JPH08325333A - Ethylene-alpha-olefin copolymer - Google Patents
Ethylene-alpha-olefin copolymerInfo
- Publication number
- JPH08325333A JPH08325333A JP17786695A JP17786695A JPH08325333A JP H08325333 A JPH08325333 A JP H08325333A JP 17786695 A JP17786695 A JP 17786695A JP 17786695 A JP17786695 A JP 17786695A JP H08325333 A JPH08325333 A JP H08325333A
- Authority
- JP
- Japan
- Prior art keywords
- group
- ethylene
- mfr
- olefin copolymer
- copolymer
- 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
- 239000004711 α-olefin Substances 0.000 title claims description 38
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title claims description 35
- 238000009826 distribution Methods 0.000 claims abstract description 36
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 44
- 239000005977 Ethylene Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 28
- 238000010828 elution Methods 0.000 claims description 24
- 238000005194 fractionation Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 23
- 229920001577 copolymer Polymers 0.000 abstract description 22
- 150000001875 compounds Chemical class 0.000 abstract description 21
- 230000000704 physical effect Effects 0.000 abstract description 15
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000000465 moulding Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 238000012937 correction Methods 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 16
- -1 Specifically Chemical group 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 150000002430 hydrocarbons Chemical group 0.000 description 12
- 238000007789 sealing Methods 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- 239000012968 metallocene catalyst Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DKVSRPILOXOTTE-UHFFFAOYSA-L CCCO[Zr](Cl)(Cl)OCCC Chemical compound CCCO[Zr](Cl)(Cl)OCCC DKVSRPILOXOTTE-UHFFFAOYSA-L 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- YGRHYJIWZFEDBT-UHFFFAOYSA-N tridecylaluminum Chemical compound CCCCCCCCCCCCC[Al] YGRHYJIWZFEDBT-UHFFFAOYSA-N 0.000 description 3
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 2
- 108091022623 Formins Proteins 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 230000005674 electromagnetic induction Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000007613 slurry method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- YPEOCTSXLWIZSO-UHFFFAOYSA-N 1,3-dimethylcyclopenta-1,3-diene Chemical compound CC1=CC(C)=CC1 YPEOCTSXLWIZSO-UHFFFAOYSA-N 0.000 description 1
- GKEUODMJRFDLJY-UHFFFAOYSA-N 1-Methylfluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2C GKEUODMJRFDLJY-UHFFFAOYSA-N 0.000 description 1
- IQSUNBLELDRPEY-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 description 1
- QMRIOEQPJDFOPT-UHFFFAOYSA-N 1-methylcyclohepta-1,3,5-triene Chemical compound CC1=CC=CC=CC1 QMRIOEQPJDFOPT-UHFFFAOYSA-N 0.000 description 1
- LZYHSPJFFHXHPW-UHFFFAOYSA-N 1H-inden-1-ylsilane Chemical compound C1=CC=C2C([SiH3])C=CC2=C1 LZYHSPJFFHXHPW-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- DKLQZDIAQKGVTA-UHFFFAOYSA-N 4,7-dimethyl-1h-indene Chemical compound CC1=CC=C(C)C2=C1CC=C2 DKLQZDIAQKGVTA-UHFFFAOYSA-N 0.000 description 1
- IRAWLGHJHQBREM-UHFFFAOYSA-N 7-Methylinden Natural products CC1=CC=CC2=C1C=CC2 IRAWLGHJHQBREM-UHFFFAOYSA-N 0.000 description 1
- AWHIZLGSPNLJRO-UHFFFAOYSA-M CCCCO[Zr](Cl)(OCCCC)OCCCC Chemical compound CCCCO[Zr](Cl)(OCCCC)OCCCC AWHIZLGSPNLJRO-UHFFFAOYSA-M 0.000 description 1
- MLOQZZUGWOLMCU-UHFFFAOYSA-N CC[Zr](CC)(CC)CC Chemical compound CC[Zr](CC)(CC)CC MLOQZZUGWOLMCU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241001293164 Eutrema japonicum Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- 235000000760 Wasabia japonica Nutrition 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CKEGKURXFKLBDX-UHFFFAOYSA-N butan-1-ol;hafnium Chemical compound [Hf].CCCCO.CCCCO.CCCCO.CCCCO CKEGKURXFKLBDX-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- DWHYOXYJRGUQEP-UHFFFAOYSA-N carbanide zirconium(4+) Chemical compound [CH3-].[CH3-].[CH3-].[CH3-].[Zr+4] DWHYOXYJRGUQEP-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- CHVJITGCYZJHLR-UHFFFAOYSA-N cyclohepta-1,3,5-triene Chemical compound C1C=CC=CC=C1 CHVJITGCYZJHLR-UHFFFAOYSA-N 0.000 description 1
- KDUIUFJBNGTBMD-VXMYFEMYSA-N cyclooctatetraene Chemical compound C1=C\C=C/C=C\C=C1 KDUIUFJBNGTBMD-VXMYFEMYSA-N 0.000 description 1
- AIRILDQHJRAOBJ-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylsilane Chemical compound [SiH3]C1C=CC=C1 AIRILDQHJRAOBJ-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- KZLUHGRPVSRSHI-UHFFFAOYSA-N dimethylmagnesium Chemical compound C[Mg]C KZLUHGRPVSRSHI-UHFFFAOYSA-N 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- KSCFJBIXMNOVSH-UHFFFAOYSA-N dyphylline Chemical group O=C1N(C)C(=O)N(C)C2=C1N(CC(O)CO)C=N2 KSCFJBIXMNOVSH-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QSLMQGXOMLSFAW-UHFFFAOYSA-N methanidylbenzene;zirconium(4+) Chemical compound [Zr+4].[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1 QSLMQGXOMLSFAW-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- NGPFLGSPZBLITO-UHFFFAOYSA-N penta-1,3-dienylsilane Chemical compound CC=CC=C[SiH3] NGPFLGSPZBLITO-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、優れた物性および加工
性を有する新規なエチレン・α−オレフィン共重合体に
関する。さらに詳しくは、分子量分布が狭いにもかかわ
らず、比較的広い組成分布を持ち、かつ低分子量成分お
よび非晶質成分の含有量が少なく、機械物性、成形加工
性、光学特性および耐熱性に優れ、特にＴダイ成形、イ
ンフレーションフィルム成形等によって製造され各種包
装用フィルム、ラミネート用原反等のフィルム成形体、
中空成形による各種容器等、射出成形による各種容器、
蓋、コンテナー等の射出成形体、あるいは電線、ケーブ
ル、鋼管等の被覆用等に好適なエチレン・α−オレフィ
ン共重合体を提供するものである。FIELD OF THE INVENTION The present invention relates to a novel ethylene / α-olefin copolymer having excellent physical properties and processability. More specifically, despite having a narrow molecular weight distribution, it has a relatively wide composition distribution and a low content of low molecular weight components and amorphous components, and is excellent in mechanical properties, moldability, optical properties and heat resistance. , In particular, film molded products such as various packaging films and original films for laminating produced by T-die molding, inflation film molding, etc.
Various containers by injection molding, various containers by hollow molding, etc.
It is intended to provide an ethylene / α-olefin copolymer suitable for injection moldings such as lids and containers, or for coating electric wires, cables, steel pipes and the like.
【０００２】[0002]
【従来の技術】チグラー型触媒で得られるエチレン・α
−オレフィン共重合体である直鎖状低密度ポリエチレン
（ＬＬＤＰＥ）は、高圧法低密度ポリエチレン（ＨＰＬ
ＤＰＥ）と比較し、強度およびじん性が大きく、フィル
ム、シート、中空成形体、射出成形体等さまざまな用途
に用いられているが、成形品の軽量化のためさらなる高
強度化が要求されている。近年、メタロセン系触媒によ
り分子量分布および組成分布が非常に狭い高強度のエチ
レン・α−オレフィン系共重合体が開発された。しかし
ながらこれらのメタロセン系エチレン・α−オレフィン
系重合体には、いくつかの欠点がある。例えば組成分布
が非常に狭いため温度に対する粘度および強度の変化が
非常に急激であり、そのため、成形加工時の温度や押し
出し条件等の適応範囲が狭く成形に難がある。また成形
品としても耐熱性や、適度なヒートシール強度あるいは
良好なホットタック強度を発現する温度範囲が狭い等の
欠点がある。例えばフィルム、シート等の分野ではヒー
トシールが容易であるため、ヒートシールし袋状として
用いられることが多く、このような用途でホットタック
特性が必要とされる。すなわち、内容物を充填する際な
どヒートシール直後にシール部分が引っ張られて荷重が
かかり、シール部が剥離する場合がある。このようなも
のではシール直後の剥離に対し強い値を示すヒートシー
ルが可能となるシールの温度範囲が広いものが好まれ
る。2. Description of the Related Art Ethylene / α obtained by Ziegler type catalyst
-Linear low-density polyethylene (LLDPE), which is an olefin copolymer, is a high-pressure low-density polyethylene (HPL).
Compared to DPE), it has higher strength and toughness and is used in various applications such as films, sheets, hollow moldings and injection moldings, but higher strength is required to reduce the weight of molded products. There is. In recent years, a high-strength ethylene / α-olefin copolymer having a very narrow molecular weight distribution and composition distribution has been developed using a metallocene catalyst. However, these metallocene ethylene / α-olefin polymers have some drawbacks. For example, since the composition distribution is very narrow, the changes in viscosity and strength with respect to temperature are extremely rapid, and therefore the applicable range of temperature and extrusion conditions during molding is narrow, and molding is difficult. Further, the molded product also has drawbacks such as a heat resistance, a narrow temperature range for exhibiting an appropriate heat seal strength or a good hot tack strength. For example, in the field of films, sheets, etc., heat sealing is easy, and therefore it is often used as a bag by heat sealing, and hot tack characteristics are required for such applications. That is, there is a case where the seal portion is pulled and a load is applied immediately after heat sealing, such as when filling the contents, and the seal portion is peeled off. In such a case, a seal having a wide temperature range that enables heat sealing exhibiting a strong value against peeling immediately after sealing is preferable.
【０００３】このようなホットタック特性を改良する試
みとして、複数のチーグラー型触媒によるポリエチレン
系樹脂を混合する試みがなされている（例えば特開平３
−２０７７３６、特開平３−２０７７３７）。しかしこ
の方法では同時に分子量分布も広がるため、強度の向上
は期待できない。As an attempt to improve such a hot tack property, an attempt has been made to mix a polyethylene resin with a plurality of Ziegler type catalysts (for example, Japanese Patent Laid-Open No. Hei 3).
-207736, JP-A-3-207737). However, in this method, since the molecular weight distribution is broadened at the same time, improvement in strength cannot be expected.
