JPH0112778B2 - - Google Patents
Info
- Publication number
- JPH0112778B2 JPH0112778B2 JP58069196A JP6919683A JPH0112778B2 JP H0112778 B2 JPH0112778 B2 JP H0112778B2 JP 58069196 A JP58069196 A JP 58069196A JP 6919683 A JP6919683 A JP 6919683A JP H0112778 B2 JPH0112778 B2 JP H0112778B2
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene
- molecular weight
- resin composition
- polyethylene resin
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 polyethylene Polymers 0.000 claims description 111
- 239000004698 Polyethylene Substances 0.000 claims description 107
- 229920000573 polyethylene Polymers 0.000 claims description 107
- 229920013716 polyethylene resin Polymers 0.000 claims description 45
- 239000011342 resin composition Substances 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 34
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 150000002902 organometallic compounds Chemical class 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 238000000071 blow moulding Methods 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 150000002681 magnesium compounds Chemical class 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 26
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 150000002430 hydrocarbons Chemical group 0.000 description 18
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 238000009826 distribution Methods 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000004898 kneading Methods 0.000 description 9
- 125000002734 organomagnesium group Chemical group 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 150000001845 chromium compounds Chemical class 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- 229940117975 chromium trioxide Drugs 0.000 description 5
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- ZQDWXGKKHFNSQK-UHFFFAOYSA-N hydroxyzine Chemical compound C1CN(CCOCCO)CCN1C(C=1C=CC(Cl)=CC=1)C1=CC=CC=C1 ZQDWXGKKHFNSQK-UHFFFAOYSA-N 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010102 injection blow moulding Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 3
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000006353 environmental stress Effects 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- CYHOFESITORDDD-UHFFFAOYSA-M C(CCC)O[Cr](=O)(=O)O Chemical group C(CCC)O[Cr](=O)(=O)O CYHOFESITORDDD-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- AHXGRMIPHCAXFP-UHFFFAOYSA-L chromyl dichloride Chemical compound Cl[Cr](Cl)(=O)=O AHXGRMIPHCAXFP-UHFFFAOYSA-L 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 108091040184 miR-43 stem-loop Proteins 0.000 description 1
- 108091076357 miR-43-1 stem-loop Proteins 0.000 description 1
- 108091037708 miR-43-2 stem-loop Proteins 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 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 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 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 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、すぐれた物理的、化学的性質と成形
加工性を有するポリエチレン樹脂組成物に関し、
とくに、中空成形、押出成形、インジエクシヨン
−ブロー成形用途等で、優れた成形加工性および
優れた耐衝撃性および耐環境応力亀裂性（以下、
ESCRと言う）等の物性を有するポリエチレン樹
脂組成物に関する。
ポリエチレンの中空、押出、インジエクシヨン
−ブロー成形用途等では分子量が比較的高く、分
子量分布の比較的広いポリマーが適している。
分子量分布の広いポリエチレンの製造方法とし
て、いくつかの方法が提案されている。
１つの方法として、高分子量のポリエチレンと
低分子量のポリエチレンとを混合する方法が提案
されている（特公昭45−3215、特公昭45−22007、
特開昭54−100444、特開昭54−100445、特開昭54
−161657、特開昭55−60542、特開昭55−60543、
特開昭56−57841、特開昭57−133136）。
又、別の方法として、２段以上の多段重合方法
が試みられてきた（特公昭46−11349、特公昭48
−42716、特開昭51−47079、特開昭52−19788）。
これらの方法によつて製造されるポリマーは、
分子量分布が広く、且つESCRが良好である。
本願発明者らは、マグネシウム化合物系チーグ
ラー型触媒によるポリエチレンで上記混合方法の
いくつかの例を検討してみると、分子量分布は広
く出来、且つESCRも改良されたが、一方、それ
らポリエチレン樹脂組成物は、衝撃強度が低い、
さらに成形加工時の溶融粘弾性特性が悪く、成形
品に厚み斑が発生し易い、あるいは複雑な形状の
成形品は成形出来ない等、実用特性の上で幾多の
欠点があることが解つた。
本発明は、これらの欠点を改良し、総合的に物
性、成形加工性ともに優れたポリエチレン樹脂組
成物を提供するものである。
すなわち、本発明は、エチレンの単独重合体及
びエチレンとα−オレフインの共重合体の群から
選ばれる３種類のポリエチレン(A)、(B)および(C)か
らなるポリエチレン樹脂組成物であり、
(i) ポリエチレン(A)および(C)はマグネシウム化合
物系チーグラー型触媒によつて、ポリエチレン
(B)は有機金属化合物を組み合せたクロム化合物
担持系触媒によつて、それぞれ重合されたもの
であり、
(ii) ポリエチレン(A)の分子量（MWA）は0.8万か
ら９万の範囲にあり、ポリエチレン(B)の分子量
（MWB）は５万から50万であり、ポリエチレン
(C)の分子量（MWC）は10万から150万であり、
(iii) MWC／MWAが４〜150であり、
(iv) ポリエチレン(A)、(B)および(C)の配合比率は、
(A)対(C)が重量比で70対30から30対70の範囲であ
り、(B)の量は組成物中、重量で10％から65％の
範囲であり、
(v) 組成物のメルトインデツクスが0.001以上10
以下であるポリエチレン樹脂組成物に係るもの
である。
本発明によれば、工業的に適用範囲の広い、優
れた耐衝撃性、ESCR、剛性などの物性と、優れ
た成形加工性を併せ有し、中空、押出、インジエ
クシヨン−ブロー成形用途等に適したポリエチレ
ン樹脂組成物が与えられる。
以下、本発明を詳細に説明する。
本発明の構成成分であるポリエチレン(A)、(B)、
(C)はエチレンの単独重合体およびエチレンとα−
オレフインとの共重合体の群から選ばれる。
共重合に用いられるα−オレフインは、炭素数
３〜14のもので、例えば、プロピレン、ブテン、
ペンテン、ヘキセン、４−メチルペンテン−１、
オクテン、デセン等が挙げられる。
ポリエチレン(A)の分子量（MWA）は0.8万から
９万であり、0.8万未満では、各成分の均一分散
性および物性が低下し、一方９万を越えると、組
成物の分子量が適度な範囲で分子量分布を広げに
くくなり、加工性が低下する。より好ましくは
1.5万〜７万である。密度は0.91〜0.98ｇ／cm3であ
る。
ポリエチレン(B)の分子量（MWB）は５万から
50万の範囲であり、密度は0.91〜0.98ｇ／cm3であ
る。なお、組成物の成形加工性、物性のバランス
を良くするために、とくに望ましい態様は、ポリ
エチレン(B)と(A)の分子量の比（MWB／MWA）が
1.2以上で、且つポリエチレン(B)と(C)との分子量
の比（MWB／MWC）が0.9以下である。
ポリエチレン(C)の分子量（MWC）は10万〜150
万で、密度は0.91〜0.97ｇ／cm3である。MWCが10
万未満のときは組成物の分子量が低下し、また
ESCRも低下するなど特長が失なわれ、一方150
万を越えるとフイツシユアイが発生したり、組成
物中の各成分の均一分散性が低下したりし、加工
性、物性ともにバランスが悪くなる。より好まし
いMWCは20万〜100万である。また、MWC／
MWAは４〜150にあり、これが４未満のときは分
子量分布が狭く、加工性が低く、150を越えると、
各成分の均一分散性が悪く、加工性、物性が低
い。好ましくは７〜100である。また、より望ま
しい実施の態様はポリエチレン(C)の密度が(A)、(B)
のいずれよりも低い事で、これがとくに0.91〜
0.95ｇ／cm3の場合は、押出性、耐衝性、ESCR等
が一段と向上する。
次に、ポリエチレン(A)、(B)および(C)の混合比率
について説明する。ポリエチレン(A)の量対ポリエ
チレン(C)の量の比は、重量で表わしたとき、70対
30から30対70の範囲で、好ましくは60対40から40
対60である。(A)または(C)が70％を越えると、分子
量分布が狭くなり、加工性、物性のバランスが悪
くなる。
また、組成物中のポリエチレン(B)の量は、重量
で10％から65％の範囲であり、好ましくは20％か
ら55％の範囲にある。(B)の量が10％未満の時は、
加工性、衝撃強度が改善されず、一方65％を越え
ると、分子量分布が狭く加工性が悪くなり、かつ
ESCRが悪くなり本願発明のポリエチレン樹脂組
成物の特徴が損なわれる。
次にポリエチレン(A)及び(C)を製造するための触
媒と(A)、(C)の製造法について説明する。
本発明で言うマグネシウム化合物系チーグラー
型触媒としては、有機マグネシウム、無機マグネ
シウムに基くいずれの系も用いることが出来る。
とくに本願発明において好ましい触媒として
は、たとえば、
(i) 一般式
M〓Mg〓R1 pR2 qXrYs
