JPWO2007083598A1 - 多層ボトル - Google Patents
多層ボトル Download PDFInfo
- Publication number
- JPWO2007083598A1 JPWO2007083598A1 JP2007554880A JP2007554880A JPWO2007083598A1 JP WO2007083598 A1 JPWO2007083598 A1 JP WO2007083598A1 JP 2007554880 A JP2007554880 A JP 2007554880A JP 2007554880 A JP2007554880 A JP 2007554880A JP WO2007083598 A1 JPWO2007083598 A1 JP WO2007083598A1
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- weight
- layer
- multilayer bottle
- barrier layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002647 polyamide Polymers 0.000 claims abstract description 130
- 239000004952 Polyamide Substances 0.000 claims abstract description 129
- 230000004888 barrier function Effects 0.000 claims abstract description 104
- 229920000728 polyester Polymers 0.000 claims abstract description 40
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000004985 diamines Chemical class 0.000 claims abstract description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 10
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002009 diols Chemical class 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 25
- 239000000194 fatty acid Substances 0.000 claims description 25
- 229930195729 fatty acid Natural products 0.000 claims description 25
- 150000004665 fatty acids Chemical class 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 8
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 8
- 239000002216 antistatic agent Substances 0.000 claims description 8
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- FQLAJSQGBDYBAL-UHFFFAOYSA-N 3-(azepane-1-carbonyl)benzamide Chemical group NC(=O)C1=CC=CC(C(=O)N2CCCCCC2)=C1 FQLAJSQGBDYBAL-UHFFFAOYSA-N 0.000 claims description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229960002684 aminocaproic acid Drugs 0.000 claims description 2
- 230000032798 delamination Effects 0.000 abstract description 28
- 238000006068 polycondensation reaction Methods 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 121
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- -1 polyethylene terephthalate Polymers 0.000 description 37
- 238000010521 absorption reaction Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 26
- 239000007789 gas Substances 0.000 description 21
- 230000002087 whitening effect Effects 0.000 description 18
- 238000000465 moulding Methods 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 238000002347 injection Methods 0.000 description 14
- 239000007924 injection Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 11
- 238000000071 blow moulding Methods 0.000 description 10
