CN101600570B - 多层容器 - Google Patents
多层容器 Download PDFInfo
- Publication number
- CN101600570B CN101600570B CN2007800511908A CN200780051190A CN101600570B CN 101600570 B CN101600570 B CN 101600570B CN 2007800511908 A CN2007800511908 A CN 2007800511908A CN 200780051190 A CN200780051190 A CN 200780051190A CN 101600570 B CN101600570 B CN 101600570B
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- Prior art keywords
- oxygen
- acid
- shielding resin
- resin composition
- resin
- Prior art date
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000001301 oxygen Substances 0.000 claims abstract description 73
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 73
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 56
- 239000011342 resin composition Substances 0.000 claims abstract description 31
- 239000007790 solid phase Substances 0.000 claims abstract description 22
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 32
- 230000001590 oxidative effect Effects 0.000 claims description 24
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 18
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 10
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 abstract description 10
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 238000002076 thermal analysis method Methods 0.000 abstract 1
- -1 polyethylene Polymers 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000000758 substrate Substances 0.000 description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 16
- 229920002647 polyamide Polymers 0.000 description 16
- 239000004952 Polyamide Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920002799 BoPET Polymers 0.000 description 6
- 239000005041 Mylar™ Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 125000006839 xylylene group Chemical group 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000004840 adhesive resin Substances 0.000 description 5
- 229920006223 adhesive resin Polymers 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 2
