CN116162299A - Ethylene resin composition and molded article - Google Patents
Ethylene resin composition and molded article Download PDFInfo
- Publication number
- CN116162299A CN116162299A CN202211487714.0A CN202211487714A CN116162299A CN 116162299 A CN116162299 A CN 116162299A CN 202211487714 A CN202211487714 A CN 202211487714A CN 116162299 A CN116162299 A CN 116162299A
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- China
- Prior art keywords
- resin composition
- density polyethylene
- temperature
- ethylene resin
- density
- 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.)
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000005977 Ethylene Substances 0.000 title claims abstract description 155
- 239000011342 resin composition Substances 0.000 title claims abstract description 149
- 238000005259 measurement Methods 0.000 claims abstract description 21
- 239000000155 melt Substances 0.000 claims abstract description 19
- 229920001684 low density polyethylene Polymers 0.000 claims description 101
- 229920001903 high density polyethylene Polymers 0.000 claims description 99
- 239000004700 high-density polyethylene Substances 0.000 claims description 99
- 238000000034 method Methods 0.000 claims description 59
- 238000002844 melting Methods 0.000 claims description 38
- 230000008018 melting Effects 0.000 claims description 38
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 28
- 229920002554 vinyl polymer Polymers 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 16
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 9
- 229920001184 polypeptide Polymers 0.000 claims description 7
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 7
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 7
- 238000001595 flow curve Methods 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 10
- 230000000877 morphologic effect Effects 0.000 abstract description 5
- 241000251468 Actinopterygii Species 0.000 abstract description 3
- 239000004702 low-density polyethylene Substances 0.000 description 98
- 238000006116 polymerization reaction Methods 0.000 description 87
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 50
- 238000004519 manufacturing process Methods 0.000 description 37
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 28
- -1 polypropylene Polymers 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000012986 chain transfer agent Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 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
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- 229940106006 1-eicosene Drugs 0.000 description 2
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- ZORJPNCZZRLEDF-UHFFFAOYSA-N (3-methoxy-3-methylbutoxy)carbonyloxy (3-methoxy-3-methylbutyl) carbonate Chemical compound COC(C)(C)CCOC(=O)OOC(=O)OCCC(C)(C)OC ZORJPNCZZRLEDF-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 description 1
- SZVMZLJAAGWNPG-UHFFFAOYSA-N 1-tert-butylperoxyoctane Chemical compound CCCCCCCCOOC(C)(C)C SZVMZLJAAGWNPG-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-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
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- IISCRELTMNKFMH-UHFFFAOYSA-N 2-methoxypropan-2-yl 2-methoxypropan-2-yloxycarbonyloxy carbonate Chemical compound COC(C)(C)OC(=O)OOC(=O)OC(C)(C)OC IISCRELTMNKFMH-UHFFFAOYSA-N 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- SCUPJVKZFHVSDD-UHFFFAOYSA-N 2-methylpentan-2-yl 3,3-dimethylbutaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)CC(C)(C)C SCUPJVKZFHVSDD-UHFFFAOYSA-N 0.000 description 1
- YMMLZUQDXYPNOG-UHFFFAOYSA-N 2-methylpentan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)CCCCCC(C)(C)C YMMLZUQDXYPNOG-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- DFSWNYUWLQKNQP-UHFFFAOYSA-N [Ti].CC=CC=C Chemical compound [Ti].CC=CC=C DFSWNYUWLQKNQP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 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
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- PRIFGVOVRHAALC-UHFFFAOYSA-N tert-butyl 3,3-dimethylbutaneperoxoate Chemical compound CC(C)(C)CC(=O)OOC(C)(C)C PRIFGVOVRHAALC-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
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- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C—CHEMISTRY; METALLURGY
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The present invention relates to an ethylene resin composition and a molded article. The invention provides an ethylene resin composition which has excellent morphological stability at high temperature and strength retention at high temperature, excellent anti-blocking property and reduced fish eyes. An ethylene resin composition satisfying the conditions (A) > < D >. The melt flow rate under conditions (A) of 190 ℃ and a load of 2.16kg is 1.0g/10 min or more and 20.0g/10 min or less. < Condition (B) > Density is 920kg/m 3 945kg/m 3 The following is given. Condition (C) > in ARES temperature increase measurement, the average value of the maximum value M and the minimum value M of tan delta in the temperature range of 30 ℃ to 150 ℃ is reachedThe temperature of (M+m)/2 is 115 ℃ or higher and 145 ℃ or lower. In the ARES temperature increase measurement, the value of tan delta at 150 ℃ is 1.00 or more and 1.50 or less.
Description
Technical Field
The present invention relates to an ethylene resin composition and a molded article.
Background
The ethylene resin composition is molded by various molding methods and is used for various applications, and the required properties are different depending on the molding method and the application.
Typical applications of the ethylene resin composition include films. Specifically, a surface protective film for an optical member or the like is known. The surface protective film is used by being adhered to the surface of an adherend such as a metal plate, a resin plate, a wooden decorative plate, a nameplate, a liquid crystal member, an electric and electronic component, a building material, and an automobile component for the purpose of preventing the occurrence of damage or stains from the outside during processing, transportation, and storage.
In order to prevent the ethylene resin composition used for the surface protective film from damaging the substrate to be protected, it is required that fish eyes (hereinafter also referred to as "FE") are small. The FE refers to a small spherical foreign matter or a defective structure in a film produced using the vinyl resin composition.
As typical methods for producing the above-described ethylene resin composition having a small FE content, for example, a method of removing the composition by a sintered filter, a method of mixing a high-density polyethylene and a low-density polyethylene, and the like are known (for example, refer to patent documents 1 to 2).
As described above, the adherend as the object protected by the surface film may be subjected to a processing step in a state where the surface protective film is attached. For example, in the case of protecting an adherend exposed to a high temperature in a drying process, a molding process, or the like, a surface protective film having high heat resistance that does not shrink or curl due to heat and having morphological stability and strength even at a high temperature so that the adherend can be protected at a high temperature is required. Further, since the surface protective film is usually produced by being fed from a roll, it is important that the ethylene resin composition is easily fed from the roll when used as the outer layer of the surface protective film.
From the above viewpoints, an ethylene resin composition having excellent heat resistance, morphological stability at high temperature, and blocking resistance, and also having moderate flexibility is required.
As a method for obtaining a surface protective film having high heat resistance and excellent blocking resistance and flexibility, a method of blending a crystalline polypropylene polymer or elastomer into an ethylene resin is disclosed (for example, refer to patent document 3). This method is not preferable from the viewpoints of economy and reuse, and has a problem that there is room for improvement in terms of stability of morphology and strength maintained at high temperature. In patent document 3, FE is not verified. Further, from the economical point of view, it is demanded that the properties such as the form stability and strength which can be maintained at a high temperature be satisfied by using the ethylene resin composition alone without blending the crystalline polypropylene polymer or elastomer, but in recent years, there is a further demand for an ethylene resin composition which is excellent in heat resistance under a high temperature condition and also excellent in flexibility. However, there is a problem that the technology described in patent document 3 has not yet been improved in general in terms of heat resistance and flexibility in a trade-off relationship.
Further, as a method for obtaining an ethylene resin composition excellent in heat resistance and transparency, a method of mixing a high-density polyethylene and a low-density polyethylene is disclosed (for example, refer to patent document 4), but patent document 4 has verified that there is a problem that there is room for improvement in heat resistance at a temperature of 120 ℃ or higher, in the form stability at a high temperature, in the maintenance of strength at a high temperature, and in the reduction of FE under a high temperature, in the high temperature condition of about 120 ℃.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 4426441
Patent document 2: japanese patent No. 6792957
Patent document 3: japanese patent No. 6593168
Patent document 4: japanese patent application laid-open No. 2018-44122
Disclosure of Invention
Problems to be solved by the invention
As described above, conventionally, there has been a demand for an ethylene resin composition which is excellent in morphological stability at high temperature, strength retention at high temperature, and blocking resistance, and which achieves FE reduction.
Accordingly, in view of the above problems of the prior art, an object of the present invention is to provide an ethylene resin composition which is excellent in form stability at high temperature and strength retention at high temperature, is excellent in blocking resistance, and realizes FE reduction.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above-described problems of the prior art, and as a result, have found that an ethylene resin composition having the composition shown below and having specific properties can solve the above-described problems of the prior art, and have completed the present invention.
