TW201936734A - Biaxially oriented polyester film - Google Patents
Biaxially oriented polyester film Download PDFInfo
- Publication number
- TW201936734A TW201936734A TW108102011A TW108102011A TW201936734A TW 201936734 A TW201936734 A TW 201936734A TW 108102011 A TW108102011 A TW 108102011A TW 108102011 A TW108102011 A TW 108102011A TW 201936734 A TW201936734 A TW 201936734A
- Authority
- TW
- Taiwan
- Prior art keywords
- film
- layer
- resin
- gas barrier
- biaxially oriented
- Prior art date
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 67
- 239000011347 resin Substances 0.000 claims abstract description 67
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 229920001225 polyester resin Polymers 0.000 claims abstract description 30
- 239000004645 polyester resin Substances 0.000 claims abstract description 30
- 230000008859 change Effects 0.000 claims abstract description 24
- -1 polybutylene terephthalate Polymers 0.000 claims abstract description 21
- 238000012360 testing method Methods 0.000 claims description 4
- 230000000930 thermomechanical effect Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 130
- 230000004888 barrier function Effects 0.000 abstract description 77
- 239000011241 protective layer Substances 0.000 abstract description 42
- 238000011282 treatment Methods 0.000 abstract description 22
- 238000005336 cracking Methods 0.000 abstract description 8
- 238000009835 boiling Methods 0.000 abstract description 7
- 230000009172 bursting Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 118
- 239000007789 gas Substances 0.000 description 73
- 238000000034 method Methods 0.000 description 45
- 239000012530 fluid Substances 0.000 description 18
- 239000000565 sealant Substances 0.000 description 18
- 238000007639 printing Methods 0.000 description 17
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 16
- 238000001816 cooling Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 230000003068 static effect Effects 0.000 description 13
- 239000010409 thin film Substances 0.000 description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 description 12
- 239000005020 polyethylene terephthalate Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910000420 cerium oxide Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000007740 vapor deposition Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 8
- 239000000314 lubricant Substances 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000009998 heat setting Methods 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 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
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000009820 dry lamination Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 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 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 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 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-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
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 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 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying 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
- 150000002466 imines Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000011129 pharmaceutical packaging material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
本發明係關於一種食品、醫藥品、工業製品等之包裝領域中所使用之聚酯膜。更詳細而言，係關於一種以聚對苯二甲酸丁二酯樹脂作為主成分之雙軸配向聚酯膜，該膜的耐針孔性、煮沸處理或蒸煮處理後的耐破袋性優異，且保護層形成步驟中的氣體阻隔層的破裂少而氣體阻隔性優異。 The present invention relates to a polyester film used in the packaging field of foods, pharmaceuticals, industrial products, and the like. More specifically, the present invention relates to a biaxially oriented polyester film having a polybutylene terephthalate resin as a main component, which is excellent in pinhole resistance, bagging resistance after boiling treatment or retort treatment, Further, the gas barrier layer in the protective layer forming step has less cracking and is excellent in gas barrier properties.
聚對苯二甲酸丁二酯(以下，將聚對苯二甲酸丁二酯簡稱為PBT)樹脂相較於聚對苯二甲酸乙二酯(以下，將聚對苯二甲酸乙二酯簡稱為PET)樹脂，在耐衝擊性、氣體阻隔性、耐化學品性優異，因此於食品包裝用膜、深拉成形用膜等膜領域中亦研究應用。 Polybutylene terephthalate (hereinafter, polybutylene terephthalate is abbreviated as PBT) resin compared to polyethylene terephthalate (hereinafter, polyethylene terephthalate is simply referred to as PET resin is excellent in impact resistance, gas barrier properties, and chemical resistance. Therefore, it is also used in film fields such as films for food packaging and films for deep drawing.
例如，於專利文獻1中，揭示有於由相對於PBT樹脂以40重量%以下之範圍調配有PBT樹脂以外的聚酯樹脂之聚酯系樹脂組成物所構成之雙軸配向PBT系膜中，藉由分子鏈主軸相對於膜的寬度方向所成之角度為30°以 下，150℃的熱收縮率於寬度方向、長度方向上均為4.0%以下，膜的固有黏度設為0.80dl/g以上且1.2dl/g以下，可較佳地用於蒸煮袋包裝或含液物包裝。 For example, Patent Document 1 discloses a biaxially oriented PBT film composed of a polyester resin composition in which a polyester resin other than a PBT resin is blended in a range of 40% by weight or less based on the PBT resin. By the angle of the main axis of the molecular chain with respect to the width direction of the film is 30° The heat shrinkage ratio at 150 ° C is 4.0% or less in the width direction and the longitudinal direction, and the intrinsic viscosity of the film is set to 0.80 dl / g or more and 1.2 dl / g or less, which can be preferably used for retort pouch packaging or Liquid packaging.
然而，可認為由於將長度方向的熱收縮率抑制為低值，故而於保護層形成步驟中膜容易於長度方向上伸長，而引起氣體阻隔性降低。 However, it is considered that since the heat shrinkage rate in the longitudinal direction is suppressed to a low value, the film is likely to be elongated in the longitudinal direction in the protective layer forming step, and the gas barrier property is lowered.
另一方面，於專利文獻2中，揭示有一種包裝構件，於將以PET樹脂為主之膜作為基材層、且具有至少一層以上之金屬氧化物層之積層膜中，藉由將150℃的熱收縮率設為0.6%至3.0%，而即便於蒸煮處理、煮沸處理等熱水處理後，亦具有充分的衝擊強度，氣體阻隔性亦優異。 On the other hand, Patent Document 2 discloses a packaging member in which a film having a PET resin-based film as a base material layer and having at least one metal oxide layer is used, by 150 ° C The heat shrinkage ratio is set to 0.6% to 3.0%, and even after hot water treatment such as retort treatment or boiling treatment, it has sufficient impact strength and is excellent in gas barrier properties.
然而，並未揭示用以滿足上述特性之具體的基材層的條件。 However, the conditions for the specific substrate layer to satisfy the above characteristics are not disclosed.
[先前技術文獻] [Previous Technical Literature]
[專利文獻] [Patent Literature]
專利文獻1：國際公開第2016/171173號。 Patent Document 1: International Publication No. 2016/171173.
專利文獻2：國際公開第2017/170574號。 Patent Document 2: International Publication No. 2017/170574.
本發明係以上述先前技術之課題為背景而完成。亦即，本發明之目的在於一種食品、醫藥品、工業製品等之包裝領域中所使用之聚酯膜。更詳細而言，本發明之目的在於獲得一種積層聚酯膜，該膜的耐針孔性、煮沸處理或蒸煮處理後的耐破袋性優異，且保護層形成步驟中的氣體阻隔層的破裂少而氣體阻隔性優異。 The present invention has been accomplished in the light of the above problems of the prior art. That is, the object of the present invention is a polyester film used in the packaging field of foods, pharmaceuticals, industrial products, and the like. More specifically, it is an object of the present invention to obtain a laminated polyester film which is excellent in pinhole resistance, bagging resistance after boiling treatment or retort treatment, and rupture of a gas barrier layer in a protective layer forming step. It is small and has excellent gas barrier properties.
本發明為了達成上述目的而進行了努力研究，結果發現，藉由將以PBT樹脂作為主體樹脂之雙軸配向拉伸膜於120℃下的尺寸變化率及熱收縮率設為特定範圍，可獲得如下之積層聚酯膜，該膜的耐針孔性、煮沸處理或蒸煮處理後的耐破袋性優異，且保護層形成步驟中的氣體阻隔層的破裂少而氣體阻隔性優異。 In order to achieve the above object, the present inventors have made intensive studies, and as a result, it has been found that a dimensional change ratio and a heat shrinkage ratio at 120 ° C of a biaxially oriented stretched film containing a PBT resin as a host resin can be obtained in a specific range. The laminated polyester film is excellent in pinhole resistance, bagging resistance after the boiling treatment or retort treatment, and has less cracking of the gas barrier layer in the protective layer forming step, and is excellent in gas barrier properties.
亦即，本發明由以下之構成所構成。 That is, the present invention consists of the following constitution.
1.一種雙軸配向聚酯膜，由含有聚對苯二甲酸丁二酯樹脂(A)60重量%至100重量%、聚對苯二甲酸丁二酯樹脂(A)以外的聚酯樹脂(B)0重量%至40重量%之聚酯樹脂組成物構成，且同時满足(a)及(b)。 A biaxially oriented polyester film comprising a polyester resin other than the polybutylene terephthalate resin (A) (60% by weight to 100% by weight) other than the polybutylene terephthalate resin (A) ( B) 0% by weight to 40% by weight of the polyester resin composition, and at the same time satisfying (a) and (b).
(a)使用TMA(Thermal Mechanical Analyzer；熱機械分析儀)所測定之溫度尺寸變化曲線中的相對於膜原長在120℃的尺寸變化率於膜的長度方向上為-2.0%至4.0%。 (a) The dimensional change ratio in the temperature dimensional change curve measured by TMA (Thermal Mechanical Analyzer) at 120 ° C with respect to the film original length was -2.0% to 4.0% in the longitudinal direction of the film.
(b)膜的長度方向在150℃的熱收縮率為1.0%至 5.0%。 (b) The thermal shrinkage of the film in the longitudinal direction at 150 ° C is 1.0% to 5.0%.
2.如1.所記載之雙軸配向聚酯膜，其中依據JIS-Z1707之穿刺強度試驗中所測定之穿刺強度的值為8.0N以上。 2. The biaxially oriented polyester film according to 1. wherein the value of the puncture strength measured in the puncture strength test according to JIS-Z1707 is 8.0 N or more.
3.如1.或2.所記載之雙軸配向聚酯膜，其中於膜的全寬的厚度精度為1%至20%。 3. The biaxially oriented polyester film of 1. or 2. wherein the thickness of the film is from 1% to 20%.
本發明者藉由上述技術，可獲得如下之積層聚酯膜，該膜的耐針孔性、煮沸處理或蒸煮處理後的耐破袋性優異，且保護層形成步驟中的氣體阻隔層的破裂少而氣體阻隔性優異。 According to the above technique, the present inventors can obtain a laminated polyester film which is excellent in pinhole resistance, bagging resistance after boiling treatment or retort treatment, and rupture of the gas barrier layer in the protective layer forming step. It is small and has excellent gas barrier properties.
以下，對本發明進行詳細的說明。 Hereinafter, the present invention will be described in detail.
[聚酯樹脂組成物] [Polyester Resin Composition]
本發明之膜中所使用之聚酯樹脂組成物係以PBT樹脂(A)作為主要構成成分，PBT樹脂(A)的含有率較佳為60重量%以上，更佳為75重量%以上，進而較佳為85重量%以上。若未達60重量%，則耐針孔性或耐破袋性降低。 The polyester resin composition used in the film of the present invention contains PBT resin (A) as a main component, and the content of PBT resin (A) is preferably 60% by weight or more, more preferably 75% by weight or more. It is preferably 85% by weight or more. If it is less than 60% by weight, pinhole resistance or bag breakage resistance is lowered.
用作主要構成成分之PBT樹脂(A)中，作為二羧酸成分之對苯二甲酸較佳為90莫耳%以上，更佳為95莫耳% 以上，進而較佳為98莫耳%以上，最佳為100莫耳%。作為二醇成分之1,4-丁二醇較佳為90莫耳%以上，更佳為95莫耳%以上，進而較佳為97莫耳%以上，最佳為不含聚合時由1,4-丁二醇的醚鍵所生成之副產物以外的成分。 In the PBT resin (A) used as a main constituent component, the terephthalic acid as the dicarboxylic acid component is preferably 90 mol% or more, more preferably 95 mol%. The above is further preferably 98% by mole or more, and most preferably 100% by mole. The 1,4-butanediol as the diol component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 97 mol% or more, and most preferably 1 in the absence of polymerization. A component other than the by-product formed by the ether bond of 4-butanediol.
