WO2017126563A1 - 二軸延伸ポリエステルフィルム、積層体及び包装用袋 - Google Patents
二軸延伸ポリエステルフィルム、積層体及び包装用袋 Download PDFInfo
- Publication number
- WO2017126563A1 WO2017126563A1 PCT/JP2017/001586 JP2017001586W WO2017126563A1 WO 2017126563 A1 WO2017126563 A1 WO 2017126563A1 JP 2017001586 W JP2017001586 W JP 2017001586W WO 2017126563 A1 WO2017126563 A1 WO 2017126563A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- resin
- polybutylene terephthalate
- polyester
- acid
- Prior art date
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 42
- 238000004806 packaging method and process Methods 0.000 title claims description 10
- -1 polybutylene terephthalate Polymers 0.000 claims abstract description 112
- 229920005989 resin Polymers 0.000 claims abstract description 98
- 239000011347 resin Substances 0.000 claims abstract description 98
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 85
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 84
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 229920001225 polyester resin Polymers 0.000 claims abstract description 38
- 239000004645 polyester resin Substances 0.000 claims abstract description 36
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010408 film Substances 0.000 claims description 165
- 239000010409 thin film Substances 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 229920000728 polyester Polymers 0.000 claims description 27
- 230000009477 glass transition Effects 0.000 claims description 21
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 18
- 238000010030 laminating Methods 0.000 claims description 10
- 239000001361 adipic acid Substances 0.000 claims description 9
- 235000011037 adipic acid Nutrition 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 150000002009 diols Chemical class 0.000 claims description 9
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims description 4
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 16
- 238000007740 vapor deposition Methods 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 11
- 238000012545 processing Methods 0.000 abstract description 10
- 239000000284 extract Substances 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 79
- 238000000034 method Methods 0.000 description 59
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000001816 cooling Methods 0.000 description 16
- 238000001125 extrusion Methods 0.000 description 16
- 239000003963 antioxidant agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 238000009998 heat setting Methods 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- 239000005020 polyethylene terephthalate Substances 0.000 description 13
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 9
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000003078 antioxidant effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 230000035699 permeability Effects 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000000565 sealant Substances 0.000 description 8
- 229910052814 silicon oxide Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
- 239000005022 packaging material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 5
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229940014772 dimethyl sebacate Drugs 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 239000005003 food packaging material Substances 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000013611 frozen food Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 230000002040 relaxant effect Effects 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- KCRLWVVFAVLSAP-UHFFFAOYSA-N octyl dihydrogen phosphite Chemical compound CCCCCCCCOP(O)O KCRLWVVFAVLSAP-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/362—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using static mixing devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/49—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using two or more extruders to feed one die or nozzle
- B29C48/495—Feed-blocks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/003—PET, i.e. poylethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
- Y10T428/1331—Single layer [continuous layer]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
- Y10T428/1345—Single layer [continuous layer]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
Definitions
- the present invention is excellent in barrier properties, dimensional stability, workability, bag-breaking resistance, chemical resistance, and there is little migration of the extract to the contents after retort treatment, and retort treatment or heat treatment in a microwave oven is possible.
- the present invention relates to a biaxially stretched polyester film that can be used publicly for food packaging materials. Furthermore, the present invention relates to a biaxially stretched polyester film that is excellent in pinhole resistance at low temperatures and suitable for frozen foods that are heat-treated by a retort treatment or a microwave oven. Furthermore, the present invention relates to a laminate and a packaging bag using these biaxially stretched polyester films.
- PET polyethylene terephthalate film
- a laminated film in which a vapor deposition layer is laminated are excellent in dimensional change and chemical resistance at the time of moisture absorption, and have low molecular components. It was known that there was little elution (for example, patent document 1). However, this conventional technique has a problem that the PET film is brittle and the contents leak when the bag is dropped, and the pinhole resistance is poor.
- a technique has been proposed in which a packaging material for boil treatment or retort treatment, which is inexpensive and excellent in low elution and transparency, can be obtained by using the layer having a transparent gas barrier film as a base layer.
- Patent Document 3 since this conventional technique is easy to peel off at the interface between the polyester-based resin layer and the polyamide-based resin layer, there is a problem that the bag is broken when the bag is dropped and the contents are likely to leak. .
- butylene terephthalate film can be a biaxially stretched polybutylene terephthalate film excellent in bag-breaking resistance, pinhole resistance and dimensional stability that can be used even under severe retort conditions of 130 ° C or higher. (For example, Patent Document 4).
- the film forming method by the tubular simultaneous biaxial stretching disclosed in the prior art has poor thickness accuracy due to the manufacturing method, and the plane orientation coefficient does not increase, so that the bag breaking resistance is inferior.
- the film tends to be stretched when it is subjected to processing such as an adhesive coating process on the film and is inferior in workability.
- 1,4-butanediol which is a monomer component of polybutylene terephthalate, and tetrahydrofuran generated by a cyclization reaction associated with a thermal decomposition product of 1,4-butanediol ( (THF) is known to be generated (for example, Non-Patent Document 1). Therefore, it has been pointed out that when a high-temperature heat treatment such as retort treatment is performed, these low molecular weight components are eluted, and the flavor of the contents is impaired (for example, Patent Document 5).
- the distribution environment is mainly a low-temperature distribution environment, so that they are loaded especially when products are transported or in large quantities.
- packaging materials made of plastic films become colder and harder and more brittle, the lower the temperature, the shape of the product stored in the packaging bag and the distribution process between the production site and the consumer
- a problem arises that the packaging bag is torn due to vibration during transportation or the like, or a bag breakage or pinhole is generated due to a drop impact due to poor handling.
- the present invention has been made against the background of the problems of the prior art. That is, the object of the present invention is excellent in barrier properties, dimensional stability, processability, bag breakage resistance, chemical resistance, and there is little migration of the extract to the contents after retorting, and the retorting or microwave oven
- An object of the present invention is to provide a biaxially stretched polyester film that can be suitably used for food packaging materials that are subjected to the above heat treatment.
- the present inventor as a result, in the production process of a biaxially stretched polybutylene terephthalate film, decomposition of the resin proceeds when the raw material polyester resin composition has a high melt extrusion temperature. As the amount of 1,4-butanediol and tetrahydrofuran remaining in the obtained biaxially stretched polybutylene terephthalate film is increased, the low molecular weight component in the film after biaxial stretching is sufficiently reduced.
- extrusion is performed at a temperature at which the resin does not decompose, and / or an antioxidant is added to suppress thermal decomposition of the resin.
- the extrusion temperature should preferably be 300 ° C. or lower.
- the extrusion temperature should preferably be 268 ° C or lower.
- the low molecular component remaining in the film is removed by performing sufficient heat treatment in the film stretching step. It is preferable that the temperature is 60 ° C. or higher in the longitudinal stretching step and 90 ° C. or higher in the horizontal stretching step.
- the temperature in the heat setting step should preferably be 205 ° C. or higher. Has been found to be important, and the present invention has been completed.
- a biaxially stretched polyester film having the following characteristics (a), (b), (c) and (d) and having a thickness of 10 to 30 ⁇ m.
- A It consists of the polyester resin composition which contains polybutylene terephthalate resin (A) in 60 mass% or more.
- B The thermal shrinkage at 150 ° C. ⁇ 30 minutes is ⁇ 2 to + 2%.
- C Thickness accuracy is 1 to 20%.
- D The total amount of 1,4-butanediol and tetrahydrofuran that volatilizes during heating for 60 minutes at a temperature of 135 ° C. is 1800 ppb or less.
- the polyester composition contains 60 to 90% by weight of the polybutylene terephthalate resin (A) and a polyester resin (B) other than the polybutylene terephthalate resin having a glass transition temperature of 0 ° C. or higher. .
- the polyester composition preferably contains 60 to 90% by weight of the polybutylene terephthalate resin (A) and a polyester resin (C) having a glass transition temperature other than 0 ° C. other than the polybutylene terephthalate resin (A). is there.
- the polyester resin (C) having a glass transition temperature of less than 0 ° C. other than the polybutylene terephthalate resin (A) is isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid And a polybutylene terephthalate resin copolymerized with at least one dicarboxylic acid selected from the group consisting of sebacic acid, or ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5 -At least selected from the group consisting of pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol and polycarbonate diol It is preferable that also at least
- a laminated film in which an inorganic thin film layer is laminated on at least one side of the biaxially stretched polyester film is suitable.
- a laminate comprising the biaxially stretched polyester film according to any one of the above and a heat-sealable resin layer is suitable.
- a packaging bag made of the laminate is preferably used.
- the present inventors can be used as a substrate film for vapor deposition, have excellent dimensional stability, processability, bag breaking resistance, chemical resistance, and can be applied to the contents even after retorting. It has become possible to obtain a biaxially stretched polyester film that can be suitably used for food packaging materials that undergo a retort treatment or a heat treatment in a microwave oven that have low migration of low molecular weight components.
- the polyester resin composition used in the present invention is mainly composed of a polybutylene terephthalate resin (A), and the content of the polybutylene terephthalate resin (A) in the polyester resin composition is 60% by mass or more. More preferably, 70 mass% or more is preferable. If it is less than 60% by mass, impact strength and pinhole resistance are lowered, and the film properties are not sufficient.
- the polybutylene terephthalate resin (A) used as the main component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, as the dicarboxylic acid component. Yes, and most preferably 100 mol%.
- 1,4-butanediol is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 97 mol% or more, and most preferably 1,4-butane during polymerization. Except for the by-product produced by the ether bond of the diol, it is not included.
- the polyester resin composition used in the present invention is a polyester resin having a glass transition temperature other than polybutylene terephthalate resin of 0 ° C. or higher for the purpose of adjusting the film forming property during biaxial stretching and the mechanical properties of the obtained film ( B) Or the polyester resin (C) whose glass transition temperature other than polybutylene terephthalate resin is less than 0 degreeC can be contained.
- polyethylene terephthalate PET
- polyethylene naphthalate PEN
- polybutylene naphthalate PBN
- polypropylene terephthalate PPT
- polybutylene terephthalate resins obtained by copolymerizing at least one acid component selected from the group consisting of isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid and sebacic acid. These have a glass transition temperature of 0 ° C. or more, and are effective in increasing the dimensional stability of the laminate.
- polyester resin (C) having a glass transition temperature other than 0 ° C. other than the polybutylene terephthalate resin (A) examples include isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid, and azelain.
- the content of the copolymer component may be adjusted. Specifically, for example, in the case of adipic acid or sebacic acid, the content may be in the range of about 30 mol% or more.
- the glass transition temperature is less than 0 ° C., there is an effect that the pinhole resistance during the frozen storage of the laminate is improved.
- 40 mass% or less is preferable, More preferably, 30 mass% or less is preferable. If it exceeds 40 mass%, the mechanical properties of polybutylene terephthalate will be impaired, impact strength, bag breakage resistance, pinhole resistance will be insufficient, and transparency and barrier properties may decrease. is there.
- the lower limit of the intrinsic viscosity of the polybutylene terephthalate resin (A) used in the present invention is preferably 0.9 dl / g, more preferably 0.95 dl / g, and still more preferably 1.0 dl / g.
- the upper limit of the intrinsic viscosity of the polybutylene terephthalate resin is preferably 1.3 dl / g.
- Addition of an antioxidant is also effective in reducing the amount of eluate such as 1,4-butanediol and tetrahydrofuran after the retort treatment of the biaxially stretched polyester film according to the present invention.
- the molecular weight of the polybutylene terephthalate resin can be suppressed, and the amount of 1,4-butanediol and tetrahydrofuran remaining in the obtained biaxially stretched polyester film can be reduced.
- polybutylene terephthalate is gradually decomposed by heating, it is effective in suppressing thermal decomposition that occurs when a packaging material using polybutylene terephthalate is retorted.
- Antioxidants used include primary antioxidants (which have a phenol-based or amine-based radical scavenging and chain termination action) and secondary antioxidants (which include phosphorus-based and sulfur-based peroxides). Any of these can be used. Specific examples include phenolic antioxidants (eg, phenol type, bisphenol type, thiobisphenol type, polyphenol type, etc.), amine antioxidants (eg, diphenylamine type, quinoline type, etc.), phosphorus antioxidants (eg, For example, phosphite type, phosphonite type, and the like) and sulfur-based antioxidants (for example, thiodipropionic acid ester type and the like).
- phenolic antioxidants eg, phenol type, bisphenol type, thiobisphenol type, polyphenol type, etc.
- amine antioxidants eg, diphenylamine type, quinoline type, etc.
- phosphorus antioxidants eg, For example, phosphite type, phosphonite
- n-octadecyl- ⁇ - (4′-hydroxy-3,5′-di-t-butylphenyl) propionate tetrakis [methylene-3- (3 ′, 5′-di-t-butyl- 4′-hydroxyphenyl) propionate] (which is commercially available as “Irganox 1010” (trade name)), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -S-triazine-2,4,6 (1H, 3H, 5H) -trione, 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (which is commercially available as “Irganox 1330” (trade name)), Tris ( Mixed mono And / or dinonylphenyl)
- antioxidants may be used alone or in combination of two or more.
- n-octadecyl- ⁇ - (4′-hydroxy-3,5′-di-t-butylphenyl) propionate, tetrakis [methylene-3- (3 ′, 5) are used from the viewpoints of availability and food hygiene.
