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
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- 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 general shape other than plane
- 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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- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- 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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- 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. .
Abstract
Disclosed is a multilayer blow-molded container having high gloss, excellent surface appearance and excellent impact resistance.
The multilayer blow-molded container is characterized in that a resin to be used for the outermost layer comprises an olefin polymer composition (E) comprising a propylene resin (A), an ethylene·α-olefin copolymer (B) and a nucleating agent (D), the propylene resin (A) comprises a copolymer of propylene and an α-olefin (A-1) and has a crystal melting point of 140 to 155˚C (A-2), the ethylene·α-olefin copolymer (B) comprises a copolymer of ethylene and at least one α-olefin having 4 to 20 carbon atoms (B-1) and has a crystal melting point of not lower than 85°C and lower than 110°C (B-2), and the olefin polymer composition (E) has an MFR value of 5 to 10 g/10 min (E-1).
Description
本発明は多層ブロー容器およびその製造方法に関する。
The present invention relates to a multilayer blow container and a manufacturing method thereof.
ブロー容器等のブロー成形体の原料としては、例えば塩化ビニル樹脂、ポリカーボネート樹脂、エチレン系樹脂、プロピレン系樹脂等の樹脂が用途に応じて用いられている。
As a raw material for blow molded articles such as blow containers, resins such as vinyl chloride resin, polycarbonate resin, ethylene resin, and propylene resin are used depending on applications.
これらの樹脂のうち、高密度ポリエチレンのような硬質のエチレン系樹脂を用いた場合には、光沢が悪く、低密度ポリエチレンのような軟質のエチレン系樹脂を用いた場合には、剛性が低いという問題がある。
Among these resins, when a hard ethylene resin such as high density polyethylene is used, the gloss is poor, and when a soft ethylene resin such as low density polyethylene is used, the rigidity is low. There's a problem.
また、塩化ビニル樹脂を用いた場合は、光沢には優れるものの、環境問題があり、ポリカーボネート樹脂を用いた場合には、光沢には非常に優れるものの、製造コストが高くなる等の問題があった。
In addition, when vinyl chloride resin is used, there is an environmental problem although it is excellent in gloss. When polycarbonate resin is used, there are problems such as high manufacturing cost although it is very excellent in gloss. .
一方、プロピレン系樹脂を用いた場合には、得られるブロー成形体は、比較的製造コストが安く、高密度ポリエチレンよりも光沢、透明性に優れるため、液体洗剤、化粧品、食品、薬品等の容器として広く用いられている。
On the other hand, when a propylene-based resin is used, 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.
ブロー成形体の光沢は、良好な外観を求める市場の要求に答えるために、従来から検討されてきた物性であるが、未だ充分な光沢と良成形性と耐衝撃性を同時に満足するブロー成形体は提案されていない。
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.
光沢に優れるブロー成形体として、プロピレン・α‐オレフィン共重合体を基材樹脂とし、結晶融点が１１０～１２５℃の線状低密度ポリエチレンを配合樹脂とし、これらの樹脂と、核剤とを含むオレフィン重合体組成物を最外層とする、多層ブロー成形体が提案されている（例えば、特許文献１参照）。しかしながら、本発明者らが検討したところ、特許文献１に記載された多層ブロー成形体であっても、未だ光沢および耐衝撃性は充分でなく、更なる改善が必要であることがわかった。
As a blow molded product with excellent gloss, a propylene / α-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). However, 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.
耐寒強度に優れる多層ボトルとして、ガスバリヤー性樹脂の芯層を有し、最外層がポリオレフィン系樹脂と、直鎖状超低密度ポリエチレン樹脂とから形成される多層ボトルが提案されている（例えば、特許文献２参照）。しかしながら、本発明者らが検討したところ、特許文献２に記載された多層ボトルであっても、未だ光沢および成形性が充分でなく、更なる改善が必要であることがわかった。
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). However, 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.
優れた光沢、表面性を有するインモールド方式によって製造されるラベル付き多層プラスチック容器として、最外層に用いられる樹脂として、エチレン分を含有するポリプロピレンランダム共重合体樹脂、ポリエチレン樹脂、造核剤、エチレン・α‐オレフィン共重合体樹脂を含むものを用いることが提案されている（例えば、特許文献３参照）。しかしながら、本発明者らが検討したところ、特許文献３に記載された多層プラスチック容器は、未だ耐衝撃性が充分でなく、更なる改善が必要であることがわかった。
As a multilayer plastic container with a label manufactured by an in-mold method with excellent gloss and surface properties, as a resin used for the outermost layer, a polypropylene random copolymer resin containing polyethylene, polyethylene resin, nucleating agent, ethylene It has been proposed to use a material containing an α-olefin copolymer resin (for example, see Patent Document 3). However, when the present inventors examined, it turned out that the multilayer plastic container described in patent document 3 is not yet sufficient in impact resistance, and needs further improvement.
容器外表面の光沢に優れた高光沢ブロー容器として、メタロセン触媒を用いて得られるポリプロピレン系樹脂と、メタロセン触媒を用いて得られるエチレン・α‐オレフィン共重合体とからなる組成物を最外層に用い、多層ブロー成形法によって成形した高光沢ブロー容器が知られている（例えば、特許文献４参照）。しかしながら、本発明者らが検討したところ、特許文献４に記載された高光沢ブロー容器は、従来の容器と比べた際には光沢に優れるが、耐熱性や光沢などの点で更なる改善の余地があることがわかった。
As a high-gloss blow container with excellent gloss on the outer surface of the container, a composition comprising a polypropylene resin obtained using a metallocene catalyst and an ethylene / α-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). However, as a result of investigations by the present inventors, 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.
本発明は、高光沢であり、表面外観に優れるとともに、耐衝撃性に優れ、かつ耐衝撃性と耐べたつき性とのバランスにも優れた多層ブロー容器を提供することを目的としている。
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.
本発明者らは、上記課題を達成するために鋭意研究を重ねた結果、特定のオレフィン重合体組成物を最外層に使用した多層ブロー容器は、高光沢であり、表面外観に優れるとともに、耐衝撃性に優れ、かつ耐衝撃性と耐べたつき性とのバランスにも優れることを見出し、本発明を完成させた。
As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that 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.
すなわち、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）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。
That is, in the multilayer blow container of the present invention, 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, (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 / α-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－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-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）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。
(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）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-1) A copolymer of ethylene and one or more α-olefins having 4 to 20 carbon atoms.
（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。
(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）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。
(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）を満たすと、多層ブロー容器の低温耐衝撃性の観点から好ましい。
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 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 / α-olefin copolymer (B): 3 ]) and the density (d F [g / cm 3 ]) measured by the density gradient method of the low density ethylene / α-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）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-1) A copolymer of ethylene and one or more α-olefins having 3 to 20 carbon atoms.
（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。
(F-2) 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.
（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。
(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）を満たすことが好ましい。
The ethylene / α-olefin copolymer (B) preferably further satisfies the following requirement (B-4).
（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。
(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）を満たすことが、多層ブロー容器の低温耐衝撃性の観点から好ましい。
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). Is preferable from the viewpoint of low-temperature impact resistance of the multilayer blow container.
（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。
(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）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。
(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）を満たすことが好ましい。
It is preferable that the propylene resin (A) further satisfies the following requirement (A-4).
（Ａ－４）ＧＰＣにより測定したＭｗ／Ｍｎが４．０以上である。
(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）を満たすことが好ましい。
It is preferable that the propylene resin (A) further satisfies the following requirement (A-3).
（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。
(A-3) According to ASTM D-1238, 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）を満たすことが好ましい。
It is preferable that the ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-5).
（Ｂ－５）ＧＰＣにより測定したＭｗ／Ｍｎが１．２～３．０である。
(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）を満たすことが好ましい。
The ethylene / α-olefin copolymer (B) preferably further satisfies the following requirement (B-3).
（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。
(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.
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が好ましい。
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
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）であることが好ましい。
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 total is preferably 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が好ましい。
The multilayer blow container is preferably obtained by molding by a direct blow molding method or an injection stretch blow molding method.
本発明の多層ブロー容器は、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を特徴とする。
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.
本発明によれば、高光沢であり、表面外観に優れるとともに、耐衝撃性に優れ、かつ耐衝撃性と耐べたつき性とのバランスにも優れる多層ブロー容器を提供することができる。
According to the present invention, it is possible to provide a multilayer blow container having high gloss, excellent surface appearance, excellent impact resistance, and excellent balance between impact resistance and stickiness resistance.
次に本発明について具体的に説明する。
Next, the present invention will be specifically described.
〔多層ブロー容器〕
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.
本発明の多層ブロー容器は、高光沢であり、表面外観に優れるとともに、耐衝撃性に優れるが、オレフィン重合体組成物（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いる態様では、さらに低温耐衝撃性にも優れる。
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 / α-olefin copolymer (F). In the embodiment formed using 0.1 to 20 parts by weight, the low temperature impact resistance is further excellent.
＜プロピレン系樹脂（Ａ）＞
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.
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.
（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。なお、炭素原子数４～２０のα‐オレフィンとしては、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-デセン、1-ドデセン、1-ヘキサドデセン、4-メチル-1-ペンテン、2-メチル-1-ブテン、3-メチル-1-ブテン、3-メチル-1-ブテン、3,3-ジメチル-1-ブテン、ジエチル-1-ブテン、トリメチル-1-ブテン、3-メチル-1-ペンテン、エチル-1-ペンテン、プロピル-1-ペンテン、ジメチル-1-ペンテン、メチルエチル-1-ペンテン、ジエチル-1-ヘキセン、トリメチル-1-ペンテン、3-メチル-1-ヘキセン、ジメチル-1-ヘキセン、3,5,5-トリメチル-1-ヘキセン、メチルエチル-1-ヘプテン、トリメチル-1-ヘプテン、エチル-1-オクテン、メチル-1-ノネンなどが挙げられる。
(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. Examples of the α-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. .
本発明に用いるプロピレン系樹脂（Ａ）としては、物性、経済性のバランスの面からプロピレンと、エチレンおよび炭素原子数４～１０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ことが好ましく、プロピレンと、エチレンおよび1-ブテンからなる群から選ばれる1種以上のα‐オレフィンとの共重合体であることがより好ましく、プロピレンとエチレンとの共重合体であることが特に好ましい。
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 α-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 α-olefins selected from the group consisting of ethylene and 1-butene, and a copolymer of propylene and ethylene It is particularly preferred that
また、本発明に用いるプロピレン系樹脂（Ａ）は、ランダム共重合体であることが好ましい。
The propylene resin (A) used in the present invention is preferably a random copolymer.
（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。結晶融点が前記範囲内にあると、多層ブロー容器の光沢および耐衝撃性に優れ、多層ブロー容器を製造する際の成形性にも優れるため好ましい。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１５５℃よりも高いと多層ブロー容器の耐衝撃性が劣る。また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℃より低いと、多層ブロー容器を製造する際の成形性に劣り、多層ブロー容器の表面にべたつきが発生する。
(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. 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. When 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. Also, if the crystal melting point measured by a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is lower than 140 ° C., the moldability at the time of producing the multilayer blow container is inferior and the surface of the multilayer blow container is sticky. .
前記プロピレン系樹脂（Ａ）の結晶融点は、ＪＩＳ－Ｋ７１２１に従って、示差走査熱量計（ＤＳＣ）（例えば、パーキンエルマー社製 Ｄｉａｍｏｎｄ ＤＳＣ）を用いて下記測定条件にて測定を行うことにより求めることができる。なお、下記測定条件で測定を行った際の、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の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。
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 ™ DSC manufactured by Perkin Elmer) according to JIS-K7121. it can. In addition, 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). When there are a plurality of endothermic peaks, the peak of the endothermic peak where the peak height is maximum is defined as the crystalline melting point (Tm).
（測定条件）
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.
第2step ： 10℃/minで60℃まで降温する。
Second step IV: Decrease the temperature to 60 ° C at 10 ° C / min.
第3step ： 10℃/minで240℃まで昇温する。
3rd step IV: Increase the temperature to 240 ° C at 10 ° C / min.
前記プロピレン系樹脂（Ａ）のＪＩＳ－Ｋ７１２１に準拠して示差走査熱量計（ＤＳＣ）で測定した結晶融点は、例えばプロピレン系樹脂（Ａ）の製造における共重合時のプロピレンと、導入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比率を変更することにより調整することができる。つまり、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、ＪＩＳ－Ｋ７１２１に準拠して示差走査熱量計（ＤＳＣ）で測定した結晶融点を低くすることができ、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、ＪＩＳ－Ｋ７１２１に準拠して示差走査熱量計（ＤＳＣ）で測定した結晶融点を高くすることができる。
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 α-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 α-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 α-olefins having 4 to 20 carbon atoms is reduced with respect to the introduction amount of propylene. By doing so, the crystal melting point measured with a differential scanning calorimeter (DSC) in accordance with JIS-K7121 can be increased.
（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。なお、ＭＦＲとはメルトフローレートを意味する。ＭＦＲが前記範囲内にあると、成形時のオレフィン重合体組成物（Ｅ）の流動性が本発明の成形に好適な範囲となり、ブロー成形における最多層のオレフィン重合体組成物（Ｅ）の厚みムラが防止され、平滑性に優れ、ひいては光沢にも優れる多層ブロー容器を製造することができる。ＡＳＴＭ Ｄ－１２３８に準拠して、測定温度２３０℃、２．１６ｋｇ荷重で測定したＭＦＲが１０ｇ／１０分より大きいと多層ブロー容器を製造する際の成形性および多層ブロー容器の耐衝撃性が劣る場合があり、ＡＳＴＭ Ｄ－１２３８に準拠して、測定温度２３０℃、２．１６ｋｇ荷重で測定したＭＦＲが５ｇ／１０分より小さいと多層ブロー容器の光沢性が劣る場合がある。
(A-3) According to ASTM D-1238, 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. In addition, MFR means a melt flow rate. When the MFR is within the above range, the fluidity of the olefin polymer composition (E) at the time of molding becomes a suitable range for molding of the present invention, and the thickness of the olefin polymer composition (E) having the highest multilayer in blow molding. Unevenness is prevented, and a multi-layer blow container having excellent smoothness and excellent gloss can be produced. In accordance with ASTM D-1238, if the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is greater than 10 g / 10 minutes, the moldability and the impact resistance of the multilayer blow container are inferior. In accordance with ASTM D-1238, if the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is less than 5 g / 10 minutes, the gloss of the multilayer blow container may be inferior.
前記プロピレン系樹脂（Ａ）のＡＳＴＭ Ｄ－１２３８に準拠して、測定温度２３０℃、２．１６ｋｇ荷重で測定したＭＦＲは、例えばプロピレン系樹脂（Ａ）の製造における共重合時、使用する連鎖移動剤（例えば水素ガス）の導入量で調整することができる。つまり、重合時に導入するプロピレンと、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の量に対する、連鎖移動剤（例えば水素ガス）の導入量を多くすることによって、プロピレン系樹脂（Ａ）の、ＡＳＴＭ Ｄ－１２３８に準拠して測定温度２３０℃、２．１６ｋｇ荷重で測定したＭＦＲを高くすることができる。また、重合時に導入するプロピレンと、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の量に対する、連鎖移動剤（例えば水素ガス）の導入量を少なくすることによって、プロピレン系樹脂（Ａ）のＡＳＴＭ Ｄ－１２３８に準拠して測定温度２３０℃、２．１６ｋｇ荷重で測定したＭＦＲを低くすることができる。
According to ASTM D-1238 of the propylene resin (A), 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 α-olefins having 4 to 20 carbon atoms. Thus, the MFR of the propylene resin (A) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 can be increased. Further, the introduction amount of chain transfer agent (for example, hydrogen gas) 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 α-olefin having 4 to 20 carbon atoms. Thus, 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.
また、重合で得られたプロピレン系樹脂を有機過酸化物等のラジカル発生剤の存在下で溶融混練処理を行うことによっても、ＡＳＴＭ Ｄ－１２３８に準拠して測定温度２３０℃、２．１６ｋｇ荷重で測定したＭＦＲを調整することができる。例えば有機過酸化物存在下で溶融混練処理を行うことによりＡＳＴＭ Ｄ－１２３８に準拠して、測定温度２３０℃、２．１６ｋｇ荷重で測定したＭＦＲは高くなる。また有機過酸化物の添加量を増やすことにより、ＡＳＴＭ Ｄ－１２３８に準拠して、測定温度２３０℃、２．１６ｋｇ荷重で測定したＭＦＲはさらに高くすることが出来る。
In addition, 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.