以調整進行雙軸拉伸時的製膜性或所獲得之膜的力學特性為目的，本發明之膜中所使用之聚酯樹脂組成物可含有PBT樹脂(A)以外的聚酯樹脂(B)。 The polyester resin composition used in the film of the present invention may contain a polyester resin other than the PBT resin (A) for the purpose of adjusting the film forming property at the time of biaxial stretching or the mechanical properties of the obtained film. ).
PBT樹脂(A)以外的聚酯樹脂(B)可列舉選自以下之樹脂中的至少1種樹脂：PET、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、聚對苯二甲酸丙二酯等聚酯樹脂；或者選自由間苯二甲酸、鄰苯二甲酸、萘二羧酸、聯苯二羧酸、環己烷二羧酸、己二酸、壬二酸及癸二酸所組成之群組中的至少1種二羧酸共聚而成之PBT樹脂；選自由乙二醇、1,3-丙二醇、1,2-丙二醇、新戊二醇、1,5-戊二醇、1,6-己二醇、二乙二醇、環己二醇、聚乙二醇、聚四亞甲基二醇及聚碳酸酯所組成之群組中的至少1種二醇成分共聚而成之PBT樹脂；選自由間苯二甲酸、鄰苯二甲酸、萘二羧酸、聯苯二羧酸、環己烷二羧酸、己二酸、壬二酸及癸二酸所組成之群組中的至少1種二羧酸共聚而成之PET樹脂；或選自由1,3-丁二醇、1,3-丙二醇、1,2-丙二醇、新戊二醇、1,5-戊二醇、1,6-己二醇、二乙二醇、環己二醇、聚乙二醇、聚四亞甲基二醇及聚碳酸酯所組成之群組中的至少1種二醇成分共聚而成之PET樹脂。 The polyester resin (B) other than the PBT resin (A) may be at least one selected from the group consisting of PET, polyethylene naphthalate, polybutylene naphthalate, and polybutylene terephthalate. a polyester resin such as propylene glycol; or a selected from the group consisting of isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, cyclohexane dicarboxylic acid, adipic acid, sebacic acid and sebacic acid a PBT resin obtained by copolymerizing at least one dicarboxylic acid in a group consisting of: ethylene glycol, 1,3-propanediol, 1,2-propanediol, neopentyl glycol, 1,5-pentanediol And copolymerizing at least one diol component in a group consisting of 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol, and polycarbonate PBT resin; selected from the group consisting of isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, cyclohexane dicarboxylic acid, adipic acid, sebacic acid and sebacic acid a PET resin obtained by copolymerizing at least one dicarboxylic acid in the group; or selected from the group consisting of 1,3-butanediol, 1,3-propanediol, 1,2-propanediol, neopentyl glycol, 1,5-pentane Alcohol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, poly A PET resin obtained by copolymerizing at least one diol component of a group consisting of ethylene glycol, polytetramethylene glycol, and polycarbonate.
其中，PET樹脂由於熔點高而耐熱性優異，故而不易發生尺寸變化，且由於與PBT樹脂之相容性亦優異，故而透明性優異，因此作為PBT樹脂(A)以外的聚酯樹脂(B)，較佳為共聚而成之PET樹脂，尤佳為PET。 Among them, the PET resin has a high melting point and is excellent in heat resistance, so that it does not easily change in size, and since it is excellent in compatibility with a PBT resin, it is excellent in transparency, and therefore, it is a polyester resin (B) other than the PBT resin (A). Preferably, the copolymerized PET resin is preferably PET.
本發明之膜中所使用之PBT樹脂(A)的固有黏度的下限較佳為0.8dl/g，更佳為0.95dl/g，進而較佳為1.0dl/g。 The lower limit of the intrinsic viscosity of the PBT resin (A) used in the film of the present invention is preferably 0.8 dl/g, more preferably 0.95 dl/g, still more preferably 1.0 dl/g.
於PBT樹脂(A)的固有黏度未達0.9dl/g之情形時，有製膜而獲得之膜的固有黏度降低，破袋強度或穿刺強度等降低之情況。 When the intrinsic viscosity of the PBT resin (A) is less than 0.9 dl/g, the inherent viscosity of the film obtained by film formation is lowered, and the bag breaking strength or puncture strength is lowered.
PBT樹脂(A)的固有黏度的上限較佳為1.3dl/g。若超過上述上限，則有膜的拉伸時的應力變得過高，製膜性惡化之情況。進而，於使用固有黏度高之PBT樹脂之情形時，樹脂的熔融黏度變高，因此必須將擠出溫度設為高溫，但若將PBT樹脂於更高溫下擠出，則有容易產生分解物之情況。 The upper limit of the intrinsic viscosity of the PBT resin (A) is preferably 1.3 dl/g. When the above upper limit is exceeded, the stress at the time of stretching of the film may be too high, and the film formability may be deteriorated. Further, when a PBT resin having a high intrinsic viscosity is used, since the melt viscosity of the resin is increased, it is necessary to set the extrusion temperature to a high temperature. However, if the PBT resin is extruded at a higher temperature, the decomposition product is likely to be generated. Happening.
作為該等PBT樹脂(A)以外的聚酯樹脂(B)的添加量的上限，較佳為40重量%以下，更佳為35重量%以下，尤佳為15重量%以下。若PBT樹脂(A)以外的聚酯樹脂(B)的添加量超過40重量%，則有耐針孔性、耐破袋性受損，此外透明性或氣體阻隔性降低之情況。 The upper limit of the amount of the polyester resin (B) other than the PBT resin (A) is preferably 40% by weight or less, more preferably 35% by weight or less, and still more preferably 15% by weight or less. When the amount of the polyester resin (B) other than the PBT resin (A) is more than 40% by weight, pinhole resistance and bag breakage resistance are impaired, and transparency or gas barrier properties may be lowered.
前述聚酯樹脂組成物亦可視需要含有先前公知的添加劑，例如潤滑劑、穩定劑、著色劑、抗氧化劑、抗靜電劑、紫外線吸收劑等。 The polyester resin composition may optionally contain previously known additives such as a lubricant, a stabilizer, a colorant, an antioxidant, an antistatic agent, an ultraviolet absorber, and the like.
作為用以調整本發明之膜的動摩擦係數之潤滑劑種，除二氧化矽、碳酸鈣、氧化鋁等無機系潤滑劑以外，較佳為有機系潤滑劑，更佳為二氧化矽、碳酸鈣，其中，就減小霧度之方面而言，尤佳為二氧化矽。可藉由該等而表現出透明性及滑動性。 The lubricant type for adjusting the dynamic friction coefficient of the film of the present invention is preferably an organic lubricant other than an inorganic lubricant such as cerium oxide, calcium carbonate or aluminum oxide, more preferably cerium oxide or calcium carbonate. Among them, in terms of reducing the haze, it is particularly preferred to be cerium oxide. The transparency and slidability can be exhibited by these.
聚酯樹脂組成物中的潤滑劑的含量的下限較佳為100重量ppm，更佳為800重量ppm，若未達100重量ppm，則有滑動性降低之情況。潤滑劑的含量的上限較佳為20000重量ppm，更佳為1000重量ppm，尤佳為1800重量ppm，若超過20000重量ppm，則有透明性降低之情況。 The lower limit of the content of the lubricant in the polyester resin composition is preferably 100 ppm by weight, more preferably 800 ppm by weight, and if it is less than 100 ppm by weight, the slidability may be lowered. The upper limit of the content of the lubricant is preferably 20,000 ppm by weight, more preferably 1000 ppm by weight, still more preferably 1800 ppm by weight, and if it exceeds 20,000 ppm by weight, transparency may be lowered.
[雙軸配向聚酯膜的製造方法] [Manufacturing method of biaxial alignment polyester film]
作為用以獲得本發明之雙軸配向聚酯膜之較佳的方法，就寬度方向的厚度精度之觀點而言，較佳為T字模方式。於吹脹(inflation)方式中，有起因於該雙軸配向聚酯膜的製造方法而拉伸倍率不易提高，產生寬度方向的厚度不良之情況。 As a preferable method for obtaining the biaxially oriented polyester film of the present invention, from the viewpoint of thickness precision in the width direction, a T-die method is preferable. In the inflation method, the method of producing the biaxially oriented polyester film is disadvantageous in that the draw ratio is not easily improved, and the thickness in the width direction is poor.
另外，作為用以獲得本發明之雙軸配向聚酯膜之較佳 的方法，可列舉：於將熔融聚酯樹脂組成物澆鑄於冷卻輥時，將相同組成的聚酯樹脂組成物原料多層化而進行澆鑄。 Further, as a preferred one for obtaining the biaxially oriented polyester film of the present invention In the method, when the molten polyester resin composition is cast on a cooling roll, the raw material of the polyester resin composition of the same composition is multilayered and cast.
由於PBT樹脂的結晶化速度快，故而於澆鑄時亦進行結晶化。此時，於未多層化而以單層澆鑄之情形時，不存在可抑制結晶生長之障壁，因此該等結晶生長成大尺寸的球晶。結果為，所獲得之未拉伸片的降伏應力變高，於長度方向的拉伸時變得容易斷裂。 Since the crystallization rate of the PBT resin is fast, crystallization is also performed at the time of casting. At this time, when it is cast in a single layer without multilayering, there is no barrier which suppresses crystal growth, and thus the crystal grows into a large-sized spherulites. As a result, the obtained unstretched sheet has a high stress, and is easily broken at the time of stretching in the longitudinal direction.
不僅如此，於長度方向的拉伸期間亦進行結晶化，因此成為如下之膜：於寬度方向的拉伸時亦容易斷裂，並且所獲得之雙軸配向聚酯膜的破袋強度或穿刺強度亦不充分。 Further, since the film is also crystallized during the stretching in the longitudinal direction, it is a film which is easily broken at the time of stretching in the width direction, and the bag breaking strength or puncture strength of the obtained biaxially oriented polyester film is also insufficient.
進而，依據寬度方向上的膜的厚度而結晶生長產生大差異，因而產生密度差。結果為，有於接下來的長度方向及寬度方向的拉伸時產生拉伸應力的不均，所獲得之雙軸配向聚酯膜的厚度精度降低之情形。 Further, a large difference in crystal growth occurs depending on the thickness of the film in the width direction, and thus a density difference occurs. As a result, unevenness in tensile stress occurs in the subsequent stretching in the longitudinal direction and the width direction, and the thickness precision of the obtained biaxial alignment polyester film is lowered.
具體而言，本發明之雙軸配向PBT膜的製造方法至少具有：步驟(1)，使包含PBT樹脂60重量%以上之聚酯樹脂組成物熔融而形成熔融流體；步驟(2)，形成由步驟(1)中所形成之熔融流體構成之積層數60以上之積層流體；步驟(3)，使步驟(2)中所形成之積層流體自模具噴出，接觸於冷卻輥而固化，從而形成積層體；及步驟(4)，將前述積層體進行雙軸拉伸。 Specifically, the method for producing a biaxially oriented PBT film of the present invention comprises at least the step (1) of melting a polyester resin composition containing 60% by weight or more of the PBT resin to form a molten fluid; and the step (2) is formed by The molten fluid formed in the step (1) constitutes a laminated fluid having a laminate number of 60 or more; in the step (3), the laminated fluid formed in the step (2) is ejected from the mold, and is solidified by contact with a cooling roll to form a laminate. And the step (4), the laminate is biaxially stretched.
於步驟(1)與步驟(2)、步驟(2)與步驟(3)之間，亦可插入其他步驟。例如，於步驟(1)與步驟(2)之間，亦可插入過濾步驟、溫度變更步驟等。另外，於步驟(2)與步驟(3)之間，亦可插入溫度變更步驟、電荷附加步驟等。但是，於步驟(2)與步驟(3)之間，不可存在破壞步驟(2)中所形成之積層結構之步驟。 Other steps may be inserted between step (1) and step (2), step (2) and step (3). For example, a filtration step, a temperature change step, and the like may be inserted between the step (1) and the step (2). Further, a temperature change step, a charge addition step, and the like may be inserted between the step (2) and the step (3). However, between step (2) and step (3), there is no step of destroying the laminated structure formed in step (2).
