JPH01279944A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPH01279944A JPH01279944A JP1004921A JP492189A JPH01279944A JP H01279944 A JPH01279944 A JP H01279944A JP 1004921 A JP1004921 A JP 1004921A JP 492189 A JP492189 A JP 492189A JP H01279944 A JPH01279944 A JP H01279944A
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- weight
- polymer
- copolymer
- component
- 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
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 30
- 239000011342 resin composition Substances 0.000 title claims abstract description 15
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 75
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 239000004793 Polystyrene Substances 0.000 claims abstract description 40
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920001400 block copolymer Polymers 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 229920005604 random copolymer Polymers 0.000 claims abstract description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 12
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 12
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 10
- 239000004952 Polyamide Substances 0.000 claims abstract description 8
- 229920002647 polyamide Polymers 0.000 claims abstract description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 5
- 229920002223 polystyrene Polymers 0.000 claims description 38
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 12
- 239000005062 Polybutadiene Substances 0.000 claims description 10
- 229920002857 polybutadiene Polymers 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 9
- 229920000515 polycarbonate Polymers 0.000 claims description 9
- 229920001195 polyisoprene Polymers 0.000 claims description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 4
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 claims description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 3
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 claims description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 3
- 229920001893 acrylonitrile styrene Polymers 0.000 claims description 3
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 claims description 3
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 26
- 239000000203 mixture Substances 0.000 abstract description 21
- 229920001971 elastomer Polymers 0.000 abstract description 12
- 239000005060 rubber Substances 0.000 abstract description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000359 diblock copolymer Polymers 0.000 abstract description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 abstract 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 abstract 1
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 239000002270 dispersing agent Substances 0.000 description 17
- 239000004743 Polypropylene Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 11
- 239000002667 nucleating agent Substances 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000454 talc Substances 0.000 description 8
- 229910052623 talc Inorganic materials 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical class CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- SYJPAKDNFZLSMV-HYXAFXHYSA-N (Z)-2-methylpropanal oxime Chemical compound CC(C)\C=N/O SYJPAKDNFZLSMV-HYXAFXHYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 4
- 229920002633 Kraton (polymer) Polymers 0.000 description 4
- 229920000297 Rayon Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002964 rayon Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 238000000944 Soxhlet extraction Methods 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 3
- 125000003011 styrenyl group Polymers [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ZKOGUIGAVNCCKH-UHFFFAOYSA-N 4-phenyl-1,3-dioxolan-2-one Chemical compound O1C(=O)OCC1C1=CC=CC=C1 ZKOGUIGAVNCCKH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003440 styrenes Polymers 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 101150083127 brox gene Proteins 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920003197 poly( p-chlorostyrene) Polymers 0.000 description 1
- 229920001620 poly(3-methyl styrene) Polymers 0.000 description 1
- 229920001627 poly(4-methyl styrene) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は熱可塑性樹脂組成物に関し、詳しくはシンジオ
タクチック構造のスチレン系重合体に、他の熱可塑性樹
脂等とともに特定のブロックあるいはグラフト共重合体
を配合してなる耐熱性、耐衝撃性等のすぐれた熱可塑性
樹脂組成物に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermoplastic resin composition, and more specifically, a styrenic polymer having a syndiotactic structure is combined with a specific block or graft copolymer along with other thermoplastic resins, etc. This invention relates to a thermoplastic resin composition containing a polymer and having excellent heat resistance, impact resistance, etc.
〔従来の技術及び発明が解決しようとする課題〕一般に
、熱可塑性樹脂は他の素材に比べて成形性にすぐれ、ま
た充分な剛性を有していることから、家庭用品をはじめ
、電気製品1機械器具の部品など様々な製品の成形材料
として用いられている。[Prior art and problems to be solved by the invention] In general, thermoplastic resins have better moldability than other materials and have sufficient rigidity, so they are used for household goods and electrical products. It is used as a molding material for various products such as parts for machinery and equipment.
しかし、熱可塑性樹脂はこのようなすぐれた性質を有し
ているものの、耐熱性の点で充分であるとは言い難いと
いう欠点がある。However, although thermoplastic resins have such excellent properties, they have the drawback of not being sufficiently heat resistant.
ところで、先般、本発明者らのグループはシンジオタク
テイシテイ−の高いスチレン系重合体を開発することに
成功し、さらにこのスチレン系重合体に他の成分を配合
した熱可塑性樹脂組成物を開発した(特開昭62−10
4818号公報、同62−257950号公報)。By the way, the group of the present inventors recently succeeded in developing a styrenic polymer with high syndiotacticity, and also developed a thermoplastic resin composition in which this styrenic polymer was blended with other components. (Unexamined Japanese Patent Publication No. 62-10
No. 4818, No. 62-257950).
しかしながら、互いに本質的に非相溶な樹脂の組成物は
、相間の界面の強度不足を避けることができないため、
配合による改質効果には限界がある。また、特願昭62
−305838号明細書には、シンジオタクチック構造
のスチレン系重合体に、ゴム状重合体を配合することに
よって、組成物に耐衝撃性を付与するものであるが、や
はり界面の強度不足を避けることができないという問題
がある。However, compositions of resins that are essentially incompatible with each other cannot avoid insufficient strength at the interface between the phases.
There are limits to the modifying effect of blending. In addition, the special request for
-305838 discloses that impact resistance is imparted to the composition by blending a rubber-like polymer with a styrene polymer having a syndiotactic structure, but it is also necessary to avoid insufficient strength at the interface. The problem is that I can't.
そこで、本発明者りよ上述した如き問題を解消し、シン
ジオタクチック構造のスチレン系重合体と他の熱可塑性
樹脂やゴム状重合体との相溶性を向上させた組成物を開
発すべく鋭意研究を重ねた。Therefore, the inventors of the present invention have conducted extensive research in order to solve the above-mentioned problems and to develop a composition that improves the compatibility between a styrene polymer with a syndiotactic structure and other thermoplastic resins and rubber-like polymers. layered.
その結果、組成物の一成分として特定のブロック共重合
体あるいはグラフト共重合体を配合することによって、
組成物の各成分間の相溶性が向上し、機械的強度が改善
されることを見出した。本発明はかかる知見に基いて完
成したものである。As a result, by incorporating a specific block copolymer or graft copolymer as a component of the composition,
It has been found that the compatibility between the components of the composition is improved and the mechanical strength is improved. The present invention was completed based on this knowledge.
すなわち本発明は、
(a)主としてシンジオタクチック構造を有するスチレ
ン系重合体5〜95重量%。That is, the present invention comprises: (a) 5 to 95% by weight of a styrenic polymer mainly having a syndiotactic structure.
(b)該スチレン系重合体以外の熱可塑性樹脂及び/又
はゴム状重合体95〜5重四%。(b) 95 to 5% by weight of a thermoplastic resin and/or rubbery polymer other than the styrene polymer.
及び前記(a)及び伽)成分の合計100重量部に対し
て、
(c) A −B型ブロック共重合体、Aグラフト化B
共重合体及びBグラフト化A共重合体のうちから選ばれ
た一種又は二種以上のブロックあるいはグラフト共重合
体0.05〜50重量部
〔ここで、Aはアククチツクポリスチレン、アクリロニ
トリル−スチレンランダム共重合体、スチレン−無水マ
レイン酸ランダム共重合体、スチレン−アクリロニトリ
ル−無水マレイミドランダム共重合体、スチレン−メチ
ルメタクリレートランダム共重合体及びスチレン−メタ
クリル酸ランダム共重合体から選ばれた一種又は二種以
上のスチレン系重合体あるいはスチレン系共重合体を示
し、Bはポリアミド、ポリメタクリル酸メチル、ポリエ
チレンテレフタレート、ポリブチレンテレフタレート、
ポリブタジェン、ポリイソプレン、水素化ポリブタジエ
ン、水素化ポリイソプレン及びポリカーボネートから選
ばれた一種又は二種以上の重合体を示す。〕
を主成分とする熱可塑性樹脂組成物を提供するものであ
る。and (c) A-B type block copolymer, A-grafted B
0.05 to 50 parts by weight of one or more block or graft copolymers selected from copolymers and B-grafted A copolymers [where A is acidic polystyrene, acrylonitrile-styrene] One or two selected from random copolymers, styrene-maleic anhydride random copolymers, styrene-acrylonitrile-maleimide anhydride random copolymers, styrene-methyl methacrylate random copolymers, and styrene-methacrylic acid random copolymers. B represents polyamide, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate,
One or more polymers selected from polybutadiene, polyisoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, and polycarbonate. ] The present invention provides a thermoplastic resin composition containing the following as a main component.