Namely, the present invention is as follows.
[1]
An ethylene resin composition satisfying the following conditions (A) > < conditions (D) >.
Condition (A) >, a method of producing a polypeptide
The melt flow rate of the ethylene resin composition under the conditions of 190 ℃ and a load of 2.16kg is 1.0g/10 min or more and 20.0g/10 min or less.
< condition (B) >)
The ethylene resin composition has a density of 920kg/m 3 945kg/m 3 The following is given.
Condition (C) >, a method of producing a polypeptide
In ARES temperature increase measurement, the average value (M+m)/2 of the maximum value M and the minimum value M of tan delta in the temperature range of 30 ℃ to 150 ℃ is 115 ℃ to 145 ℃.
Condition (D) >
In ARES temperature increase measurement, the value of tan delta at 150 ℃ is 1.00 to 1.50.
[2]
The vinyl resin composition as described in the above [1], wherein,
when the temperature is 170 ℃, the shearing speed is 10s -1 The melt viscosity of the ethylene resin composition measured under the conditions of (a) is X (Pa.s),
Will shear at 230℃for 10s -1 When the melt viscosity of the ethylene resin composition measured under the conditions of (a) is Y (Pa.s),
satisfies the following formula (1):
5≤(Y-X)/(170-230)≤25……(1)。
[3]
the vinyl resin composition as described in the above [1] or [2], wherein,
in the temperature-heat flow curve of the ethylene resin composition obtained by Differential Scanning Calorimetry (DSC), has two or more melting peaks, the melting peak temperature at the highest temperature side is 118 ℃ or more, and
the difference between the melting peak temperature at the highest temperature side and the melting peak temperature at the lowest temperature side is 10 ℃ or more and 30 ℃ or less.
[4]
As described above [1]]～[3]The ethylene resin composition according to any one of the preceding claims, wherein the ethylene resin composition has a density of 942kg/m 3 The high-density polyethylene has a density of 930kg/m 3 The following mixture of low density polyethylenes.
[5]
As described above [1]]～[4]The ethylene resin composition according to any one of claims, wherein the ethylene resin composition comprises 10 mass% or more and 50 mass% or less and has a density of 942kg/m 3 The above high density polyethylene.
[6]
A molded article of the ethylene resin composition according to any one of the above [1] to [5 ].
[7]
The molded article according to [6], wherein the molded article is a film.
Effects of the invention
According to the present invention, an ethylene resin composition having excellent morphology stability at high temperature and strength retention at high temperature, excellent blocking resistance, and reduced FE can be provided.
Drawings
Fig. 1 is a state diagram showing an example of the relationship between the maximum value M and the minimum value M of tan δ and the average value (m+m)/2 thereof in a temperature range of 30 ℃ to 150 ℃ in the ARES temperature increase measurement of the ethylene resin composition.
Detailed Description
Hereinafter, a mode for carrying out the invention of the present application (hereinafter referred to as "the present embodiment") will be described in detail.
The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following. The present invention can be implemented by various modifications within the scope of the gist thereof.
[ ethylene resin composition ]
The ethylene resin composition of the present embodiment satisfies the following conditions (A) > < conditions (D) >.
Condition (A) >, a method of producing a polypeptide
The melt flow rate of the ethylene resin composition under the conditions of 190 ℃ and a load of 2.16kg is 1.0g/10 min or more and 20.0g/10 min or less.
< condition (B) >)
The ethylene resin composition has a density of 920kg/m 3 945kg/m 3 The following is given.
Condition (C) >, a method of producing a polypeptide
In ARES temperature increase measurement, the average value (M+m)/2 of the maximum value M and the minimum value M of tan delta in the temperature range of 30 ℃ to 150 ℃ is 115 ℃ to 145 ℃.
Condition (D) >
In ARES temperature increase measurement, the value of tan delta at 150 ℃ is 1.00 to 1.50.
With the above configuration, an ethylene resin composition having excellent morphology stability at high temperature and strength retention at high temperature, excellent blocking resistance, and reduced FE can be obtained.
The ethylene resin composition of the present embodiment preferably satisfies the following conditions (E) > < conditions (G) >. Thus, an ethylene resin composition having excellent morphology stability at high temperature and strength retention at high temperature, excellent blocking resistance, and reduced FE can be obtained.
Condition (E) >, a method of producing a polypeptide
When the temperature is 170 ℃, the shearing speed is 10s -1 The melt viscosity of the ethylene resin composition measured under the conditions of (a) was X (Pa.s) and the shear rate was 10s at 230 DEG C -1 When the melt viscosity of the ethylene resin composition measured under the condition of (a) is Y (pa·s), the following formula (1) is satisfied.
(Y-X)/(170-230) 25 … … (1)
< condition (F) >)
In a temperature-heat flow curve of the ethylene resin composition obtained by Differential Scanning Calorimetry (DSC), there are two or more melting peaks, a melting peak temperature at a highest temperature side is 118 ℃ or more, and a difference between the melting peak temperature at the highest temperature side and the melting peak temperature at a lowest temperature side is 10 ℃ or more and 30 ℃ or less.
Condition (G) >
The ethylene resin composition contains 10-50 mass% of a polymer having a density of 942kg/m 3 The above high density polyethylene.
The content of the high-density polyethylene is more preferably 15 to 45% by mass, and still more preferably 20 to 40% by mass. Thus, an ethylene resin composition having excellent morphology stability at high temperature and strength retention at high temperature, excellent blocking resistance, and reduced FE can be obtained.
The ethylene resin composition of the present embodiment containsPolyethylene, particularly preferably having a density of 942kg/m 3 The high-density polyethylene has a density of 930kg/m 3 The following mixture of low density polyethylenes. Further preferably, the low density polyethylene comprises a high density polyethylene selected from the group consisting of high pressure low density polyethylene, linear low density polyethylene and other special ultra low density polyethylene. Of these, preferred are ethylene resin compositions comprising high-density polyethylene and high-pressure low-density polyethylene. Such an ethylene resin composition tends to have both heat resistance and flexibility while further reducing FE.
The polyethylene contained in the ethylene resin composition of the present embodiment may be an ethylene homopolymer or a copolymer of ethylene and an α -olefin.
The method for producing polyethylene is not particularly limited, and polyethylene produced by any one of a solution method, a high-pressure bulk method, a gas method, and a slurry method, which are generally used, may be used.
(melt flow Rate (MFR) at 190 ℃ C. Under a load of 2.16 kg)
As shown in the above-mentioned < condition (A) > the ethylene resin composition of the present embodiment has an MFR of 1.0g/10 min or more and 20.0g/10 min or less under a load of 2.16kg at 190 ℃. Preferably 2.0g/10 min or more and 15.0g/10 min or less, more preferably 3.0g/10 min or more and 10.0g/10 min or less.
The ethylene resin composition preferably has an MFR of 1.0g/10 min or more, which improves the drawdown of the film and suppresses film breakage.
Further, the ethylene resin composition preferably has an MFR of 20.0g/10 min or less, which can provide sufficient blocking resistance and is excellent in morphological stability at high temperatures.
The MFR of the ethylene resin composition can be controlled by adjusting the polymerization conditions of the polyethylene, specifically, the MFR of the ethylene resin composition can be controlled within the above numerical range by adjusting the selection of the kind of raw materials and the mixing ratio.
(Density)
The ethylene resin composition of the present embodiment has a density of 920kg/m 3 945kg/m 3 The following is given. Preferably 928kg/m 3 943kg/m of the above 3 Hereinafter, 930kg/m is more preferable 3 940kg/m above 3 The following is given.
The ethylene resin composition had a density of 920kg/m 3 The heat resistance of the film is improved as described above, and is therefore preferable. In addition, the ethylene resin composition had a density of 945kg/m 3 Hereinafter, a suitable flexibility can be obtained, and this is preferable.
The density of the ethylene resin composition was measured in accordance with JIS K7112, specifically, by the method described in examples described later.
The density of the ethylene resin composition can be controlled by adjusting the polymerization conditions of the polyethylene, specifically, the selection of the kind of raw materials and the mixing ratio are adjusted so that the density of the ethylene resin composition can be controlled within the above numerical ranges.
