JP2005306419A - Multi-layered container - Google Patents
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- Publication number
- JP2005306419A JP2005306419A JP2004124287A JP2004124287A JP2005306419A JP 2005306419 A JP2005306419 A JP 2005306419A JP 2004124287 A JP2004124287 A JP 2004124287A JP 2004124287 A JP2004124287 A JP 2004124287A JP 2005306419 A JP2005306419 A JP 2005306419A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- layer
- dicarboxylic acid
- multilayer container
- gas barrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004952 Polyamide Substances 0.000 claims abstract description 106
- 229920002647 polyamide Polymers 0.000 claims abstract description 106
- 239000010410 layer Substances 0.000 claims abstract description 85
- 230000004888 barrier function Effects 0.000 claims abstract description 65
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000155 melt Substances 0.000 claims abstract description 28
- 238000002844 melting Methods 0.000 claims abstract description 20
- 230000008018 melting Effects 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 150000004985 diamines Chemical class 0.000 claims abstract description 14
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 14
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 10
- 239000012790 adhesive layer Substances 0.000 claims abstract description 7
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- 239000004743 Polypropylene Substances 0.000 claims description 59
- -1 polypropylene Polymers 0.000 claims description 49
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 239000007790 solid phase Substances 0.000 claims description 17
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004429 atom Chemical group 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 9
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 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
- 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
- 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 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 46
- 229910052760 oxygen Inorganic materials 0.000 abstract description 46
- 239000001301 oxygen Substances 0.000 abstract description 46
- 239000007789 gas Substances 0.000 abstract description 41
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000011347 resin Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 description 29
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 22
- 235000013305 food Nutrition 0.000 description 21
- 150000003839 salts Chemical class 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 235000014113 dietary fatty acids Nutrition 0.000 description 19
- 239000000194 fatty acid Substances 0.000 description 19
- 229930195729 fatty acid Natural products 0.000 description 19
- 150000004665 fatty acids Chemical class 0.000 description 19
- 150000003863 ammonium salts Chemical class 0.000 description 18
- 238000000465 moulding Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000008188 pellet Substances 0.000 description 16
- 238000003856 thermoforming Methods 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000002087 whitening effect Effects 0.000 description 12
- 239000004840 adhesive resin Substances 0.000 description 11
- 229920006223 adhesive resin Polymers 0.000 description 11
- 239000001361 adipic acid Substances 0.000 description 11
- 235000011037 adipic acid Nutrition 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 10
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 10
- 240000007594 Oryza sativa Species 0.000 description 9
- 235000007164 Oryza sativa Nutrition 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 8
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 235000009566 rice Nutrition 0.000 description 8
- 230000001954 sterilising effect Effects 0.000 description 8
- 238000004659 sterilization and disinfection Methods 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- 230000001771 impaired effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 235000021357 Behenic acid Nutrition 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229920003188 Nylon 3 Polymers 0.000 description 3
- 229920001007 Nylon 4 Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229940116226 behenic acid Drugs 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000003827 glycol group Chemical group 0.000 description 3
- 239000011229 interlayer Substances 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
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 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
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000014347 soups Nutrition 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009966 trimming Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920003355 Novatec® Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 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
- 235000016213 coffee Nutrition 0.000 description 2
- 235000013353 coffee beverage Nutrition 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000001419 dependent effect Effects 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
- 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
- 238000009826 distribution Methods 0.000 description 2
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical class CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 235000013616 tea Nutrition 0.000 description 2
- 238000002834 transmittance Methods 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
- 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 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-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
- 229920000089 Cyclic olefin copolymer Polymers 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
- 235000009419 Fagopyrum esculentum Nutrition 0.000 description 1
- 240000008620 Fagopyrum esculentum Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical class NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 244000294411 Mirabilis expansa Species 0.000 description 1
- 235000015429 Mirabilis expansa Nutrition 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 235000007189 Oryza longistaminata Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000533293 Sesbania emerus Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-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
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 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
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- DEOSEFTVDAEGAD-UHFFFAOYSA-N benzyl-dihexadecyl-methylazanium Chemical class CCCCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCCCC)CC1=CC=CC=C1 DEOSEFTVDAEGAD-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KKWVJXUQYDCFGB-UHFFFAOYSA-N butyl(tridodecyl)azanium Chemical class CCCCCCCCCCCC[N+](CCCC)(CCCCCCCCCCCC)CCCCCCCCCCCC KKWVJXUQYDCFGB-UHFFFAOYSA-N 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
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- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
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- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- HUZVOFBJZJVUBY-UHFFFAOYSA-N methyl(trioctadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC HUZVOFBJZJVUBY-UHFFFAOYSA-N 0.000 description 1
- XJPLVFCEZXTPJP-UHFFFAOYSA-N methyl-tri(tetradecyl)azanium Chemical class CCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCC)CCCCCCCCCCCCCC XJPLVFCEZXTPJP-UHFFFAOYSA-N 0.000 description 1
- 235000013536 miso Nutrition 0.000 description 1
- 125000001421 myristyl 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])[H] 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
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- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
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- 235000013555 soy sauce Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 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
- WIMCSFQYNXRDOM-UHFFFAOYSA-N tridodecyl(ethyl)azanium Chemical class CCCCCCCCCCCC[N+](CC)(CCCCCCCCCCCC)CCCCCCCCCCCC WIMCSFQYNXRDOM-UHFFFAOYSA-N 0.000 description 1
- ADBMSVFHVFJBFR-UHFFFAOYSA-N triethyl(hexadecyl)azanium Chemical class CCCCCCCCCCCCCCCC[N+](CC)(CC)CC ADBMSVFHVFJBFR-UHFFFAOYSA-N 0.000 description 1
- CENIAFYRIODGSU-UHFFFAOYSA-N triethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](CC)(CC)CC CENIAFYRIODGSU-UHFFFAOYSA-N 0.000 description 1
- JXCCIZBMTUFJKN-UHFFFAOYSA-N triethyl(tetradecyl)azanium Chemical class CCCCCCCCCCCCCC[N+](CC)(CC)CC JXCCIZBMTUFJKN-UHFFFAOYSA-N 0.000 description 1
- AUSVCTPDUJVUGB-UHFFFAOYSA-N trimethyl(octadec-1-enyl)azanium Chemical class CCCCCCCCCCCCCCCCC=C[N+](C)(C)C AUSVCTPDUJVUGB-UHFFFAOYSA-N 0.000 description 1
- ZBMLLSYGUXEKLB-UHFFFAOYSA-N trimethyl(octadeca-1,3-dienyl)azanium Chemical class CCCCCCCCCCCCCCC=CC=C[N+](C)(C)C ZBMLLSYGUXEKLB-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は食品向け多層容器に関する。詳しくは、容器外部からの酸素透過を防止し、食品の賞味期限を延長することを可能とする多層容器に関する。 The present invention relates to a multilayer container for food. More specifically, the present invention relates to a multilayer container that can prevent oxygen permeation from the outside of the container and extend the shelf life of food.
ポリオレフィンからなる容器は、その汎用性、容易な加工性等の面から、様々な食品を収納する容器として広く利用されている。特にポリプロピレン（以下、ＰＰと略することがある）からなる容器は、同じく汎用性の高い材料として使用されているポリエチレンと比較して融点が高いことから、加熱殺菌処理を必要とする食品の保存容器としても広く利用されている。しかしながら、ＰＰは食品の劣化の原因となる酸素が透過しやすい性質を有しているため、食品を長期間保存するための容器としては性能が不十分であり、特に加熱殺菌処理される食品に適用すると、加熱殺菌処理中に食品が酸化劣化してしまうことがあった。 A container made of polyolefin is widely used as a container for storing various foods in terms of versatility and easy processability. In particular, containers made of polypropylene (hereinafter sometimes abbreviated as PP) have a higher melting point than polyethylene, which is also used as a highly versatile material. It is also widely used as a container. However, since PP has the property of easily permeating oxygen that causes deterioration of food, its performance is insufficient as a container for storing food for a long period of time. When applied, the food may be oxidized and deteriorated during the heat sterilization treatment.
食品の長期保存を可能とする方法としては、ＰＰからなる容器に中間層として酸素バリア性を持つ熱可塑性樹脂を存在させた多層容器を用いる方法が知られている。ガスバリア層を構成する樹脂としては、エチレン−ビニルアルコール共重合体（以下、ＥＶＯＨと略することがある）が知られている。ＥＶＯＨは優れた酸素バリア性を持つ樹脂であり、様々な食品を長期保存するための容器に広く利用されているが、酸素バリア性の湿度依存性が高い欠点を有する。特に加熱殺菌処理を必要とする食品を収納する場合においては、加熱殺菌処理時には熱水または水蒸気に一定時間さらされることになるため、ＥＶＯＨをガスバリア層とした多層容器は加熱殺菌処理時に大きく酸素バリア性が低下する。しかも、加熱殺菌処理後においてもＥＶＯＨは酸素バリア性が大幅に低下したままであり、経時的に元の酸素バリア性能に回復していくものの、完全な回復には長い時間を要するため、その間に大量の酸素透過を許すこととなり、結果として食品の保存性には問題が残るものであった。 As a method for enabling long-term storage of food, a method using a multilayer container in which a thermoplastic resin having an oxygen barrier property is present as an intermediate layer in a container made of PP is known. As a resin constituting the gas barrier layer, an ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) is known. EVOH is a resin having an excellent oxygen barrier property and is widely used in containers for long-term storage of various foods, but has a drawback that the oxygen barrier property is highly dependent on humidity. In particular, when foods that require heat sterilization are stored, the multilayer container using EVOH as a gas barrier layer has a large oxygen barrier during heat sterilization because it is exposed to hot water or steam for a certain period of time during heat sterilization. Sex is reduced. Moreover, even after the heat sterilization treatment, EVOH still has a significantly reduced oxygen barrier property, and although it recovers to the original oxygen barrier performance over time, it takes a long time for complete recovery. A large amount of oxygen permeation was allowed, and as a result, there was a problem in food storage stability.
ＥＶＯＨ以外に酸素バリア性に優れた熱可塑性樹脂としては、ポリメタキシリレンアジパミド（以下、Ｎ−ＭＸＤ６と略することがある）が知られており、ＰＰと組み合わせた多層容器が開示されている（特許文献１参照）。ポリメタキシリレンアジパミドはメタキシリレンジアミンとアジピン酸を重縮合させて得られるポリアミドであり、ＥＶＯＨよりも湿度依存性が低く、加熱殺菌処理時においても酸素バリア性低下が小さい特徴を有しているため、容器内部への酸素透過量を低く抑えることができ、食品の保存性を高めることができる。 In addition to EVOH, polymetaxylylene adipamide (hereinafter sometimes abbreviated as N-MXD6) is known as a thermoplastic resin excellent in oxygen barrier properties, and a multilayer container combined with PP is disclosed. (See Patent Document 1). Polymetaxylylene adipamide is a polyamide obtained by polycondensation of metaxylylenediamine and adipic acid. It is less dependent on humidity than EVOH and has a low oxygen barrier property even during heat sterilization. Therefore, the amount of oxygen permeation into the container can be kept low, and the storage stability of food can be improved.
一般的にＰＰを主体とする容器は、ＰＰからなるシートを予め作製し、これを再加熱して真空、圧空、あるいは真空と圧空を併用して金型に密着させる成形方法、いわゆる熱成形法で加工することにより得られる。通常採用される条件ではＰＰを主体とするシートの表面温度を１６０〜１７０℃付近に加熱してから容器化するが、Ｎ−ＭＸＤ６は該温度付近で比較的速い速度で結晶化する性質を持つため、ＰＰとＮ−ＭＸＤ６を複合化した多層シートから容器を成形する際においては、シートを加熱している最中にＮ−ＭＸＤ６が結晶化してその部分が延伸することができなくなり、その結果、容器の成形不良を起こすことがあった。このことから、Ｎ−ＭＸＤ６を利用した容器は種々の食品の保存性に優れるという性質を有するものの、ＰＰとの複合化を行うと容器を得ることが困難であるという欠点を有していたため、実用化が進まなかった。 In general, a container mainly composed of PP is a molding method in which a sheet made of PP is prepared in advance and re-heated to adhere to a mold using vacuum, compressed air, or a combination of vacuum and compressed air, so-called thermoforming method. It is obtained by processing with. Under normal conditions, the surface temperature of the sheet mainly composed of PP is heated to around 160 to 170 ° C. and then formed into a container, but N-MXD6 has the property of crystallizing at a relatively high rate near the temperature. Therefore, when a container is formed from a multilayer sheet in which PP and N-MXD6 are combined, N-MXD6 is crystallized while the sheet is heated, and the portion cannot be stretched. In some cases, the container was poorly molded. From this, although the container using N-MXD6 has the property of being excellent in the storage stability of various foods, it has the disadvantage that it is difficult to obtain a container when combined with PP. Practical use did not progress.