- '-Di-t-butyl-4'-hydroxyphenyl) propionate] is preferred.
- the upper limit of the antioxidant concentration in the polyester resin composition is preferably 2000 ppm, more preferably 1000 ppm. When the upper limit is exceeded, the added antioxidant itself may become an eluate.
- the polyester resin composition may contain conventionally known additives, for example, lubricants, stabilizers, colorants, antistatic agents, ultraviolet absorbers and the like, if necessary.
- lubricant in addition to inorganic lubricants such as silica, calcium carbonate, and alumina, organic lubricants are preferable, silica and calcium carbonate are more preferable, and silica is particularly preferable in terms of reducing haze. By these, transparency and slipperiness can be expressed.
- the lower limit of the lubricant concentration in the polyester resin composition is preferably 100 ppm, more preferably 500 ppm, and still more preferably 800 ppm. If it is less than the above, the slipperiness of the film may be lowered.
- the upper limit of the lubricant concentration is preferably 20000 ppm, more preferably 10,000 ppm, and even more preferably 1800 ppm. If the above is exceeded, the transparency may decrease.
- the production method for obtaining the biaxially stretched polyester film of the present invention will be specifically described below. It is not limited to these.
- the polyester resin composition as the film raw material is dried or hot air dried so that the moisture content is less than 200 ppm.
- each raw material is weighed and mixed, supplied to an extruder, and melt extruded into a sheet. Further, the molten sheet is brought into close contact with a rotating roll made of a rotating metal (casting roll) using an electrostatic application method, and is cooled and solidified to obtain an unstretched sheet.
- high-precision filtration can be performed to remove foreign substances contained in the molten polyester resin composition.
- the filter medium used for high-precision filtration of the molten resin is not particularly limited, but in the case of a stainless steel sintered filter medium, the removal performance of aggregates and high melting point organic substances mainly composed of Si, Ti, Sb, Ge, Cu Excellent and suitable.
- the lower limit of the melt extrusion temperature of the polyester resin composition is preferably 200 ° C, more preferably 250 ° C, and even more preferably 260 ° C. If it is less than the above, ejection may become unstable.
- the upper limit of the resin melting temperature is preferably 268 ° C. When the above is exceeded, the decomposition of the resin proceeds, and as a result, the amount of 1,4-butanediol and tetrahydrofuran remaining in the biaxially stretched polybutylene terephthalate film increases. When the above-mentioned antioxidant is contained in the polyester resin composition, it becomes possible to perform melt extrusion at a higher temperature, but it is necessary to make it 300 ° C. or less.
- the yield stress of the obtained unstretched sheet is increased, and not only is it easy to break during biaxial stretching, but the flexibility of the obtained biaxially stretched polyester film is impaired, and pinhole resistance and fracture resistance are reduced. It becomes a film with insufficient bag characteristics.
- the polyester resin composition is multilayered and melt extruded so that all layers have the same composition, the crystal cannot grow beyond the interface of each layer, so the yield stress of the obtained unstretched sheet
- the resulting biaxially stretched polyester film is excellent in impact strength, and has sufficient pinhole resistance and resistance to bag breakage. Further, the crystal structure is such that 1,4-butanediol and tetrahydrofuran can be easily removed in the heat treatment step after biaxial stretching.
- a general multilayering apparatus multilayer feedblock, static mixer, multilayer multimanifold, etc.
- a method of laminating thermoplastic resins sent from different flow paths using two or more extruders using a field block, a static mixer, a multi-manifold die, or the like can be used.
- the object of the present invention is achieved by introducing the multilayering apparatus described above into the melt line from the extruder to the die using only one extruder. It is also possible to fulfill.
- the lower limit of the cooling roll temperature is preferably ⁇ 10 ° C. If it is less than the above, the effect of suppressing crystallization may be saturated.
- the upper limit of the cooling roll temperature is preferably 40 ° C. If the above is exceeded, the crystallinity becomes too high and stretching may be difficult. Further, when the temperature of the cooling roll is in the above range, it is preferable to reduce the humidity of the environment near the cooling roll in order to prevent condensation.
- the surface of the cooling roll rises because high temperature resin contacts the surface.
- the cooling roll is cooled by flowing cooling water through the pipe inside, but the cooling roll is secured by securing a sufficient amount of cooling water, devising the arrangement of the pipe, and performing maintenance so that sludge does not adhere to the pipe. It is necessary to reduce the temperature difference in the width direction of the surface.
- the thickness of the unstretched sheet is preferably in the range of 15 to 2500 ⁇ m.
- the casting in the multilayer structure described above is performed with at least 60 layers, preferably 250 layers or more, more preferably 1000 layers or more. When the number of layers is small, the effect of improving stretchability is lost.
- the stretching method can be simultaneous biaxial stretching or sequential biaxial stretching, but in order to increase the piercing strength, it is necessary to increase the plane orientation coefficient, and the film forming speed is high and the productivity is high.
- sequential biaxial stretching is most preferred.
- sequential biaxial stretching the unstretched sheet is stretched in the film flow direction, so-called longitudinal direction, and then stretched in the direction perpendicular to the film flow direction, so-called transverse direction.
- the lower limit of the stretching temperature in the machine direction (hereinafter referred to as MD) is preferably 60 ° C, and more preferably 65 ° C.
- the upper limit of the MD stretching temperature is preferably 100 ° C, more preferably 95 ° C. If the temperature exceeds 100 ° C., the orientation is not applied and the mechanical properties may be deteriorated. Further, by setting the MD stretching temperature to 60 ° C. or higher, 1,4-butanediol and tetrahydrofuran remaining in the biaxially stretched polybutylene terephthalate can be further reduced.
- the lower limit of the MD draw ratio is preferably 2.6 times, particularly preferably 2.8 times. If it is less than the above, the orientation is not applied, so the mechanical properties and thickness unevenness may be deteriorated.
- the upper limit of the MD draw ratio is preferably 3.5 times, more preferably 3.0 times, and particularly preferably 3.8 times. If the above is exceeded, the effect of improving the mechanical strength and thickness unevenness may be saturated, and the vertical orientation will become stronger. The distortion may increase, and as a result, the straight tearing property in the longitudinal direction may decrease.
- the lower limit of the transverse direction (hereinafter, TD) stretching temperature is preferably 85 ° C, more preferably 90 ° C or higher. If it is less than 85 ° C., breakage may easily occur.
- the upper limit of the TD stretching temperature is preferably 100 ° C., and if it exceeds the above, since the orientation is not applied, the mechanical properties may be deteriorated. Further, by setting the TD stretching temperature to 80 ° C. or higher, 1,4-butanediol and tetrahydrofuran remaining in the biaxially stretched polybutylene terephthalate can be further reduced.
- the lower limit of the TD stretch ratio is preferably 3.5 times, more preferably 3.6 times, and particularly preferably 3.7 times. If it is less than the above, the orientation is not applied, so the mechanical properties and thickness unevenness may be deteriorated.
- the upper limit of the TD stretch ratio is preferably 5 times, more preferably 4.5 times, and particularly preferably 4.0 times. If the above is exceeded, the effect of improving mechanical strength and thickness unevenness may be saturated.
- the lower limit of the heat setting temperature is preferably 205 ° C, more preferably 210 ° C. If it is less than the above, the thermal shrinkage rate increases, and not only the displacement or shrinkage during processing may occur, but also 1,4-butanediol and tetrahydrofuran produced by thermal decomposition of polybutylene terephthalate in the resin extrusion process. It may remain in the film, and may be transferred to the contents of the packaging material by heating such as retort treatment, thereby damaging the flavor of the food.
- the upper limit of the heat setting temperature is preferably 240 ° C., and if it exceeds the above, the film will melt, and even if it does not melt, it may become extremely brittle.
- the lower limit of the TD relaxation rate is preferably 0.5%, and if it is less than the above, breakage may easily occur during heat setting.
- the upper limit of the TD relaxation rate is preferably 5%. If the upper limit is exceeded, sagging may occur and thickness unevenness may occur, and the shrinkage in the longitudinal direction during heat setting increases. The strain of molecular orientation becomes large, and the straight tearing property may be lowered.
- the lower limit of the film thickness is preferably 3 ⁇ m, more preferably 5 ⁇ m, and even more preferably 8 ⁇ m. If it is less than 3 ⁇ m, the strength as a film may be insufficient.
- the upper limit of the film thickness is preferably 100 ⁇ m, more preferably 75 ⁇ m, and still more preferably 50 ⁇ m. If it exceeds 100 ⁇ m, it may become too thick and processing for the purpose of the present invention may be difficult.
- the biaxially stretched polyester film of the present invention preferably has a resin having the same composition throughout the entire film.
- the upper limit of the thickness accuracy (Tv (%)) of the biaxially stretched polyester film of the present invention is preferably 10%, more preferably 8%. If it exceeds 10%, the film processability tends to deteriorate.
- the total amount of 1,4-butanediol and tetrahydrofuran that volatilizes while heating the biaxially stretched polyester film at a temperature of 135 ° C. for 60 minutes is preferably 1800 ppb or less.
- it is 1700 ppb, More preferably, it is 1600 ppb or less.
- it is particularly preferably 1500 ppb or less.
- the amount of 1,4-butanediol that volatilizes during heating for 60 minutes at a temperature of 135 ° C. is preferably 1800 ppb or less, and more preferably 1700 ppb. Moreover, it is especially preferable that it is 1600 ppb or less. Further, the amount of tetrahydrofuran that volatilizes during heating for 60 minutes at a temperature of 135 ° C. is preferably 200 ppb or less, more preferably 100 ppb, and most preferably 70 ppb or less.
- the lower limit of the plane orientation coefficient of the biaxially stretched polyester film of the present invention is preferably 0.1. If it is less than 0.1, the puncture strength, impact strength, etc. may be lowered.
- the upper limit of the plane orientation coefficient is preferably 0.15, and when it exceeds 0.15, productivity may be lowered and flexibility may be lowered.
- the lower limit of impact strength is preferably 0.05 J / ⁇ m. If it is less than the above, the strength may be insufficient when used as a bag.
- the upper limit of impact strength is preferably 0.2 J / ⁇ m. If the above is exceeded, the improvement effect may become saturated.
- the measurement method of impact strength is shown below. According to JIS K7160-1996, an impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used to measure the strength of the film against impact punching in an atmosphere at 23 ° C. An impact spherical surface having a diameter of 1/2 inch was used. Unit J / ⁇ m.
- the lower limit of the piercing strength of the biaxially stretched polyester film of the present invention is preferably 0.8 N / ⁇ m, more preferably 0.9 N / ⁇ m. If it is less than 0.8 N / ⁇ m, the strength at the time of processing or forming a bag may be insufficient.
- the upper limit of the piercing strength is preferably 1.5 N / ⁇ m, and if it exceeds 1.5 N / ⁇ m, the improvement effect is saturated.
- the piercing strength can be within the range by the MD magnification and the heat setting temperature. A method for measuring the piercing strength is shown below. It was measured in accordance with “2. Test methods for strength, etc.” in “Standards for Foods, Additives, etc.
- the lower limit of the thermal shrinkage after heating at 150 ° C. for 15 minutes in the MD and TD directions of the biaxially stretched polyester film of the present invention is preferably ⁇ 2.0% / ⁇ m. If it is less than the above, the effect of improvement is saturated, and it may become mechanically brittle.
- the upper limit of the heat shrinkage rate after heating at 150 ° C. for 15 minutes in the MD and TD directions of the biaxially stretched polyester film of the present invention is preferably 2.0% / ⁇ m, more preferably 1.8% / ⁇ m. More preferably, it is 1.4% / ⁇ m. If the above is exceeded, pitch deviation may occur due to dimensional changes during processing such as printing.
- the heat shrinkage rate of the film is adjusted by the processing temperature and TD relaxation rate in the TD heat setting treatment, but when the heat shrinkage rate in the MD direction is larger than 2%, the TD heat setting treatment is insufficient.
- the amount of 1,4-butanediol or tetrahydrofuran remaining in the film may not be sufficiently reduced, and the flavor of the contents may be impaired.
- the method for measuring the heat shrinkage rate is shown below. The measurement was performed by the dimensional change test method described in JIS-C-2151-2006.21 except that the test temperature was 150 ° C. and the heating time was 15 minutes. The test piece was used as described in 21.1 (a).
- the upper limit of the orientation axis angle of the film of the present invention is preferably 30 °, more preferably 28 °, and further preferably 25 °. If it is less than the above, the tear straightness when the film is torn in the longitudinal direction may be lowered.
- the upper limit of the refractive index of MD of the film of the present invention is preferably 1.640, more preferably 1.635, and still more preferably 1.630. If the above is exceeded, the effects on film mechanical properties and straight tearability may be saturated.
- the upper limit of the refractive index of MD of the film of the present invention is preferably 1.670, more preferably 1.669, and further preferably 1.668. If the above is exceeded, the effects on film mechanical properties and straight tearability may be saturated.
- the upper limit of the haze per thickness of the biaxially stretched polyester film of the present invention is preferably 0.66% / ⁇ m, more preferably 0.60% / ⁇ m, still more preferably 0.53% / ⁇ m. . If the above is exceeded, there is a possibility of degrading the quality of the printed characters and images when the film is printed.
- the biaxially stretched polyester film of the present invention can impart excellent gas barrier properties by forming a laminated film in which an inorganic thin film layer is provided on at least one side of the film.