（Ａ－４）ＧＰＣにより測定したＭｗ／Ｍｎが４．０以上である。なお、ＧＰＣとはゲルパーミエーションクロマトグラフィーを意味し、Ｍｗは重量平均分子量を意味し、Ｍｎは数平均分子量を意味し、Ｍｗ／Ｍｎは分子量分布の指標である。プロピレン系樹脂（Ａ）としては、Ｍｗ／Ｍｎが好ましくは１．５以上、より好ましくは３．０以上であるが、前記（Ａ－４）を満たす、すなわち、Ｍｗ／Ｍｎが４．０以上であると、ブロー金型の表面粗さによらず、光沢に優れたブロー成形体が得られるため特に好ましい。この理由は明らかではないが、本発明者らは以下のように考えている。すなわちＭｗ／Ｍｎが４．０以上であると、該範囲未満の場合と比べてより高分子量の部分とより低分子量の部分とが存在することになる。より高分子量の部分の存在がブロー成形時の樹脂流動変形を少なくし、より低分子量の部分の存在が、固化を早めると考えられる。このため、（Ａ）成分として上記Ｍｗ／Ｍｎの範囲のものを用いると表面粗さが大きい金型を用いた場合も、表面粗さが小さい金型を用いた場合も得られる多層ブロー容器は金型表面の粗さを転写することなく、良好な光沢になると、本発明者らは推定した。また、Ｍｗ／Ｍｎの上限としては特に限定はないが、生産性の観点から通常は５０．０、好ましくは３０．０、より好ましくは２０．０、さらに好ましくは１６．０、とりわけ好ましくは１２．０、最も好ましくは８．０である。なお、ＧＰＣによるＭｗ／Ｍｎは実施例に記載の方法で行うことができる。
(A-4) 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, and Mw / Mn is an index of molecular weight distribution. As the propylene-based resin (A), 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. That is, when Mw / Mn is 4.0 or more, a portion having a higher molecular weight and a portion having a lower molecular weight are present than in the case where the value is less than the above range. It is considered that the presence of a higher molecular weight portion reduces resin flow deformation during blow molding, and the presence of a lower molecular weight portion accelerates solidification. For this reason, the multilayer blow container which can be obtained both when a mold having a large surface roughness and a mold having a small surface roughness is used when the component (A) is in the range of Mw / Mn. The inventors estimated that the gloss would be good without transferring the roughness of the mold surface. The upper limit of 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. In addition, Mw / Mn by GPC can be performed by the method as described in an Example.
前記プロピレン系樹脂（Ａ）のＧＰＣにより測定したＭｗ／Ｍｎは、例えばプロピレン系樹脂（Ａ）の製造の際に用いる触媒の種類によって、調整することができる。例えば触媒として、チーグラーナッタ触媒、好ましくは固体状チタン触媒を用いることにより前記要件（Ａ－４）を満たすプロピレン系樹脂（Ａ）を得ることができる。また、Ｍｗ／Ｍｎを調整する別の方法の例としては、分子量の異なる２種以上のプロピレン系樹脂をブレンドする方法がある。特に固体状チタン触媒は前記のより高分子量の部分を形成する観点から有利である。
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). For example, by using a Ziegler-Natta catalyst, preferably a solid titanium catalyst, as the catalyst, the propylene-based resin (A) satisfying the requirement (A-4) can be obtained. As another example of adjusting Mw / Mn, there is a method of blending two or more propylene resins having different molecular weights. In particular, the solid titanium catalyst is advantageous from the viewpoint of forming the higher molecular weight portion.
また、プロピレン系樹脂（Ａ）としては、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、プロピレン由来の構成単位の重量が、通常は８０～９９重量％の範囲であり、好ましくは、９０～９９重量％の範囲である。また、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が、通常は１～２０重量％の範囲であり、好ましくは、１～１０重量％の範囲である。前記範囲内では、多層ブロー容器を製造する際の成形性と、多層ブロー容器のべたつき性等の物性とのバランスが良好であるため好ましい。
The propylene resin (A) is derived from one or more olefins selected from the group consisting of propylene-derived structural units and ethylene and α-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 α-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.
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、プロピレン由来の構成単位の重量は下記の条件で測定し、算出した。
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 propylene was measured and calculated under the following conditions.
（13Ｃ-ＮＭＲ測定条件）
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.
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.
文献(1)：Kakugo,M.; Naito,Y.; Mizunuma,K.; Miyatake,T., Macromolecules 1982, 15, (4), 1150-1152
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.
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.
文献(２)： James C. Randall, Macromolecules, 1978, 11, 592-597
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.
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.
また、前記プロピレン系樹脂（Ａ）は、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ランダム共重合体であることが好ましい。前記プロピレン系樹脂（Ａ）はチーグラーナッタ触媒や、メタロセン触媒存在下でプロピレンと、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を共重合、好ましくはランダム共重合することにより得ることができる。前記プロピレン系樹脂（Ａ）を重合する際に用いる触媒としては、チーグラーナッタ触媒、好ましくは固体状チタン触媒を用いると、前記要件（Ａ－４）を満たすことが可能である。また、分子量の異なる２種以上のプロピレン系樹脂（Ａ）をブレンドすることにより、要件（Ａ－４）を満たすように調整することも可能である。また、重合の際には、水素ガスに代表されるような連鎖移動剤を導入することもできる。さらに、重合で得られたプロピレン系樹脂を、有機過酸化物等のラジカル発生剤存在下で溶融混練処理を行いプロピレン系樹脂（Ａ）を得ることもできる。
The propylene resin (A) is preferably a random copolymer of propylene and one or more olefins selected from the group consisting of ethylene and α-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 α-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. When a Ziegler-Natta catalyst, preferably a solid titanium catalyst, is used as the catalyst used for polymerizing the propylene-based resin (A), 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. In the polymerization, a chain transfer agent represented by hydrogen gas can be introduced. Furthermore, 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.
前記の有機過酸化物としては、特に限定はされないが、ベンゾイルパーオキサイド、ｔ－ブチルパーベンゾエート、ｔ－ブチルパーアセテート、ｔ－ブチルパーオキシイソプロピルカーボネート、2,5－ジ－メチル－2,5－ジ－（ベンゾイルパーオキシ）ヘキサン、2,5－ジ－メチル－2,5－ジ－（ベンゾイルパーオキシ）ヘキシン－３、ｔ－ブチル－ジ－パーアジペート、ｔ－ブチルパーオキシ－3,5,5－トリメチルヘキサノエート、メチル－エチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ジキュミルパーオキサイド、2,5－ジ－メチル－2,5－ジ－（ｔ－ブチルパーオキシ）ヘキサン、2,5,－ジ－メチル－2,5－ジ－（ｔ－ブチルパーオキシ）ヘキシン－３、1,3－ビス－（ｔ－ブチルパーオキシイソプロピル）ベンゼン、ｔ－ブチルキユミルパーオキサイド、1,1－ビス－（ｔ－ブチルパーオキシ）－3,3,5－トリメチルシクロヘキサン、1,1－ビス－（ｔ－ブチルパーオキシ）シクロヘキサン、2,2－ビス－（ｔ－ブチルパーオキシ）ブタン、ｐ－メンタンハイドロパーオキサイド、ジ－イソプロピルベンゼンハイドロパーオキサイド、キユメンハイドロパーオキサイド、ｔ－ブチルハイドロパーオキサイド、ｐ－サイメンハイドロパーオキサイド、1,1,3,3－テトラ－メチルブチルハイドロパーオキサイドもしくは2,5－ジ－メチル－2,5－ジ－（ハイドロパーオキシ）ヘキサンなどの有機過酸化物を例示できる。また、これらのうち、2,5－ジ－メチル－2,5－ジ－（ベンゾイルパーオキシ）ヘキサン、1,3－ビス－（ｔ－ブチルパーオキシイソプロピル）ベンゼンがより好ましい。有機過酸化物を使用する場合、重合で得られたプロピレン系樹脂１００重量部に対して０．１重量部以下で使用することが望ましい。溶融混練処理は、プロピレン系樹脂に上記有機過酸化物を添加後、ヘンシェルミキサー、バンバリーミキサー、タンブラーミキサー等の混合機に投入し、混合を行い、次いで、得られた混合物を、一軸押出機、二軸押出機等の押出機により成形し、プロピレン系樹脂（Ａ）のストランドを得る方法が挙げられる。なお、前記ストランドは、通常ブロー成形を行う前に、ペレタイザー等を用いてペレット形状にされる。
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-3,1,3-bis- (t-butylperoxyisopropyl Pill) benzene, t-butyl chylyl peroxide, 1,1-bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis- (t-butylperoxy) cyclohexane, 2,2-bis- (t-butylperoxy) butane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, Examples thereof include organic peroxides such as 1,1,3,3-tetra-methylbutyl hydroperoxide or 2,5-di-methyl-2,5-di- (hydroperoxy) hexane. Of these, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane and 1,3-bis- (t-butylperoxyisopropyl) benzene are more preferred. When using 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. In the melt-kneading process, after adding the organic peroxide to the propylene-based resin, the mixture is introduced into a mixer such as a Henschel mixer, a Banbury mixer, or a tumbler mixer, and then mixed.The resulting mixture is then converted into a single-screw extruder, The method of shape | 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.
＜エチレン・α‐オレフィン共重合体（Ｂ）＞
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.
（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。なお、炭素原子数４～２０のα‐オレフィンとしては、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-デセン、1-ドデセン、1-ヘキサドデセン、4-メチル-1-ペンテン、2-メチル-1-ブテン、3-メチル-1-ブテン、3-メチル-1-ブテン、3,3-ジメチル-1-ブテン、ジエチル-1-ブテン、トリメチル-1-ブテン、3-メチル-1-ペンテン、エチル-1-ペンテン、プロピル-1-ペンテン、ジメチル-1-ペンテン、メチルエチル-1-ペンテン、ジエチル-1-ヘキセン、トリメチル-1-ペンテン、3-メチル-1-ヘキセン、ジメチル-1-ヘキセン、3,5,5-トリメチル-1-ヘキセン、メチルエチル-1-ヘプテン、トリメチル-1-ヘプテン、エチル-1-オクテン、メチル-1-ノネンなどが挙げられる。
(B-1) A copolymer of ethylene and one or more α-olefins having 4 to 20 carbon atoms. Examples of the α-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. .
本発明に用いるエチレン・α‐オレフィン共重合体（Ｂ）としては、物性と経済性とのバランスの観点からエチレンと、炭素原子数４～１０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ことが好ましく、エチレンと、1-ブテン、1-ヘキセンおよび1-オクテンからなる群から選ばれる1種以上のα‐オレフィンとの共重合体であることがより好ましく、エチレンと1-ヘキセンとの共重合体であることが特に好ましい。
The ethylene / α-olefin copolymer (B) used in the present invention is at least one selected from the group consisting of ethylene and α-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 α-olefins selected from the group consisting of 1-butene, 1-hexene and 1-octene. A copolymer of ethylene and 1-hexene is particularly preferable.
（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。結晶融点が前記範囲内にあると、多層ブロー容器の耐衝撃性や、最外層と他の層との接着性に優れるため好ましい。エチレン・α‐オレフィン共重合体（Ｂ）のＪＩＳ－Ｋ７１２１に準拠してＤＳＣで測定した結晶融点が１１０℃以上では接着性および耐衝撃性に劣り、ＪＩＳ－Ｋ７１２１に準拠してＤＳＣで測定した結晶融点が８５℃より低いと接着性に劣り、さらにべたつきが発生する為好ましくない。また、耐衝撃性、接着性およびべたつき性とのバランスの観点から、結晶融点は好ましくは１０９℃以下、より好ましくは１０８℃以下、特に好ましくは１０５℃以下である。
(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. 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. When the crystalline melting point of the ethylene / α-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. When the crystal melting point is lower than 85 ° C., the adhesiveness is inferior, and stickiness is generated, which is not preferable. Further, from the viewpoint of the balance between impact resistance, adhesion and stickiness, the crystal melting point is preferably 109 ° C. or lower, more preferably 108 ° C. or lower, and particularly preferably 105 ° C. or lower.
本発明に用いるエチレン・α‐オレフィン共重合体（Ｂ）のＪＩＳ－Ｋ７１２１に準拠してＤＳＣで測定した結晶融点は、エチレン・α‐オレフィン共重合体の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。
The crystalline melting point of the ethylene / α-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 / α-olefin copolymer. It can be.
より具体的には、エチレン・α-オレフィン共重合体（Ｂ）の重合において、エチレン・α-オレフィン共重合体を重合する際の、エチレンとα-オレフィンのフィード量の比率を変える事により調整可能である。具体的には、エチレンのフィード量に対するα-オレフィンのフィード量を多くする事により、ＪＩＳ－Ｋ７１２１に準拠してＤＳＣで測定した結晶融点を低くする事が可能である。また、エチレンのフィード量に対するα-オレフィンのフィード量を少なくする事により、ＪＩＳ－Ｋ７１２１に準拠してＤＳＣで測定した結晶融点を高くする事が可能である。
More specifically, in the polymerization of the ethylene / α-olefin copolymer (B), it is adjusted by changing the ratio of the feed amount of ethylene / α-olefin when the ethylene / α-olefin copolymer is polymerized. Is possible. Specifically, by increasing the feed amount of α-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 α-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.
前記エチレン・α‐オレフィン共重合体（Ｂ）の結晶融点は、ＪＩＳ－Ｋ７１２１に従って示差走査熱量計（ＤＳＣ）を用いて測定できる。具体的には、前述のプロピレン系樹脂（Ａ）の結晶融点と同様の方法で測定することができる。
The crystal melting point of the ethylene / α-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.
（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。ＭＦＲが前記範囲内にあると、エチレン・α‐オレフィン共重合体（Ｂ）のプロピレン系樹脂（Ａ）に対する分散性が良好となり、多層ブロー容器の光沢性、耐衝撃性に優れ、最外層と他の層との接着性に優れるため好ましい。
(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. When the MFR is within the above range, the dispersibility of the ethylene / α-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.
なお、エチレン・α－オレフィン共重合体（Ｂ）のＡＳＴＭ Ｄ－１２３８に準拠して、測定温度２３０℃、２．１６ｋｇ荷重で測定したＭＦＲの調整は、エチレン・α－オレフィン共重合体（Ｂ）の製造条件を調整することにより任意の値とすることができる。
The MFR of the ethylene / α-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 / α-olefin copolymer (B It can be set to an arbitrary value by adjusting the manufacturing conditions.
より具体的には、後述するエチレン・α－オレフィン共重合体（Ｂ）の重合において、重合する際のエチレンおよび／またはα－オレフィンのフィード量に対する水素ガスのフィード量を調整することで制御することが可能である。重合する際のエチレンガスのフィード量またはエチレンとα－オレフィンをフィードする場合はエチレンおよびα－オレフィンのフィード量に対する水素ガスのフィード量を多くすることでＡＳＴＭ Ｄ－１２３８に準拠して、測定温度２３０℃、２．１６ｋｇ荷重で測定したＭＦＲを高くすることが可能である。エチレンガスのフィード量またはエチレンとα－オレフィンをフィードする場合はエチレンおよびα－オレフィンのフィード量に対する水素ガスのフィード量を少なくすることでＡＳＴＭ Ｄ－１２３８に準拠して、測定温度２３０℃、２．１６ｋｇ荷重で測定したＭＦＲを低くすることが可能である。
More specifically, in the polymerization of the ethylene / α-olefin copolymer (B) described later, the amount of hydrogen gas is controlled by adjusting the feed amount of ethylene and / or α-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 α-olefin, by increasing the feed amount of hydrogen gas relative to the feed amount of ethylene and α-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 α-olefin, the measurement temperature is 230 ° C. according to ASTM D-1238 by reducing the amount of hydrogen gas to ethylene and α-olefin. It is possible to lower the MFR measured with a 16 kg load.
（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。密度が前記範囲内にあると、多層ブロー容器の光沢や耐衝撃性、最外層と他の層との接着性に優れるため好ましい。
(B-4) 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.
また、本発明の多層ブロー容器が、低温耐衝撃性が求められる用途に用いられる場合には、後述の低密度エチレン・α‐オレフィン共重合体（Ｆ）を用いると共に、エチレン・α‐オレフィン共重合体（Ｂ）が下記要件（Ｂ－４ａ）を満たすことが好ましい。
When the multilayer blow container of the present invention is used for applications requiring low temperature impact resistance, the low-density ethylene / α-olefin copolymer (F) described later is used and the ethylene / α-olefin copolymer is used. The polymer (B) preferably satisfies the following requirement (B-4a).
（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。密度が前記範囲内にあると、多層ブロー容器の光沢、耐衝撃性、低温耐衝撃性、最外層と他の層との接着性に優れ、かつべたつきが低く、さらには耐衝撃性や低温耐衝撃性などの耐衝撃特性と耐性とのバランスが良いため好ましい。
(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. When the density is within the above range, 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.