（式中、αは０または０より大きい数、ｐ、
ｑ、ｒ、ｓは０または０より大きい数で、ｐ＋
ｑ＋ｒ＋ｓ＝mα＋2βの関係を有し、Ｍは周期
律表第族ないし第族に属する金属元素、ｍ
はＭの原子価、R1、R2は同一または異なつた
炭素原子数の炭化水素基、Ｘ、Ｙは同一または
異なつた基であり、ハロゲン、OR3、
OSiR4R5R6、NR7R8、SR9なる基を表わし、
R3、R4、R5、R6、R7、R8は水素原子または炭
化水素基、R9は炭化水素基を表わす）で示さ
れる有機マグネシウム化合物と、
(ii) 少なくとも１個のハロゲン原子を含有するチ
タンまたはバナジウム化合物と、(iii)Al、Ｂ、
Si、Ge、Sn、Te、Sbのハライド化合物の(i)〜
(iii)のうち(i)と(ii)あるいは(i)と(ii)と(iii)とを反
応さ
せてなる固体触媒成分〔Ａ〕と有機金属化合物
〔Ｂ〕からなるものである。有機金属化合物
〔Ｂ〕としては、周期律表第〜族の化合物
で、特に有機アルミニウム化合物および有機マ
グネシウムを含む錯体が好ましい。
触媒成分〔Ａ〕と有機金属化合物〔Ｂ〕成分
の反応は、重合系内に両成分を添加し、重合条
件下に重合の進行とともに行わせることも可能
であり、あらかじめ重合に先立つて実施しても
よい。また触媒成分の反応比率は、〔Ａ〕成分
１ｇに対し〔Ｂ〕成分１〜3000ｍmolの範囲で
行なうことが好ましい。触媒成分〔Ａ〕の代り
に、無機のMg化合物にTi化合物を担持したも
のでもよい。
これらの触媒系の中でも、工業的に脱触媒工程
を省略出来るために、とくに望ましいものとし
て、特公昭52−36788、52−36790、52−36791、
52−36792、52−50070、52−36794、52−36795、
52−36796、52−36915、52−36917、53−6019、
特開昭50−21876、50−31835、50−72044、50−
78619、53−40696号のものがある。該触媒を用い
て、ポリエチレン(A)、(C)は懸濁重合、溶液重合、
気相重合等で製造出来る。このようにして製造さ
れるポリエチレン(A)、(C)は分子量分布が狭く、メ
ルトインデツクス（以下MIと言う）が１のとき、
メルトインデツクス比（荷重21.6KgのMI／荷重
2.16KgのMIで、以下MIRと言う）が20〜50、二
重結合の量が1000炭素数当り0.3個以下であると
いう特徴がある。また一方、該ポリエチレン(A)及
び(C)は溶融時のバラス効果が低く、実施例におい
て示す測定方法によるダイ・スウエルは40ｇ／20
cm以下である。
次にポリエチレン(B)を製造するための触媒と(B)
の製造法について説明する。
本発明で言うところの有機金属化合物を組み合
せたクロム化合物担持系触媒とは、次のようにし
てつくられる。すなわち、無機酸化物担体にクロ
ム化合物を担持した固体成分と有機金属化合物と
を組み合せたものである。
以下に、さらに具体的に説明する。
本発明に用いる無機酸化物担体としては、シリ
カ、アルミナ、シリカーアルミナ、ジルコニア、
トリア等を用いることができるが、シリカ、シリ
カ−アルミナが好ましく、市販の高活性触媒用シ
リカ（高表面積、高多孔容積）は特に好ましい。
担持するクロム化合物としてはクロムの酸化
物、または焼成によつて少なくとも部分的に酸化
クロムを形成する化合物、たとえばクロムのハロ
ゲン化物、オキシハロゲン化物、硝酸塩、酢酸
塩、硫酸塩、シユウ酸塩、アルコラート等が挙げ
られ、具体的には三酸化クロム、塩化クロミル、
重クロム酸カリウム、クロム酸アンモニウム、硝
酸クロム、酢酸クロム、クロムアセチルアセトネ
ート、ジターシヤリブチルクロメート等が挙げら
れる。三酸化クロム、酢酸クロム、クロムアセチ
ルアセトネートは特に好ましく用いられる。
担体にクロム化合物を担持させるには、含浸、
溶媒留去、昇華付着等の公知の方法によつて行な
われる。クロム化合物の種類により、水系あるい
は非水系のいずれか適当な方法で担持すればよ
く、たとえば三酸化クロムを用いる場合は水を、
クロムアセチルアセトネートを用いる場合はトル
エンなどの非水溶媒を用いればよい。担持するク
ロムの量は、担体に対するクロム原子の重量パー
セントで0.05〜５％、好ましくは0.1〜３％の範
囲である。
焼成活性化は一般に非還元性雰囲気、たとえば
酸素の存在下で行なうが、不活性ガスの存在下あ
るいは減圧下で行なうことも可能である。好まし
くは水分を実質的に含まない空気が用いられる。
焼成温度は300℃以上、好ましくは400〜900℃の
温度範囲で数分〜数十時間、好ましくは30分〜10
時間行なわれる。焼成時には充分乾燥空気を吹込
み、流動状態下で焼成活性化を行なうことが推奨
される。
なお、担持もしくは焼成時にチタネート類やフ
ツ素含有塩類等を添加して、活性や分子量等を調
節する公知の方法を併用することも勿論可能であ
る。
組み合せに使用する有機金属化合物としては、
次のものが挙げられる。
(a) 一般式
Al〓Mg〓R1 pR2 qR3 rXsYt
で示される不活性炭化水素可溶有機マグネシウ
ム錯化合物（式中、α、βは０より大きい数、
ｐ、ｑ、ｒ、ｓ、ｔは０または０より大で、０
＜（ｓ＋ｔ）／（α＋β）≦1.5かつｐ＋ｑ＋ｒ
＋ｓ＋ｔ＝3α＋2βの関係を有し、R1、R2、R3
は同一または異なつた炭素原子数１〜20の炭化
水素基、Ｘ、Ｙは同一または異なつたOR4、
OSiR5R6R7、NR8R9およびSR10から選ばれた
基を表わし、R4、R5、R6、R7、R8、R9は水素
原子または炭化水素基、R10は炭化水素基を表
わす。）
(b) 一般式
MgR′uR″vXxYy
（式中、R′、R″は炭化水素基を表わし、かつ
R′、R″の少なくとも一方が炭素原子数４〜６
である二級または三級のアルキル基であるか、
またはR′とR″とが炭素原子数の互いに相異な
るアルキル基であるか、またはR′、R″の少な
くとも一方が炭素原子数６以上の炭化水素基で
あり、Ｘ、ＹはＯ、ＮまたはＳ原子を含有する
陰性な基であり、ｕ、ｖ、ｘ、ｙは０または０
より大なる数でｕ＋ｖ＋ｘ＋ｙ＝２かつ０＜ｘ
＋ｙ≦1.5の関係にある）で示される不活性炭
化水素可溶有機マグネシウム化合物
(c) 一般式
M〓Mg〓R1 pR2 qR3 rXsYt
で示される不活性炭化水素可溶有機マグネシウ
ム錯化合物（式中、α、βは０より大きい数、
ｐ、ｑ、ｒ、ｓ、ｔは０またはは０より大で、
０≦（ｓ＋ｔ）／（α＋β）≦1.5かつｐ＋ｑ＋
ｒ＋ｓ＋ｔ＝mα＋2βの関係を有し、Ｍは亜
鉛、ホウ素、ベリリウムおよびリチウムから選
ばれた原子、ｍはＭの原子価を表わし、R1、
R2、R3は同一または異なつた炭素原子数１〜
20の炭化水素基、Ｘ、Ｙは同一または異なつた
OR4、OSiR5R6R7、NR8R9およびSR10から選
ばれた基を表わし、R4、R5、R6、R7、R8、R9
は水素原子または炭化水素基、R10は炭化水素
基を表わす。）
(d) 一般式
M〓Mg〓R1 pR2 q（OSiHR3R4）r
（式中、Ｍはアルミニウム、亜鉛、ホウ素、ベ
リリウムから成る群から選ばれた原子、R1、
R2、R3は炭素原子数１〜20の炭化水素基、R4
は水素原子または炭素原子数１〜20の炭化水素
基を表わし、α、β、ｒは０より大なる数、
ｐ、ｑは０または０より大なる数で、ｐ＋ｑ＋
ｒ＝mα＋2β、ｍはＭの原子価である）で示さ
れる有機マグネシウム化合物
(e) 一般式
AlR1 o（OSiHR2R3）3-o
（式中、R1、R2は炭素原子数１〜20の炭化水
素基、R3は水素もしくは炭素原子数１〜20の
炭化水素基を表わし、ｎは１〜３の数である）
で示される有機アルミニウム化合物
(f) 一般式
AlR1 pHq（OR2）x（OSiHR3R4）y
（式中、ｐ≧１、１≧ｑ≧０、ｘ≧0.25、ｙ≧
0.15、1.5≧ｘ＋ｙ≧0.5かつｐ＋ｑ＋ｘ＋ｙ＝
３であり、R1、R2、R3、R4は同一または異な
つた炭素原子数１〜20の炭化水素基を表わす）
で示されるアルコキシ基およびヒドロキシ基の
両方を含有する有機アルミニウム化合物。
上述したこれらの有機金属化合物を組み合せた
クロム化合物担持系触媒については、特開昭56−
79106、同56−120713、同56−131607、同57−
70108、同57−70109、特願昭56−193667に詳述さ
れている。
ポリエチレン(B)は、該有機金属化合物を組み合
せたクロム化合物担持系触媒を用いて、懸濁重
合、溶液重合、気相重合等で製造出来る。談ポリ
エチレン(B)は、本願発明における該ポリエチレン
(A)、(C)に比較して分子量分布が広く、すなわち、
MIが１のとき、MIRが50〜120であり、二重結
合の量が1000炭素数当り0.3個以上２個以下であ
り、かつ適度に高いバラス効果を示し、実施例で
示す測定方法によるダイ・スウエルは50〜80ｇ／
20cmの範囲にある。このようなMIRとバラス効
果を併せ有するのが該ポリエチレン(B)の特徴であ
る。因みに、通常実施、あるいは市販されている
クロム化合物触媒によるポリエチレンは該測定方
法によるダイ・スウエルは50ｇ／20cmに達しな
い。
本願発明におけるポリエチレン樹脂組成物が、
優れた成形加工性と物性を示す原因としては、分
子量分布が狭く、分子量およびバラス効果の低い
ポリエチレン(A)と分子量分布が狭く、バラス効果
は低いが分子量の高いポリエチレン(C)とを、中間
の分子量で、分子量分布が比較的広く、バラス効
果が適度に高いポリエチレン(B)が、連結しうまく
分子を絡み合せることにより、最適な分子構造の
形態をとるところにあると考えられる。
本願発明のポリエチレン樹脂組成物が如何に優
れているかは実施例で示す通りであるが、例えば
ポリエチレン(B)の代りに、ポリエチレン(A)、(C)で
用いたマグネシウム化合物系チーグラー型触媒に
よる分子量がポリエチレン(B)と同じ範囲にあるポ
リエチレン、あるいは、分子量が該(B)と同じ範囲
にある他のクロム化合物系触媒によるポリエチレ
ンを用いても、本願発明のポリエチレン樹脂組成
物のような優れた特性のポリエチレン組成物は得
られ難い。
ポリエチレン(A)、(B)および(C)の３成分の混合方
法は、(A)、(B)、(C)を同時に混合混練する方法、３
成分のうちのいずれか２成分をあらかじめ混合
し、続いて３番目の成分を混合混練する方法のい
ずれを用いてもかまわない。これらの混練は溶融
状態で、通常は150〜300℃の温度で一軸、二軸の
押出機、混練機等で行なわれる。
このようにして製造される組成物のMIは0.001
以上10以下にあり、密度は0.91〜0.97ｇ／cm3好ま
しくは0.935〜0.965ｇ／cm3である。分子量分布は
MIRで60以上、好ましくは75以上である。なお、
インジエクシヨン−ブロー成形用途に使用する場
合はMIが0.5以上３以下が望ましく、中空、押出
成形用には0.005以上１以下が好ましい。
該ポリエチレン樹脂組成物は、熱安定剤、酸化
防止剤、紫外線吸収剤、顔料、帯電防止剤、滑
剤、充填剤、他のポリオレフイン、熱可塑性樹
脂、ゴム等、通常ポリオレフインに添加、ブレン
ドされ得る物質は、必要に応じて使用される。ま
た、発泡剤を混入させて発泡成形することも出来
る。
本願発明のポリエチレン樹脂組成物の特徴をま
とめると下記の如くなる。
(1) 溶融時の流動特性、粘弾性特性のバランスが
よく、成形加工性に優れている。とくに、中空
成形、およびパイプ、シートなど押出成形性、
インジエクシヨン−ブロー成形性が良く、成形
品の厚み斑が小さい。
(2) 成形品の剛性、耐衝撃性およびESCRが高
く、これら全ての特性が実用的によくバランス
している。
(3) 物性、加工性に優れているため、薄肉成形品
がつくり易い。このため、省資源、省エネルギ
ーの時代に適合する。
(4) 外観のよい成形品が得られる。
(5) 容易に製造出来る。
(6) 射出、フイルム、延伸、回転および発泡成形
などの各種の成形用途にも適用出来る。
以下、実施例を挙げて本発明をさらに詳細に説
明するが、本願発明はこれらの実施例によつて何
ら制限されるものではない。
本実施例、比較例において示す記号、測定方法
および測定条件。
(i) MI；メルトインデツクスを表わし、
ASTMD−1238により、温度190℃、荷重2.16
Kgの条件下で測定した値。本願明細書でいうメ
ルトインデツクスは全てこの値であり、単位は
ｇ／10minである。
(ii) MIR；MI測定条件において荷重21.6Kgで測
定した値をMIで除した商を意味し、分子量分
布の１つの尺度であり、この値が大きい程、分
子量分布が広いことを示す。
(iii) 分子量（MW）；デカリン溶液を用い、135℃
で測定した固有粘度（η）と、ジヤーナル、オ
ブ、ポリマーサイエンス36巻91頁（1957）記載
の式、η＝6.8×10-4MW0.67からMWを求めた。
なお、本願発明における分子量は全てこの方法
によるものである。
(iv) 密度；ASTMD−1505に従つて測定した。
(v) 衝撃強さ；ASTMD−256によるノツチ付ア
イゾツト衝撃強さである。
