JP4561965B2 - Multi-layer container - Google Patents
Multi-layer container Download PDFInfo
- Publication number
- JP4561965B2 JP4561965B2 JP2004131598A JP2004131598A JP4561965B2 JP 4561965 B2 JP4561965 B2 JP 4561965B2 JP 2004131598 A JP2004131598 A JP 2004131598A JP 2004131598 A JP2004131598 A JP 2004131598A JP 4561965 B2 JP4561965 B2 JP 4561965B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polyamide resin
- layer
- multilayer container
- mol
- 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 86
- 229920005989 resin Polymers 0.000 claims description 62
- 239000011347 resin Substances 0.000 claims description 62
- 229920001225 polyester resin Polymers 0.000 claims description 35
- 239000004645 polyester resin Substances 0.000 claims description 35
- 238000002347 injection Methods 0.000 claims description 28
- 239000007924 injection Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 17
- 150000004985 diamines Chemical class 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 11
- 235000011037 adipic acid Nutrition 0.000 claims description 11
- 239000001361 adipic acid Substances 0.000 claims description 11
- 238000000071 blow moulding Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- 150000002009 diols Chemical class 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- 238000001746 injection moulding Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 2
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 114
- -1 polyethylene terephthalate Polymers 0.000 description 30
- 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
- 230000004888 barrier function Effects 0.000 description 18
- 230000002087 whitening effect Effects 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 230000032798 delamination Effects 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004952 Polyamide Substances 0.000 description 8
- 229920002647 polyamide Polymers 0.000 description 8
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 7
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 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
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 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
- 239000000203 mixture Substances 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
- 239000002253 acid Substances 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
- 239000006185 dispersion Substances 0.000 description 3
- 238000005259 measurement 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
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000012360 testing method 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
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-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
- 239000004677 Nylon Substances 0.000 description 2
- 229920002302 Nylon 6,6 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
- 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
- 239000003054 catalyst Substances 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
- 150000001875 compounds Chemical class 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000008569 process Effects 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
- 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 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
- 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
- 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
- 206010011416 Croup infectious Diseases 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
- 229920000577 Nylon 6/66 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000008271 cosmetic emulsion Substances 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 235000015071 dressings Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- PFBWBEXCUGKYKO-UHFFFAOYSA-N ethene;n-octadecyloctadecan-1-amine Chemical compound C=C.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC PFBWBEXCUGKYKO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 235000021056 liquid food Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000019992 sake Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 235000020083 shōchū Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- 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
- B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
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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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
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- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Description
本発明は多層容器の層間剥離防止に係る発明であり、詳しくは多層容器の輸送時、または落下時に衝撃を受けた際の最内層および最外層と中間層との間の層間密着性を改良して多層容器の層間剥離を防止するとともに、凹凸部、屈曲部の少ない形状にしなくても層間剥離を回避することができ、デザイン自由度が大きい多層容器に関するものである。 The present invention relates to the prevention of delamination of multilayer containers, and more specifically, improves the interlayer adhesion between the innermost layer and the outermost layer when the multilayer container is subjected to an impact during transportation or when dropped. In addition, the present invention relates to a multilayer container that can prevent delamination of the multi-layer container and can avoid delamination without having a shape with few concavo-convex parts and bent parts, and has a high degree of design freedom.
現在、ポリエチレンテレフタレート（ＰＥＴ）等のポリエステルを主体とするプラスチック容器（ボトルなど）がお茶、果汁飲料、炭酸飲料等に広く使用されている。また、プラスチック容器の中で、小型プラスチックボトルの占める割合が年々大きくなっている。ボトルは小型化するに従い単位体積当たりの表面積の割合が大きくなるため、ボトルを小型化した場合、内容物の賞味期限は短くなる傾向にある。また、近年、酸素や光の影響を受けやすいビールのプラスチックボトルでの販売やプラスチックボトル入りお茶のホット販売が行なわれ、プラスチック容器の利用範囲が広がる中、プラスチック容器に対するガスバリア性の更なる向上が要求されている。 Currently, plastic containers (such as bottles) mainly composed of polyester such as polyethylene terephthalate (PET) are widely used for tea, fruit juice drinks, carbonated drinks and the like. The proportion of small plastic bottles in plastic containers is increasing year by year. Since the ratio of the surface area per unit volume increases as the bottle becomes smaller, the shelf life of the contents tends to be shorter when the bottle is made smaller. In recent years, beer plastic bottles, which are easily affected by oxygen and light, and hot sale of plastic bottled tea have been sold, and the range of use of plastic containers has expanded, further improving the gas barrier properties of plastic containers. It is requested.
上記要求に対し、ボトルにガスバリア性を付与する方法として熱可塑性ポリエステル樹脂とガスバリア性樹脂を用いた多層ボトル、ブレンドボトル、熱可塑性ポリエステル樹脂単層ボトルにカーボンコート、蒸着、バリア樹脂の塗布を施したバリアコーティングボトル等が開発されている。 In response to the above requirements, carbon bottles, vapor deposition, and barrier resin coating are applied to multilayer bottles, blend bottles, and thermoplastic polyester resin single-layer bottles using thermoplastic polyester resin and gas barrier resin as a method of imparting gas barrier properties to the bottle. Barrier coating bottles have been developed.
多層ボトルの一例としては、最内層および最外層を形成するＰＥＴ等の熱可塑性ポリエステル樹脂とポリメタキシリレンアジパミド（ポリアミドＭＸＤ６）等の熱可塑性ガスバリア性樹脂とを射出して金型キャビティーを満たすことにより得られる３層または５層構造を有するパリソンを２軸延伸ブロー成形したボトルが実用化されている。 As an example of the multilayer bottle, a mold cavity is formed by injecting a thermoplastic polyester resin such as PET, which forms the innermost layer and the outermost layer, and a thermoplastic gas barrier resin such as polymetaxylylene adipamide (polyamide MXD6). A bottle in which a parison having a three-layer or five-layer structure obtained by filling is biaxially stretch blow molded has been put into practical use.
更に、容器外からの酸素を遮断しながら容器内の酸素を捕捉する酸素捕捉機能を有する樹脂が開発され、多層ボトルに応用されている。酸素捕捉性ボトルとしては、酸素吸収速度、透明性、強度、成形性等の面で、遷移金属系触媒を混合したポリアミドＭＸＤ６をガスバリア層として使用した多層ボトルが好適である。 Furthermore, a resin having an oxygen scavenging function for capturing oxygen in the container while blocking oxygen from outside the container has been developed and applied to a multilayer bottle. As the oxygen scavenging bottle, a multilayer bottle using polyamide MXD6 mixed with a transition metal catalyst as a gas barrier layer is preferable in terms of oxygen absorption rate, transparency, strength, moldability, and the like.
上記多層ボトルは、その良好なガスバリア性からビール、お茶、炭酸飲料等の容器に利用されている。多層ボトルがこれら用途に使用されることにより、内容物の品質維持、シェルフライフの改善がなされる一方、異なる樹脂間、例えば、最内層および最外層と中間層の間で層間剥離が起こり、商品価値を損ねてしまう問題がある。 The said multilayer bottle is utilized for containers, such as beer, tea, and a carbonated drink, from the favorable gas barrier property. Multi-layer bottles are used in these applications to maintain the quality of contents and improve shelf life, while delamination occurs between different resins, for example, the innermost layer and the outermost and intermediate layers. There is a problem that detracts from value.
このような問題点を改良する方法として、最内層および最外層を構成する樹脂を最後に金型キャビティー内に射出する際に、ガスバリア層側に一定量逆流させることが可能な逆流調節装置を使用し層間に粗混合樹脂を介在させることによって耐層間剥離性を改善することが開示記載されているが、特殊な装置を使用するという問題点がある（特許文献１参照）。
本発明の目的は、上記課題を解決し、多層容器において、落下や衝撃による剥離が起こりにくく、かつ、剥離防止のために凹凸部、屈曲部の少ない形状にする必要がなく、デザイン自由度が大きい多層容器を提供することにある。 The object of the present invention is to solve the above-mentioned problems, and in a multi-layer container, peeling due to dropping or impact is unlikely to occur, and it is not necessary to have a shape with few uneven parts and bent parts to prevent peeling, and the degree of freedom in design is increased. It is to provide a large multi-layer container.
