JP2008031374A - Resin composition for laminate and laminate - Google Patents
Resin composition for laminate and laminate Download PDFInfo
- Publication number
- JP2008031374A JP2008031374A JP2006209238A JP2006209238A JP2008031374A JP 2008031374 A JP2008031374 A JP 2008031374A JP 2006209238 A JP2006209238 A JP 2006209238A JP 2006209238 A JP2006209238 A JP 2006209238A JP 2008031374 A JP2008031374 A JP 2008031374A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- component
- polymer
- production example
- polymerization
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 30
- 239000005977 Ethylene Substances 0.000 claims abstract description 160
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 145
- 229920005989 resin Polymers 0.000 claims abstract description 91
- 239000011347 resin Substances 0.000 claims abstract description 91
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 23
- 239000004711 α-olefin Substances 0.000 claims abstract description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 18
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 72
- 238000000465 moulding Methods 0.000 claims description 30
- 238000001125 extrusion Methods 0.000 claims description 28
- 238000003475 lamination Methods 0.000 claims description 17
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 26
- 210000003739 neck Anatomy 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 246
- 238000004519 manufacturing process Methods 0.000 description 207
- 229920000573 polyethylene Polymers 0.000 description 129
- 239000011949 solid catalyst Substances 0.000 description 113
- 229920000642 polymer Polymers 0.000 description 105
- 238000006116 polymerization reaction Methods 0.000 description 91
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 90
- 150000001875 compounds Chemical class 0.000 description 76
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 74
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 73
- 239000003054 catalyst Substances 0.000 description 66
- 239000002002 slurry Substances 0.000 description 66
- 238000005259 measurement Methods 0.000 description 57
- 239000007787 solid Substances 0.000 description 53
- 238000002360 preparation method Methods 0.000 description 52
- 125000004429 atom Chemical group 0.000 description 43
- 239000000243 solution Substances 0.000 description 38
- 230000000704 physical effect Effects 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 35
- -1 ethylenebis (indenyl) hafnium dichloride Chemical compound 0.000 description 34
- 239000007789 gas Substances 0.000 description 30
- 229910052726 zirconium Inorganic materials 0.000 description 27
- 239000006228 supernatant Substances 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 18
- 238000001816 cooling Methods 0.000 description 18
- 238000010908 decantation Methods 0.000 description 18
- 229920001684 low density polyethylene Polymers 0.000 description 18
- 239000004702 low-density polyethylene Substances 0.000 description 18
- 238000002156 mixing Methods 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 150000002430 hydrocarbons Chemical group 0.000 description 14
- 229920005992 thermoplastic resin Polymers 0.000 description 14
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 150000003623 transition metal compounds Chemical class 0.000 description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 239000002685 polymerization catalyst Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000012685 gas phase polymerization Methods 0.000 description 6
- 239000012968 metallocene catalyst Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000737 periodic effect Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 150000003624 transition metals Chemical group 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920006324 polyoxymethylene Polymers 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- JJDZBQREKCLIOM-UHFFFAOYSA-L CC1=CC(C=C1)[Zr](Cl)(Cl)(C1C=CC(C)=C1)=[Si](C)C Chemical compound CC1=CC(C=C1)[Zr](Cl)(Cl)(C1C=CC(C)=C1)=[Si](C)C JJDZBQREKCLIOM-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
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- 239000004721 Polyphenylene oxide Substances 0.000 description 2
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
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- 238000000071 blow moulding Methods 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
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- 229910052735 hafnium Chemical group 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
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- LVVOITZLMNPGOL-UHFFFAOYSA-N 2-methyloxaluminane;toluene Chemical compound C[Al]1CCCCO1.CC1=CC=CC=C1 LVVOITZLMNPGOL-UHFFFAOYSA-N 0.000 description 1
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- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
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- TXDMTLNRJWRPEW-UHFFFAOYSA-N C(C)(C)=[Zr](C1=CC(=CC=2C3=CC(=CC=C3CC12)C(C)(C)C)C(C)(C)C)C1C=CC2=CC=CC=C12 Chemical compound C(C)(C)=[Zr](C1=CC(=CC=2C3=CC(=CC=C3CC12)C(C)(C)C)C(C)(C)C)C1C=CC2=CC=CC=C12 TXDMTLNRJWRPEW-UHFFFAOYSA-N 0.000 description 1
- XJTQEAXBIXXILJ-UHFFFAOYSA-L CC(C)=[Zr](Cl)(Cl)(C1C=CC=C1)C1=CC=CC2=C1CC1=CC=CC=C21 Chemical compound CC(C)=[Zr](Cl)(Cl)(C1C=CC=C1)C1=CC=CC2=C1CC1=CC=CC=C21 XJTQEAXBIXXILJ-UHFFFAOYSA-L 0.000 description 1
- LMNJIRLUFGKYMP-UHFFFAOYSA-L C[Si](C)=[Zr](Cl)(Cl)(C1C=CC=C1)C1C=CC=C1 Chemical compound C[Si](C)=[Zr](Cl)(Cl)(C1C=CC=C1)C1C=CC=C1 LMNJIRLUFGKYMP-UHFFFAOYSA-L 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
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Images
Landscapes
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、積層体用樹脂組成物および積層体に関し、さらに詳しくは、特定の物性を有するエチレン系樹脂を含む積層体用樹脂組成物および該積層体用樹脂組成物から成る層を少なくとも一層含む積層体に関する。 The present invention relates to a resin composition for a laminate and a laminate, and more specifically, includes at least one layer comprising a resin composition for a laminate containing an ethylene-based resin having specific physical properties and the resin composition for a laminate. It relates to a laminate.
エチレン系樹脂は、種々の成形方法により成形され、様々な用途に用いられている。これら成形方法や用途に応じて、エチレン系樹脂に要求される特性も異なる。例えばTダイ成形においてキャストフィルムを成形する場合、フィルム端部が中央方向へと縮んでしまうネックインが発生する。ネックインが発生すると、フィルム幅が小さくなるとともにフィルム端部の厚みがフィルム中央部に比べ厚くなってしまうため、製品の歩留まりが悪化する。ネックインを最小限に抑えるためには、エチレン系樹脂として分子量の割には、溶融張力の大きいものを選択しなければならない。同様の特性が中空成形におけるたれ下がり、あるいはちぎれを防止するために、あるいはインフレーションフィルムにおけるバブルのゆれ、あるいはちぎれを防止するために必要である。 Ethylene-based resins are molded by various molding methods and used for various applications. Depending on these molding methods and applications, the characteristics required for ethylene resins also differ. For example, when a cast film is formed in T-die molding, a neck-in in which the film end portion shrinks in the center direction occurs. When neck-in occurs, the film width becomes smaller and the thickness of the film end becomes thicker than the center of the film, so that the yield of products deteriorates. In order to minimize neck-in, an ethylene resin having a high melt tension must be selected for the molecular weight. Similar properties are necessary to prevent sagging or tearing in hollow molding, or to prevent bubble swaying or tearing in blown film.
また、Tダイ成形においてキャストフィルムを成形する場合、「引取サージング」(「ドローレゾナンス」と呼ばれる場合もある。)と呼ばれるフィルムの引き取り方向に発生する規則的な厚み変動が生じることが知られている。引取サージングが発生するとフィルムに厚薄ムラが発生し、その結果、場所毎に機械的強度にばらつきが出てしまう。このため、フィルム厚みが均質なフィルムを安定的に生産する為には、引取サージングの発生を避ける必要がある。この引取サージングの発生を抑制するためには、伸長粘度のひずみ硬化度が、ひずみ速度の増加に伴い大きくなるような樹脂特性が必要であると考えられている(例えば、非特許文献1参照)。 In addition, when forming a cast film in T-die molding, it is known that regular thickness fluctuations occur in the film take-off direction called “take-up surging” (sometimes referred to as “draw resonance”). Yes. When take-up surging occurs, thickness unevenness occurs in the film, and as a result, the mechanical strength varies from place to place. For this reason, in order to stably produce a film having a uniform film thickness, it is necessary to avoid the occurrence of take-up surging. In order to suppress the occurrence of this take-up surging, it is considered that a resin characteristic is required such that the strain hardening degree of the extension viscosity increases with an increase in strain rate (for example, see Non-Patent Document 1). .
メタロセン触媒を用いて得られた既知のエチレン系重合体は、引張強度、引裂強度あるいは耐衝撃強度などの機械的強度には優れるが、溶融張力が小さいためネックインが大きくなってしまう。また、伸長粘度がひずみ速度硬化性を示さないため、引取サージングを発生してしまう。 A known ethylene polymer obtained by using a metallocene catalyst is excellent in mechanical strength such as tensile strength, tear strength or impact strength strength, but neck-in becomes large because of low melt tension. Further, since the extension viscosity does not show strain rate curability, take-up surging occurs.
高圧法低密度ポリエチレンは、メタロセン触媒を用いて得られたエチレン系重合体と比較して溶融張力が大きいため、ネックインなどの成形性に優れる。また、伸長粘度がひずみ速度硬化性を示すため、引取サージングが発生しない。しかし高圧法低密度ポリエチレンは、複雑な長鎖分岐構造を有するため引張強度、引裂強度あるいは耐衝撃強度などの機械的強度に劣る。 The high-pressure low-density polyethylene has a higher melt tension than an ethylene polymer obtained using a metallocene catalyst, and thus has excellent moldability such as neck-in. Further, since the extension viscosity shows strain rate curability, take-up surging does not occur. However, the high-pressure low-density polyethylene has a complicated long-chain branched structure, and therefore is inferior in mechanical strength such as tensile strength, tear strength or impact strength.
そこで、ネックイン、引取サージングなどの成形性を維持しつつ、且つ機械的強度を具備させたエチレン系重合体として、メタロセン触媒を用いて得られたエチレン系重合体と高圧法低密度ポリエチレンとの組成物が特開平6-65443号公報(特許文献1)、特開平7-26079号公報(特許文献2)などに提案されている。しかし、高圧法低密度ポリエチレンの含有量が多い場合、引張強度、引裂強度あるいは耐衝撃強度などの機械的強度に劣ることが予想される。また、高圧法低密度ポリエチレンの含有量が少ない場合には溶融張力の向上が十分でないため、ネックインが大きいなど成形性の悪化が予想される。 Therefore, an ethylene polymer obtained by using a metallocene catalyst and a high-pressure method low-density polyethylene as an ethylene polymer having mechanical strength while maintaining moldability such as neck-in and take-up surging. Compositions have been proposed in JP-A-6-65443 (Patent Document 1), JP-A-7-26079 (Patent Document 2), and the like. However, when the content of the high pressure method low density polyethylene is large, it is expected that the mechanical strength such as tensile strength, tear strength or impact strength is inferior. In addition, when the content of the high-pressure method low-density polyethylene is small, the melt tension is not sufficiently improved, so that the moldability is expected to deteriorate due to a large neck-in.
このような問題を解決するため、メタロセン触媒により長鎖分岐を導入したエチレン系重合体が種々開示されている。特開平2-276807号公報(特許文献3)にはエチレンビス(インデニル)ハフニウムジクロリドとメチルアルモキサンとからなる触媒の存在下、溶液
重合により得られたエチレン系重合体が、特開平4-213309号公報(特許文献4)にはシリカに担持したエチレンビス(インデニル)ジルコニウムジクロリドとメチルアルモキサンとからなる触媒の存在下で気相重合により得られたエチレン系重合体が、国際公開第93/08221号パンフレット(特許文献5)には拘束幾何触媒の存在下で溶液重合により得られたエチレン系重合体が、特開平8-311260号公報(特許文献6)にはシリカに担持したMe2Si(2-Me-Ind)2のラセミ及びメソ異性体とメチルアルモキサンとからなる触媒の存在下で気相重合により得られたエチレン系重合体が開示されている。これらのエチレン系重合体は、長鎖分岐の無い直鎖状のエチレン系重合体に比べ溶融張力が向上し、成形性に優れる旨の記載はあるが、依然としてネックインは大きいことから、成形性の向上については不十分であると予想される。また、これらのエチレン系重合体は、高圧法低密度ポリエチレンとは異なり、伸長粘度がひずみ速度硬化性を示さないため、引取サージングの改善は見込めないと予想される。
In order to solve such problems, various ethylene polymers in which long chain branching is introduced by a metallocene catalyst have been disclosed. JP-A-2-76807 (Patent Document 3) discloses an ethylene polymer obtained by solution polymerization in the presence of a catalyst comprising ethylenebis (indenyl) hafnium dichloride and methylalumoxane. (Patent Document 4) discloses an ethylene polymer obtained by gas phase polymerization in the presence of a catalyst comprising ethylenebis (indenyl) zirconium dichloride supported on silica and methylalumoxane. No. 08221 pamphlet (Patent Document 5) discloses an ethylene polymer obtained by solution polymerization in the presence of a constrained geometric catalyst, and Japanese Patent Laid-Open No. 8-311260 (Patent Document 6) discloses Me 2 Si supported on silica. An ethylene-based polymer obtained by gas phase polymerization in the presence of a catalyst comprising a racemic and meso isomer of (2-Me-Ind) 2 and methylalumoxane is disclosed. Although these ethylene polymers are described as having improved melt tension and excellent moldability compared to linear ethylene polymers without long-chain branching, the neck-in is still large, so moldability This improvement is expected to be insufficient. In addition, unlike the high-pressure low-density polyethylene, these ethylene-based polymers are not expected to improve take-up surging because the extensional viscosity does not exhibit strain rate curability.
以上述べたように、従来技術から、ネックインや引取サージングなどの成形性に優れ、かつ高速成形性に優れたエチレン系樹脂を効率的に得ることは難しかったのである。
本発明者らは、このような状況に鑑み鋭意研究した結果、特定の分子構造と溶融特性を有するエチレン系樹脂および該樹脂を主成分とする組成物は、Tダイ成形におけるネックインが小さく、引取サージングの発生が無く、かつ高速成形性に優れることを見出し、本発明を完成するに至った。
As a result of diligent research in view of such circumstances, the inventors of the present invention have an ethylene resin having a specific molecular structure and melting characteristics and a composition containing the resin as a main component, with a small neck-in in T-die molding, The inventors have found that there is no occurrence of take-up surging and excellent high-speed moldability, and the present invention has been completed.
本発明の課題は、Tダイ成形におけるネックインが小さく、引取サージングの発生が無く、かつ高速成形性に優れる積層体用樹脂組成物および該積層体用樹脂組成物から成る層を少なくとも一層含む積層体を提供することにある。 An object of the present invention is to provide a laminate resin composition having a small neck-in in T-die molding, no occurrence of take-up surging, and excellent in high-speed moldability, and a laminate comprising at least one layer comprising the laminate resin composition To provide a body.
本発明に係る積層体用樹脂組成物は、エチレンと、炭素数4〜10のα−オレフィンとの共重合体であって、下記要件(I)〜(V)を同時に満たすエチレン系樹脂を含む;
(I)190℃における2.16kg荷重でのメルトフローレート(MFR)が0.1〜50g/10分の範囲である。
(II)密度(d)が875〜970kg/m3の範囲である
(III)190℃における溶融張力〔MT(g)〕と、200℃、角速度1.0rad/秒にお
けるせん断粘度〔η*(P)〕との比〔MT/η*(g/P)〕が1.00×10-4〜9.0
0×10-4の範囲である
(IV)13C-NMRにより測定された炭素原子1000個あたりのメチル分岐数〔A(/1000C)〕とエチル分岐数〔B(/1000C)〕との和〔(A+B)(/1000C)〕が1.8以下である
(V)200℃におけるゼロせん断粘度〔η0(P)〕とGPC-粘度検出器法(GPC-
VISCO)により測定された重量平均分子量(Mw)とが下記関係式(Eq-1)を満たす
0.01×10-13×Mw3.4≦η0≦4.5×10-13×Mw3.4 -----(Eq-1)
本発明に係る積層体は、上記積層体用樹脂組成物から成る層を少なくとも一層含む。この積層体は、例えば押出ラミネート成形によって得られる。
The resin composition for laminates according to the present invention is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, and includes an ethylene-based resin that simultaneously satisfies the following requirements (I) to (V). ;
(I) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is in the range of 0.1 to 50 g / 10 min.
(II) The density (d) is in the range of 875 to 970 kg / m 3 (III) The melt tension [MT (g)] at 190 ° C. and the shear viscosity [η * ( P)] [MT / η * (g / P)] is 1.00 × 10 −4 to 9.0.
Sum of methyl branch number [A (/ 1000C)] and ethyl branch number [B (/ 1000C)] per 1000 carbon atoms measured by (IV) 13 C-NMR in the range of 0 × 10 −4 [(A + B) (/ 1000C)] is 1.8 or less (V) Zero shear viscosity [η 0 (P)] at 200 ° C. and GPC-viscosity detector method (GPC-
The weight average molecular weight (Mw) measured by VISCO) satisfies the following relational expression (Eq-1): 0.01 × 10 −13 × Mw 3.4 ≦ η 0 ≦ 4.5 × 10 −13 × Mw 3.4 − --- (Eq-1)
The laminate according to the present invention includes at least one layer formed of the resin composition for laminate. This laminated body is obtained by, for example, extrusion lamination molding.
本発明に係る積層体用樹脂組成物は、Tダイ成形におけるネックインが小さく、引取サージングの発生が無く、かつ高速成形性に優れる。また該樹脂組成物から得られる積層体(押出ラミネート成形体)は優れたヒートシール強度を示す。 The resin composition for laminates according to the present invention has a small neck-in in T-die molding, no occurrence of take-up surging, and excellent high-speed moldability. In addition, a laminate (extruded laminate) obtained from the resin composition exhibits excellent heat seal strength.
以下、本発明に係る積層体用樹脂組成物および積層体について具体的に説明する。
本発明の積層体用樹脂組成物は、下記エチレン系樹脂[R]からなるか、または後述する
熱可塑性樹脂[R3]、添加剤を含む下記エチレン系樹脂[R]からなる。
Hereinafter, the resin composition for a laminate and the laminate according to the present invention will be specifically described.
The resin composition for laminates of the present invention comprises the following ethylene resin [R], or comprises the following thermoplastic resin [R3] and the following ethylene resin [R] containing an additive.
《エチレン系樹脂[R]》
まず、本発明で用いられるエチレン系樹脂[R]について具体的に説明する。
エチレン系樹脂[R]は、エチレン系重合体一種のみで構成されていてもよいし、二種以
上のエチレン系重合体から構成されていてもよいが必ず前記の要件(I)〜(V)を全て満たすことを特徴としている。エチレン系樹脂[R]が一種のみのエチレン系重合体から構
成される場合は、該エチレン系重合体[R1]は後述する重合方法によって効率的に製造される。エチレン系樹脂[R]が二種以上のエチレン系重合体から構成される場合は、前記エチ
レン系重合体[R1]と該[R1]以外のエチレン系重合体[R2]を含むことが好ましく、エチレン系重合体[R2]としては、例えば、メタロセン触媒又はチーグラー触媒を用いて得られる、エチレンと炭素数4〜10のα-オレフィンとの共重合体や高圧ラジカル重合法によって製造される高圧法低密度ポリエチレンを挙げることができる。二種以上のエチレン系重合体から構成される場合はエチレン系重合体[R1]とエチレン系重合体[R2]の組成比率やエチレン系重合体[R2]の種類については、[R1]と[R2]のブレンド処理が可能であり、且つブレンドされた樹脂が前記要件(I)〜(V)を同時に満たす限りは特に限定されるものではない。しかしながら、後述する産業用途に適用する場合は、通常、エチレン系樹脂[R]中のエ
チレン系重合体[R1]の組成比率は99重量%以下、好ましくは70重量%以下、さらに好ましくは30重量%以下になるように設定される。エチレン系樹脂[R]は、ブレンド等の処理工程を省略できるという視点から、通常、エチレン系重合体[R1]のみから構成される。一方、エチレン系重合体[R1]が持つ特定性能を更に顕著に促進させたい場合や、エチレン系重合体[R1]が本来保有しない新たな性能を付加させたい場合は、前記したようなエチレン系重合体[R2]を併用しブレンド形態として用いられるのである。
<< Ethylene resin [R] >>
First, the ethylene resin [R] used in the present invention will be specifically described.
The ethylene resin [R] may be composed of only one ethylene polymer, or may be composed of two or more ethylene polymers, but the requirements (I) to (V) are always included. It is characterized by satisfying all. When the ethylene resin [R] is composed of only one kind of ethylene polymer, the ethylene polymer [R1] is efficiently produced by a polymerization method described later. When the ethylene resin [R] is composed of two or more kinds of ethylene polymers, it preferably contains the ethylene polymer [R1] and an ethylene polymer [R2] other than the [R1], Examples of the ethylene polymer [R2] include a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms obtained by using a metallocene catalyst or a Ziegler catalyst, and a high pressure method produced by a high pressure radical polymerization method. Mention may be made of low-density polyethylene. When composed of two or more ethylene polymers, the composition ratio of the ethylene polymer [R1] and the ethylene polymer [R2] and the type of the ethylene polymer [R2] are [R1] and [R2]. R2] can be blended and is not particularly limited as long as the blended resin satisfies the requirements (I) to (V) at the same time. However, when applied to industrial applications described later, the composition ratio of the ethylene polymer [R1] in the ethylene resin [R] is usually 99% by weight or less, preferably 70% by weight or less, more preferably 30% by weight. It is set to be less than%. The ethylene-based resin [R] is usually composed only of the ethylene-based polymer [R1] from the viewpoint that a processing step such as blending can be omitted. On the other hand, if you want to further promote the specific performance of the ethylene polymer [R1], or if you want to add new performance that the ethylene polymer [R1] does not originally possess, The polymer [R2] is used in combination as a blend form.
エチレン系樹脂[R]は、前記した要件(I)〜(V)を同時に満たすことを特徴として
いる。以下、これらの要件(I)〜(V)について具体的に説明する。
要件 (I)
エチレン系樹脂[R]の、190℃、2.16 kg荷重におけるメルトフローレート(MFR)は0.1
〜50 g/10分、好ましくは1.0〜50 g/10分、より好ましくは3.0〜30の範囲である。MFRが0.1 g/10分以上の場合、エチレン系樹脂[R]のせん断粘度が高過ぎず成形性に優れ、例えばフィルムとした場合の外観が良好である。MFRが50 g/10分以下の場合、エチレン系樹脂[R]の引張強度やヒートシール強度が良好である。なお、MFRは、ASTM D1238-89に従い190℃、2.16 kg荷重の条件下で測定される値である。
The ethylene resin [R] is characterized by satisfying the above requirements (I) to (V) at the same time. Hereinafter, these requirements (I) to (V) will be specifically described.
Requirements (I)
The melt flow rate (MFR) of ethylene resin [R] at 190 ° C and 2.16 kg load is 0.1
-50 g / 10 min, preferably 1.0-50 g / 10 min, more preferably in the range of 3.0-30. When the MFR is 0.1 g / 10 min or more, the shear viscosity of the ethylene resin [R] is not too high and the moldability is excellent. For example, the appearance of a film is good. When the MFR is 50 g / 10 min or less, the tensile strength and heat seal strength of the ethylene-based resin [R] are good. The MFR is a value measured under conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-89.
一般に、MFRは分子量に強く依存する。すなわち、MFRが小さいほど分子量は大きく、MFRが大きいほど分子量は小さくなる。エチレン系樹脂[R]の分子量は、これを構成するエチレン系重合体を製造する際の重合系内における水素とエチレンとの組成比(水素/エチレ
ン)により決定されることが知られている(例えば、Kazuo Soga, KODANSHA"CATALYTIC OLEFIN POLYMERIZATION”, p376 (1990))。このため、水素/エチレンを増減させることで、MFRが上記範囲にあるエチレン系樹脂[R]を製造することが可能である。
In general, MFR is strongly dependent on molecular weight. That is, the smaller the MFR, the larger the molecular weight, and the larger the MFR, the smaller the molecular weight. It is known that the molecular weight of the ethylene resin [R] is determined by the composition ratio (hydrogen / ethylene) of hydrogen and ethylene in the polymerization system when the ethylene polymer constituting the ethylene resin [R] is produced ( For example, Kazuo Soga, KODANSHA “CATALYTIC OLEFIN POLYMERIZATION”, p376 (1990)). Therefore, it is possible to produce an ethylene resin [R] having an MFR in the above range by increasing / decreasing hydrogen / ethylene.
要件 (II)
エチレン系樹脂[R]の、密度(d)は、875〜970 kg/m3、好ましくは877〜965 kg/m3、より好ましくは880〜960 kg/m3の範囲にある。なお密度(d)は、測定サンプルを120℃で1時間
熱処理し、1時間かけて直線的に室温まで徐冷したのち、密度勾配管で測定される値であ
る。
Requirements (II)
The density (d) of the ethylene-based resin [R] is in the range of 875 to 970 kg / m 3 , preferably 877 to 965 kg / m 3 , more preferably 880 to 960 kg / m 3 . The density (d) is a value measured with a density gradient tube after heat-treating the measurement sample at 120 ° C. for 1 hour and linearly cooling to room temperature over 1 hour.
密度(d)が875 kg/m3以上の場合、エチレン系樹脂[R]の耐熱性が良好であり、またエチ
レン系樹脂[R]から成形されたフィルム表面のべたつきが少ない。一方、密度(d)が970 kg/m3以下の場合、エチレン系樹脂[R]の低温シール性が良好である。
When the density (d) is 875 kg / m 3 or more, the heat resistance of the ethylene resin [R] is good, and the film surface formed from the ethylene resin [R] has little stickiness. On the other hand, when the density (d) is 970 kg / m 3 or less, the low temperature sealing property of the ethylene-based resin [R] is good.
一般に、密度はエチレン系重合体のα-オレフィン含量に依存しており、α-オレフィン含量が少ないほど密度は高く、α-オレフィン含量が多いほど密度は低くなる。また、エ
チレン系重合体中のα-オレフィン含量は、重合系内におけるα-オレフィンとエチレンとの組成比(α-オレフィン/エチレン)により決定されることが知られている(例えばWalter Kaminsky, Makromol.Chem. 193, p.606(1992))。このため、エチレン系樹脂[R]を構
成するエチレン系重合体を製造する際に、α-オレフィン/エチレンを増減させることで該重合体の密度を制御することが可能であり、このような制御方法によって、密度が上記範囲にあるエチレン系樹脂[R]を製造することが可能である。
In general, the density depends on the α-olefin content of the ethylene polymer. The smaller the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density. In addition, it is known that the α-olefin content in an ethylene polymer is determined by the composition ratio of α-olefin and ethylene (α-olefin / ethylene) in the polymerization system (for example, Walter Kaminsky, Makromol). Chem. 193, p.606 (1992)). Therefore, when producing an ethylene polymer constituting the ethylene resin [R], it is possible to control the density of the polymer by increasing or decreasing α-olefin / ethylene. By the method, it is possible to produce an ethylene resin [R] having a density in the above range.