【０００４】次にメタロセン系触媒によるポリマーの成
形加工性を改良する方法としては、複数の配位子を有す
るメタロセン系触媒により、組成分布を狭く保ったまま
樹脂の溶融特性を改良する試みがなされている（例えば
特開平６−２０６９３９）。しかし、分子量分布が広が
ることあるいは長鎖分岐の生成により強度が低下すると
いう問題がある。またメタロセン系触媒とチーグラー系
触媒の混合系による成形加工性の改良も試みられている
（例えば特開平６−１５７６３１）が、分子量分布が広
がるため強度の犠牲を伴う。Next, as a method of improving the molding processability of the polymer by the metallocene catalyst, an attempt is made to improve the melting characteristics of the resin by keeping the composition distribution narrow by using the metallocene catalyst having a plurality of ligands. (For example, JP-A-6-206939). However, there is a problem that the strength is lowered due to the broadening of the molecular weight distribution or the formation of long chain branches. Attempts have also been made to improve molding processability by using a mixed system of a metallocene-based catalyst and a Ziegler-based catalyst (for example, Japanese Patent Laid-Open No. 6-157631), but the sacrifice of strength is accompanied by the broadening of the molecular weight distribution.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、チー
グラー型触媒によるＬＬＤＰＥより優れた機械的強度、
光学特性を有し、しかもメタロセン系エチレン・α−オ
レフィン共重合体と同等の低温ヒートシール性、透明性
を有しなから該メタロセン系エチレン・α−オレフィン
共重合体よりも優れた耐熱性、ホットタック特性および
成形加工性を有するエチレン・α−オレフィン共重合体
を提供することにある。The object of the present invention is to provide a mechanical strength superior to LLDPE with a Ziegler type catalyst,
It has optical properties and, at the same time, has a low temperature heat-sealing property equivalent to that of the metallocene ethylene / α-olefin copolymer and transparency, and therefore has a heat resistance superior to that of the metallocene ethylene / α-olefin copolymer, It is intended to provide an ethylene / α-olefin copolymer having hot tack characteristics and moldability.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記目的
に沿って鋭意検討した結果、分子量分布か狭いにもかか
わらず、比較的広い組成分布を持ち、なおかつ低分子量
成分および非晶質成分の含有量が少ないエチレン・α−
オレフィン共重合体を製造し、これにより上記目的を達
成するに至った。Means for Solving the Problems The inventors of the present invention have made earnest studies in accordance with the above-mentioned object, and as a result, have a relatively broad composition distribution despite having a narrow molecular weight distribution, and also have a low molecular weight component and an amorphous component. Ethylene / α- with low content of ingredients
An olefin copolymer was produced, and the above object was achieved thereby.
【０００７】すなわち、本発明は、第１に、（Ａ）密度
ｄが０．８６〜０．９６ｇ／ｃｍ３、（Ｂ）ＭＦＲが
０．０１〜２００ｇ／１０ｍｉｎ、（Ｃ）Ｍｗ／Ｍｎが
１．８〜３．５、（Ｄ）組成分布パラメーターＣｂが
１．１０〜２．００を満足することを特徴とするエチレ
ン・α−オレフィン共重合体である。That is, the present invention is, firstly, (A) the density d is 0.86 to 0.96 g / cm 3 , (B) the MFR is 0.01 to 200 g / 10 min, and the (C) Mw / Mn is The ethylene / α-olefin copolymer has a composition distribution parameter Cb of 1.8 to 3.5 and (D) of 1.10 to 2.00.
【０００８】本発明は、第２に、（Ａ）密度ｄが０．８
６〜０．９６ｇ／ｃｍ３、（Ｂ）ＭＦＲが０．０１〜２
００ｇ／ｍｉｎ、（Ｃ）Ｍｗ／Ｍｎが１．８〜３．５、
（Ｄ）組成分布パラメーターＣｂが１．１０〜２．０
０、（Ｅ）２５℃におけるＯＤＣＢ可溶分の量Ｘ（重量
％）と密度ｄおよびＭＦＲが、イ）ｄ−０．００８×ｌ
ｏｇＭＦＲ≧０．９３の場合、Ｘ＜２．０、ロ）ｄ−
０．００８×ｌｏｇＭＦＲ＜０．９３の場合、Ｘ＜９．
８×１０３×（０．９３００−ｄ＋０．００８×ｌｏｇ
ＭＦＲ）２＋２．０を満足することを特徴とするエチレ
ン・α−オレフィン共重合体である。Secondly, the present invention (A) has a density d of 0.8.
6 to 0.96 g / cm 3 , (B) MFR is 0.01 to 2
00 g / min, (C) Mw / Mn is 1.8 to 3.5,
(D) The composition distribution parameter Cb is 1.10 to 2.0
0, (E) The amount X (wt%) of the ODCB soluble component at 25 ° C, the density d and the MFR are a) d-0.008xl
When ogMFR ≧ 0.93, X <2.0, b) d−
If 0.008 × logMFR <0.93, X <9.
8 × 10 3 × (0.9300−d + 0.008 × log
It is an ethylene / α-olefin copolymer characterized by satisfying MFR) 2 +2.0.
【０００９】本発明は、第３に、（Ａ）密度ｄか０．８
６〜０．９６ｇ／ｃｍ３、（Ｂ）ＭＦＲが０．０１〜２
００ｇ／１０ｍｉｎ、（Ｃ）Ｍｗ／Ｍｎが１．８〜３．
５、（Ｄ）組成分布パラメーターＣｂが１．１０〜２．
００、（Ｅ）２５℃におけるＯＤＣＢ可溶分の量Ｘ（重
量％）と密度ｄおよびＭＦＲが、イ）ｄ−０．００８×
ｌｏｇＭＦＲ≧０．９３の場合、Ｘ＜２．０、ロ）ｄ−
０．００８×ｌｏｇＭＦＲ＜０．９３の場合、Ｘ＜９．
８×１０３×（０．９３００−ｄ＋０．００８×ｌｏｇ
ＭＦＲ）２＋２．０、（Ｆ）ＴＲＥＦによる溶出温度−
溶出量曲線のピークが複数個、を満足することを特徴と
するエチレン・α−オレフィン共重合体である。Thirdly, the present invention provides (A) the density d or 0.8.
6 to 0.96 g / cm 3 , (B) MFR is 0.01 to 2
00g / 10min, (C) Mw / Mn is 1.8-3.
5, (D) composition distribution parameter Cb is 1.10-2.
00, (E) The amount X (wt%) of the ODCB soluble component at 25 ° C, the density d and the MFR are a) d-0.008 x
When logMFR ≧ 0.93, X <2.0, b) d−
If 0.008 × logMFR <0.93, X <9.
8 × 10 3 × (0.9300−d + 0.008 × log
MFR) 2 +2.0, elution temperature by (F) TREF-
It is an ethylene / α-olefin copolymer characterized by satisfying a plurality of peaks in an elution amount curve.
【００１０】以下本発明をさらに詳細に説明する。本発
明のエチレン・α−オレフィン共重合体はエチレンと炭
素数３〜２０のα−オレフィンより選ばれた一種以上と
の共重合体である。この炭素数３〜２０のα−オレフィ
ンとしては、好ましくは炭素数３〜１２のものであり、
具体的にはプロピレン、１−ブテン、４−メチル−１−
ペンテン、１−ヘキセン、１−オクテン、１−デセン、
１−ドデセン、などが挙げられる。また、これらのα−
オレフィンの含有量は、合計で通常３０モル％以下、好
ましくは３〜２０モル％の範囲で選択されることが望ま
しい。The present invention will be described in more detail below. The ethylene / α-olefin copolymer of the present invention is a copolymer of ethylene and one or more kinds selected from α-olefins having 3 to 20 carbon atoms. The α-olefin having 3 to 20 carbon atoms is preferably one having 3 to 12 carbon atoms,
Specifically, propylene, 1-butene, 4-methyl-1-
Pentene, 1-hexene, 1-octene, 1-decene,
1-dodecene and the like. Also, these α-
It is desirable that the total content of olefins is selected in the range of usually 30 mol% or less, preferably 3 to 20 mol%.
【００１１】本発明のエチレン・α−オレフィン共重合
体の密度（Ａ）は、０．８６〜０．９６ｇ／ｃｍ３、好
ましくは０．８８〜０．９４５ｇ／ｃｍ３、より好まし
くは０．９０〜０．９３０ｇ／ｃｍ３の範囲である。密
度が０．８６未満では剛性、耐熱性が劣り、０．９６以
上では耐衝撃性が十分でない。The density (A) of the ethylene / α-olefin copolymer of the present invention is 0.86 to 0.96 g / cm 3 , preferably 0.88 to 0.945 g / cm 3 , and more preferably 0. It is in the range of 90 to 0.930 g / cm 3 . If the density is less than 0.86, the rigidity and heat resistance are poor, and if it is 0.96 or more, the impact resistance is insufficient.
【００１２】本発明のエチレン・α−オレフィン共重合
体のＭＦＲ（Ｂ）は０．０１〜２００ｇ／１０ｍｉｎ、
好ましくは０．１〜１００ｇ／１０ｍｉｎ、さらに好ま
しくは０．２〜５０ｇ／１０ｍｉｎの範囲にあることが
望ましい。ＭＦＲが０．０１未満では成形加工性が劣
り、２００以上では耐衝撃性などの機械的強度が低下す
る。The MFR (B) of the ethylene / α-olefin copolymer of the present invention is 0.01 to 200 g / 10 min,
It is preferably 0.1 to 100 g / 10 min, and more preferably 0.2 to 50 g / 10 min. When the MFR is less than 0.01, the moldability is poor, and when it is 200 or more, the mechanical strength such as impact resistance is lowered.
【００１３】本発明のエチレン・α−オレフィン共重合
体の分子量分布Ｍｗ／Ｍｎ（Ｃ）の算出方法は、ゲルバ
ーミエイションクロマトグラフィー（ＧＰＣ）により重
量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）を求め、
この比Ｍｗ／Ｍｎを求めるものである。The method of calculating the molecular weight distribution Mw / Mn (C) of the ethylene / α-olefin copolymer of the present invention is carried out by gel permeation chromatography (GPC) by weight average molecular weight (Mw) and number average molecular weight (Mn). Seeking
This ratio Mw / Mn is obtained.
【００１４】本発明のエチレン・α−オレフィン共重合
体のＭｗ／Ｍｎは１．８〜３．５であり、好ましくは
２．０〜３．０、さらに好ましくは２．２〜２．８の範
囲にあることが望ましい。Ｍｗ／Ｍｎが１．８未満では
成形加工性が劣り、３．５以上では耐衝撃性が劣る。The Mw / Mn of the ethylene / α-olefin copolymer of the present invention is 1.8 to 3.5, preferably 2.0 to 3.0, more preferably 2.2 to 2.8. It is desirable to be in the range. If the Mw / Mn is less than 1.8, the moldability is poor, and if it is 3.5 or more, the impact resistance is poor.
【００１５】本発明のエチレン・α−オレフィン共重合
体の組成分布パラメーターＣｂ（Ｄ）は１．１０〜２．
００であり、好ましくは１．１２〜１．７０、さらに好
ましくは１．１５〜１．５０の範囲にあることが望まし
い。１．１０未満では、ホットタック特性が劣り、２．
００以上では、透明性が低下し、また成形品に高分子ゲ
ルを生じる等の慮がある。The composition distribution parameter Cb (D) of the ethylene / α-olefin copolymer of the present invention is 1.10-2.
00, preferably 1.12 to 1.70, and more preferably 1.15 to 1.50. If it is less than 1.10, the hot tack property is poor, and 2.
When it is 00 or more, the transparency may be lowered, and a polymer gel may be formed in the molded product.
【００１６】本発明のエチレン・α−オレフィン共重合
体の組成分布パラメーターＣｂの測定法は下記の通りで
ある。The method for measuring the composition distribution parameter Cb of the ethylene / α-olefin copolymer of the present invention is as follows.
