JP4357924B2 - Polyolefin resin composition and use thereof - Google Patents
Polyolefin resin composition and use thereof Download PDFInfo
- Publication number
- JP4357924B2 JP4357924B2 JP2003359406A JP2003359406A JP4357924B2 JP 4357924 B2 JP4357924 B2 JP 4357924B2 JP 2003359406 A JP2003359406 A JP 2003359406A JP 2003359406 A JP2003359406 A JP 2003359406A JP 4357924 B2 JP4357924 B2 JP 4357924B2
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin resin
- resin composition
- block copolymer
- mass
- styrene
- 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.)
- Expired - Lifetime
Links
- 229920005672 polyolefin resin Polymers 0.000 title claims description 77
- 239000011342 resin composition Substances 0.000 title claims description 61
- 229920001400 block copolymer Polymers 0.000 claims description 67
- 229920000642 polymer Polymers 0.000 claims description 50
- -1 aromatic vinyl compound Chemical group 0.000 claims description 48
- 238000012644 addition polymerization Methods 0.000 claims description 33
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical group CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000010894 electron beam technology Methods 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 55
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 34
- 238000000034 method Methods 0.000 description 27
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 26
- 238000012360 testing method Methods 0.000 description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 18
- 238000005984 hydrogenation reaction Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000004132 cross linking Methods 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 229920000573 polyethylene Polymers 0.000 description 11
- 229920002223 polystyrene Polymers 0.000 description 11
- 229920000428 triblock copolymer Polymers 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920000314 poly p-methyl styrene Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920006132 styrene block copolymer Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 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
- 230000003078 antioxidant effect Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- CORMBJOFDGICKF-UHFFFAOYSA-N 1,3,5-trimethoxy 2-vinyl benzene Natural products COC1=CC(OC)=C(C=C)C(OC)=C1 CORMBJOFDGICKF-UHFFFAOYSA-N 0.000 description 1
- JPSVCKGZBDBQPG-UHFFFAOYSA-N 1,3,5-tris(chloromethyl)-2-ethenylbenzene Chemical compound ClCC1=CC(CCl)=C(C=C)C(CCl)=C1 JPSVCKGZBDBQPG-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- MLWORXSNFFNDJF-UHFFFAOYSA-N 1,3-bis(chloromethyl)-5-ethenylbenzene Chemical compound ClCC1=CC(CCl)=CC(C=C)=C1 MLWORXSNFFNDJF-UHFFFAOYSA-N 0.000 description 1
- KKLSEIIDJBCSRK-UHFFFAOYSA-N 1-(chloromethyl)-2-ethenylbenzene Chemical compound ClCC1=CC=CC=C1C=C KKLSEIIDJBCSRK-UHFFFAOYSA-N 0.000 description 1
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 1
- BCQNXDFECRPAOT-UHFFFAOYSA-N 1-(dichloromethyl)-2-ethenylbenzene Chemical compound ClC(Cl)C1=CC=CC=C1C=C BCQNXDFECRPAOT-UHFFFAOYSA-N 0.000 description 1
- IAFVZVIHAMSEDL-UHFFFAOYSA-N 1-(dichloromethyl)-3-ethenylbenzene Chemical compound ClC(Cl)C1=CC=CC(C=C)=C1 IAFVZVIHAMSEDL-UHFFFAOYSA-N 0.000 description 1
- IQXRSGMWLOIESY-UHFFFAOYSA-N 1-(dichloromethyl)-4-ethenylbenzene Chemical compound ClC(Cl)C1=CC=C(C=C)C=C1 IQXRSGMWLOIESY-UHFFFAOYSA-N 0.000 description 1
- UFFVWIGGYXLXPC-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1N1C(=O)C=CC1=O UFFVWIGGYXLXPC-UHFFFAOYSA-N 0.000 description 1
- UBRFDRBFBYCBFS-UHFFFAOYSA-N 1-ethenyl-2,4-diethylbenzene Chemical compound CCC1=CC=C(C=C)C(CC)=C1 UBRFDRBFBYCBFS-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- CCYFATPNAXTAFW-UHFFFAOYSA-N 1-ethenyl-2,4-dipropylbenzene Chemical compound CCCC1=CC=C(C=C)C(CCC)=C1 CCYFATPNAXTAFW-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- XIYATWBVQHWJPH-UHFFFAOYSA-N 1-ethenyl-2-propylbenzene Chemical compound CCCC1=CC=CC=C1C=C XIYATWBVQHWJPH-UHFFFAOYSA-N 0.000 description 1
- HVOKBODBWQEEGI-UHFFFAOYSA-N 1-ethenyl-3,5-diethylbenzene Chemical compound CCC1=CC(CC)=CC(C=C)=C1 HVOKBODBWQEEGI-UHFFFAOYSA-N 0.000 description 1
- XKMDZVINHIFHLY-UHFFFAOYSA-N 1-ethenyl-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(C=C)=C1 XKMDZVINHIFHLY-UHFFFAOYSA-N 0.000 description 1
- UTEYZSGHFLOAGG-UHFFFAOYSA-N 1-ethenyl-3,5-dipropylbenzene Chemical compound CCCC1=CC(CCC)=CC(C=C)=C1 UTEYZSGHFLOAGG-UHFFFAOYSA-N 0.000 description 1
- XGEAAAIRJFPUMU-UHFFFAOYSA-N 1-ethenyl-3-ethyl-5-methylbenzene Chemical compound CCC1=CC(C)=CC(C=C)=C1 XGEAAAIRJFPUMU-UHFFFAOYSA-N 0.000 description 1
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- CYAOHDYNSBNYPZ-UHFFFAOYSA-N 1-ethenyl-3-propylbenzene Chemical compound CCCC1=CC=CC(C=C)=C1 CYAOHDYNSBNYPZ-UHFFFAOYSA-N 0.000 description 1
- MBJWTCLMJBDAGT-UHFFFAOYSA-N 1-ethenyl-4-ethyl-2-methylbenzene Chemical compound CCC1=CC=C(C=C)C(C)=C1 MBJWTCLMJBDAGT-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- DPYJMQGTOTVJBV-UHFFFAOYSA-N 2,2-difluoroethenylbenzene Chemical compound FC(F)=CC1=CC=CC=C1 DPYJMQGTOTVJBV-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- AOGNACZDZNOTSN-UHFFFAOYSA-N 2,3-dihydroxy-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(O)(CO)C(=O)C1=CC=CC=C1 AOGNACZDZNOTSN-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-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
- 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 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- SZUWQQOPFFEVSI-UHFFFAOYSA-N 2-ethenyl-1,3,5-triethylbenzene Chemical compound CCC1=CC(CC)=C(C=C)C(CC)=C1 SZUWQQOPFFEVSI-UHFFFAOYSA-N 0.000 description 1
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 description 1
- ZWPBTHVXPHHNJX-UHFFFAOYSA-N 2-ethenyl-1,3,5-tripropylbenzene Chemical compound CCCC1=CC(CCC)=C(C=C)C(CCC)=C1 ZWPBTHVXPHHNJX-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- AXYQEGMSGMXGGK-UHFFFAOYSA-N 2-phenoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(C=1C=CC=CC=1)OC1=CC=CC=C1 AXYQEGMSGMXGGK-UHFFFAOYSA-N 0.000 description 1
- DDLXBFDBKPCGQK-UHFFFAOYSA-N 3-hydroxy-2-methoxy-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(CO)(OC)C(=O)C1=CC=CC=C1 DDLXBFDBKPCGQK-UHFFFAOYSA-N 0.000 description 1
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、ポリオレフィン系樹脂組成物に関する。本発明で得られるポリオレフィン系樹脂組成物は、柔軟性を有しつつ、特に耐熱性、力学的特性、耐溶剤性のバランスに優れ、電線被覆、各種ケーブルの被覆、チューブ、フィルム、シートなどの用途に有効に利用することができる。 The present invention relates to a polyolefin resin composition. The polyolefin-based resin composition obtained in the present invention has flexibility, particularly excellent balance of heat resistance, mechanical properties, and solvent resistance, such as wire coating, various cable coatings, tubes, films, sheets, etc. It can be used effectively for applications.
ポリオレフィン系樹脂は、一般的に適度な耐熱性を持ち、耐溶剤性に優れるという特徴を生かして、電線被覆、ケーブル被覆、チューブ、ラミネート用フィルム、農業用フィルム、ストレッチ・ラップ用フィルム、接着フィルム、医療用フィルムなどのフィルム、農業用シートなどのシート用途、加工紙、射出成型用途、パイプ、結束テープ、フラットヤーン、繊維など広範囲の用途に使用されている。しかしながら、電線被覆、チューブ、フィルム、シートなどの用途においては、さらなる物性向上、例えば耐熱性や耐溶剤性の向上が要求されているのが現状である。 Polyolefin-based resins generally have moderate heat resistance and excellent solvent resistance, and are used for wire coating, cable coating, tubes, laminating films, agricultural films, stretch wrap films, adhesive films. It is used in a wide range of applications such as films for medical films, sheets for agricultural sheets, processed paper, injection molding, pipes, binding tape, flat yarns, and fibers. However, in applications such as electric wire coverings, tubes, films, sheets, etc., there are currently demands for further improvements in physical properties such as heat resistance and solvent resistance.
ポリオレフィン系樹脂に力学的特性、耐熱性、耐溶剤性を付与する方法として、ポリオレフィン系樹脂に架橋性モノマーを混合した架橋性ポリマー組成物に活性エネルギー線を照射する方法が知られている（特許文献１参照）。また、ポリエチレンとエチレン−α−オレフィン共重合体、あるいはポリエチレンとスチレン系ブロック共重合体をブレンドする方法による試みがなされている（特許文献２参照）。
一方、炭素数８以上の非共役ジエンを共重合させた架橋性の高いエチレン共重合体をポリエチレンに配合してなる電子線架橋用ポリエチレン樹脂組成物（特許文献３参照）や、少なくとも１種の他のモノマーと共重合化されたエチレンインターポリマー（好ましくは均質分岐エチレンポリマー）を含み、硬化、照射または架橋された該エチレンポリマーを包含する成形品が提案されている（特許文献４参照）。さらに、シラン変性したポリオレフィンと、ポリプロピレンを含有する架橋組成物も提案されている（特許文献５参照）。
そして、エチレン−プロピレンゴムに結晶性ポリマー（好ましくはポリエチレン）および無機充填剤を配合した組成物を電離性放射線で架橋したエラストマーの製造方法（特許文献６参照）、スチレン−エチレン・ブチレン−スチレンブロック共重合体にポリプロピレン、油、安定剤および架橋助剤を添加してなる架橋性樹脂組成物を電子線架橋や化学架橋により架橋して、耐油性、カットスルー、加熱変形、耐はんだ性が改善された組成物（特許文献７参照）、ポリエチレンにスチレン−エチレン・ブチレン−スチレンブロック共重合体および難燃剤を配合した組成物を電子線照射または化学架橋で架橋してなる耐熱性、難燃性に優れる難燃性架橋ポリエチレン組成物が提案されている（特許文献８参照）。
As a method for imparting mechanical properties, heat resistance, and solvent resistance to a polyolefin resin, a method of irradiating a crosslinkable polymer composition in which a crosslinkable monomer is mixed with a polyolefin resin is known (patent) Reference 1). Attempts have also been made by a method of blending polyethylene and an ethylene-α-olefin copolymer, or polyethylene and a styrene block copolymer (see Patent Document 2).