於步驟(1)中，使聚酯樹脂組成物熔融而形成熔融流體之方法並無特別限定，作為較佳的方法，可列舉使用單軸擠出機或雙軸擠出機進行加熱熔融之方法。 In the step (1), the method of melting the polyester resin composition to form a molten fluid is not particularly limited, and a preferred method is a method of heating and melting using a single-axis extruder or a twin-screw extruder. .
步驟(2)中之形成積層流體之方法並無特別限定，就設備的簡易性或保養性之方面而言，更佳為靜態混合器及/或多層進料塊(feed block)。另外，就片寬度方向的均勻性之方面而言，更佳為具有矩形的熔融線(melt line)之設備。進而較佳為使用具有矩形的熔融線之靜態混合器或多層進料塊。再者，亦可使藉由使多種聚酯樹脂組成物合流而形成之由多層構成之樹脂組成物通過靜態混合器、多層進料塊及多層歧管之任1種或2種以上。 The method of forming the build-up fluid in the step (2) is not particularly limited, and is preferably a static mixer and/or a multi-layer feed block in terms of ease of use or maintainability of the apparatus. Further, in terms of uniformity in the width direction of the sheet, a device having a rectangular melt line is more preferable. It is further preferred to use a static mixer or a multi-layer feed block having a rectangular melting line. Further, the resin composition composed of a plurality of layers formed by a plurality of polyester resin compositions may be passed through one or two or more types of a static mixer, a multilayer feed block, and a multilayer manifold.
步驟(2)中的理論積層數需為60以上。理論積層數的下限較佳為200，更佳為500。若理論積層數過少，則層界面間距離變長而結晶尺寸變得過大，發生前述之拉伸時的斷裂或力學強度的降低、厚度精度的降低。另外，有片 兩端附近的結晶度增大，製膜變得不穩定，此外成型後的透明性降低之情況。步驟(2)中的理論積層數的上限並無特別限定，較佳為100000，更佳為10000，進而較佳為7000。即便使理論積層數極大，亦有積層效果飽和之情形。 The theoretical number of layers in the step (2) needs to be 60 or more. The lower limit of the theoretical number of layers is preferably 200, more preferably 500. When the number of theoretical layers is too small, the distance between the layer interfaces becomes long and the crystal size becomes excessively large, and the fracture at the time of stretching, the decrease in mechanical strength, and the decrease in thickness precision occur. In addition, there are pieces The crystallinity near the both ends is increased, the film formation becomes unstable, and the transparency after molding is lowered. The upper limit of the theoretical number of layers in the step (2) is not particularly limited, but is preferably 100,000, more preferably 10,000, still more preferably 7,000. Even if the theoretical number of layers is extremely large, there is a case where the layering effect is saturated.
於利用靜態混合器進行步驟(2)中的積層之情形時，藉由選擇靜態混合器的元件數，可調整理論積層數。靜態混合器通常作為無驅動部之靜止型混合器(管路型混合器)而為大眾所知，進入至混合器內之流體藉由元件而依序攪拌混合。但是，若使高黏度流體通過靜態混合器，則會產生高黏度流體之分割及積層，形成積層流體。每次通過靜態混合器之一元件時，高黏度流體分割成2層，繼而合流而積層。因此，若使高黏度流體通過元件數n之靜態混合器，則形成理論積層數N=2的n次方之積層流體。 In the case where the layering in the step (2) is carried out using a static mixer, the theoretical number of layers can be adjusted by selecting the number of elements of the static mixer. Static mixers are generally known as stationary mixers (line-type mixers) without a drive, and the fluid entering the mixer is sequentially agitated and mixed by means of components. However, if a high-viscosity fluid is passed through a static mixer, a high-viscosity fluid is divided and laminated to form a stratified fluid. Each time a component of the static mixer is passed, the high viscosity fluid is split into two layers, which in turn merge to form a layer. Therefore, if a high-viscosity fluid is passed through a static mixer having a number n of elements, a layered fluid having a theoretical number of layers N=2 is formed.
典型的靜態混合器元件具有將長方形的板扭轉180度之結構，根據扭轉的方向，有右元件及左元件，各元件的尺寸係以相對於直徑為1.5倍之長度為基礎。可用於本發明之靜態混合器並不限定於此種混合器。 A typical static mixer element has a structure that twists a rectangular plate by 180 degrees. Depending on the direction of twisting, there are right and left elements, each element being sized based on a length 1.5 times the diameter. Static mixers useful in the present invention are not limited to such mixers.
於利用多層進料塊進行步驟(2)中的積層之情形時，藉由選擇多層進料塊之分割、積層次數，可調整理論積層數。多層進料塊可串聯設置多個。另外，亦可將供給至多層進料塊之高黏度流體本身設為積層流體。例如，於供給 至多層進料塊之高黏度流體的積層數為p，多層進料塊的分割、積層數為q，多層進料塊的設置數為r之情形時，積層流體的積層數N成為N=p×(q的r次方)。 In the case where the layering in the step (2) is carried out by using the multilayer feeding block, the number of theoretical layers can be adjusted by selecting the number of divisions and the number of layers of the multilayer feeding block. Multiple layers of feed blocks can be placed in series. Alternatively, the high viscosity fluid supplied to the multilayer feed block itself may be used as a buildup fluid. For example, in supply The number of layers of the high-viscosity fluid to the multi-layer feed block is p, the division of the multi-layer feed block, the number of layers is q, and the number of layers of the multi-layer feed block is r, the number N of laminated fluids becomes N=p × (the rth power of q).
再者，於如本案發明般由相同組成的聚酯樹脂組成物多層化之情形時，亦可僅使用一台擠出機，於擠出至模具之熔融線導入上述之多層化裝置。 Further, in the case where the polyester resin composition having the same composition is multilayered as in the case of the present invention, it is also possible to introduce the above-mentioned multilayering apparatus into a melting line extruded into a mold using only one extruder.
於步驟(3)中，使積層流體自模具噴出，接觸於冷卻輥而固化。 In the step (3), the layered fluid is ejected from the mold and brought into contact with the cooling roll to be solidified.
模具溫度的下限較佳為255℃，更佳為260℃，尤佳為265℃，若未達上述下限，則有噴出不穩定，厚度變得不均勻之情況。 The lower limit of the mold temperature is preferably 255 ° C, more preferably 260 ° C, and particularly preferably 265 ° C. If the lower limit is not reached, the discharge is unstable and the thickness becomes uneven.
另外，有樹脂之熔融擠出步驟內所滯留之PET樹脂成為未熔融物而混入至膜中，損害膜的品質之情況。樹脂熔融溫度的上限較佳為285℃，更佳為280℃，最佳為275℃。若超過上述上限，則樹脂進行分解，膜變脆。 Further, the PET resin remaining in the melt extrusion step of the resin is mixed into the film without being melted, and the quality of the film is impaired. The upper limit of the melting temperature of the resin is preferably 285 ° C, more preferably 280 ° C, most preferably 275 ° C. When the above upper limit is exceeded, the resin is decomposed and the film becomes brittle.
模具溫度的上限較佳為320℃，更佳為300℃以下，進而較佳為280℃以下。若超過上述上限，則有厚度變得不均勻，此外引起樹脂劣化，因模唇污染等而導致外觀不良之情況。 The upper limit of the mold temperature is preferably 320 ° C, more preferably 300 ° C or less, and still more preferably 280 ° C or less. When the above upper limit is exceeded, the thickness may become uneven, and the resin may be deteriorated, and the appearance may be poor due to contamination of the lip.
冷卻輥溫度的上限較佳為40℃，更佳為20℃以下。若超過上述上限，則有熔融的聚酯樹脂組成物冷卻固化時 的結晶度變得過高而拉伸變得困難之情況。冷卻輥溫度的下限較佳為0℃，若未達上述下限，則有熔融的聚酯樹脂組成物冷卻固化時的結晶化抑制的效果飽和之情況。另外，於將冷卻輥的溫度設為上述範圍之情形時，為了防止結露，較佳為預先降低冷卻輥附近的環境的濕度。 The upper limit of the chill roll temperature is preferably 40 ° C, more preferably 20 ° C or less. If the above upper limit is exceeded, the molten polyester resin composition is cooled and solidified. The degree of crystallinity becomes too high and stretching becomes difficult. The lower limit of the chill roll temperature is preferably 0 ° C. If the lower limit is not reached, the effect of suppressing crystallization during cooling and solidification of the molten polyester resin composition may be saturated. Further, when the temperature of the cooling roll is set to the above range, in order to prevent dew condensation, it is preferable to lower the humidity of the environment in the vicinity of the cooling roll in advance.
於冷卻輥表面澆鑄熔融聚酯樹脂組成物時，由於高溫樹脂接觸於表面，故而冷卻輥表面的溫度上升。通常，冷卻輥係於內部通過配管流通冷卻水而進行冷卻，但必須減小冷卻輥表面的寬度方向的溫度差，例如確保充分的冷卻水量、研究配管的配置、以及進行維護以使沈澱物(sludge)不附著於配管等。尤其是，於不使用多層化等方法而於低溫下進行冷卻之情形時，必須注意。 When the molten polyester resin composition is cast on the surface of the chill roll, the temperature of the surface of the chill roll rises because the high temperature resin contacts the surface. Usually, the cooling roller is cooled by circulating cooling water through a pipe, but it is necessary to reduce the temperature difference in the width direction of the surface of the cooling roll, for example, to secure a sufficient amount of cooling water, to study the arrangement of piping, and to perform maintenance to make a precipitate ( Sludge) does not adhere to piping or the like. In particular, care must be taken when cooling at a low temperature without using a method such as multilayering.
此時，未拉伸片的厚度較佳為15μm至2500μm之範圍。更佳為500μm以下，進而較佳為300μm以下。 At this time, the thickness of the unstretched sheet is preferably in the range of 15 μm to 2500 μm. More preferably, it is 500 μm or less, and further preferably 300 μm or less.
上述中的以多層結構的澆鑄以至少60層以上、較佳為250層以上、進而較佳為1000層以上進行。若層數少，則不僅未拉伸片的球晶尺寸變大，拉伸性的改善效果小，而且產生所獲得之雙軸拉伸膜的力學強度的降低或厚度精度的降低。 The above-described casting with a multilayer structure is carried out at least 60 layers or more, preferably 250 layers or more, and more preferably 1000 layers or more. When the number of layers is small, not only the spherulite size of the unstretched sheet is increased, but also the effect of improving the stretchability is small, and the mechanical strength of the obtained biaxially stretched film is lowered or the thickness precision is lowered.
其次，對步驟(4)之拉伸方法進行說明。拉伸方法可為同步雙軸拉伸亦可為逐步雙軸拉伸，但自耐針孔性及耐 破袋性之觀點考慮，就容易提高面配向係數，容易提高膜厚度的寬度方向的均勻性之方面，以及製膜速度快而生產性高之方面而言，最佳為逐步雙軸拉伸。 Next, the stretching method of the step (4) will be described. The stretching method can be synchronous biaxial stretching or stepwise biaxial stretching, but self-resistant pinhole resistance and resistance From the viewpoint of the bag breaking property, it is easy to increase the surface alignment coefficient, it is easy to increase the uniformity of the film thickness in the width direction, and the film forming speed is fast and the productivity is high, and the gradual biaxial stretching is optimal.