本発明の樹脂組成物は、上述したように(a)、 (b
)。As mentioned above, the resin composition of the present invention has (a), (b)
).
(c)成分を主成分とするものである。ここで、(a)
成分は主としてシンジオタクチック構造を有するスチレ
ン系重合体であるが、このスチレン系重合体の主として
シンジオタクチック構造とは、立体化学構造が主として
シンジオタクチック構造、即ち炭素−炭素結合から形成
される主鎖に対して側鎖であるフェニル基や置換フェニ
ル基が交互に反対方向に位置する立体構造を有するもの
であり、そのタフティシティ−は同位体炭素による核磁
気共鳴法(13cmNMR法)により定量される。′3
cmNMR法により測定されるタフティシティ−は、連
続する複数個の構成単位の存在割合、例えば2個の場合
はダイアツド、3個の場合はトリアット′。The main component is component (c). Here, (a)
The component is mainly a styrenic polymer having a syndiotactic structure, but the mainly syndiotactic structure of this styrenic polymer means that the stereochemical structure is mainly formed from a syndiotactic structure, that is, carbon-carbon bonds. It has a three-dimensional structure in which side chain phenyl groups and substituted phenyl groups are alternately located in opposite directions with respect to the main chain, and its toughness is determined by nuclear magnetic resonance method (13 cm NMR method) using carbon isotopes. Quantitated. '3
Toughness measured by the cmNMR method is the proportion of a plurality of consecutive constituent units present, for example, 2 in the case of diats and 3 in the case of triat'.
5個の場合はペンタッドによって示すことができるが、
本発明に言う主としてシンジオタクチック構造を有する
スチレン系重合体とは、通常はダイアツドで75%以上
、好ましくは85%以上、若しくはペンタッド(ラセミ
ペンタッド)で30%以上、好ましくは50%以上のシ
ンジオタクテイシテイ−を有するポリスチレン、ポリ(
アルキルスチレン)、ポリ(ハロゲン化スチレン)、ポ
リ(アルコキシスチレン)、ポリ(ビニル安a 香酸エ
ステル)およびこれらの混合物、あるいはこれらを主成
分とする共重合体を指称する。なお、ここでポリ(アル
キルスチレン)としては、ポリ(メチルスチレン)、ポ
リ(エチルスチレン)。The case of 5 can be represented by a pentad, but
In the present invention, the styrenic polymer mainly having a syndiotactic structure is usually 75% or more, preferably 85% or more in terms of diad, or 30% or more, preferably 50% or more in pentad (racemic pentad). Polystyrene, poly(
Refers to poly(alkylstyrene), poly(halogenated styrene), poly(alkoxystyrene), poly(vinyl benzoic acid ester), mixtures thereof, or copolymers having these as main components. Note that poly(alkylstyrene) here includes poly(methylstyrene) and poly(ethylstyrene).
ポリ(イソプロピルスチレン)、ポリ(ターシャリ−ブ
チルスチレン)などがあり、ポリ(ハロゲン化スチレン
)としては、ポリ(クロロスチレン)。Poly(isopropylstyrene), poly(tertiary-butylstyrene), etc. Poly(halogenated styrene) includes poly(chlorostyrene).
ポリ(ブロモスチレン)、ポリ(フルオロスチレン)な
どがある、また、ポリ(アルコキシスチレン)としては
、ポリ(メトキシスチレン)、ポリ(エトキシスチレン
)などがある、これらのうち特に好ましいスチレン系重
合体としては、ポリスチレン、ポリ(p−メチルスチレ
ン)、ポリ(m−メチルスチレン)、ポリ(p−ターシ
ャリ−ブチルスチレン)、ポリ(p−クロロスチレン)
、ポリ(m−クロロスチレン)、ポリ(p−フルオロス
チレン)、更にはスチレンとp−メチルスチレンとの共
重合体をあげることができる。Examples of poly(bromostyrene) and poly(fluorostyrene) include poly(alkoxystyrene) such as poly(methoxystyrene) and poly(ethoxystyrene). Among these, particularly preferred styrenic polymers include are polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene)
, poly(m-chlorostyrene), poly(p-fluorostyrene), and copolymers of styrene and p-methylstyrene.
また、本発明に用いるスチレン系重合体は、分子量につ
いては制限はないが、重量平均分子量が10.000以
上のものが好ましく、とりわけ50.000以上のもの
が最適である。さらに、分子量分布についてもその広狭
は制約がなく、様々なものを充当することが可能である
。このような主としてシンジオタクチック構造を有する
スチレン系重合体は、例えば不活性炭化水素溶媒中また
は溶媒の不存在下に、チタン化合物、及び水とトリアル
キルアルミニウムの縮合生成物を触媒として、スチレン
系単量体(上記スチレン系重合体に対応する単量体)を
重合することにより製造することができる(特開昭62
−187708号公報)。Furthermore, the molecular weight of the styrenic polymer used in the present invention is not limited, but those having a weight average molecular weight of 10,000 or more are preferred, and those of 50,000 or more are particularly optimal. Further, there is no restriction on the width or narrowness of the molecular weight distribution, and various types can be used. Such styrenic polymers having a mainly syndiotactic structure can be produced by using a titanium compound and a condensation product of water and trialkylaluminum as catalysts, for example, in an inert hydrocarbon solvent or in the absence of a solvent. It can be produced by polymerizing monomers (monomers corresponding to the above-mentioned styrene polymers) (Japanese Patent Laid-Open No. 62
-187708).
一方、本発明の(b)成分は、(a)成分以外の熱可塑
性樹脂及びゴム状重合体のうちの一種あるいは二種以上
の混合物である。ここで熱可塑性樹脂としては、組成物
の用途等により様々なものが選定され、特に制限はない
が、上記(a)成分と非相溶性である樹脂、例えばポリ
エステル(ポリエチレンテレフタレートなど)、ポリカ
ーボネート、ポリエーテル(ポリスルホン、ポリエーテ
ルスルホンなど)、ポリアミド、ポリオキシメチレンな
どの縮合系重合体、ポリアクリル酸、ポリアクリル酸エ
ステル、ポリメチルメタクリレートなどのアクリル系重
合体、ポリエチレン、ポリプロピレン、ポリブテン、ポ
リ4−メチルペンテン−1,エチレン−プロピレン共重
合体などのポリオレフィン、あるいはポリ塩化ビニル、
ポリ塩化ビニリデン。On the other hand, component (b) of the present invention is one or a mixture of two or more of thermoplastic resins and rubbery polymers other than component (a). Here, various thermoplastic resins are selected depending on the use of the composition, etc., and there are no particular restrictions, but resins that are incompatible with the above component (a), such as polyester (polyethylene terephthalate, etc.), polycarbonate, Polyether (polysulfone, polyethersulfone, etc.), polyamide, condensation polymers such as polyoxymethylene, acrylic polymers such as polyacrylic acid, polyacrylic acid ester, polymethyl methacrylate, polyethylene, polypropylene, polybutene, poly 4 - methylpentene-1, polyolefin such as ethylene-propylene copolymer, or polyvinyl chloride,
Polyvinylidene chloride.
ポリ弗化ビニリデンなどの含ハロゲン化合物重合体など
が、本発明の目的に沿うものである。Halogen-containing compound polymers such as polyvinylidene fluoride are suitable for the purpose of the present invention.
また、(b)成分のうちのゴム状重合体についても、各
種のものが使用可能であるが、上記(a)成分と非相溶
性であるゴム状重合体、例えば天然ゴム、ポリブタジェ
ン、ポリイソプレン、ポリイソブチレン、ネオプレン、
エチレン−プロピレン共重合体ゴム、ポリスルフィドゴ
ム、チオコールゴム、アクリルゴム、ウレタンゴム、シ
リコーンゴム、エピクロルヒドリンゴム、ポリエーテル
エステルゴム、ポリエステルエステルゴムなどが、本発
明の目的に沿うものとして挙げることができる。Various types of rubber-like polymers can be used as component (b), but rubber-like polymers that are incompatible with component (a), such as natural rubber, polybutadiene, and polyisoprene, can be used. , polyisobutylene, neoprene,
Ethylene-propylene copolymer rubber, polysulfide rubber, thiol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, polyether ester rubber, polyester ester rubber, etc. can be mentioned as those that meet the purpose of the present invention.