本発明者らは、多層容器の耐層間剥離性について鋭意研究を重ねた結果、最内層および最外層を構成する樹脂と中間層を構成する樹脂の親和性を高め、かつ、ガラス転移温度の高い樹脂をブレンドすることで層間の密着性が改善され、落下時等の層間剥離を防止できることを見出した。即ち、中間層を構成する樹脂の溶解度指数と最内層および最外層を構成する樹脂の溶解度指数を近づけ、さらに中間層を構成する樹脂のブロー成形後のひずみを大きくすることにより、層間剥離が抑制された多層容器が得られることを見出し本発明に到った。 As a result of intensive studies on the delamination resistance of the multilayer container, the present inventors have improved the affinity between the resin constituting the innermost layer and the outermost layer and the resin constituting the intermediate layer, and has a high glass transition temperature. It has been found that interlaminar adhesion can be improved by blending the resin, and delamination during dropping can be prevented. In other words, delamination is suppressed by bringing the solubility index of the resin constituting the intermediate layer closer to the solubility index of the resin constituting the innermost layer and the outermost layer, and further increasing the strain after blow molding of the resin constituting the intermediate layer. The present inventors have found that a multilayered container can be obtained.
即ち本発明は、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８０〜１２０℃での定温結晶化における半結晶化時間がポリアミド樹脂Ｃの１／５以下であり、かつ下記式（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により主として構成され、該多層容器から取出した混合樹脂Ｂの引張弾性率が、混合樹脂Ｂの代わりにポリアミド樹脂Ｃを中間層として用いた以外は同様に作成した多層容器から取出したポリアミド樹脂Ｃの引張弾性率より低いことを特徴とする多層容器を提供する。
That is, the present invention is a multilayer container comprising an outermost layer, an innermost layer and at least one intermediate layer located between the outermost layer and the innermost layer, wherein the outermost layer and the innermost layer contain 80 mol% of terephthalic acid. It is mainly composed of a thermoplastic polyester resin A obtained by polymerizing a dicarboxylic acid component containing at least 80 mol% of ethylene glycol and at least one intermediate layer containing at least 70 mol% of metaxylylenediamine. The semi-crystallization time in the constant temperature crystallization at 80 to 120 ° C. and the polyamide resin C obtained by polymerizing the diamine component containing and the dicarboxylic acid component containing 70 mol% or more of adipic acid is 1/5 or less of the polyamide resin C And the following formula (1):
Sa <Sd <Sc (1)
(In the formula, Sa is the solubility index of the thermoplastic polyester resin A, Sc is the solubility index of the polyamide resin C, Sd is the solubility index of the polyamide resin D, and each solubility index is calculated by the Small method.)
The mixed resin B mainly containing the polyamide resin D satisfying the weight ratio of 99.5 / 0.5 to 80/20, and the tensile modulus of the mixed resin B taken out from the multilayer container is Instead, there is provided a multilayer container characterized by being lower than the tensile elastic modulus of the polyamide resin C taken out from the multilayer container prepared in the same manner except that the polyamide resin C is used as an intermediate layer.
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８０〜１２０℃での定温結晶化における半結晶化時間がポリアミド樹脂Ｃの１／５以下であり、かつ下記式（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。
Furthermore, the present invention uses an injection molding machine having a skin side injection cylinder and a core side injection cylinder, from an outermost layer, an innermost layer and at least one intermediate layer located between the outermost layer and the innermost layer. A thermoplastic polyester resin obtained by polymerizing a dicarboxylic acid component containing 80 mol% or more of terephthalic acid and a diol component containing 80 mol% or more of ethylene glycol from the skin-side injection cylinder. A is injected to form the innermost layer and the outermost layer, and a diamine component containing 70 mol% or more of metaxylylenediamine and a dicarboxylic acid component containing 70 mol% or more of adipic acid are polymerized from the core-side injection cylinder. The semi-crystallization time in the constant temperature crystallization at 80 to 120 ° C. with the polyamide resin C obtained in this way is 1/5 of the polyamide resin C. It is lower, and the following formula (1):
Sa <Sd <Sc (1)
(In the formula, Sa is the solubility index of the thermoplastic polyester resin A, Sc is the solubility index of the polyamide resin C, Sd is the solubility index of the polyamide resin D, and each solubility index is calculated by the Small method.)
Including a step of injecting a mixed resin B containing 99.5 / 0.5 to 80/20 in a weight ratio of the polyamide resin D satisfying the above to form at least one intermediate layer to produce a multilayer parison The manufacturing method of the multilayer container characterized by this is provided.
本発明によれば、層間剥離が起こりにくく、かつ、ガスバリア性に優れた多層容器を得ることができ、本発明の工業的意義は大きい。 According to the present invention, it is possible to obtain a multi-layer container in which delamination hardly occurs and gas barrier properties are excellent, and the industrial significance of the present invention is great.
本発明の多層容器の最外層、最内層、および場合によっては中間層の少なくとも１層を形成することもある熱可塑性ポリエステル樹脂Ａ（以下、“ポリエステル樹脂Ａ”と略称する）は、８０モル％以上、好ましくは９０モル％以上がテレフタル酸であるジカルボン酸成分と、８０モル％以上、好ましくは９０モル％以上がエチレングリコールであるジオール成分を重合反応させて得られたポリエステルである。 The thermoplastic polyester resin A (hereinafter abbreviated as “polyester resin A”) that may form at least one of the outermost layer, the innermost layer, and in some cases the intermediate layer of the multilayer container of the present invention is 80 mol%. Above, preferably a polyester obtained by polymerizing a dicarboxylic acid component whose terephthalic acid is 90 mol% or more and a diol component whose ethylenemol is 80 mol% or more, preferably 90 mol% or more.
ポリエステル樹脂Ａとしては、ポリエチレンテレフタレートが好適に使用される。ポリエチレンテレフタレートの持つ透明性、機械的強度、射出成形性、延伸ブロー成形性の全てにおいて優れた特性を発揮することが可能となる。 As the polyester resin A, polyethylene terephthalate is preferably used. It becomes possible to exhibit excellent properties in all of transparency, mechanical strength, injection moldability, and stretch blow moldability of polyethylene terephthalate.
テレフタル酸以外の他のジカルボン酸成分としては、イソフタル酸、ジフェニルエーテル−４，４−ジカルボン酸、ナフタレン−１，４又は２，６−ジカルボン酸、アジピン酸、セバシン酸、デカン−１，１０−カルボン酸、ヘキサヒドロテレフタル酸を使用することができる。またエチレングリコール以外の他のジオール成分としてはプロピレングリコール、１，４−ブタンジオール、ネオペンチルグリコール、ジエチレングリコール、シクロヘキサンジメタノール、２，２−ビス（４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシエトキシフェニル）プロパン等を使用することが出来る。更に、ポリエステル樹脂Ａの原料モノマーとして、ｐ−オキシ安息香酸等のオキシ酸を使用することもできる。 As other dicarboxylic acid components other than terephthalic acid, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, naphthalene-1,4 or 2,6-dicarboxylic acid, adipic acid, sebacic acid, decane-1,10-carboxyl Acid, hexahydroterephthalic acid can be used. As other diol components other than ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis ( 4-hydroxyethoxyphenyl) propane or the like can be used. Furthermore, as a raw material monomer for the polyester resin A, an oxyacid such as p-oxybenzoic acid may be used.
