WO2011090101A1 - Multilayer blow-molded container, and process for production thereof - Google Patents
Multilayer blow-molded container, and process for production thereof Download PDFInfo
- Publication number
- WO2011090101A1 WO2011090101A1 PCT/JP2011/050939 JP2011050939W WO2011090101A1 WO 2011090101 A1 WO2011090101 A1 WO 2011090101A1 JP 2011050939 W JP2011050939 W JP 2011050939W WO 2011090101 A1 WO2011090101 A1 WO 2011090101A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ethylene
- propylene
- olefin copolymer
- olefin
- measured
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 316
- 239000005977 Ethylene Substances 0.000 claims abstract description 316
- 239000004711 α-olefin Substances 0.000 claims abstract description 267
- 229920005989 resin Polymers 0.000 claims abstract description 209
- 239000011347 resin Substances 0.000 claims abstract description 209
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 206
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 191
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 191
- 239000000203 mixture Substances 0.000 claims abstract description 161
- 238000002844 melting Methods 0.000 claims abstract description 148
- 230000008018 melting Effects 0.000 claims abstract description 148
- 229920000098 polyolefin Polymers 0.000 claims abstract description 136
- 239000013078 crystal Substances 0.000 claims abstract description 78
- 239000002667 nucleating agent Substances 0.000 claims abstract description 72
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 37
- 229920005606 polypropylene copolymer Polymers 0.000 claims abstract description 7
- 238000005259 measurement Methods 0.000 claims description 91
- 229920000642 polymer Polymers 0.000 claims description 53
- 239000000155 melt Substances 0.000 claims description 37
- -1 aromatic phosphate ester compounds Chemical class 0.000 claims description 35
- 238000000071 blow moulding Methods 0.000 claims description 32
- 150000001336 alkenes Chemical class 0.000 claims description 25
- 229920001155 polypropylene Polymers 0.000 claims description 24
- 238000000465 moulding Methods 0.000 claims description 23
- 229910019142 PO4 Inorganic materials 0.000 claims description 22
- 239000010452 phosphate Substances 0.000 claims description 22
- 229920000573 polyethylene Polymers 0.000 claims description 16
- 229920005992 thermoplastic resin Polymers 0.000 claims description 9
- 238000010103 injection stretch blow moulding Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000011342 resin composition Substances 0.000 claims description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- 150000002484 inorganic compounds Chemical class 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 161
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- 230000000052 comparative effect Effects 0.000 description 48
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- 238000006116 polymerization reaction Methods 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 238000009826 distribution Methods 0.000 description 20
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229920001971 elastomer Polymers 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 14
- 230000008025 crystallization Effects 0.000 description 14
- 239000000806 elastomer Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 239000010936 titanium Substances 0.000 description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 229910052719 titanium Inorganic materials 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000012968 metallocene catalyst Substances 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 12
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 11
- 150000001451 organic peroxides Chemical class 0.000 description 11
- 229920006132 styrene block copolymer Polymers 0.000 description 11
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229920005604 random copolymer Polymers 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- 229920001903 high density polyethylene Polymers 0.000 description 7
- 239000004700 high-density polyethylene Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 6
- 229920005672 polyolefin resin Polymers 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- GGQHNQQPLWRNHD-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-hydroxy-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP(O)(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C GGQHNQQPLWRNHD-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005488 sandblasting Methods 0.000 description 5
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 5
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- 230000003746 surface roughness Effects 0.000 description 5
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
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- 238000007664 blowing Methods 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
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- 229920000092 linear low density polyethylene Polymers 0.000 description 4
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- WEPNJTDVIIKRIK-UHFFFAOYSA-N 2-methylhept-2-ene Chemical compound CCCCC=C(C)C WEPNJTDVIIKRIK-UHFFFAOYSA-N 0.000 description 3
- BWEKDYGHDCHWEN-UHFFFAOYSA-N 2-methylhex-2-ene Chemical compound CCCC=C(C)C BWEKDYGHDCHWEN-UHFFFAOYSA-N 0.000 description 3
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 3
- JTXUVHFRSRTSAT-UHFFFAOYSA-N 3,5,5-trimethylhex-1-ene Chemical compound C=CC(C)CC(C)(C)C JTXUVHFRSRTSAT-UHFFFAOYSA-N 0.000 description 3
- AUJLDZJNMXNESO-UHFFFAOYSA-N 3-ethylhex-3-ene Chemical compound CCC=C(CC)CC AUJLDZJNMXNESO-UHFFFAOYSA-N 0.000 description 3
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- 241000446313 Lamella Species 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
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- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
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- 238000000691 measurement method Methods 0.000 description 3
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- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
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- 125000004429 atom Chemical group 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
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- 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
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- FNWASOQFCKPKQZ-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-hydroxy-5h-benzo[d][1,3,2]benzodioxaphosphocine Chemical compound C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP(O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C FNWASOQFCKPKQZ-UHFFFAOYSA-N 0.000 description 1
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-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
- PIYNPBVOTLQBTC-UHFFFAOYSA-N 1-[8-propyl-2,6-bis(4-propylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound O1C2C(CCC)OC(C=3C=CC(CCC)=CC=3)OC2C(C(O)CO)OC1C1=CC=C(CCC)C=C1 PIYNPBVOTLQBTC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-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
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-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
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-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
- OLGHJTHQWQKJQQ-UHFFFAOYSA-N 3-ethylhex-1-ene Chemical compound CCCC(CC)C=C OLGHJTHQWQKJQQ-UHFFFAOYSA-N 0.000 description 1
- YPVPQMCSLFDIKA-UHFFFAOYSA-N 3-ethylpent-1-ene Chemical compound CCC(CC)C=C YPVPQMCSLFDIKA-UHFFFAOYSA-N 0.000 description 1
- RITONZMLZWYPHW-UHFFFAOYSA-N 3-methylhex-1-ene Chemical compound CCCC(C)C=C RITONZMLZWYPHW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- OPMUAJRVOWSBTP-UHFFFAOYSA-N 4-ethyl-1-hexene Chemical compound CCC(CC)CC=C OPMUAJRVOWSBTP-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CMBHKJNCOFBVEI-UHFFFAOYSA-N CCC(C)CC=C.CCC(C)(C)CC=C Chemical compound CCC(C)CC=C.CCC(C)(C)CC=C CMBHKJNCOFBVEI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- MBPDGMCEEVFMEH-UHFFFAOYSA-N OC1=CC=CC=2OP(OC3=C(CC21)C=CC=C3)=O Chemical compound OC1=CC=CC=2OP(OC3=C(CC21)C=CC=C3)=O MBPDGMCEEVFMEH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- RKFMOTBTFHXWCM-UHFFFAOYSA-M [AlH2]O Chemical compound [AlH2]O RKFMOTBTFHXWCM-UHFFFAOYSA-M 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001739 density measurement Methods 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
- QQRGOZKHLWDWHF-UHFFFAOYSA-H dialuminum;hexanedioate Chemical compound [Al+3].[Al+3].[O-]C(=O)CCCCC([O-])=O.[O-]C(=O)CCCCC([O-])=O.[O-]C(=O)CCCCC([O-])=O QQRGOZKHLWDWHF-UHFFFAOYSA-H 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000015071 dressings Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- QGWKRYREOQNOCC-UHFFFAOYSA-N hydrogen peroxide;1-methyl-4-propan-2-ylbenzene Chemical compound OO.CC(C)C1=CC=C(C)C=C1 QGWKRYREOQNOCC-UHFFFAOYSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N iron (II) ion Substances [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920005679 linear ultra low density polyethylene Polymers 0.000 description 1
- UADIOTAIECKQLQ-UHFFFAOYSA-M lithium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Li+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C UADIOTAIECKQLQ-UHFFFAOYSA-M 0.000 description 1
- ICGXPVHBUFIENI-UHFFFAOYSA-M lithium;1,3,7,9-tetratert-butyl-5-methyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Li+].CC1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ICGXPVHBUFIENI-UHFFFAOYSA-M 0.000 description 1
- PEZYITXKFBTLBI-UHFFFAOYSA-M lithium;1,9-ditert-butyl-3,7-diethyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Li+].C1C2=CC(CC)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(CC)C=C2C(C)(C)C PEZYITXKFBTLBI-UHFFFAOYSA-M 0.000 description 1
- DOPGPJUHBPZWQJ-UHFFFAOYSA-M lithium;1,9-ditert-butyl-3,7-dimethyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Li+].C1C2=CC(C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C)C=C2C(C)(C)C DOPGPJUHBPZWQJ-UHFFFAOYSA-M 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JGMMIGGLIIRHFV-UHFFFAOYSA-N nonane-1,2,3,4,5,6,7,8,9-nonol Chemical compound OCC(O)C(O)C(O)C(O)C(O)C(O)C(O)CO JGMMIGGLIIRHFV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- YWSUSMUSZKSAAQ-UHFFFAOYSA-M potassium;1,3,7,9-tetratert-butyl-5-methyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [K+].CC1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C YWSUSMUSZKSAAQ-UHFFFAOYSA-M 0.000 description 1
- 229920005634 random propylene copolymer resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- XEZJJVRUWKGVIA-UHFFFAOYSA-M sodium;1,3,7,9-tetraethyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].O1P([O-])(=O)OC2=C(CC)C=C(CC)C=C2CC2=CC(CC)=CC(CC)=C21 XEZJJVRUWKGVIA-UHFFFAOYSA-M 0.000 description 1
- DVSGVEPIPBNASD-UHFFFAOYSA-M sodium;1,3,7,9-tetramethyl-11-oxido-5-(2,4,4-trimethylpentan-2-yl)-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].O1P([O-])(=O)OC2=C(C)C=C(C)C=C2C(C(C)(C)CC(C)(C)C)C2=CC(C)=CC(C)=C21 DVSGVEPIPBNASD-UHFFFAOYSA-M 0.000 description 1
- SIJVPMATBIKDTJ-UHFFFAOYSA-M sodium;1,3,7,9-tetramethyl-11-oxido-5-propyl-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].O1P([O-])(=O)OC2=C(C)C=C(C)C=C2C(CCC)C2=CC(C)=CC(C)=C21 SIJVPMATBIKDTJ-UHFFFAOYSA-M 0.000 description 1
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 1
- IEFYQJPRHOKDLM-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-5-methyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].CC1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C IEFYQJPRHOKDLM-UHFFFAOYSA-M 0.000 description 1
- UXBYXHNQMORKEI-UHFFFAOYSA-M sodium;1,9-ditert-butyl-3,7-diethyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(CC)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(CC)C=C2C(C)(C)C UXBYXHNQMORKEI-UHFFFAOYSA-M 0.000 description 1
- FIAYJSUZUBQZOW-UHFFFAOYSA-M sodium;1,9-ditert-butyl-3,7-dimethyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C)C=C2C(C)(C)C FIAYJSUZUBQZOW-UHFFFAOYSA-M 0.000 description 1
- ZEYNWZNNZISTPU-UHFFFAOYSA-M sodium;1,9-ditert-butyl-5-methyl-11-oxido-3,7-dipropyl-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].CC1C2=CC(CCC)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(CCC)C=C2C(C)(C)C ZEYNWZNNZISTPU-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
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- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
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- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
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- 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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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- B29C2949/00—Indexing scheme relating to blow-moulding
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- B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
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- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
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Definitions
- the present invention relates to a multilayer blow container and a manufacturing method thereof.
- resins such as vinyl chloride resin, polycarbonate resin, ethylene resin, and propylene resin are used depending on applications.
- the resulting blow-molded product is relatively inexpensive to manufacture, and is more glossy and transparent than high-density polyethylene. Therefore, containers for liquid detergents, cosmetics, foods, medicines, etc. Is widely used.
- the gloss of the blow molded product is a physical property that has been studied in order to meet the market demand for a good appearance, but it still has sufficient gloss, good moldability and impact resistance at the same time. Has not been proposed.
- a propylene / ⁇ -olefin copolymer is used as a base resin, and a linear low density polyethylene having a crystalline melting point of 110 to 125 ° C. is used as a compounding resin, and these resins and a nucleating agent are contained.
- a multilayer blow molded article having an olefin polymer composition as an outermost layer has been proposed (see, for example, Patent Document 1).
- Patent Document 1 As a result of investigations by the present inventors, it was found that even the multilayer blow molded article described in Patent Document 1 is still insufficient in gloss and impact resistance and needs further improvement.
- Patent Document 2 As a multilayer bottle excellent in cold resistance, a multilayer bottle having a gas barrier resin core layer and having an outermost layer formed of a polyolefin resin and a linear ultra-low density polyethylene resin has been proposed (for example, Patent Document 2).
- Patent Document 2 As a result of studies by the present inventors, it was found that even the multilayer bottle described in Patent Document 2 still has insufficient gloss and moldability, and further improvement is necessary.
- a composition comprising a polypropylene resin obtained using a metallocene catalyst and an ethylene / ⁇ -olefin copolymer obtained using a metallocene catalyst as the outermost layer.
- a high-gloss blow container formed by a multilayer blow molding method is known (for example, see Patent Document 4).
- Patent Document 4 the high-gloss blown container described in Patent Document 4 is superior in gloss when compared to conventional containers, but further improved in terms of heat resistance and gloss. I found that there was room.
- An object of the present invention is to provide a multi-layer blow container having high gloss, excellent surface appearance, excellent impact resistance, and excellent balance between impact resistance and stickiness resistance.
- a multilayer blow container using a specific olefin polymer composition as the outermost layer has high gloss, excellent surface appearance, and is resistant to damage.
- the present invention has been completed by finding out that it has excellent impact resistance and also has an excellent balance between impact resistance and stickiness resistance.
- the resin used in the outermost layer is 80 to 98 parts by weight of the propylene resin (A) and 2 to 20 parts by weight of the ethylene / ⁇ -olefin copolymer (B) (however, (A) and (B) are 100 parts by weight) and a nucleating polymer composition (E) formed from 0.01 to 0.5 parts by weight of the nucleating agent (D),
- the propylene resin (A) satisfies the following requirements (A-1) and (A-2), and the ethylene / ⁇ -olefin copolymer (B) satisfies the following requirements (B-1) and (B-2):
- a multilayer blow container characterized in that the olefin polymer composition (E) satisfies the following requirement (E-1).
- A-2 The crystal melting point measured with a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is in the range of 140 to 155 ° C.
- (B-1) A copolymer of ethylene and one or more ⁇ -olefins having 4 to 20 carbon atoms.
- the crystal melting point measured by DSC in accordance with JIS-K7121 is in the range of 85 ° C. or higher and lower than 110 ° C.
- melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes.
- the olefin polymer composition (E) is further formed using 0.1 to 20 parts by weight of a low density ethylene / ⁇ -olefin copolymer (F).
- the polymer (F) satisfies the following requirements (F-1) and (F-2), and the density (d B [g / cm] measured by the density gradient method of the ethylene / ⁇ -olefin copolymer (B): 3 ]) and the density (d F [g / cm 3 ]) measured by the density gradient method of the low density ethylene / ⁇ -olefin copolymer (F) satisfy the following requirement (X-1), the multilayer blow It is preferable from the viewpoint of the low temperature impact resistance of the container.
- (F-1) A copolymer of ethylene and one or more ⁇ -olefins having 3 to 20 carbon atoms.
- the ethylene / ⁇ -olefin copolymer (B) preferably further satisfies the following requirement (B-4).
- the density measured by the density gradient tube method is in the range of 0.880 to 0.910 g / cm 3 .
- the ethylene / ⁇ -olefin copolymer (B) further satisfies the following requirement (B-4a), and the low-density ethylene / ⁇ -olefin copolymer (F) further satisfies the following requirement (F-3). Is preferable from the viewpoint of low-temperature impact resistance of the multilayer blow container.
- (B-4a) density measured by a density gradient tube method (d B [g / cm 3 ]) is in the range of 0.890 ⁇ 0.910g / cm 3.
- the density (d F [g / cm 3 ]) measured by the density gradient tube method is in the range of 0.865 to 0.900 g / cm 3 .
- the propylene resin (A) further satisfies the following requirement (A-4).
- the propylene resin (A) further satisfies the following requirement (A-3).
- the ethylene / ⁇ -olefin copolymer (B) further satisfies the following requirement (B-5).
- the ethylene / ⁇ -olefin copolymer (B) preferably further satisfies the following requirement (B-3).
- the nucleating agent (D) is one or more compounds selected from the group consisting of aromatic phosphate ester compounds, carboxylic acid metal salt nucleating agents, polymer nucleating agents, sorbitol nucleating agents and inorganic compound nucleating agents. It is preferable that
- the propylene-based resin (A) is 95.5 to 98 parts by weight, and the ethylene / ⁇ -olefin copolymer (B) is 2 to 4.5 parts by weight (provided that (A) and (B) The total is preferably 100 parts by weight.
- the multilayer blow container has a layer formed from a propylene polymer (G) or an ethylene polymer (H) as at least one inner layer.
- G propylene polymer
- H ethylene polymer
- the multilayer blow container is preferably obtained by molding by a direct blow molding method or an injection stretch blow molding method.
- the multilayer blow container of the present invention uses a thermoplastic resin composition other than the olefin polymer composition (E) and the olefin polymer composition (E) described above, and the olefin polymer composition (E) has the outermost layer. And formed by a direct blow molding method or an injection stretch blow molding method so that the thermoplastic resin composition other than the olefin polymer composition (E) forms at least one inner layer.
- the resin used for the outermost layer is an olefin polymer formed of a propylene resin (A), an ethylene / ⁇ -olefin copolymer (B), and a nucleating agent (D). It consists of a composition (E), It is characterized by the above-mentioned.
- the multilayer blow container of the present invention has high gloss, excellent surface appearance, and excellent impact resistance, but the olefin polymer composition (E) is further reduced in density ethylene / ⁇ -olefin copolymer (F). In the embodiment formed using 0.1 to 20 parts by weight, the low temperature impact resistance is further excellent.
- the propylene resin (A) used in the present invention preferably satisfies the following requirements (A-1) and (A-2), and preferably satisfies at least one of the following requirements (A-3) and (A-4): More preferably, the following requirements (A-3) and (A-4) are satisfied.
- Propylene-type resin (A) may be used individually by 1 type, or may use 2 or more types.
- olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms.
- the ⁇ -olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene and 4-methyl.
- -1-pentene 2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1-butene , 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3-methyl- Examples include 1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, ethyl-1-octene, and methyl-1-nonene. .
- the propylene-based resin (A) used in the present invention is composed of propylene and one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 10 carbon atoms in view of the balance between physical properties and economy. It is preferably a copolymer, more preferably a copolymer of propylene and one or more ⁇ -olefins selected from the group consisting of ethylene and 1-butene, and a copolymer of propylene and ethylene It is particularly preferred that
- the propylene resin (A) used in the present invention is preferably a random copolymer.
- the crystal melting point measured with a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is in the range of 140 to 155 ° C. It is preferable that the crystal melting point is in the above-mentioned range since the multilayer blow container is excellent in gloss and impact resistance and is excellent in moldability when producing the multilayer blow container.
- the crystal melting point measured by a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is higher than 155 ° C., the impact resistance of the multilayer blow container is inferior.
- the moldability at the time of producing the multilayer blow container is inferior and the surface of the multilayer blow container is sticky. .
- the crystalline melting point of the propylene-based resin (A) can be determined by measuring under the following measurement conditions using a differential scanning calorimeter (DSC) (for example, Diamond TM DSC manufactured by Perkin Elmer) according to JIS-K7121. it can.
- DSC differential scanning calorimeter
- the top of the endothermic peak in the third step when the measurement was performed under the following measurement conditions was defined as the crystalline melting point (Tm).
- Tm crystalline melting point
- Measurement condition Measurement environment: Nitrogen gas atmosphere Sample volume: 5mg Sample shape: Press film (230 ° C molding, thickness 200-400 ⁇ m) First step: The temperature is raised from 30 ° C to 240 ° C at 10 ° C / min and held for 10 min.
- Second step IV Decrease the temperature to 60 ° C at 10 ° C / min.
- 3rd step IV Increase the temperature to 240 ° C at 10 ° C / min.
- the crystal melting point of the propylene resin (A) measured by a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is, for example, propylene at the time of copolymerization in the production of the propylene resin (A), ethylene introduced, and It can be adjusted by changing the introduction ratio of one or more olefins selected from the group consisting of ⁇ -olefins having 4 to 20 carbon atoms. That is, by increasing the introduction amount of one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms with respect to the introduction amount of propylene, the differential scanning calorific value in accordance with JIS-K7121.
- the crystal melting point measured by a total (DSC) can be lowered, and the introduction amount of one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms is reduced with respect to the introduction amount of propylene.
- DSC differential scanning calorimeter
- MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes.
- MFR means a melt flow rate.
- the moldability and the impact resistance of the multilayer blow container are inferior.
- the gloss of the multilayer blow container may be inferior.
- MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is, for example, chain transfer used during copolymerization in the production of the propylene resin (A). It can adjust with the introduction amount of an agent (for example, hydrogen gas). That is, the amount of the chain transfer agent (for example, hydrogen gas) introduced is increased with respect to the amount of propylene introduced during the polymerization and one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms.
