JPH03220249A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPH03220249A JPH03220249A JP1485090A JP1485090A JPH03220249A JP H03220249 A JPH03220249 A JP H03220249A JP 1485090 A JP1485090 A JP 1485090A JP 1485090 A JP1485090 A JP 1485090A JP H03220249 A JPH03220249 A JP H03220249A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- resin
- weight
- styrene
- thermoplastic resin
- 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 14
- 239000011342 resin composition Substances 0.000 title claims description 12
- 229920001971 elastomer Polymers 0.000 claims abstract description 62
- 239000002245 particle Substances 0.000 claims abstract description 36
- 239000005060 rubber Substances 0.000 claims abstract description 32
- 229920001890 Novodur Polymers 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 15
- 239000012770 industrial material Substances 0.000 abstract description 5
- 239000007790 solid phase Substances 0.000 abstract description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 abstract description 4
- 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 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 38
- 239000004793 Polystyrene Substances 0.000 description 21
- 229920002223 polystyrene Polymers 0.000 description 21
- -1 polypropylene Polymers 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- 229920001400 block copolymer Polymers 0.000 description 7
- 150000003440 styrenes Chemical class 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 241001237745 Salamis Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 235000015175 salami Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NLBJAOHLJABDAU-UHFFFAOYSA-N (3-methylbenzoyl) 3-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C=C(C)C=CC=2)=C1 NLBJAOHLJABDAU-UHFFFAOYSA-N 0.000 description 1
- PYOLJOJPIPCRDP-UHFFFAOYSA-N 1,1,3-trimethylcyclohexane Chemical compound CC1CCCC(C)(C)C1 PYOLJOJPIPCRDP-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920004939 Cariflex™ Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 125000000174 L-prolyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])[C@@]1([H])C(*)=O 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- PBGVMIDTGGTBFS-UHFFFAOYSA-N but-3-enylbenzene Chemical compound C=CCCC1=CC=CC=C1 PBGVMIDTGGTBFS-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CSKKAINPUYTTRW-UHFFFAOYSA-N tetradecoxycarbonyloxy tetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCC CSKKAINPUYTTRW-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は新規な熱可塑性樹脂組成物、さらに詳しくは、
耐熱性や、剛性、耐衝撃性特に低温衝撃強度などの機械
的特性を十分に保持するとともに、同相接着性が良好で
、工業材料として好適なポリオレフィンを主体とする熱
可塑性樹脂組成物に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel thermoplastic resin composition, more specifically,
This article relates to thermoplastic resin compositions mainly composed of polyolefins, which have sufficient mechanical properties such as heat resistance, rigidity, impact resistance, especially low-temperature impact strength, and have good in-phase adhesion, making them suitable as industrial materials. be.
〔従来の技術］
従来、ポリオレフィン系樹脂は機械的強度、成形性、耐
薬品性などに優れていることから、多くの工業分野にお
いて幅広く用いられている。しかしながら、このポリオ
レフィン系樹脂は無極性であるため、二次加工性、特に
固相接着性に劣り、用途が制限されるのを免れないとい
う欠点を有している。[Prior Art] Conventionally, polyolefin resins have been widely used in many industrial fields because of their excellent mechanical strength, moldability, chemical resistance, and the like. However, since this polyolefin resin is non-polar, it has the disadvantage that it has poor secondary processability, particularly solid phase adhesion, and its uses are inevitably limited.
したがって、このような欠点を改良するために、これま
で種々の方法、例えばポリプロピレンに接着性の良好な
ポリマーをブレンドする方法（特開昭４８−６３４４１
号公報、特公昭５２−８１３４号公報）、ポリプロピレ
ンに、ポリスチレンとエラストマーとを組み合わせてブ
レンドする方法（特開昭５２−１４１８５４号公報、特
開昭５６−３８３３８号公報、特開昭５６−１０４９７
８号公報、特公昭５２−１７０５５号公報）などが提案
されている。Therefore, in order to improve these drawbacks, various methods have been used, such as a method of blending a polymer with good adhesiveness with polypropylene (Japanese Patent Laid-Open No. 48-63441).
JP-A No. 52-8134, JP-A-52-8134), a method of blending polypropylene in combination with polystyrene and an elastomer (JP-A-52-141854, JP-A-56-38338, JP-A-56-10497)
8, Japanese Patent Publication No. 52-17055), etc. have been proposed.
しかしながら、接着性の良好なポリマーをブレンドする
方法においては、ある程度同相接着性は改良されるもの
の、相溶性が悪いために、物性の低下を免れない上、成
形品において層剥離が生じゃすいなどの欠点がある。ま
た、ポリスチレンとエラストマーとを組み合わせてブレ
ンドする方法においては、流動性、耐熱性、剛性が大幅
に低下するなど、好ましくない事態を招来し、工業材料
としては不十分である。However, in the method of blending polymers with good adhesion, although the in-phase adhesion is improved to some extent, due to poor compatibility, the physical properties are inevitably deteriorated and the molded product is prone to delamination. There are drawbacks. Furthermore, in the method of blending polystyrene and elastomer, fluidity, heat resistance, and rigidity are significantly reduced, resulting in undesirable situations, making the material unsatisfactory as an industrial material.
［発明が解決しようとする課題］
本発明は、このような事情のもとで、耐熱性や、剛性、
耐衝撃性特に低温衝撃強度などの機械的特性を十分に保
持するとともに、固相接着性が良好で、工業材料として
好適なポリオレフィンを主体とする熱可塑性樹脂組成物
を提供することを目的としてなされたものである。[Problems to be Solved by the Invention] Under these circumstances, the present invention aims to improve heat resistance, rigidity,
The purpose of this invention is to provide a polyolefin-based thermoplastic resin composition that sufficiently maintains mechanical properties such as impact resistance, particularly low-temperature impact strength, and has good solid phase adhesion and is suitable as an industrial material. It is something that
［課題を解決するための手段１
本発明者らは、前記の好ましい性質を有する熱可塑性樹
脂組成物を開発すべく鋭意研究を重ねた結果、ポリオレ
フィン樹脂に、特定のゴム分散形態を有するゴム変性ス
チレン系責脂と相溶化剤とを特定の割合で配合した組成
物により、その目的を達成しうろことを見い出し、この
知見に基づいて本発明を完成するに至った。[Means for Solving the Problems 1] As a result of intensive research aimed at developing a thermoplastic resin composition having the above-mentioned preferable properties, the present inventors found that a rubber modified resin having a specific rubber dispersion form was added to a polyolefin resin. It was discovered that the objective could be achieved by a composition containing a styrene resin and a compatibilizer in a specific ratio, and the present invention was completed based on this knowledge.