要件 (III)
エチレン系樹脂[R]の、190℃における溶融張力[MT(g)]と、200℃、角速度1.0 rad/秒におけるせん断粘度[η*(P)]との比[MT/η*(g/P)]は、1.00×10-4〜9.00×10-4、好ましく
は、2.00×10-4〜7.00×10-4、より好ましくは、2.60×10-4〜5.00×10-4の範囲にある。MT/η*が1.00×10-4以上であるエチレン系樹脂はネックインが良好となる。
Requirements (III)
Ratio [MT / η * (g / g) of melt tension [MT (g)] at 190 ° C. and shear viscosity [η * (P)] at 200 ° C. and an angular velocity of 1.0 rad / sec. P)] is in the range of 1.00 × 10 −4 to 9.00 × 10 −4 , preferably 2.00 × 10 −4 to 7.00 × 10 −4 , more preferably 2.60 × 10 −4 to 5.00 × 10 −4 . is there. An ethylene resin having MT / η * of 1.00 × 10 −4 or more has a good neck-in.
後述する製造例31に記載した条件で製造することにより、上記下限付近のMT/η*を有するエチレン系重合体を得ることができ、製造例19に記載した条件で製造することにより、上記上限付近のMT/η*を有するエチレン系重合体を得ることができる。 By producing under the conditions described in Production Example 31 to be described later, an ethylene polymer having MT / η * near the lower limit can be obtained, and by producing under the conditions described in Production Example 19, the upper limit An ethylene-based polymer having a nearby MT / η * can be obtained.
なお、本発明においては溶融張力(MT)は溶融されたポリマーを一定速度で延伸したときの応力を測定することにより決定した。測定には東洋精機製作所製のMT測定機を用いた。測定条件は樹脂温度190℃、溶融時間6分、バレル径9.55 mmφ、押し出し速度15 mm/分、巻取り速度24 m/分(溶融フィラメントが切れてしまう場合には、巻取り速度を5 m/分ず
つ低下させる)、ノズル径 2.095 mmφ、ノズル長さ8 mmである。
In the present invention, the melt tension (MT) was determined by measuring the stress when the molten polymer was stretched at a constant speed. An MT measuring machine manufactured by Toyo Seiki Seisakusho was used for the measurement. Measurement conditions are: resin temperature 190 ° C, melting time 6 minutes, barrel diameter 9.55 mmφ,
また、200℃、角速度 1.0 rad/秒におけるせん断粘度(η*)は、測定温度 200℃にお
けるせん断粘度(η*)の角速度〔ω (rad/秒)〕分散を0.02512≦ω≦100の範囲で測定することにより決定された。測定にはレオメトリックス社製ダイナミックストレスレオメーター SR-5000を用いた。サンプルホルダーは 25 mmφのパラレルプレートを用い、サンプル厚みは約 2.0 mmとした。測定点はω一桁当たり5点とした。歪み量は、測定範囲でのトルクが検出可能で、かつトルクオーバーにならないよう、3〜10 %の範囲で適宜選択した。
せん断粘度測定に用いたサンプルは、神藤金属工業所製プレス成形機を用い、予熱温度 190℃、予熱時間5分間、加熱温度190℃、加熱時間2分間、加熱圧力 100 kg/cm2、冷却温度20℃、冷却時間5分間、冷却圧力100 kg/cm2の条件にて、測定サンプルを厚さ2 mmにプレ
ス成形することで調製した。
The shear viscosity (η * ) at 200 ° C and angular velocity of 1.0 rad / sec is the angular velocity [ω (rad / sec)] dispersion of shear viscosity (η * ) at a measurement temperature of 200 ° C in the range of 0.02512 ≦ ω ≦ 100. Determined by measuring. A dynamic stress rheometer SR-5000 manufactured by Rheometrics was used for the measurement. The sample holder was a 25 mmφ parallel plate, and the sample thickness was about 2.0 mm. The number of measurement points was 5 per ω digit. The amount of strain was appropriately selected within a range of 3 to 10% so that the torque in the measurement range could be detected and torque was not exceeded.
The sample used for shear viscosity measurement was a press molding machine manufactured by Shin-Fuji Metal Industry Co., Ltd., preheating temperature 190 ° C, preheating
要件 (IV)
エチレン系樹脂[R]の、13C-NMRにより測定されたメチル分岐数[A (/1000C)]とエチル分岐数[B (/1000C)]との和[(A+B) (/1000C)]は1.8以下、好ましくは1.3以下、より好ましくは0.8以下、特に好ましくは0.5以下である。なお、本発明で定義したメチル分岐数およびエチル分岐数は、後述するように1,000カーボンあたりの個数で定義される。
Requirement (IV)
Sum of the number of methyl branches [A (/ 1000C)] and the number of ethyl branches [B (/ 1000C)] measured by 13 C-NMR of ethylene resin [R] [(A + B) (/ 1000C) ] Is 1.8 or less, preferably 1.3 or less, more preferably 0.8 or less, and particularly preferably 0.5 or less. The number of methyl branches and the number of ethyl branches defined in the present invention are defined by the number per 1,000 carbons as described later.
エチレン系樹脂にメチル分岐、エチル分岐などの短鎖分岐が存在すると、短鎖分岐が結晶中に取り込まれ、結晶の面間隔が広がってしまうため、樹脂の機械的強度が低下することが知られている(例えば、大澤善次郎 他、「高分子の寿命予測と長寿命化技術」, p481, エヌ・ティー・エス(2002))。そのため、メチル分岐数とエチル分岐数との和(A+B)が1.8以下の場合、得られるエチレン系樹脂の機械的強度が良好となる。 It is known that when a short chain branch such as methyl branch or ethyl branch is present in an ethylene-based resin, the short chain branch is incorporated into the crystal and the interplanar spacing of the crystal widens, so that the mechanical strength of the resin decreases. (For example, Zenjiro Osawa et al., “Prediction and extension of polymer life”, p481, NTS (2002)). Therefore, when the sum (A + B) of the number of methyl branches and the number of ethyl branches (A + B) is 1.8 or less, the mechanical strength of the obtained ethylene-based resin is good.
エチレン系樹脂中のメチル分岐数、エチル分岐数は、エチレン系樹脂を構成するエチレン系重合体の重合方法に強く依存し、高圧ラジカル重合により得られたエチレン系重合体は、チーグラー型触媒系を用いた配位重合により得られたエチレン系重合体に比べ、メチル分岐数、エチル分岐数が多い。配位重合の場合、エチレン系重合体中のメチル分岐数、エチル分岐数は、重合系内におけるプロピレン、1-ブテンとエチレンとの組成比(プロ
ピレン/エチレン、1-ブテン/エチレン)に強く依存する。このため、1-ブテン/エチレ
ンを増減させることで、メチル分岐数とエチル分岐数の和(A+B)が上記範囲にあるエチレ
ン系樹脂を製造することが可能である。
The number of methyl branches and the number of ethyl branches in the ethylene resin strongly depend on the polymerization method of the ethylene polymer constituting the ethylene resin, and the ethylene polymer obtained by high-pressure radical polymerization is a Ziegler type catalyst system. The number of methyl branches and the number of ethyl branches are larger than the ethylene polymer obtained by the coordination polymerization used. In the case of coordination polymerization, the number of methyl branches and the number of ethyl branches in an ethylene polymer strongly depend on the composition ratio of propylene, 1-butene and ethylene (propylene / ethylene, 1-butene / ethylene) in the polymerization system. To do. Therefore, by increasing or decreasing 1-butene / ethylene, it is possible to produce an ethylene-based resin in which the sum of the number of methyl branches and the number of ethyl branches (A + B) is in the above range.
なお、13C-NMRにより測定されたメチル分岐数およびエチル分岐数は下記のように決定
される。測定は日本電子(株)社製ECP500型核磁気共鳴装置(1H; 500MHz)を用い、積算回数1万〜3万回にて測定した。なお、化学シフト基準として主鎖メチレンのピーク(29.97 ppm)を用いた。直径10mmの市販のNMR測定石英ガラス管中に、サンプル250〜400mgと、和光純薬工業(株)社製特級o-ジクロルベンゼン:ISOTEC社製ベンゼン-d6=5:1(体積比)の混
合液3mlを入れ、120℃にて加熱、均一分散させることにより行った。NMRスペクトルにおける各吸収の帰属は、「化学領域増刊141号 NMR-総説と実験ガイド[I]、p132〜p133に準じて行った。1,000カーボン当たりのメチル分岐数は、5〜45 ppmの範囲に現れる吸収の積分総和に対する、メチル分岐由来のメチル基の吸収(19.9ppm)の積分強度比より算出
した。また、エチル分岐数は、5〜45 ppmの範囲に現れる吸収の積分総和に対する、エチ
ル分岐由来のエチル基の吸収(10.8 ppm)の積分強度比より算出した。
The number of methyl branches and the number of ethyl branches measured by 13 C-NMR are determined as follows. The measurement was carried out using an ECP500 type nuclear magnetic resonance apparatus (1H; 500 MHz) manufactured by JEOL Ltd. at a cumulative number of 10,000 to 30,000. The main chain methylene peak (29.97 ppm) was used as the chemical shift standard. In a commercially available quartz glass tube with a diameter of 10 mm, a sample of 250 to 400 mg, Wako Pure Chemical Industries, Ltd. special grade o-dichlorobenzene: ISOTEC benzene-d 6 = 5: 1 (volume ratio) 3 ml of the above mixture was added, heated at 120 ° C., and uniformly dispersed. The assignment of each absorption in the NMR spectrum was carried out in accordance with “Chemical Region Special Issue 141 NMR-Review and Experiment Guide [I], p132-p133. The number of methyl branches per 1,000 carbons was in the range of 5-45 ppm. Calculated from the integrated intensity ratio of the absorption of methyl groups derived from methyl branching (19.9 ppm) to the integrated sum of the appearing absorption, and the number of ethyl branches is the ethyl branching relative to the integrated sum of absorption appearing in the range of 5 to 45 ppm. It was calculated from the integrated intensity ratio of the absorption (10.8 ppm) of the ethyl group derived therefrom.
要件 (V)
エチレン系樹脂[R]の、200℃におけるゼロせん断粘度[η0(P)]とGPC-粘度検出器法(GPC-VISCO)により測定された重量平均分子量(Mw)は、下記関係式(Eq-1)を満たす。
Requirements (V)
The weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) and the zero shear viscosity [η 0 (P)] at 200 ° C. of the ethylene-based resin [R] are expressed by the following equation (Eq -1) is satisfied.
0.01×10-13×Mw3.4≦η0≦4.5×10-13×Mw3.4 -----(Eq-1)
好ましくは、下記関係式(Eq-2)を満たす。
0.05×10-13×Mw3.4≦η0≦4.5×10-13×Mw3.4 -----(Eq-2)
より好ましくは、下記関係式(Eq-3)を満たす。
0.01 × 10 -13 × Mw 3.4 ≦ η 0 ≦ 4.5 × 10 -13 × Mw 3.4 ----- (Eq-1)
Preferably, the following relational expression (Eq-2) is satisfied.
0.05 × 10 -13 × Mw 3.4 ≦ η 0 ≦ 4.5 × 10 -13 × Mw 3.4 ----- (Eq-2)
More preferably, the following relational expression (Eq-3) is satisfied.
0.10×10-13×Mw3.4≦η0≦3.5×10-13×Mw3.4 -----(Eq-3)
特に好ましくは、下記関係式(Eq-4)を満たす。
0.15×10-13×Mw3.4≦η0≦1.8×10-13×Mw3.4 -----(Eq-4)
重量平均分子量(Mw)に対してゼロせん断粘度[η0(P)]を両対数プロットしたとき、長鎖分岐の無い直鎖状のエチレン系重合体のように伸長粘度がひずみ硬化性を示さない樹脂は傾きが3.4のべき乗則に則るのに対し、高圧法低密度ポリエチレンのように伸長粘度
がひずみ速度硬化性を示す樹脂はべき乗則よりも低いゼロせん断粘度[η0(P)]を示すことが知られている(C Gabriel, H.Munstedt, J.Rheol., 47(3), 619(2003))。200℃におけるゼロせん断粘度[η0(P)]が4.5×10-13×Mw3.4以下の場合、得られるエチレン系重合体
の伸長粘度がひずみ速度硬化性を示すため、引取サージングが発生しない。
0.10 × 10 -13 × Mw 3.4 ≦ η 0 ≦ 3.5 × 10 -13 × Mw 3.4 ----- (Eq-3)
Particularly preferably, the following relational expression (Eq-4) is satisfied.
0.15 × 10 -13 × Mw 3.4 ≦ η 0 ≦ 1.8 × 10 -13 × Mw 3.4 ----- (Eq-4)
When the zero shear viscosity [η 0 (P)] is log-log plotted against the weight average molecular weight (Mw), the extensional viscosity is strain-hardening like a linear ethylene polymer without long chain branching. The resin with no slope follows the power law of 3.4, whereas the low shear viscosity resin with elongation viscosity like the high pressure method low density polyethylene has lower zero shear viscosity [η 0 (P)] than the power law (C Gabriel, H. Munstedt, J. Rheol., 47 (3), 619 (2003)). When the zero shear viscosity [η 0 (P)] at 200 ° C. is 4.5 × 10 −13 × Mw 3.4 or less, the elongational viscosity of the resulting ethylene polymer exhibits strain rate curability, so that take-up surging does not occur.
エチレン系樹脂[R]が上記関係式(Eq-1)を満たすことは、エチレン系樹脂[R]のη0とMw
を両対数プロットした際に、log(η0)とlogMwが下記関係式(Eq-1')で規定される領域に存
在することと同義である。
The fact that ethylene resin [R] satisfies the above relational expression (Eq-1) indicates that η 0 and Mw of ethylene resin [R]
Is logarithmically plotted, this means that log (η 0 ) and logMw are present in the region defined by the following relational expression (Eq-1 ′).
3.4Log(Mw)−15.0000≦Log(η0)≦3.4Log(Mw)−12.3468 -------- (Eq-1')
後述する製造例に記載した全エチレン系樹脂について、log(η0)とlogMwをプロットし
た図を図1に示す。製造例2に記載した条件で製造することにより、上記パラメーター不
等式(Eq-1)で規定されるゼロせん断粘度[η0(P)]と重量平均分子量(Mw)の関係が、パラメーター不等式(Eq-1')の内、下記式(Eq-1'')で規定される境界ラインに近いエチレン系
樹脂を得ることができ、一方で、製造例29に記載した条件で製造することにより、パラメーター不等式(Eq-1')の内、下記式(Eq-1''')で規定される境界ラインに近いエチレン系樹脂を得ることができる。
3.4Log (Mw) −15.0000 ≦ Log (η 0 ) ≦ 3.4Log (Mw) −12.3468 -------- (Eq-1 ')
FIG. 1 shows a plot of log (η 0 ) and logMw for all ethylene resins described in the production examples described later. By producing under the conditions described in Production Example 2, the relationship between the zero shear viscosity [η 0 (P)] defined by the parameter inequality (Eq-1) and the weight average molecular weight (Mw) is the parameter inequality (Eq -1 ′), an ethylene-based resin close to the boundary line defined by the following formula (Eq-1 ″) can be obtained. Of the inequality (Eq-1 ′), an ethylene resin close to the boundary line defined by the following formula (Eq-1 ′ ″) can be obtained.
Log(η0)=3.4Log(Mw)−15.0000 --------- (Eq-1'')
Log(η0)=3.4Log(Mw)−12.3468 ----------(Eq-1''')
なお、200℃におけるゼロせん断粘度[η0(P)]は以下のようにして求めた。測定温度200℃におけるせん断粘度(η*)の角速度[ω(rad/秒)]分散を、0.02512≦ω≦100の範囲で測
定する。測定にはレオメトリックス社製ダイナミックストレスレオメーター SR-5000を用いた。サンプルホルダーは25 mmφのパラレルプレートを用い、サンプル厚みは約2.0 mm
とした。測定点はω一桁当たり5点とした。歪み量は、測定範囲でのトルクが検出可能で
、かつトルクオーバーにならないよう、3〜10 %の範囲で適宜選択した。せん断粘度測定
に用いたサンプルは、神藤金属工業所製プレス成形機を用い、予熱温度190℃、予熱時間 5分間、加熱温度 190℃、加熱時間 2分間、加熱圧力 100 kg/cm2、冷却温度20℃、冷却時間 5分間、冷却圧力 100kg/cm2の条件にて、測定サンプルを厚さ 2 mmにプレス成形する
ことで調製した。
Log (η 0 ) = 3.4Log (Mw) −15.0000 --------- (Eq-1``)
Log (η 0 ) = 3.4Log (Mw) −12.3468 ---------- (Eq-1 ''')
The zero shear viscosity [η 0 (P)] at 200 ° C. was determined as follows. The angular velocity [ω (rad / sec)] dispersion of the shear viscosity (η *) at a measurement temperature of 200 ° C. is measured in the range of 0.02512 ≦ ω ≦ 100. A dynamic stress rheometer SR-5000 manufactured by Rheometrics was used for the measurement. The sample holder uses a 25 mmφ parallel plate, and the sample thickness is approximately 2.0 mm.
It was. The number of measurement points was 5 per ω digit. The amount of strain was appropriately selected within a range of 3 to 10% so that the torque in the measurement range could be detected and torque was not exceeded. The sample used for shear viscosity measurement was a press molding machine manufactured by Shin-Fuji Metal Industry Co., Ltd., preheating temperature 190 ° C, preheating
ゼロせん断粘度η0は、下記数式(Eq-5)のCarreauモデルを非線形最小二乗法により実測のレオロジー曲線[せん断粘度(η*)の角速度(ω)分散]にフィッティングさせることで
算出した。
The zero shear viscosity η 0 was calculated by fitting the Carreau model of the following formula (Eq-5) to an actually measured rheological curve [angular velocity (ω) dispersion of shear viscosity (η *)] by a nonlinear least square method.
上記式(Eq-5)中、λは時間の次元を持つパラメーター、nは材料の冪法則係数(Power law index)を表す。なお、非線形最小二乗法によるフィッティングは下記数式 (Eq-6)におけるdが最小となるよう行われる。 In the above formula (Eq-5), λ is a parameter having a time dimension, and n is a power law index of the material. The fitting by the nonlinear least square method is performed so that d in the following equation (Eq-6) is minimized.
上記式(Eq-6)中、ηexp(ω)は実測のせん断粘度、ηcalc(ω)はCarreauモデルより算出したせん断粘度を表す。
GPC-VISCO法による重量平均分子量(Mw)はウォーターズ社製 GPC/V2000を用い、以下
のようにして測定した。ガードカラムはShodex AT-G、分析カラムは AT-806を2本使用し
、カラム温度は145℃とし、移動相にはo-ジクロロベンゼンおよび酸化防止剤としてBHT 0.3重量%を用い、1.0 ml/分で移動させ、試料濃度は 0.1重量%とし、検出器として示差屈
折計、3キャピラリー粘度計を用いた。標準ポリスチレンは、東ソー社製を用いた。分子
量計算は、粘度計と屈折計から実測粘度を算出し、実測ユニバーサルキャリブレーションより重量平均分子量(Mw)を算出した。
In the above formula (Eq-6), η exp (ω) represents the measured shear viscosity, and η calc (ω) represents the shear viscosity calculated from the Carreau model.
The weight average molecular weight (Mw) by GPC-VISCO method was measured as follows using GPC / V2000 manufactured by Waters. The guard column uses Shodex AT-G, the analytical column uses two AT-806, the column temperature is 145 ° C, the mobile phase is o-dichlorobenzene and BHT 0.3 wt% as an antioxidant, 1.0 ml / The sample concentration was 0.1 wt%, and a differential refractometer and 3-capillary viscometer were used as detectors. Standard polystyrene used was manufactured by Tosoh Corporation. In the molecular weight calculation, the actually measured viscosity was calculated from a viscometer and a refractometer, and the weight average molecular weight (Mw) was calculated from the actually measured universal calibration.
本発明で用いられるエチレン系樹脂[R]は、上記した要件(I)〜(V)を満たす限り
は殆どのプラスチック産業用途において後述する効果を遺憾なく発現するが、成形性や流動性の突発的な不具合を確実に防止することができると言う視点からは、上記要件(I)〜(V)に加えて下記要件(VI)を同時に満たすことが好ましい。
The ethylene-based resin [R] used in the present invention exhibits the effects described later in most plastic industrial applications as long as the above requirements (I) to (V) are satisfied. From the standpoint that certain troubles can be surely prevented, it is preferable to simultaneously satisfy the following requirement (VI) in addition to the above requirements (I) to (V).
要件 (VI)
エチレン系樹脂[R]の、135℃デカリン中で測定した極限粘度([η] (dl/g))とGPC-粘度検出器法(GPC-VISCO)により測定された重量平均分子量Mwとが下記関係式(Eq-7)を満たす
。
Requirements (VI)
The intrinsic viscosity ([η] (dl / g)) of ethylene resin [R] measured in decalin at 135 ° C and the weight average molecular weight Mw measured by the GPC-viscosity detector method (GPC-VISCO) are as follows: The relational expression (Eq-7) is satisfied.
0.80×10-4×Mw0.776≦[η]≦1.65×10-4×Mw0.776 -----(Eq-7)
より好ましくは、下記関係式(Eq-8)を満たす。
0.90×10-4×Mw0.776≦[η]≦1.55×10-4×Mw0.776 -----(Eq-8)
特に好ましくは、下記関係式(Eq-9)を満たす。
0.80 × 10 -4 × Mw 0.776 ≦ [η] ≦ 1.65 × 10 -4 × Mw 0.776 ----- (Eq-7)
More preferably, the following relational expression (Eq-8) is satisfied.
0.90 × 10 -4 × Mw 0.776 ≦ [η] ≦ 1.55 × 10 -4 × Mw 0.776 ----- (Eq-8)
Particularly preferably, the following relational expression (Eq-9) is satisfied.
0.90×10-4×Mw0.776≦[η]≦1.40×10-4×Mw0.776 -----(Eq-9)
エチレン系重合体中に長鎖分岐が導入されると、長鎖分岐の無い直鎖型エチレン系重合体に比べ、分子量の割に極限粘度[η](dl/g)が小さくなることが知られている(例えばWalther Burchard, ADVANCES IN POLYMER SCIENCE, 143, Branched PolymerII, p.137(1999))。そのため、エチレン系樹脂[R]においても、極限粘度[η] (dl/g)が1.65×10-4×Mw0.776以下の場合は多数の長鎖分岐を有しているので、成形性、流動性に優れる。
0.90 × 10 -4 × Mw 0.776 ≦ [η] ≦ 1.40 × 10 -4 × Mw 0.776 ----- (Eq-9)
It is known that when long chain branching is introduced into an ethylene polymer, the intrinsic viscosity [η] (dl / g) is smaller for the molecular weight than a straight chain ethylene polymer without long chain branching. (For example, Walther Burchard, ADVANCES IN POLYMER SCIENCE, 143, Branched Polymer II, p.137 (1999)). Therefore, even in the ethylene-based resin [R], when the intrinsic viscosity [η] (dl / g) is 1.65 × 10 −4 × Mw 0.776 or less, it has a large number of long-chain branches. Excellent in properties.
後述の製造例31に記載した条件で製造することにより、極限粘度〔[η] (dl/g)〕と重
量平均分子量(Mw)との関係を規定したパラメーター式(Eq-7)の内、0.80×10-4×Mw0.776=[η]で規定される境界ラインに近いエチレン系重合体を得ることができ、一方で製造例21に記載した条件で製造することにより、パラメーター式(Eq-7)の内、[η]=1.65×10-4
×Mw0.776で規定される境界ラインに近いエチレン系重合体を得ることができる。
By producing under the conditions described in Production Example 31 to be described later, the parameter formula (Eq-7) that defines the relationship between the intrinsic viscosity [[η] (dl / g)] and the weight average molecular weight (Mw), 0.80 × 10 −4 × Mw 0.776 = Ethylene-based polymer close to the boundary line defined by [η] can be obtained, while by producing it under the conditions described in Production Example 21, the parameter formula (Eq− 7), [η] = 1.65 × 10 -4
× Mw An ethylene polymer close to the boundary line defined by 0.776 can be obtained.
なお、極限粘度[η] (dl/g)はデカリン溶媒を用い、以下のように測定した。サンプル
約20 mgをデカリン15 mlに溶解し、135℃のオイルバス中で比粘度ηspを測定する。この
デカリン溶液にデカリン溶媒を5 ml追加して希釈後、同様にして比粘度ηspを測定する。この希釈操作をさらに2回繰り返し、濃度(C)を0に外挿した時のηsp/C値を極限粘度[η]
とした。(下式(Eq-10)参照)
[η]=lim(ηsp/C) (C→0) ---------- (Eq-10)
本発明で用いられるエチレン系樹脂[R]は、必須構成成分であるエチレン系重合体[R1]
単独から構成されていてもよいし、エチレン系樹脂[R]が前記した要件(I)〜(V)を
同時に満たす範囲でエチレン系重合体[R2]の共存が許容されることは既に述べた通りである。以下、本発明のエチレン系樹脂[R]中の必須構成成分であるエチレン系重合体[R1]の
製造方法について詳細に述べる。
The intrinsic viscosity [η] (dl / g) was measured as follows using a decalin solvent. About 20 mg of sample is dissolved in 15 ml of decalin, and the specific viscosity η sp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity η sp is measured in the same manner. This dilution operation was repeated two more times, and the η sp / C value when the concentration (C) was extrapolated to 0 was calculated as the intrinsic viscosity [η].
It was. (Refer to the following formula (Eq-10))
[η] = lim (η sp / C) (C → 0) ---------- (Eq-10)
The ethylene resin [R] used in the present invention is an essential polymer, an ethylene polymer [R1].
It has already been described that the ethylene-based polymer [R2] may be composed of a single material, and the ethylene-based polymer [R2] is allowed to coexist as long as the ethylene-based resin [R] satisfies the above requirements (I) to (V) at the same time. Street. Hereinafter, a method for producing the ethylene polymer [R1], which is an essential component in the ethylene resin [R] of the present invention, will be described in detail.