- the introduction amount of chain transfer agent for example, hydrogen gas
- the introduction amount of chain transfer agent is reduced with respect to the amount of one or more olefins selected from the group consisting of propylene introduced at the time of polymerization and ethylene and ⁇ -olefin having 4 to 20 carbon atoms.
- the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 of the propylene resin (A) can be lowered.
- the propylene-based resin obtained by polymerization is melt kneaded in the presence of a radical generator such as an organic peroxide, and the measurement temperature is 230 ° C. and the load is 2.16 kg according to ASTM D-1238.
- the MFR measured in (1) can be adjusted. For example, by performing the melt-kneading process in the presence of an organic peroxide, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is increased in accordance with ASTM D-1238. Further, by increasing the amount of the organic peroxide added, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg can be further increased in accordance with ASTM D-1238.
- Mw / Mn measured by GPC is 4.0 or more.
- GPC means gel permeation chromatography
- Mw means weight average molecular weight
- Mn means number average molecular weight
- Mw / Mn is an index of molecular weight distribution.
- Mw / Mn is preferably 1.5 or more, more preferably 3.0 or more, but satisfies the above (A-4), that is, Mw / Mn is 4.0 or more. It is particularly preferable because a blow molded article having excellent gloss can be obtained regardless of the surface roughness of the blow mold. The reason for this is not clear, but the present inventors consider as follows.
- Mw / Mn is not particularly limited, but is usually 50.0, preferably 30.0, more preferably 20.0, still more preferably 16.0, particularly preferably 12 from the viewpoint of productivity. 0.0, most preferably 8.0.
- Mw / Mn by GPC can be performed by the method as described in an Example.
- Mw / Mn measured by GPC of the propylene resin (A) can be adjusted, for example, depending on the type of catalyst used in the production of the propylene resin (A).
- a Ziegler-Natta catalyst preferably a solid titanium catalyst
- the propylene-based resin (A) satisfying the requirement (A-4) can be obtained.
- Mw / Mn there is a method of blending two or more propylene resins having different molecular weights.
- the solid titanium catalyst is advantageous from the viewpoint of forming the higher molecular weight portion.
- the propylene resin (A) is derived from one or more olefins selected from the group consisting of propylene-derived structural units and ethylene and ⁇ -olefins having 4 to 20 carbon atoms, calculated from 13 C-NMR.
- the weight of the propylene-derived structural unit when the total amount of the structural units is 100% by weight is usually in the range of 80 to 99% by weight, and preferably in the range of 90 to 99% by weight.
- the weight of the structural unit derived from one or more olefins selected from the group consisting of ethylene and an ⁇ -olefin having 4 to 20 carbon atoms is usually in the range of 1 to 20% by weight, preferably 1 to It is in the range of 10% by weight. Within the above range, it is preferable because the balance between the moldability when producing a multilayer blow container and physical properties such as stickiness of the multilayer blow container is good.
- the total of the structural unit derived from propylene calculated from 13 C-NMR and the structural unit derived from one or more olefins selected from the group consisting of ethylene and an ⁇ -olefin having 4 to 20 carbon atoms is 100% by weight.
- the weight of the structural unit derived from propylene was measured and calculated under the following conditions.
- the mole fraction of the structural unit derived from ethylene in the propylene resin (A) (mol%) (hereinafter referred to as E (mol%))
- the molar fraction (mol%) of constituent units derived from propylene (hereinafter referred to as P (mol%))
- the weight percent of the structural unit derived from propylene and the weight percent of the structural unit derived from ethylene in the propylene-based resin (A) are calculated by converting from the obtained E (mol%) and P (mol%) to weight percent. be able to.
- the molar fraction (mol%) of the structural unit derived from (hereinafter referred to as A (mol%)) and the molar fraction (mol%) of the structural unit derived from propylene (hereinafter referred to as P (mol%)) are calculated. be able to. Converted from the calculated A (mol%) and P (mol%) to wt%, derived from propylene-based constituent units in propylene resin (A) and derived from ⁇ -olefin having 4 to 20 carbon atoms The weight% of the structural unit to be calculated can be calculated.
- Adjustment of the weight of the structural unit derived from propylene can be made into arbitrary quantity by adjusting the manufacturing conditions mentioned later. More specifically, introduction of one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms with respect to the amount of propylene introduced during copolymerization in the production of propylene-based resin (A). By reducing the amount, the weight of the structural unit derived from propylene can be increased.
- the weight of the structural unit derived from propylene is reduced. be able to.
- the propylene resin (A) is preferably a random copolymer of propylene and one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms.
- the propylene resin (A) is a copolymer of propylene and one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms, preferably in the presence of a Ziegler-Natta catalyst or a metallocene catalyst. Can be obtained by random copolymerization.
- the requirement (A-4) can be satisfied. It is also possible to adjust to satisfy the requirement (A-4) by blending two or more propylene resins (A) having different molecular weights.
- a chain transfer agent represented by hydrogen gas can be introduced.
- the propylene-based resin (A) can also be obtained by subjecting the propylene-based resin obtained by polymerization to melt-kneading in the presence of a radical generator such as an organic peroxide.
- the organic peroxide is not particularly limited, but benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5 -Di- (benzoylperoxy) hexane, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexyne-3, t-butyl-diperadipate, t-butylperoxy-3, 5,5-trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di- (t -Butylperoxy) hexane, 2,5, -di-methyl-2,5-di- (t-butylperoxy) hexyne-3,1,
- 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane and 1,3-bis- (t-butylperoxyisopropyl) benzene are more preferred.
- an organic peroxide it is desirable to use it at 0.1 parts by weight or less with respect to 100 parts by weight of the propylene-based resin obtained by polymerization.
- the mixture is introduced into a mixer such as a Henschel mixer, a Banbury mixer, or a tumbler mixer, and then mixed.
- a mixer such as a Henschel mixer, a Banbury mixer, or a tumbler mixer
- the resulting mixture is then converted into a single-screw extruder,
- molding with extruders, such as a twin-screw extruder, and obtaining the strand of propylene-type resin (A) is mentioned.
- the strand is usually formed into a pellet using a pelletizer or the like before blow molding.
- ⁇ Ethylene / ⁇ -olefin copolymer (B)> The ethylene / ⁇ -olefin copolymer (B) used in the present invention satisfies the following requirements (B-1) and (B-2), and at least one of the following requirements (B-3) and (B-4): Preferably, the following requirements (B-3) and (B-4) are satisfied. It is also preferable to satisfy the following requirement (B-5).
- the ethylene / ⁇ -olefin copolymer (B) may be used alone or in combination of two or more.
- (B-1) A copolymer of ethylene and one or more ⁇ -olefins having 4 to 20 carbon atoms.
- the ⁇ -olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene and 4-methyl.
- -1-pentene 2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1-butene , 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3-methyl- Examples include 1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, ethyl-1-octene, and methyl-1-nonene. .
- the ethylene / ⁇ -olefin copolymer (B) used in the present invention is at least one selected from the group consisting of ethylene and ⁇ -olefins having 4 to 10 carbon atoms from the viewpoint of a balance between physical properties and economy. It is preferably a copolymer of olefins, more preferably a copolymer of ethylene and one or more ⁇ -olefins selected from the group consisting of 1-butene, 1-hexene and 1-octene. A copolymer of ethylene and 1-hexene is particularly preferable.
- the crystal melting point measured by DSC in accordance with JIS-K7121 is in the range of 85 ° C. or higher and lower than 110 ° C. It is preferable that the crystal melting point is in the above range because the multilayer blow container is excellent in impact resistance and adhesion between the outermost layer and other layers.
- the crystalline melting point of the ethylene / ⁇ -olefin copolymer (B) measured by DSC in accordance with JIS-K7121 is 110 ° C. or higher, the adhesion and impact resistance are inferior, and measured by DSC in accordance with JIS-K7121.
- the crystal melting point is lower than 85 ° C., the adhesiveness is inferior, and stickiness is generated, which is not preferable.
- the crystal melting point is preferably 109 ° C. or lower, more preferably 108 ° C. or lower, and particularly preferably 105 ° C. or lower.
- the crystalline melting point of the ethylene / ⁇ -olefin copolymer (B) used in the present invention measured by DSC in accordance with JIS-K7121 can be adjusted to any amount by adjusting the production conditions of the ethylene / ⁇ -olefin copolymer. It can be.
- the polymerization of the ethylene / ⁇ -olefin copolymer (B) it is adjusted by changing the ratio of the feed amount of ethylene / ⁇ -olefin when the ethylene / ⁇ -olefin copolymer is polymerized.
- the ratio of the feed amount of ethylene / ⁇ -olefin when the ethylene / ⁇ -olefin copolymer is polymerized Is possible. Specifically, by increasing the feed amount of ⁇ -olefin relative to the feed amount of ethylene, it is possible to lower the crystal melting point measured by DSC in accordance with JIS-K7121. Further, by reducing the feed amount of ⁇ -olefin relative to the feed amount of ethylene, it is possible to increase the crystalline melting point measured by DSC in accordance with JIS-K7121.
- the crystal melting point of the ethylene / ⁇ -olefin copolymer (B) can be measured using a differential scanning calorimeter (DSC) according to JIS-K7121. Specifically, it can be measured by the same method as the crystalline melting point of the propylene resin (A) described above.
- DSC differential scanning calorimeter
- (B-3) MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is in the range of 5 to 10 g / 10 min.
- the MFR is within the above range, the dispersibility of the ethylene / ⁇ -olefin copolymer (B) in the propylene resin (A) is good, the gloss of the multilayer blow container is excellent, and the impact resistance is excellent. Since it is excellent in adhesiveness with another layer, it is preferable.
- the MFR of the ethylene / ⁇ -olefin copolymer (B) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is adjusted with the ethylene / ⁇ -olefin copolymer (B It can be set to an arbitrary value by adjusting the manufacturing conditions.
- the amount of hydrogen gas is controlled by adjusting the feed amount of ethylene and / or ⁇ -olefin at the time of polymerization. It is possible. Measurement temperature in accordance with ASTM D-1238 by increasing the feed amount of ethylene gas during polymerization or when feeding ethylene and ⁇ -olefin, by increasing the feed amount of hydrogen gas relative to the feed amount of ethylene and ⁇ -olefin It is possible to increase the MFR measured at 230 ° C. and a 2.16 kg load. In the case of feeding ethylene gas or ethylene and ⁇ -olefin, the measurement temperature is 230 ° C. according to ASTM D-1238 by reducing the amount of hydrogen gas to ethylene and ⁇ -olefin. It is possible to lower the MFR measured with a 16 kg load.
- the density measured by the density gradient tube method is in the range of 0.880 to 0.910 g / cm 3 . It is preferable for the density to be in the above-mentioned range since the multilayer blow container is excellent in gloss and impact resistance and adhesion between the outermost layer and other layers.
- the low-density ethylene / ⁇ -olefin copolymer (F) described later is used and the ethylene / ⁇ -olefin copolymer is used.
- the polymer (B) preferably satisfies the following requirement (B-4a).
- (B-4a) density measured by a density gradient tube method (d B [g / cm 3 ]) is in the range of 0.890 ⁇ 0.910g / cm 3.
- the multi-layer blow container has excellent gloss, impact resistance, low temperature impact resistance, adhesion between the outermost layer and other layers, low stickiness, and further, impact resistance and low temperature resistance. It is preferable because the balance between impact resistance such as impact properties and resistance is good.
- the density measured by the density gradient tube method of the ethylene / ⁇ -olefin copolymer (B) used in the present invention should be an arbitrary amount by adjusting the production conditions of the ethylene / ⁇ -olefin copolymer (B). Can do.
- the ratio of the feed amount of ethylene and ⁇ -olefin when the ethylene / ⁇ -olefin copolymer is polymerized is changed.
- the density measured by the density gradient tube method can be lowered by increasing the feed amount of ⁇ -olefin relative to the feed amount of ethylene.
- the density measured by the density gradient tube method can be increased by reducing the feed amount of ⁇ -olefin relative to the feed amount of ethylene.
- the density measured by the density gradient tube method of the ethylene / ⁇ -olefin copolymer (B) used in the present invention is the same as that of the ethylene / ⁇ -olefin copolymer (B) strand obtained at the time of the MFR measurement. It is a measured value measured with a density gradient tube after heat treatment at 120 ° C. for 1 hour and linearly cooling to room temperature over 1 hour.
- Mw / Mn measured by GPC is 1.2 to 3.0.
- the ethylene / ⁇ -olefin copolymer (B) preferably has Mw / Mn of 1.5 to 3.0. It is preferable that Mw / Mn is within the above range because the multilayer blow container of the present invention is excellent in gloss.
- Mw / Mn measured by GPC of the ethylene / ⁇ -olefin copolymer (B) can be adjusted, for example, depending on the type of catalyst used in the production of the ethylene / ⁇ -olefin copolymer (B). .
- a metallocene catalyst as the catalyst, an ethylene / ⁇ -olefin copolymer (B) satisfying the requirement (B-5) can be obtained.
- the ethylene / ⁇ -olefin copolymer (B) can be obtained by copolymerizing ethylene and an ⁇ -olefin, but the ethylene / ⁇ -olefin copolymer is obtained using a metallocene catalyst. A polymerized one is preferred. In the polymerization, a chain transfer agent represented by hydrogen gas can be introduced.
- the ethylene / ⁇ -olefin copolymer (B) used in the present invention is an ethylene / ⁇ -olefin copolymer polymerized using a metallocene catalyst, an ethylene polymerized using a conventional so-called Ziegler-Natta catalyst is used. Since the composition distribution is more uniform than that of the ⁇ -olefin copolymer, the dispersibility with respect to the propylene-based resin (A) is improved, and the olefin polymer composition (E) having better gloss can be obtained.
- an ethylene / ⁇ -olefin copolymer polymerized using a metallocene catalyst has a narrower molecular weight distribution than that of an ethylene / ⁇ -olefin copolymer polymerized using a Ziegler-Natta catalyst. Low molecular weight components that cause deterioration are reduced.
- an ethylene / ⁇ -olefin copolymer polymerized using a metallocene catalyst has a more uniform composition distribution of the copolymer than an ethylene / ⁇ -olefin copolymer polymerized using a Ziegler-Natta catalyst. The amorphous component that causes stickiness is also reduced. Further, adhesion unevenness between the outermost layer and the other layers is reduced, and it is expected to suppress deterioration in appearance over time.
- the olefin polymer composition (E) has excellent gloss, impact resistance, and low stickiness. ) Can be obtained.
- the olefin polymer composition (E) the propylene resin (A) and the ethylene / ⁇ -olefin copolymer ( In addition to B) and the nucleating agent (D), it is preferable to use a composition formed using a low-density ethylene / ⁇ -olefin copolymer (F).
- the low-density ethylene / ⁇ -olefin copolymer (F) preferably satisfies the following requirements (F-1) and (F-2), and further satisfies the following requirement (F-3).
- the low density ethylene / ⁇ -olefin copolymer (F) may be used alone or in combination of two or more.
- (F-1) A copolymer of ethylene and one or more ⁇ -olefins having 3 to 20 carbon atoms.
- the ⁇ -olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, 4 -Methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1 -Butene, 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3- Methyl-1-hexen
- the low density ethylene / ⁇ -olefin copolymer (F) includes at least one selected from the group consisting of ethylene and ⁇ -olefins having 3 to 10 carbon atoms from the viewpoint of a balance between physical properties and economy. It is preferably a copolymer with olefin, and is a copolymer of ethylene and one or more ⁇ -olefins selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene. More preferred.
- the low density ethylene / ⁇ -olefin copolymer (F) is preferably a copolymer of ethylene and propylene, a copolymer of ethylene and 1-butene, or a copolymer of ethylene and 1-octene. More preferred is a copolymer of ethylene and 1-butene, and a copolymer of ethylene and 1-octene, and particularly preferred is a copolymer of ethylene and 1-butene.
- the crystal melting point measured by DSC according to JIS-K7121 is 89 ° C. or lower, or no peak based on the crystal melting point is observed. When it has a crystalline melting point, it is preferably 75 ° C. or lower. A crystal melting point within the above range is preferable because a multilayer blow container is excellent in low-temperature impact resistance.
- the crystal melting point of the low density ethylene / ⁇ -olefin copolymer (F) can be measured using a differential scanning calorimeter (DSC) according to JIS-K7121. Specifically, it can measure by the method as described in the below-mentioned Example.
- DSC differential scanning calorimeter
- the density (d F [g / cm 3 ]) measured by the density gradient tube method is in the range of 0.865 to 0.900 g / cm 3 .
- the density is more preferably in the range of 0.870 to 0.900 g / cm 3 . It is preferable for the density to be in the above-mentioned range since the gloss of the multilayer blow container is excellent and the low-temperature impact resistance is particularly excellent.
- the density (d F [g / cm 3 ]) measured by the public law satisfies the following requirement (X-1).
- the density difference (d B -d F ) from the density ethylene / ⁇ -olefin copolymer ( F ) is 0.010 to 0.050 [g / cm 3 ].
- the density difference (d B ⁇ d F ) is preferably 0.010 to 0.040 [g / cm 3 ].
- the density difference (d B ⁇ d F ) be in the above range because the multilayer blow container is excellent in gloss and further excellent in low-temperature impact resistance.
- the low-density ethylene / ⁇ -olefin copolymer (F) has an MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 in the range of 0.1 to 50 g / 10 min. It is preferably in the range of 0.5 to 30 g / 10 minutes, and more preferably in the range of 5 to 10 g / 10 minutes.
- the MFR is within the above range, the dispersibility of the low-density ethylene / ⁇ -olefin copolymer (F) becomes good, and the gloss and low-temperature impact properties are improved.
- the low-density ethylene / ⁇ -olefin copolymer (F) can be obtained by copolymerizing ethylene and ⁇ -olefin, and the ethylene / ⁇ -olefin copolymer is a Ziegler-Natta catalyst.
- the polymer may be polymerized using a metallocene or may be polymerized using a metallocene catalyst.
- nucleating agent (D) In the present invention, the nucleating agent (D) is used.
- the nucleating agent (D) one or more compounds selected from the group consisting of aromatic phosphate ester compounds, carboxylic acid metal salt nucleating agents, polymer nucleating agents, sorbitol nucleating agents and inorganic compound nucleating agents. Is mentioned. It is preferable that the nucleating agent (D) does not deteriorate the odor of the multilayer blow container.
- a nucleating agent (D) may be used individually by 1 type, or may use 2 or more types together.
- the aromatic phosphate compound is preferably a compound represented by the following formula [III] and / or [IV].
- R 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms
- R 2 and R 3 are each independently a hydrogen atom or 1 to 10 carbon atoms.
- a hydrocarbon group, M is a monovalent to trivalent metal atom, n is an integer of 1 to 3, and m is 1 or 2.
- aromatic phosphate compound represented by the general formula [III] include sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2 , 2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium-2 , 2'-Butyliden
- a hydroxyaluminum phosphate compound represented by the general formula [IV] can also be used.
- the compound represented by the general formula [V] in which R 2 and R 3 are both tert-butyl groups. are preferred.
- R 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and m is 1 or 2.
- a particularly preferred aromatic phosphate compound is a compound represented by the general formula [VI].
- R 1 is a methylene group or an ethylidene group.
- hydroxyaluminum-bis [2,2-methylene-bis (4,6-di-t-butyl) phosphate] (also known as bis (2, 4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) aluminum hydroxide salt), or hydroxyaluminum Bis [2,2-ethylidene-bis (4,6-di-t-butyl) phosphate].
- carboxylic acid metal salt nucleating agent for example, pt-butyl aluminum benzoate, aluminum adipate, or sodium benzoate can be used.
- a branched ⁇ -olefin polymer is preferably used as the polymer nucleating agent.
- branched ⁇ -olefin polymers include 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, a homopolymer of 3-ethyl-1-hexene, or a copolymer thereof, Can include copolymers of these with other ⁇ -olefins.
- polymer nucleating agents can be blended directly when the olefin polymer composition (E) is produced, and when the propylene resin (A) is produced, the propylene resin (A) is produced.
- the above branched ⁇ -olefin is polymerized before or after the polymerization in a block manner, and blended by using the propylene resin (A) containing the branched ⁇ -olefin polymer as the nucleating agent (D). It is also possible to use a polymer nucleating agent-containing propylene resin (A ′).
- the polymer nucleating agent contained in the polymer nucleating agent-containing propylene resin (A ′) Let the amount be the blending amount of the nucleating agent (D) in the olefin polymer composition (E). Moreover, let the part which reduced the quantity of the polymer nucleating agent from the polymer nucleating agent mixing
- the polymer nucleating agent can also be formed by prepolymerization when producing the polymer (A), the polymer (B), and the polymer (F) using a known method. ), When the polymer (F) is produced, it can also be formed by a block copolymerization method.
- a polymer nucleating agent-containing propylene resin (A ′) and a propylene resin (A) containing no polymer nucleating agent may be used in combination.
- a polymer of 3-methyl-1-butene is particularly preferable from the viewpoints of transparency, low-temperature impact resistance, rigidity properties, and economical viewpoint.