(ARES temperature increase measurement)
In the ethylene resin composition of the present embodiment, the average value (m+m)/2 of the maximum value M and the minimum value M of tan δ in the temperature range of 30 ℃ to 150 ℃ is 115 ℃ to 145 ℃ in the ARES temperature increase measurement.
In the ARES temperature increase measurement, the dynamic viscoelasticity is measured while heating the sample, so that the melting behavior of the sample and the viscoelasticity in a high temperature state can be analyzed. For example, the measurement can be performed by the following method.
The storage modulus (G ') and loss modulus (G') were measured using ARES-G2 manufactured by TA Instruments, inc., the gap distance was adjusted to 1mm to 2mm under a nitrogen atmosphere and parallel plates having a diameter of 8mm phi, and their ratio G '/G' was used as tan delta. The ethylene resin composition of the present embodiment was completely melted by heating the ethylene resin composition pellets for 30 minutes in a device set at 200 ℃. Then, the temperature was lowered from 200℃to 30℃at a rate of 5℃per minute. During cooling, considering shrinkage of the sample and the clamp caused by thermal expansion, the distance between the plates is adjusted so that normal stress is zero. Next, the dynamic viscoelasticity was measured while heating from 30℃to 150℃at a rate of 5℃per minute. The strain amount was measured while changing from 0.1% to 5.0% according to softening of the resin with temperature rise. The strain was measured from 0.1% and varied according to the softening of the resin.
(temperature at which the average value (M+m)/2 of the maximum value M and the minimum value M of tan delta is reached)
In the ethylene resin composition of the present embodiment, the average value (m+m)/2 of the maximum value M and the minimum value M of tan δ in the temperature range of 30 ℃ to 150 ℃ is 115 ℃ to 145 ℃ in the ARES temperature increase measurement. Preferably 118℃or more and 140℃or less, more preferably 120℃or more and 135℃or less.
Here, the temperature at which the average value (m+m)/2 of the maximum value M and the minimum value M of tan δ is reached represents the temperature at which the viscoelasticity of the ethylene resin composition changes viscously due to melting. Fig. 1 shows a state diagram of an example of a maximum value M and a minimum value M of tan δ and an average value (m+m)/2 thereof in a temperature range of 30 ℃ to 150 ℃ in the ARES temperature increase measurement of the ethylene resin composition.
When the temperature (M+m)/2 is 115℃or higher, the heat resistance is excellent, and when the temperature (M+m)/2 is 145℃or lower, the flexibility derived from the low-density component is preferably exhibited.
The temperature at which the average value (m+m)/2 of the maximum value M and the minimum value M of tan δ is reached can be controlled within the above-mentioned numerical range by adjusting the polymerization method, composition, and mixing method of the components contained in the ethylene resin composition. The method is not particularly limited, and for example, when the low-density polyethylene contains 10 mass% or more of a high-density polyethylene having a melting point of 118 ℃ or more, the heat resistance of the ethylene resin composition is improved, and the temperature at which the average value (m+m)/2 of the maximum value M and the minimum value M of tan δ is reached can be adjusted to 115 ℃ or more.
For example, the temperature up to (M+m)/2 can be adjusted to 145℃or lower by adding 50 mass% or less of a high-density polyethylene having a melting point of 118℃or higher to the low-density polyethylene or by not using an ultra-high molecular weight component such as an ultra-high-molecular-weight polyethylene having a weight average molecular weight of 100 ten thousand g/mol or higher.
On the other hand, high density polyethylene with a large difference in melting point is generally incompatible with low density polyethylene. When the high-density polyethylene is not sufficiently dispersed, the low-density polyethylene as a matrix is melted, and the temperature tends to be low at the average value (m+m)/2 of the maximum value M and the minimum value M of tan δ.
When the high-density polyethylene is sufficiently dispersed in the low-density polyethylene, the temperature (m+m)/2 becomes 115 ℃ or higher, and the heat resistance of the ethylene resin composition tends to be improved. The reason for this is that the high-density polyethylene is sufficiently dispersed in the low-density polyethylene at a molecular level, whereby the low-density polyethylene is hindered from relaxing in orientation and moving in molecular.
As a method for sufficiently dispersing and mixing the low-density polyethylene and the high-density polyethylene, there is no particular limitation, and a method in which the two kinds of particles are sufficiently dry-mixed with each other and then melt-blended using a single screw extruder is preferable. In addition, the high-density polyethylene and the low-density polyethylene are preferably dispersed easily and uniformly by appropriately changing the rotation speed of the extruder and controlling the variation of the resin pressure within 5 MPa. In addition, in the step of granulating the polymer powder in the slurry polymerization process of the high-density polyethylene, the low-density polyethylene is mixed in advance as about 5 mass% of the additive, and in the subsequent mixing step of the high-density polyethylene and the low-density polyethylene, the compatibility of the high-density polyethylene and the low-density polyethylene is improved, so that it is preferable. In addition, it is preferable to control the active state of the Ziegler-Natta catalyst by adjusting the composition of the liquid co-catalyst component used in the polymerization of the high-density polyethylene, and to generate trace amounts of the high-molecular weight component and the low-molecular weight component in the high-density polyethylene, thereby improving the compatibility with the low-density polyethylene.
(tan delta value at 150 ℃ C.)
In the ethylene resin composition of the present embodiment, the tan δ value at 150 ℃ in the ARES temperature increase measurement is 1.00 or more and 1.50 or less. Preferably 1.05 to 1.40, more preferably 1.10 to 1.30.
Here, the value of tan δ at 150 ℃ of the ethylene resin composition indicates viscoelasticity in a molten state at a temperature equal to or higher than the melting point, and by definition of tan δ, a smaller value of tan δ indicates more elasticity.
When the value of tan δ is 1.00 or more, the fluidity is high to some extent, and thus film molding can be performed by a T-die, which is preferable. In addition, when the value of tan δ is 1.50 or less, the melt state has sufficient elasticity, and the form stability and strength at high temperature are excellent, so that it is preferable. Further, it is preferable to disperse FE derived from the unmelted resin by having sufficient elasticity even during kneading in an extruder.
The value of tan delta at 150℃of the ethylene resin composition can be controlled within the above-mentioned numerical range by adjusting the polymerization method, composition and mixing method of the components contained in the ethylene resin composition. Examples of the method include a method of containing 50 mass% or more of a low-density polyethylene having a large number of long-chain branches. Thus, the entanglement of the molecular chains maintains a certain degree of elasticity even in a molten state, and the tan δ value at 150 ℃ tends to be 1.00 or more and 1.50 or less. The method for producing the ethylene resin composition containing 50 mass% or more of the low-density polyethylene having a large amount of long chain branches is not particularly limited, and examples thereof include a method of adjusting the polymerization temperature, the polymerization pressure, the type of the polymerization initiator or chain transfer agent, the type of the polymerization reactor, and the temperature of the ethylene gas supplied to the polymerization reactor. For example, by heating a pipe immediately before a polymerization reactor with steam or the like, and polymerizing the ethylene gas at about 150 ℃ with forced stirring, the entire polymerization reactor is in a nearly homogeneous state, and thus there is a tendency that a polymer having a large number of branching points is produced and an ethylene resin composition containing 50 mass% or more of low-density polyethylene having a large number of long-chain branches is obtained.
(melt viscosity at 170 ℃ C., 230 ℃ C.)
The ethylene resin composition of the present embodiment was subjected to shearing at 170℃for 10s -1 The melt viscosity measured under the conditions of (2) was X (Pa.s) and the shear rate was 10s at 230 DEG C -1 When the melt viscosity measured under the condition of (2) is Y (Pa.s), the ratio of (Y-X)/(170-230) is preferably 5 to 25. More preferably 7 to 22, still more preferably 10 to 20.
(Y-X)/(170-230) represents the degree of change in melt viscosity with respect to the change in temperature.
When the value of the above formula is 5 or more, film forming property and processability in a temperature range of 170 to 230 ℃ are excellent, and thus preferable. When the value of the above formula is 25 or less, the melt viscosity is not easily lowered with respect to a change in temperature, and the morphology stability at high temperature is excellent, which is preferable.