一方、ＰＰと酸素バリア性樹脂からなる多層容器に用いられるＰＰは、シート成形時や熱成形時のドローダウンを防止するために一般にメルトインデックスの低い樹脂が使用される。そのため、ＰＰと複合化される酸素バリア性樹脂は十分に高い溶融粘度を持つものでないと、ＰＰと多層化したときに厚み制御が困難になったり、シート端部に酸素バリア性樹脂が大きくはみ出して、酸素バリア性樹脂を大きくロスすることがあった。これを解決するには、酸素バリア性樹脂の溶融粘度を高めることが有効である。ポリアミドは溶融重縮合によって製造されるが、溶融重縮合では製造装置上の問題から、到達できるポリアミドの分子量には限界があり、一般にＰＰと複合化して多層シートを製造するには溶融粘度が不十分である。溶融重縮合により得られたポリアミドの分子量を更に高めるには、固相重合がよく用いられるが、ポリアミドが非晶性の場合、固相重合装置内壁にポリマーが付着してしまうため、非晶性ポリアミドでは固相重合により分子量を高めることは事実上困難であった。 On the other hand, a PP having a low melt index is generally used for PP used in a multilayer container composed of PP and an oxygen barrier resin in order to prevent drawdown during sheet molding or thermoforming. Therefore, unless the oxygen barrier resin compounded with PP has a sufficiently high melt viscosity, it becomes difficult to control the thickness when multilayered with PP, or the oxygen barrier resin protrudes greatly at the sheet edge. As a result, the oxygen barrier resin may be largely lost. In order to solve this, it is effective to increase the melt viscosity of the oxygen barrier resin. Polyamide is produced by melt polycondensation. However, in melt polycondensation, the molecular weight of the polyamide that can be reached is limited due to problems in the production equipment. Generally, melt viscosity is inadequate for producing a multilayer sheet by compounding with PP. It is enough. In order to further increase the molecular weight of the polyamide obtained by melt polycondensation, solid-phase polymerization is often used. However, if the polyamide is amorphous, the polymer will adhere to the inner wall of the solid-phase polymerization apparatus. In polyamide, it was practically difficult to increase the molecular weight by solid phase polymerization.
Ｎ−ＭＸＤ６に第３成分として芳香族ジカルボン酸を共重合させることにより結晶性が低下し、非晶化していくことが開示されている（特許文献２、３参照）。非晶化が進むと一般的に結晶化速度は遅くなる傾向にあるため、前記ポリアミドをＰＰと複合化した容器では、Ｎ−ＭＸＤ６とＰＰの複合容器で問題であった熱成形性は改善される傾向にある。しかしながら、Ｎ−ＭＸＤ６の非晶性を高めすぎると、得られたポリマーは前述のように固相重合することができないため、ＰＰと複合化して多層容器を形成する材料としての溶融粘度に調整することが困難であった。
本発明の目的は、上記課題を解決し、Ｎ−ＭＸＤ６の持つ酸素バリア性の特性を損なわずに、シート加工安定性に優れ、かつ熱成形性を改善した酸素バリア性樹脂を中間層とした多層容器を提供することにあり、特に加熱殺菌処理食品の保存に適した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 to use an oxygen barrier resin having excellent sheet processing stability and improved thermoformability as an intermediate layer without impairing the oxygen barrier properties of N-MXD6. The object is to provide a multi-layer container, and in particular to provide a multi-layer container suitable for storage of heat-sterilized food.
本発明者らは、上記多層容器について鋭意研究を重ねた結果、Ｎ−ＭＸＤ６に第３成分として芳香族ジカルボン酸を特定の範囲で共重合したポリアミドがＰＰと複合化するに適した溶融粘度まで高めることができるため、多層シート成形を安定して行うことができ、さらにこれとＰＰを複合化したシートが熱成形性に優れ、得られたＰＰ多層容器は酸素バリア性に優れると共に優れた加熱殺菌処理耐性を発揮できることを見出し、本発明を完成するに到った。 As a result of intensive research on the multilayer container, the present inventors have obtained a melt viscosity suitable for complexing with a polyamide in which a polyamide obtained by copolymerizing aromatic dicarboxylic acid as a third component in N-MXD6 in a specific range is combined. Therefore, it is possible to stably form a multilayer sheet, and a sheet obtained by combining PP and PP is excellent in thermoformability. The obtained PP multilayer container has excellent oxygen barrier properties and excellent heating. The inventors have found that sterilization resistance can be exhibited, and have completed the present invention.
すなわち本発明は、ポリプロピレンを主成分とするＰＰ層、接着性熱可塑性樹脂からなる接着層、およびメタキシリレンジアミンを７０モル％以上含むジアミン成分と７０〜９７モル％のα，ω−直鎖状脂肪族ジカルボン酸と３〜３０モル％の芳香族ジカルボン酸とからなるジカルボン酸成分とを溶融重縮合後にさらに固相重合して得られ、融点＋２０℃、剪断速度１００ｓ−１における溶融粘度が６００〜３０００Ｐａ・ｓであるポリアミドを主成分とするガスバリア層がこの順に積層された３層以上の層構成を有する多層容器に関する。 That is, the present invention relates to a PP layer mainly composed of polypropylene, an adhesive layer composed of an adhesive thermoplastic resin, and a diamine component containing 70 mol% or more of metaxylylenediamine and 70 to 97 mol% α, ω-linear chain. Obtained by melt polycondensation of a dicarboxylic acid component consisting of an aliphatic dicarboxylic acid and 3-30 mol% aromatic dicarboxylic acid after melt polycondensation, and has a melting viscosity at a melting point of + 20 ° C. and a shear rate of 100 s −1 . The present invention relates to a multilayer container having a layer structure of three or more layers in which gas barrier layers mainly composed of polyamide of 600 to 3000 Pa · s are laminated in this order.
本発明の多層容器は、安定した成形加工性を有し、かつガスバリア性に優れた多層容器であり、各種食品の包装材料として非常に有用なものであり、その工業的価値は非常に高い。 The multilayer container of the present invention is a multilayer container having stable molding processability and excellent gas barrier properties, and is very useful as a packaging material for various foods, and its industrial value is very high.
本発明の多層容器は、ＰＰ層、接着層、およびガスバリア層の少なくとも３層がこの順に積層されてなるものである。該多層容器は前記３層がその順に積層されていればよく、その層間に中間層が積層されていても良い。また、この３層の外側に更に接着層やＰＰ層、または別の樹脂からなる層が積層されていても良い。 The multilayer container of the present invention is formed by laminating at least three layers of a PP layer, an adhesive layer, and a gas barrier layer in this order. The multilayer container only needs to have the three layers stacked in that order, and an intermediate layer may be stacked between the layers. Further, an adhesive layer, a PP layer, or a layer made of another resin may be further laminated outside the three layers.
本発明の多層容器を構成するＰＰ層は、ＰＰを主成分とする層であり、ガスバリア層を食品から隔離する役割、容器に食品を収納後、トップフィルムと接着するためのシーラントとしての役割を有する。ＰＰは公知のものを使用することができる。具体的にはその化学構造から、ホモポリプロピレン、プロピレン−エチレンランダムコポリマー、プロピレン−エチレンブロックコポリマーが挙げられる。ＰＰ層にはその美観を整えるために、酸化チタン等の着色顔料を添加することができ、さらにＰＰの酸化劣化を防止するための酸化防止剤や艶消剤、耐候安定剤、紫外線吸収剤、核剤、可塑剤、難燃剤、帯電防止剤等の添加剤を加えることができる。また、場合によってはＰＰの物性を改質するためにポリエチレンやエチレン−α−オレフィン共重合体等の熱可塑性樹脂を加えることもできる。 The PP layer constituting the multilayer container of the present invention is a layer mainly composed of PP, and serves as a sealant for adhering the gas barrier layer from the food and adhering to the top film after the food is stored in the container. Have. A known PP can be used. Specific examples thereof include homopolypropylene, propylene-ethylene random copolymer, and propylene-ethylene block copolymer. In order to adjust the appearance of the PP layer, a coloring pigment such as titanium oxide can be added. Further, an antioxidant, a matting agent, a weathering stabilizer, a UV absorber, Additives such as nucleating agents, plasticizers, flame retardants and antistatic agents can be added. In some cases, a thermoplastic resin such as polyethylene or ethylene-α-olefin copolymer may be added to modify the physical properties of PP.
本発明で使用するＰＰはメルトインデックスが０．３〜５（ｇ／１０分、２３０℃、２．１６ｋｇｆ）のものを使用することが好ましく、より好ましくは０．４〜４（ｇ／１０分、２３０℃、２．１６ｋｇｆ）、さらに好ましくは０．５〜３（ｇ／１０分、２３０℃、２．１６ｋｇｆ）である。メルトインデックスが０．３（ｇ／１０分、２３０℃、２．１６ｋｇｆ）を下回ると押出加工が困難になるため好ましくない。また５（ｇ／１０分、２３０℃、２．１６ｋｇｆ）を超えると、シート製造時や熱成形による容器製造時に、シートのドローダウンが大きくなりすぎてシートの外観を損ねたり、容器成形不良を起こしやすくなるため好ましくない。 The PP used in the present invention preferably has a melt index of 0.3 to 5 (g / 10 minutes, 230 ° C., 2.16 kgf), more preferably 0.4 to 4 (g / 10 minutes). 230 ° C., 2.16 kgf), more preferably 0.5 to 3 (g / 10 min, 230 ° C., 2.16 kgf). If the melt index is less than 0.3 (g / 10 min, 230 ° C., 2.16 kgf), extrusion processing becomes difficult, which is not preferable. On the other hand, if it exceeds 5 (g / 10 min, 230 ° C., 2.16 kgf), the sheet drawdown becomes excessively large at the time of manufacturing the sheet or the container by thermoforming, and the appearance of the sheet is impaired, or the container molding is poor. It is not preferable because it tends to occur.
本発明の多層容器を構成する接着層は、ＰＰ層とガスバリア層を十分な強度で接着する役割を有する。接着層に使用される接着性熱可塑性樹脂としては、例えば、オレフィン系樹脂をアクリル酸、メタクリル酸、マレイン酸、無水マレイン酸等の不飽和カルボン酸で変性した酸変性ポリオレフィン類等が挙げられる。この中でも、ポリプロピレンを主成分とし、これを変性した系がＰＰとの接着性の面から特に好ましく用いられる。 The adhesive layer constituting the multilayer container of the present invention has a role of adhering the PP layer and the gas barrier layer with sufficient strength. Examples of the adhesive thermoplastic resin used in the adhesive layer include acid-modified polyolefins obtained by modifying an olefin resin with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, and maleic anhydride. Among these, a system mainly composed of polypropylene and modified thereof is particularly preferably used from the viewpoint of adhesiveness with PP.
本発明の多層容器を構成するガスバリア層は、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と７０〜９７モル％のα，ω−直鎖状脂肪族ジカルボン酸と３〜３０モル％の芳香族ジカルボン酸とからなるジカルボン酸成分とを重縮合して得られるポリアミドからなり、容器外部から進入する酸素を遮断し、食品の酸化劣化を防止する役割を有する。 The gas barrier layer constituting the multilayer container of the present invention comprises a diamine component containing 70% by mole or more of metaxylylenediamine, 70 to 97% by mole of α, ω-linear aliphatic dicarboxylic acid and 3 to 30% by mole of fragrance. It consists of a polyamide obtained by polycondensation with a dicarboxylic acid component consisting of a group dicarboxylic acid, and has the role of blocking oxygen entering from the outside of the container and preventing oxidative degradation of food.