本発明に用いるエチレン・α‐オレフィン共重合体（Ｂ）の密度勾配管法で測定した密度はエチレン・α‐オレフィン共重合体（Ｂ）の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。
The density measured by the density gradient tube method of the ethylene / α-olefin copolymer (B) used in the present invention should be an arbitrary amount by adjusting the production conditions of the ethylene / α-olefin copolymer (B). Can do.
より具体的には、後述するエチレン・α-オレフィン共重合体（Ｂ）の重合において、エチレン・α-オレフィン共重合体を重合する際の、エチレンとα-オレフィンのフィード量の比率を変える事により調整可能である。具体的には、エチレンのフィード量に対するα-オレフィンのフィード量を多くする事により、密度勾配管法で測定した密度を低くする事が可能である。また、エチレンのフィード量に対するα-オレフィンのフィード量を少なくする事により、密度勾配管法で測定した密度を高くする事が可能である。
More specifically, in the polymerization of the ethylene / α-olefin copolymer (B) described later, the ratio of the feed amount of ethylene and α-olefin when the ethylene / α-olefin copolymer is polymerized is changed. Can be adjusted. Specifically, the density measured by the density gradient tube method can be lowered by increasing the feed amount of α-olefin relative to the feed amount of ethylene. Further, the density measured by the density gradient tube method can be increased by reducing the feed amount of α-olefin relative to the feed amount of ethylene.
なお、本発明に用いるエチレン・α‐オレフィン共重合体（Ｂ）の密度勾配管法で測定した密度は、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）のストランドを１２０℃で１時間熱処理し、１時間かけて直線的に室温まで徐冷したのち、密度勾配管で測定した測定値である。
The density measured by the density gradient tube method of the ethylene / α-olefin copolymer (B) used in the present invention is the same as that of the ethylene / α-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.
（Ｂ－５）ＧＰＣにより測定したＭｗ／Ｍｎが１．２～３．０である。なお、エチレン・α‐オレフィン共重合体（Ｂ）としては、Ｍｗ／Ｍｎが１．５～３．０であるとより好ましい。Ｍｗ／Ｍｎが前記範囲内であると、本発明の多層ブロー容器の光沢に優れるため好ましい。
(B-5) Mw / Mn measured by GPC is 1.2 to 3.0. The ethylene / α-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.
前記エチレン・α‐オレフィン共重合体（Ｂ）のＧＰＣにより測定したＭｗ／Ｍｎは、例えばエチレン・α‐オレフィン共重合体（Ｂ）の製造の際に用いる触媒の種類によって、調整することができる。例えば触媒として、メタロセン触媒を用いることにより、前記要件（Ｂ－５）を満たすエチレン・α‐オレフィン共重合体（Ｂ）を得ることができる。
Mw / Mn measured by GPC of the ethylene / α-olefin copolymer (B) can be adjusted, for example, depending on the type of catalyst used in the production of the ethylene / α-olefin copolymer (B). . For example, by using a metallocene catalyst as the catalyst, an ethylene / α-olefin copolymer (B) satisfying the requirement (B-5) can be obtained.
また、前記エチレン・α‐オレフィン共重合体（Ｂ）は、エチレンと、α‐オレフィンとを共重合することにより得ることができるが、エチレン・α‐オレフィン共重合体は、メタロセン触媒を用いて重合されたものであることが好ましい。また、重合の際には、水素ガスに代表されるような連鎖移動剤を導入することもできる。
The ethylene / α-olefin copolymer (B) can be obtained by copolymerizing ethylene and an α-olefin, but the ethylene / α-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.
本発明に用いるエチレン・α－オレフィン共重合体（Ｂ）がメタロセン触媒を用いて重合されたエチレン・α－オレフィン共重合体であると、従来の、いわゆるチーグラーナッタ触媒を用いて重合されたエチレン・α－オレフィン共重合体よりも組成分布が均一であることからプロピレン系樹脂（Ａ）に対する分散性が良好となり、より光沢が良好なオレフィン重合体組成物（Ｅ）を得ることができる。また、メタロセン触媒を用いて重合されたエチレン・α－オレフィン共重合体であると、チーグラーナッタ触媒を用いて重合されたエチレン・α－オレフィン共重合体より分子量分布も狭くなり、耐衝撃性を悪化させる要因となる低分子量成分が少なくなる。さらにはメタロセン触媒を用いて重合されたエチレン・α－オレフィン共重合体であると、チーグラーナッタ触媒を用いて重合されたエチレン・α－オレフィン共重合体より、共重合体の組成分布も均一となり、べたつきの原因となる非晶成分も少なくなる。また、最外層と他の層との間の接着ムラも少なくなり、経時的な外観悪化を抑制することも期待される。
When the ethylene / α-olefin copolymer (B) used in the present invention is an ethylene / α-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 α-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. In addition, an ethylene / α-olefin copolymer polymerized using a metallocene catalyst has a narrower molecular weight distribution than that of an ethylene / α-olefin copolymer polymerized using a Ziegler-Natta catalyst. Low molecular weight components that cause deterioration are reduced. Furthermore, an ethylene / α-olefin copolymer polymerized using a metallocene catalyst has a more uniform composition distribution of the copolymer than an ethylene / α-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.
上記のことから、メタロセン触媒用いて重合されたエチレン・α－オレフィン共重合体（Ｂ）を用いることで光沢に優れ、さらには耐衝撃性に優れ、べたつき性が低いオレフィン重合体組成物（Ｅ）を得ることができる。
From the above, by using the ethylene / α-olefin copolymer (B) polymerized using a metallocene catalyst, the olefin polymer composition (E) has excellent gloss, impact resistance, and low stickiness. ) Can be obtained.
＜低密度エチレン・α‐オレフィン共重合体（Ｆ）＞
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).
前記低密度エチレン・α‐オレフィン共重合体（Ｆ）は、下記要件（Ｆ－１）および（Ｆ－２）を満たし、さらに下記要件（Ｆ－３）を満たすことが好ましい。低密度エチレン・α‐オレフィン共重合体（Ｆ）は一種単独で用いても、二種以上を用いてもよい。
The low-density ethylene / α-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 / α-olefin copolymer (F) may be used alone or in combination of two or more.
（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。なお、炭素原子数３～２０のα‐オレフィンとしては、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-デセン、1-ドデセン、1-ヘキサドデセン、4-メチル-1-ペンテン、2-メチル-1-ブテン、3-メチル-1-ブテン、3-メチル-1-ブテン、3,3-ジメチル-1-ブテン、ジエチル-1-ブテン、トリメチル-1-ブテン、3-メチル-1-ペンテン、エチル-1-ペンテン、プロピル-1-ペンテン、ジメチル-1-ペンテン、メチルエチル-1-ペンテン、ジエチル-1-ヘキセン、トリメチル-1-ペンテン、3-メチル-1-ヘキセン、ジメチル-1-ヘキセン、3,5,5-トリメチル-1-ヘキセン、メチルエチル-1-ヘプテン、トリメチル-1-ヘプテン、エチル-1-オクテン、メチル-1-ノネンなどが挙げられる。
(F-1) A copolymer of ethylene and one or more α-olefins having 3 to 20 carbon atoms. Examples of the α-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-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, ethyl-1-octene, methyl-1-nonene, etc. Can be mentioned.
前記低密度エチレン・α‐オレフィン共重合体（Ｆ）としては、物性と経済性とのバランスの観点からエチレンと、炭素原子数３～１０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ことが好ましく、エチレンと、プロピレン、1-ブテン、1-ヘキセンおよび1-オクテンからなる群から選ばれる1種以上のα‐オレフィンとの共重合体であることがより好ましい。前記低密度エチレン・α‐オレフィン共重合体（Ｆ）としては、中でもエチレンとプロピレンとの共重合体、エチレンと１－ブテンとの共重合体、エチレンと１‐オクテンとの共重合体が好ましく、エチレンと１－ブテンとの共重合体、エチレンと１‐オクテンとの共重合体より好ましく、エチレンと１－ブテンとの共重合体が特に好ましい。
The low density ethylene / α-olefin copolymer (F) includes at least one selected from the group consisting of ethylene and α-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 α-olefins selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene. More preferred. The low density ethylene / α-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.
（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。結晶融点を有する場合には、７５℃以下であることが好ましい。結晶融点が前記範囲内にあると、多層ブロー容器が低温耐衝撃性にすぐれるため好ましい。
(F-2) 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.
前記低密度エチレン・α‐オレフィン共重合体（Ｆ）の結晶融点は、ＪＩＳ－Ｋ７１２１に従って示差走査熱量計（ＤＳＣ）を用いて測定できる。具体的には、後述の実施例に記載の方法で測定することができる。
The crystal melting point of the low density ethylene / α-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.
（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。前記密度は、０．８７０～０．９００ｇ／ｃｍ3の範囲であることがより好ましい。密度が前記範囲内にあると、多層ブロー容器の光沢に優れ、低温耐衝撃性に特に優れるため好ましい。
(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 . 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.
また、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］）は下記要件（Ｘ－１）を満たす。
The density (d B [g / cm 3 ]) measured by the density gradient method of the ethylene / α-olefin copolymer (B) and the density gradient of the low density ethylene / α-olefin copolymer (F) The density (d F [g / cm 3 ]) measured by the public law satisfies the following requirement (X-1).
（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。すなわち、低密度エチレン・α‐オレフィン共重合体（Ｆ）の密度は、前記エチレン・α‐オレフィン共重合体（Ｂ）の密度よりも小さく、エチレン・α‐オレフィン共重合体（Ｂ）と低密度エチレン・α‐オレフィン共重合体（Ｆ）との密度差（ｄB－ｄF）が０．０１０～０．０５０［ｇ／ｃｍ3］である。なお、密度差（ｄB－ｄF）は０．０１０～０．０４０［ｇ／ｃｍ3］であることが好ましい。
(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 ]. That is, the density of the low-density ethylene / α-olefin copolymer (F) is smaller than the density of the ethylene / α-olefin copolymer (B), which is lower than that of the ethylene / α-olefin copolymer (B). The density difference (d B -d F ) from the density ethylene / α-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 ].
密度差（ｄB－ｄF）が前記範囲内にあると、多層ブロー容器の光沢に優れ、さらには低温耐衝撃性に優れるため好ましい。
It is preferable that 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.
また低密度エチレン・α‐オレフィン共重合体（Ｆ）としては、ＡＳＴＭ Ｄ－１２３８に準拠して、測定温度２３０℃、２．１６ｋｇ荷重で測定したＭＦＲが０．１～５０ｇ／１０分の範囲であることが好ましく、０．５～３０ｇ／１０分の範囲であることがより好ましく、特に５～１０ｇ／１０分の範囲にあることが好ましい。ＭＦＲが前記範囲内にあると、低密度エチレン・α‐オレフィン共重合体（Ｆ）の分散性が良好となり、光沢、低温衝撃性が向上する。
The low-density ethylene / α-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. When the MFR is within the above range, the dispersibility of the low-density ethylene / α-olefin copolymer (F) becomes good, and the gloss and low-temperature impact properties are improved.
また、前記低密度エチレン・α‐オレフィン共重合体（Ｆ）は、エチレンと、α‐オレフィンとを共重合することにより得ることができるが、エチレン・α‐オレフィン共重合体は、チーグラーナッタ触媒を用いて重合されたものでも、メタロセン触媒を用いて重合されたものでもよい。
The low-density ethylene / α-olefin copolymer (F) can be obtained by copolymerizing ethylene and α-olefin, and the ethylene / α-olefin copolymer is a Ziegler-Natta catalyst. The polymer may be polymerized using a metallocene or may be polymerized using a metallocene catalyst.
＜核剤（Ｄ）＞
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.
前記芳香族リン酸エステル化合物としては、以下の式［ＩＩＩ］および／または［ＩＶ］で表わされる化合物であることが好ましい。
The aromatic phosphate compound is preferably a compound represented by the following formula [III] and / or [IV].
前記式［III］、［IV］中、Ｒ1は、炭素原子数１～１０の２価炭化水素基であり、Ｒ2およびＲ3はそれぞれ独立に、水素原子または炭素原子数１～１０の炭化水素基であり、Ｍは、１～３価の金属原子であり、ｎは１～３の整数であり、ｍは１または２である。
In the formulas [III] and [IV], R 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and 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.
一般式［III］で表わされる芳香族リン酸エステル化合物の具体例としては、ナトリウム-2,2'-メチレン-ビス（4,6-ジ-t-ブチルフェニル)フォスフェート、ナトリウム-2,2'-エチリデン-ビス（4,6-ジ-t-ブチルフェニル)フォスフェート、リチウム-2,2'-メチレン-ビス（4,6-ジ-t-ブチルフェニル）フォスフェート、リチウム-2,2'-エチリデン-ビス（4,6-ジ-t-ブチルフェニル）フォスフェート、ナトリウム-2,2'-エチリデン-ビス（4-i-プロピル-6-t-ブチルフェニル）フォスフェート、リチウム-2,2'-メチレン-ビス（4-メチル-6-t-ブチルフェニル）フォスフェート、リチウム-2,2'-メチレン-ビス（4-エチル-6-t-ブチルフェニル）フォスフェート、ナトリウム-2,2'-ブチリデン-ビス（4,6-ジ-メチルフェニル）フォスフェート、ナトリウム-2,2'-ブチリデン-ビス（4,6-ジ-t-ブチルフェニル）フォスフェート、ナトリウム-2,2'-t-オクチルメチレン-ビス（4,6-ジ-メチルフェニル）フォスフェート、ナトリウム-2,2'-t-オクチルメチレン-ビス（4,6-ジ-t-ブチルフェニル）フォスフェート、カルシウム-ビス-（2,2'-メチレン-ビス（4,6-ジ-t-ブチルフェニル）フォスフェート）、マグネシウム-ビス［2,2'-メチレン-ビス（4,6-ジ-t-ブチルフェニル）フォスフェート］、バリウム-ビス［2,2'-メチレン-ビス（4,6-ジ-t-ブチルフェニル）フォスフェート］、ナトリウム-2,2'-メチレン-ビス（4-メチル-6-t-ブチルフェニル）フォスフェート、ナトリウム-2,2'-メチレン-ビス（4-エチル-6-t-ブチルフェニル）フォスフェート、ナトリウム-2,2'-エチリデン-ビス（4-m-ブチル-6-t-ブチルフェニル）フォスフェート、ナトリウム-2,2'-メチレン-ビス（4,6-ジ-メチルフェニル）フォスフェート、ナトリウム-2,2'-メチレン-ビス（4,6-ジ-エチルフェニル）フォスフェート、カリウム-2,2'-エチリデン-ビス（4,6-ジ-t-ブチルフェニル）フォスフェート、カルシウム-ビス［2,2'-エチリデン-ビス（4,6-ジ-t-ブチルフェニル）フオスフェート］、マグネシウム-ビス［2,2'-エチリデン-ビス（4,6-ジ-t-ブチルフェニル）フォスフェート］、バリウム-ビス［2,2'-エチリデン-ビス（4,6-ジ-t-ブチルフェニル）フォスフェート］、アルミニウム-トリス［2,2'-メチレン-ビス（4,6-ジ-t-ブチルフェル）フォスフェート］、アルミニウム-トリス［2,2'-エチリデン-ビス（4,6-ジ-t-ブチルフェニル）フォスフェート］、およびこれらの二種以上の混合物などを挙げることができる。
Specific examples of the 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'-Butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-t-butylphenyl) Nyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di) -t-butylphenyl) phosphate, calcium-bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2 ' -Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium-2,2 ' -Ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) ) Phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate Fate, calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphato], magnesium-bis [2,2'-ethylidene-bis (4,6-di-t- Butylphenyl) phosphate], barium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4, 6-di-t-butylfell) phosphate], aluminum-tris [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], and mixtures of two or more of these Can be mentioned.
芳香族リン酸エステル化合物としては、一般式［IV］で表わされるヒドロキシアルミニウムフォスフェート化合物も使用可能であり、特にＲ2およびＲ3が共にtert-ブチル基である、一般式［V］で表わされる化合物が好ましい。
As the aromatic phosphate compound, a hydroxyaluminum phosphate compound represented by the general formula [IV] can also be used. In particular, the compound represented by the general formula [V] in which R 2 and R 3 are both tert-butyl groups. Are preferred.
式［Ｖ］において、Ｒ1は、炭素原子数１～１０の２価炭化水素基であり、ｍは１または２である。特に好ましい芳香族リン酸エステル化合物は、一般式［VI］で表わされる化合物である。
In the formula [V], 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].