さらに、ら)成分としては上記のゴム状重合体成分を含
有する熱可塑性樹脂、例えばEPR含有ブロックポリプ
ロピレン、ポリエーテルエステルゴム含有ポリエステル
等を用いることも可能である。Further, as component (3), it is also possible to use a thermoplastic resin containing the above-mentioned rubbery polymer component, such as EPR-containing block polypropylene, polyether ester rubber-containing polyester, and the like.
本発明の樹脂組成物では、上記(a)、 (b)成分の
配合割合は、(a)、 (b)成分の合計量に対して(
a)成分を5〜95重量%、好ましくは15〜85重量
%とし、ら)成分を95〜5重景%、好ましくは85〜
15重景%とする。ここで、(a)成分であるシンジオ
タクチック構造のスチレン系重合体の配合割合が、5重
量%未満では、組成物に耐熱性や耐薬品性を付与するこ
とができず、また95重量%を超えると、組成物の機械
的強度の改善効果が充分に発現されない。In the resin composition of the present invention, the blending ratio of the components (a) and (b) is (with respect to the total amount of the components (a) and (b)).
Component a) is 5 to 95% by weight, preferably 15 to 85% by weight, and component ra) is 95 to 5% by weight, preferably 85 to 85% by weight.
15% heavy view. Here, if the blending ratio of the styrene-based polymer having a syndiotactic structure, which is component (a), is less than 5% by weight, heat resistance and chemical resistance cannot be imparted to the composition, or 95% by weight If it exceeds this amount, the effect of improving the mechanical strength of the composition will not be sufficiently expressed.
本発明の樹脂組成物は、上記(a)、 (b)成分にさ
らに(c)成分であるブロックあるいはグラフト共重合
体を配合する。ここで(c)成分として用いるブロック
共重合体は、様々なものが使用できるが、ブロック共重
合体をA−B型として表示したときに、Aに相当するも
のとしてアタクチックポリスチレン、アクリロニトリル
−スチレンランダム共重合体(アクリロニトリル単位の
モル比2〜40%)。The resin composition of the present invention further contains component (c), a block or graft copolymer, in addition to components (a) and (b). Various types of block copolymers can be used as the component (c), but when the block copolymer is expressed as an A-B type, those corresponding to A are atactic polystyrene, acrylonitrile-styrene, etc. Random copolymer (molar ratio of acrylonitrile units 2-40%).
スチレン−無水マレイン酸ランダム共重合体(無水マレ
イン酸単位のモル比2〜50%)、スチレン−アクリロ
ニトリル−無水マレイミドランダム共重合体(スチレン
単位のモル比55〜75%。Styrene-maleic anhydride random copolymer (mole ratio of maleic anhydride units 2-50%), styrene-acrylonitrile-maleimide anhydride random copolymer (mole ratio of styrene units 55-75%).
アクリロニトリル単位のモル比10〜30%、無水マレ
イミド単位のモル比5〜25%)、スチレン−メチルメ
タクリレートランダム共重合体(メチルメタクリレート
単位のモル比2〜30%)及びスチレン−メタクリル酸
ランダム共重合体(メタクリル酸単位のモル比2〜25
%)から選ばれた一種又は二種以上のスチレン系(共)
重合体を挙げることができる。なお、上記スチレン系共
重合体の括弧内の各単位のモル比は、好ましい範囲であ
るが、この範囲であれば(a)成分との親和性が極めて
良好である。また、已に相当するものとしてポリアミド
、ポリメタクリル酸メチル、ポリエチレンテレフタレー
ト、ポリブチレンテレフタレート、ポリブタジェン、ポ
リイソプレン、水素化ポリブタジェン、水素化ポリイソ
プレン及びポリカーボネートから選ばれた一種又は二種
以上の重合体を挙げることができる。10-30% molar ratio of acrylonitrile units, 5-25% molar ratio of maleimide anhydride units), styrene-methyl methacrylate random copolymer (2-30% molar ratio of methyl methacrylate units), and styrene-methacrylic acid random copolymer. Coalescence (molar ratio of methacrylic acid units 2 to 25
%) or two or more styrene-based (co-) selected from
Polymers may be mentioned. The molar ratio of each unit in the parentheses of the above styrene copolymer is within a preferable range, and within this range, the affinity with component (a) is extremely good. In addition, one or more polymers selected from polyamide, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polybutadiene, polyisoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, and polycarbonate can be used as equivalent materials. can be mentioned.
さらに、(c)成分として用いるグラフト共重合体につ
いても、様々なものが使用できるが、ここで使用可能な
グラフト共重合体を前述のA、Bを用いて表示すれば、
Aグラフト化B共重合体あるいはBグラフト化A共重合
体の如く表わすことができる。Furthermore, various graft copolymers can be used as component (c), but if the graft copolymers that can be used here are expressed using the above-mentioned A and B,
It can be expressed as an A-grafted B copolymer or a B-grafted A copolymer.
上記A、Bから構成されるブロックあるいはグラフト共
重合体は、一般にAの部分が(a)成分と良好な親和性
を示し、Bの部分が(b)成分と良好な親和性を示すも
のである。In the block or graft copolymer composed of A and B described above, the A portion generally exhibits good affinity with component (a), and the B portion exhibits good affinity with component (b). be.
このような観点から、(c)成分におけるBの部分は、
Φ)成分によって適切な種類のものを選択することが望
ましい、すなわち(b)成分が、低密度ポリエチレン(
LDPE)、直鎖状低密度ポリエチレン(LLDPE)
、高密度ポリエチレン(HDPE)、ポリプロピレン(
PP)、ポリブテン−1(PB−1)、ポリ4−メチル
ペンテン−1などのポリオレフィンのときは、(c)成
分として具体的には、スチレン−ブタジェンブロック共
重合体(SB、SBS、BSBなど)、スチレン−水素
化ブタジェンブロック共重合体(SEBS、SEBなど
)、スチレン−イソプレンブロック共重合体(SI、S
IS、ISIなど)、スチレン−水素化イソプレンブロ
ック共重合体(SEP、5EPSなど)が好ましい、こ
れは、上記ブロック共重合体中のブタジェン、水素化ブ
タジェン、イソプレンあるいは水素化イソプレン成分が
、ポリオレフィンと良好な親和性を示すためである。ま
た、(b)成分がポリブタジェンのときは、(c)成分
としてポリスチレングラフト化ポリブタジェンあるいは
ポリスチレン−ポリブタジェンブロック共重合体が好ま
しく、(b)成分がナイロンのときは、(c)成分とし
てスチレングラフト化ポリアミドが好ましく、(b)成
分がポリカーボネートのときは、(c)成分としてポリ
スチレン−ポリカーボネートブロック共重合体が好まし
く用いられる。このように(c)成分は、℃)成分の種
類に応じて適時選択されるべきである。From this point of view, the part B in component (c) is
Φ) It is desirable to select an appropriate type of component depending on the component, that is, component (b) is low density polyethylene (
LDPE), linear low density polyethylene (LLDPE)
, high density polyethylene (HDPE), polypropylene (
In the case of polyolefins such as PP), polybutene-1 (PB-1), and poly4-methylpentene-1, specifically, styrene-butadiene block copolymers (SB, SBS, BSB) are used as component (c). ), styrene-hydrogenated butadiene block copolymers (SEBS, SEB, etc.), styrene-isoprene block copolymers (SI, S
IS, ISI, etc.), styrene-hydrogenated isoprene block copolymers (SEP, 5EPS, etc.) are preferred, because the butadiene, hydrogenated butadiene, isoprene, or hydrogenated isoprene component in the block copolymer is a polyolefin. This is because it shows good affinity. When the component (b) is polybutadiene, the component (c) is preferably polystyrene-grafted polybutadiene or a polystyrene-polybutadiene block copolymer, and when the component (b) is nylon, the component (c) is styrene. Grafted polyamide is preferred, and when component (b) is polycarbonate, polystyrene-polycarbonate block copolymer is preferably used as component (c). In this way, component (c) should be appropriately selected depending on the type of component (° C.).