On the other hand, a polyethylene resin composition for electron beam cross-linking obtained by blending polyethylene with a highly cross-linkable ethylene copolymer obtained by copolymerizing a non-conjugated diene having 8 or more carbon atoms (see Patent Document 3), or at least one kind There has been proposed a molded article containing an ethylene interpolymer (preferably a homogeneous branched ethylene polymer) copolymerized with another monomer and including the cured, irradiated or crosslinked ethylene polymer (see Patent Document 4). Furthermore, a crosslinked composition containing a silane-modified polyolefin and polypropylene has also been proposed (see Patent Document 5).
Then, a method for producing an elastomer obtained by crosslinking a composition in which a crystalline polymer (preferably polyethylene) and an inorganic filler are blended with ethylene-propylene rubber with ionizing radiation (see Patent Document 6), styrene-ethylene-butylene-styrene block Crosslinkable resin composition made by adding polypropylene, oil, stabilizer and crosslinking aid to copolymer is crosslinked by electron beam crosslinking or chemical crosslinking to improve oil resistance, cut-through, heat deformation, and solder resistance. Composition (see Patent Document 7), heat resistance and flame resistance obtained by crosslinking a composition obtained by blending polyethylene with a styrene-ethylene / butylene-styrene block copolymer and a flame retardant by electron beam irradiation or chemical crosslinking Has been proposed (see Patent Document 8).
しかしながら、架橋性モノマーを混合し、活性エネルギー線を照射する特許文献１の方法は、架橋性ポリマー組成物に必ずしも充分な耐熱性や耐溶剤性を付与することができない。一方、ポリエチレンとエチレン−α−オレフィン共重合体、あるいはポリエチレンとスチレン系ブロック共重合体を混合する特許文献２の方法においては、ポリエチレンにエチレン−α−オレフィン共重合体を混合しても耐熱性付与効果は小さい。また、ポリエチレンにスチレン系ブロック共重合体を混合した場合には、得られる組成物の耐溶剤性が悪化する傾向となる問題点も有しており、必ずしも柔軟性と耐熱性とのバランスのとれた組成物は得られていない。
特許文献３〜特許文献５記載の方法では、架橋性が向上し、耐熱性が改良されるものの、柔軟性の改良効果は少なく、柔軟性が要求される用途には適さない。
また、特許文献６〜特許文献８記載の方法では、弾性を有する成分としてエチレン−プロピレン共重合ゴムあるいはスチレン−エチレン・ブチレン−スチレンブロック共重合体を配合しているので柔軟性の改善については一定の効果が見られる。しかし、いずれの組成物においてもその架橋性は必ずしも充分であるとはいえないため、耐熱性の改良レベルについても、例えば自動車のエンジンルーム内で使用する電線被覆材のような高い耐熱性が要求される用途においては充分ではない。
よって、電線被覆、ケーブル被覆、チューブ、フィルム、シートなどの用途において有効に使用可能な、柔軟性、力学的特性、耐熱性、耐溶剤性のバランスに優れたポリオレフィン系樹脂組成物が望まれていた。
However, the method of Patent Document 1 in which a crosslinkable monomer is mixed and irradiated with active energy rays cannot always give sufficient heat resistance and solvent resistance to the crosslinkable polymer composition. On the other hand, in the method of Patent Document 2 in which polyethylene and ethylene-α-olefin copolymer or polyethylene and styrene block copolymer are mixed, heat resistance is maintained even if ethylene-α-olefin copolymer is mixed with polyethylene. The grant effect is small. In addition, when a styrene block copolymer is mixed with polyethylene, there is a problem that the solvent resistance of the resulting composition tends to deteriorate, and the balance between flexibility and heat resistance is not necessarily achieved. No composition has been obtained.
In the methods described in Patent Documents 3 to 5, although the crosslinkability is improved and the heat resistance is improved, the effect of improving the flexibility is small and it is not suitable for applications requiring flexibility.
Further, in the methods described in Patent Documents 6 to 8, since an ethylene-propylene copolymer rubber or a styrene-ethylene-butylene-styrene block copolymer is blended as an elastic component, the improvement in flexibility is constant. The effect is seen. However, since the crosslinkability is not necessarily sufficient in any composition, the heat resistance improvement level also requires high heat resistance such as a wire covering material used in an engine room of an automobile. Is not sufficient for certain applications.
Therefore, there is a demand for a polyolefin resin composition having an excellent balance of flexibility, mechanical properties, heat resistance, and solvent resistance that can be effectively used in applications such as wire coating, cable coating, tubes, films, and sheets. It was.
しかして、本発明の目的は、上記従来技術の問題を解決し、柔軟性、耐熱性、力学的特性および耐溶剤性のバランスに優れたポリオレフィン系樹脂組成物を提供することにある。 Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art and provide a polyolefin resin composition having an excellent balance of flexibility, heat resistance, mechanical properties, and solvent resistance.
本発明によれば、上記の目的は、
〔１〕 炭素数１〜８のアルキル基の少なくとも１個がベンゼン環に結合したアルキルスチレン由来構造単位（ａ）（以下、構造単位（ａ）と略称することがある）を１０質量％以上有する芳香族ビニル化合物単位を主体とする重合体ブロックＡを１個以上と、共役ジエン化合物単位を主体とする重合体ブロックＢを１個以上有し、少なくとも重合体ブロックＡ部分が活性エネルギー線によって架橋可能なブロック共重合体およびその水素添加物から選ばれる少なくとも１種の付加重合系ブロック共重合体（Ｉ）とポリオレフィン系樹脂（ＩＩ）を、付加重合系ブロック共重合体（Ｉ）／ポリオレフィン系樹脂（ＩＩ）＝８０／２０〜１／９９（質量比）の割合で含有してなり、成形後に活性エネルギー線によって架橋を行うことを特徴とするポリオレフィン系樹脂組成物；
〔２〕 炭素数１〜８のアルキル基の少なくとも１個がベンゼン環に結合したアルキルスチレン由来構造単位（ａ）がｐ−メチルスチレン単位であることを特徴とする〔１〕のポリオレフィン系樹脂組成物；
〔３〕 活性エネルギー線として電子線を用いることを特徴とする〔１〕または〔２〕のポリオレフィン系樹脂組成物；
〔４〕 〔１〕〜〔３〕のいずれかのポリオレフィン系樹脂組成物から得られる成形品；
および、
〔５〕 〔１〕〜〔３〕のいずれかのポリオレフィン系樹脂組成物からなる層を含有する
積層体；を提供することによって達成される。
According to the present invention, the above object is
[1] 10 % by mass or more of an alkylstyrene-derived structural unit (a) (hereinafter sometimes abbreviated as structural unit (a)) in which at least one alkyl group having 1 to 8 carbon atoms is bonded to a benzene ring. It has at least one polymer block A mainly composed of aromatic vinyl compound units and one or more polymer blocks B mainly composed of conjugated diene compound units, and at least the polymer block A part is crosslinked by active energy rays. At least one addition polymerization block copolymer (I) and polyolefin resin (II) selected from possible block copolymers and hydrogenated products thereof are added to the addition polymerization block copolymer (I) / polyolefin system. Resin (II) is contained at a ratio of 80/20 to 1/99 (mass ratio), and is crosslinked by active energy rays after molding. Polyolefin resin composition;
[2] Polyolefin resin composition according to [1], wherein the alkylstyrene-derived structural unit (a) in which at least one alkyl group having 1 to 8 carbon atoms is bonded to a benzene ring is a p-methylstyrene unit. object;
[3] A polyolefin resin composition according to [1] or [2], wherein an electron beam is used as an active energy ray;
[ 4] A molded product obtained from the polyolefin resin composition according to any one of [1] to [ 3 ];
and,
[ 5 ] It is achieved by providing a laminate comprising a layer made of the polyolefin resin composition of any one of [1] to [ 3 ].
本発明によれば、柔軟性、耐熱性、力学的特性および耐溶剤性のバランスに優れたポリオレフィン系樹脂組成物を得ることができる。 According to the present invention, a polyolefin resin composition having an excellent balance of flexibility, heat resistance, mechanical properties and solvent resistance can be obtained.
以下に本発明について詳細に説明する。
本発明のポリオレフィン系樹脂組成物を構成する付加重合系ブロック共重合体（Ｉ）は、炭素数１〜８のアルキル基の少なくとも１個がベンゼン環に結合したアルキルスチレン由来構造単位（ａ）を１０質量％以上有する芳香族ビニル化合物単位を主体とする重合体ブロックＡを１個以上と、共役ジエン化合物単位を主体とする重合体ブロックＢを１個以上有し、少なくとも重合体ブロックＡ部分が活性エネルギー線によって架橋可能なブロック共重合体およびその水素添加物から選ばれる少なくとも１種の付加重合系ブロック共重合体である。
The present invention is described in detail below.
The addition polymerization block copolymer (I) constituting the polyolefin resin composition of the present invention comprises an alkylstyrene-derived structural unit (a) in which at least one alkyl group having 1 to 8 carbon atoms is bonded to a benzene ring. Having at least one polymer block A mainly composed of an aromatic vinyl compound unit having at least 10 % by mass and at least one polymer block B mainly composed of a conjugated diene compound unit, wherein at least the polymer block A part is It is at least one addition polymerization block copolymer selected from a block copolymer crosslinkable by active energy rays and a hydrogenated product thereof.
重合体ブロックＡにおいて、構造単位（ａ）を構成するアルキルスチレンとしては、例えば、アルキル基の炭素数が１〜８であるｏ−アルキルスチレン、ｍ−アルキルスチレン、ｐ−アルキルスチレン、２，４−ジアルキルスチレン、３，５−ジアルキルスチレン、２，４，６−トリアルキルスチレン、前記したアルキルスチレン類におけるアルキル基の水素原子の１個または２個以上がハロゲン原子で置換されたハロゲン化アルキルスチレン類などを挙げることができる。より具体的には、構造単位（ａ）を構成するアルキルスチレンとしては、例えばｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、２，４−ジメチルスチレン、３，５−ジメチルスチレン、２，４，６−トリメチルスチレン、ｏ−エチルスチレン、ｍ−エチルスチレン、ｐ−エチルスチレン、２，４−ジエチルスチレン、３，５−ジエチルスチレン、２，４，６−トリエチルスチレン、ｏ−プロピルスチレン、ｍ−プロピルスチレン、ｐ−プロピルスチレン、２，４−ジプロピルスチレン、３，５−ジプロピルスチレン、２，４，６−トリプロピルスチレン、２−メチル−４−エチルスチレン、３−メチル−５−エチルスチレン、ｏ−クロロメチルスチレン、ｍ−クロロメチルスチレン、ｐ−クロロメチルスチレン、２，４−ビス（クロロメチル）スチレン、３，５−ビス（クロロメチル）スチレン、２，４，６−トリ（クロロメチル）スチレン、ｏ−ジクロロメチルスチレン、ｍ−ジクロロメチルスチレン、ｐ−ジクロロメチルスチレンなどを挙げることができる。 In the polymer block A, as the alkyl styrene constituting the structural unit (a), for example, o-alkyl styrene, m-alkyl styrene, p-alkyl styrene whose alkyl group has 1 to 8 carbon atoms, 2, 4 -Dialkyl styrene, 3,5-dialkyl styrene, 2,4,6-trialkyl styrene, halogenated alkyl styrene in which one or more of the hydrogen atoms of the alkyl group in the aforementioned alkyl styrenes are substituted with halogen atoms And the like. More specifically, examples of the alkylstyrene constituting the structural unit (a) include o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 3,5-dimethylstyrene, 2 , 4,6-trimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 2,4-diethylstyrene, 3,5-diethylstyrene, 2,4,6-triethylstyrene, o-propylstyrene M-propyl styrene, p-propyl styrene, 2,4-dipropyl styrene, 3,5-dipropyl styrene, 2,4,6-tripropyl styrene, 2-methyl-4-ethyl styrene, 3-methyl- 5-ethylstyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, 2,4- (Chloromethyl) styrene, 3,5-bis (chloromethyl) styrene, 2,4,6-tri (chloromethyl) styrene, o-dichloromethylstyrene, m-dichloromethylstyrene, p-dichloromethylstyrene, etc. Can be mentioned.