式［VI］において、Ｒ1は、メチレン基またはエチリデン基である。一般式［VI］で表わされる化合物としては、具体的には、ヒドロキシアルミニウム-ビス［2,2-メチレン-ビス（4,6-ジ-t-ブチル）フォスフェート］（別名：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）、またはヒドロキシアルミニウム-ビス［2,2-エチリデン-ビス（4,6-ジ-t-ブチル）フォスフェート］である。
In the formula [VI], R 1 is a methylene group or an ethylidene group. As the compound represented by the general formula [VI], specifically, 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].
カルボン酸金属塩造核剤としては例えば、ｐ－ｔ－ブチル安息香酸アルミニウム塩、アジピン酸アルミニウム、安息香酸ナトリウムを用いることができる。
As the carboxylic acid metal salt nucleating agent, for example, pt-butyl aluminum benzoate, aluminum adipate, or sodium benzoate can be used.
ポリマー造核剤としては分岐状α－オレフィン重合体が好適に用いられる。分岐状α－オレフィン重合体の例として、３－メチル－１－ブテン、３－メチル－１－ペンテン、３－エチル－１－ペンテン、４－メチル－１－ペンテン、４－メチル－１－ヘキセン、４，４－ジメチル－１－ヘキセン、４，４－ジメチル－１－ペンテン、４－エチル－１－ヘキセン、３－エチル－１－ヘキセンの単独重合体、あるいはそれら相互の共重合体、さらにはそれらと他のα－オレフィンとの共重合体を挙げることができる。
As the polymer nucleating agent, a branched α-olefin polymer is preferably used. Examples of branched α-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 α-olefins.
これらのポリマー造核剤は、オレフィン系重合体組成物（Ｅ）を製造する際に、直接配合することも可能であるし、プロピレン系樹脂（Ａ）製造の際、プロピレン系樹脂（Ａ）の重合の前、あるいは後でブロック的に上記分岐状α－オレフィンの重合を行い、核剤（Ｄ）として分岐状α－オレフィン重合体を含んだプロピレン系樹脂（Ａ）を用いることにより配合してもよい（ポリマー造核剤配合プロピレン系樹脂（Ａ'）とする）。ポリマー造核剤配合プロピレン系樹脂（Ａ'）をオレフィン系重合体組成物（Ｅ）の原料として使用する場合、ポリマー造核剤配合プロピレン系樹脂（Ａ'）中に含まれるポリマー造核剤の量をオレフィン系重合体組成物（Ｅ）中の核剤（Ｄ）の配合量とする。また、ポリマー造核剤配合プロピレン系樹脂（Ａ'）からポリマー造核剤の量を減じた分を、オレフィン系重合体組成物（Ｅ）中のプロピレン系樹脂（Ａ）とする。
These 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 α-olefin is polymerized before or after the polymerization in a block manner, and blended by using the propylene resin (A) containing the branched α-olefin polymer as the nucleating agent (D). It is also possible to use a polymer nucleating agent-containing propylene resin (A ′). When using the polymer nucleating agent-containing propylene resin (A ′) as a raw material for the olefin polymer composition (E), 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 | blending propylene-type resin (A ') be the propylene-type resin (A) in an olefin type polymer composition (E).
また、上記ポリマー造核剤は、公知の方法を用いて重合体（Ａ）、重合体（Ｂ）、重合体（Ｆ）を製造する際の予備重合で形成することもでき、重合体（Ｂ）、重合体（Ｆ）を製造する際にブロック共重合法で形成することもできる。
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.
なお、その際、ポリマー造核剤配合プロピレン系樹脂（Ａ'）と、ポリマー造核剤を含まないプロピレン系樹脂（Ａ）とを併用してもよい。また、ポリマー造核剤配合プロピレン系樹脂（Ａ'）と、他の核剤（Ｄ）を併用してもよい。
At that time, a polymer nucleating agent-containing propylene resin (A ′) and a propylene resin (A) containing no polymer nucleating agent may be used in combination. Moreover, you may use together a polymer nucleating agent mixing | blending propylene-type resin (A '), and another nucleating agent (D).
これらのポリマー造核剤は、オレフィン系重合体組成物（Ｅ）が後述するその他の樹脂類を含有する場合には、その他の樹脂類と、ポリマー増核剤とを含有するマスターバッチを、オレフィン系重合体組成物（Ｅ）を製造する際に用いることにより配合してもよい。該マスターバッチをオレフィン系重合体組成物（Ｅ）の原料として使用する場合、マスターバッチ中に含まれるポリマー増核剤の量をオレフィン系重合体組成物（Ｅ）中の核剤（Ｄ）の配合量とする。なお、マスターバッチと他の核剤（Ｄ）とを併用し、オレフィン系重合体組成物を製造してもよい。
When these polymer nucleating agents contain other resins described later in the olefin polymer composition (E), master batches containing other resins and a polymer nucleating agent are used as olefins. You may mix | blend by using when manufacturing a type | system | group polymer composition (E). When the master batch is used as a raw material for the olefin polymer composition (E), the amount of the polymer nucleating agent contained in the master batch is determined based on the nucleating agent (D) in the olefin polymer composition (E). The blending amount. The master batch and other nucleating agent (D) may be used in combination to produce an olefin polymer composition.
ポリマー造核剤としては透明性、低温耐衝撃性、剛性の特性が良好であること、および経済性の観点から、特に、３－メチル－１－ブテンの重合体が好ましい。
As the polymer nucleating agent, a polymer of 3-methyl-1-butene is particularly preferable from the viewpoints of transparency, low-temperature impact resistance, rigidity properties, and economical viewpoint.
ソルビトール系造核剤としては、ノニトール，１，２，３－トリデオキシ－４，６：５，７－ビス－Ｏ－[（４－プロピルフェニル）メチレン]を好ましく利用することができる。
As the sorbitol nucleating agent, nonitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] can be preferably used.
無機化合物造核剤としては例えば、タルク、マイカ、炭酸カルシウムを用いることができる。
As the inorganic compound nucleating agent, for example, talc, mica, calcium carbonate can be used.
これらの核剤（Ｄ）の中でも、透明性、低温耐衝撃性、剛性および低臭気であるとの観点からノニトール，１，２，３－トリデオキシ－４，６：５，７－ビス－Ｏ－［（４－プロピルフェニル）メチレン］、およびビス（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から選択される少なくとも１種の造核剤を用いることが好ましい。これらのうちでもビス（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用いることがより好ましい。
Among these 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. [(4-propylphenyl) methylene] and bis (2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin It is preferred to use at least one nucleating agent selected from -6-oxide) aluminum hydroxide salts. Of these, bis (2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) hydroxylation More preferably, an aluminum salt is used.
本発明に用いる核剤（Ｄ）としては、市販品を用いることができ、例えば、アデカスタブＮＡ－２１（ＡＤＥＫＡ社製）はビス（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造核剤として市販されており、ノニトール，１，２，３－トリデオキシ－４，６：５，７－ビス－Ｏ－［（４－プロピルフェニル）メチレン］は、ミラードＮＸ８０００（ミリケン社製）の商品名で市販されている。
A commercially available product can be used as the nucleating agent (D) used in the present invention. For example, ADK STAB NA-21 (manufactured by 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).
＜オレフィン重合体組成物（Ｅ）＞
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.
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.
なお、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）０．１～２０重量部を用いて形成される組成物を用いることが好ましい。
When the multilayer blow container of the present invention is required to have low temperature impact resistance, as described above, the olefin polymer composition (E) is composed of propylene resin (A) and ethylene / α-olefin copolymer. It is preferable to use a composition formed by using 0.1 to 20 parts by weight of a low density ethylene / α-olefin copolymer (F) in addition to the coalescence (B) and the nucleating agent (D). .
また、多層ブロー容器に低温耐衝撃性が求められない場合には、オレフィン重合体組成物（Ｅ）が、低密度エチレン・α‐オレフィン共重合体（Ｆ）を用いずに形成される組成物であることも好ましい。
When the multilayer blow container does not require low temperature impact resistance, the olefin polymer composition (E) is formed without using the low density ethylene / α-olefin copolymer (F). It is also preferable.
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）の使用量は、べたつき性が良好であるという観点、および経済性と生産性の観点から、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）であることが好ましい。
The amount of the propylene-based resin (A) and the ethylene / α-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 / α-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
オレフィン重合体組成物（Ｅ）を得るために用いる前記プロピレン系樹脂（Ａ）が９８重量部より多く、前記エチレン・α‐オレフィン共重合体（Ｂ）が２重量部より少ない場合、多層ブロー容器の耐衝撃性、他の層との接着性が劣り、オレフィン重合体組成物（Ｅ）に配合される前記プロピレン系樹脂（Ａ）が８０重量部より少なく、前記エチレン・α‐オレフィン共重合体（Ｂ）が２０重量部より多い場合べたつきが発生するため好ましくない。
When the amount of the propylene-based resin (A) used to obtain the olefin polymer composition (E) is more than 98 parts by weight and the amount of the ethylene / α-olefin copolymer (B) is less than 2 parts by weight, 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 / α-olefin copolymer is inferior in impact resistance and adhesion to other layers. When (B) is more than 20 parts by weight, stickiness occurs, which is not preferable.
また、多層ブロー容器が、低温耐衝撃性を求められる場合には、べたつきと経済性の観点からオレフィン重合体組成物（Ｅ）に配合される、前記低密度エチレン・α‐オレフィン共重合体（Ｆ）が３～１５重量部であることが好ましい。
When the multilayer blow container is required to have low temperature impact resistance, the low-density ethylene / α-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.
核剤（Ｄ）はプロピレン系樹脂（Ａ）とエチレン・α-オレフィン共重合体（Ｂ）との合計量１００重量部に対し、０．０１～０．５重量部用いることにより、多層ブロー容器の光沢性を向上させる効果が得られる。核剤（Ｄ）の添加量が０．０１重量部より少ないと光沢性を向上する効果が少ない。核剤（Ｄ）の添加量が０．５重量部より多く添加しても、効果が変わらないばかりでなく、経済的に不利となるため好ましくない。
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 / α-olefin copolymer (B). The effect of improving the glossiness of the film can be obtained. When 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.
前記オレフィン重合体組成物（Ｅ）は、下記要件（Ｅ－１）を満たす。
The olefin polymer composition (E) satisfies the following requirement (E-1).
（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。ＭＦＲが前記範囲内にあると、成形時のオレフィン重合体組成物（Ｅ）の流動性が成形に好適な範囲となり、成形時に発生する微細なメルトフラクチャー（ＭＦ）を抑制することができる。また、ブロー成形におけるオレフィン重合体組成物（Ｅ）の厚みムラが防止され、平滑性に優れる多層ブロー容器を得ることができる。
(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. When the MFR is within the above range, 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. Moreover, 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.
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１０ｇ／１０分より高いと、成形性に劣り、５ｇ／１０分より低いと光沢性に劣る。
In accordance with ASTM D-1238, when the 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. Inferior to
オレフィン重合体組成物（Ｅ）に関わる要件（Ｅ－１）、つまり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）は、使用するプロピレン系樹脂（Ａ）と、エチレン・α-オレフィン共重合体（Ｂ）と、必要に応じて用いられる低密度エチレン・α‐オレフィン共重合体（Ｆ）とを適宜選択することにより調整が可能である。
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 / α-olefin copolymer (B), and the low density ethylene / α-olefin copolymer (F) used as necessary. is there.
使用するプロピレン系樹脂（Ａ）とエチレン・α-オレフィン共重合体（Ｂ）が、共に、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分の範囲である場合には、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、必要に応じて用いられる低密度エチレン・α‐オレフィン共重合体（Ｆ）とを適宜選択することで（Ｅ－１）の要件を満たすことが可能である。
Both the propylene-based resin (A) and the ethylene / α-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 / α-olefin copolymer (B), and the low-density ethylene / α-olefin copolymer used as necessary. The requirement (E-1) can be satisfied by appropriately selecting the polymer (F).
また、これ以外の場合、例えば、プロピレン系樹脂（Ａ）として、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５ｇ／１０分未満程度の、比較的ＭＦＲが低いものを用いる場合には、プロピレン系樹脂（Ａ）、エチレン・α‐オレフィン共重合体（Ｂ）および核剤（Ｄ）、ならびに必要に応じて用いられる低密度エチレン・α‐オレフィン共重合体（Ｆ）からオレフィン重合体組成物（Ｅ）を形成する際に、有機過酸化物存在下で溶融混練を行うことにより、プロピレン系樹脂（Ａ）やエチレン・α‐オレフィン共重合体（Ｂ）、あるいは必要に応じて用いられる低密度エチレン・α‐オレフィン共重合体（Ｆ）の変性を行い、オレフィン重合体組成物（Ｅ）のＭＦＲを、前記範囲内に調整することができる。なお、有機過酸化物としては、前記＜プロピレン系樹脂（Ａ）＞の項で記載したものと同様のものが挙げられる。
In other cases, for example, as a propylene resin (A), 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. When a relatively low MFR is used, propylene resin (A), ethylene / α-olefin copolymer (B) and nucleating agent (D), and low-density ethylene used as necessary・ When forming the olefin polymer composition (E) from the α-olefin copolymer (F), by performing melt-kneading in the presence of an organic peroxide, the propylene-based resin (A) or ethylene / α- The olefin copolymer (B) or the low density ethylene / α-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. In addition, as an organic peroxide, the thing similar to what was described by the term of the said <propylene-type resin (A)> is mentioned.
また、別の例としては、プロピレン系樹脂（Ａ）としてＭＦＲが１０ｇ／１０分を超える、比較的ＭＦＲが高いものを用いる場合には、組み合わせるエチレン・α-オレフィン共重合体（Ｂ）、必要に応じて用いられる低密度エチレン・α‐オレフィン共重合体（Ｆ）としてＭＦＲの低いものを用いることにより、オレフィン重合体組成物（Ｅ）のＭＦＲを前記範囲内に調整することができる。
As another example, when a propylene resin (A) having an MFR of more than 10 g / 10 minutes and a relatively high MFR is used, an ethylene / α-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 / α-olefin copolymer (F) used depending on
前記オレフィン重合体組成物（Ｅ）は、ＪＩＳ－Ｋ７１２１に準拠してＤＳＣで測定した結晶融点が１４０～１５５℃の範囲であることが好ましい。結晶融点が前記範囲内にあると、光沢が良好であり、耐衝撃性の良好な多層ブロー容器を得ることができる。
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.
前記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）を用いて測定できる。具体的には、前述のプロピレン系樹脂（Ａ）の結晶融点と同様の方法で測定することができる。
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.
また、前記オレフィン重合体組成物（Ｅ）は、半結晶化時間（t1/2）が５０～１０００秒の範囲であることが好ましく、１００～５００秒の範囲であることがより好ましい。前記範囲内では、ブロー成形時に金型転写性が良好となり、光沢の良好な多層ブロー容器を得ることができる。
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.
なお、半結晶化時間（t1/2）は、１２５℃等温条件下オレフィン重合体組成物（Ｅ）で結晶化させて、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として測定することができる。
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.
前記オレフィン重合体組成物（Ｅ）の半結晶化時間（t1/2）は、オレフィン重合体組成物（Ｅ）に含まれる核剤（Ｄ）の量で調整することができる。オレフィン重合体組成物（Ｅ）に含まれる核剤（Ｄ）の量を増やすことで半結晶化時間（t1/2）を速くすることが可能で、逆に、核剤（Ｄ）の量を減らすことで半結晶化時間（t1/2）を遅くすることが可能である。
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.
本発明のオレフィン重合体組成物（Ｅ）には、前述のプロピレン系樹脂（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）、および核剤（Ｄ）以外の成分が含有されていてもよい。
The olefin polymer composition (E) of the present invention includes the propylene resin (A), the ethylene / α-olefin copolymer (B), the low density ethylene / α-olefin copolymer (F), and Components other than the nucleating agent (D) may be contained.
前記（Ａ）、（Ｂ）、（Ｆ）および（Ｄ）以外の成分としては、その他の樹脂類、各種添加剤等が挙げられる。
As components other than the above (A), (B), (F) and (D), other resins, various additives and the like can be mentioned.
その他の樹脂類としては、例えば、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）および核剤（Ｄ）以外のポリオレフィン系樹脂が挙げられる。
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.
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.
また、その他の樹脂として、例えばスチレン系エラストマーまたはその水素添加物（Ｓ）を例示することもできる。なお、光沢の金型表面粗さ依存性を小さくしたい場合には、スチレン系エラストマーまたはその水素添加物（Ｓ）を添加しないことが好ましい態様である。
Further, as other resins, for example, styrene elastomers or hydrogenated products (S) thereof can be exemplified. When it is desired to reduce the gloss mold surface roughness dependency, it is preferable that no styrene elastomer or its hydrogenated product (S) is added.