- nonitol, 1,2,3-trideoxy-4,6 5,7-bis-O-[(4-propylphenyl) methylene] can be preferably used.
- inorganic compound nucleating agent for example, talc, mica, calcium carbonate can be used.
- nucleating agents (D) nonitol, 1,2,3-trideoxy-4,6: 5,7-bis-O— is preferred in terms of transparency, low-temperature impact resistance, rigidity and low odor.
- a commercially available product can be used as the nucleating agent (D) used in the present invention.
- ADK STAB NA-21 manufactured by ADEKA
- ADEKA is bis (2,4,8,10-tetra-t-butyl-6-).
- Hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) is commercially available as a nucleating agent containing aluminum hydroxide as a main component.
- 3-Trideoxy-4,6 5,7-bis-O-[(4-propylphenyl) methylene] is commercially available under the trade name Millard NX8000 (Milken).
- the olefin polymer composition (E) used in the present invention is a resin used for the outermost layer of the multilayer blow container of the present invention.
- the propylene-based resin (A) is 80 to 98 parts by weight and an ethylene / ⁇ -olefin.
- the olefin polymer composition (E) is composed of propylene resin (A) and ethylene / ⁇ -olefin copolymer. It is preferable to use a composition formed by using 0.1 to 20 parts by weight of a low density ethylene / ⁇ -olefin copolymer (F) in addition to the coalescence (B) and the nucleating agent (D). .
- the olefin polymer composition (E) is formed without using the low density ethylene / ⁇ -olefin copolymer (F). It is also preferable.
- the amount of the propylene-based resin (A) and the ethylene / ⁇ -olefin copolymer (B) used is such that the propylene-based resin (A) is used from the viewpoint of good stickiness and economical and productivity. 95.5 to 98 parts by weight, and the ethylene / ⁇ -olefin copolymer (B) is 2 to 4.5 parts by weight (provided that the total of (A) and (B) is 100 parts by weight) It is preferable that
- a multilayer blow container The propylene-based resin (A) blended in the olefin polymer composition (E) is less than 80 parts by weight, and the ethylene / ⁇ -olefin copolymer is inferior in impact resistance and adhesion to other layers.
- (B) is more than 20 parts by weight, stickiness occurs, which is not preferable.
- the low-density ethylene / ⁇ -olefin copolymer (E) is blended into the olefin polymer composition (E) from the viewpoints of stickiness and economy.
- F) is preferably 3 to 15 parts by weight.
- the nucleating agent (D) is used in an amount of 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the total amount of the propylene resin (A) and the ethylene / ⁇ -olefin copolymer (B).
- the effect of improving the glossiness of the film can be obtained.
- the addition amount of the nucleating agent (D) is less than 0.01 parts by weight, the effect of improving the glossiness is small. Even if the addition amount of the nucleating agent (D) is more than 0.5 parts by weight, the effect is not changed, and it is not preferable because it is economically disadvantageous.
- the olefin polymer composition (E) satisfies the following requirement (E-1).
- the melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes.
- MFR melt flow rate
- the fluidity of the olefin polymer composition (E) at the time of molding becomes a range suitable for molding, and fine melt fracture (MF) generated at the time of molding can be suppressed.
- MF fine melt fracture
- the thickness nonuniformity of the olefin polymer composition (E) in blow molding is prevented, and the multilayer blow container excellent in smoothness can be obtained.
- melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is higher than 10 g / 10 minutes, the moldability is inferior, and when it is lower than 5 g / 10 minutes, the glossiness is obtained.
- the melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with the requirements (E-1) relating to the olefin polymer composition (E), that is, ASTM D-1238, is propylene used Can be adjusted by appropriately selecting the resin (A), the ethylene / ⁇ -olefin copolymer (B), and the low density ethylene / ⁇ -olefin copolymer (F) used as necessary. is there.
- both the propylene-based resin (A) and the ethylene / ⁇ -olefin copolymer (B) used were measured in accordance with ASTM D-1238 at a measurement temperature of 230 ° C. and a load of 2.16 kg (MFR). ) In the range of 5 to 10 g / 10 min, the propylene resin (A), the ethylene / ⁇ -olefin copolymer (B), and the low-density ethylene / ⁇ -olefin copolymer used as necessary.
- the requirement (E-1) can be satisfied by appropriately selecting the polymer (F).
- a melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is less than 5 g / 10 minutes.
- the propylene-based resin (A) or ethylene / ⁇ - The olefin copolymer (B) or the low density ethylene / ⁇ -olefin copolymer (F) used as necessary is modified to give an MF of the olefin polymer composition (E).
- The can be adjusted within the above range.
- an organic peroxide the thing similar to what was described by the term of the said ⁇ propylene-type resin (A)> is mentioned.
- an ethylene / ⁇ -olefin copolymer (B) to be combined is necessary.
- the MFR of the olefin polymer composition (E) can be adjusted within the above range by using a low density ethylene / ⁇ -olefin copolymer (F) used depending on
- the olefin polymer composition (E) preferably has a crystal melting point measured by DSC according to JIS-K7121 in the range of 140 to 155 ° C. When the crystal melting point is within the above range, a multi-layer blow container having good gloss and good impact resistance can be obtained.
- the crystal melting point of the olefin polymer composition (E) can be measured using a differential scanning calorimeter (DSC) according to JIS-K7121. Specifically, it can be measured by the same method as the crystalline melting point of the propylene resin (A) described above.
- DSC differential scanning calorimeter
- the olefin polymer composition (E) preferably has a half crystallization time (t 1/2 ) in the range of 50 to 1000 seconds, and more preferably in the range of 100 to 500 seconds. Within the above range, the mold transferability becomes good at the time of blow molding, and a multi-layer blow container with good gloss can be obtained.
- the half crystallization time (t 1/2 ) was crystallized with the olefin polymer composition (E) under an isothermal condition of 125 ° C., and the calorific value associated with crystallization was measured at this time to start the heat generation (crystallization It can be measured as the time from the start) until the calorific value becomes half the total calorific value.
- the half crystallization time (t 1/2 ) of the olefin polymer composition (E) can be adjusted by the amount of the nucleating agent (D) contained in the olefin polymer composition (E). By increasing the amount of the nucleating agent (D) contained in the olefin polymer composition (E), it is possible to increase the half crystallization time (t 1/2 ), and conversely, the amount of the nucleating agent (D). It is possible to slow down the half crystallization time (t 1/2 ) by reducing.
- the olefin polymer composition (E) of the present invention includes the propylene resin (A), the ethylene / ⁇ -olefin copolymer (B), the low density ethylene / ⁇ -olefin copolymer (F), and Components other than the nucleating agent (D) may be contained.
- Examples of other resins include polyolefins other than propylene resin (A), ethylene / ⁇ -olefin copolymer (B), low density ethylene / ⁇ -olefin copolymer (F), and nucleating agent (D).
- Examples of the polyolefin resin include propylene resins (P) other than the propylene resin (A).
- Examples of the propylene resin (P) include propylene homopolymers (including syndiotactic propylene homopolymers) different from the propylene resin (A).
- Tm of propylene-based resin (P) measured by a differential scanning calorimeter (DSC) according to JISK7121 is 140 to 155 ° C.
- the MFR of propylene resin (P) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is preferably 0.01 to 20 g / 10 min, particularly 0.1 to 5 g / 10 min is preferred.
- styrene elastomers or hydrogenated products (S) thereof can be exemplified.
- S hydrogenated product
- the styrenic elastomer or hydrogenated product (S) thereof has a styrene content of 10 to 70% by weight, preferably 10 to 65% by weight, more preferably 10 to 40% by weight, and a conjugated diene content of 30 to 90% by weight.
- the styrenic elastomer or the hydrogenated product (S) thereof is preferably 35 to 90% by weight, more preferably 60 to 90% by weight.
- styrene-type elastomer or its hydrogenated substance As said styrene-type elastomer or its hydrogenated substance (S), a styrene-type polymer block component (it may hereafter be called a styrene block) and a conjugated diene-type polymer block component (it may be hereafter called a diene block). And a styrene / butadiene random copolymer, a styrene / isoprene random copolymer, a styrene / chloroprene random copolymer, and hydrogenated products thereof. Of these, styrene block copolymers are preferred.
- the styrenic polymer block component constituting the styrenic block copolymer is composed of styrene or a derivative thereof.
- Specific examples of the monomer include styrene, ⁇ -methylstyrene, p-methylstyrene, chlorostyrene, and vinylnaphthalene. Etc. Of these, styrene is preferred. These monomers are used alone or in combination of two or more.
- the monomer constituting the conjugated diene polymer block include butadiene, isoprene, chloroprene and the like. Of these, butadiene and isoprene are preferred. These monomers are used alone or in combination of two or more.
- the bonding form of the styrene block and the diene block in the styrenic block copolymer is not particularly limited, but the styrene block / diene block or styrene block / [diene block / styrene block] n (where n is 1 to 5) Form is preferred.
- the content of the styrene polymer block component in the styrene block copolymer is 10 to 70% by weight, preferably 10 to 65% by weight, more preferably 10 to 40% by weight, and the content of the conjugated diene polymer block component
- the amount is desirably 30 to 90% by weight, preferably 35 to 90% by weight, and more preferably 60 to 90% by weight.
- the styrene block copolymer has a melt flow rate (MFR) measured at 230 ° C. and a load of 2160 g in accordance with ASTM D-1238 at 0.1 g / 10 min or more, preferably 0.3 to 20 g / 10 min, particularly Preferably, it is 5 to 10 g / 10 min.
- MFR melt flow rate
- styrenic block copolymers include styrene / ethylene / butene / styrene block copolymers (SEBS), styrene / ethylene / propylene / styrene block copolymers (SEPS), and styrene / butadiene / stin blocks.
- SEBS styrene / ethylene / butene / styrene block copolymers
- SEPS styrene / ethylene / propylene / styrene block copolymers
- SEPS styrene / butadiene / stin blocks.
- SBS copolymer
- SIS styrene / isoprene / styrene block copolymer
- SEP styrene / ethylene / propylene block copolymer
- the upper limit is usually 20 parts by weight or less, more preferably with respect to 100 parts by weight of the total of (A) and (B). Is 10 parts by weight or less, more preferably 5 parts by weight or less, and the lower limit is usually 0.1 parts by weight.
- the upper limit of the propylene resin (P) is usually 20 parts by weight with respect to a total of 100 parts by weight of the (A) and (B). Below, more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less, and the lower limit is usually 0.1 parts by weight.
- the styrene elastomer or its hydrogenated product (S) is in a total of 100 parts by weight of (A) and (B).
- the upper limit is usually 20 parts by weight or less, more preferably 10 parts by weight or less, further preferably 5 parts by weight or less, and the lower limit is usually 0.1 parts by weight.
- the propylene resin (P) and the styrene elastomer or hydrogenated product (S) are used as the other resin
- the propylene resin (P) and the styrene elastomer or hydrogenated product thereof are used.
- the upper limit of the total of (S) is usually 20 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less based on 100 parts by weight of the total of (A) and (B).
- the lower limit is usually 0.1 parts by weight.
- an embodiment in which the propylene resin (P) is not added and an embodiment in which the styrene elastomer or its hydrogenated product (S) is not added are more desirable. It is an aspect and the aspect which does not add the said propylene-type resin (P) and the said styrene-type elastomer, or its hydrogenated substance (S) is a more desirable aspect.
- the low density ethylene / ⁇ -olefin copolymer (F) is in a small amount or not present in terms of stickiness.
- Olefin polymer composition (E) consisting essentially of 0 to 20 parts by weight of at least one polymer selected from S) (in an amount relative to a total of 100 parts by weight of (A) and (B))
- Olefin polymer composition (E) consisting essentially of 0 to 20 parts by weight of at least one polymer selected from S) (in an amount relative to a total of 100 parts by weight of (A) and (B))
- the total of the propylene resin (P) having a Tm of 140 to 155 ° C. and the styrene elastomer or its hydrogenated product (S) is 0 with respect to 100 parts by weight of the total of (A) and (B).
- the case of parts by weight is also included.
- “substantially” means that the olefin polymer composition (E) may contain additives as other components within the range not impairing the effects of the present invention, but other components are included. Indicates no.
- Additives include antioxidants, hydrochloric acid absorbers, heat stabilizers, light stabilizers, UV absorbers, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, copper damage inhibitors, neutralizing agents, Examples thereof include foaming agents, plasticizers, anti-bubble agents, crosslinkers, flowability improvers such as peroxides, weld strength improvers, and the like.
- these additives For example, a commercial item can be used.
- the amount of the olefin polymer composition (E) is not particularly limited as long as it is within the range where the effects of the present invention can be obtained. It is usually 0.01 to 1.00 parts by weight with respect to 100 parts by weight in total with B).
- the olefin polymer composition (E) used in the present invention has a MFR in a specific range, it is difficult to blow mold only with the olefin polymer composition (E), but as a surface layer of a multilayer blow molded article. It can be used, and when used as a surface layer, it exhibits excellent gloss and has excellent physical properties.
- the method for preparing the olefin polymer composition (E) is not particularly limited.
- a propylene resin (A), an ethylene / ⁇ -olefin copolymer (B) and a nucleating agent (D) can be arbitrarily used.
- the strand is usually formed into pellets using a pelletizer or the like before blow molding.
- the propylene resin (A) the propylene resin (A), the ethylene / ⁇ -olefin copolymer (B) or a low-density ethylene / ⁇ -olefin copolymer (F) used as necessary may be modified.
- a reactive additive such as a peroxide such as an organic peroxide or a crosslinking agent
- the reason why the multilayer blow container formed using the olefin polymer composition (E) as a resin for forming the outermost layer exhibits good physical properties is not clear, but ethylene / ⁇ -olefin having a crystal melting point in a specific range.
- the copolymer (B) it is considered that the ethylene / ⁇ -olefin copolymer (B) is finely dispersed in the propylene-based resin (A). It is considered that the impact resistance is high and the impact resistance is high, and furthermore, the impact resistance and the low stickiness are compatible.
- the resin used for the outermost layer is composed of the above-mentioned olefin polymer composition (E).
- the multilayer blow container of the present invention has at least one inner layer as a layer other than the outermost layer.
- the other layer (inner layer) forming the multilayer blow container is not particularly limited and is usually made of a thermoplastic resin other than the olefin polymer composition (E).
- examples thereof include vinyl copolymers, polyvinyl alcohol resins or polyvinyl chloride resins, polyvinyl chloride resins, and modified polyolefin resins.
- a mixture of two or more of the above resins can also be used.
- a propylene polymer (G) and an ethylene polymer (H) are preferable.
- the propylene polymer (G) is a propylene polymer having a propylene-derived constitutional unit of 51 mol% or more, and the ethylene polymer (H) is an ethylene-derived constitutional unit of 51 mol% or more. It is an ethylene polymer.
- Multi-layer blow container is formed from styrene polymer or other polar resin such as polyethylene terephthalate resin, polyamide resin, ABS resin, ethylene-vinyl acetate copolymer, polyvinyl alcohol resin, polyvinyl chloride resin as other layer (inner layer)
- styrene polymer or other polar resin such as polyethylene terephthalate resin, polyamide resin, ABS resin, ethylene-vinyl acetate copolymer, polyvinyl alcohol resin, polyvinyl chloride resin as other layer (inner layer)
- the outermost layer of the multilayer blow container of the present invention that is, the layer formed from the olefin polymer composition (E) is highly glossy.
- the multilayer blow container is also excellent in impact resistance.
- the MFR which is an index of fluidity of the olefin polymer composition (E) is in a specific range. Yes. For this reason, in blow molding, it is estimated that the surface of the heated molten resin immediately before contacting the mold is easily smoothed, and the surface is likely to be smooth even after blow molding, thereby providing excellent surface gloss. It is considered that a multilayer blow container can be obtained. Moreover, since MFR which is an index of fluidity of the olefin polymer composition (E) is in a specific range, the surface appearance is also good.
- an ethylene / ⁇ -olefin copolymer (B) is used as a raw material of the composition. Since the ethylene / ⁇ -olefin copolymer (B) has a crystal melting point in a specific range, the obtained molded product exhibits excellent properties such as the above-described correlated adhesiveness and low stickiness, Even when the amount of the ethylene / ⁇ -olefin copolymer (B) used relative to the propylene resin (A) is small, the impact resistance can be improved efficiently.
- a low density ethylene / ⁇ -olefin copolymer (F) is used as a raw material of the composition as required.
- the low-density ethylene / ⁇ -olefin copolymer (F) can efficiently improve the low-temperature impact resistance even when the amount used for the propylene-based resin (A) is small.
- the multilayer blow container of the present invention has high gloss and excellent impact resistance, and when the low density ethylene / ⁇ -olein copolymer (F) is used, low temperature impact resistance is achieved.
- the present inventors have estimated that it is also excellent.
- the multilayer blow container of the present invention Since the multilayer blow container of the present invention has excellent impact resistance, cracks and the like due to external impact are suppressed, and since the outermost layer is highly glossy, the container has gloss with a transparent feeling. In addition, since the multilayer blow container of the present invention is excellent in low-temperature impact resistance, even when the multilayer blow container is filled with contents and transported, stored, etc. under low temperature conditions, it is due to impact from the outside. Cracks and the like are suppressed.
- the layer structure of the multilayer blow container of the present invention is not particularly limited as long as the outermost layer is a layer made of the olefin polymer composition (E).
- the outermost layer made of the olefin polymer composition (E) A two-layer configuration with the innermost layer (layer configuration arranged in order of outermost layer / innermost layer), an outermost layer made of the olefin polymer composition (E), an intermediate layer adjacent to the outermost layer, Three-layer configuration with the innermost layer adjacent to the intermediate layer (layer configuration arranged in order of outermost layer / intermediate layer / innermost layer), outermost layer made of the olefin polymer composition (E), and adjacent to the outermost layer A four-layer structure (outermost layer / intermediate layer (1) /) of the intermediate layer (1), the intermediate layer (2) adjacent to the intermediate layer (1), and the innermost layer adjacent to the intermediate layer (2).
- a layer located inside the outermost layer is defined as an inner layer. That is, in the present invention, the innermost layer and the intermediate layer correspond to inner layers, and the multilayer blow container of the present invention may have at least one inner layer and may have two or more layers.
- the layer adjacent to the outermost layer is formed from the propylene polymer (G) or the ethylene polymer (H), so-called Even without using an adhesive resin, strong adhesiveness was exhibited.
- the layer adjacent to the outermost layer made of the olefin polymer composition (E) is a propylene polymer ( G) or an ethylene polymer (H) is preferable.
- the layer adjacent to the olefin polymer composition (E) is a layer other than the propylene polymer (G) and the ethylene polymer (H), the olefin polymer composition (E). From the viewpoint of adhesiveness with the outermost layer made of, it is preferable that the outermost layer made of the olefin polymer composition (E) and other layers are formed via the adhesive resin layer.
- the multilayer blow container of the present invention may have any layer colored.
- the propylene polymer (G) is not particularly limited, and examples thereof include homopolypropylene, propylene / ⁇ -olefin random copolymer, propylene / ⁇ -olefin block copolymer, and the like.
- the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is preferably in the range of 0.1 to 20.0 g / 10 minutes. In particular, 0.1 to 5 g / 10 min is preferable.
- the crystal melting point measured with a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is preferably in the range of 100 to 168 ° C.
- the ethylene polymer (H) is not particularly limited, and examples thereof include so-called high density polyethylene, linear low density polyethylene, and low density polyethylene.
- the density of the ethylene polymer (H) measured by the density gradient tube method is preferably 0.860 to 0.980 g / cm 3 , and the measurement temperature is 230 ° C. according to ASTM D-1238.
- the MFR measured under a 16 kg load is preferably 0.01 to 20 g / 10 min, and particularly preferably 0.1 to 5 g / 10 min.
- the modified polyolefin resin (I) is not particularly limited, and generally an acid-modified polyolefin can be used.
- the acid used for the acid modification include an ethylenically unsaturated carboxylic acid such as maleic anhydride, acrylic acid, methacrylic acid, and itaconic anhydride, or an anhydride thereof.
- the polyolefin resin used for modification is preferably an ethylene / ⁇ -olefin copolymer, a propylene homopolymer, or a propylene / ⁇ -olefin copolymer.
- the inner layer other than the layer adjacent to the outermost layer in the multilayer blow container is composed of a propylene polymer (G), an ethylene polymer (H), a styrene polymer, a polyethylene terephthalate resin, a polyamide resin, an ABS resin.
- G propylene polymer
- H ethylene polymer
- H styrene polymer
- polyethylene terephthalate resin a polyamide resin
- ABS resin an ABS resin.
- a layer formed of at least one resin selected from ethylene-vinyl acetate copolymer, polyvinyl alcohol resin or polyvinyl chloride resin is preferable.
- any method may be used as long as it is blow molding.
- the molding method include a direct blow molding method (hollow molding method), an injection stretch blow molding method (injection hollow molding method), an extrusion stretch blow molding method, and a sheet blow molding method.
- the multilayer blow container is preferably obtained by molding by a direct blow molding method or an injection stretch blow molding method from the viewpoint of productivity in mass production.
