JP4720102B2 - 多層容器 - Google Patents
多層容器 Download PDFInfo
- Publication number
- JP4720102B2 JP4720102B2 JP2004131597A JP2004131597A JP4720102B2 JP 4720102 B2 JP4720102 B2 JP 4720102B2 JP 2004131597 A JP2004131597 A JP 2004131597A JP 2004131597 A JP2004131597 A JP 2004131597A JP 4720102 B2 JP4720102 B2 JP 4720102B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- resin
- weight
- multilayer container
- 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.)
- Expired - Fee Related
Links
- 229920006122 polyamide resin Polymers 0.000 claims description 99
- 229920005989 resin Polymers 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 28
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 230000008961 swelling Effects 0.000 claims description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 15
- 150000004985 diamines Chemical class 0.000 claims description 15
- 230000009477 glass transition Effects 0.000 claims description 13
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 11
- 239000004677 Nylon Substances 0.000 claims description 10
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 10
- 239000001361 adipic acid Substances 0.000 claims description 10
- 235000011037 adipic acid Nutrition 0.000 claims description 10
- 229920001778 nylon Polymers 0.000 claims description 10
- 150000002009 diols Chemical class 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 111
- -1 polyethylene terephthalate Polymers 0.000 description 39
- 229920001225 polyester resin Polymers 0.000 description 31
- 239000004645 polyester resin Substances 0.000 description 31
- 230000004888 barrier function Effects 0.000 description 22
- 150000003839 salts Chemical class 0.000 description 22
- 230000032798 delamination Effects 0.000 description 21
- 235000014113 dietary fatty acids Nutrition 0.000 description 21
- 239000000194 fatty acid Substances 0.000 description 21
- 229930195729 fatty acid Natural products 0.000 description 21
- 150000004665 fatty acids Chemical class 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- 239000007789 gas Substances 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 230000002087 whitening effect Effects 0.000 description 18
- 150000003863 ammonium salts Chemical class 0.000 description 17
- 238000002347 injection Methods 0.000 description 17
- 239000007924 injection Substances 0.000 description 17
- 239000002184 metal Substances 0.000 description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 10
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 9
- 238000000071 blow moulding Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000004898 kneading Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004952 Polyamide Substances 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 229920002647 polyamide Polymers 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 235000021357 Behenic acid Nutrition 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