スチレン系エラストマーまたはその水素添加物（Ｓ）としては、スチレン含有量１０～７０重量％、好ましくは１０～６５重量％、さらに好ましくは１０～４０重量％、および共役ジエン含有量３０～９０重量％、好ましくは３５～９０重量％、さらに好ましくは６０～９０重量％のスチレン系エラストマーまたはその水素添加物（Ｓ）が挙げられる。
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.
上記スチレン系エラストマーまたはその水素添加物（Ｓ）としては、スチレン系重合体ブロック成分（以下、スチレンブロックという場合がある）と、共役ジエン系重合体ブロック成分（以下、ジエンブロックという場合がある）とからなるスチレン系ブロック共重合体や、スチレン・ブタジエンランダム共重合体、スチレン・イソプレンランダム共重合体、スチレン・クロロプレンランダム共重合体およびこれらの水素添加物などがあげられる。これらの中ではスチレン系ブロック共重合体が好ましい。
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.
上記スチレン系ブロック共重合体を構成するスチレン系重合体ブロック成分はスチレンまたはその誘導体から構成され、モノマーの具体的なものとしてはスチレン、α－メチルスチレン、ｐ－メチルスチレン、クロロスチレン、ビニルナフタレンなどがあげられる。これらの中では、スチレンが好ましい。これらのモノマーは１種単独で、または２種以上が組み合されて用いられる。
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, α-methylstyrene, p-methylstyrene, chlorostyrene, and vinylnaphthalene. Etc. Of these, styrene is preferred. These monomers are used alone or in combination of two or more.
前記共役ジエン系重合体ブロックを構成するモノマーの具体的なものとしては、ブタジエン、イソプレン、クロロプレンなどがあげられる。これらの中では、ブタジエン、イソプレンが好ましい。これらのモノマーは１種単独で、または２種以上が組み合されて用いられる。
Specific examples of 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.
スチレン系ブロック共重合体におけるスチレンブロックとジエンブロックとの結合形態は特に限定されないが、スチレンブロック・ジエンブロックまたはスチレンブロック・［ジエンブロック・スチレンブロック］ｎ（ここで、ｎは１～５）の形態が好ましい。
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.
スチレン系ブロック共重合体中のスチレン系重合体ブロック成分の含有量は１０～７０重量％、好ましくは１０～６５重量％、さらに好ましくは１０～４０重量％、共役ジエン系重合体ブロック成分の含有量は３０～９０重量％、好ましくは３５～９０重量％、さらに好ましくは６０～９０重量％であるのが望ましい。
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.
スチレン系ブロック共重合体は、ＡＳＴＭ Ｄ－１２３８に準拠して、２３０℃、荷重２１６０ｇで測定したメルトフローレート（ＭＦＲ）が０．１ｇ／１０ｍｉｎ以上、好ましくは０．３～２０ｇ／１０ｍｉｎ、特に好ましくは５～１０ｇ／１０ｍｉｎであるのが望ましい。
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.
スチレン系ブロック共重合体の具体的なものとしては、スチレン・エチレン・ブテン・スチレンブロック共重合体（ＳＥＢＳ）、スチレン・エチレン・プロピレン・スチレンブロック共重合体（ＳＥＰＳ）、スチレン・ブタジエン・スチンブロック共重合体（ＳＢＳ）、スチレン・イソプレン・スチレンブロック共重合体（ＳＩＳ）、およびスチレン・エチレン・プロピレンブロック共重合体（ＳＥＰ）などがあげられる。
Specific examples of styrenic block copolymers include styrene / ethylene / butene / styrene block copolymers (SEBS), styrene / ethylene / propylene / styrene block copolymers (SEPS), and styrene / butadiene / stin blocks. Examples thereof include a copolymer (SBS), a styrene / isoprene / styrene block copolymer (SIS), and a styrene / ethylene / propylene block copolymer (SEP).
オレフィン重合体組成物（Ｅ）が、その他の樹脂類を含有する場合には、前記（Ａ）と（Ｂ）との合計１００重量部に対して、上限が通常は２０重量部以下、より好ましくは１０重量部以下、さらに好ましくは５重量部以下であり、下限が通常は０．１重量部である。
When the olefin polymer composition (E) contains other resins, 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.
その他の樹脂として、前記プロピレン系樹脂（Ｐ）を用いる場合、前記プロピレン系樹脂（Ｐ）は、前記（Ａ）と（Ｂ）との合計１００重量部に対して、上限が通常は２０重量部以下、より好ましくは１０重量部以下、さらに好ましくは５重量部以下であり、下限が通常は０．１重量部である。
When the propylene resin (P) is used as the other resin, 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.
その他の樹脂として、前記スチレン系エラストマーまたはその水素添加物（Ｓ）を用いる場合、前記スチレン系エラストマーまたはその水素添加物（Ｓ）は、前記（Ａ）と（Ｂ）との合計１００重量部に対して、上限が通常は２０重量部以下、より好ましくは１０重量部以下、さらに好ましくは５重量部以下であり、下限が通常は０．１重量部である。
When the styrene elastomer or its hydrogenated product (S) is used as the other resin, the styrene elastomer or its hydrogenated product (S) is in a total of 100 parts by weight of (A) and (B). On the other hand, 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.
その他の樹脂として、前記プロピレン系樹脂（Ｐ）および前記スチレン系エラストマーまたはその水素添加物（Ｓ）の少なくともいずれかを用いる場合、前記プロピレン系樹脂（Ｐ）と前記スチレン系エラストマーまたはその水素添加物（Ｓ）との合計は、前記（Ａ）と（Ｂ）との合計１００重量部に対して、上限が通常は２０重量部以下、より好ましくは１０重量部以下、さらに好ましくは５重量部以下であり、下限が通常は０．１重量部である。
When at least one of the propylene resin (P) and the styrene elastomer or hydrogenated product (S) is 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.
また、光沢の金型表面粗さ依存性が少ないことが望ましい場合は、前記プロピレン系樹脂（Ｐ）を添加しない態様、前記スチレン系エラストマーまたはその水素添加物（Ｓ）を添加しない態様がより望ましい態様であり、前記プロピレン系樹脂（Ｐ）および前記スチレン系エラストマーまたはその水素添加物（Ｓ）を添加しない態様がさらに望ましい態様である。
Further, when it is desirable that the gloss mold surface roughness dependency is small, 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.
また、前記スチレン系エラストマーまたはその水素添加物（Ｓ）を用いる場合、べたつきの点から、前記低密度エチレン・α‐オレフィン共重合体（Ｆ）が少量であるかまたは存在しないことが好ましい態様のひとつである。
In the case of using the styrenic elastomer or the hydrogenated product (S) thereof, it is preferable that the low density ethylene / α-olefin copolymer (F) is in a small amount or not present in terms of stickiness. One.
前記低密度エチレン・α‐オレフィン共重合体（Ｆ）を用いない場合には、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、任意成分であるＴｍが１４０～１５５℃のプロピレン系樹脂（Ｐ）およびスチレン系エラストマーまたはその水素添加物（Ｓ）から選択される少なくとも一種の重合体０～２０重量部（（Ａ）と（Ｂ）との合計１００重量部に対する量である）とから実質的になるオレフィン系重合体組成物（Ｅ）を用いることも本発明の好適態様の一つである。この中にはＴｍが１４０～１５５℃のプロピレン系樹脂（Ｐ）およびスチレン系エラストマーまたはその水素添加物（Ｓ）との合計が（Ａ）と（Ｂ）との合計１００重量部に対して０重量部である場合も含まれる。なお、実質的になるとは、オレフィン系重合体組成物（Ｅ）が、その他の成分として、本発明の効果を損なわない範囲で添加剤を含んでいてもよいが、それ以外の成分が含まれないことを示す。
When the low density ethylene / α-olefin copolymer (F) is not used, 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) are used. Parts (provided that the total of (A) and (B) is 100 parts by weight), propylene resin (P) having an optional component Tm of 140 to 155 ° C. and a styrene elastomer or a hydrogenated product thereof ( 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)) It is also a preferred embodiment of the present invention to use. Among these, 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. As used herein, “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.
添加剤としては、酸化防止剤、塩酸吸収剤、耐熱安定剤、光安定剤、紫外線吸収剤、滑剤、帯電防止剤、難燃剤、顔料、染料、分散剤、銅害防止剤、中和剤、発泡剤、可塑剤、気泡防止剤、架橋剤、過酸化物などの流れ性改良剤、ウェルド強度改良剤などが挙げられる。これらの添加剤としては、特に限定はなく、例えば市販品を用いることができる。
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. There is no limitation in particular as these additives, For example, a commercial item can be used.
オレフィン重合体組成物（Ｅ）が、添加剤を含有する場合にはその量としては、本発明の効果を得られる範囲の量であればよく、特に限定はないが、前記（Ａ）と（Ｂ）との合計１００重量部に対して、通常は０．０１～１．００重量部である。
When the olefin polymer composition (E) contains an additive, 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).
本発明に用いるオレフィン重合体組成物（Ｅ）は、ＭＦＲが特定の範囲にあるため、オレフィン重合体組成物（Ｅ）のみではブロー成形することが困難であるが、多層ブロー成形体の表層として用いることが可能であり、表層として用いることにより、優れた光沢を示し、優れた物性を有する。
Since 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.
オレフィン重合体組成物（Ｅ）の調製方法としては特に限定はなく、例えばプロピレン系樹脂（Ａ）、エチレン・α‐オレフィン共重合体（Ｂ）および核剤（Ｄ）、任意に用いることが可能な低密度エチレン・α‐オレフィン共重合体（Ｆ）、その他の樹脂類および添加剤を、ヘンシェルミキサー、バンバリーミキサー、タンブラーミキサー等の混合機に投入し、混合を行い、次いで、得られた混合物を、一軸押出機、二軸押出機等の押出機により成形し、オレフィン重合体組成物（Ｅ）のストランドを得る方法が挙げられる。なお、前記ストランドは、通常ブロー成形を行う前に、ペレタイザー等を用いてペレットに成形される。
The method for preparing the olefin polymer composition (E) is not particularly limited. For example, a propylene resin (A), an ethylene / α-olefin copolymer (B) and a nucleating agent (D) can be arbitrarily used. A low density ethylene / α-olefin copolymer (F), other resins and additives into a mixer such as a Henschel mixer, Banbury mixer, tumbler mixer, etc., followed by mixing, and then the resulting mixture Is formed by an extruder such as a single screw extruder or a twin screw extruder to obtain a strand of the olefin polymer composition (E). The strand is usually formed into pellets using a pelletizer or the like before blow molding.
また、前記添加剤として、有機過酸化物等の過酸化物、架橋剤等の反応性の添加剤を用いた場合には、前記混合機による混合の際に、プロピレン系樹脂（Ａ）や、エチレン・α‐オレフィン共重合体（Ｂ）や、必要に応じて用いられる低密度エチレン・α‐オレフィン共重合体（Ｆ）の変性を伴ってもよい。
Further, when a reactive additive such as a peroxide such as an organic peroxide or a crosslinking agent is used as the additive, at the time of mixing by the mixer, the propylene resin (A), The ethylene / α-olefin copolymer (B) or a low-density ethylene / α-olefin copolymer (F) used as necessary may be modified.
また、最外層を形成する樹脂としてオレフィン重合体組成物（Ｅ）を用いて形成された多層ブロー容器が良好な物性を示す理由は明らかでないが、特定範囲の結晶融点を有するエチレン・α‐オレフィン共重合体（Ｂ）を用いることにより、プロピレン系樹脂（Ａ）へ、エチレン・α‐オレフィン共重合体（Ｂ）が微分散すると考えられ、そのため、得られる多層ブロー容器の光沢、表面外観に優れ、耐衝撃性が高くなり、さらには、耐衝撃性と低いべたつき性とが両立しうると考えられる。さらには、最外層と接する内層を形成する重合体として、後述のプロピレン系重合体（Ｇ）またはエチレン系重合体（Ｈ）を用いた場合には、該層と最外層との接着点となるエチレン・α‐オレフィン共重合体（Ｂ）が微分散するため、接着点の数が多くなり、内層との接着性にも優れると考えられる。また、低密度エチレン・α‐オレフィン共重合体（Ｆ）を用いた場合には、エチレン・α‐オレフィン共重合体（Ｂ）の介在下では、低密度エチレン・α‐オレフィン共重合体（Ｆ）は、プロピレン系樹脂（Ａ）に微分散すると考えられ、そのため、光沢、表面外観に優れ、耐衝撃性および低温耐衝撃性が高くなり、さらに微分散するためべたつき性も低く抑えられると考えられる。
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 / α-olefin having a crystal melting point in a specific range. By using the copolymer (B), it is considered that the ethylene / α-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. Furthermore, when a later-described propylene polymer (G) or ethylene polymer (H) is used as the polymer forming the inner layer in contact with the outermost layer, it becomes an adhesion point between the layer and the outermost layer. Since the ethylene / α-olefin copolymer (B) is finely dispersed, the number of adhesion points increases, and it is considered that the adhesion to the inner layer is excellent. Further, when the low density ethylene / α-olefin copolymer (F) is used, the low density ethylene / α-olefin copolymer (F) is interposed in the presence of the ethylene / α-olefin copolymer (B). ) Is considered to be finely dispersed in the propylene-based resin (A). Therefore, it is considered that the gloss and surface appearance are excellent, the impact resistance and the low-temperature impact resistance are high, and the stickiness is also suppressed to be low because of fine dispersion. It is done.
＜多層ブロー容器＞
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.
多層ブロー容器を形成する他の層（内層）としては特に限定はなく、通常はオレフィン重合体組成物（Ｅ）以外の熱可塑性樹脂からなる。
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).
オレフィン重合体組成物（Ｅ）以外の熱可塑性樹脂としては、プロピレン系重合体（Ｇ）、エチレン系重合体（Ｈ）、スチレン系重合体、ポリエチレンテレフタレート樹脂、ポリアミド樹脂、ＡＢＳ樹脂、エチレン・酢酸ビニル共重合体、ポリビニルアルコール樹脂またはポリ塩化ビニル樹脂、ポリ塩化ビニル樹脂および変性ポリオレフィン樹脂等が挙げられ、上記樹脂２種以上の混合物も用いることができる。このうち、プロピレン系重合体（Ｇ）、エチレン系重合体（Ｈ）が好ましい。
As thermoplastic resins other than the olefin polymer composition (E), propylene polymer (G), ethylene polymer (H), styrene polymer, polyethylene terephthalate resin, polyamide resin, ABS resin, ethylene / acetic acid 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. Among these, a propylene polymer (G) and an ethylene polymer (H) are preferable.
なお、プロピレン系重合体（Ｇ）とは、プロピレン由来の構成単位を５１モル％以上有するプロピレン系重合体であり、エチレン系重合体（Ｈ）とは、エチレン由来の構成単位を５１モル％以上有するエチレン系重合体である。
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.
多層ブロー容器が、他の層（内層）としてスチレン系重合体または、ポリエチレンテレフタレート樹脂、ポリアミド樹脂、ＡＢＳ樹脂、エチレン－酢酸ビニル共重合体、ポリビニルアルコール樹脂、ポリ塩化ビニル樹脂等の極性樹脂から形成される層を有する場合には、最外層と、スチレン系重合体または極性樹脂から形成される層との間に、変性ポリオレフィン樹脂（Ｉ）から形成される層を有することが、層間の接着強度の観点から好ましい。
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) In the case of having a layer to be formed, it is necessary to have a layer formed from the modified polyolefin resin (I) between the outermost layer and the layer formed from the styrenic polymer or the polar resin. From the viewpoint of
本発明の多層ブロー容器の最外層、すなわちオレフィン重合体組成物（Ｅ）から形成される層は、高光沢である。また、多層ブロー容器は耐衝撃性にも優れる。
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.
本発明の多層ブロー容器の最外層、すなわちオレフィン重合体組成物（Ｅ）から形成される層は、オレフィン重合体組成物（Ｅ）の、流動性の指標であるＭＦＲが特定の範囲となっている。このため、ブロー成形において、金型に接触する直前の加熱溶融樹脂の表面が容易に平滑になりやすく、ブロー成形した後においても表面が平滑になりやすいと推定され、これにより表面光沢性に優れた多層ブロー容器を得ることができるものと考えられる。また、オレフィン重合体組成物（Ｅ）の、流動性の指標であるＭＦＲが特定の範囲となっているため、表面外観も良好となる。
In the outermost layer of the multilayer blow container of the present invention, that is, the layer formed from the olefin polymer composition (E), 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.
