WO2021117736A1 - 二軸配向ポリエステルフィルム及びその製造方法 - Google Patents
二軸配向ポリエステルフィルム及びその製造方法 Download PDFInfo
- Publication number
- WO2021117736A1 WO2021117736A1 PCT/JP2020/045721 JP2020045721W WO2021117736A1 WO 2021117736 A1 WO2021117736 A1 WO 2021117736A1 JP 2020045721 W JP2020045721 W JP 2020045721W WO 2021117736 A1 WO2021117736 A1 WO 2021117736A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- biaxially oriented
- less
- oriented polyester
- polyester film
- Prior art date
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 163
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 239000004645 polyester resin Substances 0.000 claims abstract description 179
- 229920001225 polyester resin Polymers 0.000 claims abstract description 179
- 239000002245 particle Substances 0.000 claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 239000002994 raw material Substances 0.000 claims description 86
- 229920005989 resin Polymers 0.000 claims description 77
- 239000011347 resin Substances 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 57
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 34
- 238000004804 winding Methods 0.000 claims description 31
- 239000002344 surface layer Substances 0.000 claims description 30
- 238000004140 cleaning Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 230000007547 defect Effects 0.000 claims description 15
- 229920000728 polyester Polymers 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 7
- 238000009736 wetting Methods 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 abstract description 36
- 238000007740 vapor deposition Methods 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 18
- 238000000576 coating method Methods 0.000 abstract description 18
- 239000010408 film Substances 0.000 description 367
- 239000010410 layer Substances 0.000 description 127
- 229920000139 polyethylene terephthalate Polymers 0.000 description 70
- 239000005020 polyethylene terephthalate Substances 0.000 description 70
- 230000003068 static effect Effects 0.000 description 53
- 230000004888 barrier function Effects 0.000 description 42
- 239000007789 gas Substances 0.000 description 40
- 239000002585 base Substances 0.000 description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- 239000010409 thin film Substances 0.000 description 29
- 238000011156 evaluation Methods 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 208000028659 discharge Diseases 0.000 description 21
- 239000000126 substance Substances 0.000 description 21
- 239000011241 protective layer Substances 0.000 description 20
- 239000000565 sealant Substances 0.000 description 19
- 239000012790 adhesive layer Substances 0.000 description 17
- 238000007639 printing Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 239000008188 pellet Substances 0.000 description 15
- -1 polyethylene Polymers 0.000 description 14
- 229910052814 silicon oxide Inorganic materials 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- 230000005611 electricity Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000010954 inorganic particle Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000004594 Masterbatch (MB) Substances 0.000 description 7
- 239000004840 adhesive resin Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010030 laminating Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000005204 segregation Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000003851 corona treatment Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000037303 wrinkles Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000007790 solid phase 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000011146 organic particle Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000000427 thin-film deposition Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-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
- 229920000742 Cotton Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920002799 BoPET Polymers 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- MPCKOQMIBZHVGJ-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;ethane-1,2-diol Chemical group OCCO.OC(=O)C1=CC=CC(C(O)=O)=C1 MPCKOQMIBZHVGJ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001569 carbon dioxide Substances 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical group OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 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
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 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 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011242 organic-inorganic particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- 238000005019 vapor deposition process Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
-
- 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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/275—Recovery or reuse of energy or materials
- B29C48/277—Recovery or reuse of energy or materials of materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/28—Storing of extruded material, e.g. by winding up or stacking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/49—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using two or more extruders to feed one die or nozzle
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Definitions
- the present invention relates to a biaxially oriented polyester film and a method for producing the same, and more specifically, the present invention is suitable for performing secondary processing such as coating and vapor deposition to further enhance the function of the biaxially oriented polyester film, and is suitable for a PET bottle.
- It is an environmentally friendly polyester film by using polyester resin recycled from the market and society (hereinafter sometimes referred to as "polyester resin made by recycling PET bottles"), and has a long winding length.
- the present invention relates to a biaxially oriented polyester film having little variation in physical properties in the longitudinal direction even if it is a long film roll, and a method for producing the same.
- biaxially oriented polyester films have been widely used in a wide range of fields such as packaging materials and industrial materials due to their excellent mechanical strength, thermal properties, optical properties, and the like.
- Biaxially oriented polyester films have excellent oxygen barrier properties, and in packaging applications such as general foods, retort pouch foods, and pharmaceuticals, there are increasing demands for oxygen barrier properties and water vapor barrier properties related to deterioration and deterioration of the contents. There is a problem that the contents are deteriorated or deteriorated.
- the biaxially oriented polyester film used for general foods, retort pouch foods, and packaging applications such as pharmaceuticals further improves the adhesion to printing inks and further improves the gas barrier property in oxygen, water vapor, and the like. Measures have been taken.
- a method for improving the gas barrier property a method of laminating a film made of a resin having a good gas barrier property such as polyvinylidene chloride or a polyethylene vinyl alcohol copolymer to a biaxially oriented polyester film, or a liquid in which these resins are dissolved.
- a vapor-deposited polyester film in which a metal oxide is provided on the film surface is often used because it is excellent in heat resistance and transparency in addition to gas barrier properties.
- a metal oxide thin film such as silicon oxide or an aluminum oxide film having good gas barrier properties on the film surface.
- the gas barrier property of the vapor-deposited polyester film is improved by controlling the surface state of the biaxially oriented polyester film used as the base material of the vapor-deposited polyester film, and the central surface of the biaxially oriented polyester film is improved.
- Those that specify the surface roughness and the number of protrusions see, for example, Patent Document 1
- those that specify the centerline surface roughness of the biaxially oriented polyester film see, for example, Patent Document 2 have been proposed.
- All of these films focus only on improving the gas barrier property after the metal oxide thin film is provided, but when the film is wound on the film roll after the film is manufactured, the film roll is wrinkled or the films in the film roll are placed together.
- the improvement of close contact, so-called blocking, was not sufficient.
- the performance after secondary processing such as coating and vapor deposition was not sufficient.
- Patent Document 4 a biaxially oriented polyethylene terephthalate film using a PET bottle recycled materials, melt specific resistance at temperature 285 ° C. is within 1.0 ⁇ 10 8 ⁇ ⁇ cm, sodium contained in the film Biaxially oriented polyester films having a content of more than 0 ppm and a potassium content of 150 ppm or less are disclosed. According to such a technique, there is little residual cleaning liquid component used when making a recycled material for PET bottles, excellent thermal stability, few foreign substances, stable specific resistance at the time of melting, film productivity, and film productivity. A biaxially oriented polyester film that does not impair quality can be obtained.
- polyester resin recycled from the market and society, including PET bottles which has excellent transparency as described above, is easy to perform secondary processing such as coating and vapor deposition, and has excellent characteristics after secondary processing.
- a polyester resin composition containing a polyester resin containing particles mixed with a polyester resin recycled from the market or society, including a PET bottle is biaxially stretched. It can be expected that this can be achieved, and it is common to mix a resin chip having a normal specific gravity and a resin chip having a large specific gravity containing particles to form a film.
- An object of the present invention is to improve the problems of the prior art, to have excellent transparency, to easily perform secondary processing such as coating and vapor deposition, to have excellent characteristics after secondary processing, and to include PET bottles on the market. It is to provide an environment-friendly biaxially oriented polyester film and a method for producing the same by using a polyester resin recycled from the above and the society, and more preferably, the biaxially oriented polyester film in which the usage ratio of the recycled PET bottle raw material is further increased. To provide a polyester film and a method for producing the same, more preferably to provide a biaxially oriented polyester film having less foreign matter and a method for producing the same, and particularly preferably to use a long film roll having a long winding length. It is an object of the present invention to provide a biaxially oriented polyester film roll having little variation in physical properties in the longitudinal direction and a method for producing the same.
- Static marks which are locally charged parts, and static mark discharge marks due to the discharge of stored static electricity are likely to occur, and coated dissolved resin and vapor-deposited inorganic oxidation are likely to occur in these parts. It has been found that it is difficult for the substance molecules to form a thin film regularly and uniformly on the film surface without defects.
- a biaxial orientation obtained by biaxially stretching a polyester resin composition containing a polyester resin containing particles with respect to a polyester resin recycled from the market or society, including a PET bottle.
- the rest angle of the polyester resin pellets containing particles is set to a specific range, and when mixing the resin chips as the raw material, the hopper contains a PET bottle from above, which is recycled from the market and society.
- the polyester resin chips containing particles are supplied through a pipe having an outlet directly above the extruder in the hopper (hereinafter, may be referred to as an inner pipe), and both chips are mixed.
- the present invention has the following configuration.
- 1. A biaxially oriented polyester film comprising a polyester resin obtained from recycled PET bottles and a polyester resin composition containing particles, wherein at least one surface satisfies all of the following requirements (1) to (3).
- the number of fine protrusions with a height of less than 3 nm per area of 4 ⁇ 10 -12 m 2 is 250 or more and 600 or less.
- the number of fine protrusions having a height of 3 nm or more per area of 4 ⁇ 10 -12 m 2 is 300 or more and 600 or less.
- the arithmetic mean height Sa is 0.010 ⁇ m or more and 0.025 ⁇ m or less.
- the content of the polyester resin obtained by recycling PET bottles in the polyester resin composition constituting the biaxially oriented polyester film is 50% by mass or more and 100% by mass or less.
- the number of defects of 1 mm or more per 1 m 2 of the film is less than 1.0.
- ⁇ 3. The biaxially oriented polyester film according to any one of.
- polyester resin obtained by recycling the PET bottle is subjected to at least one alkaline washing.
- ⁇ 4 The biaxially oriented polyester film according to any one of.
- the coefficient of kinetic friction between the surface satisfying all the requirements (1) to (3) of the biaxially oriented polyester film and the opposite surface is 0.20 or more and 0.60 or less.
- the wetting tension of the surface of the biaxially oriented polyester film that satisfies all of the above requirements (1) to (3) is 50 mN / m or more.
- the outer haze of the biaxially oriented polyester film is 1.8% or less, and the internal haze is 2.0% or less. ⁇ 7.
- a film roll obtained by winding the biaxially oriented polyester film according to any one of the above in a roll shape, and has an area of 4 ⁇ 10 -12 when the film roll is sampled from the surface layer to the core in the longitudinal direction of the film every 1000 m. wherein the m number of fine protrusions height less than 3nm per 2, and area 4 ⁇ 10 -12 m 2 per height 3nm or more microprojections number of variations is equal to or less than 40% both, biaxial Oriented polyester film roll. (Variation is expressed by the following formula [1] when the maximum value is Xmax, the minimum value is Xmin, and the average value is Xave. Variation (%) 100x (Xmax-Xmin) / Xave ... [1] ])
- a method for producing a biaxially oriented polyester film which comprises a melt extrusion step of a polyester raw material resin and a biaxial stretching step, and in the melt extrusion step of the polyester raw material resin, the PET bottle is recycled from above to a hopper.
- Raw material resin chips of the polyester resin composition containing the particles having a rest angle of 30 degrees or more and 40 degrees or less through a pipe having an outlet directly above the extruder in the hopper while supplying the raw material resin chips of the polyester resin. 1. It is characterized by having a step of supplying, mixing both chips, and melting and extruding. ⁇ 8.
- the method for producing a polyester film according to any one of.
- a method for producing a biaxially oriented polyester film roll which comprises a melt extrusion step of the polyester raw material resin, a biaxial stretching step, and a step of winding the film after the biaxial stretching into a roll shape.
- a raw resin chip of polyester resin obtained by recycling the PET bottle is supplied to the hopper from above, and the rest angle is 30 degrees or more and 40 degrees through a pipe having an outlet in the hopper and directly above the extruder.
- It is characterized by having a step of supplying a raw material resin chip of a polyester resin composition containing the following particles, mixing the two chips, and melt-extruding the two chips.
- the method for producing a biaxially oriented polyester film roll according to any one of.
- the transparency is excellent, wrinkles are less likely to occur on the film roll when the film is wound on the film roll after production, and there is little adhesion between the films in the film roll (so-called blocking phenomenon).
- the length in the width direction and the length in the longitudinal direction of the biaxially oriented polyester film roll (hereinafter referred to as the master roll) to be wound first through the stretching step have been increased.
- the master roll the length in the width direction and the length in the longitudinal direction of the biaxially oriented polyester film roll (hereinafter referred to as the master roll) to be wound first through the stretching step.
- wrinkles and blocking are few even in a film roll having such a large size, it is easy to perform secondary processing, and the performance after secondary processing, for example, the gas barrier property of a vapor-deposited film can be satisfied.
- a biaxially oriented polyester film can be obtained. The same applies to the film roll obtained by slitting the master roll into small pieces.
- FIG. 5 is a partially enlarged view of FIG.
- polyester resin made from recycled PET bottles For the biaxially oriented polyester film in the present invention, it is preferable to use a polyester resin recycled from the market or society, including the following PET bottles. By using polyester resin recycled from the market and society, including PET bottles, the ratio of recycled raw materials in the film can be increased, and it becomes possible to obtain an environment-friendly film.
- the polyester resin recycled from the market and society including the PET bottle used for the biaxially oriented polyester film of the present invention, is mainly a recycled product of a vessel mainly composed of polyethylene terephthalate, for example, a tea beverage.
- Recycled products of beverage containers such as soft drinks can be preferably used, and may be appropriately oriented and colorless, but may contain some coloring components.
- Recycled raw materials recycled from the market and society including PET bottles that can be preferably used, are polyesters produced and molded by ordinary polymerization methods and solid-phase polymerization methods, and preferably are mainly composed of polyethylene terephthalate. It may contain other polyester components and copolymerization components.
- a metal compound such as antimony, germanium, or titanium may be contained as a catalyst, or a phosphorus compound as a stabilizer may be contained.
- germanium is often used as a catalyst in polyester for PET bottles, and if a PET bottle recycled material is used to form a film, the film contains 1 ppm or more of germanium. However, since it is the content of the catalyst to the last, it is usually 100 ppm or less at most, and usually 50 ppm or less.
- the collected used recycled PET bottles are sorted so as not to be mixed with other materials and dust, and after removing labels and the like, they are crushed into flakes. Foreign matter is often attached to or mixed with these flakes. It is also conceivable that consumers fill used PET bottles with chemical substances such as chemicals and solvents. For example, detergents such as tableware, pesticides, herbicides, pesticides and various oils can be considered. Alkaline cleaning is preferable because the chemical substances adsorbed on the surface of the PET bottle cannot be sufficiently removed by ordinary cleaning. As the alkali metal hydroxide solution used in this cleaning step, a sodium hydroxide solution or a potassium hydroxide solution is used. In such a cleaning step, pre-cleaning may be performed before alkaline cleaning.
- the concentration of the aqueous alkali metal hydroxide solution used in the cleaning step depends on the temperature, time, and stirring condition, but is usually in the range of 1 to 10% by weight.