【００１７】試料に耐熱安定剤を加え、ＯＤＣＢに試料
温度が０．２重量％となるように１３５℃で加熱溶解す
る。この加熱溶液を、けい藻土（セライト５４５）を充
填したカラムに移送し充満後０．１℃／ｍｉｎで２５℃
まで冷却し、試料をセライト表面に析出沈着する。次
に、このカラムにＯＤＣＢを一定流量で流しながら、カ
ラム温度を５℃きざみに１２０℃まで段階的に昇温しな
がら、各温度において、試料を溶解した溶液を採取す
る。この溶液を冷却後メタノールで試料を再枕後、濾
過、乾燥し、各溶出温度における試料を得る。この分別
された試料の重量分率および分岐度（炭素数１０００個
あたりの分岐数）を測定する。分岐度の測定は１３Ｃ−
ＮＭＲにより求める。A heat-resistant stabilizer is added to the sample, and the sample is heated and dissolved in ODCB at 135 ° C. so that the sample temperature becomes 0.2% by weight. This heated solution was transferred to a column packed with diatomaceous earth (Celite 545) and filled to 25 ° C at 0.1 ° C / min.
The sample is deposited and deposited on the surface of Celite. Next, while flowing ODCB at a constant flow rate through this column and gradually increasing the column temperature by 5 ° C. to 120 ° C., a solution in which the sample is dissolved is collected at each temperature. After cooling this solution, the sample is re-pillowed with methanol, filtered and dried to obtain a sample at each elution temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) of this separated sample are measured. Measurement of branching degree is 13C-
Determined by NMR.
【００１８】このような方法で３０℃から９０℃で採取
した各フラクションについては次のような、分岐度の補
正を行う。すなわち、溶出温度に対して測定した分岐度
をプロットし、相関関係を最小自乗法で直線に近似し、
検量線を作成する。この近似の相関係数は十分大きい。
この検量線により求めた値を各フラクションの分岐度と
する。なお、溶出温度９５℃以上で採取したフラクショ
ンについては溶出温度と分岐度に必ずしも直線関係が成
立しないのでこの補正は行わない。For each fraction collected at 30 ° C. to 90 ° C. by such a method, the branching degree is corrected as follows. That is, the degree of branching measured against the elution temperature is plotted, and the correlation is approximated to a straight line by the method of least squares,
Create a calibration curve. The correlation coefficient of this approximation is sufficiently large.
The value obtained from this calibration curve is the branching degree of each fraction. This correction is not performed for the fractions collected at an elution temperature of 95 ° C or higher, because the elution temperature and the degree of branching do not always have a linear relationship.
【００１９】次にそれぞれのフラクションの重量分率ｗ
ｉを、溶出温度５℃当たりの分岐度ｂｉの変化量（ｂｉ
−ｂｉ−ｌ）で割って相対濃度ｃｉを求め、分岐度に対
して相対濃度をプロットし、組成分布曲線を得る。この
組成分布曲線を一定の幅で分割し、次式より組成分布パ
ラメーターＣｂを算出する。Next, the weight fraction w of each fraction
The i, the amount of change in the degree of branching b i per the elution temperature 5 ° C. (b i
-B i-1 ) to obtain the relative concentration c i , plot the relative concentration against the branching degree, and obtain a composition distribution curve. This composition distribution curve is divided with a constant width, and the composition distribution parameter Cb is calculated from the following equation.
【００２０】[0020]
【式１】 (Equation 1)
【００２１】ここでｃｊとｂｊはそれぞれｊ番目の区分
の相対濃度と分岐度である。組成分布パラメーターＣｂ
は試料の組成が均一である場合に１．０となり、組成分
布が広がるに従って値が大きくなる。Here, c j and b j are the relative density and branching degree of the j-th section, respectively. Composition distribution parameter Cb
Is 1.0 when the composition of the sample is uniform, and increases as the composition distribution spreads.
【００２２】なお、エチレン・α−オレフィン共重合体
の組成分布を記述する方法は多くの提案がなされてい
る。例えば特開昭６０−８８０１６号では、試料を溶剤
分別して得た各分別試料の分岐数に対して、累積重量分
率が特定の分布（対数正規分布）をすると仮定して数値
処理を行い、重量平均分岐度（Ｃｗ）と数平均分岐度
（Ｃｎ）の比を求めている。この近似計算は、試料の分
岐数と累積重量分率が対数正規分布からずれると精度が
下がり、市販のＬＬＤＰＥについて測定を行うと相関係
数Ｒ２はかなり低く、値の精度は充分でない。このＣｗ
／Ｃｎと本発明のＣｂとは、定義および測定方法が異な
る。Many proposals have been made for the method of describing the composition distribution of the ethylene / α-olefin copolymer. For example, in JP-A-60-88016, numerical processing is performed assuming that the cumulative weight fraction has a specific distribution (logarithmic normal distribution) with respect to the number of branches of each fractionated sample obtained by solvent fractionation of the sample, The ratio between the weight average branching degree (Cw) and the number average branching degree (Cn) is determined. The accuracy of this approximate calculation is low when the number of branches of the sample and the cumulative weight fraction deviate from the lognormal distribution, and the correlation coefficient R 2 is considerably low when the measurement is performed on commercially available LLDPE, and the accuracy of the value is not sufficient. This Cw
/ Cn and Cb of the present invention have different definitions and measurement methods.
【００２３】本発明のエチレン・α−オレフィン共重合
体は、２５℃におけるＯＤＣＢ可溶分の量Ｘは、エチレ
ン・α−オレフィン共重合体に含まれる高分岐度成分お
よび低分子量成分の割合を示すものであり、耐熱性の低
下や成形品表面のベタツキの原因となるため少ないこと
が望ましい。ＯＤＣＢ可溶分の量は、共重合体全体のα
−オレフィンの含有量および平均分子量、すなわち密度
とＭＦＲに影響される。In the ethylene / α-olefin copolymer of the present invention, the amount X of the ODCB-soluble component at 25 ° C. is the ratio of the highly branched component and the low molecular weight component contained in the ethylene / α-olefin copolymer. However, it is desirable that the amount is small because it causes deterioration of heat resistance and stickiness of the surface of the molded product. The amount of ODCB-soluble component is α of the whole copolymer.
Influenced by olefin content and average molecular weight, ie density and MFR.
【００２４】従って、前記ＯＤＣＢ可溶分の量Ｘ（重量
％）は密度ｄとＭＦＲの関係が、ｄ−０．００８×ｌｏ
ｇＭＦＲ≧０．９３を満たす場合は２重量％未満、好ま
しくは１重量％未満、さらに好ましくは０．５重量％未
満である。Therefore, the amount X (wt%) of the ODCB-soluble component has a relationship between the density d and the MFR: d-0.008 × lo
When gMFR ≧ 0.93 is satisfied, it is less than 2% by weight, preferably less than 1% by weight, and more preferably less than 0.5% by weight.
【００２５】また、ｄとＭＦＲの関係が、ｄ−０．００
８×ｌｏｇＭＦＲ＜０．９３を満たす場合はＸ＜９．８
×１０３×（０．９３００−ｄ＋０．００８×ｌｏｇＭ
ＦＲ）２＋２．０の関係を満足し、好ましくはＸ＜７．
４×１０３×（０．９３００−ｄ＋０．００８×ｌｏｇ
ＭＦＲ）２＋１．０、さらに好ましくはＸ＜５．６×１
０３×（０．９３００−ｄ＋０．００８×ｌｏｇＭＦ
Ｒ）２＋０．５の範囲である。The relationship between d and MFR is d-0.00
X <9.8 when 8 × log MFR <0.93 is satisfied.
× 10 3 × (0.9300-d + 0.008 × logM
FR) 2 +2.0, preferably X <7.
4 × 10 3 × (0.9300-d + 0.008 × log
MFR) 2 +1.0, more preferably X <5.6 × 1
0 3 × (0.9300-d + 0.008 × logMF
R) 2 +0.5.
【００２６】密度、ＭＦＲとＯＤＣＢ可溶分の量が上記
の関係を満たすことは、共重合体全体に含まれているα
−オレフィンが遍在していないことを示している。The fact that the density, the MFR and the amount of the ODCB-soluble component satisfy the above-mentioned relations means that α contained in the whole copolymer.
-Indicating that the olefins are not ubiquitous.
【００２７】なお、前記の２５℃におけるＯＤＣＢ可溶
分Ｘは、下記の方法により測定する。すなわち試料０．
５ｇを２０ｍｌのＯＤＣＢに加え１３５℃で２時間加熱
し、試料を完全に溶解した後、２５℃まで冷却する。こ
の溶液を２５℃で一晩放置後、テフロン製フィルターで
濾過して濾液を採取する。試料溶液である濾液を赤外分
光器によりメチレンの非対称伸縮振動の波数２９２５ｃ
ｍ−１付近の吸収ピーク強度を測定し、あらかじめ作成
した検量線により濾液中の試料濃度を算出する。この値
より、２５℃におけるＯＤＣＢ可溶分を求める。The ODCB-soluble component X at 25 ° C. is measured by the following method. That is, sample 0.
5 g is added to 20 ml of ODCB and heated at 135 ° C. for 2 hours to completely dissolve the sample, and then cooled to 25 ° C. The solution is left at 25 ° C. overnight and then filtered through a Teflon filter to collect the filtrate. The filtrate, which is a sample solution, was analyzed by infrared spectroscopy for the wave number 2925c of the asymmetric stretching vibration of methylene.
The absorption peak intensity around m −1 is measured, and the sample concentration in the filtrate is calculated from the calibration curve prepared in advance. From this value, the ODCB-soluble component at 25 ° C. is determined.
【００２８】本発明のエチレン・α−オレフィン共重合
体は、連続昇温溶出分別法（ＴＲＥＦ）により求めた溶
出温度−溶出量曲線において、ピークが複数個（Ｆ）あ
ることが好ましく、さらにその高温側のピークが８５℃
から１００℃の間に存在することが特に好ましい。この
ピークが存在することにより、融点が高くなりまた結晶
化度が上昇し成形体の耐熱性および剛性が向上する。図
１に本発明の共重合体の溶出温度−溶出量曲線を示し、
図２にいわゆるメタロセン触媒による共重合体の溶出温
度−溶出量曲線を示した。The ethylene / α-olefin copolymer of the present invention preferably has a plurality of peaks (F) in the elution temperature-elution amount curve determined by the continuous temperature rising elution fractionation method (TREF). High temperature peak is 85 ℃
It is particularly preferred that it is present between 1 and 100 ° C. The presence of this peak raises the melting point and crystallinity, and improves the heat resistance and rigidity of the molded body. FIG. 1 shows an elution temperature-elution amount curve of the copolymer of the present invention,
FIG. 2 shows an elution temperature-elution amount curve of a copolymer with a so-called metallocene catalyst.