すなわち、本発明は、（Ａ）ポリオレフィン樹脂５０〜
９５重量％と（Ｂ）分散ゴム形態がオクルー’；ａン構
造を有するゴム変性スチレン系樹脂５０〜５重量％との
樹脂混合物１００重量部に対して、（Ｃ）相溶化剤５〜
４０重量部を配合して成る熱可塑性樹脂組成物を提供す
るものである。That is, the present invention provides (A) polyolefin resin 50 to
(B) 50 to 5 weight % of a rubber-modified styrenic resin having an occluded rubber structure and (C) 5 to 5 weight % of a compatibilizer (C)
40 parts by weight of the thermoplastic resin composition is provided.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明組成物において、（Ａ）成分として用いられるポ
リオレフィン樹脂としては、例えばエチレン、プロピレ
ン、ブテン−１，３−メチルブテン−１，３−メチルペ
ンテン−１，４−メチルペンテン−１などのσ−オレフ
ィンの単独重合体やこれらの共重合体、あるいはこれら
と他の共重合可能な不飽和単量体との共重合体などが挙
げられる。代表例としては、高密度、中密度、低密度ポ
リエチレンや、直鎖状低密度ポリエチレン、超高分子量
ポリエチレン、エチレン−酢酸ビニル共重合体、エチレ
ン−アクリル酸エチル共重合体などのポリエチレン類、
プロピレン単独重合体、プロピレン−エチレンブロック
共重合体やランダム共重合体、プロピレン−エチレン−
ジエン化合物共重合体などのポリプロピレン類、ポリブ
テン−１、ポリ４−メチルペンテン−１などを挙げるこ
とができるが、これらの中で結晶性のポリエチレン及び
結晶性のポリプロピレンが好ましく、特に結晶性のポリ
プロピレンが好適である。In the composition of the present invention, examples of the polyolefin resin used as component (A) include ethylene, propylene, and σ- such as butene-1,3-methylbutene-1,3-methylpentene-1,4-methylpentene-1 Examples include olefin homopolymers, copolymers thereof, and copolymers of these and other copolymerizable unsaturated monomers. Typical examples include high-density, medium-density, and low-density polyethylene, linear low-density polyethylene, ultra-high molecular weight polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and other polyethylenes.
Propylene homopolymer, propylene-ethylene block copolymer and random copolymer, propylene-ethylene-
Examples include polypropylenes such as diene compound copolymers, polybutene-1, poly-4-methylpentene-1, etc., but among these, crystalline polyethylene and crystalline polypropylene are preferable, particularly crystalline polypropylene. is suitable.
結晶性のポリプロピレンとしては、例えば結晶性を有す
るアイソタクチックプロピレン単独重合体や、エチレン
単位の含有量が少ないエチレンプロピレンランダム共重
合体から成る共重合部又はプロピレン単独重合体から成
るホモ重合部とエチレン単位の含有量が比較的多いエチ
レンプロピレンランダム共重合体から成る共重合部とか
ら構成された、いわゆるプロピレンブロック共重合体と
して市販されている実質上結晶性のプロピレンとエチレ
ンとのブロック共重合体、あるいはこのブロック共重合
体における各ホモ重合部又は共重合部が、さらに、ブテ
ン−１などのσ−オレフィンを共重合したものから成る
実質上結晶性のプロピレン−エチレン−ａ−オレフィン
共重合体などが好ましく挙げられる。Crystalline polypropylene includes, for example, an isotactic propylene homopolymer having crystallinity, a copolymer part made of an ethylene propylene random copolymer with a low content of ethylene units, or a homopolymer part made of a propylene homopolymer. A block copolymer of substantially crystalline propylene and ethylene, which is commercially available as a so-called propylene block copolymer, and is composed of a copolymer part consisting of an ethylene-propylene random copolymer with a relatively high content of ethylene units. A substantially crystalline propylene-ethylene-a-olefin copolymer in which each homopolymerization part or copolymerization part in this block copolymer is further copolymerized with a σ-olefin such as butene-1. Preferred examples include combination.
該（Ａ）成分として用いられるポリオレフィン樹脂はメ
ルトインデックス（Ｍ Ｉ ）力；５〜６０９ ／１０
分の範囲にあるものが好ましい。The polyolefin resin used as the component (A) has a melt index (M I ) power of 5 to 609/10.
Preferably in the range of minutes.
このＭＩが５９／１０分未満では成形性が悪いし、６０
９／１０分を超えると耐衝撃性が低下する傾向がみられ
る。また、このポリオレフィン樹脂は１種用いてもよい
し、２種以上を組み合わせて用いてもよい。If this MI is less than 59/10 minutes, moldability is poor;
If the time exceeds 9/10 minutes, there is a tendency for impact resistance to decrease. Moreover, one type of this polyolefin resin may be used, or two or more types may be used in combination.
本発明組成物においては、（Ｂ）成分として、分散ゴム
形態がオクルージョン構造を有するゴム変性スチレン系
樹脂が用いられる。ここでオクルージョン構造とは、一
つのゴム粒子中に、コアがスチレン系重合体で、シェル
がゴム状重合体から成る内包オクルージョンが５個以下
含まれており、かつそのうちの少なくとも５０％が内包
オクルージョンが１個で′ある構造のことをいう。In the composition of the present invention, a rubber-modified styrenic resin whose dispersed rubber form has an occlusion structure is used as the component (B). Here, the occlusion structure means that one rubber particle contains 5 or less encapsulated occlusions in which the core is made of a styrene polymer and the shell is made of a rubber-like polymer, and at least 50% of them are encapsulated occlusions. It refers to a structure where there is one '.
該（Ｂ）成分のゴム変性スチレン系樹脂は、分散ゴム形
態が、前記のようなオクルージョン構造を７０％以上有
することが必要で、サラミ構造などの粒子が３０％以上
混在すると、本発明の目的が十分に達せられない。した
がって、本発明においては、内包オクルージョンを６ａ
以上含有する、通常サラミ構造を有する耐衝撃性ポリス
チレン（ＨＩＰＳ）を、ゴム粒子数で３０％未満の割合
であれば配合することもできる。The rubber-modified styrenic resin as the component (B) must have a dispersed rubber form of 70% or more of the above-mentioned occlusion structure, and if 30% or more of particles such as salami structures are mixed, the objective of the present invention will be impaired. cannot be fully achieved. Therefore, in the present invention, the inclusion occlusion is defined as 6a
The above-contained high impact polystyrene (HIPS), which usually has a salami structure, can be blended in a ratio of less than 30% in terms of the number of rubber particles.
前記ゴム変性スチレン系樹脂の中で対称面をもつオクル
ージョン構造を膏し、かつ面積平均粒子径がＯ，ｌ＝０
．７．ｕｍ、好ましくは０．２−０−６μｍで、数平均
粒子径に対する面積平均粒子径の比が１．０〜２，５、
好ましくは１．０〜１．８の範囲にあるゴム重合体粒子
をスチレン系樹脂中に分散させたものが好適である。さ
らに、ゴム変性スチレン系樹脂としては、ゴム状重合体
粒子の体積分率（Ｉｍ）、ゴム状重合体粒子の面積平均
粒子径（直径） （ＤＳ）及びゴム状重合体相の厚さ
（λ）を因子とする関係式
％式％）
）
（ただしλは０．１０μｍ以下である）で求められるＫ
が０．１８以上、好ましくは０．２０以上、より好まし
くは０．２２以上であるものが好適である。The rubber-modified styrenic resin has an occlusion structure with a symmetrical plane, and has an area average particle diameter of O, l=0.
．． 7. um, preferably 0.2-0-6 μm, the ratio of area average particle size to number average particle size is 1.0 to 2.5,
Preferably, rubber polymer particles having a particle size in the range of 1.0 to 1.8 are dispersed in a styrene resin. Furthermore, as for the rubber-modified styrenic resin, the volume fraction (Im) of the rubbery polymer particles, the area average particle diameter (diameter) (DS) of the rubbery polymer particles, and the thickness (λ ) as a factor %) ) (However, λ is 0.10 μm or less)
is preferably 0.18 or more, preferably 0.20 or more, more preferably 0.22 or more.
