミド、マレインイミド、フ
タルイミド、イタコンイミド、５−ノルボーネン−２，
３−カルボンイミド、テトラヒドロフタルイミド、Ｎ−
フェニルマレインイミド、Ｎ−フェニルフマールイミド
、Ｎ−フェニルイタコンイミド、Ｎ−フェニル−５−ノ
ルボーネン−２，３−カルボンイミド、Ｎ−フェニルテ
トラヒドロフタルイミドなどが挙げられ、なかでも、ア
クリル酸、メタクリル酸、無水マレイン酸、無水イタコ
ン酸、テトラヒドロフタル酸無水物、アクリル酸グリシ
ジル、メタクリル酸グリシジル、マレイン酸ジグリシジ
ル、テトラヒドロフタル酸ジグリシジル、ダイマー酸ジ
グリシジル、アクリルアミド、メタクリルアミド、マレ
インイミド、Ｎ−フェニルマレインイミドなどが好まし
く挙げられる。N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-dimethylcrotonamide, N,N
, N', N'-tetramethylmaleamide, N, N,
N', N'-tetramethylthumaruamide, N, N
, N', N'-tetramethylitaconamide,
N, N, N', N'-tetramethyl-5-norbornene-2,3-carbonamide, N, N, N', N'-tetramethyltetrahydrophthalamide, N, N, N', N
'-tetramethyl dimeramide, maleimide, phthalimide, itaconimide, 5-norbornene-2,
3-carbonimide, tetrahydrophthalimide, N-
Examples include phenylmaleimide, N-phenyl fumarimide, N-phenyl itaconimide, N-phenyl-5-norbornene-2,3-carbonimide, N-phenyltetrahydrophthalimide, among others, acrylic acid, methacrylic acid, Maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, glycidyl acrylate, glycidyl methacrylate, diglycidyl maleate, diglycidyl tetrahydrophthalate, diglycidyl dimerate, acrylamide, methacrylamide, maleimide, N-phenylmaleimide, etc. Preferably.
エチレン系共重合体に不飽和カルボン酸、またはその誘
導体をグラフト共重合する方法はかならずしも限定され
るものではないが、エチレン系共重合体をベンゼン、ト
ルエン等の溶媒に加熱溶解せしめ、これに不飽和カルボ
ン酸および／または不飽和カルボン酸誘導体、およびラ
ジカル発生剤を添加反応させる方法、エチレン系共重合
体、不飽和カルボン酸および／または不飽和カルボン酸
誘導体およびラジカル発生剤を押出機、ニーダ−等を用
いて、溶融混線反応させる方法などが挙げられる。The method of graft copolymerizing an unsaturated carboxylic acid or its derivative to an ethylene copolymer is not necessarily limited, but the ethylene copolymer is heated and dissolved in a solvent such as benzene or toluene, and the A method of adding and reacting a saturated carboxylic acid and/or an unsaturated carboxylic acid derivative, and a radical generator, an ethylene copolymer, an unsaturated carboxylic acid and/or an unsaturated carboxylic acid derivative, and a radical generator by an extruder, a kneader, etc. For example, a method of causing a melt crosstalk reaction using, for example,
グラフト共重合する不飽和カルボン酸または不飽和カル
ボン酸誘導体の量は、変性エチレン共重合体中０．０１
〜１０重量％、好ましくは０゜１〜３重量％である。グ
ラフト量が０．０１重量％未満では、芳香族ポリエステ
ルの耐衝撃性改良効果が充分でなく、また１０重量％を
越える場合は、樹脂組成物の成形流動性が低下する問題
がありいずれも好ましくない。The amount of unsaturated carboxylic acid or unsaturated carboxylic acid derivative to be graft copolymerized is 0.01 in the modified ethylene copolymer.
-10% by weight, preferably 0.1-3% by weight. If the amount of grafting is less than 0.01% by weight, the effect of improving the impact resistance of the aromatic polyester will not be sufficient, and if it exceeds 10% by weight, there will be a problem that the molding fluidity of the resin composition will decrease, so both are preferred. do not have.
さらに少量であれば、そのほかのモノマー、例えばスチ
レン、アクリロニトリル、ブタジェン等をグラフト成分
モノマーとして同時に用いてもよい。Furthermore, other monomers such as styrene, acrylonitrile, butadiene, etc. may be used simultaneously as graft component monomers, provided they are in small amounts.