- the time required for washing is in the range of 10 to 100 minutes, and it is preferable to carry out the washing while stirring in order to enhance the effect.
- Alkaline cleaning and rinsing cleaning may be repeated several times.
- the aqueous component of the alkali metal hydroxide used in the cleaning in the alkaline cleaning step remains in the flakes, so that the final result is obtained by going through the melt extrusion step in the subsequent pellet granulation step and the melt extrusion step in the film forming process. It may affect the physical properties of the film obtained.
- the concentration of sodium and potassium in the film finally obtained by using the polyester resin recycled from the market and society including these PET bottles is preferably more than 0 ppm and 150 ppm or less, more preferably 3 to 3 to. It is 120 ppm, more preferably 5 to 80 ppm. If the concentration of sodium or potassium contained in the film is higher than 150 ppm, the heat resistance and thermal stability of the film are lowered or the film is colored, which is not preferable. Further, if there is no diethylene glycol at all, the effect of suppressing the production of diethylene glycol is diminished, which is not preferable. In addition, polyester resins recycled from the market and society, including PET bottles, may contain some of these components, and it is difficult to eliminate them at all.
- a part of PET bottle flakes is hydrolyzed by an aqueous solution of alkali metal hydroxide.
- the degree of polymerization of the resin is reduced by heating when molding the PET bottle. Further, the degree of polymerization is lowered due to the influence of heat and moisture applied when the recovered PET bottle is crushed for reuse and then melted and pelletized again. It can be reused as it is, but depending on the intended use, if the degree of polymerization is lowered, the moldability, strength, transparency, heat resistance, etc. may be inferior and it may not be possible to reuse it as it is.
- the washed flakes or flakes that are melt-extruded and pelletized are continuously solid-phase polymerized in an inert gas such as nitrogen gas or noble gas at 180 to 245 ° C., preferably 200 to 240 ° C. It can be done by.
- an inert gas such as nitrogen gas or noble gas
- the process of pelletizing flakes will be explained.
- the flakes are melted, extruded, cooled and granulated using an extruder with degassing and filtering means.
- the melting step in the extruder can be carried out by melting and kneading at 260 to 300 ° C., preferably 265 to 295 ° C.
- the flakes obtained by crushing the PET bottle to be charged need to be sufficiently dried, and it is preferable to carry out the drying under the conditions of 5 to 200, preferably 10 to 100 ppm, and further 15 to 50 ppm.
- the hydrolysis reaction proceeds in the melting step, and the ultimate viscosity of the obtained polyester resin decreases.
- the degassing means those having at least one vacuum vent in the melting zone of the resin are preferable.
- the extruder has a filter capable of filtering and removing solid foreign matter having a diameter of 25 ⁇ m or more, preferably 15 ⁇ m or more, more preferably 10 ⁇ m or more of the molten resin as a filtering means.
- the biaxially oriented polyester film in the present invention comprises a polyester resin composition containing the following polyester resin as a main component.
- the polyester resin constituting the biaxially oriented polyester film of the present invention is a polymer synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
- polyethylene terephthalate polybutylene terephthalate, and polyethylene-2,6-naphthalate can be mentioned, and polyethylene terephthalate is preferable from the viewpoint of mechanical properties, heat resistance, cost, and the like.
- the main component here means that the content in the polyester resin composition is 80% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more, and 98% by weight or more. Most preferred.
- the copolymerization component examples include isophthalic acid, naphthalene dicarboxylic acid, 4,4-diphenyldicarboxylic acid, adipic acid, sebacic acid and ester-forming derivatives thereof.
- examples of the diol component include diethylene glycol, hexamethylene glycol, neopentyl glycol, and cyclohexanedimethanol.
- polyoxyalkylene glycols such as polyethylene glycol and polypropylene glycol can also be mentioned.
- the copolymerization amount is preferably 10 mol% or less, more preferably 5 mol% or less, and most preferably 3 mol% or less per constituent repeating unit.
- the above-mentioned dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof are mainly used as starting materials according to a conventional method.
- Examples thereof include a method of producing by performing an esterification or transesterification reaction and then performing a polycondensation reaction at a high temperature and under reduced pressure.
- the ultimate viscosity of the polyester resin constituting the biaxially oriented polyester film of the present invention is preferably in the range of 0.50 to 0.9 dl / g, more preferably 0.55, from the viewpoint of film forming property and recoverability. It is in the range of ⁇ 0.8 dl / g.
- the number of fine protrusions with a height of less than 3 nm per area of 4 ⁇ 10 -12 m 2 is 250 or more.
- the number of fine protrusions having a height of 3 nm or more per area of 4 ⁇ 10 -12 m 2 is 300 or more and 600 or less.
- the arithmetic mean height Sa is 0.010 ⁇ m or more and 0.025 ⁇ m or less.
- examples of the inorganic particles used include particles composed of silica (silicon oxide), alumina (aluminum oxide), titanium dioxide, calcium carbonate, kaolin, and barium sulfate.
- examples of the organic particles include particles made of acrylic resin particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene. Among them, particles made of silica (silicon oxide), calcium carbonate, or alumina (aluminum oxide), or particles made of polymethacrylate, polymethylacrylate, or a derivative thereof are preferable, and particles made of silica (silicon oxide) or calcium carbonate are preferable. More preferably, inorganic particles made of silica (silicon oxide) are particularly preferable.
- the particle size distribution of the particles used in the present invention is preferably monodisperse.
- the shape of the inorganic fine particles is not particularly limited, but the closer to the spherical shape, the larger the number of fine protrusions having a height of 3 nm or more and the number of fine protrusions having a height of less than 3 nm can be increased without significantly changing the arithmetic mean height Sa. ..
- the weight average particle diameter measured by the Coulter counter of the particles in the present invention is preferably in the range of 0.8 to 1.8 ⁇ m.
- the weight average particle size of the particles is 0.8 ⁇ m or more, the number of fine protrusions having a height of less than 3 nm and the arithmetic mean height Sa are likely to be set to the lower limit values of (1) and (3) above, respectively.
- the weight average particle size of the particles is 1.8 ⁇ m or less, the arithmetic average height Sa is likely to be equal to or less than the upper limit value of (3) above, and the number of fine protrusions having a height of less than 3 nm is equal to or more than the lower limit value of (1) above. Also suitable for.
- the lower limit of the content of particles in the polyester resin composition containing particles (masterbatch) in the present invention is 1000 ppm by mass, more preferably 1300 ppm by mass, and particularly preferably 1400 ppm by mass.
- the upper limit of the particle content is preferably 3000 ppm by weight, more preferably 2500 ppm by weight, still more preferably 2200 ppm by weight, and particularly preferably 1800 ppm by weight.
- the concentration of the inorganic particles in the masterbatch is preferably 7,000 to 400,000 ppm, more preferably 8,000 to 350,000 ppm, and particularly preferably 9000 to 300,000 ppm.
- concentration of the inorganic particles in the masterbatch is less than 7,000 ppm, the addition ratio of the masterbatch containing the inorganic particles is large, and the ratio of the polyester resin recycled from the market and society including the PET bottle which is the main raw material is high. The number will decrease, and it will not be possible to effectively obtain inexpensive resins and resin properties for environmental consideration.
- the angle of repose of the master pellet is preferably 25 to 40 degrees, more preferably 30 to 40 degrees. If the angle of repose is larger than 40 degrees, segregation is likely to occur before being supplied to the extruder after being mixed with polyester resin recycled from the market or society, including PET bottles, and the resulting film has a large variation in the longitudinal direction. Prone.
- the rest angle of the master pellet can be adjusted by changing the shape and size of the pellet. The closer the pellet is to a spherical shape, the smaller the angle of repose, and the longer the pellet, the larger the angle of repose. Also, the smaller the pellet size, the smaller the angle of repose.
- any one of a step of esterification for producing a polyester resin, a step after the completion of the transesterification reaction, or a step before the start of the polycondensation reaction can be added in the step, it is preferable to add it as a slurry dispersed in ethylene glycol or the like to proceed with the polycondensation reaction.
- a method of blending a slurry of particles dispersed in ethylene glycol or water using a kneading extruder with a vent and a polyester resin raw material or a method of blending dried particles and a polyester resin raw material using a kneading extruder. It is also preferable to carry out by a method of blending with and the like.
- the step of mixing the particles and the polyester resin raw material it is preferable to reduce the agglomerates of the particles as much as possible in order to stably obtain the desired surface condition, but the film formation of the biaxially oriented polyester film after the mixing step is preferable. The influence can be reduced by adjusting the process conditions.
- polyester resin composition of the present invention a small amount of other polymers, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, plasticizers, pigments or the like, as long as the object of the present invention is not impaired.
- Other additives and the like may be contained.
- the polyester film obtained as described above contains the content of the isophthalic acid component with respect to 100 mol% of the total dicarboxylic acid component in the biaxially oriented polyester film in the range of 0.02 mol% or more and 2.0 mol% or less. Is preferable. Crystallinity is controlled in the polyester generally used for PET bottles in order to improve the appearance of the bottle, and as a result, polyester containing 10 mol% or less of an isophthalic acid component is used. is there. Therefore, the polyester film of the present invention contains a certain amount of a material containing an isophthalic acid component, and by containing a specific amount of the isophthalic acid component in the film, the present invention further adheres to the sealant. Adhesive strength can be improved.
- the lower limit of the amount of the isophthalic acid component in the total dicarboxylic acid components constituting the polyester resin contained in the film is preferably 0.02 mol%, more preferably 0.05 mol%, and further preferably 0. It is 1 mol%, particularly preferably 0.15 mol%.
- some polyester resins recycled from the market and society, including PET bottles contain a large amount of isophthalic acid components, so that the isophthalic acid component constituting the polyester resin in the film is 0.02 mol%. If it is less than, it becomes difficult to produce a polyester film having a high ratio of recycled resin, which is not so preferable.
- the upper limit of the amount of the isophthalic acid component in the total dicarboxylic acid components constituting the polyester resin contained in the film is preferably 2 mol%, more preferably 1.5 mol%, still more preferably 1.0 mol. %. If it exceeds 2.0 mol%, the crystallinity is lowered, so that the mechanical strength of the film may be lowered, which is not very preferable. Further, it is preferable to set the content of the isophthalic acid component in the above range because it is easy to produce a film having excellent lamination strength, shrinkage and thickness unevenness.
- the upper limit of the ultimate viscosity of polyester resins recycled from the market and society, including PET bottles, is preferably 0.9 dl / g, more preferably 0.8 dl / g, and even more preferably 0.75 dl / g. Yes, particularly preferably 0.69 dl / g. If it exceeds 0.9 dl / g, it may be difficult to discharge the resin from the extruder and the productivity may decrease, which is not very preferable.
- the lower limit of the content of the polyester resin recycled from the market or society, including the PET bottle is preferably 50% by weight, more preferably 70% by weight, still more preferably 90% by weight. It is by weight%, particularly preferably 100% by weight. If it is less than 50% by weight, the content of the recycled resin is poor and it is not very preferable in terms of contributing to environmental protection.
- the content of the recycled polyester resin is 100% by mass when the particles are contained in an amount of 0.5% by mass or less (that is, when the content of the recycled polyester resin is 99.5% by mass or more). )including.
- polyester resin recycled from the market and society, including PET bottles as a master batch (high-concentration-containing resin) used when adding lubricants and additives such as inorganic particles to improve the function of the film. it can.
- the biaxially oriented polyester film of the present invention is an extruder equipped with a polyester resin chip recycled from the market or society and a chip of a polyester resin composition containing polyester resin as a main component, including the above-mentioned PET bottle, in a hopper. It can be obtained by supplying and mixing with a resin, melt-extruding with an extruder to form an unstretched sheet, and stretching the unstretched sheet. Suitable examples are given below, but are not limited thereto.
- the film of the present invention may have a single-layer structure of at least one layer, or may have a laminated structure of two or more layers. It may be 2 layers, 3 layers, 4 layers or 5 layers. In the case of two layers, it is a laminated portion / base layer portion, in the case of three layers, it is a laminated portion (A) / base layer portion / laminated portion (B), and in the case of three layers, the laminated portion (A) and the laminated portion (B) are It may have the same composition and composition, or may have a different composition, for example, a particle-free layer / base layer / particle-containing layer. Further, the thickness may be substantially the same, or may be different. Preferably, it is desirable that the laminated portion (A) and the laminated portion (B) are designed to have the same composition for easy production.
- the film of the present invention it is preferable that at least one layer of each of the above-mentioned layers constituting the film is biaxially oriented.
- the two or more laminated structures it is particularly preferable that all the layers are biaxially oriented. If all layers are non-oriented or uniaxially oriented, it is difficult to use for body-wrapping labels, which is not very preferable.
- the hopper When mixing the resin chips that are the raw materials, the hopper is supplied with polyester resin chips that are recycled from the market and society, including PET bottles, and pipes that have an outlet in the hopper and directly above the extruder (hereinafter referred to as “the pipe”). It is preferable to supply the chips of the polyester resin composition through (sometimes referred to as an inner pipe), mix the two chips, and melt-extrude them.
- the pipe polyester resin chips recycled from the market and society, including PET bottles, and chips of polyester resin composition are mixed and placed in the hopper on the extruder, resin chips with different specific gravity and chip shape are placed in the hopper.
- FIG. 4 shows an example of a specific mixing procedure.
- FIG. 4 is a schematic view showing an example of the relationship between the extruder 2 provided with the hopper 1 and the inner pipe 3.
- resins other than the polyester resin chips recycled from the market and society including the PET bottle which is the main raw material of the polyester film of the present invention, are supplied through the inner pipe 3, and the chips of the polyester resin composition are supplied. It is supplied from the upper part of the hopper 1. Since the outlet 4 of the inner pipe 3 is directly above the extruder (to be exact, directly above the resin supply port 5 of the extruder 2), the mixing ratio of the raw materials can be kept constant.
- melt-extruding a polyester resin and a polyester resin composition recycled from the market or society, including PET bottles it is preferable to dry them using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer. After drying the polyester resin and the polyester resin composition recycled from the market and society, including PET bottles, the polyester resin reaches the melting point of the polyester resin or higher and at a temperature of 200 to 300 ° C. using an extruder. Melt and extrude into a film. Alternatively, the polyester resin, particles and, if necessary, additives may be sent out by separate extruders, merged, mixed and melted, and extruded into a sheet. When extruding the molten resin composition, any existing method such as the T-die method and the tubular method can be adopted.
- the unstretched sheet can be obtained by quenching the sheet-shaped molten polyester resin after extrusion.
- a method for rapidly cooling the molten polyester resin a method of casting the molten polyester resin from a base onto a rotating drum and quenching and solidifying the molten polyester resin to obtain a substantially unoriented resin sheet can be preferably adopted.