前記ゴム状重合体の粒子の体積分率（１，）は、式 ％式％） （１１） によって求めることができる。The volume fraction (1,) of the particles of the rubbery polymer is expressed by the formula %formula%) (11) It can be found by
ここでＰ６はゴム状重合体の比重であり、０．９０を用
いる。またρ２．はスチレン系重合体の比重であり、１
．０５を用いる。ざらにＷｌはゴム変性スチレン系樹脂
に含まれるゴム状重合体の重量分率で、式
％式％］
とができる。すなわち、配向の小さいゴム変性スチレン
系樹脂のペレットを３重量％の四酸化オスミウム水溶液
にて剋理したものを超ミクロトームにより薄片化したの
ち、このものの透過型電子顕微鏡像を得、画像上のゴム
状重合体粒子の長径方向の直径（Ｄ）を１０００個の粒
子について測定し、その面積平均値を次式に従って求め
ることにより、ゴム状１合体粒子の面積平均粒子径（直
径）（Ｄ、）及び（Ｄ、）が得られる。Here, P6 is the specific gravity of the rubbery polymer, and 0.90 is used. Also ρ2. is the specific gravity of the styrene polymer, and 1
．． 05 is used. Roughly, Wl is the weight fraction of the rubbery polymer contained in the rubber-modified styrenic resin, and can be expressed as follows. Specifically, pellets of a rubber-modified styrenic resin with small orientation were sliced with a 3% by weight osmium tetroxide aqueous solution and sliced using an ultramicrotome, and a transmission electron microscope image of the pellet was obtained. By measuring the diameter (D) of 1000 particles in the major axis direction of the rubber-like polymer particles and calculating the area average value according to the following formula, the area average particle diameter (diameter) (D, and (D,) are obtained.
で求めることができる。It can be found by
ゴム状重合体粒子の面積平均粒子径（直径）（Ｄ、）及
び（Ｄ、）は、次のようにして求めるこ）
（ｎは直径りのゴム状重合体粒子の個数）また、ゴム状
重合体相の厚さ（λ）は、前記と同様にして透過型電子
ｌｌｌ微鏡像を得、ゴム状重合体粒子のうち、ゴム状重
合体相が周辺のみに存在するもの、すなわち、中心付近
で切削されたゴム状重合体粒子のゴム状重合体相の厚さ
λｉを１００個の粒子について測定し、その数平均値を
次式に従って求めることにより、得られる。The area average particle size (diameter) (D, ) and (D, ) of the rubbery polymer particles can be determined as follows: (n is the number of rubbery polymer particles with diameter) The thickness (λ) of the polymer phase was determined by obtaining a transmission electron microscopic image in the same manner as described above. It can be obtained by measuring the thickness λi of the rubbery polymer phase of the rubbery polymer particles cut with respect to 100 particles and finding the number average value according to the following formula.
λ−（λ１＋λ２＋λ、＋・・・・・・＋λ、。。）／
１００また、同様にして透過型電子顕微鏡像を得、無作
為に抽出した１ｏｏｏ個の粒子に対するオクルージョン
構造粒子の数の比率を求め、オクルージコン構造粒子の
比率を評価した。λ-(λ1+λ2+λ, +...+λ,...)/
100 In addition, a transmission electron microscope image was similarly obtained, and the ratio of the number of occlusion structure particles to 100 randomly extracted particles was determined to evaluate the ratio of occlusion structure particles.
該ゴム変性スチレン系樹脂においては、ゴム重合体粒子
は特定のミクロ構造を有することが好ましい。すなわち
、ゲル量がゴム状重合体に対して１．１〜４．０重量比
、好ましくは１．４〜３．６重量比の範囲にあることが
望ましく、またその膨潤指数が５〜２０′、好ましくは
７〜１８の範囲にあることが望ましい。In the rubber-modified styrenic resin, the rubber polymer particles preferably have a specific microstructure. That is, it is desirable that the amount of gel is in the range of 1.1 to 4.0 weight ratio, preferably 1.4 to 3.6 weight ratio to the rubbery polymer, and the swelling index is 5 to 20'. , preferably in the range of 7 to 18.
該（Ｂ）ｆｆ分として、前記した条件を満たすゴム変性
スチレン系樹脂を用いることにより、本発明の目的がよ
り効果的に達せられる。The object of the present invention can be more effectively achieved by using a rubber-modified styrene resin that satisfies the above conditions as the (B) ff component.
該ゴム変性スチレン系樹脂においては、スチレン系重合
体とゴム状重合体は、それぞれ７０〜９２重量％及び３
０〜８重量％、好ましくは７２〜９０重量％及び２８〜
１０重量％の割合で含有することが望ましい。ゴム状重
合体の含有量が８重量％未満では耐衝撃性の改良効果が
十分に発揮されないし、３０重量％を超えると流動性が
低下する傾向が生じる。In the rubber-modified styrenic resin, the styrenic polymer and the rubbery polymer are 70 to 92% by weight and 3% by weight, respectively.
0-8% by weight, preferably 72-90% and 28-8% by weight
The content is preferably 10% by weight. If the content of the rubbery polymer is less than 8% by weight, the effect of improving impact resistance will not be sufficiently exhibited, and if it exceeds 30% by weight, fluidity will tend to decrease.
また、該ゴム変性スチレン系樹脂においては、ゴム状重
合体相の厚さ（λ）が０．１０μｍ以下であることが好
ましい。ゴム状重合体相の厚さ（λ）が０．１０μｍ以
上にするためには、使用されるゴム状重合体の分子量を
高くする必要がある（例えば、スチレン−ブタンジエン
系ブロック共重合体ゴムを用いる場合、ブタンジエン重
合体ブロック部の分子量をおよそ８００，０００以上に
する必要がある）。Further, in the rubber-modified styrenic resin, the thickness (λ) of the rubbery polymer phase is preferably 0.10 μm or less. In order to make the thickness (λ) of the rubbery polymer phase 0.10 μm or more, it is necessary to increase the molecular weight of the rubbery polymer used (for example, styrene-butanediene block copolymer rubber (If used, the molecular weight of the butane diene polymer block portion must be approximately 800,000 or higher).
このような高分子量のゴム状重合体を用いて、ゴム変性
スチレン系樹脂を製造すると、重合反応溶液の粘度が著
しく高（なり好ましくない。ゴム状重合体相の厚さ（λ
）はｏ−ｏｏｓ〜０．０７μｍにすることが好ましい。When a rubber-modified styrenic resin is produced using such a high molecular weight rubbery polymer, the viscosity of the polymerization reaction solution becomes extremely high (which is undesirable).The thickness of the rubbery polymer phase (λ
) is preferably o-oos to 0.07 μm.