ポリアミドを構成するジアミン成分としては、メタキシリレンジアミンが７０モル％以上含まれることが必要であり、より好ましくは８０モル％以上、さらに好ましくは９０モル％以上である。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、それから得られるポリアミドは優れたガスバリア性を発現することができる。メタキシリレンジアミン以外に使用できるジアミンとしては、パラキシリレンジアミン、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、テトラメチレンジアミン、ヘキサメチレンジアミン、ノナメチレンジアミン、２−メチル−１，５−ペンタンジアミン等が例示できるが、これらに限定されるものではない。 The diamine component constituting the polyamide is required to contain 70 mol% or more of metaxylylenediamine, more preferably 80 mol% or more, and still more preferably 90 mol% or more. When the metaxylylenediamine in the diamine component is 70 mol% or more, the polyamide obtained therefrom can exhibit excellent gas barrier properties. Examples of diamines that can be used in addition to metaxylylenediamine include paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, tetramethylenediamine, hexamethylenediamine, and nonamethylenediamine. , 2-methyl-1,5-pentanediamine and the like, but are not limited thereto.
またポリアミドを構成するジカルボン酸成分は、７０〜９７モル％のα，ω−直鎖状脂肪族ジカルボン酸と３〜３０モル％の芳香族ジカルボン酸とからなり、好ましくは、７５〜９６モル％のα，ω−直鎖状脂肪族ジカルボン酸と４〜２５モル％の芳香族ジカルボン酸、より好ましくは、８０〜９５モル％のα，ω−直鎖状脂肪族ジカルボン酸と５〜２０モル％の芳香族ジカルボン酸である。α，ω−直鎖状脂肪族ジカルボン酸としては、炭素数４〜２０のα，ω−直鎖状脂肪族ジカルボン酸のうち１種以上が使用され、特に好ましくはアジピン酸が使用される。また、芳香族ジカルボン酸としてはイソフタル酸、および２，６−ナフタレンジカルボン酸から選ばれる１種以上が使用され、特に好ましくはイソフタル酸である。ジカルボン酸成分のうち、α，ω−直鎖状脂肪族ジカルボン酸が７０モル％以上であると、ガスバリア性の低下や結晶性の過度の低下を避けることができる。また芳香族ジカルボン酸が３モル％以上であると、ポリアミドの非晶性が増加して結晶化速度が低下するため、容器成形時の熱成形性が良好になる。ただし、芳香族ジカルボン酸が３０モル％を超えると、ポリアミドは結晶性をほとんど示さなくなるため、固相重合することが困難となり、所望の溶融粘度を有するポリアミドに加工することができなくなるため好ましくない。 The dicarboxylic acid component constituting the polyamide is composed of 70 to 97 mol% α, ω-linear aliphatic dicarboxylic acid and 3 to 30 mol% aromatic dicarboxylic acid, preferably 75 to 96 mol%. Of α, ω-linear aliphatic dicarboxylic acid and 4 to 25 mol% of aromatic dicarboxylic acid, more preferably 80 to 95 mol% of α, ω-linear aliphatic dicarboxylic acid and 5 to 20 mol % Aromatic dicarboxylic acid. As the α, ω-linear aliphatic dicarboxylic acid, one or more of α, ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms are used, and adipic acid is particularly preferably used. As the aromatic dicarboxylic acid, at least one selected from isophthalic acid and 2,6-naphthalenedicarboxylic acid is used, and isophthalic acid is particularly preferable. Among the dicarboxylic acid components, when the α, ω-linear aliphatic dicarboxylic acid is 70 mol% or more, it is possible to avoid a decrease in gas barrier properties and an excessive decrease in crystallinity. On the other hand, if the aromatic dicarboxylic acid content is 3 mol% or more, the amorphous property of the polyamide increases and the crystallization rate decreases, so that the thermoformability at the time of molding the container is improved. However, if the aromatic dicarboxylic acid exceeds 30 mol%, the polyamide hardly exhibits crystallinity, so that it is difficult to perform solid-phase polymerization, and it is not preferable because it cannot be processed into a polyamide having a desired melt viscosity. .
上記のポリアミドは、溶融重縮合法により製造された後、さらに固相重合されたものである。溶融重縮合法としては、例えばジアミン成分とジカルボン酸成分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、ジアミン成分を溶融状態のジカルボン酸成分に直接加えて、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、ジアミン成分をジカルボン酸成分に連続的に加え、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。溶融重縮合で得られたポリマーは一旦取り出された後、さらに固相重合する。固相重合で用いられる加熱装置としては、連続式の加熱装置より、気密性に優れ高度に酸素とポリアミドとの接触を絶つことができる回分式加熱装置が好ましく、特にタンブルドライヤー、コニカルドライヤー、ロータリードライヤー等と称される回転ドラム式の加熱装置およびナウタミキサーと称される内部に回転翼を備えた円錐型の加熱装置が好適に使用できるが、これらに限定されるものではない。 The above polyamide is produced by a melt polycondensation method and then further solid phase polymerized. As the melt polycondensation method, for example, there is a method in which a nylon salt composed of a diamine component and a dicarboxylic acid component 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 a diamine component is directly added to a molten dicarboxylic acid component and polycondensed. In this case, in order to keep the reaction system in a uniform liquid state, the diamine component is continuously added to the dicarboxylic acid component, and the reaction system is heated up so that the reaction temperature does not fall below the melting point of the generated oligoamide and polyamide. However, polycondensation proceeds. The polymer obtained by melt polycondensation is once taken out and further solid-phase polymerized. The heating device used in the solid-phase polymerization is preferably a batch heating device that is superior in air tightness and capable of cutting off the contact between oxygen and polyamide at a higher level than a continuous heating device, particularly a tumble dryer, a conical dryer, and a rotary. A rotating drum type heating device called a drier or the like and a conical heating device called a Nauta mixer with rotating blades inside can be preferably used, but are not limited thereto.
ポリアミドの固相重合工程は、例えば、ポリアミドペレット同士が融着したり、ポリアミドペレットが装置内壁に付着しないよう、ポリアミドの結晶化度を高める第一の工程、ポリアミドの分子量を高める第二の工程、所望の分子量まで固相重合を進めた後にポリアミドを冷却する第三の工程により進められる。第一の工程はポリアミドのガラス転移温度以下で行うことが好ましい。第二の工程は減圧下でポリアミドの融点よりも低い温度で行うことが好ましいが、本発明で行われるポリアミドの固相重合はこれに限定されるものではない。 The solid phase polymerization step of polyamide is, for example, a first step of increasing the degree of crystallinity of polyamide so that the polyamide pellets are not fused to each other or adhered to the inner wall of the apparatus, and a second step of increasing the molecular weight of polyamide. The solid phase polymerization is advanced to a desired molecular weight, and then the polyamide is cooled in the third step. The first step is preferably performed at a temperature below the glass transition temperature of the polyamide. The second step is preferably performed at a temperature lower than the melting point of the polyamide under reduced pressure, but the solid phase polymerization of the polyamide performed in the present invention is not limited to this.
本発明で用いられるポリアミドは、融点＋２０℃、剪断速度１００ｓ−１における溶融粘度が６００〜３０００Ｐａ・ｓであることが好ましく、より好ましくは７００〜２８００Ｐａ・ｓであり、さらに好ましくは８００〜２６００Ｐａ・ｓである。溶融粘度が６００Ｐａ・ｓを下回ると、多層容器の前駆体である多層シートを製造する際に、ポリアミドがシートの両端に大きくはみ出してしまい、シート幅方向のガスバリア層の厚みバランスが損なわれたりするため好ましくない。また３０００Ｐａ・ｓを上回ると、ポリアミドの溶融粘度が高すぎて多層シートの押し出し加工性を損なうことがあるため好ましくない。ポリアミドの溶融粘度を上記範囲に設定することで、ＰＰと複合化しても厚みバランスを良好に保ちながら多層シートを製造することができる。なお、ポリアミドの溶融粘度はＰＰのメルトインデックスが比較的低い場合は高めに、ＰＰのメルトインデックスが比較的高い場合は低めに設定することが好ましい。 The polyamide used in the present invention preferably has a melt viscosity of 600 to 3000 Pa · s at a melting point of + 20 ° C. and a shear rate of 100 s −1 , more preferably 700 to 2800 Pa · s, and still more preferably 800 to 2600 Pa · s. s. When the melt viscosity is less than 600 Pa · s, when the multilayer sheet which is a precursor of the multilayer container is produced, the polyamide greatly protrudes at both ends of the sheet, and the thickness balance of the gas barrier layer in the sheet width direction is impaired. Therefore, it is not preferable. On the other hand, if it exceeds 3000 Pa · s, the melt viscosity of the polyamide is too high, and the extrusion processability of the multilayer sheet may be impaired. By setting the melt viscosity of the polyamide within the above range, a multilayer sheet can be produced while maintaining a good thickness balance even when combined with PP. The melt viscosity of polyamide is preferably set high when the PP melt index is relatively low, and low when the PP melt index is relatively high.
上記のポリアミドには、溶融成形時の加工安定性を高めるため、あるいはポリアミドの着色を防止するためにリン化合物が含まれていても良い。リン化合物としてはアルカリ金属又はアルカリ土類金属を含むリン化合物が好適に使用され、例えば、ナトリウム、マグネシウム、カルシウム等のリン酸塩、次亜リン酸塩、亜リン酸塩が挙げられ、アルカリ金属又はアルカリ土類金属の次亜リン酸塩を使用したものがポリアミドの着色防止効果に特に優れるため好ましく用いられる。また、上記ポリアミドには上記のリン化合物の他に本発明の効果を損なわない範囲で滑剤、艶消剤、耐熱安定剤、耐候安定剤、紫外線吸収剤、核剤、可塑剤、難燃剤、帯電防止剤、着色防止剤、ゲル化防止剤等の添加剤等を加えることもできるが、以上に示したものに限定されることなく、種々の材料を混合しても良い。 The above polyamide may contain a phosphorus compound in order to increase the processing stability during melt molding or to prevent the polyamide from being colored. As the phosphorus compound, a phosphorus compound containing an alkali metal or an alkaline earth metal is preferably used. Examples thereof include phosphates such as sodium, magnesium and calcium, hypophosphites and phosphites, and alkali metals. Alternatively, a material using an alkaline earth metal hypophosphite is preferably used because it is particularly excellent in the anti-coloring effect of the polyamide. In addition to the above phosphorus compounds, the above-mentioned polyamides include lubricants, matting agents, heat stabilizers, weather stabilizers, UV absorbers, nucleating agents, plasticizers, flame retardants, electrification, as long as the effects of the present invention are not impaired. Additives such as an inhibitor, an anti-coloring agent, and an anti-gelling agent can be added, but the present invention is not limited to those shown above, and various materials may be mixed.
また、本発明の特徴を損なわない範囲で上記ポリアミドには、他の熱可塑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、例えばポリエチレンやポリプロピレン等の各種ポリオレフィン、ＰＥＴやポリエチレン−２，６−ナフタレンジカルボキシレート等の各種ポリエステル、ポリアミド６やポリアミド６６、非晶性ポリアミド等の各種ポリアミド、熱可塑性エラストマー、ポリスチレン、アイオノマー等、種々の熱可塑性樹脂が挙げられる。 Moreover, the said polyamide can be mix | blended and used for the said polyamide in the range which does not impair the characteristic of this invention. Examples of other thermoplastic resins include various polyolefins such as polyethylene and polypropylene, various polyesters such as PET and polyethylene-2,6-naphthalene dicarboxylate, various polyamides such as polyamide 6 and polyamide 66, amorphous polyamide, and heat. Various thermoplastic resins such as plastic elastomer, polystyrene, ionomer and the like can be mentioned.
本発明で使用するポリアミドは、場合によっては吸水によって結晶化して白化し、多層容器の外観を損なうことがある。このような現象を防ぐために、本発明ではポリアミドに、白化防止剤として、特定の脂肪酸金属塩、ジアミド化合物あるいはジエステル化合物を添加したものを容器のガスバリア層として使用することが好ましく行われる。このようにすることで内容物を充填した多層容器を長期間保存してもポリアミドの白化が防止される。 In some cases, the polyamide used in the present invention crystallizes and whitens due to water absorption, which may impair the appearance of the multilayer container. In order to prevent such a phenomenon, in the present invention, it is preferable to use a polyamide obtained by adding a specific fatty acid metal salt, diamide compound or diester compound as a whitening inhibitor to the gas barrier layer of the container. By doing so, the whitening of the polyamide is prevented even when the multilayer container filled with the contents is stored for a long period of time.