- PZNPLUBHRSSFHT-RRHRGVEJSA-N 1-hexadecanoyl-2-octadecanoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[C@@H](COP([O-])(=O)OCC[N+](C)(C)C)COC(=O)CCCCCCCCCCCCCCC PZNPLUBHRSSFHT-RRHRGVEJSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical compound CC1CCC(N)CC1 KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- QCTBMLYLENLHLA-UHFFFAOYSA-N aminomethylbenzoic acid Chemical compound NCC1=CC=C(C(O)=O)C=C1 QCTBMLYLENLHLA-UHFFFAOYSA-N 0.000 description 2
- 229960003375 aminomethylbenzoic acid Drugs 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- CTIHZTFULZJBGQ-UHFFFAOYSA-L cobalt(2+);decanoate Chemical compound [Co+2].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O CTIHZTFULZJBGQ-UHFFFAOYSA-L 0.000 description 2
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
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- 239000004701 medium-density polyethylene Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- CNVZJPUDSLNTQU-SEYXRHQNSA-N petroselinic acid Chemical compound CCCCCCCCCCC\C=C/CCCCC(O)=O CNVZJPUDSLNTQU-SEYXRHQNSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- FKSDBOYUTQOSSU-UHFFFAOYSA-N 1,3-diphenylpropane-1,3-dione methane Chemical compound C(C1=CC=CC=C1)(=O)CC(C1=CC=CC=C1)=O.C FKSDBOYUTQOSSU-UHFFFAOYSA-N 0.000 description 1
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 description 1
- YDBHSDRXUCPTQQ-UHFFFAOYSA-N 1-methylcyclohexan-1-amine Chemical compound CC1(N)CCCCC1 YDBHSDRXUCPTQQ-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- DBLXXVQTWJFJFI-UHFFFAOYSA-N 1-phenyloctadecan-1-one Chemical compound CCCCCCCCCCCCCCCCCC(=O)C1=CC=CC=C1 DBLXXVQTWJFJFI-UHFFFAOYSA-N 0.000 description 1
- VGYZKPWMARHMDW-UHFFFAOYSA-N 1-phenyltetradecane-1,3-dione Chemical compound CCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 VGYZKPWMARHMDW-UHFFFAOYSA-N 0.000 description 1
- OXEDXHIBHVMDST-UHFFFAOYSA-N 12Z-octadecenoic acid Natural products CCCCCC=CCCCCCCCCCCC(O)=O OXEDXHIBHVMDST-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- MOMFXATYAINJML-UHFFFAOYSA-N 2-Acetylthiazole Chemical group CC(=O)C1=NC=CS1 MOMFXATYAINJML-UHFFFAOYSA-N 0.000 description 1