このＣＢ）成分のゴム変性スチレン系樹脂は、ゴム状重
合体の存在下に、スチレン又はスチレンと共重合可能な
単量体とを重合させることによって調製することができ
る。スチレンと共重合可能な単量体としては、例えばα
−メチルスチレン、ビニルトルエン、ビニルエチルベン
ゼン、ビニルキシレン、ｐ−、ｔ−ブチルスチレン、α
−メチル−ｐ−メチルスチレン、ビニルナフタレンなど
の芳香族モノビニル化合物、アクリロニトリル、メタク
リル酸メチル、アクリル酸メチル、メタクリル酸、アク
リル酸、無水マレイン酸、フェニルマレイミドなどを挙
げることができる。これらの単量体は１種用いてもよい
し、２種以上を組み合わせて用いてもよいが、スチレン
を含む全単量体に対して、通常５０重量％以下、好まし
くは４０重量％以下の割合で用いられる。The rubber-modified styrenic resin of component CB) can be prepared by polymerizing styrene or a monomer copolymerizable with styrene in the presence of a rubbery polymer. Examples of monomers copolymerizable with styrene include α
-Methylstyrene, vinyltoluene, vinylethylbenzene, vinylxylene, p-, t-butylstyrene, α
Examples include aromatic monovinyl compounds such as -methyl-p-methylstyrene and vinylnaphthalene, acrylonitrile, methyl methacrylate, methyl acrylate, methacrylic acid, acrylic acid, maleic anhydride, and phenylmaleimide. These monomers may be used alone or in combination of two or more types, but they usually account for 50% by weight or less, preferably 40% by weight or less, based on the total monomers containing styrene. Used in percentages.
一方、ゴム状重合体の種類については特に制限はなく、
従来ゴム変性スチレン系樹脂に慣用されているもの、例
えば天然ゴムや、ポリブタジェンゴム、ポリインブレン
ゴム、スチレン−ブタジェン系共重合体ゴム、スチレン
−イソグレン系共重合体ゴム、ブチルゴム、エチレンー
プロヒレン系共重合体ゴムなどの合成ゴム、あるいはこ
れらのゴムとスチレンとのグラフト共重合体ゴムなどを
用いることができるが、これらの中でスチレン−ブタジ
ェン系ブロック共重合体ゴムカ好適である。このスチレ
ン−ブタジェン系ブロック共重合体ゴムとしては、分子
量がｓｏ、ｏｏｏ〜ｓｏｏ、ｏｏｏの範囲にあり、かつ
スチレン類で形成される重合体ブロックの含有量が１０
〜６０重量％の範囲にあるものが特に好ましい。該分子
量がｓｏ、ｏｏｏ未溝のものでは耐衝撃性が十分ではな
いし、ｓｏｏ、ｏｏｏを超えると成形時の流動性が低下
するようになり、好ましくない。まｔ；、このスチレン
−ブタジェン系ブロック共重合体ゴムに、分子量がｓ
ｏ 、ｏ ｏ ｏ〜ｓｏｏ、ｏｏ。On the other hand, there are no particular restrictions on the type of rubber-like polymer;
Conventionally used rubber-modified styrene resins, such as natural rubber, polybutadiene rubber, polyimbrene rubber, styrene-butadiene copolymer rubber, styrene-isogrene copolymer rubber, butyl rubber, and ethylene-propylene rubber. Synthetic rubbers such as hyrene copolymer rubbers or graft copolymer rubbers of these rubbers and styrene can be used, but among these, styrene-butadiene block copolymer rubbers are preferred. This styrene-butadiene block copolymer rubber has a molecular weight in the range of so, ooo to soo, ooo, and has a content of polymer blocks formed from styrenes of 10
Particularly preferred are those in the range of 60% by weight. If the molecular weight is so or ooo without grooves, the impact resistance will not be sufficient, and if it exceeds soo or ooo, the fluidity during molding will decrease, which is not preferable. Also, this styrene-butadiene block copolymer rubber has a molecular weight of s.
o, o o o ~ soo, oo.
程度のポリブタジェンゴムを適宜配合して用いてもよい
。A certain amount of polybutadiene rubber may be appropriately blended and used.
重合方法については特に１１Ｊ＠はなく、従来慣用され
ている方法、例えば乳化重合法、塊状重合法、溶液重合
法、懸濁重合法、あるいは塊状−懸濁二段重合法のよう
な多段重合法などを用いることができる。Regarding the polymerization method, there is no particular 11J@, and conventionally used methods such as emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or multi-stage polymerization methods such as bulk-suspension two-stage polymerization method are used. etc. can be used.
次に、塊状−懸濁二段重合法によるゴム変性スチレン系
樹脂の好適な製造方法の１例について説明すると、まず
スチレン又はスチレンと共重合可能な巣量体との混合物
に、ゴム状重合体を添加し、必要に応じ加熱して溶解さ
せる。この溶解はできるだけ均一に行うことが好ましい
。Next, to explain one example of a suitable method for producing a rubber-modified styrenic resin by a bulk-suspension two-stage polymerization method, first, a rubber-like polymer is added to a mixture of styrene or a styrene copolymerizable polymer. Add and heat as necessary to dissolve. It is preferable to perform this dissolution as uniformly as possible.
次に、この溶液に、アルキルメルカプタンなどの分子量
調節剤（連鎖移動剤）及び必要に応じて用いられる有機
過酸化物などの重合開始剤を加え、７０〜１５０℃程度
の温度に加熱しながら、撹拌下に重合度が１０〜６０％
になるまで塊状重合法による予備重合を行う。この予備
重合工程において該ゴム状重合体は撹拌により粒子状に
分散される。Next, a molecular weight regulator (chain transfer agent) such as an alkyl mercaptan and a polymerization initiator such as an organic peroxide used as necessary are added to this solution, and while heating to a temperature of about 70 to 150 °C, Degree of polymerization is 10-60% under stirring
Prepolymerization is carried out by bulk polymerization until . In this prepolymerization step, the rubbery polymer is dispersed into particles by stirring.
次いで、前記予備重合液を第三リン酸カルシウムやポリ
ビニルアルコールなどを懸濁剤として、水相に懸濁し、
通常、重合度が１００％近くなるまで懸濁重合（主重合
）を行う。なお、必要に応じ、この主重合工程の後、さ
らに加熱を続けてもよい。Next, the prepolymerization solution is suspended in an aqueous phase using tricalcium phosphate, polyvinyl alcohol, or the like as a suspending agent,
Usually, suspension polymerization (main polymerization) is carried out until the degree of polymerization approaches 100%. Note that, if necessary, heating may be continued after this main polymerization step.
前記分子量調節剤としては、例えばσ−メチルスチレン
ダイマー、ｎ−ドデシルメルカプタン、ｔ−Ｆデシルメ
ルカプタン、ｌ−フェニルブテン−２−フルオレン、ジ
ペンテン、クロロホルムなどのメルカプタン類、テルペ
ン類、／Ｓロゲン化合物などを挙げることができる。Examples of the molecular weight regulator include mercaptans such as σ-methylstyrene dimer, n-dodecylmercaptan, t-Fdecylmercaptan, l-phenylbutene-2-fluorene, dipentene, and chloroform, terpenes, and /S rogen compounds. can be mentioned.
まｔ；、所望に応じて用いられる重合開始剤としては、
例えば１．１−ビス（ヒープチルペルオキシ）シクロヘ
キサン、１．１−ｔ”ス（１−ブチルぺＪレオキシ）−
３，３，５−トリメチルシクロヘキサンなどのペルオキ
シケタール類、ジクミルペルオキシド、ジ−ｔ−ブチル
ペルオキシド、２．５−ジメチル−２，５−ジ（ｔ−ブ
チルペルオキシ）ヘキサンなどのジアルキルペルオキシ
ド類、ベンゾイルペルオキシド、ｍ−トルオイルペルオ
キシドなどのジアリールペルオキシド類、ジミリスチル
ペルオキシジカーポネートなどのペルオキシジカーボネ
ート類、ｔ−プチルペルオキシイソグロビルカーポネー
トなどのペルオキシエステル類、シクロヘキサノンペル
オキシドなどのケトンペルオキシド類、ｐ−メンタンヒ
ドロペルオキンドなどのヒドロペルオキシド類などの有
機過酸化物などを挙げることができる。As the polymerization initiator used as desired,
For example, 1.1-bis(heeptylperoxy)cyclohexane, 1.1-t"su(1-butylperoxy)-
Peroxyketals such as 3,3,5-trimethylcyclohexane, dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, benzoyl Peroxide, diaryl peroxides such as m-toluoyl peroxide, peroxydicarbonates such as dimyristyl peroxydicarbonate, peroxyesters such as t-butylperoxyisoglobil carbonate, ketone peroxides such as cyclohexanone peroxide, p -Organic peroxides such as hydroperoxides such as menthane hydroperoquinde, and the like.