(vi) ESCR；環境応力破壊抵抗力を示す。
50mm径スクリユー付中空成形機を用い、シリ
ンダー温度190℃、金型温度40℃にて成形した
2000ml容量の把手付きボトル（重量95ｇ）に、
ノニオン系界面活性剤33％の水溶液200mlを充
填、密栓し、60℃のオーブンに入れ、ボトルに
クラツクが発生するまでの時間を測定する。
(vii) ボトルの耐衝撃性；上記のボトルに冷水（13
℃）を満し、密栓し、1.9ｍの高さからコンク
リート面に繰り返し落下し、ボトルが破壊され
るまでの回数を測定する。
(viii) 押出加工性；上記中空成形機を用い、シリン
ダー温度190℃、スクリユー回転数46rpmで押
出した時の押出量を測定する。
(ix) ダイ・スウエル；外径15mm、内径10mmの中空
成形用ダイを用い、上記(viii)の条件で押出した時
の20cm長さのパリソンの重量で表す。本願明細
書で言うダイスウエルは全てこのようにして測
定されたものである。
(x) ボトルの肉厚斑；上記(vi)の時につくつたボト
ルについて、とくに厚さが薄くなり易いハンド
ル部のピンチオフ溶着部の肉厚状態を肉眼で観
察し、非常に良好な状態を◎、良好な状態を
〇、一寸悪い状態を△、および非常に悪い状態
を×で表わす。
実施例 １−１
(1) ポリエチレン(A)および(C)用の触媒の合成
トリクロルシラン（HSiCl3）１モル／の
ヘキサン溶液を２を８のオートクレーブに
入れ、50℃に保つた。これに組成AlMg6.0
（C2H5）2.0（ｎ−C4H9）9.5（OC4H9）3.5の有機ア
ルミニウム−マグネシウム錯体の１モル／ヘ
キサン溶液２を撹拌下に２時間かけて滴下
し、さらにこの温度で２時間反応させた。生成
した固体成分を２のヘキサンで２回沈降法に
よつて洗浄した。この固体成分を含むスラリー
に四塩化チタン２を仕込み、130℃にて２時
間反応させた後、固体触媒を単離、遊離のハロ
ゲンが検出されなくなるまでヘキサンで洗浄し
た。この固体触媒は2.1％のチタンを含有して
いた。
(2) ポリエチレン(A)および(C)の製造
反応容積200のステンレス製重合機を用い、
連続重合によりポリエチレンを製造した。重合
温度は86℃、重合圧力は12Kg／cm2Ｇで、８Kg／
Hrの生成量となるよう重合をコントロールし
た。触媒はトリエチルアルミニウムを0.5ｍ
mol／の濃度で、また固体触媒は重合生成量
が８Kg／Hrとなるよう30／Hrのヘキサンと
ともに導入した。水素を分子量調節剤として用
いた。
低分子量ポリエチレン(A)はMWAが21000とな
るように重合を行なつた。水素濃度は約75％、
触媒効率は10万ｇポリマー／ｇTiであつた。
高分子量のポリエチレン(C)はブテン−１を共
重合し、密度0.938、MWC420000となるように
気相組成を調節した。水素濃度は約５％、ブテ
ン−１濃度は約4.5％であり、触媒効率は76万
ｇポリマー／ｇTiであつた。
(3) ポリエチレン(B)用の触媒の合成
(i) 固体成分(a)の合成
三酸化クロム10ｇを蒸留水2000mlに溶解
し、この溶液中にシリカ（富士デヴイソン社
製Grade952）500ｇを浸漬し、室温にて１時
間撹拌した。このスラリーを加熱して水を留
去し、続いて120℃にて10時間減圧乾燥を行
なつた。この固体を乾燥空気流通下、700℃
で５時間焼成して固体成分(a)を得た。得られ
た固体成分(a)はクロムを１重量％含有し、窒
素雰囲気下室温にて貯蔵した。
(ii) 有機アルミニウム成分(b)の合成
トリエチルアルミニウム100ｍmol、メチ
ルヒドロポリシロキサン（30℃における粘
度：30センチストークス）50ｍmol（Si基
準）、ｎ−ヘプタン150mlを窒素雰囲気下ガラ
ス製耐圧容器に秤取し、磁気撹拌子を用いて
撹拌下100℃において24時間反応させてAl
（C2H5）2.5（OSi・Ｈ・CH3・C2H5）0.5ヘプタ
ン溶液を合成した。次にこの溶液100ｍmol
（Al基準）を窒素雰囲気下200mlフラスコに
秤取し、滴下ロートよりエタノール50ｍmol
とｎ−ヘプタン50mlの混合溶液を氷冷撹拌下
に滴下し、滴下後室温にて１時間反応させて
Al（C2H5）2.0（OC2H5）0.5（OSi・Ｈ・CH3・
C2H5）0.5ヘプタン溶液を合成した。
(4) ポリエチレン(B)の製造
(2)で使用した重合機を用い、連続重合によつ
てポリエチレンを製造した。重合温度は83℃、
重合圧力は11Kg／cm2Ｇで、10.5Kg／Hrの生成
量となるように重合をコントロールした。触媒
は(3)−(i)で合成した固体成分(a)77mg／の濃度
で、(3)−(ii)で合成した有機アルミニウム成分(b)
0.075ｍmol／の濃度で、40／Hrのヘキサ
ンとともに導入した。水素を分子量調節剤とし
て用い、水素濃度を約30％にし、分子量約11
万、MIR58、密度0.967のポリエチレン(B)を製
造した。
(5) ポリエチレン樹脂組成物の製造
上記の如くして製造したポリエチレン(A)、(B)
及び(C)のパウダーを重量比で40対20対40の割合
で混合し、次いでこの混合物に熱、酸化防止剤
としてテトラキス〔メチレン−３−（3′，5′−
ジ−ｔ−ブチル−4′−ヒドロキシフエニル）プ
ロピオネート〕メタンを300ppm、およびジラ
ウリル−３，3′−チオジプロピオン酸エステル
を300ppmを添加し、ヘンシエルミキサー中で
十分撹拌混合した。この混合物をフアレル社製
FCMで220℃の温度で混練し、次いでこの混練
物を一軸押出機で200℃の温度で押出し、ペン
タイズをし、ポリエチレン樹脂組成物を製造し
た。このポリエチレン樹脂組成物の性能は第１
表に示す通り、成形加工性及び物性ともに非常
に優れた性能を示す。
実施例 １−２、１−３
実施例１−１で製造したポリエチレンパウダー
(A)、(B)及び(C)を、第１表に示すような配合量にし
て混合した以外は、添加剤、混合、混練及び押出
条件などは、実施例１−１と同様にしてポリエチ
レン樹脂組成物を製造し、その性能を評価した結
果を第１表に示す。
比較例 １−１〜１−３
実施例１−１で製造したポリエチレンパウダー
(A)、(B)及び(C)を、第１表に示すような配合量にし
て混合した以外は、添加剤、混合、混練及び押出
条件などは、実施例１−１と同様にしてポリエチ
レン樹脂組成物を製造し、その性能を評価した結
果を第１表に示す。
比較例 １−４〜１−５
実施例１−１で製造したポリエチレンパウダー
(A)と(C)及びフイリツプス社製マーレツクス
HHM5502を第１表に示すように配合量で混合し
た以外は、添加剤、混合、混練及び押出条件など
は、実施例１−１と同様にしてポリエチレン樹脂
組成物を製造し、その性能を評価した結果を第１
表に示す。
比較例 １−６
実施例１−１で製造したポリエチレンパウダー
(B)を添加剤、混練押出条件などは実施例１−１と
同様にしてペレツトにし、その性能を評価した。
結果は第１表に示す。
比較例 １−７
比較例１−４及び１−５で使用したマーレツク
スHHM5502の性能を評価し、その結果を第１表
に示す。
The present invention relates to a polyethylene resin composition having excellent physical and chemical properties and moldability,
In particular, it is suitable for use in blow molding, extrusion molding, injection blow molding, etc., with excellent molding processability and excellent impact resistance and environmental stress cracking resistance (hereinafter referred to as
It relates to polyethylene resin compositions having physical properties such as ESCR. Polymers with relatively high molecular weights and relatively wide molecular weight distributions are suitable for use in polyethylene hollow molding, extrusion, injection blow molding, and the like. Several methods have been proposed as methods for producing polyethylene with a wide molecular weight distribution. As one method, a method of mixing high molecular weight polyethylene and low molecular weight polyethylene has been proposed (Japanese Patent Publication No. 45-3215, Japanese Patent Publication No. 45-22007,
JP-A-54-100444, JP-A-54-100445, JP-A-54
−161657, JP-A-55-60542, JP-A-55-60543,
(Japanese Patent Publication No. 56-57841, Japanese Patent Application Publication No. 57-133136). In addition, as another method, a multi-stage polymerization method of two or more stages has been attempted (Japanese Patent Publication No. 46-11349, Special Publication No. 11349, No. 48)
-42716, JP-A-51-47079, JP-A-52-19788). Polymers produced by these methods are
It has a wide molecular weight distribution and good ESCR. The inventors of the present application investigated several examples of the above-mentioned mixing method for polyethylene using a magnesium compound-based Ziegler type catalyst, and found that the molecular weight distribution was wide and the ESCR was improved, but on the other hand, those polyethylene resin compositions objects have low impact strength,
Furthermore, it has been found that it has a number of drawbacks in terms of practical properties, such as poor melt viscoelastic properties during molding, which tends to cause uneven thickness in molded products, and the inability to mold molded products with complex shapes. The present invention aims to improve these drawbacks and provide a polyethylene resin composition that has comprehensively excellent physical properties and moldability. That is, the present invention is a polyethylene resin composition consisting of three types of polyethylene (A), (B) and (C) selected from the group of ethylene homopolymers and copolymers of ethylene and α-olefin, (i) Polyethylene (A) and (C) are converted into polyethylene using a magnesium compound-based Ziegler catalyst.