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229940116226 behenic acid Drugs 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- 235000014171 carbonated beverage Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000013461 design Methods 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
- 125000003827 glycol group Chemical group 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000005259 measurement Methods 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
- 230000035699 permeability Effects 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 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
- SWTNRXKFJNGFRF-UHFFFAOYSA-N 14-aminotetradecanoic acid Chemical compound NCCCCCCCCCCCCCC(O)=O SWTNRXKFJNGFRF-UHFFFAOYSA-N 0.000 description 2
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 125000000217 alkyl group Chemical group 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
- 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
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 2
- 235000019993 champagne Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- QQJDHWMADUVRDL-UHFFFAOYSA-N didodecyl(dimethyl)azanium Chemical class CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC QQJDHWMADUVRDL-UHFFFAOYSA-N 0.000 description 2
- SWSFKKWJEHRFFP-UHFFFAOYSA-N dihexadecyl(dimethyl)azanium Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCC SWSFKKWJEHRFFP-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 2
- CJBMLKNLJXFFGD-UHFFFAOYSA-N dimethyl-di(tetradecyl)azanium Chemical class CCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCC CJBMLKNLJXFFGD-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical class CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000014347 soups Nutrition 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 2
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical class CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 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 compound 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
- XAUQWYHSQICPAZ-UHFFFAOYSA-N 10-amino-decanoic acid Chemical compound NCCCCCCCCCC(O)=O XAUQWYHSQICPAZ-UHFFFAOYSA-N 0.000 description 1
- QJGFZBNNVXTCLL-UHFFFAOYSA-N 16-aminohexadecanoic acid Chemical compound NCCCCCCCCCCCCCCCC(O)=O QJGFZBNNVXTCLL-UHFFFAOYSA-N 0.000 description 1
- ACQSOZZSYSEKHC-UHFFFAOYSA-N 18-aminooctadecanoic acid Chemical compound NCCCCCCCCCCCCCCCCCC(O)=O ACQSOZZSYSEKHC-UHFFFAOYSA-N 0.000 description 1
- 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 compound 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