なお、ゴム状重合体相の厚さλは、ゴム状重合体として
、例えばスチレン−ブタジェン系ブロック共重合体ゴム
を用いる場合、ブタジェン重合体ブロック部の分子量を
変化させることにより制御することができる。すなわち
、ブタジェン重合体ブロック部の分子量を小さくすれば
λは減少し、大きくするとλは増大する。一方、ゴム状
重合体粒子の半径Ｒは重合中の撹拌速度、ゴム状重合体
としてスチレン−ブタジェン系ブロック共重合体ゴムを
用いる場合はスチレン重合体ブロック部の分子量、さら
に連鎖移動剤の使用の有無、スチレン−ブタジェン系ブ
ロック共重合体ゴムに配合されるポリブタジェンゴムの
有無などによって制御することができる。すなわち、重
合中の撹拌速度が早いとＲは減少し、遅いと増大する。The thickness λ of the rubbery polymer phase can be controlled by changing the molecular weight of the butadiene polymer block when, for example, a styrene-butadiene block copolymer rubber is used as the rubbery polymer. . That is, if the molecular weight of the butadiene polymer block portion is decreased, λ will be decreased, and if it is increased, λ will be increased. On the other hand, the radius R of the rubbery polymer particles depends on the stirring speed during polymerization, the molecular weight of the styrene polymer block when a styrene-butadiene block copolymer rubber is used as the rubbery polymer, and the use of a chain transfer agent. It can be controlled by the presence or absence of polybutadiene rubber blended with the styrene-butadiene block copolymer rubber. That is, when the stirring speed during polymerization is fast, R decreases, and when it is slow, R increases.
スチレン重合体ブロック部の分子量を大さくするとＲは
減少し、小さくするとＲは増大する。まｔ：、連鎖移動
剤を使用しない場合Ｒは小さし１が、使用すると増大す
るし、ポリブタジェンゴムを用いるとＲは増大するが、
使用しない場合Ｒは小さい。When the molecular weight of the styrene polymer block portion is increased, R decreases, and when it is decreased, R increases. When a chain transfer agent is not used, R is small (1), but when it is used, it increases, and when polybutadiene rubber is used, R increases, but
If not used, R is small.
次に、このようにして得られたスラリーを、通常の手段
により地理して、ビーズ状反応物を取り出し、乾燥した
のち、常法に従いベレット化することにより、所望のゴ
ム変性スチレン系樹脂が得られる。このようにして得ら
れたゴム変性スチレン系樹脂のマトリックス部の分子量
は１００，０００〜３００，０００．好ましくは１３０
．０００〜２８０．０００の範囲にあるのが有利である
。この分子量が１００，０００未満では耐衝撃性に劣る
し、３００ 、ＯＯＯを超えると成形時における流動性
が不十分となる。Next, the slurry thus obtained is divided by conventional means to remove the bead-shaped reactants, dried, and pelletized according to a conventional method to obtain the desired rubber-modified styrenic resin. It will be done. The molecular weight of the matrix portion of the rubber-modified styrenic resin thus obtained is 100,000 to 300,000. Preferably 130
．． Advantageously, it lies in the range from 000 to 280.000. If the molecular weight is less than 100,000, the impact resistance will be poor, and if it exceeds 300,000, the fluidity during molding will be insufficient.
本発明組成物においては、前記（Ａ）成分のポリオレフ
ィン樹脂と（Ｂ）成分のゴム変性スチレン系樹脂との配
合割合については、（Ａ）成分と（Ｂ）成分との合計重
量に基づき、（Ａ）成分が５０〜９５重量％、好ましく
は６０〜８５重量％、（Ｂ）成分が５０〜５重量％、好
ましくは４０〜１５重量％になるような割合で配合する
ことが必要である。（Ａ）成分の配合量が５０重量％未
満では成形性に劣るおそれがあるし、９５重量％を超え
ると剛性が低下する傾向がみられる。In the composition of the present invention, the blending ratio of the polyolefin resin as the component (A) and the rubber-modified styrene resin as the component (B) is determined based on the total weight of the components (A) and (B). It is necessary to blend component A) in a proportion of 50 to 95% by weight, preferably 60 to 85% by weight, and component (B) in a proportion of 50 to 5% by weight, preferably 40 to 15% by weight. If the amount of component (A) is less than 50% by weight, moldability may be poor, and if it exceeds 95% by weight, there is a tendency for stiffness to decrease.
本発明組成物においては、（Ｃ）成分として相溶化剤が
用いられる。この相比溶剤については、ポリオレフィン
樹脂とゴム変性スチレン系樹脂とを相溶化させる性質を
有するものであればよく、特に制限はない。該相溶化剤
としては、例えばスチレン−ブタジェン共重合体やスチ
レン−イソプレン共重合体などのスチレン系熱可塑性エ
ラストマー、アクリル系熱可塑性エラストマー、エチレ
ン−エチルアクリレート−無水マレイン酸共重合体など
が挙げられる。このような相溶化剤を用いることにより
、ポリオレフィン樹脂中にゴム変性スチレン系樹脂が極
めて均質に分数し、優れた物性を有する組成物が得られ
る。In the composition of the present invention, a compatibilizer is used as component (C). This compatible solvent is not particularly limited as long as it has the property of making the polyolefin resin and rubber-modified styrene resin compatible. Examples of the compatibilizing agent include styrene thermoplastic elastomers such as styrene-butadiene copolymers and styrene-isoprene copolymers, acrylic thermoplastic elastomers, and ethylene-ethyl acrylate-maleic anhydride copolymers. . By using such a compatibilizing agent, the rubber-modified styrenic resin is fractionated extremely homogeneously in the polyolefin resin, and a composition having excellent physical properties can be obtained.
本発明組成物においては、これらの相溶化剤は１種用い
てもよいし、２種以上を組み合わせて用いてもよく、そ
の配合量は、該（Ａ）成分のポリオレフィン樹脂と（Ｂ
）成分のゴム変性スチレン系樹脂との合計量１００重量
部に対し、５〜４０重量部、好ましくは１０〜３５重量
部の範囲で選ばれる。この量が５重量部未満では耐衝撃
性に劣るし、４０重量部を超えると剛性が低下する傾向
がみられる。In the composition of the present invention, one type of these compatibilizers may be used, or two or more types may be used in combination, and the blending amount is determined based on the polyolefin resin of the component (A) and
The amount is selected in the range of 5 to 40 parts by weight, preferably 10 to 35 parts by weight, based on 100 parts by weight of the total amount of the component () and the rubber-modified styrene resin. If this amount is less than 5 parts by weight, impact resistance will be poor, and if this amount exceeds 40 parts by weight, there will be a tendency for stiffness to decrease.