さらにオレフィン重合体組成物（Ｅ）は、該組成物の原料としてエチレン・α-オレフィン共重合体（Ｂ）が用いられる。前記エチレン・α‐オレフィン共重合体（Ｂ）は、特定範囲の結晶融点を有するため、得られた成形体は前述の相関接着性が優れる、べたつき性が低いなどの優れた特性を示すほか、エチレン・α‐オレフィン共重合体（Ｂ）のプロピレン系樹脂（Ａ）に対する使用量が少ない場合でも、効率的に耐衝撃性を改良することが可能となった。この理由は定かではないが、特定範囲の融点を持つエチレン・α-オレフィン共重合体（Ｂ）を選択することにより、適度なラメラ厚みを持ち、ラメラとラメラをつなぐタイ分子の量も最適なものとなっていると推測される。
Further, in the olefin polymer composition (E), an ethylene / α-olefin copolymer (B) is used as a raw material of the composition. Since the ethylene / α-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 / α-olefin copolymer (B) used relative to the propylene resin (A) is small, the impact resistance can be improved efficiently. The reason for this is not clear, but by selecting an ethylene / α-olefin copolymer (B) having a melting point in a specific range, it has an appropriate lamella thickness and the amount of tie molecules that connect the lamella and lamella is also optimal. It is presumed to be a thing.
さらにオレフィン重合体組成物（Ｅ）は、該組成物の原料として、必要に応じて低密度エチレン・α‐オレフィン共重合体（Ｆ）が用いられる。前記低密度エチレン・α‐オレフィン共重合体（Ｆ）は、プロピレン系樹脂（Ａ）に対する使用量が少ない場合でも、効率的に低温耐衝撃性を改良することが可能である。
Further, in the olefin polymer composition (E), a low density ethylene / α-olefin copolymer (F) is used as a raw material of the composition as required. The low-density ethylene / α-olefin copolymer (F) can efficiently improve the low-temperature impact resistance even when the amount used for the propylene-based resin (A) is small.
以上のようなことから、本発明の多層ブロー容器は高光沢であると同時に耐衝撃性に優れ、前記低密度エチレン・α‐オレイン共重合体（Ｆ）を用いた場合には低温耐衝撃性にも優れていると本発明者等は推定した。
As described above, the multilayer blow container of the present invention has high gloss and excellent impact resistance, and when the low density ethylene / α-olein copolymer (F) is used, low temperature impact resistance is achieved. The present inventors have estimated that it is also excellent.
本発明の多層ブロー容器は、耐衝撃性に優れるため、外部からの衝撃によるクラック等が抑制され、最外層が高光沢であるため、容器が透明感のある光沢性を有する。また、本発明の多層ブロー容器は、低温耐衝撃性に優れるため、多層ブロー容器に内容物が充填され、低温条件で、輸送、貯蔵等されている場合であっても、外部からの衝撃によるクラック等が抑制される。
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.
本発明の多層ブロー容器の層構成としては、最外層がオレフィン重合体組成物（Ｅ）からなる層であればよく、特に限定はないが、例えばオレフィン重合体組成物（Ｅ）からなる最外層と、最内層との二層構成（最外層／最内層の順で配置された層構成）、オレフィン重合体組成物（Ｅ）からなる最外層と、該最外層に隣接する中間層と、該中間層に隣接する最内層との三層構成（最外層／中間層／最内層の順で配置された層構成）、オレフィン重合体組成物（Ｅ）からなる最外層と、該最外層に隣接する中間層（１）と、該中間層（１）に隣接する中間層（２）と、該中間層（２）に隣接する最内層との四層構成（最外層／中間層（１）／中間層（２）／最内層の順で配置された層構成）等が挙げられる。
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). For example, 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). Intermediate layer (2) / layer structure arranged in the order of the innermost layer).
なお、本発明においては、最外層よりも内側に位置する層を、内層と定義する。すなわち、本発明において前記最内層、中間層は内層に該当し、本発明の多層ブロー容器は、内層を少なくとも一層を有し、二層以上有していてもよい。
In the present invention, 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.
オレフィン重合体組成物（Ｅ）を最外層にもつ本発明の多層ブロー容器において、最外層に隣接する層がプロピレン系重合体（Ｇ）またはエチレン系重合体（Ｈ）から形成される場合、いわゆる接着樹脂を用いなくても強固な接着性を発現した。本発明の多層ブロー容器のオレフィン重合体組成物（Ｅ）からなる最外層との接着性の観点から、オレフィン重合体組成物（Ｅ）からなる最外層と隣接する層は、プロピレン系重合体（Ｇ）またはエチレン系重合体（Ｈ）であることが好ましい。
In the multilayer blow container of the present invention having the olefin polymer composition (E) in the outermost layer, when 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. From the viewpoint of adhesiveness with the outermost layer made of the olefin polymer composition (E) of the multilayer blow container of the present invention, 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.
なお、オレフィン重合体組成物（Ｅ）と隣接する層が、前記プロピレン系重合体（Ｇ）、およびエチレン系重合体（Ｈ）以外の層である場合には、オレフィン重合体組成物（Ｅ）からなる最外層との接着性の観点から、接着性樹脂層を介して、オレフィン重合体組成物（Ｅ）からなる最外層と、他の層が形成されることが好ましい。
When 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.
本発明の多層ブロー容器は、任意の層が着色されていてもよい。
The multilayer blow container of the present invention may have any layer colored.
前記プロピレン系重合体（Ｇ）としては、特に限定はなく、ホモポリプロピレン、プロピレン・α‐オレフィンランダム共重合体、プロピレン・α‐オレフィンブロック共重合体等が挙げられる。プロピレン系重合体（Ｇ）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、０．１～２０．０ｇ／１０分の範囲であることが好ましく、特に０．１～５ｇ／１０分であることが好ましい。また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１００～１６８℃の範囲であることが好ましい。
The propylene polymer (G) is not particularly limited, and examples thereof include homopolypropylene, propylene / α-olefin random copolymer, propylene / α-olefin block copolymer, and the like. According to ASTM D-1238 of the propylene polymer (G), 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.
前記エチレン系重合体（Ｈ）としては、特に限定はなく、いわゆる高密度ポリエチレン、直鎖状低密度ポリエチレン、低密度ポリエチレンが挙げられる。エチレン系重合体（Ｈ）の密度勾配管法で測定した密度は０．８６０～０．９８０ｇ／ｃｍ3であることが好ましく、また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。
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.
前記変性ポリオレフィン樹脂（Ｉ）としては、特に限定無く、一般的には酸変性ポリオレフィンを使用することができる。酸変性に使用される酸は、例えば無水マレイン酸、アクリル酸、メタクリル酸、無水イタコン酸といったエチレン系不飽和カルボン酸あるいはその無水物が挙げられる。また、変性に使用するポリオレフィン樹脂としてはエチレン・α-オレフィン共重合体、プロピレン単独重合体、プロピレン・α-オレフィン共重合体が好ましい。
The modified polyolefin resin (I) is not particularly limited, and generally an acid-modified polyolefin can be used. Examples of 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 / α-olefin copolymer, a propylene homopolymer, or a propylene / α-olefin copolymer.
また、多層ブロー容器中の、最外層と隣接する層以外の内層は、プロピレン系重合体（Ｇ）、エチレン系重合体（Ｈ）、スチレン系重合体または、ポリエチレンテレフタレート樹脂、ポリアミド樹脂、ＡＢＳ樹脂、エチレン－酢酸ビニル共重合体、ポリビニルアルコール樹脂またはポリ塩化ビニル樹脂から選ばれる少なくとも１種の樹脂から形成される層であることが好ましい。
Further, 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. A layer formed of at least one resin selected from ethylene-vinyl acetate copolymer, polyvinyl alcohol resin or polyvinyl chloride resin is preferable.
また、最外層以外の層には、その他の樹脂類、各種添加剤が含まれていてもよい。
Moreover, other resins and various additives may be contained in layers other than the outermost layer.
本発明の多層ブロー容器の成形法としては、ブロー成形であればどのような方法でもよい。成形法としては、ダイレクトブロー成形法（中空成形法）、射出延伸ブロー成形法（射出中空成形法）、押出延伸ブロー成形法、シートブロー成形法等が挙げられる。多層ブロー容器としては、大量生産を行う際の生産性の観点から、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が好ましい。
As a method for forming the multilayer blow container of the present invention, any method may be used as long as it is blow molding. Examples of 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.
ダイレクトブロー成形法により、多層ブロー容器を成形する場合には例えば、多層ブロー用ダイを用いて、オレフィン重合体組成物（Ｅ）およびその他の樹脂を、オレフィン重合体組成物（Ｅ）が最外層になるように、パイプ状に押出し、得られたパリソンがまだ溶融状態にある間に、ブロー型で挟んで、パリソン内に流体を吹き込んで所定形状に成形する。オレフィン重合体組成物（Ｅ）から形成される層が、最外層となるため、高光沢の多層ブロー容器を得ることができる。
When forming a multilayer blow container by the direct blow molding method, for example, using a multilayer blow die, 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.
そして（Ｅ）は、そのＭＦＲを鑑みると、単独ではブロー成形に制約を受けるケース（例えば大型ブロー成形にはやや困難がある場合がある）があるが、本願発明の技術を用いれば、最外層以外の層を適宜選択することにより（例えば（Ｇ）や（Ｈ）を適宜選択することにより）、光沢などと大型化等とを同時に達成することもできる。
And (E), in view of the MFR, there are cases where blow molding is restricted by itself (for example, there may be some difficulties in large blow molding), but if the technique of the present invention is used, the outermost layer By appropriately selecting a layer other than (for example, by appropriately selecting (G) and (H)), it is possible to simultaneously achieve gloss and the like and enlargement.
成形条件は、樹脂の性状にもよるが、流体を吹き込む際の樹脂の温度、すなわち成形温度が１２０～２６０℃であることが好ましく、流体の吹き込み圧力が２～１０ｋｇ／ｃｍ2であることが好ましく、ブロー比が１．２～５．０であることが成形性の観点から好ましい。
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.
ここでいうブロー比とは押出機ダイ部より押し出された筒状溶融パリソンの外径で、成形されるボトルの外径を割った値を言う。
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.
射出延伸ブロー成形法により、多層ブロー容器を成形する場合には例えば、オレフィン重合体組成物（Ｅ）およびその他の樹脂を、オレフィン重合体組成物（Ｅ）が最外層になるように、射出成形することによりプリフォームを成形する。次いでこのプリフォームが溶融状態あるいは軟化状態にある状況で、あるいは一旦プリフォームを固化させた後再加熱した後、このプリフォームを延伸棒等を用いて、強制的に縦延伸し、その後横方向にさらに延伸するためにプリフォーム内に加圧流体を圧入することにより多層ブロー容器を得ることができる。射出成形によりプリフォームを成形する際には、オレフィン重合体組成物（Ｅ）の射出温度が通常は１６０～２６０℃の範囲である。前記縦延伸直前のプリフォームの温度は１１０～１５０℃であることが好ましく、縦延伸倍率は１．５～４．０倍であることが好ましく、横延伸倍率は１．５～３．０倍であることが好ましい。
When molding a multilayer blow container by the injection stretch blow molding method, for example, the olefin polymer composition (E) and other resins are injection molded so that the olefin polymer composition (E) is the outermost layer. To form a preform. Next, in a state where the preform is in a molten state or a softened state, or after re-heating after the preform is solidified, 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. When a preform is formed by injection molding, 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, and the transverse stretching ratio is 1.5 to 3.0 times. It is preferable that
本発明の多層ブロー容器の厚さ、サイズは、多層ブロー容器の用途等によって適宜決定されるが、通常は、厚さ０．３～１０．０ｍｍ、サイズは直径１０～３００ｍｍ、高さ１０～３００ｍｍである。
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.
本発明の多層ブロー容器の最外層の厚さは、外層とその他の内層との厚さの比（外層／内層）が、好ましくは５０／５０～５／９５、より好ましくは３０／７０～１０／９０であるのが好ましい。前記範囲内では、外層の高光沢が最も発現されやすく、成形性も良好となるため好ましい。
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.
本発明の多層ブロー容器は、最外層以外の層にも透明樹脂を用いた場合には、透明性に優れる。具体的には、ＪＩＳ－Ｋ７１０５に準拠してヘイズメーターを用いて測定した曇値（ヘイズ）が３０以下であることが好ましく、２０以下であることがより好ましい。前記範囲内では内容物の視認性が極めて良好な、付加価値の高いボトルを得る事が出来る。
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. Specifically, 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.
本発明の多層ブロー容器は、光沢に優れるが、具体的には、最外層のＪＩＳ－Ｋ７１０５に準拠して光沢計で測定した６０度光沢度が、７０以上であることが好ましく、７５以上であることがより好ましい。前記範囲内では優れた光沢外観を示す、付加価値の高いボトルを得る事が出来る。
The multilayer blow container of the present invention is excellent in gloss. Specifically, 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.
本発明に係る多層ブロー容器は、各種用途に用いることができるが、例えばソース、ドレッシング、ジュース、フルーツ、甘味、水煮野菜等の食品を充填する容器、化粧品、シャンプーなどのトイレタリー用品を充填する容器、液体洗剤などのサニタリー用品を充填する容器として好適である。
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.
〔多層ブロー容器の製造方法〕
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.
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.
本発明の製造方法に用いられる、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）、核剤（Ｄ）、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としては、前述の〔多層ブロー容器〕の項で説明したものを用いることができ、〔多層ブロー容器〕の項で説明した、その他の樹脂類、各種添加剤も用いることができる。
Propylene resin (A), ethylene / α-olefin copolymer (B), low density ethylene / α-olefin copolymer (F), nucleating agent (D), olefin heavy used in the production method of the present invention As the 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.
本発明の製造方法では、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、最外層がオレフィン重合体組成物（Ｅ）から形成される多層ブロー容器を成形する。このため、得られる多層ブロー容器は、該多層ブロー容器の最外層にエチレン・α‐オレフィン共重合体（Ｂ）が含有されるため、高光沢である。また、多層ブロー容器は耐衝撃性にも優れる。
In the production method of the present invention, 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 / α-olefin copolymer (B). The multilayer blow container is also excellent in impact resistance.
本発明の製造方法により得られる多層ブロー容器は、耐衝撃性に優れるため、外部からの衝撃によるクラック等が抑制され、最外層が高光沢であるため、容器が透明感のある光沢性を有する。
Since 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. .
次に本発明について実施例を示してさらに詳細に説明するが、本発明はこれらによって限定されるものではない。
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
〔プロピレン系樹脂（Ａ－１）の製造〕
（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.
（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.
このようにして得られた均一溶液を室温に冷却した後、－２０℃に保持した四塩化チタン２００ｍｌ中に、この均一溶液の７５ｍｌを１時間にわたって滴下装入した。装入終了後、この混合液の温度を４時間かけて１１０℃に昇温し、１１０℃に達したところでフタル酸ジイソブチル（DIBP）５．２２ｇを添加し、これより２時間同温度にて攪拌保持した。
After cooling the homogeneous solution thus obtained to room temperature, 75 ml of this homogeneous solution was charged dropwise into 200 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the completion of charging, the temperature of the mixed solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added, followed by stirring at the same temperature for 2 hours. Retained.
２時間の反応終了後、熱濾過にて固体部を採取し、この固体部を２７５ｍｌの四塩化チタンに再懸濁させた後、再び１１０℃で２時間加熱した。反応終了後、再び熱濾過にて固体部を採取し、１１０℃のデカンおよびヘキサンにて溶液中に遊離のチタン化合物が検出されなくなるまで充分洗浄した。洗浄後の固体部を、固体状チタン触媒成分（Ａ）とした。固体状チタン触媒成分（Ａ）は、デカンスラリーとして保存したが、この内の一部を触媒組成を調べる目的で乾燥した。前記固体状チタン触媒成分（Ａ）の組成は、チタン２．３重量％、塩素６１重量％、マグネシウム１９重量％、DIBP １２．５重量％であった。
After completion of the reaction for 2 hours, the solid part was collected by hot filtration, and the solid part was resuspended in 275 ml of titanium tetrachloride and then heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was again collected by hot filtration, and washed thoroughly with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution. 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.
なお、前記遊離チタン化合物の検出は次の方法で行った。予め窒素置換した１００ｍｌの枝付きシュレンクに上記固体触媒成分の上澄み液１０ｍｌを注射器で採取し装入した。次に、窒素気流にて溶媒ヘキサンを乾燥し、さらに３０分間真空乾燥した。これに、イオン交換水４０ｍｌ、５０容量％硫酸１０ｍｌを装入し３０分間攪拌した。この水溶液をろ紙を通して１００ｍｌメスフラスコに移し、続いて鉄（ＩＩ）イオンのマスキング剤としてｃｏｎｃ．Ｈ3ＰＯ4 １ｍｌとチタンの発色試薬として３％Ｈ2Ｏ2水溶液 ５ｍｌを加え、さらにイオン交換水で１００ｍｌにメスアップした。このメスフラスコを振り混ぜ、２０分後にＵＶを用い４２０ｎｍの吸光度を観測し遊離チタンの検出を行った。この吸収が観測されなくなるまで遊離チタンの洗浄除去および遊離チタンの検出を行った。
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. 1 ml of H 3 PO 4 and 5 ml of 3% H 2 O 2 aqueous solution were added as a coloring reagent for titanium, and the volume was further increased to 100 ml with ion-exchanged water. The volumetric flask was shaken and mixed, and after 20 minutes, the absorbance at 420 nm was observed using UV to detect free titanium. Free titanium was removed by washing and free titanium was detected until this absorption was not observed.