重合体ブロックＡは、構造単位（ａ）として前記したアルキルスチレンおよびハロゲン化アルキルスチレンのうちの１種または２種以上からなる単位を有することができる。そのうちでも、構造単位（ａ）としては、ｐ−メチルスチレン単位が架橋反応性に優れ、入手が容易な点から好ましい。 The polymer block A can have a unit consisting of one or more of the above-described alkylstyrene and halogenated alkylstyrene as the structural unit (a). Among them, as the structural unit (a), a p-methylstyrene unit is preferable because it has excellent crosslinking reactivity and is easily available.
また構造単位（ａ）以外の芳香族ビニル化合物単位としては、例えばスチレン、α−メチルスチレン、β−メチルスチレン、モノフルオロスチレン、ジフルオロスチレン、モノクロロスチレン、ジクロロスチレン、メトキシスチレン、ビニルナフタレン、ビニルアントラセン、インデン、アセトナフチレンなどからなる単位を挙げることができ、中でもスチレン、α−メチルスチレンからなる単位が好ましい。 Examples of the aromatic vinyl compound unit other than the structural unit (a) include styrene, α-methylstyrene, β-methylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene, and vinylanthracene. , Indene, acetonaphthylene, and the like. Among these, units consisting of styrene and α-methylstyrene are preferable.
付加重合系ブロック共重合体（Ｉ）において、重合体ブロックＡは熱可塑性エラストマーのハードセグメントに相当し、構造単位（ａ）におけるベンゼン環に結合したアルキル基は、活性エネルギー線の照射による静的な架橋反応により、重合体ブロックＡからなるハードセグメントに架橋を導入する役割を有する。 In the addition polymerization block copolymer (I), the polymer block A corresponds to the hard segment of the thermoplastic elastomer, and the alkyl group bonded to the benzene ring in the structural unit (a) is statically irradiated by active energy rays. It has a role which introduce | transduces bridge | crosslinking into the hard segment which consists of polymer block A by an appropriate crosslinking reaction.
重合体ブロックＡにおける構造単位（ａ）の割合は、付加重合系ブロック共重合体（Ｉ）を構成する重合体ブロックＡの質量［付加重合系ブロック共重合体（Ｉ）が２個以上の重合体ブロックＡを有する場合はその合計質量］に対し１０質量％以上であり、４０質量％以上であるのがより好ましく、さらにすべての単位が構造単位（ａ）からなっていてもよい。構造単位（ａ）の割合が１質量％未満であると、重合体ブロックＡに架橋が充分に導入されず、得られるポリオレフィン系樹脂組成物において充分な耐熱性および力学的特性が発現しない。重合体ブロックＡにおける構造単位（ａ）とそれ以外の芳香族ビニル化合物単位との結合形態は、ランダム、ブロック、テーパードなどのいずれの形態であってもよい。 The proportion of the structural unit (a) in the polymer block A is the mass of the polymer block A constituting the addition polymerization block copolymer (I) [the weight of the addition polymerization block copolymer (I) is 2 or more. polymer block Ri der 1 0 wt% or more against its total mass] If with a, more preferably 40 mass% or more, even all the unit may be made of the structural units (a) . When the proportion of the structural unit (a) is less than 1% by mass, crosslinking is not sufficiently introduced into the polymer block A, and sufficient heat resistance and mechanical properties are not exhibited in the resulting polyolefin resin composition. The bonding form of the structural unit (a) and the other aromatic vinyl compound unit in the polymer block A may be any form such as random, block, and tapered.
付加重合系ブロック共重合体（Ｉ）における重合体ブロックＡの含有量は１０〜４０質量％が好ましい。１０質量％より少ない場合には架橋効果が充分に発現せず、充分な耐熱性、力学的特性を示さない傾向となる。また、４０質量％より多い場合、ポリオレフィン系樹脂組成物が充分な柔軟性を示さなくなる傾向となる。 The content of the polymer block A in the addition polymerization block copolymer (I) is preferably 10 to 40% by mass. When the amount is less than 10% by mass, the crosslinking effect is not sufficiently exhibited, and sufficient heat resistance and mechanical properties tend not to be exhibited. Moreover, when more than 40 mass%, it will become the tendency for a polyolefin-type resin composition not to show sufficient softness | flexibility.
重合体ブロックＡは、構造単位（ａ）を含む芳香族ビニル化合物からなる構造単位と共に、必要に応じて他の重合性単量体からなる構造単位を少量有していてもよい。その場合の他の重合性単量体からなる構造単位の割合は、付加重合系ブロック共重合体（Ｉ）を構成する重合体ブロックＡの質量［付加重合系ブロック共重合体（Ｉ）が２個以上の重合体ブロックＡを有する場合はその合計質量］に基づいて３０質量％以下であることが好ましく、１０質量％以下であることがより好ましい。その場合の他の重合性単量体としては、例えば１−ブテン、ペンテン、ヘキセン、ブタジエン、イソプレン、メチルビニルエーテルなどを挙げることできる。 The polymer block A may have a small amount of structural units composed of other polymerizable monomers as necessary together with the structural units composed of the aromatic vinyl compound containing the structural unit (a). In this case, the proportion of the structural units composed of other polymerizable monomers is the mass of the polymer block A constituting the addition polymerization block copolymer (I) [addition polymerization block copolymer (I) is 2 In the case of having at least one polymer block A, the total mass] is preferably 30% by mass or less, and more preferably 10% by mass or less. Examples of the other polymerizable monomer in that case include 1-butene, pentene, hexene, butadiene, isoprene, methyl vinyl ether, and the like.
本発明に用いる付加重合系ブロック共重合体（Ｉ）は、上記の構造単位（ａ）を含む芳香族ビニル化合物単位からなる重合体ブロックＡの他に、構造単位（ａ）を含まない芳香族ビニル化合物単位からなる重合体ブロックを有していてもよい。 The addition polymerization block copolymer (I) used in the present invention is an aromatic that does not contain a structural unit (a) in addition to the polymer block A composed of an aromatic vinyl compound unit containing the structural unit (a). You may have a polymer block which consists of a vinyl compound unit.
一方、付加重合系ブロック共重合体（Ｉ）における共役ジエン化合物単位を主体とする重合体ブロックＢを構成する共役ジエン化合物としては、例えばブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、１，３−ヘキサジエンなどが挙げられる。重合体ブロックＢはこれらの共役ジエン化合物の１種類のみから構成されていてもよいし、２種以上から構成されていてもよい。中でもブタジエン、イソプレンまたはブタジエンとイソプレンの混合物から構成されているのが好ましい。なお、重合体ブロックＢのミクロ構造の種類および含有量に特に制限はない。また、２種以上の共役ジエン化合物を併用した場合、それらの結合形態はランダム、ブロック、テーパード、またはそれらの２種以上の組み合わせからなっていることができる。 On the other hand, examples of the conjugated diene compound constituting the polymer block B mainly composed of the conjugated diene compound unit in the addition polymerization block copolymer (I) include butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. 1,3-pentadiene, 1,3-hexadiene and the like. The polymer block B may be comprised only from 1 type of these conjugated diene compounds, and may be comprised from 2 or more types. Among these, it is preferable to be composed of butadiene, isoprene or a mixture of butadiene and isoprene. The type and content of the microstructure of the polymer block B are not particularly limited. Further, when two or more kinds of conjugated diene compounds are used in combination, their bonding form can be random, block, tapered, or a combination of two or more thereof.
重合体ブロックＢは、共役ジエン化合物からなる構造単位とともに、必要に応じて他の重合性単量体からなる構造単位を少量有していてもよい。その場合の他の重合性単量体の割合は、付加重合系ブロック共重合体（Ｉ）を構成する重合体ブロックＢの質量［付加重合系ブロック共重合体（Ｉ）が２個以上の重合体ブロックＢを有する場合はその合計質量］に基づいて３０質量％以下であることが好ましく、１０質量％以下であることがより好ましい。その場合の他の重合性単量体としては、例えばスチレン、α−メチルスチレン、構造単位（ａ）を構成する前記したアルキルスチレン（好適にはｐ−メチルスチレン）などを挙げることができる。 The polymer block B may have a small amount of a structural unit composed of another polymerizable monomer as necessary, together with a structural unit composed of a conjugated diene compound. In this case, the ratio of the other polymerizable monomer is the mass of the polymer block B constituting the addition polymerization block copolymer (I) [the addition polymerization block copolymer (I) has two or more weights. When the combined block B is included, the total mass] is preferably 30% by mass or less, and more preferably 10% by mass or less. Examples of the other polymerizable monomer in that case include styrene, α-methylstyrene, and the above-described alkylstyrene (preferably p-methylstyrene) constituting the structural unit (a).
そのうちでも、重合体ブロックＢは、イソプレン単位からなるポリイソプレンブロックまたは該イソプレン単位に基づく炭素−炭素二重結合の一部または全部が水素添加された水添ポリイソプレンブロック；ブタジエン単位からなるポリブタジエンブロックまたは該ブタジエン単位に基づく炭素−炭素二重結合の一部または全部が水素添加された水添ポリブタジエンブロック；或いはイソプレン単位とブタジエン単位からなるイソプレンとブタジエンの混合物からなる共重合体ブロックまたは該イソプレン単位およびブタジエン単位に基づく炭素−炭素二重結合の一部または全部が水素添加された共重合体ブロックであることが好ましい。 Among them, the polymer block B is a polyisoprene block composed of isoprene units or a hydrogenated polyisoprene block in which part or all of carbon-carbon double bonds based on the isoprene units are hydrogenated; a polybutadiene block composed of butadiene units. Or a hydrogenated polybutadiene block in which some or all of carbon-carbon double bonds based on the butadiene unit are hydrogenated; or a copolymer block comprising a mixture of isoprene and butadiene comprising isoprene units and butadiene units, or the isoprene units. And a copolymer block in which part or all of carbon-carbon double bonds based on butadiene units are hydrogenated.