- a thin film made of a metal or an inorganic oxide is preferably used as the inorganic thin film layer.
- the material for forming the inorganic thin film layer is not particularly limited as long as it can be formed into a thin film, but from the viewpoint of gas barrier properties, inorganic oxidation such as silicon oxide (silica), aluminum oxide (alumina), a mixture of silicon oxide and aluminum oxide, etc. A thing is mentioned preferably.
- a composite oxide of silicon oxide and aluminum oxide is preferable from the viewpoint that both flexibility and denseness of the thin film layer can be achieved.
- the mixing ratio of silicon oxide and aluminum oxide is preferably such that the mass ratio of Al 2 O 3 is in the range of 20 to 70%.
- Al 2 O 3 is less than 20%, the water vapor barrier property may be lowered.
- the inorganic thin film layer tends to be hard, and the film may be broken during the secondary processing such as printing or laminating, and the barrier property may be lowered.
- silicon oxide is various silicon oxides such as SiO and SiO 2 or a mixture thereof
- aluminum oxide is various aluminum oxides such as AlO and Al 2 O 3 or a mixture thereof.
- the film thickness of the inorganic thin film layer is usually 1 to 800 nm, preferably 5 to 500 nm. If the film thickness of the inorganic thin film layer is less than 1 nm, satisfactory gas barrier properties may be difficult to obtain. On the other hand, even if the thickness exceeds 800 nm, the corresponding gas barrier property improvement effect is obtained. However, it is disadvantageous in terms of bending resistance and manufacturing cost.
- the method for forming the inorganic thin film layer is not particularly limited.
- a known vapor deposition method such as a vacuum vapor deposition method, a sputtering method, a physical vapor deposition method such as an ion plating method (PVD method), or a chemical vapor deposition method (CVD method).
- PVD method physical vapor deposition method
- CVD method chemical vapor deposition method
- a typical method for forming the inorganic thin film layer will be described by taking a silicon oxide / aluminum oxide thin film as an example.
- a vacuum deposition method a mixture of SiO 2 and Al 2 O 3 or a mixture of SiO 2 and Al is preferably used as a deposition material.
- particles are used as these vapor deposition materials.
- the size of each particle is desirably such that the pressure during vapor deposition does not change, and the preferred particle diameter is 1 mm to 5 mm.
- heating methods such as resistance heating, high frequency induction heating, electron beam heating, and laser heating can be employed.
- reactive vapor deposition using oxygen, nitrogen, hydrogen, argon, carbon dioxide gas, water vapor or the like as a reactive gas, or using means such as ozone addition or ion assist.
- the film forming conditions can be arbitrarily changed, for example, by applying a bias to the deposition target (film to be deposited) or heating or cooling the deposition target.
- a bias to the deposition target (film to be deposited) or heating or cooling the deposition target.
- Such a vapor deposition material, reaction gas, bias of the deposition target, heating / cooling, and the like can be similarly changed when a sputtering method or a CVD method is employed.
- the biaxially stretched polyester film of the present invention can be provided with an adhesion layer between the biaxially stretched polybutylene terephthalate film and the inorganic thin film layer for the purpose of ensuring the barrier properties and laminate strength after retorting.
- an adhesion layer provided between the biaxially stretched polypolyester film and the inorganic thin film layer resins such as urethane, polyester, acrylic, titanium, isocyanate, imine, polybutadiene, epoxy, isocyanate And those added with a curing agent such as a melamine or a melamine.
- the solvent examples include aromatic solvents such as benzene and toluene; alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate and butyl acetate; Examples thereof include polyhydric alcohol derivatives such as glycol monomethyl ether.
- the resin composition used for these adhesion layers preferably contains a silane coupling agent having at least one organic functional group. Examples of the organic functional group include an alkoxy group, an amino group, an epoxy group, and an isocyanate group.
- the resin compositions used for the adhesion layer it is preferable to use a mixture of a resin containing an oxazoline group, an acrylic resin, and a urethane resin.
- the oxazoline group has a high affinity with the inorganic thin film, and can react with the oxygen deficient part of the inorganic oxide and metal hydroxide generated during the formation of the inorganic thin film layer, and exhibits strong adhesion with the inorganic thin film layer.
- the unreacted oxazoline group present in the coating layer can react with the carboxylic acid terminal generated by hydrolysis of the base film and the coating layer to form a crosslink.
- the method for forming the adhesion layer is not particularly limited, and a conventionally known method such as a coating method can be employed.
- Preferred examples of the coating method include an offline coating method and an in-line coating method.
- the drying and heat treatment conditions during coating depend on the thickness of the coat and the conditions of the equipment, but are sent to the right-angled stretching process immediately after coating and stretched. It is preferable to dry in the preheating zone or the stretching zone of the process. In such a case, it is usually preferable to set the temperature to about 50 to 250 ° C.
- a laminate in which a heat sealable resin layer called a sealant is laminated is often used.
- the biaxially stretched polyester film may be laminated with a layer made of another material such as a heat-sealable resin layer, and as a method, the biaxially stretched polyester film of the present invention is bonded after production, Layers made of other materials such as a heat-sealable resin layer can be laminated in the process of producing a biaxially stretched polyester film.
- the heat-sealable resin layer is usually formed by an extrusion lamination method or a dry lamination method.
- thermoplastic polymer for forming the heat-sealable resin layer is not particularly limited as long as the sealant adhesiveness can be sufficiently exhibited, such as polyethylene resins such as HDPE, LDPE, LLDPE, polypropylene resin, and ethylene-vinyl acetate copolymer. , Ethylene- ⁇ -olefin random copolymers, ionomer resins, and the like can be used. Among them, a polypropylene resin is preferable as a material having heat resistance capable of withstanding retort processing.
- the total amount of 1,4-butanediol and THF transferred to the inside of the bag after heating at a temperature of 135 ° C. for 60 minutes is preferably 1000 ppb or less, and more preferably 800 ppb or less.
- a biaxially stretched polyester film has a heat-sealable resin layer on the inorganic thin film layer side surface of the laminated film provided with an inorganic thin film layer on at least one side of the film, and the inorganic thin film layer side. What laminated
- stacked the other thermoplastic resin layer on the opposite surface is preferable.
- thermoplastic resin layer a film obtained by melt-extruding a thermoplastic tree and stretching, cooling, and heat-setting in the longitudinal direction and / or the width direction can be used as necessary.
- plastics include polyamides represented by nylon 4,6, nylon 6, nylon 6,6, nylon 12, etc .; polyesters represented by polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, etc .; polyethylene, polypropylene
- polyolefins such as polybutene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, wholly aromatic polyamide, polyamideimide, polyimide, polyetherimide, polysulfone, polystyrene, and polylactic acid.
- polyester is preferable in terms of heat resistance, step stability, and transparency
- polyethylene terephthalate or a copolymer obtained by copolymerizing polyethylene terephthalate with other components is particularly preferable.
- the inorganic vapor deposition layer is excellent in gas barrier properties, so that 1,4 generated from the polybutylene terephthalate film -Butanediol or tetrahydrofuran may not escape to the outside of the bag, resulting in an increased amount of transfer to the bag contents.
- the biaxially stretched polyester film of the present invention since the biaxially stretched polyester film of the present invention generates a small amount of THF or 1,4-butanediol even in the retort treatment, even when used in such a configuration, even after the retort treatment. It is considered that the amount of 1,4-butanediol or tetrahydrofuran transferred to the contents can be reduced.
- the pinhole resistance of the laminate of the present invention is preferably 20 or less, more preferably 10 or less, and most preferably 6 or less.
- the pinhole resistance measurement method is shown below.
- the laminate was cut into a size of 20.3 cm (8 inches) ⁇ 27.9 cm (11 inches), and the rectangular test film after cutting was cut at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more. Leave to condition. Thereafter, the rectangular test film is wound to form a cylindrical shape having a length of 20.32 cm (8 inches).
- one end of the cylindrical film is fixed to the outer periphery of a disk-shaped fixed head of a gelbo flex tester (manufactured by Rigaku Kogyo Co., Ltd., NO.901 type) (conforming to MIL-B-131C standard).
- the other end of the tester was fixed to the outer periphery of a disk-shaped movable head of a tester facing the fixed head at a distance of 17.8 cm (7 inches).
- the movable head is rotated 440 ° while approaching the fixed head in the direction of 7.6 cm (3.5 inches) along the axis of both heads opposed in parallel, and then 6.4 cm (without rotation) 2.5-inch)
- a one-cycle bending test in which the movement is performed in the reverse direction and the movable head is returned to the initial position is performed continuously for 2000 cycles at a rate of 40 cycles per minute. Repeated. Implementation was at 5 ° C. Thereafter, the number of pinholes generated in a portion within 17.8 cm (7 inches) ⁇ 27.9 cm (11 inches) excluding the portion fixed to the outer periphery of the fixed head and the movable head of the tested film was measured (ie, The number of pinholes per 77 square inches was measured).
- the number of drops is preferably 30 or more, more preferably 40 or more, further preferably 50 or more, and 60 or more. Most preferred.
- the method for measuring the bag resistance is shown below. Cut the laminate to a size of 15cm square, superimpose two sheets so that the sealant is inside, and heat-seal the three sides at a seal temperature of 160 ° C and a seal width of 1.0cm. A three-side sealed bag was obtained. After filling the obtained three-side seal bag with 250 mL of water, the mouth of the fourth side was closed by heat sealing to prepare a four-side seal bag filled with water. The resulting four-side sealed bag was placed at room temperature 5 ° C. and humidity 35% R.D. H. In this environment, the sample was dropped onto a concrete plate from a position with a height of 100 cm, and the number of drops until a tear or pinhole was generated was counted.
- the oxygen permeability of the laminate of the present invention is preferably 10 ml / m 2 ⁇ day ⁇ MPa or less.
- the measuring method of oxygen permeability is shown below. In accordance with JIS K7126-2 A method, the oxygen permeability was measured under the conditions of 23 ° C. and 65% RH using an oxygen permeability measuring device (“OX-TRAN 2/21” manufactured by MOCON). The measurement was performed in a direction in which oxygen permeates from the base film side on which the inorganic thin film layer is not laminated to the inorganic thin film layer side.
- the water vapor permeability of the laminate of the present invention is preferably 8 g / m 2 ⁇ day or less.
- a method for measuring the water vapor transmission rate is shown below. In accordance with JIS K7129 B method, measurement was performed using a water vapor transmission rate measuring device (“PERMATRAN-W 3/31” manufactured by MOCON) under the conditions of 40 ° C. and 90% RH. The measurement was performed in a direction in which oxygen permeates from the base film side on which the inorganic thin film layer is not laminated to the inorganic thin film layer side.
- Tv (%) ⁇ (Tmax ⁇ Tmin) / Tave ⁇ ⁇ 100 (%) (1)
- the layer was formed by electron beam evaporation.
- As the evaporation source particulate SiO 2 (purity 99.9%) and A1 2 O 3 (purity 99.9%) of about 3 mm to 5 mm were used.
- the film thickness of the inorganic thin film layer (SiO 2 / A1 2 O 3 composite oxide layer) thus obtained was 13 nm.
- a urethane-based two-component curable adhesive (“Takelac (registered trademark) A525S” and “Takenate (registered trademark) A50” manufactured by Mitsui Chemicals, Inc.) is 13.5: 1 (mass ratio).
- an unstretched polypropylene film having a thickness of 70 ⁇ m (“P1147” manufactured by Toyobo Co., Ltd.) as a heat-sealable resin layer by dry laminating using a dry laminating method, and aging at 40 ° C. for 4 days A laminated gas barrier laminate for evaluation was obtained.
- all the thickness after drying of the adhesive bond layer formed with a urethane type 2 liquid curable adhesive was about 4 micrometers.
- a urethane-based two-component curable adhesive (“Takelac (registered trademark) A525S” and “Takenate (registered trademark) A50” manufactured by Mitsui Chemicals, Inc.) is 13.5: 1 (mass ratio).
- a laminate gas barrier laminate for evaluation was prepared by laminating an unstretched polypropylene film (“P1147” manufactured by Toyobo Co., Ltd.) having a thickness of 70 ⁇ m as a heat-sealable resin layer on the opposite surface and aging at 40 ° C. for 4 days.
- An unstretched polypropylene film (“P1147” manufactured by Toyobo Co., Ltd.) was bonded and subjected to aging at 40 ° C. for 4 days to obtain a laminate gas barrier laminate for evaluation.
- all the thickness after drying of the adhesive bond layer formed with a urethane type 2 liquid curable adhesive was about 4 micrometers.
- the other end of the film was fixed to the outer periphery of a tester disk-shaped movable head facing the fixed head at a distance of 17.8 cm (7 inches). Then, the movable head is rotated 440 ° while approaching the fixed head in the direction of 7.6 cm (3.5 inches) along the axis of both heads opposed in parallel, and then 6.4 cm (without rotation) 2.5-inch)
- a one-cycle bending test in which the movement is performed in the reverse direction and the movable head is returned to the initial position is performed continuously for 2000 cycles at a rate of 40 cycles per minute. Repeated. Implementation was at 5 ° C.