- BSELJBOMYPMBNL-UHFFFAOYSA-N 2-acetyl-3,4-dihydro-2h-naphthalen-1-one Chemical compound C1=CC=C2C(=O)C(C(=O)C)CCC2=C1 BSELJBOMYPMBNL-UHFFFAOYSA-N 0.000 description 1
- OEKATORRSPXJHE-UHFFFAOYSA-N 2-acetylcyclohexan-1-one Chemical group CC(=O)C1CCCCC1=O OEKATORRSPXJHE-UHFFFAOYSA-N 0.000 description 1
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 1
- CTUQBZGKHZPYJF-UHFFFAOYSA-N 2-benzoyl-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(C(=O)C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 CTUQBZGKHZPYJF-UHFFFAOYSA-N 0.000 description 1
- HUCQLDZSDDSFKF-UHFFFAOYSA-N 2-benzoyl-3,4-dihydro-2h-naphthalen-1-one Chemical group C1CC2=CC=CC=C2C(=O)C1C(=O)C1=CC=CC=C1 HUCQLDZSDDSFKF-UHFFFAOYSA-N 0.000 description 1
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical group C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 description 1
- QDOGDTXCIBHAMV-UHFFFAOYSA-N 2-hexadecyl-3,4-dihydro-2H-naphthalen-1-one Chemical compound C(CCCCCCCCCCCCCCC)C1C(C2=CC=CC=C2CC1)=O QDOGDTXCIBHAMV-UHFFFAOYSA-N 0.000 description 1
- VKZYRCUVDRFYEZ-UHFFFAOYSA-N 2-icosylpropanedioic acid Chemical compound CCCCCCCCCCCCCCCCCCCCC(C(O)=O)C(O)=O VKZYRCUVDRFYEZ-UHFFFAOYSA-N 0.000 description 1
- NVHGRUYAFQFUJE-UHFFFAOYSA-N 2-octadecanoyl-3,4-dihydro-2h-naphthalen-1-one Chemical compound C1=CC=C2C(=O)C(C(=O)CCCCCCCCCCCCCCCCC)CCC2=C1 NVHGRUYAFQFUJE-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-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
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/10—Forming by pressure difference, e.g. vacuum
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- 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
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- 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
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/002—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor characterised by the choice of material