《エチレン系重合体[R1]の製造方法》
本発明で用いられるエチレン系重合体[R1]は、
(S) 固体状担体と
(A)下記一般式(I)示される周期表第4族のメタロセン化合物(a-1)及び下記一般式(II)で表される周期表第4族の遷移金属化合物(a-2)から選ばれる少なくても一種の化合物
(B)下記一般式(III)示される周期表第4族のメタロセン化合物と、
(C) (c-1) 有機金属化合物
(c-2) 有機アルミニウムオキシ化合物、および
(c-3) 成分(A)、成分(B)と反応してイオン対を形成する化合物
よりなる群から選ばれる少なくとも1種の化合物、
から得られる粒子状の触媒成分〔以下の説明では、該触媒成分を「固体触媒成分(K)」と
略称する場合がある〕、および必要に応じて
(D) 有機アルミニウム化合物
の存在下、エチレンと、炭素数4〜10のα-オレフィンから選ばれる少なくとも1種のα−オレフィンとを重合することによって効率的に製造することができる。
<< Method for Producing Ethylene Polymer [R1] >>
The ethylene polymer [R1] used in the present invention is:
(S) with solid carrier
(A) From the metallocene compound (a-1) of the
(B) a metallocene compound of
(C) (c-1) Organometallic compound
(c-2) an organoaluminum oxy compound, and
(c-3) at least one compound selected from the group consisting of compounds that react with component (A) and component (B) to form ion pairs;
(In the following description, the catalyst component may be abbreviated as “solid catalyst component (K)”), and as necessary
(D) It can be efficiently produced by polymerizing ethylene and at least one α-olefin selected from α-olefins having 4 to 10 carbon atoms in the presence of an organoaluminum compound.
固体触媒成分(K)を調製する際の、前記各成分の接触順序の詳細については後記するが
、通常は、接触処理操作が簡便であるという視点から、下記方法[a]および方法[b]が好んで採用される。
[a] 成分(S)と成分(C)を混合接触させ、次いで成分(A)および成分(B)の混合成分を接触させて固体触媒成分(K)を調製する方法、
[b] 成分(S)と成分(C)を混合接触させ、次いで成分(A)を混合接触させて固体触媒成分(K-1)を調製し、別途、成分(S)と成分(C)を混合接触させ、次いで成分(B)を混合接触させて
固体触媒成分(K-2)を調製し、該固体触媒成分(K-1)と該固体触媒成分(K2)をブレンドして固体触媒成分(K)を調製する方法。
The details of the contact order of the components when preparing the solid catalyst component (K) will be described later. Usually, from the viewpoint that the contact treatment operation is simple, the following method [a] and method [b] Is preferred.
[a] a method of preparing a solid catalyst component (K) by mixing and contacting the component (S) and the component (C) and then contacting the mixed components of the component (A) and the component (B);
[b] Component (S) and component (C) are mixed and contacted, and then component (A) is mixed and contacted to prepare a solid catalyst component (K-1). Separately, component (S) and component (C) Are mixed and contacted, and then component (B) is mixed and contacted to prepare a solid catalyst component (K-2), and the solid catalyst component (K-1) and the solid catalyst component (K2) are blended to obtain a solid catalyst. A method of preparing component (K).
炭素数4〜10のα-オレフィンとしては、1-ブテン、1-ヘキセン、4-メチル-1-ペンテン
、1-オクテン、1-デセンなどが挙げられる。好ましくは炭素数6〜10のα-オレフィンであり、より好ましくは1-ヘキセンである。炭素数4〜10のα-オレフィンとして、異なる二種以上を使用することもできる。なお、α-オレフィンとして1-ブテンを使用する場合には
、炭素数6〜10のα-オレフィンの併用が好ましい。
Examples of the α-olefin having 4 to 10 carbon atoms include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene. An α-olefin having 6 to 10 carbon atoms is preferable, and 1-hexene is more preferable. Two or more different kinds of α-olefins having 4 to 10 carbon atoms can be used. In addition, when 1-butene is used as the α-olefin, it is preferable to use an α-olefin having 6 to 10 carbon atoms.
次に、各成分(A)、(B)、(C)および(D)について具体的に述べる。
成分(A)
成分(A)は、化合物(a-1)単独で構成されるか、化合物(a-2)単独で構成されるか、また
は化合物(a-1)と化合物(a-2)の併用で構成される。
Next, each component (A), (B), (C) and (D) will be specifically described.
Ingredient (A)
Component (A) is composed of compound (a-1) alone, compound (a-2) alone, or a combination of compound (a-1) and compound (a-2) Is done.
メタロセン化合物(a-1)は、下記一般式(I)で示される周期表第4族のメタロセン化合
物である。
The metallocene compound (a-1) is a metallocene compound belonging to
一般式(I)中、R1〜R8は水素原子、炭素数1〜20の炭化水素基(アルキル基、シクロアルキル基、アルケニル基、アリール基、アリールアルキル基)からなる群から選ばれる基であり、それぞれ同一でも異なってもよく、Q1は炭素数1〜20のアルキレン基、アルキリデ
ン基、ケイ素含有基からなる群から選ばれる基であり、Xは、それぞれ独立に、水素原子
、ハロゲン原子、炭素数1〜20の炭化水素基、炭素数1〜20のハロゲン含有炭化水素基、珪
素含有基、酸素含有基、イオウ含有基、窒素含有基およびリン含有基から選択された基である。Mはチタン、ジルコニウムまたはハフニウムである。
In the general formula (I), R 1 to R 8 are groups selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms (alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group). Each may be the same or different, and Q 1 is a group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms, an alkylidene group, and a silicon-containing group, and X is independently a hydrogen atom, a halogen atom, A group selected from an atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, and a phosphorus-containing group. . M is titanium, zirconium or hafnium.
好ましいメタロセン化合物(a-1)として、ジメチルシリレン基で架橋されたメタロセン
化合物が選ばれ、中でも、特に好ましい化合物しては、ジメチルシリレンビス(シクロペ
ンタジエニル)ジルコニウムジクロリド、ジメチルシリレンビス(2-メチルシクロペンタジエニル)ジルコニウムジクロリド、ジメチルシリレンビス(3-メチルシクロペンタジエニ
ル)ジルコニウムジクロリド、ジメチルシリレンビス(2-n-ブチルシクロペンタジエニル)ジルコニウムジクロリド、ジメチルシリレンビス(3-n-ブチルシクロペンタジエニル)ジルコニウムジクロリドが選ばれる。なお、後述する製造例で使用した化合物(a-1)は、
下記式(A-1)または下記式(A-2)で表される化合物であるが、本発明においてはこれら二種の化合物に何ら限定されるものではない。
As the preferred metallocene compound (a-1), a metallocene compound crosslinked with a dimethylsilylene group is selected, and among them, particularly preferred compounds are dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2- Methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3-n-butyl) Cyclopentadienyl) zirconium dichloride is chosen. In addition, the compound (a-1) used in the production examples described later is
Although it is a compound represented by the following formula (A-1) or the following formula (A-2), it is not limited to these two kinds of compounds in the present invention.
遷移金属化合物(a-2)は、下記一般式(II)で示される周期表第4族の遷移金属化合物である。
The transition metal compound (a-2) is a
一般式(II)中、Mは周期表第4族遷移金属原子を示し、mは、1〜4の整数を示し、R9は、
下記一般式(II-1)または(II-2)で表され、R10〜R14は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの2個以上が互いに連結して環を形成していても
よい。また、mが2の場合にはR10〜R14で示される基のうち2個の基が連結されていてもよ
く(但し、R9同士が結合されることはない)。nは、Mの価数を満たす数であり、Xは、水
素原子、ハロゲン原子、C1〜C20の炭化水素基、C1〜C20のハロゲン含有炭化水素基、珪素含有基、酸素含有基、イオウ含有基、窒素含有基およびリン含有基から選択された基を示し、nが2以上の場合は、Xで示される複数の基は互いに同一でも異なっていてもよく、ま
たXで示される複数の基は互いに結合して環を形成してもよい。
In the general formula (II), M represents a
It is represented by the following general formula (II-1) or (II-2), and R 10 to R 14 may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue , An oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these are linked to each other to form a ring It may be formed. When m is 2, two groups out of the groups represented by R 10 to R 14 may be linked (however, R 9 are not bonded to each other). n is a number that satisfies the valence of M, and X is a hydrogen atom, halogen atom, C1-C20 hydrocarbon group, C1-C20 halogen-containing hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing A group selected from a group, a nitrogen-containing group and a phosphorus-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X May combine with each other to form a ring.
(式中、Raは水素原子、脂肪族炭化水素基または脂環族炭化水素基を示し、Rb、Rcは水素原子あるいはメチル基を示し、互いに同一でも異なっていてもよい) (In the formula, Ra represents a hydrogen atom, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, Rb and Rc represent a hydrogen atom or a methyl group, and may be the same or different from each other)
(式中、破線は2つのCβが直接結合するか、炭素数1以上の炭化水素基により、2つのCβ
と結合していることを示す)
遷移金属化合物(a-2)の中で、前記一般式(II)において、R9が、メチル、エチル、n-プ
ロピル、n-ヘキシル、n-オクタデシル、シクロヘキシル、シクロヘプチル、シクロオクチル、4-tert-ブチルシクロヘキシル、メチレンシクロヘキシル、イソプロピル、1-メチル
ヘキシル、1,5-ジメチルヘキシルである化合物が好んで用いられる。なお、後述する製造例で使用した化合物(a-2)は、下記式(A-3)で表される化合物であるが、本発明においてはこの化合物に何ら限定されるものではない。
(In the formula, the broken line indicates that two Cβs are directly bonded to each other, or two Cβs are bound by a hydrocarbon group having 1 or more carbon atoms.
Indicates that it is combined with
Among the transition metal compounds (a-2), in the general formula (II), R 9 is methyl, ethyl, n-propyl, n-hexyl, n-octadecyl, cyclohexyl, cycloheptyl, cyclooctyl, 4- Compounds which are tert-butylcyclohexyl, methylenecyclohexyl, isopropyl, 1-methylhexyl, 1,5-dimethylhexyl are preferably used. In addition, the compound (a-2) used in the production examples described later is a compound represented by the following formula (A-3), but is not limited to this compound in the present invention.
成分(B)
成分(B)は、下記一般式(III)で示される周期表第4族のメタロセン化合物である。
Ingredient (B)
Component (B) is a metallocene compound belonging to
一般式(III)中、R9〜R20は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの2個以上が互いに連結して環を形成していてもよい。Q2は、二つの配
位子を結合する二価の基であって、炭素数1〜20の炭化水素基、炭素数1〜20のハロゲン含有炭化水素基、ケイ素含有基またはゲルマニウム或いはスズ含有基であり、Xは、それぞ
れ独立に、水素原子、ハロゲン原子、炭素数1〜20の炭化水素基、炭素数1〜20のハロゲン含有炭化水素基、珪素含有基、酸素含有基、イオウ含有基、窒素含有基およびリン含有基から選択された基であり、Mは、チタン、ジルコニウムおよびハフニウムから選ばれた遷
移金属である。
In general formula (III), R 9 to R 20 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or a boron-containing group. A group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring. Q 2 is a divalent group that binds two ligands and contains a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, germanium, or tin. X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. , A group selected from a nitrogen-containing group and a phosphorus-containing group, and M is a transition metal selected from titanium, zirconium and hafnium.
このうち好ましい成分(B)としては、イソプロピリデン(シクロペンタジエニル)(フルオレニル)ジルコニウムジクロリド、イソプロピリデン(シクロペンタジエニル)(2,7-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド、イソプロピリデン(シクロペンタジエニル)(3,6-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド、イソプロピリデン(シクロペンタジエニル)(オクタメチルオクタヒドリドジベンズフルオレニル)ジルコニウムジ
クロリド、シクロヘキシリデン(シクロペンタジエニル)(フルオレニル)ジルコニウムジクロリド、シクロヘキシリデン(シクロペンタジエニル)(2,7-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド、シクロヘキシリデン(シクロペンタジエニル)(3,6-ジ-tert-ブ
チルフルオレニル)ジルコニウムジクロリド、シクロヘキシリデン(シクロペンタジエニル)(オクタメチルオクタヒドリドジベンズフルオレニル)ジルコニウムジクロリド、ジメチ
ルシリル(シクロペンタジエニル)(フルオレニル)ジルコニウムジクロリド、ジメチルシリル(シクロペンタジエニル)(2,7-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド、ジメチルシリル(シクロペンタジエニル)(3,6-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド、ジメチルシリル(シクロペンタジエニル)(オクタメチルオクタヒドリドジベ
ンズフルオレニル)ジルコニウムジクロリド、イソプロピリデン(インデニル)(フルオレニル)ジルコニウムジクロリド、イソプロピリデン(インデニル)(2,7-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド、イソプロピリデン(インデニル)(3,6-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド、イソプロピリデン(インデニル)(オクタメチルオクタヒドリドジベンズフルオレニル)ジルコニウムジクロリド、シクロヘキシリデン(インデニル)(フルオレニル)ジルコニウムジクロリド、シクロヘキシリデン(インデニル)(2,7-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド、シクロヘキシリデン(インデニル)(3,6-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド、シクロヘキシリデン(インデニル)(オクタメチルオクタヒドリドジベンズフルオレニル)ジルコニウムジクロリド、ジ
メチルシリル(インデニル)(フルオレニル)ジルコニウムジクロリド、ジメチルシリル(イ
ンデニル)(2,7-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド、ジメチルシリル(インデニル)(3,6-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド、ジメチルシリ
ル(インデニル)(オクタメチルオクタヒドリドジベンズフルオレニル)ジルコニウムジクロリドが挙げられる。なお、後述する製造例で使用した成分(B)は、下記式(B-1)または下記式(B-2)で表されるメタロセン化合物であるが、本発明においてはこの化合物に何ら限定
されるものではない。
Among these, preferred components (B) include isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene. Liden (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene ( Cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6 -Di-tert-butylfluorenyl) zirconium dichloride, cyclohexyl Den (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (2,7-di- tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (octamethyloctahydridodibenz Fluorenyl) zirconium dichloride, isopropylidene (indenyl) (fluorenyl) zirconium dichloride, isopropylidene (indenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (indenyl) (3,6- Di-tert-butylfluorenyl) zirconium Loride, isopropylidene (indenyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene (indenyl) (fluorenyl) zirconium dichloride, cyclohexylidene (indenyl) (2,7-di-tert-butylfur Olenyl) zirconium dichloride, cyclohexylidene (indenyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (indenyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dimethyl Silyl (indenyl) (fluorenyl) zirconium dichloride, dimethylsilyl (indenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (indenyl) (3,6-di-tert-butylfluorenyl) ) Zirconium dichloride, dimethylsilyl (Indenyl) (octamethyl octa hydride blunder benz fluorenyl) zirconium dichloride. The component (B) used in the production examples described later is a metallocene compound represented by the following formula (B-1) or the following formula (B-2), but is not limited to this compound in the present invention. It is not something.
成分(C)
成分(C)は、(c-1) 有機金属化合物、(c-2) 有機アルミニウムオキシ化合物、および(c-3)成分(A)、成分(B)と反応してイオン対を形成する化合物から選ばれる少なくとも1種
の化合物である。これらの化合物については、本出願人による特開平11-315109号公報やEP0874005A1中に開示された化合物を制限無く使用することができるが、好ましい態様を以下に述べる。
Ingredient (C)
Component (C) is (c-1) an organometallic compound, (c-2) an organoaluminum oxy compound, and (c-3) a compound that reacts with component (A) and component (B) to form an ion pair. At least one compound selected from the group consisting of: As these compounds, compounds disclosed in Japanese Patent Application Laid-Open No. 11-315109 and EP0874005A1 by the present applicant can be used without limitation, but preferred embodiments are described below.
(c-1) 有機金属化合物としては、有機アルミニウム化合物が好ましく、1種単独または2種以上を組み合わせて用いられる。
(c-2) 有機アルミニウムオキシ化合物としては、トリアルキルアルミニウム、トリシクロアルキルアルミニウムから調製された有機アルミニウムオキシ化合物が好ましく、トリメチルアルミニウムまたはトリイソブチルアルミニウムから調製された有機アルミニウムオキシ化合物が特に好ましい。このような有機アルミニウムオキシ化合物は、1種単独ま
たは2種以上を組み合わせて用いられる。
(c-1) The organometallic compound is preferably an organoaluminum compound, and is used alone or in combination of two or more.
(c-2) The organoaluminum oxy compound is preferably an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum, and particularly preferably an organoaluminum oxy compound prepared from trimethylaluminum or triisobutylaluminum. Such organoaluminum oxy compounds are used singly or in combination of two or more.
(c-3) 成分(A)、成分(B)と反応してイオン対を形成する化合物としては、特開平1-501950号公報、特開平1-502036号公報、特開平3-179005号公報、特開平3-179006号公報、特開平3-207703号公報、特開平3-207704号公報、US5321106号公報などに記載されたルイス
酸、イオン性化合物、ボラン化合物およびカルボラン化合物や、さらにはヘテロポリ化合物およびイソポリ化合物を制限無く使用することができる。
(c-3) As compounds that react with component (A) and component (B) to form ion pairs, JP-A-1-501950, JP-A-1-502036, JP-A-3-17905 Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US5321106, etc. Compounds and isopoly compounds can be used without limitation.
成分(D)
エチレン系重合体[R1]の重合において任意成分として用いられる成分(D)は、前記成分(c-1)と同様の有機アルミニウム化合物が用いられる。後述する製造例ではトリイソブチルアルミニウムを用いているが本発明においてはこの化合物に何ら限定されるものではない。
Ingredient (D)
As the component (D) used as an optional component in the polymerization of the ethylene polymer [R1], the same organoaluminum compound as the component (c-1) is used. In the production examples described later, triisobutylaluminum is used, but the present invention is not limited to this compound.
なお、後述する製造例において使用した成分(C)は、上記(c-2)としての、トリメチルアルミニウムから調製された有機アルミニウムオキシ化合物(=メチルアルミノキサン)である。 The component (C) used in the production examples described later is an organoaluminum oxy compound (= methylaluminoxane) prepared from trimethylaluminum as the above (c-2).
成分(S)
エチレン系重合体[R1]を製造する際に用いられる固体触媒成分は、上記成分(A)、成分(B)と、成分(C)が、固体状担体(S)に担持されていることを特徴としている。
Ingredient (S)
The solid catalyst component used in producing the ethylene polymer [R1] is that the component (A), the component (B), and the component (C) are supported on the solid carrier (S). It is a feature.
固体状担体(S)は、無機または有機の化合物であって、顆粒状ないしは微粒子状の固体
である。
このうち無機化合物としては、多孔質酸化物、無機ハロゲン化物、粘土、粘土鉱物またはイオン交換性層状化合物が好ましく、多孔質酸化物がより好ましい。
The solid carrier (S) is an inorganic or organic compound and is a granular or particulate solid.
Among these, as the inorganic compound, porous oxides, inorganic halides, clays, clay minerals or ion-exchangeable layered compounds are preferable, and porous oxides are more preferable.
このような多孔質酸化物は、種類および製法によりその性状は異なるが、本発明に好ましく用いられる担体は、粒径が1〜300μm、好ましくは3〜200μmであって、比表面積が50〜1000m2/g、好ましくは100〜800m2/gの範囲にあり、細孔容積が0.3〜3.0 cm3/gの範囲にあることが望ましい。このような担体は、必要に応じて80〜1000℃、好ましくは100〜800℃で焼成して使用される。 Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 1 to 300 μm, preferably 3 to 200 μm, and a specific surface area of 50 to 1000 m. 2 / g, preferably in the range of 100 to 800 m 2 / g, and the pore volume is in the range of 0.3 to 3.0 cm 3 / g. Such a carrier is used after being calcined at 80 to 1000 ° C., preferably 100 to 800 ° C., if necessary.
後述する製造例で用いた担体は、平均粒子径が12μmであるシリカと、平均粒子系が50
μmであるシリカの二種類である。
固体触媒成分の調製
次に、前記した成分(S)、成分(A)、成分(B)および成分(C)から、固体触媒成分の調製する方法について記載する。
The carrier used in the production examples described later is silica having an average particle diameter of 12 μm and an average particle system of 50 μm.
There are two types of silica that are μm.
Preparation of Solid Catalyst Component Next, a method for preparing a solid catalyst component from the aforementioned component (S), component (A), component (B) and component (C) will be described.
固体触媒成分(K)は、成分(A)、成分(B)、成分(C)および、固体状担体(S)を不活性炭化
水素中で混合接触させることにより調製することができる。
この際の各成分の混合順序は任意であるが、好ましい接触順序としては、例えば、
i) 成分(S)と成分(C)を混合接触させ、次いで成分(A)を混合接触させて粒子状触媒成分(K-1)を調製し、別途、成分(S)と成分(C)を混合接触させ、次いで成分(B)を混合接触させて固体触媒成分(K-2)を調製し、該固体触媒成分(K-1)と該固体触媒成分(K-2)をブレンド
して固体触媒成分(K)を調製する方法。
The solid catalyst component (K) can be prepared by mixing and contacting the component (A), the component (B), the component (C), and the solid support (S) in an inert hydrocarbon.
The mixing order of the components at this time is arbitrary, but as a preferred contact order, for example,
i) Component (S) and component (C) are mixed and contacted, and then component (A) is mixed and contacted to prepare particulate catalyst component (K-1). Separately, component (S) and component (C) Then, the solid catalyst component (K-2) is prepared by mixing and contacting the component (B), and the solid catalyst component (K-1) and the solid catalyst component (K-2) are blended. A method for preparing the solid catalyst component (K).
ii) 成分(A)と成分(C)とを混合接触させ、次いで成分(S)を接触させて粒子状触媒成分(K-1)を調製し、別途、成分(B)と成分(C)とを混合接触させ、次いで成分(S)を接触させて
固体触媒成分(K-2)を調製し、該固体触媒成分(K-1)と該固体触媒成分(K2)をブレンドして固体触媒成分(K)を調製する方法。
ii) Component (A) and component (C) are mixed and contacted, and then component (S) is contacted to prepare particulate catalyst component (K-1). Separately, component (B) and component (C) Are mixed and contacted, and then the component (S) is contacted to prepare a solid catalyst component (K-2), and the solid catalyst component (K-1) and the solid catalyst component (K2) are blended to obtain a solid catalyst A method of preparing component (K).
iii) 成分(S)と成分(C)を混合接触させ、次いで成分(A)を接触させた後に、成分(B)を
接触させて粒子状触媒成分(K)を調製する方法
iv) 成分(S)と成分(C)を混合接触させ、次いで成分(B)を接触させた後に、成分(A)を接触させて粒子状触媒成分(K)を調製する方法
v) 成分(S)と成分(C)を混合接触させ、次いで成分(A)および成分(B)の混合成分を接触
させて粒子状触媒成分(K)を調製する方法
vi) 成分(A)と成分(B)の混合成分と成分(C)を接触させ、次いで成分(S)を接触させて粒子状触媒成分(K)を調製する方法
などが挙げられる。このうち、特に好ましい接触順序は、前記したように、上記i)とv)の接触方法である。上記の接触方法によって得られる固体触媒成分(K)、固体触媒成分(K-1)および固体触媒成分(K-2)は、重合時にそのままの形態で重合系に添加されてもよいし
、予めオレフィンを予備重合させた予備重合触媒成分として用いてもよい。予備重合においては、エチレン又はエチレンを主成分とするオレフィンが用いられ、予備重合量は、固体触媒成分1gあたり、0.01〜1,000g、好ましくは0.1〜800g、さらに好ましくは0.2〜500gである。
iii) A method in which the component (S) and the component (C) are mixed and contacted, and then the component (A) is contacted, and then the component (B) is contacted to prepare the particulate catalyst component (K).
iv) A method in which the component (S) and the component (C) are mixed and contacted, and then the component (B) is contacted, and then the component (A) is contacted to prepare the particulate catalyst component (K).
v) A method of preparing the particulate catalyst component (K) by bringing the component (S) and the component (C) into contact with each other and then contacting the mixed component of the component (A) and the component (B).
vi) A method of preparing the particulate catalyst component (K) by bringing the mixed component of the component (A) and the component (B) into contact with the component (C) and then contacting the component (S). Among these, a particularly preferable contact order is the contact method i) and v) described above. The solid catalyst component (K), solid catalyst component (K-1) and solid catalyst component (K-2) obtained by the above contact method may be added to the polymerization system as they are during polymerization, You may use as a prepolymerization catalyst component which prepolymerized the olefin. In the prepolymerization, ethylene or an olefin mainly composed of ethylene is used, and the prepolymerization amount is 0.01 to 1,000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g, per 1 g of the solid catalyst component.
固体触媒成分の調製に用いる溶媒としては、不活性炭化水素溶媒があげられ、具体的には、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、灯油等の脂肪族炭化水素;シクロペンタン、シクロヘキサン、メチルシクロペンタン等の脂環族炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素;エチレンクロリド
、クロルベンゼン、ジクロロメタン等のハロゲン化炭化水素またはこれらの混合物等を挙げることができる。成分(A)と成分(B)の予備接触時間は、通常0〜5時間、好ましくは0〜1時間、特に好ましくは0〜30分であり、その後の成分(C)と固体状担体(S)との接触物に接
触させる時間は、通常0〜24時間、好ましくは0〜5時間、特に好ましくは0〜2時間である
。これらの担持操作は、通常-50〜200℃、好ましくは-50〜50℃、特に好ましくは0〜40℃で行われる。
Examples of the solvent used for the preparation of the solid catalyst component include inert hydrocarbon solvents, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; And alicyclic hydrocarbons such as pentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures thereof. . The pre-contact time between the component (A) and the component (B) is usually 0 to 5 hours, preferably 0 to 1 hour, particularly preferably 0 to 30 minutes. Thereafter, the component (C) and the solid carrier (S The contact time with the contact product is usually 0 to 24 hours, preferably 0 to 5 hours, particularly preferably 0 to 2 hours. These loading operations are usually performed at -50 to 200 ° C, preferably -50 to 50 ° C, particularly preferably 0 to 40 ° C.