(B) is polymerized using a chromium compound-supported catalyst combined with an organometallic compound, and (ii) the molecular weight (MW A ) of polyethylene (A) is in the range of 80,000 to 90,000. , the molecular weight (MW B ) of polyethylene (B) is from 50,000 to 500,000, and polyethylene
(C) has a molecular weight (MW C ) of 100,000 to 1,500,000, (iii) MW C /MW A of 4 to 150, and (iv) a blend of polyethylene (A), (B) and (C). The ratio is
(A) to (C) in a weight ratio ranging from 70:30 to 30:70; the amount of (B) in the composition ranges from 10% to 65% by weight; and (v) the composition Melt index of 0.001 or more 10
This relates to the following polyethylene resin composition. According to the present invention, it has both excellent physical properties such as impact resistance, ESCR, and rigidity, which have a wide range of industrial applications, and excellent molding processability, and is suitable for hollow, extrusion, injection blow molding, etc. A polyethylene resin composition is provided. The present invention will be explained in detail below. Polyethylene (A), (B), which is a component of the present invention,
(C) is an ethylene homopolymer and ethylene and α-
selected from the group of copolymers with olefins. The α-olefin used in copolymerization has 3 to 14 carbon atoms, such as propylene, butene,
Pentene, hexene, 4-methylpentene-1,
Examples include octene and decene. The molecular weight (MW A ) of polyethylene (A) is 80,000 to 90,000. If it is less than 0,800, the uniform dispersibility and physical properties of each component will deteriorate, while if it exceeds 90,000, the molecular weight of the composition will be moderate. Within this range, it becomes difficult to widen the molecular weight distribution and processability decreases. More preferably
15,000 to 70,000. The density is 0.91-0.98 g/ cm3 . The molecular weight (MW B ) of polyethylene (B) is from 50,000
500,000, and the density is 0.91-0.98 g/ cm3 . In order to improve the balance between moldability and physical properties of the composition, a particularly desirable embodiment is such that the molecular weight ratio (MW B /MW A ) of polyethylene (B) and (A) is
1.2 or more, and the ratio of the molecular weights of polyethylene (B) and (C) (MW B /MW C ) is 0.9 or less. The molecular weight (MW C ) of polyethylene (C) is 100,000 to 150
The density is 0.91 to 0.97 g/cm 3 . MW C is 10
When it is less than 10,000, the molecular weight of the composition decreases, and
ESCR also decreased and other features were lost, while 150
If it exceeds 10,000, hard eyes may occur or the uniform dispersibility of each component in the composition may decrease, resulting in poor balance in both processability and physical properties. A more preferable MW C is 200,000 to 1,000,000. Also, MW C /
MW A ranges from 4 to 150; when it is less than 4, the molecular weight distribution is narrow and processability is low; when it exceeds 150,
Uniform dispersibility of each component is poor, and processability and physical properties are poor. Preferably it is 7-100. In addition, in a more desirable embodiment, the density of polyethylene (C) is (A), (B)
This is especially lower than 0.91~
In the case of 0.95 g/cm 3 , extrudability, impact resistance, ESCR, etc. are further improved. Next, the mixing ratio of polyethylene (A), (B) and (C) will be explained. The ratio of the amount of polyethylene (A) to the amount of polyethylene (C) is 70 to
In the range of 30 to 30:70, preferably 60:40 to 40
It is against 60. When (A) or (C) exceeds 70%, the molecular weight distribution becomes narrow and the balance between processability and physical properties becomes poor. Also, the amount of polyethylene (B) in the composition ranges from 10% to 65% by weight, preferably from 20% to 55%. When the amount of (B) is less than 10%,
Processability and impact strength are not improved, and if it exceeds 65%, the molecular weight distribution becomes narrow and processability deteriorates.
The ESCR deteriorates and the characteristics of the polyethylene resin composition of the present invention are impaired. Next, a catalyst for producing polyethylene (A) and (C) and a method for producing (A) and (C) will be explained. As the magnesium compound-based Ziegler type catalyst referred to in the present invention, any system based on organic magnesium or inorganic magnesium can be used. Particularly preferred catalysts in the present invention include, for example, (i) the general formula M〓Mg〓R 1 p R 2 q X r Y s (where α is 0 or a number larger than 0, p,
q, r, s are 0 or a number larger than 0, p+
The relationship is q+r+s=mα+2β, where M is a metal element belonging to Group 1 or Group 3 of the periodic table, and m
is the valence of M, R 1 and R 2 are hydrocarbon groups having the same or different numbers of carbon atoms, X and Y are the same or different groups, and halogen, OR 3 ,
represents a group OSiR 4 R 5 R 6 , NR 7 R 8 , SR 9 ;
R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are hydrogen atoms or hydrocarbon groups; R 9 is a hydrocarbon group); (ii) at least one halogen; a titanium or vanadium compound containing atoms; and (iii) Al, B,
(i) of halide compounds of Si, Ge, Sn, Te, and Sb
Of (iii), it consists of a solid catalyst component [A] obtained by reacting (i) and (ii) or (i), (ii) and (iii), and an organometallic compound [B]. The organometallic compound [B] is a compound of groups 1 to 10 of the periodic table, and a complex containing an organoaluminum compound and an organomagnesium is particularly preferable. The reaction between the catalyst component [A] and the organometallic compound [B] component can be carried out by adding both components into the polymerization system and carrying out the reaction under polymerization conditions as the polymerization progresses. It's okay. The reaction ratio of the catalyst components is preferably in the range of 1 to 3000 mmol of component [B] per 1 g of component [A]. Instead of the catalyst component [A], a Ti compound supported on an inorganic Mg compound may be used. Among these catalyst systems, Japanese Patent Publications No. 52-36788, No. 52-36790, No. 52-36791,
52−36792, 52−50070, 52−36794, 52−36795,
52−36796, 52−36915, 52−36917, 53−6019,
Unexamined Japanese Patent Publication No. 50-21876, 50-31835, 50-72044, 50-
78619, No. 53-40696. Using this catalyst, polyethylene (A) and (C) can be subjected to suspension polymerization, solution polymerization,
It can be manufactured by gas phase polymerization, etc. Polyethylene (A) and (C) produced in this way have a narrow molecular weight distribution, and when the melt index (hereinafter referred to as MI) is 1,
Melt index ratio (MI/load of 21.6Kg load)
It has an MI of 2.16 kg, has an MI of 20 to 50 (hereinafter referred to as MIR), and has less than 0.3 double bonds per 1000 carbon atoms. On the other hand, the polyethylenes (A) and (C) have a low balancing effect during melting, and the die swell according to the measurement method shown in the example is 40g/20.
cm or less. Next, a catalyst for producing polyethylene (B) and (B)
The manufacturing method will be explained. The chromium compound-supported catalyst combined with an organometallic compound referred to in the present invention is produced in the following manner. That is, it is a combination of a solid component in which a chromium compound is supported on an inorganic oxide carrier and an organic metal compound. This will be explained in more detail below. Examples of the inorganic oxide carrier used in the present invention include silica, alumina, silica alumina, zirconia,
Although thoria and the like can be used, silica and silica-alumina are preferred, and commercially available silica for highly active catalysts (high surface area, high pore volume) is particularly preferred. Supported chromium compounds include chromium oxides, or compounds which at least partially form chromium oxide upon calcination, such as chromium halides, oxyhalides, nitrates, acetates, sulfates, oxalates, alcoholates. Specifically, chromium trioxide, chromyl chloride,
Potassium dichromate, ammonium chromate, chromium nitrate, chromium acetate, chromium acetylacetonate, ditertiary butyl chromate, and the like. Chromium trioxide, chromium acetate, and chromium acetylacetonate are particularly preferably used. In order to support the chromium compound on the carrier, impregnation,
This is carried out by known methods such as solvent distillation and sublimation deposition. Depending on the type of chromium compound, it may be supported using an appropriate method, either aqueous or non-aqueous. For example, when using chromium trioxide, water may be supported.
When using chromium acetylacetonate, a non-aqueous solvent such as toluene may be used. The amount of chromium supported ranges from 0.05 to 5%, preferably from 0.1 to 3%, in weight percent of chromium atoms relative to the support. Calcination activation is generally carried out in a non-reducing atmosphere, for example in the presence of oxygen, but it can also be carried out in the presence of an inert gas or under reduced pressure. Preferably, air substantially free of moisture is used.
The firing temperature is 300℃ or higher, preferably in the temperature range of 400 to 900℃ for several minutes to several tens of hours, preferably 30 minutes to 10
Time is done. During firing, it is recommended to blow in sufficient dry air and activate firing under a fluidized state. Of course, it is also possible to use a known method of controlling activity, molecular weight, etc. by adding titanates, fluorine-containing salts, etc. during supporting or firing. The organometallic compounds used in the combination include:
These include: (a) An inert hydrocarbon soluble organomagnesium complex compound represented by the general formula Al〓Mg〓R 1 p R 2 q R 3 r X s Y t (wherein α and β are numbers greater than 0,
p, q, r, s, t are 0 or greater than 0, and 0
<(s+t)/(α+β)≦1.5 and p+q+r
+s+t=3α+2β, R 1 , R 2 , R 3
are the same or different hydrocarbon groups having 1 to 20 carbon atoms, X and Y are the same or different OR 4 ,
Represents a group selected from OSiR 5 R 6 R 7 , NR 8 R 9 and SR 10 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are hydrogen atoms or hydrocarbon groups, and R 10 is a hydrogen atom or a hydrocarbon group. Represents a hydrocarbon group. ) (b) General formula MgR′ u R″ v X x Y y (wherein, R′ and R″ represent a hydrocarbon group, and
At least one of R′ and R″ has 4 to 6 carbon atoms
is a secondary or tertiary alkyl group,
Or, R' and R'' are alkyl groups having different numbers of carbon atoms, or at least one of R' and R'' is a hydrocarbon group having 6 or more carbon atoms, and X and Y are O, N or a negative group containing an S atom, and u, v, x, y are 0 or 0
A larger number such that u+v+x+y=2 and 0<x
+y≦1.5) An inert hydrocarbon-soluble organomagnesium compound (c) An inert hydrocarbon-soluble organomagnesium compound with the general formula M〓Mg〓R 1 p R 2 q R 3 r X s Y t Dissolved organomagnesium complex compound (wherein α and β are numbers larger than 0,
p, q, r, s, t are 0 or greater than 0,
0≦(s+t)/(α+β)≦1.5 and p+q+
It has the relationship r + s + t = mα + 2β, M is an atom selected from zinc, boron, beryllium and lithium, m represents the valence of M, R 1 ,
R 2 and R 3 have the same or different number of carbon atoms from 1 to
20 hydrocarbon groups, X and Y are the same or different
Represents a group selected from OR 4 , OSiR 5 R 6 R 7 , NR 8 R 9 and SR 10 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9
represents a hydrogen atom or a hydrocarbon group, and R 10 represents a hydrocarbon group. ) (d) General formula M〓Mg〓R 1 p R 2 q (OSiHR 3 R 4 ) r (wherein M is an atom selected from the group consisting of aluminum, zinc, boron, beryllium, R 1 ,
R 2 and R 3 are hydrocarbon groups having 1 to 20 carbon atoms, R 4
represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, α, β, and r are numbers greater than 0,
p and q are 0 or a number greater than 0, p+q+
(e) General formula AlR 1 o (OSiHR 2 R 3 ) 3-o (wherein R 1 and R 2 have 1 carbon atom) ~20 hydrocarbon groups, R 3 represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and n is a number from 1 to 3)
Organoaluminum compound (f) with the general formula AlR 1 p H q (OR 2 ) x (OSiHR 3 R 4 ) y (wherein p≧1, 1≧q≧0, x≧0.25, y≧
0.15, 1.5≧x+y≧0.5 and p+q+x+y=
3, and R 1 , R 2 , R 3 , and R 4 represent the same or different hydrocarbon groups having 1 to 20 carbon atoms)
An organoaluminum compound containing both an alkoxy group and a hydroxy group. Chromium compound-supported catalysts combining these organometallic compounds mentioned above are described in Japanese Patent Application Laid-Open No. 1986-
79106, 56-120713, 56-131607, 57-
No. 70108, No. 57-70109, and Japanese Patent Application No. 56-193667. Polyethylene (B) can be produced by suspension polymerization, solution polymerization, gas phase polymerization, etc. using a chromium compound supported catalyst in combination with the organometallic compound. The polyethylene (B) is the polyethylene in the present invention.