【００２９】ＴＲＥＦの測定方法は下記のとおりであ
る。即ち、試料に耐熱安定剤を加え、ＯＤＣＢに試料濃
度０．０５重量％となるように１３５℃で加熱溶解す
る。この加熱溶液５ｍｌを、ガラスビーズを充填したカ
ラムに注入した後、０．１℃／ｍｉｎの冷却速度で２５
℃まで冷却し、試料をガラスビーズ表面に沈着する。次
に、このカラムにＯＤＣＢを一定流量で流しながら、カ
ラム温度を５０℃／ｈｒの一定速度で昇温し、各温度に
おいて溶液に溶解可能な試料を順次溶出させる。この
際、溶剤中の試料濃度はメチレンの非対称伸縮振動の波
数２９２５ｃｍ−１に対する吸収を赤外検出器で連続的
に検出される。この濃度から、溶出温度−溶出量曲線を
得ることができる。The method of measuring TREF is as follows. That is, a heat resistance stabilizer was added to the sample, and the sample was heated and dissolved in ODCB at 135 ° C. so that the sample concentration was 0.05% by weight. 5 ml of this heated solution was injected into a column filled with glass beads, and then 25 ° C. at a cooling rate of 0.1 ° C./min.
Cool to 0 ° C. and deposit sample on glass bead surface. Next, while flowing ODCB at a constant flow rate through this column, the column temperature is raised at a constant rate of 50 ° C./hr to sequentially elute the sample soluble in the solution at each temperature. At this time, as for the sample concentration in the solvent, the absorption of the asymmetric stretching vibration of methylene at a wave number of 2925 cm −1 is continuously detected by an infrared detector. From this concentration, an elution temperature-elution amount curve can be obtained.
【００３０】ＴＲＥＦ分析は極少量の試料で、温度変化
に対する溶出速度の変化を連続的に分析出来るため、分
別法では検出出来ない比較的細かいピークの検出が可能
である。Since the TREF analysis can continuously analyze the change in the elution rate with respect to the temperature change with a very small amount of sample, it is possible to detect a relatively fine peak which cannot be detected by the fractionation method.
【００３１】本発明の特定のエチレン・α−オレフィン
共重合体の製造は、上記（Ａ）〜（Ｄ）、好ましくは
（Ａ）〜（Ｅ）、より好ましくは（Ａ）〜（Ｆ）の性状
を満足すればよく、チグラー触媒、フイリップス触媒、
メタロセン触媒等により製造してもよいが、好ましくは
以下のＣ１〜Ｃ５からなる触媒で重合することが望まし
い。The production of the specific ethylene / α-olefin copolymer of the present invention is carried out according to the above (A) to (D), preferably (A) to (E), more preferably (A) to (F). As long as the properties are satisfied, Ziegler catalyst, Phillips catalyst,
It may be produced with a metallocene catalyst or the like, but it is preferable to polymerize with a catalyst having the following C1 to C5.
【００３２】すなわち、Ｃ１：一般式Ｍｅ１Ｒ１ ｐ（Ｏ
Ｒ２）ｑＸ１ ４−ｐ−ｑで表される化合物（式中Ｍｅ１
はＺｒ、Ｔｉ、Ｈｆを示し、Ｒ１およびＲ２は各々炭素
数１〜２４の炭化水素基、Ｘ１はハロゲン原子を示し、
ｐ、ｑおよびｒは各々０≦ｐ＜４、０≦ｐ＋ｑ≦４の範
囲を満たす整数である）、Ｃ２：一般式Ｍｅ２Ｒ３
ｍ（ＯＲ４） ｎＸ２ ｚ−ｍ−ｎで表される化合物（式中
Ｍｅ２は周期律表第Ｉ〜ＩＩＩ族元素、Ｒ３およびＲ４
は各々炭素数１〜２４の炭化水素基、Ｘ２はハロゲン原
子または水素原子（ただし、Ｘ２が水素原子の場合はＭ
ｅ２は周期律表第ＩＩＩ族元素の場合に限る）を示し、
ｚはＭｅ２の価数を示し、ｍおよびｎは各々０≦ｍ≦
ｚ、０≦ｎ≦ｚの範囲を満たす整数であり、かつ、０≦
ｍ＋ｎ≦ｚである）、Ｃ３：共役二重結合を持つ有機環
状化合物、およびＣ４：有機アルミニウム化合物と水と
の反応によって得られるＡｌ−Ｏ−Ａｌ結合を含む変性
有機アルミニウム化合物、Ｃ５：無機担体および／また
は粒子状ポリマー担体を相互に接触させて得られる触媒
である。That is, C1: general formula Me 1 R 1 p (O
R 2 ) q X 1 4- pq A compound represented by the formula (Me 1 in the formula)
Represents Zr, Ti, Hf, R 1 and R 2 each represent a hydrocarbon group having 1 to 24 carbon atoms, X 1 represents a halogen atom,
p, q and r are integers satisfying the ranges of 0 ≦ p <4 and 0 ≦ p + q ≦ 4, respectively, C2: general formula Me 2 R 3
A compound represented by m (OR 4 ) n X 2 z-mn (wherein Me 2 is an element of Group I to III of the periodic table, R 3 and R 4).
Are each a hydrocarbon group having 1 to 24 carbon atoms, X 2 is a halogen atom or a hydrogen atom (provided that when X 2 is a hydrogen atom, M is
e 2 represents only a group III element of the periodic table)
z represents the valence of Me 2 , and m and n are each 0 ≦ m ≦.
z, an integer satisfying the range of 0 ≦ n ≦ z, and 0 ≦
m + n ≦ z), C3: an organic cyclic compound having a conjugated double bond, and C4: a modified organoaluminum compound containing an Al—O—Al bond obtained by the reaction of an organoaluminum compound and water, C5: an inorganic carrier. And / or a catalyst obtained by bringing the particulate polymer supports into contact with each other.
【００３３】上記触媒成分（Ｃ１）の一般式Ｍｅ１Ｒ１
ｐ（ＯＲ２）ｑＸ１ ４−ｐ−ｑで表される化合物の式中
Ｍｅ１はＺｒ、Ｔｉ、Ｈｆを示す。これらの遷移金属の
種類は限定されるものではなく、複数を用いることもで
きるが、共重合体の耐候性がより優れる点でＺｒが含ま
れることが特に好ましい。Ｒ１およびＲ２は各々炭素数
１〜２４の炭化水素基で、好ましくは炭素数１〜１２、
さらに好ましくは炭素数１〜８の炭化水素基であり、具
体的にはメチル基、エチル基、プロピル基、イソプロピ
ル基、ブチル基などのアルキル基；ビニル基、アリル基
などのアルケニル基；フェニル基、トリル基、キシリル
基、メシチル基、インデニル基、ナフチル基などのアリ
ール基；ベンジル基、トリチル基、フェネチル基、スチ
リル基、ベンズヒドリル基、フェニルブチル基、ネオフ
イル基などのアラルキル基などが挙げられる。これらは
分岐があってもよい。Ｘ１はフッ素、ヨウ素、塩素およ
び臭素などのハロゲン原子を示し、ｐおよびｑはそれぞ
れ０≦ｐ＜４、０≦ｑ＜４、０≦ｐ＋ｑ≦４の範囲を満
たし、好ましくは０≦ｐ＋ｑ≦４の範囲である。The above catalyst component (C1) has the general formula Me 1 R 1
Me < 1 > shows Zr, Ti, and Hf in the formula of the compound represented by p (OR < 2 >) qX < 1 > 4- pq. The type of these transition metals is not limited, and a plurality of transition metals may be used, but it is particularly preferable that Zr is contained from the viewpoint that the weather resistance of the copolymer is more excellent. R 1 and R 2 are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms,
More preferably, it is a hydrocarbon group having 1 to 8 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group; an alkenyl group such as a vinyl group and an allyl group; a phenyl group. Aryl groups such as tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group; aralkyl groups such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group and neophyl group. These may have branches. X 1 represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p and q satisfy the ranges of 0 ≦ p <4, 0 ≦ q <4, 0 ≦ p + q ≦ 4, and preferably 0 ≦ p + q ≦ The range is 4.
【００３４】上記触媒成分（Ｃ１）一般式で示される化
合物の例としては、テトラメチルジルコニウム、テトラ
エチルジルコニウム、テトラベンジルジルコニウム、テ
トラプロポキシジルコニウム、トリプロポキシモノクロ
ロジルコニウム、ジプロポキシジクロロジルコニウム、
テトラブトキシジルコニウム、トリブトキシモノクロロ
ジルコニウム、ジブトキシジクロロジルコニウム、テト
ラブトキシチタン、テトラブトキシハフニウムなどが挙
げられ、これらを２種以上混合して用いても差し支えな
い。Examples of the compound represented by the above general formula of the catalyst component (C1) include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium,
Examples thereof include tetrabutoxyzirconium, tributoxymonochlorozirconium, dibutoxydichlorozirconium, tetrabutoxytitanium, and tetrabutoxyhafnium. These may be used as a mixture of two or more.
【００３５】上記触媒成分（Ｃ２）の一般式Ｍｅ２Ｒ３
ｍ（ＯＲ４）ｎＸ２ ｚ−ｍ−ｎで表される化合物の式中
Ｍｅ２は周期律表第Ｉ〜ＩＩＩ族元素を示し、リチウ
ム、ナトリウム、カリウム、マグネシウム、カルシウ
ム、亜鉛、ホウ素、アルミニウムなどである。Ｒ３およ
ひＲ４は各々炭素数１〜２４の炭化水素基、好ましくは
炭素数１〜１２、さらに好ましくは炭素数１〜８の炭化
水素基であり、具体的にはメチル基、エチル基、プロピ
ル基、イソプロピル基、ブチル基などのアルキル基；ビ
ニル基、アリル基などのアルケニル基；フェニル基、ト
リル基、キシリル基、メシチル基、インデニル基、ナフ
チル基などのアリール基；ベンジル基、トリチル基、フ
ェネチル基、スチリル基、ベンズヒドリル基、フェニル
ブチル基、ネオフィル基などのアラルキル基などが挙げ
られる。これらは分岐があってもよい。Ｘ２はフッ素、
ヨウ素、塩素および臭素などのハロゲン原子または水素
原子を示すものである。ただし、Ｘ２が水素原子の場合
はＭｅ２はホウ素、アルミニウムなどに例示される周期
律表第ＩＩＩ族元素の場合に限るものである。また、ｚ
はＭｅ２の価数を示し、ｍおよびｎは各々０≦ｍ≦ｚ、
０≦ｎ≦ｚの範囲を満たす整数であり、かつ、０≦ｍ＋
ｎ≦ｚである。The above catalyst component (C2) has the general formula Me 2 R 3
m (OR 4) wherein Me 2 in n X compounds represented by 2 z-m-n represents the periodic table I~III group element, lithium, sodium, potassium, magnesium, calcium, zinc, boron, Such as aluminum. R 3 and R 4 are each a hydrocarbon group having 1 to 24 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 8 carbon atoms, and specifically, methyl group, ethyl group. Groups, alkyl groups such as propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group; benzyl group Examples thereof include aralkyl groups such as a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neophyll group. These may have branches. X 2 is fluorine
It represents a halogen atom or hydrogen atom such as iodine, chlorine and bromine. However, when X 2 is a hydrogen atom, Me 2 is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. Also, z
Represents the valence of Me 2 , m and n are 0 ≦ m ≦ z,
An integer satisfying the range of 0 ≦ n ≦ z, and 0 ≦ m +
n ≦ z.