ポリエステル樹脂Ａの固有粘度は、０．５５〜１．５０、好ましくは０．６５〜１．４０である。固有粘度が上記０．５５以上であると多層パリソンを透明な非晶状態で得ることが可能であり、また得られる多層容器の機械的強度も満足するものとなる。また固有粘度が前記１．５０以下の場合、粘度上昇による成形のトラブルを回避することができる。 The intrinsic viscosity of the polyester resin A is 0.55 to 1.50, preferably 0.65 to 1.40. When the intrinsic viscosity is 0.55 or more, the multilayer parison can be obtained in a transparent amorphous state, and the mechanical strength of the obtained multilayer container is also satisfied. Further, when the intrinsic viscosity is 1.50 or less, it is possible to avoid molding troubles due to an increase in viscosity.
また、本発明の特徴を損なわない範囲でポリエステル樹脂Ａに他の熱可塑性樹脂を配合して使用することができる。他の熱可塑性樹脂としては、ポリエチレン−２，６−ナフタレンジカルボキシレート等の熱可塑性ポリエステル樹脂、ポリオレフィン系樹脂、ポリカーボネート、ポリアクリロニトリル、ポリ塩化ビニル、ポリスチレン等が例示できる。他の熱可塑性樹脂の配合量は、ポリエステル樹脂Ａの１０重量％以下であるのが好ましい。 Further, other thermoplastic resins can be blended with the polyester resin A within a range not impairing the characteristics of the present invention. Examples of other thermoplastic resins include thermoplastic polyester resins such as polyethylene-2,6-naphthalenedicarboxylate, polyolefin resins, polycarbonate, polyacrylonitrile, polyvinyl chloride, polystyrene, and the like. The blending amount of the other thermoplastic resin is preferably 10% by weight or less of the polyester resin A.
本発明の多層容器の中間層の少なくとも１層は、下記ポリアミド樹脂Ｃとポリアミド樹脂Ｄとの混合樹脂Ｂにより形成される。
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。
At least one of the intermediate layers of the multilayer container of the present invention is formed of a mixed resin B of the following polyamide resin C and polyamide resin D.
The polyamide resin C is obtained by polymerizing a diamine component containing 70 mol% or more of metaxylylenediamine and a dicarboxylic acid component containing 70 mol% or more of adipic acid. When the amount of metaxylylenediamine in the diamine component is 70 mol% or more, excellent gas barrier properties can be maintained. When the adipic acid in the dicarboxylic acid component is 70 mol% or more, it is possible to prevent a decrease in gas barrier properties and a decrease in crystallinity.
ポリエステル樹脂Ａ（ポリエチレンテレフタレート）との共射出成形性、共延伸ブロー成形性において優れた特性を発揮するので、ポリアミド樹脂Ｃとしては、ポリメタキシリレンアジパミド（ポリアミドＭＸＤ６）が好適に使用される。 Polyamidexylene adipamide (polyamide MXD6) is preferably used as the polyamide resin C because it exhibits excellent properties in co-injection moldability and co-stretch blow moldability with polyester resin A (polyethylene terephthalate). .
メタキシリレンジアミン以外に使用できるジアミン成分として、テトラメチレンジアミン、ペンタメチレンジアミン、２−メチルペンタンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ドデカメチレンジアミン、２，２，４−トリメチルヘキサメチレンジアミン、２，４，４−トリメチルヘキサメチレンジアミン等の脂肪族ジアミン；１，３−ビス（アミノメチル）シクロヘキサン、１，４−ビス（アミノメチル）シクロヘキサン、１，３−ジアミノシクロヘキサン、１，４−ジアミノシクロヘキサン、ビス（４−アミノシクロヘキシル）メタン、２，２−ビス（４−アミノシクロヘキシル）プロパン、ビス（アミノメチル）デカリン、ビス（アミノメチル）トリシクロデカン等の脂環族ジアミン；ビス（４−アミノフェニル）エーテル、パラフェニレンジアミン、パラキシリレンジアミン、ビス（アミノメチル）ナフタレン等の芳香環を有するジアミン類等が例示できるが、これらに限定されるものではない。 As diamine components that can be used in addition to metaxylylenediamine, tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, Aliphatic diamines such as 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine; 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1 , 3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) decalin, bis (amino Examples thereof include alicyclic diamines such as methyl) tricyclodecane; diamines having an aromatic ring such as bis (4-aminophenyl) ether, paraphenylenediamine, paraxylylenediamine, bis (aminomethyl) naphthalene, and the like. It is not limited to these.
アジピン酸以外に使用できるジカルボン酸成分として、スベリン酸、アゼライン酸、セバシン酸、１，１０−デカンジカルボン酸、テレフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸等が例示できるが、これらに限定されるものではない。
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。
Examples of dicarboxylic acid components that can be used in addition to adipic acid include suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and the like. Is not to be done.
Further, the polyamide resin C may contain a small amount of monoamine or monocarboxylic acid used as a molecular weight regulator during production.
上記のポリアミド樹脂Ｃは、ジアミン成分とジカルボン酸成分とを溶融重縮合することにより、又は溶融重縮合後更に固相重合することにより製造される。
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。
The polyamide resin C is produced by melt polycondensation of a diamine component and a dicarboxylic acid component, or by further solid phase polymerization after melt polycondensation.
As the melt polycondensation method, for example, there is a method in which a nylon salt composed of metaxylylenediamine and adipic acid is heated in the presence of water under pressure and polymerized in a molten state while removing added water and condensed water. . It can also be produced by a method in which metaxylylenediamine is directly added to molten adipic acid and polycondensed. In this case, in order to keep the reaction system in a uniform liquid state, metaxylylenediamine is continuously added to adipic acid, and during this time, the reaction system is raised so that the reaction temperature does not fall below the melting point of the generated oligoamide and polyamide. The polycondensation proceeds while warming.
溶融重縮合により得られる比較的低分子量のポリアミドの相対粘度（ポリアミド樹脂１ｇを９６％硫酸１００ｍｌに溶解し、２５℃で測定した値、以下同じ）は通常、２．２８程度である。溶融重縮合後の相対粘度が２．２８以下であると、ゲル状物の生成が少なく、色調が良好な高品質のポリアミドが得られる。溶融重縮合により得られた比較的低分子量のポリアミドは次いで固相重合してもよい。固相重合は、溶融重縮合により得られた比較的低分子量のポリアミドをペレットあるいは粉末にし、これを減圧下あるいは不活性ガス雰囲気下に、１５０℃以上、かつ、ポリアミドの融点以下の温度に加熱することにより実施される。固相重合ポリアミドの相対粘度は２．３〜４．２が望ましい。この範囲であると、中空容器、フィルム、シートへの成形が良好で、且つ得られる中空容器、フィルム、シートの性能、特に機械的性能が良好である。溶融重縮合後の比較的低分子量のポリアミドを用いても本発明の効果は一部得られるが、機械的強度、特に耐衝撃性が十分ではなく、中空容器用材料として実用的ではない。 The relative viscosity of polyamide having a relatively low molecular weight obtained by melt polycondensation (1 g of polyamide resin dissolved in 100 ml of 96% sulfuric acid and measured at 25 ° C., hereinafter the same) is usually about 2.28. When the relative viscosity after melt polycondensation is 2.28 or less, a high-quality polyamide having a good color tone is obtained with less formation of a gel-like product. The relatively low molecular weight polyamide obtained by melt polycondensation may then be subjected to solid state polymerization. In solid-phase polymerization, a relatively low molecular weight polyamide obtained by melt polycondensation is made into pellets or powder, and this is heated to a temperature of 150 ° C. or higher and a melting point of polyamide or lower under reduced pressure or in an inert gas atmosphere. It is carried out by doing. The relative viscosity of the solid phase polymerized polyamide is preferably 2.3 to 4.2. Within this range, molding into a hollow container, film, or sheet is good, and the performance of the resulting hollow container, film, or sheet, particularly mechanical performance, is good. Even if a polyamide having a relatively low molecular weight after melt polycondensation is used, some of the effects of the present invention can be obtained, but mechanical strength, particularly impact resistance is not sufficient, and it is not practical as a material for a hollow container.