The molecular weight distribution is wider compared to (A) and (C), that is,
When MI is 1, MIR is 50 to 120, the number of double bonds is 0.3 or more and 2 or less per 1000 carbons, and a moderately high balance effect is exhibited, and the measurement method shown in the example shows that・Swell is 50-80g/
It is in the range of 20cm. The polyethylene (B) is characterized by having both such MIR and a balancing effect. Incidentally, the die swell of polyethylene catalyzed by a chromium compound, which is commonly practiced or commercially available, does not reach 50 g/20 cm by this measuring method. The polyethylene resin composition in the present invention is
The reason for the excellent moldability and physical properties is that polyethylene (A) has a narrow molecular weight distribution and low molecular weight and balance effect, and polyethylene (C) has a narrow molecular weight distribution and low balance effect but has a high molecular weight. It is thought that polyethylene (B), which has a molecular weight of , a relatively wide molecular weight distribution, and a moderately high balancing effect, takes the form of an optimal molecular structure by linking and entangling the molecules. The superiority of the polyethylene resin composition of the present invention is as shown in the examples. Even if polyethylene having a molecular weight in the same range as polyethylene (B) or polyethylene produced by another chromium compound catalyst and having a molecular weight in the same range as said (B) is used, the excellent properties of the polyethylene resin composition of the present invention can be obtained. It is difficult to obtain polyethylene compositions with such characteristics. The methods of mixing the three components of polyethylene (A), (B) and (C) include a method of simultaneously mixing and kneading (A), (B), and (C);
Any two of the components may be mixed in advance, and then the third component may be mixed and kneaded. These kneading processes are carried out in a molten state, usually at a temperature of 150 to 300°C, using a single-screw or twin-screw extruder, kneader, or the like. The MI of the composition thus produced is 0.001
The density is 0.91 to 0.97 g/cm 3 and preferably 0.935 to 0.965 g/cm 3 . The molecular weight distribution is
MIR is 60 or more, preferably 75 or more. In addition,
When used for injection blow molding, MI is preferably 0.5 or more and 3 or less, and for hollow or extrusion molding, MI is preferably 0.005 or more and 1 or less. The polyethylene resin composition contains substances that can be normally added or blended with polyolefins, such as heat stabilizers, antioxidants, ultraviolet absorbers, pigments, antistatic agents, lubricants, fillers, other polyolefins, thermoplastic resins, rubbers, etc. is used as necessary. Further, foam molding can be carried out by mixing a foaming agent. The characteristics of the polyethylene resin composition of the present invention are summarized as follows. (1) Good balance between fluidity and viscoelastic properties when melted, and excellent moldability. In particular, it is suitable for blow molding, extrusion molding of pipes, sheets, etc.
In-die extension - Good blow moldability and small thickness unevenness of the molded product. (2) The molded product has high rigidity, impact resistance, and ESCR, and all these properties are well balanced for practical use. (3) It has excellent physical properties and processability, making it easy to make thin-walled molded products. Therefore, it is suitable for the era of resource saving and energy saving. (4) Molded products with good appearance can be obtained. (5) Easy to manufacture. (6) Can be applied to various molding applications such as injection, film, stretching, rotation and foam molding. Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Symbols, measurement methods, and measurement conditions shown in Examples and Comparative Examples. (i) MI; represents melt index;
According to ASTMD-1238, temperature 190℃, load 2.16
Values measured under Kg conditions. All melt indexes referred to in this specification are this value, and the unit is g/10min. (ii) MIR; means the quotient obtained by dividing the value measured under MI measurement conditions at a load of 21.6 kg by MI, and is one measure of molecular weight distribution; the larger this value is, the wider the molecular weight distribution is. (iii) Molecular weight (MW); using decalin solution, 135℃
The MW was determined from the intrinsic viscosity (η) measured by the method and the formula described in Journal of Polymer Science, Vol. 36, p. 91 (1957), η=6.8×10 −4 MW 0.67 .
Note that all molecular weights in the present invention are determined by this method. (iv) Density: Measured according to ASTM D-1505. (v) Impact strength: Notched isot impact strength according to ASTM D-256. (vi) ESCR: Indicates environmental stress fracture resistance. Molded using a blow molding machine with a 50mm diameter screw at a cylinder temperature of 190℃ and a mold temperature of 40℃.
2000ml capacity bottle with handle (weight 95g),
Fill the bottle with 200ml of a 33% nonionic surfactant aqueous solution, seal it, put it in an oven at 60℃, and measure the time until cracks appear in the bottle. (vii) Impact resistance of the bottle;
°C), tightly capped, and repeatedly dropped from a height of 1.9 m onto a concrete surface to measure the number of times it takes for the bottle to break. (viii) Extrusion processability: Using the above blow molding machine, measure the extrusion amount when extruding at a cylinder temperature of 190°C and a screw rotation speed of 46 rpm. (ix) Die swell: Expressed as the weight of a 20 cm long parison when extruded under the conditions of (viii) above using a blow molding die with an outer diameter of 15 mm and an inner diameter of 10 mm. All die swells referred to in this specification were measured in this manner. (x) Thickness unevenness on the bottle: For the bottle made in (vi) above, visually observe the wall thickness of the pinch-off weld on the handle, which tends to become thinner, and find that it is in very good condition. , a good condition is represented by ○, a slightly worse condition is represented by △, and a very bad condition is represented by ×. Example 1-1 (1) Synthesis of catalysts for polyethylene (A) and (C) A 1 mol/hexane solution of trichlorosilane (HSiCl 3 ) was placed in a 2 to 8 autoclave and maintained at 50°C. This has a composition AlMg 6.0
(C 2 H 5 ) 2.0 (n-C 4 H 9 ) 9.5 (OC 4 H 9 ) 3.5 1 mol/hexane solution 2 of the organoaluminium-magnesium complex was added dropwise with stirring over 2 hours, and further at this temperature. The mixture was allowed to react for 2 hours. The produced solid component was washed twice with hexane by the precipitation method. Titanium tetrachloride 2 was added to the slurry containing this solid component and reacted at 130° C. for 2 hours. The solid catalyst was isolated and washed with hexane until no free halogen was detected. This solid catalyst contained 2.1% titanium. (2) Production of polyethylene (A) and (C) Using a stainless steel polymerization machine with a reaction volume of 200,
Polyethylene was produced by continuous polymerization. The polymerization temperature was 86℃, the polymerization pressure was 12Kg/cm 2 G, and the polymerization rate was 8Kg/cm 2 G.
The polymerization was controlled to maintain the amount of Hr produced. The catalyst is triethylaluminum 0.5m
The solid catalyst was introduced with hexane at a concentration of 30/Hr to give a polymerization yield of 8 Kg/Hr. Hydrogen was used as a molecular weight regulator. Low molecular weight polyethylene (A) was polymerized so that MW A was 21,000. Hydrogen concentration is approximately 75%,
The catalyst efficiency was 100,000 g polymer/g Ti. High molecular weight polyethylene (C) was copolymerized with butene-1, and the gas phase composition was adjusted to have a density of 0.938 and a MW C of 420,000. The hydrogen concentration was about 5%, the butene-1 concentration was about 4.5%, and the catalyst efficiency was 760,000 g polymer/g Ti. (3) Synthesis of catalyst for polyethylene (B) (i) Synthesis of solid component (a) 10 g of chromium trioxide was dissolved in 2000 ml of distilled water, and 500 g of silica (Grade 952 manufactured by Fuji Davison) was immersed in this solution. , and stirred at room temperature for 1 hour. This slurry was heated to distill off water, and then dried under reduced pressure at 120°C for 10 hours. Dry this solid at 700℃ under air circulation.
The mixture was calcined for 5 hours to obtain solid component (a). The obtained solid component (a) contained 1% by weight of chromium and was stored at room temperature under a nitrogen atmosphere. (ii) Synthesis of organoaluminium component (b) Weigh out 100 mmol of triethylaluminum, 50 mmol of methylhydropolysiloxane (viscosity at 30°C: 30 centistokes) (based on Si), and 150 ml of n-heptane in a glass pressure-resistant container under a nitrogen atmosphere. Al
(C 2 H 5 ) 2.5 (OSi·H·CH 3 ·C 2 H 5 ) 0.5 heptane solution was synthesized. Next, 100 mmol of this solution
(Al standard) was weighed into a 200 ml flask under nitrogen atmosphere, and 50 mmol of ethanol was added from the dropping funnel.
A mixed solution of 50 ml of n-heptane was added dropwise while stirring on ice, and after the dropwise addition, the mixture was allowed to react at room temperature for 1 hour.
Al (C 2 H 5 ) 2.0 (OC 2 H 5 ) 0.5 (OSi・H・CH 3・
C 2 H 5 ) 0.5 heptane solution was synthesized. (4) Production of polyethylene (B) Polyethylene was produced by continuous polymerization using the polymerization machine used in (2). Polymerization temperature was 83℃,
The polymerization pressure was 11 Kg/cm 2 G, and the polymerization was controlled so that the production amount was 10.5 Kg/Hr. The catalyst was the solid component (a) synthesized in (3)-(i) at a concentration of 77 mg/, and the organoaluminum component (b) synthesized in (3)-(ii).
A concentration of 0.075 mmol/h was introduced together with 40/Hr of hexane. Using hydrogen as a molecular weight regulator, the hydrogen concentration is approximately 30%, and the molecular weight is approximately 11.