【００３６】上記触媒成分（Ｃ２）の一般式で示される
化合物の例としては、メチルリチウム、エチルリチウム
などの有機リチウム化合物；ジメチルマグネシウム、ジ
エチルマグネシウム、メチルマグネシウムクロライド、
エチルマグネシウムクロライドなどの有機マグネシウム
化合物；ジメチル亜鉛、ジエチル亜鉛などの有機亜鉛化
合物；トリメチルボロン、トリエチルボロンなどの有機
ボロン化合物；トリメチルアルミニウム、トリエチルア
ルミニウム、トリイソブチルアルミニウム、トリヘキシ
ルアルミニウム、トリデシルアルミニウム、ジエチルア
ルミニウムクロライド、エチルアルミニウムジクロライ
ド、エチルアルミニウムセスキクロライド、ジエチルア
ルミニウムエトキサイド、ジエチルアルミニウムハイド
ライドなどの有機アルミニウム化合物等の誘導体が挙げ
られる。Examples of the compound represented by the general formula of the catalyst component (C2) include organic lithium compounds such as methyllithium and ethyllithium; dimethylmagnesium, diethylmagnesium, methylmagnesium chloride,
Organomagnesium compounds such as ethylmagnesium chloride; Organozinc compounds such as dimethylzinc and diethylzinc; Organoboron compounds such as trimethylboron and triethylboron; Trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethyl Examples thereof include derivatives of organic aluminum compounds such as aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide and diethyl aluminum hydride.
【００３７】上記触媒成分（Ｃ３）の共役二重結合を持
つ有機環状化合物とは、環状で共役二重結合を２個以
上、好ましくは２〜４個、さらに好ましくは２〜３個有
する環を１個または２個以上もち、全炭素数が４〜２
４、好ましくは４〜１２である環状炭化水素化合物；前
記環状炭化水素化合物が部分的に１〜６個の炭化水素残
基（典型的には、炭素数１〜１２のアルキル基またはア
ラルキル基）で置換された環状炭化水素化合物；共役二
重結合を２個以上、好ましくは２〜４個、さらに好まし
くは２〜３個有する環を１個または２個以上もち、全炭
素数が４〜２４、好ましくは４〜１２である環状炭化水
素基を有する有機ケイ素化合物；前記環状炭化水素基が
部分的に１〜６個の炭化水素残基またはアルカリ金属塩
（ナトリウムまたはリチウム塩）で置換された有機ケイ
素化合物が含まれる。特に好ましくは分子中のいずれか
にシクロペンタジエン構造をもつものが望ましい。The organic cyclic compound having a conjugated double bond of the catalyst component (C3) is a cyclic ring having two or more conjugated double bonds, preferably 2 to 4 and more preferably 2 to 3. It has 1 or 2 or more, and the total carbon number is 4 to 2.
4, preferably 4 to 12 cyclic hydrocarbon compounds; wherein the cyclic hydrocarbon compounds are partially 1 to 6 hydrocarbon residues (typically, alkyl groups or aralkyl groups having 1 to 12 carbon atoms) A cyclic hydrocarbon compound substituted by; a compound having 2 or more, preferably 2 to 4, more preferably 2 to 3 rings having a conjugated double bond and having a total carbon number of 4 to 24 An organosilicon compound having a cyclic hydrocarbon group which is preferably 4 to 12; said cyclic hydrocarbon group being partly substituted with 1 to 6 hydrocarbon residues or an alkali metal salt (sodium or lithium salt) Includes organosilicon compounds. Particularly preferably, one having a cyclopentadiene structure in any of the molecules is desirable.
【００３８】上記の好適な化合物としては、シクロペン
タジエン、インデン、アズレンまたはこれらのアルキ
ル、アリール、アラルキル、アルコキシまたはアリール
オキシ誘導体などが挙げられる。また、これらの化合物
がアルキレン基（その炭素数は通常２〜８、好ましくは
２〜３）を介して結合（架橋）した化合物も好適に用い
られる。Examples of the above-mentioned suitable compounds include cyclopentadiene, indene, azulene or their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Moreover, the compound which these compounds couple | bonded (bridge | crosslink) through the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.
【００３９】環状炭化水素基を有する有機ケイ素化合物
は、下記一般式で表示することができる。The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula.
【００４０】ＡＬＳｉＲ４−ＬALSiR 4 -L
【００４１】ここで、Ａはシクロペンタジエニル基、置
換シクロペンタジエニル基、インデニル基、置換インデ
ニル基で例示される前記環状水素基を示し、Ｒはメチル
基、エチル基、プロピル基、イソプロピル基、ブチル基
などのアルキル基；メトキシ基、エトキシ基、プロポキ
シ基、ブトキシ基などのアルコキシ基；フェニル基など
のアリール基；フェノキシ基などのアリールオキシ基；
ベンジル基などのアラルキル基で示され、炭素数１〜２
４、好ましくは１〜１２の炭化水素残基または水素を示
し、Ｌは１≦Ｌ≦４、好ましくは１≦Ｌ≦３である。Here, A represents the above-mentioned cyclic hydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group, a propyl group, an isopropyl group. Group, alkyl group such as butyl group; alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group; aryl group such as phenyl group; aryloxy group such as phenoxy group;
It is represented by an aralkyl group such as a benzyl group and has 1 to 2 carbon atoms.
4, preferably 1 to 12 hydrocarbon residues or hydrogen, L is 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.
【００４２】上記成分（Ｃ３）の有機環状炭化水素化合
物の具体例は、シクロペンタジエン、メチルシクロペン
タジエン、エチルシクロペンタジエン、１，３−ジメチ
ルシクロペンタジエン、インデン、４−メチル−１−イ
ンデン、４，７−ジメチルインデン、シクロヘプタトリ
エン、メチルシクロヘプタトリエン、シクロオクタテト
ラエン、アズレン、フルオレン、メチルフルオレンのよ
うな炭素数７〜２４のシクロポリエンまたは置換シクロ
ポリエン、モノシクロペンタジエニルシラン、ビスシク
ロペンタジエニルシラン、トリスシクロペンタジエニル
シラン、モノインデニルシラン、ビスインデニルシラ
ン、トリスインデニルシラン等が挙げられる。Specific examples of the organic cyclic hydrocarbon compound of the above component (C3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4, 7-Dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene-containing cyclopolyene or substituted cyclopolyene, monocyclopentadienylsilane, biscyclo Examples thereof include pentadienylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.
【００４３】触媒成分（Ｃ４）有機アルミニウム化合物
と水との反応によって得られるＡｌ−Ｏ−Ａｌ結合を含
む変性有機アルミニウム化合物とは、アルキルアルミニ
ウム化合物と水とを反応させることにより、通常アルミ
ノキサンと称される変性有機アルミニウムか得られ、分
子中に通常１〜１００個、好ましくは１〜５０個のＡｌ
−Ｏ−Ａｌ結合を含有する。また、変性有機アルミニウ
ム化合物は線状でも環状でもいずれでもよい。The modified organoaluminum compound containing an Al--O--Al bond obtained by the reaction of the catalyst component (C4) organoaluminum compound with water is usually referred to as an aluminoxane by reacting an alkylaluminum compound with water. The modified organoaluminum obtained is obtained, and usually 1 to 100, preferably 1 to 50 Al in the molecule.
It contains a —O—Al bond. The modified organoaluminum compound may be linear or cyclic.
【００４４】有機アルミニウムと水との反応は通常不活
性炭化水素中で行われる。該不活性炭化水素としては、
ペンタン、ヘキサン、ヘプタン、シクロヘキサン、ベン
ゼン、トルエン、キシレン等の脂肪族、脂環族、芳香族
炭化水素が好ましい。The reaction of organoaluminum with water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon,
Aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferable.
【００４５】水と有機アルミニウム化合物との反応比
（水／Ａｌモル比）は通常０．２５／１〜１．２／１、
好ましくは０．５／１〜１／１であることが望ましい。The reaction ratio of water and the organoaluminum compound (water / Al molar ratio) is usually 0.25 / 1 to 1.2 / 1,
It is preferably 0.5 / 1 to 1/1.
【００４６】触媒成分（Ｃ５）無機物担体および／また
は粒子状ポリマー担体とは、炭素質物、金属、金属酸化
物、金属塩化物、金属炭酸塩またはこれらの混合物ある
いは熱可塑性樹脂、熱硬化性樹脂等が挙げられる。該無
機物担体に用いることができる好適な金属としては、
鉄、アルミニウム、ニッケルなどが挙げられる。The catalyst component (C5) inorganic carrier and / or particulate polymer carrier means a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate or a mixture thereof, or a thermoplastic resin, a thermosetting resin or the like. Is mentioned. Suitable metals that can be used for the inorganic carrier include
Examples include iron, aluminum and nickel.
【００４７】具体的にはＳｉＯ２、Ａｌ２Ｏ３、Ｍｇ
Ｏ、ＺｒＯ２、ＴｉＯ２、Ｂ２Ｏ３、ＣａＯ、ＺｎＯ、
ＢａＯ、ＴｈＯ２等またはこれらの混合物が挙げられ、
ＳｉＯ２−Ａｌ２Ｏ３、ＳｉＯ２−Ｖ２Ｏ５、ＳｉＯ２
−ＴｉＯ２、ＳｉＯ２−Ｖ２Ｏ５、ＳｉＯ２−ＭｇＯ、
ＳｉＯ２−Ｃｒ２Ｏ３等が挙げられる。これらの中でも
ＳｉＯ２およびＡｌ２Ｏ３からなる群から選択された少
なくとも１種の成分を主成分とするものが好ましい。Specifically, SiO 2 , Al 2 O 3 , Mg
O, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO,
BaO, ThO 2, etc. or a mixture thereof may be mentioned.
SiO 2 -Al 2 O 3, SiO 2 -V 2 O 5, SiO 2
-TiO 2, SiO 2 -V 2 O 5, SiO 2 -MgO,
Like SiO 2 -Cr 2 O 3 and the like. Among these, those containing, as a main component, at least one component selected from the group consisting of SiO 2 and Al 2 O 3 .
【００４８】また、有機化合物としては、熱可塑性樹
脂、熱硬化性樹脂のいずれも使用でき、具体的には、粒
子状のポリオレフィン、ポリエステル、ポリアミド、ポ
リ塩化ビニル、ポリ（メタ）アクリル酸メチル、ポリス
チレン、ポリノルボルネン、各種天然高分子およびこれ
らの混合物等が挙げられる。As the organic compound, either a thermoplastic resin or a thermosetting resin can be used, and specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, poly (meth) acrylate, Examples thereof include polystyrene, polynorbornene, various natural polymers, and mixtures thereof.
【００４９】上記無機物担体および／または粒子状ポリ
マー担体は、このまま使用することもできるが、好まし
くは予備処理としてこれらの担体を有機アルミニウム化
合物やＡｌ−Ｏ−Ａｌ結合を含む変性有機アルミニウム
化合物などで接触処理させた後に成分（Ｃ５）として用
いることもできる。The above inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are treated with an organoaluminum compound or a modified organoaluminum compound containing an Al--O--Al bond. It can also be used as the component (C5) after the contact treatment.
【００５０】本発明のエチレン・α−オレフィン共重合
体の製造方法は、気相法、スラリー法、溶液法等で製造
され、一段重合法、多段重合法など特に限定されるもの
ではない。The method for producing the ethylene / α-olefin copolymer of the present invention is produced by a gas phase method, a slurry method, a solution method or the like, and is not particularly limited such as a one-step polymerization method and a multi-step polymerization method.