- the temperature of the rotating drum is preferably set to 40 ° C. or lower.
- the biaxially oriented polyester film of the present invention can be obtained by combining the obtained unstretched sheet with the following steps such as stretching steps in the longitudinal direction and the width direction, a heat fixing step, and a heat relaxation step. It will be possible. This will be described in detail below.
- the longitudinal direction means the direction in which the unstretched sheet is run
- the width direction means the direction perpendicular to it.
- the stretching method can be simultaneous biaxial stretching in which stretching in the longitudinal direction and width direction is performed at the same time, or sequential biaxial stretching in which either the longitudinal direction or the width direction is performed first, but the film forming speed is high. Sequential biaxial stretching is most preferable because of its high productivity and excellent thickness uniformity of the finally obtained biaxially oriented polyester film.
- the film-forming speed referred to here means the traveling speed (m / min) of the biaxially oriented polyester film when it is wound on the master roll through the stretching step.
- the temperature during stretching of the unstretched sheet in the longitudinal direction is in the range of (Tg + 15) to (Tg + 55) ° C. using the glass transition temperature (hereinafter, Tg) of the polyester resin as an index, and the stretching ratio is 4.2 to 4.
- the range is preferably 7 times.
- the stretching temperature is (Tg + 55) ° C. or lower and 4.2 times or more, the number of fine protrusions having a height of less than 3 nm is likely to be equal to or higher than the lower limit of (1) above, and the molecules in the longitudinal direction and the width direction. It is preferable that the orientation is well-balanced and the difference in physical properties between the longitudinal direction and the width direction is small.
- the flatness of the obtained biaxially stretched polyester film is also good and preferable.
- the stretching temperature in the longitudinal direction is (Tg + 15) ° C. or higher and the stretching ratio is 4.7 times or less
- the arithmetic mean height Sa is likely to be equal to or lower than the upper limit value of (3) above. It is preferable that the tensile stress (Boeing phenomenon) generated in the direction opposite to the traveling direction of the film in the thermal relaxation step does not become too large.
- the stretching speed is not increased so much in the longitudinal direction. Since the draw ratio of the film can be increased, the difference in physical properties in the film width direction can be further reduced, which is preferable. Two-stage or three-stage stretching is preferable from the viewpoint of effect, equipment, and cost.
- a film obtained by stretching an unstretched sheet in the longitudinal direction is subjected to surface treatment such as corona treatment or plasma treatment as necessary, and then imparted with functions such as slipperiness, adhesiveness, and antistatic property.
- surface treatment such as corona treatment or plasma treatment as necessary, and then imparted with functions such as slipperiness, adhesiveness, and antistatic property.
- a resin dispersion or a resin solution can also be applied to at least one surface of the film.
- the film obtained by stretching the unstretched sheet in the longitudinal direction is stretched in the width direction
- the film is guided to a tenter device, both ends of the film stretched in the longitudinal direction are gripped by clips, and the film is pressed by hot air. After heating to a predetermined temperature, the film can be stretched in the width direction by increasing the distance between the clips while transporting the film in the longitudinal direction.
- the stretching temperature in the width direction is Tg + 5 ° C. or higher, the arithmetic mean height Sa is likely to be the upper limit value of (3) above, and breakage is less likely to occur during stretching, which is preferable. Further, when the stretching temperature is Tg + 40 ° C.
- the number of fine protrusions having a height of less than 3 nm is likely to be equal to or higher than the lower limit of the above (1), and uniform stretching in the width direction is easily performed, resulting in thickness unevenness in the width direction. Is not likely to increase, so that the variation in the winding hardness of the film roll surface in the width direction is unlikely to increase, which is preferable. More preferably, it is Tg + 8 ° C. or higher and Tg + 37 ° C. or lower, and even more preferably Tg + 11 ° C. or higher and Tg + 34 ° C. or lower.
- the stretch ratio in the width direction of the film obtained by stretching the unstretched sheet in the longitudinal direction is preferably 4.0 times or more and 6 times or less.
- the stretching ratio in the width direction is 4.0 times or more, the number of fine protrusions having a height of less than 3 nm is likely to be equal to or higher than the lower limit of (1) above, and a high yield in terms of mass balance is likely to be obtained. It is preferable that the strength does not decrease, the thickness unevenness in the width direction is less likely to increase, and the winding hardness of the film roll in the width direction is less likely to vary.
- the stretch ratio in the width direction is more preferably 4.1 times or more, and further preferably 4.2 times or more. Further, when the stretching ratio in the width direction is 6 times or less, the arithmetic mean height Sa is likely to be set to the upper limit value or less of the above (3), and it is difficult to break during stretching film formation, which is preferable.
- the heat fixing step is performed after the stretching step in the width direction, and the heat fixing temperature of the film obtained by stretching the unstretched sheet in the longitudinal direction and stretching in the width direction is preferably 240 ° C. or higher and 250 ° C. or lower.
- the heat fixing temperature is 240 ° C. or higher, the number of fine protrusions having a height of less than 3 nm is likely to be set to be equal to or higher than the lower limit of (1) above, and the heat shrinkage rate does not become too high in both the longitudinal direction and the width direction. This is preferable because it improves thermal dimensional stability.
- the heat fixing temperature is 250 ° C. or lower, Boeing is unlikely to increase, which is preferable.
- the heat relaxation treatment step is performed, but it may be performed separately from the heat fixing step after the heat fixing step, or may be performed at the same time as the heat fixing step.
- the relaxation rate in the film width direction in the heat relaxation treatment step is preferably 4% or more and 8% or less. When the relaxation rate is 4% or more, the heat shrinkage rate in the width direction of the obtained biaxially oriented polyester film does not become too high, and the dimensional stability during the vapor deposition process is improved, which is preferable.
- the binding force in the width direction is reduced by the weight of the film obtained by stretching the unstretched sheet in the longitudinal direction until the film stretched in the width direction is contracted by heat relaxation. Since the film may loosen or swell due to the accompanying airflow of hot air blown from the nozzles installed above and below the film, the film is in a situation where it is very likely to fluctuate up and down, and the resulting biaxial stretching is achieved. The amount of change in the orientation angle and the diagonal heat shrinkage difference of the polyester film is likely to fluctuate greatly. As a method for reducing these, for example, the films are kept parallel by adjusting the wind speed of the hot air blown from the upper and lower nozzles.
- the biaxially oriented polyester film for vapor deposition of the present invention may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, surface roughening treatment, as long as the object of the present invention is not impaired, and is known.
- Anchor coating, printing, decoration, etc. may be applied.
- the wide biaxially oriented polyester film stretched and formed by the above method is wound by a winder device to prepare a master roll.
- the width of the master roll is preferably 5000 mm or more and 10000 mm or less. When the width of the roll is 5000 mm or more, the cost per film area is lowered in the subsequent stepping process, thin film deposition processing, and printing processing, which is preferable.
- the winding length of the master roll is preferably 10,000 m or more and 100,000 m or less. When the winding length of the roll is 5000 m or more, the cost per film area is lowered in the subsequent slitting process, thin film deposition processing, and printing processing, which is preferable.
- the winding width of the film roll slit from the master roll is preferably 400 mm or more and 3000 mm or less.
- the winding width is 400 mm or more, the time and effort required to frequently replace the film roll in the printing process is reduced, which is preferable in terms of cost.
- it is preferable that the winding width is long, but when it is 3000 mm or less, the roll width does not become too large, the roll weight does not become too heavy, and the handleability is not deteriorated, which is preferable.
- the winding length of the film roll is preferably 2000 m or more and 65000 m or less.
- the winding length is 2000 m or more, the time and effort required to frequently replace the film roll in the printing process is reduced, which is preferable in terms of cost. Further, it is preferable that the winding length is long, but when it is 65,000 m or less, the roll diameter does not become too large, the roll weight does not become too heavy, and the handleability is not deteriorated, which is preferable.
- the number of fine protrusions with a height of less than 3 nm per area of 4 ⁇ 10 -12 m 2 is 250 or more and 600 or less.
- the number of fine protrusions having a height of 3 nm or more per area of 4 ⁇ 10 -12 m 2 is 300 or more and 600 or less.
- the arithmetic mean height Sa is 0.010 ⁇ m or more and 0.025 ⁇ m or less.
- the film and metal roll are used in the process of transporting or winding the produced film.
- the area where the film surface and the metal roll come into contact with each other becomes extremely small even when the high protrusions on the film surface are pushed in by strong force, so the amount of charge due to friction becomes small, and as a result, the static mark and the static mark discharge mark Is thought to decrease. It is more preferably 300 or more, more preferably 400 or more, and particularly preferably 500 or more. This tendency also applies to the friction that occurs when the films come into contact with each other.
- the number of fine protrusions having a height of less than 3 nm does not further improve the slipperiness of the film or lower the blocking property, and has a feature that the gas barrier property of the inorganic thin film layer formed on the film surface is not adversely affected. Further, even if the number of fine protrusions having a height of less than 3 nm is in the range of 600 or less, the static marks and the static mark discharge marks are sufficiently small.
- the arithmetic mean height Sa of at least one surface of the biaxially oriented polyester film of the present invention is preferably 0.010 or more and 0.025 ⁇ m or less.
- the arithmetic mean height Sa is 0.010 ⁇ m or more, adhesion (blocking phenomenon) between the films in the film roll of the recesses formed between the films and between the protrusions on the film surface is unlikely to occur, and the film has two. This is preferable because the next processing can be performed smoothly. It is more preferably 0.013 ⁇ m or more, and more preferably 0.015 ⁇ m or more.
- the arithmetic mean height Sa is 0.025 ⁇ m or less, the haze of the biaxially oriented polyester film, particularly the external haze, is lowered and the transparency is excellent, which is preferable. It is more preferably 0.023 ⁇ m or less, more preferably 0.020 ⁇ m or less, and particularly preferably 0.017 ⁇ m or less.
- the arithmetic mean height Sa of the other film surface is preferably in the same range.
- the coefficient of kinetic friction between one surface of the biaxially oriented polyester film of the present invention and the opposite surface is preferably 0.20 or more and 0.60 or less. When it is 0.20 or more, the films do not slip too much, and when the film roll is wound by the winder device at the time of film production or slitting, the film roll is less likely to wrinkle and the secondary workability is less likely to be deteriorated. It is more preferably 0.30 or more, and most preferably 0.45 or more.
- the films slip with each other, so that when the film roll is wound by the winder device at the time of film production or slitting, the film roll is less likely to be misaligned and the secondary workability is less likely to be deteriorated. It is more preferably 0.50 or less, and most preferably 0.44 or less.
- the coefficient of static friction between one surface of the biaxially oriented polyester film of the present invention and the opposite surface is preferably 0.20 or more and 0.60 or less. When it is 0.20 or more, the films do not slip too much, and when the film roll is wound by the winder device at the time of film production or slitting, the film roll is less likely to wrinkle and the secondary workability is less likely to be deteriorated. It is more preferably 0.30 or more, and most preferably 0.45 or more.
- the films slip with each other, so that when the film roll is wound by the winder device at the time of film production or slitting, the film roll is less likely to be misaligned and the secondary workability is less likely to be deteriorated. It is more preferably 0.50 or less, and most preferably 0.44 or less.
- the maximum height Sz of the surface satisfying all of the above (1) to (3) of the biaxially oriented polyester film of the present invention is preferably 0.5 ⁇ m or more and 2.0 ⁇ m or less.
- the maximum height Sz is 0.5 ⁇ m or more, the amount of air entrained between the films in contact with each other is large when winding the master roll or when the master roll is slit and the biaxially oriented polyester film is wound around the core. It is hard to become, and there is little elongation or deformation of the film. In addition, the film in the roll is less likely to loosen after the air in the film roll is released.
- the maximum height Sz tends to be 0.5 ⁇ m or more.
- the coating film and the inorganic thin film layer after the secondary processing on the surface of the biaxially oriented polyester film are less likely to come off or have defects.
- the stretching temperature in the longitudinal direction is Tg + 40 ° C. or lower, or the stretching ratio is 4.2 times or more, the maximum height Sz tends to be 2.0 ⁇ m or less. The same applies to the maximum height Sz of the other film surface.
- the external haze of the biaxially oriented polyester film of the present invention is preferably 1.8% or less.
- the smoothness of the film surface is less likely to be impaired, and in the film manufacturing process, charging due to contact with or peeling from the transport roll is less likely to occur, and static marks, static mark discharge marks, etc. It is preferable because quality defects due to charging are unlikely to occur. It is more preferably 1.6% or less, more preferably 1.4% or less, particularly preferably 1.2% or less, and most preferably 1.0% or less.
- the internal haze of the biaxially oriented polyester film of the present invention is preferably 2.5% or less.
- the transparency is less likely to decrease, which is preferable. It is more preferably 2.0% or less, more preferably 1.8% or less, and particularly preferably 1.6% or less.
- One surface of the biaxially oriented polyester film of the present invention may be surface-modified by surface treatment such as low-temperature plasma treatment or corona discharge treatment.
- the wetting tension of the surface of the biaxially oriented polyester film of the present invention that satisfies all of the above (1) to (3) is preferably 50 mN / m or more, and more preferably 52 mN / m or more. There is no particular upper limit, but even a range of 55 mN / m or less is sufficient for performance after performing a secondary processing coating or a thin-film deposition thin film.
- the film thickness of the biaxially oriented polyester film of the present invention is preferably 5 to 40 ⁇ m.
- the thickness of the film is more preferably 8 to 30 ⁇ m, particularly preferably 9 ⁇ m to 20 ⁇ m.
- the biaxially oriented polyester film of the present invention preferably contains less than one foreign substance of 1 mm or more per 1 m 2 of the film from the viewpoint of film quality, and can be said to be a film having good quality while using a recycled polyester raw material.
- a gas barrier layer such as an inorganic thin film layer or a metal foil such as an aluminum foil can be provided on at least one surface of the biaxially oriented polyester film of the present invention that satisfies all of the following (1) to (3).
- the number of fine protrusions with a height of less than 3 nm per area of 4 ⁇ 10 -12 m 2 is 250 or more and 600 or less.
- the number of fine protrusions having a height of 3 nm or more per area of 4 ⁇ 10 -12 m 2 is 300 or more and 600 or less.
- the arithmetic mean height Sa is 0.01 ⁇ m or more and 0.025 ⁇ m or less.
- the inorganic thin film layer is a thin film made of metal or an inorganic oxide.
- the material for forming the inorganic thin film layer is not particularly limited as long as it can be formed into a thin film, but from the viewpoint of gas barrier properties, inorganic oxidation such as silicon oxide (silica), aluminum oxide (alumina), and a mixture of silicon oxide and aluminum oxide. Things are preferred.