ポリアミド樹脂Ｄは、８０℃〜１２０℃での定温結晶化における半結晶化時間が、同条件におけるポリアミド樹脂Ｃの半結晶化時間の１／５以下であり、好ましくは、１／１０以下、さらに好ましくは１／２０以下である。前記半結晶化時間がポリアミド樹脂Ｃの１／５より大きくなると、中間層を構成する混合樹脂Ｂの収縮率が小さくなり、最内層および最外層を構成するポリエステル樹脂Ａに対する密着性効果が小さくなり好ましくない。 The polyamide resin D has a half crystallization time in constant temperature crystallization at 80 ° C. to 120 ° C. is 1/5 or less of the half crystallization time of the polyamide resin C under the same conditions, preferably 1/10 or less, Preferably it is 1/20 or less. When the semi-crystallization time is longer than 1/5 of the polyamide resin C, the shrinkage rate of the mixed resin B constituting the intermediate layer is reduced, and the adhesion effect to the polyester resin A constituting the innermost layer and the outermost layer is reduced. It is not preferable.
また、ポリアミド樹脂Ｄは、下記式（１）を満たす樹脂である。
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。
The polyamide resin D is a resin that satisfies the following formula (1).
Sa <Sd <Sc (1)
(In the formula, Sa is the solubility index of the thermoplastic polyester resin A, Sc is the solubility index of the polyamide resin C, and Sd is the solubility index of the polyamide resin D.)
The solubility index is calculated by the Small method (see Japan Adhesion Association, Vol. 22, No. 10, p. 51 (1986)).
In the polyamide resin D, it is important that the value of Sd is between Sa and Sc in order to increase the affinity between the innermost and outer layers (polyester resin A layer) and the intermediate layer (gas barrier layer). When Sd exceeds this range, the affinity between the polyester resin A constituting the innermost layer and the outermost layer and the mixed resin B constituting the intermediate layer is lowered, and the adhesion between layers is lowered, which is not preferable for preventing delamination.
Such a polyamide resin D can be obtained by designing a skeleton segment in the polymer so as to satisfy the above formula (1) from the solubility index of the polyester resin A and the polyamide resin C obtained from the calculation by the Small method. .
上記したように、本発明においては、透明性、機械的強度、射出成形性、延伸ブロー成形性が優れているので、ポリエステル樹脂Ａとしてポリエチレンテレフタレートが好適に使用される。また、ポリエチレンテレフタレートとの共射出成形性、共延伸ブロー成形性が優れているので、ポリアミド樹脂ＣとしてはポリアミドＭＸＤ６が好適に使用される。ポリエステル樹脂Ａとしてポリエチレンテレフタレートを、ポリアミド樹脂ＣとしてポリアミドＭＸＤ６を使用する場合、ポリアミド樹脂Ｄの溶解度指数は１１〜１３が好ましく、１２．０ 〜１２．９がより好ましい。具体的には、ナイロン６、ナイロン６６、ナイロン６／６６、ナイロン６６／６等の脂肪族ポリアミドが挙げられ、この中でもナイロン６が特に好ましい。 As described above, in the present invention, since the transparency, mechanical strength, injection moldability, and stretch blow moldability are excellent, polyethylene terephthalate is preferably used as the polyester resin A. Further, since the co-injection moldability with polyethylene terephthalate and the co-stretch blow moldability are excellent, polyamide MXD6 is suitably used as the polyamide resin C. When polyethylene terephthalate is used as the polyester resin A and polyamide MXD6 is used as the polyamide resin C, the solubility index of the polyamide resin D is preferably 11 to 13, and more preferably 12.0 to 12.9. Specific examples include aliphatic polyamides such as nylon 6, nylon 66, nylon 6/66, and nylon 66/6. Among these, nylon 6 is particularly preferable.
混合樹脂Ｂは、ポリアミド樹脂Ｃとポリアミド樹脂Ｄのペレットを乾式で混合して射出成形機ホッパーにより再ペレット化するドライブレンド法、もしくは、ポリアミド樹脂Ｃとポリアミド樹脂Ｄを溶融押出しして再ペレット化するメルトブレンド法のいずれによっても製造することができる。なお、用途、使用条件、機械的性能等に応じて適切な配合処方が選択される。 The mixed resin B is a dry blend method in which pellets of polyamide resin C and polyamide resin D are mixed in a dry manner and re-pelletized by an injection molding machine hopper, or polyamide resin C and polyamide resin D are melt-extruded and re-pelletized. It can be produced by any melt blending method. An appropriate formulation is selected according to the application, use conditions, mechanical performance, and the like.
混合樹脂Ｂ中のポリアミド樹脂Ｃとポリアミド樹脂Ｄの重量比は、９９．５／０．５〜８０／２０、好ましくは９９／１〜８５／１５、さらに好ましくは９５／５〜９０／１０である。ポリアミド樹脂Ｄの重量比が０．５％より小さいと、顕著な耐剥離性改善効果が得られない。また、ポリアミド樹脂Ｄの重量比が２０％を超えると耐剥離性改善に効果は見られるがポリアミド樹脂Ｃの良好なバリア性が多層容器に寄与されず実用的ではない。 The weight ratio of the polyamide resin C and the polyamide resin D in the mixed resin B is 99.5 / 0.5 to 80/20, preferably 99/1 to 85/15, more preferably 95/5 to 90/10. is there. When the weight ratio of the polyamide resin D is less than 0.5%, a remarkable peel resistance improvement effect cannot be obtained. Further, if the weight ratio of the polyamide resin D exceeds 20%, an effect is seen in improving the peel resistance, but the good barrier property of the polyamide resin C is not contributed to the multilayer container and is not practical.
本発明の多層容器では、パリソンと容器の形状によっては低延伸倍率（１〜２．５ 倍）の部分が生じることがある。低延伸倍率部の中間層が吸水すると白化することがある。必要に応じて混合樹脂Ｂに白化防止剤を添加することにより白化が抑制され透明性の良好な多層容器が得られる。 In the multilayer container of the present invention, a portion having a low draw ratio (1 to 2.5 times) may occur depending on the shape of the parison and the container. When the intermediate layer of the low draw ratio part absorbs water, it may whiten. By adding an anti-whitening agent to the mixed resin B as necessary, whitening is suppressed and a multilayer container with good transparency is obtained.
本発明に用いる白化防止剤は、炭素数１８〜５０、好ましくは１８〜３４の脂肪酸金属塩である。炭素数が１８以上で白化防止が期待できる。また、炭素数が５０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、ステアリン酸(Ｃ１８)、エイコサン酸(Ｃ２０)、ベヘン酸(Ｃ２２)、モンタン酸(Ｃ２８)、トリアコンタン酸(Ｃ３０)などの直鎖飽和脂肪酸が好ましい。脂肪酸と塩を形成する金属に特に制限はないが、ナトリウム、カリウム、リチウム、カルシウム、バリウム、マグネシウム、ストロンチウム、アルミニウム、亜鉛等が例示され、ナトリウム、カリウム、リチウム、カルシウム、アルミニウム、および亜鉛が特に好ましい。 The whitening inhibitor used in the present invention is a fatty acid metal salt having 18 to 50 carbon atoms, preferably 18 to 34 carbon atoms. With 18 or more carbon atoms, whitening prevention can be expected. Further, when the carbon number is 50 or less, uniform dispersion in the mixed resin B is good. Fatty acids may have side chains or double bonds, but linear saturated such as stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28), triacontanoic acid (C30) Fatty acids are preferred. The metal that forms a salt with the fatty acid is not particularly limited, but sodium, potassium, lithium, calcium, barium, magnesium, strontium, aluminum, zinc, etc. are exemplified, and sodium, potassium, lithium, calcium, aluminum, and zinc are particularly preferable.