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 241001122767 Theaceae Species 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 235000014171 carbonated beverage Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 235000021357 Behenic acid Nutrition 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 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 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229940116226 behenic acid Drugs 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000001470 diamides Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920000393 Nylon 6/6T Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 2
- 235000013405 beer Nutrition 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 2
- 229920000136 polysorbate Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
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- 230000002000 scavenging effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- XAUQWYHSQICPAZ-UHFFFAOYSA-N 10-amino-decanoic acid Chemical compound NCCCCCCCCCC(O)=O XAUQWYHSQICPAZ-UHFFFAOYSA-N 0.000 description 1
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- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- BDBZTOMUANOKRT-UHFFFAOYSA-N 4-[2-(4-aminocyclohexyl)propan-2-yl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1C(C)(C)C1CCC(N)CC1 BDBZTOMUANOKRT-UHFFFAOYSA-N 0.000 description 1
- OECUQWQIGXMPAN-UHFFFAOYSA-N 6-oxo-6-pyrrolidin-1-ylhexanamide Chemical compound NC(=O)CCCCC(=O)N1CCCC1 OECUQWQIGXMPAN-UHFFFAOYSA-N 0.000 description 1
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 description 1
- JXGAUFIBOJVEJJ-UHFFFAOYSA-N 9-(azepan-1-yl)-9-oxononanamide Chemical compound NC(=O)CCCCCCCC(=O)N1CCCCCC1 JXGAUFIBOJVEJJ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
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- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 description 1
- WPWNSTTVSOUHRP-UHFFFAOYSA-N [1-(aminomethyl)naphthalen-2-yl]methanamine Chemical group C1=CC=CC2=C(CN)C(CN)=CC=C21 WPWNSTTVSOUHRP-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical group NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910000316 alkaline earth metal phosphate Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
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- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
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Abstract
Description
一方、多層ボトル中のポリアミド(B)の吸水量を高めるために、ボトル成形時に水分率の高いポリアミドMXD6を使用すると、成形中に加えられる熱によって水分が蒸発し発泡し、商品にならないという問題があった。通常、成形時には発泡を抑制するために、ポリアミド(B)は数百ppm程度以下に乾燥させて用いられる。
そこで、ポリアミド(B)よりも飽和水分率の高いポリアミド(C)をブレンドすることによって、ボトル成形後のバリア層の吸水率が高まり、柔軟性、層間の密着性が改善され、耐層間剥離性能が良好になることを見出した。