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- 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
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/14—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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Abstract
本发明目的在于,提供一种多层容器,其成形时的加工性优异、具有由吸氧性屏蔽树脂组合物形成的中间层。本发明提供一种多层容器,该多层容器具有包含烯烃树脂的内外层和在前述内外层间的由吸氧性屏蔽树脂组合物形成的中间层,其中,吸氧性屏蔽树脂组合物的降温结晶化峰值温度低于构成吸氧性屏蔽树脂组合物的基材树脂(氧屏蔽树脂),前述多层容器是在低于基材树脂的降温结晶化起始温度(Tc2)1~15℃的温度范围内进行固相成形而成的,在容器体部的热分析中,以100℃/分钟的速度从30℃升温至130℃后的等温结晶化带来的发热量低于0.5J/g。
Description
技术领域
本发明涉及成形时的加工性优异的、具有由吸氧性屏蔽树脂组合物形成的中间层的多层容器。
背景技术
氧屏蔽性树脂、例如乙烯-乙烯醇共聚物(EVOH)被用作与聚烯烃等热塑性树脂层进行层压而形成多层容器的树脂(参照专利文献1)。
但是,在成形以乙烯-乙烯醇共聚物等氧屏蔽性树脂作为中间层的多层片材时,从提高透明性、机械特性的观点来看,采用固相成形,在进行固相成形时,存在氧屏蔽性树脂层的切断、厚度不均等问题。
专利文献1:日本特开2005-187808号公报
发明内容
本发明的目的在于,提供固相成形时的加工性优异的、具有由吸氧性屏蔽树脂组合物形成的中间层的多层容器。
本发明提供一种多层容器,该多层容器具有包含烯烃树脂的内外层和在前述内外层间的由吸氧性屏蔽树脂组合物形成的中间层,其中,吸氧性屏蔽树脂组合物的降温结晶化峰值温度低于构成吸氧性屏蔽树脂组合物的氧屏蔽树脂,氧屏蔽树脂是乙烯-乙烯醇共聚物树脂,吸氧性屏蔽树脂组合物包含在氧屏蔽树脂中配合具有不饱和烯键的氧化性聚合物以及氧化催化剂得到的树脂,前述多层容器是在低于氧屏蔽树脂的降温结晶化起始温度1~15℃的温度范围内进行固相成形而成的,在容器体部的热分析中,以100℃/分钟的速度从30℃升温至130℃并保持30分钟时的由等温结晶化带来的发热量低于0.5J/g,至少在容器体部测得的X射线衍射谱去除空气散射后的、2θ=14.5°的峰值强度I与2θ=15.5°的峰值强度I0的强度比I/I0为4以上,所述降温结晶化起始温度是利用DSC差示扫描量热计求得的。
根据本发明的多层容器,能够获得固相成形时的加工性优异的、具有由吸氧性屏蔽树脂组合物形成的中间层的多层容器。
具体实施方式
本发明的多层容器具有包含烯烃树脂的内外层和由吸氧性屏蔽树脂组合物形成的中间层。
作为烯烃树脂,可以列举低密度聚乙烯(LDPE)、中密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)、线性低密度聚乙烯(LLDPE)、线性超低密度聚乙烯(LVLDPE)等聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物、聚丁烯-1、乙烯-丁烯-1共聚物、丙烯-丁烯-1共聚物、乙烯-丙烯-丁烯-1共聚物、乙烯-乙酸乙烯酯共聚物、离子交联烯烃共聚物(离聚物)或它们的混合物等。
作为阻气性树脂,可以列举乙烯-乙烯醇共聚物、聚酰胺树脂、聚酯树脂。这些树脂可以单独使用,也可以2种以上组合使用。
在本发明中,作为对于氧、香气成分的屏蔽性特别优异的树脂,使用乙烯-乙烯醇共聚物是理想的。作为乙烯-乙烯醇共聚物,可以使用那些本身公知的任何物质,例如,可以使用对乙烯含量为20~60摩尔%,特别为25~50摩尔%的乙烯-乙酸乙烯共聚物进行皂化处理,使得皂化度为96摩尔%以上,特别为99摩尔%以上而得到的共聚物皂化物。
该乙烯-乙烯醇共聚物皂化物应当具有可足以形成薄膜的分子量,一般来说,理想的是,在苯酚∶水的重量比为85∶15的混合溶剂中,在30℃下进行测定时,具有0.01dL/g以上,尤其为0.05dL/g以上的粘度。
作为聚酰胺树脂,可以列举:(a)由二羧酸成分和二胺成分衍生出的脂肪族、脂环族或半芳香族聚酰胺;(b)由氨基羧酸或其内酰胺衍生出的聚酰胺、或者它们的共聚酰胺或它们的混合物。
作为二羧酸成分,例如,可以列举琥珀酸、己二酸、癸二酸、癸烷二羧酸、十一烷二羧酸、十二烷二羧酸等碳原子数4~15的脂肪族二羧酸,对苯二甲酸、间苯二甲酸等芳香族二羧酸。