本発明における（Ｄ）不飽和カルボン酸またはその誘導
体０．０１〜１０重量％をグラフト共重合した変性エチ
レン系共重合体の添加量は、芳香族ポリエステル１００
重量部に対して１〜７０重量部、好ましくは２〜５０重
量部、より好ましくは３〜４０重量部である。添加量が
１重量部未満では、芳香族ポリエステルの耐衝撃性の改
良効果が充分でなく、７０重量部を越えると、かえって
芳香族ポリエステルの機械的特性を損なう傾向にありい
ずれも好ましくない。In the present invention, the amount of the modified ethylene copolymer (D) graft copolymerized with 0.01 to 10% by weight of an unsaturated carboxylic acid or its derivative is 100% by weight of the aromatic polyester.
The amount is 1 to 70 parts by weight, preferably 2 to 50 parts by weight, and more preferably 3 to 40 parts by weight. If the amount added is less than 1 part by weight, the effect of improving the impact resistance of the aromatic polyester will not be sufficient, and if it exceeds 70 parts by weight, the mechanical properties of the aromatic polyester will tend to be impaired, and both are not preferred.
本発明組成物は、（Ａ）芳香族ポリエステル、ＣＢ）無
機充填剤および（Ｃ）エポキシ化合物を溶融混合した後
、（Ｄ）不飽和カルボン酸またはその誘導体０．０１〜
１０重量％をグラフト共重合したエチレン系共重合体を
溶融混合した場合に最高の性能を発揮する。The composition of the present invention is prepared by melt-mixing (A) aromatic polyester, CB) inorganic filler, and (C) epoxy compound, and then (D) unsaturated carboxylic acid or its derivative from 0.01 to
The best performance is achieved when 10% by weight of an ethylene copolymer is melt-blended.
すなわち、本発明の特徴は、上記本発明の製造方法に従
って（混合順序にしたがって）芳香族ポリエステル、無
機充填剤、エポキシ化合物、曹２．ヤ＃１８体。□、ユ
ウヶうお、２．８よ。That is, the feature of the present invention is that aromatic polyester, inorganic filler, epoxy compound, soda 2. Ya #18 body. □, Yuugao, 2.8.
きに限って、耐衝撃性、引張り強さなどの機械的性質に
優れると共に、良好な耐ヒートサイクル性、耐加水分解
性を有する芳香族ポリエステル樹脂組成物が得られるこ
とにある。In this case, it is possible to obtain an aromatic polyester resin composition that has excellent mechanical properties such as impact resistance and tensile strength, as well as good heat cycle resistance and hydrolysis resistance.
例えば、（Ａ）芳香族ポリエステル、（Ｂ）無機充填剤
、（Ｃ）エポキシ化合物および（Ｄ）変性エチレン系共
重合体の４者を同時に溶融混合した場合には、耐衝撃性
はもちろんのこと、優れた耐ヒートサイクル性を有した
樹脂組成物は得られない。For example, when four components, (A) aromatic polyester, (B) inorganic filler, (C) epoxy compound, and (D) modified ethylene copolymer, are melt-mixed at the same time, not only impact resistance but also impact resistance is obtained. However, a resin composition having excellent heat cycle resistance cannot be obtained.
さらに、（Ａ）芳香族ポリエステル、（Ｂ）無機充填剤
を溶融混合した後、（Ｄ）変性エチレン系共重合体を溶
融混合、した場合には、ある程度耐衝撃性は向上するも
のの、引張り強度などの機械物性や、耐加水分解性に問
題がある。Furthermore, if (A) the aromatic polyester and (B) the inorganic filler are melt-mixed and then (D) the modified ethylene copolymer is melt-mixed, although the impact resistance improves to some extent, the tensile strength There are problems with mechanical properties such as, and hydrolysis resistance.
ｔ？＝、（Ａ）芳香族ポリエステル、（Ｄ）変性エチレ
ン系共重合体を溶融混合した後、（Ｂ）無機充填剤、（
Ｃ）エポキシ化合物を溶融混合した場合には、耐衝撃性
、引張り強さなどの機械的性質が不十分な樹脂組成物し
か得られない。T? =, After melt-mixing (A) aromatic polyester and (D) modified ethylene copolymer, (B) inorganic filler, (
C) When epoxy compounds are melt-mixed, only resin compositions with insufficient mechanical properties such as impact resistance and tensile strength are obtained.