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- UQXNEWQGGVUVQA-UHFFFAOYSA-N 8-aminooctanoic acid Chemical compound NCCCCCCCC(O)=O UQXNEWQGGVUVQA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- QFCZZHLPPALBGT-UHFFFAOYSA-N CCCCCCCCC(=C(C)N(C)C)C Chemical class CCCCCCCCC(=C(C)N(C)C)C QFCZZHLPPALBGT-UHFFFAOYSA-N 0.000 description 1
- 206010011416 Croup infectious Diseases 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical class CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- IIHKGAZZIDXOAT-UHFFFAOYSA-N NCC12CCCCC2(CCCC1)CN Chemical compound NCC12CCCCC2(CCCC1)CN IIHKGAZZIDXOAT-UHFFFAOYSA-N 0.000 description 1
- DHJQXXSAGLAJOR-UHFFFAOYSA-M NCCCC(=O)[O-].C(CCCCCCCCCCC)[N+](CCCC)(CCCCCCCCCCCC)CCCCCCCCCCCC Chemical compound NCCCC(=O)[O-].C(CCCCCCCCCCC)[N+](CCCC)(CCCCCCCCCCCC)CCCCCCCCCCCC DHJQXXSAGLAJOR-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241001312297 Selar Species 0.000 description 1
- 229920003365 Selar® Polymers 0.000 description 1
- 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 compound 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
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
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- 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 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- HNTQYVHJXDXWDT-UHFFFAOYSA-N tributyl(hexadecyl)azanium Chemical class CCCCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC HNTQYVHJXDXWDT-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
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- B29C2949/00—Indexing scheme relating to blow-moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
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- B29C2949/3038—Preforms or parisons made of several components having components being injected having two or more components being injected having three or more components being injected having more than three components being injected
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Description
Sa<Sd<Sc (1)
(式中、Saは熱可塑性ポリエステル樹脂Aの溶解度指数、Scはポリアミド樹脂Cの溶解度指数、Sdはポリアミド樹脂Dの溶解度指数であり、各溶解度指数は、Small法により計算される。)を満たすポリアミド樹脂Dを99.5/0.5〜80/20の重量比で含有する混合樹脂Bにより主として構成され、該ポリアミド樹脂Dのガラス転移温度が該ポリアミド樹脂Cのガラス転移温度より高く、かつ、130℃以下であることを特徴とする多層容器を提供する。
さらに、本発明は、スキン側射出シリンダーおよびコア側射出シリンダーを有する射出成形機を用いて、最外層、最内層および該最外層と該最内層との間に位置する少なくとも1層の中間層からなる多層容器を製造する方法であって、該スキン側射出シリンダーから、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Aを射出して該最内層および該最外層を形成し、該コア側射出シリンダーから、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およびアジピン酸を70モル%以上含むジカルボン酸成分を重合して得たポリアミド樹脂Cと下記式(1):
Sa<Sd<Sc (1)
(式中、Saは熱可塑性ポリエステル樹脂Aの溶解度指数、Scはポリアミド樹脂Cの溶解度指数、Sdはポリアミド樹脂Dの溶解度指数であり、各溶解度指数は、Small法により計算される。)
を満たすポリアミド樹脂Dを99.5/0.5〜80/20の重量比で含有する混合樹脂Bを射出して該中間層の少なくとも1層を形成して多層パリソンを製造する工程を含むことを特徴とする多層容器の製造方法を提供する。
ポリアミド樹脂Cは、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およびアジピン酸を70モル%以上含むジカルボン酸成分を重合して得られる。ジアミン成分中のメタキシリレンジアミンが70モル%以上であると、優れたガスバリア性が維持できる。ジカルボン酸成分中のアジピン酸が70モル%以上であると、ガスバリア性の低下や結晶性の低下を防止することができる。