脂肪酸金属塩は、１種類でもよいし、２種以上を併用してもよい。本発明では、脂肪酸金属塩の粒径に特に制限はないが、粒径が小さい方が混合樹脂Ｂ中に均一に分散することが容易になるため、粒径は０．２ｍｍ以下が好ましい。 One type of fatty acid metal salt may be used, or two or more types may be used in combination. In the present invention, the particle diameter of the fatty acid metal salt is not particularly limited, but the smaller the particle diameter, the easier it is to disperse uniformly in the mixed resin B, so the particle diameter is preferably 0.2 mm or less.
脂肪酸金属塩の添加量は、ポリアミド樹脂Ｃとポリアミド樹脂Ｄの合計量１００重量部に対して好ましくは０．００５〜１．０重量部、より好ましくは０．０５〜０．５重量部、特に好ましくは０．１２〜０．５重量部である。合計量１００重量部に対して０．００５重量部以上添加することにより白化防止効果が期待できる。また、添加量が合計量１００重量部に対して１．０重量部以下であると得られる多層容器の曇価を低く保つことが可能となる。 The addition amount of the fatty acid metal salt is preferably 0.005 to 1.0 part by weight, more preferably 0.05 to 0.5 part by weight, particularly preferably 100 parts by weight of the total amount of the polyamide resin C and the polyamide resin D. Preferably it is 0.12-0.5 weight part. Addition of 0.005 part by weight or more with respect to 100 parts by weight of the total amount can be expected to prevent whitening. Moreover, it becomes possible to keep the cloudiness of the multilayer container obtained that the addition amount is 1.0 part by weight or less with respect to 100 parts by weight of the total amount.
上記脂肪酸金属塩の代わりに、下記のジアミド化合物およびジエステル化合物から選ばれた化合物を白化防止剤として添加してもよい。１種または２種以上のジアミド化合物を添加してもよいし、１種または２種以上のジエステル化合物を添加してもよいし、１種または２種以上のジアミド化合物と１種または２種以上のジエステル化合物を併用してもよい。 Instead of the fatty acid metal salt, a compound selected from the following diamide compounds and diester compounds may be added as a whitening inhibitor. One or two or more diamide compounds may be added, one or two or more diester compounds may be added, one or two or more diamide compounds and one or two or more types These diester compounds may be used in combination.
ジアミド化合物は、炭素数８〜３０の脂肪酸と炭素数２〜１０のジアミンから得られる。脂肪酸の炭素数が８以上、ジアミンの炭素数が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、ジアミンの炭素数が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。 The diamide compound is obtained from a fatty acid having 8 to 30 carbon atoms and a diamine having 2 to 10 carbon atoms. When the fatty acid has 8 or more carbon atoms and the diamine has 2 or more carbon atoms, an effect of preventing whitening can be expected. Further, when the fatty acid has 30 or less carbon atoms and the diamine has 10 or less carbon atoms, uniform dispersion in the mixed resin B is good. The fatty acid may have a side chain or a double bond, but a linear saturated fatty acid is preferred.
ジアミド化合物の脂肪酸成分として、ステアリン酸（Ｃ１８）、エイコサン酸（Ｃ２０）、ベヘン酸（Ｃ２２）、モンタン酸（Ｃ２８）、トリアコンタン酸（Ｃ３０）が例示できる。ジアミド化合物のジアミン成分として、エチレンジアミン、ブチレンジアミン、ヘキサンジアミン、キシリレンジアミン、ビス（アミノメチル）シクロヘキサン等が例示できる。これらを組み合わせて得られるジアミド化合物が本発明に用いられる。炭素数８〜３０の脂肪酸と主としてエチレンジアミンから成るジアミンから得られるジアミド化合物、または主としてモンタン酸からなる脂肪酸と炭素数２〜１０のジアミンから得られるジアミド化合物が好ましい。
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。
Examples of the fatty acid component of the diamide compound include stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28), and triacontanoic acid (C30). Examples of the diamine component of the diamide compound include ethylenediamine, butylenediamine, hexanediamine, xylylenediamine, and bis (aminomethyl) cyclohexane. A diamide compound obtained by combining these is used in the present invention. A diamide compound obtained from a diamine composed mainly of a fatty acid having 8 to 30 carbon atoms and mainly ethylenediamine, or a diamide compound obtained from a fatty acid mainly composed of montanic acid and a diamine having 2 to 10 carbon atoms is preferred.
The diester compound is obtained from a fatty acid having 8 to 30 carbon atoms and a diol having 2 to 10 carbon atoms. When the fatty acid has 8 or more carbon atoms and the diol has 2 or more carbon atoms, an effect of preventing whitening can be expected. Further, when the fatty acid has 30 or less carbon atoms and the diol has 10 or less carbon atoms, uniform dispersion in the mixed resin B is good. The fatty acid may have a side chain or a double bond, but a linear saturated fatty acid is preferred.
ジエステル化合物の脂肪酸成分として、ステアリン酸（Ｃ１８）、エイコ酸（Ｃ２０）、ベヘン酸（Ｃ２２）、モンタン酸（Ｃ２８）、トリアコンタン酸（Ｃ３０）等が例示できる。ジエステル化合物のジオール成分として、エチレングリコール、プロパンジオール、ブタンジオール、ヘキサンジオール、キシリレングリコール、シクロヘキサンジメタノール等が例示できる。これらを組み合わせて得られるジエステル化合物が本発明に用いられる。主としてモンタン酸からなる脂肪酸と主としてエチレングリコールおよび／または１，３−ブタンジオールからなるジオールから得られるジエステル化合物が特に好ましい。 Examples of the fatty acid component of the diester compound include stearic acid (C18), eicoic acid (C20), behenic acid (C22), montanic acid (C28), triacontanoic acid (C30), and the like. Examples of the diol component of the diester compound include ethylene glycol, propanediol, butanediol, hexanediol, xylylene glycol, and cyclohexanedimethanol. A diester compound obtained by combining these is used in the present invention. Particularly preferred are diester compounds obtained from fatty acids composed mainly of montanic acid and diols composed mainly of ethylene glycol and / or 1,3-butanediol.
ジアミド化合物および／またはジエステル化合物の添加量は、ポリアミド樹脂Ｃとポリアミド樹脂Ｄの合計量１００重量部に対して好ましくは０．００５〜１．０重量部、より好ましくは０．０５〜０．５重量部、特に好ましくは０．１２〜０．５重量部である。合計量１００重量部に対して０．００５重量部以上添加することにより白化防止効果が期待できる。また、添加量が合計量１００重量部に対して１．０重量部以下であると、得られる多層容器の曇価を低く保つことが可能となる。 The addition amount of the diamide compound and / or diester compound is preferably 0.005 to 1.0 part by weight, more preferably 0.05 to 0.5 part per 100 parts by weight of the total amount of the polyamide resin C and the polyamide resin D. Part by weight, particularly preferably 0.12 to 0.5 part by weight. Addition of 0.005 part by weight or more with respect to 100 parts by weight of the total amount can be expected to prevent whitening. Further, when the addition amount is 1.0 part by weight or less with respect to the total amount of 100 parts by weight, the haze value of the resulting multilayer container can be kept low.
混合樹脂Ｂへの白化防止剤の添加は従来から公知の混合法を適用できる。たとえば、回転中空容器内にポリアミド樹脂ＣおよびＤのペレット、金属触媒化合物、白化防止剤を投入し混合して使用してもよい。また、高濃度の白化防止剤を含有するポリアミド樹脂組成物を製造した後、白化防止剤を含有しないポリアミド樹脂ペレットで所定の濃度で希釈し、これを溶融混練する方法、溶融混連後、引き続き、射出成形などにより成形する方法などが採用される。 A conventionally known mixing method can be applied to the addition of the whitening inhibitor to the mixed resin B. For example, polyamide resin C and D pellets, a metal catalyst compound, and a whitening inhibitor may be put into a rotating hollow container and mixed for use. Further, after producing a polyamide resin composition containing a high concentration of whitening inhibitor, it is diluted with a polyamide resin pellet containing no whitening agent at a predetermined concentration, and this is melt kneaded, continuously after melt mixing. A method of molding by injection molding or the like is employed.