重合条件
成分(A)と成分(B)の使用比は、所望するエチレン系重合体の分子量及び分子量分布によっても異なるが、通常は成分(A)に起因する生成ポリマー重量(WA)と成分(B)に起因する生成ポリマー重量(WB)の比率[=WA/WB]が、40/60〜95/5、好ましくは、50/50〜95/5、特に好ましくは、60/40〜95/5になるように成分(A)と成分(B)の使用比が決められる。後述する
製造例で用いた成分(A)および成分(B)については、成分(A)と成分(B)のモル比[=成分(A)のモル量/成分(B)のモル量]として0.1〜50程度である。
Polymerization conditions The ratio of component (A) to component (B) used varies depending on the molecular weight and molecular weight distribution of the desired ethylene polymer, but usually the polymer weight (W A ) and component resulting from component (A) the ratio of the produced polymer weight resulting from (B) (W B) [ = W a / W B] is 40 / 60-95 / 5, preferably 50 / 50-95 / 5, particularly preferably 60 / The usage ratio of component (A) and component (B) is determined so as to be 40 to 95/5. For component (A) and component (B) used in the production examples described later, the molar ratio of component (A) to component (B) [= molar amount of component (A) / molar amount of component (B)] It is about 0.1-50.
なお、担体(S)に担持された成分(A)及び成分(B)中の全遷移金属原子(M)は、誘導結合プラズマ発光分析法(ICP分析法)により求めることができる。
成分(c-1)は、成分(c-1)と、成分(A)及び成分(B)中の全遷移金属原子(M)とのモル比[(c-1)/M]が、通常0.01〜100,000、好ましくは0.05〜50,000となるような量で用いられる
。成分(c-2)は、成分(c-2)中のアルミニウム原子と成分(A)及び成分(B)中の全遷移金属原子(M)とのモル比[(c-2)/M]が、通常10〜500,000、好ましくは20〜100,000となるような量で用いられる。成分(c-3)は、成分(c-3)と、成分(A)及び成分(B)中の全遷移金属原子(M)
とのモル比[(c-3)/M]が、通常1〜10、好ましくは1〜5となるような量で用いられる。
The total transition metal atoms (M) in the component (A) and the component (B) supported on the carrier (S) can be obtained by inductively coupled plasma emission analysis (ICP analysis).
Component (c-1) usually has a molar ratio [(c-1) / M] of component (c-1) to all transition metal atoms (M) in component (A) and component (B). It is used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. Component (c-2) is a molar ratio [(c-2) / M] of aluminum atoms in component (c-2) to all transition metal atoms (M) in component (A) and component (B). Is usually used in an amount of 10 to 500,000, preferably 20 to 100,000. Component (c-3) includes component (c-3) and all transition metal atoms (M) in component (A) and component (B).
The molar ratio [(c-3) / M] is usually 1 to 10, preferably 1 to 5.
エチレン系重合体[R1]は、上記した固体触媒成分の存在下に、エチレンと炭素数4〜10
のα-オレフィンを重合または共重合することにより得られる。
重合は溶解重合、懸濁重合等の液相重合法または気相重合法のいずれにおいても実施できるが、懸濁重合法または気相重合法が好ましい。
In the presence of the above-described solid catalyst component, the ethylene polymer [R1] has ethylene and 4 to 10 carbon atoms.
It is obtained by polymerizing or copolymerizing the α-olefin.
The polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method, but a suspension polymerization method or a gas phase polymerization method is preferred.
液相重合法において用いられる不活性炭化水素媒体として具体的には、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、灯油等の脂肪族炭化水素;シクロペンタン、シクロヘキサン、メチルシクロペンタン等の脂環族炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素;エチレンクロリド、クロルベンゼン、ジクロロメタン等のハロゲン化炭化水素またはこれらの混合物等を挙げることができ、オレフィン自身を溶媒として用いることもできる。 Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and the like aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, or a mixture thereof. You can also.
上記のような重合触媒を用いて重合を行うに際して、成分(A)及び成分(B)は、合計で反応容積1リットル当り、通常10-12〜10-1モル、好ましくは10-8〜10-2モルになるような量で用いられる。 In carrying out the polymerization using the polymerization catalyst as described above, the component (A) and the component (B) are generally 10 -12 to 10 -1 mol, preferably 10 -8 to 10 mol per liter of the reaction volume in total. Used in such an amount as to be -2 mol.
また、このような重合触媒を用いた重合温度は、通常-50〜+200℃、好ましくは0〜170℃、特に好ましくは60〜170℃の範囲である。重合圧力は、通常、常圧〜100kg/cm2、好ましくは常圧〜50kg/cm2 の条件下であり、重合反応は、回分式、半連続式、連続式のいず
れの方法においても行うことができる。さらに重合を反応条件の異なる2段以上に分けて
行うことも可能である。
The polymerization temperature using such a polymerization catalyst is usually in the range of -50 to + 200 ° C, preferably 0 to 170 ° C, particularly preferably 60 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm 2 , preferably from normal pressure to 50 kg / cm 2 , and the polymerization reaction is carried out in any of batch, semi-continuous and continuous methods. Can do. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions.
得られるエチレン系重合体[R1]の分子量は、重合系に水素を存在させるか、または重合温度を変化させることによって調節することができる。
また、重合を円滑に進行させる目的で、帯電防止剤やアンチファウリング剤などを併用したり、担体上に担持しても良い。
The molecular weight of the resulting ethylene polymer [R1] can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature.
Further, for the purpose of allowing the polymerization to proceed smoothly, an antistatic agent, an anti-fouling agent, or the like may be used in combination or supported on a carrier.
エチレン系樹脂[R1]の製造において使用できるオレフィン種については既に述べた通りであるが、エチレン系樹脂[R1]が兼ね備えるべき要件(I)〜(V)を満たす範囲において、次のようなオレフィンを併用することを何ら制限するものではない。炭素原子数が3
〜30、好ましくは炭素原子数が5〜20の環状オレフィン、たとえばシクロペンテン、シク
ロヘプテン、ノルボルネン、5-メチル-2-ノルボルネン、テトラシクロドデセン等;極性
モノマー、たとえば、アクリル酸、メタクリル酸、フマル酸、無水マレイン酸等;アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸等のα,β-不飽和カルボン酸エステル;酢酸ビニル、プロピオン酸ビニル等のビニルエステル類;アクリル酸グリシジル、メタクリル酸グリシジル等の不飽和グリシジル類;フッ化ビニル、塩化ビニル等のハロゲン化オレフィン類;ビニルシクロヘキサン、ジエンまたはポリエン;スチレン等の芳香族ビニル化合物;ジビニルベンゼン等の官能基含有スチレン誘導体等。
The olefin species that can be used in the production of the ethylene-based resin [R1] are as described above, but within the range that satisfies the requirements (I) to (V) that the ethylene-based resin [R1] should have, the following olefins It is not intended to limit the combined use. 3 carbon atoms
-30, preferably cyclic olefins having 5 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, etc .; polar monomers such as acrylic acid, methacrylic acid, fumaric acid , Maleic anhydride, etc .; α, β-unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid; vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid Unsaturated glycidyls such as glycidyl and glycidyl methacrylate; halogenated olefins such as vinyl fluoride and vinyl chloride; vinylcyclohexane, diene or polyene; aromatic vinyl compounds such as styrene; functional group-containing styrene derivatives such as divinylbenzene .
エチレン系重合体[R2]
エチレン系樹脂[R]を構成する任意成分としてのエチレン系重合体[R2]は、前記要件(
I)〜(V)のいずれか一つ、または二つ以上の要件を充足しないエチレン系重合体として定義される。このようなエチレン系重合体[R2]としては、ウルトゼックス15150J、ウルトゼックス20100J(商品名、株式会社プライムポリマー社製)などのチーグラーナッタ触媒で製造される低密度ポリエチレン、エボリューSP1540、エボリューSP2040(商品名、株式会社プライムポリマー社製)などのメタロセン触媒で製造される低密度ポリエチレン、ミラソン11P、ミラソン14P(商品名、株式会社プライムポリマー社製)などの高圧法低密度ポリエチレンを例示することができる。後述する製造例32には、エチレン系重合体[R2]として、株式会社プライムポリマー製造のエチレン・4-メチル-1-ペンテン共重合体(商品名: ウルトゼックスUZ15150J)が用いた例を示す。通常、エチレン系樹脂[R]中のエチレン系重合体[R1]の組成比率は99重量%以下、好ましくは70重量%以下、さらに好ましくは30重量%以下である。
Ethylene polymer [R2]
The ethylene-based polymer [R2] as an optional component constituting the ethylene-based resin [R]
It is defined as an ethylene polymer that does not satisfy any one of I) to (V), or two or more requirements. Examples of such an ethylene polymer [R2] include low density polyethylene, Evolue SP1540, Evolue SP2040 (produced by Ziegler-Natta catalysts such as Ultzex 15150J and Ultzex 20100J (trade name, manufactured by Prime Polymer Co., Ltd.). Examples include low-density polyethylene produced by metallocene catalysts such as trade name, manufactured by Prime Polymer Co., Ltd., and high-pressure low-density polyethylene such as Mirason 11P and Mirason 14P (trade name, manufactured by Prime Polymer Co., Ltd.). it can. Production Example 32 described later shows an example in which an ethylene-4-methyl-1-pentene copolymer (trade name: ULTZEX UZ15150J) manufactured by Prime Polymer Co., Ltd. was used as the ethylene polymer [R2]. Usually, the composition ratio of the ethylene polymer [R1] in the ethylene resin [R] is 99% by weight or less, preferably 70% by weight or less, and more preferably 30% by weight or less.
《熱可塑性樹脂[R3]》
エチレン系樹脂[R]は、エチレン系重合体[R1]およびエチレン系重合体[R2]以外の熱可
塑性樹脂[R3]とブレンドすることにより、成形性に優れ、かつ機械的強度に優れた組成物となる場合がある。エチレン系樹脂[R]と、熱可塑性樹脂[R3]とのブレンド比率([R]/[R3])は、通常は99.9/0.1〜0.1/99.9、好ましくは99.9/0.1〜30/70、より好ましくは99.9/0.1〜70/30である。なお、積層体用樹脂組成物は、熱可塑性樹脂[R3]、下記添加剤を含む
場合であっても、上記要件(I)〜(V)を全て満たすことが好ましい。
《Thermoplastic resin [R3]》
Ethylene resin [R] is a composition with excellent moldability and mechanical strength by blending with thermoplastic resin [R3] other than ethylene polymer [R1] and ethylene polymer [R2]. It can be a thing. Blend ratio ([R] / [R3]) of ethylene resin [R] and thermoplastic resin [R3] is usually 99.9 / 0.1 to 0.1 / 99.9, preferably 99.9 / 0.1 to 30/70 Preferably it is 99.9 / 0.1-70 / 30. In addition, even if it is a case where the resin composition for laminated bodies contains thermoplastic resin [R3] and the following additive, it is preferable to satisfy | fill all the said requirements (I)-(V).
熱可塑性樹脂[R3]としては、ポリオレフィン、ポリアミド、ポリエステルおよびポリアセタール等の結晶性熱可塑性樹脂; ポリスチレン、アクリロニトリル・ブタジエン・スチレン共重合体(ABS)、ポリカーボネート、ポリフェニレンオキサイド、ポリアクリレート等の非結晶性熱可塑性樹脂; ポリ塩化ビニル等を例示することができる。 As thermoplastic resin [R3], crystalline thermoplastic resins such as polyolefin, polyamide, polyester and polyacetal; non-crystalline such as polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate, polyphenylene oxide, polyacrylate Thermoplastic resin; Polyvinyl chloride and the like can be exemplified.
上記ポリオレフィンとして具体的には、プロピレン系重合体、ブテン系重合体、4-メチル-1-ペンテン系重合体、3-メチル-1-ブテン系重合体、ヘキセン系重合体などが挙げられる。中でも、プロピレン系重合体、4-メチル-1-ペンテン系重合体が好ましい。 Specific examples of the polyolefin include a propylene polymer, a butene polymer, a 4-methyl-1-pentene polymer, a 3-methyl-1-butene polymer, and a hexene polymer. Of these, propylene polymers and 4-methyl-1-pentene polymers are preferred.
上記ポリアミドとして具体的には、ナイロン-6、ナイロン-66、ナイロン-10、ナイロン-12、ナイロン-46等の脂肪族ポリアミド、芳香族ジカルボン酸と脂肪族ジアミンより製造される芳香族ポリアミドなどを挙げることができる。 Specific examples of the polyamide include aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12, and nylon-46, and aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines. Can be mentioned.
上記ポリエステルとして具体的には、ポリエチレンテレフタレート、ポリエチレンナフ
タレート、ポリブチレンテレフタレート等の芳香族系ポリエステル;ポリカプロラクトン、ポリヒドロキシブチレートなどを挙げることができる。
Specific examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polycaprolactone, polyhydroxybutyrate, and the like.
上記ポリアセタールとして具体的には、ポリホルムアルデヒド(ポリオキシメチレン)、ポリアセトアルデヒド、ポリプロピオンアルデヒド、ポリブチルアルデヒドなどを挙げることができる。中でも、ポリホルムアルデヒドが特に好ましい。 Specific examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde and the like. Among these, polyformaldehyde is particularly preferable.
上記ポリスチレンは、スチレンの単独重合体であってもよく、スチレンとアクリロニトリル、メタクリル酸メチル、α-メチルスチレンとの二元共重合体であってもよい。
上記ABSとしては、アクリロニトリルから誘導される構成単位を20〜35モル%の量で含有し、ブタジエンから誘導される構成単位を20〜30モル%の量で含有し、スチレンから誘導
される構成単位を40〜60モル%の量で含有するABSが好ましく用いられる。
The polystyrene may be a homopolymer of styrene, or a binary copolymer of styrene and acrylonitrile, methyl methacrylate, or α-methylstyrene.
The ABS includes a structural unit derived from acrylonitrile in an amount of 20 to 35 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, and a structural unit derived from styrene. Is preferably used in an amount of 40 to 60 mol%.
上記ポリカーボネートとしては、ビス(4-ヒドロキシフェニル)メタン、1,1-ビス(4-ヒ
ドロキシフェニル)エタン、2,2-ビス(4-ヒドロキシフェニル)プロパン、2,2-ビス(4-ヒドロキシフェニル)ブタンなどから得られるポリマーを挙げることができる。中でも、2,2-
ビス(4-ヒドロキシフェニル)プロパンから得られるポリカーボネートが特に好ましい。
Examples of the polycarbonate include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyphenyl). And polymers obtained from butane and the like. Among them, 2,2-
Polycarbonate obtained from bis (4-hydroxyphenyl) propane is particularly preferred.
上記ポリフェニレンオキシドとしては、ポリ(2,6-ジメチル-1,4-フェニレンオキシド)
を用いることが好ましい。
上記ポリアクリレートとしては、ポリメチルメタクリレート、ポリブチルアクリレートを用いることが好ましい。
As the above polyphenylene oxide, poly (2,6-dimethyl-1,4-phenylene oxide)
Is preferably used.
As the polyacrylate, polymethyl methacrylate or polybutyl acrylate is preferably used.
上記のような熱可塑性樹脂[R3]は、単独で用いてもよく、また二種以上組み合わせて用いてもよい。
《添加剤》
エチレン系樹脂[R]は、本発明の目的を損なわない範囲で、耐候性安定剤、耐熱安定剤
、帯電防止剤、スリップ防止剤、アンチブロッキング剤、防曇剤、滑剤、顔料、染料、核剤、可塑剤、老化防止剤、塩酸吸収剤、酸化防止剤等の添加剤が配合されていてもよい。
The thermoplastic resins [R3] as described above may be used alone or in combination of two or more.
"Additive"
The ethylene-based resin [R] is within a range that does not impair the object of the present invention, and is a weather resistance stabilizer, heat resistance stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, lubricant, pigment, dye, nucleus. Additives such as an agent, a plasticizer, an anti-aging agent, a hydrochloric acid absorbent, and an antioxidant may be blended.
《積層体》
エチレン系樹脂[R]および必要に応じて熱可塑性樹脂[R3]や添加剤を含む樹脂組成物は
、成形性に優れ、この組成物を加工することにより、機械的強度に優れた多層成形体、好ましくは多層フィルムが得られる。
<Laminate>
A resin composition containing an ethylene-based resin [R] and, if necessary, a thermoplastic resin [R3] and additives is excellent in moldability, and by processing this composition, a multilayer molded article excellent in mechanical strength A multilayer film is preferably obtained.
エチレン系樹脂[R]および必要に応じて熱可塑性樹脂[R3]や添加剤を含む樹脂組成物は
、一般のフィルム成形やブロー成形、インジェクション成形及び押出成形により加工される。フィルム成形では押出ラミネート成形、Tダイフィルム成形、インフレーション成形(空冷、水冷、多段冷却、高速加工)などが挙げられる。得られたフィルムは単層でも使用することができるが、多層(積層体)とすることでさらに様々な機能を付与することができる。その場合には、前記各成形法における共押出法が挙げられる。一方押出ラミネート成形やドライラミネート法のような貼合ラミネート成形法によって、共押出が困難な紙やバリアフィルム(アルミ箔、蒸着フィルム、コーティングフィルムなど)との積層が挙げられる。ブロー成形やインジェクション成形、押出成形での、共押出法による多層化での高機能製品の作製については、フィルム成形と同様に可能である。
The resin composition containing the ethylene-based resin [R] and, if necessary, the thermoplastic resin [R3] and additives is processed by general film molding, blow molding, injection molding, and extrusion molding. Examples of film molding include extrusion lamination molding, T-die film molding, and inflation molding (air cooling, water cooling, multistage cooling, high-speed processing), and the like. The obtained film can be used as a single layer, but various functions can be imparted by forming a multilayer (laminate). In that case, the coextrusion method in each said shaping | molding method is mentioned. On the other hand, lamination with paper and barrier films (aluminum foil, vapor-deposited film, coating film, etc.) that are difficult to co-extrusion by a lamination method such as extrusion lamination or dry lamination is mentioned. Production of high-functional products by multilayering by co-extrusion methods in blow molding, injection molding, and extrusion molding is possible in the same manner as film molding.
エチレン系樹脂[R]および必要に応じて熱可塑性樹脂[R3]や添加剤を含む樹脂組成物を
加工することにより得られる多層成形体としては、フィルム、ブロー輸液バック、ブローボトル、ガソリンタンク、押出成形によるチューブ、パイプ、引きちぎりキャップ、日用雑貨品等射出成形物、繊維、回転成形による大型成形品などが挙げられる。
As a multilayer molded body obtained by processing a resin composition containing an ethylene resin [R] and, if necessary, a thermoplastic resin [R3] or an additive, a film, a blow infusion bag, a blow bottle, a gasoline tank, Examples include extrusion molded tubes, pipes, tear caps, daily miscellaneous products, such as injection molded articles, fibers, and large molded articles by rotational molding.
さらに、エチレン系樹脂[R]および必要に応じて熱可塑性樹脂[R3]や添加剤を含む樹脂
組成物を加工することにより得られる多層フィルムとしては水物包装袋、液体スープ包袋、液体紙器、ラミ原反、特殊形状液体包装袋(スタンディングパウチ等)、規格袋、重袋、ラップフィルム、砂糖袋、油物包装袋、食品包装用等の各種包装用フィルム、プロテクトフィルム、輸液バック、農業用資材等に好適である。また、ナイロン、ポリエステル等の基材と貼り合わせて、多層フィルムとして用いることもできる。
Furthermore, multilayer films obtained by processing a resin composition containing an ethylene-based resin [R] and, if necessary, a thermoplastic resin [R3] and additives include water packaging bags, liquid soup bags, and liquid paper containers. , Lami fabric, special shape liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, wrap films, sugar bags, oil packaging bags, food packaging packaging films, protective films, infusion bags, agriculture Suitable for materials for use. It can also be used as a multilayer film by being bonded to a base material such as nylon or polyester.
エチレン系樹脂[R]および必要に応じて熱可塑性樹脂[R3]や添加剤を含む樹脂組成物は
、特に押出ラミネート加工による積層体用途に好適に使用される。
積層体用樹脂組成物を押出ラミネート加工する場合の基材としては、高密度ポリエチレン、中・低密度ポリエチレン、ポリプロピレン、ポリスチレン、ポリアミド、ポリエステル、エチレン−酢酸ビニル共重合体、ポリビニルアルコール、エチレン−ビニルアルコール共重合体、ポリカーボネートなどの樹脂フィルムまたはシート;アルミニウム、鉄、銅、またはこれらを主成分とする合金などの金属箔または金属板;セロファン、布、織布、不織布などが挙げられる。本発明の積層体用樹脂組成物と上記基材の接着強度を向上させるために、必要に応じて基材の表面にコロナ放電処理、フレーム処理、オゾン処理などの処理を行ったり、該樹脂組成物と基材の間に接着剤を介在させてもよい。
A resin composition containing an ethylene-based resin [R] and, if necessary, a thermoplastic resin [R3] or an additive is suitably used particularly for laminate applications by extrusion lamination.
High-density polyethylene, medium / low-density polyethylene, polypropylene, polystyrene, polyamide, polyester, ethylene-vinyl acetate copolymer, polyvinyl alcohol, ethylene-vinyl are used as base materials for extrusion laminate processing of laminate resin compositions. Examples thereof include resin films or sheets such as alcohol copolymers and polycarbonates; metal foils or metal plates such as aluminum, iron, copper, or alloys based on these; cellophane, cloth, woven cloth, and non-woven cloth. In order to improve the adhesive strength between the resin composition for laminates of the present invention and the substrate, the surface of the substrate is subjected to treatment such as corona discharge treatment, flame treatment, ozone treatment, etc., if necessary, or the resin composition An adhesive may be interposed between the article and the substrate.
本発明の積層体用樹脂組成物を押出ラミネート加工するための装置としては通常のT−ダイ方式の装置を用いることができる。ラミネートの厚さには特に制限はなく、目的に応じた厚さを適宜選択すれば良い。本発明の積層体用樹脂組成物は、基材の少なくとも一表面に押出ラミネート加工することに用いられる。また基材の片面に一層の該樹脂組成物を押出ラミネートする場合に限らず、多層T−ダイ押出機を用いて、基材の片面に二層以上を押出ラミネートしても良い。その場合、該樹脂組成物を最外層に用いるか内層に用いるかは製品の使用目的に応じて選択すれば良い。 As an apparatus for extrusion laminating the resin composition for a laminate of the present invention, an ordinary T-die type apparatus can be used. There is no restriction | limiting in particular in the thickness of a laminate, What is necessary is just to select the thickness according to the objective suitably. The resin composition for laminates of the present invention is used for extrusion lamination processing on at least one surface of a substrate. Moreover, it is not limited to the case where one layer of the resin composition is extruded and laminated on one side of the substrate, and two or more layers may be extruded and laminated on one side of the substrate using a multilayer T-die extruder. In this case, whether the resin composition is used for the outermost layer or the inner layer may be selected according to the purpose of use of the product.
[実施例]
以下、本発明について実施例に基づいて具体的に説明するが、本発明はかかる実施例によって何ら制限を受けるものではない。なお、エチレン系樹脂の分析方法および評価方法の中で、以上の説明中に記述されていない方法は以下の通りである。
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not restrict | limited at all by this Example. Of the ethylene resin analysis and evaluation methods, methods not described in the above description are as follows.
[m1] 数平均分子量(Mn)、Z平均分子量(Mz)、重量平均分子量と数平均分子量との比(Mw/Mn)、Z平均分子量と重量平均分子量との比(Mz/Mw)
数平均分子量(Mn)、Z平均分子量(Mz)、重量平均分子量と数平均分子量との比(Mw/Mn)、Z平均分子量と重量平均分子量との比(Mz/Mw)はウォーターズ社製GPC/V2000を用い、以下のようにして測定した。ガードカラムはShodex AT-G、分析カラムはAT-806を2本使用し、カラム温度は145℃とし、移動相にはo-ジクロロベンゼンおよび酸化防止剤とし
てBHT 0.3重量%を用い、1.0 ml/分で移動させ、試料濃度は0.1重量%とし、検出器として
示差屈折計、3キャピラリー粘度計を用いた。標準ポリスチレンは、東ソー社製を用いた
。分子量計算は、粘度計と屈折計から実測粘度を算出し、実測ユニバーサルキャリブレーションより算出した。
[m2] ネックイン
得られたエチレン系重合体を、65 mmφの押出機とダイ幅500 mmのTダイを有する住友重機社製ラミネーターを用いて、基材である50 g/m2のクラフト紙上に下記条件にて押出ラ
ミネートした。
・エアギャップ: 130 mm
・ダイ下樹脂温度: 295℃
・引取速度:80 m/分、120 m/分、200 m/分
・膜厚:引取速度80 m/分の時は20μm、引取速度120 m/分の時は13μm、引取速度200 m/
分の時は8μm
Tダイの幅をL0、各引取速度にてクラフト紙上にラミネートされたフィルムの幅をLとしたとき、ネックインはL0−Lにより算出される。
[m3] 膜切れ速度、引取サージング発生速度
得られたエチレン系重合体を、65 mmφの押出機とダイ幅500 mmのTダイを有する住友重機社製ラミネーターを用いて、基材である50 g/m2のクラフト紙上に、エアギャップ130 mm、ダイ下樹脂温度295℃の条件にて押出ラミネートした。押出量は引取速度80 m/分の時
の膜厚が20μmになるよう設定した。
[m1] Number average molecular weight (Mn), Z average molecular weight (Mz), Ratio of weight average molecular weight to number average molecular weight (Mw / Mn), Ratio of Z average molecular weight to weight average molecular weight (Mz / Mw)
Number average molecular weight (Mn), Z average molecular weight (Mz), ratio of weight average molecular weight to number average molecular weight (Mw / Mn), ratio of Z average molecular weight to weight average molecular weight (Mz / Mw) is GPC manufactured by Waters Using / V2000, measurement was performed as follows. The guard column uses Shodex AT-G, the analytical column uses two AT-806, the column temperature is 145 ° C, the mobile phase uses o-dichlorobenzene and 0.3% by weight BHT as an antioxidant, 1.0 ml / The sample concentration was 0.1 wt%, and a differential refractometer and 3-capillary viscometer were used as detectors. Standard polystyrene used was manufactured by Tosoh Corporation. The molecular weight was calculated by measuring the measured viscosity from a viscometer and a refractometer, and calculating from the measured universal calibration.