本発明組成物には、本発明の貝、的を損なわない範囲で
必要に応じ公知の各種添加成分、例えば炭酸カルシウム
、タルク、マイカ、シリカ、アスベストなどの無機光て
ん剤、ガラス繊維、炭素繊維、金属ウィスカーなどの補
強剤、酸化防止剤、紫外線吸収剤、熱安定剤、滑剤、難
熱剤、帯電防止剤などの添加剤を含有させてもよいし、
また他の熱可塑性樹脂、例えばポリ塩化ビニル系樹脂、
ポリアミド系樹脂、ポリイミド系樹脂、ポリエステル系
樹脂、ポリカーボネート系樹脂、ポリアセタール系−脂
、ポリ芳香族エーテルケトン系樹脂、ポリフェニレンエ
ーテル系樹ｍ、ポリフェニレンスルフィド系樹脂、ポリ
芳香族エステル系樹脂、ポリスルホン系樹脂、他のスチ
レン系樹脂、アクリレート系樹脂などを配合してもよい
。The composition of the present invention includes the shellfish of the present invention, various known additive components as necessary within a range that does not impair the target, such as inorganic photoresist agents such as calcium carbonate, talc, mica, silica, and asbestos, glass fibers, and carbon fibers. , reinforcing agents such as metal whiskers, antioxidants, ultraviolet absorbers, heat stabilizers, lubricants, heat retardants, antistatic agents, and other additives may be included.
In addition, other thermoplastic resins, such as polyvinyl chloride resins,
Polyamide resin, polyimide resin, polyester resin, polycarbonate resin, polyacetal resin, polyaromatic ether ketone resin, polyphenylene ether resin, polyphenylene sulfide resin, polyaromatic ester resin, polysulfone resin , other styrene resins, acrylate resins, etc. may be blended.
本発明組成物は、例えば前記（Ａ）成分、（Ｂ）成分、
（Ｃ）成分及び必要に応じて用いられる各種添加成分を
、それぞれ所定の割合で配合し、バンバリーミキサ−１
単軸スクリユ一押出機、二軸スクリュー押出機、コニー
ダ、多軸スクリュー押出機などにより、１８０〜２４０
℃の範囲の温度で十分に混練することにより、調製する
ことができる。The composition of the present invention includes, for example, the above-mentioned component (A), component (B),
Component (C) and various additive components used as necessary are blended in predetermined proportions, and Banbury mixer-1
180 to 240
It can be prepared by thorough kneading at a temperature in the range of °C.
このようにして得られた本発明組成物は、例えば射出成
形法や押出成形法など、通常用いられている方法に゛従
って、所望形状の成形品に成形することができる。The composition of the present invention thus obtained can be molded into a molded article of a desired shape by a commonly used method such as injection molding or extrusion molding.
［実施例Ｊ
次に、実施例により本発明をさらに詳細に説明するが、
本発明はこれらの例によってなんら限定されるものでは
ない。[Example J] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.
なお、ゴム変性ポリスチレン及び樹脂組成物の物性は次
のようにして求めた。The physical properties of the rubber-modified polystyrene and resin composition were determined as follows.
（１）ゲル量、膨潤指数
サンプルＷＣ（９）をトルエンに溶解し、１５０００ｒ
ｐｍで６０分間遠心分離後、上澄液をデカンテインヨン
し、膨潤した不溶成分量ＷＳ（９）を求め、次にこの膨
潤した不溶成分を６０℃で２４時間真空乾燥して、乾燥
不溶成分量Ｗｇ（ｇ）を求める。(1) Gel amount and swelling index Dissolve sample WC (9) in toluene and
After centrifugation at pm for 60 minutes, the supernatant was decanted to determine the amount of swollen insoluble components WS (9), and then the swollen insoluble components were vacuum dried at 60°C for 24 hours to obtain the dry insoluble components. Find the amount Wg (g).
ゲル量（ｗｔ％）＝ （Ｗｇ／Ｗｃ） Ｘ Ｉ ＯＯ膨
潤指数−Ｗ ｓ ／ Ｗ ｇ
（２）光沢度
ＪＩＳＫ−７１０５に準拠して求めた。Gel amount (wt%) = (Wg/Wc)
（３）アイゾツト衝撃強度
ＪＩＳＫ−７１１０に準拠して求めた。ゴム変性ポリス
チレンの場合は２３℃、ノツチ付の条件で、組成物の場
合は一３０℃、ノツチ付の条件で求めた。(3) Izot impact strength was determined in accordance with JISK-7110. In the case of rubber-modified polystyrene, it was determined at 23°C with a notch, and in the case of the composition, it was determined at -30°C with a notch.
（４）熱変形温度 ＪＩＳＫ−７１０，２に準拠して求めた。(4) Heat distortion temperature It was determined in accordance with JISK-710.2.
（５）曲げ弾性率 ＡＳＴＭ Ｄ−７９０に準拠して求めた。(5) Flexural modulus It was determined in accordance with ASTM D-790.
（６）メルトインデックス［ＭＩ］ ｌ５ＯＲ−１１３３に準拠して求めた。(6) Melt index [MI] It was determined in accordance with 15OR-1133.
（７）落錘衝撃強度
（イ）ゴム変性ポリスチレンの場合
２７０ｘ７０Ｘ３ｍｍの射出成形板のゲート位Ｉｔ（成
形板の末端）より１２５ｍｍ地点で板幅（７０ｍｍ）の
中央部にて、荷重３．７６ｋｇ、速度３−５ ｍ／秒、
試料固定部の穴径２インチ、温度２３°Ｃの条件で、レ
オメトリックス社製自動落錘衝撃試験機ＲＤＴ５０００
を用いて測定し、力と変位の曲線で最初に力が急激な減
少を示す時点までのエネルギーを求め、落錘衝撃強度と
した。(7) Falling weight impact strength (a) In the case of rubber-modified polystyrene: A load of 3.76 kg at the center of the plate width (70 mm) at a point 125 mm from the gate position It (end of the molded plate) of a 270 x 70 x 3 mm injection molded plate, Speed 3-5 m/s,
Under the conditions of a hole diameter of 2 inches in the sample fixing part and a temperature of 23°C, an automatic falling weight impact tester RDT5000 manufactured by Rheometrics was used.
The energy up to the point where the force first shows a sudden decrease in the force-displacement curve was determined and used as the falling weight impact strength.
（ロ）組成物の場合
前記方法において、速度をｌ１ｍ／秒、温度を一３０’
Ｃとした以外は、同様にして落錘衝撃強度を求めた。(b) In the case of a composition, in the above method, the speed is 11 m/sec and the temperature is 130'.
The falling weight impact strength was determined in the same manner except that C was used.
製造例１ 単一オフルーシコンゴム変性ポリスチレンの
製造
内容量５１Ｉのオートクレーブに重量平均分子量１０万
、スチレン単位の含有量２２．６重量％のＳＢブロック
共重合体〔日本ゼオン（株）製、商品名：ＺＬＳ−０１
）６５９ｇ、スチレン３０００９及び連鎖移動剤として
のｎ−ドデシルメルカプタン１ｇを入れ、３００ｒｐｍ
で撹拌しながら１３０℃、４時間反応を行った。Production Example 1 Production of a single ophthalmic rubber-modified polystyrene SB block copolymer with a weight average molecular weight of 100,000 and a styrene unit content of 22.6% by weight [manufactured by Nippon Zeon Co., Ltd., product] was placed in an autoclave with a content of 51 I. Name: ZLS-01
) 659 g, styrene 30009 and 1 g of n-dodecyl mercaptan as a chain transfer agent, and the mixture was heated at 300 rpm.