(Y-X)/(170-230) can be controlled by adjusting the branched structure of the polyethylene contained in the vinyl resin composition. As a method for adjusting the branched structure of polyethylene, there is mentioned a method for adjusting polymerization conditions such as polymerization temperature, polymerization pressure, and kind of polymerization initiator.
Further, in order to produce an ethylene resin composition in which the value of (Y-X)/(170-230) is controlled in the range of 5 to 25, it is effective to control the branched structure of the low-density polyethylene more precisely. As a method for this, for example, a method of adjusting the type of the polymerization reactor and the temperature of the ethylene gas supplied to the polymerization reactor is effective. By heating a pipe immediately before the polymerization reactor with steam or the like, ethylene gas is adjusted to about 150 ℃ and polymerization is carried out under forced agitation, whereby the polymerization reactor as a whole becomes a nearly homogeneous state, and thus polyethylene having a large number of branching points is easily produced. The low-density polyethylene obtained by polymerization in this manner is preferably used as a raw material because the decrease in melt viscosity due to temperature change is small. That is, by adjusting the content of polyethylene having a large number of branching points, the degree of decrease in melt viscosity under a temperature change can be controlled, and the value of (Y-X)/(170-230) can be controlled within the numerical range of 5 to 25 as described above.
The melt viscosity of the ethylene resin composition can be measured by the method described in examples described below.
(temperature-heat flow curve obtained by Differential Scanning Calorimetry (DSC))
The ethylene resin composition of the present embodiment has two or more melting peaks in a temperature-heat flow curve (hereinafter also referred to as "DSC curve") obtained by Differential Scanning Calorimetry (DSC), and the melting peak temperature on the highest temperature side is 118 ℃ or higher, and the difference between the melting peak temperature on the highest temperature side and the melting peak temperature on the lowest temperature side is preferably 10 ℃ or higher and 30 ℃ or lower. More preferably at 12℃to 28℃and still more preferably at 15℃to 25 ℃.
By observing two or more melting peaks, it was found that the high-density polyethylene and the low-density polyethylene were contained.
Examples of the method for obtaining the above-mentioned ethylene resin composition include a method of mixing a high-density polyethylene with a low-density polyethylene. In particular, by mixing a high-density polyethylene having a melting point of 118 ℃ or higher with a low-density polyethylene having a melting point of 108 ℃ or lower, an ethylene resin composition having a melting peak temperature of 118 ℃ or higher on the highest temperature side and a difference between the melting peak temperature on the highest temperature side and the melting peak temperature on the lowest temperature side of 10 ℃ or higher and 30 ℃ or lower can be obtained.
The difference between the melting peak temperature at the highest temperature side and the melting peak temperature at the lowest temperature side is 10 ℃ or more, whereby a vinyl resin composition and a film having both heat resistance by high-density polyethylene and flexibility by low-density polyethylene can be obtained, which is preferable. The difference between the melting peak temperature at the highest temperature side and the melting peak temperature at the lowest temperature side is 30 ℃ or less, and the high-density polyethylene and the low-density polyethylene are preferably mixed appropriately.
Measurement by DSC was performed by the method described in the examples.
[ molded article ]
The molded article of the present embodiment is a molded article of the ethylene resin composition of the present embodiment, and examples thereof include films. When the film is a multilayer film, the ethylene resin composition of the present embodiment may be used for the outermost layer or the intermediate layer.
[ method for producing vinyl resin composition ]
The ethylene resin composition of the present embodiment can be produced by, for example, melt-kneading a high-density polyethylene (a) and a low-density polyethylene (B), but is not particularly limited.
Examples of the melt kneader used in the kneading operation include a single screw extruder, a twin screw extruder, a vented extruder, and a tandem extruder. In particular, in order to improve the dispersibility of the high-density polyethylene and the low-density polyethylene, it is preferable that the pellets are sufficiently dry-blended with each other and then melt-kneaded by a single screw extruder. In order to suppress the uneven mixing of the high-density polyethylene and the low-density polyethylene, it is preferable to appropriately change the rotation speed of the extruder and to control the variation of the resin pressure to 5MPa or less.
(Process for producing high-Density polyethylene)
The high-density polyethylene (a) can be produced, for example, by a continuous slurry polymerization method.
The catalyst used in the production is not particularly limited, and examples thereof include: metallocene catalysts, ziegler-Natta catalysts, phillips catalysts, and the like. By using a Ziegler-Natta catalyst having a plurality of active sites, the molecular weight distribution becomes broader, and the compatibility with low-density polyethylene is improved, so that it is preferable. In general, the physical properties of the high-density polyethylene (a) can be controlled by adjusting the comonomer concentration, the hydrogen concentration, and the cocatalyst type in addition to the polymerization temperature, the polymerization pressure, and the catalyst type.
In the case where the high-density polyethylene (a) and the low-density polyethylene (B) described later are copolymers of ethylene and other comonomers, examples of the comonomers include: a compound selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, styrene, and derivatives thereof; a cyclic olefin having 3 to 20 carbon atoms selected from the group consisting of cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene and 2-methyl-1, 4,5, 8-dimethylene-1, 2,3, 4a,5,8 a-octahydronaphthalene; the linear, branched or cyclic diene having 4 to 20 carbon atoms selected from the group consisting of 1, 3-butadiene, 1, 4-pentadiene, 1, 5-hexadiene, 1, 4-hexadiene, 1, 7-octadiene and cyclohexadiene, but is not limited thereto. In this embodiment, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like are particularly preferable.
The polymerization temperature of the high-density polyethylene (A) is preferably 30℃or more and 100℃or less. The polymerization temperature is 30 ℃ or higher, whereby an industrially more efficient production can be achieved, while the polymerization temperature is 100 ℃ or lower, whereby a more stable operation can be continuously achieved.
The polymerization pressure of the high-density polyethylene (a) is usually preferably not less than normal pressure and not more than 2MPa, more preferably not less than 0.1MPa and not more than 1.5MPa, still more preferably not less than 0.1MPa and not more than 1.0 MPa.
In order to produce the high-density polyethylene (a), it is preferable to use a cocatalyst and add the cocatalyst in order to exhibit polymerization activity by reducing a titanium source.
Examples of the cocatalyst include: triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and the like. Triethylaluminum and triisobutylaluminum are particularly preferable. In addition, when two cocatalysts having different reducibility are simultaneously added to the polymerization reactor, polymerization is performed in a state having a plurality of active sites, and a trace amount of low molecular weight component and high molecular weight component are produced, so that compatibility with the low density polyethylene (B) described later is improved, and thus it is preferable.
Examples of the method for adjusting the molecular weight of the high-density polyethylene (a) include: as described in the specification of german patent application publication No. 3127133, a method of allowing hydrogen to exist in a polymerization system and a method of changing a polymerization temperature are disclosed. The molecular weight can be controlled within an appropriate range by adding hydrogen as a chain transfer agent to the polymerization system.
As a method for adjusting the density of the high-density polyethylene (a), for example, there may be mentioned: and a method for incorporating the above comonomer in the polymerization system. By adding a comonomer in the polymerization system, the density can be controlled within an appropriate range.
Examples of the solvent separation method include decantation, centrifugation, and filter filtration, and more preferably centrifugation with good separation efficiency of the ethylene polymer from the solvent.
The polymer powder of the high-density polyethylene (A) is pelletized into pellets by means of a single screw extruder, a twin screw extruder, a vented extruder, a tandem extruder, or the like. The type of extruder and the number of extrusion times are not particularly limited, and kneading is preferably performed by a twin-screw extruder. In addition, when kneading by a twin screw extruder, the addition of the low-density polyethylene (B) described below in an amount of about 5 mass% relative to the powder obtained by slurry polymerization is preferable because the compatibility with the low-density polyethylene (B) is improved in the subsequent mixing step.
(Process for producing Low Density polyethylene)
As the low-density polyethylene (B), a high-pressure process low-density polyethylene is preferable.
The high-pressure low-density polyethylene can be obtained, for example, by radical polymerization of ethylene in an autoclave reactor or a tubular reactor, but is not particularly limited. In the case of using an autoclave type reactor, the polymerization conditions may be set to a temperature of 200 to 300 ℃ and a polymerization pressure of 100 to 250MPa in the presence of a peroxide, while in the case of using a tubular reactor, the polymerization conditions may be set to a polymerization peak temperature of 180 to 400 ℃ and a polymerization pressure of 100 to 400MPa in the presence of a peroxide and a chain transfer agent.