另外,作为二胺成分,可以列举1,6-二氨基己烷、1,8-二氨基辛烷、1,10-二氨基癸烷、1,12-二氨基十二烷等碳原子数4~25、尤其为6~18的直链状或支链状亚烷基二胺、双(氨基甲基)环己烷、双(4-氨基环己基)甲烷、4,4’-二氨基-3,3’-二甲基二环己基甲烷,尤其是双(4-氨基环己基)甲烷、1,3-双(氨基环己基)甲烷、1,3-双(氨基甲基)环己烷等脂环族二胺、间亚二甲苯基二胺和/或对亚二甲苯基二胺等芳香脂肪族二胺。
作为氨基羧酸成分,可以列举脂肪族氨基羧酸,例如ω-氨基己酸、ω-氨基辛酸、ω-氨基十一烷酸、ω-氨基十二烷酸、对氨基甲基安息香酸、对氨基苯乙酸等芳香脂肪族氨基羧酸等。
在这些聚酰胺中,优选含亚二甲苯基的聚酰胺,具体地可列举,聚间亚二甲苯基己二酰胺、聚间亚二甲苯基癸二酰胺、聚间亚二甲苯基辛酰胺、聚对亚二甲苯基庚二酰胺、聚间亚二甲苯基壬二酰胺等均聚物以及间亚二甲苯基/对亚二甲苯基己二酰胺共聚物、间亚二甲苯基/对亚二甲苯基庚二酰胺共聚物、间亚二甲苯基/对亚二甲苯基癸二酰胺共聚物、间亚二甲苯基/对亚二甲苯基壬二酰胺共聚物等共聚物、或者对这些均聚物或共聚物的成分和如六亚甲基二胺那样的脂肪族二胺、如哌嗪那样的脂环式二胺、如对双(2-氨基乙基)苯那样的芳香族二胺、如对苯二甲酸那样的芳香族二羧酸、如ε-己内酰胺那样的内酰胺、如7-氨基庚酸那样的ω-氨基羧酸、如对氨基甲基安息香酸那样的芳香族氨基羧酸等进行共聚得到的共聚物,其中,可以特别合适地使用由以间亚二甲苯基二胺和/或对亚二甲苯基二胺为主成分的二胺成分和脂肪族二羧酸和/或芳香族二羧酸得到的聚酰胺。
与其他聚酰胺树脂相比,这些含亚二甲苯基的聚酰胺的阻气性更优异,是用于本发明目的的优选物质。
本发明中。从抑制聚酰胺树脂的氧化劣化的观点来看,优选聚酰胺树脂的末端氨基浓度为40eq/106g以上、尤其是末端氨基浓度超过50eq/106g的聚酰胺树脂。
聚酰胺树脂的氧化劣化即吸氧与聚酰胺树脂的末端氨基浓度有密切关系。即,当聚酰胺树脂的末端氨基浓度在上述较高值的范围时,能够将吸氧速度抑制到几乎为零或者接近零的值,与此相对,当聚酰胺树脂的末端氨基浓度低于前述范围时,聚酰胺树脂的吸氧速度有增大的倾向。
这些聚酰胺还应该具有足以形成薄膜的分子量,理想的是,在浓硫酸中的浓度为1.0g/dl,而且在30℃温度下测得的相对粘度(ηrel)为1.1以上,特别为1.5以上。
作为聚酯树脂,可以列举由对苯二甲酸、间苯二甲酸这样的芳香族二羧酸和乙二醇这样的二醇类衍生出的热塑性聚酯,即所谓的阻气性聚酯。在该阻气性聚酯的聚合物链中含有摩尔比为T∶I=95∶5~5∶95,特别为75∶25~25∶75的对苯二甲酸成分(T)和间苯二甲酸成分(I),并且还含有摩尔比为E∶BHEB=99.999∶0.001~2.0∶98.0,特别为99.95∶0.05~40∶60的乙二醇成分(E)和双(2-羟基乙氧基)苯成分(BHEB)。作为BHEB,优选1,3-双(2-羟基乙氧基)苯。
该聚酯至少应该具有足以形成薄膜的分子量,理想的是,通常在重量比为60∶40的苯酚与四氯乙烷的混合溶剂中,在30℃温度下测定时,具有0.3~2.8dl/g,特别为0.4~1.8dl/g的特性粘度[η]。
还可以使用将主体为聚乙二醇酸的聚酯树脂或由该聚酯树脂、前述芳香族二羧酸、二醇类衍生出的聚酯树脂进行混合而获得的聚酯树脂。
吸氧性屏蔽树脂组合物优选含有氧化性聚合物。其中,氧化性聚合物是指通过被氧化而显示吸氧作用的聚合物。
作为氧化性聚合物,可以列举具有不饱和烯键的氧化性聚合物等,例如以多烯为单体而衍生出的聚合物。作为多烯的适当例子,可以列举丁二烯、异戊二烯等共轭二烯等。可以使用多烯的均聚物、或者组合2种以上前述多烯或与其他单体组合而获得的无规共聚物、嵌段共聚物等作为氧化性聚合物。在由多烯衍生的聚合物中,合适的是聚丁二烯、聚异戊二烯、天然橡胶、腈-丁二烯橡胶、苯乙烯-丁二烯橡胶、氯丁二烯橡胶、乙烯-丙烯-二烯橡胶等,当然不限于这些化合物。
另外,作为具有不饱和烯键的氧化性聚合物,优选具有官能团。作为官能团,可以列举羧酸基、羧酸酐基、羧酸酯基、羧酸酰胺基、环氧基、羟基、氨基、羰基等,从相容性等方面来看,特别优选羧酸基、羧酸酐基。这些官能团可以位于树脂的侧链,也可以位于末端。
作为用于导入这些官能团的单体,可以列举具有前述官能团的烯属不饱和单体。
作为用于向具有不饱和烯键的氧化性聚合物导入羧酸基或羧酸酐基的单体,使用不饱和羧酸或者它们的衍生物是理想的,具体地可以列举丙烯酸、甲基丙烯酸、马来酸、富马酸、衣康酸、柠康酸、四氢苯二甲酸等α,β-不饱和羧酸、双环[2,2,1]庚-2-烯-5,6-二羧酸等不饱和羧酸、马来酸酐、衣康酸酐、柠康酸酐、四氢苯二甲酸酐等α,β-不饱和羧酸酐、双环[2,2,1]庚-2-烯-5,6-二羧酸酐等不饱和羧酸酐。