本発明の樹脂組成物では、上記(c)成分を(a)、
(b)成分の合計100重量部に対して、0.05〜5
0′重量部、好ましくは0,5〜20重量部の割合で配
合する。この(c)成分の配合割合が、0.05重量部
未満では、これによる分散相の均一化や微細化の効果が
充分に発現できず、組成物の機械的強度の向上が期待で
きない。一方、50重量部を超えても配合量に相当する
効果は期待できず、むしろ耐熱性やその他の物性の低下
を招く。In the resin composition of the present invention, the above-mentioned (c) component is (a),
(b) 0.05 to 5 parts by weight per 100 parts by weight of components in total
It is blended in an amount of 0' parts by weight, preferably 0.5 to 20 parts by weight. If the blending ratio of component (c) is less than 0.05 part by weight, the effects of homogenizing and finely dispersing the dispersed phase cannot be sufficiently expressed, and no improvement in the mechanical strength of the composition can be expected. On the other hand, even if the amount exceeds 50 parts by weight, no effect corresponding to the amount blended can be expected, but rather leads to a decrease in heat resistance and other physical properties.
本発明の樹脂組成物は、上述した(a)、 (b)及び
(c)成分を主成分とするものであるが、この各成分の
特質を阻害しない範囲で、無機充填材や核剤、滑剤、可
塑剤、酸化防止剤、紫外線吸収剤、熱安定剤、難燃剤、
帯電防止剤2着色剤等の各種添加剤を配合することもで
きる。ここで、無機充填材としては、各種のものがあり
、目的に応じて適宜選定すればよい。具体的にはガラス
繊維、炭素繊維。The resin composition of the present invention has the above-mentioned components (a), (b), and (c) as main components, but may contain inorganic fillers, nucleating agents, Lubricants, plasticizers, antioxidants, ultraviolet absorbers, heat stabilizers, flame retardants,
Various additives such as an antistatic agent 2 and a coloring agent can also be blended. Here, there are various types of inorganic fillers, and they may be appropriately selected depending on the purpose. Specifically, glass fiber and carbon fiber.
アルミナ繊維、カーボンブラック、グラファイト。Alumina fiber, carbon black, graphite.
二酸化チタン、シリカ、タルク、マイカ、炭酸カルシウ
ム、硫酸カルシウム、炭酸バリウム、炭酸マグネシウム
、硫酸マグネシウム、硫酸バリウム。Titanium dioxide, silica, talc, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate.
オキシサルフエイト、酸化スズ、アルミナ、カオリン、
炭化ケイ素、金属粉末あるいはこれらの混合物をあげる
ことができる。Oxysulfate, tin oxide, alumina, kaolin,
Silicon carbide, metal powder or a mixture thereof can be mentioned.
本発明の樹脂組成物は、上述した(a)、 (b)及び
(c)成分並びに必要に応じて加える無機充填材や各種
添加剤を配合し、ブレンドすることによって調製するが
、このブレンドの方法としては、従来から知られている
溶融混練法、溶液ブレンド法等状況に応じて適宜手法に
よればよい。一般にはバンバリーミキサ−、ヘンシェル
ミキサーや混練ロールによる通常の溶融混練によること
が好ましい。The resin composition of the present invention is prepared by blending and blending the above-mentioned components (a), (b), and (c) as well as inorganic fillers and various additives added as necessary. The method may be any conventionally known melt kneading method, solution blending method, or other appropriate method depending on the situation. Generally, it is preferable to use conventional melt-kneading using a Banbury mixer, Henschel mixer, or kneading rolls.
次に、本発明を実施例及び比較例により更に詳しく説明
する。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
参考例1(主としてシンジオタクチック構造を有するポ
リスチレンの製造)
反応容器に、反応溶媒としてトルエン21と触媒成分と
してテトラエトキシチタン5ミリモルおよびメチルアル
ミノキサンをアルミニウム原子として500ミリモル入
れ、50″Cにおいてスチレン15Nを加え、4時間重
合反応を行った。Reference Example 1 (Production of polystyrene mainly having a syndiotactic structure) In a reaction vessel, 21 toluene as a reaction solvent, 5 mmol of tetraethoxytitanium as a catalyst component, and 500 mmol of methylaluminoxane as an aluminum atom were placed, and styrene 15N was added at 50''C. was added to carry out a polymerization reaction for 4 hours.
反応終了後、生成物を塩酸とメタノールとの混合液で洗
浄して、触媒成分を分解除去した0次いで乾燥すること
により、スチレン系重合体(ポリスチレン)2.5kg
を得た0次に、この重合体を、メチルエチルケトンを溶
媒としてソックスレー抽出し、抽出残分95重量%を得
た。この抽出残分の重量平均分子量はsoo、oooで
あった。また、この重合体は”C−NMRによる分析(
溶媒:1゜2−ジクロロベンゼン)から、シンジオタク
チック構造に基因する145.35ppmに吸収が認め
られ、そのピーク面積がら算出したラセミペンタッドで
のシンジオタクテイシテイ−は96%であった。After the reaction, the product was washed with a mixture of hydrochloric acid and methanol to decompose and remove the catalyst component.Then, the product was dried to produce 2.5 kg of styrene polymer (polystyrene).
Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue of 95% by weight. The weight average molecular weight of this extraction residue was soo, ooo. In addition, this polymer was analyzed by C-NMR (
Solvent: 1°2-dichlorobenzene), absorption was observed at 145.35 ppm due to the syndiotactic structure, and the syndiotacticity in racemic pentad calculated from the peak area was 96%.
参考例2(ポリスチレングラフト化ポリブチレンテレフ
タレートの製造)
末端をジヒドロキジル基で変成した数平均分子1600
0のポリスチレン(東亜合成化学工業■製、商品名:H
3−6)20重量部、1.4−ブタンジオール20重量
部及びポリブチレンテレフタレート(バロックス31O
,エンジニアリング・プラスチック■製)100重量部
を、ステンレス類のセパラブルフラスコに入れ、窒素気
流中、常圧下で、180℃にて2時間加熱した。Reference Example 2 (Production of polystyrene-grafted polybutylene terephthalate) Number average molecule 1600 whose terminal was modified with a dihydroxyl group
0 polystyrene (manufactured by Toagosei Kagaku Kogyo ■, product name: H
3-6) 20 parts by weight, 20 parts by weight of 1,4-butanediol and polybutylene terephthalate (Valox 31O
, Engineering Plastics Ltd.) was placed in a stainless steel separable flask and heated at 180° C. for 2 hours under normal pressure in a nitrogen stream.
次いで、フラスコを5.0wHgに減圧して200°C
で2時間攪拌した。その後、生成物をトルエンで20時
間ソックスレー抽出した。押出残分を120°Cで40
時間真空乾燥した後、13C−NMRを測定したところ
、ポリエステルに起因するピークのほかに、ポリスチレ
ンに起因するピークが認められ、ポリエステルにポリス
チレンがグラフト重合していることが確認できた。Next, the flask was depressurized to 5.0wHg and heated to 200°C.
The mixture was stirred for 2 hours. The product was then Soxhlet extracted with toluene for 20 hours. The extrusion residue was heated at 120°C for 40
After vacuum drying for an hour, 13C-NMR was measured, and in addition to the peak due to polyester, a peak due to polystyrene was observed, confirming that polystyrene was graft polymerized to polyester.
参考例3(ポリスチレングラフト化ポリアミドの製造)
末端をジカルボキシル基で変成した数平均分子量600
0のポリスチレン(東亜合成化学工業■製、商品名:C
5−6)100重量部及びナイロン6(宇部興産■製、
商品名二宇部ナイロン1013B)100重量部をラボ
プラストミル内に投入して、270℃にて50rpa+
の条件下で5分間混練した。Reference Example 3 (Manufacture of polystyrene-grafted polyamide) Number average molecular weight 600 with terminal modified with dicarboxyl group
0 polystyrene (manufactured by Toagosei Kagaku Kogyo ■, product name: C
5-6) 100 parts by weight and nylon 6 (manufactured by Ube Industries ■,
100 parts by weight of Niube Nylon 1013B (trade name) was put into a laboplast mill and heated to 50 rpa+ at 270°C.