1,000, produced polyethylene (B) with MIR58 and density 0.967. (5) Production of polyethylene resin composition Polyethylene (A) and (B) produced as above
The powders of (C) and (C) were mixed in a weight ratio of 40:20:40, and then this mixture was heated and treated with tetrakis[methylene-3-(3',5'-
300 ppm of di-t-butyl-4'-hydroxyphenyl)propionate]methane and 300 ppm of dilauryl-3,3'-thiodipropionic acid ester were added, and the mixture was sufficiently stirred and mixed in a Henschel mixer. This mixture is manufactured by Fuarel.
The mixture was kneaded using FCM at a temperature of 220°C, and then this kneaded product was extruded using a single screw extruder at a temperature of 200°C and pentized to produce a polyethylene resin composition. The performance of this polyethylene resin composition is the first
As shown in the table, it shows very excellent performance in both moldability and physical properties. Examples 1-2, 1-3 Polyethylene powder produced in Example 1-1
The additives, mixing, kneading, and extrusion conditions were the same as in Example 1-1, except that (A), (B), and (C) were mixed in the amounts shown in Table 1. Table 1 shows the results of producing a polyethylene resin composition and evaluating its performance. Comparative Examples 1-1 to 1-3 Polyethylene powder produced in Example 1-1
The additives, mixing, kneading, and extrusion conditions were the same as in Example 1-1, except that (A), (B), and (C) were mixed in the amounts shown in Table 1. Table 1 shows the results of producing a polyethylene resin composition and evaluating its performance. Comparative Examples 1-4 to 1-5 Polyethylene powder produced in Example 1-1
(A) and (C) and Philips Marex
A polyethylene resin composition was produced in the same manner as in Example 1-1, except that HHM5502 was mixed in the amount shown in Table 1, using additives, mixing, kneading, and extrusion conditions, and its performance was evaluated. The first result is
Shown in the table. Comparative Example 1-6 Polyethylene powder produced in Example 1-1
(B) was made into pellets using the same additives, kneading and extrusion conditions as in Example 1-1, and its performance was evaluated.
The results are shown in Table 1. Comparative Example 1-7 The performance of Marex HHM5502 used in Comparative Examples 1-4 and 1-5 was evaluated, and the results are shown in Table 1.
【表】
＊；把手部のピンチオフ溶着部付近でクラツク
が入つた。その他のものは底部にクラツクが入つた。
＊＊；マーレツクスHHM5502を使用。
実施例 ２−１
(1) ポリエチレン(A)および(C)用の触媒の合成
ジ−ｎ−ブチルマグネシウム138ｇをトリエ
チルアルミニウム19ｇとをｎ−ヘプタン２と
ともに容量４の撹拌槽に送入し、80℃で２時
間反応させることにより、組成AlMg6（C2H5）3
（ｎ−C4H9）12の有機アルミニウム−マグネシ
ウム錯体を合成した。この錯体400ｍmol（54
ｇ）を含むｎ−ヘプタン溶液800mlと四塩化チ
タン400ｍmolを含有するｎ−ヘプタン溶液800
mlを、乾燥窒素置換によつて水分と酸素を除去
した後、−20℃で撹拌下４時間反応させた。生
成した炭化水素不溶性固体を単離し、ｎ−ヘプ
タンで洗浄し106ｇの固体を得た。
(2) ポリエチレン(A)および(C)の製造
上記の触媒を使用し、低分子量ポリエチレン
(A)および(C)を、下記の方法、条件で製造して、
ポリエチレン樹脂組成物の原料にした。
実施例１−１と同じ重合機を用い、実施例１
−１と同じ重合温度、圧力で重合した。触媒は
トリエチルアルミニウムを0.5ｍmol／の濃
度で、また固体触媒は重合生成量が８Kg／Hr
となるように30／Hrのヘキサンとともに導
入した。水素を分子量調節剤として用いた。コ
モノマーはブテン−１を用いた。低分子量ポリ
エチレン(A)は、そのMWA35000、密度0.950と
なるように気相組成を調節した。水素濃度は約
48％であり、ブテン−１濃度は約７％で、触媒
効率は17万ｇポリマー／ｇTiであつた。高分
子量のポリエチレン(C)はMWC280000、密度
0.935ｇ／cm3となるように気相組成を調節した。
水素濃度は約10％であり、ブテン−１濃度は約
６％であり、触媒効率は41万ｇポリマー／ｇ
Tiであつた。
(3) ポリエチレン(B)用触媒の合成
(i) 固体成分(a)の合成
三酸化クロム10ｇを用いる代りに酢酸クロ
ム（）１水塩25ｇを用いること、および焼
成温度を600℃にすること以外は、実施例１
−１と同様にして、固体成分(a)の合成を行な
い、貯蔵した。
(‐1) 有機マグネシウム成分（ｂ−１）の合
成
ジ−ｎ−ブチルマグネシウム13.80ｇと
トリエチルアルミニウム2.85ｇとを、ｎ−
ヘプタン200mlとともに500mlフラスコに入
れ、80℃にて２時間撹拌下で反応させるこ
とにより、組成AlMg4（C2H5）3（ｎ−
C4H9）8に相当する有機マグネシウム錯体
を合成した。続いてこの溶液を10℃に冷却
し、ｎ−オクタノール50ｍmolを含有する
ｎ−ヘプタン溶液50mlを、反応混合物を冷
却しつつ１時間かけて滴々添加し、アルコ
キシ含有有機マグネシウム錯体溶液を得
た。この溶液の一部分を分取し、乾燥空気
で酸化し、次いで加水分解することによ
り、アルキル基およびアルコキシ基をすべ
てアルコールとし、ガスクロマトグラフに
て分析した。エタノール、ｎ−ブタノー
ル、ｎ−オクタノールの分析値から、上記
錯体の組成はAlMg4（C2H5）2.70（ｎ−
C4H9）6.28（OH−C8H17）2.02であることが
判明した。
(4) ポリエチレン（Ｂ−１）の製造
実施例１−１と同じ重合機、重合温度、圧力
で、触媒は(3)−(i)で合成した固体成分(a)73mg／
の濃度で、(3)−（−１）で合成した有機ア
ルミニウム成分（ｂ−１）0.075ｍmol／の
濃度で、40／Hrのヘキサンとともに導入し
た。水素濃度約12％、ブテン−１濃度約1.5％
で分子量150000、MIR95、密度0.959ｇ／cm3の
ポリエチレン（Ｂ−１）を製造した。
(5) ポリエチレン樹脂組成物の製造
上記の如くして製造したポリエチレン(A)、
（Ｂ−１）及び(C)のパウダーを重量比で38対35
対27の割合で混合し、次いでこの混合物に熱、
酸化防止剤として、ｎ−オクタデシル−β−
（4′−ヒドロキシ−3′，5′−ジ−ｔ−ブチルフエ
ニル）プロピオネート500ppm、テトラキス
（２，４−ジタ−シヤリブチルフエニール）４，
4′−ビフエニレンジフオスフオナイト200ppm
およびステアリン酸カルシウム500ppmを添加
し、混合、混練および押出等の条件は実施例１
−１と同様にして、ポリエチレン樹脂組成物を
製造した。その性能は第２表に示す。
実施例 ２−２
実施例２−１で使用した固体触媒成分(a)と下記
の有機マグネシウム成分（ｂ−２）と組合せた。
(1) 有機マグネシウム成分（ｂ−２）の合成
ジ−ｎ−ブチルマグネシウム13.80ｇとジエ
チル亜鉛2.06ｇとをｎ−ヘプタン200mlととも
に500mlのフラスコに入れ、80℃で２時間撹拌
下に反応させることにより、組成ZnMg6
（C2H5）2（ｎ−C4H9）12の有機マグネシウム錯体
ヘプタン溶液を得た。
(2) ポリエチレン（Ｂ−２）の製造
実施例１−１と同じ重合機、重合温度、圧力
で、触媒は実施例２−１で合成した固体成分(a)
62mg／の濃度で、有機マグネシウム成分（ｂ
−２）0.065ｍmol／の濃度で、40／Hrの
ヘキサンとともに導入した。水素濃度約15％、
ブテン−１濃度約1.5％で分子量140000、
MIR88、密度0.959ｇ／cm3のポリエチレン(B)を
製造した。
(3) ポリエチレン樹脂組成物の製造
実施例２−１で製造したポリエチレン(A)、(C)
とポリエチレン（Ｂ−２）を使用した以外は実
施例２−１と同様にしてポリエチレン樹脂組成
物を製造した。その性能は第２表に示す。
比較例 ２−１
実施例２−１で製造したポリエチレン(A)と(C)の
２者を用い、第２表に示す配合比で、添加剤、混
合、混練押出条件は実施例２−１と同様にしてポ
リエチレン樹脂組成物を製造した。その性能は第
２表に示す。
比較例 ２−２
実施例２−１におけるポリエチレン(A)、(C)をつ
くるのに使用した触媒を用い、ポリエチレン（Ｂ
−３）を製造した。ポリエチレン(A)、（Ｂ−３）
及び(C)のパウダーを使用した以外は全て実施例２
−１と同様にしてポリエチレン樹脂組成物を製造
した。その性能は第２表に示す。
ポリエチレン（Ｂ−３）の製造条件は下記の通
りである。
水素濃度は約32％、ブテン−１濃度は約0.3％、
にした以外、ポリエチレン(A)、(C)と同様にして重
合した。このポリエチレン（Ｂ−３）の分子量
160000、MIR43、密度は0.960ｇ／cm3であつた。[Table] *; A crack appeared near the pinch-off weld on the handle. Others had cracks at the bottom.
**; Uses Marex HHM5502.
Example 2-1 (1) Synthesis of catalysts for polyethylene (A) and (C) 138 g of di-n-butylmagnesium, 19 g of triethylaluminum, and 22 g of n-heptane were fed into a stirring tank with a capacity of 4, By reacting for 2 hours at °C, the composition AlMg 6 (C 2 H 5 ) 3
An organoaluminum-magnesium complex of (n- C4H9 ) 12 was synthesized. 400 mmol (54
800 ml of n-heptane solution containing g) and 800 ml of n-heptane solution containing 400 mmol of titanium tetrachloride.
ml was subjected to dry nitrogen purging to remove moisture and oxygen, and then reacted at -20°C for 4 hours with stirring. The resulting hydrocarbon-insoluble solid was isolated and washed with n-heptane to yield 106 g of solid. (2) Production of polyethylene (A) and (C) Using the above catalyst, low molecular weight polyethylene
(A) and (C) are produced by the following method and conditions,
It was used as a raw material for polyethylene resin compositions. Using the same polymerization machine as in Example 1-1, Example 1
Polymerization was carried out at the same polymerization temperature and pressure as in -1. The catalyst is triethylaluminum at a concentration of 0.5 mmol/solid catalyst, and the polymerization amount is 8 Kg/Hr.
It was introduced together with hexane at a rate of 30/Hr. Hydrogen was used as a molecular weight regulator. Butene-1 was used as the comonomer. The gas phase composition of the low molecular weight polyethylene (A) was adjusted so that its MW A was 35000 and the density was 0.950. Hydrogen concentration is approx.