[m2] Neck-in The obtained ethylene-based polymer was placed on a base material of 50 g / m 2 kraft paper using a 65 mmφ extruder and a Sumitomo Heavy Industries laminator having a die D of 500 mm. Were extruded and laminated under the following conditions.
・ Air gap: 130 mm
・ Resin temperature under die: 295 ℃
・ Take-off speed: 80 m / min, 120 m / min, 200 m / min ・ Film thickness: 20 μm at take-up speed of 80 m / min, 13 μm at take-up speed of 120 m / min, take-up speed 200 m / min
8μm for minutes
When the width of the T die is L 0 and the width of the film laminated on the kraft paper at each take-off speed is L, the neck-in is calculated by L 0 -L.
[m3] Film breakage speed, take-off surging generation speed The obtained ethylene-based polymer was added to a base material of 50 g by using a 65 mmφ extruder and a Sumitomo Heavy Industries Laminator having a T die having a die width of 500 mm. / m 2 craft paper was extrusion-laminated at an air-gap 130 mm, die under a resin temperature 295 ° C. conditions. The amount of extrusion was set so that the film thickness was 20 μm when the take-up speed was 80 m / min.
引取速度を上昇させていき、溶融膜が切れたときの引取速度を膜切れ速度とした。
また、引取速度を上昇させていき、各引取速度におけるネックインを5回測定し、そのネ
ックインの平均値に対して±1.5 mm以上になる値が2回以上測定された時の引取速度を引
取サージング発生速度とした。
[m4] 樹脂圧力
得られたエチレン系重合体を、65 mmφの押出機とダイ幅500 mmのTダイを有する住友重機社製ラミネーターを用いて、基材である50 g/m2のクラフト紙上に、エアギャップ130 mm、ダイ下樹脂温度295℃、引取速度80 m/minの条件下で膜厚20μmになるよう押出ラミネ
ートした。そのときのクロスヘッド部の樹脂圧力を測定した。
[m5] ヒートシール強度
得られたエチレン系重合体を、65 mmφの押出機とダイ幅500 mmのTダイを有する住友重機社製ラミネーターを用いて、基材上にエアギャップ130 mm、ダイ下樹脂温度295℃、引
取速度80 m/minの条件下で、膜厚25μmになるよう押出ラミネートした。基材には、厚さ15μmの二軸延伸ナイロンフィルム(商品名 エンブレムONM、ユニチカ(株)製)の片面に、ウレタン系アンカーコート剤を塗布し、その後、チーグラー触媒により得られた直鎖状低密度ポリエチレンと高圧法低密度ポリエチレンをそれぞれ50重量部ずつブレンドしたエチレン系混合樹脂を25μmの厚さで押出ラミネートした積層体を用いた。なお、エチレン
系重合体は上記積層体のエチレン系混合樹脂層側に押出ラミネートされる。
The take-up speed was increased, and the take-off speed when the molten film was cut was defined as the film cut-off speed.
Also, increase the take-up speed, measure the neck-in at each take-up
[m4] Resin pressure The obtained ethylene-based polymer was applied to a base material of 50 g / m 2 kraft paper using a 65 mmφ extruder and a Sumitomo Heavy Industries laminator having a T die with a die width of 500 mm. The laminate was extruded and laminated to a film thickness of 20 μm under the conditions of an air gap of 130 mm, a resin temperature under the die of 295 ° C., and a take-off speed of 80 m / min. The resin pressure of the crosshead part at that time was measured.
[m5] Heat seal strength The obtained ethylene-based polymer was placed on a substrate with a 65 mmφ extruder and a Sumitomo Heavy Industries laminator having a T die with a die width of 500 mm. Extrusion lamination was carried out so that the film thickness was 25 μm under the conditions of a resin temperature of 295 ° C. and a take-up speed of 80 m / min. The base material was coated with a urethane anchor coating agent on one side of a 15-μm thick biaxially stretched nylon film (trade name Emblem ONM, manufactured by Unitika Ltd.), and then the linear shape obtained with a Ziegler catalyst. A laminate obtained by extrusion laminating an ethylene-based mixed resin in which 50 parts by weight of low-density polyethylene and high-pressure method low-density polyethylene were blended at a thickness of 25 μm was used. The ethylene polymer is extrusion-laminated on the ethylene mixed resin layer side of the laminate.
この押出ラミネートフィルムのエチレン系重合体層同士のヒートシール強度を下記方法に従って測定ないし評価した。
・片面加熱バーシーラーを使用
・ヒートシール圧力:2 kg/cm2
・ヒートシール時間:0.5秒
・シールバーの幅:10 mm
・試験片幅:15 mm
・剥離角度:180度
・剥離速度:30 mm/分
[m6] 造粒方法
得られたエチレン系重合体、単軸65 mmφ押出機(株式会社プラコー製)を用い、設定
温度180℃、スクリュー回転数50 rpmで溶融混練し、樹脂組成物とした後、ストランド状
に押出し、カッターにてペレットとした。
[m7] 樹脂圧力、モーター負荷
得られたエチレン系重合体を、65 mmφの押出機とダイ幅500 mmのTダイを有する住友重機社製ラミネーターを用いて、基材である50 g/m2のクラフト紙上に、エアギャップ130 mm、ダイ下樹脂温度295℃、引取速度80 m/minの条件下で膜厚20μmになるよう押出ラミネ
ートした。そのときのクロスヘッド部の樹脂圧力およびスクリューを駆動させるモーターの負荷を測定した。
[製造例1]
[固体成分(S-1)の調製]
内容積260リットルの攪拌機付き反応器に、窒素雰囲気下、250℃で10時間乾燥したシリ
カ(SiO2:平均粒子径12μm)10kgを90.5リットルのトルエンに懸濁した後、0〜5℃まで
冷却した。この懸濁液にメチルアルモキサンのトルエン溶液(Al原子換算で3.0mmol/ml)45.5リットルを30分間かけて滴下した。この際、系内の温度を0〜5℃に保った。引き続き0〜5℃で30分間反応させた後、約1.5時間かけて95〜100℃まで昇温して、引き続き95〜100℃で4時間反応させた。その後常温まで降温して、上澄み液をデカンテーションにより除去した。このようにして得られた固体成分をトルエンで2回洗浄した後、トルエンを加え
て全量129リットルとし、固体成分(S-1)のトルエンスラリーを調製した。得られた固体成分の一部を採取し、濃度を調べたところ、スラリー濃度:137.5g/L、Al濃度:1.1mol/Lであった。
The heat seal strength between the ethylene polymer layers of this extruded laminate film was measured or evaluated according to the following method.
・ Uses single-sided heating bar sealer ・ Heat seal pressure: 2 kg / cm 2
・ Heat seal time: 0.5 seconds ・ Width of seal bar: 10 mm
・ Specimen width: 15 mm
・ Peeling angle: 180 degrees ・ Peeling speed: 30 mm / min
[m6] Granulation method After the obtained ethylene polymer was melt-kneaded at a set temperature of 180 ° C. and a screw rotation speed of 50 rpm using a single-axis 65 mmφ extruder (manufactured by Placo Corporation), a resin composition was obtained. Then, it was extruded into a strand shape and pelletized with a cutter.
[m7] Resin pressure, motor load The obtained ethylene-based polymer was added to a base material of 50 g / m 2 using a Sumitomo Heavy Industries Laminator having a 65 mmφ extruder and a T die having a die width of 500 mm. Was extruded and laminated to a film thickness of 20 μm under the conditions of an air gap of 130 mm, a resin temperature under the die of 295 ° C., and a take-off speed of 80 m / min. The resin pressure of the crosshead part at that time and the load of the motor that drives the screw were measured.
[Production Example 1]
[Preparation of solid component (S-1)]
In a reactor equipped with a stirrer with an internal volume of 260 liters, 10 kg of silica (SiO 2 :
[固体触媒成分(X-1)の調製] エチレン系樹脂[R1]
内容積114リットルの攪拌機付き反応器に、窒素雰囲気下、トルエン21.0リットルと上
記で調製した固体成分(S-1)のトルエンスラリー15.8リットル(固体成分で2400g)を添加した。一方、内容積100リットルの攪拌機付き反応器に、窒素雰囲気下、トルエン31.0リ
ットルを張り込み、攪拌下、メタロセン化合物(A-1)のトルエン溶液(Zr原子換算で8.25mmol/L)10.0リットルを投入し、続いてメタロセン化合物(B-1)のトルエン溶液(Zr原子換算で2.17mmol/L) 2.0リットルを投入し数分間混合した〔(A-1)/(B-1)モル比=95/5〕。続いて、調製した混合溶液を予め固体成分(S-1)のトルエンスラリーを張り込んだ上記反応
器に圧送した。圧送後、内温20〜25℃で1時間反応させた。その後、上澄み液をデカンテ
ーションにより除去した。このようにして得られた固体触媒成分をヘキサンで3回洗浄し
た後、ヘキサンを加えて全量56リットルとし、固体触媒成分(X-1)のヘキサンスラリーを
調製した。
[Preparation of solid catalyst component (X-1)] Ethylene resin [R1]
Under a nitrogen atmosphere, 21.0 liters of toluene and 15.8 liters of the toluene slurry of the solid component (S-1) prepared above (2400 g as the solid component) were added to a reactor equipped with a stirrer having an internal volume of 114 liters. On the other hand, 31.0 liters of toluene was placed in a reactor with an internal volume of 100 liters under a nitrogen atmosphere, and 10.0 liters of a toluene solution of metallocene compound (A-1) (8.25 mmol / L in terms of Zr atoms) was added with stirring. Subsequently, 2.0 liters of a toluene solution of metallocene compound (B-1) (2.17 mmol / L in terms of Zr atoms) was added and mixed for several minutes [(A-1) / (B-1) molar ratio = 95 / Five〕. Subsequently, the prepared mixed solution was pumped to the reactor in which the toluene slurry of the solid component (S-1) was previously applied. After pumping, the reaction was carried out at an internal temperature of 20 to 25 ° C. for 1 hour. Thereafter, the supernatant was removed by decantation. The solid catalyst component thus obtained was washed three times with hexane, and then hexane was added to make a total volume of 56 liters to prepare a hexane slurry of the solid catalyst component (X-1).
[予備重合触媒(XP-1)の調製]
引き続き、上記で得られた固体触媒成分(X-1)のヘキサンスラリーを10℃まで冷却した
後、常圧下でエチレンを系内に連続的に数分間供給した。この間、系内の温度は10〜15℃に保持した。その後、トリイソブチルアルミニウム(TIBAL)2.8molと1-ヘキセン157mlを添加した。1-ヘキセン添加後にエチレンを1.8 kg/hrで再度供給し予備重合を開始した。
予備重合を開始してから40分後に系内温度は24℃まで上昇し、それ以降の系内温度は24〜26℃に保持した。予備重合を開始してから70分後に1-ヘキセン79.0mlを添加、140分後に
も1-ヘキセン79.0mlを添加した。
[Preparation of prepolymerization catalyst (XP-1)]
Subsequently, after the hexane slurry of the solid catalyst component (X-1) obtained above was cooled to 10 ° C., ethylene was continuously supplied into the system for several minutes under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, 2.8 mol of triisobutylaluminum (TIBAL) and 157 ml of 1-hexene were added. After the addition of 1-hexene, ethylene was supplied again at 1.8 kg / hr to start prepolymerization.
After 40 minutes from the start of the prepolymerization, the system temperature rose to 24 ° C, and the subsequent system temperature was maintained at 24-26 ° C. 70 minutes after the start of the prepolymerization, 79.0 ml of 1-hexene was added, and 79.0 ml of 1-hexene was added 140 minutes later.
予備重合開始から220分後に、エチレン供給を停止し系内を窒素により置換し、予備重
合を停止した。その後、上澄み液をデカンテーションにより除去した。このようにして得られた予備重合触媒をヘキサンで6回洗浄し、固体触媒成分1g当り2.87gのポリマーが重合された予備重合触媒(XP-1)を得た。得られた予備重合触媒成分の一部を乾燥し、組成を調べたところ、固体触媒成分1g当たりZr原子が0.72mg含まれていた。
220 minutes after the start of prepolymerization, the ethylene supply was stopped, the inside of the system was replaced with nitrogen, and the prepolymerization was stopped. Thereafter, the supernatant was removed by decantation. The prepolymerized catalyst thus obtained was washed 6 times with hexane to obtain a prepolymerized catalyst (XP-1) in which 2.87 g of polymer was polymerized per 1 g of the solid catalyst component. A portion of the obtained prepolymerized catalyst component was dried and the composition was examined. As a result, 0.72 mg of Zr atoms were contained per 1 g of the solid catalyst component.
[重合]
内容積290リットルの完全攪拌混合型重合槽において、上記予備重合触媒(XP-1)を用い
て、エチレン系重合体の製造を行った。
[polymerization]
An ethylene polymer was produced using the pre-polymerization catalyst (XP-1) in a completely stirred and mixed polymerization tank having an internal volume of 290 liters.
重合槽内に、溶媒ヘキサンを45L/h、予備重合触媒(XP-1)をZr原子に換算して0.44mmol/h、トリイソブチルアルミニウムを20.0mmol/hr、エチレンを6.6kg/hr、1-ヘキセンを500g/hrの割合となる様に連続的に供給した。かつ重合槽内の溶媒量が一定となる様に重合槽
より重合体スラリーを連続的に抜き出し、全圧0.8MPa-G、重合温度80℃、滞留時間2.6hr
という条件で重合を行った。重合槽から連続的に抜き出された重合体スラリーは、フラッシュドラムで未反応エチレンが実質的に除去される。その後、重合体スラリー中のヘキサンを溶媒分離装置で除去し、乾燥し、エチレン系重合体を4.4kg/hrで得た(第1表参照)
。
In the polymerization tank, the solvent hexane is 45 L / h, the prepolymerization catalyst (XP-1) is converted to Zr atoms, 0.44 mmol / h, triisobutylaluminum is 20.0 mmol / hr, ethylene is 6.6 kg / hr, 1- Hexene was continuously supplied at a rate of 500 g / hr. In addition, the polymer slurry is continuously withdrawn from the polymerization tank so that the amount of solvent in the polymerization tank is constant, and the total pressure is 0.8 MPa-G, the polymerization temperature is 80 ° C., and the residence time is 2.6 hours.
Polymerization was performed under the conditions. From the polymer slurry continuously extracted from the polymerization tank, unreacted ethylene is substantially removed by a flash drum. Thereafter, hexane in the polymer slurry was removed with a solvent separator and dried to obtain an ethylene polymer at 4.4 kg / hr (see Table 1).
.
得られたエチレン系重合体に、耐熱安定剤としてIrganox1076(チバスペシャリティケ
ミカルズ社製)を0.1重量%、Irgafos168(チバスペシャリティケミカルズ社製)を0.1重
量%になるように加え、株式会社プラコー社製の単軸65mmφ押出機を用い、設定温度180℃、スクリュー回転数50rpmの条件にて溶融混練した後、ストランド状に押出し、カッター
にてペレットとしたものを測定試料とした。該試料を用いて物性測定、押出ラミネート成形を行った結果を第5表および第10表に示す。
[製造例2]〜[製造例4]
[重合]
製造例1において、重合条件を第1表に示す条件に変えた以外は、製造例1と同様にして
エチレン系重合体を得た(第1表参照)。得られたエチレン系重合体を用い、製造例1と同様の方法にて測定試料を調製した。該試料を用いて物性測定、押出ラミネート成形を行った結果を第5表と第10表に示す。
[製造例5]
[固体触媒成分(X-2)の調製]
内容積114リットルの攪拌機付き反応器に、窒素雰囲気下、トルエン18.6リットルと上
記で調製した固体成分(S-1)のトルエンスラリー 7.9リットル(固体成分で1200g)を添加した。一方、内容積100リットルの攪拌機付き反応器に、窒素雰囲気下、トルエン14.5リ
ットルを張り込み、攪拌下、メタロセン化合物(A-1)のトルエン溶液(Zr原子換算で7.81mmol/L) 5.0リットルを投入し、続いてメタロセン化合物(B-1)のトルエン溶液(Zr原子換算で2.17mmol/L) 2.0リットルを投入し数分間混合した〔(A-1)/(B-1)モル比=85/15〕。
続いて、調製した混合溶液を予め固体成分(S-1)のトルエンスラリーを張り込んだ上記反
応器に圧送した。圧送後、内温20〜25℃で1時間反応させた。その後、上澄み液をデカン
テーションにより除去した。このようにして得られた固体触媒成分をヘキサンで3回洗浄
した後、ヘキサンを加えて全量30リットルとし、固体触媒成分(X-2)のヘキサンスラリー
を調製した。
To the obtained ethylene polymer, Irganox 1076 (manufactured by Ciba Specialty Chemicals) was added as a heat-resistant stabilizer to 0.1% by weight and Irgafos168 (manufactured by Ciba Specialty Chemicals) was added to 0.1% by weight. Using a single-shaft 65 mmφ extruder, melt kneading was carried out under the conditions of a set temperature of 180 ° C. and a screw rotation speed of 50 rpm, and then extruded into a strand shape and pelletized with a cutter as a measurement sample. Tables 5 and 10 show the results of physical property measurement and extrusion laminate molding using the sample.
[Production Example 2] to [Production Example 4]
[polymerization]
In Production Example 1, an ethylene-based polymer was obtained in the same manner as Production Example 1 except that the polymerization conditions were changed to the conditions shown in Table 1 (see Table 1). Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Production Example 1. Tables 5 and 10 show the results of physical property measurement and extrusion lamination molding using the sample.
[Production Example 5]
[Preparation of solid catalyst component (X-2)]
Under a nitrogen atmosphere, 18.6 liters of toluene and 7.9 liters of the toluene slurry of the solid component (S-1) prepared above (1200 g of the solid component) were added to a reactor equipped with a stirrer having an internal volume of 114 liters. On the other hand, 14.5 liters of toluene was placed in a reactor with a stirrer with an internal volume of 100 liters under a nitrogen atmosphere, and 5.0 liters of a toluene solution of metallocene compound (A-1) (7.81 mmol / L in terms of Zr atoms) was added with stirring. Subsequently, 2.0 liters of a toluene solution of metallocene compound (B-1) (2.17 mmol / L in terms of Zr atom) was added and mixed for several minutes [(A-1) / (B-1) molar ratio = 85 / 15].
Subsequently, the prepared mixed solution was pumped to the reactor in which the toluene slurry of the solid component (S-1) was previously applied. After pumping, the reaction was carried out at an internal temperature of 20 to 25 ° C. for 1 hour. Thereafter, the supernatant was removed by decantation. The solid catalyst component thus obtained was washed three times with hexane, and then hexane was added to make a total volume of 30 liters to prepare a hexane slurry of the solid catalyst component (X-2).
[予備重合触媒(XP-2)の調製]
引き続き、上記で得られた固体触媒成分(X-2)のヘキサンスラリーを10℃まで冷却した
後、常圧下でエチレンを系内に連続的に数分間供給した。この間、系内の温度は10〜15℃に保持した。その後、トリイソブチルアルミニウム1.6molと1-ヘキセン80mlを添加した。1-ヘキセン添加後にエチレンを1.8kg/hrで再度供給し予備重合を開始した。予備重合を開始してから25分後に系内温度は24℃まで上昇し、それ以降の系内温度は24〜26℃に保持した。予備重合を開始してから35分後に1-ヘキセン39.0mlを添加、60分後にも1-ヘキセン39.0mlを添加した。
[Preparation of prepolymerization catalyst (XP-2)]
Subsequently, after the hexane slurry of the solid catalyst component (X-2) obtained above was cooled to 10 ° C., ethylene was continuously supplied into the system for several minutes under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, 1.6 mol of triisobutylaluminum and 80 ml of 1-hexene were added. After the addition of 1-hexene, ethylene was supplied again at 1.8 kg / hr to start prepolymerization. After 25 minutes from the start of the prepolymerization, the system temperature rose to 24 ° C, and the subsequent system temperature was maintained at 24-26 ° C. 35 minutes after the start of prepolymerization, 39.0 ml of 1-hexene was added, and 39.0 ml of 1-hexene was also added 60 minutes later.
予備重合開始から85分後に、エチレン供給を停止し系内を窒素により置換し、予備重合を停止した。その後、上澄み液をデカンテーションにより除去した。このようにして得られた予備重合触媒をヘキサンで4回洗浄し、固体触媒成分1g当り2.93gのポリマーが重合された予備重合触媒(XP-2)を得た。得られた予備重合触媒成分の一部を乾燥し、組成を調べ
たところ、固体触媒成分1g当たりZr原子が0.72mg含まれていた。
85 minutes after the start of the prepolymerization, the ethylene supply was stopped, the inside of the system was replaced with nitrogen, and the prepolymerization was stopped. Thereafter, the supernatant was removed by decantation. The prepolymerized catalyst thus obtained was washed four times with hexane to obtain a prepolymerized catalyst (XP-2) in which 2.93 g of polymer was polymerized per 1 g of the solid catalyst component. A portion of the obtained prepolymerized catalyst component was dried and the composition was examined. As a result, 0.72 mg of Zr atoms were contained per 1 g of the solid catalyst component.
[重合]
予備重合触媒(XP-2)を用い、重合条件を第1表に示す条件に変えた以外は、製造例1と同様にしてエチレン系重合体を得た。得られたエチレン系重合体を用い、製造例1と同様の
方法にて測定試料を調製した。該試料を用いて物性測定、押出ラミネート成形を行った結果を第5表、第10表に示す。
[製造例6]〜[製造例8]
[重合]
製造例5において、重合条件を第1表に示す条件に変えた以外は、製造例5と同様にして
エチレン系重合体を得た。得られたエチレン系重合体を用い、製造例1と同様の方法にて
測定試料を調製した。該試料を用いて物性測定、押出ラミネート成形を行った結果を第5
表、第10表に示す(製造例6は物性測定のみを実施)。
[製造例9]
[重合]
製造例5において、重合条件を第1表に示す条件に変えた以外は、製造例5と同様にして
エチレン系重合体を得た。但し、該重合体の密度が935kg/m3を下回ると、重合槽より抜き出した重合体スラリーの上澄み液は白濁し、該重合体の密度が920kg/m3に到達してから8hr後には重合体と溶媒が分離せずスラリー性状が悪化したため、連続運転を中止した。運転中止前に得られたエチレン系重合体を用い、製造例1と同様の方法にて測定試料を調製
した。該試料を用いて物性測定、押出ラミネート成形を行った結果を第5表、第10表に示
す。
[製造例10]
[固体成分(S-2)の調製]
窒素流通下、250℃で10時間乾燥したシリカ(SiO2:平均粒子径50μm) 30gを、460ml
のトルエンに懸濁した後、0℃まで冷却した。この懸濁液にメチルアルモキサンのトルエ
ン溶液(Al原子換算で1.52mmol/ml) 140mlを1時間かけて滴下した。この際、系内の温度を0〜2℃に保った。引き続き、0℃で30分間反応させた後、1.5時間かけて95℃まで昇温し、その温度で4時間反応させた。その後60℃まで降温し、上澄み液をデカンテーションに
より除去した。このようにして得られた固体成分をトルエンで3回洗浄した後、トルエン
を加え、固体成分(S-2)のトルエンスラリーを調製した。得られた固体成分(S-2)の一部を採取し、濃度を調べたところ、スラリー濃度:0.1665g/ml、Al濃度:0.697mmol/mlであった。
[polymerization]
An ethylene polymer was obtained in the same manner as in Production Example 1, except that the prepolymerization catalyst (XP-2) was used and the polymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Production Example 1. Tables 5 and 10 show the results of physical property measurement and extrusion lamination molding using the sample.
[Production Example 6] to [Production Example 8]
[polymerization]
An ethylene polymer was obtained in the same manner as in Production Example 5, except that the polymerization conditions in Production Example 5 were changed to the conditions shown in Table 1. Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Production Example 1. The results of physical property measurement and extrusion lamination molding using the sample are shown in No. 5
The results are shown in Table 10 and Table 10 (Production Example 6 only measures physical properties).
[Production Example 9]
[polymerization]
An ethylene polymer was obtained in the same manner as in Production Example 5, except that the polymerization conditions in Production Example 5 were changed to the conditions shown in Table 1. However, when the density of the polymer is lower than 935 kg / m 3 , the supernatant of the polymer slurry extracted from the polymerization tank becomes cloudy, and after 8 hours from the arrival of the polymer density of 920 kg / m 3 Since the coalescence and the solvent were not separated and the slurry properties deteriorated, the continuous operation was stopped. A measurement sample was prepared in the same manner as in Production Example 1 using the ethylene polymer obtained before the operation was stopped. Tables 5 and 10 show the results of physical property measurement and extrusion lamination molding using the sample.
[Production Example 10]
[Preparation of solid component (S-2)]
460 ml of 30 g of silica (SiO 2 : average particle size 50 μm) dried at 250 ° C. for 10 hours under nitrogen flow
After being suspended in toluene, the mixture was cooled to 0 ° C. To this suspension, 140 ml of a toluene solution of methylalumoxane (1.52 mmol / ml in terms of Al atom) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 to 2 ° C. Subsequently, after reacting at 0 ° C. for 30 minutes, the temperature was raised to 95 ° C. over 1.5 hours and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by decantation. The solid component thus obtained was washed three times with toluene, and then toluene was added to prepare a toluene slurry of the solid component (S-2). A part of the obtained solid component (S-2) was collected and examined for concentration. As a result, the slurry concentration was 0.1665 g / ml, and the Al concentration was 0.697 mmol / ml.
[固体触媒成分(X-3)の調製]
窒素置換した200mlのガラス製フラスコにトルエン50mlを入れ、攪拌下、上記で調製し
た固体成分(S-2)のトルエンスラリー(固体部換算で1.0g)を装入した。次に、あらかじ
め混合したメタロセン化合物(A-1)のトルエン溶液(Zr原子換算で0.0015mmol/ml) 11.2mlとメタロセン化合物(B-1)のトルエン溶液(Zr原子換算で0.0015mmol/ml) 2.8mlの混合
液を滴下し、室温で1時間反応させた。その後、上澄み液をデカンテーションにより除去
し、デカンで2回洗浄し、デカンスラリーとした〔固体触媒成分(X-3)〕。固体触媒成分調製時のメタロセン化合物(A-1)と(B-1)の混合モル比は、(A-1)/(B-1)=80/20である。また
、得られた固体触媒成分(X-3)のデカンスラリーの一部を採取して濃度を調べたところ、Zr濃度0.037mg/ml、Al濃度2.27mg/mlであった。
[Preparation of solid catalyst component (X-3)]
50 ml of toluene was placed in a 200 ml glass flask purged with nitrogen, and the toluene slurry (1.0 g in terms of solid part) of the solid component (S-2) prepared above was charged with stirring. Next, a premixed toluene solution of metallocene compound (A-1) (0.0015 mmol / ml in terms of Zr atom) 11.2 ml and a toluene solution of metallocene compound (B-1) (0.0015 mmol / ml in terms of Zr atom) 2.8 A mixed solution of ml was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a decane slurry [solid catalyst component (X-3)]. The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 80/20. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-3) was sampled to examine the concentration, the Zr concentration was 0.037 mg / ml and the Al concentration was 2.27 mg / ml.