付加重合系ブロック共重合体（Ｉ）は、重合体ブロックＡと重合体ブロックＢとが結合している限りは、その結合形式は限定されず、直鎖状、分岐状、放射状、またはそれらの２つ以上が組合わさった結合形式のいずれでもよい。それらのうちでも、重合体ブロックＡと重合体ブロックＢの結合形式は直鎖状であることが好ましく、その例としては重合体ブロックＡをＡで、また重合体ブロックＢをＢで表したときに、Ａ−Ｂ−Ａで示されるトリブロック共重合体、Ａ−Ｂ−Ａ−Ｂで示されるテトラブロック共重合体、Ａ−Ｂ−Ａ−Ｂ−Ａで示されるペンタブロック共重合体などを挙げることができる。それらのうちでも、トリブロック共重合体（Ａ−Ｂ−Ａ）が、付加重合系ブロック共重合体（Ｉ）の製造の容易性、柔軟性などの点から好ましく用いられる。 As long as the polymer block A and the polymer block B are bonded to the addition polymerization block copolymer (I), the bonding type is not limited and is linear, branched, radial, or those Any of two or more combined forms may be used. Among them, it is preferable that the bond form of the polymer block A and the polymer block B is a linear form, for example, when the polymer block A is represented by A and the polymer block B is represented by B. Further, a triblock copolymer represented by A-B-A, a tetrablock copolymer represented by A-B-A-B, a pentablock copolymer represented by A-B-A-B-A, etc. Can be mentioned. Among them, the triblock copolymer (ABA) is preferably used from the viewpoints of ease of production of the addition polymerization block copolymer (I) and flexibility.
本発明において使用する付加重合系ブロック共重合体（Ｉ）の数平均分子量は特に制限されないが、好ましくは３００００〜１００００００の範囲であり、より好ましくは４００００〜３０００００の範囲である。なお、ここでいう数平均分子量とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で求めたポリスチレン換算の数平均分子量を意味する。 The number average molecular weight of the addition polymerization block copolymer (I) used in the present invention is not particularly limited, but is preferably in the range of 30000 to 1000000, more preferably in the range of 40000 to 300000. In addition, the number average molecular weight here means the number average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC).
付加重合系ブロック共重合体（Ｉ）は、例えば、次のような公知のアニオン重合法によって製造することができる。すなわち、アルキルリチウム化合物などを開始剤として、ｎ−ヘキサン、シクロヘキサンなどの重合反応に不活性な有機溶媒中で、構造単位（ａ）を構成するアルキルスチレンまたは構造単位（ａ）を構成するアルキルスチレンと芳香族ビニル化合物の混合物、共役ジエン化合物を逐次重合させてブロック共重合体（すなわち未水添の付加重合系ブロック共重合体（Ｉ））を形成する。
また、得られた該ブロック共重合体は、必要に応じてさらに水素添加される。かかる水素添加反応は、例えば、該ブロック共重合体をシクロヘキサンなどの飽和炭化水素系溶媒中で、ラネーニッケル；Ｐｔ、Ｐｄ、Ｒｕ、Ｒｈ、Ｎｉ等の金属をカーボン、アルミナ、硅藻土等の担体に担持させた不均一触媒；コバルト、ニッケルなどの第９族または第１０族の金属からなる有機金属化合物とトリエチルアルミニウム、トリイソブチルアルミニウムなどの有機アルミニウム化合物または有機リチウム化合物等の組み合わせからなるチーグラー系の触媒；チタン、ジルコニウム、ハフニウムなどの遷移金属のビス（シクロペンタジエニル）化合物とリチウム、ナトリウム、カリウム、アルミニウム、亜鉛またはマグネシウムなどからなる有機金属化合物の組み合わせからなるメタロセン系触媒などの水素添加触媒の存在下で、通常、反応温度として２０〜１００℃の範囲で、水素圧力０．１〜１０ＭＰａの範囲の条件下で行うことができ、該ブロック共重合体の水素添加物（すなわち、水素添加されている付加重合系ブロック共重合体（Ｉ））を得ることができる。
The addition polymerization block copolymer (I) can be produced, for example, by the following known anionic polymerization method. That is, the alkyl styrene constituting the structural unit (a) or the alkyl styrene constituting the structural unit (a) in an organic solvent inert to the polymerization reaction such as n-hexane or cyclohexane using an alkyl lithium compound as an initiator. And a mixture of an aromatic vinyl compound and a conjugated diene compound are sequentially polymerized to form a block copolymer (that is, an unhydrogenated addition polymerization block copolymer (I)).
Moreover, the obtained block copolymer is further hydrogenated as necessary. Such a hydrogenation reaction is carried out, for example, by using the block copolymer in a saturated hydrocarbon solvent such as cyclohexane, Raney nickel; a metal such as Pt, Pd, Ru, Rh, or Ni as a support such as carbon, alumina, or diatomaceous earth. A heterogeneous catalyst supported on a Ziegler system comprising a combination of an organometallic compound comprising a Group 9 or 10 metal such as cobalt or nickel and an organoaluminum compound or organolithium compound such as triethylaluminum or triisobutylaluminum Hydrogenation of metallocene catalysts composed of combinations of bis (cyclopentadienyl) compounds of transition metals such as titanium, zirconium and hafnium and organometallic compounds composed of lithium, sodium, potassium, aluminum, zinc or magnesium In the presence of a catalyst Usually, the reaction can be carried out under the conditions of a reaction temperature of 20 to 100 ° C. and a hydrogen pressure of 0.1 to 10 MPa, and the hydrogenated product of the block copolymer (that is, addition polymerization in which hydrogenation is performed). A system block copolymer (I)) can be obtained.
水素添加率は、本発明のポリオレフィン系樹脂組成物に要求される物性に応じて適宜調整することができるが、耐熱性、耐候性および耐オゾン性を重視する場合、かかる付加重合系ブロック共重合体（Ｉ）を構成する重合体ブロックＢの共役ジエン化合物単位に基づく炭素−炭素二重結合の７０％以上が水素添加されていることが好ましく、８５％以上であることがより好ましく、９５％以上が水素添加されていることがさらに好ましい。
なお、重合体ブロックＢの共役ジエン化合物単位に基づく炭素−炭素二重結合の水素添加率は、ヨウ素価滴定、赤外分光光度計、核磁気共鳴などの測定手段により水素添加反応前後における重合体ブロックＢ中の炭素−炭素二重結合の量を測定し、その測定値から算出することができる。
The hydrogenation rate can be appropriately adjusted according to the physical properties required for the polyolefin resin composition of the present invention. However, when importance is attached to heat resistance, weather resistance and ozone resistance, such an addition polymerization block copolymer is used. 70% or more of the carbon-carbon double bond based on the conjugated diene compound unit of the polymer block B constituting the polymer (I) is preferably hydrogenated, more preferably 85% or more, and 95% More preferably, the above is hydrogenated.
The hydrogenation rate of the carbon-carbon double bond based on the conjugated diene compound unit of the polymer block B is determined by measuring the polymer before and after the hydrogenation reaction by measuring means such as iodine titration, infrared spectrophotometer, nuclear magnetic resonance, etc. The amount of the carbon-carbon double bond in the block B can be measured and calculated from the measured value.
本発明のポリオレフィン系樹脂組成物を構成するポリオレフィン樹脂（ＩＩ）としては、例えば、高密度ポリエチレン（ＨＤＰＥ）、中密度ポリエチレンおよび低密度ポリエチレン（ＬＤＰＥ）、ポリプロピレンのような単独重合体；エチレン−プロピレン共重合体、エチレン−１−ブテン共重合体、エチレン−１−ヘキセン共重合体、エチレン−１−ヘプテン共重合体、エチレン−１−オクテン共重合体、エチレン−４−メチル−１−ペンテン共重合体、エチレン−１−ノネン共重合体およびエチレン−１−デセン共重合体などのようなエチレン−α−オレフィン共重合体；エチレン−１，７−オクタジエン共重合体のような架橋性エチレン系共重合体；エチレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体、エチレン−アクリル酸エステル共重合体、エチレン−メタクリル酸共重合体、エチレン−メタクリル酸エステル共重合体およびこれらを無水マレイン酸などで変性した樹脂などが挙げられる。これらの中でも高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、ポリプロピレン、エチレン−ポリプロピレン共重合体、エチレン−α−オレフィン共重合体を用いるのが好ましい。 Examples of the polyolefin resin (II) constituting the polyolefin resin composition of the present invention include homopolymers such as high density polyethylene (HDPE), medium density polyethylene and low density polyethylene (LDPE), and polypropylene; ethylene-propylene Copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-heptene copolymer, ethylene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer Polymers, ethylene-α-olefin copolymers such as ethylene-1-nonene copolymers and ethylene-1-decene copolymers; crosslinkable ethylene systems such as ethylene-1,7-octadiene copolymers Copolymer; ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic Acid ester copolymer, ethylene - methacrylic acid copolymer, ethylene - methacrylic acid ester copolymer and modified resin of these, such as with maleic acid. Among these, high-density polyethylene, medium-density polyethylene, low-density polyethylene, polypropylene, ethylene-polypropylene copolymer, and ethylene-α-olefin copolymer are preferably used.
本発明のポリオレフィン系樹脂組成物は、付加重合系ブロック共重合体（Ｉ）とポリオレフィン系樹脂（ＩＩ）が、質量比として、付加重合系ブロック共重合体（Ｉ）／ポリオレフィン系樹脂（ＩＩ）＝８０／２０〜１／９９の割合で配合されており、８０／２０〜２０／８０であるのがより好ましい。ポリオレフィン系樹脂（ＩＩ）の割合が、付加重合系ブロック共重合体（Ｉ）とポリオレフィン系樹脂（ＩＩ）の合計質量に対して１０質量％未満であるか、または９９質量％を超えた場合には、いずれも、柔軟性、耐熱性、力学的特性および耐溶剤性のバランスに優れたポリオレフィン系樹脂組成物を得られない傾向となる。 In the polyolefin resin composition of the present invention, the addition polymerization block copolymer (I) and the polyolefin resin (II) have a mass ratio of addition polymerization block copolymer (I) / polyolefin resin (II). = it is blended in a ratio of 80/20 to 1/99, and more preferably 80/20 to 20/80. When the proportion of the polyolefin resin (II) is less than 10% by mass or more than 99% by mass with respect to the total mass of the addition polymerization block copolymer (I) and the polyolefin resin (II) In either case, there is a tendency that a polyolefin resin composition having an excellent balance of flexibility, heat resistance, mechanical properties and solvent resistance cannot be obtained.
本発明のポリオレフィン系樹脂組成物において、構成成分である付加重合系ブロック共重合体（Ｉ）の少なくとも重合体ブロックＡ部分を架橋するのに用いられる活性エネルギー線としては、粒子線、電磁波、およびこれらの組み合わせが挙げられる。粒子線としては電子線（ＥＢ）、α線、電磁波としては紫外線（ＵＶ）、可視光線、赤外線、γ線、Ｘ線などが挙げられる。これらの中でも、電子線（ＥＢ）または紫外線（ＵＶ）が好ましい。
これらの活性エネルギー線は、公知の装置を用いて照射することができる。電子線（ＥＢ）の場合の加速電圧としては０．１〜１０ＭｅＶ、照射線量としては１〜５００ｋＧｙの範囲が適当である。紫外線（ＵＶ）の場合、その線源として放射波長が２００ｎｍ〜４５０ｎｍのランプを好適に用いることができる。線源としては、電子線（ＥＢ）の場合は、例えばタングステンフィラメントが挙げられ、紫外線（ＵＶ）の場合は、例えば低圧水銀灯、高圧水銀灯、紫外線用水銀灯、カーボンアーク灯、キセノンランプ、ジルコニウムランプなどが挙げられる。
In the polyolefin resin composition of the present invention, the active energy rays used to crosslink at least the polymer block A portion of the addition polymerization block copolymer (I) as a constituent component include particle beams, electromagnetic waves, and These combinations are mentioned. Examples of the particle beam include electron beams (EB) and α rays, and examples of the electromagnetic waves include ultraviolet rays (UV), visible rays, infrared rays, γ rays, and X rays. Among these, an electron beam (EB) or an ultraviolet ray (UV) is preferable.