長度方向(以下稱為MD(Machine Direction；縱向))的拉伸溫度的下限較佳為55℃，更佳為60℃。若未達55℃，則不僅有容易引起斷裂之情況，而且藉由低溫下的拉伸而縱向的配向變強，因此有因熱固定處理時的收縮應力變大，而寬度方向的分子配向的應變變大，結果長度方向的直行撕裂性降低之情況。MD拉伸溫度的上限較佳為100℃，更佳為95℃。若超過100℃，則無法施加配向，因此有力學特性降低之情況。 The lower limit of the stretching temperature in the longitudinal direction (hereinafter referred to as MD (Machine Direction)) is preferably 55 ° C, more preferably 60 ° C. If it is less than 55 ° C, not only is it easy to cause breakage, but also the longitudinal alignment becomes stronger by stretching at a low temperature. Therefore, the shrinkage stress at the time of heat fixation treatment is increased, and the molecular orientation in the width direction is increased. The strain becomes large, and as a result, the straight tearing property in the longitudinal direction is lowered. The upper limit of the MD stretching temperature is preferably 100 ° C, more preferably 95 ° C. If it exceeds 100 ° C, the alignment cannot be applied, and thus the mechanical properties may be lowered.
MD拉伸倍率的下限較佳為2.5倍，尤佳為2.7倍。若未達上述下限，則不易施加配向，因此有力學特性降低之情況。 The lower limit of the MD stretching ratio is preferably 2.5 times, and particularly preferably 2.7 times. If the lower limit is not reached, the alignment is not easily applied, so that the mechanical properties are lowered.
MD拉伸倍率的上限較佳為3.8倍，更佳為3.4倍，尤佳為3.0倍。若超過上述上限，則有力學強度或厚度不均改善的效果飽和之情況。 The upper limit of the MD stretching ratio is preferably 3.8 times, more preferably 3.4 times, and particularly preferably 3.0 times. If the above upper limit is exceeded, the effect of improving the mechanical strength or thickness unevenness may be saturated.
寬度方向(以下稱為TD(Transverse Direction；橫向))的拉伸溫度的下限較佳為60℃，若未達上述下限，則有容易引起斷裂之情況。TD拉伸溫度的上限較佳為100℃，若超過上述上限，則無法施加配向，因此有力學特性降低 之情況。 The lower limit of the stretching temperature in the width direction (hereinafter referred to as TD (Transverse Direction)) is preferably 60 ° C. If the lower limit is not reached, the fracture may easily occur. The upper limit of the TD stretching temperature is preferably 100 ° C. If the above upper limit is exceeded, the alignment cannot be applied, so that the mechanical properties are lowered. The situation.
TD拉伸倍率的下限較佳為3.5倍，更佳為3.6倍，尤佳為3.7倍。若未達上述下限，則寬度方向的配向度變小，因此有力學強度或厚度不均變差之情況。TD拉伸倍率的上限較佳為5倍，更佳為4.6倍，尤佳為4.2倍。若超過上述上限，則有力學強度或厚度不均改善的效果飽和之情況。 The lower limit of the TD stretching ratio is preferably 3.5 times, more preferably 3.6 times, and particularly preferably 3.7 times. If the lower limit is not reached, the degree of alignment in the width direction becomes small, so that the mechanical strength or thickness unevenness may be deteriorated. The upper limit of the TD stretching ratio is preferably 5 times, more preferably 4.6 times, and particularly preferably 4.2 times. If the above upper limit is exceeded, the effect of improving the mechanical strength or thickness unevenness may be saturated.
TD熱固定溫度的下限較佳為185℃，更佳為190℃。若未達上述下限，則有熱收縮率變大，保護層形成步驟中膜收縮，積層後的氣體阻隔層破裂，結果導致氣體阻隔性降低之情況。TD熱固定溫度的上限較佳為210℃，若超過上述上限，則膜熔融，此外即便於不熔融之情形時，亦有顯著變脆之情況，不僅如此，亦有MD方向的熱收縮率變小，保護層形成步驟中膜伸長，積層後的氣體阻隔層破裂，結果導致氣體阻隔性降低之情況。 The lower limit of the TD heat setting temperature is preferably 185 ° C, more preferably 190 ° C. If the lower limit is not reached, the heat shrinkage rate increases, and the film shrinks during the protective layer forming step, and the gas barrier layer after the laminate is broken, resulting in a decrease in gas barrier properties. The upper limit of the TD heat setting temperature is preferably 210 ° C. If the upper limit is exceeded, the film is melted, and even if it is not melted, it is significantly brittle, and not only the heat shrinkage rate in the MD direction is also changed. Small, the film is elongated in the protective layer forming step, and the gas barrier layer after the lamination is broken, resulting in a decrease in gas barrier properties.
TD鬆弛率的下限較佳為0.5%，若未達上述下限，則有於熱固定時容易引起斷裂之情況。TD鬆弛率的上限較佳為10%，若超過上述上限，則不僅有產生應變等而發生厚度不均之情況，而且有熱固定時朝長度方向的收縮變大，結果端部的分子配向的應變變大，於寬度方向上尺寸穩定性等變得不均勻之情況。 The lower limit of the TD relaxation rate is preferably 0.5%, and if the lower limit is not reached, the fracture tends to occur at the time of heat fixation. The upper limit of the TD relaxation rate is preferably 10%. When the above-mentioned upper limit is exceeded, not only the strain or the like is generated, but the thickness is not uniform, and the shrinkage in the longitudinal direction is increased when the heat is fixed, and the molecular alignment of the end portion is caused. The strain becomes large, and dimensional stability and the like in the width direction become uneven.
[雙軸配向聚酯膜的特性] [Characteristics of Biaxially Oriented Polyester Film]
於本發明之雙軸配向聚酯膜中，膜厚度的下限較佳為3μm，更佳為5μm，進而較佳為8μm。若未達3μm，則有作為膜之強度不足之情況。 In the biaxially oriented polyester film of the present invention, the lower limit of the film thickness is preferably 3 μm, more preferably 5 μm, still more preferably 8 μm. If it is less than 3 μm, the strength of the film may be insufficient.
膜厚度的上限較佳為100μm，更佳為75μm，進而較佳為50μm。若超過100μm，則有變得過厚而本發明的目標的加工變得困難之情況。 The upper limit of the film thickness is preferably 100 μm, more preferably 75 μm, still more preferably 50 μm. If it exceeds 100 μm, the processing of the object of the present invention may become difficult.
本發明之雙軸配向PBT膜的固有黏度的下限較佳為0.80dl/g，更佳為0.85dl/g，進而較佳為0.90dl/g，尤佳為0.95dl/g。若為上述下限以上，則可改善衝擊強度或耐穿刺性等。 The lower limit of the intrinsic viscosity of the biaxially oriented PBT film of the present invention is preferably 0.80 dl/g, more preferably 0.85 dl/g, still more preferably 0.90 dl/g, still more preferably 0.95 dl/g. When it is more than the above lower limit, impact strength, puncture resistance, and the like can be improved.
雙軸配向PBT膜的固有黏度的上限較佳為1.2dl/g，進而較佳為1.1dl/g。若超過上述上限，則拉伸時的應力變得過高，製膜性惡化。 The upper limit of the intrinsic viscosity of the biaxially oriented PBT film is preferably 1.2 dl/g, and more preferably 1.1 dl/g. When the above upper limit is exceeded, the stress at the time of stretching becomes too high, and the film formability is deteriorated.
本發明之雙軸配向PBT膜較佳為遍及膜整個區域而具有相同組成的樹脂。 The biaxially oriented PBT film of the present invention is preferably a resin having the same composition throughout the entire area of the film.
本發明之雙軸配向聚酯膜的面配向度(△P)的下限較佳為0.145，更佳為0.148，進而較佳為0.151。若未達上述下限，則有面配向弱，穿刺強度降低，耐破袋性降低之情況。 The lower limit of the surface orientation (?P) of the biaxially oriented polyester film of the present invention is preferably 0.145, more preferably 0.148, still more preferably 0.151. If the lower limit is not reached, the surface alignment is weak, the puncture strength is lowered, and the breakage resistance is lowered.
本發明之雙軸配向聚酯膜的△P的上限較佳為0.200。若超過上述上限，則有改善的效果飽和之情況。 The upper limit of ΔP of the biaxially oriented polyester film of the present invention is preferably 0.200. If the above upper limit is exceeded, there is a case where the effect of the improvement is saturated.
本發明之雙軸配向聚酯膜的MD方向上的於150℃加熱15分鐘後的熱收縮率的上限為5.0%，較佳為4.0%，進而較佳為3.3%。若為上述範圍內，則於施加張力之保護層形成步驟中可抑制膜之伸縮，可抑制由氣體阻隔層的破裂所致之氣體阻隔性的降低。若超過上述上限，則有於保護層形成步驟中膜收縮，引起氣體阻隔層的破裂，結果氣體阻隔性降低之情況。 The upper limit of the heat shrinkage ratio after heating at 150 ° C for 15 minutes in the MD direction of the biaxially oriented polyester film of the present invention is 5.0%, preferably 4.0%, and more preferably 3.3%. When it is in the above range, the expansion and contraction of the film can be suppressed in the protective layer forming step of applying tension, and the decrease in gas barrier properties due to the crack of the gas barrier layer can be suppressed. When the above upper limit is exceeded, the film shrinks during the protective layer forming step, causing cracking of the gas barrier layer, and as a result, the gas barrier properties are lowered.
本發明之雙軸配向聚酯膜的MD方向上的於150℃加熱15分鐘後的熱收縮率的下限為1.0%，尤佳為2.0%。若為上述範圍內，則於施加張力之保護層形成步驟中可抑制膜之伸縮，可抑制由氣體阻隔層的破裂所致之氣體阻隔性的降低。若未達上述下限，則有於保護層形成步驟中膜伸長，引起氣體阻隔層的破裂，結果氣體阻隔性降低之情況。 The lower limit of the heat shrinkage ratio after heating at 150 ° C for 15 minutes in the MD direction of the biaxially oriented polyester film of the present invention is 1.0%, and particularly preferably 2.0%. When it is in the above range, the expansion and contraction of the film can be suppressed in the protective layer forming step of applying tension, and the decrease in gas barrier properties due to the crack of the gas barrier layer can be suppressed. If the lower limit is not reached, the film is elongated in the protective layer forming step, causing cracking of the gas barrier layer, and as a result, the gas barrier property is lowered.
本發明之雙軸配向聚酯膜的使用TMA所測定之假定保護層形成步驟之MD方向上的120℃的尺寸變化率的上限為4.0%，較佳為3.0%。若為上述範圍內，則於施加張力之保護層形成步驟中可抑制膜之伸長，可抑制由氣體阻隔層的破裂所致之氣體阻隔性的降低。若超過上述上限，則有於保護層形成步驟中膜伸長，引起氣體阻隔層的破 裂，結果氣體阻隔性降低之情況。本發明之雙軸配向聚酯膜的MD方向上的120℃的尺寸變化率的下限為-2.0%，較佳為0%。若為上述範圍內，則於施加張力之保護層形成步驟中可抑制膜之收縮，可抑制由氣體阻隔層的破裂所致之氣體阻隔性的降低。若未達上述下限，則有於保護層形成步驟中膜收縮，引起氣體阻隔層的破裂，結果氣體阻隔性降低之情況。 The upper limit of the dimensional change ratio of 120 ° C in the MD direction of the assumed protective layer forming step measured by TMA of the biaxially oriented polyester film of the present invention is 4.0%, preferably 3.0%. When it is in the above range, the elongation of the film can be suppressed in the protective layer forming step of applying tension, and the decrease in gas barrier properties due to the crack of the gas barrier layer can be suppressed. If the upper limit is exceeded, the film is elongated in the protective layer forming step, causing breakage of the gas barrier layer. Crack, resulting in a decrease in gas barrier properties. The lower limit of the dimensional change ratio of 120 ° C in the MD direction of the biaxially oriented polyester film of the present invention is -2.0%, preferably 0%. When it is in the above range, shrinkage of the film can be suppressed in the protective layer forming step of applying tension, and deterioration of gas barrier properties due to cracking of the gas barrier layer can be suppressed. If the lower limit is not reached, the film shrinks during the protective layer forming step, causing cracking of the gas barrier layer, and as a result, the gas barrier properties are lowered.