- the above laminate laminate was measured under the conditions of 23 ° C. and 65% RH using an oxygen permeability measuring device (“OX-TRAN 2/21” manufactured by MOCON) according to JIS K7126-2 A method. The measurement was performed in a direction in which oxygen permeates from the base film side on which the inorganic thin film layer is not laminated to the inorganic thin film layer side. Also, cut the above laminate laminate into 15cm square size, superimpose two sheets so that the sealant is inside, and heat-seal the three sides at 160 ° C sealing temperature and 1.0cm sealing width. Thus, a three-side sealed bag having an inner size of 13 cm was obtained.
- the above laminate laminate was measured according to JIS K7129 B method using a water vapor transmission rate measuring device (“PERMATRAN-W 3/31” manufactured by MOCON) under the conditions of 40 ° C. and 90% RH. The measurement was performed in a direction in which oxygen permeates from the base film side on which the inorganic thin film layer is not laminated to the inorganic thin film layer side. Also, cut the above laminate laminate into 15cm square size, superimpose two sheets so that the sealant is inside, and heat-seal the three sides at 160 ° C sealing temperature and 1.0cm sealing width. Thus, a three-side sealed bag having an inner size of 13 cm was obtained.
- Polybutylene terephthalate resin 1-2 (Polybutylene terephthalate resin 1-2; Examples 1-6 and 1-9)
- a resin composition containing 0.2% by weight of the antioxidant Irganox 1010 in the polybutylene terephthalate resin 1-1 was prepared as a master batch.
- a flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer was charged with 460.6 parts of isopropyl alcohol and heated to 80 ° C. while gently flowing nitrogen gas.
- a monomer mixture consisting of 126 parts of methyl methacrylate, 210 parts of 2-isopropenyl-2-oxazoline and 84 parts of methoxypolyethylene glycol acrylate prepared in advance, and 2,2′-azobis as a polymerization initiator.
- acrylic resin (B-1) As an acrylic resin, a commercially available 25% by weight emulsion of an acrylic ester copolymer (“MOVINE (registered trademark) 7980” manufactured by Nichigo Movinyl Co., Ltd.) was prepared. The acid value of this acrylic resin (B-1) ( Theoretical value) was 4 mg KOH / g.
- reaction solution reached a predetermined amine equivalent.
- 9 parts of triethylamine was added to obtain a polyurethane prepolymer solution (isocyanate group-terminated prepolymer).
- 450 parts of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring, adjusted to 25 ° C., stirred and mixed at 2000 min ⁇ 1, and the polyurethane prepolymer solution obtained above (isocyanate group). The total amount of the terminal prepolymer was added and dispersed in water.
- the acid value (theoretical value) of the obtained urethane resin (C-1) was 25 mgKOH / g.
- Example 1-1 was carried out in the same manner as Example 1-1 except that the raw material composition and film forming conditions were changed to the biaxially stretched films described in Tables 1 and 2.
- Example 1-1 was carried out in the same manner as Example 1-1 except that the raw material composition and film forming conditions were changed to the biaxially stretched film described in Table 2. Specifically, in the film forming step of the biaxially stretched film shown in Example 1-1, the coating solution (adhesive layer resin composition) was applied by fountain bar coating after MD stretching. Then, it led to the tenter while drying, and the solvent was volatilized and dried at a preheating temperature of 70 ° C. Next, the film was stretched 4.0 times in the transverse direction at a temperature of 90 ° C., and heat-fixed at 210 ° C.
- the coating solution adheresive layer resin composition
- polyester film having a thickness of 15 ⁇ m.
- a two-layer film having a coating layer formed on one side of the substrate film was obtained.
- Example 1-1 was carried out in the same manner as Example 1-1 except that the raw material composition and film forming conditions were changed to the biaxially stretched film described in Table 2. Specifically, in the film-forming step of the biaxially stretched film shown in Example 1-6, the coating solution (adhesive layer resin composition) was applied by fountain bar coating after MD stretching. Then, it led to the tenter while drying, and the solvent was volatilized and dried at a preheating temperature of 70 ° C. Next, one side of a 15 ⁇ m thick biaxially stretched polyester film was stretched 4.0 times in the transverse direction at a temperature of 90 ° C. and heat-fixed at 210 ° C. while relaxing in the transverse direction of 5%. A two-layer film having a coating layer formed thereon was obtained.
- the coating solution adheresive layer resin composition
- Example 1-1 was carried out in the same manner as Example 1-1 except that the raw material composition and film forming conditions were changed to the biaxially stretched film described in Table 3.
- Table 3 shows the film forming conditions, physical properties, and evaluation results of the obtained film.
- the biaxially stretched polybutylene terephthalate films (Examples 1-1 to 1-9) obtained by the present invention are not only excellent in impact resistance and puncture resistance, but also at the retorting temperature. Even after the corresponding heating at 135 ° C., a film with little generation of 1,4-butanediol and tetrahydrofuran was obtained.
- the laminate laminates using the biaxially stretched polybutylene terephthalate films of Examples 1-1 to 1-9 had excellent oxygen barrier properties and water vapor barriers even after retorting. At the same time, it was excellent in pinhole resistance, bag breaking resistance, and fragrance retention.
- Comparative Example 1-1 when the PET content in the film is large, impact strength and puncture strength are lowered, and pinhole resistance and bag breaking resistance are insufficient. .
- Comparative Example 1-2 when the extrusion temperature at the time of film formation is high, the low molecular weight component in the film increases due to thermal decomposition of the resin. Will increase.
- Comparative Example 1-3 if the heat setting treatment temperature during film formation is low, the low molecular weight component generated in the extrusion process cannot be sufficiently removed, so the amount of low molecular weight component generated from the film Will increase.
- Comparative Example 1-4 when the draw ratio is low, the degree of plane orientation does not increase, so that not only the impact strength and piercing properties of the film are deteriorated, but also the thickness accuracy is poor, and the intended characteristics are satisfied. I can't.
- the laminate laminate using the biaxially stretched polybutylene terephthalate film of Example 1-10 has a small amount of tetrahydrofuran and 1,4-butanediol generated from the film, so that Even when the sealant had a structure in which a thermoplastic film was laminated on the opposite surface, the pinhole resistance, the bag breaking resistance, and the fragrance retention were excellent.
- Polymerization was performed in the same manner to obtain an adipic acid copolymerized polybutylene terephthalate resin (polyester 2-2).
- Table 4 shows the glass transition temperature.
- Polymerization was carried out in the same manner as in Example 1 to obtain a sebacic acid copolymerized polybutylene terephthalate resin (polyester 2-3).
- Table 4 shows the glass transition temperature.
- polyester 2-5 (Polyester 2-5; Example 2-5, Comparative Example 2-4)
- Table 5 shows the glass transition temperature.
- polyester 2-6 Example 2-6
- the polyester 2-1 described above except that the ratio of dimethyl terephthalate, dimethyl adipate and 1,4-butanediol was changed to dimethyl terephthalate / dimethyl adipate // 1,4-butanediol 80/20 // 100 (mol%)
- Polymerization was conducted in the same manner to obtain an adipic acid copolymerized polybutylene terephthalate resin (polyester 2-6).
- Table 5 shows the glass transition temperature.
- Example 2-1 Using a single-screw extruder, 80 parts by weight of polybutylene terephthalate resin, 20 parts by weight of polyester 2-1 (adipic acid copolymerized PET resin) and 1600 ppm in terms of silica particles having an average particle size of 2.4 ⁇ m as inert particles After melting at 290 ° C., the melt line was introduced into a 12-element static mixer. Thus, the polybutylene terephthalate melt was divided and laminated to obtain a multilayer melt made of the same raw material. The sheet was cast from a T-die at 270 ° C., and adhered to a cooling roll at 25 ° C. by an electrostatic adhesion method to obtain an unstretched sheet.
- the film was stretched 3.3 times in the machine direction (MD) at 70 ° C., then stretched 4.2 times in the transverse direction (TD) at 90 ° C. through a tenter, and subjected to a tension heat treatment at 210 ° C. for 3 seconds.
- TD transverse direction
- the gripping portions at both ends were cut and removed by 10% each to obtain a mill roll of a biaxially stretched polybutylene terephthalate film having a thickness of 15 ⁇ m.
- Table 5 shows the film forming conditions, physical properties, and evaluation results of the obtained film.
- Example 2-1 was carried out in the same manner as Example 2-1 except that the raw material composition and film forming conditions were changed to those described in Table 5.
- Example 2-1 was carried out in the same manner as Example 2-1 except that the raw material composition and film forming conditions were changed to those described in Table 5.
- Example 2-1 was carried out in the same manner as Example 2-1 except that the raw material composition and film forming conditions were changed to those described in Table 6.
- the laminates using the biaxially stretched polybutylene terephthalate films of Examples 2-1 to 2-4 have pinhole resistance, bag breakage resistance and incense retention at low temperatures. It was excellent in nature.
- the laminate laminates using the biaxially stretched polybutylene terephthalate films of Examples 2-5 and 2-6 were excellent in fragrance retention.
- the biaxially stretched polybutylene terephthalate film of Comparative Example 2-1 has a low molecular weight component in the film when the temperature during stretching in the TD direction is low. The occurrence of low molecular weight components increases.
- the biaxially stretched polybutylene terephthalate film of Comparative Example 2-2 has a low molecular weight component from the film because the low molecular weight component generated in the extrusion process cannot be sufficiently removed if the extrusion temperature during film formation is high. The amount of generation increases.
- the biaxially stretched polybutylene terephthalate film of Comparative Example 2-4 has a low molecular weight from the film because the low molecular weight component generated in the extrusion process cannot be sufficiently removed if the heat setting temperature during film formation is low. The amount of components generated increases.
- the present invention can also be used as a raw material for vapor deposition, has excellent barrier properties, dimensional stability, processability, bag-breaking resistance, chemical resistance, and excellent migration of the extract to the contents after retorting.