The physical properties of the resulting low-density polyethylene (B) can be controlled by adjusting the polymerization temperature, polymerization pressure, type of peroxide, and presence or absence of a chain transfer agent.
The peroxide is not particularly limited, and examples thereof include: methyl ethyl ketone peroxide, ketone peroxide (specifically, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) cyclohexane, 2-bis (t-butylperoxy) octane, n-butyl 4, 4-bis (t-butylperoxy) valerate, 2-bis (t-butylperoxy) butane, etc.), hydroperoxides (specifically, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1, 3-tetramethylbutyl hydroperoxide, etc.), dialkyl peroxides (specifically, di-t-butyl peroxide, dicumyl peroxide, bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-di (t-butylperoxy) -3-hexyne, etc.), diacyl peroxide (specifically, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, 3, 5-trimethylhexanoyl peroxide, benzoyl peroxide, etc.), peroxydicarbonates (specifically, diisopropyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, di (methoxyisopropyl) peroxydicarbonate, etc.), and the like, bis (3-methyl-3-methoxybutyl) peroxydicarbonate, diallyl peroxydicarbonate, and the like), peroxyesters (specifically, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxyoctoate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3, 5, 6-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, cumyl peroxyoctoate, t-hexyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxyneohexanoate, t-hexyl peroxyneohexanoate, cumyl peroxyneohexanoate, and the like), acetyl cyclohexyl sulfonyl peroxide, t-butyl peroxyallylcarbonate, and the like.
The chain transfer agent is not particularly limited, and various physical properties can be adjusted by stopping radicals of the growing polymer by using hydrocarbon compounds such as propane, propylene, butane, and the like.
Further, since the temperature of ethylene supplied to the polymerization reactor and the temperature of the polymer immediately after the discharge from the polymerization reactor affect the branched structure of the polymer, it is preferable to control the temperature of ethylene supplied to the polymerization reactor to 150 ℃ or higher by heating the pipe immediately before the polymerization reactor with steam as described above, since the polymerization reactor is in a homogeneous state, free radicals are easily brought into contact with the polymer, and a polymer having a large number of branching points is easily produced.
Examples of the method for controlling the molecular weight and density of the low-density polyethylene include: a method of changing the polymerization temperature or pressure, and a method of allowing the chain transfer agent described above to be present in the polymerization system. By adjusting the above conditions, the molecular weight and density can be controlled within appropriate ranges.
(additive)
The ethylene resin composition of the present embodiment may further contain additives such as antioxidants, light stabilizers, slip agents, fillers, antistatic agents, and the like.
Examples
The present embodiment will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples.
The measurement method and evaluation method of each physical property and characteristic are described below.
[ method for measuring physical Properties ]
((physical Property 1) Melt Flow Rate (MFR) at 190 ℃ C., load of 2.16 kg)
The ethylene resin compositions and raw materials obtained in examples and comparative examples were numbered D by JIS K7210: 1999 (temperature=190 ℃, load=2.16 kg) the melt flow rate (g/10 min) was measured.
((physical Property 2) Density)
The ethylene-based compositions and raw materials obtained in examples and comparative examples were prepared by the method of JIS K7112: 1999. density (kg/m) was measured by the Density gradient tube method (23 ℃ C.) 3 )。
(physical Property 3) ARES temperature increase measurement
The storage modulus (G ') and loss modulus (G') were measured using a parallel plate having a diameter of 8mm phi under a nitrogen atmosphere with the gap distance set to 1mm to 2mm using ARES-G2 manufactured by TA Instruments, and their ratio G '/G' was used as tan delta.
The ethylene resin compositions of examples and comparative examples described below were heated in a device set at 200℃for 10 minutes to 30 minutes to completely melt the compositions. Then, the temperature was lowered from 200℃to 30℃at a rate of 5℃per minute. During cooling, considering shrinkage of the sample and the clamp caused by thermal expansion, the distance between the plates is adjusted so that normal stress is zero. Next, the dynamic viscoelasticity was measured while heating from 30℃to 150℃at a rate of 5℃per minute. The strain amount was measured while changing from 0.1% to 5.0% according to softening of the resin with temperature rise. The strain was measured from 0.1% and changed according to the softening of the vinyl resin composition. Specifically, the strain is increased so that the torque is not less than 1g cm. The strain at 30℃was 0.1% and the strain at 150℃was 5.0%.
The device comprises: ARES-G2 (TA Instruments Co., ltd.)
Atmosphere: nitrogen gas
Geometry: 8mm phi parallel plate
Gap: 1.0mm to 2.0mm
Strain: 0.1% -5.0% (changed according to the state)
Measuring temperature: 30-150 DEG C
Heating/cooling rate: 5 ℃/min
The tan delta obtained by the ARES temperature increase measurement was calculated, and the temperature (. Degree.C.) at which the average value (M+m)/2 of the maximum value M and the minimum value M was reached was calculated. Further, the value of tan delta at 150℃was obtained.
(determination of melt viscosity of physical Property 4)
Melt viscosities of the ethylene resin compositions of examples and comparative examples described below were measured using a capillograph 1D manufactured by Toyo Seisakusho Co., ltd. And using a capillary having a capillary length of 50.80mm and a capillary diameter of 0.77mm under conditions that the piston lowering speed was 0.15 mm/min to 40.00 mm/min.
The measurement was performed at a temperature of 170℃and 230 ℃.
The shear rate was calculated from the piston descent rate and capillary diameter, and the shear rate was set at 170℃for 10s -1 The melt viscosity measured under the conditions of (2) was X (Pa.s) and the shear rate was 10s at 230 DEG C -1 The melt viscosity measured under the conditions of (3) was defined as Y (Pa.s), and the value of (Y-X)/(170-230) was calculated.
(physical Property 5) DSC measurement
Differential scanning calorimetric analysis (DSC) was performed using a DSC-7 type differential scanning calorimeter manufactured by Perkin Elmer, and a DSC curve (temperature-heat flow curve) was obtained under the following conditions in accordance with the following procedure.
(1) About 5mg of the ethylene resin compositions produced in examples and comparative examples were charged into an aluminum pan, heated to 200℃at 200℃per minute, and held at 200℃for 5 minutes.
(2) Then, the temperature was lowered from 200℃to 50℃at a temperature-lowering rate of 10℃per minute, and the mixture was kept for 5 minutes after the completion of the temperature lowering.
(3) Then, the temperature was raised from 50℃to 200℃at a temperature-raising rate of 10℃per minute.
The highest temperature at the position of the melting peak was taken as the melting point (. Degree. C.) according to the DSC curve observed during the above-mentioned (3).
In the DCS curves, the number of melting peaks, the melting peak temperature (c) at the highest temperature side, and the difference (c) between the melting peak temperature at the highest temperature side and the melting peak temperature at the lowest temperature side were calculated.
[ evaluation method ]
(evaluation 1) number of FE' s
The ethylene resin composition was molded using a T-die film-forming machine (HM 40N, screw diameter 40mm, die width 300mm, manufactured by North Ind Co., ltd.) at a barrel temperature of 200℃and a die temperature of 210℃with an extrusion amount of 5 kg/hr.
The film comprising the ethylene resin composition was obtained by trimming 50mm on each of both ends to a thickness of 35. Mu.m, and the film area was visually evaluated for 400cm 2 The length of the long axis is more than 0.1mm and the number N3 of FE.
The index X of FE was defined by "x=n3/(n1×a+n2×b)" using the number N1 of FEs of the high-density polyethylene (a) alone film as a raw material, the mass ratio a of the high-density polyethylene (a) when the entire ethylene resin composition was 1, the number N2 of FEs of the low-density polyethylene (B) alone film as a raw material, and the mass ratio B of the low-density polyethylene (B) when the entire ethylene resin composition was 1, and evaluated as follows.
In the case of using two or more kinds of low-density polyethylene (B), the term of the low-density polyethylene as a denominator is increased according to the number.