The mixture was kneaded for 5 minutes under these conditions.
その後、混練物をトルエンで20時間ソックスレー抽出
した。抽出残分を120℃で40時間真空乾燥した後、
”C−NMRを測定したところ、ナイロンに起因するピ
ークのほかに、ポリスチレンに起因するピークが認めら
れ、ナイロンにポリスチレンがグラフト重合しているこ
とが確認できた。Thereafter, the kneaded material was subjected to Soxhlet extraction with toluene for 20 hours. After vacuum drying the extraction residue at 120°C for 40 hours,
``When C-NMR was measured, in addition to the peak due to nylon, a peak due to polystyrene was observed, confirming that polystyrene was graft polymerized to nylon.
実施例1
上記参考例1で得られたシンジオタクチック構造のポリ
スチレン19.8重量%、熱可塑性樹脂としてポリエチ
レンテレフタレート(商品名:ダイヤナイトMA−52
3,(η)=0.78d/g。Example 1 19.8% by weight of the syndiotactic polystyrene obtained in Reference Example 1, polyethylene terephthalate (trade name: Dyanite MA-52) as a thermoplastic resin
3, (η)=0.78d/g.
三菱レイヨン■製)79.2重量%及び分散剤((c)
成分)として参考例2で得られたポリスチレングラフト
化ポリブチレンテレフタレート1重量%を混合し、得ら
れた組成物全体100重量部に対して、核剤としてタル
ク(商品名:FFR,平均粒径0.6μm、浅田製粉■
製)を1重量部加え、内径25■の単軸押出機にて混練
し、ミニマット成形機により射出成形した。Mitsubishi Rayon ■) 79.2% by weight and dispersant ((c)
1% by weight of the polystyrene grafted polybutylene terephthalate obtained in Reference Example 2 was mixed as a nucleating agent (trade name: FFR, average particle size: 0 .6μm, Asada Seifun ■
1 part by weight of (manufactured by) was added, kneaded using a single screw extruder with an inner diameter of 25 mm, and injection molded using a mini mat molding machine.
得られた試験片についてJIS−に7110に従ったア
イゾツト衝撃試験、JIS−に7113に従った引張試
験及びJIS−に7206に従ったビカット軟化点測定
を行った。結果を第1表に示す。The obtained test piece was subjected to an Izot impact test according to JIS-7110, a tensile test according to JIS-7113, and a Vicat softening point measurement according to JIS-7206. The results are shown in Table 1.
実施例2
シンジオタクチック構造のポリスチレンの配合割合を4
1.7重量%、ポリエチレンテレフタレートの配合割合
を41.7重量%、ポリスチレングラフト化ポリブチレ
ンテレフタレートの配合割合を16.6重量%とじたこ
と以外は、実施例1と同様の操作を行った。結果を第1
表に示す。Example 2 The blending ratio of polystyrene with syndiotactic structure was 4
The same operation as in Example 1 was performed except that the blending ratio of polyethylene terephthalate was 41.7% by weight, and the blending ratio of polystyrene grafted polybutylene terephthalate was 16.6% by weight. Results first
Shown in the table.
実施例3
シンジオタクチック構造のポリスチレンの配合割合を6
3.6重量%、熱可塑性樹脂としてポリブチレンテレフ
タレート(商品名:バロックス310エンジニアリング
・プラスチック■製)27.3重量%、ポリスチレング
ラフト化ポリブチレンテレフタレートの配合割合を9.
1重量%としたこと以外は、実施例1と同様の操作を行
った。結果を第1表に示す。Example 3 The blending ratio of polystyrene with syndiotactic structure was 6
3.6% by weight, 27.3% by weight of polybutylene terephthalate (product name: Valox 310 manufactured by Engineering Plastics ■) as a thermoplastic resin, and 9.9% by weight of polystyrene grafted polybutylene terephthalate.
The same operation as in Example 1 was performed except that the amount was 1% by weight. The results are shown in Table 1.
実施例4
シンジオタクチック構造のポリスチレンの配合割合を6
6.7重量%、ゴム状重合体としてエチレン−プロピレ
ンゴム(商品名:EPO2P、 日本合成ゴム■製)2
8.6重量%2分散剤としてスチレン−水素化ブタジェ
ンブロック共重合体(商品名:G−1652,シェル化
学社製)4.7重量%とじたこと以外は、実施例1と同
様の操作を行った。結果を第1表に示す。Example 4 The blending ratio of polystyrene with syndiotactic structure was 6
6.7% by weight, ethylene-propylene rubber (trade name: EPO2P, manufactured by Japan Synthetic Rubber) 2 as a rubbery polymer
8.6% by weight 2 The same operation as in Example 1 except that 4.7% by weight of styrene-hydrogenated butadiene block copolymer (trade name: G-1652, manufactured by Shell Chemical Co., Ltd.) was used as the dispersant. I did it. The results are shown in Table 1.
実施例5
シンジオタクチック構造のポリスチレン・の配合割合を
49.7重量%、熱可塑性樹脂としてナイロン6(商品
名:UBEナイロン1013B、宇部興産■製)49.
7重量%9分散剤として参考例3で得られたポリスチレ
ングラフト化ポリアミド0.6重量%とじたこと以外は
、実施例1と同様の操作を行った。結果を第1表に示す
。Example 5 The blending ratio of polystyrene with a syndiotactic structure was 49.7% by weight, and the thermoplastic resin was nylon 6 (trade name: UBE Nylon 1013B, manufactured by Ube Industries, Ltd.) 49.
The same operation as in Example 1 was performed except that 0.6% by weight of the polystyrene grafted polyamide obtained in Reference Example 3 was used as the dispersant. The results are shown in Table 1.
実施例6
シンジオタクチック構造のポリスチレンの配合割合を6
6.7重量%、熱可塑性樹脂として直鎖状低密度ポリエ
チレン(商品名:出光ポリエチレンL1014D、出光
石油化学■製)28.6重量%2分散剤としてスチレン
−水素化ブタジェンブロック共重合体(商品名:G−1
652,シェル化学社製)4.7重量%とじたこと以外
は、実施例1と同様の操作を行った。結果を第1表に示
す。Example 6 The blending ratio of polystyrene with syndiotactic structure was 6
6.7% by weight, 28.6% by weight of linear low-density polyethylene (trade name: Idemitsu Polyethylene L1014D, manufactured by Idemitsu Petrochemical) as a thermoplastic resin, 2 Styrene-hydrogenated butadiene block copolymer as a dispersant ( Product name: G-1
652, manufactured by Shell Chemical Co., Ltd.) The same operation as in Example 1 was performed, except that the content was 4.7% by weight. The results are shown in Table 1.
実施例7
シンジオタクチック構造のポリスチレンの配合割合を4
5.5重量%、熱可塑性樹脂としてポリカーボネート(
商品名:タフロンA−2500.出光石油化学■製)4
5.5重量%1分散剤としてスチレン−カーボネートブ
ロック共重合体(特開昭61−1078617号公報に
したがって調製したもの)9.0重量%としたこと以外
は、実施例1と同様の操作を行った。結果を第1表に示
す。Example 7 The blending ratio of polystyrene with syndiotactic structure was 4
5.5% by weight, polycarbonate (as thermoplastic resin)
Product name: Taflon A-2500. Manufactured by Idemitsu Petrochemical ■) 4
The same procedure as in Example 1 was carried out, except that 9.0% by weight of styrene-carbonate block copolymer (prepared according to JP-A-61-1078617) was used as the dispersant. went. The results are shown in Table 1.
実施例8
シンジオタクチック構造のポリスチレンの配合割合を8
4.5重量%、熱可塑性樹脂としてポリカーボネート(
商品名:タフロンA−2500,出光石油化学■製)6
.4重量%2分散剤としてスチレン−カーボネートブロ
ック共重合体(特開昭61−1078617号公報にし
たがって調製したもの)9.1重量%とじたこと以外は
、実施例1と同様の操作を行った。結果を第1表に示す
。Example 8 The blending ratio of polystyrene with syndiotactic structure was 8
4.5% by weight, polycarbonate (as thermoplastic resin)
Product name: Taflon A-2500, manufactured by Idemitsu Petrochemical ■) 6
.. The same operation as in Example 1 was carried out, except that 9.1% by weight of a styrene-carbonate block copolymer (prepared according to JP-A-61-1078617) was used as the dispersant. . The results are shown in Table 1.