本発明に用いる脂肪酸金属塩は、炭素数１８〜５０、好ましくは、炭素数１８〜３４の脂肪酸金属塩である。炭素数が１８以上であればポリアミドが吸水した際の白化が防止できる。また、炭素数が５０以下で樹脂組成物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 fatty acid metal salt used in the present invention is a fatty acid metal salt having 18 to 50 carbon atoms, preferably 18 to 34 carbon atoms. If the carbon number is 18 or more, whitening when the polyamide absorbs water can be prevented. Moreover, carbon number is 50 or less, and uniform dispersion | distribution in a resin composition becomes favorable. Fatty acids may have side chains or double bonds, but linear saturated such as stearic acid (C18), eicoic 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.
本発明に用いられる脂肪酸金属塩は、上記のうち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、脂肪酸金属塩の形状に特に制限はないが、粒径が小さい方が樹脂組成物中に均一に分散させることが容易に行えるため、その粒径は０．２ｍｍ以下が好ましい。 One type of fatty acid metal salt used in the present invention may be used, or two or more types may be used in combination. In the present invention, the shape of the fatty acid metal salt is not particularly limited. However, the smaller the particle size, the easier it can be uniformly dispersed in the resin composition, and therefore the particle size is preferably 0.2 mm or less.
本発明において、脂肪酸金属塩の添加量は、ポリアミド１００重量部に対して０．００５〜１．０重量部、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。脂肪酸金属塩の添加量が０．００５重量部未満であると実用的な白化防止効果が得られない。また、１．０重量部より多いと脂肪酸金属塩の影響でポリアミドが白くにごるため好ましくない。 In the present invention, the addition amount of the fatty acid metal salt is 0.005 to 1.0 part by weight, preferably 0.05 to 0.5 part by weight, particularly preferably 0.12 to 0. 5 parts by weight. If the added amount of the fatty acid metal salt is less than 0.005 parts by weight, a practical whitening prevention effect cannot be obtained. On the other hand, when the amount is more than 1.0 part by weight, the polyamide becomes white due to the influence of the fatty acid metal salt, which is not preferable.
本発明で用いられるジアミド化合物は、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ジアミド化合物である。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以下で組成物中への均一分散が良好となる。 The diamide compound used in the present invention is a diamide compound obtained from a fatty acid having 8 to 30 carbon atoms and a diamine having 2 to 10 carbon atoms. The effect of preventing whitening can be expected when the fatty acid has 8 or more carbon atoms and the diamine has 2 or more carbon atoms. Moreover, the carbon number of the fatty acid is 30 or less and the carbon number of the diamine is 10 or less, so that uniform dispersion in the composition is good.
ジアミド化合物に用いられる脂肪酸は、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。例として、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）が例示でき、中でもモンタン酸が好ましい。ジアミド化合物に用いられるジアミンとして、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、中でもエチレンジアミンが好ましい。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。ジアミド化合物は１種類でも良いし、２種類以上を併用してもよい。 The fatty acid used in the diamide compound may have a side chain or a double bond, but is preferably a linear saturated fatty acid. Examples include stearic acid (C18), eicoic acid (C20), behenic acid (C22), montanic acid (C28), and triacontanoic acid (C30). Of these, montanic acid is preferred. Examples of the diamine used in the diamide compound include ethylene diamine, butylene diamine, hexane diamine, xylylene diamine, and bis (aminomethyl) cyclohexane. Among them, ethylene diamine is preferable. A diamide compound obtained by combining these is used in the present invention. One kind of diamide compound may be used, or two or more kinds may be used in combination.
本発明で用いられ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ジエステル化合物である。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以下で組成物中への均一分散が良好となる。 The diester compound used in the present invention is a diester compound 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, a whitening prevention effect 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 composition becomes good.
ジエステル化合物に使用される脂肪酸として、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、中でもモンタン酸が好ましい。ジエステル化合物に使用されるジオールとして、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、中でもエチレングリコールあるいは１，３−ブタンジオールが好ましい。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。ジエステル化合物は１種類でも良いし、２種以上を併用しても良い。 Examples of the fatty acid used in the diester compound include stearic acid (C18), eicoic acid (C20), behenic acid (C22), montanic acid (C28), triacontanoic acid (C30), and among them, montanic acid is preferable. Examples of the diol used in the diester compound include ethylene glycol, propanediol, butanediol, hexanediol, xylylene glycol, and cyclohexanedimethanol, and ethylene glycol or 1,3-butanediol is particularly preferable. A diester compound obtained by combining these is used in the present invention. One type of diester compound may be used, or two or more types may be used in combination.
本発明において用いられるジアミド化合物とジエステル化合物は単独で用いても良いし、併用して用いても良い。
本発明において、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１００重量部に対して０．００５〜１．０重量部、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。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が０．００５重量部未満であると実用的な白化防止効果が得られない。また、１．０重量部より多いとジアミド化合物および／またはジエステル化合物の影響でポリアミドが白くにごるため好ましくない。
The diamide compound and diester compound used in the present invention may be used alone or in combination.
In the present invention, the addition amount of the diamide compound and / or diester compound is 0.005 to 1.0 part by weight, preferably 0.05 to 0.5 part by weight, particularly preferably 0.005 part by weight based on 100 parts by weight of the polyamide. 12 to 0.5 parts by weight. When the addition amount of the diamide compound and / or diester compound is less than 0.005 parts by weight, a practical whitening prevention effect cannot be obtained. On the other hand, when the amount is more than 1.0 part by weight, the polyamide becomes white due to the influence of the diamide compound and / or diester compound, which is not preferable.
ポリアミドに上記白化防止剤を添加する方法は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ペレットと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ペレットで所定の濃度で希釈し、これらを溶融混練する方法、溶融混練後、引き続き、射出成形などにより成形体を得る方法などが採用される。 A known mixing method can be applied to the method of adding the whitening inhibitor to the polyamide. For example, polyamide pellets and a whitening inhibitor may be charged and mixed in a rotating hollow container. In addition, after manufacturing a composition containing a high concentration whitening inhibitor, a method of diluting the polyamide pellets containing no whitening inhibitor at a predetermined concentration and then melt-kneading them, followed by melt-kneading, injection molding, etc. For example, a method of obtaining a molded body by the method is adopted.
本発明では、さらに優れた酸素バリア性を付与するために、上記ポリアミドに元素周期律表の第VIII族の遷移金属、マンガン、銅及び亜鉛から選択された一種以上の金属原子を混合して、ガスバリア層に酸素吸収機能を付与することができる。 In the present invention, in order to impart further excellent oxygen barrier properties, the polyamide is mixed with one or more metal atoms selected from Group VIII transition metals of the Periodic Table of Elements, manganese, copper and zinc, An oxygen absorbing function can be imparted to the gas barrier layer.
本発明において前記金属原子をポリアミド中に添加、混合するには金属原子を含有する化合物（以下、金属触媒化合物と称する）を用いることが好ましい。金属触媒化合物は前記金属原子の低価数の無機酸塩、有機酸塩又は錯塩の形で使用される。無機酸塩としては、塩化物や臭化物等のハロゲン化物、硫酸塩、硝酸塩、リン酸塩、ケイ酸塩等が挙げられる。一方、有機酸塩としては、カルボン酸塩、スルホン酸塩、ホスホン酸塩等が挙げられる。また、β−ジケトンまたはβ−ケト酸エステル等との遷移金属錯体も利用することができる。特に本発明では酸素吸収機能が良好であることから、前記金属原子を含むカルボン酸塩、ハロゲン化物、アセチルアセトネート錯体を使用することが好ましい。本発明において、ポリアミドには上記金属触媒化合物のうち一種以上を添加することができるが、コバルト金属原子を含むものが特に酸素吸収機能に優れており、好ましく用いられる。 In the present invention, a compound containing a metal atom (hereinafter referred to as a metal catalyst compound) is preferably used for adding and mixing the metal atom in the polyamide. The metal catalyst compound is used in the form of a low-valent inorganic acid salt, organic acid salt or complex salt of the metal atom. Examples of inorganic acid salts include halides such as chlorides and bromides, sulfates, nitrates, phosphates, silicates, and the like. On the other hand, examples of the organic acid salt include a carboxylate, a sulfonate, and a phosphonate. Also, transition metal complexes with β-diketone or β-keto acid ester can be used. In particular, in the present invention, since the oxygen absorption function is good, it is preferable to use a carboxylate, a halide or an acetylacetonate complex containing the metal atom. In the present invention, one or more of the above metal catalyst compounds can be added to the polyamide, but those containing cobalt metal atoms are particularly excellent in oxygen absorption function and are preferably used.
本発明でポリアミドに添加できる前記金属原子の濃度は特に制限はないが、ポリアミド１００重量部に対して金属原子を０．０１〜０．１０重量部の範囲で添加することが好ましく、より好ましくは０．０２〜０．０８重量部である。金属原子の添加量が０．０１重量部より少ない場合、酸素吸収機能が十分に発現せず、多層容器の酸素バリア性の向上効果も低いものとなる。また０．１０重量部より多い場合、多層容器の酸素バリア性向上効果に変化はないため、不経済である。 The concentration of the metal atom that can be added to the polyamide in the present invention is not particularly limited, but it is preferable to add the metal atom in the range of 0.01 to 0.10 parts by weight, more preferably 100 parts by weight of the polyamide. 0.02 to 0.08 part by weight. When the addition amount of the metal atom is less than 0.01 parts by weight, the oxygen absorption function is not sufficiently exhibited, and the effect of improving the oxygen barrier property of the multilayer container is low. On the other hand, when the amount is more than 0.10 parts by weight, the effect of improving the oxygen barrier property of the multilayer container is not changed, which is uneconomic.
ポリアミドに金属触媒化合物を添加する方法は、ポリアミドと金属触媒化合物を押出機等を用いて溶融混合する方法、金属触媒化合物を溶媒と混合して溶解又はスラリー状にした後、ポリアミドと混合してから溶媒を除去してポリアミドに付着させる方法、多層容器を製造する装置に金属触媒化合物を添加できる装置を設けてポリアミドに金属触媒化合物を添加する方法等を用いることができるが、これらの中でも容易に金属触媒化合物をポリアミド中に混合することが可能であることからポリアミドと金属触媒化合物を押出機等を用いて溶融混合する方法が好ましく行われる。 The method of adding the metal catalyst compound to the polyamide is a method of melt-mixing the polyamide and the metal catalyst compound using an extruder, etc., mixing the metal catalyst compound with a solvent to form a solution or slurry, and then mixing with the polyamide. For example, a method of removing the solvent from the polyamide and attaching it to the polyamide, a method of adding a metal catalyst compound to a device for manufacturing a multilayer container, and a method of adding the metal catalyst compound to the polyamide can be used. Since the metal catalyst compound can be mixed in the polyamide, a method of melt-mixing the polyamide and the metal catalyst compound using an extruder or the like is preferably performed.
さらに本発明では、前記ポリアミドに層状珪酸塩を添加したものをガスバリア層として使用することもできる。このようにすることで容器の酸素バリア性だけではなく、炭酸ガス等の他のガスに対するバリア性も向上させることができる。 Furthermore, in this invention, what added layered silicate to the said polyamide can also be used as a gas barrier layer. By doing in this way, not only the oxygen barrier property of a container but the barrier property with respect to other gas, such as a carbon dioxide gas, can also be improved.
層状珪酸塩は、０．２５〜０．６の電荷密度を有する２−八面体型や３−八面体型の層状珪酸塩であり、２−八面体型としては、モンモリロナイト、バイデライト等、３−八面体型としてはヘクトライト、サボナイト等が挙げられる。これらの中でも、モンモリロナイトが好ましい。 The layered silicate is a 2-octahedral or 3-octahedral layered silicate having a charge density of 0.25 to 0.6. Examples of the 2-octahedral type include montmorillonite, beidellite, and the like. Examples of the octahedron type include hectorite and saponite. Among these, montmorillonite is preferable.
層状珪酸塩は、高分子化合物や有機系化合物等の有機膨潤化剤を予め層状珪酸塩に接触させて、層状珪酸塩の層間を拡げたものとすることが好ましい。有機膨潤化剤として、第４級アンモニウム塩が好ましく使用できるが、好ましくは、炭素数１２以上のアルキル基又はアルケニル基を少なくとも一つ以上有する第４級アンモニウム塩が用いられる。 The layered silicate is preferably obtained by expanding an interlayer of the layered silicate by previously bringing an organic swelling agent such as a polymer compound or an organic compound into contact with the layered silicate. As the organic swelling agent, a quaternary ammonium salt can be preferably used. Preferably, a quaternary ammonium salt having at least one alkyl group or alkenyl group having 12 or more carbon atoms is used.