具有不饱和烯键的氧化性聚合物的酸改性通过如下来制造:以具有不饱和烯键的氧化性共聚物作为基底聚合物,利用那些本身已知的方法使不饱和羧酸或其衍生物与该基底聚合物进行接枝共聚而制造,还可以通过使前述具有不饱和烯键的氧化性聚合物与不饱和羧酸或其衍生物进行无规共聚而制造。
从在氧屏蔽树脂中的分散性方面来看,特别合适的具有羧酸或羧酸酐基的、含不饱和烯键的氧化性聚合物优选液态树脂,该液态树脂以酸值为5KOHmg/g以上的量含有羧酸或其衍生物。
如果不饱和羧酸或其衍生物的含量在前述范围内,具有不饱和烯键的氧化性聚合物在氧屏蔽树脂中的分散性就很好,同时还可以顺利地吸收氧。
当在氧屏蔽树脂中配合具有不饱和烯键的氧化性聚合物时,优选的是,在过渡金属催化剂的存在下,在常温下,每1g具有不饱和烯键的氧化性聚合物,具有吸收2×10-3mol以上的氧,尤其是4×10-3mol以上的氧的能力。即,当吸氧能力为前述值以上时,无需为了显示出良好的氧屏蔽性而在氧屏蔽性树脂中配合大量的具有不饱和烯键的氧化性聚合物,因此不会引起配合而成的树脂组合物的加工性、成形性的降低。
本发明中使用的具有不饱和烯键的氧化性聚合物中的碳-碳双键没有特殊限制,可以是以亚乙烯基的形式位于主链中,还可以是以乙烯基的形式位于侧链中,关键是只要能够氧化就可以。
相对于吸氧性屏蔽树脂组合物,具有不饱和烯键的氧化性聚合物的含量优选为1~30重量%,特别优选为3~20重量%的范围。如果具有不饱和烯键的氧化性聚合物的配合量在前述范围内,吸氧性层具有足够的吸氧性能,还能够维持树脂组合物的成形性。
吸氧性屏蔽树脂组合物优选含有氧化催化剂。
作为氧化催化剂,优选为铁、钴、镍等元素周期表第VIII族金属成分,另外,可以列举含铜、银等第I族金属,锡、钛、锆等第IV族金属,第V族钒、第VI族铬等、第VII族锰等金属成分的过渡金属催化剂等。在这些金属成分中,钴成分的吸氧速度大,特别适合于本发明的目的。
过渡金属催化剂一般以前述过渡金属的低价态的无机酸盐、有机酸盐或络合盐的形式使用。
作为无机酸盐,可以列举氯化物等卤化物、硫酸盐等硫的含氧酸盐、硝酸盐等氮的含氧酸盐、磷酸盐等磷氧酸盐、硅酸盐等。
另一方面,作为有机酸盐,可以列举羧酸盐、磺酸盐、膦酸盐等,羧酸盐适合于本发明的目的,其具体例子可以列举乙酸、丙酸、异丙酸、丁酸、异丁酸、戊酸、异戊酸、己酸、庚酸、异庚酸、辛酸、2-乙基己酸、壬酸、3,5,5-三甲基己酸、癸酸、新癸酸、十一烷酸、月桂酸、豆蔻酸、棕榈酸、十七烷酸、硬脂酸、花生酸、十二碳-5-烯酸、十四碳烯-4-酸、十八碳-6-烯酸、油酸、亚油酸、亚麻酸、二十四碳四烯酸、甲酸、草酸、氨基磺酸、环烷酸等的过渡金属盐。
另一方面,作为过渡金属的络合物,可以使用与β-二酮或β-酮酸酯的络合物,作为β-二酮或β-酮酸酯,可以使用例如乙酰丙酮、乙酰乙酸乙酯、1,3-环己二酮、亚甲基双-1,3-环己二酮、2-苄基-1,3-环己二酮、乙酰四氢萘酮、棕榈酰四氢萘酮、硬脂酰四氢萘酮、苯甲酰四氢萘酮、2-乙酰环己酮、2-苯甲酰环己酮、2-乙酰基-1,3-环己烷二酮、苯甲酰基-对氯苯甲酰甲烷、双(4-甲基苯甲酰基)甲烷、双(2-羟基苯甲酰基)甲烷、苯甲酰丙酮、三苯甲酰甲烷、二乙酰苯甲酰甲烷、硬脂酰苯甲酰甲烷、棕榈酰苯甲酰甲烷、月桂酰苯甲酰甲烷、二苯甲酰甲烷、双(4-氯苯甲酰基)甲烷、双(亚甲基-3,4-二氧基苯甲酰基)甲烷、苯甲酰乙酰苯甲烷、硬脂酰(4-甲氧基苯甲酰基)甲烷、丁酰丙酮、二硬脂酰甲烷、乙酰丙酮、硬脂酰丙酮、双(环己酰基)-甲烷和二新戊酰甲烷等。
前述具有不饱和烯键的氧化性聚合物的含量为:本领域技术人员都能够容易地设定,并使得前述降温结晶化峰值温度低于基材树脂,一般来说,相对于吸氧性屏蔽树脂组合物的总重量,前述具有不饱和烯键的氧化性聚合物的含量为1~30重量%,优选为3~20重量%。
另外,氧化催化剂的含量为:本领域技术人员都能够容易地设定,并使得前述降温结晶化峰值温度低于基材树脂,一般来说,相对于吸氧性屏蔽树脂组合物的总重量,以金属量计为100~1000ppm,优选为200~500ppm。
吸氧性屏蔽树脂组合物可以是氧屏蔽树脂和氧化性聚合物的混合物,还可以配合作为第三成分的成核剂、相容化剂等添加剂。特别是从提高吸氧性、加工性、透明性等方面来看,优选氧化性聚合物或添加剂与氧屏蔽性树脂键合。前述键合可以利用核磁共振、傅立叶变换红外分光光度计等来进行确认。
在本发明的多层容器中,吸氧性屏蔽树脂组合物的降温结晶化峰值温度比构成吸氧性屏蔽树脂组合物的基材树脂(氧屏蔽树脂)还要低。
通过将前述降温结晶化峰值温度设定成上述这样的条件,可以获得固相成形时的结晶化得到抑制或降低的、加工性优异的吸氧性屏蔽树脂组合物。
并且,本发明的多层容器是在低于基材树脂的降温结晶化起始温度(Tc2)1~15℃的温度范围内进行固相成形而成的。通过设定这样的成形条件,可以使后述的发热量控制在合适的范围内,从而能够获得具有吸氧性能的、氧屏蔽性优异的多层容器。本发明的多层容器优选在低于Tc2 1~15℃的温度范围内进行固相成形,更优选在低于Tc2 3~14℃的温度范围内进行固相成形。