実施例9
シンジオタクチック構造のポリスチレンの配合割合を6
6.7重量%、熱可塑性樹脂として高密度ポリエチレン
(商品名:出光ポリエチレン110J、出光石油化学■
製)28.6重量%1分散剤としてスチレン−水素化ブ
タジェンブロック共重合体(商品名:G−1652,シ
ェル化学■製)4.7重量%としたこと以外は、実施例
1と同様の操作を行った。結果を第1表に示す。Example 9 The blending ratio of polystyrene with syndiotactic structure was 6
6.7% by weight, high-density polyethylene as thermoplastic resin (product name: Idemitsu Polyethylene 110J, Idemitsu Petrochemical ■
Same as Example 1 except that the dispersant was 4.7% by weight of styrene-hydrogenated butadiene block copolymer (trade name: G-1652, manufactured by Shell Chemical Company). The operation was performed. The results are shown in Table 1.
実施例10
シンジオタクチック構造のポリスチレンの配合割合を6
9.3重量%、熱可塑性樹脂としてポリプロピレン(商
品名:出光ポリプロピレンJ−700G、出光石油化学
■製)29.7重量%9分散剤としてスチレン−水素化
ブタジエンブロソク共重合体(商品名:G−1652,
シェル化学社製)1.0重量%とじたこと以外は、実施
例1と同様の操作を行った。結果を第1表に示す。Example 10 The blending ratio of polystyrene with syndiotactic structure was 6
9.3% by weight as a thermoplastic resin, polypropylene (product name: Idemitsu Polypropylene J-700G, manufactured by Idemitsu Petrochemical ■) 29.7% by weight 9. Styrene-hydrogenated butadiene brox copolymer as a dispersant (product name: G-1652,
The same operation as in Example 1 was carried out, except that the content was 1.0% by weight (manufactured by Shell Chemical Co., Ltd.). The results are shown in Table 1.
比較例1
シンジオタクチック構造のポリスチレンの配合割合を2
0.0重世%、熱可塑性樹脂としてポリエチレンテレフ
タレート(商品名:ダイヤナイトMA−523,(η)
=0.78d/g、三菱レイヨン■製)80.0重量
%とじて、分散剤を加えなかったこと以外は、実施例1
と同様の操作を行った。Comparative Example 1 The blending ratio of polystyrene with syndiotactic structure was 2
0.0%, polyethylene terephthalate (trade name: Diamondite MA-523, (η)) as thermoplastic resin
= 0.78 d/g, manufactured by Mitsubishi Rayon ■) 80.0% by weight, and Example 1 except that no dispersant was added.
The same operation was performed.
結果を第1表に示す。The results are shown in Table 1.
比較例2
シンジオタクチック構造のポリスチレンの配合割合を5
0.0重量%、熱可塑性樹脂としてポリエチレンテレフ
タレート(商品名:ダイヤナイトMA−523,(η)
=0.78d1/g、三liレイヨン■製)50.0重
量%として、分散剤を加えなかったこと以外は、実施例
1と同様の操作を行った。Comparative Example 2 The blending ratio of polystyrene with syndiotactic structure was 5
0.0% by weight, polyethylene terephthalate (trade name: Dyanite MA-523, (η)) as thermoplastic resin
= 0.78 d1/g, manufactured by Sanli Rayon ■) 50.0% by weight, and the same operation as in Example 1 was performed except that no dispersant was added.
結果を第1表に示す。The results are shown in Table 1.
比較例3
シンジオタクチック構造のポリスチレンの配合割合を7
0.0重量%、熱可塑性樹脂としてポリブチレンテレフ
タレート(商品名:バロックス31o。Comparative Example 3 The blending ratio of polystyrene with syndiotactic structure was 7
0.0% by weight, polybutylene terephthalate (trade name: Valox 31o) as a thermoplastic resin.
エンジニアリング・プラスチック株製)30.0重量%
として、分散剤を加えなかったこと以外は、実施例1と
同様の操作を行った。結果を第1表に示す。Engineering Plastics Co., Ltd.) 30.0% by weight
The same operation as in Example 1 was performed except that no dispersant was added. The results are shown in Table 1.
比較例4
シンジオタクチック構造のポリスチレンの配合割合を7
0.0重量%、ゴム状重合体としてエチレン−プロピレ
ンゴム(商品名:EPO2P、 日本合成ゴム■製)3
0.0重量%として、分散剤を加えなかったこと以外は
、実施例1と同様の操作を行った。結果を第1表に示す
。Comparative Example 4 The blending ratio of polystyrene with syndiotactic structure was 7
0.0% by weight, ethylene-propylene rubber (trade name: EPO2P, manufactured by Japan Synthetic Rubber) 3 as a rubbery polymer
The same operation as in Example 1 was performed except that the dispersant was added at 0.0% by weight and no dispersant was added. The results are shown in Table 1.
比較例5
シンジオタクチック構造のポリスチレンの配合割合を2
0.0重量%5分散剤として参考例2で得られたポリス
チレングラフト化ポリブチレンチレフタレ−)80.0
重量%とじて、熱可塑性樹脂を加えなかったこと以外は
、実施例1と同様の操作を行った。結果を第1表に示す
。Comparative Example 5 The blending ratio of polystyrene with syndiotactic structure was 2
0.0% by weight 5 Polystyrene grafted polybutylene ethylene terephthalate obtained in Reference Example 2 as a dispersant) 80.0
The same operation as in Example 1 was performed except that no thermoplastic resin was added in terms of weight percent. The results are shown in Table 1.
比較例6
熱可塑性樹脂としてポリエチレンテレフタレート(商品
名:ダイヤナイトMA−523,(η)−〇、78di
/g、三菱レイヨン■製)80.0重量%。Comparative Example 6 Polyethylene terephthalate (trade name: Dyanite MA-523, (η)-〇, 78di) as a thermoplastic resin
/g, manufactured by Mitsubishi Rayon■) 80.0% by weight.
分散剤として参考例2で得られたポリスチレングラフト
化ポリブチレンテレフタレート20.0重量%とじて、
シンジオタクチック構造のポリスチレンを加えなかった
こと以外は、実施例1と同様の操作を行った。結果を第
1表に示す。With 20.0% by weight of polystyrene grafted polybutylene terephthalate obtained in Reference Example 2 as a dispersant,
The same operation as in Example 1 was performed except that polystyrene having a syndiotactic structure was not added. The results are shown in Table 1.
参考例4
シンジオタクチック構造のポリスチレン100重量部に
核剤としてのタルクを0.5重量部加えたものについて
、実施例1と同様の操作を行った。Reference Example 4 The same operation as in Example 1 was carried out using 100 parts by weight of polystyrene having a syndiotactic structure and 0.5 parts by weight of talc as a nucleating agent.
結果を第1表に示す。The results are shown in Table 1.
参考例5
ポリエチレンテレフタレート(商品名:ダイヤナイトM
A−523,(η) =0.78社/g、 三菱レイ
ヨン■製)100重量部に核剤としてのタルクを0.5
重量部加えたものについて、実施例1と同様の操作を行
った。結果を第1表に示す。Reference example 5 Polyethylene terephthalate (product name: Diamondite M
A-523, (η) = 0.78/g, manufactured by Mitsubishi Rayon ■) 0.5 parts by weight of talc as a nucleating agent
The same operation as in Example 1 was performed for the product to which the weight part was added. The results are shown in Table 1.
参考例6
ポリブチレンテレフタレート(商品名:バロックス31
O,エンジニアリング・プラスチック■製)100重量
部に核剤としてのタルクを0.5重量部加えたものにつ
いて、実施例1と同様の操作を行った。結果を第1表に
示す。Reference example 6 Polybutylene terephthalate (product name: Valox 31
The same operation as in Example 1 was carried out using 100 parts by weight of 0.5 parts by weight of talc as a nucleating agent. The results are shown in Table 1.
参考例7
ナイロン6(商品名:UBEナイロン1013B、宇部
興産■製)100重量部に核剤としてのタルクを0.5
重量部加えたものについて、実施例1と同様の操作を行
った。結果を第1表に示す。Reference Example 7 0.5 parts of talc as a nucleating agent was added to 100 parts by weight of nylon 6 (trade name: UBE Nylon 1013B, manufactured by Ube Industries).