有機膨潤化剤の具体例として、トリメチルドデシルアンモニウム塩、トリメチルテトラデシルアンモニウム塩、トリメチルヘキサデシルアンモニウム塩、トリメチルオクタデシルアンモニウム塩、トリメチルエイコシルアンモニウム塩等のトリメチルアルキルアンモニウム塩；トリメチルオクタデセニルアンモニウム塩、トリメチルオクタデカジエニルアンモニウム塩等のトリメチルアルケニルアンモニウム塩；トリエチルドデシルアンモニウム塩、トリエチルテトラデシルアンモニウム塩、トリエチルヘキサデシルアンモニウム塩、トリエチルオクタデシルアンモニウム等のトリエチルアルキルアンモニウム塩；トリブチルドデシルアンモニウム塩、トリブチルテトラデシルアンモニウム塩、トリブチルヘキサデシルアンモニウム塩、トリブチルオクタデシルアンモニウム塩等のトリブチルアルキルアンモニウム塩；ジメチルジドデシルアンモニウム塩、ジメチルジテトラデシルアンモニウム塩、ジメチルジヘキサデシルアンモニウム塩、ジメチルジオクタデシルアンモニウム塩、ジメチルジタロウアンモニウム塩等のジメチルジアルキルアンモニウム塩；ジメチルジオクタデセニルアンモニウム塩、ジメチルジオクタデカジエニルアンモニウム塩等のジメチルジアルケニルアンモニウム塩；ジエチルジドデジルアンモニウム塩、ジエチルジテトラデシルアンモニウム塩、ジエチルジヘキサデシルアンモニウム塩、ジエチルジオクタデシルアンモニウム等のジエチルジアルキルアンモニウム塩；ジブチルジドデシルアンモニウム塩、ジブチルジテトラデシルアンモニウム塩、ジブチルジヘキサデシルアンモニウム塩、ジブチルジオクタデシルアンモニウム塩等のジブチルジアルキルアンモニウム塩；メチルベンジルジヘキサデシルアンモニウム塩等のメチルベンジルジアルキルアンモニウム塩；ジベンジルジヘキサデシルアンモニウム塩等のジベンジルジアルキルアンモニウム塩；トリドデシルメチルアンモニウム塩、トリテトラデシルメチルアンモニウム塩、トリオクタデシルメチルアンモニウム塩等のトリアルキルメチルアンモニウム塩；トリドデシルエチルアンモニウム塩等のトリアルキルエチルアンモニウム塩；トリドデシルブチルアンモニウム塩等のトリアルキルブチルアンモニウム塩；４−アミノ−ｎ−酪酸、６−アミノ−ｎ−カプロン酸、８−アミノカプリル酸、１０−アミノデカン酸、１２−アミノドデカン酸、１４−アミノテトラデカン酸、１６−アミノヘキサデカン酸、１８−アミノオクタデカン酸等のω−アミノ酸などが挙げられる。また、水酸基及び／又はエーテル基含有のアンモニウム塩、中でも、メチルジアルキル（ＰＡＧ）アンモニウム塩、エチルジアルキル（ＰＡＧ）アンモニウム塩、ブチルジアルキル（ＰＡＧ）アンモニウム塩、ジメチルビス（ＰＡＧ）アンモニウム塩、ジエチルビス（ＰＡＧ）アンモニウム塩、ジブチルビス（ＰＡＧ）アンモニウム塩、メチルアルキルビス（ＰＡＧ)アンモニウム塩、エチルアルキルビス（ＰＡＧ)アンモニウム塩、ブチルアルキルビス（ＰＡＧ)アンモニウム塩、メチルトリ（ＰＡＧ）アンモニウム塩、エチルトリ（ＰＡＧ）アンモニウム塩、ブチルトリ（ＰＡＧ）アンモニウム塩、テトラ（ＰＡＧ）アンモニウム塩（ただし、アルキルはドデシル、テトラデシル、ヘキサデシル、オクタデシル、エイコシルなどの炭素数１２以上のアルキル基を表し、ＰＡＧはポリアルキレングリコール残基、好ましくは、炭素数２０以下のポリエチレングリコール残基またはポリプロピレングリコール残基を表す）などの少なくとも一のアルキレングリコール残基を含有する４級アンモニウム塩も有機膨潤化剤として使用することができる。中でもトリメチルドデシルアンモニウム塩、トリメチルテトラデシルアンモニウム塩、トリメチルヘキサデシルアンモニウム塩、トリメチルオクタデシルアンモニウム塩、ジメチルジドデシルアンモニウム塩、ジメチルジテトラデシルアンモニウム塩、ジメチルジヘキサデシルアンモニウム塩、ジメチルジオクタデシルアンモニウム塩、ジメチルジタロウアンモニウム塩が好ましい。なお、これらの有機膨潤化剤は、単独でも複数種類の混合物としても使用できる。 Specific examples of organic swelling agents include trimethyl dodecyl ammonium salt, trimethyl tetradecyl ammonium salt, trimethyl hexadecyl ammonium salt, trimethyl octadecyl ammonium salt, trimethyl alkyl decyl ammonium salt, trimethyl alkyl decyl ammonium salt; trimethyl octadecenyl ammonium salt Trimethylalkenylammonium salts such as trimethyloctadecadienylammonium salt; triethylalkylammonium salts such as triethyldodecylammonium salt, triethyltetradecylammonium salt, triethylhexadecylammonium salt, triethyloctadecylammonium salt; tributyldodecylammonium salt, tributyltetradecyl Ammonium salt, tributyl hexadecyl ammonium salt, tri Tributylalkylammonium salts such as tiloctadecylammonium salt; dimethyldialkylammonium salts such as dimethyldidodecylammonium salt, dimethylditetradecylammonium salt, dimethyldihexadecylammonium salt, dimethyldioctadecylammonium salt, dimethylditallowammonium salt; dimethyl Dioctadecenyl ammonium salt, dimethyl dialkenyl ammonium salt such as dimethyl dioctadecadienyl ammonium salt; diethyl didodecyl ammonium salt, diethyl ditetradecyl ammonium salt, diethyl dihexadecyl ammonium salt, diethyl dioctadecyl ammonium salt, etc. Diethyl dialkyl ammonium salt; dibutyl didodecyl ammonium salt, dibutyl ditetradecyl ammonium salt, dibu Dibutyl dialkyl ammonium salts such as rudihexadecyl ammonium salt and dibutyl dioctadecyl ammonium salt; methyl benzyl dialkyl ammonium salts such as methyl benzyl dihexadecyl ammonium salt; dibenzyl dialkyl ammonium salts such as dibenzyl dihexadecyl ammonium salt; tridodecyl Trialkylmethylammonium salts such as methylammonium salt, tritetradecylmethylammonium salt, trioctadecylmethylammonium salt; trialkylethylammonium salts such as tridodecylethylammonium salt; trialkylbutylammonium salts such as tridodecylbutylammonium salt; 4-amino-n-butyric acid, 6-amino-n-caproic acid, 8-aminocaprylic acid, 10-aminodecanoic acid, 12-aminodode Examples include ω-amino acids such as canic acid, 14-aminotetradecanoic acid, 16-aminohexadecanoic acid, and 18-aminooctadecanoic acid. In addition, hydroxyl group and / or ether group-containing ammonium salts, among them, methyl dialkyl (PAG) ammonium salt, ethyl dialkyl (PAG) ammonium salt, butyl dialkyl (PAG) ammonium salt, dimethyl bis (PAG) ammonium salt, diethyl bis (PAG) ) Ammonium salt, dibutyl bis (PAG) ammonium salt, methyl alkyl bis (PAG) ammonium salt, ethyl alkyl bis (PAG) ammonium salt, butyl alkyl bis (PAG) ammonium salt, methyl tri (PAG) ammonium salt, ethyl tri (PAG) ammonium Salt, butyltri (PAG) ammonium salt, tetra (PAG) ammonium salt (wherein alkyl has 12 carbon atoms such as dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl) A quaternary ammonium containing at least one alkylene glycol residue such as a polyalkylene glycol residue, preferably a polyethylene glycol residue or a polypropylene glycol residue having 20 or less carbon atoms) Salts can also be used as organic swelling agents. Among them, trimethyldodecyl ammonium salt, trimethyl tetradecyl ammonium salt, trimethyl hexadecyl ammonium salt, trimethyl octadecyl ammonium salt, dimethyl didodecyl ammonium salt, dimethyl ditetradecyl ammonium salt, dimethyl dihexadecyl ammonium salt, dimethyl dioctadecyl ammonium salt, dimethyl A ditallow ammonium salt is preferred. These organic swelling agents can be used alone or as a mixture of a plurality of types.
本発明では、ポリアミド１００重量部に対し、有機膨潤化剤で処理した層状珪酸塩を０．５〜８重量部添加したものが好ましく用いられ、より好ましくは１〜６重量部、さらに好ましくは２〜５重量部である。層状珪酸塩の添加量が０．５重量部より少ないとガスバリア性の改善効果が小さいため好ましくない。また８重量部より多いとガスバリア層が濁って容器の透明性が損なわれるため好ましくない。 In this invention, what added 0.5-8 weight part of layered silicate processed with the organic swelling agent with respect to 100 weight part of polyamide is used preferably, More preferably, it is 1-6 weight part, More preferably, 2 ~ 5 parts by weight. If the amount of layered silicate added is less than 0.5 parts by weight, the effect of improving gas barrier properties is small, which is not preferable. On the other hand, when the amount is more than 8 parts by weight, the gas barrier layer becomes turbid and the transparency of the container is impaired.
ポリアミドにおいて、層状珪酸塩は局所的に凝集することなく均一に分散していることが好ましい。ここでいう均一分散とは、ポリアミド中において層状珪酸塩が平板状に分離し、それらの５０％以上が５ｎｍ以上の層間距離を有することをいう。ここで層間距離とは平板状物の重心間距離のことをいう。この距離が大きい程分散状態が良好となり、透明性等の外観が良好で、かつ酸素、炭酸ガス等のガスバリア性を向上させることができる。 In polyamide, the layered silicate is preferably uniformly dispersed without locally agglomerating. Here, the uniform dispersion means that the layered silicate is separated into a flat plate shape in the polyamide, and 50% or more of them have an interlayer distance of 5 nm or more. Here, the interlayer distance refers to the distance between the centers of gravity of the flat objects. The larger the distance, the better the dispersion state, the better the appearance such as transparency, and the better the gas barrier properties such as oxygen and carbon dioxide.
ポリアミドと層状珪酸塩を混合する方法としては、特に制限はないが、本発明では溶融混練法が好ましく用いられる。例えば、ポリアミドの重縮合中に層状珪酸塩を添加し攪拌する方法、単軸もしくは二軸押出機等の通常用いられる種々の押出機を用いて溶融混練する方法等の公知の方法を利用することができるが、これらのなかでも、二軸押出機を用いて溶融混練する方法が本発明において好ましい方法である。 The method of mixing the polyamide and the layered silicate is not particularly limited, but the melt kneading method is preferably used in the present invention. For example, a known method such as a method of adding and stirring a layered silicate during polycondensation of polyamide, a method of melt kneading using various commonly used extruders such as a single-screw or twin-screw extruder, etc. Among these, a method of melt kneading using a twin screw extruder is a preferable method in the present invention.
以上述べたように、本発明の多層容器におけるガスバリア層を構成するポリアミドには白化防止剤や、酸素吸収機能を付与する金属触媒化合物、あるいはガスバリア性を高める効果を有する層状珪酸塩を添加することができる。これらの添加物は組み合わせて使用しても良い。 As described above, the polyamide constituting the gas barrier layer in the multilayer container of the present invention should be added with a whitening inhibitor, a metal catalyst compound that imparts an oxygen absorption function, or a layered silicate having an effect of enhancing gas barrier properties. Can do. These additives may be used in combination.