(1)ポリアミド(B)あるいはポリアミド(C)の単層フィルムを面積倍率で8〜13倍に二軸延伸する(熱固定は無し)。
(2)得られた延伸フィルムを23℃、50%RH、1atmの条件下で4週間保存する。
(3)保存後の延伸フィルムの水分率を、カールフィッシャー法により、235℃、30分の条件で測定し、その測定値を飽和水分率とする。
脂肪族ポリアミド(ポリアミド(C1))として例えば、ポリ(カプロラクタム)としても知られるポリ(6−アミノヘキサン酸)(PA−6)、ポリ(ヘキサメチレンアジパミド)(PA−6,6)、ポリ(7−アミノヘプタン酸)(PA−7)、ポリ(10−アミノデカン酸)(PA−10)、ポリ(11−アミノウンデカン酸)(PA−11)、ポリ(ヘキサメチレンセバカミド)(PA−6,10)、ポリ(ヘキサメチレンアゼラミド)(PA−6,9)、ポリ(テトラメチレンアジパミド)(PA−4,6)といったホモポリマー、カプロラクタム/ヘキサメチレンアジパミドコポリマー(PA−6,6/6))、ヘキサメチレンアジパミド/カプロラクタムコポリマー(PA−6/6,6)などなどの脂肪族ポリアミドを例示できる。これらの中でも、PA−6、PA−6,6が特に好ましく使用できる。ポリアミド(C1)の数平均分子量は、10000〜30000が好ましく、より好ましくは、12500〜25000である。
10000〜30000である。
(1)あらかじめ乾燥済みのペレットを23℃、50%RH、1atmの条件下で24時間保存する。
(2)保存前後のペレットの水分率を、カールフィッシャー法により、235℃、30分の条件で測定し、吸水後の水分率と吸水前の水分率を(T)1/2(Tは保存時間=24時間)で除した値を吸水速度とした。
なお、(T)1/2で除するのは、吸水開始直後の吸水速度は、徐々に遅くなり刻々と変化するため、その影響を平均化するためである。ただし、Tで除しても、その値は異なるが、実質的な意味は変わらない。
一方、ポリアミド(C)の23℃、50%RH、1atmでの吸水速度は250〜1500ppm/hr1/2であることが好ましく、より好ましくは300〜1300ppm/hr1/2、特に好ましくは500〜1200ppm/hr1/2である。ポリアミド(C)の吸水速度が上記範囲であると、ボトルをブロー成形後にすみやかに吸水したポリアミド(C)からポリアミド(B)へ水分がすみやかに供給され、ポリアミド(B)が柔軟になり、ボトルに衝撃が加わったときのバリア層の最外層および最内層に対する追従性が良好となることから、耐層間剥離性への効果に優れたものとなる。
なお、多層プリフォームを製造する方法は、上記方法だけに限定されるものではない。
ASTM D2463−95 ProcedureBに基づき、容器の落下試験により層間剥離高さを求めて評価した。層間剥離高さが高いほど、耐層間剥離性が良好であることを示す。まず、多層容器に水を満たしキャップをした後、多層容器を落下させ層間剥離の有無を目視で判定した。多層容器は底部が床に接触するように垂直落下させた。落下高さを15cm間隔で増減させながらテストを繰り返した。テストボトル数は30本。
23℃、ボトル内部100%RH、ボトル外部50%RHの雰囲気下にてASTM D3985に準じてボトルの酸素透過率を測定した。測定は、モダンコントロールズ社製、OX−TRAN 2/61を使用した。値が低いほど酸素バリア性が良好であることを示す。
また、ボトルバリア層の酸素透過係数(OTR)は、ボトルを丁寧に解体しバリア層のみを取り出し、60%RH、23℃の条件で測定した。測定には、モダンコントロールズ社製、OX−TRAN 2/61を使用した。
ボトル(内容積:500ml)に4G.V.(ガスボリューム:ボトル内容積の4倍量(標準状態))の二酸化炭素を含む炭酸水を充填した。これを23℃、50%RHの雰囲気下に保存し、ボトル内部圧力の時間的変化を継続して測定した。ボトル内部の二酸化炭素は時間とともにボトル壁面から透過するので圧力は時間とともに減少する。初期の圧力を100%とし、90%まで減少するまでの日数をシェルフライフとしてボトルの二酸化炭素バリア性を評価した。値が大きいほど二酸化炭素バリア性が良好であることを示す。
23℃、50%RH、1atmの条件でポリアミドの延伸フィルム(面積倍率10倍)を4週間保存し、平沼産業(株)製AQ−2000を用い、カールフィッシャー法により水分率を測定した。測定値をもって飽和水分率とした。測定温度は235℃、測定時間は30minであった。また、ボトル丁寧に解体して取り出したバリア層の飽和水分率を同様に測定した。
下記の条件により、ポリエステル(A)層/バリア層/ポリエステル(A)層からなる3層プリフォーム(27g)を射出成形し、冷却後、プリフォームを加熱し2軸延伸ブロー成形を行い、多層ボトルを得た。
ポリエチレンテレフタレート(日本ユニペット製 RT543C)
固有粘度:0.75dl/g(フェノール/テトラクロロエタン=6/4(重量比)の混合溶媒を使用し、30℃で測定)
バリア層
ポリアミド(B):ポリメタキシリレンアジパミド(三菱ガス化学株式会社製 MXナイロンS6007)95重量%
ポリアミド(C):ナイロン6(宇部興産株式会社製 1015B)5重量%
全長95mm
外径22mm
肉厚4.2mm
3層プリフォームの製造には、名機製作所(株)製の射出成形機(型式:M200、4個取り)を使用した。
スキン側射出シリンダー温度:280℃
コア側射出シリンダー温度 :250℃
金型内樹脂流路温度 :280℃
金型冷却水温度 :15℃
プリフォーム中のバリア層樹脂の割合:5重量%
全長223mm
外径65mm
内容積500ml
底部形状:シャンパンタイプ
胴部ディンプル:無し
2軸延伸ブロー成形はフロンティア社製ブロー成形機(型式:EFB1000ET)を使用した。
プリフォーム加熱温度:103℃
延伸ロッド用圧力:0.5MPa
一次ブロー圧力:1.0MPa
二次ブロー圧力:2.5MPa