[重合]
充分に窒素置換した内容積1リットルのSUS製オートクレーブに精製ヘプタン 500mlを入れ、エチレンを流通し、液相および気相をエチレンで飽和させた。次に、水素−エチレン混合ガス(水素濃度:0.45vol%)を用いて、系内を置換した後、1-ヘキセン10ml、トリイソブチルアルミニウム 0.375mmol、ジルコニウム換算で0.01ミリモルの固体触媒成分(X-3
)をこの順に装入した。80℃に昇温して、0.78MPa-Gにて90分間重合を行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体87.4gを得た。なお、製造例10で得られ
た重合体の製造条件に関しては、第2表に記載した。
[polymerization]
Purified heptane (500 ml) was placed in a 1-liter SUS autoclave thoroughly purged with nitrogen, ethylene was circulated, and the liquid phase and gas phase were saturated with ethylene. Next, after replacing the system with a hydrogen-ethylene mixed gas (hydrogen concentration: 0.45 vol%), 1 ml of 1-hexene, 0.375 mmol of triisobutylaluminum, 0.01 mmol of a solid catalyst component (X- Three
) In this order. The temperature was raised to 80 ° C., and polymerization was carried out at 0.78 MPa-G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 87.4 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 10 are shown in Table 2.
測定試料を調製するため、得られたエチレン系重合体に、耐熱安定剤としてIrganox1076(チバスペシャリティケミカルズ社製)を0.1重量%になるように、Irgafos168(チバス
ペシャリティケミカルズ社製)を0.1重量%になるように加え、(前述のとおり、)東洋精機製作所製ラボプラストミルを用い、樹脂温度180℃、回転数50rpmで5分間溶融混練した
。さらに、この溶融ポリマーを、神藤金属工業所製プレス成形機を用い、冷却温度20℃、冷却時間5分間、冷却圧力100kg/cm2の条件にて冷却した。該試料を用いて物性測定を行
った結果を第6表に示す。
[製造例11]
[固体触媒成分(X-4)の調製]
窒素置換した200mlのガラス製フラスコにトルエン38.9mlを入れ、攪拌下、製造例1で調製した固体成分(S-1)のトルエンスラリー(固体部換算で2.0g)を装入した。次に、あら
かじめ混合したメタロセン化合物(A-1)のトルエン溶液(Zr原子換算で0.002mmol/ml) 34.4mlとメタロセン化合物(B-1)のトルエン溶液(Zr原子換算で0.001mmol/ml)3.6mlの混合液を滴下し、室温で1時間反応させた。その後、上澄み液をデカンテーションにより除去
し、デカンで2回洗浄し、デカンスラリーとした〔固体触媒成分(X-4)〕。固体触媒成分調製時のメタロセン化合物(A-1)と(B-1)の混合モル比は、(A-1)/(B-1)=95/5である。また、得られた固体触媒成分(X-4)のデカンスラリーの一部を採取して濃度を調べたところ、Zr
濃度0.062mg/ml、Al濃度3.64mg/mlであった。
In order to prepare a measurement sample, Irgafos168 (manufactured by Ciba Specialty Chemicals) was added to 0.1% by weight so that Irganox 1076 (manufactured by Ciba Specialty Chemicals) would be 0.1% by weight as a heat stabilizer. In addition, as described above, the mixture was melt kneaded for 5 minutes at a resin temperature of 180 ° C. and a rotation speed of 50 rpm using a lab plast mill manufactured by Toyo Seiki Seisakusho. Further, this molten polymer was cooled using a press molding machine manufactured by Shindo Metal Industry Co., Ltd. under the conditions of a cooling temperature of 20 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg / cm 2 . Table 6 shows the results of physical properties measured using the sample.
[Production Example 11]
[Preparation of solid catalyst component (X-4)]
38.9 ml of toluene was placed in a 200 ml glass flask purged with nitrogen, and the toluene slurry of solid component (S-1) prepared in Production Example 1 (2.0 g in terms of solid part) was charged with stirring. Next, 34.4 ml of a premixed metallocene compound (A-1) in toluene solution (0.002 mmol / ml in terms of Zr atoms) and a metallocene compound (B-1) in toluene solution (0.001 mmol / ml in terms of Zr atoms) 3.6 A mixed solution of ml was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a decane slurry [solid catalyst component (X-4)]. The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 95/5. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-4) was collected and the concentration was examined, Zr
The concentration was 0.062 mg / ml, and the Al concentration was 3.64 mg / ml.
[重合]
製造例10の重合において、水素−エチレン混合ガス(水素濃度:0.2vol%)、ジルコニ
ウム換算で0.0025ミリモルの固体触媒成分(X-4)を用いた以外は、製造例10と同様の方法
で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体71.1gを得た。な
お、製造例11で得られた重合体の製造条件に関しては、第2表に記載した。得られたエチ
レン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第6表に示す。
[製造例12]
[固体触媒成分(X−5)の調製]
窒素置換した200mlのガラス製フラスコにトルエン50mlを入れ、攪拌下、上記で調製し
た固体成分(S-1)のトルエンスラリー(固体部換算で2.0g)を装入した。次に、あらかじ
め混合したメタロセン化合物(A-1)のトルエン溶液(Zr原子換算で0.0015mmol/ml) 44.0mlとメタロセン化合物(B-1)のトルエン溶液(Zr原子換算で0.0015mmol/ml) 1.83mlの混合液を滴下し、室温で1時間反応させた。その後、上澄み液をデカンテーションにより除去
し、デカンで2回洗浄し、デカンスラリーとした〔固体触媒成分(X-5)〕。固体触媒成分調製時のメタロセン化合物(A-1)と(B-1)の混合モル比は、(A-1)/(B-1)=96/4である。また、得られた固体触媒成分(X-5)のデカンスラリーの一部を採取して濃度を調べたところ、Zr
濃度0.061mg/ml、Al濃度3.71mg/mlであった。
[polymerization]
The polymerization in Production Example 10 was carried out in the same manner as in Production Example 10, except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.2 vol%) and 0.0025 mmol of the solid catalyst component (X-4) in terms of zirconium were used. It was. The obtained polymer was vacuum-dried for 10 hours to obtain 71.1 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 11 are shown in Table 2. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 6 shows the results of physical properties measured using the sample.
[Production Example 12]
[Preparation of solid catalyst component (X-5)]
50 ml of toluene was placed in a 200 ml glass flask purged with nitrogen, and the toluene slurry (2.0 g in terms of solid part) of the solid component (S-1) prepared above was charged with stirring. Next, a premixed toluene solution of metallocene compound (A-1) (0.0015 mmol / ml in terms of Zr atoms) and 44.0 ml of a toluene solution of metallocene compound (B-1) (0.0015 mmol / ml in terms of Zr atoms) 1.83 A mixed solution of ml was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a decane slurry [solid catalyst component (X-5)]. The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 96/4. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-5) was collected and examined for concentration, Zr
The concentration was 0.061 mg / ml, and the Al concentration was 3.71 mg / ml.
[重合]
製造例10の重合において、水素−エチレン混合ガス(水素濃度:0.1vol%)、ジルコニ
ウム換算で0.0025ミリモルの固体触媒成分(X-5)を用いた以外は、製造例10と同様の方法
で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体46.2gを得た。な
お、製造例12で得られた重合体の製造条件に関しては、第2表に記載した。得られたエチ
レン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第6表に示す。
[製造例13]
製造例12の重合において、水素−エチレン混合ガス(水素濃度:0.2vol%)、を用いた
以外は、製造例12と同様の方法で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体52.2gを得た。なお、製造例13で得られた重合体の製造条件に関しては、第2表に記載した。得られたエチレン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第6表に示す。
[製造例14]
製造例12の重合において、水素−エチレン混合ガス(水素濃度:0.25vol%)、を用いた以外は、製造例12と同様の方法で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体58.6gを得た。なお、製造例14で得られた重合体の製造条件に関しては、第2表に記載した。得られたエチレン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第6表に示す。
[製造例15]
[固体触媒成分(X-6)の調製]
製造例12の固体触媒成分(X-5)の調製において、固体成分(S-1)のトルエンスラリーの装入量を固体部換算で1.9gとし、かつ、メタロセン化合物(A-1)のトルエン溶液(Zr原子換
算で0.0015mmol/ml) 40.3ml、メタロセン化合物(B-1)のトルエン溶液(Zr原子換算で0.0015mmol/ml) 5.50mlを使用した以外は、製造例12と同様の方法で固体触媒成分(X-6)を調製した。固体触媒成分調製時のメタロセン化合物(A-1)と(B-1)の混合モル比は、(A-1)/(B-1)=88/12である。また、得られた固体触媒成分(X-6)のデカンスラリーの一部を採取して濃度を調べたところ、Zr濃度0.059mg/ml、Al濃度3.43mg/mlであった。
[polymerization]
The polymerization in Production Example 10 was performed in the same manner as in Production Example 10, except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.1 vol%) and 0.0025 mmol of the solid catalyst component (X-5) in terms of zirconium were used. It was. The obtained polymer was vacuum-dried for 10 hours to obtain 46.2 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 12 are shown in Table 2. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 6 shows the results of physical properties measured using the sample.
[Production Example 13]
The polymerization in Production Example 12 was performed in the same manner as in Production Example 12 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.2 vol%) was used. The obtained polymer was vacuum-dried for 10 hours to obtain 52.2 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 13 are shown in Table 2. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 6 shows the results of physical properties measured using the sample.
[Production Example 14]
The polymerization in Production Example 12 was carried out in the same manner as in Production Example 12 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.25 vol%) was used. The obtained polymer was vacuum-dried for 10 hours to obtain 58.6 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 14 are shown in Table 2. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 6 shows the results of physical properties measured using the sample.
[Production Example 15]
[Preparation of solid catalyst component (X-6)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, the amount of the toluene slurry charged with the solid component (S-1) was 1.9 g in terms of solid part, and the toluene of the metallocene compound (A-1) Solution (0.0015 mmol / ml in terms of Zr atoms) 40.3 ml, toluene solution of metallocene compound (B-1) (0.0015 mmol / ml in terms of Zr atoms) Except for using 5.50 ml, the same method as in Production Example 12 A solid catalyst component (X-6) was prepared. The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 88/12. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-6) was sampled to examine the concentration, it was found that the Zr concentration was 0.059 mg / ml and the Al concentration was 3.43 mg / ml.
[重合]
製造例10の重合において、水素−エチレン混合ガス(水素濃度:0.75vol%)、ジルコニウム換算で0.0025ミリモルの固体触媒成分(X-6)を用いた以外は、製造例10と同様の方法
で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体71.3gを得た。な
お、製造例15で得られた重合体の製造条件に関しては、第2表に記載した。得られたエチ
レン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第6表に示す。
[製造例16]
製造例15の重合において、水素−エチレン混合ガス(水素濃度:0.83vol%)、を用いた以外は、製造例15と同様の方法で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体65.9gを得た。なお、製造例16で得られた重合体の製造条件に関しては、第2表に記載した。得られたエチレン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第6表に示す。
[製造例17]
[固体触媒成分(X-7)の調製]
製造例12の固体触媒成分(X-5)の調製において、固体成分(S-1)のトルエンスラリーの装入量を固体部換算で1.0gとし、かつ、メタロセン化合物(A-1)のトルエン溶液(Zr原子換
算で0.002mmol/ml) 16.6ml、メタロセン化合物(B-1)のトルエン溶液(Zr原子換算で0.001mmol/ml) 2.89mlを使用した以外は、製造例12と同様の方法で固体触媒成分(X-7)を調製した。固体触媒成分調製時のメタロセン化合物(A-1)と(B-1)の混合モル比は、(A-1)/(B-1)=92/8である。また、得られた固体触媒成分(X-7)のデカンスラリーの一部を採取して濃
度を調べたところ、Zr濃度0.058mg/ml、Al濃度3.52mg/mlであった。
[polymerization]
The polymerization in Production Example 10 was carried out in the same manner as in Production Example 10, except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.75 vol%) and 0.0025 mmol of the solid catalyst component (X-6) in terms of zirconium were used. It was. The obtained polymer was vacuum-dried for 10 hours to obtain 71.3 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 15 are shown in Table 2. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 6 shows the results of physical properties measured using the sample.
[Production Example 16]
The polymerization in Production Example 15 was performed in the same manner as in Production Example 15 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.83 vol%) was used. The obtained polymer was vacuum-dried for 10 hours to obtain 65.9 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 16 are shown in Table 2. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 6 shows the results of physical properties measured using the sample.
[Production Example 17]
[Preparation of solid catalyst component (X-7)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, the amount of the toluene slurry of the solid component (S-1) was 1.0 g in terms of solid part, and the toluene of the metallocene compound (A-1) 16.6 ml of solution (0.002 mmol / ml in terms of Zr atoms), toluene solution of metallocene compound (B-1) (0.001 mmol / ml in terms of Zr atoms) A solid catalyst component (X-7) was prepared. The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 92/8. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-7) was collected to examine the concentration, the Zr concentration was 0.058 mg / ml and the Al concentration was 3.52 mg / ml.
[重合]
製造例10の重合において、水素−エチレン混合ガス(水素濃度:0.65vol%)、を用い、1-ヘキセン量を3mlに変更し、ジルコニウム換算で0.0026ミリモルの固体触媒成分(X-7)を用いた以外は、製造例10と同様の方法で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体63.9gを得た。なお、製造例17で得られた重合体の製造条件に関して
は、第3表に記載した。得られたエチレン系重合体を用い、製造例10と同様の方法にて測
定試料を調製した。該試料を用いて物性測定を行った結果を第7表に示す。
[製造例18]
[固体触媒成分(X-8)の調製]
製造例12の固体触媒成分(X-5)の調製において、メタロセン化合物(A-1)のトルエン溶液(Zr原子換算で0.002mmol/ml) 32.5ml、メタロセン化合物(B-1)のトルエン溶液(Zr原子換算で0.001mmol/ml) 7.23mlを使用した以外は、製造例12と同様の方法で固体触媒成分(X-8)を調製した。固体触媒成分調製時のメタロセン化合物(A-1)と(B-1)の混合モル比は、(A-1)/(B-1)=90/10である。また、得られた固体触媒成分(X-8)のデカンスラリーの一部を採取して濃度を調べたところ、Zr濃度0.065mg/ml、Al濃度3.77mg/mlであった。
[polymerization]
In the polymerization of Production Example 10, a hydrogen-ethylene mixed gas (hydrogen concentration: 0.65 vol%) was used, the amount of 1-hexene was changed to 3 ml, and the solid catalyst component (X-7) of 0.0026 mmol in terms of zirconium was used. The procedure was the same as in Production Example 10 except that The obtained polymer was vacuum-dried for 10 hours to obtain 63.9 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 17 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.
[Production Example 18]
[Preparation of solid catalyst component (X-8)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, 32.5 ml of a toluene solution of metallocene compound (A-1) (0.002 mmol / ml in terms of Zr atom), a toluene solution of metallocene compound (B-1) ( The solid catalyst component (X-8) was prepared in the same manner as in Production Example 12, except that 7.23 ml was used (0.001 mmol / ml in terms of Zr atoms). The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 90/10. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-8) was collected to examine the concentration, the Zr concentration was 0.065 mg / ml and the Al concentration was 3.77 mg / ml.
[重合]
製造例10の重合において、重合温度を70℃とし、水素−エチレン混合ガス(水素濃度:0.064vol%)を用い、1-ヘキセン量を30mlに変更し、ジルコニウム換算で0.0026ミリモル
の固体触媒成分(X-8)を用いた以外は、製造例10と同様の方法で行った。得られたポリマ
ーを10時間、真空乾燥し、エチレン系重合体92.9gを得た。なお、製造例18で得られた重
合体の製造条件に関しては、第3表に記載した。得られたエチレン系重合体を用い、製造
例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第7
表に示す。
[polymerization]
In the polymerization of Production Example 10, the polymerization temperature was set to 70 ° C., a hydrogen-ethylene mixed gas (hydrogen concentration: 0.064 vol%) was used, the amount of 1-hexene was changed to 30 ml, and the solid catalyst component (0.0026 mmol in terms of zirconium) The procedure was the same as in Production Example 10 except that X-8) was used. The obtained polymer was vacuum-dried for 10 hours to obtain 92.9 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 18 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. The results of physical property measurement using the sample are shown in No. 7
Shown in the table.
[製造例19]
製造例18の重合において、固体触媒成分(X-7) 0.1gを用いた以外は、製造例18と同様の方法で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体44.5gを得た
。なお、製造例19で得られた重合体の製造条件に関しては、第3表に記載した。得られた
エチレン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第7表に示す。
[Production Example 19]
The polymerization in Production Example 18 was carried out in the same manner as in Production Example 18, except that 0.1 g of the solid catalyst component (X-7) was used. The obtained polymer was vacuum-dried for 10 hours to obtain 44.5 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 19 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.
[製造例20]
[予備重合触媒(XP-4)の調製]
窒素置換した200mlのガラス製フラスコにヘキサン52.7mlを入れ、上記で調製した固体
触媒成分(X-4)のヘキサンスラリー(固体部換算で4.0g)を装入した。次に、10℃まで冷
却した後、TIBAL 5.32mmol、1-ヘキセン0.535mlを添加し、常圧下30L/hrでエチレンのフィードを開始した。25℃において、固体触媒成分によるエチレンの積算吸収量が10.3リットルになるまで重合を行い、重合終了後、系内を窒素に置換し予備重合を終了した。その後、上澄み液をデカンテーションにより除去し、デカンで3回洗浄し、デカンスラリーと
し予備重合触媒(XP-4)を調製した。得られた予備重合触媒(XP-4)のデカンスラリーの一部を採取して濃度を調べたところ、Zr濃度0.067mg/ml、Al濃度4.77mg/mlであった。
[Production Example 20]
[Preparation of prepolymerization catalyst (XP-4)]
52.7 ml of hexane was placed in a 200 ml glass flask purged with nitrogen, and the hexane slurry (4.0 g in terms of solid part) of the solid catalyst component (X-4) prepared above was charged. Next, after cooling to 10 ° C., 5.32 mmol of TIBAL and 0.535 ml of 1-hexene were added, and ethylene feeding was started at 30 L / hr under normal pressure. Polymerization was carried out at 25 ° C. until the cumulative amount of ethylene absorbed by the solid catalyst component reached 10.3 liters. After completion of the polymerization, the system was replaced with nitrogen to complete the prepolymerization. Thereafter, the supernatant was removed by decantation and washed with decane three times to prepare a decane slurry to prepare a prepolymerized catalyst (XP-4). A portion of the resulting decane slurry of the prepolymerized catalyst (XP-4) was collected and examined for concentration. As a result, the Zr concentration was 0.067 mg / ml, and the Al concentration was 4.77 mg / ml.
[重合]
製造例10の重合において、重合温度を70℃とし、エチレンガスを用い、1-ヘキセン量を30mlに変更し、ジルコニウム換算で0.0026ミリモルの予備重合触媒(XP-4)を用いた以外は、製造例10と同様の方法で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体60.8gを得た。なお、製造例20で得られた重合体の製造条件に関しては、第3表に記載した。得られたエチレン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第7表に示す。
[polymerization]
In the polymerization of Production Example 10, the polymerization temperature was set to 70 ° C., ethylene gas was used, the amount of 1-hexene was changed to 30 ml, and a prepolymerization catalyst (XP-4) of 0.0026 mmol in terms of zirconium was used. In the same manner as in Example 10. The obtained polymer was vacuum-dried for 10 hours to obtain 60.8 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 20 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.
[製造例21]
[予備重合触媒(XP-9)の調製]
製造例12の固体触媒成分(X-5)の調製において、メタロセン化合物(A-1)のトルエン溶液(Zr原子換算で0.004mmol/ml) 14.5ml、メタロセン化合物(B-1)のトルエン溶液(Zr原子換算で0.002mmol/ml) 7.23mlを使用した以外は、製造例12と同様の方法で固体触媒成分(
X-9)を調製した。固体触媒成分調製時のメタロセン化合物(A-1)と(B-1)の混合モル比は、(A-1)/(B-1)=80/20である。また、引き続き、製造例20の予備重合触媒(XP-4)の調製と同
様の方法で、予備重合触媒(XP-9)のデカンスラリーを調製した。得られた予備重合触媒(XP-9)のデカンスラリーの一部を採取して濃度を調べたところ、Zr濃度0.062mg/ml、Al濃度4.16mg/mlであった。
[Production Example 21]
[Preparation of prepolymerization catalyst (XP-9)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, 14.5 ml of a toluene solution of metallocene compound (A-1) (0.004 mmol / ml in terms of Zr atom), a toluene solution of metallocene compound (B-1) ( The solid catalyst component (0.002 mmol / ml in terms of Zr atom) was the same as in Production Example 12 except that 7.23 ml was used.
X-9) was prepared. The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 80/20. Subsequently, a decane slurry of the prepolymerized catalyst (XP-9) was prepared in the same manner as the preparation of the prepolymerized catalyst (XP-4) of Production Example 20. A portion of the resulting decane slurry of the prepolymerized catalyst (XP-9) was collected and examined for concentration. As a result, the Zr concentration was 0.062 mg / ml and the Al concentration was 4.16 mg / ml.
[重合]
製造例10の重合において、重合温度を50℃とし、エチレンガスを用い、1-ヘキセン量を50mlに変更し、ジルコニウム換算で0.0012ミリモルの予備重合触媒(XP-9)を用いた以外は、製造例10と同様の方法で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体25.6gを得た。なお、製造例21で得られた重合体の製造条件に関しては、第3表に記載した。得られたエチレン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第7表に示す。
[polymerization]
In the polymerization of Production Example 10, the polymerization temperature was 50 ° C., ethylene gas was used, the amount of 1-hexene was changed to 50 ml, and a prepolymerization catalyst (XP-9) of 0.0012 mmol in terms of zirconium was used. In the same manner as in Example 10. The obtained polymer was vacuum-dried for 10 hours to obtain 25.6 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 21 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.
[製造例22]
[予備重合触媒(XP-10)の調製]
製造例12の固体触媒成分(X-5)の調製において、メタロセン化合物(A-1)のトルエン溶液(Zr原子換算で0.004mmol/ml) 12.7ml、メタロセン化合物(B-1)のトルエン溶液(Zr原子換算で0.002mmol/ml) 10.8mlを使用した以外は、製造例12と同様の方法で固体触媒成分(X-10)を調製した。固体触媒成分調製時のメタロセン化合物(A-1)と(B-1)の混合モル比は
、(A-1)/(B-1)=70/30である。また、引き続き、製造例20の予備重合触媒(XP-4)の調製と
同様の方法で、予備重合触媒(XP-10)のデカンスラリーを調製した。得られた予備重合触
媒(XP-10)のデカンスラリーの一部を採取して濃度を調べたところ、Zr濃度0.060mg/ml、Al濃度4.12mg/mlであった。
[Production Example 22]
[Preparation of prepolymerization catalyst (XP-10)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, 12.7 ml of a toluene solution of metallocene compound (A-1) (0.004 mmol / ml in terms of Zr atom), a toluene solution of metallocene compound (B-1) ( A solid catalyst component (X-10) was prepared in the same manner as in Production Example 12, except that 10.8 ml was used (0.002 mmol / ml in terms of Zr atoms). The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 70/30. Subsequently, a decane slurry of the prepolymerized catalyst (XP-10) was prepared in the same manner as the preparation of the prepolymerized catalyst (XP-4) of Production Example 20. A portion of the resulting decane slurry of the prepolymerized catalyst (XP-10) was sampled and examined for concentration. As a result, the Zr concentration was 0.060 mg / ml and the Al concentration was 4.12 mg / ml.
[重合]
製造例10の重合において、重合温度を50℃とし、エチレンガスを用い、1-ヘキセン量を50mlに変更し、ジルコニウム換算で0.002ミリモルの予備重合触媒(XP-10)を用いた以外は、製造例10と同様の方法で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体56.6gを得た。なお、製造例22で得られた重合体の製造条件に関しては、第3表に記載した。得られたエチレン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第7表に示す。
[polymerization]
In the polymerization of Production Example 10, the polymerization temperature was 50 ° C., ethylene gas was used, the amount of 1-hexene was changed to 50 ml, and a prepolymerization catalyst (XP-10) of 0.002 mmol in terms of zirconium was used. In the same manner as in Example 10. The obtained polymer was vacuum-dried for 10 hours to obtain 56.6 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 22 are shown in Table 3. A measurement sample was prepared in the same manner as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.
[製造例23]
製造例22の重合において、1-ヘキセン量を40mlに変更した以外は、製造例22と同様の方法で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体50.3gを得た。
なお、製造例23で得られた重合体の製造条件に関しては、第3表に記載した。得られたエ
チレン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第7表に示す。
[Production Example 23]
The polymerization in Production Example 22 was carried out in the same manner as in Production Example 22, except that the amount of 1-hexene was changed to 40 ml. The obtained polymer was vacuum-dried for 10 hours to obtain 50.3 g of an ethylene polymer.
The production conditions for the polymer obtained in Production Example 23 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.
[製造例24]
[予備重合触媒(XP-11)の調製]
製造例12の固体触媒成分(X-5)の調製において、メタロセン化合物(A-1)のトルエン溶液(Zr原子換算で0.004mmol/ml) 18.1mlのみを用いた以外は、製造例12と同様の方法で固
体触媒成分(X-11)を調製した。また、引き続き、製造例20の予備重合触媒(XP-4)の調製と同様の方法で、予備重合触媒(XP-11)のデカンスラリーを調製した。得られた予備重合触
媒(XP-11)のデカンスラリーの一部を採取して濃度を調べたところ、Zr濃度0.065mg/ml、Al濃度5.46mg/mlであった。
[Production Example 24]
[Preparation of prepolymerization catalyst (XP-11)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, the same as Production Example 12 except that only 18.1 ml of a toluene solution of metallocene compound (A-1) (0.004 mmol / ml in terms of Zr atom) was used. The solid catalyst component (X-11) was prepared by the method described above. Subsequently, a decane slurry of the prepolymerized catalyst (XP-11) was prepared in the same manner as the preparation of the prepolymerized catalyst (XP-4) of Production Example 20. A portion of the resulting decane slurry of the prepolymerized catalyst (XP-11) was collected and examined for concentration. As a result, the Zr concentration was 0.065 mg / ml and the Al concentration was 5.46 mg / ml.