本発明の多層容器の製造方法は、例えば、３台の押出機、フィードブロック、Ｔダイ、冷却ロール、巻き取り機等を備えた多層シート製造装置を用い、１台目の押出機からＰＰを、２台目の押出機から接着性樹脂を、３台目の押出機からガスバリア性樹脂をそれぞれ押し出し、フィードブロックを介してＰＰ層／接着性樹脂層／ガスバリア層／接着性樹脂層／ＰＰ層の３種５層構造の多層シートを製造し、これを加熱軟化した後、真空、圧空、又は真空と圧空を併用した熱成形法によってシートを金型に密着させて容器形状に成形し、これをトリミングして容器を得る方法が挙げられる。なお、多層シート製造装置や容器の成形方法についてはこれらに限定されるものではなく、公知の方法を適用することができる。 The multilayer container manufacturing method of the present invention uses, for example, a multilayer sheet manufacturing apparatus equipped with three extruders, a feed block, a T-die, a cooling roll, a winder, etc., to produce PP from the first extruder. Adhesive resin is extruded from the second extruder, and gas barrier resin is extruded from the third extruder, and PP layer / adhesive resin layer / gas barrier layer / adhesive resin layer / PP layer are fed through the feed block. After producing a multi-layered sheet of 3 types and 5 layers and heat-softening it, the sheet is brought into close contact with a mold by vacuum, compressed air, or a thermoforming method using both vacuum and compressed air, and formed into a container shape. The container is obtained by trimming. The multilayer sheet manufacturing apparatus and the container forming method are not limited to these, and a known method can be applied.
本発明の多層容器におけるガスバリア層の厚みは、総厚みに対して２〜１５％の範囲に設定することが好ましく、より好ましくは３〜１２％であり、さらに好ましくは４〜１０％である。ガスバリア層の厚み比（ガスバリア層の厚み／総厚み）が２％を下回ると、多層容器の形状によっては所望のガスバリア性能を発揮できなくなることがある。また１５％を超えると、容器のガスバリア性能は優れたものになるものの、容器のコストが高くなるため不経済であり、場合によっては隣接する層との流速バランスが崩れて多層シートの外観が悪化することがある。 The thickness of the gas barrier layer in the multilayer container of the present invention is preferably set in the range of 2 to 15% with respect to the total thickness, more preferably 3 to 12%, and further preferably 4 to 10%. If the thickness ratio of the gas barrier layer (the thickness of the gas barrier layer / the total thickness) is less than 2%, the desired gas barrier performance may not be exhibited depending on the shape of the multilayer container. If it exceeds 15%, the gas barrier performance of the container will be excellent, but the cost of the container will be high, which is uneconomical. In some cases, the flow rate balance with adjacent layers will be disrupted and the appearance of the multilayer sheet will deteriorate There are things to do.
本発明の多層容器は、必要に応じてＰＰ層、接着性樹脂層、ガスバリア層以外に各種熱可塑性樹脂層を積層することができる。例えば、多層シート及び多層容器製造時にトリミングしてできたトリミングくずを粉砕して、粉砕物を単独で、又はＰＰや他の熱可塑性樹脂と混合してリサイクル樹脂層としてＰＰと接着性樹脂層の間に中間層として積層することができる。また、多層容器に特徴を持たせるためにＰＰ層の表側に、ポリカーボネートや各種イージーピール性樹脂からなる熱可塑性樹脂層を積層することができる。これらに限らず、目的に応じて様々な熱可塑性樹脂層を積層することが可能である。
さらに本発明の多層容器には、そのフランジ部分にイージーピール機能を付与するための特殊加工を施すことが可能である。
The multilayer container of the present invention can be laminated with various thermoplastic resin layers in addition to the PP layer, the adhesive resin layer, and the gas barrier layer as necessary. For example, the trimming scraps produced by trimming at the time of manufacturing the multilayer sheet and the multilayer container are pulverized, and the pulverized product alone or mixed with PP or other thermoplastic resin is used as a recycled resin layer of PP and the adhesive resin layer. It can be laminated as an intermediate layer. Moreover, in order to give a characteristic to a multilayer container, the thermoplastic resin layer which consists of a polycarbonate and various easy-peeling resin can be laminated | stacked on the front side of PP layer. Not limited to these, various thermoplastic resin layers can be laminated according to the purpose.
Furthermore, the multilayer container of the present invention can be subjected to special processing for imparting an easy peel function to the flange portion.
本発明の多層容器は、特定の組成、物性を持つポリアミドを組み合わせたことにより、熱成形性に優れ、かつガスバリア性に優れたものであり、特に加熱殺菌処理時のガスバリア性に優れたものである。本発明の多層容器には、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、マヨネーズ、味噌、すり下ろし香辛料等の調味料、ジャム、クリーム、チョコレートペースト等のペースト状食品、液体スープ、煮物、漬物、シチュー等の液体加工食品に代表される液体系食品やそば、うどん、ラーメン等の生麺及びゆで麺、精米、調湿米、無洗米等の調理前の米類や調理された炊飯米、五目飯、赤飯、米粥等の加工米製品類、粉末スープ、だしの素等の粉末調味料、ゼリー、プリン等に代表される高水分食品、乾燥野菜、コーヒー豆、コーヒー粉、お茶、穀物を原料としたお菓子等に代表される低水分食品、その他農薬や殺虫剤等の固体状や溶液状の化学薬品、液体及びペースト状の医薬品、化粧水、化粧クリーム、化粧乳液、整髪料、染毛剤、シャンプー、石鹸、洗剤等、種々の物品を収納することができる。 The multilayer container of the present invention is a combination of a polyamide having a specific composition and physical properties, so that it has excellent thermoformability and excellent gas barrier properties, and particularly excellent in gas barrier properties during heat sterilization treatment. is there. In the multilayer container of the present invention, for example, carbonated drinks, juice, water, milk, sake, whiskey, shochu, coffee, tea, jelly drinks, health drinks and other liquid drinks, seasoning liquids, sauces, soy sauce, dressings, liquid stocks , Seasonings such as mayonnaise, miso, grated spices, pasty foods such as jam, cream, chocolate paste, liquid foods such as liquid processed foods such as liquid soups, boiled foods, pickles, stews, soba, udon, Raw noodles such as ramen and boiled noodles, polished rice, moisture-conditioned rice, unwashed rice, and other uncooked rice, cooked cooked rice, processed rice products such as gomoku rice, red rice, rice bran, powder soup, dashi soup High-moisture foods such as jelly and pudding, low-moisture foods such as dried vegetables, coffee beans, coffee powder, tea, and confectionery made from grains, and other pesticides To store various articles such as solid and solution chemicals such as insecticides, liquid and paste pharmaceuticals, lotion, cosmetic cream, cosmetic milk, hair conditioner, hair dye, shampoo, soap, detergent, etc. Can do.
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。なお、本実施例において各種測定は以下の方法により行った。
（１）ポリアミドの融点
島津製作所（株）製、ＤＳＣ−５０を用いて測定した。
測定条件；昇温速度１０℃／ｍｉｎ、窒素気流下
（２）ポリアミドの溶融粘度
東洋精機製作所製、キャピログラフ１Ｃを用いて測定した。
測定条件；シリンダー径９．５５ｍｍφ、キャピラリ１ｍｍφ×１０ｍｍＬ
（３）多層容器の酸素透過率
モダンコントロールズ社製、ＯＸ−ＴＲＡＮ １０／５０Ａを使用した。
測定条件；２３℃、成形体及び包装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。
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. In this example, various measurements were performed by the following methods.
(1) Melting | fusing point of polyamide It measured using Shimadzu Corporation | KK DSC-50.
Measurement conditions: Temperature rising rate 10 ° C./min, under nitrogen stream (2) Melt viscosity of polyamide Measured using Capillograph 1C manufactured by Toyo Seiki Seisakusho.
Measurement conditions: cylinder diameter 9.55 mmφ, capillary 1 mmφ × 10 mmL
(3) Oxygen permeability of multilayer container OX-TRAN 10 / 50A manufactured by Modern Controls was used.
Measurement conditions: Measured according to ASTM D3985 in an atmosphere of 23 ° C., 100% relative humidity inside the molded body and the packaging container, and 50% relative humidity outside.
実施例１（４ｍｏｌ）
攪拌機、分縮器、全縮器、温度計、滴下ロート及び窒素導入管、ストランドダイを備えた内容積５０リットルの反応容器に、精秤したアジピン酸９３８０ｇ（６４．１９ｍｏｌ）とイソフタル酸４４４ｇ（２．６７ｍｏｌ）を入れ、十分に窒素置換した後、さらに少量の窒素気流下で系内を攪拌しながら１７０℃まで加熱した。これにメタキシリレンジアミン９０４４ｇ（６６．４０ｍｏｌ）を攪拌下に滴下し、生成する縮合水を系外へ除きながら系内を連続的に昇温した。メタキシリレンジアミンの滴下終了後、内温を２５５℃として４０分反応を継続した。その後、系内を窒素で加圧し、ストランドダイからポリマーを取り出してこれをペレット化し、約１６ｋｇのポリマーを得た。
次いで、窒素ガス導入管、真空ライン、真空ポンプ、内温測定用の熱伝対を設けたジャケット付きのタンブルドライヤーにポリマーを仕込み、一定速度で回転させつつ、タンブルドライヤー内部を純度が９９容量％以上の窒素ガスで十分に置換した後、同窒素ガス気流下でタンブルドライヤーを加熱し、約１５０分かけてペレット温度を１５０℃に昇温した。ペレット温度が１５０℃に達した時点で系内の圧力を１ｔｏｒｒ以下に減圧した。さらに昇温を続け、約７０分かけてペレット温度を２００℃まで昇温した後、２００℃で４０分保持した。次いで、系内に純度が９９容量％以上の窒素ガスを導入して、タンブルドライヤーを回転させたまま冷却してポリアミド１を得た。得られたポリアミド１の融点は２３５℃であり、２５５℃、剪断速度１００ｓ−１での溶融粘度は１０００Ｐａ・ｓであった。
次いで、３台の押出機、フィードブロック、Ｔダイ、冷却ロール、巻き取り機等を備えた多層シート製造装置を用い、１台目の押出機からＰＰ（日本ポリプロ社製、商品名；ノバテックＰＰ、グレード名；ＥＣ９、メルトインデックス；０．５）を２４０℃で、２台目の押出機から接着性樹脂（三井化学社製、商品名；アドマー、グレード；ＱＢ５５０）を２３０℃で、３台目の押出機からポリアミド１を２５５℃でそれぞれ押し出し、フィードブロックを介してＰＰ層／接着性樹脂層／ガスバリア層／接着性樹脂層／ＰＰ層の３種５層構造の多層シートを製造した。なお各層の厚みは、３００／２０／４０／２０／３００（μｍ）とした。
次いで、プラグアシストを備えた真空圧空成形機を使用して、シート表面温度が１７０℃に達した時点で熱成形を行い、口径６２ｍｍ×底径５２ｍｍ×深さ２８ｍｍ、表面積７３ｃｍ２、容積７０ｍｌのカップ状容器を得た。
次いで、容器内に水を７０ｍｌ入れ、ＰＰ／アルミ箔／ＰＥＴ＝５０／９／１２（μｍ）のフィルムで開口部をヒートシールした後、オートクレーブを使用して、３０分間、１２１℃で密封容器をレトルト処理した。次いで、フィルムに穴を開けて水を６０ｍｌ抜いた後、ガス導入管及びガス排出管を挿しこみ、挿しこみ部をエポキシ系接着剤で固めて封した後、酸素透過率測定装置を用いて酸素透過率を測定した。結果を表１に示す。
Example 1 (4 mol)
Into a reaction vessel having an internal volume of 50 liters equipped with a stirrer, a partial condenser, a full condenser, a thermometer, a dropping funnel and a nitrogen introduction tube, and a strand die, 9380 g (64.19 mol) of adipic acid and 444 g of isophthalic acid were precisely weighed ( 2.67 mol) was added, and after sufficient nitrogen substitution, the system was heated to 170 ° C. with stirring in a small amount of nitrogen stream. To this, 9044 g (66.40 mol) of metaxylylenediamine was added dropwise with stirring, and the inside of the system was continuously heated while removing the generated condensed water. After completion of the dropwise addition of metaxylylenediamine, the internal temperature was set to 255 ° C. and the reaction was continued for 40 minutes. Thereafter, the inside of the system was pressurized with nitrogen, and the polymer was taken out from the strand die and pelletized to obtain about 16 kg of polymer.