白化防止剤を使用した場合、多層容器を製造した直後に混合樹脂Ｂからなる中間層が白化するのを防止することができる。また、白化しない、あるいは白化が増大しない条件で多層容器を長期保存した後に、混合樹脂Ｂからなる中間層が白化するのを防止することができる。すなわち、白化防止剤を添加しなくとも白化しない、あるいは白化が増大しない条件、たとえば温度２３℃、湿度５０％ＲＨ雰囲気下に長期保存した後に、多層容器を高湿度にさらしたり、水や沸騰水と接触させたり、あるいはガラス転移温度以上に加熱しても成形直後と同様に白化が抑制される。 When the anti-whitening agent is used, it is possible to prevent the intermediate layer made of the mixed resin B from being whitened immediately after manufacturing the multilayer container. In addition, it is possible to prevent the intermediate layer made of the mixed resin B from being whitened after the multilayer container has been stored for a long period of time without whitening or increasing whitening. That is, even if a whitening inhibitor is not added, it does not whiten or does not increase in whitening, for example, after long-term storage in an atmosphere at a temperature of 23 ° C. and a humidity of 50% RH, the multilayer container is exposed to high humidity, or water or boiling water Even if it is brought into contact with the glass or heated to a temperature higher than the glass transition temperature, whitening is suppressed as in the case immediately after molding.
本発明の多層容器は２つの射出シリンダーを有する射出成形機を使用して、ポリエステル樹脂Ａとガスバリア性を有する混合樹脂Ｂとをスキン側、コア側それぞれの射出シリンダーから金型ホットランナーを通して金型キャビティー内に射出して得られた多層パリソンを更に２軸延伸ブロー成形することにより得られる。多層パリソンのブロー成形は従来公知の方法で行えばよく、例えば、多層パリソンの表面を８０〜１２０℃に加熱した後にブロー成形する方法、多層パリソンの口部を結晶化させ、表面を８０〜１２０℃に加熱した後に９０〜１５０℃の金型内でブロー成形する方法が採用される。ブロー圧は、通常、２〜４ＭＰａである。 The multilayer container of the present invention uses an injection molding machine having two injection cylinders to mold polyester resin A and mixed resin B having gas barrier properties from the injection cylinders on the skin side and core side through the mold hot runner. The multilayer parison obtained by injection into the cavity is further obtained by biaxial stretch blow molding. The blow molding of the multilayer parison may be performed by a conventionally known method. For example, the surface of the multilayer parison is heated to 80 to 120 ° C. and then blow molded, the mouth of the multilayer parison is crystallized, and the surface is 80 to 120. A method of blow molding in a 90 to 150 ° C. mold after heating to 0 ° C. is employed. The blow pressure is usually 2 to 4 MPa.
スキン側射出シリンダーから最内層および最外層を構成するポリエステル樹脂Ａを射出し、コア側射出シリンダーから中間層を構成する混合樹脂Ｂを射出する工程で、先ず、ポリエステル樹脂Ａを射出し、次いで混合樹脂Ｂとポリエステル樹脂Ａを同時に射出し、次にポリエステル樹脂Ａを必要量射出して金型キャビティーを満たすことにより３層構造（ポリエステル樹脂Ａ／混合樹脂Ｂ／ポリエステル樹脂Ａ）の多層パリソンが製造できる。 In the process of injecting the polyester resin A constituting the innermost layer and the outermost layer from the skin side injection cylinder and injecting the mixed resin B constituting the intermediate layer from the core side injection cylinder, first the polyester resin A is injected and then mixed. By injecting resin B and polyester resin A simultaneously, and then injecting the required amount of polyester resin A to fill the mold cavity, a multilayer parison with a three-layer structure (polyester resin A / mixed resin B / polyester resin A) is obtained. Can be manufactured.
スキン側射出シリンダーから最内層および最外層を構成するポリエステル樹脂Ａを射出し、コア側射出シリンダーから中間層を構成する混合樹脂Ｂを射出する工程で、先ずポリエステル樹脂Ａを射出し、次いで混合樹脂Ｂを単独で射出し、最後にポリエステル樹脂Ａを射出して金型キャビティーを満たすことにより、５層構造（ポリエステル樹脂Ａ／混合樹脂Ｂ／ポリエステル樹脂Ａ／混合樹脂Ｂ／ポリエステル樹脂Ａ）の多層パリソンが製造できる。なお、多層パリソンを製造する方法は、上記方法だけに限定されるものではない。 In the process of injecting the polyester resin A constituting the innermost layer and the outermost layer from the skin side injection cylinder, and injecting the mixed resin B constituting the intermediate layer from the core side injection cylinder, first the polyester resin A is injected, and then the mixed resin By injecting B alone and finally injecting polyester resin A to fill the mold cavity, a five-layer structure (polyester resin A / mixed resin B / polyester resin A / mixed resin B / polyester resin A) A multi-layer parison can be manufactured. The method for producing the multilayer parison is not limited to the above method.
多層容器中の、ポリエステル樹脂Ａからなる層の厚さは０．０１〜１．０ｍｍであるのが好ましく、混合樹脂Ｂからなる層の厚さは０．００５〜０．２ｍｍであるのが好ましい。また、多層容器の厚さは容器全体で一定である必要はなく、通常、０．２〜１．０ｍｍの範囲である。 The thickness of the layer made of polyester resin A in the multilayer container is preferably 0.01 to 1.0 mm, and the thickness of the layer made of mixed resin B is preferably 0.005 to 0.2 mm. . Moreover, the thickness of a multilayer container does not need to be constant throughout the container, and is usually in the range of 0.2 to 1.0 mm.
多層パリソンを２軸延伸ブロー成形して得られる多層容器において、少なくとも多層容器の胴部に混合樹脂Ｂからなる中間層が存在していればガスバリア性能は発揮できるが、多層容器の口栓部先端付近まで中間層が延びている方がガスバリア性能は更に良好である。 In a multilayer container obtained by biaxial stretch blow molding of a multilayer parison, the gas barrier performance can be exhibited if the intermediate layer made of the mixed resin B is present at least in the barrel part of the multilayer container. The gas barrier performance is better when the intermediate layer extends to the vicinity.
本発明の多層容器において混合樹脂Ｂからなる層の重量は、多層容器総重量に対して１〜２０重量％とすることが好ましく、より好ましくは２〜１５重量％である。混合樹脂Ｂからなる層の重量が１重量％より少ないと多層容器のガスバリア性が十分でなくなることがあるため好ましくない。また混合樹脂Ｂからなる層の重量が２０重量％より多いと前駆体である多層パリソンを多層容器に成形しにくくなることがあるため好ましくない。 In the multilayer container of the present invention, the weight of the layer made of the mixed resin B is preferably 1 to 20% by weight, more preferably 2 to 15% by weight, based on the total weight of the multilayer container. If the weight of the layer made of the mixed resin B is less than 1% by weight, the gas barrier property of the multilayer container may not be sufficient, which is not preferable. On the other hand, if the weight of the layer made of the mixed resin B is more than 20% by weight, it may be difficult to form the precursor multi-layer parison into the multi-layer container.