また、ポリアミド樹脂Cは、製造時に分子量調節剤として使用される少量のモノアミン、モノカルボン酸を含んでいても良い。
溶融重縮合法としては、例えばメタキシリレンジアミンとアジピン酸からなるナイロン塩を水の存在下に、加圧下で昇温し、加えた水および縮合水を除きながら溶融状態で重合させる方法がある。また、メタキシリレンジアミンを溶融状態のアジピン酸に直接加えて、重縮合する方法によっても製造される。この場合、反応系を均一な液状状態に保つために、メタキシリレンジアミンをアジピン酸に連続的に加え、その間、反応温度が生成するオリゴアミドおよびポリアミドの融点よりも下回らないように反応系を昇温しつつ、重縮合が進められる。
Sa<Sd<Sc (1)
(式中、Saは熱可塑性ポリエステル樹脂Aの溶解度指数、Scはポリアミド樹脂Cの溶解度指数、Sdはポリアミド樹脂Dの溶解度指数である。)
溶解度指数はSmall法により計算される(日本接着協会誌、Vol.22、No.10、p.51(1986)参照)。
ポリアミド樹脂Dは、最内外層(ポリエステル樹脂A層)と中間層(ガスバリア層)の親和性を高めるためSdの値がSaとScの間にあることが重要である。Sdがこの範囲を超えると、最内層および最外層を構成するポリエステル樹脂Aと中間層を構成する混合樹脂Bの親和性が低くなり、層間の密着性が低下し層間剥離性防止に好ましくない。
このようなポリアミド樹脂Dは、Small法による計算から求めたポリエステル樹脂Aとポリアミド樹脂Cの溶解度指数から、上記式(1)を満たすようにポリマー中の骨格セグメントを設計することにより得ることができる。
ジエステル化合物は、炭素数8〜30の脂肪酸と炭素数2〜10のジオールから得られる。脂肪酸の炭素数が8以上、ジオールの炭素数が2以上であると白化防止効果が期待できる。また、脂肪酸の炭素数が30以下、ジオールの炭素数が10以下であると混合樹脂B中への均一分散が良好となる。脂肪酸は側鎖や二重結合があってもよいが、直鎖飽和脂肪酸が好ましい。
(1)ポリエチレンテレフタレートの固有粘度[η]: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。測定温度30℃。
(2)ポリアミドMXD6の相対粘度[ηrel]:樹脂1g/96%硫酸100ml、測定温度25℃。
(3)溶解度指数の算出:Small法により計算(日本接着協会誌、Vol.22、No.10、p.51(1986)参照。)。
(4)ガラス転移温度:島津製作所製の熱流束示差走査熱量計(型式:DSC−50)により測定。昇温速度10℃/min
(5)曇価:JIS K−7105、ASTM D1003に準じて、日本電色工業社製の曇価測定装置(型式:COH−300A)により測定した。
(6)層間剥離性:容器の落下試験により評価した。
落下試験方法:多層容器に水を満たしキャップをした後、24時間静置した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75cm。50本落下させたときの層間剥離したボトルの本数で層間剥離性を評価。
(7)多層容器の酸素透過率: 23℃、多層容器内部の相対湿度100%、外部の相対湿度50%の雰囲気下にてASTM D3985に準じて測定した。測定は、モダンコントロールズ社製、OX-TRAN 10/50Aを使用した。
3層パリソン形状:全長95mm、外径22mm、肉厚4.2mm。なお、3層パリソンの製造には、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。
3層パリソン成形条件
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 :260℃
金型内樹脂流路温度 :280℃
金型冷却水温度 :15℃
パリソン中の混合樹脂Bの割合:8重量%
多層容器形状:全長223mm、外径65mm、内容積500ml、ポリエステル樹脂A層/混合樹脂B層/ポリエステル樹脂A層=0.28mm/0.056mm/0.10mm、底部形状はシャンパンタイプ。なお、2軸延伸ブロー成形はブロー成形機(クルップ コーポプラスト(KRUPP CORPOPLAST)社製、型式:LB−01)を使用した。
2軸延伸ブロー成形条件
パリソン加熱温度:100℃
ブロー圧力 :2.7MPa
下記の材料を使用し、3層構成の多層容器を成形した。
最内層および最外層
ポリエステル樹脂A:固有粘度が0.75のポリエチレンテレフタレート(日本ユニペット製 RT543C)。溶解度指数は11.1。
中間層
混合樹脂B:ポリアミド樹脂Cとポリアミド樹脂Dの90/10(重量比)ドライブレンド
ポリアミド樹脂C:相対粘度が2.70のポリアミドMXD6(三菱ガス化学製 MXナイロン S6007)。溶解度指数は13.0、ガラス転移温度は80℃。
ポリアミド樹脂D:ナイロン6IT(三井・デュポンポリケミカル(株)製 Selar PA 3426)。溶解度指数は12.6、ガラス転移温度は125℃。
層間剥離性の評価結果を表1に示す。
ポリアミド樹脂Cとポリアミド樹脂Dを95/5(重量比)で混合した以外は実施例1と同様にして3層構成の多層容器を成形した。得られた3層容器の層間剥離性評価の結果を表1に示す。
ポリアミド樹脂Cとポリアミド樹脂Dを99/1(重量比)で混合した以外は実施例1と同様にして3層構成の多層容器を成形した。得られた3層容器の層間剥離性の評価結果を表1に示す。
ポリアミド樹脂Dは使用せず、中間層をポリアミド樹脂C単独で構成した以外は実施例1と同様にして3層構成の多層容器を成形した。得られた3層容器の層間剥離性の評価結果を表1に示す。
相対粘度が2.70のポリアミドMXD6(三菱ガス化学製 MXナイロン S6007)と有機膨潤化剤で処理した層状珪酸塩(クニミネ工業製「クニピア」、有機膨潤化剤としてオクタデシルアンモニウムを30重量%含有する層状珪酸塩)を97/3(重量比)でドライブレンドした。得られた混合物を、逆エレメントによる滞留部を有するスクリューを設置した、シリンダー径20mmの同方向回転型2軸押出機に6kg/hrの速度で供給し、シリンダー温度270℃の条件で溶融混練し、押出機ヘッドからストランド状に押し出し、冷却後、ペレット化した。これを、ポリアミド樹脂Cとして使用した以外は実施例2と同様にして3層構成の多層容器を成形した。得られた3層容器の酸素透過率、層間剥離性の評価結果を表2に示す。