Next, the polymer is charged into a tumble dryer with a jacket provided with a nitrogen gas inlet tube, a vacuum line, a vacuum pump, and a thermocouple for measuring the internal temperature. The purity of the tumble dryer is 99% by volume while rotating at a constant speed. After sufficiently replacing with the above nitrogen gas, the tumble dryer was heated under the same nitrogen gas stream, and the pellet temperature was raised to 150 ° C. over about 150 minutes. When the pellet temperature reached 150 ° C., the pressure in the system was reduced to 1 torr or less. The temperature was further raised, and the pellet temperature was raised to 200 ° C. over about 70 minutes, and then held at 200 ° C. for 40 minutes. Next, a nitrogen gas having a purity of 99% by volume or more was introduced into the system, and the polyamide 1 was obtained by cooling while rotating the tumble dryer. The obtained polyamide 1 had a melting point of 235 ° C., and had a melt viscosity of 1000 Pa · s at 255 ° C. and a shear rate of 100 s −1 .
Next, using a multilayer sheet manufacturing apparatus equipped with three extruders, a feed block, a T die, a cooling roll, a winder, etc., PP (from Nippon Polypro Co., Ltd., trade name: Novatec PP) , Grade name: EC9, melt index: 0.5) at 240 ° C., adhesive resin (trade name; Admer, grade: QB550, manufactured by Mitsui Chemicals, Inc.) from the second extruder, 3 units at 230 ° C. Polyamide 1 was extruded from an eye extruder at 255 ° C., and a multilayer sheet having a three-kind five-layer structure of PP layer / adhesive resin layer / gas barrier layer / adhesive resin layer / PP layer was produced through a feed block. The thickness of each layer was 300/20/40/20/300 (μm).
Next, using a vacuum / pneumatic molding machine equipped with plug assist, when the sheet surface temperature reaches 170 ° C., thermoforming is performed, and the caliber is 62 mm × bottom diameter 52 mm × depth 28 mm, surface area 73 cm 2 , volume 70 ml. A cup-shaped container was obtained.
Next, 70 ml of water is put in the container, and the opening is heat sealed with a film of PP / aluminum foil / PET = 50/9/12 (μm), and then sealed in an airtight container at 121 ° C. for 30 minutes using an autoclave. Was retorted. Next, after making a hole in the film and removing 60 ml of water, the gas introduction tube and the gas discharge tube were inserted, the insertion portion was sealed with an epoxy adhesive, and then sealed using an oxygen permeability measuring device. The transmittance was measured. The results are shown in Table 1.
実施例２（６ｍｏｌ）
アジピン酸の重量を９１８５ｇ（６２．８５ｍｏｌ）、イソフタル酸の重量を６６６ｇ（６．６９ｍｏｌ）としたこと以外は実施例１と同様にしてポリアミド２を得た。得られたポリアミド２の融点は２３２℃であり、２５２℃、剪断速度１００ｓ−１での溶融粘度は１１７０Ｐａ・ｓであった。
次いでポリアミド２の押出温度を２５０℃としたこと以外は実施例１と同様にして多層シート成形、および熱成形を行ってカップ状容器を作製し、レトルト処理後の酸素透過率を測定した。結果を表１に示す。
Example 2 (6 mol)
A polyamide 2 was obtained in the same manner as in Example 1 except that the weight of adipic acid was 9185 g (62.85 mol) and the weight of isophthalic acid was 666 g (6.69 mol). The obtained polyamide 2 had a melting point of 232 ° C., a melt viscosity of 1170 Pa · s at 252 ° C. and a shear rate of 100 s −1 .
Next, a multilayered sheet molding and thermoforming were performed in the same manner as in Example 1 except that the extrusion temperature of polyamide 2 was 250 ° C., to prepare a cup-shaped container, and the oxygen permeability after retorting was measured. The results are shown in Table 1.
実施例３（１０ｍｏｌ）
アジピン酸の重量を８７９４ｇ（６０．１７ｍｏｌ）、イソフタル酸の重量を１１１１ｇ（４．０１ｍｏｌ）としたこと以外は実施例１と同様にしてポリアミド３を得た。得られたポリアミド３の融点は２２５℃であり、２４５℃、剪断速度１００ｓ−１での溶融粘度は１５５０Ｐａ・ｓであった。
次いでポリアミド３の押出温度を２４５℃としたこと以外は実施例１と同様にして多層シート成形、および熱成形を行ってカップ状容器を作製し、レトルト処理後の酸素透過率を測定した。結果を表１に示す。
Example 3 (10 mol)
Polyamide 3 was obtained in the same manner as in Example 1 except that the weight of adipic acid was 8794 g (60.17 mol) and the weight of isophthalic acid was 1111 g (4.01 mol). The obtained polyamide 3 had a melting point of 225 ° C. and a melt viscosity of 1550 Pa · s at 245 ° C. and a shear rate of 100 s −1 .
Subsequently, except that the extrusion temperature of polyamide 3 was 245 ° C., multilayer sheet molding and thermoforming were performed in the same manner as in Example 1 to produce a cup-shaped container, and the oxygen permeability after retorting was measured. The results are shown in Table 1.
実施例４（１５ｍｏｌ）
アジピン酸の重量を８３０５ｇ（５６．８３ｍｏｌ）、イソフタル酸の重量を１６６６ｇ（１０．０３ｍｏｌ）としたこと以外は実施例１と同様にして溶融重合を行い、ポリマーを得た後、実施例１と同様のタンブルドライヤーにポリマーを仕込み、一定速度で回転させつつ、タンブルドライヤー内部を純度が９９容量％以上の窒素ガスで十分に置換した後、同窒素ガス気流下でタンブルドライヤーを加熱し、約１８０分かけてペレット温度を１５０℃に昇温した。ペレット温度が１５０℃に達した時点で系内の圧力を１ｔｏｒｒ以下に減圧した。さらに昇温を続け、約７０分かけてペレット温度を２００℃まで昇温した後、２００℃で２０分保持した。次いで、系内に純度が９９容量％以上の窒素ガスを導入して、タンブルドライヤーを回転させたまま冷却してポリアミド４を得た。得られたポリアミド４の融点は２１７℃であり、２３７℃、剪断速度１００ｓ−１での溶融粘度は１９２０Ｐａ・ｓであった。
次いで、実施例１と同様の多層シート製造装置を用い、ポリアミド４の押出温度を２４０℃としたこと以外は実施例１と同様にして多層シート成形、および熱成形を行ってカップ状容器を作製し、レトルト処理後の酸素透過率を測定した。結果を表１に示す。
Example 4 (15 mol)
Except that the weight of adipic acid was 8305 g (56.83 mol) and the weight of isophthalic acid was 1666 g (10.03 mol), melt polymerization was performed in the same manner as in Example 1 to obtain a polymer. A polymer is charged in a similar tumble dryer and rotated at a constant speed, and the inside of the tumble dryer is sufficiently replaced with nitrogen gas having a purity of 99% by volume or more. The pellet temperature was raised to 150 ° C. over a period of minutes. When the pellet temperature reached 150 ° C., the pressure in the system was reduced to 1 torr or less. The temperature was further raised, and the pellet temperature was raised to 200 ° C. over about 70 minutes, and then held at 200 ° C. for 20 minutes. Next, nitrogen gas having a purity of 99% by volume or more was introduced into the system, and the tumble dryer was rotated while cooling to obtain polyamide 4. The obtained polyamide 4 had a melting point of 217 ° C., and a melt viscosity at 237 ° C. and a shear rate of 100 s −1 was 1920 Pa · s.
Next, using the same multilayer sheet manufacturing apparatus as in Example 1, a cup-shaped container was produced by performing multilayer sheet molding and thermoforming in the same manner as in Example 1 except that the extrusion temperature of polyamide 4 was 240 ° C. Then, the oxygen transmission rate after the retort treatment was measured. The results are shown in Table 1.
実施例５（２０ｍｏｌ）
アジピン酸の重量を７８１７ｇ（５３．４９ｍｏｌ）、イソフタル酸の重量を２２２１ｇ（１３．３７ｍｏｌ）としたこと以外は実施例１と同様にして溶融重合を行い、ポリマーを得た後、実施例１と同様のタンブルドライヤーにポリマーを仕込み、一定速度で回転させつつ、タンブルドライヤー内部を純度が９９容量％以上の窒素ガスで十分に置換した後、同窒素ガス気流下でタンブルドライヤーを加熱し、約２００分かけてペレット温度を１５０℃に昇温した。ペレット温度が１５０℃に達した時点で系内の圧力を１ｔｏｒｒ以下に減圧した。さらに昇温を続け、約７０分かけてペレット温度を２００℃まで昇温した後、２００℃で２０分保持した。次いで、系内に純度が９９容量％以上の窒素ガスを導入して、タンブルドライヤーを回転させたまま冷却してポリアミド５を得た。得られたポリアミド５の融点は２０８℃であり、２２８℃、剪断速度１００ｓ−１での溶融粘度は２３４０Ｐａ・ｓであった。
次いで、実施例１と同様の多層シート製造装置を用い、ポリアミド５の押出温度を２３０℃としたこと以外は実施例１と同様にして多層シート成形、および熱成形を行ってカップ状容器を作製し、レトルト処理後の酸素透過率を測定した。結果を表１に示す。
Example 5 (20 mol)
Except that the weight of adipic acid was 7817 g (53.49 mol) and the weight of isophthalic acid was 2221 g (13.37 mol), melt polymerization was performed in the same manner as in Example 1 to obtain a polymer. A polymer is charged in the same tumble dryer and rotated at a constant speed, and the inside of the tumble dryer is sufficiently replaced with nitrogen gas having a purity of 99% by volume or more. The pellet temperature was raised to 150 ° C. over a period of minutes. When the pellet temperature reached 150 ° C., the pressure in the system was reduced to 1 torr or less. The temperature was further raised, and the pellet temperature was raised to 200 ° C. over about 70 minutes, and then held at 200 ° C. for 20 minutes. Next, nitrogen gas having a purity of 99% by volume or more was introduced into the system, and the tumble dryer was rotated and cooled to obtain polyamide 5. The obtained polyamide 5 had a melting point of 208 ° C. and a melt viscosity of 2340 Pa · s at 228 ° C. and a shear rate of 100 s −1 .
Next, using the same multilayer sheet manufacturing apparatus as in Example 1, except that the extrusion temperature of polyamide 5 was 230 ° C., multilayer sheet molding and thermoforming were performed in the same manner as in Example 1 to produce a cup-shaped container. Then, the oxygen transmission rate after the retort treatment was measured. The results are shown in Table 1.
実施例６（２５ｍｏｌ）
アジピン酸の重量を７３２８ｇ（５０．１５ｍｏｌ）、イソフタル酸の重量を２７７７ｇ（１６．７２ｍｏｌ）としたこと以外は実施例１と同様にして溶融重合を行い、ポリマーを得た後、実施例１と同様のタンブルドライヤーにポリマーを仕込み、一定速度で回転させつつ、タンブルドライヤー内部を純度が９９容量％以上の窒素ガスで十分に置換した後、同窒素ガス気流下でタンブルドライヤーを加熱し、約２３０分かけてペレット温度を１５０℃に昇温した。ペレット温度が１５０℃に達した時点で系内の圧力を１ｔｏｒｒ以下に減圧した。さらに昇温を続け、約７０分かけてペレット温度を２００℃まで昇温した後、２００℃で２０分保持した。次いで、系内に純度が９９容量％以上の窒素ガスを導入して、タンブルドライヤーを回転させたまま冷却してポリアミド６を得た。得られたポリアミド６の融点は２００℃であり、２２０℃、剪断速度１００ｓ−１での溶融粘度は２７５０Ｐａ・ｓであった。
次いで、実施例１と同様の多層シート製造装置を用い、ポリアミド６の押出温度を２２０℃としたこと以外は実施例１と同様にして多層シート成形、および熱成形を行ってカップ状容器を作製し、レトルト処理後の酸素透過率を測定した。結果を表１に示す。
Example 6 (25 mol)
Except that the weight of adipic acid was 7328 g (50.15 mol) and the weight of isophthalic acid was 2777 g (16.72 mol), melt polymerization was performed in the same manner as in Example 1 to obtain a polymer. A polymer is charged in the same tumble dryer and rotated at a constant speed, and the inside of the tumble dryer is sufficiently replaced with nitrogen gas having a purity of 99% by volume or more. Then, the tumble dryer is heated under the same nitrogen gas stream, and about 230 The pellet temperature was raised to 150 ° C. over a period of minutes. When the pellet temperature reached 150 ° C., the pressure in the system was reduced to 1 torr or less. The temperature was further raised, and the pellet temperature was raised to 200 ° C. over about 70 minutes, and then held at 200 ° C. for 20 minutes. Next, a nitrogen gas having a purity of 99% by volume or more was introduced into the system, and the polyamide 6 was obtained by cooling while rotating the tumble dryer. The obtained polyamide 6 had a melting point of 200 ° C. and a melt viscosity of 2750 Pa · s at 220 ° C. and a shear rate of 100 s −1 .