- a composite oxide of silicon oxide and aluminum oxide is preferable from the viewpoint of both flexibility and denseness of the thin film layer and transparency.
- the mixing ratio of silicon oxide and aluminum oxide is preferably in the range of 20 to 70% of Al in terms of the weight ratio of the metal content. If the Al concentration is less than 20%, the water vapor gas barrier property may be lowered. On the other hand, if it exceeds 70%, the inorganic thin film layer tends to be hard, and the film may be destroyed during secondary processing such as printing or laminating, and the gas barrier property may be lowered.
- the silicon oxide referred to here is various silicon oxides such as SiO and SiO 2 or a mixture thereof
- aluminum oxide is various aluminum oxides such as AlO and Al 2 O 3 or a mixture thereof.
- the film thickness of the inorganic thin film layer is usually 1 to 100 nm, preferably 5 to 50 nm. If the film thickness of the inorganic thin film layer is less than 1 nm, it may be difficult to obtain a satisfactory gas barrier property. On the other hand, even if the thickness exceeds 100 nm, the corresponding improvement effect of the gas barrier property can be obtained. This is not possible, and it is rather disadvantageous in terms of bending resistance and manufacturing cost.
- the method for forming the inorganic thin film layer is not particularly limited, and is known, for example, a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method (CVD method).
- PVD method physical vapor deposition method
- CVD method chemical vapor deposition method
- the method may be adopted as appropriate.
- a typical method for forming the inorganic thin film layer will be described by taking a silicon oxide / aluminum oxide thin film as an example.
- a mixture of SiO 2 and Al 2 O 3 or a mixture of SiO 2 and Al is preferably used as the vapor deposition raw material.
- Particles are usually used as these vapor deposition raw materials, but at that time, it is desirable that the size of each particle is such that the pressure at the time of vapor deposition does not change, and the particle size is preferably 1 mm to 5 mm.
- heating methods such as resistance heating, high frequency induction heating, electron beam heating, and laser heating can be adopted.
- oxygen, nitrogen, hydrogen, argon, carbon dioxide gas, water vapor or the like as the reaction gas, or to adopt reactive vapor deposition using means such as ozone addition and ion assist.
- the film forming conditions can be arbitrarily changed, such as applying a bias to the film to be vapor-deposited (laminated film to be subjected to vapor deposition) or heating or cooling the film to be vapor-deposited.
- a bias to the film to be vapor-deposited (laminated film to be subjected to vapor deposition) or heating or cooling the film to be vapor-deposited.
- Such vapor deposition material, reaction gas, bias of the vapor deposition body, heating / cooling, and the like can be similarly changed when the sputtering method or the CVD method is adopted.
- a printing layer may be laminated on the inorganic thin film layer.
- the gas barrier layer made of metal oxide is not a completely dense film, but is dotted with minute defects.
- the resin in the protective layer resin composition permeates the defective portion of the metal oxide layer.
- the effect of stabilizing the gas barrier property can be obtained.
- the gas barrier performance of the laminated film is greatly improved.
- Examples of the protective layer include urethane-based, polyester-based, acrylic-based, titanium-based, isocyanate-based, imine-based, and polybutadiene-based resins to which epoxy-based, isocyanate-based, and melamine-based curing agents are added. ..
- 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; ethyl acetate and acetate.
- Esther-based solvents such as butyl; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and the like can be mentioned.
- the polar group of the urethane bond interacts with the inorganic thin film layer and also has flexibility due to the presence of the amorphous portion, so that damage to the inorganic thin film layer is suppressed even when a bending load is applied. It is preferable because it can be used.
- the acid value of the urethane resin is preferably in the range of 10 to 60 mgKOH / g. More preferably, it is in the range of 15 to 55 mgKOH / g, and even more preferably, it is in the range of 20 to 50 mgKOH / g.
- the acid value of the urethane resin is within the above range, the liquid stability is improved when it is made into an aqueous dispersion, and the protective layer can be uniformly deposited on the highly polar inorganic thin film, so that the appearance of the coat is good. It becomes.
- the urethane resin has a glass transition temperature (Tg) of preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
- Tg glass transition temperature
- the ratio of aromatic or aromatic aliphatic diisocyanate in the urethane resin is preferably in the range of 50 mol% or more (50 to 100 mol%) in 100 mol% of the polyisocyanate component (F).
- the ratio of the total amount of the aromatic or aromatic aliphatic diisocyanate is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%.
- the "Takelac (registered trademark) WPB” series commercially available from Mitsui Chemicals, Inc. can be preferably used. If the ratio of the total amount of aromatic or aromatic aliphatic diisocyanates is less than 50 mol%, good gas barrier properties may not be obtained.
- the urethane resin preferably has a carboxylic acid group (carboxyl group) from the viewpoint of improving the affinity with the inorganic thin film layer.
- a carboxylic acid (salt) group for example, a polyol compound having a carboxylic acid group such as dimethylolpropionic acid or dimethylolbutanoic acid may be introduced as a copolymerization component as a polyol component.
- the carboxylic acid group-containing urethane resin is synthesized and then neutralized with a salt-forming agent, an aqueous dispersion urethane resin can be obtained.
- the salt forming agent examples include trialkylamines such as ammonia, trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine and tri-n-butylamine, and N such as N-methylmorpholine and N-ethylmorpholine.
- trialkylamines such as ammonia, trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine and tri-n-butylamine
- N such as N-methylmorpholine and N-ethylmorpholine.
- N-dialkylalkanolamines such as -alkylmorpholins, N-dimethylethanolamine and N-diethylethanolamine. These may be used alone or in combination of two or more.
- the biaxially oriented polyester film of the present invention may be used as a base film, and layers of other materials may be laminated to form a laminated body.
- a biaxially oriented polyester film can be bonded after being produced, or can be bonded during film formation.
- the biaxially oriented polyester film of the present invention or the biaxially oriented polyester film of the present invention provided with an inorganic vapor deposition layer may be further formed with a thermosetting resin layer called a sealant and used as a packaging material. it can.
- the heat-sealing resin layer is usually formed by an extrusion laminating method or a dry laminating method.
- the thermoplastic polymer that forms the heat-sealable resin layer may be any as long as it can sufficiently exhibit sealant adhesiveness, and polyethylene resins such as HDPE, LDPE, and LLDPE, and polypropylene resins. Ethylene-vinyl acetate copolymer, ethylene- ⁇ -olefin random copolymer, ionomer resin and the like can be used.
- the sealant layer may be a single-layer film or a multilayer film, and may be selected according to the required function.
- a multilayer film in which a resin such as an ethylene-cyclic olefin copolymer or polymethylpentene is interposed can be used.
- the sealant layer may contain various additives such as a flame retardant, a slip agent, an antiblocking agent, an antioxidant, a light stabilizer, and a tackifier.
- the thickness of the sealant layer is preferably 10 to 100 ⁇ m, more preferably 20 to 60 ⁇ m.
- the layer structure of the laminate for packaging materials using the biaxially oriented polyester film of the present invention as a base film includes, for example, a base film / gas barrier layer / protective layer, a base film / gas barrier layer / protective layer / adhesive.
- the laminate using the biaxially oriented polyester film of the present invention can be suitably used for applications such as packaging products, various label materials, lid materials, sheet molded products, and laminated tubes.
- it is used for packaging bags (for example, pillow bags, pouches such as standing pouches and 4-way pouches).
- the thickness of the laminate can be appropriately determined according to the application. For example, it is used in the form of a film or sheet having a thickness of about 5 to 500 ⁇ m, preferably about 10 to 300 ⁇ m.
- the evaluation method of the polyester resin is as follows. [Glass transition (Tg)] Using a differential scanning calorimeter (DSC6220 type manufactured by SII Nanotechnology Co., Ltd.), 5 mg of the resin sample was melted to 280 ° C. in a nitrogen atmosphere, held for 5 minutes, then rapidly cooled in liquid nitrogen, and cooled to room temperature. The measurement was carried out under the condition of a temperature rising rate of 20 ° C./min.
- the evaluation method of the polyester film is as follows. [Film thickness] It was measured using a dial gauge in accordance with JIS K7130-199 A method.
- the external haze is a value obtained by subtracting the internal haze from the total haze. Note that all haze, internal haze, and external haze all refer to haze for all wavelengths of visible light.
- the measurement points were measured at 10 points at arbitrary points of a sample of 10 cm ⁇ 10 cm, and the average values were taken as the arithmetic mean height Sa and the maximum height Sz, respectively.
- the variation (%) of the arithmetic mean height Sa was sampled every 1000 m from the surface layer of the film roll to the winding core in the longitudinal direction of the obtained polyester film roll (width 2080 mm, winding length 63,000 m). Each sampled film was measured under the above conditions.
- the maximum value of the obtained arithmetic mean height Sa was Xmax (N), the minimum value was Xmin (N), and the average value was Xave, and the variation in the longitudinal direction represented by the following equation [1] was obtained.
- a sample film was prepared by cutting out the obtained film into an area of 400 mm in the longitudinal direction and 100 mm in the width direction. This was aged for 12 hours in an atmosphere of 23 ° C. and 65% RH, and divided into a test piece of 300 mm in the vertical direction ⁇ 100 mm in the horizontal direction for the test table and a test piece of 100 mm in the longitudinal direction ⁇ 100 mm in the width direction for the sliding piece. ..
- the test piece for the test table is set on the test table, and the test piece for the slip piece is cast on the bottom surface of the slide piece (area size is 39.7 mm 2 , square) with a metal load of 1.5 kg.
- the sliding speed of the test piece is 200 mm / min, 23 ° C., 65% RH, and the others are in accordance with JIS K-7125, and the coefficient of dynamic friction and the coefficient of static friction are measured respectively, and the average of three measurements is used. There was.
- Counting was performed within 4 ⁇ 10 -12 m 2 (2 ⁇ m ⁇ 2 ⁇ m square). The number of particles (number of protrusions) less than 3 nm was counted as 0.01 nm or more. The measurement was performed 5 times at different locations, and the average value of 3 times excluding the one with the largest number of counts and the one with the smallest number of counts was calculated and used as the number of fine protrusions.
- Friction band voltage A sample film was prepared by cutting out the obtained film into an area of 80 mm in the longitudinal direction and 50 mm in the width direction. This was aged for 16 hours in an atmosphere of 23 ° C. and 50% RH.
- the friction band voltage was measured using a friction band voltage measuring machine (RST-300a) manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd. Sample The sample was fixed to a rotating device, and the static electricity generated by rubbing against a metal plate at a drum rotation speed of 400 rpm for 60 seconds was measured, and the maximum value was taken as the friction band voltage.
- the measured friction band voltage was evaluated according to the following criteria. ⁇ : Friction band voltage less than 200V ⁇ : Friction band voltage 200V or more and less than 500V ⁇ : Friction band voltage 500V or more and less than 1000V ⁇ : Friction band voltage 1000V or more
- the film was unwound from the film edge on the outermost surface of the obtained film roll, and after removing 2 m from the film edge, the film was sampled at a length of 10 cm at the center in the width direction and 10 cm in the longitudinal direction, manufactured by Kasuga Electric Works Ltd.
- the charged state of the film surface was visualized using the charge distribution determination toner of.
- the chargeability of the film roll was evaluated according to the following criteria. ⁇ : No static mark, static mark discharge mark, or toner adhesion. ⁇ : No static mark or static mark discharge mark is observed, but toner is attached. X: Static marks and static mark discharge marks are observed.
- the obtained film was cut into an area of 250 mm in the longitudinal direction and 250 mm in the width direction to prepare a sample film.
- the number of foreign substances having a diameter of 1 mm or more is measured in the entire range of 250 mm in the longitudinal direction ⁇ 250 mm in the width direction (0.0625 m 2). This is performed with respect to 20 sheets sample film, by dividing the total number of the resulting foreign object by the total observation area (1.25 m 2), in terms of the number of unit area 1 m 2 per foreign substances (pieces / m 2), point The first digit has been rounded off.
- the evaluation was made according to the following criteria based on the number of foreign substances in the measured film. ⁇ : Number of foreign substances in the film (number of defects) 1.0 / m 2 or less ⁇ : Number of foreign substances in the film (number of defects) 1.0 / m 2 or more
- the wet tension is determined by observing the liquid film of the test mixture in a bright place and in the state of the liquid film after 3 seconds. It is wet that the liquid film is kept in the state when it is applied for 3 seconds or more without causing tearing. If the wetting is maintained for 3 seconds or longer, the next step is to proceed to a mixture having a higher surface tension. On the contrary, if the liquid film breaks in 3 seconds or less, the process proceeds to the next mixed liquid having a low surface tension. Repeat this operation to select a mixture that can accurately wet the surface of the test piece in 3 seconds. A new cotton swab is used for each test.
- Brushes or wire bars should be washed with methanol and dried after each use as the residual liquid will change composition and surface tension due to evaporation.
- the operation of selecting a mixed solution capable of wetting the surface of the corona-treated surface in 3 seconds is performed at least 3 times.
- the surface tension of the mixture thus selected is reported as the wetting tension of the film.
- polyester resin A As the PET resin regenerated from the PET bottle used in the production of the biaxially stretched polyester film described later, one synthesized by the following method was used. Foreign substances such as the remaining beverages were washed away from the PET bottles for beverages, and then crushed to obtain flakes. The obtained flakes were washed with a 3.5% by weight sodium hydroxide solution under the conditions of a flake concentration of 10% by weight, 85 ° C., and 30 minutes under stirring. After the alkaline washing, the flakes were taken out and washed with distilled water under the conditions of a flake concentration of 10% by weight, 25 ° C., and 20 minutes under stirring.
- This washing with water was repeated twice more by exchanging distilled water.
- the flakes are dried and then melted with an extruder, and the filter is changed to a finer one with an opening size in sequence, and finer foreign substances are filtered out twice, and the third time with the smallest opening size of 50 ⁇ m.
- the polyester resin A having an intrinsic viscosity of 0.69 dl / g, an isophthalic acid content of 2 mol%, and an angle of repose of 46 degrees was obtained by filtration through a filter.
- polyester resin B A polyester resin having an intrinsic viscosity of 0.69 dl / g, an isophthalic acid content of 2 mol%, and a rest angle of 46 degrees in the same manner as the polyester resin A, except that alkaline cleaning was not performed in the production process of the polyester resin A. B was obtained.
- silica particles are particles obtained by preparing an ethylene glycol slurry in advance, centrifuging it to cut 35% of coarse particles, and then filtering it with a metal filter having an opening of 5 ⁇ m.
- polyester resin D having an ultimate viscosity of 0.60 dl / g and a rest angle of 37 degrees. It was.
- Polyester resin EP Polyester resins E to P were obtained in the same manner as the polyester resin D except that the shape, average particle size and content of the silica particles were changed.
- the raw material resin chips are as shown in Table 1.