本發明之雙軸配向聚酯膜的穿刺強度的下限較佳為8N。若未達上述下限，則於用作袋時，有強度不足之情況。穿刺強度的上限較佳為20N。若超過上述上限，則有改善的效果飽和之情況。 The lower limit of the puncture strength of the biaxially oriented polyester film of the present invention is preferably 8N. If the lower limit is not reached, there is a case where the strength is insufficient when used as a bag. The upper limit of the puncture strength is preferably 20N. If the above upper limit is exceeded, there is a case where the effect of the improvement is saturated.
作為用以提高本發明之雙軸配向聚酯膜的加工性之方法，有效的是調整膜的至少單面的滑動性。作為膜的至少單面的動摩擦係數的上限，較佳為0.4以下，更佳為0.39以下，最佳為0.38以下。 As a method for improving the workability of the biaxially oriented polyester film of the present invention, it is effective to adjust the slidability of at least one side of the film. The upper limit of the dynamic friction coefficient of at least one side of the film is preferably 0.4 or less, more preferably 0.39 or less, and most preferably 0.38 or less.
本發明之雙軸配向聚酯膜的每單位厚度的霧度的上限較佳為0.66%/μm，更佳為0.60%/μm，進而較佳為0.53%/μm。若超過上述上限，則於對膜施加印刷時，有可能損害所印刷之文字或圖像的品質。 The upper limit of the haze per unit thickness of the biaxially oriented polyester film of the present invention is preferably 0.66% / μm, more preferably 0.60% / μm, still more preferably 0.53% / μm. If the above upper limit is exceeded, the quality of the printed characters or images may be impaired when printing is applied to the film.
於本發明之雙軸配向聚酯膜中亦可積層印刷層。 A printed layer may also be laminated in the biaxially oriented polyester film of the present invention.
作為形成印刷層之印刷油墨，可較佳地使用水性及溶媒系的含樹脂之印刷油墨。此處，作為用於印刷油墨之樹脂，可例示：丙烯酸系樹脂、胺基甲酸酯系樹脂、聚酯系樹脂、氯乙烯系樹脂、乙酸乙烯酯共聚樹脂及該等之混合物。於印刷油墨中，亦可含有抗靜電劑、光線阻斷劑、紫外線吸收劑、塑化劑、潤滑劑、填料、著色劑、穩定劑、潤滑劑、消泡劑、交聯劑、耐黏連劑、抗氧化劑等公知的添加劑。 As the printing ink for forming the printing layer, an aqueous and solvent-based resin-containing printing ink can be preferably used. Here, examples of the resin used for the printing ink include an acrylic resin, a urethane resin, a polyester resin, a vinyl chloride resin, a vinyl acetate copolymer resin, and a mixture thereof. In printing ink, it may also contain antistatic agent, light blocker, ultraviolet absorber, plasticizer, lubricant, filler, colorant, stabilizer, lubricant, defoamer, crosslinker, and adhesion resistance. A known additive such as a agent or an antioxidant.
作為用以設置印刷層之印刷方法並無特別限定，可使用膠版印刷法、凹版印刷法、網版印刷法等公知的印刷方法。印刷後的溶媒的乾燥可使用熱風乾燥、熱輥乾燥、紅外線乾燥等公知的乾燥方法。 The printing method for providing the printing layer is not particularly limited, and a known printing method such as an offset printing method, a gravure printing method, or a screen printing method can be used. A known drying method such as hot air drying, hot roll drying, or infrared drying can be used for drying the solvent after printing.
另外，對於本發明之雙軸配向聚酯膜，只要無損本發明的目的，則可實施電暈放電處理、輝光放電處理、火焰處理、表面粗面化處理，另外，亦可實施公知的錨固塗佈處理、印刷、裝飾等。 Further, the biaxially oriented polyester film of the present invention may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, surface roughening treatment, or a known anchor coating treatment as long as the object of the present invention is not impaired. Cloth treatment, printing, decoration, etc.
可於本發明之雙軸配向聚酯膜的至少單面設置無機薄膜層或如鋁箔之金屬箔等氣體阻隔層。 An inorganic thin film layer or a gas barrier layer such as a metal foil of an aluminum foil may be provided on at least one side of the biaxially oriented polyester film of the present invention.
作為使用無機薄膜層作為氣體阻隔層之情形時的無機薄膜層，為由金屬或無機氧化物構成之薄膜。形成無機 薄膜層之材料只要為可形成薄膜之材料，則並無特別限制，就氣體阻隔性之觀點而言，可較佳地列舉氧化矽(矽氧)、氧化鋁(鋁氧)、氧化矽與氧化鋁之混合物等無機氧化物。尤其是，就可兼顧薄膜層的柔軟性及緻密性之方面而言，較佳為氧化矽與氧化鋁之複合氧化物。 The inorganic thin film layer in the case where an inorganic thin film layer is used as the gas barrier layer is a thin film made of a metal or an inorganic oxide. Forming inorganic The material of the film layer is not particularly limited as long as it is a material capable of forming a film, and from the viewpoint of gas barrier properties, cerium oxide (oxygen oxide), aluminum oxide (aluminum oxide), cerium oxide, and oxidation are preferably exemplified. An inorganic oxide such as a mixture of aluminum. In particular, a composite oxide of cerium oxide and aluminum oxide is preferred in terms of both flexibility and compactness of the film layer.
於該複合氧化物中，氧化矽與氧化鋁之混合比較佳為以金屬份之重量比計Al為20%至70%之範圍。若Al濃度未達20%，則有水蒸氣氣體阻隔性變低之情形。另一方面，若超過70%，則有無機薄膜層變硬之傾向，有於印刷或層壓等二次加工時膜遭破壞而氣體阻隔性降低之虞。再者，此處所謂之氧化矽，係指SiO或SiO2等各種矽氧化物或該等之混合物，所謂氧化鋁，係指AlO或Al2O3等各種鋁氧化物或該等之混合物。 In the composite oxide, the mixing of cerium oxide and aluminum oxide is preferably in the range of 20% to 70% by weight of Al by weight of the metal component. If the Al concentration is less than 20%, the water vapor barrier property may be lowered. On the other hand, when it exceeds 70%, the inorganic thin film layer tends to be hard, and when the secondary processing such as printing or lamination is performed, the film is broken and the gas barrier properties are lowered. In addition, the term "cerium oxide" as used herein means various cerium oxides such as SiO or SiO 2 or a mixture thereof, and the term "alumina" means various aluminum oxides such as AlO or Al 2 O 3 or a mixture thereof.
無機薄膜層的膜厚通常為1nm至100nm，較佳為5nm至50nm。若無機薄膜層的膜厚未達1nm，則有不易獲得令人滿意的氣體阻隔性之情形，另一方面，即便超過100nm而過度增厚，亦無法獲得與厚度相當的氣體阻隔性提高的效果，就耐彎曲性或製造成本之方面而言，反而不利。 The film thickness of the inorganic thin film layer is usually from 1 nm to 100 nm, preferably from 5 nm to 50 nm. When the film thickness of the inorganic thin film layer is less than 1 nm, it is difficult to obtain satisfactory gas barrier properties. On the other hand, even if it is excessively thicker than 100 nm, the effect of improving gas barrier properties equivalent to the thickness cannot be obtained. In terms of bending resistance or manufacturing cost, it is not good.
作為形成無機薄膜層之方法並無特別限制，例如適宜採用真空蒸鍍法、濺鍍法、離子鍍覆法等物理蒸鍍法 (PVD(Physical Vapor Deposition)法)、或者化學蒸鍍法(CVD(Chemical Vapor Deposition)法)等公知的蒸鍍法即可。以下，以氧化矽-氧化鋁系薄膜為例，對形成無機薄膜層之典型的方法進行說明。例如，於採用真空蒸鍍法之情形時，作為蒸鍍原料，可較佳地使用SiO2與Al2O3之混合物、或者SiO2與Al之混合物等。作為該等蒸鍍原料，通常使用粒子，此時，各粒子的大小較理想為蒸鍍時的壓力不變化之程度的大小，較佳的粒徑為1mm至5mm。加熱可採用電阻加熱、高頻感應加熱、電子束加熱、雷射加熱等方式。另外，亦可採用反應性蒸鍍，該反應性蒸鍍係導入氧、氮、氫、氬、二氧化碳、水蒸氣等作為反應氣體，使用臭氧添加、離子輔助等方法。進而，可對被蒸鍍體(供於蒸鍍之積層膜)施加偏壓，或者將被蒸鍍體進行加熱或冷卻等，成膜條件亦可任意地變更。此種蒸鍍材料、反應氣體、被蒸鍍體之偏壓、加熱、冷卻等於採用濺鍍法或CVD法之情形時亦可同樣地變更。進而，亦可於上述無機薄膜層上積層印刷層。 The method for forming the inorganic thin film layer is not particularly limited. For example, a physical vapor deposition method (PVD (Physical Vapor Deposition) method) such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method (CVD) is preferably used. A known vapor deposition method such as (Chemical Vapor Deposition) method can be used. Hereinafter, a typical method of forming an inorganic thin film layer will be described by taking a ruthenium oxide-alumina-based thin film as an example. For example, in the case of using a vacuum deposition method, as a vapor deposition material, a mixture of SiO 2 and Al 2 O 3 or a mixture of SiO 2 and Al or the like can be preferably used. As the vapor deposition material, particles are usually used. In this case, the size of each particle is preferably such a size that the pressure at the time of vapor deposition does not change, and the preferred particle diameter is 1 mm to 5 mm. Heating can be by means of resistance heating, high frequency induction heating, electron beam heating, laser heating, and the like. Further, reactive vapor deposition may be employed, in which oxygen, nitrogen, hydrogen, argon, carbon dioxide, water vapor or the like is introduced as a reaction gas, and methods such as ozone addition and ion assist are used. Further, a bias voltage may be applied to the vapor-deposited body (the laminated film to be deposited by vapor deposition), or the vapor-deposited body may be heated or cooled, and the film formation conditions may be arbitrarily changed. The vapor deposition material, the reaction gas, the bias of the vapor-deposited body, heating, and cooling can be similarly changed in the case of the sputtering method or the CVD method. Further, a printed layer may be laminated on the inorganic thin film layer.
本發明中，較佳為於前述氣體阻隔層上設置保護層。由金屬氧化物構成之氣體阻隔層並非完全緻密的膜，而是散佈有微小的缺損部分。於金屬氧化物層上塗敷後述之特定的保護層用樹脂組成物而形成保護層，藉此保護層用樹脂組成物中的樹脂滲透至金屬氧化物層的缺損部分，結果可獲得氣體阻隔性穩定之效果。此外，藉由於保護層本身 亦使用具有氣體阻隔性之材料，積層膜的氣體阻隔性能亦大幅提高。 In the present invention, it is preferred to provide a protective layer on the gas barrier layer. The gas barrier layer composed of a metal oxide is not a completely dense film but is scattered with a minute defect portion. A protective layer is formed by coating a specific resin composition for a protective layer described later on the metal oxide layer, whereby the resin in the resin composition for the protective layer penetrates into the defective portion of the metal oxide layer, and as a result, gas barrier properties are stabilized. The effect. In addition, by the protective layer itself The gas barrier property is also used, and the gas barrier properties of the laminated film are also greatly improved.
作為前述保護層，可列舉：於胺基甲酸酯系、聚酯系、丙烯酸系、鈦系、異氰酸酯系、亞胺系、聚丁二烯系等樹脂中，添加有環氧系、異氰酸酯系、三聚氰胺系等硬化劑之層。作為形成保護層時所使用之溶媒(溶劑)，例如可列舉：苯、甲苯等芳香族系溶劑；甲醇、乙醇等醇系溶劑；丙酮、甲基乙基酮等酮系溶劑；乙酸乙酯、乙酸丁酯等酯系溶劑；乙二醇單甲醚等多元醇衍生物等。 The protective layer may be an epoxy-based or isocyanate-based resin such as a urethane-based, polyester-based, acrylic-based, titanium-based, isocyanate-based, imine-based or polybutadiene-based resin. A layer of a hardener such as melamine. Examples of the solvent (solvent) used for forming the protective layer include aromatic solvents such as benzene and toluene; alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; and ethyl acetate. An ester solvent such as butyl acetate; a polyol derivative such as ethylene glycol monomethyl ether or the like.