And (3) the following materials: 0.5 or less
O: greater than 0.5 and less than or equal to 0.7
Delta: greater than 0.7 and less than or equal to 1.0
X: greater than 1.0
(evaluation 2) evaluation of Heat shrinkage resistance
The film obtained in the above (evaluation 1) was cut into a width of 5 cm. Times.length of 5cm, and the heat shrinkage resistance was tested in an atmosphere of 130℃under 2 atmospheres and a humidity of 100% RH.
The temperature was raised from normal temperature to 130℃and then kept at 130℃for 20 minutes. The pressure was reduced and cooled for 5 minutes, and then the sample was taken out. When the length of the side having the greatest shrinkage was L (cm), the heat shrinkage (%) was calculated from (5-L)/5X 100, and evaluated according to the following criteria.
And (3) the following materials: less than 20%
O: more than or equal to 20 percent and less than 30 percent
Delta: more than or equal to 30 percent and less than 40 percent
X: more than 40 percent
(evaluation 3 evaluation of strength retention at high temperature)
The film obtained in the above (evaluation 1) was cut into 5cm width by 5cm length, and four corners of the film were attached to a slide glass using a double-sided tape cut into 0.5cm width by 0.5cm length, thereby preparing a sample.
The sample was subjected to an evaluation test for strength retention in an atmosphere of 2 atmospheres at 150℃and 100% RH.
The temperature was raised from normal temperature to 150℃and then kept at 150℃for 20 minutes.
After this sample was taken out, a scratch test was performed in accordance with the method described in JIS K5600-5-4 within 5 minutes.
The surface of the slide after the test using a pencil of hardness F was observed, and the strength retention at high temperature was evaluated according to the following criteria.
And (2) the following steps: no scratches were observed on the slide.
Delta: a few scratches were observed on the slide.
X: a large number of scratches were observed on the slide.
((evaluation 4) 20 degree gloss)
The GLOSS was measured at an incident angle of 20℃in accordance with ASTM D523 (2457) for 10-point film samples randomly cut from the film obtained in the above (evaluation 1) using GLOSS METER GM-26D manufactured by color technology research, inc.
The average value of the obtained gloss values was used as an index of blocking resistance and evaluated as follows.
And (3) the following materials: less than 15.0%
O: 15.0% or more and 30.0% or less
Delta: 30.0% or more and 45.0% or less
X: 45.0% or more
[ preparation of the ingredients used in examples and comparative examples ]
(high Density polyethylene (A))
Preparation of Ziegler-Natta catalyst (a)
Into an 8L stainless steel autoclave which had been sufficiently replaced with nitrogen gas, 2mol/L of hydroxyl group was charged1000mL of a hexane solution of chlorotrichlorosilane was stirred at 65℃and AlMg was added dropwise over 4 hours 5 (C 4 H 9 ) 11 (OC 4 H 9 ) 2 2550mL (equivalent to 2.68 moles of magnesium) of a hexane solution of the organomagnesium compound was shown, and then the reaction was continued while stirring at 65℃for 1 hour.
After the completion of the reaction, the supernatant was removed, and the mixture was washed with 1800mL of hexane 4 times to obtain a solid as a carrier. As a result of analysis of this solid, the amount of magnesium contained in each 1g of the solid was 8.31 mmol.
110mL of a hexane solution of 1mol/L titanium tetrachloride and 1mol/L AlMg were simultaneously added to 1970mL of a hexane slurry containing 110g of the above carrier with stirring at a temperature of 10℃for 1 hour 5 (C 4 H 9 ) 11 (OSiH) 2 110mL of a hexane solution of the organomagnesium compound shown. After the addition, the reaction was continued at 10℃for 1 hour. After the completion of the reaction, 1100mL of the supernatant was removed and washed 2 times with 1100mL of hexane, thereby preparing a Ziegler-Natta catalyst (a).
Preparation of metallocene catalyst (b)
Average particle diameter of 15 μm and surface area of 70m 2 The spherical silica having/g and an intraparticle pore volume of 1.8mL/g was calcined at 500℃for 5 hours under a nitrogen atmosphere to be dehydrated, thereby obtaining dehydrated silica.
The amount of surface hydroxyl groups of dehydrated silica relative to 1g of SiO 2 1.85 mmoles/g.
40g of the dehydrated silica was dispersed in 800mL of hexane in an autoclave having a capacity of 1.8L under a nitrogen atmosphere, to thereby obtain a slurry. 80mL of a hexane solution of triethylaluminum (concentration: 1 mol/L) was added to the obtained slurry while keeping at 50℃with stirring, and then, triethylaluminum was allowed to react with the surface hydroxyl groups of silica with stirring for 2 hours, thereby obtaining a composition containing triethylaluminum-treated silica and supernatant and in which the surface hydroxyl groups of triethylaluminum-treated silica were blocked with triethylaluminum.
Then, the supernatant in the resulting reaction mixture was removed by decantation, thereby removing unreacted triethylaluminum in the supernatant.
Then, an appropriate amount of hexane was added to obtain 880mL of hexane slurry of triethylaluminum-treated silica (component [ c ]).
On the other hand, [ (N-tert-butylamino) (tetramethyl-. Eta.5-cyclopentadienyl) dimethylsilane]200 mmol of titanium-1, 3-pentadiene (hereinafter referred to as "titanium complex") was dissolved in 1000mL of Isopar E (trade name of hydrocarbon mixture manufactured by Exxon chemical Co., ltd., U.S.A.), and AlMg of the formula previously synthesized from triethylaluminum and dibutylmagnesium was added 6 (C 2 H 5 ) 3 (n-C 4 H 9 ) y 20mL of 1mol/L hexane solution, and then hexane was added to adjust the concentration of the titanium complex to 0.1mol/L, thereby obtaining component [ d ]]。
In addition, 5.7g of bis (hydrogenated tallow) methyl ammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter referred to as "borate compound") was added and dissolved in 50mL of toluene, to thereby obtain a 100 mmol/L toluene solution of the borate compound. To the toluene solution of the borate compound was added 5mL of a 1mol/L hexane solution of diethylaluminum ethoxide at room temperature, and then hexane was added so that the borate concentration in the solution reached 70 mmol/L. Then, the mixture was stirred at room temperature for 1 hour, thereby obtaining a reaction mixture containing a borate compound.
46mL of this reaction mixture containing a borate compound was added to 800mL of the slurry of the component [ c ] obtained above while stirring at 15℃to 20℃to support the borate compound on silica. Thus, a slurry of silica loaded with a borate compound was obtained. Then, 32mL of the above-obtained component [ d ] was added thereto, and the mixture was stirred for 3 hours to react the titanium complex with the borate compound. Thus, a supported metallocene catalyst (b) comprising silica and a supernatant and having a catalyst active material formed on the silica was obtained.
< production of high Density polyethylene (A-1) >)
A vessel-type 280L polymerization reactor equipped with a stirring device was used to conduct continuous polymerization at a polymerization temperature of 80℃under a polymerization pressure of 0.80MPa and an average residence time of 1.6 hours. Dehydrated n-hexane was supplied as a solvent at 40L/hr, the Ziegler-Natta catalyst [ a ] was supplied as a catalyst at 0.4 g/hr, triisobutylaluminum was supplied as a liquid co-catalyst component at 12 mmol/hr in terms of Al atom, and triethylaluminum was supplied at 12 mmol/hr in terms of Al atom. The hydrogen for adjusting the molecular weight was supplied in a manner of 40.2 mol% with respect to the gas phase concentration of ethylene and 1-butene, and 1-butene was supplied in a manner of 0.52 mol% with respect to the gas phase concentration of ethylene, thereby polymerizing ethylene and 1-butene.
The dehydrated n-hexane was supplied from the bottom of the polymerization reactor, the hydrogen was supplied from the middle between the liquid surface and the bottom of the polymerization reactor together with the catalyst from the catalyst introduction line for the purpose of contact with the catalyst in advance, and the ethylene was supplied from the bottom of the polymerization reactor.
The polymerization slurry in the polymerization reactor was introduced into a flash tank having a pressure of 0.08MPa and a temperature of 75 ℃ in such a manner that the liquid surface of the polymerization reactor was kept constant, and unreacted ethylene, 1-butene and hydrogen were separated.