- the biaxially stretched polyester film can be obtained, and can be widely applied as a packaging material particularly preferably used for retort pouch packaging.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Wrappers (AREA)
Abstract
Description
更には、低温での耐ピンホール性に優れる、レトルト処理や電子レンジなどによる加熱処理される冷凍食品用に適した二軸延伸ポリエステルフィルムに関する。
更には、これらの二軸延伸ポリエステルフィルム使用した積層体、包装袋に関する。
また、ポリブチレンテレフタレート樹脂に対して加熱を行うと、ポリブチレンテレフタレートのモノマー成分である1,4-ブタンジオールや、1,4-ブタンジオールの熱分解物に伴う環化反応によって生成するテトラヒドロフラン(THF)が発生することが知られている(例えば非特許文献1)
そのため、レトルト処理のような高温加熱処理を行うと、これらの低分子量成分が溶出し、内容物の風味が損なわれてしまうことが指摘されている(例えば特許文献5)。
(2)フィルムの延伸工程で十分な熱処理を行うことでフィルム内に残存する低分子成分を除去すること。縦延伸工程においては60℃以上とし、横延伸工程においては90℃以上とすることが好ましいこと。
(3)横延伸工程後に、熱固定工程を設けることで、フィルムの結晶化度を高くすることで熱分解しやすい非晶成分の量を低減すること。熱固定工程における温度は205℃以上とすることが好ましいこと。
が重要であるということを見出し、本発明の完成に至った。
1.下記(a)、(b)、(c)及び(d)の特徴を有し、厚み10~30μmである二軸延伸ポリエステルフィルムである。
(a)ポリブチレンテレフタレート樹脂(A)を60質量%以上の範囲で含有するポリエステル樹脂組成物からなる。
(b)150℃×30分での熱収縮率が-2~+2%である。
(c)厚み精度が1~20%である。
(d)温度135℃で60分間加熱している間に揮発する1,4-ブタンジオール及びテトラヒドロフランの総量が1800ppb以下である。
本発明に用いられるポリエステル樹脂組成物は、ポリブチレンテレフタレート樹脂(A)を主たる構成成分とするものであり、ポリエステル樹脂組成物中のポリブチレンテレフタレート樹脂(A)の含有率は60質量%以上が好ましく、さらには70質量%以上が好ましい。60質量%未満であるとインパクト強度および耐ピンホール性が低下してしまい、フィルム特性としては十分なものでなくなってしまう。
主たる構成成分として用いるポリブチレンテレフタレート樹脂(A)は、ジカルボン酸成分として、テレフタル酸が90モル%以上であることが好ましく、より好ましくは95モル%以上であり、さらに好ましくは98モル%以上であり最も好ましくは100モル%である。グリコール成分として1,4-ブタンジオールが90モル%以上であることが好ましく、より好ましくは95モル%以上であり、さらに好ましくは97モル%以上であり、最も好ましくは重合時に1,4-ブタンジオールのエーテル結合により生成する副生物以外は含まれないことである。
ポリブチレンテレフタレート以外のガラス転移温度が0℃以上であるポリエステル樹脂(B)としては、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリブチレンナフタレート(PBN)、ポリプロピレンテレフタレート(PPT)又は、イソフタル酸、オルソフタル酸、ナフタレンジカルボン酸、ビフェニルジカルボン酸、シクロヘキサンジカルボン酸、アジピン酸、アゼライン酸及びセバシン酸からなる群から選ばれる少なくとも一種の酸成分を共重合したポリブチレンテレフタレート樹脂が挙げられる。これらは、ガラス転移温度が0℃以上であり、積層体の寸法安定性をより大きくする効果がある。
ポリブチレンテレフタレート樹脂(A)以外のポリエステル樹脂(C)のガラス転移温度が0℃未満とするには、上記共重合成分の含有量を調整することが挙げられる。具体的には、例えばアジピン酸やセバシン酸の場合にはその含有量を約30モル%以上の範囲とすればよい。
ガラス転移温度が0℃未満の場合は、積層体の冷凍保管時における耐ピンホール性が向上するという効果がある。
ポリブチレンテレフタレート樹脂(A)の固有粘度が0.9dl/g未満の場合、製膜して得られるフィルムの固有粘度が低下し、突き刺し強度、衝撃強度、耐破袋性などが低下するとなることがある。
ポリブチレンテレフタレート樹脂の固有粘度の上限は好ましくは1.3dl/gである。上記を越えるとポリエステル樹脂組成物を溶融押出しして得られる未延伸シートを延伸する時の応力が高くなりすぎ、製膜性が悪化することがある。固有粘度の高いポリブチレンテレフタレート樹脂(A)を使用した場合、ポリエステル樹脂組成物の溶融粘度が高くなるため押出し温度を高温にする必要があるが、ポリエステル樹脂組成物をより高温で押出しすると分解物が出やすくなり、得られた二軸延伸ポリブチレンテレフタレートフィルムに残存する1,4-ブタンジオールや、1,4-ブタンジオールの熱分解物に伴う環化反応によって生成するテトラヒドロフラン(THF)が多くなる。また、このフィルムを使用した包装材料をレトルト処理すると1,4-ブタンジオールやテトラヒドロフランが溶出する。
ポリエステル樹脂組成物の溶融押出し工程においてポリブチレンテレフタレート樹脂の分子量低下を抑制し、得られた二軸延伸ポリエステルフィルム中に残存する1,4-ブタンジオールやテトラヒドロフランの量を少なくすることができる。また、ポリブチレンテレフタレートは加熱によって徐々に分解が進行するため、ポリブチレンテレフタレートを使用した包装材料をレトルト処理した時に起きる熱分解を抑制させる上でも効果的である。
具体的には、n-オクタデシル-βー(4‘-ヒドロキシ-3,5’-ジ-t-ブチルフェニル)プロピオネート、テトラキス[メチレン-3-(3‘,5’-ジ-t-ブチル-4‘-ヒドロキシフェニル)プロピオネート](これは、「イルガノックス1010」(商品名)として市販されている)、1,1,3-トリス(2-メチル-4-ヒドロキシ-5-t-ブチルフェニル)ブタン、1,3,5-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-S-トリアジン-2,4,6(1H,3H,5H)-トリオン、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)ベンゼン(これは、「イルガノックス1330」(商品名)として市販されている)、トリス(ミックスドモノおよび/またはジノニルフェニル)ホスファイト、サイクリックネオペンタンテトライルビス(オクタデシルホスファイト)、トリス(2,4-ジ-t-ブチルフェニルホスファイト)、2,2-メチレンビス(4,6-ジ-t-ブチルフェニル)オクチルホスファイト、ジ-ラウリル-チオジプロピオネート、ジ-ミリスチル-チオジプロピオネート、ジ-ステアリル-チオジプロピオネートなどが挙げられる。これらの酸化防止剤は、1種類で用いてもよいし、2種以上を併用してもよい。これらの中でも、入手性、食品衛生性の観点からn-オクタデシル-βー(4‘-ヒドロキシ-3,5’-ジ-t-ブチルフェニル)プロピオネート、テトラキス[メチレン-3-(3‘,5’-ジ-t-ブチル-4‘-ヒドロキシフェニル)プロピオネート](イルガノックス1010)が好ましい。
ポリエステル樹脂組成物に上述の酸化防止剤を含有する場合は、より高温での溶融押し出しが可能になるが、300℃以下にする必要がある。
ポリブチレンテレフタレート樹脂(A)は結晶化速度が速いため、冷却固化している間にも結晶化が進行する。従来のように、なにもせず単層のままでキャスティングした場合には、得られた未延伸シート中では、結晶の成長を抑制しうるような障壁が存在しないために、これらの結晶はサイズの大きな球晶へと成長してしまう。その結果、得られた未延伸シートの降伏応力が高くなり、二軸延伸時に破断しやすくなるばかりでなく、得られた二軸延伸ポリエステルフィルムの柔軟性が損なわれ、耐ピンホール性や耐破袋性が不十分なフィルムとなってしまう。
一方で、ポリエステル樹脂組成物をいずれの層も同一の組成となるように多層化して溶融押出しすると、各層の界面を越えて結晶が成長することができないため、得られた未延伸シートの降伏応力が小さくなり、二軸延伸時に破断しにくくなるばかりでなく、得られた二軸延伸ポリエステルフィルムはインパクト強度に優れ、耐ピンホール性や耐破袋性も十分なフィルムとなる。
また、二軸延伸後の工程である熱処理工程で1,4-ブタンジオールやテトラヒドロフランを除去しやすい結晶構造となる。
例えば、二台以上の押出機を用いて異なる流路から送り出された熱可塑性樹脂をフィールドブロックやスタティックミキサー、マルチマニホールドダイ等を用いて多層に積層する方法等を使用することができる。なお、本発明のように同一の組成で多層化する場合、一台の押出機のみを用いて、押出機からダイまでのメルトラインに上述の多層化装置を導入することで本発明の目的を果たすことも可能である。
また、MD延伸温度を60℃以上とすることで、二軸延伸ポリブチレンテレフタレートに残存する1,4-ブタンジオールやテトラヒドロフランをより低減することができる。
また、TD延伸温度を80℃以上とすることで、二軸延伸ポリブチレンテレフタレートに残存する1,4-ブタンジオールやテトラヒドロフランをより低減することができる。
フィルム厚みの上限は好ましくは100μmであり、より好ましくは75μmであり、さらに好ましくは50μmである。100μmを越えると厚くなりすぎて本発明の目的における加工が困難となることがある。
得られたフィルムロールの中央部から縦方向にフィルム片を切り出し、5cmピッチで、100箇所をダイアルゲージを用いて測定したときの最大厚みをTmax,最小厚みをTmin、平均厚みをTaveとし、下記の式(1)より厚み精度(Tv)を求めた。Tv(%)={(Tmax-Tmin)/Tave}×100 (%)・・・(1)
このとき、温度135℃で60分間加熱している間に揮発する1,4-ブタンジオールの量は1800ppb以下であることが好ましく、1700ppbであることがより好ましい。また、1600ppb以下であることが特に好ましい。
また、温度135℃で60分間加熱している間に揮発するテトラヒドロフランの量は200ppb以下であることが好ましく、100ppbであることがより好ましく、70ppb以下であることがもっとも好ましい。
サンプルについてJIS K 7142-1996 A法により、ナトリウムD線を光源としてアッベ屈折計によりフィルム長手方向の屈折率(nx)、幅方向の屈折率(ny)を測定し、下記式の計算式により面配向係数を算出した。
面配向係数(ΔP)=(nx+ny)/2-nz
JIS K7160-1996に準じて、株式会社東洋精機製作所製のインパクトテスターを用い、23℃の雰囲気下におけるフィルムの衝撃打ち抜きに対する強度を測定した。衝撃球面は、直径1/2インチのものを用いた。単位J/μm。
食品衛生法における「食品、添加物等の規格基準 第3:器具及び容器包装」(昭和57年厚生省告示第20号)の「2.強度等試験法」に準拠して測定した。先端部直径0.7mmの針を、突刺し速度50mm/分でフィルムに突き刺し、針がフィルムを貫通する際の強度を測定して、突き刺し強度とした。測定は常温(23℃)で行い、単位は[N/μm]である。
試験温度150℃、加熱時間15分間とした以外は、JIS-C-2151-2006.21に記載の寸法変化試験法で測定した。試験片は21.1(a)に記載に従い使用した。
上記を超えるとフィルムに印刷を施した際に、印刷された文字や画像の品位を損ねる可能性がある。
無機薄膜層を形成する材料は、薄膜にできるものなら特に制限はないが、ガスバリア性の観点から、酸化ケイ素(シリカ)、酸化アルミニウム(アルミナ)、酸化ケイ素と酸化アルミニウムとの混合物等の無機酸化物が好ましく挙げられる。特に、薄膜層の柔軟性と緻密性を両立できる点からは、酸化ケイ素と酸化アルミニウムとの複合酸化物が好ましい。
この複合酸化物において、酸化ケイ素と酸化アルミニウムとの混合比は、Al2O3の質量比が20~70%の範囲であることが好ましい。Al2O3が20%未満であると、水蒸気バリア性が低くなる場合がある。一方、70%を超えると、無機薄膜層が硬くなる傾向があり、印刷やラミネートといった二次加工の際に膜が破壊されてバリア性が低下する虞がある。なお、ここでいう酸化ケイ素とはSiOやSiO2等の各種珪素酸化物又はそれらの混合物であり、酸化アルミニウムとは、AlOやAl2O3等の各種アルミニウム酸化物又はそれらの混合物である。
加熱には、抵抗加熱、高周波誘導加熱、電子ビーム加熱、レーザー加熱などの方式を採用することができる。また、反応ガスとして酸素、窒素、水素、アルゴン、炭酸ガス、水蒸気等を導入したり、オゾン添加、イオンアシスト等の手段を用いた反応性蒸着を採用することも可能である。さらに、被蒸着体(蒸着に供するフィルム)にバイアスを印加したり、被蒸着体を加熱もしくは冷却するなど、成膜条件も任意に変更することができる。このような蒸着材料、反応ガス、被蒸着体のバイアス、加熱・冷却などは、スパッタリング法やCVD法を採用する場合にも同様に変更可能である。
二軸延伸ポリポリエステルフィルムと前記無機薄膜層との間に設ける密着層としては、ウレタン系、ポリエステル系、アクリル系、チタン系、イソシアネート系、イミン系、ポリブタジエン系等の樹脂に、エポキシ系、イソシアネート系、メラミン系等の硬化剤を添加したものが挙げられる。前記溶媒(溶剤)としては、例えば、ベンゼン、トルエン等の芳香族系溶剤;メタノール、エタノール等のアルコール系溶剤;アセトン、メチルエチルケトン等のケトン系溶剤;酢酸エチル、酢酸ブチル等のエステル系溶剤;エチレングリコールモノメチルエーテル等の多価アルコール誘導体等が挙げられる。これらの密着層に用いる樹脂組成物は、有機官能基を少なくとも1種類以上有するシランカップリング剤を含有することが好ましい。前記有機官能基としては、アルコキシ基、アミノ基、エポキシ基、イソシアネート基等が挙げられる。前記シランカップリング剤の添加によって、レトルト処理後のラミネート強度がより向上する。
ヒートシール性樹脂層を形成する熱可塑性重合体としては、シーラント接着性が十分に発現できるものであればよく、HDPE、LDPE、LLDPEなどのポリエチレン樹脂類、ポリプロピレン樹脂、エチレン-酢酸ビニル共重合体、エチレン-α-オレフィンランダム共重合体、アイオノマー樹脂等を使用できる。中でもレトルト処理に耐えうる耐熱性を有するものとしては、ポリプロピレン樹脂が好ましい。
一方、本発明の二軸延伸ポリエステルフィルムは、レトルト処理においてもTHFや1,4-ブタンジオールの発生量が少ないので、このような構成で使用された場合においても、レトルト処理後であっても内容物への1,4-ブタンジオールやテトラヒドロフランの移行量を少なくすることができるものと考えられる。
積層体を20.3cm(8インチ)×27.9cm(11インチ)の大きさに切断し、その切断後の長方形テストフィルムを、温度23℃の相対湿度50%の条件下に、24時間以上放置してコンディショニングした。しかる後、その長方形テストフィルムを巻架して長さ20.32cm(8インチ)の円筒状にする。そして、その円筒状フィルムの一端を、ゲルボフレックステスター(理学工業社製、NO.901型)(MIL-B-131Cの規格に準拠)の円盤状固定ヘッドの外周に固定し、円筒状フィルムの他端を、固定ヘッドと17.8cm(7インチ)隔てて対向したテスターの円盤状可動ヘッドの外周に固定した。