The same operation as in Example 1 was performed for the product to which the weight part was added. The results are shown in Table 1.
参考例8
直鎖状低密度ポリエチレン(商品名:出光ポリエチレン
L1014D、出光石油化学■製)100重量部に核剤
としてのタルクを0.5重量部加えたものについて、実
施例1と同様の操作を行った。結果を第1表に示す。Reference Example 8 The same operation as in Example 1 was carried out using 100 parts by weight of linear low-density polyethylene (trade name: Idemitsu Polyethylene L1014D, manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.5 parts by weight of talc as a nucleating agent. I did it. The results are shown in Table 1.
参考例9
ポリプロピレン(商品名:出光ポリプロピレンJ−70
0G、出光石油化学■製)100重量部に核剤としての
タルクを0.5重量部加えたものについて、実施例1と
同様の操作を行った。結果を第1表に示す。Reference Example 9 Polypropylene (Product name: Idemitsu Polypropylene J-70
The same operation as in Example 1 was carried out using 100 parts by weight of 0G (manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.5 parts by weight of talc as a nucleating agent. The results are shown in Table 1.
参考例10
高密度ポリエチレン(商品名:出光ポリエチレンll0
J、出光石油化学■製)100重量部に核剤としてのタ
ルクを0.5重量部加えたものについて、実施例1と同
様の操作を行った。結果を第1表に示す。Reference example 10 High-density polyethylene (product name: Idemitsu polyethylene ll0
The same operation as in Example 1 was carried out using 100 parts by weight of 0.5 parts by weight of talc as a nucleating agent. The results are shown in Table 1.
参考例11
ポリカーボネート(商品名:タフロンA−2500、出
光石油化学■製)について、実施例1と同様の操作を行
った。結果を第1表に示す。Reference Example 11 The same operation as in Example 1 was performed on polycarbonate (trade name: Taflon A-2500, manufactured by Idemitsu Petrochemical Co., Ltd.). The results are shown in Table 1.
(以下余白)
参考例12(主としてシンジオタクチック構造を存する
ポリスチレンの製造)
反応容器に溶媒としてトルエン32j1!と触媒成分で
あるメチルアルミノキサンをアルミニウム原子として1
335ミリモルおよびテトラエトキシチタン13.4ミ
リモルを加え、次いでこれにスチレン15kgを加えた
。(Left below) Reference Example 12 (Production of polystyrene mainly having a syndiotactic structure) Toluene 32j1! as a solvent was placed in a reaction vessel. and methylaluminoxane, which is a catalyst component, as an aluminum atom.
335 mmol and 13.4 mmol of tetraethoxytitanium were added, followed by 15 kg of styrene.
次に、55℃に昇温しで2時間重合反応を行った0反応
終了後、得られた生成物を水酸化ナトリウム−メタノー
ル混合溶液で洗浄し、触媒成分を分解除去した。その後
、これを乾燥して重合体2.1kgを得た。Next, the temperature was raised to 55° C. and a polymerization reaction was carried out for 2 hours. After the completion of the reaction, the obtained product was washed with a sodium hydroxide-methanol mixed solution to decompose and remove the catalyst component. Thereafter, this was dried to obtain 2.1 kg of polymer.
更に、この重合体をメチルエチルケトンを溶媒としてソ
ックスレー抽出し、抽出残分95重憧%を得た。このよ
うにして得られた重合体(抽出残分)は重量平均分子量
が400,000であり、融点270°Cであった。ま
た、この重合体は”C−NMRによる分析から、シンジ
オタクチック構造に起因する1 45.351)I)1
1に吸収が認められ、そのピーク面積から算出したラセ
ミペンタッドでのシンジオタクテイシテイ−は98%で
あった。Further, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue of 95% by weight. The polymer thus obtained (extraction residue) had a weight average molecular weight of 400,000 and a melting point of 270°C. In addition, this polymer was found to have a syndiotactic structure due to "145.351)I)1" from C-NMR analysis.
Absorption was observed in 1, and the syndiotacticity for racemic pentad calculated from the peak area was 98%.
実施例11
参考例12で得られた主としてシンジオタクチック構造
を有するポリスチレン75重量部、(b)成分としてメ
ルトインデックスが10 g / 10分。Example 11 75 parts by weight of the polystyrene mainly having a syndiotactic structure obtained in Reference Example 12, with a melt index of 10 g/10 minutes as component (b).
EPR成分を15重量%含有するブロックポリプロピレ
ン(出光ポリプロピレンJ−785H,出光石油化学■
製)25重量部及び分散剤((c)成分)としてスチレ
ン−水素化イソプレンブロック共重合体(SEP)(商
品名: Kraton GX L 701゜シェル化
学■製)を15重量部加え、内径20Mの単軸混練押出
機を用いて290℃で押し出し、ペレット化した後、新
潟鉄工■製のMIN−7射出成形機で射出成形した。Block polypropylene containing 15% by weight of EPR component (Idemitsu Polypropylene J-785H, Idemitsu Petrochemical ■
) and 15 parts by weight of styrene-hydrogenated isoprene block copolymer (SEP) (trade name: Kraton GX L 701° manufactured by Shell Chemical ■) as a dispersant (component (c)) were added, and a The mixture was extruded at 290° C. using a single-screw kneading extruder, pelletized, and then injection molded using a MIN-7 injection molding machine manufactured by Niigata Tekko ■.
得られた試験片についてJIS−に7110に従ったア
イゾツト衝撃試験、JIS−に7203に従った曲げ試
験及びJIS−K 7206に従ったビカット軟化点
測定を行った。配合組成を第2表に示し、結果を第3表
に示す。The obtained test piece was subjected to an Izot impact test according to JIS-7110, a bending test according to JIS-7203, and a Vicat softening point measurement according to JIS-K 7206. The composition is shown in Table 2, and the results are shown in Table 3.
実施例12〜18及び比較例7〜9
各成分の種類及び配合組成を変えたこと以外は、上記実
施例11と同様の操作を行った。配合組成を第2表に示
し、結果を第3表に示す。Examples 12 to 18 and Comparative Examples 7 to 9 The same operations as in Example 11 were performed, except that the types and composition of each component were changed. The composition is shown in Table 2, and the results are shown in Table 3.
(以下余白)
11 参考例10で得られた主としてシンジオタクチッ
ク構造を有するポリスチレン
*2 ポリプロピレン(出光ポリプロピレンJ−785
H,出光石油化学■製)
*3 5EP(Kra’tonGX−1701,シェル
化学■製)
*4 スチレン−イソプレン−スチレンブロック共重合
体(Kraton D −1111、シェル化学■製)
*5 スチレン−水素化ブタジエンースチレンブo7り
共重合体(Kraton G −1650゜シェル化学
■製)
*6 直鎖状低密度ポリエチレン(出光モアチック01
38N、出光石油化学■製)
*7 スチレン−ブタジェン−スチレンブロック共重合
体(Kraton D −,1101、シェル化学■製
)
*8 実施例18には、(c)成分としてSBSとSI
sの二種類の分散剤を用いた。(The following is a blank space) 11 Polystyrene mainly having a syndiotactic structure obtained in Reference Example 10 *2 Polypropylene (Idemitsu Polypropylene J-785
H, manufactured by Idemitsu Petrochemical ■) *3 5EP (Kra'ton GX-1701, manufactured by Shell Chemical ■) *4 Styrene-isoprene-styrene block copolymer (Kraton D-1111, manufactured by Shell Chemical ■) *5 Styrene-hydrogen butadiene-styrene copolymer (Kraton G-1650° manufactured by Shell Chemical Co., Ltd.) *6 Linear low-density polyethylene (Idemitsu Moretic 01
38N, manufactured by Idemitsu Petrochemical ■) *7 Styrene-butadiene-styrene block copolymer (Kraton D-, 1101, manufactured by Shell Chemical ■) *8 Example 18 contains SBS and SI as component (c).
Two types of dispersants were used.