前述之胺基甲酸酯樹脂由於胺基甲酸酯鍵的極性基與無機薄膜層相互作用，並且藉由存在非晶部分而亦具有柔軟性，故而即便於施加彎曲負載時亦可抑制對無機薄膜層之損傷，故而較佳。 The aforementioned urethane resin interacts with the inorganic thin film layer due to the polar group of the urethane bond, and also has flexibility by the presence of the amorphous portion, so that the inorganic substance can be suppressed even when a bending load is applied. The damage of the film layer is preferred.
胺基甲酸酯樹脂的酸值較佳為10mgKOH/g至60mgKOH/g之範圍內。更佳為15mgKOH/g至55mgKOH/g之範圍內，進而較佳為20mgKOH/g至50mgKOH/g之範圍內。若胺基甲酸酯樹脂的酸值為前述範圍，則於製成水分散液時液穩定性提高，另外，保護層可均勻地堆積於高極性的無機薄膜上，因此塗佈外觀變得良好。 The acid value of the urethane resin is preferably in the range of 10 mgKOH/g to 60 mgKOH/g. More preferably, it is in the range of 15 mgKOH/g to 55 mgKOH/g, and further preferably in the range of 20 mgKOH/g to 50 mgKOH/g. When the acid value of the urethane resin is in the above range, the liquid stability is improved when the aqueous dispersion is prepared, and the protective layer can be uniformly deposited on the highly polar inorganic film, so that the coating appearance is good. .
前述之胺基甲酸酯樹脂的玻璃轉移溫度(Tg)較佳為80℃以上，更佳為90℃以上。藉由將Tg設為80℃以上， 可減少濕熱處理過程(升溫~保溫~降溫)中的由分子運動所致之保護層的膨潤。 The glass transition temperature (Tg) of the aforementioned urethane resin is preferably 80 ° C or higher, more preferably 90 ° C or higher. By setting the Tg to 80 ° C or higher, It can reduce the swelling of the protective layer caused by molecular motion in the wet heat treatment process (heating ~ heat preservation ~ cooling).
就氣體阻隔性提高之方面而言，前述之胺基甲酸酯樹脂更佳為使用含有芳香族或芳香脂肪族二異氰酸酯成分作為主要構成成分之胺基甲酸酯樹脂。 The urethane resin is more preferably a urethane resin containing an aromatic or aromatic aliphatic diisocyanate component as a main constituent component in terms of improvement in gas barrier properties.
其中，尤佳為含有間苯二甲基二異氰酸酯成分。藉由使用上述樹脂，可藉由芳香環彼此的堆疊效果而進一步提高胺基甲酸酯鍵的凝聚力，結果可獲得良好的氣體阻隔性。 Among them, it is particularly preferable to contain a metaxylylene diisocyanate component. By using the above resin, the cohesive force of the urethane bond can be further enhanced by the effect of stacking the aromatic rings, and as a result, good gas barrier properties can be obtained.
本發明中，較佳為將胺基甲酸酯樹脂中的芳香族或芳香脂肪族二異氰酸酯的比率設為聚異氰酸酯成分(F)100莫耳%中為50莫耳%以上(50莫耳%至100莫耳%)之範圍。芳香族或芳香脂肪族二異氰酸酯的合計量的比率較佳為60莫耳%至100莫耳%，更佳為70莫耳%至100莫耳%，進而較佳為80莫耳%至100莫耳%。作為此種樹脂，可較佳地使用由三井化學公司市售之「Takelac(註冊商標)WPB」系列。若芳香族或芳香脂肪族二異氰酸酯的合計量的比率未達50莫耳%，則有可能無法獲得良好的氣體阻隔性。 In the present invention, the ratio of the aromatic or aromatic aliphatic diisocyanate in the urethane resin is preferably 50 mol% or more (50 mol% in 100 mol% of the polyisocyanate component (F). Up to 100% of the range). The ratio of the total amount of the aromatic or aromatic aliphatic diisocyanate is preferably from 60 mol% to 100 mol%, more preferably from 70 mol% to 100 mol%, still more preferably from 80 mol% to 100 mol%. ear%. As such a resin, a "Takelac (registered trademark) WPB" series commercially available from Mitsui Chemicals Co., Ltd. can be preferably used. If the total ratio of the aromatic or aromatic aliphatic diisocyanate is less than 50 mol%, good gas barrier properties may not be obtained.
就與無機薄膜層之親和性提高之觀點而言，前述胺基甲酸酯樹脂較佳為具有羧酸基(羧基)。為了於胺基甲酸酯 樹脂中導入羧酸(鹽)基，例如導入作為多元醇成分之二羥甲基丙酸、二羥甲基丁酸等具有羧酸基之多元醇化合物作為共聚成分即可。另外，若於合成含羧酸基之胺基甲酸酯樹脂後，藉由鹽形成劑進行中和，則可獲得水分散體之胺基甲酸酯樹脂。作為鹽形成劑的具體例，可列舉：氨、三甲基胺、三乙基胺、三異丙基胺、三正丙基胺、三正丁基胺等三烷基胺類、N-甲基嗎啉、N-乙基嗎啉等N-烷基嗎啉類、N-二甲基乙醇胺、N-二乙基乙醇胺等N-二烷基烷醇胺類等。該等可單獨使用，亦可併用2種以上。 The urethane resin preferably has a carboxylic acid group (carboxyl group) from the viewpoint of improving the affinity with the inorganic thin film layer. For urethane In the carboxylic acid (salt) group, a carboxylic acid group-containing polyol compound such as dimethylolpropionic acid or dimethylolbutyric acid as a polyol component may be introduced as a copolymerization component. Further, after synthesizing the carboxylic acid group-containing urethane resin and neutralizing it with a salt forming agent, an aqueous dispersion of the urethane resin can be obtained. Specific examples of the salt forming agent include trialkylamines such as ammonia, trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, and tri-n-butylamine, and N-methyl. N-alkylmorpholine such as morpholine or N-ethylmorpholine, N-dialkylalkanolamine such as N-dimethylethanolamine or N-diethylethanolamine, and the like. These may be used alone or in combination of two or more.
亦可於本發明之雙軸配向聚酯膜積層其他素材之層，作為積層方法，可於製作雙軸配向聚酯膜後貼合，或於製膜中貼合。 The layer of the other material of the biaxial alignment polyester film of the present invention may be laminated as a method of laminating the polyester film after the biaxial alignment, or may be bonded to the film.
本發明之雙軸配向聚酯膜例如可於本發明之雙軸配向聚酯膜設置無機蒸鍍層，進而形成稱為密封劑之熱封性樹脂層，用作包裝材料。通常藉由擠出層壓法或乾式層壓法而形成熱封性樹脂層。作為形成熱封性樹脂層之熱塑性聚合物，只要為可充分地表現密封劑接著性之聚合物即可，可使用HDPE(High Density Polyethylene；高密度聚乙烯)、LDPE(Low Density Polyethylene；低密度聚乙烯)、LLDPE(Linear Low Density Polyethylene；線性低密度聚乙烯)等聚乙烯樹脂類、聚丙烯樹脂。乙烯-乙酸乙烯酯共聚物、乙烯-α-烯烴無規共聚物、離子聚合物樹脂等。 The biaxially oriented polyester film of the present invention can be provided, for example, by providing an inorganic deposited layer on the biaxially oriented polyester film of the present invention, and further forming a heat sealable resin layer called a sealant, which is used as a packaging material. The heat-sealable resin layer is usually formed by an extrusion lamination method or a dry lamination method. As the thermoplastic polymer forming the heat-sealable resin layer, a polymer which can sufficiently exhibit the sealant adhesion property can be used, and HDPE (High Density Polyethylene) or LDPE (Low Density Polyethylene) can be used. Polyethylene resin, polyethylene resin such as LLDPE (Linear Low Density Polyethylene), polypropylene resin. An ethylene-vinyl acetate copolymer, an ethylene-α-olefin random copolymer, an ionic polymer resin, or the like.
密封劑層可為單層膜，亦可為多層膜，根據所需功能而進行選擇即可。例如，就賦予防濕性之方面而言，可使用介置有乙烯-環狀烯烴共聚物或聚甲基戊烯等樹脂之多層膜。另外，密封劑層亦可調配阻燃劑、滑澤劑、抗黏連劑、抗氧化劑、光穩定劑、黏著賦予劑等各種添加劑。 The sealant layer may be a single layer film or a multilayer film, and may be selected according to the desired function. For example, a multilayer film in which a resin such as an ethylene-cyclic olefin copolymer or polymethylpentene is interposed may be used in terms of imparting moisture resistance. In addition, the sealant layer may be formulated with various additives such as a flame retardant, a slip agent, an anti-blocking agent, an antioxidant, a light stabilizer, and an adhesion-imparting agent.
密封劑層的厚度較佳為10μm至100μm，更佳為20μm至60μm。 The thickness of the sealant layer is preferably from 10 μm to 100 μm, more preferably from 20 μm to 60 μm.
本發明之雙軸配向聚酯膜可用作包裝材料用的積層體的基材膜。作為積層體的層構成，例如可列舉：基材層/氣體阻隔層/保護層、基材層/氣體阻隔層/保護層/密封劑層、基材層/氣體阻隔層/保護層/樹脂層/密封劑層、基材層/樹脂層/氣體阻隔層/保護層/密封劑層、基材層/氣體阻隔層/保護層/印刷層/密封劑層、基材層/印刷層/氣體阻隔層/保護層/密封劑層、基材層/氣體阻隔層/保護層/樹脂層/印刷層/密封劑層、基材層/樹脂層/印刷層/氣體阻隔層/保護層/密封劑層、基材層/印刷層/氣體阻隔層/保護層/樹脂層/密封劑層、基材層/印刷層/樹脂層/氣體阻隔層/保護層/密封劑層、基材層/樹脂層/氣體阻隔層/保護層/印刷層/密封劑層等。 The biaxially oriented polyester film of the present invention can be used as a substrate film of a laminate for a packaging material. Examples of the layer constitution of the laminate include a base material layer/gas barrier layer/protective layer, a base material layer/gas barrier layer/protective layer/sealant layer, a base material layer/gas barrier layer/protective layer/resin layer. / sealant layer, substrate layer / resin layer / gas barrier layer / protective layer / sealant layer, substrate layer / gas barrier layer / protective layer / printing layer / sealant layer, substrate layer / printing layer / gas barrier Layer/Protective Layer/Sealant Layer, Substrate Layer/Gas Barrier Layer/Protective Layer/Resin Layer/Print Layer/Sealant Layer, Substrate Layer/Resin Layer/Print Layer/Gas Barrier Layer/Protective Layer/Sealant Layer , substrate layer / printing layer / gas barrier layer / protective layer / resin layer / sealant layer, substrate layer / printing layer / resin layer / gas barrier layer / protective layer / sealant layer, substrate layer / resin layer / Gas barrier layer / protective layer / printing layer / sealant layer, and the like.
使用本發明之雙軸配向聚酯膜之積層體可較佳地用 於包裝製品、各種標籤材料、蓋材、片成型品、層壓管等用途。尤其是，可用於包裝用袋(例如枕形袋、自立袋或四方袋等袋)。積層體的厚度可根據積層體的用途而適宜決定。例如以5μm至500μm、較佳為10μm至300μm左右的厚度的膜或片狀的形態使用。 The laminate using the biaxially oriented polyester film of the present invention can be preferably used. For packaging products, various label materials, cover materials, sheet moldings, laminated tubes and other applications. In particular, it can be used for packaging bags (for example, pillow bags, stand-up bags or square bags). The thickness of the laminate can be appropriately determined depending on the use of the laminate. For example, it is used in the form of a film or sheet having a thickness of about 5 μm to 500 μm, preferably about 10 μm to 300 μm.