- the abbreviations in the table are as follows.
- TPA EG terephthalate: ethylene glycol
- Example 1 A film having a three-layer structure was formed using three extruders.
- the base layer (B) contains 98.7% by mass of polyester resin A and 1.3% by mass of polyester resin D
- the surface layer (A) contains 93.3% by mass of polyester resin A and 6.7% by mass of polyester resin D.
- the polyester resin D was put in using an inner pipe as shown in FIG. 4 so as to be mixed with other raw materials before entering the extruder. After drying each of the raw material resins, the surface layer (A) forming mixed resin is melt-extruded from the first and third extruders at a resin temperature of 285 ° C., and the base layer (B) forming mixed resin is melt-extruded by the second extruder.
- the thickness ratio is 1/10 / 10 in the T-die in the order of surface layer (A) / base layer (B) / surface layer (A) from the side in contact with the casting drum. It was merged and laminated so as to be 1 ( ⁇ m), discharged from a T-shaped base, cooled and solidified with a casting drum having a surface temperature of 30 ° C., and an unstretched polyethylene terephthalate sheet was obtained. At that time, static electricity was applied using a wire-shaped electrode having a diameter of 0.15 mm, and the film was brought into close contact with a cooling drum to obtain a three-layer unstretched film.
- the obtained unstretched film was heated to 115 ° C., and the total draw ratio was 4 by three-stage stretching in which the first stage was 1.24 times, the second stage was 1.4 times, and the third stage was 2.6 times. It was stretched 5 times in the longitudinal direction. Subsequently, the film was stretched in the width direction at a temperature of 140 ° C. and a stretching ratio of 4.3 times, heat-fixed at 245 ° C., heat-relaxed by 5% in the width direction, and 40 W.
- a master roll (roll length 26000 m, width 8000 mm) of a biaxially oriented polyester film having a thickness of 12 ⁇ m was prepared by performing corona treatment under the condition of min / m 2 and winding the film in a roll shape with a winder.
- a biaxially oriented polyester film is unwound from the obtained master roll, and while slitting a 6-inch (152.2 mm) diameter core with a width of 2200 mm, a contact roll is used to apply surface pressure to the film roll, and a biaxial turret winder is used.
- the film roll was wound while applying tension to the film.
- Table 2 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 2 A biaxially stretched film was formed in the same manner as in Example 1 except that the polyester resin A of the surface layer (A) was changed to 95.0% by mass and the polyester resin D was changed to 5.0% by mass as raw materials.
- a biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained.
- Table 2 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 3 A biaxially stretched film was formed in the same manner as in Example 1 except that the polyester resin A of the surface layer (A) was changed to 96.0% by mass and the polyester resin E was changed to 4.0% by mass as raw materials.
- a biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained.
- Table 2 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 4 A biaxially stretched film was formed in the same manner as in Example 1 except that the polyester resin A of the surface layer (A) was changed to 92.0% by mass and the polyester resin F was changed to 8.0% by mass as raw materials.
- a biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained.
- Table 2 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 1 A biaxially stretched film was formed in the same manner as in Example 1 except that the polyester resin of the surface layer (A) was changed to polyester resin C as a raw material to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
- Table 2 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 2 A biaxially stretched film was formed in the same manner as in Example 1 except that the polyester resin A of the surface layer (A) was changed to 95.0% by mass and the polyester resin G was changed to 5.0% by mass as raw materials. A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained. Table 2 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 3 A biaxially stretched film was formed in the same manner as in Example 1 except that the polyester resin A of the surface layer (A) was changed to 95.0% by mass and the polyester resin H was changed to 5.0% by mass as raw materials. A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained. Table 2 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 5 A biaxially stretched film was formed in the same manner as in Comparative Example 1 except that the polyester resin of the surface layer (A) was changed to polyester resin B as a raw material to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
- Table 2 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 1 As in Example 1, a film having a three-layer structure was formed using three extruders.
- the base layer (B) contains 98.7% by mass of polyester resin A and 1.3% by mass of polyester resin D, and the surface layer (A) contains 93.3% by mass of polyester resin A and 6.7% by mass of polyester resin D. And said.
- the polyester resin A and the polyester resin D were all put into the extruder in a mixed state. That is, the polyester resin D entered the extruder in a state of being mixed at the upper part of the hopper without using the inner pipe.
- the surface layer (A) forming mixed resin is melt-extruded from the first and third extruders at a resin temperature of 285 ° C.
- the base layer (B) forming mixed resin is melt-extruded by the second extruder. It melts at a resin temperature of 285 ° C., and the thickness ratio is 1/10 / 10 in the T-die in the order of surface layer (A) / base layer (B) / surface layer (A) from the side in contact with the casting drum.
- a master roll (roll length 26000 m, width 8000 mm) of a biaxially oriented polyester film having a thickness of 12 ⁇ m was prepared by performing corona treatment under the condition of min / m 2 and winding the film in a roll shape with a winder.
- a biaxially oriented polyester film is unwound from the obtained master roll, and while slitting a 6-inch (152.2 mm) diameter core with a width of 2200 mm, a contact roll is used to apply surface pressure to the film roll, and a biaxial turret winder is used. The film roll was wound while applying tension to the film.
- Table 2 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- the films of Examples 1 to 4 are static because the number of fine protrusions having a height of 3 nm or more, the number of fine protrusions having a height of less than 3 nm, and the arithmetic average height Sa are within the specified ranges.
- Comparative Example 1 since the number of fine protrusions having a height of 3 nm or more, the number of fine protrusions having a height of less than 3 nm, and the arithmetic mean height Sa of the obtained film are within the specified ranges, static marks, static mark discharge marks, etc. There are few quality defects due to charging, and the performance after secondary processing such as coating and vapor deposition is excellent, but because it is a conventional fossil fuel-derived polyester resin, it was inferior as an environmentally friendly polyester film. ..
- Comparative Example 2 Although the number of fine protrusions having a height of 3 nm or more was within the range, the friction band voltage was high and the static mark evaluation was poor because the number of fine protrusions having a height of less than 3 nm was small. It was. Moreover, since the arithmetic mean height Sa is too large, the external haze is large and the transparency is inferior.
- Comparative Example 3 Although the number of fine protrusions having a height of 3 nm or more was within the range, the friction band voltage was high and the static mark evaluation was poor because the number of fine protrusions having a height of less than 3 nm was small. It was.
- Example 5 since the number of fine protrusions having a height of 3 nm or more, the number of fine protrusions having a height of less than 3 nm, and the arithmetic mean height Sa of the obtained film are within the specified ranges, static marks, static mark discharge marks, etc. There are few quality defects due to charging, and the performance after secondary processing such as coating and vapor deposition is excellent, but because polyester resin recycled from the market and society, including PET bottles that have not been alkaline-cleaned, is used, the film There were many foreign substances inside.
- Example 6 As raw materials, the polyester resin A of the surface layer (A) was 98.0% by mass, the polyester resin I was 2.0% by mass, the polyester resin A of the base layer (B) was 99.6% by mass, and the polyester resin I was 0.
- a biaxially stretched film was formed in the same manner as in Example 1 except that the content was changed to 4% by mass to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
- Table 3 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 7 As raw materials, the polyester resin A of the surface layer (A) was 99.33% by mass, the polyester resin J was 0.67% by mass, the polyester resin A of the base layer (B) was 99.87% by mass, and the polyester resin J was 0.
- a biaxially stretched film was formed in the same manner as in Example 1 except that the content was changed to 13% by mass to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
- Table 3 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 8 As raw materials, the polyester resin A of the surface layer (A) was 99.5% by mass, the polyester resin J was 0.5% by mass, the polyester resin A of the base layer (B) was 99.87% by mass, and the polyester resin J was 0.
- a biaxially stretched film was formed in the same manner as in Example 1 except that the content was changed to 13% by mass to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
- Table 3 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 9 As raw materials, the polyester resin A of the surface layer (A) was 99.6% by mass, the polyester resin M was 0.4% by mass, the polyester resin A of the base layer (B) was 99.87% by mass, and the polyester resin M was 0.
- a biaxially stretched film was formed in the same manner as in Example 1 except that the content was changed to 13% by mass to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
- Table 3 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 10 As raw materials, the polyester resin A of the surface layer (A) was 99.2% by mass, the polyester resin N was 0.8% by mass, the polyester resin A of the base layer (B) was 99.87% by mass, and the polyester resin N was 0.
- a biaxially stretched film was formed in the same manner as in Example 1 except that the content was changed to 13% by mass to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
- Table 3 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- the polyester resin A of the surface layer (A) was 99.5% by mass
- the polyester resin O was 0.5% by mass
- the polyester resin A of the base layer (B) was 99.87% by mass
- the polyester resin O was 0.
- a biaxially stretched film was formed in the same manner as in Example 1 except that the content was changed to 13% by mass to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
- Table 3 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- the polyester resin A of the surface layer (A) was 99.5% by mass
- the polyester resin P was 0.5% by mass
- the polyester resin A of the base layer (B) was 99.87% by mass
- the polyester resin P was 0.
- a biaxially stretched film was formed in the same manner as in Example 1 except that the content was changed to 13% by mass to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
- Table 3 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- Example 11 As raw materials, the surface layer (A) polyester resin A is 90.0% by mass, the polyester resin K is 10.0% by mass, the base layer (B) polyester resin A is 97.4% by mass, and the polyester resin K is 2.
- a biaxially stretched film was formed in the same manner as in Example 1 except that the content was changed to 6% by mass to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
- Table 3 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- a biaxially stretched film was formed in the same manner as in Implementation 6 except that the polyester resin of the surface layer (A) and the base layer (B) was changed to the polyester resin L, and a biaxially oriented polyester film having a thickness of 12 ⁇ m was formed.
- Got Table 3 shows the raw material composition and film forming conditions of the obtained film, the physical characteristics of the obtained film, and the evaluation results. The film was evaluated on the surface of layer A on the side in contact with the chill roll.
- the films of Examples 5 to 9 are static because the number of fine protrusions having a height of 3 nm or more, the number of fine protrusions having a height of less than 3 nm, and the arithmetic average height Sa are within the specified ranges.
- Comparative Example 4 Although the number of fine protrusions having a height of 3 nm or more was within the range, the friction band voltage was high and the static mark evaluation was poor because the number of fine protrusions having a height of less than 3 nm was small. It was. Moreover, since the arithmetic mean height Sa is too large, the external haze is large and the transparency is inferior.
- Comparative Example 5 Although the number of fine protrusions having a height of 3 nm or more was within the range, the friction band voltage was high and the static mark evaluation was poor because the number of fine protrusions having a height of less than 3 nm was small. It was.
- Example 11 since the content of the particles of the polyester resin composition containing particles is small, the proportion of the recycled PET bottle raw material used is slightly reduced, but the films and film rolls have the same good physical characteristics as in Examples 6 to 10. Met.
- the biaxially oriented polyester film of the present invention has excellent transparency, wrinkles are less likely to occur on the film roll when the film is wound on the film roll during film production or after fisslit, and the film is easily unwound from the film roll, so that the film is coated or vapor-deposited. It is easy to perform secondary processing such as. In addition, since there are few quality defects due to static electricity marks and static mark discharge marks, polyester resin that has excellent performance after secondary processing such as coating and vapor deposition, and is recycled from the market and society, including PET bottles, is used.