本発明の製造法にしたがえば（混合順序にしたがえば）
具体的な溶融混合法は必ずしも限定されるものでないが
、好ましくは、芳香族ポリエステル、無機充填剤、エポ
キシ化合物の３者を押出機を使用して、溶融混合・ペレ
ット化し、仁のペレットを変性エチレン系共重合体と共
に再び押出機を使用して溶融混合する方法や、押出機の
吐出口から最も遠いホッパーより芳香族ポリエステル、
無機充填剤、エポキシ化合物の３者を投入し、吐出口に
近いホッパーより変性エチレン系共重合体を加る方法な
どが挙げられる。According to the manufacturing method of the present invention (according to the mixing order)
Although the specific melt-mixing method is not necessarily limited, preferably, the aromatic polyester, the inorganic filler, and the epoxy compound are melt-mixed and pelletized using an extruder, and the kernel pellets are modified. Aromatic polyester is melt-mixed with the ethylene copolymer using an extruder again, or the hopper farthest from the extruder outlet is
Examples include a method in which an inorganic filler and an epoxy compound are charged, and a modified ethylene copolymer is added from a hopper near the discharge port.
本発明により得られた樹脂組成物は、射出成形、押出成
形などの通常の方法で容易に成形することが可能であり
、得られた成形品は優れた性能を発揮する。The resin composition obtained according to the present invention can be easily molded by ordinary methods such as injection molding and extrusion molding, and the obtained molded product exhibits excellent performance.
さらに本発明組成物に対して、本発明の目的を損なわな
い範囲で、酸化防止剤、熱安定剤、紫外線吸収剤、滑剤
、離型剤、染料・顔料を含む着色剤、核剤などの通常の
添加剤を１種以上任意の時点で添加することができる。Furthermore, the composition of the present invention may be added with conventional additives such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, colorants including dyes and pigments, and nucleating agents, to the extent that the purpose of the present invention is not impaired. One or more types of additives can be added at any time.
また少量の熱可塑性樹脂（例えば、ポリフェニレンオキ
サイド、ポリカーボネート、ポリアミド、ポリプロピレ
ンなど）を同様に添加することもできる。It is also possible to add a small amount of a thermoplastic resin (eg, polyphenylene oxide, polycarbonate, polyamide, polypropylene, etc.).
〈実施例〉
以下実施例・比較例を挙げて本発明の効果をさらに詳述
する。<Example> The effects of the present invention will be explained in further detail below with reference to Examples and Comparative Examples.
参考例１〜２
表１に示す幹ポリマ−１００重量部に対して、無水マレ
イン酸またはグリシジルメタクリレート２重量部および
１．３−ビス（ｔ−ブチルペルオキシ−イソプロビル）
ベンゼン０．２重ｆｆｉ部をＶ−ブレンダーでトライブ
レンドし、３０Ｗ夏２軸押出機を用いて、２００’Ｃで
溶融混線後ペレット化し、変性エチレン系共重合体（イ
）および（ロ）を製造した。Reference Examples 1 to 2 2 parts by weight of maleic anhydride or glycidyl methacrylate and 1,3-bis(t-butylperoxy-isopropyl) per 100 parts by weight of the backbone polymer shown in Table 1.
Tri-blend 0.2 parts of benzene with a V-blender, melt and mix at 200'C using a 30W summer twin-screw extruder, and pelletize the modified ethylene copolymers (a) and (b). Manufactured.
得られたペレットについて、ソックスレー抽出機を用い
て、未反応のカルボン酸誘導体を抽出後、ＩＲスペクト
ルによってグラフト率を定量した。結果を表１に示す。After extracting unreacted carboxylic acid derivatives from the obtained pellets using a Soxhlet extractor, the grafting rate was determined by IR spectrum. The results are shown in Table 1.
表 １
実施例！
相対粘度Ｌ４５のポリブチレンテレフタレート７５重量
部に対して、ガラス繊維（ａｆｌ長、チョツプドストラ
ンドタイプ）１５重量部、エポキシ化合物（ハ）１重量
部をＶ−ブレンダーにてトライブレンド後、３０ｆｆダ
２軸押出機を用いて、２５０℃で溶融混線後ペレット化
した。Table 1 Example! 75 parts by weight of polybutylene terephthalate having a relative viscosity of L45, 15 parts by weight of glass fiber (AFL length, chopped strand type) and 1 part by weight of an epoxy compound (c) were tri-blended in a V-blender, and then mixed with 30 ff da Using a twin-screw extruder, the mixture was melted and mixed at 250°C and then pelletized.
このペレット９１重量部を、１３０℃で５時間乾燥後、
参考例１にて製造した変性エチレン系共重合体（イ）１
０重量部をトライブレンドし、再び３０ｆｉダ２軸押出
機を用いて、２５０℃で溶融混線後ペレット化した。After drying 91 parts by weight of this pellet at 130°C for 5 hours,
Modified ethylene copolymer (A) 1 produced in Reference Example 1
0 parts by weight were triblended, melt mixed at 250° C. again using a 30 fi twin screw extruder, and then pelletized.