【００５１】本発明においては、本発明の共重合体の特
性を本質的に損なわない範囲において、必要に応じて酸
化防止剤は勿論のこと造核剤、滑剤、帯電防止剤、防曇
剤、顔料、紫外線吸収剤、分散剤などの公知の添加剤を
添加することができる。また、本発明のエチレン・α−
オレフィン共重合体は他の熱可塑性樹脂、例えば低密度
ポリエチレン、中密度ポリエチレン、高密度ポリエチレ
ン、ポリプロピレン等のポリオレフィンとブレンドして
使用することもできる。In the present invention, antioxidants, as well as nucleating agents, lubricants, antistatic agents, antifog agents, and Known additives such as pigments, ultraviolet absorbers and dispersants can be added. Further, the ethylene / α-of the present invention
The olefin copolymer can also be used by blending with other thermoplastic resins, for example, polyolefins such as low density polyethylene, medium density polyethylene, high density polyethylene and polypropylene.
【００５２】[0052]
【発明の効果】本発明のエチレン・α−オレフィン共重
合体は、チーグラー触媒によるエチレン・α−オレフィ
ン共重合体より優れた機械的強度、光学的特性を有し、
かつメタロセン触媒によるエチレン・α−オレフィン共
重合体のもつ低温ヒートシール性、透明性を保持しなが
らホットタック性等の特性に優れており、特にＴダイ成
形、インフレーションフィルム成形等によって製造され
る各種包装用フィルム、ラミネート用原反等のフィルム
成形体として好適である。また、本発明のエチレン・α
−オレフィン共重合体は、マヨネーズ用容器、わさび等
用のチューブ状容器、段ボール等の内装用肉薄容器、液
体洗剤用容器等の中空成形体、栓、キャップ、容器の
蓋、スキーシューズ等の射出成形体、電線、ケーブルの
被覆、鋼管の被覆等の用途にも好適である。本発明のエ
チレン・α−オレフィン共重合体は、ドライラミネート
法、共押出法、押出ラミネート法により各種多層フィル
ムあるいは積層シートとして使用することもできる。The ethylene / α-olefin copolymer of the present invention has mechanical strength and optical characteristics superior to those of the Ziegler-catalyzed ethylene / α-olefin copolymer.
Moreover, it has excellent properties such as hot tack property while maintaining low-temperature heat-sealing property and transparency of the ethylene / α-olefin copolymer with a metallocene catalyst. Especially, various products produced by T-die molding, inflation film molding, etc. It is suitable as a film molded product such as a packaging film and a laminate original fabric. Further, the ethylene / α of the present invention
-Olefin copolymers are used for containers such as mayonnaise, tubular containers for wasabi, etc., thin containers for interior such as cardboard, hollow molded products such as containers for liquid detergent, stoppers, caps, container lids, injection of ski shoes, etc. It is also suitable for applications such as moldings, wires, cables, and steel pipes. The ethylene / α-olefin copolymer of the present invention can also be used as various multilayer films or laminated sheets by a dry laminating method, a coextrusion method, or an extrusion laminating method.
【００５３】[0053]
【実施例】次に実施例により本発明を更に詳しく説明す
るが、本発明はこれらによって限定されるものではな
い。The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention.
【００５４】なお本実験例に用いた試験方法は以下の通
りである。 （物性試験方法） 密度 ：ＪＩＳ Ｋ６７６０に準拠し
た。 ＭＦＲ ：ＪＩＳ Ｋ６７６０に準拠し
た。 ＤＳＣによる測定 ：厚さ０．２ｍｍのシートを熱プ
レスで成形し約５ｍｇの試料を打ち抜き２３０℃で１０
ｍｉｎ保持後２℃／ｍｉｎにて０℃迄冷却、後再び１０
℃／ｍｉｎで１７０℃迄昇温し、現れた最高温ピークの
頂点の温度を最高ピーク温度Ｔｍとする。 Ｍｗ／Ｍｎ ：ＧＰＣ ウォータース１５０型 溶媒：ＯＤＣＢ １３５℃ カラム：東ソ−ＧＭＨＨＲ−Ｈ（Ｓ）The test method used in this experimental example is as follows. (Physical property test method) Density: Based on JIS K6760. MFR: Based on JIS K6760. Measurement by DSC: A sheet having a thickness of 0.2 mm is formed by hot pressing and a sample of about 5 mg is punched out at 230 ° C. for 10 minutes.
After holding for min, cool to 0 ° C at 2 ° C / min, and then 10 again
The temperature is raised to 170 ° C. at a rate of ° C./min, and the temperature at the peak of the highest temperature peak that appears is the highest peak temperature Tm. Mw / Mn: GPC Waters 150 type Solvent: ODCB 135 ° C Column: Toso-GMHHR-H (S)
【００５５】（インフレーションフィルム成形）重合し
た共重合体粉末は造粒して、５０ｍｍφのＬＬＤＰＥフ
ィルム専用成形機に直径１００ｍｍφ、リップギャップ
２ｍｍのダイスを取りつけ、ブロー比１．９、引き取り
速度２０ｍ／ｍｉｎ、成形温度２００℃の成形条件で厚
さ３０μｍのフィルムを成形した。(Inflation Film Molding) The polymerized copolymer powder was granulated, and a die with a diameter of 100 mmφ and a lip gap of 2 mm was attached to a 50 mmφ LLDPE film-only molding machine, a blow ratio of 1.9 and a take-up speed of 20 m / min. A film having a thickness of 30 μm was molded under the molding conditions of the molding temperature of 200 ° C.
【００５６】（フィルム性能評価） ダート衝撃強度 ：ＡＳＴＭ Ｄ １７０９に準拠
した。 引張弾性率 ：試料を引張り試験機に取付け、
５ｍｍ／ｍｉｎの速度で引っ張り、１％伸びた時の応力
と断面積から引張弾性率を求めた。 ヘイズ ：ＡＳＴＭ Ｄ１００３−６１に
準拠した。 グロス ：ＪＩＳ Ｚ８７４１準拠に準拠
した。 ホットタック性 ：１５μｍのナイロン基材フィル
ムにエーテル系アンカーコート剤を塗布し、これに前記
フィルム成形法により製造した共重合体フィルムをドラ
イラミし複合フィルムを得た。このフィルムを２５ｍｍ
幅で切り出し、シールバー幅５ｍｍの熱板式ヒートシー
ル試験機に挟み込んだ。複合フィルムの一方の端には滑
車を介して４５ｇの荷重をかけて置く。シール圧力２ｋ
ｇ／ｃｍ２、シール時間０．５秒で、複合フィルムを２
枚重ねヒートシールを行い、シールバーを開いてシール
が終了すると同時にフィルムに荷重がかかり、シール面
を剥離する。シール温度を何点か変え、シールを行い、
その温度と剥離した距離の関係を調べた。剥離した距離
が短いシールが可能であったシール温度の範囲が広いも
のほどホットタック特性が優れている。(Film Performance Evaluation) Dirt Impact Strength: In accordance with ASTM D1709. Tensile modulus: Attach the sample to the tensile tester,
The tensile modulus was determined from the stress and the cross-sectional area when the sample was pulled at a speed of 5 mm / min and elongated by 1%. Haze: According to ASTM D1003-61. Gloss: Compliant with JIS Z8741. Hot tack property: A 15 μm nylon base film was coated with an ether anchor coating agent, and the copolymer film produced by the film forming method was dry-laminated to obtain a composite film. This film is 25mm
It was cut out in a width and sandwiched in a hot plate heat seal tester having a seal bar width of 5 mm. A load of 45 g is placed on one end of the composite film via a pulley. Seal pressure 2k
2 g of composite film at g / cm 2 and sealing time of 0.5 seconds
The sheets are stacked and heat-sealed, the seal bar is opened, and the sealing is completed. Sealing is performed by changing the sealing temperature at several points.
The relationship between the temperature and the peeled distance was investigated. The shorter the peeled distance was, the wider the seal temperature range was, and the better the hot tack property was.
【００５７】（シート成形法）共重合体をロールで均一
化した後、切断してチップ状とし、これを１８０℃でプ
レス成形しシートを得た。 （射出成形機による試験片の成形条件）射出成形機
：（株）日本製鋼所 ＪＳＷ１００ 型締力１０
０ＴＯＮ 成形樹脂温度 ：２２０℃ クッション成形 金型温度 ：５０℃ （シートおよび射出試験片の評価） 引張衝撃試験 ：ＡＳＴＭＤ１８２２に準拠して
求めた。 引張弾性率 ：試料を引張り試験機に取付け、
５ｍｍ／ｍｉｎの速度で引張り、１％伸びた時の応力と
断面積から引張弾性率を求めた。 引張降伏強さ、破壊強さおよび引張伸び ：ＪＩＳ Ｋ６７６０に準拠して求めた。(Sheet Forming Method) The copolymer was homogenized with a roll and then cut into chips, which were press-molded at 180 ° C. to obtain sheets. (Molding conditions of test piece by injection molding machine) Injection molding machine
: Japan Steel Works, Ltd. JSW100 Mold clamping force 10
0TON Molding resin temperature: 220 ° C. Cushion molding mold temperature: 50 ° C. (Evaluation of sheet and injection test piece) Tensile impact test: Determined according to ASTM D1822. Tensile modulus: Attach the sample to the tensile tester,
The tensile elastic modulus was determined from the stress and the cross-sectional area when stretched by 1% at a rate of 5 mm / min. Tensile yield strength, fracture strength and tensile elongation: determined in accordance with JIS K6760.
【００５８】実施例１〜５で用いた試料Ａ１〜Ａ５は以
下の方法で重合した。Samples A1 to A5 used in Examples 1 to 5 were polymerized by the following method.
【００５９】（固体触媒の調製）窒素下で電磁誘導攪拌
機付き触媒調製器（Ｎｏ．１）に精製トルエンを加え、
ついでジプロポキシジクロロジルコニウム（Ｚｒ（ＯＰ
ｒ）２Ｃ１２）２８ｇおよびメチルシクロペンタジエン
４８ｇを加え、０℃に系を保持しながらトリデシルアル
ミニウムを４５ｇを滴下し、滴下終了後、反応系を５０
℃に保持して１６時間攪拌した。この溶液をＡ液とす
る。次に窒素下で別の攪拌器付き触媒調製器（Ｎｏ．
２）２に精製トルエンを加え、前記Ａ溶液と、ついでメ
チルアルミノキサン６．４ｍｏｌのトルエン溶液を添加
し反応させた。これをＢ液とする。(Preparation of Solid Catalyst) Purified toluene was added to a catalyst preparation device (No. 1) equipped with an electromagnetic induction stirrer under nitrogen,
Then dipropoxydichlorozirconium (Zr (OP
28 g of r) 2 C 12 ) and 48 g of methylcyclopentadiene were added, 45 g of tridecylaluminum was added dropwise while maintaining the system at 0 ° C., and after completion of the addition, the reaction system was adjusted to 50
The mixture was kept at 0 ° C. and stirred for 16 hours. This solution is referred to as solution A. Next, under nitrogen, another stirrer catalyst preparation device (No.
2) Purified toluene was added to 2 and the above solution A and then a toluene solution of 6.4 mol of methylaluminoxane were added and reacted. This is designated as solution B.