These active energy rays can be irradiated using a known apparatus. In the case of an electron beam (EB), an acceleration voltage of 0.1 to 10 MeV and an irradiation dose of 1 to 500 kGy are appropriate. In the case of ultraviolet (UV), a lamp having a radiation wavelength of 200 nm to 450 nm can be suitably used as the radiation source. Examples of the radiation source include an electron beam (EB), for example, a tungsten filament, and ultraviolet rays (UV), for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultraviolet mercury lamp, a carbon arc lamp, a xenon lamp, and a zirconium lamp. Is mentioned.
本発明のポリオレフィン系樹脂組成物において、構成成分である付加重合系ブロック共重合体（Ｉ）の少なくとも重合体ブロックＡ部分を架橋させるために活性エネルギー線を照射する際には、重合体ブロックＡ部分に架橋が生成するほかにも、付加重合系ブロック共重合体（Ｉ）の重合体ブロックＢ部分、ポリオレフィン系樹脂（ＩＩ）にも一部架橋が生成し得る。しかしながら、これらの架橋が生成しても本発明の目的を何ら阻害するものではない。 In the polyolefin resin composition of the present invention, when the active energy ray is irradiated to crosslink at least the polymer block A portion of the addition polymerization block copolymer (I) as a constituent component, the polymer block A In addition to the formation of crosslinks in the part, partial crosslinks may also be generated in the polymer block B part of the addition polymerization block copolymer (I) and the polyolefin resin (II). However, the formation of these crosslinks does not inhibit the purpose of the present invention.
本発明のポリオレフィン系樹脂組成物には必要に応じて、特に活性エネルギー線として紫外線（ＵＶ）を用いる場合、光重合開始剤をさらに配合することができる。使用できる光重合開始剤としては、例えばベンゾフェノン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、α−メチロールベンゾイン、α−メチロールベンゾインメチルエーテル、α−メトキシベンゾインメチルエーテル、ベンゾインフェニルエーテル、α−ｔ−ブチルベンゾインなどが挙げられるが、これらに限定されるものではない。これらの光重合開始剤は単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。光重合開始剤を配合する場合、そのポリオレフィン系樹脂組成物中の含有量に特に制限はないが、通常、付加重合系ブロック共重合体（Ｉ）とポリオレフィン系樹脂（ＩＩ）の合計質量に対して０．０１〜５質量％の範囲であるのが好ましい。 In the polyolefin resin composition of the present invention, a photopolymerization initiator can be further blended as necessary, particularly when ultraviolet rays (UV) are used as active energy rays. Usable photopolymerization initiators include, for example, benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylol benzoin, α-methylol benzoin methyl ether, α-methoxybenzoin methyl ether, benzoin phenyl ether, α Examples thereof include, but are not limited to, -t-butylbenzoin. These photopolymerization initiators may be used alone or in combination of two or more. When blending the photopolymerization initiator, the content in the polyolefin resin composition is not particularly limited, but is usually based on the total mass of the addition polymerization block copolymer (I) and the polyolefin resin (II). The range of 0.01 to 5% by mass is preferable.
本発明のポリオレフィン系樹脂組成物には、必要に応じて架橋助剤をさらに配合することができる。使用できる架橋助剤にはトリアリルイソシアヌレート、トリアリルシアヌレート、Ｎ，Ｎ’−フェニレンビスマレイミド、エチレングリコールジ（メタ）アクリレート、プロパンジオールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ノナンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレートなどが挙げられる。これらの架橋助剤は１種類を単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。架橋助剤を配合する場合、そのポリオレフィン系樹脂組成物中の含有量に特に制限はないが、通常、付加重合系ブロック共重合体（Ｉ）とポリオレフィン系樹脂（ＩＩ）の合計質量に対して０．０１〜５質量％の範囲であるのが好ましい。 In the polyolefin resin composition of the present invention, a crosslinking aid can be further blended as necessary. The crosslinking aids that can be used include triallyl isocyanurate, triallyl cyanurate, N, N′-phenylenebismaleimide, ethylene glycol di (meth) acrylate, propanediol di (meth) acrylate, butanediol di (meth) acrylate, Examples include hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. These crosslinking aids may be used alone or in combination of two or more. When the crosslinking aid is blended, the content in the polyolefin resin composition is not particularly limited, but is usually based on the total mass of the addition polymerization block copolymer (I) and the polyolefin resin (II). The range of 0.01 to 5% by mass is preferable.
本発明のポリオレフィン系樹脂組成物には、必要に応じて軟化剤をさらに配合することができる。使用できる軟化剤としては、パラフィン系、ナフテン系、芳香族系のプロセスオイルなどの石油系軟化剤；流動パラフィン；落花生油、ロジンなどの植物油系軟化剤などが挙げられる。これらの軟化剤は１種類を単独で、或いは２種類以上を混合して用いることができる。軟化剤を配合する場合、そのポリオレフィン系樹脂組成物中の含有量は、本発明の趣旨を損なわない限り特に制限はないが、通常、付加重合系ブロック共重合体（Ｉ）１００質量部に対して３００質量部以下であり、１００質量部以下であるのが好ましい。 The polyolefin resin composition of the present invention may further contain a softener as necessary. Examples of the softener that can be used include petroleum softeners such as paraffinic, naphthenic and aromatic process oils; liquid paraffin; vegetable oil softeners such as peanut oil and rosin. These softeners can be used alone or in combination of two or more. When blending the softening agent, the content in the polyolefin-based resin composition is not particularly limited as long as it does not impair the gist of the present invention, but is usually based on 100 parts by mass of the addition-polymerized block copolymer (I). 300 parts by mass or less, and preferably 100 parts by mass or less.
本発明のポリオレフィン系樹脂組成物には、充填効果、耐熱性付与、剛性補強などの改質を目的としてフィラーをさらに配合することができる。フィラーとしては、例えばタルク、ガラス繊維、マイカ、カオリン、酸化チタンタルク、クレー、ケイ酸カルシウム、ガラス、ガラス中空球、炭酸カルシウム、炭酸マグネシウム、水酸化アルミニウム、水酸化マグネシウム、カルシウムアルミネート、水酸化カルシウム、ホウ酸亜鉛、ドーソナイト、ポリリン酸アンモニウム、ハイドロタルサイト類、シリカ、アルミナ、酸化チタン、酸化鉄、酸化亜鉛、酸化マグネシウム、酸化スズ、酸化アンチモン、バリウムフェライト、ストロンチウムフェライト、カーボンブラック、グラファイト、炭素繊維、活性炭、炭素中空球、チタン酸カルシウム、炭化ケイ素、木粉、でんぷんなどが挙げられる。 In the polyolefin resin composition of the present invention, a filler can be further blended for the purpose of modification such as filling effect, imparting heat resistance, and rigidity reinforcement. Examples of fillers include talc, glass fiber, mica, kaolin, titanic oxide, clay, calcium silicate, glass, glass hollow sphere, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, calcium aluminate, and hydroxide. Calcium, zinc borate, dosonite, ammonium polyphosphate, hydrotalcite, silica, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbon black, graphite, Examples thereof include carbon fiber, activated carbon, carbon hollow sphere, calcium titanate, silicon carbide, wood flour, and starch.
本発明のポリオレフィン系樹脂組成物には、本発明の趣旨を損なわない範囲内で、例えば熱安定剤、光安定剤、紫外線吸収剤、酸化防止剤、滑剤、着色剤、帯電防止剤、難燃剤、発泡剤、撥水剤、防水剤、蛍光剤、アンチブロッキング剤、金属不活性化剤、抗菌剤などの他の添加剤を配合してもよい。 The polyolefin resin composition of the present invention includes, for example, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antioxidant, a lubricant, a colorant, an antistatic agent, and a flame retardant, as long as the gist of the present invention is not impaired. Other additives such as a foaming agent, a water repellent, a waterproofing agent, a fluorescent agent, an antiblocking agent, a metal deactivator, and an antibacterial agent may be blended.
本発明のポリオレフィン系樹脂組成物には、本発明の趣旨を損なわない範囲内で、柔軟性および流動性などの改質を目的として他の重合体、例えば天然ゴム、合成ポリイソプレンゴム、液状ポリイソプレンゴムおよびその水素添加物、ポリブタジエンゴム、液状ポリブタジエンゴムおよびその水素添加物、スチレン−ブタジエンゴム、クロロプレンゴム、エチレン−プロピレンゴム、アクリルゴム、ブチルゴム、アクリロニトリル−ブタジエンゴム、ポリスチレン−ポリイソプレン−ポリスチレンブロック共重合体やポリスチレン−ポリブタジエン−ポリスチレンブロック共重合体またはそれらの水素添加物などのスチレン系エラストマーなどを配合することが可能である。 The polyolefin resin composition of the present invention includes other polymers such as natural rubber, synthetic polyisoprene rubber, liquid polymer for the purpose of modifying flexibility and fluidity within the scope of the present invention. Isoprene rubber and its hydrogenated product, polybutadiene rubber, liquid polybutadiene rubber and its hydrogenated product, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, acrylic rubber, butyl rubber, acrylonitrile-butadiene rubber, polystyrene-polyisoprene-polystyrene block It is possible to blend a styrene-based elastomer such as a copolymer, a polystyrene-polybutadiene-polystyrene block copolymer, or a hydrogenated product thereof.
本発明のポリオレフィン系樹脂組成物には、本発明の趣旨を損なわない範囲で、耐熱性や耐溶剤性などのバランスをとる補強性樹脂として、比較的分子量の低い熱可塑性ポリエステル樹脂、ポリアミド樹脂、ポリフェニレンエーテル樹脂などを配合することが可能である。 The polyolefin-based resin composition of the present invention has a relatively low molecular weight thermoplastic polyester resin, polyamide resin, as a reinforcing resin that balances heat resistance, solvent resistance, and the like within a range that does not impair the spirit of the present invention. A polyphenylene ether resin or the like can be blended.