[予備重合触媒(XP-12)の調製]
製造例12の固体触媒成分(X-5)の調製において、メタロセン化合物(B-1)のトルエン溶液(Zr原子換算で0.004mmol/ml) 18.1mlのみを用いた以外は、製造例12と同様の方法で固
体触媒成分(X-12)を調製した。また、引き続き、製造例20の予備重合触媒(XP-4)の調製と同様の方法で、予備重合触媒(XP-12)のデカンスラリーを調製した。得られた予備重合触
媒(XP-12)のデカンスラリーの一部を採取して濃度を調べたところ、Zr濃度0.063mg/ml、Al濃度3.72mg/mlであった。
[Preparation of prepolymerization catalyst (XP-12)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, the same as Production Example 12 except that only 18.1 ml of a toluene solution of metallocene compound (B-1) (0.004 mmol / ml in terms of Zr atoms) was used. The solid catalyst component (X-12) was prepared by the method described above. Further, a decane slurry of the prepolymerized catalyst (XP-12) was prepared in the same manner as in the preparation of the prepolymerized catalyst (XP-4) of Production Example 20. A portion of the resulting decane slurry of the prepolymerized catalyst (XP-12) was collected and examined for concentration. As a result, the Zr concentration was 0.063 mg / ml and the Al concentration was 3.72 mg / ml.
[重合]
充分に窒素置換した内容積1リットルのSUS製オートクレーブに精製ヘプタン 500mlを入れ、エチレンを流通し、液相および気相をエチレンで飽和させた。次に、水素−エチレン混合ガス(水素濃度:0.20vol%)を用いて、系内を置換した後、1-ヘキセン3ml、トリイ
ソブチルアルミニウム 0.375mmolを添加し、さらに予備重合触媒(XP-11)をジルコニウム
換算で0.0025ミリモル、予備重合触媒(XP-12)をジルコニウム換算で0.00028ミリモル装入した〔ジルコニウムのモル比で、予備重合触媒(XP-11)/予備重合触媒(XP-12)=90/10〕。 80℃に昇温して、0.78MPa-Gにて90分間重合を行った。得られたポリマーを10時間、真空
乾燥し、エチレン系重合体55.3gを得た。なお、製造例24で得られた重合体の製造条件に
関しては、第3表に記載した。得られたエチレン系重合体を用い、製造例10と同様の方法
にて測定試料を調製した。該試料を用いて物性測定を行った結果を第7表に示す。
[polymerization]
Purified heptane (500 ml) was placed in a 1-liter SUS autoclave thoroughly purged with nitrogen, ethylene was circulated, and the liquid phase and gas phase were saturated with ethylene. Next, after substituting the inside of the system using a hydrogen-ethylene mixed gas (hydrogen concentration: 0.20 vol%), 1 ml of 1-hexene and 0.375 mmol of triisobutylaluminum were added, and a prepolymerization catalyst (XP-11) 0.0025 mmol in terms of zirconium and 0.00028 mmol in the pre-polymerization catalyst (XP-12) were charged (in terms of the molar ratio of zirconium, pre-polymerization catalyst (XP-11) / pre-polymerization catalyst (XP-12) = 90 /Ten〕. The temperature was raised to 80 ° C., and polymerization was carried out at 0.78 MPa-G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 55.3 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 24 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.
[製造例25]
製造例24の重合において、重合温度を70℃とし、エチレンガスを用い、1-ヘキセン量を30mlに変更した以外は、製造例24と同様の方法で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体76.8gを得た。なお、製造例25で得られた重合体の製造条件
に関しては、第4表に記載した。得られたエチレン系重合体を用い、製造例10と同様の方
法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第8表に示す。
[Production Example 25]
The polymerization in Production Example 24 was carried out in the same manner as in Production Example 24 except that the polymerization temperature was 70 ° C., ethylene gas was used, and the amount of 1-hexene was changed to 30 ml. The obtained polymer was vacuum-dried for 10 hours to obtain 76.8 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 25 are shown in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.
[製造例26]
製造例25の重合において、エチレンガスの代わりに、水素−エチレン混合ガス(水素濃度:0.20vol%)を用いた以外は、製造例25と同様の方法で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体62.8gを得た。なお、製造例26で得られた重合体の
製造条件に関しては、第4表に記載した。得られたエチレン系重合体を用い、製造例10と
同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第8表に示
す。
[Production Example 26]
The polymerization in Production Example 25 was performed in the same manner as in Production Example 25 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.20 vol%) was used instead of ethylene gas. The obtained polymer was vacuum-dried for 10 hours to obtain 62.8 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 26 are shown in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.
[製造例27]
製造例25の重合において、エチレンガスの代わりに、水素−エチレン混合ガス(水素濃度:0.31vol%)を用いた以外は、製造例25と同様の方法で行った。得られたポリマーを10時間、真空乾燥しエチレン系重合体72.3gを得た。なお、製造例27で得られた重合体の製
造条件に関しては、第4表に記載した。得られたエチレン系重合体を用い、製造例10と同
様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第8表に示す
。
[Production Example 27]
The polymerization in Production Example 25 was performed in the same manner as in Production Example 25 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.31 vol%) was used instead of ethylene gas. The obtained polymer was vacuum-dried for 10 hours to obtain 72.3 g of an ethylene-based polymer. The production conditions for the polymer obtained in Production Example 27 are shown in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.
[製造例28]
充分に窒素置換した内容積1リットルのSUS製オートクレーブに精製ヘプタン 500mlを入れ、エチレンを流通し系内を置換した。次に、1-ヘキセン30ml、トリイソブチルアルミニウム 0.375mmolを添加し、さらに予備重合触媒(XP-11)をジルコニウム換算で0.00238ミリモル、予備重合触媒(XP-12)をジルコニウム換算で0.00013ミリモル装入した〔ジルコニウムのモル比で、予備重合触媒(XP-11)/予備重合触媒(XP-12)=95/5〕。70℃に昇温して、0.78MPa-Gにて90分間重合を行った。得られたポリマーを10時間、真空乾燥し、エチレン系
重合体60.9gを得た。なお、製造例28で得られた重合体の製造条件に関しては、第4表に記
載した。得られたエチレン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第8表に示す。
[Production Example 28]
Purified heptane (500 ml) was placed in a 1-liter SUS autoclave sufficiently purged with nitrogen, and ethylene was passed through to replace the system. Next, 30 ml of 1-hexene and 0.375 mmol of triisobutylaluminum were added, and 0.00238 mmol of the prepolymerized catalyst (XP-11) was added in terms of zirconium and 0.00013 mmol of the prepolymerized catalyst (XP-12) was charged in terms of zirconium. [Preliminary polymerization catalyst (XP-11) / Preliminary polymerization catalyst (XP-12) = 95/5 in terms of the molar ratio of zirconium]. The temperature was raised to 70 ° C., and polymerization was carried out at 0.78 MPa-G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 60.9 g of an ethylene-based polymer. The production conditions for the polymer obtained in Production Example 28 are shown in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.
[製造例29]
[固体触媒成分(X-13)の調製]
窒素置換した200mlのガラス製フラスコにトルエン50mlを入れ、攪拌下、上記で調製し
た固体成分(S-2)のトルエンスラリー(固体部換算で2.0g)を装入した。次に、あらかじ
め混合したメタロセン化合物(A-1)のトルエン溶液(Zr原子換算で0.001mmol/ml) 37.6mlとメタロセン化合物(B−2)のトルエン溶液(Zr原子換算で0.001mmol/ml) 4.18mlの混合液を滴下し、室温で1時間反応させた。その後、上澄み液をデカンテーションにより除
去し、デカンで2回洗浄し、デカンスラリーとした〔固体触媒成分(X-13)〕。固体触媒成
分調製時のメタロセン化合物(A-1)と(B-2)の混合モル比は、(A-1)/(B-2)=90/10である。
また、得られた固体触媒成分(X-13)のデカンスラリーの一部を採取して濃度を調べたところ、Zr濃度0.035mg/ml、Al濃度2.46mg/mlであった。
[Production Example 29]
[Preparation of solid catalyst component (X-13)]
50 ml of toluene was placed in a 200 ml glass flask purged with nitrogen, and the toluene slurry (2.0 g in terms of solid part) of the solid component (S-2) prepared above was charged with stirring. Next, 37.6 ml of a premixed metallocene compound (A-1) in toluene solution (0.001 mmol / ml in terms of Zr atoms) and a metallocene compound (B-2) in toluene solution (0.001 mmol / ml in terms of Zr atoms) 4.18 A mixed solution of ml was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a decane slurry [solid catalyst component (X-13)]. The mixing molar ratio of the metallocene compounds (A-1) and (B-2) during the preparation of the solid catalyst component is (A-1) / (B-2) = 90/10.
Further, when a part of the resulting decane slurry of the solid catalyst component (X-13) was sampled to examine the concentration, it was found that the Zr concentration was 0.035 mg / ml and the Al concentration was 2.46 mg / ml.
[重合]
製造例10の重合において、水素−エチレン混合ガス(水素濃度:0.31vol%)、ジルコニウム換算で0.003ミリモルの固体触媒成分(X-13)を用いた以外は、製造例10と同様の方法
で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体38.4gを得た。
なお、製造例29で得られた重合体の製造条件に関しては、第4表に記載した。得られたエ
チレン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第8表に示す。
[polymerization]
The polymerization in Production Example 10 was carried out in the same manner as in Production Example 10, except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.31 vol%) and 0.003 mmol of the solid catalyst component (X-13) in terms of zirconium were used. It was. The obtained polymer was vacuum-dried for 10 hours to obtain 38.4 g of an ethylene polymer.
The production conditions for the polymer obtained in Production Example 29 are shown in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.
[製造例30]
[固体触媒成分(X-14)の調製]
窒素置換した200mlのガラス製フラスコにトルエン50mlを入れ、攪拌下、上記で調製し
た固体成分(S-2)のトルエンスラリー(固体部換算で1.0g)を装入した。次に、あらかじ
め混合したメタロセン化合物(A-2)のトルエン溶液(Zr原子換算で0.002mmol/ml) 2.25mlとメタロセン化合物(B-1)のトルエン溶液(Zr原子換算で0.002mmol/ml) 9.01mlの混合液を滴下し、室温で1時間反応させた。その後、上澄み液をデカンテーションにより除去し
、デカンで2回洗浄し、デカンスラリーとした〔固体触媒成分(X-14)〕。固体触媒成分調
製時のメタロセン化合物(A-2)と(B-1)の混合モル比は、(A-2)/(B-1)=20/80である。また
、得られた固体触媒成分(X-14)のデカンスラリーの一部を採取して濃度を調べたところ、Zr濃度0.015mg/ml、Al濃度1.27mg/mlであった。
[Production Example 30]
[Preparation of solid catalyst component (X-14)]
50 ml of toluene was placed in a 200 ml glass flask purged with nitrogen, and the toluene slurry (1.0 g in terms of solid part) of the solid component (S-2) prepared above was charged with stirring. Next, a premixed toluene solution of metallocene compound (A-2) (0.002 mmol / ml in terms of Zr atoms) 2.25 ml and a toluene solution of metallocene compound (B-1) (0.002 mmol / ml in terms of Zr atoms) 9.01 A mixed solution of ml was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a decane slurry [solid catalyst component (X-14)]. The mixing molar ratio of the metallocene compound (A-2) and (B-1) during the preparation of the solid catalyst component is (A-2) / (B-1) = 20/80. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-14) was collected and examined for concentration, it was found that the Zr concentration was 0.015 mg / ml and the Al concentration was 1.27 mg / ml.
[重合]
製造例10の重合において、エチレンガスを用い、重合温度70℃、ジルコニウム換算で0.0005ミリモルの固体触媒成分(X-14)を用いた以外は、製造例10と同様の方法で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体72.0gを得た。なお、製造例30
で得られた重合体の製造条件に関しては、第4表に記載した。得られたエチレン系重合体
を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第8表に示す。
[polymerization]
The polymerization in Production Example 10 was carried out in the same manner as in Production Example 10, except that ethylene gas was used, the polymerization temperature was 70 ° C., and 0.0005 mmol of the solid catalyst component (X-14) in terms of zirconium was used. The obtained polymer was vacuum-dried for 10 hours to obtain 72.0 g of an ethylene polymer. Production Example 30
The production conditions of the polymer obtained in 1 were described in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.
[製造例31]
[固体触媒成分(X-15)の調製]
窒素置換した200mlのガラス製フラスコにトルエン50mlを入れ、攪拌下、上記で調製し
た固体成分(S-2)のトルエンスラリー(固体部換算で1.0g)を装入した。次に、あらかじ
め混合した遷移金属化合物(A-3)のトルエン溶液(Zr原子換算で0.001mmol/ml) 4.18mlとメタロセン化合物(B-1)のトルエン溶液(Zr原子換算で0.0015mmol/ml) 11.15mlの混合液を滴下し、室温で1時間反応させた。その後、上澄み液をデカンテーションにより除去し
、デカンで2回洗浄し、デカンスラリーとした〔固体触媒成分(X-15)〕。固体触媒成分調
製時の遷移金属化合物(A-3)とメタロセン化合物(B-1)の混合モル比は、(A-3)/(B-1)=20/80である。また、得られた固体触媒成分(X-15)のデカンスラリーの一部を採取して濃度を
調べたところ、Zr濃度0.034mg/ml、Al濃度2.17mg/mlであった。
[Production Example 31]
[Preparation of solid catalyst component (X-15)]
50 ml of toluene was placed in a 200 ml glass flask purged with nitrogen, and the toluene slurry (1.0 g in terms of solid part) of the solid component (S-2) prepared above was charged with stirring. Next, 4.18 ml of a premixed transition metal compound (A-3) in toluene solution (0.001 mmol / ml in terms of Zr atoms) and a metallocene compound (B-1) in toluene solution (0.0015 mmol / ml in terms of Zr atoms) 11.15 ml of the mixed solution was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a decane slurry [solid catalyst component (X-15)]. The mixing molar ratio of the transition metal compound (A-3) and the metallocene compound (B-1) during the preparation of the solid catalyst component is (A-3) / (B-1) = 20/80. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-15) was sampled to examine its concentration, it was found that the Zr concentration was 0.034 mg / ml and the Al concentration was 2.17 mg / ml.
[重合]
製造例10の重合において、水素−エチレン混合ガス(水素濃度:0.02vol%)、ジルコニウム換算で0.001ミリモルの固体触媒成分(X-15)を用いた以外は、製造例10と同様の方法
で行った。得られたポリマーを10時間、真空乾燥し、エチレン系重合体67.7gを得た。な
お、製造例31で得られた重合体の製造条件に関しては、第4表に記載した。得られたエチ
レン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第8表に示す。
〔比較製造例1〕
株式会社プライムポリマーより市販されている溶液重合法によるエチレン・4-メチル-1-ペンテン共重合体(商品名:ウルトゼックス20100J)は製品ペレットを測定試料とし、
物性評価、押出ラミネート成形を行った。結果を第9表、第10表に示す。
[polymerization]
The polymerization in Production Example 10 was carried out in the same manner as in Production Example 10, except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.02 vol%) and 0.001 mmol of the solid catalyst component (X-15) in terms of zirconium were used. It was. The obtained polymer was vacuum-dried for 10 hours to obtain 67.7 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 31 are shown in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.
[Comparative Production Example 1]
Ethylene 4-methyl-1-pentene copolymer (trade name: Ultozex 20100J) by the solution polymerization method marketed by Prime Polymer Co., Ltd. uses product pellets as measurement samples.
Physical property evaluation and extrusion lamination were performed. The results are shown in Tables 9 and 10.
比較製造例1は、MT/η*に関して請求項1に記載の要件から外れている。このため、製造例に比べネックインが大きい。
〔比較製造例2〕
株式会社プライムポリマーより市販されている高圧ラジカル重合法によるポリエチレン(商品名:ミラソン11)は製品ペレットを測定試料とし、物性評価、押出ラミネート成形を行った。結果を第9表、第10表に示す。
Comparative Production Example 1 deviates from the requirement described in claim 1 with respect to MT / η *. For this reason, a neck-in is large compared with a manufacture example.
[Comparative Production Example 2]
Polyethylene (trade name: Mirason 11) by high pressure radical polymerization commercially available from Prime Polymer Co., Ltd. was subjected to physical property evaluation and extrusion lamination molding using a product pellet as a measurement sample. The results are shown in Tables 9 and 10.
比較製造例2は、メチル分岐数とエチル分岐数の和(A+B)に関して請求項1に記載の要件
から外れている。このため、ヒートシール強度が製造例に比べ劣る。
〔比較製造例3〕
[固体成分(S-3)の調製]
内容積180リットルの攪拌機付き反応器に、窒素雰囲気下、250℃で10時間乾燥したシリカ(SiO2)10kgを77リットルのトルエンに懸濁した後、0〜5℃まで冷却した。この懸濁液にメチルアルモキサンのトルエン溶液(Al原子換算で1.79mmol/ml)39.5リットルを1時間かけて滴下した。この際、系内の温度を0〜5℃に保った。引続き0〜5℃で30分間反応させ、次いで1.5時間かけて95〜100℃まで昇温し、その温度で4時間反応させた。その後55〜60℃まで降温し、上澄み液をデカンテーションにより除去した。このようにして得られた
固体成分をトルエンで4回洗浄した後、トルエンを加えて全量166.3リットルとし、固体成分(S-3)のトルエンスラリーを調製した。得られた固体成分(S-3)の一部を採取し、濃度を調べたところ、スラリー濃度:84.6g/L、Al濃度:0.422mol/Lであった。
Comparative Production Example 2 deviates from the requirement described in claim 1 regarding the sum of the number of methyl branches and the number of ethyl branches (A + B). For this reason, heat seal strength is inferior compared with a manufacture example.
[Comparative Production Example 3]
[Preparation of solid component (S-3)]
In a reactor equipped with a stirrer with an internal volume of 180 liters, 10 kg of silica (SiO 2 ) dried at 250 ° C. for 10 hours in a nitrogen atmosphere was suspended in 77 liters of toluene, and then cooled to 0 to 5 ° C. To this suspension, 39.5 liters of methylalumoxane in toluene (1.79 mmol / ml in terms of Al atoms) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 to 5 ° C. Subsequently, the mixture was reacted at 0 to 5 ° C. for 30 minutes, then heated to 95 to 100 ° C. over 1.5 hours, and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 55-60 ° C., and the supernatant was removed by decantation. The solid component thus obtained was washed four times with toluene, and then toluene was added to make a total volume of 166.3 liters to prepare a toluene slurry of the solid component (S-3). A part of the obtained solid component (S-3) was collected and examined for concentration. As a result, the slurry concentration was 84.6 g / L and the Al concentration was 0.422 mol / L.
[固体触媒成分(X-16)の調製]
次に、内容積114リットルの攪拌機付き反応器に、窒素雰囲気下、上記で調製した固体
成分(S-3)のトルエンスラリー11.8リットル(固体成分で1000g)を添加した後、攪拌下、エチレンビス(インデニル)ジルコニウムジクロリドのトルエン溶液(Zr原子換算で0.0017mmol/ml) 14.7リットルを78〜80℃で30分間かけて滴下し、この温度で2時間反応させ
た。その後、上澄み液を除去し、ヘキサンで2回洗浄した後、ヘキサンを加えて全量25リ
ットルとし、固体触媒成分(X-16)のヘキサンスラリーを調製した。
[Preparation of solid catalyst component (X-16)]
Next, 11.8 liters of the toluene slurry of the solid component (S-3) prepared above (1000 g of the solid component) was added to a reactor equipped with a stirrer with an internal volume of 114 liters under a nitrogen atmosphere. 14.7 liters of a toluene solution of (indenyl) zirconium dichloride (0.0017 mmol / ml in terms of Zr atoms) was added dropwise at 78 to 80 ° C. over 30 minutes, and reacted at this temperature for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane, and then hexane was added to a total volume of 25 liters to prepare a hexane slurry of the solid catalyst component (X-16).
[予備重合触媒(XP-16)の調製]
上記で得られた固体触媒成分(X-16)のヘキサンスラリーを5℃まで冷却した後、常圧下
でエチレンを系内に連続的に供給した。この間、系内の温度は10〜15℃に保持した。その後、トリイソブチルアルミニウムのヘキサン溶液(Al原子換算で40.0mmol/L) 1.9リットルと1-ヘキセン65.3mlを添加し、予備重合を開始した。1時間後に系内の温度は35℃まで
上昇したが、その後は系内温度を34〜35℃に保持した。予備重合を開始してから70分後に、再び1-ヘキセン65.3mlを添加した。
[Preparation of prepolymerization catalyst (XP-16)]
After cooling the hexane slurry of the solid catalyst component (X-16) obtained above to 5 ° C., ethylene was continuously supplied into the system under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, 1.9 liters of a hexane solution of triisobutylaluminum (40.0 mmol / L in terms of Al atom) and 65.3 ml of 1-hexene were added to start prepolymerization. After 1 hour, the temperature in the system rose to 35 ° C, but thereafter, the temperature in the system was maintained at 34 to 35 ° C. 70 minutes after the start of prepolymerization, 65.3 ml of 1-hexene was added again.
その後、予備重合開始から4時間後に、系内を窒素により置換し、予備重合を停止した
。次いで、上澄み液を除去し、ヘキサンで4回洗浄し、固体触媒成分(X-16) 1g当り3gのポリマーが予備重合された予備重合触媒(XP-16)を得た。その後、系内温度を34〜35℃まで
昇温し、エマルゲン108(花王(株)製ポリオキシエチレンラウリルエーテル)のヘキサ
ン溶液10リットル(エマルゲンの濃度で1.0g/L)を添加した。この温度で2時間攪拌し、
予備重合触媒(XP-16)にエマルゲンを担持させた予備重合触媒(XPV-16)を得た。
Thereafter, 4 hours after the start of the prepolymerization, the system was replaced with nitrogen, and the prepolymerization was stopped. Next, the supernatant was removed and washed 4 times with hexane to obtain a prepolymerized catalyst (XP-16) in which 3 g of polymer was prepolymerized per 1 g of the solid catalyst component (X-16). Thereafter, the temperature inside the system was raised to 34 to 35 ° C., and 10 liters of a hexane solution of Emulgen 108 (polyoxyethylene lauryl ether manufactured by Kao Corporation) (1.0 g / L in the concentration of Emulgen) was added. Stir at this temperature for 2 hours,
A prepolymerization catalyst (XPV-16) in which emulgen was supported on the prepolymerization catalyst (XP-16) was obtained.
[重合]
連続式流動床気相重合装置を用い、全圧2.0MPa-G、重合温度70℃、ガス線速度0.8m/secでエチレンと1-ヘキセンとの共重合を行った。上記で調製した予備重合触媒(XPV-16)を乾燥し、25〜30g/hrの割合で連続的に供給し、重合の間一定のガス組成を維持するためにエ
チレン、1-ヘキセン、水素および窒素を連続的に供給した(ガス組成:1-ヘキセン/エチ
レン=1.1〜1.3×10-2、エチレン濃度=71.4%)。得られたエチレン系重合体の収量は、5.3kg/hrであった。
[polymerization]
Using a continuous fluidized bed gas phase polymerization apparatus, ethylene and 1-hexene were copolymerized at a total pressure of 2.0 MPa-G, a polymerization temperature of 70 ° C., and a gas linear velocity of 0.8 m / sec. The pre-polymerized catalyst (XPV-16) prepared above is dried and continuously fed at a rate of 25-30 g / hr to maintain a constant gas composition during the polymerization, ethylene, 1-hexene, hydrogen and Nitrogen was continuously supplied (gas composition: 1-hexene / ethylene = 1.1 to 1.3 × 10 −2 , ethylene concentration = 71.4%). The yield of the obtained ethylene polymer was 5.3 kg / hr.
得られたエチレン系重合体を用い、製造例1と同様の方法にて測定試料を調製した。該
試料を用いて物性測定、押出ラミネート成形を行った。結果を第9表、第10表に示す。
比較製造例3は、MT/η*に関して請求項1に記載の要件から外れている。このため、製造例に比べ成形時のネックインが大きい。さらに、ゼロせん断粘度(η0)と重量平均分子
量(Mw)との関係に関して請求項1に記載の要件から外れている。このため、製造例とは
異なり、引取サージングが発生する。
Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Production Example 1. Using this sample, physical properties were measured and extrusion lamination was performed. The results are shown in Tables 9 and 10.
Comparative Production Example 3 deviates from the requirement described in claim 1 with respect to MT / η *. For this reason, the neck-in at the time of shaping | molding is large compared with the manufacture example. Furthermore, the relationship between the zero shear viscosity (η 0 ) and the weight average molecular weight (Mw) deviates from the requirement described in claim 1. For this reason, unlike the manufacturing example, takeover surging occurs.
〔比較製造例4〕
[固体触媒成分(X-17)の調製]
窒素置換した200mlのガラス製フラスコにトルエン100mlを入れ,攪拌した,上記で調製した固体成分(S-3)のトルエンスラリー(固体部換算で2.0g)を装入した。次に、Me2Si(Ind)2ZrCl2(成分A)のトルエン溶液(Zr原子換算で0.0015mmol/ml) 32.1mlを滴下し、
室温で1時間反応させた。その後、上澄み液をデカンテーションにより除去し、デカンで2回洗浄し、100mlのデカンスラリーとした〔固体触媒成分(X-17)〕。得られた固体触媒成
分(X-17)のデカンスラリーの一部を採取して濃度を調べたところ、Zr濃度0.043mg/ml、Al濃度2.49mg/mlであった。
[Comparative Production Example 4]
[Preparation of solid catalyst component (X-17)]
100 ml of toluene was placed in a 200 ml glass flask purged with nitrogen and stirred, and the toluene slurry of the solid component (S-3) prepared above (2.0 g in terms of solid part) was charged. Next, 32.1 ml of a toluene solution of Me 2 Si (Ind) 2 ZrCl 2 (component A) (0.0015 mmol / ml in terms of Zr atoms) was added dropwise,
The reaction was allowed to proceed for 1 hour at room temperature. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain 100 ml of decane slurry [solid catalyst component (X-17)]. A portion of the resulting decane slurry of the solid catalyst component (X-17) was collected and examined for concentration. As a result, the Zr concentration was 0.043 mg / ml, and the Al concentration was 2.49 mg / ml.