【００６０】次に窒素下で攪拌器付き調製器（Ｎｏ．
１）に精製トルエンを加え、ついであらかじめ４００℃
で所定時間焼成処理したシリカ（富士デビソン社製、グ
レード＃９５２、表面積３００ｍ２／ｇ）１４００ｇを
加えた後、前記Ｂ溶液の全量を添加し、室温で攪拌し
た。ついで窒素ブローにて溶媒を除去して流動性の良い
固体触媒粉末を得た。これを触媒Ｃとする。Next, under nitrogen, a preparer with a stirrer (No.
Purified toluene was added to 1) and then 400 ° C in advance.
After adding 1400 g of silica (manufactured by Fuji Devison Co., Ltd., grade # 952, surface area 300 m 2 / g), which was calcined for a predetermined time, the whole amount of the solution B was added and stirred at room temperature. Then, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This is designated as catalyst C.
【００６１】（試料Ａ１の重合）連続式の流動床気相法
重合装置を用い、重合温度７０℃、全圧２０ｋｇｆ／ｃ
ｍ２Ｇでエチレンと１−ブテンの共重合を行った。系内
のガス組成は、１−ブテン／エチレンモル比０．１２、
エチレン濃度６０ｍｏｌ％とした。前記触媒Ｃを連続的
に供給して重合を行い、系内のガス組成を一定に保つた
め、各ガスを連続的に供給した。なお、生成した共重合
体の物性は表１に示した。(Polymerization of Sample A1) Using a continuous fluidized bed gas phase polymerization apparatus, the polymerization temperature was 70 ° C. and the total pressure was 20 kgf / c.
Copolymerization of ethylene and 1-butene was carried out with m 2 G. The gas composition in the system is 1-butene / ethylene molar ratio 0.12,
The ethylene concentration was 60 mol%. The catalyst C was continuously supplied to carry out polymerization, and each gas was continuously supplied to keep the gas composition in the system constant. The physical properties of the produced copolymer are shown in Table 1.
【００６２】（試料Ａ２の重合）１−ブテン／エチレン
のモル比を変化させたこと以外は（Ａ１）と同様の操作
を行って重合した。共重合体の物性は実験結果と併せて
表１に示した。(Polymerization of Sample A2) Polymerization was carried out in the same manner as in (A1) except that the molar ratio of 1-butene / ethylene was changed. The physical properties of the copolymer are shown in Table 1 together with the experimental results.
【００６３】（試料Ａ３〜Ａ５の重合）（Ａ３）、（Ａ
４）、（Ａ５）はコモノマーをそれぞれ１−ペンテン、
１−ヘキセン、４−メチル−ペンテン−１とした以外は
（Ａ１）と同様の操作を行って重合した。共重合体の物
性は実験結果と併せて表１に示した。(Polymerization of Samples A3 to A5) (A3), (A
4) and (A5) are comonomer 1-pentene,
Polymerization was performed in the same manner as in (A1) except that 1-hexene and 4-methyl-pentene-1 were used. The physical properties of the copolymer are shown in Table 1 together with the experimental results.
【００６４】（試料Ａ７〜Ａ１０の重合）１−ブテン／
エチレンのモル比を変化させたこと以外は（Ａ１）と同
様の操作を行って重合した。共重合体の物性は実験結果
と併せて表２または表３に示した。(Polymerization of Samples A7 to A10) 1-Butene /
Polymerization was performed in the same manner as in (A1) except that the molar ratio of ethylene was changed. The physical properties of the copolymer are shown in Table 2 or Table 3 together with the experimental results.
【００６５】（試料Ｂ２の重合）窒素で置換した攪拌機
付きの５０Ｌ加圧反応器に精製トルエン２５Ｌ入れた。
次いで、ブテン−１を１８３ｇ添加し、更にビス（ｎ−
ブチルシクロペンタジエニル）ジルコニウムジクロライ
ド、メチルアルモキサン〔ＭＡＯ〕の混合液を（Ａｌ／
Ｚｒモル比＝５００）をＺｒとして０．３３ミリモルと
なるように加えた後、８０℃に昇温した。次にエチレン
９ｋｇ／ｃｍ２Ｇとなるように張り込み重合を開始し
た。エチレンを連続的に重合しつつ全圧を９ｋｇ／ｃｍ
２Ｇに維持して１時間重合を行い共重合体を製造した。
共重合体の物性は実験結果と併せて表１に示した。(Polymerization of Sample B2) 25 L of purified toluene was placed in a 50 L pressure reactor equipped with a stirrer and purged with nitrogen.
Next, 183 g of butene-1 was added, and bis (n-
A mixed solution of butylcyclopentadienyl) zirconium dichloride and methylalumoxane [MAO] (Al /
Zr molar ratio = 500) was added as Zr so as to be 0.33 mmol, and then the temperature was raised to 80 ° C. Next, the polymerization was initiated so that the ethylene content was 9 kg / cm 2 G. The total pressure is 9 kg / cm while continuously polymerizing ethylene.
Polymerization was carried out by maintaining the temperature at 2 G for 1 hour to produce a copolymer.
The physical properties of the copolymer are shown in Table 1 together with the experimental results.
【００６６】（試料Ｂ８の重合）１−ブテンを４１０ｇ
添加した以外は（Ｂ２）と同様の操作を行って重合し
た。共重合体の物性は実験結果と併せて表３に示した。(Polymerization of Sample B8) 410 g of 1-butene
Polymerization was performed in the same manner as in (B2) except that the addition was performed. The physical properties of the copolymer are shown in Table 3 together with the experimental results.
【００６７】上記以外に用いた試料（Ｂ１）、（Ｂ
３）、（Ｂ７）、（Ｂ９）は四塩化チタン、トリエチル
アルミニウム触媒を用い気相法またはスラリー法にてエ
チレンと１−ブテンを共重合して得たＬＬＤＰＥまたは
ＶＬＤＰＥである。また（Ｂ４）は市販ウルトゼックス
３０１０Ｆ（三井石油化学（株）製）である。その物性
は実験結果と併せて表１〜表３に示した。Samples (B1) and (B
3), (B7) and (B9) are LLDPE or VLDPE obtained by copolymerizing ethylene and 1-butene by a gas phase method or a slurry method using titanium tetrachloride and a triethylaluminum catalyst. Further, (B4) is a commercially available Ultzex 3010F (manufactured by Mitsui Petrochemical Co., Ltd.). The physical properties are shown in Tables 1 to 3 together with the experimental results.
【００６８】実施例１〜５ 表１には前記手順により造粒した後インフレーションフ
ィルム成形し、各種物性の比較を行ったものである。Examples 1 to 5 Table 1 shows a comparison of various physical properties after granulation according to the above procedure and then blown film molding.
【００６９】比較例１〜４ 実施例１〜５との比較をするため表１に示した樹脂を用
い同様の操作を行ったものである。結果を表１に示し
た。比較例１はダート衝撃強度と透明性が、比較例２は
表１に示したように融点が低く耐熱性が劣り、また比較
例３、４は使用したα−オレフィンの種類を勘案して実
施例３、４と比べるとダート強度と透明性が劣る。Comparative Examples 1 to 4 In order to make a comparison with Examples 1 to 5, the same operations were performed using the resins shown in Table 1. The results are shown in Table 1. Comparative Example 1 had a dart impact strength and transparency, Comparative Example 2 had a low melting point and poor heat resistance as shown in Table 1, and Comparative Examples 3 and 4 were carried out in consideration of the type of α-olefin used. The dirt strength and transparency are inferior to those of Examples 3 and 4.
【００７０】実施例６、比較例５〜６ 実施例２で得たフィルムを用いホットタック特性を測定
し、比較例１、２で得たフィルムで測定した比較例５、
６と比較した。結果を表３に示す。実施例６は剥離距離
の短いシール温度範囲が広い。Example 6, Comparative Examples 5 to 6 The hot tack characteristics were measured using the film obtained in Example 2, and the comparative example 5 was measured using the film obtained in Comparative Examples 1 and 2.
Compared to 6. The results are shown in Table 3. Example 6 has a wide seal temperature range with a short peel distance.
【００７１】実施例７〜８、比較例７〜８ 前記の方法でシートを成形し物性試験を行い表３に示し
た。比較例７は引っ張り衝撃強度が劣り、比較例７は耐
熱性が劣る。Examples 7 to 8 and Comparative Examples 7 to 8 Sheets were molded by the above-mentioned method and physical properties were tested. Comparative Example 7 is inferior in tensile impact strength, and Comparative Example 7 is inferior in heat resistance.
【００７２】実施例９〜１０、比較例９ 前記の方法で射出成形による試験片を成形し物性試験を
行い表４に示した。比較例９は引っ張り衝撃強度および
引っ張り破壊強さが劣る。Examples 9 to 10 and Comparative Example 9 Test pieces by injection molding were molded by the above-mentioned method and the physical properties were tested. Comparative Example 9 is inferior in tensile impact strength and tensile fracture strength.
【００７３】[0073]
【表１】 [Table 1]
【００７４】[0074]
【表２】 [Table 2]
【００７５】[0075]
【表３】 [Table 3]
【００７６】[0076]
【表４】 [Table 4]
【図１】本発明共重合体のＴＲＥＦにより求めた溶出温
度−溶出量曲線。FIG. 1 is an elution temperature-elution amount curve of the copolymer of the present invention determined by TREF.
【図２】メタロセン触媒による共重合体のＴＲＥＦによ
り求めた溶出温度−溶出量曲線。FIG. 2 is an elution temperature-elution amount curve obtained by TREF of a copolymer with a metallocene catalyst.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成７年８月３０日[Submission date] August 30, 1995
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】以下本発明をさらに詳細に説明する。本発
明のエチレン・α−オレフィン共重合体はエチレンと炭
素数３〜２０のα−オレフィンより選ばれた一種以上と
の共重合体である。この炭素数３〜２０のα−オレフィ
ンとしては、好ましくは炭素数３〜１２のものであり、
具体的にはプロピレン、１−ブテン、１−ペンテン、４
−メチル−１−ペンテン、１−ヘキセン、１−オクテ
ン、１−デセン、１−ドデセン、などが挙げられる。ま
た、これらのα−オレフィンの含有量は、合計で通常３
０モル％以下、好ましくは３〜２０モル％の範囲で選択
されることが望ましい。The present invention will be described in more detail below. The ethylene / α-olefin copolymer of the present invention is a copolymer of ethylene and one or more kinds selected from α-olefins having 3 to 20 carbon atoms. The α-olefin having 3 to 20 carbon atoms is preferably one having 3 to 12 carbon atoms,
Specifically, propylene, 1-butene, 1-pentene, 4
-Methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like. The total content of these α-olefins is usually 3
It is desirable to select 0 mol% or less, preferably 3 to 20 mol%.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００５４[Correction target item name] 0054
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００５４】なお本実験例に用いた試験方法は以下の通
りである。 （物性試験方法） 密度 ：ＪＩＳ Ｋ６７６０に準拠し
た。 ＭＦＲ ：ＪＩＳ Ｋ６７６０に準拠し
た。 ＤＳＣによる測定 ：厚さ０．２ｍｍのシートを熱プ
レスで成形し約５ｍｇの試料を打ち抜き２３０℃で１０
ｍｉｎ保持後２℃／ｍｉｎにて０℃迄冷却、後再び１０
℃／ｍｉｎで１７０℃迄昇温し、現れた最高温ピークの
頂点の温度を最高ピーク温度Ｔｍとする。 Ｍｗ／Ｍｎ ：ＧＰＣ ウォータース１５０型 溶媒：ＯＤＣＢ １３５℃ カラム：東ソ−ＧＭＨＨＲ−Ｈ（Ｓ）検出器：示差屈折率 The test method used in this experimental example is as follows. (Physical property test method) Density: Based on JIS K6760. MFR: Based on JIS K6760. Measurement by DSC: A sheet having a thickness of 0.2 mm is formed by hot pressing and a sample of about 5 mg is punched out at 230 ° C. for 10 minutes.