- the olefin polymer composition (E) and other resins are used, and the olefin polymer composition (E) is the outermost layer. Then, while the obtained parison is still in a molten state, it is sandwiched between blow molds, and fluid is blown into the parison to be molded into a predetermined shape. Since the layer formed from the olefin polymer composition (E) is the outermost layer, a high gloss multilayer blow container can be obtained.
- the molding conditions depend on the properties of the resin, but the temperature of the resin when the fluid is blown, that is, the molding temperature is preferably 120 to 260 ° C., and the fluid blowing pressure is 2 to 10 kg / cm 2.
- a blow ratio of 1.2 to 5.0 is preferable from the viewpoint of moldability.
- the blow ratio here refers to the outer diameter of the cylindrical molten parison extruded from the extruder die, and the value obtained by dividing the outer diameter of the bottle to be formed.
- the olefin polymer composition (E) and other resins are injection molded so that the olefin polymer composition (E) is the outermost layer.
- the preform is forcibly stretched longitudinally using a stretching rod or the like, and then the transverse direction.
- a multilayer blow container can be obtained by press-fitting a pressurized fluid into the preform for further stretching.
- the injection temperature of the olefin polymer composition (E) is usually in the range of 160 to 260 ° C.
- the temperature of the preform immediately before the longitudinal stretching is preferably 110 to 150 ° C.
- the longitudinal stretching ratio is preferably 1.5 to 4.0 times
- the transverse stretching ratio is 1.5 to 3.0 times. It is preferable that
- the thickness and size of the multilayer blow container of the present invention are appropriately determined depending on the use of the multilayer blow container and the like. Usually, the thickness is 0.3 to 10.0 mm, the size is 10 to 300 mm in diameter, and the height is 10 to 300 mm.
- the thickness of the outermost layer of the multilayer blow container of the present invention is preferably the ratio of the thickness of the outer layer to the other inner layer (outer layer / inner layer), preferably 50/50 to 5/95, more preferably 30/70 to 10 / 90 is preferred. Within the above-mentioned range, the high gloss of the outer layer is most easily expressed and the moldability is good, which is preferable.
- the multilayer blow container of the present invention is excellent in transparency when a transparent resin is used for layers other than the outermost layer.
- the haze value (haze) measured using a haze meter in accordance with JIS-K7105 is preferably 30 or less, and more preferably 20 or less. Within the above range, it is possible to obtain a high value-added bottle with very good contents visibility.
- the multilayer blow container of the present invention is excellent in gloss.
- the 60 ° gloss measured with a gloss meter in accordance with JIS-K7105 of the outermost layer is preferably 70 or more, and 75 or more. More preferably. Within the above range, it is possible to obtain a high value-added bottle exhibiting an excellent gloss appearance.
- the multi-layer blow container according to the present invention can be used for various applications, for example, filling containers such as sauces, dressings, juices, fruits, sweets, boiled vegetables, toiletries such as cosmetics and shampoos. It is suitable as a container for filling sanitary goods such as containers and liquid detergents.
- the method for producing a multilayer blow container of the present invention uses a thermoplastic resin composition other than the olefin polymer composition (E) and the olefin polymer composition (E) described above, and the olefin polymer composition (E) It is preferable that the outermost layer is formed and molded by a direct blow molding method or an injection stretch blow molding method so that the thermoplastic resin composition other than the olefin polymer composition (E) forms at least one inner layer.
- thermoplastic resin other than the coalescence composition (E) and the olefin polymer composition (E) those described in the above-mentioned section [Multilayer Blow Container] can be used.
- Other resins and various additives described above can also be used.
- a multilayer blow container in which the outermost layer is formed from the olefin polymer composition (E) is molded by a direct blow molding method or an injection stretch blow molding method. For this reason, the resulting multilayer blow container is highly glossy because the outermost layer of the multilayer blow container contains the ethylene / ⁇ -olefin copolymer (B). The multilayer blow container is also excellent in impact resistance.
- the multilayer blow container obtained by the production method of the present invention has excellent impact resistance, cracks due to external impact are suppressed, and the outermost layer is highly glossy, so that the container has gloss with a transparent feeling. .
- the solid part after washing was defined as a solid titanium catalyst component (A).
- the solid titanium catalyst component (A) was stored as a decane slurry, but a portion thereof was dried for the purpose of examining the catalyst composition.
- the composition of the solid titanium catalyst component (A) was 2.3 wt% titanium, 61 wt% chlorine, 19 wt% magnesium, and 12.5 wt% DIBP.
- the free titanium compound was detected by the following method. 10 ml of the supernatant of the above solid catalyst component was collected with a syringe into a 100 ml branched Schlenk previously purged with nitrogen and charged. Next, the solvent hexane was dried in a nitrogen stream, and further vacuum-dried for 30 minutes. This was charged with 40 ml of ion-exchanged water and 10 ml of 50% by volume sulfuric acid and stirred for 30 minutes. This aqueous solution was transferred to a 100 ml volumetric flask through a filter paper, followed by conc. As a masking agent for iron (II) ions.
- the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based resin (A-1) was calculated from 7.0 C / 10 min, 13 C-NMR.
- the weight of the structural unit derived from ethylene is 3.2% by weight when the total of the structural unit derived from propylene and the structural unit derived from ethylene is 100% by weight, DSC melting point (measured by DSC based on JIS-K7121) Crystal melting point) was 145 ° C. and Mw / Mn (molecular weight distribution) was 5.3.
- the resulting propylene-based resin (A-2) had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) calculated from 7.0 C / 10 min, 13 C-NMR.
- MFR melt flow rate
- the weight of ethylene-derived constitutional unit when the total of propylene-derived constitutional unit and ethylene-derived constitutional unit is 100% by weight is 4.8% by weight
- DSC melting point measured by DSC based on JIS-K7121
- Crystal melting point was 136 ° C.
- Mw / Mn molecular weight distribution
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the obtained propylene resin (A-3) was calculated from 7.0 C / 10 min, 13 C-NMR.
- the weight of the structural unit derived from ethylene is 1.0% by weight when the total of the structural unit derived from propylene and the structural unit derived from ethylene is 100% by weight.
- DSC melting point (measured by DSC based on JIS-K7121) Crystal melting point) was 156 ° C. and Mw / Mn (molecular weight distribution) was 5.0.
- the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based resin (A-4) was calculated from 13 C-NMR at 3.0 g / 10 min.
- the weight of the structural unit derived from ethylene is 3.2% by weight when the total of the structural unit derived from propylene and the structural unit derived from ethylene is 100% by weight, DSC melting point (measured by DSC based on JIS-K7121) Crystal melting point) was 145 ° C. and Mw / Mn (molecular weight distribution) was 5.3.
- the resulting propylene resin (A-5) had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) calculated from 13 C-NMR at 15.0 g / 10 min.
- MFR melt flow rate
- the weight of the structural unit derived from ethylene is 3.2% by weight when the total of the structural unit derived from propylene and the structural unit derived from ethylene is 100% by weight, DSC melting point (measured by DSC based on JIS-K7121) Crystal melting point) was 145 ° C. and Mw / Mn (molecular weight distribution) was 5.3.
- the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 1.5 hours, and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.
- the solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene to make a total volume of 160 liters.
- ethylene supply was started again at a flow rate of 8 Nm 3 / hr. After 15 minutes, the ethylene flow rate was lowered to 2 Nm 3 / hr, and the pressure in the system was adjusted to 0.08 MPaG. During this time, the temperature in the system rose to 35 ° C. Thereafter, ethylene was supplied at a flow rate of 4 Nm 3 / hr for 3.5 hours while adjusting the temperature in the system to 32 to 35 ° C. During this time, the pressure in the system was maintained at 0.07 to 0.08 MPaG. Next, after the inside of the system was replaced with nitrogen, the supernatant was removed and washed twice with hexane. Thus, a prepolymerized catalyst (2) in which 3 g of polymer was prepolymerized per 1 g of the solid catalyst component was obtained.
- Polymerization was started while continuously supplying 4.1 g / hr of the prepolymerized catalyst (2) prepared above and TIBA at a rate of 5 mmol / hr.
- the yield of the obtained ethylene / 1-hexene copolymer was 6.0 kg / hr, the DSC melting point (crystal melting point measured by DSC according to JIS-K7121) was 98 ° C., measured by the density gradient tube method. Density was 0.903 g / cm 3 , MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg) was 7.0 g / 10 min, and Mw / Mn (molecular weight distribution) was 2.6. .
- the obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / ⁇ -olefin copolymer (B-1).
- the yield of the obtained ethylene / 1-hexene copolymer was 6.0 kg / hr, the DSC melting point (crystal melting point measured by DSC according to JIS-K7121) was 113 ° C., measured by the density gradient tube method. Density was 0.913 g / cm 3 , MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg) was 7.0 g / 10 min, and Mw / Mn (molecular weight distribution) was 2.6. .
- the obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / ⁇ -olefin copolymer (B-2).
- the yield of the obtained ethylene / 1-hexene copolymer is 5.8 kg / hr
- DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) is 120 ° C., measured by density gradient tube method Density was 0.924 g / cm 3
- MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg) was 7.0 g / 10 min
- Mw / Mn molecular weight distribution
- the obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / ⁇ -olefin copolymer (B-3).
- Example A1 97 parts by weight of propylene-based resin (A-1), 3 parts by weight of ethylene / ⁇ -olefin copolymer (B-1), and ADEKA STAB NA-21 (manufactured by ADEKA: bis (2 , 4,8,10-Tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) aluminum hydroxide as a main component 0.15 parts by weight of an aromatic phosphate ester compound nucleating agent) and a phenolic antioxidant [pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) as an additive ) Propionate]], 0.10 parts by weight of a phosphorous antioxidant [Tris (2,4-di-t-butylphenyl) phosphite], and calcium stearate as a neutralizing agent 0.09 part by weight of
- melt flow rate (MFR) of the olefin polymer composition (E-1) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) is 7.0 g / 10 min, DSC melting point (according to JIS-K7121) Crystal melting point measured by DSC) was 147 ° C.
- the molding temperature is set to 200 ° C. and the fluid blowing pressure is set to 5.0 kg / cm 2 .
- a molten parison having an outer diameter of 20.0 mm was formed by a crosshead die having a die hole size of 14.0 mm and a core size of 12.5 mm, weight 34 g, inner capacity 780 ml, mouth screw outer diameter 27.0 mm, waist circumference
- a cylindrical multilayer blow container having a two-layer structure having an outer diameter of 72 mm and a waistline average thickness of 0.5 mmt was manufactured.
- a propylene-based random copolymer B251VT (Co., Ltd.) is used for a base material (inner layer) by using an intermediate layer and an outer layer extruder having a cylinder temperature set at 200 ° C. without using an inner layer extruder.
- melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.2 g / 10 min
- DSC melting point accordinging to JIS-K7121, crystal melting point measured by DSC) ) Is 146 ° C.
- E-1 olefin polymer composition
- blow mold After forming a molten parison in the shape of a mold, it was sandwiched between blow molds adjusted to a temperature of 25 ° C. by a water circulation circuit, stretched and adhered to the mold with compressed air, and cooled and solidified to obtain a multilayer blow container.
- the blow mold two types of molds, that is, a mold subjected to sandblasting # 400 as a surface treatment and a mold subjected to sandblasting # 200, are used, and a multilayer blow container is formed using each mold. Obtained.
- haze, gloss (gross), moldability, adhesiveness, impact resistance (full water drop impact strength) and stickiness were measured by the following evaluation methods.
- a multilayer blow container was prepared using two types of molds, and the gloss of each was evaluated. These results are shown in the table.
- Example A2 The same procedure as in Example A1 was carried out except that the ratio of 95.5 parts by weight of the propylene resin (A-1) and 4.5 parts by weight of the ethylene / ⁇ -olefin copolymer (B-1) was changed.
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-2) obtained in Example A2 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- Example A3 At the time of multilayer blow molding, instead of propylene random copolymer B251VT (manufactured by Prime Polymer Co., Ltd.) for the base material (inner layer), propylene random block copolymer B511QA (manufactured by Prime Polymer Co., Ltd., melt) Flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.2 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC is 158 ° C.) The same procedure as in Example A2 was carried out except that the intermediate layer was used.
- MFR Flow rate
- Example A4 In the case of multilayer blow molding, instead of the propylene random copolymer B251VT (manufactured by Prime Polymer Co., Ltd.) for the base material (inner layer), PE resin HDPE, HZ-6008B (manufactured by Prime Polymer Co., Ltd.) Rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 0.7 g / 10 min, density measured by density gradient tube method is 0.958 g / cm 3 )
- Example A2 was carried out in the same manner as in Example A2.
- Example A5 The same procedure as in Example A1 was carried out except that the ratio of propylene resin (A-1) was 80.0 parts by weight and that of ethylene / ⁇ -olefin copolymer (B-1) was 20.0 parts by weight.
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-3) obtained in Example A5 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 148 ° C.
- ADEKA STAB NA-21 manufactured by ADEKA
- melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-7) obtained in Example A6 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 149 ° C.
- Example A7 When propylene resin (A-1) is stirred and mixed with a Henschel mixer instead of propylene resin (A-4), [2,5-di-methyl-2,5- The same procedure as in Example A2 except that 0.006 part by weight of di- (benzoylperoxy) hexane] was added.
- melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-20) obtained in Example A7 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- MFR melt flow rate
- DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- the results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
- Example A1 The same procedure as in Example A1 was carried out except that the proportion of propylene resin (A-1) was changed to 100 parts by weight and that of ethylene / ⁇ -olefin copolymer (B-1) was changed to 0 part by weight.
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-4) obtained in Comparative Example A1 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- Comparative Example A1 since the ethylene / ⁇ -olefin copolymer (B) is not blended, the requirements of this claim are not satisfied. Since the ethylene / ⁇ -olefin copolymer (B) is not blended, the adhesiveness and impact resistance (full water impact resistance) are inferior.
- Example A2 The same procedure as in Example A1 was carried out except that the ratio of propylene-based resin (A-1) was changed to 70.0 parts by weight and that of ethylene / ⁇ -olefin copolymer (B-1) was changed to 30.0 parts by weight.
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-5) obtained in Comparative Example A2 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- Example A3 The same procedure as in Example A2 was conducted, except that ADK STAB NA-21 (manufactured by ADEKA) was not added as the nucleating agent (D).
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-6) obtained in Comparative Example A3 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 145 ° C.
- Example A4 The same procedure as in Example A2 was conducted except that the propylene resin (A-2) was changed to the propylene resin (A-2).
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-8) obtained in Comparative Example A4 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, the crystalline melting point measured by DSC) was 138 ° C.
- Example A5 The same procedure as in Example A2 was conducted except that the propylene resin (A-3) was changed to the propylene resin (A-3).
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-9) obtained in Comparative Example A5 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 158 ° C.
- Example A6 The same procedure as in Example A2 was conducted except that the propylene resin (A-4) was changed to the propylene resin (A-4).
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-10) obtained in Comparative Example A6 is 3.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- Example A7 The same procedure as in Example A2 was carried out except that the propylene resin (A-5) was replaced with a propylene resin (A-5).
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-11) obtained in Comparative Example A7 is 15.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- melt flow rate (MFR) ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg
- MFR melt flow rate
- Example A8 The same procedure as in Example A2 was conducted except that the ethylene / ⁇ -olefin copolymer (B-2) was changed to the ethylene / ⁇ -olefin copolymer (B-1).
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-12) obtained in Comparative Example A8 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- the ethylene / ⁇ -olefin copolymer (B-2) used in Comparative Example A8 has a DSC melting point (crystal melting point measured by DSC according to JIS-K7121) of the ethylene / ⁇ -olefin copolymer (B). It is higher than the range specified in the claims. For this reason, adhesiveness and impact resistance (full drop impact strength) are inferior. Furthermore, the balance between impact resistance and stickiness is not good.
- Comparative Example A9 The same procedure as in Comparative Example A8 was carried out except that the ratio of propylene resin (A-1) was 90.0 parts by weight and that of ethylene / ⁇ -olefin copolymer (B-2) was 10.0 parts by weight.
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-13) obtained in Comparative Example A9 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- the ethylene / ⁇ -olefin copolymer (B-2) used in Comparative Example A9 has a DSC melting point (crystal melting point measured by DSC according to JIS-K7121) of the ethylene / ⁇ -olefin copolymer (B). It is higher than the range specified in the claims. For this reason, adhesiveness and impact resistance (full drop impact strength) are inferior. Furthermore, the balance between impact resistance and stickiness is not good.
- Comparative Example A10 The procedure was the same as Comparative Example A8 except that the ratio of propylene resin (A-1) was 80.0 parts by weight and that of ethylene / ⁇ -olefin copolymer (B-2) was 20.0 parts by weight.
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-14) obtained in Comparative Example A10 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- the ethylene / ⁇ -olefin copolymer (B-2) used in Comparative Example A10 has a DSC melting point (crystal melting point measured by DSC according to JIS-K7121) of the ethylene / ⁇ -olefin copolymer (B). It is higher than the range specified in the claims. For this reason, adhesiveness and impact resistance (full drop impact strength) are inferior. Furthermore, the balance between impact resistance and stickiness is not good.
- Example A11 The same procedure as in Example A2 was conducted, except that the ethylene / ⁇ -olefin copolymer (B-3) was replaced with the ethylene / ⁇ -olefin copolymer (B-3).
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-15) obtained in Comparative Example A11 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- the ethylene / ⁇ -olefin copolymer (B-3) used in Comparative Example A11 has a DSC melting point (crystal melting point measured by DSC according to JIS-K7121) of the ethylene / ⁇ -olefin copolymer (B). It is higher than the range specified in the claims. For this reason, gloss (gross), adhesiveness, and impact resistance (full water drop impact strength) are inferior. Furthermore, the balance between impact resistance and stickiness is not good.
- melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-16) obtained in Comparative Example A12 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- ULTRAZEX 1030L was used in place of the ethylene / ⁇ -olefin copolymer (B).
- the DSC melting point of ULTZEX 1030L (according to JIS-K7121, crystal melting point measured by DSC) is 115 ° C., which is higher than the DSC melting point range of the ethylene / ⁇ -olefin copolymer (B) defined in the claims. .
- Ultzex 1030L is polymerized with a Ziegler-Natta catalyst that is not a metallocene catalyst, the multilayer blow container formed from the olefin polymer composition (E-16) has adhesiveness, stickiness and impact resistance (full water). Drop impact strength is inferior. Furthermore, the balance between impact resistance and stickiness is not good.
- melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-17) obtained in Comparative Example A13 is 8.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- HZ-2100J was used in place of the ethylene / ⁇ -olefin copolymer (B).
- the DSC melting point of HZ-2100J (according to JIS-K7121, crystal melting point measured by DSC) is 131 ° C., which is higher than the DSC melting point range of the ethylene / ⁇ -olefin copolymer (B) specified in the claims.
- the density measured by the density gradient tube method of HZ-2100J is 0.956 g / cm 3 .
- the multilayer blow container formed from the olefin polymer composition (E-17) is inferior in adhesion and impact resistance (full water drop impact strength). Furthermore, the balance between impact resistance and stickiness is not good.
- Tuffmer P-0680 polyethylene rubber (EPR), manufactured by Mitsui Chemicals, Inc., density 0. 870 g / cm 3 , melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.0 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) ) Is not measured.), And Tufmer P-0680 (manufactured by Mitsui Chemicals, Inc.) as propylene resin (A-1) as 90.0 parts by weight and ethylene / ⁇ -olefin copolymer (B) was carried out in the same manner as in Example A1, except that the ratio was changed to 10.0 parts by weight.
- EPR polyethylene rubber
- MFR melt flow rate
- melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-18) obtained in Comparative Example A14 is 6.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- Tuffmer P-0680 manufactured by Mitsui Chemicals, Inc.
- Tuffmer P-0680 does not correspond to an ethylene / ⁇ -olefin copolymer (B) because its DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) is not measured.
- the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) was 1.0 g / 10 min, and the density measured by the density gradient tube method was 0.870 g / cm 3 . .
- the multilayer blow container formed from the olefin polymer composition (E-18) is inferior in glossiness (gloss), adhesiveness and stickiness.
- Tuffmer P-0180 polyethylene rubber (EPR), manufactured by Mitsui Chemicals, Inc., density 0. 0
- EPR polyethylene rubber
- melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 8.0 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) ) Is not measured.), And 90.0 parts by weight of propylene resin (A-1) and ethylene / ⁇ -olefin copolymer (B) as Toughmer P-0180 (manufactured by Mitsui Chemicals, Inc.) was carried out in the same manner as in Example A1, except that the ratio was changed to 10.0 parts by weight.
- MFR melt flow rate
- melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-19) obtained in Comparative Example A15 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
- Tuffmer P-0180 (manufactured by Mitsui Chemicals, Inc.) is used in place of the ethylene / ⁇ -olefin copolymer (B).
- Tuffmer P-0180 does not correspond to an ethylene / ⁇ -olefin copolymer (B) because the DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) is not measured.
- the density was 0.870 g / cm 3 . For this reason, the multilayer blow container formed from the olefin polymer composition (E-19) has poor adhesion and stickiness.