仁のペレットを１３０℃で５時間乾燥後、２５０℃に設
定した５オンスのスクリューインライン型射出成形機を
用いて金型温度８０℃、成形サイクル（射出時間／冷却
時１！ｌ／中間時間）１５秒／２０秒／１０秒で成形し
、ＡＳＴＭＩ号ダンベル、ｌ／８’ 幅アイゾツト衝
撃試験片を各々得るとともに、金型内に樹脂を充填する
のに必要な最小圧力である成形下限圧（ゲージ圧）を測
定した。After drying the kernel pellets at 130°C for 5 hours, the mold temperature was 80°C using a 5-ounce screw in-line injection molding machine set at 250°C, and the molding cycle (injection time/cooling time 1!L/intermediate time) Molding was performed for 15 seconds, 20 seconds, and 10 seconds to obtain ASTMI dumbbell, 1/8' width Izot impact test specimens, and the lower limit pressure for molding (the minimum pressure required to fill the resin into the mold). gauge pressure) was measured.
得られた、ＡＳＴＭＩ号ダンベルについて、１００℃熱
水中１５日間の熱水処理試験を、また、１５０℃で２時
間、ひき続き一４０℃で２時間を１サイクルとして、１
５０サイクルの熱衝撃を与えるヒートサイクル試験を行
った。The resulting ASTMI dumbbell was subjected to a 15-day hot water treatment test at 100°C, with one cycle of 2 hours at 150°C, followed by 2 hours at -40°C.
A heat cycle test was conducted in which 50 cycles of thermal shock were applied.
得られた試験片について、・ＡＳＴＭ Ｄ−６３８に
したがい引張り試験を、ＡＳＴＭ Ｄ−２５６にした
がいア、イゾット試験を行った。結果を表２に示す。The obtained test piece was subjected to a tensile test according to ASTM D-638 and an Izod test according to ASTM D-256. The results are shown in Table 2.
ＯＣＲ，、Ｑ
表 ２
注：※ｌ 成形下限圧：値が小さい程、成形時の流動性
が良好。OCR,,Q Table 2 Note: *l Lower limit pressure for molding: The smaller the value, the better the fluidity during molding.
実施例２〜４、比較例１〜４
また実施例１において、変性エチレン系共重合体を（口
〕に変えたのみの例（実施例２）、使用するエポキシ化
合物を（ニ）に変えたのみの例（実施例３）および（ホ
）に変えたのみの例（実施例４）についても、実施例１
と同様にして、溶融混合、成形・評価を行った。結果を
表２に示す。Examples 2 to 4, Comparative Examples 1 to 4 In addition, in Example 1, the modified ethylene copolymer was only changed to (Example 2), and the epoxy compound used was changed to (D). Example 1 also applies to the example (Example 3) in which only
Melt mixing, molding, and evaluation were performed in the same manner as above. The results are shown in Table 2.
さらにエポキシ化合物（ハ）未添加の例（比較例１）、
実施例１の混合順序を変えた例、すなわち、ＰＢＴ、ガ
ラス繊維、変性エチレン共重合体（イ）およびエポキシ
化合物（ハ）を同時にトライブレンドした例（比較例２
） 、ＰＢＴと変性エチレン系共重合体（イ）を溶融混
合、ペレット化後、このペレットに対して、ガラス繊維
とエポキシ化合物（ハ）を溶融混合した例（比較例３）
、ＰＢＴ、ガラス繊維および変性エチレン系共重合体
（イ）を溶融混練−ペレット化後、このペレットに対し
てエポキシ化合物（ハ）を溶融混練した例（比較例４）
についても実施例１と同様にして成形評価を行った。結
果を表２に示す。Furthermore, an example in which the epoxy compound (c) was not added (Comparative Example 1),
An example in which the mixing order of Example 1 was changed, that is, an example in which PBT, glass fiber, modified ethylene copolymer (a), and epoxy compound (c) were simultaneously triblended (Comparative Example 2)
), an example in which PBT and modified ethylene copolymer (a) were melt-mixed and pelletized, and then glass fiber and epoxy compound (c) were melt-mixed with the pellets (Comparative Example 3)
, PBT, glass fiber and modified ethylene copolymer (A) were melt-kneaded and pelletized, and then the epoxy compound (C) was melt-kneaded with the pellets (Comparative Example 4)
Molding evaluation was also performed in the same manner as in Example 1. The results are shown in Table 2.