另外,本发明的多层容器在容器体部的热分析中,以100℃/分钟的速度从30℃升温至130℃后的等温结晶化带来的发热量低于0.5J/g。通过将前述发热量控制在这样的范围内,可以制得容器外观、机械特性良好,具有吸氧性能的氧屏蔽性优异的多层容器。
此外,本发明的多层容器至少在容器体部通过X射线衍射测定的(110)面的强度(I)与基线(I0)的强度之比I/I0优选为4以上。通过将前述强度比I/I0设定在这样的范围内,可以获得透明性、机械特性更加良好,具有吸氧性能的氧屏蔽性优异的多层容器。前述强度比I/I0更优选为4~10。
根据需要,本发明的多层容器还可以在各树脂层间插入粘合剂树脂。
作为这样的粘合剂树脂,可以列举如下所述聚合物:在主链或侧链上以1~700毫克当量(meq)/100g树脂,优选以10~500meq/100g树脂的浓度含有羧酸、羧酸酐的聚合物。
作为粘合剂树脂,例如是乙烯-丙烯酸共聚物、离子交联烯烃共聚物、马来酸酐接枝聚乙烯、马来酸酐接枝聚丙烯、丙烯酸接枝聚烯烃、乙烯-乙酸乙烯酯共聚物、共聚聚酯、共聚聚酰胺等,还可以是组合上述2种以上的聚合物得到的物质。
这些粘合剂树脂在利用同时挤出或夹芯层压等进行层压时有用。另外,还可以使用异氰酸酯系或环氧系等热固化型粘合剂树脂。
使用本发明的吸氧性屏蔽树脂组合物的层压结构可以根据使用状态、所需功能来适当地选择。尤其,至少具有一层氧屏蔽层的结构能够提高吸氧层的寿命,因此优选。
在使用本发明的吸氧性屏蔽树脂组合物的层压体中,为了捕集吸氧时产生的副产物,优选在吸氧层或其他任何层,尤其是在比吸氧层更内侧的一层配合除臭剂或氧化副产物的吸附剂。
作为这些除臭剂或吸附剂,可以使用本身已知的物质,例如天然沸石、合成沸石、硅胶、活性碳、浸渍活性碳、活性白土、活性氧化铝、粘土、硅藻土、高岭土、滑石、膨润土、海泡石、绿坡缕石、氧化镁、氧化铁、氢氧化铝、氢氧化镁、氢氧化铁、硅酸镁、硅酸铝、合成水滑石、胺负载多孔质二氧化硅。其中,从与作为氧化副产物的醛的反应性方面来看,优选胺负载多孔二氧化硅,另外,从对各种氧化副产物显示优异的吸附性、而且透明方面来看,优选二氧化硅/氧化铝之比较大的所谓的高硅沸石。
作为高硅沸石,优选二氧化硅/氧化铝之比(摩尔比)为80以上,更优选为90以上,进一步优选为100~700。
这种二氧化硅/氧化铝之比的沸石,在二氧化硅/氧化铝之比较低的沸石吸附性降低的高湿条件下反而具有能提高氧化副产物的包装性能的性质,用作包装含水分的内容品的包装材料是非常有效的。高硅沸石的交换阳离子必须是钠、锂、钾等碱金属、钙、镁等碱土类金属的1种或2种以上的混合物。在这种情况下,作为交换阳离子,优选至少含有钠离子,作为特别优选的物质,可以列举基本全部的交换阳离子是钠。
本发明的多层容器由凸缘部、体部、底部构成,从加工性方面来看,多层容器的高度H与口径D之比H/D为2.0以下的范围,更优选为1.6~0.8。
并且,使用本发明的多层结构体的包装容器可以用作能够防止氧引起的内容物香气降低的容器。
作为能够填充的内容物,可以列举啤酒、葡萄酒、果汁、碳酸软饮料、乌龙茶、绿茶等饮料,水果、坚果、蔬菜、肉制品、婴儿食品、咖啡、果酱、蛋黄酱、番茄酱、食用油、调味品、酱汁类、成烹海味类、乳制品等,以及医药品、化妆品、汽油等,在氧存在下容易发生劣化的内容品等,但不仅限于这些例子。
实施例
通过实施例进一步说明本发明,但本发明并不限于这些实施例。
1.测定方法
(1)在低于基材树脂的降温结晶化起始温度(Tc2)1~15℃的温度范围内的固相成形
从多层容器的体部切取测定样品,利用DSC差示扫描量热计(DSC6220:SII公司制造),以10℃/分钟的速度,从0℃升温至230℃,保持5分钟后,以10℃/分钟的速度降温至0℃,求得基材树脂的降温结晶化起始温度(Tc2),结果为162℃。
该降温结晶化起始温度162℃(Tc2)减去成形温度(T),求得温度差(Tc2)-(T),从而证实是否在低于基材树脂的降温结晶化起始温度162℃(Tc2)1~15℃的温度范围内进行固相成形。
(2)等温结晶化带来的发热量
从多层容器的体部切取测定样品,使用DSC差示扫描量热计(DSC6220:SII公司制造),求得以100℃/分钟的速度从30℃升温至130℃并保持30分钟时的由等温结晶化带来的发热量。
(3)X射线衍射强度比I/I0
从多层容器的体部切取测定样品,利用微型X射线衍射装置(PSPC-150C:理学电气(株)制造)测定衍射谱。测定过程如下:利用准直仪使X射线成为细光束,并垂直入射试样面,安装成容器高度方向垂直(高度方向的取向的强度)于包含X射线光轴和弯曲型PSPC的面,利用弯曲PSPC测算布拉格角2θ=0~100°下的衍射强度。从所得X射线衍射谱去除空气散射后,将2θ=14.5°的峰值强度(相当于聚丙烯的110面)作为I,将2θ=15.5°的峰值强度作为I0,计算强度比I/I0。