そして、可動ヘッドを固定ヘッドの方向に、平行に対向した両ヘッドの軸に沿って7.6cm(3.5インチ)接近させる間に440゜回転させ、続いて回転させることなく6.4cm(2.5インチ)直進させた後、それらの動作を逆向きに実行させて可動ヘッドを最初の位置に戻すという1サイクルの屈曲テストを、1分間あたり40サイクルの速度で、連続して2000サイクル繰り返した。実施は5℃で行った。
しかる後に、テストしたフィルムの固定ヘッドおよび可動ヘッドの外周に固定した部分を除く17.8cm(7インチ)×27.9cm(11インチ)内の部分に生じたピンホール数を計測した(すなわち、497cm2 (77平方インチ)当たりのピンホール数を計測した)。
積層体を15cm四方の大きさにカットし、シーラントが内側になるように2枚を重ね合わせ、3方を160℃のシール温度、シール幅1.0cmにてヒートシールすることで内寸13cmの3方シール袋を得た。
得られた3方シール袋に水250mLを充填した後、ヒートシールにて4方目の口を閉じ、水の充填された4方シール袋を作製した。
得られた4方シール袋を室温5℃、湿度35%R.H.の環境下、高さ100cmの位置からコンクリート板の上に落下させ、破れやピンホールが発生するまでの落下回数を数えた。
JIS K7126-2 A法に準じて、酸素透過率測定装置(MOCON社製「OX-TRAN 2/21」)を用い、23℃、65%RHの条件下で測定した。なお測定に際しては、無機薄膜層を積層していない基材フィルム側から無機薄膜層側に酸素が透過する方向で行った。
JIS K7129 B法に準じて、水蒸気透過率測定装置(MOCON社製「PERMATRAN-W 3/31」)を用い、40℃、90%RHの条件下で測定した。なお測定に際しては、無機薄膜層を積層していない基材フィルム側から無機薄膜層側に酸素が透過する方向で行った。
JIS K7130-1999 A法に準拠し、ダイアルゲージを用いて測定した。
JIS-K-7105に準ずる方法で、試料をヘイズメーター(日本電色製、NDH2000)を用いて異なる箇所3ヶ所について測定し、その平均値をヘイズとした。
単位は[%]である。
得られたフィルムロールの中央部から縦方向にフィルム片を切り出し、5cmピッチで、100箇所をダイアルゲージを用いて測定したときの最大厚みをTmax,最小厚みをTmin、平均厚みをTaveとし、下記の式(1)より厚み精度(Tv)を求めた。
Tv(%)={(Tmax-Tmin)/Tave}×100 (%)・・・(1)
得られたフィルム中から発生する低分子量成分量の測定方法を以下に示す。
装置:HP-7890/HP-5975(Agilent)
カラム:Rxi-lms(長さ30ms、内径0.25mm、膜厚1.0μm)
注入口温度:250℃
オーブン温度:50℃(2分)、10℃/min、250℃(2分)
カラム流量:1mL/min、スプリット比20
尚、事前に既知の量の1,4-ブタンジオール及びTHFのTICクロマトグラムから得たピーク強度と各成分濃度の関係を示す検量線をもとに、先のサンプルのTICクロマトグラムにおける1,4-ブタンジオール及びTHFに起因するピーク強度での成分濃度を求めた。
サンプルについてJIS K 7142-1996 A法により、ナトリウムD線を光源としてアッベ屈折計によりフィルム長手方向の屈折率(nx)、幅方向の屈折率(ny)を測定し、式(2)の計算式により面配向係数を算出した。
面配向係数(ΔP)=(nx+ny)/2-nz (2)
食品衛生法における「食品、添加物等の規格基準 第3:器具及び容器包装」(昭和57年厚生省告示第20号)の「2.強度等試験法」に準拠して測定した。先端部直径0.7mmの針を、突刺し速度50mm/分でフィルムに突き刺し、針がフィルムを貫通する際の強度を測定して、突き刺し強度とした。測定は常温(23℃)で行い、単位は[N/μm]である。
JIS K7160-1996に準じて、株式会社東洋精機製作所製のインパクトテスターを用い、23℃の雰囲気下におけるフィルムの衝撃打ち抜きに対する強度を測定した。衝撃球面は、直径1/2インチのものを用いた。単位J/μm。
ポリエステルフィルムの熱収縮率は試験温度150℃、加熱時間15分間とした以外は、JIS-C-2151-2006.21に記載の寸法変化試験法で測定した。
試験片は21.1(a)に記載に従い使用した。
後述する実施例1-1~1-9および比較例1-1~1-4で得られた各二軸延伸ポリブチレンテレフタレートフィルムの片面に、無機薄膜層として二酸化ケイ素と酸化アルミニウムの複合酸化物層を電子ビーム蒸着法で形成した。蒸着源としては、3mm~5mm程度の粒子状SiO2(純度99.9%)とA12O3(純度99.9%)とを用いた。このようにして得られた無機薄膜層(SiO2/A12O3複合酸化物層)の膜厚は13nmであった。またこの複合酸化物層の組成は、SiO2/A12O3(質量比)=60/40であった。
さらに、無機薄膜層の上に、ウレタン系2液硬化型接着剤(三井化学社製「タケラック(登録商標)A525S」と「タケネート(登録商標)A50」を13.5:1(質量比)の割合で配合)を用いてドライラミネート法により、ヒートシール性樹脂層として厚さ70μmの無延伸ポリプロピレンフィルム(東洋紡株式会社製「P1147」)を貼り合わせ、40℃にて4日間エージングを施すことにより、評価用のラミネートガスバリア性積層体を得た。なお、ウレタン系2液硬化型接着剤で形成される接着剤層の乾燥後の厚みはいずれも約4μmであった。
後述する実施例1-1および比較例1-3で得られた各二軸延伸ポリブチレンテレフタレートフィルムの片面に、無機薄膜層として二酸化ケイ素と酸化アルミニウムの複合酸化物層を電子ビーム蒸着法で形成した。蒸着源としては、3mm~5mm程度の粒子状SiO2(純度99.9%)とA12O3(純度99.9%)とを用いた。このようにして得られた無機薄膜層(SiO2/A12O3複合酸化物層)の膜厚は13nmであった。またこの複合酸化物層の組成は、SiO2/A12O3(質量比)=60/40であった。
さらに、無機薄膜層の上に、ウレタン系2液硬化型接着剤(三井化学社製「タケラック(登録商標)A525S」と「タケネート(登録商標)A50」を13.5:1(質量比)の割合で配合)を用いてドライラミネート法により、熱可塑性プラスチックフィルムとして、厚さ12μmの二軸延伸ポリエチレンテレフタレートフィルム(東洋紡株式会社製「E5102」)を貼り合せた後、同様の接着剤を用いて反対面にヒートシール性樹脂層として厚さ70μmの無延伸ポリプロピレンフィルム(東洋紡株式会社製「P1147」)を貼り合わせ、40℃にて4日間エージングを施すことにより、評価用のラミネートガスバリア性積層体を得た。
後述する実施例2-1~2-6および比較例2-1~2-4で得られた各二軸延伸ポリブチレンテレフタレートフィルムの上に、ウレタン系2液硬化型接着剤(三井化学社製「タケラック(登録商標)A525S」と「タケネート(登録商標)A50」を13.5:1(質量比)の割合で配合)を用いてドライラミネート法により、ヒートシール性樹脂層として厚さ70μmの無延伸ポリプロピレンフィルム(東洋紡株式会社製「P1147」)を貼り合わせ、40℃にて4日間エージングを施すことにより、評価用のラミネートガスバリア性積層体を得た。なお、ウレタン系2液硬化型接着剤で形成される接着剤層の乾燥後の厚みはいずれも約4μmであった。
前述のラミネート積層体を20.3cm(8インチ)×27.9cm(11インチ)の大きさに切断し、その切断後の長方形テスト積層体を、温度23℃の相対湿度50%の条件下に、24時間以上放置してコンディショニングした。しかる後、その長方形テスト積層体を巻架して長さ20.32cm(8インチ)の円筒状にする。そして、その円筒状積層体の一端を、ゲルボフレックステスター(理学工業社製、NO.901型)(MIL-B-131Cの規格に準拠)の円盤状固定ヘッドの外周に固定し、円筒状フィルムの他端を、固定ヘッドと17.8cm(7インチ)隔てて対向したテスターの円盤状可動ヘッドの外周に固定した。
そして、可動ヘッドを固定ヘッドの方向に、平行に対向した両ヘッドの軸に沿って7.6cm(3.5インチ)接近させる間に440゜回転させ、続いて回転させることなく6.4cm(2.5インチ)直進させた後、それらの動作を逆向きに実行させて可動ヘッドを最初の位置に戻すという1サイクルの屈曲テストを、1分間あたり40サイクルの速度で、連続して2000サイクル繰り返した。実施は5℃で行った。
しかる後に、テストしたフィルムの固定ヘッドおよび可動ヘッドの外周に固定した部分を除く17.8cm(7インチ)×27.9cm(11インチ)内の部分に生じたピンホール数を計測した(すなわち、497cm2(77平方インチ)当たりのピンホール数を計測した)。
前述のラミネート積層体を15cm四方の大きさにカットし、シーラントが内側になるように2枚を重ね合わせ、3方を160℃のシール温度、シール幅1.0cmにてヒートシールすることで内寸13cmの3方シール袋を得た。
得られた3方シール袋に水250mLを充填した後、ヒートシールにて4方目の口を閉じ、水の充填された4方シール袋を作製した。
得られた4方シール袋を室温5℃、湿度35%R.H.の環境下、高さ100cmの位置からコンクリート板の上に落下させ、破れやピンホールが発生するまでの落下回数を数えた。
前述のラミネート積層体を15cm四方の大きさにカットし、シーラントが内側になるように2枚を重ね合わせ、3方を160℃のシール温度、シール幅1.0cmにてヒートシールすることで内寸13cmの3方シール袋を得た。
得られた3方シール袋に、イオン交換水を充填し、残る1方を同様にヒートシールした後に、レトルト処理機で135℃、1時間のレトルト処理を行い、しかる後、80℃にて1週間保管した。その浸漬液を用いて30人のパネラーにて試飲テストを行い、比較用のイオン交換水と比較した。比較用のイオン交換水と較べて味の変化を感じた人数が30人中3人以下の場合を○、4~10人の場合を△、11人以上の場合を×とした。
前述のラミネート積層体をJIS K7126-2 A法に準じて、酸素透過率測定装置(MOCON社製「OX-TRAN 2/21」)を用い、23℃、65%RHの条件下で測定した。なお測定に際しては、無機薄膜層を積層していない基材フィルム側から無機薄膜層側に酸素が透過する方向で行った。
また、前述のラミネート積層体を15cm四方の大きさにカットし、シーラントが内側になるように2枚を重ね合わせ、3方を160℃のシール温度、シール幅1.0cmにてヒートシールすることで内寸13cmの3方シール袋を得た。
得られた3方シール袋に、イオン交換水を充填し、残る1方を同様にヒートシールした後に、レトルト処理機で135℃、1時間のレトルト処理を行った後も、同様に測定を行った。
前述のラミネート積層体をJIS K7129 B法に準じて、水蒸気透過率測定装置(MOCON社製「PERMATRAN-W 3/31」)を用い、40℃、90%RHの条件下で測定した。なお測定に際しては、無機薄膜層を積層していない基材フィルム側から無機薄膜層側に酸素が透過する方向で行った。
また、前述のラミネート積層体を15cm四方の大きさにカットし、シーラントが内側になるように2枚を重ね合わせ、3方を160℃のシール温度、シール幅1.0cmにてヒートシールすることで内寸13cmの3方シール袋を得た。
得られた3方シール袋に、イオン交換水を充填し、残る1方を同様にヒートシールした後に、レトルト処理機で135℃、1時間のレトルト処理を行った後も、同様に測定を行った。
(ポリブチレンテレフタレート樹脂1-1;実施例1-1~1-9、比較例1-1~1-4)
後述する実施例1-1~1-9、比較例1-1~1-4のフィルム作製において、主原料であるポリブチレンテレフタレート樹脂は1100-211XG(CHANG CHUN PLASTICS CO.,LTD.、固有粘度1.28dl/g)を用いた。
ポリブチレンテレフタレート樹脂1-2として前記ポリブチレンテレフタレート樹脂1-1に酸化防止剤Irganox1010を0.2重量%含有する樹脂組成物を作製し、マスターバッチとした。
被覆層の形成に用いた各材料は以下のようにして調製した。
反応中は窒素ガスを流し続け、フラスコ内の温度を80±1℃に保った。その後、反応液を冷却し、得られた重合体をイオン交換水に溶解させ、固形分濃度25%のオキサゾリン基を有する樹脂(A-1)を得た。得られたオキサゾリン基を有する樹脂(A-1)のオキサゾリン基量は4.3mmol/gであり、GPC(ゲルパーミエーションクロマトグラフィ)により測定した数平均分子量は20000であった。
アクリル樹脂として、市販のアクリル酸エステル共重合体の25質量%エマルジョン(ニチゴー・モビニール(株)社製「モビニール(登録商標)7980」を用意した。このアクリル樹脂(B-1)の酸価(理論値)は4mgKOH/gであった。
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管および温度計を備えた4つ口フラスコに、1,3-ビス(イソシアネートメチル)シクロヘキサン72.96部と、ジメチロールプロピオン酸12.60部と、ネオペンチルグリコール11.74部と、数平均分子量2000のポリエステルジオール112.70部と、溶剤としてアセトニトリル85.00部およびN-メチルピロリドン5.00部とを投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次いで、この反応液を40℃にまで降温した後、トリエチルアミン9.03部を添加し、ポリウレタンプレポリマー溶液(イソシアネート基末端プレポリマー)を得た。
次に、高速攪拌可能なホモディスパーを備えた反応容器に、水450部を添加し、25℃に調整して2000min-1で攪拌混合しながら、上記で得られたポリウレタンプレポリマー溶液(イソシアネート基末端プレポリマー)の全量を添加して水分散させた。その後、減圧下で、アセトニトリルおよび水の一部を除去することにより、固形分濃度30%の水溶性ポリウレタン樹脂(C-1)を調製した。得られたウレタン樹脂(C-1)の酸価(理論値)は25mgKOH/gであった。
下記の配合比率で各材料を混合し、塗布液(被覆層用樹脂組成物)を作製した。なお、得られた塗布液中のオキサゾリン基を有する樹脂、アクリル樹脂およびウレタン樹脂の固形分換算の質量比は表1に示す通りである。
水 67.53質量%
イソプロパノール 5.00質量%
オキサゾリン基を有する樹脂(A-2) 20.00質量%
アクリル樹脂(B-1) 4.80質量%
ウレタン樹脂(C-1) 2.67質量%
一軸押出機を用い、ポリブチレンテレフタレート樹脂1-1とテレフタル酸//エチレングリコール=100//100(モル%)からなる固有粘度0.62dl/gのポリエチレンテレフタレート樹脂、不活性粒子として平均粒径2.4μmのシリカ粒子をシリカ濃度として1600ppmとなるように配合したものを290℃で溶融させた後、メルトラインを12エレメントのスタティックミキサーに導入した。これにより、ポリブチレンテレフタレート溶融体の分割・積層を行い、同一の原料からなる多層溶融体を得た。265℃のT-ダイスからキャストし、15℃の冷却ロールに静電密着法により密着させて未延伸シートを得た。