Next, the polymerization slurry is continuously fed into a centrifuge in such a manner that the liquid surface of the polymerization reactor is kept constant, and the polymer and the solvent or the like other than the polymer are separated. The content of the solvent or the like in this case was 45%.
The separated high-density polyethylene powder was dried at 85 ℃ while blowing nitrogen.
Next, 300 mass ppm of pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] as an antioxidant was added to the obtained powder, and then 5 mass% of pellets of the low density polyethylene (B-1) described below were added, and melt-kneaded and pelletized at a temperature of 200℃by using a TEX-44 twin screw extruder manufactured by Nippon Steel Co., ltd.) to obtain a high density polyethylene (A-1).
The density of the resulting high-density polyethylene (A-1) was 960kg/m 3 MFR of 10.0g/10 min.
< production of high Density polyethylene (A-2) >)
The same procedure as for the above-mentioned high-density polyethylene (A-1) was conducted except that the low-density polyethylene (B-1) was not added to the polymer powder, thereby obtaining a high-density polyethylene (A-2). The density of the resulting high-density polyethylene (A-2) was 965kg/m 3 The MFR was 12.0g/10 min.
< production of high Density polyethylene (A-3) >)
The same operation as that of the above-mentioned high-density polyethylene (A-1) was conducted except that triisobutylaluminum as a liquid cocatalyst component was supplied at 24 mmol/hr in terms of Al atom, thereby obtaining a high-density polyethylene (A-3).
The density of the resulting high-density polyethylene (A-3) was 960kg/m 3 The MFR was 11.0g/10 min.
< production of high Density polyethylene (A-4) >)
The same operation as that of the above-mentioned high-density polyethylene (A-1) was conducted except that triisobutylaluminum as a liquid cocatalyst component was supplied at 24 mmol/hr in terms of Al atom and the low-density polyethylene (B-1) was not added to the polymerization powder, thereby obtaining a high-density polyethylene (A-4).
The density of the resulting high-density polyethylene (A-4) was 960kg/m 3 The MFR was 11.0g/10 min.
< production of high Density polyethylene (A-5) >)
The same operation as that of the high-density polyethylene (A-1) was conducted except that the hydrogen gas for adjusting the molecular weight was supplied so as to be 20.2 mol% with respect to the gas phase concentration of ethylene and 1-butene, and 1-butene was supplied so as to be 0.96 mol% with respect to the gas phase concentration of ethylene, thereby obtaining a high-density polyethylene (A-5).
The density of the resulting high-density polyethylene (A-5) was 945kg/m 3 The MFR was 5.0g/10 min.
< production of high Density polyethylene (A-6) >)
The prepared supported metallocene catalyst (b), liquid co-catalyst component, hexane as a solvent, and ethylene as a monomer were used to perform continuous secondary polymerization, thereby producing high-density polyethylene (a-6).
In the first stage reaction polymerizer, the temperature was 60℃and the total pressure was 0.25MPa, the 1-butene content was 0.05 mol% with respect to the gas phase concentration of ethylene, and the hydrogen content was 0.13 mol% with respect to the gas phase concentration of ethylene and 1-butene.
In the second stage reaction polymerizer, the temperature was 75℃and the total pressure was 0.85MPa, the 1-butene content was 1.2 mol% with respect to the gas phase concentration of ethylene, and the hydrogen content was 0.11 mol% with respect to the gas phase concentration of ethylene and 1-butene.
The obtained high-density polyethylene powder was melt kneaded at a temperature of 200℃and pelletized by a TEX-44 twin-screw extruder manufactured by Nippon Steel Co., ltd., without using an additive such as a neutralizing agent or an antioxidant, thereby obtaining high-density polyethylene (A-6).
The density of the resulting high-density polyethylene (A-6) was 941kg/m 3 The MFR was 1.0g/10 min.
< production of high Density polyethylene (A-7) >)
The hydrogen for adjusting the molecular weight was supplied at a concentration of 60.2 mol% relative to the gas phase concentration of ethylene and 1-butene, and 1-butene was not used. The same operation as that of the above-mentioned high-density polyethylene (A-1) was conducted under other conditions, whereby a high-density polyethylene (A-7) was obtained.
The density of the resulting high-density polyethylene (A-7) was 965kg/m 3 The MFR was 28.0g/10 min.
(Low Density polyethylene (B))
< production of Low Density polyethylene (B-1) >)
In an autoclave reactor, a polymerization temperature was 259℃and a polymerization pressure was 128.1MPa, and a low-density polyethylene (B-1) was obtained by polymerization using t-butyl peroxyacetate as a polymerization initiator.
The temperature of ethylene supplied to the polymerization reactor was adjusted to 165℃by heating the pipe immediately before the polymerization reactor with steam.
The obtained productThe resulting low-density polyethylene (B-1) was processed into pellets using a single screw extruder. Density of 920kg/m 3 The MFR was 2.0g/10 min.
< production of Low Density polyethylene (B-2) >)
In a tubular reactor, the polymerization temperature was 280℃and the polymerization pressure was 200MPa, and 1.2 mol% of the ethylene raw material was changed to propylene by using tert-butyl peroxy-2-ethylhexanoate as a polymerization initiator, and polymerization was carried out, thereby obtaining a low-density polyethylene (B-2).
The temperature of ethylene supplied to the polymerization reactor was adjusted to 155℃by heating the pipe immediately before the polymerization reactor with steam.
The density of the resulting low-density polyethylene (B-2) was 924kg/m 3 The MFR was 4.0g/10 min.
< production of Low Density polyethylene (B-3) >)
The same operation as that of the low-density polyethylene (B-1) was performed except that the pipe immediately before the polymerization reactor was not heated with steam, thereby obtaining a low-density polyethylene (B-3).
The temperature of the ethylene fed to the polymerization reactor was 115 ℃.
The density of the resulting low-density polyethylene (B-3) was 920kg/m 3 The MFR was 2.0g/10 min.
< production of Low Density polyethylene (B-4) >)
The same operation as for the low-density polyethylene (B-1) was conducted except that the polymerization temperature was 245℃and the polymerization pressure was 170.0MPa, 18.5 mol% of the ethylene raw material was changed to butane, and the piping immediately before the polymerization reactor was not heated, thereby obtaining a low-density polyethylene (B-4).
The ethylene supplied to the polymerization reactor had a temperature of 110 ℃.
The density of the resulting low-density polyethylene (B-4) was 923kg/m 3 The MFR was 3.8g/10 min.
< production of Low Density polyethylene (B-5) >)
The same operation as for the low-density polyethylene (B-1) was conducted except that the polymerization temperature was 200℃and the polymerization pressure was 150.0MPa, 7.5 mol% of the ethylene raw material was changed to butane, and the piping immediately before the polymerization reactor was not heated, thereby obtaining a low-density polyethylene (B-5).
The temperature of ethylene supplied to the polymerization reactor was 104 ℃.
The density of the resulting low-density polyethylene (B-5) was 931kg/m 3 The MFR was 5.0g/10 min.
< production of Low Density polyethylene (B-6) >)
The same operation as for the low-density polyethylene (B-1) was conducted except that the polymerization temperature was changed to 250℃and the polymerization pressure was changed to 110.0MPa, thereby obtaining a low-density polyethylene (B-6).
The temperature of ethylene supplied to the polymerization reactor was 161 ℃.
The density of the resulting low-density polyethylene (B-6) was 920kg/m 3 The MFR was 15.0g/10 min.
(ethylene resin composition)
Example 1 production of vinyl resin composition (C-1)
The high-density polyethylene (a-1) and the low-density polyethylene (B-1) were melt-kneaded at 200℃using a single screw extruder (screw diameter: 50mm, L/d=24) manufactured by japan steel corporation so that the high-density polyethylene (a-1) and the low-density polyethylene (B-1) were 30 mass% and 70 mass%, respectively, and pelletized.
Further, the fluctuation of the resin pressure is controlled to be within 5MPa by adjusting the screw rotation speed of the extruder in the range of 50rpm to 150 rpm.
Example 2 production of vinyl resin composition (C-2)
The high-density polyethylene (A-2) and the low-density polyethylene (B-2) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the amounts of the high-density polyethylene (A-2) and the low-density polyethylene (B-2) were adjusted to 20 mass% and 80 mass%, respectively.