The reaction was carried out at 130° C. for 4 hours while stirring.
次いで１０Ｍのオートクレーブに、前記反応混合物３０
００９．水３０００ｇ、懸濁安定剤としてのポリビニル
アルコール１０９、重合開始剤としてのベンゾイルペル
オキシド６ｇ及びジクミルペルオキシド３ｇを入れ、３
００ｒｐｍで撹拌しながら、８０℃から３０℃／ ｈ
ｒの昇温速度で１４０℃まで昇温し、その温度でさらに
４時間反応させて、ゴム変性ポリスチレンのビーズを得
た。Then 30% of the reaction mixture was placed in a 10M autoclave.
009. Add 3000 g of water, 109% polyvinyl alcohol as a suspension stabilizer, 6 g of benzoyl peroxide and 3 g of dicumyl peroxide as polymerization initiators,
80℃ to 30℃/h while stirring at 00rpm
The temperature was raised to 140° C. at a heating rate of r, and the reaction was continued at that temperature for an additional 4 hours to obtain rubber-modified polystyrene beads.
次に、得られたビーズを２２０℃の単軸押出機にてペレ
ット化したのち、成形を行った。Next, the obtained beads were pelletized using a single-screw extruder at 220° C., and then molded.
得られた成形品の物性の測定結果及びゴム変性ポリスチ
レンの特性を第１表に示す。Table 1 shows the measurement results of the physical properties of the obtained molded article and the properties of the rubber-modified polystyrene.
製造例２ 単一オクルージョンゴム変性ポリスチレンの
製造
内容１に５【のオートクレーブにＳＢブロック共重合体
〔日本ゼオン（株）製、商品名：ＺＬＳ−０１，スチレ
ン単位の含有量２２６重量％、分子量１０万）７０４９
、スチレン３０００ｇ及び連鎖移動剤としてのｎ−ドデ
シルメルカプタン１ｇを入れ、３００ｒｐｍで撹拌しな
から１３０°Ｃ１４時間反応を行い、予備重合物（１）
を得た。Production Example 2 Production details of single occlusion rubber modified polystyrene 1 to 5 [SB block copolymer [manufactured by Nippon Zeon Co., Ltd., trade name: ZLS-01, styrene unit content 226% by weight, molecular weight 10] million) 7049
, 3000 g of styrene and 1 g of n-dodecyl mercaptan as a chain transfer agent were added, and the reaction was carried out at 130°C for 14 hours while stirring at 300 rpm to obtain a prepolymerized product (1).
I got it.
また、同様にポリブタジェン〔旭化成（株）製、商品名
：ＮＦ３５ＡＳ）４０９９とｎ−ドデシルメルカプタン
１ｇを用いて予備重合物（Ｉ［）を得た（ゴム構造はそ
れぞれ下記のような懸濁重合条件でビーズを合成し電子
Ｈ微鏡にてそれぞれ０．４μｍのオクルージョンと１．
２μｍのサラミ構造を確認した）。次いで、１０ｔのオ
ートクレーブに得られた予備重合物（Ｉ）２５５０ｚ、
予備重合物（ＩＩ）４５０ｇ、水３０００９、懸濁安定
剤としてのポリビニルアルコールｌｏｇ、重合開始剤と
してのペンゾイルベルオキンド６ｇ及びジクミルペルオ
キシド３ｇを入れ５００ｒｐｍで撹拌しつつ、８０℃か
ら３０℃／時間の昇温速度で１４０’ｃまで昇温し、さ
らに４時間反応させてゴム変性ポリスチレンのビーズを
得た（電子顕＠鏡にてオクルージョンが０．４μｍ１サ
ラミが１．２μｍであることを確認し、た）。得られた
ビーズを２２０°Ｃの単軸押出機にてペレット化しｔ；
のち、成形を行った。Similarly, a prepolymer (I[) was obtained using polybutadiene (manufactured by Asahi Kasei Corporation, trade name: NF35AS) 4099 and 1 g of n-dodecyl mercaptan (the rubber structure was obtained under the following suspension polymerization conditions). Beads were synthesized using an electron H-microscope with an occlusion of 0.4 μm and an occlusion of 1.
A salami structure of 2 μm was confirmed). Next, the prepolymer (I) 2550z obtained in a 10 t autoclave,
Add 450 g of prepolymerized product (II), 30009 water, log of polyvinyl alcohol as a suspension stabilizer, 6 g of penzoylberoquinde as a polymerization initiator, and 3 g of dicumyl peroxide, and stir at 500 rpm while stirring from 80°C to 30°C/ The temperature was raised to 140'C at a heating rate of 1 hour, and the reaction was continued for another 4 hours to obtain beads of rubber-modified polystyrene. did). The obtained beads were pelletized using a single screw extruder at 220°C;
Afterwards, it was molded.
得られた成形品の物性の測定結果及びゴム変性ポリスチ
レンの特性を第１表に示す。Table 1 shows the measurement results of the physical properties of the obtained molded article and the properties of the rubber-modified polystyrene.
（以下余白）
第 １
表
＊製造例１．２ともに電子顕微鏡にて対称面を有するオ
クルージョン構造を確認した。(Margin below) Table 1 *Production Examples 1 and 2 were both confirmed to have an occlusion structure with a plane of symmetry using an electron microscope.
実施例１
製造例１で得たオクルージョン構造を有するゴム変性ポ
リスチレン１５重量部、プロ／クポリプロピレン（ＭＩ
ＩＯ）８５重量部及び相溶化剤としてのＳＢＳ （スチ
レン−ブタジェン−スチレン共重合体、ンエル化学社製
、カリフレックスＴＲ１１０２）１２重量部をトライブ
レンドしたのち、単軸混練機を用いて、温度２００℃、
回転数８Ｏｒｐｍの条件で混練してペレットを得た。Example 1 15 parts by weight of rubber-modified polystyrene having an occlusion structure obtained in Production Example 1, Pro/Cu polypropylene (MI
After tri-blending 85 parts by weight of IO) and 12 parts by weight of SBS (styrene-butadiene-styrene copolymer, manufactured by Neru Chemical Co., Ltd., CARIFLEX TR1102) as a compatibilizer, the mixture was mixed using a single-shaft kneader at a temperature of 200°C. °C,
Pellets were obtained by kneading at a rotation speed of 8 rpm.
次に、このペレットを用いて射出成形により試験片を作
製し、アイゾツト衝撃強度、落錘衝撃強度、曲げ弾性率
、熱変形温度を求めた。その結果を第２表に示す。Next, a test piece was prepared by injection molding using this pellet, and the Izot impact strength, falling weight impact strength, flexural modulus, and heat distortion temperature were determined. The results are shown in Table 2.
実施例２
実施例１において、ブロックポリプロピレン及び製造例
１で得たゴム変性ポリスチレンの配合量を、それぞれ７
０重量部及び３０重量部に変えた以外は、実施例１と同
様な操作を行った。その結果を第２表に示す。Example 2 In Example 1, the blending amounts of block polypropylene and rubber-modified polystyrene obtained in Production Example 1 were changed to 7.
The same operation as in Example 1 was performed except that the amounts were changed to 0 parts by weight and 30 parts by weight. The results are shown in Table 2.