本発明のポリオレフィン系樹脂組成物は、例えば、通常の槽式混合機、高速攪拌機、密閉式ニーダー、インターナルミキサー、一軸押出機や二軸押出機などの押出機などを用いて、必要に応じて窒素雰囲気中で、通常、１３０℃〜２３０℃の範囲で付加重合系ブロック共重合体（Ｉ）、ポリオレフィン系樹脂（ＩＩ）、必要に応じて光重合開始剤、架橋助剤、軟化剤、その他の任意添加成分を溶融混練して調製することができる。得られるポリオレフィン系樹脂組成物は、その用途、使用態様などに応じて適切な形態にしておくことができ、例えばブロック状、粒状、フレーク状、ペレット状、棒状、フィルム状、シート状などの形態において、それぞれ電線被覆、各種ケーブルの被覆、チューブ、フィルム、シート用途などに用いることができる。 The polyolefin resin composition of the present invention can be used, for example, by using an ordinary tank mixer, a high speed stirrer, a closed kneader, an internal mixer, an extruder such as a single screw extruder or a twin screw extruder, and the like. In a nitrogen atmosphere, usually in the range of 130 ° C. to 230 ° C., an addition polymerization block copolymer (I), a polyolefin resin (II), if necessary, a photopolymerization initiator, a crosslinking aid, a softening agent, Other optional additives can be prepared by melt-kneading. The resulting polyolefin-based resin composition can be made into an appropriate form according to its use, usage mode, etc., for example, in the form of a block, granule, flake, pellet, rod, film, sheet, etc. Can be used for wire coating, various cable coatings, tubes, films, sheets and the like.
なお、上記混練中に、無水マレイン酸および過酸化物（例えば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）をさらに添加することにより、付加重合系ブロック共重合体（Ｉ）およびポリオレフィン系樹脂（ＩＩ）の一方または両方が無水マレイン酸変性され、フィラー分散性および／またはポリアミド、ポリカーボネート、ポリブチレンテレフタレート、ポリエチレンテレフタレートなどの極性樹脂との複層成形性、接着特性などの特性がさらに付与されたポリオレフィン系樹脂組成物を得ることもできる。 During the kneading, maleic anhydride and peroxide (for example, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane) are further added. As a result, one or both of the addition polymerization block copolymer (I) and the polyolefin resin (II) are modified with maleic anhydride, and the filler dispersibility and / or the polarity of polyamide, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, etc. It is also possible to obtain a polyolefin resin composition further imparted with properties such as multi-layer moldability with resin and adhesive properties.
上記の方法で得られたポリオレフィン系樹脂組成物は、各種成形法、例えば射出成形法（インサート成形法、二色成形法、サンドイッチ成形法、ガスインジェクション成形法など）、押出成形法、インフレーション成形法、Ｔダイフィルム成形法、ラミネート成形法、ブロー成形法、中空成形法、圧縮成形法、カレンダー成形法などの成形法により成形、加工した後、活性エネルギー線を照射することで架橋を生成させることができる。
このようにして成形および加工された成形品は、電線被覆材、食品包装用フィルム、繊維包装用フィルムなどのフィルム、加工紙、パイプ、シート、文具、食品容器、日用雑貨品などの用途に使用できる。
The polyolefin-based resin composition obtained by the above method can be produced by various molding methods such as injection molding methods (insert molding method, two-color molding method, sandwich molding method, gas injection molding method, etc.), extrusion molding method, inflation molding method. , After forming and processing by T die film molding method, laminate molding method, blow molding method, hollow molding method, compression molding method, calender molding method, etc., to generate a crosslink by irradiating with active energy rays Can do.
Molded products molded and processed in this way are used for applications such as electric wire coating materials, films for food packaging, films for textile packaging, processed paper, pipes, sheets, stationery, food containers, daily goods, etc. Can be used.
また、上記の方法で得られたポリオレフィン系樹脂組成物は、かかるポリオレフィン系樹脂組成物によって形成される層と、ポリオレフィン系樹脂、例えばポリプロピレンなどの他のポリオレフィン系樹脂によって形成される層、さらに必要に応じて接着層などの他の層を設けて積層させることによって、柔軟性を有する積層体として使用することができる。 In addition, the polyolefin resin composition obtained by the above method includes a layer formed from the polyolefin resin composition, a layer formed from a polyolefin resin, for example, another polyolefin resin such as polypropylene, and the like. Accordingly, by providing and laminating other layers such as an adhesive layer, it can be used as a flexible laminate.
さらに、上記の方法で得られたポリオレフィン系樹脂組成物にロジン系樹脂、テルペン系樹脂、脂肪族系石油樹脂、芳香族系石油樹脂、脂環族系石油樹脂、クマロン・インデン樹脂、スチレン系樹脂、アルキルフェノール樹脂、キシレン樹脂などの粘着付与樹脂を、該ポリオレフィン系樹脂組成物に対して好ましくは１〜５００質量部の範囲で配合して粘着性を付与し、得られた該組成物を例えばフィルムに成形して、接着性を有するフィルムとして使用することもできる。 Furthermore, the rosin resin, terpene resin, aliphatic petroleum resin, aromatic petroleum resin, alicyclic petroleum resin, coumarone / indene resin, styrene resin are added to the polyolefin resin composition obtained by the above method. A tackifying resin such as an alkylphenol resin or a xylene resin, preferably in the range of 1 to 500 parts by mass with respect to the polyolefin-based resin composition to impart tackiness. It can also shape | mold and use as a film which has adhesiveness.
以下、実施例などにより本発明をさらに具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。
なお、以下の実施例および比較例では、次の方法により、得られたポリオレフィン系樹脂組成物の硬度、力学的特性（破断強度、破断伸度）、耐熱性および耐溶剤性の評価を行なった。
EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, this invention is not limited to these Examples at all.
In the following examples and comparative examples, the hardness, mechanical properties (breaking strength, breaking elongation), heat resistance and solvent resistance of the obtained polyolefin resin compositions were evaluated by the following methods. .
１）硬度
ＪＩＳ Ｋ ６２５３に記載された方法に従って測定した。すなわち、実施例および比較例で得られたポリオレフィン系樹脂組成物より作製した縦１５ｃｍ×横１５ｃｍ×厚さ０．２ｃｍのシートを３枚重ねて、ＡＳＴＭ Ｄ硬度計を用いて測定し、柔軟性の指標とした。
1) Hardness Measured according to the method described in JIS K 6253. That is, three sheets of 15 cm long × 15 cm wide × 0.2 cm thick produced from the polyolefin resin compositions obtained in the examples and comparative examples were stacked and measured using an ASTM D hardness meter, It was used as an index.
２）力学的特性（破断強度、破断伸度）
ＪＩＳ Ｋ ６２５１に記載された方法に従って測定した。すなわち、実施例および比較例で得られたポリオレフィン系樹脂組成物より作製した縦１５ｃｍ×横１５ｃｍ×厚さ０．１ｃｍのシートからダンベル状５号形の試験片を打ち抜き、インストロン万能試験機を使用して、２３℃および８０℃の２種の条件下で、引張速度５００ｍｍ／ｍｉｎで引張試験を行い、破断強度（ＭＰａ）および破断伸度（％）を測定した。
2) Mechanical properties (breaking strength, breaking elongation)
The measurement was performed according to the method described in JIS K 6251. That is, a dumbbell-shaped No. 5 test piece was punched out from a sheet of 15 cm long × 15 cm wide × 0.1 cm thick prepared from the polyolefin resin compositions obtained in Examples and Comparative Examples, and an Instron universal testing machine was used. In use, a tensile test was performed at a tensile speed of 500 mm / min under two conditions of 23 ° C. and 80 ° C., and the breaking strength (MPa) and the breaking elongation (%) were measured.
３）耐熱性
３−１）破断強度残率、破断伸度残率
ＪＩＳ Ｃ ３００５の第１７項に記載された方法に準じて測定した。すなわち、実施例および比較例で得られたポリオレフィン系樹脂組成物より作製した縦１５ｃｍ×横１５ｃｍ×厚さ０．１ｃｍのシートを１２０℃下で９６時間放置し、該シートよりＪＩＳ Ｋ ６２５１に規定されたダンベル状５号形の試験片を打ち抜き、インストロン万能試験機を使用して、２３℃の条件下で、引張速度５００ｍｍ／ｍｉｎで引張試験を行い、破断強度（ＭＰａ）および破断伸度（％）を測定し、次式により破断強度残率および破断伸度残率を算出した。
破断強度残率（％）＝１００×Ｆ１／Ｆ０
但し、Ｆ０：加熱前の破断強度（ＭＰａ）
Ｆ１：加熱処理後の破断強度（ＭＰａ）
破断伸度残率（％）＝１００×Ｌ１／Ｌ０
但し、Ｌ０：加熱前の破断伸度（％）
Ｌ１：加熱処理後の破断伸度（％）
3) Heat resistance 3-1) Breaking strength residual rate, breaking elongation residual rate It measured according to the method described in the 17th item of JISC3005. That is, a sheet of length 15 cm × width 15 cm × thickness 0.1 cm prepared from the polyolefin resin compositions obtained in Examples and Comparative Examples was allowed to stand at 120 ° C. for 96 hours, and the sheet was specified in JIS K 6251. The dumbbell-shaped No. 5 specimen was punched out, and a tensile test was conducted at 23 ° C. and a tensile speed of 500 mm / min using an Instron universal testing machine, and the breaking strength (MPa) and breaking elongation were measured. (%) Was measured, and the residual strength at break and the residual elongation at break were calculated by the following equations.
Breaking strength residual rate (%) = 100 × F 1 / F 0
However, F 0 : Breaking strength before heating (MPa)
F 1 : Breaking strength after heat treatment (MPa)
Breaking elongation residual rate (%) = 100 × L 1 / L 0
Where L 0 : elongation at break (%) before heating
L 1 : Elongation at break after heat treatment (%)
３−２）加熱変形率
ＪＩＳ Ｃ ３００５の第２３項に記載された方法に準じて測定した。すなわち、実施例および比較例で得られたポリオレフィン系樹脂組成物より作製した縦１５ｃｍ×横１５ｃｍ×厚さ０．２ｃｍのシートから長さ３ｃｍ×幅１．５ｃｍの試験片を打ち抜いた。その試験片と加熱変形試験機を予め１５０℃で３０分間加熱した後、試験片を測定装置の平行板間の半径５ｍｍ、長さ３５ｍｍの半円状の丸棒の上に置き、平行板の上から１ｋｇの荷重を加え、さらに同温度で３０分間静置した後、そのままの状態で試験片の厚さを測り、加熱後の厚さと加熱前の厚さから加熱変形率を次式によって算出した。加熱変形率が小さいほど、耐熱性に優れるといえる。
加熱変形率（％）＝１００×（Ｍ０−Ｍ１）／Ｍ０
但し、Ｍ０：加熱前の試験片の厚さ（ｍｍ）
Ｍ１：加熱変形後の試験片の厚さ（ｍｍ）
3-2) Heat distortion rate Measured according to the method described in item 23 of JIS C 3005. That is, a test piece having a length of 3 cm and a width of 1.5 cm was punched from a sheet having a length of 15 cm, a width of 15 cm, and a thickness of 0.2 cm prepared from the polyolefin resin compositions obtained in Examples and Comparative Examples. The test piece and the heat deformation tester were previously heated at 150 ° C. for 30 minutes, and then the test piece was placed on a semicircular round bar having a radius of 5 mm and a length of 35 mm between the parallel plates of the measuring apparatus. After applying a 1 kg load from the top and allowing to stand at the same temperature for 30 minutes, measure the thickness of the test piece as it is, and calculate the heating deformation rate from the thickness after heating and the thickness before heating by the following formula: did. It can be said that the smaller the heating deformation rate, the better the heat resistance.