- Example B1 97 parts by weight of propylene-based resin (A-1), 3 parts by weight of ethylene / ⁇ -olefin copolymer (B-1), and ADEKA STAB NA-21 (manufactured by ADEKA: bis (2 , 4,8,10-Tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) aluminum hydroxide as a main component Tafmer P-0280 (ethylene-propylene copolymer, manufactured by Mitsui Chemicals, Ltd.) as 0.15 parts by weight of an aromatic phosphate ester compound nucleating agent) as a low density ethylene / ⁇ -olefin copolymer (F) the density was measured by a density gradient tube method: 0.870 g / cm 3, Ziegler-Natta catalyst, DSC melting point (according to JIS-K7121, the crystalline melting point was measured by DSC): not
- melt flow rate (MFR) of the propylene resin composition (E-21) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 7.0 g / 10 min, DSC melting point (according to JIS-K7121) Crystal melting point measured by DSC) was 147 ° C.
- the molding temperature is set to 200 ° C. and the fluid blowing pressure is set to 5.0 kg / cm 2 .
- a molten parison having an outer diameter of 20.0 mm was formed by a crosshead die having a die hole size of 14.0 mm and a core size of 12.5 mm, weight 34 g, inner capacity 780 ml, mouth screw outer diameter 27.0 mm, waist circumference
- a cylindrical multilayer blow container having a two-layer structure having an outer diameter of 72 mm and a waistline average thickness of 0.5 mmt was manufactured.
- a propylene-based random copolymer B251VT (Co., Ltd.) is used for a base material (inner layer) by using an intermediate layer and an outer layer extruder having a cylinder temperature set at 200 ° C. without using an inner layer extruder.
- melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.2 g / 10 min
- DSC melting point accordinging to JIS-K7121, crystal melting point measured by DSC)
- Is 146 ° C. with an intermediate layer extruder and the olefin polymer composition (E-21) is dissolved with an outer layer extruder so that the outer layer thickness ratio is 15%.
- blow mold After forming a molten parison in the shape of a mold, it was sandwiched between blow molds adjusted to a temperature of 25 ° C. by a water circulation circuit, stretched and adhered to the mold with compressed air, and cooled and solidified to obtain a multilayer blow container.
- the blow mold two types of molds, that is, a mold subjected to sandblasting # 400 as a surface treatment and a mold subjected to sandblasting # 200, are used, and a multilayer blow container is formed using each mold. Obtained.
- Example B2 Low density ethylene / ⁇ -olefin copolymer (F) was measured by Mitsui Chemicals, Inc., Tafmer A-4085S (ethylene-butene copolymer, density gradient tube method) from Mitsui Chemicals, Inc., Tafmer P-0280.
- a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
- Example B3 The propylene resin (A-1) was changed to 90 parts by weight, the ethylene / ⁇ -olefin copolymer (B-1) was changed to 10 parts by weight, and the low density ethylene / ⁇ -olefin copolymer (F) was changed to Mitsui A strand was obtained in the same manner as in Example B1, except that Tuffmer P-0280 manufactured by Kagaku Co., Ltd. was changed to Tuffmer A-4085S manufactured by Mitsui Chemicals, and the blending amount was changed from 15 parts by weight to 5 parts by weight. It was.
- a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
- Example B4 The low density ethylene / ⁇ -olefin copolymer (F) was changed in the same manner as in Example B1 except that Mitsui Chemicals Co., Ltd., Tafmer P-0280 was changed to Mitsui Chemicals Co., Ltd., Tafmer A-4085S. Obtained.
- a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
- Example B5 A strand was obtained in the same manner as in Example B1 except that the low-density ethylene / ⁇ -olefin copolymer (F) was not used.
- a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
- Example B6 The propylene-based resin (A-1) was changed to 95.5 parts by weight and the ethylene / ⁇ -olefin copolymer (B-1) was changed to 4.5 parts by weight to obtain a low density ethylene / ⁇ -olefin copolymer (F ) Was used, and a strand was obtained in the same manner as in Example B1 except that 0.1 part by weight of stearic acid monoglyceride was used as an antistatic agent.
- a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
- Example B7 The propylene resin (A-1) was changed to 90 parts by weight and the ethylene / ⁇ -olefin copolymer (B-1) was changed to 10 parts by weight, and the low density ethylene / ⁇ -olefin copolymer (F) was not used. A strand was obtained in the same manner as in Example B1.
- a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
- a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
- Tuffmer P-0275 ethylene-propylene copolymer, density measured by density gradient tube method: 0.860 g / cm 3 , DSC melting point (according to JIS-K7121, crystal melting point measured by DSC): not observed , MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg): 5.4 g / 10 min) was carried out in the same manner as in Example B1 to obtain a strand.
- a multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
- MFR Melt flow rate
- the MFR of the propylene resin (A), the ethylene / ⁇ -olefin copolymer (B), the low density ethylene / ⁇ -olefin copolymer (F), and the olefin polymer composition (E) is ASTM D- It was measured according to 1238, measurement temperature 230 ° C., load 2.16 kg.
- the strand obtained at the time of MFR measurement is collected and used for the following density measurement.
- Crystalline melting points of the propylene resin (A), the ethylene / ⁇ -olefin copolymer (B), the low density ethylene / ⁇ -olefin copolymer (F) and the olefin polymer composition (E) are in accordance with JIS-K7121.
- the measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer).
- the peak of the endothermic peak at the third step measured here was defined as the crystalline melting point (Tm).
- Tm crystalline melting point
- Measurement condition Measurement environment: Nitrogen gas atmosphere Sample volume: 5mg Sample shape: Press film (230 ° C molding, thickness 200-400 ⁇ m) First step: The temperature is raised from 30 ° C to 240 ° C at 10 ° C / min and held for 10 min.
- Second step IV Decrease the temperature to 60 ° C at 10 ° C / min.
- 3rd step IV Increase the temperature to 240 ° C at 10 ° C / min.
- the half crystallization time (T 1/2 ) of the olefin polymer composition (E) was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer (DSC7)).
- the olefin polymer composition (E) is crystallized under an isothermal condition of 125 ° C., and the calorific value associated with the crystallization is measured at this time, and the calorific value from the start of the exotherm (crystallization start) is half the total calorific value.
- the time (seconds) until the crystallization time was measured as the half crystallization time (t 1/2 ).
- a smaller half crystallization time (t 1/2 ) means a faster crystallization rate.
- Measurement condition Measurement environment: Nitrogen gas atmosphere Sample volume: 5mg Sample shape: Press film (230 ° C molding, thickness 200-400 ⁇ m) First step: The temperature is increased from 30 ° C to 220 ° C at 10 ° C / min and held for 3 min.
- 2nd step IV Decrease the temperature to 125 ° C at 60 ° C / min.
- the density of the ethylene / ⁇ -olefin copolymer (B) and the low density ethylene / ⁇ -olefin copolymer (F) is the same as that of the ethylene / ⁇ -olefin copolymer (B) and the low density obtained during the MFR measurement.
- the strands of the density ethylene / ⁇ -olefin copolymer (F) were each heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured with a density gradient tube.
- Mw / Mn molecular weight distribution
- Mw and Mn were measured as follows using GPC-150C Plus manufactured by Waters.
- TSKgel GMH6-HT and TSKgel GMH6-HTL were used as separation columns, the column size was 7.5 mm in inner diameter and 600 mm in length, the column temperature was 140 ° C., and o-dichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase.
- Yakuhin Kogyo Co., Ltd. and 0.025% by weight of BHT (Wako Pure Chemical Industries, Ltd.) as an antioxidant, moved at 1.0 ml / min, sample concentration of 0.1% by weight, sample injection The amount was 500 microliters, and a differential refractometer was used as a detector.
- Standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw ⁇ 1000 and Mw> 4 ⁇ 10 6 , and used by Pressure Chemical Co. for 1000 ⁇ Mw ⁇ 4 ⁇ 10 6 .
- the glossiness was evaluated by the following gloss measurement.
- the measurement site was cut out from the container body, and the 60-degree glossiness of the outer layer was measured with a gloss meter (NIPPON DENSHOKU (VG2000)) in accordance with JIS-K7105. It can be said that the larger the gloss value, the better the glossiness.
- AA Appearance is poor and adhesion is good
- BB Appearance is poor and adhesion is slightly inferior when observed closely
- CC Clear appearance is poor and adhesion is inferior [Odor]
- the odor of the olefin polymer composition (E) was obtained by putting 10 g of the composition pellets in a 100 ml Erlenmeyer flask, sealing with a cap, taking out after heating in an oven at 100 ° C. for 1 hour, and immediately opening the cap. The generated odor was judged as superior or inferior in the sensory test as follows.
- AA No odor
- BB Some odor
- CC Some odor [impact resistance]
- the impact resistance was evaluated based on the presence or absence of surface cracks by the full water drop impact strength measurement method described below.
- a multi-layer blow container (with an internal capacity of 780 ml) filled with water was cooled to 5 ° C. (evaluation of impact resistance), and each of the 10 containers cooled to each temperature had a bottom of 1 m from the concrete surface. It was dropped vertically from the height position and evaluated according to the following drop criteria. The determination of the crack was made based on whether or not a surface crack was generated.
- Weight of structural unit derived from ⁇ -olefin in propylene resin calculated from 13 C-NMR The total of the structural unit derived from propylene calculated from 13 C-NMR and the structural unit derived from one or more olefins selected from the group consisting of ethylene and an ⁇ -olefin having 4 to 20 carbon atoms is 100% by weight.
- the weight of the structural unit derived from one or more olefins selected from the group consisting of ethylene and ⁇ -olefins having 4 to 20 carbon atoms is measured and calculated as follows based on the measurement of 13 C-NMR. I decided.
- E (mol%) Mole fraction of structural units derived from ethylene (mol%)
- P (mol%) mole fraction of structural units derived from propylene (mol%)
- the weight percent of the structural unit derived from propylene and the weight percent of the structural unit derived from ethylene in the propylene-based resin (A) were calculated from the calculated E (mol%) and P (mol%) in weight percent. .
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Abstract
Description
本発明の多層ブロー容器は、最外層に使用される樹脂が、プロピレン系樹脂(A)とエチレン・α‐オレフィン共重合体(B)と、核剤(D)とから形成されるオレフィン重合体組成物(E)からなることを特徴とする。 [Multi-layer blow container]
In the multilayer blow container of the present invention, the resin used for the outermost layer is an olefin polymer formed of a propylene resin (A), an ethylene / α-olefin copolymer (B), and a nucleating agent (D). It consists of a composition (E), It is characterized by the above-mentioned.
本発明に用いるプロピレン系樹脂(A)は、下記要件(A-1)および(A-2)を満たし、さらに下記要件(A-3)、(A-4)の少なくとも一方を満たすことが好ましく、下記要件(A-3)および(A-4)を満たすことがより好ましい。プロピレン系樹脂(A)は一種単独で用いても、二種以上を用いてもよい。 <Propylene resin (A)>
The propylene resin (A) used in the present invention preferably satisfies the following requirements (A-1) and (A-2), and preferably satisfies at least one of the following requirements (A-3) and (A-4): More preferably, the following requirements (A-3) and (A-4) are satisfied. Propylene-type resin (A) may be used individually by 1 type, or may use 2 or more types.
測定環境:窒素ガス雰囲気
サンプル量 : 5mg
サンプル形状 : プレスフィルム(230℃成形、厚み200~400μm)
第1step : 30℃より10℃/minで240℃まで昇温し、10min間保持する。 (Measurement condition)
Measurement environment: Nitrogen gas atmosphere Sample volume: 5mg
Sample shape: Press film (230 ° C molding, thickness 200-400μm)
First step: The temperature is raised from 30 ° C to 240 ° C at 10 ° C / min and held for 10 min.
測定装置:日本電子製LA400型核磁気共鳴装置
測定モード:BCM(Bilevel Complete decoupling)
観測周波数:100.4MHz
観測範囲:17006.8Hz
パルス幅:C核45°(7.8μ秒)
パルス繰り返し時間:5秒
試料管:5mmφ
試料管回転数:12Hz
積算回数:20000回
測定温度:125℃
溶媒:1,2,4-トリクロロベンゼン:0.35ml/重ベンゼン:0.2ml
試料量:約40mg
(プロピレン由来の構成単位の重量の算出)
エチレンおよび炭素原子数4~20のα‐オレフィンからなる群から選ばれる1種以上のオレフィン(すなわちコモノマー)がエチレンである場合、得られた13C-NMRスペクトルから下記文献(1)に準じて、モノマー連鎖分布(ダイアッド(2連子)分布)の比率を決定することにより、プロピレン系樹脂(A)中のエチレンに由来する構成単位のモル分率(mol%) (以下E(mol%)と記す)およびプロピレンに由来する構成単位のモル分率(mol%) (以下P(mol%)と記す)を算出することができる。求められたE(mol%)およびP(mol%)から重量%に換算しプロピレン系樹脂(A)中のプロピレンに由来する構成単位の重量%およびエチレンに由来する構成単位の重量%を算出することができる。 ( 13 C-NMR measurement conditions)
Measuring apparatus: LA400 type nuclear magnetic resonance apparatus manufactured by JEOL Measurement mode: BCM (Bilevel Complete Decoupling)
Observation frequency: 100.4 MHz
Observation range: 17006.8Hz
Pulse width: C nucleus 45 ° (7.8 μsec)
Pulse repetition time: 5 seconds Sample tube: 5 mmφ
Sample tube rotation speed: 12Hz
Integration count: 20000 times Measurement temperature: 125 ° C
Solvent: 1,2,4-trichlorobenzene: 0.35 ml / heavy benzene: 0.2 ml
Sample amount: about 40mg
(Calculation of weight of structural unit derived from propylene)
When one or more olefins selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms (that is, a comonomer) is ethylene, the obtained 13 C-NMR spectrum is used according to the following document (1). By determining the ratio of the monomer chain distribution (dyad (doubled) distribution), the mole fraction of the structural unit derived from ethylene in the propylene resin (A) (mol%) (hereinafter referred to as E (mol%)) And the molar fraction (mol%) of constituent units derived from propylene (hereinafter referred to as P (mol%)) can be calculated. The weight percent of the structural unit derived from propylene and the weight percent of the structural unit derived from ethylene in the propylene-based resin (A) are calculated by converting from the obtained E (mol%) and P (mol%) to weight percent. be able to.
エチレンおよび炭素原子数4~20のα‐オレフィンからなる群から選ばれる1種以上のオレフィン(すなわちコモノマー)が炭素原子数4~20のα‐オレフィンの場合、得られた13C-NMRスペクトルから、下記文献(2)に準じて、モノマー連鎖分布(ダイアッド(2連子)分布)の比率を決定することにより、プロピレン系樹脂の(A)中の炭素原子数4~20のα‐オレフィンに由来する構成単位のモル分率(mol%) (以下A(mol%)と記す)およびプロピレンに由来する構成単位のモル分率(mol%) (以下P(mol%)と記す)を算出することができる。求められたA(mol%)およびP(mol%)から重量%に換算しプロピレン系樹脂(A)中のプロピレンに由来する構成単位の重量%および炭素原子数4~20のα‐オレフィンに由来する構成単位の重量%を算出することができる。 Reference (1): Kakugo, M .; Naito, Y .; Mizunuma, K .; Miyatake, T., Macromolecules 1982, 15, (4), 1150-1152
When one or more olefins selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms (that is, a comonomer) is an α-olefin having 4 to 20 carbon atoms, the obtained 13 C-NMR spectrum In accordance with the following document (2), by determining the ratio of the monomer chain distribution (dyad (doublet) distribution), the α-olefin having 4 to 20 carbon atoms in (A) of the propylene resin is obtained. The molar fraction (mol%) of the structural unit derived from (hereinafter referred to as A (mol%)) and the molar fraction (mol%) of the structural unit derived from propylene (hereinafter referred to as P (mol%)) are calculated. be able to. Converted from the calculated A (mol%) and P (mol%) to wt%, derived from propylene-based constituent units in propylene resin (A) and derived from α-olefin having 4 to 20 carbon atoms The weight% of the structural unit to be calculated can be calculated.
プロピレンに由来する構成単位の重量の調整は、後述する製造条件を調整することにより任意の量とすることができる。より詳細には、プロピレン系樹脂(A)の製造における共重合時の、プロピレンの導入量に対する、エチレンおよび炭素原子数4~20のα-オレフィンからなる群から選ばれる1種以上のオレフィンの導入量を少なくすることにより、プロピレン由来の構成単位の重量を多くすることができる。また、プロピレンの導入量に対する、エチレンおよび炭素原子数4~20のα-オレフィンからなる群から選ばれる1種以上のオレフィンの導入量を多くすることにより、プロピレン由来の構成単位の重量を少なくすることができる。 Reference (2): James C. Randall, Macromolecules, 1978, 11, 592-597
Adjustment of the weight of the structural unit derived from propylene can be made into arbitrary quantity by adjusting the manufacturing conditions mentioned later. More specifically, introduction of one or more olefins selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms with respect to the amount of propylene introduced during copolymerization in the production of propylene-based resin (A). By reducing the amount, the weight of the structural unit derived from propylene can be increased. Further, by increasing the amount of one or more olefins selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms with respect to the amount of propylene introduced, the weight of the structural unit derived from propylene is reduced. be able to.
本発明に用いるエチレン・α‐オレフィン共重合体(B)は、下記要件(B-1)および(B-2)を満たし、さらに下記要件(B-3)、(B-4)の少なくとも一方を満たすことが好ましく、下記要件(B-3)および(B-4)を満たすことがより好ましい。また、下記要件(B-5)を満たすことも好ましい。エチレン・α‐オレフィン共重合体(B)は一種単独で用いても、二種以上を用いてもよい。 <Ethylene / α-olefin copolymer (B)>
The ethylene / α-olefin copolymer (B) used in the present invention satisfies the following requirements (B-1) and (B-2), and at least one of the following requirements (B-3) and (B-4): Preferably, the following requirements (B-3) and (B-4) are satisfied. It is also preferable to satisfy the following requirement (B-5). The ethylene / α-olefin copolymer (B) may be used alone or in combination of two or more.
本発明の多層ブロー容器が、低温耐衝撃性を求められる場合には、前述のようにオレフィン重合体組成物(E)として、プロピレン系樹脂(A)と、エチレン・α‐オレフィン共重合体(B)と、核剤(D)とに加えて、さらに低密度エチレン・α‐オレフィン共重合体(F)を用いて形成される組成物を用いることが好ましい。 <Low density ethylene / α-olefin copolymer (F)>
When the multilayer blow container of the present invention is required to have low temperature impact resistance, as described above, as the olefin polymer composition (E), the propylene resin (A) and the ethylene / α-olefin copolymer ( In addition to B) and the nucleating agent (D), it is preferable to use a composition formed using a low-density ethylene / α-olefin copolymer (F).
本発明には核剤(D)を用いる。核剤(D)としては、芳香族リン酸エステル化合物、カルボン酸金属塩造核剤、ポリマー造核剤、ソルビトール系造核剤および無機化合物造核剤からなる群から選ばれる1種以上の化合物が挙げられる。核剤(D)は、多層ブロー容器の臭気を悪化させないことが好ましい。核剤(D)は一種単独で用いても、二種以上を併用してもよい。 <Nucleating agent (D)>
In the present invention, the nucleating agent (D) is used. As the nucleating agent (D), one or more compounds selected from the group consisting of aromatic phosphate ester compounds, carboxylic acid metal salt nucleating agents, polymer nucleating agents, sorbitol nucleating agents and inorganic compound nucleating agents. Is mentioned. It is preferable that the nucleating agent (D) does not deteriorate the odor of the multilayer blow container. A nucleating agent (D) may be used individually by 1 type, or may use 2 or more types together.
本発明に用いるオレフィン重合体組成物(E)は、本発明の多層ブロー容器の最外層に使用される樹脂であり、前述のプロピレン系樹脂(A)80~98重量部とエチレン・α‐オレフィン共重合体(B)2~20重量部(ただし、(A)と(B)との合計は100重量部である)と、核剤(D)0.01~0.5重量部とから形成される組成物である。 <Olefin polymer composition (E)>
The olefin polymer composition (E) used in the present invention is a resin used for the outermost layer of the multilayer blow container of the present invention. The propylene-based resin (A) is 80 to 98 parts by weight and an ethylene / α-olefin. Formed from 2 to 20 parts by weight of copolymer (B) (however, the sum of (A) and (B) is 100 parts by weight) and 0.01 to 0.5 parts by weight of nucleating agent (D) Composition.
ポリオレフィン系樹脂としては、プロピレン系樹脂(A)以外のプロピレン系樹脂(P)を例示することができる。プロピレン系樹脂(P)としては、プロピレン系樹脂(A)とは異なるプロピレンの単独重合体(シンジオタクチックプロピレン単独重合体などを含む)等が挙げられる。通常、プロピレン系樹脂(P)の、JISK7121に準拠して示差走査熱量計(DSC)により測定したTmは140~155℃である。また、プロピレン系樹脂(P)の、ASTM D-1238に準拠して、測定温度230℃、2.16kg荷重で測定したMFRとしては0.01~20g/10分が好ましく、特に0.1~5g/10分であることが好ましい。 Examples of other resins include polyolefins other than propylene resin (A), ethylene / α-olefin copolymer (B), low density ethylene / α-olefin copolymer (F), and nucleating agent (D). Based resins.