The butene-1 concentration was approximately 7%, and the catalyst efficiency was 170,000 g polymer/g Ti. High molecular weight polyethylene (C) has MW C 280000, density
The gas phase composition was adjusted to 0.935 g/cm 3 .
The hydrogen concentration is about 10%, the butene-1 concentration is about 6%, and the catalyst efficiency is 410,000 g polymer/g.
It was Ti. (3) Synthesis of catalyst for polyethylene (B) (i) Synthesis of solid component (a) Use 25 g of chromium acetate () monohydrate instead of 10 g of chromium trioxide, and set the calcination temperature to 600°C. Other than that, Example 1
Solid component (a) was synthesized and stored in the same manner as in -1. (-1) Synthesis of organomagnesium component (b-1) 13.80 g of di-n-butylmagnesium and 2.85 g of triethylaluminum were combined with n-
The composition AlMg 4 (C 2 H 5 ) 3 (n-
An organomagnesium complex corresponding to C 4 H 9 ) 8 was synthesized. Subsequently, this solution was cooled to 10° C., and 50 ml of n-heptane solution containing 50 mmol of n-octanol was added dropwise over 1 hour while cooling the reaction mixture to obtain an alkoxy-containing organomagnesium complex solution. A portion of this solution was taken, oxidized with dry air, and then hydrolyzed to convert all alkyl groups and alkoxy groups into alcohols, which was analyzed using a gas chromatograph. From the analytical values of ethanol, n-butanol, and n-octanol, the composition of the above complex is AlMg 4 (C 2 H 5 ) 2.70 (n-
It was found to be C 4 H 9 ) 6.28 (OH−C 8 H 17 ) 2.02 . (4) Production of polyethylene (B-1) Using the same polymerization machine, polymerization temperature, and pressure as in Example 1-1, the catalyst was 73 mg/g of the solid component (a) synthesized in (3)-(i).
The organoaluminum component (b-1) synthesized in (3)-(-1) was introduced at a concentration of 0.075 mmol/h together with 40/Hr of hexane. Hydrogen concentration approximately 12%, butene-1 concentration approximately 1.5%
Polyethylene (B-1) having a molecular weight of 150,000, an MIR of 95, and a density of 0.959 g/cm 3 was produced. (5) Production of polyethylene resin composition Polyethylene (A) produced as described above,
(B-1) and (C) powders in a weight ratio of 38:35
Mix in a ratio of 27 parts to 27 parts, then heat this mixture,
As an antioxidant, n-octadecyl-β-
(4'-hydroxy-3',5'-di-t-butylphenyl)propionate 500ppm, tetrakis(2,4-dithyabutylphenyl) 4,
4'-biphenylene diphosphonite 200ppm
and 500 ppm of calcium stearate, and the conditions of mixing, kneading, extrusion, etc. are as in Example 1.
A polyethylene resin composition was produced in the same manner as in Example 1-1. Its performance is shown in Table 2. Example 2-2 The solid catalyst component (a) used in Example 2-1 was combined with the following organic magnesium component (b-2). (1) Synthesis of organomagnesium component (b-2) Put 13.80 g of di-n-butylmagnesium and 2.06 g of diethylzinc into a 500 ml flask with 200 ml of n-heptane, and react with stirring at 80°C for 2 hours. According to the composition ZnMg 6
A heptane solution of an organomagnesium complex of (C 2 H 5 ) 2 (n-C 4 H 9 ) 12 was obtained. (2) Production of polyethylene (B-2) Using the same polymerization machine, polymerization temperature, and pressure as in Example 1-1, the catalyst was the solid component (a) synthesized in Example 2-1.
At a concentration of 62mg/organomagnesium component (b
-2) Introduced with hexane at a concentration of 0.065 mmol/40/Hr. Hydrogen concentration approximately 15%,
Molecular weight 140,000 at a butene-1 concentration of approximately 1.5%,
Polyethylene (B) with an MIR of 88 and a density of 0.959 g/cm 3 was produced. (3) Production of polyethylene resin composition Polyethylene (A) and (C) produced in Example 2-1
A polyethylene resin composition was produced in the same manner as in Example 2-1 except that polyethylene (B-2) was used. Its performance is shown in Table 2. Comparative Example 2-1 Using two polyethylenes (A) and (C) produced in Example 2-1, the additives, mixing, kneading and extrusion conditions were as shown in Table 2, and the additives, mixing, kneading and extrusion conditions were as in Example 2-1. A polyethylene resin composition was produced in the same manner. Its performance is shown in Table 2. Comparative Example 2-2 Using the catalyst used to produce polyethylene (A) and (C) in Example 2-1, polyethylene (B
-3) was produced. Polyethylene (A), (B-3)
All Example 2 except that powders of (C) and (C) were used.
A polyethylene resin composition was produced in the same manner as in -1. Its performance is shown in Table 2. The manufacturing conditions for polyethylene (B-3) are as follows. Hydrogen concentration is approximately 32%, butene-1 concentration is approximately 0.3%,
Polymerization was carried out in the same manner as polyethylene (A) and (C), except that Molecular weight of this polyethylene (B-3)
160000, MIR43, and density 0.960 g/cm 3 .
【表】【table】
【表】
実施例 ３
(1) ポリエチレン(A)、(C)の製造
実施例１−１でポリエチレン(A)、(C)をつくる
のに使用した触媒を用い、実施例１−１におけ
る重合機、温度、圧力でポリエチレン(A)及び(C)
を重合した。
ポリエチレン(A)は分子量12000になるよう水
素濃度を調節した。一方、ポリエチレン(C)は分
子量700000、密度0.942になるよう水素濃度と
オクテン−１の濃度を調節した。水素濃度は
各々約88％、約３％であり、(C)の場合のオクテ
ン−１の濃度は約３％であつた。
(2) ポリエチレン(B)の製造
実施例１−１でポリエチレン(B)をつくるのに
使用した触媒を用い、分子量が250000になるよ
う水素濃度を約１％にした以外は、実施例１−
１と同様にして、ポリエチレン(B)を製造した。
(3) ポリエチレン樹脂組成物の製造
ポリエチレン(A)、(B)及び(C)を第３表に示す配
合比で混合し、その他の条件は実施例１−１と
同様にしてポリエチレン樹脂組成物を製造し
た。その性能は第３表に示す。
比較例 ３−１
ポリエチレン(A)と(C)で第３表に示す配合比にし
た以外は実施例１−１と同様にしてポリエチレン
樹脂組成物を製造した。その性能は第３表に示
す。
比較例 ３−２
ポリエチレン(B)の代りに、フイリツプス社製マ
ーレツクスHXM50100を使用した以外は実施例
３と同様にしてポリエチレン樹脂組成物を製造し
た。その性能は第３表に示す。[Table] Example 3 (1) Production of polyethylene (A) and (C) Polymerization in Example 1-1 was carried out using the catalyst used to produce polyethylene (A) and (C) in Example 1-1. Polyethylene (A) and (C) under machine, temperature and pressure
was polymerized. The hydrogen concentration of polyethylene (A) was adjusted so that the molecular weight was 12,000. On the other hand, the hydrogen concentration and octene-1 concentration of polyethylene (C) were adjusted so that the molecular weight was 700,000 and the density was 0.942. The hydrogen concentrations were about 88% and about 3%, respectively, and the octene-1 concentration in case (C) was about 3%. (2) Production of polyethylene (B) Example 1-1 was performed except that the catalyst used to produce polyethylene (B) in Example 1-1 was used and the hydrogen concentration was adjusted to about 1% so that the molecular weight was 250,000.
Polyethylene (B) was produced in the same manner as in Example 1. (3) Manufacture of polyethylene resin composition Polyethylene (A), (B), and (C) were mixed at the compounding ratio shown in Table 3, and the other conditions were the same as in Example 1-1 to prepare a polyethylene resin composition. was manufactured. Its performance is shown in Table 3. Comparative Example 3-1 A polyethylene resin composition was produced in the same manner as in Example 1-1, except that polyethylene (A) and polyethylene (C) were used in the blending ratio shown in Table 3. Its performance is shown in Table 3. Comparative Example 3-2 A polyethylene resin composition was produced in the same manner as in Example 3, except that Marex HXM50100 manufactured by Phillips was used instead of polyethylene (B). Its performance is shown in Table 3.
【表】【table】
【表】
(注) ＊；把手部のピンチオフ部が完全に融着
せず成形出来なかつた。
＊＊；マーレツクスHXM−50100を使用。
以上実施例、比較例各々１〜３に示すように、
本願発明によるポリエチレン(A)、(B)及び(C)から成
るポリエチレン樹脂組成物は、成形加工性及び成
形品の物性に極めて優れた特性を示し、また、そ
れらが高いレベルでよくバランスしている。これ
に対し、ポリエチレン(A)と(C)の２者から成るポリ
エチレン樹脂組成物は、成形加工性が劣り、ま
た、成形品の物性も劣つている。一方、市販のク
ロム系触媒からつくられるポリエチレンを(B)の代
りに用いた場合は、ポリエチレン(A)と(C)の２者か
ら成るポリエチレン樹脂組成物にくらべ成形加工
性、物性ともに、幾分改善されるが本願発明のポ
リエチレン樹脂組成物のレベルよりは相当低い。
他方ポリエチレン(A)、(C)と同じ系の触媒からつく
られるポリエチレンを(B)の代りに用いた場合は、
その成形加工性、物性ともにポリエチレン(A)と(C)
の２者から成るポリエチレン樹脂組成物に近く、
低いレベルにある。すなわち、本願発明は上述の
如く、それぞれの触媒によるポリマーの特性を生
かすことによつて成されたものである。[Table] (Note) *; The pinch-off part of the handle was not completely fused and could not be formed.
**; Using Marex HXM-50100.
As shown in Examples and Comparative Examples 1 to 3 above,
The polyethylene resin composition composed of polyethylene (A), (B), and (C) according to the present invention exhibits extremely excellent properties in molding processability and physical properties of molded products, and also has a high level of well-balanced properties. There is. On the other hand, polyethylene resin compositions consisting of polyethylene (A) and polyethylene (C) have poor moldability and also have poor physical properties of molded products. On the other hand, when polyethylene made from a commercially available chromium-based catalyst is used instead of (B), the moldability and physical properties are much lower than that of a polyethylene resin composition consisting of polyethylene (A) and (C). However, it is considerably lower than the level of the polyethylene resin composition of the present invention.
On the other hand, if polyethylene made from the same catalyst as polyethylene (A) and (C) is used instead of (B),
Its moldability and physical properties are similar to that of polyethylene (A) and (C).
It is close to a polyethylene resin composition consisting of two components,
It's at a low level. That is, as described above, the present invention has been achieved by taking advantage of the characteristics of the polymers produced by each catalyst.