Example 3 production of vinyl resin composition (C-3)
The high-density polyethylene (A-3) and the low-density polyethylene (B-1) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the amounts of the high-density polyethylene and the low-density polyethylene were adjusted to 30 mass% and 70 mass%, respectively.
Example 4 production of vinyl resin composition (C-4)
The high-density polyethylene (A-4) and the low-density polyethylene (B-2) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the amounts of the high-density polyethylene and the low-density polyethylene were adjusted to 40 mass% and 60 mass%, respectively.
Example 5 production of vinyl resin composition (C-5)
The high-density polyethylene (A-1) and the low-density polyethylene (B-3) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the screw speed of the extruder was adjusted to 30 mass% and 70 mass%, respectively, and the screw speed was kept constant at 100 rpm.
Example 6 production of vinyl resin composition (C-6)
The high-density polyethylene (A-1) and the low-density polyethylene (B-4) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the amounts of the high-density polyethylene and the low-density polyethylene were adjusted to 30 mass% and 70 mass%, respectively.
Example 7 production of vinyl resin composition (C-7)
The high-density polyethylene (A-2) and the low-density polyethylene (B-2) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the screw speed of the extruder was kept constant at 100rpm while adjusting to 10 mass% and 90 mass% respectively.
Example 8 production of vinyl resin composition (C-8)
The high-density polyethylene (A-1) and the low-density polyethylene (B-1) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the amounts of the high-density polyethylene (A-1) and the low-density polyethylene (B-1) were adjusted to 55 mass% and 45 mass%, respectively.
Example 9 production of vinyl resin composition (C-9)
The high-density polyethylene (A-5) and the low-density polyethylene (B-3) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the amounts of the high-density polyethylene and the low-density polyethylene were adjusted to 35% by mass and 65% by mass, respectively.
Comparative example 1 production of vinyl resin composition (C-10)
The high-density polyethylene (A-1) and the low-density polyethylene (B-1) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the amounts of the high-density polyethylene (A-1) and the low-density polyethylene (B-1) were adjusted to 70 mass% and 30 mass%, respectively.
Comparative example 2 production of vinyl resin composition (C-11)
The high-density polyethylene (A-6) and the low-density polyethylene (B-1) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the amounts of the high-density polyethylene and the low-density polyethylene were adjusted to 40 mass% and 60 mass%, respectively.
Comparative example 3 production of vinyl resin composition (C-12)
The high-density polyethylene (A-4) and the low-density polyethylene (B-4) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the amounts of the high-density polyethylene and the low-density polyethylene were adjusted to 30 mass% and 70 mass%, respectively.
Comparative example 4 production of vinyl resin composition (C-13)
The high-density polyethylene (A-2) and the low-density polyethylene (B-4) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the screw speed of the extruder was kept constant at 100rpm while adjusting to 40 mass% and 60 mass% respectively.
Comparative example 5 production of vinyl resin composition (C-14)
The high-density polyethylene (A-7) and the low-density polyethylene (B-6) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the screw speed of the extruder was kept constant at 100rpm while adjusting to 45 mass% and 55 mass% respectively.
Comparative example 6 production of vinyl resin composition (C-15)
The low-density polyethylene (B-5) was melt kneaded using a single screw extruder (screw diameter: 50mm, L/d=24) manufactured by japan steel corporation at a screw speed of 100rpm at 200 ℃ and pelletized.
Comparative example 7 production of vinyl resin composition (C-16)
The high-density polyethylene (A-6) and the low-density polyethylene (B-5) were melt-kneaded and pelletized by the same operation as the above-mentioned ethylene resin composition (C-1), except that the screw speed of the extruder was adjusted to 70 mass% and 30 mass%, respectively, and the screw speed was kept constant at 100 rpm.
Comparative example 8 production of vinyl resin composition (C-17)
An ethylene resin composition (C-17) was obtained in the same manner as in example 2 described in Japanese patent No. 6912290.
Comparative example 9 production of vinyl resin composition (C-18)
An ethylene resin composition (C-18) was obtained in the same manner as in example 9 described in Japanese patent No. 6912290.
Comparative example 10 production of vinyl resin composition (C-19)
An ethylene resin composition (C-19) was obtained in the same manner as in example 3 described in Japanese patent No. 6243195.
Industrial applicability
The ethylene resin composition of the present invention is industrially useful as a raw material for, for example, a protective film in film applications where fish eye quality is particularly important.
Claims (7)
1. An ethylene resin composition satisfying the following < condition (A) > < condition (D) >:
condition (A) >, a method of producing a polypeptide
The melt flow rate of the ethylene resin composition under the conditions of 190 ℃ and a load of 2.16kg is 1.0g/10 min or more and 20.0g/10 min or less;
< condition (B) >)
The ethylene resin composition has a density of 920kg/m 3 945kg/m 3 The following are set forth;
condition (C) >, a method of producing a polypeptide
In ARES temperature increase measurement, the average value (M+m)/2 of the maximum value M and the minimum value M of tan delta in the temperature range of 30 ℃ to 150 ℃ is 115 ℃ to 145 ℃;
Condition (D) >
In ARES temperature increase measurement, the value of tan delta at 150 ℃ is 1.00 to 1.50.
2. The vinyl resin composition according to claim 1, wherein,
when the temperature is 170 ℃, the shearing speed is 10s -1 The melt viscosity of the ethylene resin composition measured under the conditions of (a) is X (Pa.s),
Will shear at 230℃for 10s -1 When the melt viscosity of the ethylene resin composition measured under the conditions of (a) is Y (Pa.s),
satisfies the following formula (1):
5≤(Y-X)/(170-230)≤25……(1)。
3. the vinyl resin composition according to claim 1, wherein,
in the temperature-heat flow curve of the ethylene resin composition obtained by Differential Scanning Calorimetry (DSC), has two or more melting peaks, the melting peak temperature at the highest temperature side is 118 ℃ or more, and
the difference between the melting peak temperature at the highest temperature side and the melting peak temperature at the lowest temperature side is 10 ℃ or more and 30 ℃ or less.
4. The ethylene resin composition according to claim 1, wherein the ethylene resin composition has a density of 942kg/m 3 The high-density polyethylene has a density of 930kg/m 3 The following mixture of low density polyethylenes.
5. The ethylene resin composition according to claim 1, wherein the ethylene resin composition has a density of 942kg/m of 10 mass% or more and 50 mass% or less 3 The above high density polyethylene.
6. A molded article comprising the ethylene resin composition according to any one of claims 1 to 5.
7. The molded article according to claim 6, wherein the molded article is a film.
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| JP2021191043 | 2021-11-25 | ||
| JP2021-191043 | 2021-11-25 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010242082A (en) * | 2009-03-19 | 2010-10-28 | Asahi Kasei Chemicals Corp | Film polyethylene resin |
| JP2012255138A (en) * | 2011-05-16 | 2012-12-27 | Asahi Kasei Chemicals Corp | Polyethylene resin composition for surface protective film |
| JP6243195B2 (en) * | 2013-11-07 | 2017-12-06 | 旭化成株式会社 | Polyethylene resin composition and film for surface protective film |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4931187B2 (en) * | 2006-03-30 | 2012-05-16 | 旭化成ケミカルズ株式会社 | Polyethylene resin composition for T-die molding and T-die molded film comprising the composition |
| JP2013237791A (en) * | 2012-05-16 | 2013-11-28 | Sumitomo Chemical Co Ltd | Low density polyethylene, film, and method of manufacturing multilayer film |
| JP2016108383A (en) * | 2014-12-03 | 2016-06-20 | 三井・デュポンポリケミカル株式会社 | Resin composition for surface protective member and surface protective film or sheet using the same |
| JP6792957B2 (en) * | 2016-04-21 | 2020-12-02 | 旭化成株式会社 | Polyethylene composition and film |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010242082A (en) * | 2009-03-19 | 2010-10-28 | Asahi Kasei Chemicals Corp | Film polyethylene resin |
| JP2012255138A (en) * | 2011-05-16 | 2012-12-27 | Asahi Kasei Chemicals Corp | Polyethylene resin composition for surface protective film |
| JP6243195B2 (en) * | 2013-11-07 | 2017-12-06 | 旭化成株式会社 | Polyethylene resin composition and film for surface protective film |
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