[實施例] [Examples]
其次，藉由實施例更詳細地說明本發明，但本發明並不限定於以下之例。再者，膜之評價藉由以下之測定法進行。 Next, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. Further, the evaluation of the film was carried out by the following measurement method.
[120℃下的尺寸變化率] [Dimensional change rate at 120 ° C]
使用島津製作所公司製造之TMA(熱機械分析儀)自室溫升溫至200℃而進行測定。其中，升溫速度係設為10℃/min，測定樣品的寬度係設為4mm，測定樣品的長度係設為10mm，初期張力係設為400mN。 The measurement was carried out by heating from room temperature to 200 ° C using a TMA (thermo-mechanical analyzer) manufactured by Shimadzu Corporation. The temperature increase rate was set to 10 ° C/min, the width of the measurement sample was set to 4 mm, the length of the measurement sample was set to 10 mm, and the initial tension system was set to 400 mN.
讀取所獲得之溫度變化曲線中的120℃的尺寸變化率(%)。 The dimensional change rate (%) at 120 ° C in the obtained temperature change curve was read.
[膜的厚度] [Thickness of film]
依據JIS K7130-1999 A法，使用度盤規進行測定。 The measurement was carried out using a gauge according to JIS K7130-1999 A method.
[厚度精度] [thickness accuracy]
沿所獲得之膜輥的寬度方向切取膜片，以5cm間隔使用度盤規進行測定，將此時的最大厚度設為Tmax，將 最小厚度設為Tmin，將平均厚度設為Tave，根據下述式(1)求出厚度精度。 The film was cut along the width direction of the obtained film roll, and measured at a distance of 5 cm using a gauge, and the maximum thickness at this time was set to Tmax. The minimum thickness is Tmin, the average thickness is Tave, and the thickness accuracy is obtained according to the following formula (1).
厚度精度(%)={(Tmax-Tmin)/Tave}×100% (1) Thickness accuracy (%)={(Tmax-Tmin)/Tave}×100% (1)
[膜的面配向度△P] [Film alignment degree ΔP]
針對樣品，藉由JIS K 7142-1996 A法，以鈉D射線作為光源，藉由阿貝折射計測定膜長度方向的折射率(Nx)、寬度方向的折射率(Ny)、厚度方向的折射率(Nz)，藉由式(2)之計算式算出△P。 For the sample, the refractive index (Nx) in the longitudinal direction of the film, the refractive index (Ny) in the width direction, and the refractive index in the thickness direction were measured by an Abbe refractometer using a sodium D-ray as a light source by the method of JIS K 7142-1996 A. The rate (Nz) is calculated by the calculation formula of the formula (2).
配向係數(AP)=(Nx+Ny)/2-Nz (2) Orientation coefficient (AP)=(Nx+Ny)/2-Nz (2)
[熱收縮率] [heat shrinkage rate]
關於聚酯膜的熱收縮率，除設為試驗溫度150℃、加熱時間15分鐘以外，利用JIS-C-2151-2006.21中所記載之尺寸變化試驗法進行測定。試驗片係依據21.1(a)中的記載而使用。 The heat shrinkage rate of the polyester film was measured 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 in accordance with the description in 21.1 (a).
[穿刺強度] [Puncture strength]
聚酯膜的穿刺強度係利用JIS-Z1707中所記載之試驗法進行測定。 The puncture strength of the polyester film was measured by the test method described in JIS-Z1707.
[氣體阻隔層之製作] [Production of gas barrier layer]
對後述之實施例及比較例所示之基材層進行氧化鋁之蒸鍍。將膜設置於連續式真空蒸鍍機的捲出側，經由冷 卻金屬轉筒使之移行而捲取膜。此時，將連續式真空蒸鍍機減壓至10-4Torr以下，自冷卻轉筒的下部，於氧化鋁製坩堝中裝填純度99.99%之金屬鋁，使金屬鋁加熱蒸鍍，一面對金屬鋁的蒸汽中供給氧而進行氧化反應，一面附著沉積於膜上，形成厚度30nm之氧化鋁膜。 The base material layers shown in the examples and comparative examples described later were subjected to vapor deposition of alumina. The film was placed on the unwinding side of the continuous vacuum vapor deposition machine, and the film was wound by cooling the metal drum to take up the film. At this time, the continuous vacuum vapor deposition machine is depressurized to 10 -4 Torr or less, and the aluminum alloy having a purity of 99.99% is filled in the alumina crucible from the lower portion of the cooling drum, and the metal aluminum is heated and vapor-deposited. Oxygen is supplied to the vapor of the metal aluminum to carry out an oxidation reaction, and is deposited on the film to form an aluminum oxide film having a thickness of 30 nm.
[保護層之製作] [Production of protective layer]
藉由線棒塗佈法，於前述蒸鍍而形成之氣體阻隔層的無機蒸鍍薄膜層上塗佈混合有水60重量%、異丙醇30重量%、胺基甲酸酯樹脂10重量%之溶液，於150℃乾燥30秒，獲得保護層。乾燥後的塗佈量為0.190g/m2(以固形物成分計)。 By using a wire bar coating method, 60% by weight of water, 30% by weight of isopropyl alcohol, and 10% by weight of urethane resin are applied and mixed on the inorganic vapor-deposited film layer of the gas barrier layer formed by the vapor deposition. The solution was dried at 150 ° C for 30 seconds to obtain a protective layer. The coating amount after drying was 0.190 g/m 2 (based on the solid content).
胺基甲酸酯樹脂：作為胺基甲酸酯樹脂，準備市售之含間苯二甲基之胺基甲酸酯樹脂的分散液(三井化學公司製造的「Takelac(註冊商標)WPB341」；固形物成分30%)。該胺基甲酸酯樹脂的酸價為25mgKOH/g，利用DSC(Differential Scanning Calorimetry；示差掃描熱量計)所測定之玻璃轉移溫度為130℃。另外，藉由1H-NMR(Nuclear Magnetic Resonance；核磁共振)所測定之芳香族或芳香脂肪族二異氰酸酯相對於聚異氰酸酯成分整體之比率為85莫耳%。 A urethane resin: a dispersion of a commercially available metaxylylene urethane resin (Takelac (registered trademark) WPB341, manufactured by Mitsui Chemicals, Inc.) as a urethane resin; Solid content component 30%). The urethane resin had an acid value of 25 mgKOH/g, and the glass transition temperature measured by DSC (Differential Scanning Calorimetry) was 130 °C. Further, the ratio of the aromatic or aromatic aliphatic diisocyanate to the entire polyisocyanate component measured by 1 H-NMR (Nuclear Magnetic Resonance) was 85 mol %.
[評價用層壓積層體之製作] [Production of laminated laminate for evaluation]
於在前述之基材膜上具備氣體阻隔層/保護層之積 層膜的保護層上，使用胺基甲酸酯系2液硬化型接著劑(將三井化學公司製造的「Takelac(註冊商標)A525S」與「Takenate(註冊商標)A50」以13.5：1(重量比)之比率進行調配)，藉由乾式層壓法，貼合厚度70μm之未拉伸聚丙烯膜(東洋紡股份有限公司製造的「P1147」)作為熱封性樹脂層，於40℃實施4天老化，藉此獲得評價用的層壓氣體阻隔性積層體。再者，由胺基甲酸酯系2液硬化型接著劑形成之接著劑層的乾燥後的厚度均為約4μm。 Providing a product of a gas barrier layer/protective layer on the aforementioned substrate film On the protective layer of the film, a urethane-based two-liquid-curing adhesive ("Takelac (registered trademark) A525S" manufactured by Mitsui Chemicals Co., Ltd. and "Takenate (registered trademark) A50" was used at 13.5:1 (weight). In the dry lamination method, an unstretched polypropylene film ("P1147" manufactured by Toyobo Co., Ltd.) having a thickness of 70 μm was bonded as a heat-sealable resin layer, and it was carried out at 40 ° C for 4 days. The laminate was aged to obtain a laminated gas barrier laminate for evaluation. Further, the thickness of the adhesive layer formed of the urethane-based two-liquid curing adhesive was about 4 μm.
[蒸煮處理後的耐破袋性] [break-resistant bagging after cooking]
將前述之層壓積層體切割成15cm見方之大小，以密封劑成為內側之方式將2片重疊，將三邊以160℃之密封溫度、密封寬度1.0cm進行熱封，藉此獲得內部尺寸13cm之三邊密封袋。 The laminated laminate was cut into a size of 15 cm square, two sheets were overlapped so that the sealant became inside, and the three sides were heat-sealed at a sealing temperature of 160 ° C and a sealing width of 1.0 cm, thereby obtaining an internal size of 13 cm. Three sides sealed bag.
於所獲得之三邊密封袋中填充水250mL後，利用熱封封閉第四邊之口，製作填充有水之四邊密封袋。 After filling the obtained three-side sealed bag with 250 mL of water, the fourth side of the mouth was sealed by heat sealing to prepare a four-side sealed bag filled with water.
針對所獲得之四邊密封袋，進行於130℃之熱水中保持30分鐘之濕熱處理後，於室溫5℃、濕度35%R.H.之環境下，使之自高度100cm之位置掉落至混凝土板上，計數直至發生破損或針孔為止的掉落次數。 The obtained four-side sealed bag was subjected to a wet heat treatment in a hot water of 130 ° C for 30 minutes, and then dropped to a concrete slab at a height of 100 cm at a room temperature of 5 ° C and a humidity of 35% RH. Up, count the number of drops until damage or pinholes occur.
[積層體的氣體阻隔性：透氧率(OTR；Oxygen Transmission Rate)] [Gas barrier properties of the laminate: Oxygen Transmission Rate (OTR)]
針對前述之層壓積層體，依據JIS-K7126-2之電解感 測器法(附錄A)，使用透氧率測定裝置(MOCON公司製造的「OX-TRAN 2/20」)，於溫度23℃、相對濕度65%之氛圍下，測定常態下的透氧率。再者，透氧率之測定係於氧自基材膜側往密封劑側透過之方向上進行。 For the aforementioned laminated laminate, the electrolytic sensation according to JIS-K7126-2 In the detector method (Appendix A), the oxygen permeability in a normal state was measured using an oxygen permeability measuring device ("OX-TRAN 2/20" manufactured by MOCON Corporation) under an atmosphere of a temperature of 23 ° C and a relative humidity of 65%. Further, the measurement of the oxygen permeability is carried out in the direction in which oxygen permeates from the substrate film side to the sealant side.
[積層體的氣體阻隔性：水蒸氣透過率(WVTR；Water Vapor Transmission Rate)] [Gas barrier properties of the laminate: Water Vapor Transmission Rate (WVTR)]
針對前述之層壓積層體，依據JIS-K7129-1992 B法，使用水蒸氣透過率測定裝置(MOCON公司製造的「PERMATRAN-WIA」)，於溫度40度、相對濕度90%之氛圍下，測定常態下的水蒸氣透過率。再者，水蒸氣透過率之測定係於水蒸氣自基材層膜側往密封劑側透過之方向上進行。 In the above-mentioned laminated laminate, a water vapor transmission rate measuring device ("PERMATRAN-WIA" manufactured by MOCON Corporation) was used in accordance with JIS-K7129-1992 B, and the temperature was measured at 40 ° C and a relative humidity of 90%. Water vapor transmission rate under normal conditions. In addition, the measurement of the water vapor transmission rate is performed in the direction in which the water vapor permeates from the basement film side to the sealant side.