- biaxially oriented polyester film which is an environment-friendly polyester film, has few foreign substances, and has little variation in physical properties in the longitudinal direction even if it is a long film roll having a long winding length, and a method for producing the same. It has become possible. Therefore, it is useful in food packaging applications, especially applications for films having gas barrier properties, and is expected to greatly contribute to the industrial world.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
例えば、ガスバリア性を向上させる方法として、二軸配向ポリエステルフィルムにポリ塩化ビニリデンやポリエチレンビニルアルコール共重合体などのガスバリア性の良好な樹脂からなるフィルムを張り合わせる方法、これらの樹脂を溶解させた液をコートし、薄膜を積層する方法、あるいはアルミニウムなどの金属や酸化アルミニウムなどの金属酸化物を蒸着させ、薄膜をフィルム表面に形成させる方法がある。
しかしながら、良好なガスバリア性を有する、酸化珪素や酸化アルミニウム膜などの金属酸化物薄膜をフィルム表面に設けた蒸着ポリエステルフィルムを工業的に安定して得ることは容易ではなかった。
かかる技術によれば、ペットボトル再生原料を作る際に使用する洗浄液成分の残存が少なく熱安定性に優れ、異物も少なく、且つ溶融時の比抵抗が安定しており、フィルムの生産性、及び品位を損なうことがない二軸配向ポリエステルフィルムが得られるというものである。
1.ペットボトルをリサイクル使用したポリエステル樹脂と粒子を含むポリエステル樹脂組成物からなる二軸配向ポリエステルフィルムであって、少なくとも一方の面が下記要件(1)~(3)をすべて満たす二軸配向ポリエステルフィルム。
(1)面積4×10-12m2あたりの高さ3nm未満の微細突起数が250ケ以上600ケ以下である。
(2)面積4×10-12m2あたりの高さ3nm以上の微細突起数が300ケ以上600ケ以下である。
(3)算術平均高さSaが0.010μm以上0.025μm以下である。
がいずれも40%以下であることを特徴とする、二軸配向ポリエステルフィルムロール。
(バラつきは、最大値をXmax、最小値をXmin、平均値をXaveとしたときの、下記式[1]で表される
バラつき(%)=100x(Xmax-Xmin)/Xave・・・[1])
(バラつきは、算術平均高さSaの最大値をXmax、最小値をXmin、平均値をXaveとしたときの、下記式[2]で表される。
バラつき(%)=100x(Xmax-Xmin)/Xave・・・[2])
マスターロールをスリットし小分けにしたフィルムロールも同様である。
[ペットボトルをリサイクル使用したポリエステル樹脂]
本発明における二軸配向ポリエステルフィルムは下記のペットボトルを含む、市場や社会からリサイクルされたポリエステル樹脂を用いることが好ましい。ペットボトルを含む、市場や社会からリサイクルされたポリエステル樹脂を用いることで、フィルム中のリサイクル原料比率を上げることができ、環境配慮されたフィルムを得ることが可能となる。
アルカリ洗浄を行わないと、原料の樹脂中に異物として残存してしまうため、これらが混入して製膜時の破断のきっかけとなり生産性を低下させてしまうばかりか、フィルム中に異物として残り、フィルムの外観や、後に行われる印刷工程での印刷抜けの原因となりうる。
ぎ洗浄は数回繰り返して行っても良い。アルカリ洗浄工程において洗浄で用いるアルカリ金属水酸化物の水溶液成分がフレークに残存することにより、その後のペレット造粒工程における溶融押出工程やフィルム製膜時における溶融押出工程を経由することにより、最終的に得られるフィルムの物性に影響を与えることがある。
[ポリエステル樹脂組成物]
本発明における二軸配向ポリエステルフィルムは下記のポリエステル樹脂を主成分として含むポリエステル樹脂組成物からなる。
本発明の二軸配向ポリエステルフィルムを構成するポリエステル樹脂は、ジカルボン酸またはそのエステル形成性誘導体と、ジオールまたはそのエステル形成性誘導体から合成されるポリマーである。例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレン-2,6-ナフタレートが挙げられ、機械的特性および耐熱性、コストなどの観点からポリエチレンテレフタレートが好ましい。
ここでの主成分とはポリエステル樹脂組成物中の含有率が80重量%以上であることを意味し、90重量%以上であることが好ましく、95重量%以上がより好ましく、98重量%以上が最も好ましい。
(1)面積4×10-12m2あたりの高さ3nm未満の微細突起数が250ケ以上である。
(2)面積4×10-12m2あたりの高さ3nm以上の微細突起数が300ケ以上600ケ
以下である。
(3)算術平均高さSaが0.010μm以上0.025μm以下である。
有機粒子としては、例えば、アクリル系樹脂粒子、メラミン樹脂粒子、シリコーン樹脂粒子、架橋ポリスチレンからなる粒子を挙げることができる。中でもシリカ(酸化珪素)、炭酸カルシウム、又はアルミナ(酸化アルミニウム)からなる粒子、若しくはポリメタクリレート、ポリメチルアクリレート、又はその誘導体からなる粒子が好ましく、シリカ(酸化珪素)、又は炭酸カルシウムからなる粒子がより好ましく、シリカ(酸化珪素)からなる無機粒子が特に好ましい。
無機系微粒子の形状は特に限定されないが、球状に近いほど高さ3nm以上の微細突起数、算術平均高さSaをさほど変化させずに、高さ3nm未満の微細突起数を大きくすることができる。
粒子の重量平均粒径が0.8μm以上であると高さ3nm未満の微細突起数、算術平均高さSaをそれぞれ上記(1)、(3)の下限値以上としやすい。
粒子の重量平均粒径が1.8μm以下であると算術平均高さSaを上記(3)の上限値以下としやすく、高さ3nm未満の微細突起数を上記(1)の下限値以上とするのにも適している。
粒子の含有量の上限は好ましくは3000重量ppmであり、より好ましくは2500重量ppmであり、さらに好ましくは2200重量ppmであり、特に好ましくは1800重量ppmである。
マスターバッチ中の無機粒子の濃度は7000~400000ppmが好ましく、8000~350000ppmがより好ましく、9000~300000ppmが特に好ましい。マスターバッチ中の無機粒子の濃度が7000ppmより小さい場合は、無機粒子を含有するマスターバッチの添加比率が大きくなり、主原料となるペットボトルを含む、市場や社会からリサイクルされたポリエステル樹脂の割合が少なくなり、安価な樹脂や環境配慮などへの樹脂特性を効果的に得られなくなる。マスターバッチ中の無機粒子の濃度が400000ppmより大きいと、原料の偏析のために長手方向で原料比率の変動が大きくなるため、得られたフィルムの長手方向のバラつきが大きくなりやすい。
マスターペレット(マスターバッチ)の安息角は25度から40度であることが好ましく、30度から40度であることがより好ましい。安息角40度より大きいと、ペットボトルを含む、市場や社会からリサイクルされたポリエステル樹脂と混合した後に押出機に供給されるまでに偏析しやすくなり、得られたフィルムの長手方向のバラつきが大きくなりやすい。なお、前記マスターペレットの安息角度は、ペレットの形状やサイズを変更することにより調整できる。ペレットが球状に近いほど安息角は小さくなり、細長い形状とすれば大きくなる。また、ペレットのサイズが小さくなると安息角は小さくなる。
また、ベント付き混練押出し機を用いてエチレングリコールまたは水等に分散させた粒子のスラリーとポリエステル系樹脂原料とをブレンドする方法、または混練押出し機を用いて、乾燥させた粒子とポリエステル系樹脂原料とをブレンドする方法等によって行うのも好ましい。
このため本発明のポリエステルフィルム中には、イソフタル酸成分を含む材料が一定量含まれることとなり、フィルム中に特定量のイソフタル酸成分を含有することにより、本発明ではさらに、シーラントと接着した際の接着強度を向上させることが出来る。
フィルム中にイソフタル酸成分を含有することによりシーラントとの接着性が向上する理由は明らかではないが、イソフタル酸-エチレングリコールユニットはテレフタル酸-エチレングリコールユニットと比べて結晶化しにくいため、フィルム中に非晶成分が多く残存し、その結果、コロナ処理などのフィルムの表面処理によって改質されやすくなるばかりか、フィルムのごく表面が溶剤に対して溶解されやすくなり、シーラントと接着する際に用いられる接着剤との親和性が増すことが要因であるものと推定される。
。先に述べたようにペットボトルを含む、市場や社会からリサイクルされたポリエステル樹脂は、イソフタル酸成分を多く含むものがあるため、フィルム中のポリエステル樹脂を構成するイソフタル酸成分が0.02モル%未満であることは、リサイクル樹脂の比率の高いポリエステルフィルムの製造が結果として困難になり、あまり好ましくない。フィルム中に含まれるポリエステル樹脂を構成する全ジカルボン酸成分に占めるイソフタル酸成分の量の上限は好ましくは2モル%であり、より好ましくは1.5モル%であり、さらに好ましくは1.0モル%である。2.0モル%を超えると結晶性が低下するため、フィルムとしての力学強度が低下することがあり、あまり好ましくない。また、イソフタル酸成分の含有率を上記範囲とすることでラミネート強度、収縮率、厚みムラに優れたフィルムの作成が容易となり好ましい。
本発明の二軸配向ポリエステルフィルムは、例えば上記のペットボトルを含む、市場や社会からリサイクルされたポリエステル樹脂チップとポリエステル樹脂を主成分とするポリエステル樹脂組成物のチップとをホッパーに備えた押出機に供給及び混合し、押出機により溶融押し出しして未延伸シートを形成し、その未延伸シートを延伸することによって得ることができる。
下記に好適な例を述べるが、これらに制限されものではない。
溶融樹脂組成物の押し出しに際しては、Tダイ法、チューブラー法等、既存の任意の方法を採用することができる。
以下に詳細に説明する。長手方向とは、未延伸シートを走行させる方向を、幅方向とはそれと直角方向を意味する。
ここでいう製膜速度とは、延伸工程を経てマスターロールに巻き取られる際の二軸配向ポリエステルフィルムの走行速度(m/分)を意味する。
延伸時温度が(Tg+55)℃以下であり、さらに4.2倍以上である場合、高さ3nm未満の微細突起数を上記(1)の下限値以上としやすく、また長手方向と幅方向の分子配向のバランスがよく、長手方向と幅方向の物性差が小さく好ましい。また、得られる二軸延伸ポリエステルフィルムの平面性も良く好ましい。
一方、長手方向の延伸温度が(Tg+15)℃以上であり、さらに延伸倍率が4.7倍以下の場合、算術平均高さSaを上記(3)の上限値以下としやすい。熱弛緩工程におけるフィルムの走行方向とは逆方向に生じる引張応力(ボーイング現象)が大きくなり過ぎず好ましい。
幅方向の延伸時温度がTg+5℃以上であると、算術平均高さSaを上記(3)の上限値としやすく、また延伸時に破断が生じにくくなり、好ましい。
また延伸時温度がTg+40℃以下であると、高さ3nm未満の微細突起数を上記(1)の下限値以上としやすく、また、均一な幅方向の延伸がしやすくなり、幅方向の厚み斑が大きくなりにくいため、フィルムロール表面の巻硬度の幅方向のばらつきが大きくなりにくく好ましい。
より好ましくはTg+8℃以上Tg+37℃以下であり、更に好ましくはTg+11℃以上Tg+34℃以下である。
未延伸シートを長手方向に延伸して得られたフィルムの幅方向への延伸倍率は4.0倍以上6倍以下が好ましい。
幅方向延伸倍率が4.0倍以上であると、高さ3nm未満の微細突起数を上記(1)の下限値以上としやすく、また物質収支的に高い収率が得られやすい上に、力学強度が低下しないほか、幅方向の厚み斑が大きくなりにくく、フィルムロールの幅方向の巻硬さのばらつきが生じにくく好ましい。幅方向延伸倍率はが4.1倍以上がより好ましく、4.2倍以上がさらに好ましい。
また幅方向延伸倍率が6倍以下であると、算術平均高さSaを上記(3)の上限値以下としやすく、また延伸製膜時に破断しにくくなり好ましい。
熱固定温度が240℃以上の場合、高さ3nm未満の微細突起数を上記(1)の下限値以上としやすく、また長手方向および幅方向ともに熱収縮率が高くなりすぎず、蒸着加工時の熱寸法安定性が良くなるため好ましい。
一方、熱固定温度が250℃以下の場合、ボーイングが増加しにくく好ましい。
弛緩率が4%以上の場合、得られる二軸配向ポリエステルフィルムの幅方向の熱収縮率が高くなりすぎず、蒸着加工時の寸法安定性が良きなるため好ましい。
一方、弛緩率が8%以下の場合、フィルムの幅方向中央部のフィルムの走行方向とは逆方向に生じる引張応力(ボーイング現象)が大きくなり過ぎず、幅方向のフィルム厚み変動率が大きくならず好ましい。
これらを軽減させる方法としては、例えば、上下部のノズルから吹き出す熱風の風速を調整することで、フィルムが平行になるように保つことが挙げられる。
マスターロールの巻長は10000m以上100000m以下が好ましい。ロールの巻長が5000m以上であると、その後スリット工程、蒸着加工や印刷加工においてフィルム面積あたりのコストが低くなり好ましい。
また、マスターロールよりスリットしたフィルムロールの巻幅は400mm以上3000mm以下であることが好ましい。巻幅が400mm以上であると、印刷工程において頻繁にフィルムロールを交換する手間が少なくなり、コストの面で好ましい。また、巻幅は長い方が好ましいが、3000mm以下であるとロール幅が大きくなりすぎない他、ロール重量が重くなりすぎず、ハンドリング性が低下せず好ましい。
フィルムロールの巻長は2000m以上65000m以下であることが好ましい。巻長が2000m以上であると、印刷工程において頻繁にフィルムロールを交換する手間が少なくなり、コストの面で好ましい。また、巻長は長い方が好ましいが、65000m以下であるとロール径が大きくなりすぎない他、ロール重量が重くなりすぎず、ハンドリング性が低下せず好ましい。
本発明のペットボトルを含む、市場や社会からリサイクルされたポリエステル樹脂と粒子を含むポリエステル樹脂組成物からなる二軸配向ポリエステルフィルムの少なくとも一方の面は下記(1)~(3)をすべて満たすのが好ましい。それぞれについて詳細に説明する。
(1)面積4×10-12m2あたりの高さ3nm未満の微細突起数が250ケ以上600ケ以下である。
(2)面積4×10-12m2あたりの高さ3nm以上の微細突起数が300ケ以上600ケ以下である。
(3)算術平均高さSaが0.010μm以上0.025μm以下である。
二軸配向ポリエステルフィルムは電気絶縁性を有するためフィルム製造工程や加工工程で搬送ロールとの接触、剥離などにより部分的に帯電した部分であるスタティックマークや、蓄えられた静電気が放電すること等に起因するスタティックマーク放電痕が発生しやすいが、面積4×10-12m2あたりの高さ3nm未満の微細突起数が250ケ以上であるとスタティックマークやスタティックマーク放電痕が少なくなり、コート層を形成後にコート斑が生じにくかったり、形成した無機薄膜層のガスバリア性能が向上したり、二次加工後の性能が向上しやすい。
その理由は、面積4×10-12m2あたりの高さ3nm未満の微細突起数が250ケ以上であると、製造されたフィルムを搬送したり、それを巻取る工程において、フィルムと金属ロールが強い力で接触し、フィルム表面の高い突起が押し込まれた場合でもフィルム表面と金属ロールが接する面積は極めて小さくなるため、摩擦による帯電量が小さくなり、その結果、スタティックマークとスタティックマーク放電痕が少なくなると考えられる。さらに好ましくは300ヶ以上であり、より好ましくは400ヶ以上であり、特に好ましくは500ヶ以上である。この傾向はフィルム同士が接触して起こる摩擦の場合にもあてはまる。
高さ3nm未満の微細突起数はフィルムの滑り性をより向上させたり、ブロッキング性を低下させるものではなく、フィルム表面に形成した無機薄膜層のガスバリア性にも悪影響を与えにくいという特徴をもつ。
また、高さ3nm未満の微細突起数が600ケ以下の範囲であってもスタティックマークやスタティックマーク放電痕は十分少ない。