（２）予備重合触媒成分の調製
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.
（３）重合
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%.
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%.
内温８０℃、全圧０．８MPa-Gに系内が安定した後、上記予備重合触媒成分（Ｂ）をＴｉ原子換算で０．１０mmol含んだヘプタンスラリー２０．８ｍｌを加え、全圧とエチレン濃度とを保つようにプロピレンおよびエチレンを連続的に供給しながら８０℃で３時間重合をおこなった。
After the inside of the system was stabilized at an internal temperature of 80 ° C. and a total pressure of 0.8 MPa-G, 20.8 ml of heptane slurry containing 0.10 mmol of the prepolymerized catalyst component (B) in terms of Ti atoms was added, and the total pressure and ethylene were added. Polymerization was carried out at 80 ° C. for 3 hours while continuously supplying propylene and ethylene so as to maintain the concentration.
所定時間経過したところで５０ｍｌのメタノールを添加し反応を停止し、降温、脱圧した。内容物を全量フィルター付きろ過槽へ移し６０℃に昇温し固液分離した。さらに、６０℃のヘプタン６Ｌで固体部を２回洗浄した。このようにして得られたプロピレン/エチレン共重合体（プロピレン系樹脂（Ａ－１））を真空乾燥した。
When a predetermined time had elapsed, 50 ml of methanol was added to stop the reaction, and the temperature was lowered and the pressure was released. The entire contents were transferred to a filtration tank equipped with a filter, heated to 60 ° C., and solid-liquid separated. Further, the solid part was washed twice with 6 L of heptane at 60 ° C. The propylene / ethylene copolymer (propylene resin (A-1)) thus obtained was vacuum dried.
得られたプロピレン系樹脂（Ａ－１）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、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由来の構成単位との合計を１００重量％とした際のエチレン由来の構成単位の重量が３．２重量％、ＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が１４５℃、Ｍｗ／Ｍｎ（分子量分布）は５．３であった。
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.
〔プロピレン系樹脂（Ａ－２）の製造〕
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.
得られたプロピレン系樹脂（Ａ－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、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由来の構成単位との合計を１００重量％とした際のエチレン由来の構成単位の重量が４．８重量％、ＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が１３６℃、Ｍｗ／Ｍｎ（分子量分布）は５．５であった。
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. 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., and Mw / Mn (molecular weight distribution) was 5.5.
〔プロピレン系樹脂（Ａ－３）の製造〕
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、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.
得られたプロピレン系樹脂（Ａ－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、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由来の構成単位との合計を１００重量％とした際のエチレン由来の構成単位の重量が１．０重量％、ＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が１５６℃、Ｍｗ／Ｍｎ（分子量分布）は５．０であった。
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.
〔プロピレン系樹脂（Ａ－４）の製造〕
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０．１５ＭＰａ－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.
得られたプロピレン系樹脂（Ａ－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３．０ｇ／１０分、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由来の構成単位との合計を１００重量％とした際のエチレン由来の構成単位の重量が３．２重量％、ＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が１４５℃、Ｍｗ／Ｍｎ（分子量分布）は５．３であった。
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.
〔プロピレン系樹脂（Ａ－５）の製造〕
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.
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.
得られたプロピレン系樹脂（Ａ－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１５．０ｇ／１０分、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由来の構成単位との合計を１００重量％とした際のエチレン由来の構成単位の重量が３．２重量％、ＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が１４５℃、Ｍｗ／Ｍｎ（分子量分布）は５．３であった。
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. 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.
〔エチレン・α－オレフィン共重合体（Ｂ－１）の製造〕
（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.
（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.
引続き０℃で３０分間反応させ、次いで１．５時間かけて９５℃まで昇温し、その温度で４時間反応させた。その後６０℃まで降温し、上澄み液をデカンテーション法により除去した。このようにして得られた固体成分をトルエンで２回洗浄した後、トルエン１００リットルで再懸濁し、全量を１６０リットルとした。
Subsequently, 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.
このようにして得られた懸濁液に、ビス（１，３－ｎ－ブチルメチルシクロペンタジエニル）ジルコニウムジクロリドのトルエン溶液（Ｚｒ＝２５．６ミリモル／リットル）２０．０リットルを３５℃で３０分間かけて滴下し、さらに３５℃で２時間反応させた。その後、上澄み液を除去し、ヘキサンで２回洗浄することにより、固体触媒成分１ｇ当り３．２ｍｇのジルコニウムを含有する固体触媒成分（１）を得た。
To the suspension thus obtained, 20.0 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr = 25.6 mmol / liter) was added at 35 ° C. The solution was added dropwise over 30 minutes and further reacted at 35 ° C. for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst component (1) containing 3.2 mg of zirconium per 1 g of the solid catalyst component.
（２）予備重合触媒成分の調製
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.
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.
（３）重合
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.
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.
上記で調製した予備重合触媒（２）を４．１ｇ／ｈｒおよびＴＩＢＡを５ミリモル／ｈｒの割合で連続的に供給しながら重合を開始した。重合の間一定のガス組成を維持するためにエチレン、1-ヘキセン、水素、窒素を連続的に供給した（ガス組成（ｍｏｌ比）；１－ヘキセン／エチレン＝０．０４、水素／エチレン＝４．０×１０-4、エチレン濃度＝７１％）。
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. In order to maintain a constant gas composition during the polymerization, ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied (gas composition (molar ratio); 1-hexene / ethylene = 0.04, hydrogen / ethylene = 4). 0.0 × 10 −4 , ethylene concentration = 71%).
得られたエチレン・１－ヘキセン共重合体の収量は６．０ｋｇ／ｈｒであり、ＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が９８℃であり、密度勾配管法で測定した密度が０．９０３ｇ／ｃｍ3であり、ＭＦＲ（ＡＳＴＭ－１２３８、測定温度２３０℃、荷重２．１６ｋｇ）が７．０ｇ／１０分、Ｍｗ／Ｍｎ（分子量分布）は２．６であった。
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. .
なお、得られたエチレン・１－ヘキセン共重合体をエチレン・α－オレフィン共重合体（Ｂ－１）とも記す。
The obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B-1).
〔エチレン・α－オレフィン共重合体（Ｂ－２）の製造〕
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＝０．０３、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%.
得られたエチレン・１－ヘキセン共重合体の収量は６．０ｋｇ／ｈｒであり、ＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が１１３℃であり、密度勾配管法で測定した密度が０．９１３ｇ／ｃｍ3であり、ＭＦＲ（ＡＳＴＭ－１２３８、測定温度２３０℃、荷重２．１６ｋｇ）が７．０ｇ／１０分、Ｍｗ／Ｍｎ（分子量分布）は２．６であった。
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. .
なお、得られたエチレン・１－ヘキセン共重合体をエチレン・α－オレフィン共重合体（Ｂ－２）とも記す。
The obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B-2).
〔エチレン・α－オレフィン共重合体（Ｂ－３）の製造〕
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%.
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%.
得られたエチレン・１－ヘキセン共重合体の収量は５．８ｋｇ／ｈｒであり、ＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が１２０℃であり、密度勾配管法で測定した密度が０．９２４ｇ／ｃｍ3であり、ＭＦＲ（ＡＳＴＭ－１２３８、測定温度２３０℃、荷重２．１６ｋｇ）が７．０ｇ／１０分、Ｍｗ／Ｍｎ（分子量分布）は２．６であった。
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, and Mw / Mn (molecular weight distribution) was 2.6. .
なお、得られたエチレン・１－ヘキセン共重合体をエチレン・α－オレフィン共重合体（Ｂ－３）とも記す。
The obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B-3).
〔実施例Ａ１〕
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.
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.
（二軸押出機条件）
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).
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).
オレフィン重合体組成物（Ｅ－１）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。
The 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.
結果を半結晶化時間、臭気の測定結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time and odor measurement results.
次いで、該ペレットを用いてブロー成形を実施した。
Next, blow molding was performed using the pellets.
３種３層多層ダイレクトブロー成形機（株式会社プラコー社製、３Ｂ５０・４０・４０ブロー成形機）を用い、成形条件としてシリンダ温度が２００℃、流体の吹き込み圧力を５．０ｋｇ／ｃｍ2で設定し、ダイ孔サイズ１４．０ｍｍ、コアサイズ１２．５ｍｍのクロスヘッドダイにより外径２０．０ｍｍ筒状の溶融パリソンを成形し、重量３４ｇ、内容量７８０ｍｌ、口部ネジ外径２７．０ｍｍ、胴回り外径７２ｍｍ、胴回り平均肉厚０．５ｍｍｔの２層構造の円筒状多層ブロー容器を製造した。
Using three types of three-layer multi-layer direct blow molding machine (Placo Co., Ltd., 3B50 / 40/40 blow molding machine), the molding temperature is set to 200 ° C. and the fluid blowing pressure is set to 5.0 kg / cm 2 . Then, 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.
具体的には、内層の押出機を用いず、シリンダ温度を２００℃に設定した中間層と外層の押出機を用いて、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、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１４６℃）を中間層の押出機にて、オレフィン重合体組成物（Ｅ－１）を外層の押出機にて、外層肉厚比率１５％となるように溶解し、クロスヘッドダイにより筒状の溶融パリソンを成形した後、水循環回路により２５℃に温度調整したブロー金型で挟み、圧縮空気にて金型に延伸密着させて冷却固化し、多層ブロー容器を得た。なお、ブロー金型としては、表面処理としてサンドブラスト処理＃４００を行った金型およびサンドブラスト処理＃２００を行った金型の二種類の金型を用い、それぞれの金型を用いて多層ブロー容器を得た。
Specifically, 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. Made by Prime Polymer, 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 146 ° C.) with an intermediate layer extruder and the olefin polymer composition (E-1) is melted with an outer layer extruder so that the outer layer thickness ratio is 15%. 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. As 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.
得られた多層ブロー容器を試験用ボトルとして用いて、下記記載の評価方法によりヘイズ、光沢（グロス）、成形性、接着性、耐衝撃性（満水落下耐衝撃強度）、べたつき性を測定した。なお、金型の表面処理が得られる多層ブロー容器の光沢に影響するかどうかを調べるため、二種類の金型を用いて多層ブロー容器を作成し、それぞれの光沢を評価した。これらの結果を表に示した。
Using the obtained multilayer blow container as a test bottle, haze, gloss (gross), moldability, adhesiveness, impact resistance (full water drop impact strength) and stickiness were measured by the following evaluation methods. In order to investigate whether the surface treatment of the mold affects the gloss of the multilayer blow container, 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.
〔実施例Ａ２〕
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.
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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
〔実施例Ａ３〕
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.
結果を表に示した。
The results are shown in the table.
〔実施例Ａ４〕
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.
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.
結果を表に示した。
The results are shown in the table.
〔実施例Ａ５〕
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.
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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
〔実施例Ａ６〕
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.
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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
〔実施例Ａ７〕
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、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.
実施例Ａ７で得られたオレフィン重合体組成物（Ｅ－２０）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。結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The 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. The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
〔比較例Ａ１〕
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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ１では、エチレン・α－オレフィン共重合体（Ｂ）を配合していない為、本請求項の要件を満たさない。エチレン・α－オレフィン共重合体（Ｂ）を配合していない為ため接着性と耐衝撃性（満水落下耐衝撃強度）が劣っている。
In Comparative Example A1, since the ethylene / α-olefin copolymer (B) is not blended, the requirements of this claim are not satisfied. Since the ethylene / α-olefin copolymer (B) is not blended, the adhesiveness and impact resistance (full water impact resistance) are inferior.
〔比較例Ａ２〕
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.
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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ２では、エチレン・α－オレフィン共重合体（Ｂ）の配合量が請求項に規定の範囲より多い。このためべたつき性が劣っている。
In Comparative Example A2, the blending amount of the ethylene / α-olefin copolymer (B) is larger than the range specified in the claims. For this reason, stickiness is inferior.
〔比較例Ａ３〕
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.
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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ３では、核剤（Ｄ）を配合していない為、本請求項１の案件を満たさない。このため光沢（グロス）が劣っている。
In Comparative Example A3, the case of Claim 1 is not satisfied because the nucleating agent (D) is not blended. For this reason, gloss is inferior.
〔比較例Ａ４〕
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－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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ４では、プロピレン系樹脂（Ａ）のＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が請求項に規定された範囲より低い。このため成形性とべたつき性が劣っている。
In Comparative Example A4, the DSC melting point (crystal melting point measured by DSC in accordance with JIS-K7121) of the propylene-based resin (A) is lower than the range specified in the claims. For this reason, formability and stickiness are inferior.
〔比較例Ａ５〕
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－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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ５では、プロピレン系樹脂（Ａ）のＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が請求項に規定された範囲より高い。このため耐衝撃性（満水落下耐衝撃強度）が劣っている。
In Comparative Example A5, the DSC melting point (crystal melting point measured by DSC according to JIS-K7121) of the propylene-based resin (A) is higher than the range specified in the claims. For this reason, impact resistance (full water impact resistance) is inferior.
〔比較例Ａ６〕
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－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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ６では、オレフィン重合体組成物（Ｅ）のメルトフローレート（ＭＦＲ）（ＡＳＴＭ Ｄ－１２３８、測定温度２３０℃、荷重２．１６ｋｇ）が請求項に規定された範囲より低い。このため光沢（グロス）が劣っている。
In Comparative Example A6, the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E) is lower than the range specified in the claims. For this reason, gloss is inferior.
〔比較例Ａ７〕
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.
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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ７では、オレフィン重合体組成物（Ｅ）のメルトフローレート（ＭＦＲ）（ＡＳＴＭ Ｄ－１２３８、測定温度２３０℃、荷重２．１６ｋｇ）が請求項に規定された範囲より高い。このため成形性と耐衝撃性（満水落下耐衝撃強度）が劣っている。
In Comparative Example A7, the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E) is higher than the range specified in the claims. For this reason, moldability and impact resistance (full drop impact strength) are inferior.
〔比較例Ａ８〕
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.
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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ８で用いたエチレン・α－オレフィン共重合体（Ｂ－２）は、エチレン・α－オレフィン共重合体（Ｂ）のＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が請求項に規定された範囲より高い。このため接着性と耐衝撃性（満水落下耐衝撃強度）が劣っている。さらには耐衝撃性とべたつき特性とのバランスが良くない。
The ethylene / α-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 / α-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.
〔比較例Ａ９〕
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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ９で用いたエチレン・α－オレフィン共重合体（Ｂ－２）は、エチレン・α－オレフィン共重合体（Ｂ）のＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が請求項に規定された範囲より高い。このため接着性と耐衝撃性（満水落下耐衝撃強度）が劣っている。さらには耐衝撃性とべたつき特性とのバランスが良くない。
The ethylene / α-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 / α-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.
〔比較例Ａ１０〕
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.
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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ１０で用いたエチレン・α－オレフィン共重合体（Ｂ－２）は、エチレン・α－オレフィン共重合体（Ｂ）のＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が請求項に規定された範囲より高い。このため接着性と耐衝撃性（満水落下耐衝撃強度）が劣っている。さらには耐衝撃性とべたつき特性とのバランスが良くない。
The ethylene / α-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 / α-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.
〔比較例Ａ１１〕
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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ１１で用いたエチレン・α－オレフィン共重合体（Ｂ－３）は、エチレン・α－オレフィン共重合体（Ｂ）のＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が請求項に規定された範囲より高い。このため光沢（グロス）と接着性と耐衝撃性（満水落下耐衝撃強度）が劣っている。さらには耐衝撃性とべたつき特性とのバランスが良くない。
The ethylene / α-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 / α-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.
〔比較例Ａ１２〕
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.).
比較例Ａ１２で得られたオレフィン重合体組成物（Ｅ－１６）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。
The 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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ１２ではエチレン・α－オレフィン共重合体（Ｂ）に代えて、ウルトゼックス１０３０Ｌを用いた。ウルトゼックス１０３０ＬのＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）は１１５℃であり、請求項に規定されたエチレン・α－オレフィン共重合体（Ｂ）のＤＳＣ融点の範囲より高い。さらにウルトゼックス１０３０Ｌは、メタロセン触媒ではない、チーグラーナッタ触媒で重合されるため、オレフィン重合体組成物（Ｅ－１６）から形成される多層ブロー容器は、接着性、べたつき性と耐衝撃性（満水落下耐衝撃強度）が劣っている。さらには耐衝撃性とべたつき特性とのバランスが良くない。
In Comparative Example A12, ULTRAZEX 1030L was used in place of the ethylene / α-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 / α-olefin copolymer (B) defined in the claims. . Furthermore, since 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.