次いで、60℃で縦方向(MD)に3.0倍ロール延伸し、次いで、テンターに通して90℃で横方向(TD)に4.0倍延伸し、210℃で3秒間の緊張熱処理と1秒間5%の緩和処理を実施した後、両端の把持部を10%ずつ切断除去して厚みが15μmのポリブチレンテレフタレートフィルムのミルロールを得た。得られたフィルムの製膜条件、物性および評価結果を表1に示した。
実施例1-1において、原料組成、製膜条件を表1及び表2に記載した二軸延伸フィルムに変えた以外は実施例1-1と同様に行った。
実施例1-1において、原料組成、製膜条件を表2に記載した二軸延伸フィルムに変えた以外は実施例1-1と同様に行った。
詳しくは、実施例1-1で示した二軸延伸フィルムの製膜工程において、MD延伸後に前記塗布液(密着層用樹脂組成物)をファウンテンバーコート法により塗布した。その後、乾燥しながらテンターに導き、予熱温度70℃で溶媒を揮発、乾燥させた。次いで、温度90℃で横方向に4.0倍に延伸し、5%の横方向の弛緩を行いながら、210℃で熱固定処理を行うことにより、厚さ15μmの二軸延伸ポリエステルフィルム(プラスチック基材フィルム)の片面に被覆層が形成された2層フィルム(プラスチック基材フィルム/被覆層)を得た。
実施例1-1において、原料組成、製膜条件を表2に記載した二軸延伸フィルムに変えた以外は実施例1-1と同様に行った。
詳しくは、実施例1-6で示した二軸延伸フィルムの製膜工程において、MD延伸後に前記塗布液(密着層用樹脂組成物)をファウンテンバーコート法により塗布した。その後、乾燥しながらテンターに導き、予熱温度70℃で溶媒を揮発、乾燥させた。次いで、温度90℃で横方向に4.0倍に延伸し、5%の横方向の弛緩を行いながら、210℃で熱固定処理を行うことにより、厚さ15μmの二軸延伸ポリエステルフィルムの片面に被覆層が形成された2層フィルムを得た。
実施例1-1において、原料組成、製膜条件を表3に記載した二軸延伸フィルムに変えた以外は実施例1-1と同様に行った。
得られたフィルムの製膜条件、物性および評価結果を表3に示した。
また、比較例1-2に示すように、フィルム製膜時の押出し温度が高いと、樹脂の熱分解によりフィルム中の低分子量成分が多くなるために、フィルムの加熱後の低分子量成分の発生が多くなる。
また、比較例1-3に示すように、フィルム製膜時の熱固定処理温度が低いと、押出し工程で発生した低分子量成分を充分に除去できないために、フィルムからの低分子量成分の発生量が多くなる。
さらに比較例1-4に示すように、延伸倍率が低いと面配向度が高くならないためにフィルムの衝撃強度や突刺し性が悪化するばかりか、厚み精度も悪く、目的としている特性を満足させることが出来ない。
(ポリブチレンテレフタレート樹脂2;実施例2-1~2-5、比較例2-1~2-4)
後述する実施例2-1~2-5、比較例2-1~2-4のフィルム作製において、主原料であるポリブチレンテレフタレート樹脂2は1100-211XG(CHANG CHUN PLASTICS CO.,LTD.、固有粘度1.28dl/g)を用いた。
ジメチルテレフタレート、ジメチルアジペートおよび1、4-ブタンジオールの比率をジメチルテレフタレート/ジメチルアジペート//1,4-ブタンジオール=40/60//100(mol%)となるように撹拌機を有した金属性のオートクレーブにとり、さらに触媒としてテトラ-n-ブチルチタネートを(ポリマーに対してチタン金属換算で21ppm)を加えた後、常圧下室温から4時間で徐々に210℃まで昇温し210℃で20分反応させ、生成するメタノールを反応系外に除去して低重合度ブチレンテレフタレートを調製した。この低重合度ブチレンテレフタレートを真空ポンプを有するオートクレーブに移液し、2時間で徐々に減圧昇温し、245℃1.0mmHgとしてこの状態で2時間15分反応させた。反応後の窒素加圧により排出し、水で急冷しカッターにより切断し、アジピン酸共重合ポリブチレンテレフタレート樹脂(ポリエステル2-1)を得た。
得られた樹脂の上記成分に由来する成分の比率は、ジメチルテレフタレート/ジメチルアジペート//1,4-ブタンジオール=40/60//100(mol%)であった。ガラス転移温度を表5、表6に示す。
ジメチルテレフタレート、ジメチルアジペートおよび1、4-ブタンジオールの比率をジメチルテレフタレート/ジメチルアジペート//1,4-ブタンジオール=65/35//100(mol%)とした以外は上述したポリエステル2-1と同様にして重合を行い、アジピン酸共重合ポリブチレンテレフタレート樹脂(ポリエステル2-2)を得た。
得られた樹脂の上記成分に由来する成分の比率は、ジメチルテレフタレート由来成分/ジメチルアジペート由来成分//1,4-ブタンジオール由来成分=65/35//100(mol%)であった。ガラス転移温度を表4に示す。
ジメチルテレフタレート、ジメチルセバケートおよび1、4-ブタンジオールの比率をジメチルテレフタレート/ジメチルセバケート//1,4-ブタンジオール=53/47//100(mol%)とした以外は上述したポリエステル2-1と同様にして重合を行い、セバシン酸共重合ポリブチレンテレフタレート樹脂(ポリエステル2-3)を得た。
得られた樹脂の上記成分に由来する成分の比率は、ジメチルテレフタレート由来成分/ジメチルセバケート由来成分//1,4-ブタンジオール由来成分=53/47//100(mol%)であった。ガラス転移温度を表4に示す。
ジメチルテレフタレートおよび1、4-ブタンジオール、ポリテトラメチレングリコール(PTMG、Mw=1000)の比率をジメチルテレフタレート//1,4-ブタンジオール/PTMG=100//85/15(mol%)とした以外は上述したポリエステル2-1と同様にして重合を行い、PTMG共重合ポリブチレンテレフタレート樹脂(ポリエステル2-4)を得た。
得られた樹脂の上記成分に由来する成分の比率は、ジメチルテレフタレート由来成分//1,4-ブタンジオール由来成分/PTMG由来成分=100//85/15(mol%)であった。ガラス転移温度を表4に示す。
後述する実施例2-5のフィルム作製において、テレフタル酸//エチレングリコール=100//100(モル%)からなる固有粘度0.62dl/gのポリエチレンテレフタレート樹脂をポリエステル2-5として用いた。
得られた樹脂の上記成分に由来する成分の比率は、テレフタル酸由来成分//エチレングリコール由来成分=100//100(モル%)であった。ガラス転移温度を表5に示す。
ジメチルテレフタレート、ジメチルアジペートおよび1、4-ブタンジオールの比率をジメチルテレフタレート/ジメチルアジペート//1,4-ブタンジオール=80/20//100(mol%)とした以外は上述したポリエステル2-1と同様にして重合を行い、アジピン酸共重合ポリブチレンテレフタレート樹脂(ポリエステル2-6)を得た。
得られた樹脂の上記成分に由来する成分の比率は、ジメチルテレフタレート由来成分/ジメチルアジペート由来成分//1,4-ブタンジオール由来成分=80/20//100(mol%)であった。ガラス転移温度を表5に示す。
一軸押出機を用い、ポリブチレンテレフタレート樹脂を80重量部とポリエステル2-1(アジピン酸共重合PET樹脂)を20重量部と不活性粒子として平均粒径2.4μmのシリカ粒子をシリカ濃度として1600ppmとなるように配合したものを290℃で溶融させた後、メルトラインを12エレメントのスタティックミキサーに導入した。これにより、ポリブチレンテレフタレート溶融体の分割・積層を行い、同一の原料からなる多層溶融体を得た。270℃のT-ダイスからキャストし、25℃の冷却ロールに静電密着法により密着させて未延伸シートを得た。
次いで、70℃で縦方向(MD)に3.3倍ロール延伸し、次いで、テンターに通して90℃で横方向(TD)に4.2倍延伸し、210℃で3秒間の緊張熱処理と1秒間の緩和率が5%の緩和処理を実施した後、両端の把持部を10%ずつ切断除去して厚みが15μmの二軸延伸ポリブチレンテレフタレートフィルムのミルロールを得た。得られたフィルムの製膜条件、物性および評価結果を表5に示した。
実施例2-1において、原料組成、製膜条件を表5に記載したものに変えた以外は実施例2-1と同様に行った。
実施例2-1において、原料組成、製膜条件を表5に記載したものに変えた以外は実施例2-1と同様に行った。
実施例2-1において、原料組成、製膜条件を表6に記載したものに変えた以外は実施例2-1と同様に行った。
Claims (7)
- 下記(a)、(b)、(c)及び(d)の特徴を有し、厚み10~30μmである二軸延伸ポリエステルフィルム。
(a)ポリブチレンテレフタレート樹脂(A)を60質量%以上の範囲で含有するポリエステル樹脂組成物からなる。
(b)150℃×30分での熱収縮率が-2~+2%である。
(c)厚み精度が1~20%である。
(d)温度135℃で60分間加熱している間に揮発する1,4-ブタンジオール及びテトラヒドロフランの総量が1800ppb以下である。 - ポリエステル組成物がポリブチレンテレフタレート樹脂(A)を60~90重量%、ポリブチレンテレフタレート樹脂(A)以外のガラス転移温度が0℃以上であるポリエステル樹脂(B)を含有する請求項1記載の二軸延伸ポリエステルフィルム。
- ポリエステル組成物がポリブチレンテレフタレート樹脂(A)を60~90重量%、ポリブチレンテレフタレート樹脂(A)以外のガラス転移温度が0℃未満であるポリエステル樹脂(C)を含有する請求項1記載の二軸延伸ポリエステルフィルム。
- 前記ポリブチレンテレフタレート樹脂(A)以外のガラス転移温度が0℃未満であるポリエステル樹脂C)が、イソフタル酸、オルソフタル酸、ナフタレンジカルボン酸、ビフェニルジカルボン酸、シクロヘキサンジカルボン酸、アジピン酸、アゼライン酸及びセバシン酸からなる群から選ばれる少なくとも一種のジカルボン酸が共重合されたポリブチレンテレフタレート樹脂、または、エチレングリコール、1,3-プロピレングリコール、1,2-プロピレングリコール、ネオペンチルグリコール、1,5-ペンタンジオール、1,6-ヘキサンジオール、ジエチレングリコール、シクロヘキサンジオール、ポリエチレングリコール、ポリテトラメチレングリコール及びポリカーボネートジオールからなる群から選ばれる少なくとも一種のジオール成分が共重合されたポリブチレンテレフタレート樹脂から選ばれる少なくとも1種の樹脂である請求項3に記載の二軸延伸ポリエステルフィルム。
- 請求項1~4のいずれかに記載の二軸延伸ポリエステルフィルムの少なくとも片面に無機薄膜層が積層されてなる積層フィルム。
- 請求項1~4のいずれかに記載の二軸延伸ポリエステルフィルム又は請求項5の無機薄膜層側の面にヒートシール性樹脂層が積層された積層体。
- 請求項6の積層体からなる包装用袋。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017562859A JPWO2017126563A1 (ja) | 2016-01-22 | 2017-01-18 | 二軸延伸ポリエステルフィルム、積層体及び包装用袋 |
CN201780007326.9A CN108472860A (zh) | 2016-01-22 | 2017-01-18 | 双轴拉伸聚酯薄膜、层叠体和包装用袋 |
EP17741440.6A EP3406421B1 (en) | 2016-01-22 | 2017-01-18 | Biaxially-stretched polyester film, laminate and packaging bag |
KR1020187023716A KR20180108670A (ko) | 2016-01-22 | 2017-01-18 | 2축 연신 폴리에스테르 필름, 적층체 및 포장용 주머니 |
US16/071,292 US20210198477A1 (en) | 2016-01-22 | 2017-01-18 | Biaxially-stretched polyester film, laminate and packaging bag |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016-010665 | 2016-01-22 | ||
JP2016010665 | 2016-01-22 | ||
JP2016-068816 | 2016-03-30 | ||
JP2016068816 | 2016-03-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017126563A1 true WO2017126563A1 (ja) | 2017-07-27 |
Family
ID=59362240
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/001586 WO2017126563A1 (ja) | 2016-01-22 | 2017-01-18 | 二軸延伸ポリエステルフィルム、積層体及び包装用袋 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20210198477A1 (ja) |
EP (1) | EP3406421B1 (ja) |
JP (1) | JPWO2017126563A1 (ja) |
KR (1) | KR20180108670A (ja) |
CN (1) | CN108472860A (ja) |
TW (1) | TW201736453A (ja) |
WO (1) | WO2017126563A1 (ja) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018052042A1 (ja) * | 2016-09-15 | 2018-03-22 | 大日本印刷株式会社 | 袋 |
WO2019021759A1 (ja) * | 2017-07-26 | 2019-01-31 | 東洋紡株式会社 | ポリブチレンテレフタレートフィルムを用いた包装袋 |
JP2019029589A (ja) * | 2017-08-02 | 2019-02-21 | ユニチカ株式会社 | 半導体パッケージの製造工程用離型フィルムおよびその製造方法 |
JP2019093649A (ja) * | 2017-11-24 | 2019-06-20 | ポリプラスチックス株式会社 | 多層フィルム及び包装袋 |
JP2019155845A (ja) * | 2018-03-16 | 2019-09-19 | 東洋紡株式会社 | ラミネート積層体 |
WO2019187694A1 (ja) * | 2018-03-30 | 2019-10-03 | 東洋紡株式会社 | ポリエステルフィルムロール |
JP2019171587A (ja) * | 2018-03-27 | 2019-10-10 | 東洋紡株式会社 | ポリエステルフィルムおよびガスバリア性積層フィルム |
WO2020031712A1 (ja) * | 2018-08-08 | 2020-02-13 | 東洋紡株式会社 | ガスバリア性積層フィルムおよびその製造方法 |
WO2020050351A1 (ja) * | 2018-09-06 | 2020-03-12 | ユニチカ株式会社 | ポリエステルフィルムおよびその製造方法 |
WO2020080131A1 (ja) * | 2018-10-16 | 2020-04-23 | 東洋紡株式会社 | 積層フィルム |