本発明の樹脂組成物は、主としてシンジオタクチック構
造を有するスチレン系重合体が配合されているとともに
、各成分間の相溶性が良好であるため、耐熱性にすぐれ
ると同時に、耐衝撃強度。The resin composition of the present invention mainly contains a styrene polymer having a syndiotactic structure and has good compatibility between each component, so it has excellent heat resistance and high impact resistance.
引張強度2弾性率等の力学的物性のすぐれたものである
。It has excellent mechanical properties such as tensile strength and modulus of elasticity.
したがって、本発明の樹脂組成物は、耐熱性や各種の力
学的物性の要求される産業用資材1機械部品用素材等と
して幅広くかつ有効な利用が期待される。Therefore, the resin composition of the present invention is expected to be widely and effectively used as a material for industrial materials, mechanical parts, etc. that require heat resistance and various mechanical properties.
特許出願人 出光興産株式会社 代理人 弁理士 大 谷 保Patent applicant: Idemitsu Kosan Co., Ltd. Agent Patent Attorney Tamotsu Otani
Claims (1)
スチレン系重合体5〜95重量%、 (b)該スチレン系重合体以外の熱可塑性樹脂及び/又
はゴム状重合体95〜5重量%、 及び前記(a)及び(b)成分の合計100重量部に対
して、 (c)A−B型ブロック共重合体、Aグラフト化B共重
合体及びBグラフト化A共重合体のうちから選ばれた一
種又は二種以上のブロックあるいはグラフト共重合体0
.05〜50重量部〔ここで、Aはアタクチックポリス
チレン、アクリロニトリル−スチレンランダム共重合体
、スチレン−無水マレイン酸ランダム共重合体、スチレ
ン−アクリロニトリル−無水マレイミドランダム共重合
体、スチレン−メチルメタクリレートランダム共重合体
及びスチレン−メタクリル酸ランダム共重合体から選ば
れた一種又は二種以上のスチレン系重合体あるいはスチ
レン系共重合体を示し、Bはポリアミド、ポリメタクリ
ル酸メチル、ポリエチレンテレフタレート、ポリブチレ
ンテレフタレート、ポリブタジエン、ポリイソプレン、
水素化ポリブタジエン、水素化ポリイソプレン及びポリ
カーボネートから選ばれた一種又は二種以上の重合体を
示す。〕を主成分とする熱可塑性樹脂組成物。(1) (a) 5 to 95% by weight of a styrenic polymer mainly having a syndiotactic structure, (b) 95 to 5% by weight of a thermoplastic resin and/or rubbery polymer other than the styrenic polymer, and For a total of 100 parts by weight of the components (a) and (b), (c) selected from A-B block copolymers, A-grafted B copolymers, and B-grafted A copolymers; One or more block or graft copolymers 0
.. 05 to 50 parts by weight [Here, A is atactic polystyrene, acrylonitrile-styrene random copolymer, styrene-maleic anhydride random copolymer, styrene-acrylonitrile-anhydride maleimide random copolymer, styrene-methyl methacrylate random copolymer B represents one or more styrene polymers or styrene copolymers selected from polymers and styrene-methacrylic acid random copolymers, and B represents polyamide, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polybutadiene, polyisoprene,
One or more polymers selected from hydrogenated polybutadiene, hydrogenated polyisoprene, and polycarbonate. A thermoplastic resin composition containing ] as a main component.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1004921A JP2768483B2 (en) | 1988-01-13 | 1989-01-13 | Thermoplastic resin composition |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP384488 | 1988-01-13 | ||
JP63-3844 | 1988-01-13 | ||
JP1004921A JP2768483B2 (en) | 1988-01-13 | 1989-01-13 | Thermoplastic resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01279944A true JPH01279944A (en) | 1989-11-10 |
JP2768483B2 JP2768483B2 (en) | 1998-06-25 |
Family
ID=26337484
Family Applications (1)
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---|---|---|---|
JP1004921A Expired - Fee Related JP2768483B2 (en) | 1988-01-13 | 1989-01-13 | Thermoplastic resin composition |
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Country | Link |
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JP (1) | JP2768483B2 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01197547A (en) * | 1988-02-01 | 1989-08-09 | Asahi Chem Ind Co Ltd | Heat-resistant resin composition |
JPH01197546A (en) * | 1988-02-01 | 1989-08-09 | Asahi Chem Ind Co Ltd | Heat-resistant resin composition |
WO1993018087A1 (en) * | 1992-03-04 | 1993-09-16 | Idemitsu Kosan Co., Ltd. | Styrenic resin composition |
JPH1095886A (en) * | 1996-09-23 | 1998-04-14 | Bridgestone Corp | Extended polymer composition formed from blend of elastomer with syndiotactic polystyrene |
WO2002014425A1 (en) * | 2000-08-14 | 2002-02-21 | Samsung General Chemicals Co., Ltd. | Reactor alloy of syndiotactic polystyrene having high impact resistance |
KR100330352B1 (en) * | 1999-07-02 | 2002-04-01 | 유현식 | Syndiotactic Polystyrene Compositions having Improved Impact Strength |
JP2008174675A (en) * | 2007-01-22 | 2008-07-31 | Idemitsu Kosan Co Ltd | Polystyrenic resin composition |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100762609B1 (en) * | 2001-07-25 | 2007-10-04 | 삼성토탈 주식회사 | Polypropylene-syndiotactic polystyrene resin composition |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4925044A (en) * | 1969-02-27 | 1974-03-06 | ||
JPS5192856A (en) * | 1975-02-14 | 1976-08-14 | NANNENSEIJUSHISOSEIBUTSU | |
JPS6092344A (en) * | 1983-10-27 | 1985-05-23 | Toagosei Chem Ind Co Ltd | Thermoplastic resin composition |
JPS61126159A (en) * | 1984-11-26 | 1986-06-13 | Toagosei Chem Ind Co Ltd | Resin composition |
JPS62187708A (en) * | 1985-11-11 | 1987-08-17 | Idemitsu Kosan Co Ltd | Production of styrene polymer |
JPS62257950A (en) * | 1986-05-06 | 1987-11-10 | Idemitsu Kosan Co Ltd | Thermoplastic resin composition |
-
1989
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4925044A (en) * | 1969-02-27 | 1974-03-06 | ||
JPS5192856A (en) * | 1975-02-14 | 1976-08-14 | NANNENSEIJUSHISOSEIBUTSU | |
JPS6092344A (en) * | 1983-10-27 | 1985-05-23 | Toagosei Chem Ind Co Ltd | Thermoplastic resin composition |
JPS61126159A (en) * | 1984-11-26 | 1986-06-13 | Toagosei Chem Ind Co Ltd | Resin composition |
JPS62187708A (en) * | 1985-11-11 | 1987-08-17 | Idemitsu Kosan Co Ltd | Production of styrene polymer |
JPS62257950A (en) * | 1986-05-06 | 1987-11-10 | Idemitsu Kosan Co Ltd | Thermoplastic resin composition |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01197547A (en) * | 1988-02-01 | 1989-08-09 | Asahi Chem Ind Co Ltd | Heat-resistant resin composition |
JPH01197546A (en) * | 1988-02-01 | 1989-08-09 | Asahi Chem Ind Co Ltd | Heat-resistant resin composition |
WO1993018087A1 (en) * | 1992-03-04 | 1993-09-16 | Idemitsu Kosan Co., Ltd. | Styrenic resin composition |
US5391611A (en) * | 1992-03-04 | 1995-02-21 | Idemitsu Kosan Co., Ltd. | Styrenic resin composition |
JPH1095886A (en) * | 1996-09-23 | 1998-04-14 | Bridgestone Corp | Extended polymer composition formed from blend of elastomer with syndiotactic polystyrene |
KR100330352B1 (en) * | 1999-07-02 | 2002-04-01 | 유현식 | Syndiotactic Polystyrene Compositions having Improved Impact Strength |
WO2002014425A1 (en) * | 2000-08-14 | 2002-02-21 | Samsung General Chemicals Co., Ltd. | Reactor alloy of syndiotactic polystyrene having high impact resistance |
US6780938B2 (en) | 2000-08-14 | 2004-08-24 | Samsung Atofina Co. Ltd. | Reactor alloy of syndiotactic polystyrene having high impact resistance |
JP2008174675A (en) * | 2007-01-22 | 2008-07-31 | Idemitsu Kosan Co Ltd | Polystyrenic resin composition |
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