After holding for min, cool to 0 ° C at 2 ° C / min, and then 10 again
The temperature is raised to 170 ° C. at a rate of ° C./min, and the temperature at the peak of the highest temperature peak that appears is the highest peak temperature Tm. Mw / Mn: GPC Waters 150 type Solvent: ODCB 135 ° C Column: Toso-GMHHR-H (S) Detector: Differential refractive index
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００５９[Correction target item name] 0059
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００５９】（固体触媒の調製）窒素下で電磁誘導攪拌
機付き触媒調製器（Ｎｏ．１）に精製トルエンを加え、
ついでジプロポキシジクロロジルコニウム（Ｚｒ（ＯＰ
ｒ） ２Ｃｌ２ ）２８ｇおよびメチルシクロペンタジエン
４８ｇを加え、０℃に系を保持しながらトリデシルアル
ミニウムを４５ｇを滴下し、滴下終了後、反応系を５０
℃に保持して１６時間攪拌した。この溶液をＡ液とす
る。次に窒素下で別の攪拌器付き触媒調製器（Ｎｏ．
２）２に精製トルエンを加え、前記Ａ溶液と、ついでメ
チルアルミノキサン６．４ｍｏｌのトルエン溶液を添加
し反応させた。これをＢ液とする。(Preparation of Solid Catalyst) Purified toluene was added to a catalyst preparation device (No. 1) equipped with an electromagnetic induction stirrer under nitrogen,
Then dipropoxydichlorozirconium (Zr (OP
28 g of r) 2 Cl 2 ) and 48 g of methylcyclopentadiene were added, and 45 g of tridecylaluminum was added dropwise while maintaining the system at 0 ° C. After completion of the addition, the reaction system was adjusted to 50
The mixture was kept at 0 ° C. and stirred for 16 hours. This solution is referred to as solution A. Next, under nitrogen, another stirrer catalyst preparation device (No.
2) Purified toluene was added to 2, and the above solution A and then a toluene solution of 6.4 mol of methylaluminoxane were added and reacted. This is designated as solution B.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００７１[Correction target item name] 0071
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００７１】実施例７〜８、比較例７〜８ 前記の方法でシートを成形し物性試験を行い表３に示し
た。比較例７は引っ張り衝撃強度が劣り、比較例８は耐
熱性が劣る。Examples 7 to 8 and Comparative Examples 7 to 8 Sheets were molded by the above-mentioned method and physical properties were tested. Comparative Example 7 is inferior in tensile impact strength, and Comparative Example 8 is inferior in heat resistance.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００７３[Correction target item name] 0073
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００７３】[0073]
【表１】 [Table 1]
Claims (3)
・α−オレフィン共重合体。 （Ａ）密度 ０．８６〜０．９６ｇ／ｃｍ３ （Ｂ）メルトフローレート（ＭＦＲ） ０．０１〜２００ｇ／１０ｍｉｎ （Ｃ）分子量分布（Ｍｗ／Ｍｎ） １．８〜３．５ （Ｄ）組成分布パラメーターＣｂ １．１０〜２．００1. An ethylene / α-olefin copolymer satisfying the following (A) to (D): (A) Density 0.86 to 0.96 g / cm 3 (B) Melt flow rate (MFR) 0.01 to 200 g / 10 min (C) Molecular weight distribution (Mw / Mn) 1.8 to 3.5 (D) Composition distribution parameter Cb 1.10 to 2.00
・α−オレフィン共重合体。 （Ａ）密度 ０．８６〜０．９６ｇ／ｃｍ３ （Ｂ）メルトフローレート（ＭＦＲ） ０．０１〜２００ｇ／１０ｍｉｎ （Ｃ）分子量分布（Ｍｗ／Ｍｎ） １．８〜３．５ （Ｄ）組成分布パラメーターＣｂ １．１０〜２．００ （Ｅ）２５℃におけるオルソジクロロベンゼン（ＯＤＣ
Ｂ）可溶分の量Ｘ（重量％）と密度ｄおよびＭＦＲが次
の関係を満足する イ）ｄ−０．００８×ｌｏｇＭＦＲ≧０．９３の場合 Ｘ＜２．０ ロ）ｄ−０．００８×ｌｏｇＭＦＲ＜０．９３の場合 Ｘ＜９．８×１０３×（０．９３００−ｄ＋０．００８
×ｌｏｇＭＦＲ）２＋２．０ （式１）2. An ethylene / α-olefin copolymer satisfying the following (A) to (E). (A) Density 0.86 to 0.96 g / cm 3 (B) Melt flow rate (MFR) 0.01 to 200 g / 10 min (C) Molecular weight distribution (Mw / Mn) 1.8 to 3.5 (D) Composition distribution parameter Cb 1.10 to 2.00 (E) Orthodichlorobenzene (ODC) at 25 ° C.
B) The amount X (% by weight) of the soluble content and the densities d and MFR satisfy the following relationships: a) In the case of d-0.008 × log MFR ≧ 0.93 X <2.0 b) d-0. When 008 × logMFR <0.93 X <9.8 × 10 3 × (0.9300−d + 0.008
× logMFR) 2 +2.0 (Equation 1)
・α−オレフィン共重合体。 （Ａ）密度 ０．８６〜０．９６ｇ／ｃｍ３ （Ｂ）メルトフローレート（ＭＦＲ） ０．０１〜２００ｇ／１０ｍｉｎ （Ｃ）分子量分布（Ｍｗ／Ｍｎ） １．８〜３．５ （Ｄ）組成分布パラメーターＣｂ １．１〜２．００ （Ｅ）２５℃におけるオルソジクロロベンゼン（ＯＤＣ
Ｂ）可溶分の量Ｘ（重量％）と密度ｄおよびＭＦＲが次
の関係を満足する イ）ｄ−０．００８×ｌｏｇＭＦＲ≧０．９３の場合 Ｘ＜２．０ ロ）ｄ−０．００８×ｌｏｇＭＦＲ＜０．９３の場合 Ｘ＜９．８×１０３×（０．９３００−ｄ＋０．００８
×ｌｏｇＭＦＲ）２＋２．０ （式１） （Ｆ）連続昇温溶出分別法（ＴＲＥＦ）による溶出温度
−溶出量曲線のピークが複数個3. An ethylene / α-olefin copolymer satisfying the following (A) to (F): (A) Density 0.86 to 0.96 g / cm 3 (B) Melt flow rate (MFR) 0.01 to 200 g / 10 min (C) Molecular weight distribution (Mw / Mn) 1.8 to 3.5 (D) Composition distribution parameter Cb 1.1-2.00 (E) Ortho-dichlorobenzene (ODC) at 25 ° C.
B) The amount X (% by weight) of the soluble content and the densities d and MFR satisfy the following relationships: a) In the case of d-0.008 × log MFR ≧ 0.93 X <2.0 b) d-0. When 008 × logMFR <0.93 X <9.8 × 10 3 × (0.9300−d + 0.008
× logMFR) 2 +2.0 (Equation 1) (F) Multiple peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17786695A JP3539801B2 (en) | 1995-03-28 | 1995-06-12 | Ethylene / α-olefin copolymer |
| SG1996006457A SG55111A1 (en) | 1995-03-28 | 1996-03-26 | Enthylene-alfa-olefin copolymer and composition and film laminate and electrical insulating material comprising same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-106797 | 1995-03-28 | ||
| JP10679795 | 1995-03-28 | ||
| JP17786695A JP3539801B2 (en) | 1995-03-28 | 1995-06-12 | Ethylene / α-olefin copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08325333A true JPH08325333A (en) | 1996-12-10 |
| JP3539801B2 JP3539801B2 (en) | 2004-07-07 |
Family
ID=26446906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17786695A Expired - Fee Related JP3539801B2 (en) | 1995-03-28 | 1995-06-12 | Ethylene / α-olefin copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3539801B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999065957A1 (en) * | 1998-06-19 | 1999-12-23 | Japan Polyolefins Co., Ltd. | ETHYLENE/α-OLEFIN COPOLYMER, COMPOSITION THEREOF, FILM THEREOF, AND USES OF THESE |
| JP2007039603A (en) * | 2005-08-05 | 2007-02-15 | Nippon Polyethylene Kk | Catalyst composition for olefin polymerization |
| WO2009020121A1 (en) * | 2007-08-09 | 2009-02-12 | Tosoh Corporation | Ethylene polymer and film thereof |
| JP2012503689A (en) * | 2008-09-25 | 2012-02-09 | バーゼル・ポリオレフィン・ゲーエムベーハー | Impact resistant LLDPE composition and film produced therefrom |
| WO2021071154A1 (en) * | 2019-10-11 | 2021-04-15 | 주식회사 엘지화학 | Polyethylene and preparation method therefor |
| CN113166321A (en) * | 2019-10-11 | 2021-07-23 | 株式会社Lg化学 | Polyethylene and process for its preparation |
-
1995
- 1995-06-12 JP JP17786695A patent/JP3539801B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999065957A1 (en) * | 1998-06-19 | 1999-12-23 | Japan Polyolefins Co., Ltd. | ETHYLENE/α-OLEFIN COPOLYMER, COMPOSITION THEREOF, FILM THEREOF, AND USES OF THESE |
| US6492475B1 (en) | 1998-06-19 | 2002-12-10 | Japan Polyolefins Co., Ltd. | Ethylene/α-olefin copolymer |
| JP2007039603A (en) * | 2005-08-05 | 2007-02-15 | Nippon Polyethylene Kk | Catalyst composition for olefin polymerization |
| WO2009020121A1 (en) * | 2007-08-09 | 2009-02-12 | Tosoh Corporation | Ethylene polymer and film thereof |
| JP2009040894A (en) * | 2007-08-09 | 2009-02-26 | Tosoh Corp | Ethylene polymer and film comprising the same |
| JP2012503689A (en) * | 2008-09-25 | 2012-02-09 | バーゼル・ポリオレフィン・ゲーエムベーハー | Impact resistant LLDPE composition and film produced therefrom |
| US8846188B2 (en) | 2008-09-25 | 2014-09-30 | Basell Poliolefine GmbH | Impact resistant LLDPE composition and films made thereof |
| WO2021071154A1 (en) * | 2019-10-11 | 2021-04-15 | 주식회사 엘지화학 | Polyethylene and preparation method therefor |
| CN113166321A (en) * | 2019-10-11 | 2021-07-23 | 株式会社Lg化学 | Polyethylene and process for its preparation |
| CN113166321B (en) * | 2019-10-11 | 2023-07-07 | 株式会社Lg化学 | Polyethylene and preparation method thereof |
| US12098224B2 (en) | 2019-10-11 | 2024-09-24 | Lg Chem, Ltd. | Polyethylene and method for preparing the same |
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