Next, using the same multilayer sheet manufacturing apparatus as in Example 1, a cup-shaped container was produced by performing multilayer sheet molding and thermoforming in the same manner as in Example 1 except that the extrusion temperature of polyamide 6 was 220 ° C. Then, the oxygen transmission rate after the retort treatment was measured. The results are shown in Table 1.
比較例１（０ｍｏｌ）
アジピン酸の重量を９７７１ｇ（６６．８６ｍｏｌ）、イソフタル酸の重量を０ｇ（０ｍｏｌ）としたこと以外は実施例１と同様にしてポリアミド７を得た。得られたポリアミド７の融点は２４２℃であり、２６０℃、剪断速度１００ｓ−１での溶融粘度は９００Ｐａ・ｓであった。
次いで、実施例１と同様の多層シート製造装置を用い、ポリアミド７の押出温度を２６０℃としたこと以外は実施例１と同様にして多層シート成形を行った。次いで、熱成形を行ったが、ガスバリア層を構成するポリアミド７がシート加熱時に結晶化してしまい、得られた成形品は外観不良であった。
Comparative Example 1 (0 mol)
Polyamide 7 was obtained in the same manner as in Example 1 except that the weight of adipic acid was 9771 g (66.86 mol) and the weight of isophthalic acid was 0 g (0 mol). The obtained polyamide 7 had a melting point of 242 ° C. and a melt viscosity of 900 Pa · s at 260 ° C. and a shear rate of 100 s −1 .
Next, using the same multilayer sheet manufacturing apparatus as in Example 1, multilayer sheet molding was performed in the same manner as in Example 1 except that the extrusion temperature of polyamide 7 was 260 ° C. Subsequently, thermoforming was performed, but the polyamide 7 constituting the gas barrier layer was crystallized when the sheet was heated, and the obtained molded product had a poor appearance.
比較例２（２ｍｏｌ）
アジピン酸の重量を９５７６ｇ（６５．５２ｍｏｌ）、イソフタル酸の重量を２２２ｇ（１．３４ｍｏｌ）としたこと以外は実施例１と同様にしてポリアミド８を得た。得られたポリアミド８の融点は２３８℃であり、２５７℃、剪断速度１００ｓ−１での溶融粘度は９５０Ｐａ・ｓであった。
次いで、実施例１と同様の多層シート製造装置を用い、ポリアミド８の押出温度を２６０℃としたこと以外は実施例１と同様にして多層シート成形を行った。次いで、熱成形を行ったが、ガスバリア層を構成するポリアミド８がシート加熱時に結晶化してしまい、得られた成形品は外観不良であった。
Comparative Example 2 (2 mol)
Polyamide 8 was obtained in the same manner as in Example 1 except that the weight of adipic acid was 9576 g (65.52 mol) and the weight of isophthalic acid was 222 g (1.34 mol). Polyamide 8 obtained had a melting point of 238 ° C., a melt viscosity of 950 Pa · s at 257 ° C. and a shear rate of 100 s −1 .
Next, using the same multilayer sheet manufacturing apparatus as in Example 1, multilayer sheet molding was performed in the same manner as in Example 1 except that the extrusion temperature of polyamide 8 was 260 ° C. Next, thermoforming was performed, but the polyamide 8 constituting the gas barrier layer was crystallized when the sheet was heated, and the resulting molded product had a poor appearance.
比較例３（３５ｍｏｌ）
アジピン酸の重量を６３５１ｇ（４３．４６ｍｏｌ）、イソフタル酸の重量を３８８８ｇ（２３．４０ｍｏｌ）としたこと以外は実施例１と同様にして溶融重合を行いポリマーを得た後、固相重合を行おうとしたが、得られたポリマーは１５０℃まで昇温する最中に結晶化しなかったため、固相重合装置内壁に付着したり、ペレット同士が融着し、固相重合を行うことができなかった。
Comparative Example 3 (35 mol)
Except that the weight of adipic acid was 6351 g (43.46 mol) and the weight of isophthalic acid was 3888 g (23.40 mol), a melt polymerization was performed in the same manner as in Example 1 to obtain a polymer, followed by solid phase polymerization. However, since the obtained polymer was not crystallized during the heating up to 150 ° C., it adhered to the inner wall of the solid phase polymerization apparatus, or the pellets were fused together, and solid phase polymerization could not be performed. .
比較例４（４ｍｏｌの固相未実施品）
実施例１の溶融重合工程で得たポリマーを真空乾燥機を用いて、２４時間、１００℃で乾燥してポリアミド１０を得た。得られたポリアミド１０の融点は２３５℃であり、２５５℃、剪断速度１００ｓ−１での溶融粘度は４００Ｐａ・ｓであった。
次いで、実施例１と同様にして多層シート成形を行ったが、シート端部にポリアミド１０が大きくはみ出してしまい、実施例１と比較して同様の材料構成を有する多層シートを製造するのに１．３倍のポリアミドを消費した。
Comparative Example 4 (4 mol of solid phase incomplete product)
The polymer obtained in the melt polymerization step of Example 1 was dried at 100 ° C. for 24 hours using a vacuum dryer to obtain polyamide 10. The obtained polyamide 10 had a melting point of 235 ° C., a melt viscosity of 400 Pa · s at 255 ° C. and a shear rate of 100 s −1 .
Next, multilayer sheet molding was performed in the same manner as in Example 1, but the polyamide 10 protruded greatly at the sheet end, and it was 1 for producing a multilayer sheet having the same material structure as in Example 1. .3 times more polyamide was consumed.
比較例５（ＥＶＯＨ）
３台の押出機、フィードブロック、Ｔダイ、冷却ロール、巻き取り機等を備えた多層シート製造装置を用い、１台目の押出機からＰＰ（日本ポリプロ社製、商品名；ノバテックＰＰ、グレード名；ＥＣ９、メルトインデックス；０．５）を２２０℃で、２台目の押出機から接着性樹脂（三井化学社製、商品名；アドマー、グレード；ＱＦ５５１）を２１０℃で、３台目の押出機からエチレン−ビニルアルコール共重合体（クラレ社製、商品名；エバール、グレード；Ｆ１０１Ｂ、融点；１７５℃）を２２０℃でそれぞれ押し出し、フィードブロックを介してＰＰ層／接着性樹脂層／ガスバリア層／接着性樹脂層／ＰＰ層の３種５層構造の多層シートを製造した。なお各層の厚みは、３００／２０／４０／２０／３００（μｍ）とした。
次いで、プラグアシストを備えた真空圧空成形機を使用して、シート表面温度が１７５℃に達した時点で熱成形を行い、口径６２ｍｍ×底径５２ｍｍ×深さ２８ｍｍ、表面積７３ｃｍ２、容積７０ｍｌのカップ状容器を得た。
次いで、容器内に水を７０ｍｌ入れ、ＰＰ／アルミ箔／ＰＥＴ＝５０／９／１２（μｍ）のフィルムで開口部をヒートシールした後、オートクレーブを使用して、３０分間、１２１℃で密封容器をレトルト処理した。次いで、フィルムに穴を開けて水を６０ｍｌ抜いた後、ガス導入管及びガス排出管を挿しこみ、挿しこみ部をエポキシ系接着剤で固めて封した後、酸素透過率測定装置を用いて酸素透過率を測定した。結果を表１に示す。
Comparative Example 5 (EVOH)
Using multilayer sheet manufacturing equipment equipped with 3 extruders, feed block, T-die, cooling roll, winder, etc., PP (from Nippon Polypro Co., Ltd., trade name: Novatec PP, grade) Name: EC9, melt index: 0.5) at 220 ° C. Adhesive resin (Mitsui Chemicals, trade name: Admer, Grade: QF551) from the second extruder at 210 ° C. Extrude an ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., trade name: Eval, grade; F101B, melting point: 175 ° C.) from the extruder at 220 ° C., and feed PP layer / adhesive resin layer / gas barrier through the feed block. A multilayer sheet having a three-kind five-layer structure of layer / adhesive resin layer / PP layer was produced. The thickness of each layer was 300/20/40/20/300 (μm).
Next, using a vacuum / pressure forming machine equipped with plug assist, when the sheet surface temperature reaches 175 ° C., thermoforming is performed, and the diameter is 62 mm × bottom diameter 52 mm × depth 28 mm, surface area 73 cm 2 , volume 70 ml. A cup-shaped container was obtained.
Next, 70 ml of water is put in the container, and the opening is heat sealed with a film of PP / aluminum foil / PET = 50/9/12 (μm), and then sealed in an airtight container at 121 ° C. for 30 minutes using an autoclave. Was retorted. Next, after making a hole in the film and removing 60 ml of water, the gas introduction tube and the gas discharge tube were inserted, the insertion portion was sealed with an epoxy adhesive, and then sealed using an oxygen permeability measuring device. The transmittance was measured. The results are shown in Table 1.
以上の実施例及び比較例の結果から、発明の詳細な説明に示したように特定の組成、溶融粘度を有するポリアミドをバリア層として積層した実施例１乃至６はシート成形、熱成形において問題なく加工を行うことができ、しかも得られた容器は加熱処理を行った後でも酸素透過率の上昇は小さく、容器内へ透過する酸素量を少なくすることができるものであった。一方、本発明のポリアミドの組成とは異なり、イソフタル酸のモル比が小さい比較例１、比較例２は、熱成形時にシートを加熱した際、ポリアミドの結晶化が起こって腑型性が悪化し、満足な容器を得ることができなかった。逆にイソフタル酸のモル比が大きい比較例３は、ポリマーの結晶性が損なわれたため、ポリアミドの分子量を十分なものとする固相重合を行うことができなかった。溶融粘度が小さい比較例４では、多層シート成形時ポリアミドの溶融粘度が低すぎてシート端部に大きくはみ出し、実施例と同等の厚みを有する多層シートを得るにはポリアミドの消費量が多くなり不経済であった。またシート幅方向の厚み分布のバラツキも大きい傾向があり、シート製造が困難であった。また、ＥＶＯＨをガスバリア層とした比較例５では、シート成形、熱成形に問題は無かったものの、レトルト処理した後の酸素透過率が大幅に上昇し、実施例と比べて実質的に酸素バリア性に劣るものであった。 From the results of the above Examples and Comparative Examples, Examples 1 to 6 in which polyamide having a specific composition and melt viscosity was laminated as a barrier layer as shown in the detailed description of the present invention were satisfactory in sheet molding and thermoforming. Processing was possible, and the obtained container had a small increase in oxygen permeability even after heat treatment, and the amount of oxygen permeated into the container could be reduced. On the other hand, unlike the polyamide composition of the present invention, Comparative Example 1 and Comparative Example 2 in which the molar ratio of isophthalic acid is small, when the sheet is heated during thermoforming, the crystallization of the polyamide occurs and the moldability deteriorates. Could not get a satisfactory container. On the contrary, in Comparative Example 3 having a large isophthalic acid molar ratio, the crystallinity of the polymer was impaired, so that solid phase polymerization with sufficient polyamide molecular weight could not be performed. In Comparative Example 4 where the melt viscosity is small, the polyamide melt viscosity is too low at the time of forming the multi-layer sheet and protrudes greatly at the end of the sheet. To obtain a multi-layer sheet having the same thickness as that of the example, the amount of polyamide consumed is increased. It was an economy. Further, the variation in the thickness distribution in the sheet width direction tends to be large, and sheet production is difficult. In Comparative Example 5 in which EVOH was used as a gas barrier layer, there was no problem in sheet molding and thermoforming, but the oxygen permeability after retort treatment was significantly increased, and the oxygen barrier property substantially compared with the Examples. It was inferior to.
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