Heat deformation rate (%) = 100 × (M 0 −M 1 ) / M 0
However, M 0 : thickness of the test piece before heating (mm)
M 1 : thickness of the test piece after heat deformation (mm)
３−３）変形温度
実施例および比較例で得られたポリオレフィン系樹脂組成物より作製した縦１５ｃｍ×横１５ｃｍ×厚さ０．１ｃｍのシートから、ＪＩＳ Ｋ ６２５１に規定されたダンベル状６号形の試験片を打ち抜いた。該試験片をオーブン中に７２ｇの荷重をかけた状態で吊り下げ、３℃／ｍｉｎでオーブン内を昇温し、試験片が１００％伸びた時の温度を測定し、耐熱性の指標とした。
3-3) Deformation temperature A dumbbell-shaped No. 6 defined in JIS K 6251 from a sheet of 15 cm long × 15 cm wide × 0.1 cm thick prepared from the polyolefin resin compositions obtained in Examples and Comparative Examples The test piece was punched out. The test piece was suspended in an oven under a load of 72 g, the inside of the oven was heated at 3 ° C./min, and the temperature when the test piece was 100% stretched was measured as a heat resistance index. .
４）トルエン抽出率
容量５０ｍｌのスクリュー管にトルエン３０ｍｌを入れ、その中に、力学的特性の測定に使用したダンベル状５号形試験片の一部を切り取って予め質量を精秤した試験片（約０．３ｇ）を入れた。このスクリュー管を、振盪機を用いて２５℃で１２時間振盪した後、試験片を取り出して、１００℃、１８０分間減圧下に乾燥し、乾燥後の試験片の質量を測定した。得られた値から、下式に従ってトルエン抽出率を算出し、その結果を耐溶剤性の指標とした。
トルエン抽出率（％）＝１００×（Ａ０−Ａ１）／Ａ０
但し、Ａ０：試験前の試験片の質量（ｇ）
Ａ１：試験後の試験片の質量（ｇ）
4) Toluene extraction rate 30 ml of toluene was put into a screw tube with a capacity of 50 ml, and a part of the dumbbell-shaped No. 5 test piece used for measuring the mechanical properties was cut out and the mass was precisely weighed in advance ( About 0.3 g). The screw tube was shaken at 25 ° C. for 12 hours using a shaker, and then the test piece was taken out and dried under reduced pressure at 100 ° C. for 180 minutes, and the mass of the dried test piece was measured. From the obtained value, the toluene extraction rate was calculated according to the following formula, and the result was used as an index of solvent resistance.
Toluene extraction rate (%) = 100 × (A 0 −A 1 ) / A 0
However, A0 : Mass (g) of the test piece before a test
A 1 : Mass of the test piece after the test (g)
参考例１
撹拌装置付き耐圧容器中に、シクロヘキサン３９ｋｇ、ｓｅｃ−ブチルリチウム（１１質量％、シクロヘキサン溶液）１８０ｍｌを加え、この溶液にｐ−メチルスチレンとスチレンの混合液（ｐ−メチルスチレン／スチレン＝５０／５０（質量比））１．３２ｋｇを３０分かけて加えて５０℃で６０分間重合し、次にイソプレンとブタジエンの混合物（イソプレン／ブタジエン＝５０／５０（質量比））１０．７ｋｇを６０分かけて加えて５０℃で９０分間重合し、さらにｐ−メチルスチレンとスチレンの混合液（ｐ−メチルスチレン／スチレン＝５０／５０（質量比））１．３２ｋｇを３０分かけて加えて５０℃で６０分間重合することで、ポリ（ｐ−メチルスチレン／スチレン）−ポリ（イソプレン／ブタジエン）−ポリ（ｐ−メチルスチレン／スチレン）トリブロック共重合体を含む反応混合液を得た。得られたブロック共重合体の数平均分子量は９４０００であり、１Ｈ−ＮＭＲによって測定したｐ−メチルスチレンとスチレンを合わせた含有量は２０質量％であった。
上記ブロック共重合体を含む反応混合液に、オクチル酸ニッケル（６４質量％、シクロヘキサン溶液）５６ｇにトリイソプロピルアルミニウム（２０質量％、シクロヘキサン溶液）３８０ｇを加えて別途調製した水素添加触媒を添加し、８０℃、１ＭＰａの水素雰囲気下で水素添加反応を行ない、上記したポリ（ｐ−メチルスチレン／スチレン）−ポリ（イソプレン／ブタジエン）−ポリ（ｐ−メチルスチレン／スチレン）トリブロック共重合体の水素添加物（以下、これをブロック共重合体（Ｉ）−１と称する）を得た。得られたブロック共重合体（Ｉ）−１の数平均分子量は１０００００であり、１Ｈ−ＮＭＲによって測定した、ｐ−メチルスチレンとスチレンを合わせた含有量および水素添加率はそれぞれ１９質量％、９７％であった。
Reference example 1
In a pressure vessel equipped with a stirrer, 39 kg of cyclohexane and 180 ml of sec-butyllithium (11% by mass, cyclohexane solution) were added, and a mixed solution of p-methylstyrene and styrene (p-methylstyrene / styrene = 50/50) was added to this solution. (Mass ratio)) 1.32 kg was added over 30 minutes, polymerized at 50 ° C. for 60 minutes, and then 10.7 kg of a mixture of isoprene and butadiene (isoprene / butadiene = 50/50 (mass ratio)) over 60 minutes. Then, polymerization is carried out at 50 ° C. for 90 minutes, and 1.32 kg of a mixed solution of p-methylstyrene and styrene (p-methylstyrene / styrene = 50/50 (mass ratio)) is added over 30 minutes at 50 ° C. By polymerizing for 60 minutes, poly (p-methylstyrene / styrene) -poly (isoprene / butadiene) -poly (p-methyls) To obtain a reaction mixture containing alkylene / styrene) triblock copolymer. The number average molecular weight of the obtained block copolymer was 94000, and the combined content of p-methylstyrene and styrene measured by 1 H-NMR was 20% by mass.
A hydrogenation catalyst prepared separately by adding 380 g of triisopropylaluminum (20 mass%, cyclohexane solution) to 56 g of nickel octylate (64 mass%, cyclohexane solution) is added to the reaction mixture containing the block copolymer, Hydrogenation reaction is performed in a hydrogen atmosphere at 80 ° C. and 1 MPa, and hydrogen of the poly (p-methylstyrene / styrene) -poly (isoprene / butadiene) -poly (p-methylstyrene / styrene) triblock copolymer described above An additive (hereinafter referred to as block copolymer (I) -1) was obtained. The number average molecular weight of the obtained block copolymer (I) -1 is 100,000, and the content and hydrogenation rate of p-methylstyrene and styrene, as measured by 1 H-NMR, are 19% by mass, 97%.
参考例２
撹拌装置付き耐圧容器中に、シクロヘキサン３９ｋｇ、ｓｅｃ−ブチルリチウム（１１質量％、シクロヘキサン溶液）２６５ｍｌを加え、この溶液にｐ−メチルスチレン２．２５ｋｇを３０分かけて加えて５０℃で６０分間重合し、次にテトラヒドロフラン１００ｍｌを加えたのち、ブタジエン１０．５ｋｇを６０分かけて加えて５０℃で９０分間重合し、さらにｐ−メチルスチレン２．２５ｋｇを３０分かけて加えて５０℃で６０分間重合することで、ポリｐ−メチルスチレン−ポリブタジエン−ポリｐ−メチルスチレントリブロック共重合体を含む反応混合液を得た。得られたブロック共重合体の数平均分子量は８００００であり、１Ｈ−ＮＭＲによって測定したｐ−メチルスチレンの含有量は３０質量％であった。
上記ブロック共重合体を含む反応混合液に、オクチル酸ニッケル（６４質量％、シクロヘキサン溶液）５６ｇにトリイソプロピルアルミニウム（２０質量％、シクロヘキサン溶液）３８０ｇを加えて別途調製した水素添加触媒を添加し、８０℃、１ＭＰａの水素雰囲気下で水素添加反応を行い、上記したポリｐ−メチルスチレン−ポリブタジエン−ポリｐ−メチルスチレントリブロック共重合体の水素添加物（以下、これをブロック共重合体（Ｉ）−２と称する）を得た。得られたブロック共重合体（Ｉ）−２の数平均分子量は８１０００であり、１Ｈ−ＮＭＲによって測定したｐ−メチルスチレン含有量および水素添加率はそれぞれ２９質量％、９７％であった。
Reference example 2
In a pressure-resistant vessel equipped with a stirrer, 39 kg of cyclohexane and 265 ml of sec-butyllithium (11% by mass, cyclohexane solution) are added, and 2.25 kg of p-methylstyrene is added to this solution over 30 minutes, and polymerization is performed at 50 ° C. for 60 minutes. Next, after adding 100 ml of tetrahydrofuran, 10.5 kg of butadiene was added over 60 minutes and polymerized at 50 ° C. for 90 minutes, and 2.25 kg of p-methylstyrene was added over 30 minutes and then at 50 ° C. for 60 minutes. By polymerization, a reaction mixture containing a poly p-methylstyrene-polybutadiene-poly p-methylstyrene triblock copolymer was obtained. The number average molecular weight of the obtained block copolymer was 80000, and the content of p-methylstyrene measured by 1 H-NMR was 30% by mass.
A hydrogenation catalyst prepared separately by adding 380 g of triisopropylaluminum (20 mass%, cyclohexane solution) to 56 g of nickel octylate (64 mass%, cyclohexane solution) is added to the reaction mixture containing the block copolymer, A hydrogenation reaction is carried out in a hydrogen atmosphere at 80 ° C. and 1 MPa, and a hydrogenated product of the above-mentioned poly p-methylstyrene-polybutadiene-poly p-methylstyrene triblock copolymer (hereinafter referred to as a block copolymer (I ) -2). The number average molecular weight of the obtained block copolymer (I) -2 was 81000, and the p-methylstyrene content and the hydrogenation rate measured by 1 H-NMR were 29% by mass and 97%, respectively.
参考例３
撹拌装置付き耐圧容器中に、シクロヘキサン３９ｋｇ、ｓｅｃ−ブチルリチウム（１１質量％、シクロヘキサン溶液）１８０ｍｌを加え、この溶液にスチレン１．３２ｋｇを３０分かけて加えて５０℃で３０分間重合し、次にイソプレンとブタジエンの混合物（イソプレン／ブタジエン＝５０／５０（質量比））１０．７ｋｇを６０分かけて加えて５０℃で９０分間重合し、さらにスチレン１．３２ｋｇを３０分かけて加えて５０℃で６０分間重合することで、ポリスチレン−ポリ（イソプレン／ブタジエン）−ポリスチレントリブロック共重合体を含む反応混合液を得た。得られたブロック共重合体の数平均分子量は９４０００であり、１Ｈ−ＮＭＲによって測定したスチレン含有量は２０質量％であった。
上記ブロック共重合体を含む反応混合液に、オクチル酸ニッケル（６４質量％、シクロヘキサン溶液）５６ｇにトリイソプロピルアルミニウム（２０質量％、シクロヘキサン溶液）３８０ｇを加えて別途調製した水素添加触媒を添加し、８０℃、１ＭＰａの水素雰囲気下で水素添加反応を行い、上記したポリスチレン−ポリ（イソプレン／ブタジエン）−ポリスチレントリブロック共重合体の水素添加物（以下、これをブロック共重合体１と称する）を得た。得られたブロック共重合体１の数平均分子量は１０００００であり、１Ｈ−ＮＭＲによって測定したスチレン含有量および水素添加率はそれぞれ１９質量％、９７％であった。
Reference example 3
In a pressure vessel equipped with a stirrer, 39 kg of cyclohexane and 180 ml of sec-butyllithium (11% by mass, cyclohexane solution) are added, 1.32 kg of styrene is added to this solution over 30 minutes, and polymerization is performed at 50 ° C. for 30 minutes. 10.7 kg of a mixture of isoprene and butadiene (isoprene / butadiene = 50/50 (mass ratio)) was added over 60 minutes to polymerize at 50 ° C. for 90 minutes, and 1.32 kg of styrene was further added over 30 minutes to 50 Polymerization was carried out at 60 ° C. for 60 minutes to obtain a reaction mixture containing a polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer. The number average molecular weight of the obtained block copolymer was 94000, and the styrene content measured by 1 H-NMR was 20% by mass.