本発明の多層容器では、該多層容器から取出した混合樹脂Ｂの引張弾性率が、混合樹脂Ｂの代わりにポリアミド樹脂Ｃを中間層として用いた以外は同様に作成した多層容器から取出したポリアミド樹脂Ｃの引張弾性率より低いことが重要である。混合樹脂Ｂの引張弾性率がポリアミド樹脂Ｃの引張弾性率以上であると、中間層を構成する混合樹脂Ｂの柔軟性が十分とは言えず、層間密着性を改善することが難しくなるので好ましくない。 In the multi-layer container of the present invention, the polyamide resin taken out from the multi-layer container prepared in the same manner except that the tensile modulus of the mixed resin B taken out from the multi-layer container was used as the intermediate layer instead of the mixed resin B. It is important that it be lower than the tensile modulus of C. If the tensile modulus of the mixed resin B is equal to or higher than that of the polyamide resin C, the mixed resin B constituting the intermediate layer cannot be said to have sufficient flexibility, and it is difficult to improve interlayer adhesion. Absent.
本発明の多層容器は、落下や衝撃による層間剥離が起こりにくい。また、凹凸部、屈曲部を含む形状であっても層間剥離が起こりにくいので、多層容器の形状は凹凸部、屈曲部の少ない形状に限定されず、デザイン自由度が大きくなる。本発明の多層容器は、例えば、炭酸飲料、ジュース、水、牛乳、日本酒、ウイスキー、焼酎、コーヒー、茶、ゼリー飲料、健康飲料等の液体飲料、調味液、ソース、醤油、ドレッシング、液体だし等の調味料、液体スープ等の液体系食品、液状の医薬品、化粧水、化粧乳液、整髪料、染毛剤、シャンプー等、種々の物品の収納、保存に好適である。 In the multilayer container of the present invention, delamination hardly occurs due to dropping or impact. In addition, since the delamination hardly occurs even in a shape including an uneven portion and a bent portion, the shape of the multilayer container is not limited to a shape having few uneven portions and a bent portion, and the degree of freedom in design is increased. The multilayer container of the present invention is, for example, a carbonated beverage, juice, water, milk, sake, whiskey, shochu, coffee, tea, jelly beverage, health beverage or other liquid beverage, seasoning liquid, sauce, soy sauce, dressing, liquid soup, etc. It is suitable for storage and storage of various articles such as liquid seasonings, liquid foods such as liquid soup, liquid pharmaceuticals, skin lotions, cosmetic emulsions, hair conditioners, hair dyes, shampoos and the like.
以下実施例及び比較例により、本発明を更に詳細に説明するが本発明はこれら実施例に限定されるものではない。実施例等で測定した特性の測定法を以下に示す。
（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）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。
（５）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。
（６）結晶化速度：コタキ製作所（株）製半結晶化時間測定器を用いて測定した。試料を２８０℃／３分間保持したのち、１２０℃の油浴での半結晶化時間を測定した。
（７）引張弾性率：ＡＳＴＭ Ｄ８８２に準じて、東洋精機（株）製ＳＴＯＲＯＧＲＡＰＨ Ｖ１−Ｃを用いて多層容器から取出した中間層の引張弾性率を測定した。
試験片 １００ｍｍ×１０ｍｍ。試験速度 ５０ｍｍ／ｍｉｎ。
（８）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。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The measuring method of the characteristic measured in the Example etc. is shown below.
(1) Use of a mixed solvent of intrinsic viscosity [η] of polyethylene terephthalate: phenol / tetrachloroethane = 6/4 (weight ratio). Measurement temperature 30 ° C.
(2) Relative viscosity [η rel ] of polyamide MXD6: resin 1 g / 96% sulfuric acid 100 ml, measurement temperature 25 ° C.
(3) Calculation of solubility index: Calculated by the Small method (see Japan Adhesion Association, Vol. 22, No. 10, p. 51 (1986)).
(4) Haze value: Measured with a haze value measuring apparatus (model: COH-300A) manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K-7105 and ASTM D1003.
(5) Delamination property: Evaluated by a container drop test.
Drop test method: After a multilayer container was filled with water and capped, the multilayer container left for 24 hours was dropped, and the presence or absence of delamination was visually determined. The multilayer container was dropped vertically so that the bottom part was in contact with the floor. Drop height 75cm. The delamination property was evaluated by the number of delaminated bottles when 50 bottles were dropped.
(6) Crystallization rate: Measured using a semi-crystallization time measuring device manufactured by Kotaki Seisakusho. After holding the sample at 280 ° C./3 minutes, the half crystallization time in an oil bath at 120 ° C. was measured.
(7) Tensile elastic modulus: According to ASTM D882, the tensile elastic modulus of the intermediate layer taken out from the multilayer container was measured using STOROGRAPH V1-C manufactured by Toyo Seiki Co., Ltd.
Test piece 100 mm × 10 mm. Test speed 50 mm / min.
(8) Oxygen permeability of multilayer container: Measured according to ASTM D3985 in an atmosphere of 23 ° C., relative humidity of 100% inside multilayer container, and 50% relative humidity outside. The measurement used OX-TRAN 10 / 50A made by Modern Controls.
実施例１〜３および比較例１〜２に用いた多層容器は下記の方法で製造した。
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
The multilayer containers used in Examples 1 to 3 and Comparative Examples 1 and 2 were produced by the following method.
Three-layer parison shape: total length 95 mm, outer diameter 22 mm, wall thickness 4.2 mm. For the production of the three-layer parison, an injection molding machine (model: M200, 4 pieces) manufactured by Meiki Seisakusho Co., Ltd. was used.
Three-layer parison molding conditions Skin side injection cylinder temperature: 280 ° C
Core side injection cylinder temperature: 260 ° C
Resin channel temperature in mold: 280 ° C
Mold cooling water temperature: 15 ° C
Ratio of mixed resin B in parison: 8% by weight
Multilayer container shape: total length 223 mm, outer diameter 65 mm, inner volume 500 ml, polyester resin A layer / mixed resin B layer / polyester resin A layer = 0.28 mm / 0.056 mm / 0.10 mm, bottom shape is champagne type. The biaxial stretch blow molding used a blow molding machine (KRUPP CORPLAST, model: LB-01).
Biaxial stretch blow molding conditions Parison heating temperature: 100 ° C
Blow pressure: 2.7 MPa
＜実施例１＞
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）を使用した。溶解度指数は１３．０、１００℃における半結晶化時間は２００秒である。
ポリアミド樹脂Ｄ：Ｎ−６（宇部興産製 １０１５Ｂ）を使用した。溶解度指数は１２．６、１００℃における半結晶化時間は６秒である。
得られた３層容器について層間剥離性を評価した。また、容器の中間層を取り出し引張弾性率を測定した。結果を表１に示す。
<Example 1>
A multilayer container having a three-layer structure was formed using the following materials.
Innermost layer and outermost layer polyester resin A: Polyethylene terephthalate having an intrinsic viscosity of 0.75 (RT543C manufactured by Nihon Unipet). The solubility index is 11.1.
Intermediate layer Mixed resin B: 90/10 (weight ratio) of polyamide resin C and polyamide resin D Dry blend polyamide resin C: Polyamide MXD6 (MX nylon S6007 manufactured by Mitsubishi Gas Chemical) having a relative viscosity of 2.70 was used. The solubility index is 13.0 and the half crystallization time at 100 ° C. is 200 seconds.
Polyamide resin D: N-6 (Ube Industries 1015B) was used. The solubility index is 12.6 and the half crystallization time at 100 ° C. is 6 seconds.
The resulting three-layer container was evaluated for delamination. Moreover, the intermediate | middle layer of the container was taken out and the tensile elasticity modulus was measured. The results are shown in Table 1.
＜実施例２＞
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３層構成の多層容器を成形した。評価結果を表１に示す。
<Example 2>
A multilayer container having a three-layer structure was molded in the same manner as in Example 1 except that the polyamide resin C and the polyamide resin D were mixed in a 95/5 weight ratio. The evaluation results are shown in Table 1.
＜実施例３＞
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３層構成の多層容器を成形した。評価結果を表１に示す。
<Example 3>
A multilayer container having a three-layer structure was molded in the same manner as in Example 1 except that the polyamide resin C and the polyamide resin D were mixed in a 99/1 weight ratio. The evaluation results are shown in Table 1.