相対粘度が2.70のポリアミドMXD6(三菱ガス化学製 MXナイロン S6007)とステアリン酸コバルトを99.5/0.5(重量比)でドライブレンドした後、2軸押出機でシリンダー温度270℃の条件で溶融混練し、押出機ヘッドからストランド状に押し出し、冷却後、ペレット化した。これをポリアミド樹脂Cとして使用した以外は実施例2と同様にして3層構成の多層容器を成形した。得られた3層容器の酸素透過率、層間剥離性の評価結果を表2に示す。
比較例1で成形した3層容器の酸素透過率を測定した。結果を表2に示す。
ポリアミド樹脂Cとポリアミド樹脂Dの混合時に白化防止剤としてモンタン酸ナトリウム塩(商品名ホスタモントNaV101、クラリアントジャパン(株)製)をポリアミド樹脂の合計量100重量部に対して0.2重量部添加し、また、容器の形状を下記のように変更した以外は実施例1と同様にして3層構成の多層容器を成形した。
多層容器形状:全長170mm、容積330ml、首径25mm、胴径66mm、ポリエステル樹脂A層/混合樹脂B層/ポリエステル樹脂A層=0.33mm/0.066mm/0.12mm、底部形状はシャンパンタイプ。
得られた3層容器の層間剥離性の評価結果、および、水を330ml充填した3層容器を40℃/80%RH下で6ヶ月間保存した後、容器の低延伸倍率部分(延伸倍率1〜1.5倍)より取り出した中間層の曇価を測定した結果を表3に示す。
白化防止剤をエチレンビスステアリルアミド(商品名アルフローH−50T、日本油脂(株)製)に変更した以外は実施例6と同様にして3層構成の多層容器を成形した。
実施例6と同様にして得た評価結果を表3に示す。
ポリアミド樹脂Dは使用せず、中間層をポリアミド樹脂C単独で使用した以外は実施例6と同様にして3層構成の多層容器を成形した。実施例6と同様にして得た評価結果を表3に示す。
Claims (6)
- 最外層、最内層および最外層と最内層との間に位置する少なくとも1層の中間層からなる多層容器であって、
該最外層および最内層が、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Aにより主として構成され、
該中間層の少なくとも1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およびアジピン酸を70モル%以上含むジカルボン酸成分を重合して得たポリアミド樹脂Cと下記式(1):
Sa<Sd<Sc (1)
(式中、Saは熱可塑性ポリエステル樹脂Aの溶解度指数、Scはポリアミド樹脂Cの溶解度指数、Sdはポリアミド樹脂Dの溶解度指数であり、各溶解度指数は、Small法により計算される。)
を満たすナイロン6IT及びナイロン6I6Tから選ばれるポリアミド樹脂Dを99/1〜85/15の重量比で含有する混合樹脂Bにより主として構成され、該ポリアミド樹脂Dのガラス転移温度が該ポリアミド樹脂Cのガラス転移温度より高く、かつ、130℃以下であることを特徴とする多層容器。 - 前記ポリアミド樹脂C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およびアジピン酸を70モル%以上含むジカルボン酸成分とを溶融重縮合して得られたポリアミド樹脂を、更に固相重合することにより得られた固相重合ポリアミド樹脂であることを特徴とする請求項1記載の多層容器。
- 前記混合樹脂Bが、さらに、有機膨潤化剤で処理した層状珪酸塩をポリアミド樹脂Cとポリアミド樹脂Dの合計量の0.5〜8重量%含有することを特徴とする請求項1又は2に記載の多層容器。
- 前記混合樹脂Bが、さらに、元素周期律表第VIII族の遷移金属、マンガン、銅及び亜鉛からなる群より選択された一種以上の金属元素をポリアミド樹脂Cとポリアミド樹脂Dの合計量の0.01〜0.10重量%含有することを特徴とする請求項1〜3のいずれかに記載の多層容器。
- 前記混合樹脂Bが、さらに、白化防止剤をポリアミド樹脂Cおよびポリアミド樹脂Dの合計量100重量部に対して0.005〜1.0重量部含有することを特徴とする請求項1〜4のいずれかに記載の多層容器。
- 多層容器総重量に対する前記混合樹脂Bの重量比が1〜20重量%であることを特徴とする請求項1〜5のいずれかに記載の多層容器。
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JPH1086291A (ja) * | 1995-12-27 | 1998-04-07 | Mitsubishi Gas Chem Co Inc | 脱酸素性多層体及びこれよりなる包装容器 |
JP2000297245A (ja) * | 1999-04-14 | 2000-10-24 | Shin Etsu Polymer Co Ltd | プラスチック被覆用導電性組成物 |
WO2001015900A1 (fr) * | 1999-08-27 | 2001-03-08 | Toray Industries, Inc. | Couche mince stratifiee et couche mince a depot par evporation l'utilisant |
JP2001199024A (ja) * | 2000-01-21 | 2001-07-24 | Mitsubishi Gas Chem Co Inc | 多層容器 |
JP2001354222A (ja) * | 2000-06-08 | 2001-12-25 | Mitsubishi Gas Chem Co Inc | 多層容器 |
JP2002322350A (ja) * | 2001-04-24 | 2002-11-08 | Mitsui Chemicals Inc | ポリエステル組成物製中空成形体およびその製造方法 |
JP2003012944A (ja) * | 2001-04-26 | 2003-01-15 | Toyo Seikan Kaisha Ltd | 成形性及びガス遮断性に優れた樹脂組成物及び包装材料 |
JP2003020023A (ja) * | 2001-07-03 | 2003-01-21 | Toyo Seikan Kaisha Ltd | プラスチック多層容器 |
JP2004352361A (ja) * | 2003-05-06 | 2004-12-16 | Mitsubishi Gas Chem Co Inc | 多層容器 |
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