WO2020138048A1 (ja) * | 2018-12-28 | 2020-07-02 | 東洋紡株式会社 | 積層体及びそれを用いた包装体 |
WO2020145254A1 (ja) * | 2019-01-10 | 2020-07-16 | 東洋紡株式会社 | 積層フィルム |
JP2020147020A (ja) * | 2018-09-28 | 2020-09-17 | 大日本印刷株式会社 | バリア性積層フィルム及びバリア性積層フィルムの製造方法、並びにバリア性積層フィルムを備える包装材料 |
WO2020203105A1 (ja) * | 2019-03-29 | 2020-10-08 | 東洋紡株式会社 | ポリエステルフィルム及びその製造方法 |
WO2020203106A1 (ja) * | 2019-03-29 | 2020-10-08 | 東洋紡株式会社 | ポリエステルフィルム及びその製造方法 |
WO2021100558A1 (ja) * | 2019-11-20 | 2021-05-27 | 東洋紡株式会社 | 積層フィルム |
JP6934268B1 (ja) * | 2020-03-10 | 2021-09-15 | ユニチカ株式会社 | ポリエステルフィルムおよびその製造方法 |
JP7469087B2 (ja) | 2020-03-18 | 2024-04-16 | 住友化学株式会社 | 光学フィルム及びフレキシブル表示装置 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108883604B (zh) * | 2016-04-01 | 2021-09-03 | 凸版印刷株式会社 | 阻气膜 |
WO2018159157A1 (ja) * | 2017-02-28 | 2018-09-07 | 東洋紡株式会社 | 積層フィルム |
TWI705097B (zh) * | 2018-10-19 | 2020-09-21 | 南亞塑膠工業股份有限公司 | 一種用於模內裝飾膜的易延伸改性聚酯膜 |
TWI822929B (zh) * | 2019-01-28 | 2023-11-21 | 日商東洋紡股份有限公司 | 雙軸配向聚醯胺膜以及聚醯胺膜修邊捲筒 |
KR102612318B1 (ko) * | 2019-02-26 | 2023-12-12 | 도요보 가부시키가이샤 | 2축 배향 폴리에스테르 필름, 및 2축 배향 폴리에스테르 필름의 제조 방법 |
KR20220016073A (ko) * | 2019-05-31 | 2022-02-08 | 이데미쓰 유니테크 가부시키가이샤 | 지퍼 테이프 및 지퍼 테이프가 부착된 용기 |
CN111406551B (zh) * | 2020-01-21 | 2022-04-01 | 国网浙江省电力有限公司湖州供电公司 | 一种节能智慧种植大棚及其控制方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004048071A1 (ja) * | 2002-11-26 | 2004-06-10 | Seiji Kagawa | ポリブチレンテレフタレートフィルムの製造方法 |
JP2005097560A (ja) * | 2003-08-19 | 2005-04-14 | Toyobo Co Ltd | ポリエステルフィルム |
JP2008291238A (ja) * | 2007-04-24 | 2008-12-04 | Toyobo Co Ltd | ポリエステルエラストマー組成物及びその用途、並びにポリエステルエラストマー組成物の製造方法 |
WO2014077197A1 (ja) * | 2012-11-16 | 2014-05-22 | 東洋紡株式会社 | 二軸延伸ポリエステルフィルムおよびその製造方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08276553A (ja) * | 1995-04-04 | 1996-10-22 | Teijin Ltd | 金属板貼合せ成形加工用ポリエステルフイルム |
JPH09194604A (ja) * | 1996-01-24 | 1997-07-29 | Unitika Ltd | 金属ラミネート用フィルム |
CN1835994B (zh) * | 2003-08-19 | 2010-08-25 | 东洋纺织株式会社 | 聚酯薄膜 |
JP5822611B2 (ja) * | 2011-09-06 | 2015-11-24 | ユニチカ株式会社 | 二軸延伸ポリエステルフィルムおよびその製造方法 |
-
2017
- 2017-01-18 US US16/071,292 patent/US20210198477A1/en not_active Abandoned
- 2017-01-18 WO PCT/JP2017/001586 patent/WO2017126563A1/ja active Application Filing
- 2017-01-18 KR KR1020187023716A patent/KR20180108670A/ko not_active Application Discontinuation
- 2017-01-18 JP JP2017562859A patent/JPWO2017126563A1/ja active Pending
- 2017-01-18 CN CN201780007326.9A patent/CN108472860A/zh active Pending
- 2017-01-18 EP EP17741440.6A patent/EP3406421B1/en active Active
- 2017-01-20 TW TW106102141A patent/TW201736453A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004048071A1 (ja) * | 2002-11-26 | 2004-06-10 | Seiji Kagawa | ポリブチレンテレフタレートフィルムの製造方法 |
JP2005097560A (ja) * | 2003-08-19 | 2005-04-14 | Toyobo Co Ltd | ポリエステルフィルム |
JP2008291238A (ja) * | 2007-04-24 | 2008-12-04 | Toyobo Co Ltd | ポリエステルエラストマー組成物及びその用途、並びにポリエステルエラストマー組成物の製造方法 |
WO2014077197A1 (ja) * | 2012-11-16 | 2014-05-22 | 東洋紡株式会社 | 二軸延伸ポリエステルフィルムおよびその製造方法 |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018052042A1 (ja) * | 2016-09-15 | 2018-03-22 | 大日本印刷株式会社 | 袋 |
US11433653B2 (en) | 2017-07-26 | 2022-09-06 | Toyobo Co., Ltd. | Packaging bag using polybutylene terephthalate film |
WO2019021759A1 (ja) * | 2017-07-26 | 2019-01-31 | 東洋紡株式会社 | ポリブチレンテレフタレートフィルムを用いた包装袋 |
JP2019029589A (ja) * | 2017-08-02 | 2019-02-21 | ユニチカ株式会社 | 半導体パッケージの製造工程用離型フィルムおよびその製造方法 |
JP2019093649A (ja) * | 2017-11-24 | 2019-06-20 | ポリプラスチックス株式会社 | 多層フィルム及び包装袋 |
JP7028619B2 (ja) | 2017-11-24 | 2022-03-02 | ポリプラスチックス株式会社 | 多層フィルム及び包装袋 |
JP7060842B2 (ja) | 2018-03-16 | 2022-04-27 | 東洋紡株式会社 | ラミネート積層体 |
JP2019155845A (ja) * | 2018-03-16 | 2019-09-19 | 東洋紡株式会社 | ラミネート積層体 |
JP2019171587A (ja) * | 2018-03-27 | 2019-10-10 | 東洋紡株式会社 | ポリエステルフィルムおよびガスバリア性積層フィルム |
WO2019187694A1 (ja) * | 2018-03-30 | 2019-10-03 | 東洋紡株式会社 | ポリエステルフィルムロール |
JPWO2019187694A1 (ja) * | 2018-03-30 | 2020-10-22 | 東洋紡株式会社 | ポリエステルフィルムロール |
WO2020031712A1 (ja) * | 2018-08-08 | 2020-02-13 | 東洋紡株式会社 | ガスバリア性積層フィルムおよびその製造方法 |
JPWO2020031712A1 (ja) * | 2018-08-08 | 2020-08-20 | 東洋紡株式会社 | ガスバリア性積層フィルムおよびその製造方法 |
JPWO2020050351A1 (ja) * | 2018-09-06 | 2020-09-10 | ユニチカ株式会社 | ポリエステルフィルムおよびその製造方法 |
JP2020041122A (ja) * | 2018-09-06 | 2020-03-19 | ユニチカ株式会社 | ポリエステルフィルムおよびその製造方法 |
WO2020050351A1 (ja) * | 2018-09-06 | 2020-03-12 | ユニチカ株式会社 | ポリエステルフィルムおよびその製造方法 |
JP2020147020A (ja) * | 2018-09-28 | 2020-09-17 | 大日本印刷株式会社 | バリア性積層フィルム及びバリア性積層フィルムの製造方法、並びにバリア性積層フィルムを備える包装材料 |
JP7296050B2 (ja) | 2018-09-28 | 2023-06-22 | 大日本印刷株式会社 | バリア性積層フィルム及びバリア性積層フィルムの製造方法、並びにバリア性積層フィルムを備える包装材料 |
JPWO2020080131A1 (ja) * | 2018-10-16 | 2021-02-15 | 東洋紡株式会社 | 積層フィルム |
WO2020080131A1 (ja) * | 2018-10-16 | 2020-04-23 | 東洋紡株式会社 | 積層フィルム |
WO2020138048A1 (ja) * | 2018-12-28 | 2020-07-02 | 東洋紡株式会社 | 積層体及びそれを用いた包装体 |
WO2020145254A1 (ja) * | 2019-01-10 | 2020-07-16 | 東洋紡株式会社 | 積層フィルム |
EP3909767A4 (en) * | 2019-01-10 | 2022-09-21 | Toyobo Co., Ltd. | COMPOSITE FILM |
WO2020203106A1 (ja) * | 2019-03-29 | 2020-10-08 | 東洋紡株式会社 | ポリエステルフィルム及びその製造方法 |
WO2020203105A1 (ja) * | 2019-03-29 | 2020-10-08 | 東洋紡株式会社 | ポリエステルフィルム及びその製造方法 |
WO2021100558A1 (ja) * | 2019-11-20 | 2021-05-27 | 東洋紡株式会社 | 積層フィルム |
JP6934268B1 (ja) * | 2020-03-10 | 2021-09-15 | ユニチカ株式会社 | ポリエステルフィルムおよびその製造方法 |
JP7469087B2 (ja) | 2020-03-18 | 2024-04-16 | 住友化学株式会社 | 光学フィルム及びフレキシブル表示装置 |
Also Published As
Publication number | Publication date |
---|---|
CN108472860A (zh) | 2018-08-31 |
EP3406421A1 (en) | 2018-11-28 |
EP3406421A4 (en) | 2019-09-25 |
TW201736453A (zh) | 2017-10-16 |
JPWO2017126563A1 (ja) | 2018-11-08 |
EP3406421B1 (en) | 2020-10-21 |
US20210198477A1 (en) | 2021-07-01 |
KR20180108670A (ko) | 2018-10-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2017126563A1 (ja) | 二軸延伸ポリエステルフィルム、積層体及び包装用袋 | |
JP6970390B2 (ja) | ポリブチレンテレフタレートフィルムを用いた包装袋 | |
JP2018020844A (ja) | ポリブチレンテレフタレートフィルムを用いた包装袋 | |
JP6874277B2 (ja) | 二軸延伸ポリエステルフィルムおよびその製造方法 | |
JP6962364B2 (ja) | 積層フィルム | |
WO2018225559A1 (ja) | 二軸配向ポリエステルフィルム | |
JP6927336B2 (ja) | ガスバリア性積層フィルムおよびその製造方法 | |
JP7006445B2 (ja) | ポリエステルフィルムおよびガスバリア性積層フィルム | |
JPWO2019187694A1 (ja) | ポリエステルフィルムロール | |
WO2018179726A1 (ja) | 二軸配向ポリエステルフィルム及びその製造方法 | |
JP6879473B2 (ja) | 二軸配向ポリエステルフィルム | |
JP7060842B2 (ja) | ラミネート積層体 | |
WO2020145254A1 (ja) | 積層フィルム | |
WO2019142781A1 (ja) | 二軸配向ポリエステルフィルム | |
JP7310876B2 (ja) | ポリエステルフィルムおよびガスバリア性積層フィルム |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17741440 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017562859 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20187023716 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020187023716 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2017741440 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2017741440 Country of ref document: EP Effective date: 20180822 |