Examples of the polyolefin resin include propylene resins (P) other than the propylene resin (A). Examples of the propylene resin (P) include propylene homopolymers (including syndiotactic propylene homopolymers) different from the propylene resin (A). Usually, Tm of propylene-based resin (P) measured by a differential scanning calorimeter (DSC) according to JISK7121 is 140 to 155 ° C. Further, the MFR of propylene resin (P) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is preferably 0.01 to 20 g / 10 min, particularly 0.1 to 5 g / 10 min is preferred.
本発明の多層ブロー容器は、最外層に使用される樹脂が、前述のオレフィン重合体組成物(E)からなる。本発明の多層ブロー容器は最外層以外の層として、少なくとも一つの内層を有する。 <Multilayer blow container>
In the multilayer blow container of the present invention, the resin used for the outermost layer is composed of the above-mentioned olefin polymer composition (E). The multilayer blow container of the present invention has at least one inner layer as a layer other than the outermost layer.
本発明の多層ブロー容器の製造方法は、前述のオレフィン重合体組成物(E)およびオレフィン重合体組成物(E)以外の熱可塑性樹脂組成物を用い、前記オレフィン重合体組成物(E)が最外層を形成し、前記オレフィン重合体組成物(E)以外の熱可塑性樹脂組成物が少なくとも一つの内層を形成するように、ダイレクトブロー成形法または射出延伸ブロー成形法により成形することが好ましい。 [Method for producing multilayer blow container]
The method for producing a multilayer blow container of the present invention uses a thermoplastic resin composition other than the olefin polymer composition (E) and the olefin polymer composition (E) described above, and the olefin polymer composition (E) It is preferable that the outermost layer is formed and molded by a direct blow molding method or an injection stretch blow molding method so that the thermoplastic resin composition other than the olefin polymer composition (E) forms at least one inner layer.
(1)固体触媒成分の調製
無水塩化マグネシウム95.2g、デカン442mlおよび2-エチルヘキシルアルコール390.6gを130℃で2時間加熱反応を行って均一溶液とした後、この溶液中に無水フタル酸21.3gを添加し、さらに130℃にて1時間攪拌混合を行い、無水フタル酸を溶解させた。 [Production of propylene-based resin (A-1)]
(1) Preparation of solid catalyst component An anhydrous magnesium chloride 95.2 g, decane 442 ml, and 2-ethylhexyl alcohol 390.6 g were heated at 130 ° C. for 2 hours to form a homogeneous solution. .3 g was added, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.
内容積500mlの攪拌機付きの三つ口フラスコを窒素ガスで置換した後、脱水処理したヘプタンを400ml、トリエチルアルミニウム19.2mmol、ジシクロペンチルジメトキシシラン3.8mmol、上記固体状チタン触媒成分(A)4gを加えた。内温を20℃に保持し、攪拌しながらプロピレンガスを8g/hrの速度で連続的に導入した。1時間後、攪拌を停止し結果的に固体状チタン触媒成分(A)1g当たり2gのプロピレンが重合した予備重合触媒成分(B)を得た。 (2) Preparation of prepolymerization catalyst component A three-necked flask with a stirrer having an internal volume of 500 ml was replaced with nitrogen gas, and then 400 ml of dehydrated heptane, 19.2 mmol of triethylaluminum, 3.8 mmol of dicyclopentyldimethoxysilane, and the above 4 g of solid titanium catalyst component (A) was added. While maintaining the internal temperature at 20 ° C., propylene gas was continuously introduced at a rate of 8 g / hr while stirring. After 1 hour, stirring was stopped, and as a result, a prepolymerized catalyst component (B) in which 2 g of propylene was polymerized per 1 g of the solid titanium catalyst component (A) was obtained.
内容積10Lの攪拌機付きステンレス製オートクレーブを十分乾燥し、窒素置換の後、脱水処理したヘプタン6L、トリエチルアルミニウム12.5mmol、ジシクロペンチルジメトキシシラン0.6mmolを加えた。系内の窒素をプロピレンで置換した後に、水素を0.30MPa-G装入し、続いて攪拌しながらプロピレンおよびエチレンを導入した。なお、導入量は、重合槽内の気相部のエチレン濃度が1.5mol%となるように調整した。 (3) Polymerization A stainless steel autoclave with a stirrer with an internal volume of 10 L was sufficiently dried, and after substitution with nitrogen, 6 L of dehydrated heptane, 12.5 mmol of triethylaluminum, and 0.6 mmol of dicyclopentyldimethoxysilane were added. After replacing nitrogen in the system with propylene, hydrogen was charged at 0.30 MPa-G, and then propylene and ethylene were introduced with stirring. The amount introduced was adjusted so that the ethylene concentration in the gas phase in the polymerization tank was 1.5 mol%.
プロピレン系重合体(A-1)の製造において、重合槽内の気相部のエチレン濃度が2.2mol%となるように調整した以外は、プロピレン系重合体(A-1)の製造と同様にして重合を行った。 [Production of propylene-based resin (A-2)]
The production of the propylene polymer (A-1) was the same as the production of the propylene polymer (A-1) except that the ethylene concentration in the gas phase in the polymerization tank was adjusted to 2.2 mol%. Polymerization was carried out.
プロピレン系重合体(A-1)の製造において、重合槽内の気相部のエチレン濃度が0.8mol%となるように調整した以外は、プロピレン系重合体(A-1)の製造と同様にして重合を行った。 [Production of propylene resin (A-3)]
The production of the propylene polymer (A-1) was the same as the production of the propylene polymer (A-1) except that the ethylene concentration in the gas phase portion in the polymerization tank was adjusted to 0.8 mol%. Polymerization was carried out.
プロピレン系重合体(A-1)の製造において、系内の窒素をプロピレンで置換した後に、水素を0.15MPa-G装入した以外は、プロピレン系重合体(A-1)の製造と同様にして重合を行った。 [Production of propylene resin (A-4)]
The production of the propylene polymer (A-1) was the same as the production of the propylene polymer (A-1) except that the nitrogen in the system was replaced with propylene and hydrogen was charged at 0.15 MPa-G. Polymerization was carried out.
プロピレン系重合体(A-1)の製造において、系内の窒素をプロピレンで置換した後に、水素を0.45MPa-G装入した以外は、プロピレン系重合体(A-1)の製造と同様にして重合を行った。 [Production of propylene resin (A-5)]
The production of the propylene polymer (A-1) was the same as the production of the propylene polymer (A-1), except that nitrogen in the system was replaced with propylene and hydrogen was charged at 0.45 MPa-G. Polymerization was carried out.
(1)触媒の調製
充分に窒素置換した300リットルの反応器に600℃で10時間乾燥したシリカ10.0kgとトルエン154リットルとを装入し、懸濁状にして0℃まで冷却した。その後、この懸濁液に、メチルアルミノキサンのトルエン溶液(Al=3.02モル/リットル)23.4リットルを1時間かけて滴下した。この際、系内の温度を0~5℃の範囲に保った。 [Production of ethylene / α-olefin copolymer (B-1)]
(1) Preparation of catalyst 10.0 kg of silica dried at 600 ° C. for 10 hours and 154 liters of toluene were charged in a 300 liter reactor sufficiently purged with nitrogen, and the suspension was cooled to 0 ° C. Thereafter, 23.4 liters of a toluene solution of methylaluminoxane (Al = 3.02 mol / liter) was dropped into the suspension over 1 hour. At this time, the temperature in the system was kept in the range of 0 to 5 ° C.
充分に窒素置換した350リットルの反応器に、上記で調製した固体触媒成分(1)7.0kgとヘキサンを装入し、全容積を285リットルにした。系内を10℃まで冷却した後、エチレンを8Nm3/hrの流量で5分間ヘキサン中に吹き込んだ。この間、系内の温度は、10~15℃に保持した。その後、エチレンの供給を停止し、ジイソブチルアルミニウムハイドライド(DIBALH)を2.4モルおよび1-ヘキセンを1.2kg装入した。系内を密閉系にした後、8Nm3/hrの流量でエチレンの供給を再度開始した。15分後、エチレンの流量を2Nm3/hrに下げ、系内の圧力を0.08MPaGにした。この間に、系内の温度は35℃まで上昇した。その後、系内の温度を32~35℃に調節しながら、エチレンを4Nm3/hrの流量で3.5時間供給した。この間、系内の圧力は0.07~0.08MPaGに保持されていた。次いで、系内を窒素により置換を行った後、上澄み液を除去し、ヘキサンで2回洗浄した。このようにして固体触媒成分1g当たり3gのポリマーが予備重合された予備重合触媒(2)を得た。 (2) Preparation of prepolymerization catalyst component In a 350 liter reactor sufficiently purged with nitrogen, 7.0 kg of the solid catalyst component (1) prepared above and hexane were charged to a total volume of 285 liters. After cooling the system to 10 ° C., ethylene was blown into hexane at a flow rate of 8 Nm 3 / hr for 5 minutes. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, the ethylene supply was stopped, and 2.4 mol of diisobutylaluminum hydride (DIBALH) and 1.2 kg of 1-hexene were charged. After the inside of the system was closed, ethylene supply was started again at a flow rate of 8 Nm 3 / hr. After 15 minutes, the ethylene flow rate was lowered to 2 Nm 3 / hr, and the pressure in the system was adjusted to 0.08 MPaG. During this time, the temperature in the system rose to 35 ° C. Thereafter, ethylene was supplied at a flow rate of 4 Nm 3 / hr for 3.5 hours while adjusting the temperature in the system to 32 to 35 ° C. During this time, the pressure in the system was maintained at 0.07 to 0.08 MPaG. Next, after the inside of the system was replaced with nitrogen, the supernatant was removed and washed twice with hexane. Thus, a prepolymerized catalyst (2) in which 3 g of polymer was prepolymerized per 1 g of the solid catalyst component was obtained.
連続式流動床気相重合装置を用い、全圧2.0MPaG、重合温度70℃、ガス線速0.7m/秒で、エチレンと1-ヘキセンとの共重合を行った。 (3) Polymerization Copolymerization of ethylene and 1-hexene was carried out using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 2.0 MPaG, a polymerization temperature of 70 ° C., and a gas linear velocity of 0.7 m / sec.
エチレン・α-オレフィン共重合体(B-1)の製造において、重合温度を80℃に変更し、ガス組成(mol比)を1-ヘキセン/エチレン=0.03、水素/エチレン=4.2×10-4、エチレン濃度=71%に変更した以外は、エチレン・α-オレフィン共重合体(B-1)の製造と同様にしてエチレン・1-ヘキセン共重合体を得た。 [Production of ethylene / α-olefin copolymer (B-2)]
In the production of the ethylene / α-olefin copolymer (B-1), the polymerization temperature was changed to 80 ° C., and the gas composition (mol ratio) was 1-hexene / ethylene = 0.03, hydrogen / ethylene = 4.2. An ethylene / 1-hexene copolymer was obtained in the same manner as in the production of the ethylene / α-olefin copolymer (B-1) except that the ethylene concentration was changed to × 10 −4 and ethylene concentration = 71%.
エチレン・α-オレフィン共重合体(B-1)の製造において、重合温度を80℃に変更し、ガス組成(mol比)を1-ヘキセン/エチレン=0.02、水素/エチレン=4.6×10-4、エチレン濃度=70%に変更した以外は、エチレン・α-オレフィン共重合体(B-1)の製造と同様にしてエチレン・1-ヘキセン共重合体を得た。 [Production of ethylene / α-olefin copolymer (B-3)]
In the production of the ethylene / α-olefin copolymer (B-1), the polymerization temperature was changed to 80 ° C., and the gas composition (mol ratio) was 1-hexene / ethylene = 0.02, hydrogen / ethylene = 4.6. An ethylene / 1-hexene copolymer was obtained in the same manner as in the production of the ethylene / α-olefin copolymer (B-1) except that the ethylene concentration was changed to × 10 −4 and ethylene concentration = 70%.
プロピレン系樹脂(A-1)を97重量部およびエチレン・α-オレフィン共重合体(B-1)を3重量部、さらに核剤(D)としてアデカスタブNA-21(ADEKA社製:ビス(2,4,8,10-テトラ-t-ブチル-6-ヒドロキシ-12H-ジベンゾ〔d,g〕〔1,3,2〕ジオキサホスホシン-6-オキシド)水酸化アルミニウム塩を主成分として含んだ芳香族リン酸エステル化合物系造核剤)を0.15重量部、および添加剤としてフェノール系酸化防止剤[ペンタエリスリトール テトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]]を0.10重量部、リン系酸化防止剤[トリス(2,4-ジ-t-ブチルフェニル)フォスファイト]を0.10重量部、中和剤としてステアリン酸カルシウムを0.09重量部、帯電防止剤としてステアリン酸モノグリセライドを0.10重量部、ヘンシェルミキサーにて攪拌混合し、その混合物をナカタニ機械社製の二軸押出機(NR-36)を用いて下記条件にて溶融混練しストランドを得た。 [Example A1]
97 parts by weight of propylene-based resin (A-1), 3 parts by weight of ethylene / α-olefin copolymer (B-1), and ADEKA STAB NA-21 (manufactured by ADEKA: bis (2 , 4,8,10-Tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) aluminum hydroxide as a main component 0.15 parts by weight of an aromatic phosphate ester compound nucleating agent) and a phenolic antioxidant [pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) as an additive ) Propionate]], 0.10 parts by weight of a phosphorous antioxidant [Tris (2,4-di-t-butylphenyl) phosphite], and calcium stearate as a neutralizing agent 0.09 part by weight of the rubber and 0.10 part by weight of stearic acid monoglyceride as an antistatic agent were stirred and mixed with a Henschel mixer, and the mixture was mixed using a twin-screw extruder (NR-36) manufactured by Nakatani Machinery Co., Ltd. A strand was obtained by melt-kneading under the following conditions.
型式:NR-36
スクリュー回転数250rpm
樹脂温度200℃
得られたストランドを水冷後ペレタイザーにて切断する事によりオレフィン重合体組成物(E-1)のペレットを得た。 (Twin screw extruder conditions)
Model: NR-36
Screw rotation speed 250rpm
Resin temperature 200 ℃
The obtained strand was cooled with water and then cut with a pelletizer to obtain pellets of the olefin polymer composition (E-1).
プロピレン系樹脂(A-1)を95.5重量部およびエチレン・α-オレフィン共重合体(B-1)を4.5重量部の比率に変更した以外は実施例A1と同様に行った。実施例A2で得られたオレフィン重合体組成物(E-2)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が147℃であった。 [Example A2]
The same procedure as in Example A1 was carried out except that the ratio of 95.5 parts by weight of the propylene resin (A-1) and 4.5 parts by weight of the ethylene / α-olefin copolymer (B-1) was changed. The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-2) obtained in Example A2 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
多層ブロー成形の際、基材(内層)用にプロピレン系ランダム共重合体B251VT((株)プライムポリマー社製)に代えてプロピレン系ランダムブロック共重合体B511QA((株)プライムポリマー社製、メルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は1.2g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が158℃)を中間層にて用いた以外は実施例A2と同様に行った。 [Example A3]
At the time of multilayer blow molding, instead of propylene random copolymer B251VT (manufactured by Prime Polymer Co., Ltd.) for the base material (inner layer), propylene random block copolymer B511QA (manufactured by Prime Polymer Co., Ltd., melt) Flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.2 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC is 158 ° C.) The same procedure as in Example A2 was carried out except that the intermediate layer was used.
多層ブロー成形の際、基材(内層)用にプロピレン系ランダム共重合体B251VT((株)プライムポリマー社製)に代えてPE系樹脂HDPE、HZ-6008B((株)プライムポリマー社製メルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は0.7g/10分、密度勾配管法で測定した密度が0.958g/cm3)を中間層にて用いた以外は実施例A2と同様に行った。 [Example A4]
In the case of multilayer blow molding, instead of the propylene random copolymer B251VT (manufactured by Prime Polymer Co., Ltd.) for the base material (inner layer), PE resin HDPE, HZ-6008B (manufactured by Prime Polymer Co., Ltd.) Rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 0.7 g / 10 min, density measured by density gradient tube method is 0.958 g / cm 3 ) Example A2 was carried out in the same manner as in Example A2.
プロピレン系樹脂(A-1)を80.0重量部およびエチレン・α-オレフィン共重合体(B-1)を20.0重量部の比率に変更した以外は実施例A1と同様に行った。実施例A5で得られたオレフィン重合体組成物(E-3)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が148℃であった。 [Example A5]
The same procedure as in Example A1 was carried out except that the ratio of propylene resin (A-1) was 80.0 parts by weight and that of ethylene / α-olefin copolymer (B-1) was 20.0 parts by weight. The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-3) obtained in Example A5 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 148 ° C.
核剤(D)としてアデカスタブNA-21(ADEKA社製)を0.15重量部に代えてゲルオールMD(新日本理化(株)社製品名、化学名=1,3,2,4-ジ-(p-メチルベンジリデン)ソルビトール、表中にG-MDと記載)を0.30重量部に変更した以外は、実施例A2と同様に行った。実施例A6で得られたオレフィン重合体組成物(E-7)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が149℃であった。 [Example A6]
As a nucleating agent (D), ADEKA STAB NA-21 (manufactured by ADEKA) was replaced by 0.15 parts by weight, and Gelol MD (product name of Shin Nippon Rika Co., Ltd., chemical name = 1, 3, 2, 4-di-) The procedure was the same as Example A2 except that (p-methylbenzylidene) sorbitol (described as G-MD in the table) was changed to 0.30 part by weight. The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-7) obtained in Example A6 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 149 ° C.
プロピレン系樹脂(A-1)を、プロピレン系樹脂(A-4)に代えて、ヘンシェルミキサーにて攪拌混合する際に、有機過酸化物として[2,5-ジ-メチル-2,5-ジ-(ベンゾイルパーオキシ)ヘキサン]を0.006重量部加えた以外は実施例A2と同様に行った。 [Example A7]
When propylene resin (A-1) is stirred and mixed with a Henschel mixer instead of propylene resin (A-4), [2,5-di-methyl-2,5- The same procedure as in Example A2 except that 0.006 part by weight of di- (benzoylperoxy) hexane] was added.
プロピレン系樹脂(A-1)を100重量部およびエチレン・α-オレフィン共重合体(B-1)を0重量部の比率に変更した以外は実施例A1と同様に行った。比較例A1で得られたオレフィン重合体組成物(E-4)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が147℃であった。 [Comparative Example A1]
The same procedure as in Example A1 was carried out except that the proportion of propylene resin (A-1) was changed to 100 parts by weight and that of ethylene / α-olefin copolymer (B-1) was changed to 0 part by weight. The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-4) obtained in Comparative Example A1 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
プロピレン系樹脂(A-1)を70.0重量部およびエチレン・α-オレフィン共重合体(B-1)を30.0重量部の比率に変更した以外は実施例A1と同様に行った。比較例A2で得られたオレフィン重合体組成物(E-5)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が147℃であった。 [Comparative Example A2]
The same procedure as in Example A1 was carried out except that the ratio of propylene-based resin (A-1) was changed to 70.0 parts by weight and that of ethylene / α-olefin copolymer (B-1) was changed to 30.0 parts by weight. The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-5) obtained in Comparative Example A2 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
核剤(D)としてアデカスタブNA-21(ADEKA社製)を添加しなかった以外は、実施例A2と同様に行った。比較例A3で得られたオレフィン重合体組成物(E-6)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が145℃であった。 [Comparative Example A3]
The same procedure as in Example A2 was conducted, except that ADK STAB NA-21 (manufactured by ADEKA) was not added as the nucleating agent (D). The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-6) obtained in Comparative Example A3 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 145 ° C.
プロピレン系樹脂(A-1)に代えてプロピレン系樹脂(A-2)に変更した以外は実施例A2と同様に行った。比較例A4で得られたオレフィン重合体組成物(E-8)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が138℃であった。 [Comparative Example A4]
The same procedure as in Example A2 was conducted except that the propylene resin (A-2) was changed to the propylene resin (A-2). The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-8) obtained in Comparative Example A4 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, the crystalline melting point measured by DSC) was 138 ° C.
プロピレン系樹脂(A-1)に代えてプロピレン系樹脂(A-3)に変更した以外は実施例A2と同様に行った。比較例A5で得られたオレフィン重合体組成物(E-9)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が158℃であった。 [Comparative Example A5]
The same procedure as in Example A2 was conducted except that the propylene resin (A-3) was changed to the propylene resin (A-3). The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-9) obtained in Comparative Example A5 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 158 ° C.