＜比較例１＞
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１と同様に３層構成の多層容器を成形した。評価結果を表２に示す。
<Comparative Example 1>
A multi-layer container having a three-layer structure was formed in the same manner as in Example 1 except that the polyamide resin D was not used and the intermediate layer was used alone as the polyamide resin C. The evaluation results are shown in Table 2.
＜比較例２＞
ポリアミド樹脂Ｃとポリアミド樹脂Ｄを７０／３０重量比で混合した以外は実施例１と同様に３層構成の多層容器を成形した。評価結果を表２に示す。
<Comparative example 2>
A multilayer container having a three-layer structure was formed in the same manner as in Example 1 except that the polyamide resin C and the polyamide resin D were mixed at a weight ratio of 70/30. The evaluation results are shown in Table 2.
＜実施例４＞
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。
<Example 4>
When mixing polyamide resin C and polyamide resin D, 0.2 part by weight of montanic acid sodium salt (trade name Hostamont NaV101, manufactured by Clariant Japan Co., Ltd.) as an anti-whitening agent is added to 100 parts by weight of the total amount of polyamide resin. Further, a multilayer container having a three-layer structure was formed in the same manner as in Example 1 except that the shape of the container was changed as follows.
Multi-layer container shape: total length 170 mm, volume 330 ml, neck diameter 25 mm, trunk diameter 66 mm, polyester resin A layer / mixed resin B layer / polyester resin A layer = 0.33 mm / 0.066 mm / 0.12 mm, bottom shape is champagne type .
The evaluation result of the delamination property of the obtained three-layer container and the three-layer container filled with 330 ml of water were stored at 40 ° C./80% RH for 6 months, and then the low stretch ratio part (stretch ratio 1) Table 3 shows the results of measuring the haze value of the intermediate layer taken out from (1.5 times).
＜実施例５＞
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４と同様にして３層構成の多層容器を成形した。
実施例４と同様にして得た評価結果を表３に示す。
<Example 5>
A multilayer container having a three-layer structure was formed in the same manner as in Example 4 except that the whitening inhibitor was changed to ethylene bisstearylamide (trade name Alflow H-50T, manufactured by NOF Corporation).
Table 3 shows the evaluation results obtained in the same manner as in Example 4.
＜比較例３＞
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４と同様にして３層構成の多層容器を成形した。実施例４と同様にして得た評価結果を表３に示す。
<Comparative Example 3>
A multi-layer container having a three-layer structure was formed in the same manner as in Example 4 except that the polyamide resin D was not used and the intermediate layer was used alone as the polyamide resin C. Table 3 shows the evaluation results obtained in the same manner as in Example 4.
Claims (12)
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の重量比で含有し、かつ該多層容器から取出した混合樹脂Ｂの引張弾性率が、混合樹脂Ｂの代わりにポリアミド樹脂Ｃを中間層として用いた以外は同様に作成した多層容器から取出したポリアミド樹脂Ｃの引張弾性率より低いことを特徴とする多層容器。 At least one layer located between the outermost layer, the innermost layer and the outermost layer and the innermost layer, obtained by further biaxially stretching blow molding the multilayer parison obtained by injecting the polyester resin A and the mixed resin B A multilayer container comprising an intermediate layer, wherein the outermost layer and the innermost layer are composed of a polyester resin A, at least one of the intermediate layers is composed of a mixed resin B, and the polyester resin A contains 80 mol% of terephthalic acid. A thermoplastic polyester resin obtained by polymerizing a dicarboxylic acid component containing at least 80 mol% of ethylene glycol and a mixed resin B comprising a diamine component containing at least 70 mol% of metaxylylenediamine and adipic acid. Polyamide resin C obtained by polymerizing a dicarboxylic acid component containing 70 mol% or more and constant temperature crystallization at 80 to 120 ° C. Definitive half-crystallization time is not more than 1/5 of the polyamide resin C, and the following formula (1):
Sa <Sd <Sc (1)
(In the formula, Sa is the solubility index of the thermoplastic polyester resin A, Sc is the solubility index of the polyamide resin C, Sd is the solubility index of the polyamide resin D, and each solubility index is calculated by the Small method.)
The polyamide resin D satisfying the weight ratio of 99.5 / 0.5 to 80/20 , and the tensile modulus of the mixed resin B taken out from the multilayer container is polyamide resin C instead of the mixed resin B. A multilayer container characterized by being lower than the tensile elastic modulus of the polyamide resin C taken out from the multilayer container prepared in the same manner except that it is used as an intermediate layer.
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。 A multilayer container comprising an outermost layer, an innermost layer and at least one intermediate layer located between the outermost layer and the innermost layer is manufactured using an injection molding machine having a skin side injection cylinder and a core side injection cylinder. In this method, a thermoplastic polyester resin A obtained by polymerizing a dicarboxylic acid component containing 80 mol% or more of terephthalic acid and a diol component containing 80 mol% or more of ethylene glycol is injected from the skin-side injection cylinder. Polyamide resin C obtained by polymerizing a diamine component containing 70 mol% or more of metaxylylenediamine and a dicarboxylic acid component containing 70 mol% or more of adipic acid from the core side injection cylinder, forming the innermost layer and the outermost layer And half-crystallization time in constant temperature crystallization at 80 to 120 ° C. is 1/5 or less of polyamide resin C, and Equation (1):
Sa <Sd <Sc (1)
(In the formula, Sa is the solubility index of the thermoplastic polyester resin A, Sc is the solubility index of the polyamide resin C, Sd is the solubility index of the polyamide resin D, and each solubility index is calculated by the Small method.)
Including a step of injecting a mixed resin B containing 99.5 / 0.5 to 80/20 in a weight ratio of the polyamide resin D satisfying the above to form at least one intermediate layer to produce a multilayer parison A method for producing a multi-layer container.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4720102B2 (en) * | 2003-05-06 | 2011-07-13 | 三菱瓦斯化学株式会社 | Multi-layer container |
| JP4730046B2 (en) * | 2005-10-06 | 2011-07-20 | 東洋製罐株式会社 | Multilayer polyester container and method for producing the same |
| US8778470B2 (en) | 2006-01-18 | 2014-07-15 | Mitsubishi Gas Chemical Company, Inc. | Multi-layer bottle |
| JP4821353B2 (en) * | 2006-02-09 | 2011-11-24 | 三菱瓦斯化学株式会社 | Multilayer bottle |
| JP5076541B2 (en) * | 2007-02-19 | 2012-11-21 | 三菱瓦斯化学株式会社 | Multi-layer injection molded product with excellent barrier properties |
| EP2979984B8 (en) * | 2013-03-28 | 2020-02-26 | Mitsubishi Gas Chemical Company, Inc. | Delamination container and method of producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52141785A (en) * | 1976-05-20 | 1977-11-26 | Toyo Seikan Kaisha Ltd | Container |
| JPS63178930A (en) * | 1986-12-27 | 1988-07-23 | 三菱瓦斯化学株式会社 | Multilayer vessel |
| JPH04120168A (en) * | 1990-09-11 | 1992-04-21 | Mitsubishi Gas Chem Co Inc | Polyamide resin composition and polyamide film |
| JP2001199024A (en) * | 2000-01-21 | 2001-07-24 | Mitsubishi Gas Chem Co Inc | Multilayered container |
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2004
- 2004-04-27 JP JP2004131598A patent/JP4561965B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52141785A (en) * | 1976-05-20 | 1977-11-26 | Toyo Seikan Kaisha Ltd | Container |
| JPS63178930A (en) * | 1986-12-27 | 1988-07-23 | 三菱瓦斯化学株式会社 | Multilayer vessel |
| JPH04120168A (en) * | 1990-09-11 | 1992-04-21 | Mitsubishi Gas Chem Co Inc | Polyamide resin composition and polyamide film |
| JP2001199024A (en) * | 2000-01-21 | 2001-07-24 | Mitsubishi Gas Chem Co Inc | Multilayered container |
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