Claims (1)
オレフインの共重合体の群から選ばれる３種類の
ポリエチレン(A)、(B)および(C)とから成るポリエチ
レン樹脂組成物であり、 (i) ポリエチレン(A)と(C)はマグネシウム化合物系
チーグラー型触媒によつて、ポリエチレン(B)は
有機金属化合物を組み合せたクロム化合物担持
系触媒によつて、それぞれ重合されたものであ
り、 (ii) ポリエチレン(A)の分子量は0.8万から９万で
あり、ポリエチレン(C)の分子量は10万から150
万であり、ポリエチレン(B)の分子量は５万から
50万であり、 (iii) ポリエチレン(C)の分子量／ポリエチレン(A)の
分子量が４〜150であり、 (iv) ポリエチレン(A)、(B)および(C)の配合比は、(A)
対(C)が重量比で70対30から30対70の範囲であ
り、(B)の量は組成物中、重量で10％から65％の
範囲であり、 (v) 組成物のメルトインデツクスが0.001以上10
以下であるポリエチレン樹脂組成物。 ２ ポリエチレン(C)の密度が、ポリエチレン(A)、
(B)の密度のいずれよりも低い特許請求の範囲第１
項記載のポリエチレン樹脂組成物。 ３ ポリエチレン(B)の分子量が(A)の分子量の1.2
倍以上で、且つ(C)の分子量の0.9倍以下である特
許請求の範囲第１項記載のポリエチレン樹脂組成
物。 ４ ポリエチレン(A)、(B)および(C)の配合比が、(A)
対(C)は重量比で60対40から40対60の範囲であり、
(B)の量が組成物中、重量で20％から55％の範囲で
ある特許請求の範囲第１、２又は３項記載のポリ
エチレン樹脂組成物。 ５ ポリエチレン(A)の分子量が1.5万から７万で
あり、ポリエチレン(C)の分子量が20万から100万
であり、その分子量の比（(C)の分子量／(A)の分子
量）が７〜100である特許請求の範囲第１、２、
３又は４項記載のポリエチレン樹脂組成物。 ６ 組成物の密度が0.935以上0.965ｇ／cm3以下で
ある特許請求の範囲第１、２、３、４又は５項記
載のポリエチレン樹脂組成物。 ７ 組成物のメルトインデツクスが0.005以上１
以下の範囲にある特許請求の範囲第１、２、３、
４、５又は６項記載の中空成形用ポリエチレン樹
脂組成物。 ８ 組成物のメルトインデツクスが0.005以上１
以下の範囲にある特許請求の範囲第１、２、３、
４、５又は６項記載の押出成形用ポリエチレン樹
脂組成物。 ９ 組成物のメルトインデツクスが0.5以上３以
下の範囲にある特許請求の範囲第１、２、３、
４、５又は６項記載のインジエクシヨン−ブロー
成形用ポリエチレン樹脂組成物。[Claims] 1. Ethylene homopolymer and ethylene and α-
A polyethylene resin composition consisting of three types of polyethylene (A), (B) and (C) selected from the group of olefin copolymers, (i) polyethylene (A) and (C) are magnesium compound-based Polyethylene (B) is polymerized using a Ziegler-type catalyst and a chromium compound-supported catalyst combined with an organometallic compound. (ii) The molecular weight of polyethylene (A) is 80,000 to 90,000. The molecular weight of polyethylene (C) is 100,000 to 150
The molecular weight of polyethylene (B) is from 50,000 to 50,000.
500,000, (iii) the molecular weight of polyethylene (C)/the molecular weight of polyethylene (A) is 4 to 150, (iv) the blending ratio of polyethylene (A), (B) and (C) is (A )
(C) in a weight ratio ranging from 70:30 to 30:70; the amount of (B) in the composition ranges from 10% to 65% by weight; (v) the melt index of the composition; Tsukusu is 0.001 or more 10
A polyethylene resin composition as follows. 2 The density of polyethylene (C) is polyethylene (A),
Claim 1 lower than any of the densities in (B)
The polyethylene resin composition described in . 3 The molecular weight of polyethylene (B) is 1.2 of that of (A).
2. The polyethylene resin composition according to claim 1, which has a molecular weight of at least twice that of (C) and no more than 0.9 times that of (C). 4 The blending ratio of polyethylene (A), (B) and (C) is (A)
Pair (C) ranges from 60:40 to 40:60 in weight ratio,
The polyethylene resin composition according to claim 1, 2 or 3, wherein the amount of (B) in the composition ranges from 20% to 55% by weight. 5 The molecular weight of polyethylene (A) is 15,000 to 70,000, the molecular weight of polyethylene (C) is 200,000 to 1,000,000, and the ratio of their molecular weights (molecular weight of (C) / molecular weight of (A)) is 7. ~100 Claims 1, 2,
The polyethylene resin composition according to item 3 or 4. 6. The polyethylene resin composition according to claim 1, 2, 3, 4, or 5, wherein the composition has a density of 0.935 or more and 0.965 g/cm 3 or less. 7 The melt index of the composition is 0.005 or more1
Claims 1, 2, 3 within the following scope,
The polyethylene resin composition for blow molding according to item 4, 5 or 6. 8 The melt index of the composition is 0.005 or more1
Claims 1, 2, 3 within the following scope,
The polyethylene resin composition for extrusion molding according to item 4, 5 or 6. 9 Claims 1, 2, 3, in which the melt index of the composition is in the range of 0.5 or more and 3 or less
The polyethylene resin composition for in-die extension blow molding according to item 4, 5 or 6.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6919683A JPS59196346A (en) | 1983-04-21 | 1983-04-21 | Polyethylene resin composition |
| US06/599,401 US4536550A (en) | 1983-04-21 | 1984-04-12 | Polyethylene composition |
| CA000451826A CA1218181A (en) | 1983-04-21 | 1984-04-12 | Polyethylene composition |
| EP84302681A EP0129312B1 (en) | 1983-04-21 | 1984-04-19 | Polyethylene composition |
| DE8484302681T DE3470168D1 (en) | 1983-04-21 | 1984-04-19 | Polyethylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6919683A JPS59196346A (en) | 1983-04-21 | 1983-04-21 | Polyethylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59196346A JPS59196346A (en) | 1984-11-07 |
| JPH0112778B2 true JPH0112778B2 (en) | 1989-03-02 |
Family
ID=13395728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6919683A Granted JPS59196346A (en) | 1983-04-21 | 1983-04-21 | Polyethylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59196346A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009147967A1 (en) | 2008-06-05 | 2009-12-10 | 株式会社Adeka | Aluminum phenoxides and process for production of stabilized polymers by using the aluminum phenoxides |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6036549A (en) * | 1983-08-09 | 1985-02-25 | Showa Denko Kk | Ethylenic polymer composition for lamination |
| JPS63154753A (en) * | 1986-12-18 | 1988-06-28 | Nippon Oil Co Ltd | Polyethylene composition |
| WO1993000400A1 (en) * | 1991-06-21 | 1993-01-07 | The Dow Chemical Company | Polyethylene blends for molding |
| DE69829371T2 (en) * | 1997-06-24 | 2006-04-06 | Japan Polyolefins Co. Ltd. | ETHYLENE COPOLYMERS AND COMPOSITE FILMS AND HOLLOW BODIES MANUFACTURED THEREOF |
| US6716385B2 (en) | 1997-06-24 | 2004-04-06 | Japan Polyolefins Co., Ltd. | Ethylene (co) polymers, and laminate and hollow molding made by using the same |
| DE19945980A1 (en) * | 1999-09-24 | 2001-03-29 | Elenac Gmbh | Polyethylene molding compound with improved ESCR stiffness ratio and swelling rate, process for its production and hollow bodies made from it |
| JP4596510B2 (en) * | 2002-11-18 | 2010-12-08 | 旭化成ケミカルズ株式会社 | Polyethylene composition |
| JP4641842B2 (en) * | 2005-03-25 | 2011-03-02 | 旭化成ケミカルズ株式会社 | Polyethylene resin composition for extrusion lamination |
| JP5054947B2 (en) * | 2006-08-30 | 2012-10-24 | 日本ポリエチレン株式会社 | Polyethylene resin molding material for hollow molding and hollow molded body comprising the same |
| JP5054946B2 (en) * | 2006-08-30 | 2012-10-24 | 日本ポリエチレン株式会社 | Method for producing polyethylene resin molding material for hollow molding |
| GB2498936A (en) * | 2012-01-31 | 2013-08-07 | Norner Innovation As | Polyethylene with multi-modal molecular weight distribution |
| JP6187332B2 (en) * | 2013-03-28 | 2017-08-30 | 日本ポリエチレン株式会社 | Polyethylene for pipes and joints and molded articles thereof |
| EP2818508A1 (en) * | 2013-06-25 | 2014-12-31 | Basell Polyolefine GmbH | Polyethylene composition having high impact and stress cracking resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4934758A (en) * | 1972-08-01 | 1974-03-30 | ||
| JPS4934759A (en) * | 1972-07-31 | 1974-03-30 | ||
| JPS50122584A (en) * | 1974-03-08 | 1975-09-26 | ||
| JPS54100445A (en) * | 1978-01-26 | 1979-08-08 | Showa Denko Kk | Polyethylene resin composition for injection molding |
| JPS54100444A (en) * | 1978-01-26 | 1979-08-08 | Showa Denko Kk | Polyethylene resin composition |
| JPS55152735A (en) * | 1979-05-18 | 1980-11-28 | Asahi Chem Ind Co Ltd | Polyethylene composition |
| JPS5731945A (en) * | 1980-08-04 | 1982-02-20 | Asahi Chem Ind Co Ltd | Polyethylene composition and preparation of the same |
| JPS57159834A (en) * | 1981-03-30 | 1982-10-02 | Idemitsu Petrochem Co Ltd | Ethylene polymer composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6412777A (en) * | 1987-07-07 | 1989-01-17 | Pioneer Electronic Corp | Information recording system |
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1983
- 1983-04-21 JP JP6919683A patent/JPS59196346A/en active Granted
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4934759A (en) * | 1972-07-31 | 1974-03-30 | ||
| JPS4934758A (en) * | 1972-08-01 | 1974-03-30 | ||
| JPS50122584A (en) * | 1974-03-08 | 1975-09-26 | ||
| JPS54100445A (en) * | 1978-01-26 | 1979-08-08 | Showa Denko Kk | Polyethylene resin composition for injection molding |
| JPS54100444A (en) * | 1978-01-26 | 1979-08-08 | Showa Denko Kk | Polyethylene resin composition |
| JPS55152735A (en) * | 1979-05-18 | 1980-11-28 | Asahi Chem Ind Co Ltd | Polyethylene composition |
| JPS5731945A (en) * | 1980-08-04 | 1982-02-20 | Asahi Chem Ind Co Ltd | Polyethylene composition and preparation of the same |
| JPS57159834A (en) * | 1981-03-30 | 1982-10-02 | Idemitsu Petrochem Co Ltd | Ethylene polymer composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009147967A1 (en) | 2008-06-05 | 2009-12-10 | 株式会社Adeka | Aluminum phenoxides and process for production of stabilized polymers by using the aluminum phenoxides |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59196346A (en) | 1984-11-07 |
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