プロピレン系樹脂(A-1)に代えてプロピレン系樹脂(A-4)に変更した以外は実施例A2と同様に行った。比較例A6で得られたオレフィン重合体組成物(E-10)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は3.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が147℃であった。 [Comparative Example A6]
The same procedure as in Example A2 was conducted except that the propylene resin (A-4) was changed to the propylene resin (A-4). The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-10) obtained in Comparative Example A6 is 3.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
プロピレン系樹脂(A-1)に代えてプロピレン系樹脂(A-5)に変更した以外は実施例A2と同様に行った。比較例A7で得られたオレフィン重合体組成物(E-11)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は15.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が147℃であった。 [Comparative Example A7]
The same procedure as in Example A2 was carried out except that the propylene resin (A-5) was replaced with a propylene resin (A-5). The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-11) obtained in Comparative Example A7 is 15.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
エチレン・α-オレフィン共重合体(B-1)に代えてエチレン・α-オレフィン共重合体(B-2)に変更した以外は実施例A2と同様に行った。比較例A8で得られたオレフィン重合体組成物(E-12)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が147℃であった。 [Comparative Example A8]
The same procedure as in Example A2 was conducted except that the ethylene / α-olefin copolymer (B-2) was changed to the ethylene / α-olefin copolymer (B-1). The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-12) obtained in Comparative Example A8 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
プロピレン系樹脂(A-1)を90.0重量部およびエチレン・α-オレフィン共重合体(B-2)を10.0重量部の比率に変更した以外は比較例A8と同様に行った。比較例A9で得られたオレフィン重合体組成物(E-13)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が147℃であった。 [Comparative Example A9]
The same procedure as in Comparative Example A8 was carried out except that the ratio of propylene resin (A-1) was 90.0 parts by weight and that of ethylene / α-olefin copolymer (B-2) was 10.0 parts by weight. The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-13) obtained in Comparative Example A9 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
プロピレン系樹脂(A-1)を80.0重量部およびエチレン・α-オレフィン共重合体(B-2)を20.0重量部の比率に変更した以外は比較例A8と同様に行った。比較例A10で得られたオレフィン重合体組成物(E-14)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が147℃であった。 [Comparative Example A10]
The procedure was the same as Comparative Example A8 except that the ratio of propylene resin (A-1) was 80.0 parts by weight and that of ethylene / α-olefin copolymer (B-2) was 20.0 parts by weight. The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-14) obtained in Comparative Example A10 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
エチレン・α-オレフィン共重合体(B-1)に代えてエチレン・α-オレフィン共重合体(B-3)に変更した以外は実施例A2と同様に行った。比較例A11で得られたオレフィン重合体組成物(E-15)のメルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が147℃であった。 [Comparative Example A11]
The same procedure as in Example A2 was conducted, except that the ethylene / α-olefin copolymer (B-3) was replaced with the ethylene / α-olefin copolymer (B-3). The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-15) obtained in Comparative Example A11 is 7.0 g / 10 min, DSC melting point (According to JIS-K7121, crystal melting point measured by DSC) was 147 ° C.
エチレン・α-オレフィン共重合体(B-1)に代えてメタロセン触媒ではない、チーグラーナッタ触媒にて製造されるPE系樹脂L-LDPE(直鎖状低密度ポリエチレン)、ウルトゼックス1030L((株)プライムポリマー社製、密度0.909g/cm3、メルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は7.0g/10min、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が115℃)に変更した以外は実施例A2と同様に行った。 [Comparative Example A12]
PE-based resin L-LDPE (linear low density polyethylene) produced by a Ziegler-Natta catalyst, which is not a metallocene catalyst, instead of an ethylene / α-olefin copolymer (B-1), Ultzex 1030L ) Prime polymer, density 0.909 g / cm 3 , melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 7.0 g / 10 min, DSC melting point (according to JIS-K7121) This was carried out in the same manner as in Example A2 except that the crystal melting point measured by DSC was 115 ° C.).
エチレン・α-オレフィン共重合体(B-1)に代えてPE系樹脂HDPE(高密度ポリエチレン)、HZ-2100J((株)プライムポリマー社製、密度0.956g/cm3、メルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は11.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が131℃、Mw/Mn(分子量分布)は7.0)に変更し、プロピレン系樹脂(A-1)を90.0重量部およびPE系樹脂HDPE、HZ-2100J((株)プライムポリマー社製)を10.0重量部の比率に変更した以外は実施例A1と同様に行った。 [Comparative Example A13]
Instead of the ethylene / α-olefin copolymer (B-1), a PE resin HDPE (high density polyethylene), HZ-2100J (manufactured by Prime Polymer Co., Ltd., density 0.956 g / cm 3 , melt flow rate ( MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 11.0 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) is 131 ° C., Mw / Mn ( The molecular weight distribution was changed to 7.0), and 90.0 parts by weight of the propylene resin (A-1) and 10.0 parts by weight of the PE resin HDPE, HZ-2100J (manufactured by Prime Polymer Co., Ltd.) The same procedure as in Example A1 was conducted except that the ratio was changed.
エチレン・α-オレフィン共重合体(B-1)に代えてエチレン・α-オレフィン共重合体(B)としてタフマーP-0680(ポリエチレンラバー(EPR)、三井化学(株)社製、密度0.870g/cm3、メルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は1.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が測定されない。)に変更し、プロピレン系樹脂(A-1)を90.0重量部およびエチレン・α-オレフィン共重合体(B)としてタフマーP-0680(三井化学(株)社製)を10.0重量部の比率に変更した以外は実施例A1と同様に行った。 [Comparative Example A14]
Instead of ethylene / α-olefin copolymer (B-1), Tuffmer P-0680 (polyethylene rubber (EPR), manufactured by Mitsui Chemicals, Inc., density 0. 870 g / cm 3 , melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.0 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) ) Is not measured.), And Tufmer P-0680 (manufactured by Mitsui Chemicals, Inc.) as propylene resin (A-1) as 90.0 parts by weight and ethylene / α-olefin copolymer (B) Was carried out in the same manner as in Example A1, except that the ratio was changed to 10.0 parts by weight.
エチレン・α-オレフィン共重合体(B-1)に代えてエチレン・α-オレフィン共重合体(B)としてタフマーP-0180(ポリエチレンラバー(EPR)、三井化学(株)社製、密度0.870g/cm3、メルトフローレート(MFR)(ASTM D-1238、測定温度230℃、荷重2.16kg)は8.0g/10分、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点)が測定されない。)に変更し、プロピレン系樹脂(A-1)を90.0重量部およびエチレン・α-オレフィン共重合体(B)としてタフマーP-0180(三井化学(株)社製)を10.0重量部の比率に変更した以外は実施例A1と同様に行った。 [Comparative Example A15]
Instead of the ethylene / α-olefin copolymer (B-1), Tuffmer P-0180 (polyethylene rubber (EPR), manufactured by Mitsui Chemicals, Inc., density 0. 0) was used as the ethylene / α-olefin copolymer (B). 870 g / cm 3 , melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 8.0 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) ) Is not measured.), And 90.0 parts by weight of propylene resin (A-1) and ethylene / α-olefin copolymer (B) as Toughmer P-0180 (manufactured by Mitsui Chemicals, Inc.) Was carried out in the same manner as in Example A1, except that the ratio was changed to 10.0 parts by weight.
プロピレン系樹脂(A-1)を97重量部およびエチレン・α-オレフィン共重合体(B-1)を3重量部、さらに核剤(D)としてアデカスタブNA-21(ADEKA社製:ビス(2,4,8,10-テトラ-t-ブチル-6-ヒドロキシ-12H-ジベンゾ〔d,g〕〔1,3,2〕ジオキサホスホシン-6-オキシド)水酸化アルミニウム塩を主成分として含んだ芳香族リン酸エステル化合物系造核剤)を0.15重量部、低密度エチレン・α‐オレフィン共重合体(F)として、三井化学社製、タフマーP-0280(エチレン-プロピレン共重合体、密度勾配管法で測定した密度:0.870g/cm3、チーグラーナッタ触媒、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点):観察されず、MFR(ASTM-1238、測定温度230℃、荷重2.16kg):5.4g/10分)を15重量部、および添加剤としてフェノール系酸化防止剤[ペンタエリスリトール テトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]を0.10重量部、リン系酸化防止剤[トリス(2,4-ジ-t-ブチルフェニル)フォスファイト]]を0.10重量部、中和剤としてステアリン酸カルシウムを0.09重量部を、ヘンシェルミキサーにて攪拌混合し、その混合物をナカタニ機械社製の二軸押出機(NR-36)を用いて下記条件にて溶融混練しストランドを得た。 [Example B1]
97 parts by weight of propylene-based resin (A-1), 3 parts by weight of ethylene / α-olefin copolymer (B-1), and ADEKA STAB NA-21 (manufactured by ADEKA: bis (2 , 4,8,10-Tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) aluminum hydroxide as a main component Tafmer P-0280 (ethylene-propylene copolymer, manufactured by Mitsui Chemicals, Ltd.) as 0.15 parts by weight of an aromatic phosphate ester compound nucleating agent) as a low density ethylene / α-olefin copolymer (F) the density was measured by a density gradient tube method: 0.870 g / cm 3, Ziegler-Natta catalyst, DSC melting point (according to JIS-K7121, the crystalline melting point was measured by DSC): not observed, MFR (AST -1238, measuring temperature 230 ° C., load 2.16 kg): 5.4 g / 10 min) 15 parts by weight, and phenolic antioxidant [pentaerythritol tetrakis [3- (3,5-di-t] as an additive -Butyl-4-hydroxyphenyl) propionate] in 0.10 parts by weight, phosphorus antioxidant [Tris (2,4-di-t-butylphenyl) phosphite]] in 0.10 parts by weight, neutralizing agent As a mixture, 0.09 part by weight of calcium stearate was stirred and mixed with a Henschel mixer, and the mixture was melt-kneaded using a twin screw extruder (NR-36) manufactured by Nakatani Machinery Co., Ltd. under the following conditions to obtain a strand. .
型式:NR-36
スクリュー回転数250rpm
樹脂温度200℃
得られたストランドを水冷後ペレタイザーにて切断する事によりオレフィン重合体組成物(E-21)のペレットを得た。 (Twin screw extruder conditions)
Model: NR-36
Screw rotation speed 250rpm
Resin temperature 200 ℃
The obtained strand was cooled with water and then cut with a pelletizer to obtain pellets of the olefin polymer composition (E-21).
低密度エチレン・α‐オレフィン共重合体(F)を、三井化学社製、タフマーP-0280から、三井化学社製、タフマーA-4085S(エチレン-ブテン共重合体、密度勾配管法で測定した密度:0.885g/cm3、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点):70℃、MFR(ASTM-1238、測定温度230℃、荷重2.16kg):6.7g/10分)に変更し、その配合量を15重量部から7重量部に変更し、帯電防止剤としてステアリン酸モノグリセライドを0.1重量部用いたこと以外は実施例B1と同様に行い、ストランドを得た。 [Example B2]
Low density ethylene / α-olefin copolymer (F) was measured by Mitsui Chemicals, Inc., Tafmer A-4085S (ethylene-butene copolymer, density gradient tube method) from Mitsui Chemicals, Inc., Tafmer P-0280. Density: 0.885 g / cm 3 , DSC melting point (according to JIS-K7121, crystal melting point measured by DSC): 70 ° C., MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg): 6.7 g / 10 minutes), the blending amount was changed from 15 parts by weight to 7 parts by weight, and the same procedure as in Example B1 was conducted except that 0.1 part by weight of stearic acid monoglyceride was used as an antistatic agent. Obtained.
プロピレン系樹脂(A-1)を90重量部、エチレン・α-オレフィン共重合体(B-1)を10重量部に変更し、低密度エチレン・α‐オレフィン共重合体(F)を、三井化学社製、タフマーP-0280から、三井化学社製、タフマーA-4085Sに変更し、その配合量を15重量部から5重量部に変更した以外は実施例B1と同様に行い、ストランドを得た。 [Example B3]
The propylene resin (A-1) was changed to 90 parts by weight, the ethylene / α-olefin copolymer (B-1) was changed to 10 parts by weight, and the low density ethylene / α-olefin copolymer (F) was changed to Mitsui A strand was obtained in the same manner as in Example B1, except that Tuffmer P-0280 manufactured by Kagaku Co., Ltd. was changed to Tuffmer A-4085S manufactured by Mitsui Chemicals, and the blending amount was changed from 15 parts by weight to 5 parts by weight. It was.
低密度エチレン・α‐オレフィン共重合体(F)を、三井化学社製、タフマーP-0280から、三井化学社製、タフマーA-4085Sに変更した以外は実施例B1と同様に行い、ストランドを得た。 [Example B4]
The low density ethylene / α-olefin copolymer (F) was changed in the same manner as in Example B1 except that Mitsui Chemicals Co., Ltd., Tafmer P-0280 was changed to Mitsui Chemicals Co., Ltd., Tafmer A-4085S. Obtained.
低密度エチレン・α‐オレフィン共重合体(F)を用いなかったこと以外は実施例B1と同様に行い、ストランドを得た。 [Example B5]
A strand was obtained in the same manner as in Example B1 except that the low-density ethylene / α-olefin copolymer (F) was not used.
プロピレン系樹脂(A-1)を95.5重量部、エチレン・α-オレフィン共重合体(B-1)を4.5重量部に変更し、低密度エチレン・α‐オレフィン共重合体(F)を用いず、帯電防止剤としてステアリン酸モノグリセライドを0.1重量部用いたこと以外は実施例B1と同様に行い、ストランドを得た。 [Example B6]
The propylene-based resin (A-1) was changed to 95.5 parts by weight and the ethylene / α-olefin copolymer (B-1) was changed to 4.5 parts by weight to obtain a low density ethylene / α-olefin copolymer (F ) Was used, and a strand was obtained in the same manner as in Example B1 except that 0.1 part by weight of stearic acid monoglyceride was used as an antistatic agent.
プロピレン系樹脂(A-1)を90重量部、エチレン・α-オレフィン共重合体(B-1)を10重量部に変更し、低密度エチレン・α‐オレフィン共重合体(F)を用いなかった以外は実施例B1と同様に行い、ストランドを得た。 [Example B7]
The propylene resin (A-1) was changed to 90 parts by weight and the ethylene / α-olefin copolymer (B-1) was changed to 10 parts by weight, and the low density ethylene / α-olefin copolymer (F) was not used. A strand was obtained in the same manner as in Example B1.
プロピレン系樹脂(A-1)を95.5重量部、エチレン・α-オレフィン共重合体(B-1)を4.5重量部に変更し、低密度エチレン・α‐オレフィン共重合体(F)を15重量部から25重量部に変更した以外は実施例B1と同様に行い、ストランドを得た。 [Reference Example B1]
The propylene-based resin (A-1) was changed to 95.5 parts by weight and the ethylene / α-olefin copolymer (B-1) was changed to 4.5 parts by weight to obtain a low density ethylene / α-olefin copolymer (F ) Was changed from 15 parts by weight to 25 parts by weight in the same manner as in Example B1 to obtain a strand.
エチレン・α-オレフィン共重合体(B-1)を、エチレン・α-オレフィン共重合体(B-2)に変更し、プロピレン系樹脂(A-1)を95.5重量部に変更し、エチレン・α-オレフィン共重合体(B-2)を4.5重量部用い、低密度エチレン・α‐オレフィン共重合体(F)を、三井化学社製、タフマーP-0280から、三井化学社製、タフマーP-0275(エチレン-プロピレン共重合体、密度勾配管法で測定した密度:0.860g/cm3、DSC融点(JIS-K7121に準拠、DSCで測定した結晶融点):観察されず、MFR(ASTM-1238、測定温度230℃、荷重2.16kg):5.4g/10分)に変更した以外は実施例B1と同様に行い、ストランドを得た。 [Comparative Example B1]
The ethylene / α-olefin copolymer (B-1) was changed to the ethylene / α-olefin copolymer (B-2), and the propylene resin (A-1) was changed to 95.5 parts by weight. Using 4.5 parts by weight of ethylene / α-olefin copolymer (B-2), a low density ethylene / α-olefin copolymer (F) was obtained from Mitsui Chemicals, Tuffmer P-0280, and Mitsui Chemicals. Manufactured by Tuffmer P-0275 (ethylene-propylene copolymer, density measured by density gradient tube method: 0.860 g / cm 3 , DSC melting point (according to JIS-K7121, crystal melting point measured by DSC): not observed , MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg): 5.4 g / 10 min) was carried out in the same manner as in Example B1 to obtain a strand.
以下に記載の方法に従い、プロピレン系重合体(A)、エチレン・α-オレフィン共重合体(B)、低密度エチレン・α‐オレフィン共重合体(F)またはオレフィン重合体組成物(E)の物性を測定した。結果を表に示す。 〔Evaluation methods〕
According to the method described below, the propylene polymer (A), the ethylene / α-olefin copolymer (B), the low density ethylene / α-olefin copolymer (F) or the olefin polymer composition (E) Physical properties were measured. The results are shown in the table.
前記プロピレン系樹脂(A)、エチレン・α-オレフィン共重合体(B)、低密度エチレン・α‐オレフィン共重合体(F)、およびオレフィン重合体組成物(E)のMFRは、ASTM D-1238、測定温度230℃、荷重2.16kgに従って測定した。 [MFR (melt flow rate)]
The MFR of the propylene resin (A), the ethylene / α-olefin copolymer (B), the low density ethylene / α-olefin copolymer (F), and the olefin polymer composition (E) is ASTM D- It was measured according to 1238, measurement temperature 230 ° C., load 2.16 kg.
前記プロピレン系樹脂(A)、エチレン・α-オレフィン共重合体(B)、低密度エチレン・α‐オレフィン共重合体(F)およびオレフィン重合体組成物(E)の結晶融点はJIS-K7121に従って、示差走査熱量計(DSC、パーキンエルマー社製(Diamond DSC))を用いて測定を行った。ここで測定した第3stepにおける吸熱ピークの頂点を結晶融点(Tm)と定義した。吸熱ピークが複数ある場合はピーク高さが最大となる吸熱ピーク頂点を結晶融点(Tm)と定義する。 [Melting point (Tm)]
Crystalline melting points of the propylene resin (A), the ethylene / α-olefin copolymer (B), the low density ethylene / α-olefin copolymer (F) and the olefin polymer composition (E) are in accordance with JIS-K7121. The measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). The peak of the endothermic peak at the third step measured here was defined as the crystalline melting point (Tm). When there are a plurality of endothermic peaks, the endothermic peak vertex at which the peak height is maximum is defined as the crystalline melting point (Tm).
測定環境:窒素ガス雰囲気
サンプル量 : 5mg
サンプル形状 : プレスフィルム(230℃成形、厚み200~400μm)
第1step : 30℃より10℃/minで240℃まで昇温し、10min間保持する。 (Measurement condition)
Measurement environment: Nitrogen gas atmosphere Sample volume: 5mg
Sample shape: Press film (230 ° C molding, thickness 200-400μm)
First step: The temperature is raised from 30 ° C to 240 ° C at 10 ° C / min and held for 10 min.
オレフィン重合体組成物(E)の半結晶化時間(T1/2)は、示差走査熱量計(DSC、パーキンエルマー社製(DSC7))を用いて測定を行った。125℃等温条件下でオレフィン重合体組成物(E)を結晶化させて、この時結晶化に伴う発熱量を測定し、発熱開始(結晶化開始)から発熱量がトータル発熱量の半分の値になるまでの時間(秒)を半結晶化時間(t1/2)として測定した。半結晶化時間(t1/2)の値が小さいほど結晶化速度が速いことを意味する。 [Semi-crystallization time (T 1/2 )]
The half crystallization time (T 1/2 ) of the olefin polymer composition (E) was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer (DSC7)). The olefin polymer composition (E) is crystallized under an isothermal condition of 125 ° C., and the calorific value associated with the crystallization is measured at this time, and the calorific value from the start of the exotherm (crystallization start) is half the total calorific value. The time (seconds) until the crystallization time was measured as the half crystallization time (t 1/2 ). A smaller half crystallization time (t 1/2 ) means a faster crystallization rate.
測定環境:窒素ガス雰囲気
サンプル量 : 5mg
サンプル形状 : プレスフィルム(230℃成形、厚み200~400μm)
第1step : 30℃より10℃/minで220℃まで昇温し、3min間保持する。 (Measurement condition)
Measurement environment: Nitrogen gas atmosphere Sample volume: 5mg
Sample shape: Press film (230 ° C molding, thickness 200-400μm)
First step: The temperature is increased from 30 ° C to 220 ° C at 10 ° C / min and held for 3 min.
エチレン・α-オレフィン共重合体(B)および低密度エチレン・α‐オレフィン共重合体(F)の密度は、前記MFRの測定時に得られる、エチレン・α-オレフィン共重合体(B)および低密度エチレン・α‐オレフィン共重合体(F)のストランドをそれぞれ120℃で1時間熱処理し、1時間かけて室温まで徐冷したのち、密度勾配管で測定した。 〔density〕
The density of the ethylene / α-olefin copolymer (B) and the low density ethylene / α-olefin copolymer (F) is the same as that of the ethylene / α-olefin copolymer (B) and the low density obtained during the MFR measurement. The strands of the density ethylene / α-olefin copolymer (F) were each heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured with a density gradient tube.
前記プロピレン系樹脂(A)およびエチレン・α-オレフィン共重合体(B)のMw/Mnは、下記測定法で測定した重量平均分子量(Mw)および数平均分子量(Mn)より求めた。 [Mw / Mn (molecular weight distribution)]
The Mw / Mn of the propylene resin (A) and the ethylene / α-olefin copolymer (B) was determined from the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by the following measurement method.