高さ3nm以上の微細突起数が300ケ以上であるとフィルム同士の動摩擦係数が小さくなりすぎず、二軸配向ポリエステルフィルムは電気絶縁性を有するためフィルム製造工程や加工工程で搬送ロールとの接触、剥離などにより部分的に帯電した部分であるスタティックマークや、蓄えられた静電気が放電すること等に起因するスタティックマーク放電痕をより発生しにくくできるため好ましい。さらに好ましくは400ヶ以上であり、より好ましくは500ヶ以上である。
高さ3nm以上の微細突起数が600ケ以下であれば、形成した無機薄膜層のガスバリア性も十分に得られる。
本発明の二軸配向ポリエステルフィルムの少なくとも一方の面の算術平均高さSaは、0.010以上0.025μm以下が好ましい。
算術平均高さSaが0.010μm以上であるとフィルム間及びフィルム表面に形成された突起と突起の間の凹部のフィルムロール内のフィルム同士の癒着(ブロッキング現象)が発生しにくく、フィルムの二次加工をスムーズに行えるため好ましい。さらに好ましくは0.013μm以上であり、より好ましくは0.015μm以上である。
算術平均高さSaが0.025μm以下であると、二軸配向ポリエステルフィルムのヘイズ、特に外部ヘイズが低下し、透明性に優れるため好ましい。さらに好ましくは0.023μm以下であり、より好ましくは0.020μm以下であり、特に好ましくは0.017μm以下である。
もう一方のフィルム表面の算術平均高さSaも同様の範囲が好ましい。
本発明の二軸配向ポリエステルフィルムの一方の面とその反対面の間の動摩擦係数は0.20以上0.60以下であることが好ましい。
0.20以上であるとフィルム同士が滑りすぎず、フィルム製造時あるいはスリット時にワインダー装置によりフィルムロールを巻き取る時に、フィルムロールにシワが生じにくく、二次加工性が低下しにくい。さらに好ましくは0.30以上であり、最も好ましくは0.45以上である。
また、0.60以下であるとフィルム同士が滑るので、フィルム製造時あるいはスリット時にワインダー装置によりフィルムロールを巻き取る時に、フィルムロールに巻ズレが生じにくく、二次加工性が低下しにくい。さらに好ましくは0.50以下であり、最も好ましくは0.44以下である。
本発明の二軸配向ポリエステルフィルムの一方の面とその反対面の間の静止摩擦係数は0.20以上0.60以下であることが好ましい。
0.20以上であるとフィルム同士が滑りすぎず、フィルム製造時あるいはスリット時にワインダー装置によりフィルムロールを巻き取る時に、フィルムロールにシワが生じにくく、二次加工性が低下しにくい。さらに好ましくは0.30以上であり、最も好ましくは0.45以上である。
また、0.60以下であると、フィルム同士が滑るので、フィルム製造時あるいはスリット時にワインダー装置によりフィルムロールを巻き取る時に、フィルムロールに巻ズレが生じにくく、二次加工性が低下しにくい。さらに好ましくは0.50以下であり、最も好ましくは0.44以下である。
本発明の二軸配向ポリエステルフィルムの上記(1)~(3)すべてを満たす面の最大高さSzが0.5μm以上2.0μm以下が好ましい。
最大高さSzが0.5μm以上であるとマスターロールを巻き取る際、あるいはマスターロールをスリットし、巻芯に二軸配向ポリエステルフィルムを巻き取る時に互いに接するフィルムの間に巻き込む空気の量が多くなりにくく、フィルムの伸びや変形が少ない。また、フィルムロール中の空気が抜けた後のロール中のフィルムが弛みにくい。ポリエステル樹脂に含まれる粒子の重量平均粒径が0.8μm以上であると最大高さSzを0.5μm以上としやすい。
最大高さSzが2.0μm以下であると二軸配向ポリエステルフィルムの表面上における、二次加工後のコート膜や無機薄膜層の抜けや欠陥などが少なくなる。長手方向の延伸時温度がTg+40℃以下であるか、延伸倍率が4.2倍以上であると、最大高さSzを2.0μm以下としやすい。
もう一方のフィルム表面の最大高さSzも同様である。
本発明の二軸配向ポリエステルフィルムの外部ヘイズが1.8%以下であることが好ましい。外部ヘイズが1.8%以下であるとフィルム表面の平滑性を損ないにくく、フィルム製造工程では搬送ロールとの接触、剥離などによる帯電が発生しにくく、スタチックマークやスタチックマーク放電痕などの帯電による品質不良が発生しにくいため好ましい。さらに好ましくは1.6%以下であり、より好ましくは1.4%下であり、特に好ましくは1.2%以下であり、最も好ましくは1.0%以下である。
本発明の二軸配向ポリエステルフィルムの内部ヘイズが2.5%以下であることが好ましい。内部ヘイズが2.5%以下であると透明性が低下しにくく好ましい。さらに好ましくは2.0%以下であり、より好ましくは1.8%以下であり、特に好ましくは1.6%以下である。
本発明の二軸配向ポリエステルフィルムの一方の面には、低温プラズマ処理やコロナ放電処理等の表面処理による表面改質が行われてもよい。
このとき、本発明の二軸配向ポリエステルフィルムの上記(1)~(3)すべてを満たす面の濡れ張力は50mN/m以上が好ましく、52mN/m以上がより好ましい。
上限は特に無いが、55mN/m以下の範囲であっても、二次加工のコートや蒸着薄膜を行った後の性能には十分である。
本発明の二軸配向ポリエステルフィルムのフィルム厚みは、5~40μmが好ましい。5μm以上であるとフィルムとしての強度やコシ感が低下せず、ワインダー装置により巻き取る際、フィルムロールにシワが入りにくく好ましい。一方、フィルム厚みは40μm以下の範囲であれば強度やコシ感は十分に得られ、コストの観点から薄肉化することが好ましい。フィルムの厚みは8~30μmがより好ましく、9μm~20μmが特に好ましい。
本発明の二軸配向ポリエステルフィルムは、フィルム1m2当たり1mm以上の異物が1個未満であることがフィルム品位の観点から好ましく、ポリエステル再生原料を用いながらも品位のよいフィルムであると言える。
本発明の二軸配向ポリエステルフィルムの下記(1)~(3)すべてを満たす少なくとも一方の面に無機薄膜層やアルミ箔のような金属箔などのガスバリア層を設けることができる。
(1)面積4×10-12m2あたりの高さ3nm未満の微細突起数が250ケ以上600ケ以下である。
(2)面積4×10-12m2あたりの高さ3nm以上の微細突起数が300ケ以上600ケ以下である。
(3)算術平均高さSaが0.01μm以上0.025μm以下である。
ウレタン樹脂の酸価は10~60mgKOH/gの範囲内であるのが好ましい。より好しくは15~55mgKOH/gの範囲内、さらに好ましくは20~50mgKOH/gの範囲内である。ウレタン樹脂の酸価が前記範囲であると、水分散液とした際に液安定性が向上し、また保護層は高極性の無機薄膜上に均一に堆積することができるため、コート外観が良好となる。
前記のウレタン樹脂は、ガスバリア性向上の面から、芳香族又は芳香脂肪族ジイソシアネート成分を主な構成成分として含有するウレタン樹脂を用いることがより好ましい。
その中でも、メタキシリレンジイソシアネート成分を含有することが特に好ましい。上記樹脂を用いることで、芳香環同士のスタッキング効果によりウレタン結合の凝集力を一層高めることができ、結果として良好なガスバリア性が得られる。
本発明においては、ウレタン樹脂中の芳香族又は芳香脂肪族ジイソシアネートの割合を、ポリイソシアネート成分(F)100モル%中、50モル%以上(50~100モル%)の範囲とすることが好ましい。芳香族又は芳香脂肪族ジイソシアネートの合計量の割合は、60~100モル%が好ましく、より好ましくは70~100モル%、さらに好ましくは80~100モル%である。このような樹脂として、三井化学社から市販されている「タケラック(登録商標)WPB」シリーズは好適に用いることが出来る。芳香族又は芳香脂肪族ジイソシアネートの合計量の割合が50モル%未満であると、良好なガスバリア性が得られない可能性がある。
本発明の二軸配向ポリエステルフィルムを基材フィルムとして他素材の層を積層し、積層体としても良い。その方法として、二軸配向ポリエステルフィルムを作製後に貼り合わせるか、製膜中に貼り合わせることができる。
ヒートシール性樹脂層の形成は、通常押出しラミネート法あるいはドライラミネート法によりなされる。
ヒートシール性樹脂層を形成する熱可塑性重合体としては、シーラント接着性が充分に発現できるものであればよく、HDPE、LDPE、LLDPEなどのポリエチレン樹脂類、ポリプロピレン樹脂。エチレン-酢酸ビニル共重合体、エチレン-α-オレフィンランダム共重合体、アイオノマー樹脂等を使用できる。
シーラント層の厚さは、10~100μmが好ましく、20~60μmがより好ましい。
[ガラス転移転(Tg)]
示差走査熱量分析装置(エスアイアイ・ナノテクノロジー株式会社製DSC6220型)を用いて、樹脂試料5mgを窒素雰囲気下にて280℃まで溶融し、5分間保持した後、液体窒素にて急冷し、室温より昇温速度20℃/分の条件にて測定した。
ポリエステル樹脂0.2gをフェノール/1,1,2,2-テトラクロルエタン(60/40(重量比))の混合溶媒50ml中に溶解し、30℃でオストワルド粘度計を用いて測定した。単位はdl/gである。
クロロホルムD(ユーリソップ社製)とトリフルオロ酢酸D1(ユーリソップ社製)を10:1(体積比)で混合した溶媒に溶解させて、試料溶液を調製し、NMR(「GEMINI-200」;Varian社製)を用いて、温度23℃、積算回数64回の測定条件で試料溶液のプロトンのNMRを測定した。NMR測定では、所定のプロトンのピーク強度を算出して、酸成分100モル%中のテレフタル酸成分およびイソフタル酸成分の含有率(モル%)を算出した。
直径50mm、高さ10mmの金属円筒の端面中央部に、ポリエチレン製漏斗(口径10mm)を用いてペレットを落下させた。金属円筒の平面とペレットの綾線の作る角度を分度器を用いて測定したものを安息角とした。
[フィルムの厚み]
JIS K7130-1999 A法に準拠し、ダイアルゲージを用いて測定した。
得られたフィルムから縦方向5cm×横方向5cmの面積に切り出し、日本電色工業株式会社製の濁度計(NDH5000)を用いて、25℃で可視光線の全波長に対して、JIS-K7136に準拠して、全ヘイズを測定した。
同様にして、石英ガラス板2枚の間にツェーデル油のみを挟んだ構成の積層体のヘイズ(以下、「ヘイズH1」)、及び、ツェーデル油で表面を均一に濡らしたポリエステルフィルムを石英ガラス板2枚の間に挟んだ構成の積層体のヘイズ(以下、「ヘイズH2」)を測定した。
次いで、下記式に従って内部ヘイズを求める。
内部ヘイズ=ヘイズ(H2)-ヘイズ(H1)・・・式1
外部ヘイズは、全ヘイズから内部ヘイズを差し引くことによって求められる値とする。
なお、全ヘイズ、内部ヘイズ、及び外部ヘイズは、いずれも可視光線の全波長に対する
ヘイズを指す。
得られたフィルムから縦方向10cm×横方向10cmの面積に切り出し、Zygo社製の白色レーザー干渉計(NEW VIEW8300)を使用した。
干渉計に20倍レンズを取り付けて、走査を行い、算術平均高さ(μm)と最大高さ(μm)を測定した。測定は、一方の表面のMD方向に0.82μm、 幅方向に0.82μmの範囲で行い、未溶融物や埃等の異物を除く表面を対象とした。
測定箇所は10cm×10cmのサンプルの任意の箇所10点で測定し、その平均値をそれぞれ算術平均高さSa、最大高さSzとした。
算術平均高さSaのバラつき(%)は、得られたポリエステルフィルムロール(幅2080mm、巻き長63,000m)について、長手方向にフィルムロールの表層から巻き芯まで1000m毎にサンプリングした。サンプリングした各フィルムについて、上記の条件にて測定を行った。得られた算術平均高さSaの最大値をXmax(N)、最小値をXmin(N)、平均値をXaveとし、下記式[1]で表される長手方向のバラつきを求めた。
得られたフィルムから長手方向400mm×幅方向100mmの面積に切り出し、試料フィルムを作製した。これを23℃、65%RHの雰囲気下で12時間エージングし、試験テーブル用として縦方向300mm×横方向100mmの試験片、滑り片用に縦長手方向100mm×幅方向100mmの試験片に分けた。
試験テーブル用試験片を試験テーブルにセットし、滑り片用試験片は、金属製の荷重が1.5kgの滑り片の底面(面積の大きさが39.7mm2、正方形)に、それぞれがキャスティングドラムに接した面が対面するように、両面テープで貼りつけた。
試験片の滑り速度を200mm/分、23℃、65%RH条件下で、その他はJIS K-7125に準拠し、動摩擦係数と静止摩擦係数とをそれぞれ測定し、3回の測定の平均を用いた。
得られたフィルムから長手方向10mm×幅方向10mmの面積に切り出し、 島津製作所社製の走査型プローブ顕微鏡(SPM-9700)を用い、下記の観察条件にて測定を行い、測定面の画像を取り込んだ。
得られた画像(高さトレース)について、下記の条件にて画像処理を行った。
SPM-9700シリーズの粒子解析ソフトウェアを用いて、下記の粒子解析条件で抽出する粒子のしきい値を3nmとして3nm以上の粒子数(突起数)および3nm未満の粒子数(突起数)を、面積4×10-12m2(2μm×2μm角)内でカウントした。なお、3nm未満の粒子数(突起数)は0.01nm以上のものをカウントした。
測定は場所を変えて5回行い、カウント数の最も多いものと少ないものを除いた3回の平均値を計算し、微細突起数とした。
(観察条件)
・カンチレバー:Si(シリコン)製
・走査モード:位相モード
・走査速度:2Hz
・走査範囲:2μm
・画素数:256×256
・オフセットX:0μm
・オフセットY:0μm
・走査角度:0°
・オペレーティングポイント:1.0V
・Pゲイン:0.001
・Iゲイン:1500
・オフセットZ:0μm
・Zレンジ:×2
・走査モード:力一定
(画像処理)
・傾き補正:X方向の平均値(X)、Y方向の平均値(Y)、ラインフィット(L)
・ノイズラインの除去:モード(範囲指定)、自動選択
(粒子解析)
・ターゲットの形状:粒子
・XYしきい値:30%
・無視するピクセル数:5
微細突起数のバラつき(%)は、得られたポリエステルフィルムロール(幅2080mm、巻き長63,000m)について、長手方向にフィルムロールの表層から巻き芯まで1000m毎にサンプリングした。サンプリングした各フィルムについて、上記の条件にて測定を行った。得られた微細突起数の最大値をXmax(N)、最小値をXmin(N)、平均値をXaveとし、下記式[1]で表される長手方向のバラつきを求めた。
得られたフィルムから長手方向80mm×幅方向50mmの面積に切り出し、試料フィルムを作製した。これを23℃、50%RHの雰囲気下で16時間エージングした。大栄科学精器製作所社製の摩擦帯電圧測定機(RST-300a)を用いて、摩擦帯電圧の測定を行った。
試料サンプルを回転装置に固定し、ドラム回転速度400rpmで60秒間、金属板と摩擦し発生した静電気を測定し、最大値を摩擦帯電圧とした。測定した摩擦帯電圧により以下の判定基準で評価した。
◎:摩擦帯電圧200V未満
○:摩擦帯電圧200V以上、500V未満
△:摩擦帯電圧500V以上、1000V未満
×:摩擦帯電圧1000V以上
得られた幅方向に550mm、長手方向に500mで巻き取った2軸配向ポリエステル
フィルムローを西村製作所社製のスリッター(FN105E型)を用いて、速度15m/min、巻取張力100N/m(ユニット張力設定)で巻き返しを実施した。
このときの静電除去は、スリッターについている静電除去装置をONとし、巻出ロールと傾き調整ローラの間に除電ブラシ(アキレス社製「NSP-2S」)をフィルムの上下面側に設置して静電除去を行った。
得られたフィルムロール最表面のフィルム端部からフィルムを巻き出して、フィルム端部から2m除去した後にフィルムを幅方向の中央部10cm、長手方向に10cmの長さでサンプリングし、春日電機社製の帯電分布判定トナーを使用し、フィルム表面の帯電状態を可視化した。以下の判定基準でフィルムロールの帯電性を評価した。
◎:スタティックマークやスタティックマーク放電痕やトナー付着がない。
〇:スタティックマークやスタティックマーク放電痕が観察されないが、トナーが付着している。
×:スタティックマークやスタティックマーク放電痕が観察される。
[フィルム中の異物(欠点数)]
得られたフィルムを長手方向250mm×幅方向250mmの面積に切り出し、試料フィルムを作製した。これをスケール付き顕微鏡で、フィルム面に対して垂直方向から観察した時の1mm以上の直径を有する異物の数を長手方向250mm×幅方向250mm(0.0625m2)の範囲すべてについて計測する。これを試料フィルム20枚に対して行い、得られた異物の総数を総観察面積(1.25m2)で除し、単位面積1m2当たり異物の個数(個/m2)に換算し、小数点第1位の桁を四捨五入した。測定したフィルム中の異物の数により以下の判定基準で評価した。
〇:フィルム中の異物の数(欠点数)1.0個/m2未満
×:フィルム中の異物の数(欠点数)1.0個/m2以上