2.评价
目视观察多层容器的外观,确认纵条状的不均(成形时的拉伸不均)、表面的凹凸、白浊、壁厚的均匀性(容器壁厚的偏差)这样的容器外观,以及耐冲击性(落下强度)这样的机械特性,并将没有发生这些现象的情况记做○,将发生这些现象的情况己做×。
(实施例1)
利用滚筒混合由乙烯-乙烯醇共聚物树脂(共聚32mol%的乙烯)(EP-F171B:(株)クラレ)形成的基材树脂(氧屏蔽树脂)颗粒和由新癸酸钴(钴含有率为14wt%)(DICANATE5000:大日本油墨化学工业(株))形成的过渡金属催化剂,将以钴量计350ppm的新癸酸钴均匀地粘附于前述基材树脂颗粒表面。
接着,使用在出口部分安装有股线模(strand die)的双螺杆挤出机(TEM-35B:东芝机械(株)),螺杆转速100rpm,通过排气口抽成低真空,利用液体给料器,相对950重量份粘附有钴的基材树脂,滴入50重量份酸值40mgKOH/g的马来酸酐改性聚丁二烯(M-2000-20:日本石油化学(株)),在成形温度200℃下牵引出绞线(strand),制造吸氧性屏蔽树脂组合物颗粒。
并且,利用聚丙烯树脂(EC9J:日本ポリプロ(株))、粘合树脂(ADMER QF551:三井化学(株)),并利用前述制造的吸氧性屏蔽树脂组合物的颗粒,制造3种5层的多层片材。
层构成和厚度如下:聚丙烯层(557μm)/粘合树脂层(24μm)/吸氧性屏蔽树脂组合物层(38μm)/粘合树脂层(24μm)/聚丙烯层(557μm),总厚度为1200μm。
将该多层片材切成30cm见方后,利用远红外加热器将片材加热至148℃,利用柱塞辅助真空压空成形机,对牵引比H/D=1.3的多层容器进行固相成形。
测定基材树脂的降温结晶化起始温度162℃(Tc2)减去成形温度(T)的温度差(Tc2-T)、等温结晶化带来的发热量、X射线衍射强度比I/I0,对容器进行评价。
(实施例2)
除了使片材加热温度为159℃以外,与实施例1同样地对多层容器进行固相成形,并进行测定和评价。
(实施例3)
除了使牵引比H/D=1.6以外,与实施例1同样地对多层容器进行固相成形,并进行测定和评价。
(比较例1)
除了使中间层为基材树脂以外,与实施例1同样地对多层容器进行固相成形,并进行测定和评价。
(比较例2)
除了使中间层为基材树脂,使片材的加热温度为158℃以外,与实施例1同样地对多层容器进行固相成形,并进行测定和评价。
(比较例3)
除了使中间层为基材树脂,使成形时的牵引比为1.6以外,与实施例1同样地对多层容器进行固相成形,在该条件下不能进行固相成形,不进行等温结晶化带来的发热量、X射线衍射强度比I/I0的测定以及容器的评价。
(比较例4)
除了使片材的加热温度为130℃以外,与实施例1同样地对多层容器进行成形,并进行测定和评价。
(比较例5)
除了使中间层为基材树脂,使片材的加热温度为130℃以外,与实施例1同样地对多层容器进行成形,并进行测定和评价。
(比较例6)
除了使片材的加热温度为180℃,使牵引比H/D=0.8以外,与实施例1同样地对多层容器进行成形,并进行测定和评价。
表1示出了从降温结晶化起始温度162℃(Tc2)减去成形温度(T)的温度差(Tc2-T)的证实、等温结晶化带来的发热量、X射线衍射强度比I/I0的测定结果,表2示出了多层容器的评价结果。
由表2可知,通过本发明,能够获得固相成形时的加工性优异的、具有由吸氧性屏蔽树脂组合物形成的中间层的多层容器,能够形成容器外观、机械特性优异的多层容器。
表2固相成形
Claims (1)
1.一种多层容器,该多层容器具有包含烯烃树脂的内外层和在前述内外层间的由吸氧性屏蔽树脂组合物形成的中间层,其中,
吸氧性屏蔽树脂组合物的降温结晶化峰值温度低于构成吸氧性屏蔽树脂组合物的氧屏蔽树脂,
氧屏蔽树脂是乙烯-乙烯醇共聚物树脂,
吸氧性屏蔽树脂组合物包含在氧屏蔽树脂中配合具有不饱和烯键的氧化性聚合物以及氧化催化剂得到的树脂,
前述多层容器是在低于氧屏蔽树脂的降温结晶化起始温度1~15℃的温度范围内进行固相成形而成的,
在容器体部的热分析中,以100℃/分钟的速度从30℃升温至130℃并保持30分钟时的由等温结晶化带来的发热量低于0.5J/g,
至少在容器体部测得的X射线衍射谱去除空气散射后的、2θ=14.5°的峰值强度I与2θ=15.5°的峰值强度I0的强度比I/I0为4以上,
所述降温结晶化起始温度是利用DSC差示扫描量热计求得的。
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