多層ブロー容器のヘイズは、容器胴部から測定部位を切り出し、JIS-K7105に準拠してヘイズメーター(NIPPON DENSHOKU(NDH2000))にてヘイズ(曇値)を測定した。ヘイズの値が小さいほど透明性に優れているといえる。 [Haze]
For the haze of the multilayer blow container, the measurement site was cut out from the container body, and the haze (cloudiness value) was measured with a haze meter (NIPPON DENSHOKU (NDH2000)) in accordance with JIS-K7105. It can be said that the smaller the haze value, the better the transparency.
光沢性の評価は下記のグロスの測定により評価した。多層ブロー容器のグロスは、容器胴部から測定部位を切り出し、JIS-K7105に準拠して光沢計(NIPPON DENSHOKU(VG2000))で、外層の60度光沢度を測定した。グロスの値が大きいほど、優れた光沢性を持っているといえる。 [Glossy]
The glossiness was evaluated by the following gloss measurement. For the gloss of the multilayer blow container, the measurement site was cut out from the container body, and the 60-degree glossiness of the outer layer was measured with a gloss meter (NIPPON DENSHOKU (VG2000)) in accordance with JIS-K7105. It can be said that the larger the gloss value, the better the glossiness.
多層ブロー容器の成形性は、得られた容器外観を観察し、容器胴部にブロー時の溶融パリソン表面肌荒れによる皺の有無で評価した。 [Formability]
The moldability of the multi-layer blow container was evaluated by observing the appearance of the obtained container and the presence or absence of wrinkles due to the rough surface of the melted parison during blowing on the container body.
BB:皺が観察できるかまたは目立ち、成形性が劣る
〔接着性〕
多層ブロー容器の本願オレフィン重合体組成物(E)から形成される最外層と隣接する層との層間において、容器成形時にバリカット部すなわち容器上部及び容器下部ピンチオフ部に発生する層剥離によるひも状や帯状に観察される外観不良の有無を評価する。 AA: No wrinkles or not noticeable, good moldability BB: Wrinkles can be observed or noticeable, and moldability is poor [Adhesiveness]
Between the outermost layer formed from the olefin polymer composition (E) of the present invention and the adjacent layer of the multilayer blow container, a string-like shape due to delamination that occurs in the burr cut part, that is, the container upper part and the container lower pinch-off part at the time of container molding Evaluate the presence or absence of appearance defects observed in strips.
BB:よく見ると外観不良が観察でき、接着性がやや劣る
CC:明らかな外観不良が有り、接着性が劣る
〔臭気〕
オレフィン重合体組成物(E)の臭気は、該組成物のペレット10gを100ml三角フラスコに入れ、蓋栓をして密封し、100℃オーブンで1時間加熱後取出し、直後に蓋栓を開け、発生した臭気を官能試験にて以下のように優劣判断した。 AA: Appearance is poor and adhesion is good BB: Appearance is poor and adhesion is slightly inferior when observed closely CC: Clear appearance is poor and adhesion is inferior [Odor]
The odor of the olefin polymer composition (E) was obtained by putting 10 g of the composition pellets in a 100 ml Erlenmeyer flask, sealing with a cap, taking out after heating in an oven at 100 ° C. for 1 hour, and immediately opening the cap. The generated odor was judged as superior or inferior in the sensory test as follows.
BB・・・若干臭気有り
CC・・・臭気有り
〔耐衝撃性〕
耐衝撃性の評価は、下記満水落下衝撃強度測定法による表面亀裂の発生有無により評価した。多層ブロー容器(内容量780ml)に水を満注した充填容器を5℃(耐衝撃性の評価)に冷却し、各温度に冷却したそれぞれ10本の容器を容器の底面がコンクリート面から1mの高さになる位置より垂直落下させ、次の落下基準に従い評価を行った。割れの判定は表層亀裂の発生有無にて判断した。 AA: No odor BB: Some odor CC: Some odor [impact resistance]
The impact resistance was evaluated based on the presence or absence of surface cracks by the full water drop impact strength measurement method described below. A multi-layer blow container (with an internal capacity of 780 ml) filled with water was cooled to 5 ° C. (evaluation of impact resistance), and each of the 10 containers cooled to each temperature had a bottom of 1 m from the concrete surface. It was dropped vertically from the height position and evaluated according to the following drop criteria. The determination of the crack was made based on whether or not a surface crack was generated.
BB:半数以上で、表面に亀裂が発生しないが、少なくとも1本で表面に亀裂が発生する
CC:過半数で表面に亀裂が発生する
満水落下耐衝撃強度測定法の評価が良好であるほど、耐衝撃性が良好であるといえる。 AA: No cracks occur on the surface in all cases BB: More than half, no cracks occur on the surface, but cracks occur on the surface with at least one CC: Cracks occur on the surface with a majority The full drop impact strength measurement The better the evaluation of the method, the better the impact resistance.
低温耐衝撃性の評価は、下記満水落下衝撃強度測定法による表面亀裂の発生有無により評価した。多層ブロー容器(内容量780ml)に、エチレングリコール/水=5/5(体積/体積)からなる液を満注した充填容器を-5℃(低温耐衝撃性の評価)に冷却し、各温度に冷却したそれぞれ10本の容器を容器の底面がコンクリート面から1mの高さになる位置より垂直落下させ、次の落下基準に従い評価を行った。割れの判定は表層亀裂の発生有無にて判断した。 (Low temperature impact resistance)
The low temperature impact resistance was evaluated by the presence or absence of surface cracks by the full water drop impact strength measurement method described below. Cool a filled container filled with a solution consisting of ethylene glycol / water = 5/5 (volume / volume) to a multilayer blow container (internal capacity 780 ml) to −5 ° C. (evaluation of low temperature impact resistance), Each of the 10 containers cooled in the vertical direction was dropped vertically from the position where the bottom surface of the container was 1 m above the concrete surface, and the evaluation was performed according to the following drop criteria. The determination of the crack was made based on whether or not a surface crack was generated.
BB:半数以上で、表面に亀裂が発生しないが、少なくとも1本で表面に亀裂が発生する
CC:過半数で表面に亀裂が発生する
満水落下耐衝撃強度測定法の評価が良好であるほど、低温耐衝撃性が良好であるといえる。 AA: No cracks occur on the surface in all cases BB: More than half, no cracks occur on the surface, but cracks occur on the surface with at least one CC: Cracks occur on the surface with a majority The full drop impact strength measurement The better the evaluation of the method, the better the low-temperature impact resistance.
多層ブロー容器の表面の手触りについて、成形後48~72時間23℃で状態調整したボトルの表面について、べたべたとした触感の有無を官能試験にて以下のように優劣判断した。 [Stickiness]
Regarding the touch of the surface of the multi-layer blow container, the presence or absence of a sticky tactile sensation on the surface of the bottle which was conditioned at 23 ° C. for 48 to 72 hours after molding was judged as superior or inferior as follows.
BB:殆どべたつきを感じない
CC:多少べたつきを感じる
DD:べたつきを感じる
本願請求の多層ブロー容器においては、べたつきの無いものが好ましく、べたつきが発生するものはべたつき性に劣るとした。 AA: No stickiness at all BB: Little stickiness CC: Some stickiness DD: Feeling sticky In the multilayer blow container claimed in the present application, a non-sticky one is preferable, and a sticky one is sticky. I was inferior.
13C-NMRより算出した、プロピレン由来の構成単位と、エチレンおよび炭素原子数4~20のα‐オレフィンからなる群から選ばれる1種以上のオレフィン由来の構成単位との合計を100重量%とした際の、エチレンおよび炭素原子数4~20のα‐オレフィンからなる群から選ばれる1種以上のオレフィン由来の構成単位の重量は13C-NMRの測定に基づき下記のようにして測定・算出し決定した。 [Weight of structural unit derived from α-olefin in propylene resin calculated from 13 C-NMR]
The total of the structural unit derived from propylene calculated from 13 C-NMR and the structural unit derived from one or more olefins selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms is 100% by weight. The weight of the structural unit derived from one or more olefins selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms is measured and calculated as follows based on the measurement of 13 C-NMR. I decided.
測定装置:日本電子製LA400型核磁気共鳴装置
測定モード:BCM(Bilevel Complete decoupling)
観測周波数:100.4MHz
観測範囲:17006.8Hz
パルス幅:C核45°(7.8μ秒)
パルス繰り返し時間:5秒
試料管:5mmφ
試料管回転数:12Hz
積算回数:20000回
測定温度:125℃
溶媒:1,2,4-トリクロロベンゼン:0.35ml/重ベンゼン:0.2ml
試料量:約40mg
コモノマーがエチレンの場合、得られた13C-NMRスペクトルを下記文献(1)に準じて、モノマー連鎖分布(ダイアッド(2連子)分布)の比率を決定し、プロピレン系樹脂の(A)中のエチレンに由来する構成単位のモル分率(mol%) (以下E(mol%)と記す)およびプロピレンに由来する構成単位のモル分率(mol%) (以下P(mol%)と記す)を算出した。求められたE(mol%)およびP(mol%)から重量%に換算しプロピレン系樹脂(A)中のプロピレンに由来する構成単位の重量%およびエチレンに由来する構成単位の重量%を算出した。 13 C-NMR measurement conditions Measurement device: LA400 type nuclear magnetic resonance apparatus manufactured by JEOL Measurement mode: BCM (Bilevel Complete Decoupling)
Observation frequency: 100.4 MHz
Observation range: 17006.8Hz
Pulse width: C nucleus 45 ° (7.8 μsec)
Pulse repetition time: 5 seconds Sample tube: 5 mmφ
Sample tube rotation speed: 12Hz
Integration count: 20000 times Measurement temperature: 125 ° C
Solvent: 1,2,4-trichlorobenzene: 0.35 ml / heavy benzene: 0.2 ml
Sample amount: about 40mg
When the comonomer is ethylene, the ratio of the obtained 13 C-NMR spectrum is determined according to the following document (1) to determine the ratio of the monomer chain distribution (dyad (doubled) distribution). Mole fraction of structural units derived from ethylene (mol%) (hereinafter referred to as E (mol%)) and mole fraction of structural units derived from propylene (mol%) (hereinafter referred to as P (mol%)) Was calculated. The weight percent of the structural unit derived from propylene and the weight percent of the structural unit derived from ethylene in the propylene-based resin (A) were calculated from the calculated E (mol%) and P (mol%) in weight percent. .
なお、多層ブロー容器の物性についての評価の内、ヘイズ、成形性、接着性、耐衝撃性、低温耐衝撃性およびべたつき性については、サンドブラスト処理#400を行った金型を用いて作成された多層ブロー容器について測定した。 Reference (1): Kakugo, M .; Naito, Y .; Mizunuma, K .; Miyatake, T., Macromolecules 1982, 15, (4), 1150-1152
Of the evaluation of the physical properties of the multilayer blow container, the haze, moldability, adhesiveness, impact resistance, low temperature impact resistance and stickiness were prepared using a mold subjected to sandblasting # 400. Measurements were made on multilayer blow containers.
Claims (13)
- 最外層に使用される樹脂が、プロピレン系樹脂(A)80~98重量部とエチレン・α‐オレフィン共重合体(B)2~20重量部(ただし、(A)と(B)との合計は100重量部である)と、核剤(D)0.01~0.5重量部とから形成されるオレフィン重合体組成物(E)からなり、
前記プロピレン系樹脂(A)が下記要件(A-1)および(A-2)を満たし、
前記エチレン・α‐オレフィン共重合体(B)が下記要件(B-1)および(B-2)を満たし、
前記オレフィン重合体組成物(E)が下記要件(E-1)を満たすことを特徴とする多層ブロー容器。
(A-1)プロピレンと、エチレンおよび炭素原子数4~20のα‐オレフィンからなる群から選ばれる1種以上のオレフィンとの共重合体である。
(A-2)JIS-K7121に準拠して示差走査熱量計(DSC)で測定した結晶融点が140~155℃の範囲である。
(B-1)エチレンと、炭素原子数4~20の1種以上のα‐オレフィンとの共重合体である。
(B-2)JIS-K7121に準拠してDSCで測定した結晶融点が85℃以上、110℃未満の範囲である。
(E-1)ASTM D-1238に準拠して、測定温度230℃、2.16kg荷重で測定したメルトフローレート(MFR)が5~10g/10分の範囲である。 The resin used in the outermost layer is 80 to 98 parts by weight of the propylene resin (A) and 2 to 20 parts by weight of the ethylene / α-olefin copolymer (B) (however, the sum of (A) and (B)) Is 100 parts by weight) and an olefin polymer composition (E) formed from 0.01 to 0.5 parts by weight of the nucleating agent (D),
The propylene resin (A) satisfies the following requirements (A-1) and (A-2):
The ethylene / α-olefin copolymer (B) satisfies the following requirements (B-1) and (B-2):
A multilayer blow container, wherein the olefin polymer composition (E) satisfies the following requirement (E-1).
(A-1) A copolymer of propylene and one or more olefins selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms.
(A-2) The crystal melting point measured with a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is in the range of 140 to 155 ° C.
(B-1) A copolymer of ethylene and one or more α-olefins having 4 to 20 carbon atoms.
(B-2) The crystal melting point measured by DSC in accordance with JIS-K7121 is in the range of 85 ° C. or higher and lower than 110 ° C.
(E-1) According to ASTM D-1238, the melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes. - 前記オレフィン系重合体組成物(E)が、さらに低密度エチレン・α‐オレフィン共重合体(F)0.1~20重量部を用いて形成されており、
前記低密度エチレン・α‐オレフィン共重合体(F)が下記要件(F-1)および(F-2)を満たし、
前記エチレン・α‐オレフィン共重合体(B)の密度勾配官法で測定した密度(dB[g/cm3])および低密度エチレン・α‐オレフィン共重合体(F)の密度勾配官法で測定した密度(dF[g/cm3])が下記要件(X-1)を満たす請求項1に記載の多層ブロー容器。
(F-1)エチレンと、炭素原子数3~20の1種以上のα-オレフィンとの共重合体である。
(F-2)JIS-K7121に準拠してDSCで測定した結晶融点が89℃以下であるか、または、結晶融点に基づくピークが観測されない。
(X-1)dB[g/cm3]>dF[g/cm3]であり、0.010[g/cm3]≦(dB-dF)[g/cm3]≦0.050[g/cm3]である。 The olefin polymer composition (E) is further formed using 0.1 to 20 parts by weight of a low density ethylene / α-olefin copolymer (F),
The low density ethylene / α-olefin copolymer (F) satisfies the following requirements (F-1) and (F-2):
The density (d B [g / cm 3 ]) measured by the density gradient method of the ethylene / α-olefin copolymer (B) and the density gradient method of the low density ethylene / α-olefin copolymer (F) The multilayer blow container according to claim 1, wherein the density (d F [g / cm 3 ]) measured in step 1 satisfies the following requirement (X-1).
(F-1) A copolymer of ethylene and one or more α-olefins having 3 to 20 carbon atoms.
(F-2) The crystalline melting point measured by DSC according to JIS-K7121 is 89 ° C. or lower, or no peak based on the crystalline melting point is observed.
(X-1) d B [g / cm 3 ]> d F [g / cm 3 ], 0.010 [g / cm 3 ] ≦ (d B −d F ) [g / cm 3 ] ≦ 0 0.050 [g / cm 3 ]. - 前記エチレン・α‐オレフィン共重合体(B)がさらに下記要件(B-4)を満たすことを特徴とする請求項1に記載の多層ブロー容器。
(B-4)密度勾配管法で測定した密度が0.880~0.910g/cm3の範囲である。 The multilayer blow container according to claim 1, wherein the ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-4).
(B-4) The density measured by the density gradient tube method is in the range of 0.880 to 0.910 g / cm 3 . - 前記エチレン・α‐オレフィン共重合体(B)がさらに下記要件(B-4a)を満たし、前記低密度エチレン・α‐オレフィン共重合体(F)がさらに下記要件(F-3)を満たすことを特徴とする請求項2に記載の多層ブロー容器。
(B-4a)密度勾配管法で測定した密度(dB[g/cm3])が0.890~0.910g/cm3の範囲である。
(F-3)密度勾配管法で測定した密度(dF[g/cm3])が0.865~0.900g/cm3の範囲である。 The ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-4a), and the low density ethylene / α-olefin copolymer (F) further satisfies the following requirement (F-3). The multilayer blow container according to claim 2.
(B-4a) density measured by a density gradient tube method (d B [g / cm 3 ]) is in the range of 0.890 ~ 0.910g / cm 3.
(F-3) The density (d F [g / cm 3 ]) measured by the density gradient tube method is in the range of 0.865 to 0.900 g / cm 3 . - 前記プロピレン系樹脂(A)がさらに下記要件(A-4)を満たすことを特徴とする請求項1~4のいずれか一項に記載の多層ブロー容器。
(A-4)GPCにより測定したMw/Mnが4.0以上である。 The multilayer blow container according to any one of claims 1 to 4, wherein the propylene-based resin (A) further satisfies the following requirement (A-4).
(A-4) Mw / Mn measured by GPC is 4.0 or more. - 前記プロピレン系樹脂(A)がさらに下記要件(A-3)を満たすことを特徴とする請求項1~5のいずれか一項に記載の多層ブロー容器。
(A-3)ASTM D-1238に準拠して、測定温度230℃、2.16kg荷重で測定したMFRが5~10g/10分の範囲である。 The multilayer blow container according to any one of claims 1 to 5, wherein the propylene-based resin (A) further satisfies the following requirement (A-3).
(A-3) According to ASTM D-1238, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes. - 前記エチレン・α‐オレフィン共重合体(B)がさらに下記要件(B-5)を満たすことを特徴とする請求項1~6のいずれか一項に記載の多層ブロー容器。
(B-5)GPCにより測定したMw/Mnが1.2~3.0である。 The multilayer blow container according to any one of claims 1 to 6, wherein the ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-5).
(B-5) Mw / Mn measured by GPC is 1.2 to 3.0. - 前記エチレン・α‐オレフィン共重合体(B)がさらに下記要件(B-3)を満たすことを特徴とする請求項1~7のいずれか一項に記載の多層ブロー容器。
(B-3)ASTM D-1238に準拠して、測定温度230℃、2.16kg荷重で測定したMFRが5~10g/10分の範囲である。 The multilayer blow container according to any one of claims 1 to 7, wherein the ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-3).
(B-3) According to ASTM D-1238, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes. - 前記核剤(D)が、芳香族リン酸エステル化合物、カルボン酸金属塩造核剤、ポリマー造核剤、ソルビトール系造核剤および無機化合物造核剤からなる群から選ばれる1種以上の化合物であることを特徴とする請求項1~8のいずれか一項に記載の多層ブロー容器。 The nucleating agent (D) is one or more compounds selected from the group consisting of aromatic phosphate ester compounds, carboxylic acid metal salt nucleating agents, polymer nucleating agents, sorbitol nucleating agents and inorganic compound nucleating agents. The multilayer blow container according to any one of claims 1 to 8, wherein
- 前記プロピレン系樹脂(A)が95.5~98重量部であり、前記エチレン・α‐オレフィン共重合体(B)が2~4.5重量部(ただし、(A)と(B)との合計は100重量部である)であることを特徴とする請求項1~9のいずれか一項に記載の多層ブロー容器。 The propylene-based resin (A) is 95.5 to 98 parts by weight, and the ethylene / α-olefin copolymer (B) is 2 to 4.5 parts by weight (provided that (A) and (B) The multilayer blow container according to any one of claims 1 to 9, wherein the total is 100 parts by weight.
- 前記多層ブロー容器が、少なくとも一つの内層として、プロピレン系重合体(G)またはエチレン系重合体(H)から形成される層を有することを特徴とする請求項1~10のいずれか一項に記載の多層ブロー容器。 The multilayer blow container has a layer formed from a propylene polymer (G) or an ethylene polymer (H) as at least one inner layer. The multilayer blow container described.
- 前記多層ブロー容器が、ダイレクトブロー成形法または射出延伸ブロー成形法により成形して得られたものであることを特徴とする請求項1~11のいずれか一項に記載の多層ブロー容器。 The multilayer blow container according to any one of claims 1 to 11, wherein the multilayer blow container is obtained by molding by a direct blow molding method or an injection stretch blow molding method.
- 請求項1~9のいずれか一項に記載のオレフィン重合体組成物(E)およびオレフィン重合体組成物(E)以外の熱可塑性樹脂組成物を用い、
前記オレフィン重合体組成物(E)が最外層を形成し、前記オレフィン重合体組成物(E)以外の熱可塑性樹脂組成物が少なくとも一つの内層を形成するように、ダイレクトブロー成形法または射出延伸ブロー成形法により成形することを特徴とする多層ブロー容器の製造方法。 A thermoplastic resin composition other than the olefin polymer composition (E) and the olefin polymer composition (E) according to any one of claims 1 to 9,
The direct blow molding method or injection stretching so that the olefin polymer composition (E) forms the outermost layer and the thermoplastic resin composition other than the olefin polymer composition (E) forms at least one inner layer. A method for producing a multilayer blow container, characterized by molding by a blow molding method.
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