A hydrogenation catalyst prepared separately by adding 380 g of triisopropylaluminum (20 mass%, cyclohexane solution) to 56 g of nickel octylate (64 mass%, cyclohexane solution) is added to the reaction mixture containing the block copolymer, A hydrogenation reaction is carried out in a hydrogen atmosphere at 80 ° C. and 1 MPa, and the above hydrogenated product of polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer (hereinafter referred to as block copolymer 1) is obtained. Obtained. The number average molecular weight of the obtained block copolymer 1 was 100,000, and the styrene content and hydrogenation rate measured by 1 H-NMR were 19% by mass and 97%, respectively.
参考例４
撹拌装置付き耐圧容器中に、シクロヘキサン３９ｋｇ、ｓｅｃ−ブチルリチウム（１１質量％、シクロヘキサン溶液）２６５ｍｌを加え、この溶液にスチレン２．２５ｋｇを３０分かけて加えて５０℃で３０分間重合し、次にテトラヒドロフラン１００ｍｌを加えたのち、ブタジエン１０．５ｋｇを６０分かけて加えて５０℃で９０分間重合し、さらにスチレン２．２５ｋｇを３０分かけて加えて５０℃で３０分間重合することで、ポリスチレン−ポリブタジエン−ポリスチレントリブロック共重合体を含む反応混合液を得た。得られたブロック共重合体の数平均分子量は８００００であり、１Ｈ−ＮＭＲによって測定した、スチレンの含有量は３０質量％であった。
上記ブロック共重合体を含む反応混合液に、オクチル酸ニッケル（６４質量％、シクロヘキサン溶液）５６ｇにトリイソプロピルアルミニウム（２０質量％、シクロヘキサン溶液）３８０ｇを加えて別途調製した水素添加触媒を添加し、８０℃、１ＭＰａの水素雰囲気下で水素添加反応を行い、上記したポリスチレン−ポリブタジエン−ポリスチレントリブロック共重合体の水素添加物（以下、これをブロック共重合体２と称する）を得た。得られたブロック共重合体２の数平均分子量は８１０００であり、１Ｈ−ＮＭＲによって測定した、スチレン含有量および水素添加率はそれぞれ２９質量％、９７％であった。
Reference example 4
In a pressure vessel equipped with a stirrer, 39 kg of cyclohexane and 265 ml of sec-butyllithium (11% by mass, cyclohexane solution) are added, and 2.25 kg of styrene is added to this solution over 30 minutes, followed by polymerization at 50 ° C. for 30 minutes. After adding 100 ml of tetrahydrofuran to 10.5 kg of butadiene over 60 minutes and polymerizing at 50 ° C. for 90 minutes, further adding 2.25 kg of styrene over 30 minutes and polymerizing at 50 ° C. for 30 minutes, polystyrene A reaction mixture containing a polybutadiene-polystyrene triblock copolymer was obtained. The number average molecular weight of the obtained block copolymer was 80000, and the styrene content measured by 1 H-NMR was 30% by mass.
A hydrogenation catalyst prepared separately by adding 380 g of triisopropylaluminum (20 mass%, cyclohexane solution) to 56 g of nickel octylate (64 mass%, cyclohexane solution) is added to the reaction mixture containing the block copolymer, Hydrogenation reaction was performed in a hydrogen atmosphere at 80 ° C. and 1 MPa to obtain a hydrogenated product of the above-described polystyrene-polybutadiene-polystyrene triblock copolymer (hereinafter referred to as block copolymer 2). The number average molecular weight of the obtained block copolymer 2 was 81000, and the styrene content and the hydrogenation rate measured by 1 H-NMR were 29% by mass and 97%, respectively.
〈実施例１〜６〉
参考例１および２で得られたブロック共重合体（Ｉ）−１、ブロック共重合体（Ｉ）−２、ポリオレフィン系樹脂［ＰＥ１：「ノバテックＬＤ ＥＨ３０」（商品名、日本ポリケム（株）社製、低密度ポリエチレン、ＭＦＲ（１９０℃、２．１６ｋｇ荷重）＝２．０ｇ／１０分）、ＰＥ２：「ウルトゼックス １５２０Ｌ」（商品名、三井化学（株）社製、線状低密度ポリエチレン、ＭＦＲ（１９０℃、２．１６ｋｇ荷重）＝２．３ｇ／１０分）］、および酸化防止剤を表１に示す配合（すべて質量部）で、二軸押出機にて２００℃で溶融混練してポリオレフィン系樹脂組成物を得た。得られたポリオレフィン系樹脂組成物より、プレス成形（成形温度２００℃、プレス圧力１０ＭＰａ、プレス時間３分）によって縦１５ｃｍ×横１５ｃｍ×厚さ０．１ｃｍのシートおよび縦１５ｃｍ×横１５ｃｍ×厚さ０．２ｃｍのシートを作製した後、電子線を加速電圧５．０ＭｅＶで２００ｋＧｙ照射した。このようにして得られたポリオレフィン系樹脂組成物のシートを用いて、上記した各種性能を評価した。結果を表１に示す。
<Examples 1-6>
Block copolymer (I) -1, block copolymer (I) -2 obtained in Reference Examples 1 and 2, polyolefin resin [PE1: “Novatech LD EH30” (trade name, Nippon Polychem Co., Ltd.) Manufactured, low density polyethylene, MFR (190 ° C., 2.16 kg load) = 2.0 g / 10 min), PE2: “Ultzex 1520L” (trade name, manufactured by Mitsui Chemicals, Inc., linear low density polyethylene, MFR (190 ° C., 2.16 kg load) = 2.3 g / 10 min)], and the antioxidants shown in Table 1 (all parts by mass) were melt kneaded at 200 ° C. in a twin screw extruder. A polyolefin resin composition was obtained. From the obtained polyolefin-based resin composition, a sheet of 15 cm long × 15 cm wide × 0.1 cm thick and 15 cm long × 15 cm wide × thickness by press molding (molding temperature 200 ° C., press pressure 10 MPa, press time 3 minutes). After producing a 0.2 cm sheet, an electron beam was irradiated with an acceleration voltage of 5.0 MeV at 200 kGy. Using the polyolefin resin composition sheet thus obtained, the various performances described above were evaluated. The results are shown in Table 1.
〈比較例１〜６〉
実施例１〜６において、ポリオレフィン系樹脂組成物よりプレス成形によってシートを作製した後、電子線を照射せずに、得られたシートの上記した各種性能を評価した。結果を表２に示す。
<Comparative Examples 1-6>
In Examples 1-6, after producing a sheet | seat by press molding from the polyolefin-type resin composition, various above-described performances of the obtained sheet | seat were evaluated, without irradiating an electron beam. The results are shown in Table 2.
〈比較例７〜１２〉
参考例１および２で得られたブロック共重合体（Ｉ）−１、ブロック共重合体（Ｉ）−２の代わりに、参考例３および４で得られたブロック共重合体１、ブロック共重合体２を用いた以外は実施例１〜６と同様にしてポリオレフィン系樹脂組成物のシートを作製し、上記した各種性能を評価した。結果を表３および表４に示す。
<Comparative Examples 7-12>
Instead of the block copolymer (I) -1 and the block copolymer (I) -2 obtained in Reference Examples 1 and 2, the block copolymer 1 and the block copolymer obtained in Reference Examples 3 and 4 were used. Except having used the union 2, the sheet | seat of the polyolefin-type resin composition was produced like Example 1-6, and the above-mentioned various performance was evaluated. The results are shown in Table 3 and Table 4.
〈比較例１３〜１４〉
参考例１〜４で得られたブロック共重合体のいずれをも配合せず、ポリオレフィン系樹脂（ＰＥ１またはＰＥ２）および酸化防止剤のみを配合して、実施例１〜６と同様にしてシートを作製し、上記した各種性能を評価した。結果を表４に示す。
<Comparative Examples 13-14>
Neither of the block copolymers obtained in Reference Examples 1 to 4 were blended, but only a polyolefin resin (PE1 or PE2) and an antioxidant were blended, and sheets were obtained in the same manner as in Examples 1 to 6. It produced and evaluated various performances mentioned above. The results are shown in Table 4.
表１および表２の結果より、実施例１〜６のポリオレフィン系樹脂組成物より得られる成形体は、比較例１〜６の成形体に比べて、活性エネルギー線を照射して架橋することにより、力学的特性、耐熱性、耐溶剤性に優れることがわかる。 From the results of Table 1 and Table 2, the molded bodies obtained from the polyolefin-based resin compositions of Examples 1 to 6 are crosslinked by irradiating active energy rays as compared with the molded bodies of Comparative Examples 1 to 6. It can be seen that it is excellent in mechanical properties, heat resistance and solvent resistance.
また、表１、表３および表４の結果より、実施例１〜６のポリオレフィン系樹脂組成物より得られる成形体は、スチレン単位のみからなるブロックをハードセグメントとするブロック共重合体を用いた比較例７〜１２のポリオレフィン系樹脂組成物より得られる成形体に比べ、特に耐熱性および耐溶剤性に優れ、比較例１３〜１４のポリオレフィン系樹脂のみより得られる成形体に比べ、特に柔軟性および耐熱性に優れることがわかる。 Moreover, from the results of Tables 1, 3 and 4, the molded products obtained from the polyolefin resin compositions of Examples 1 to 6 were block copolymers having a hard segment as a block composed only of styrene units. Compared to molded articles obtained from the polyolefin resin compositions of Comparative Examples 7 to 12, particularly excellent heat resistance and solvent resistance, and particularly flexible compared to molded articles obtained only from the polyolefin resins of Comparative Examples 13 to 14. It can also be seen that it has excellent heat resistance.
本発明によれば、柔軟性、耐熱性、力学的特性および耐溶剤性のバランスに優れたポリオレフィン系樹脂組成物を得ることができる。得られるポリオレフィン系樹脂組成物は、かかる特徴を活かして、電線被覆、各種ケーブルの被覆、チューブ、食品包装用フィルム、繊維包装用フィルムなどのフィルム、加工紙、パイプ、シート、文具、食品容器、日用雑貨品などの用途に有効に使用することができる。
According to the present invention, a polyolefin resin composition having an excellent balance of flexibility, heat resistance, mechanical properties and solvent resistance can be obtained. Taking advantage of such characteristics, the polyolefin resin composition obtained is a wire coating, various cable coatings, tubes, films for food packaging, films for textile packaging, processed paper, pipes, sheets, stationery, food containers, It can be used effectively for daily goods.
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