実施例３
実施例１において、ＳＢＳの代りに５ＥＢＳ（ＳＢＳの
水添物、ンエル化学社製）を用いた以外は、実施例１と
同様な操作を行った。その結果を第２表に示す。Example 3 The same operation as in Example 1 was performed except that 5EBS (hydrogenated SBS, manufactured by Neru Kagaku Co., Ltd.) was used instead of SBS. The results are shown in Table 2.
実施例４
実施例１において、製造例１で得Ｉ；ゴム変性ポリスチ
レンの代りに、製造例２で得たゴム変性ポリスチレンを
用いた以外は、実施例１と同様の操作を行った。その結
果を第２表に示す。Example 4 In Example 1, the same operation as in Example 1 was performed except that the rubber-modified polystyrene obtained in Production Example 2 was used instead of the rubber-modified polystyrene obtained in Production Example 1. The results are shown in Table 2.
実施例５
実施例３において、製造例１で得たゴム変性ポリスチレ
ンの代りに、製造例２で得たゴム変性ポリスチレンを用
いた以外は、実施例３と同様な操作を行っｔ；。その結
果を第２表に示す。Example 5 In Example 3, the same operations as in Example 3 were performed, except that the rubber-modified polystyrene obtained in Production Example 2 was used instead of the rubber-modified polystyrene obtained in Production Example 1. The results are shown in Table 2.
比較例１
実施例１において、製造例１で得たゴム変性ポリスチレ
ンの代りに、ゴム変性ポリスチレン「出光スチロールＨ
Ｔ−５１Ｊ （出光石油化学社製、ＭＩ２．０）を用
いた以外は、実施例１と同様な操作を行った。その結果
を第２表に示す。Comparative Example 1 In Example 1, rubber modified polystyrene "Idemitsu Styrene H" was used instead of the rubber modified polystyrene obtained in Production Example 1.
The same operation as in Example 1 was performed except that T-51J (manufactured by Idemitsu Petrochemical Co., Ltd., MI2.0) was used. The results are shown in Table 2.
比較例２
実施例２において、製造例１で得たゴム変性ポリスチレ
ンの代りに、ゴム変性ポリスチレン「出光スチロールＨ
Ｔ−５１Ｊを用いた以外は、実施例２と同様な操作を行
った。その結果を第２表に示す。Comparative Example 2 In Example 2, rubber modified polystyrene "Idemitsu Styrene H" was used instead of the rubber modified polystyrene obtained in Production Example 1.
The same operation as in Example 2 was performed except that T-51J was used. The results are shown in Table 2.
（以下余白）
［発明の効果］
本発明の熱可塑性樹脂組成物は、ポリオレフィン樹脂に
、分散ゴム形態がオクルージョン構造を有するゴム変性
スチレン系樹脂と相溶化剤とを配合しＩ；ものであって
、耐熱性や剛性、耐衝撃性特に低温衝撃強度などの機械
的特性を十分に保持するとともに、固相接着性が良好で
、工業材料として、例えば自動車分野における外板など
に好適に用いられる。(The following is a blank space) [Effects of the Invention] The thermoplastic resin composition of the present invention is one in which a polyolefin resin is blended with a rubber-modified styrenic resin whose dispersed rubber form has an occlusion structure and a compatibilizer. It sufficiently maintains mechanical properties such as heat resistance, rigidity, impact resistance, especially low-temperature impact strength, and has good solid phase adhesion, so it is suitably used as an industrial material, for example, for outer panels in the automobile field.
Claims (1)
分散ゴム形態がオクルージョン構造を有するゴム変性ス
チレン系樹脂５０〜５重量％との樹脂混合物１００重量
部に対して、（Ｃ）相溶化剤５〜４０重量部を配合して
成る熱可塑性樹脂組成物。 ２ ゴム変性スチレン系樹脂が、ゴム状重合体を、対称
面をもつオクルージョン構造を有し、かつ面積平均粒子
径が０．１〜０．７μｍで、数平均粒子径に対する面積
平均粒子径の比が１．０〜２．５の粒子としてスチレン
系重合体中に分散させたものである請求項１記載の熱可
塑性樹脂組成物。 ３ ゴム状重合体の分散粒子が、 関係式 Ｋ＝φ＿Ｒ｛１−［〔（Ｄ＿Ｓ／２）−λ〕／（Ｄ＿Ｓ
／２）］＾３｝＾−＾１（式中のφ＿Ｒはゴム変性スチ
レン系樹脂中のゴム状重合体の体積分率を示し、Ｄ＿Ｓ
はゴム状重合体の面積平均粒子径（直径）を示し、λは
ゴム状重合体相の厚さで０．１０μｍ以下である） で求められるＫが０．１８以上のものである請求項２記
載の熱可塑性樹脂組成物。[Claims] 1 (A) 50 to 95% by weight of polyolefin resin and (B)
A thermoplastic resin composition comprising 5 to 40 parts by weight of (C) a compatibilizer to 100 parts by weight of a resin mixture with 50 to 5% by weight of a rubber-modified styrenic resin whose dispersed rubber form has an occlusion structure. . 2. The rubber-modified styrenic resin contains a rubber-like polymer, has an occlusion structure with a plane of symmetry, has an area average particle diameter of 0.1 to 0.7 μm, and has a ratio of the area average particle diameter to the number average particle diameter. 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is dispersed in a styrenic polymer as particles having a particle size of 1.0 to 2.5. 3 Dispersed particles of rubbery polymer meet the relational expression K=φ_R{1-[[(D_S/2)-λ]/(D_S
/2)]^3}^-^1 (φ_R in the formula indicates the volume fraction of the rubbery polymer in the rubber-modified styrenic resin, and D_S
is the area average particle size (diameter) of the rubbery polymer, and λ is the thickness of the rubbery polymer phase and is 0.10 μm or less. The thermoplastic resin composition described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014850A JPH0621199B2 (en) | 1990-01-26 | 1990-01-26 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014850A JPH0621199B2 (en) | 1990-01-26 | 1990-01-26 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03220249A true JPH03220249A (en) | 1991-09-27 |
| JPH0621199B2 JPH0621199B2 (en) | 1994-03-23 |
Family
ID=11872515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014850A Expired - Fee Related JPH0621199B2 (en) | 1990-01-26 | 1990-01-26 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0621199B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004307734A (en) * | 2003-04-10 | 2004-11-04 | Techno Polymer Co Ltd | Thermoplastic resin composition and molded article |
| WO2009003114A1 (en) * | 2007-06-27 | 2008-12-31 | Inteva Products | Thermoplastic polyolefin compositions having improved adhesion to polymer foams and/or coatings and methods of making and using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182361A (en) * | 1987-01-23 | 1988-07-27 | Mitsui Toatsu Chem Inc | Slidable styrene resin composition |
-
1990
- 1990-01-26 JP JP2014850A patent/JPH0621199B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182361A (en) * | 1987-01-23 | 1988-07-27 | Mitsui Toatsu Chem Inc | Slidable styrene resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004307734A (en) * | 2003-04-10 | 2004-11-04 | Techno Polymer Co Ltd | Thermoplastic resin composition and molded article |
| WO2009003114A1 (en) * | 2007-06-27 | 2008-12-31 | Inteva Products | Thermoplastic polyolefin compositions having improved adhesion to polymer foams and/or coatings and methods of making and using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0621199B2 (en) | 1994-03-23 |
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