[重合]
充分に窒素置換した内容積1リットルのSUS製オートクレーブに精製ヘプタン 500mlを入れ、エチレンを流通し、液相および気相をエチレンで飽和させた。次に、水素−エチレン混合ガス(水素濃度:0.54vol%)を用いて、系内を置換した後、1-ヘキセン15ml、トリイソブチルアルミニウム 0.375mmol、固体触媒成分(X-17) 0.5gをこの順に装入した。80℃
に昇温して、0.78MPa-Gにて90分間重合を行った。得られたポリマーを10時間、真空乾燥
し、エチレン系重合体86.7gを得た。
[polymerization]
Purified heptane (500 ml) was placed in a 1-liter SUS autoclave thoroughly purged with nitrogen, ethylene was circulated, and the liquid phase and gas phase were saturated with ethylene. Next, after replacing the inside of the system with a hydrogen-ethylene mixed gas (hydrogen concentration: 0.54 vol%), 1 ml of 1-hexene, 0.375 mmol of triisobutylaluminum, 0.5 g of the solid catalyst component (X-17) We inserted in order. 80 ℃
The temperature was raised to 0.78 MPa-G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 86.7 g of an ethylene polymer.
得られたエチレン系重合体を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第9表に示す。
〔比較製造例5〕
ダウ・ケミカル・カンパニーより市販されている溶液重合法によるエチレン・1-オクテン共重合体(商品名:アフィニティーPF1140)は製品ペレットを測定試料とし、物性評価を行った。結果を第9表に示す。
A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 9 shows the results of physical properties measured using the sample.
[Comparative Production Example 5]
The ethylene 1-octene copolymer (trade name: Affinity PF1140) by the solution polymerization method marketed by Dow Chemical Company was evaluated for physical properties using the product pellet as a measurement sample. The results are shown in Table 9.
比較製造例4、5は、MT/η*に関して請求項1に記載の要件から外れている。このため、
製造例に比べネックインが大きいと推定される。さらに、ゼロせん断粘度(η0)と重量
平均分子量(Mw)との関係に関して請求項1に記載の要件から外れている。このため、製
造例とは異なり引取サージングが発生すると推定される。
Comparative production examples 4 and 5 deviate from the requirements described in claim 1 with respect to MT / η *. For this reason,
It is estimated that the neck-in is larger than the manufacturing example. Furthermore, the relationship between the zero shear viscosity (η 0 ) and the weight average molecular weight (Mw) deviates from the requirement described in claim 1. For this reason, it is estimated that takeover surging occurs unlike the manufacturing example.
〔エチレン系重合体[R1-1]〕
製造例11と同様の方法にてエチレン系重合体[R1-1]を製造した。得られたエチレン系重合体[R1-1]を用い、製造例10と同様の方法にて測定試料を調製した。該試料を用いて物性測定を行った結果を第11表に示す。
〔エチレン系重合体[R2-1]〕
エチレン系重合体[R2-1]として、株式会社プライムポリマーより市販されているエチレン・4-メチル-1-ペンテン共重合体(商品名:ウルトゼックスUZ15150J)を用いた。製品
ペレットを測定試料とし、物性評価を行った結果を第11表に示す。
〔エチレン系樹脂〕
エチレン系重合体[R1-1]とエチレン系重合体[R2-1]とを重量比([R1-1]/[R2-1]= 30/70)でドライブレンドした後、東洋精機製作所製ラボプラストミルを用い、樹脂温度180℃
、回転数50rpmで5分間溶融混練してエチレン系樹脂を得た。さらに、この溶融ポリマーを、神藤金属工業所製プレス成形機を用い、冷却温度20℃、冷却時間5分間、冷却圧力100 kg/cm2の条件にて冷却した。該試料を用いて物性測定を行った結果を第12表に示す。
[Ethylene polymer [R1-1]]
Ethylene polymer [R1-1] was produced in the same manner as in Production Example 11. Using the obtained ethylene polymer [R1-1], a measurement sample was prepared in the same manner as in Production Example 10. Table 11 shows the results of physical properties measured using the sample.
[Ethylene polymer [R2-1]]
As the ethylene-based polymer [R2-1], an ethylene-4-methyl-1-pentene copolymer (trade name: Ultzex UZ15150J) commercially available from Prime Polymer Co., Ltd. was used. Table 11 shows the results of physical property evaluation using product pellets as measurement samples.
[Ethylene resin]
After dry blending ethylene polymer [R1-1] and ethylene polymer [R2-1] at a weight ratio ([R1-1] / [R2-1] = 30/70), manufactured by Toyo Seiki Seisakusho Using Laboplast Mill, resin temperature 180 ° C
Then, it was melt-kneaded for 5 minutes at a rotation speed of 50 rpm to obtain an ethylene-based resin. Further, this molten polymer was cooled using a press molding machine manufactured by Shindo Metal Industry Co., Ltd. under the conditions of a cooling temperature of 20 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg / cm 2 . Table 12 shows the results of physical properties measured using the sample.
[エチレン系重合体の合成]
製造例1において、エチレン・1-ヘキセン共重合を第13表に示す条件に変えた以外は、製造例1と同様にしてエチレン系重合体を得た。
[Synthesis of ethylene polymer]
An ethylene polymer was obtained in the same manner as in Production Example 1 except that the ethylene / 1-hexene copolymerization was changed to the conditions shown in Table 13 in Production Example 1.
[積層体の調製]
得られたエチレン系重合体を、65 mmφの押出機とダイ幅500 mmのTダイを有する住友重機社製ラミネーターを用いて、基材上にエアギャップ130 mm、ダイ下樹脂温度295℃、引
取速度80 m/minの条件下で、膜厚25μmになるよう押出ラミネートした。基材には、厚さ15μmの二軸延伸ナイロンフィルム(商品名 エンブレムONM、ユニチカ(株)製)の片
面に、ウレタン系アンカーコート剤を塗布し、その後、チーグラー触媒により得られた直鎖状低密度ポリエチレンと高圧法低密度ポリエチレンをそれぞれ50重量部ずつブレンドしたエチレン系混合樹脂を25μmの厚さで押出ラミネートした積層体を用いた。なお、エチ
レン系重合体は上記積層体のエチレン系混合樹脂層側に押出ラミネートした。
[Preparation of laminate]
The obtained ethylene-based polymer was taken up using a Sumitomo Heavy Industries Laminator having a 65 mmφ extruder and a T die with a die width of 500 mm, with an air gap of 130 mm on the substrate and a resin temperature under the die of 295 ° C. Extrusion lamination was carried out under the condition of a speed of 80 m / min so that the film thickness was 25 μm. The base material was coated with a urethane anchor coating agent on one side of a biaxially stretched nylon film (trade name Emblem ONM, manufactured by Unitika Ltd.) with a thickness of 15 μm, and then a linear shape obtained with a Ziegler catalyst. A laminate obtained by extrusion laminating an ethylene-based mixed resin in which 50 parts by weight of low-density polyethylene and high-pressure method low-density polyethylene were blended at a thickness of 25 μm was used. The ethylene polymer was extrusion laminated on the ethylene mixed resin layer side of the laminate.
この押出ラミネートフィルムのエチレン系重合体層同士のヒートシール強度を上記方法に従って測定ないし評価した。 The heat seal strength between the ethylene polymer layers of this extruded laminate film was measured or evaluated according to the above method.
[固体成分(S-3)の調製]
内容積260Lの攪拌機付き反応器に、窒素雰囲気下、250℃で10時間乾燥したシリカ(SiO2:平均粒子径65μm)10kgを88.5Lのトルエンに懸濁した後、
0〜5℃まで冷却した。この懸濁液にメチルアルモキサンのトルエン溶液(Al原子換算で3.0mmol/mL)78.2Lを60分間かけて滴下した。この際、系内の温度を0〜5℃に保った。引き続き0〜5℃で30分間反応させた後、約1.5時間かけて95〜100℃まで昇温して、引き続き95〜100℃で4時間反応させた。その後60℃まで降温して、上澄み液をデカンテーションにより除去した。このようにして得られた固体成分をトルエンで4回洗浄した後、トルエンを加えて全量130Lとし、固体成分(S-
3)のトルエンスラリーを調製した。得られた固体成分の一部を採取し、濃度を調べたところ、スラリー濃度:138.5g/L、Al濃度:1.0mol/Lであった。
[Preparation of solid component (S-3)]
In a reactor equipped with a stirrer with an internal volume of 260 L, 10 kg of silica (SiO 2 : average particle diameter 65 μm) dried at 250 ° C. for 10 hours under a nitrogen atmosphere was suspended in 88.5 L of toluene,
Cooled to 0-5 ° C. To this suspension, 78.2 L of a methylalumoxane toluene solution (3.0 mmol / mL in terms of Al atom) was added dropwise over 60 minutes. At this time, the temperature in the system was kept at 0 to 5 ° C. Subsequently, the mixture was reacted at 0 to 5 ° C. for 30 minutes, then heated to 95 to 100 ° C. over about 1.5 hours, and then reacted at 95 to 100 ° C. for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by decantation. The solid component thus obtained was washed four times with toluene, and then toluene was added to make a total volume of 130 L. The solid component (S-
The toluene slurry of 3) was prepared. A part of the obtained solid component was collected and examined for concentration. As a result, the slurry concentration was 138.5 g / L and the Al concentration was 1.0 mol / L.
[固体触媒成分(X-4)の調製]
内容積114Lの攪拌機付き反応器に、窒素雰囲気下、トルエン21.0Lと上記で調製した固体成分(S-3)のトルエンスラリー16.2L(固体成分で1865g)を添
加した。一方、内容積100Lの攪拌機付き反応器に、窒素雰囲気下、トルエン36.1Lを張り込み、攪拌下、メタロセン化合物(A-1)のトルエン溶液(Zr原子換算で7
.40mmol/L)5.5リットルを投入し、続いてメタロセン化合物(B-1)のト
ルエン溶液(Zr原子換算で3.20mmol/L)5.0Lを投入し数分間混合した((A-1)/(B-1)のモル比=70/30)。続いて、調製した混合溶液を予め固体成分(S-3)のトルエンスラリーを張り込んだ上記反応器に圧送した。圧送後、内温20
〜25℃で1時間反応させた。その後、上澄み液をデカンテーションにより除去した。このようにして得られた固体触媒成分をヘキサンで3回洗浄した後、ヘキサンを加えて全量47Lとし、固体触媒成分(X-4)のヘキサンスラリーを調製した。
[Preparation of solid catalyst component (X-4)]
Under a nitrogen atmosphere, 21.0 L of toluene and 16.2 L of a toluene slurry of the solid component (S-3) prepared above (1865 g as a solid component) were added to a reactor having an internal volume of 114 L with a stirrer. On the other hand, in a reactor with a stirrer having an internal volume of 100 L, 36.1 L of toluene was put under a nitrogen atmosphere, and under stirring, a toluene solution of the metallocene compound (A-1) (7 in terms of Zr atoms).
. (40 mmol / L) 5.5 liters was added, and then 5.0 L of a toluene solution of metallocene compound (B-1) (3.20 mmol / L in terms of Zr atoms) was added and mixed for several minutes ((A-1 ) / (B-1) molar ratio = 70/30). Subsequently, the prepared mixed solution was pumped to the reactor in which the toluene slurry of the solid component (S-3) was previously put. After pumping,
It was made to react at -25 degreeC for 1 hour. Thereafter, the supernatant was removed by decantation. The solid catalyst component thus obtained was washed with hexane three times, and then hexane was added to a total volume of 47 L to prepare a hexane slurry of the solid catalyst component (X-4).
[予備重合触媒(XP-4)の調製]
引き続き、上記で得られた固体触媒成分(X-1)のヘキサンスラリーを10℃まで冷
却した後、常圧下でエチレンを系内に連続的に数分間供給した。この間、系内の温度は10〜15℃に保持した。その後、トリイソブチルアルミニウム(TiBAl)2.5molと1-ヘキセン123mLを添加した。1-ヘキセン添加後にエチレンを1.8kg/hで再度供給し予備重合を開始した。予備重合を開始してから35分後に系内温度は23℃まで上昇し、それ以降の系内温度は24〜26℃に保持した。予備重合を開始してから87分後に1-ヘキセン61.0mLを添加、150分後にも1-ヘキセン61.0mLを添加した。
[Preparation of prepolymerization catalyst (XP-4)]
Subsequently, the solid catalyst component (X-1) hexane slurry obtained above was cooled to 10 ° C., and then ethylene was continuously fed into the system for several minutes under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, 2.5 mol of triisobutylaluminum (TiBAl) and 123 mL of 1-hexene were added. After the addition of 1-hexene, ethylene was supplied again at 1.8 kg / h to start prepolymerization. 35 minutes after the start of prepolymerization, the system temperature rose to 23 ° C, and the system temperature thereafter was maintained at 24-26 ° C. 87 minutes after the start of prepolymerization, 61.0 mL of 1-hexene was added, and 61.0 mL of 1-hexene was added 150 minutes later.
予備重合開始から212分後に、エチレン供給を停止し系内を窒素により置換し、予備重合を停止した。その後、上澄み液をデカンテーションにより除去した。このようにして得られた予備重合触媒をヘキサンで6回洗浄し、固体触媒成分1g当り3.03gのポリマーが重合された予備重合触媒(XP-4)を得た。得られた予備重合触媒成分の一部を
乾燥し、組成を調べたところ、固体触媒成分1g当たりZr原子が0.60mg含まれていた。
After 212 minutes from the start of the prepolymerization, the ethylene supply was stopped, the inside of the system was replaced with nitrogen, and the prepolymerization was stopped. Thereafter, the supernatant was removed by decantation. The prepolymerized catalyst thus obtained was washed 6 times with hexane to obtain a prepolymerized catalyst (XP-4) in which 3.03 g of polymer was polymerized per 1 g of the solid catalyst component. A part of the obtained prepolymerized catalyst component was dried and the composition was examined. As a result, 0.60 mg of Zr atom was contained per 1 g of the solid catalyst component.
内容積43Lの攪拌機付き蒸発乾燥機に、窒素雰囲気下、予備重合触媒(XP-4)の
ヘキサンスラリー25L(固体予備重合触媒で3330g)を移液した。移液後、乾燥機内を約3.5時間かけて−65KPaGまで減圧し、−65KPaGに到達したところで約4.0時間真空乾燥しヘキサン、予備重合触媒の揮発分を除去した。更に−100KPaGまで減圧し、−100KPaGに到達したところで6時間真空乾燥した。得られた予備重合触媒(XP-4)のトータル揮発分は、0.3wt%含まれていた。
[重合]
内容積1.7m3の流動層型気相重合反応器に上記で得られた予備重合触媒成分(XP-4)をZr原子換算で0.06mmol/hrで供給した。エチレンの分圧を1.5MP
a・A、気相1-ヘキセン/エチレン比=0.014m.r.、反応器中のガス線速が0.7m/sとなるように、窒素、エチレン、1-ヘキセンを供給した。かつ重合反応器中の重
合体が一定量となるように、重合反応器より重合体を連続的に抜き出し、全圧2.0MPaG、重合温度80℃、滞留時間7.3hという条件で重合を行った。重合反応器から連続的に抜き出された重合体は、フラッシュホッパーで未反応エチレンが実質的に除去される。その後、重合体を乾燥装置で乾燥し、エチレン系重合体を3.3kg/hで得た。(表14参照)得られたエチレン系重合体を用い、実施例1と同様にしてヒートシール強度を測定ないし評価した。
25 L of hexane slurry (3330 g as a solid prepolymerization catalyst) of the prepolymerization catalyst (XP-4) was transferred to an evaporation dryer with a stirrer having an internal volume of 43 L under a nitrogen atmosphere. After the liquid transfer, the inside of the dryer was depressurized to -65 KPaG over about 3.5 hours, and when it reached -65 KPaG, vacuum drying was performed for about 4.0 hours to remove volatile components of hexane and the prepolymerized catalyst. Furthermore, the pressure was reduced to −100 KPaG, and when the pressure reached −100 KPaG, vacuum drying was performed for 6 hours. The total volatile content of the obtained prepolymerized catalyst (XP-4) was 0.3 wt%.
[polymerization]
The prepolymerized catalyst component (XP-4) obtained above was supplied at 0.06 mmol / hr in terms of Zr atoms to a fluidized bed gas phase polymerization reactor having an internal volume of 1.7 m 3 . The partial pressure of ethylene is 1.5MP
a, A, gas phase 1-hexene / ethylene ratio = 0.014 m.r. Nitrogen, ethylene, and 1-hexene were supplied so that the gas linear velocity in the reactor was 0.7 m / s. In addition, the polymer is continuously withdrawn from the polymerization reactor so that the amount of the polymer in the polymerization reactor becomes a constant amount, and polymerization is performed under the conditions of a total pressure of 2.0 MPaG, a polymerization temperature of 80 ° C., and a residence time of 7.3 h. It was. From the polymer continuously withdrawn from the polymerization reactor, unreacted ethylene is substantially removed by a flash hopper. Thereafter, the polymer was dried with a drying apparatus to obtain an ethylene-based polymer at 3.3 kg / h. (See Table 14) Using the obtained ethylene polymer, the heat seal strength was measured or evaluated in the same manner as in Example 1.
実施例2において、エチレン・1-ヘキセン共重合を第14表に示す条件に変えた以外は、実施例2と同様にしてエチレン系重合体を得た。得られたエチレン系重合体を用い、実施例1と同様にしてヒートシール強度を測定ないし評価した。
〔比較例1〕
実施例1においてエチレン系重合体に代えて高圧法低密度ポリエチレン(商品名:ミラソン11P、株式会社プライムポリマー社製)を用いたこと以外は実施例1と同様にしてヒートシール強度を測定ないし評価した。
〔比較例2〕
実施例1においてエチレン系重合体に代えて低密度ポリエチレン(商品名:ウルトゼックス20100J、株式会社プライムポリマー社製)を用いたこと以外は実施例1と同様にしてヒートシール強度を測定ないし評価した。
〔比較例3〕
製造比較例3のエチレン系重合体を用いたこと以外は実施例1と同様にしてヒートシール強度を測定ないし評価した。
In Example 2, an ethylene polymer was obtained in the same manner as in Example 2, except that the ethylene / 1-hexene copolymerization was changed to the conditions shown in Table 14. Using the obtained ethylene polymer, the heat seal strength was measured or evaluated in the same manner as in Example 1.
[Comparative Example 1]
In Example 1, heat seal strength was measured or evaluated in the same manner as in Example 1 except that high-pressure low-density polyethylene (trade name: Mirason 11P, manufactured by Prime Polymer Co., Ltd.) was used instead of the ethylene polymer. did.
[Comparative Example 2]
In Example 1, the heat seal strength was measured or evaluated in the same manner as in Example 1 except that low density polyethylene (trade name: ULTZEX 20100J, manufactured by Prime Polymer Co., Ltd.) was used instead of the ethylene polymer. .
[Comparative Example 3]
Heat seal strength was measured or evaluated in the same manner as in Example 1 except that the ethylene-based polymer of Production Comparative Example 3 was used.
以上の結果を下記第15表に示す。 The above results are shown in Table 15 below.
Claims (3)
(I)190℃における2.16kg荷重でのメルトフローレート(MFR)が0.1〜50g/10分の範囲である。
(II)密度(d)が875〜970kg/m3の範囲である
(III)190℃における溶融張力〔MT(g)〕と、200℃、角速度1.0rad/秒におけるせん断粘度〔η*(P)〕との比〔MT/η*(g/P)〕が1.00×10-4〜9.0
0×10-4の範囲である
(IV)13C-NMRにより測定された炭素原子1000個あたりのメチル分岐数〔A(/1000C)〕とエチル分岐数〔B(/1000C)〕との和〔(A+B)(/1000C)〕が1.8以下である
(V)200℃におけるゼロせん断粘度〔η0(P)〕とGPC-粘度検出器法(GPC-
VISCO)により測定された重量平均分子量(Mw)とが下記関係式(Eq-1)を満たす
0.01×10-13×Mw3.4≦η0≦4.5×10-13×Mw3.4 -----(Eq-1) A resin composition for a laminate, which is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, and includes an ethylene-based resin that simultaneously satisfies the following requirements (I) to (V):
(I) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is in the range of 0.1 to 50 g / 10 min.
(II) The density (d) is in the range of 875 to 970 kg / m 3 (III) The melt tension [MT (g)] at 190 ° C. and the shear viscosity [η * ( P)] [MT / η * (g / P)] is 1.00 × 10 −4 to 9.0.
Sum of methyl branch number [A (/ 1000C)] and ethyl branch number [B (/ 1000C)] per 1000 carbon atoms measured by (IV) 13 C-NMR in the range of 0 × 10 −4 [(A + B) (/ 1000C)] is 1.8 or less (V) Zero shear viscosity [η 0 (P)] at 200 ° C. and GPC-viscosity detector method (GPC-
The weight average molecular weight (Mw) measured by VISCO) satisfies the following relational expression (Eq-1): 0.01 × 10 −13 × Mw 3.4 ≦ η 0 ≦ 4.5 × 10 −13 × Mw 3.4 − --- (Eq-1)
The laminate according to claim 2 obtained by extrusion lamination molding.
Priority Applications (6)
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JP2006209238A JP5174333B2 (en) | 2006-07-31 | 2006-07-31 | Laminate resin composition and laminate |
CN2007800276255A CN101490116B (en) | 2006-07-31 | 2007-07-31 | Film or laminate comprising ethylene resin or ethylene resin composition |
KR1020097004012A KR101096836B1 (en) | 2006-07-31 | 2007-07-31 | Film or laminate comprising ethylene resin or ethylene resin composition |
EP07791698.9A EP2050771B1 (en) | 2006-07-31 | 2007-07-31 | Film or laminate comprising ethylene resin or ethylene resin composition |
US12/309,598 US8299193B2 (en) | 2006-07-31 | 2007-07-31 | Film or laminate comprising ethylene-based resin or ethylene-based resin composition |
PCT/JP2007/065014 WO2008016059A1 (en) | 2006-07-31 | 2007-07-31 | Film or laminate comprising ethylene resin or ethylene resin composition |
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Cited By (2)
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JP2008031378A (en) * | 2006-07-31 | 2008-02-14 | Mitsui Chemicals Inc | Resin composition for adhesion and packaging material |
JP2008031382A (en) * | 2006-07-31 | 2008-02-14 | Mitsui Chemicals Inc | Blow-molded article comprising polyethylene-based resin |
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EP2402376A1 (en) * | 2010-06-29 | 2012-01-04 | Borealis AG | Process for producing a prepolymerised catalyst, such prepolymerised catalyst and its use for producing a polymer |
CN104024326B (en) * | 2011-12-28 | 2016-11-23 | 三井化学株式会社 | Ethylene polymer composition and formed body therefrom |
ES2659232T3 (en) | 2013-02-20 | 2018-03-14 | Prime Polymer Co., Ltd. | Biaxially stretched film, and ethylene type polymer composition |
CN103275377B (en) * | 2013-06-04 | 2014-04-30 | 汕头保税区联通工业有限公司 | Easy-to-tear plastic film material and preparation technology thereof |
CN108677599A (en) * | 2018-05-28 | 2018-10-19 | 无锡上美纸制品有限公司 | One kind easily tearing environmentally friendly brown paper protective film and preparation method thereof |
CN114478889B (en) * | 2020-10-26 | 2024-06-04 | 中国石油化工股份有限公司 | Ethylene polymer and preparation method and application thereof |
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JPH07252311A (en) * | 1993-12-21 | 1995-10-03 | Union Carbide Chem & Plast Technol Corp | Production of polyolefin with long-chain branch by vapor phase method |
JP2002105132A (en) * | 2000-07-26 | 2002-04-10 | Mitsui Chemicals Inc | Polymer and method for producing the same |
JP2004217924A (en) * | 2002-12-27 | 2004-08-05 | Mitsui Chemicals Inc | Ethylene polymer and molded product obtained therefrom |
WO2004104055A1 (en) * | 2003-05-20 | 2004-12-02 | Mitsui Chemicals, Inc. | Ethylene polymer |
JP2005002333A (en) * | 2003-05-20 | 2005-01-06 | Mitsui Chemicals Inc | Ethylene-based polymer |
JP2006233207A (en) * | 2005-01-31 | 2006-09-07 | Mitsui Chemicals Inc | Ethylene polymer and molding obtained therefrom |
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CN1067945C (en) * | 1994-04-28 | 2001-07-04 | 旭化成宝利积层股份有限公司 | Web of layered film used in sealed bag and sealed bag made of same |
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Patent Citations (6)
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JPH07252311A (en) * | 1993-12-21 | 1995-10-03 | Union Carbide Chem & Plast Technol Corp | Production of polyolefin with long-chain branch by vapor phase method |
JP2002105132A (en) * | 2000-07-26 | 2002-04-10 | Mitsui Chemicals Inc | Polymer and method for producing the same |
JP2004217924A (en) * | 2002-12-27 | 2004-08-05 | Mitsui Chemicals Inc | Ethylene polymer and molded product obtained therefrom |
WO2004104055A1 (en) * | 2003-05-20 | 2004-12-02 | Mitsui Chemicals, Inc. | Ethylene polymer |
JP2005002333A (en) * | 2003-05-20 | 2005-01-06 | Mitsui Chemicals Inc | Ethylene-based polymer |
JP2006233207A (en) * | 2005-01-31 | 2006-09-07 | Mitsui Chemicals Inc | Ethylene polymer and molding obtained therefrom |
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JP2008031378A (en) * | 2006-07-31 | 2008-02-14 | Mitsui Chemicals Inc | Resin composition for adhesion and packaging material |
JP2008031382A (en) * | 2006-07-31 | 2008-02-14 | Mitsui Chemicals Inc | Blow-molded article comprising polyethylene-based resin |
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CN101490116A (en) | 2009-07-22 |
JP5174333B2 (en) | 2013-04-03 |
CN101490116B (en) | 2011-09-07 |
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