一次ブロー遅延時間:0.35sec
一次ブロー時間:0.28sec
二次ブロー時間:2.0sec
ブロー排気時間:0.6sec
金型温度:30℃
バリア層組成を表1に記載のものに変更した以外は実施例1と同様にして多層ボトルを得た。多層ボトルの評価結果を第1表に示す。
(1)S6007:ポリメタキシリレンアジパミド(三菱ガス化学株式会社製 MXナイロンS6007 固相重合品)
数平均分子量:23500
相対粘度:2.70(樹脂1g/96%硫酸100ml、測定温度25℃、以下同様)
飽和水分率:3.4重量%
吸水速度:280ppm/h1/2
(2)S6121:ポリメタキシリレンアジパミド(三菱ガス化学株式会社製 MXナイロンS6121 固相重合品)
数平均分子量:40000
相対粘度:3.94
飽和水分率:3.4重量%
吸水速度:270ppm/h1/2)
(3)1015B:ナイロン6(宇部興産株式会社製 グレード:1015B)
数平均分子量:15000
飽和水分率:7.1重量%
吸水速度:1090ppm/h1/2
(4)1020B:ナイロン6(宇部興産株式会社製 グレード:1020B)
数平均分子量:20000
飽和水分率:7.1重量%
吸水速度:1070ppm/h1/2
(5)2020B:ナイロン66(宇部興産株式会社製 グレード:2020B)
数平均分子量:20000
飽和水分率:6.3重量%
吸水速度:1000ppm/h1/2
(6)X21F07:ナイロン6I/6T(三菱エンジニアリングプラスチックス社製 グレード:ノバミッドX21F07)
飽和水分率:11重量%
吸水速度:910ppm/h1/2
(7)3024:ナイロン12(宇部興産株式会社製 グレード:3024NUX)
飽和水分率:1.2重量%
吸水速度:100ppm/h1/2
Claims (15)
- ポリエステル(A)により主として構成された最外層および最内層、ならびに、該最外層と最内層との間に位置する少なくとも1層のバリア層を含む多層ボトルであって、
該ポリエステル(A)がテレフタル酸を80モル%以上含むジカルボン酸成分およびエチレングリコールを80モル%以上含むジオール成分を重合して得た熱可塑性ポリエステル樹脂であり、かつ、
該バリア層がメタキシリレンジアミンを70モル%以上含むジアミン成分と、炭素数4〜20のα,ω−直鎖脂肪族ジカルボン酸を70モル%以上含むジカルボン酸成分とを重縮合して得られるポリアミド(B)と、23℃、50%RH、1atmで測定した飽和水分率が、ポリアミド(B)よりも高いポリアミド(C)を含み、かつ、ポリアミド(C)の重量が、バリア層重量に対して20重量%以下である多層ボトル。 - 前記ポリアミド(B)の飽和水分率が2.5〜5重量%である請求項1記載の多層ボトル。
- 前記ポリアミド(C)の飽和水分率が3〜13重量%である請求項1記載の多層ボトル。
- ポリアミド(C)が、バリア層重量に対して1〜20重量%含まれる請求項1記載の多層ボトル。
- 前記ポリアミド(C)が、脂肪族ポリアミドおよび非晶質半芳香族ポリアミドから選ばれる少なくとも1種のポリアミドである請求項1記載の多層ボトル。
- 前記ポリアミド(C)が、脂肪族ポリアミドおよび非晶質半芳香族ポリアミドの組み合わせである請求項5記載の多層ボトル。
- 前記脂肪族ポリアミドがポリ(6−アミノヘキサン酸)及び/又はポリ(ヘキサメチレンアジパミド)であり、前記非晶質半芳香族ポリアミドがヘキサメチレンイソフタラミド/ヘキサメチレンテレフタラミドコポリマーである請求項5記載の多層ボトル。
- 脂肪族ポリアミド1重量部に対して、非晶質半芳香族ポリアミドを0.25〜4重量部含む請求項5記載の多層ボトル。
- 前記バリア層が、バリア層の合計量100重量部に対して、炭素数18〜50の脂肪酸金属塩を0.005〜1.0重量部含有する請求項1記載の多層ボトル。
- 前記バリア層が、帯電防止剤を1〜1000ppm含有する請求項1記載の多層ボトル。
- 前記ポリアミド(B)の数平均分子量が18000〜43500である請求項1記載の多層ボトル。
- ポリエステル(A)層/バリア層/ポリエステル(A)層の3層構造を有する請求項1に記載の多層ボトル。
- ポリエステル(A)層/バリア層/ポリエステル(A)層/バリア層/ポリエステル(A)層の5層構造を有する請求項1に記載の多層ボトル。
- 多層ボトル総重量に対する前記バリア層の重量比が1〜20重量%である請求項1に記載の多層ボトル。
- 前記バリア層が、ポリアミド(B)とポリアミド(C)のドライブレンドから形成された層である請求項1に記載の多層ボトル。
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KR101330500B1 (ko) | 2013-11-15 |
US20100233401A1 (en) | 2010-09-16 |
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WO2007083598A1 (ja) | 2007-07-26 |
EP1974901B1 (en) | 2011-09-21 |
RU2415015C2 (ru) | 2011-03-27 |
RU2008133600A (ru) | 2010-02-27 |
CN101360601B (zh) | 2012-05-09 |
EP1974901A1 (en) | 2008-10-01 |
KR20080083655A (ko) | 2008-09-18 |
UA96437C2 (ru) | 2011-11-10 |
EP1974901A4 (en) | 2009-12-16 |
US8778470B2 (en) | 2014-07-15 |
JP5104318B2 (ja) | 2012-12-19 |
ATE525295T1 (de) | 2011-10-15 |
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