[實施例1] [Example 1]
使用單軸擠出機，將PBT樹脂(1100-211XG(CHANG CHUN PLASTICS CO.,LTD.，固有黏度1.28dl/g)、由對苯二甲酸//乙二醇=100//100(莫耳%)所構成之固有黏度0.62dl/g之PET樹脂、及作為惰性粒子之平均粒徑2.4μm之二氧化矽粒子，以二氧化矽濃度成為0.16重量%之方式調配而形成混合物，使所形成之混合物於290℃下熔融後，將熔融線導入至12元件之靜態混合器。藉此，進行熔融體之分割、積層，獲得由相同原料構成之多層熔融體。自270℃之T型模進行澆鑄，藉由靜電密接法密接於 15℃之冷卻輥而獲得未拉伸片。 Using a single-axis extruder, PBT resin (1100-211XG (CHANG CHUN PLASTICS CO., LTD., intrinsic viscosity 1.28 dl / g), from terephthalic acid / / ethylene glycol = 100 / / 100 (mole %) The PET resin having an intrinsic viscosity of 0.62 dl/g and the cerium oxide particles having an average particle diameter of 2.4 μm as inert particles are blended so as to have a cerium oxide concentration of 0.16% by weight to form a mixture. After the mixture was melted at 290 ° C, the molten wire was introduced into a static mixer of 12 elements, whereby the melt was divided and laminated to obtain a multilayered melt composed of the same raw material, and a T-die of 270 ° C was used. Casting, intimately bonded by electrostatic bonding A 15 ° C cooling roll was used to obtain an unstretched sheet.
繼而，於60℃沿長度方向(MD)進行2.9倍輥拉伸，繼而，通入至拉幅機而於85℃沿寬度方向(TD)進行4.3倍拉伸，於200℃下實施3秒之張緊熱處理及1秒之9%之鬆弛處理後，將兩端之固持部切斷去除各10%而獲得厚度為15μm之膜之磨輥(mill roll)。所獲得之膜的製膜條件、物性及評價結果示於表1。 Then, 2.9 times of roll stretching was carried out in the longitudinal direction (MD) at 60 ° C, and then, it was passed to a tenter and stretched 4.3 times in the width direction (TD) at 85 ° C, and 3 seconds at 200 ° C. After the tension heat treatment and the relaxation treatment of 9% of 1 second, the holding portions at both ends were cut and removed by 10% each to obtain a mill roll of a film having a thickness of 15 μm. The film forming conditions, physical properties, and evaluation results of the obtained film are shown in Table 1.
[實施例2至實施例6] [Example 2 to Example 6]
於實施例1中，將原料組成、製膜條件變更為表1中所記載之雙軸拉伸膜，除此以外，與實施例1同樣地進行。 In the same manner as in Example 1, except that the raw material composition and the film forming conditions were changed to the biaxially stretched film described in Table 1 in the first embodiment.
[比較例1至比較例8] [Comparative Example 1 to Comparative Example 8]
使用單軸擠出機，藉由表2記載之條件獲得膜。所獲得之膜的製膜條件、物性及評價結果示於表2。 The film was obtained by the conditions described in Table 2 using a single-axis extruder. The film formation conditions, physical properties, and evaluation results of the obtained film are shown in Table 2.
(比較例1) (Comparative Example 1)
將熱固定溫度變更為表2中所記載之值，除此以外，利用與實施例1相同的方法實施。所獲得之膜的耐針孔性良好，但穿刺強度為6.5N，耐破袋性為60%而不良。另外，由於尺寸變化率為4.10%而較大，故而氣體阻隔性不良。結果示於表2。 The same procedure as in Example 1 was carried out except that the heat setting temperature was changed to the value described in Table 2. The obtained film had good pinhole resistance, but the puncture strength was 6.5 N, and the bag breaking resistance was 60%, which was poor. Further, since the dimensional change rate is 4.10%, it is large, and thus the gas barrier property is poor. The results are shown in Table 2.
(比較例2) (Comparative Example 2)
將熱固定溫度變更為表2中所記載之值，除此以外，利用與實施例1相同的方法實施。所獲得之膜的耐針孔性及耐破袋性良好，但由於熱收縮率為5.5%而較大，尺寸變化率為-2.20%，故而氣體阻隔性不良。 The same procedure as in Example 1 was carried out except that the heat setting temperature was changed to the value described in Table 2. The film obtained was excellent in pinhole resistance and bag break resistance, but was large in heat shrinkage ratio of 5.5%, and the dimensional change rate was -2.20%, so that the gas barrier property was poor.
(比較例3) (Comparative Example 3)
將聚酯樹脂組成變更為表2中所記載之值，除此以外，利用與實施例1相同的方法實施。所獲得之膜的氣體阻隔性良好，但由於PBT的含量少，故而所獲得之膜的穿刺強度為7.2N，耐破袋性及耐針孔性不良。 The same procedure as in Example 1 was carried out except that the polyester resin composition was changed to the values described in Table 2. The gas barrier property of the obtained film was good, but since the content of PBT was small, the obtained film had a puncture strength of 7.2 N, and was resistant to bag breakage and pinhole resistance.
(比較例4) (Comparative Example 4)
利用表2中所記載之方法實施。所獲得之膜的穿刺強度為8.9N，耐針孔性及耐破袋性良好，但由於尺寸變化率為4.30%而較大，故而氣體阻隔性不良。 It was carried out by the method described in Table 2. The obtained film had a puncture strength of 8.9 N, and was excellent in pinhole resistance and bag break resistance. However, the film had a large dimensional change rate of 4.30%, and thus the gas barrier property was poor.
(比較例5) (Comparative Example 5)
利用表2中所記載之方法實施。所獲得之膜的耐針孔性及耐破袋性良好，但由於尺寸變化率為4.10%而較大，故而氣體阻隔性不良。 It was carried out by the method described in Table 2. The film obtained was excellent in pinhole resistance and bag break resistance, but was large in size change rate of 4.10%, and thus had poor gas barrier properties.
(比較例6) (Comparative Example 6)
利用表2中所記載之方法實施。所獲得之膜的穿刺強度為7.3N，耐破袋性及耐針孔性不良。另外，由於尺寸變化率為4.40%而較大，故而氣體阻隔性不良。 It was carried out by the method described in Table 2. The obtained film had a puncture strength of 7.3 N, and was resistant to bag breakage and pinhole resistance. Further, since the dimensional change rate is 4.40%, it is large, and thus the gas barrier property is poor.
(比較例7) (Comparative Example 7)
利用表2中所記載之方法實施。所獲得之膜的穿刺強度為7.5N，耐破袋性及耐針孔性不良。另外，由於尺寸變化率為4.10%而較大，故而氣體阻隔性不良。 It was carried out by the method described in Table 2. The obtained film had a puncture strength of 7.5 N, and was resistant to bag breakage and pinhole resistance. Further, since the dimensional change rate is 4.10%, it is large, and thus the gas barrier property is poor.
(比較例8) (Comparative Example 8)
利用表2中所記載之方法實施。所獲得之膜的穿刺強度為7.3N，耐破袋性及耐針孔性不良。另外，由於熱收縮率為0.8%而較小，尺寸變化率為4.10%而較大，故而氣體阻隔性不良。 It was carried out by the method described in Table 2. The obtained film had a puncture strength of 7.3 N, and was resistant to bag breakage and pinhole resistance. In addition, since the heat shrinkage rate is small at 0.8%, the dimensional change rate is 4.10%, which is large, and thus the gas barrier property is poor.
(參考例1) (Reference example 1)
於實施例1中，未於熔融線中導入靜態混合器，除此 以外，同樣地製膜。製膜中，頻繁發生膜的斷裂，無法以50m以上之長度獲得膜。所獲得之膜的厚度精度為30%以上。 In Example 1, the static mixer was not introduced into the molten wire, except Film formation was carried out in the same manner. In the film formation, film breakage frequently occurs, and the film cannot be obtained in a length of 50 m or more. The thickness of the obtained film was 30% or more.
(參考例2) (Reference example 2)
針對市售之利用吹脹方式製膜之以PBT作為主成分之雙軸配向膜(總厚度15μm、寬度840mm)，測定厚度精度。厚度精度為28%，較本發明之膜差。 The biaxial alignment film (total thickness: 15 μm, width: 840 mm) containing PBT as a main component, which was formed by inflation in a commercially available film, was measured for thickness precision. The thickness accuracy is 28%, which is inferior to the film of the present invention.
(產業可利用性) (industry availability)
根據本發明，可獲得如下之積層聚酯膜，該膜的耐針孔性、煮沸處理或蒸煮處理後的耐破袋性優異，且保護層形成步驟中的氣體阻隔層的破裂少而氣體阻隔性優異，可廣泛地用作食品包裝或醫藥品包裝材料，故而可期待較大地貢獻於產業界。 According to the present invention, it is possible to obtain a laminated polyester film which is excellent in pinhole resistance, bagging resistance after boiling treatment or retort treatment, and has less cracking of the gas barrier layer in the protective layer forming step and gas barrier It is excellent in properties and can be widely used as a food packaging or pharmaceutical packaging material, so it can be expected to contribute greatly to the industry.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018008055 | 2018-01-22 | ||
| JP2018-008055 | 2018-01-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW201936734A true TW201936734A (en) | 2019-09-16 |
Family
ID=67302389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW108102011A TW201936734A (en) | 2018-01-22 | 2019-01-18 | Biaxially oriented polyester film |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2019142781A1 (en) |
| TW (1) | TW201936734A (en) |
| WO (1) | WO2019142781A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW202012191A (en) * | 2018-08-08 | 2020-04-01 | 日商東洋紡股份有限公司 | Gas barrier laminate film and the method thereof, laminating body, packaging bag |
| KR20230084191A (en) * | 2020-10-07 | 2023-06-12 | 도요보 가부시키가이샤 | Biaxially oriented polyester films and laminates |
| CN121086479A (en) * | 2025-09-06 | 2025-12-09 | 广东华炜新材料科技有限公司 | Thermal shrinkage film for battery packaging, preparation method and application |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004250624A (en) * | 2003-02-21 | 2004-09-09 | Teijin Dupont Films Japan Ltd | Transparent polyester film |
| DE602004019940D1 (en) * | 2003-08-19 | 2009-04-23 | Toyo Boseki | POLYESTER FILM |
| MY195397A (en) * | 2015-04-24 | 2023-01-18 | Toyo Boseki | Biaxially Stretched Polyester Film, and Production Method Therefor |
| CN110382222A (en) * | 2017-02-28 | 2019-10-25 | 东洋纺株式会社 | laminated film |
-
2019
- 2019-01-15 JP JP2019566466A patent/JPWO2019142781A1/en active Pending
- 2019-01-15 WO PCT/JP2019/000918 patent/WO2019142781A1/en not_active Ceased
- 2019-01-18 TW TW108102011A patent/TW201936734A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019142781A1 (en) | 2019-07-25 |
| JPWO2019142781A1 (en) | 2020-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI686433B (en) | Biaxially stretched polyester film and manufacturing method thereof | |
| JP6962364B2 (en) | Laminated film | |
| JP6874277B2 (en) | Biaxially stretched polyester film and its manufacturing method | |
| CN110691809A (en) | Biaxially Oriented Polyester Film | |
| JP6927336B2 (en) | Gas barrier laminated film and its manufacturing method | |
| JPWO2020080131A1 (en) | Laminated film | |
| TW201704013A (en) | Biaxially stretched polyester film, and production method therefor | |
| JP6819816B2 (en) | Polyester film roll | |
| JP6879473B2 (en) | Biaxially oriented polyester film | |
| JP7006445B2 (en) | Polyester film and gas barrier laminated film | |
| TW201936734A (en) | Biaxially oriented polyester film | |
| TW202043047A (en) | Laminated film | |
| JP2020012086A (en) | Polyester-based film roll | |
| JP7310876B2 (en) | Polyester film and gas barrier laminated film | |
| JP7365569B2 (en) | Biaxially oriented polyester film and method for producing biaxially oriented polyester film | |
| JP6826784B2 (en) | Biaxially oriented polyester film and method for producing biaxially oriented polyester film | |
| JP2019171587A (en) | Polyester film and gas barrier laminate film | |
| TW201905048A (en) | Biaxially-oriented polyester film and laminated film | |
| WO2020175066A1 (en) | Biaxially oriented polyester film, and production method for biaxially oriented polyester film | |
| TW202112922A (en) | Biaxially oriented polyester film and method of producing the same |