表２の結果から明らかなように、本発明の混合順序にし
たがって製造した場合（実施例１〜４）には成形品の引
張り強度、衝撃強度が優れるばかりでなく、耐加水分解
性、耐ヒートサイクル性も極めて良好であり、中でもエ
ポキシ化合物（ハ）を使用した場合の性能が最も優れる
ことがわかる。As is clear from the results in Table 2, when manufactured according to the mixing order of the present invention (Examples 1 to 4), the molded products not only have excellent tensile strength and impact strength, but also hydrolysis resistance and heat resistance. It can be seen that the cycleability is also very good, and that the performance when using the epoxy compound (c) is the best.
これに対し、エポキシ化合物未添加の場合（比較例１）
や、本発明の混合順序と異なる場合（比較例２〜４）に
は機械的性質が低いばかりでなく、耐加水分解性、耐ヒ
ートサイクル性も劣っている。In contrast, when no epoxy compound was added (Comparative Example 1)
When the mixing order is different from the mixing order of the present invention (Comparative Examples 2 to 4), not only the mechanical properties are poor but also the hydrolysis resistance and heat cycle resistance are poor.
〈発明の効果〉
本発明によって製造された組成物の与える成形品は、衝
撃強度、引張り強度に代表される機械物性に優れるばか
りでなく、耐加水分解性、耐ヒートサイクル性も極めて
良好であり、機械機構部品、自動車部品等の用途に有用
である。<Effects of the Invention> Molded articles produced by the composition produced by the present invention not only have excellent mechanical properties such as impact strength and tensile strength, but also have extremely good hydrolysis resistance and heat cycle resistance. It is useful for applications such as mechanical parts, automobile parts, etc.
特許出願人 東 し 株 式 会 社Patent applicant Higashi Shikikai Co., Ltd.
Claims (1)
の誘導体０．０１〜１０重量％をグラフト共重合した変
性エチレン系共重合体１〜７０重量部からなる樹脂組成
物を製造するに際し、 （Ａ）、（Ｂ）および（Ｃ）を溶融混合した後、（Ｄ）
を溶融混合することを特徴とする芳香族ポリエステル樹
脂組成物の製造方法。Scope of Claims: (A) Based on 100 parts by weight of aromatic polyester (B) 1 to 120 parts by weight of inorganic filler (C) 0.01 to 10 parts by weight of epoxy compound (D) To ethylene copolymer (A), (B) and (C ) After melt-mixing (D)
A method for producing an aromatic polyester resin composition, which comprises melt-mixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33502587A JPH01174555A (en) | 1987-12-28 | 1987-12-28 | Production of aromatic polyester resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33502587A JPH01174555A (en) | 1987-12-28 | 1987-12-28 | Production of aromatic polyester resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01174555A true JPH01174555A (en) | 1989-07-11 |
| JPH0563504B2 JPH0563504B2 (en) | 1993-09-10 |
Family
ID=18283901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33502587A Granted JPH01174555A (en) | 1987-12-28 | 1987-12-28 | Production of aromatic polyester resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01174555A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001031851A (en) * | 1999-07-23 | 2001-02-06 | Toray Ind Inc | Polybutylene terephthalate resin composition and molded product |
| DE112004002063B4 (en) * | 2003-10-28 | 2009-04-16 | Asahi Kasei Chemicals Corp. | Polytrimethylene terephthalate reinforced resin composition and use thereof |
| WO2013101821A1 (en) * | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Toughened polyester blends |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007127369A2 (en) | 2006-04-26 | 2007-11-08 | Quellan, Inc. | Method and system for reducing radiated emissions from a communications channel |
| CN115175818B (en) * | 2020-10-07 | 2023-04-11 | 住友橡胶工业株式会社 | Tyre for vehicle wheels |
-
1987
- 1987-12-28 JP JP33502587A patent/JPH01174555A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001031851A (en) * | 1999-07-23 | 2001-02-06 | Toray Ind Inc | Polybutylene terephthalate resin composition and molded product |
| DE112004002063B4 (en) * | 2003-10-28 | 2009-04-16 | Asahi Kasei Chemicals Corp. | Polytrimethylene terephthalate reinforced resin composition and use thereof |
| WO2013101821A1 (en) * | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Toughened polyester blends |
| US8753728B2 (en) | 2011-12-28 | 2014-06-17 | E I Du Pont De Nemours And Company | Toughened polyester blends |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0563504B2 (en) | 1993-09-10 |
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