〔比較例Ａ１３〕
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.
比較例Ａ１３で得られたオレフィン重合体組成物（Ｅ－１７）の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１４７℃であった。
The 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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ１３ではエチレン・α－オレフィン共重合体（Ｂ）に代えて、ＨＺ－２１００Ｊを用いた。ＨＺ－２１００ＪのＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）は１３１℃であり、請求項に規定されたエチレン・α－オレフィン共重合体（Ｂ）のＤＳＣ融点の範囲より高い。さらに、ＨＺ－２１００Ｊの密度勾配管法で測定した密度が０．９５６ｇ／ｃｍ3である。このためオレフィン重合体組成物（Ｅ－１７）から形成される多層ブロー容器は、接着性と耐衝撃性（満水落下耐衝撃強度）が劣っている。さらには耐衝撃性とべたつき特性とのバランスが良くない。
In Comparative Example A13, HZ-2100J was used in place of the ethylene / α-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 / α-olefin copolymer (B) specified in the claims. . Furthermore, the density measured by the density gradient tube method of HZ-2100J is 0.956 g / cm 3 . For this reason, 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.
〔比較例Ａ１４〕
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－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.
比較例Ａ１４で得られたオレフィン重合体組成物（Ｅ－１８）のメルトフローレート（ＭＦＲ）（ＡＳＴＭ Ｄ－１２３８、測定温度２３０℃、荷重２．１６ｋｇ）は６．０ｇ／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。
The 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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ１４ではエチレン・α－オレフィン共重合体（Ｂ）に代えて、タフマーＰ－０６８０（三井化学(株)社製）を用いている。タフマーＰ－０６８０は、ＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が測定されず、エチレン・α－オレフィン共重合体（Ｂ）に該当しない。さらに、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、密度勾配管法で測定した密度も０．８７０ｇ／ｃｍ3であった。
In Comparative Example A14, Tuffmer P-0680 (manufactured by Mitsui Chemicals, Inc.) is used in place of the ethylene / α-olefin copolymer (B). Tuffmer P-0680 does not correspond to an ethylene / α-olefin copolymer (B) because its DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) is not measured. Further, 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 . .
このためオレフィン重合体組成物（Ｅ－１８）から形成される多層ブロー容器は、光沢性（グロス）、接着性とべたつき性が劣っている。
Therefore, the multilayer blow container formed from the olefin polymer composition (E-18) is inferior in glossiness (gloss), adhesiveness and stickiness.
〔比較例Ａ１５〕
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.
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.
比較例Ａ１５で得られたオレフィン重合体組成物（Ｅ－１９）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。
The 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.
結果を半結晶化時間、臭気の測定結果および多層ブロー容器試験結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.
比較例Ａ１５ではエチレン・α－オレフィン共重合体（Ｂ）に代えて、タフマーＰ－０１８０（三井化学（株）社製）を用いている。タフマーＰ－０１８０は、ＤＳＣ融点（ＪＩＳ－Ｋ７１２１に準拠、ＤＳＣで測定した結晶融点）が測定されず、エチレン・α－オレフィン共重合体（Ｂ）に該当しない。さらに、密度は０．８７０ｇ／ｃｍ3、であった。このためオレフィン重合体組成物（Ｅ－１９）から形成される多層ブロー容器は、接着性とべたつき性が劣っている。
In Comparative Example A15, Tuffmer P-0180 (manufactured by Mitsui Chemicals, Inc.) is used in place of the ethylene / α-olefin copolymer (B). Tuffmer P-0180 does not correspond to an ethylene / α-olefin copolymer (B) because the DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) is not measured. Furthermore, 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.
〔実施例Ｂ１〕
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. .
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. .
（二軸押出機条件）
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).
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).
プロピレン系樹脂組成物（Ｅ－２１）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。
The 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.
結果を半結晶化時間、臭気の測定結果と併せて表に示した。
The results are shown in the table together with the semi-crystallization time and odor measurement results.
次いで、該ペレットを用いてブロー成形を実施した。
Next, blow molding was performed using the pellets.
３種３層多層ダイレクトブロー成形機（株式会社プラコー社製、３Ｂ５０・４０・４０ブロー成形機）を用い、成形条件としてシリンダ温度が２００℃、流体の吹き込み圧力を５．０ｋｇ／ｃｍ2で設定し、ダイ孔サイズ１４．０ｍｍ、コアサイズ１２．５ｍｍのクロスヘッドダイにより外径２０．０ｍｍ筒状の溶融パリソンを成形し、重量３４ｇ、内容量７８０ｍｌ、口部ネジ外径２７．０ｍｍ、胴回り外径７２ｍｍ、胴回り平均肉厚０．５ｍｍｔの２層構造の円筒状多層ブロー容器を製造した。
Using three types of three-layer multi-layer direct blow molding machine (Placo Co., Ltd., 3B50 / 40/40 blow molding machine), the molding temperature is set to 200 ° C. and the fluid blowing pressure is set to 5.0 kg / cm 2 . Then, 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.
具体的には、内層の押出機を用いず、シリンダ温度を２００℃に設定した中間層と外層の押出機を用いて、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、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１４６℃）を中間層の押出機にて、オレフィン重合体組成物（Ｅ－２１）を外層の押出機にて、外層肉厚比率１５％となるように溶解し、クロスヘッドダイにより筒状の溶融パリソンを成形した後、水循環回路により２５℃に温度調整したブロー金型で挟み、圧縮空気にて金型に延伸密着させて冷却固化し、多層ブロー容器を得た。なお、ブロー金型としては、表面処理としてサンドブラスト処理＃４００を行った金型およびサンドブラスト処理＃２００を行った金型の二種類の金型を用い、それぞれの金型を用いて多層ブロー容器を得た。
Specifically, 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. Made by Prime Polymer, 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 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%. 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. As 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.
得られた多層ブロー容器を試験用ボトルとして用いて、下記記載の評価方法によりヘイズ、光沢（グロス）、成形性、接着性、べたつき、耐衝撃性（満水落下耐衝撃強度）および低温耐衝撃性（満水落下耐衝撃強度）を測定した。なお、金型の表面処理が得られる多層ブロー容器の光沢に影響するかどうかを調べるため、二種類の金型を用いて多層ブロー容器を作成し、それぞれの光沢を評価した。これらの結果を表に示した。
Using the resulting multilayer blow container as a test bottle, haze, gloss (gross), formability, adhesiveness, stickiness, impact resistance (full water drop impact strength) and low temperature impact resistance by the following evaluation methods (Full water drop impact strength) was measured. In order to investigate whether the surface treatment of the mold affects the gloss of the multilayer blow container, 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.
〔実施例Ｂ２〕
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.
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.
該ストランドを用いたこと以外は、実施例Ｂ１と同様に行い、多層ブロー容器を得た。
A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
結果を表に示した。
The results are shown in the table.
〔実施例Ｂ３〕
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.
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.
該ストランドを用いたこと以外は、実施例Ｂ１と同様に行い、多層ブロー容器を得た。
A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
結果を表に示した。
The results are shown in the table.
〔実施例Ｂ４〕
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、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.
該ストランドを用いたこと以外は、実施例Ｂ１と同様に行い、多層ブロー容器を得た。
A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
結果を表に示した。
The results are shown in the table.
〔実施例Ｂ５〕
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.
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.
該ストランドを用いたこと以外は、実施例Ｂ１と同様に行い、多層ブロー容器を得た。
A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
結果を表に示した。
The results are shown in the table.
〔実施例Ｂ６〕
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.
該ストランドを用いたこと以外は、実施例Ｂ１と同様に行い、多層ブロー容器を得た。
A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
結果を表に示した。
The results are shown in the table.
〔実施例Ｂ７〕
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.
該ストランドを用いたこと以外は、実施例Ｂ１と同様に行い、多層ブロー容器を得た。
A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
結果を表に示した。
The results are shown in the table.
〔参考例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.
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.
該ストランドを用いたこと以外は、実施例Ｂ１と同様に行い、多層ブロー容器を得た。
A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
結果を表に示した。
The results are shown in the table.
〔比較例Ｂ１〕
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.
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.
該ストランドを用いたこと以外は、実施例Ｂ１と同様に行い、多層ブロー容器を得た。
A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.
結果を表に示した。
The results are shown in the table.
〔評価方法〕
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.
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.
〔ＭＦＲ（メルトフローレート）〕
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.
ＡＳＴＭ Ｄ－１２３８に基づき、ＭＦＲ計測時に得られるストランドを採取し、下記密度の測定に使用する。
Based on ASTM D-1238, the strand obtained at the time of MFR measurement is collected and used for the following density measurement.
〔融点（Ｔｍ）〕
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).
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).
（測定条件）
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.
第2step ： 10℃/minで60℃まで降温する。
Second step IV: Decrease the temperature to 60 ° C at 10 ° C / min.
第3step ： 10℃/minで240℃まで昇温する。
3rd step IV: Increase the temperature to 240 ° C at 10 ° C / min.
〔半結晶化時間（Ｔ1/2）〕
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.
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.
（測定条件）
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.
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.
第2step ： 60℃/minで125℃まで降温する。
2nd step IV: Decrease the temperature to 125 ° C at 60 ° C / min.
〔密度〕
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.
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.
〔Ｍｗ／Ｍｎ（分子量分布）〕
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.
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.
ＭｗおよびＭｎは、ウォーターズ社製ＧＰＣ‐１５０Ｃ Ｐｌｕｓを用い以下の様にして測定した。
Mw and Mn were measured as follows using GPC-150C Plus manufactured by Waters.
分離カラムには、ＴＳＫｇｅｌ ＧＭＨ６－ＨＴおよびＴＳＫｇｅｌ ＧＭＨ６－ＨＴＬを用い、カラムサイズはそれぞれ内径７．５ｍｍ、長さ６００ｍｍであり、カラム温度は１４０℃とし、移動相にはｏ‐ジクロロベンゼン（和光純薬工業(株)）および酸化防止剤としてＢＨＴ（和光純薬工業(株)）０．０２５重量％を用い、１．０ｍｌ／分で移動させ、試料濃度は０．１重量％とし、試料注入量は５００マイクロリットルとし、検出器として示差屈折計を用いた。
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.
標準ポリスチレンは、分子量がＭｗ＜１０００およびＭｗ＞４×１０6については東ソー（株）製を用い、１０００≦Ｍｗ≦４×１０6についてはプレッシャーケミカル社製を用いた。
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 .
〔ヘイズ〕
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.
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〕
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.
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.
〔成形性〕
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.
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.
ＡＡ：皺が全くないかまたは目立たなく、成形性が良好
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：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.
ＡＡ：外観不良が無く、接着性が良好である
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：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.
ＡＡ・・・臭気無し
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・・・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.
ＡＡ：全数で表面に亀裂が発生しない
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.
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〕
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.
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.
ＡＡ：全数で表面に亀裂が発生しない
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.
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.
〔べたつき性〕
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.
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.
ＡＡ：全くべたつきを感じない
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.
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系樹脂中のα-オレフィン由来の構成単位の重量〕
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.
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.
13Ｃ-ＮＭＲ測定条件
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. .
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. .
文献(1)：Kakugo,M.; Naito,Y.; Mizunuma,K.; Miyatake,T., Macromolecules 1982, 15, (4), 1150-1152
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.
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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| JP (1) | JP5379247B2 (en) |
| KR (1) | KR101333450B1 (en) |
| CN (1) | CN102712186B (en) |
| WO (1) | WO2011090101A1 (en) |
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| WO2015137268A1 (en) * | 2014-03-10 | 2015-09-17 | 株式会社プライムポリマー | Propylene resin composition and stretched container made from same |
| WO2016114393A1 (en) * | 2015-01-16 | 2016-07-21 | 株式会社プライムポリマー | Laminate, container, method for producing container, and sheet for laminate raw material |
| JP2018203297A (en) * | 2017-05-31 | 2018-12-27 | 株式会社プライムポリマー | Sterilization container |
| JP2019031314A (en) * | 2017-08-09 | 2019-02-28 | 住友化学株式会社 | Hollow container and its manufacturing method, and polypropylene resin composition for blow fill seal |
| JP2019119814A (en) * | 2018-01-09 | 2019-07-22 | 日本ポリプロ株式会社 | Propylene-based resin composition and molded body thereof |
| US20210039364A1 (en) * | 2018-03-20 | 2021-02-11 | Prime Polymer Co., Ltd. | Laminates and liquid packaging bags |
| WO2022006196A1 (en) * | 2020-06-30 | 2022-01-06 | Fina Technology, Inc. | Clear polypropylene composition for thermoforming |
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| CN104077956B (en) * | 2013-03-28 | 2017-05-17 | 优泊公司 | Label for intramode molding and labeled plastic container utilizing label for intramode molding |
| US10173813B2 (en) * | 2016-09-29 | 2019-01-08 | Dow Global Technologies Llc | Flexible container with pop-up spout |
| US20220135779A1 (en) * | 2018-09-26 | 2022-05-05 | Borealis Ag | Propylene copolymer composition with excellent optical and mechanical properties |
| KR102157673B1 (en) * | 2020-04-28 | 2020-09-21 | 라니홀딩스(주) | Container for food packaging |
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| JPH0631796A (en) * | 1992-07-14 | 1994-02-08 | Chisso Corp | Polyolefin resin-made hollow container |
| JPH09165476A (en) * | 1995-12-15 | 1997-06-24 | Chisso Corp | Multilayer hollow vessel |
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|---|---|---|---|---|
| WO2015137268A1 (en) * | 2014-03-10 | 2015-09-17 | 株式会社プライムポリマー | Propylene resin composition and stretched container made from same |
| US10053554B2 (en) | 2014-03-10 | 2018-08-21 | Prime Polymer Co., Ltd. | Propylene resin composition and stretched container formed of the same |
| JPWO2015137268A1 (en) * | 2014-03-10 | 2017-04-06 | 株式会社プライムポリマー | Propylene-based resin composition and stretching container comprising the same |
| KR20170104998A (en) * | 2015-01-16 | 2017-09-18 | 가부시키가이샤 프라임 폴리머 | Laminate, container and manufacturing method thereof, and sheet for use as raw material of laminate |
| JPWO2016114393A1 (en) * | 2015-01-16 | 2017-10-26 | 株式会社プライムポリマー | LAMINATE, CONTAINER, MANUFACTURING METHOD THEREOF, AND LAMINATE MATERIAL SHEET |
| EP3246158A4 (en) * | 2015-01-16 | 2018-07-18 | Prime Polymer Co., Ltd. | Laminate, container, method for producing container, and sheet for laminate raw material |
| WO2016114393A1 (en) * | 2015-01-16 | 2016-07-21 | 株式会社プライムポリマー | Laminate, container, method for producing container, and sheet for laminate raw material |
| KR102460745B1 (en) | 2015-01-16 | 2022-10-28 | 가부시키가이샤 프라임 폴리머 | Laminate, container and manufacturing method thereof, and sheet for use as raw material of laminate |
| JP2018203297A (en) * | 2017-05-31 | 2018-12-27 | 株式会社プライムポリマー | Sterilization container |
| JP7055598B2 (en) | 2017-05-31 | 2022-04-18 | 株式会社プライムポリマー | Sterilization container |
| JP2019031314A (en) * | 2017-08-09 | 2019-02-28 | 住友化学株式会社 | Hollow container and its manufacturing method, and polypropylene resin composition for blow fill seal |
| JP2019119814A (en) * | 2018-01-09 | 2019-07-22 | 日本ポリプロ株式会社 | Propylene-based resin composition and molded body thereof |
| US20210039364A1 (en) * | 2018-03-20 | 2021-02-11 | Prime Polymer Co., Ltd. | Laminates and liquid packaging bags |
| WO2022006196A1 (en) * | 2020-06-30 | 2022-01-06 | Fina Technology, Inc. | Clear polypropylene composition for thermoforming |
| US11859072B2 (en) | 2020-06-30 | 2024-01-02 | Fina Technology, Inc. | Clear polypropylene composition for thermoforming |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011090101A1 (en) | 2013-05-23 |
| KR101333450B1 (en) | 2013-11-26 |
| JP5379247B2 (en) | 2013-12-25 |
| CN102712186B (en) | 2014-07-16 |
| KR20120104436A (en) | 2012-09-20 |
| CN102712186A (en) | 2012-10-03 |
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