得られたフィルムから長手方向400mm×幅方向300mmの面積に切り出し、温度23℃、相対湿度50%で24時間エージング後、温度23℃、相対湿度50%の試験室雰囲気とした以外は、JIS-K-7100に準拠しコロナ処理面を下記手順で測定した。
試験片をハンドコータの基板の上に置き、試験片の上に試験用混合液を数滴滴下して、直ちにワイヤバーを引いて広げる。綿棒又はブラシを使用して試験用混合液を広げる場合は、液体は少なくとも6cm2以上の面積に速やかに広げる。液体の量は、たまりを作らないで、薄層を形成する程度にする。
濡れ張力の判定は,試験用混合液の液膜を明るいところで観察し、3秒後の液膜の状態で行う。液膜破れを生じないで、3秒以上、塗布されたときの状態を保っているのは、ぬれていることになる。
濡れが3秒以上保つ場合は、さらに、次に表面張力の高い混合液に進む。
また逆に、3秒以下で液膜が破れる場合は、次の表面張力の低い混合液に進む。この操作を繰り返し、試験片の表面を正確に、3秒間で濡らすことができる混合液を選ぶ。
各々の試験には,新しい綿棒を使用する。ブラシ又はワイヤバーは,残留する液体が蒸発によって組成及び表面張力を変化させるので、使用ごとにメタノールで洗浄し、乾燥させる。
コロナ処理面の表面を3秒間でぬらすことができる混合液を選ぶ操作を少なくとも3回行う。このようにして選ばれた混合液の表面張力をフィルムの濡れ張力として報告する。
ポリエステルフィルム上にウレタン系2液効果型接着剤(三井化学社製「タケラック(登録商標)A525S」と「タケネート(登録商標)A50」を13.5:1(重量比)の割合で配合)を用いてドライラミネート法により、ヒートシール性樹脂層として厚さ70μmの無延伸ポリプロピレンフィルム(東洋紡株式会社製「P1147」)を張り合わせ、40℃にて4日間エージングを施すことにより、ラミネート積層体を得た。なお、ウレタン系2液硬化型接着剤で形成される接着剤層の乾燥後の厚みはいずれも約4μmであった。
前述のラミネート積層体に対して、幅15mm、長さ200mmに切り出して試験片とし、温度23℃、相対湿度65%の条件下で、テンシロン万能材料試験機(東洋ボールドウイン社製「テンシロンUMT-II-500型」)を用いてラミネート強度を測定した。
ラミネート強度は、引張速度を200mm/分とし、積層フィルムとヒートシール性樹脂層との間を、剥離角度180度で剥離させたときの強度とした。
(ポリエステル樹脂A)
後述する二軸延伸ポリエステルフィルムの作製において使用するペットボトルより再生されたPET樹脂として、以下の方法を用いて合成したものを用いた。
飲料用ペットボトルから残りの飲料などの異物を洗い流した後、粉砕してフレークを得た。得られたフレークをフレーク濃度10重量%、85℃、30分の条件で3.5重量%の水酸化ナトリウム溶液で攪拌下で洗浄を行った。アルカリ洗浄後、フレークを取り出し、フレーク濃度10重量%、25℃、20分の条件で蒸留水を用いて攪拌下で洗浄を行った。この水洗を蒸留水を交換してさらに2回繰り返し実施した。水洗後、フレークを乾燥した後、押出機で溶融し、順次目開きサイズの細かなものにフィルターを変えて2回更に細かな異物を濾別し、3回目に50μmの最も小さな目開きサイズのフィルターで濾別して、固有粘度0.69dl/g、イソフタル酸含有率2モル%、安息角46度のポリエステル樹脂Aを得た。
(ポリエステル樹脂B)
前記ポリエステル樹脂Aの製造工程において、アルカリ洗浄を行わなかった以外は、上記ポリエステル樹脂Aと同様にして、固有粘度0.69dl/g、イソフタル酸含有率2モル%、安息角46度のポリエステル樹脂Bを得た。
(ポリエステル樹脂C)
後述する二軸配向ポリエステルフィルムの作製において使用する化石燃料由来PET樹脂として、テレフタル酸//エチレングリコール=100//100(モル%)(東洋紡社製、固有粘度0.62dl/g、安息角45度)を用いた。
(ポリエステル樹脂D)
エステル化反応缶を昇温して200℃に到達した時点で、テレフタル酸[86.4質量部]及びエチレングリコール[64.4質量部]からなるスラリーを仕込み、撹拌しながら、触媒として三酸化アンチモン[0.017質量部]及びトリエチルアミン[0.16質量部]を添加した。次いで加熱昇温を行い、ゲージ圧0.34MPa、240℃の条件で加圧エステル化反応を行った。その後、エステル化反応缶内を常圧に戻し、酢酸マグネシウム4水塩[0.071質量部]、次いでリン酸トリメチル[0.014質量部]を添加した。さらに、15分かけて260℃に昇温した後、リン酸トリメチル[0.012質量部]、次いで酢酸ナトリウム[0.0036質量部]を添加した後、15分後に、高圧分散機で分散処理を行い、さらに平均粒子径1.3μmの不定形シリカ粒子のエチレングリコールスラリーを粒子含有量を基準として3.0重量部添加した。このシリカ粒子は、エチレングリコールスラリーを予め調製し、これを遠心分離処理して粗粒部を35%カットし、その後、目開き5μmの金属フィルターでろ過処理を行って得られた粒子である。15分後に、得られたエステル化反応生成物を重縮合反応缶に移送し、280℃で減圧下重縮合反応を行い、極限粘度0.60dl/g、安息角37度のポリエステル樹脂Dを得た。
(ポリエステル樹脂E~P)
シリカ粒子の形状及び平均粒子径と含有量を変更した以外はポリエステル樹脂Dと同様の方法でポリエステル樹脂E~Pを得た。
TPA:テレフタル酸
EG:エチレングリコール
3台の押出し機を用いて3層構成のフィルムを製膜した。基層(B)はポリエステル樹脂Aを98.7質量%、ポリエステル樹脂Dを1.3質量%、表面層(A)はポリエステル樹脂Aを93.3質量%、ポリエステル樹脂Dを6.7質量%とした。ここでポリエステル樹脂Dは、押出し機に入る前に他原料と混合するように図4に示すようなインナーパイプを用いて入れた。それぞれの原料樹脂を乾燥後、第1、第3の押出機より表面層(A)形成混合樹脂を285℃の樹脂温度で溶融押出しし、第2の押出機により基層(B)形成混合樹脂を285℃の樹脂温度にて溶融し、キャススティングドラムに接触する側から表面層(A)/基層(B)/表面層(A)の順番に、Tダイ内にて厚み比が1/10/1(μm)になるように合流積層し、T字の口金から吐出させ、表面温度が30℃のキャスティングドラムにて冷却固化させ、未延伸のポリエチレンテレフタレートシートを得た。
その際、直径0.15mmのワイヤー状電極を使用して静電印加し、冷却ドラムに密着させて3層未延伸フィルムを得た。
得られた未延伸フィルムを115℃に加熱し、一段目を1.24倍、二段目を1.4倍、3段目を2.6倍とした三段延伸にて、全延伸倍率4.5倍で長手方向に延伸した。
引き続き、温度140℃、延伸倍率4.3倍にて幅方向に延伸し、245℃で熱固定し、幅方向に5%熱弛緩処理を行い、チルロールに接触した側のA層表面に40W・min/m2の条件でコロナ処理を行い、ワインダーでロール状に巻取ることで、厚み12μmの二軸配向ポリエステルフィルムのマスターロール(巻長26000m、幅8000mm)を作製した。
得られたマスターロールから二軸配向ポリエステルフィルムを巻出し、直径6インチ(152.2mm)の巻芯に、2200mm幅でスリットしながら、コンタクトロールでフィルムロールに面圧と、2軸ターレットワインダーでフィルムに張力をかけながら、フィルムロールを巻き取った。
得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表2に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを95.0質量%、ポリエステル樹脂Dを5.0質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表2に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを96.0質量%、ポリエステル樹脂Eを4.0質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表2に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを92.0質量%、ポリエステル樹脂Fを8.0質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表2に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂をポリエステル樹脂Cに変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表2に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを95.0質量%、ポリエステル樹脂Gを5.0質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表2に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを95.0質量%、ポリエステル樹脂Hを5.0質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表2に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂をポリエステル樹脂Bに変更した以外は、比較例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表2に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
実施例1と同じように、3台の押出し機を用いて3層構成のフィルムを製膜した。基層(B)はポリエステル樹脂Aを98.7質量%、ポリエステル樹脂Dを1.3質量%、表面層(A)はポリエステル樹脂Aを93.3質量%、ポリエステル樹脂Dを6.7質量%とした。しかし、ポリエステル樹脂A、ポリエステル樹脂Dは全て混合された状態で押出し機に入れた。つまり、ポリエステル樹脂Dはインナーパイプを用いずに、ホッパー上部で混合した状態で押出し機に入った。それぞれの原料樹脂を乾燥後、第1、第3の押出機より表面層(A)形成混合樹脂を285℃の樹脂温度で溶融押出しし、第2の押出機により基層(B)形成混合樹脂を285℃の樹脂温度にて溶融し、キャススティングドラムに接触する側から表面層(A)/基層(B)/表面層(A)の順番に、Tダイ内にて厚み比が1/10/1(μm)になるように合流積層し、T字の口金から吐出させ、表面温度が30℃のキャスティングドラムにて冷却固化させ、未延伸のポリエチレンテレフタレートシートを得た。その際、直径0.15mmのワイヤー状電極を使用して静電印加し、冷却ドラムに密着させて3層未延伸フィルムを得た。
得られた未延伸フィルムを115℃に加熱し、一段目を1.24倍、二段目を1.4倍、3段目を2.6倍とした三段延伸にて、全延伸倍率4.5倍で長手方向に延伸した。
引き続き、温度140℃、延伸倍率4.3倍にて幅方向に延伸し、245℃で熱固定し、幅方向に5%熱弛緩処理を行い、チルロールに接触した側のA層表面に40W・min/m2の条件でコロナ処理を行い、ワインダーでロール状に巻取ることで、厚み12μmの二軸配向ポリエステルフィルムのマスターロール(巻長26000m、幅8000mm)を作製した。
得られたマスターロールから二軸配向ポリエステルフィルムを巻出し、直径6インチ(152.2mm)の巻芯に、2200mm幅でスリットしながら、コンタクトロールでフィルムロールに面圧と、2軸ターレットワインダーでフィルムに張力をかけながら、フィルムロールを巻き取った。
得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表2に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを98.0質量%、ポリエステル樹脂Iを2.0質量%、基層(B)のポリエステル樹脂Aを99.6質量%、ポリエステル樹脂Iを0.4質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表3に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを99.33質量%、ポリエステル樹脂Jを0.67質量%、基層(B)のポリエステル樹脂Aを99.87質量%、ポリエステル樹脂Jを0.13質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表3に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを99.5質量%、ポリエステル樹脂Jを0.5質量%、基層(B)のポリエステル樹脂Aを99.87質量%、ポリエステル樹脂Jを0.13質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表3に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを99.6質量%、ポリエステル樹脂Mを0.4質量%、基層(B)のポリエステル樹脂Aを99.87質量%、ポリエステル樹脂Mを0.13質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表3に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを99.2質量%、ポリエステル樹脂Nを0.8質量%、基層(B)のポリエステル樹脂Aを99.87質量%、ポリエステル樹脂Nを0.13質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表3に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを99.5質量%、ポリエステル樹脂Oを0.5質量%、基層(B)のポリエステル樹脂Aを99.87質量%、ポリエステル樹脂Oを0.13質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表3に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを99.5質量%、ポリエステル樹脂Pを0.5質量%、基層(B)のポリエステル樹脂Aを99.87質量%、ポリエステル樹脂Pを0.13質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表3に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)のポリエステル樹脂Aを90.0質量%、ポリエステル樹脂Kを10.0質量%、基層(B)のポリエステル樹脂Aを97.4質量%、ポリエステル樹脂Kを2.6質量%に変更した以外は、実施例1と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表3に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
原料として、表面層(A)および基層(B)のポリエステル樹脂をポリエステル樹脂Lに変更した以外は、実施6と同様に二軸延伸フィルムを製膜して、厚さ12μmの二軸配向ポリエステルフィルムを得た。得られたフィルムの原料組成および製膜条件、得られたフィルムの物性及び評価結果を表3に示す。フィルムの評価はチルロールに接触した側のA層表面で行った。
また、スタティックマークやスタティックマーク放電痕などの帯電による品質不良が少ないため、コートや蒸着などの二次加工後の性能に優れ、且つペットボトルを含む、市場や社会からリサイクルされたポリエステル樹脂を用いることにより環境配慮されたポリエステルフィルムであり、異物が少なく、巻き長の長い長尺のフィルムロールであっても長手方向の物性のバラつきが少ない二軸配向ポリエステルフィルム及びその製造方法を提供することが可能となった。
したがって、食品包装用途、特にガスバリア性を有するフィルムへの用途において有用であり、産業界に大きく寄与することが期待される。
Claims (12)
- ペットボトルをリサイクル使用したポリエステル樹脂と粒子を含むポリエステル樹脂組成物からなる二軸配向ポリエステルフィルムであって、少なくとも一方の面が下記要件(1)~(3)をすべて満たす二軸配向ポリエステルフィルム。
(1)面積4×10-12m2あたりの高さ3nm未満の微細突起数が250ケ以上600ケ以下である。
(2)面積4×10-12m2あたりの高さ3nm以上の微細突起数が300ケ以上600ケ以下である。
(3)算術平均高さSaが0.010μm以上0.025μm以下である。 - 前記二軸配向ポリエステルフィルムを構成するポリエステル樹脂組成物中の全ジカルボン酸成分100モル%に対するイソフタル酸成分の含有率が0.02モル%以上2.0モル%以下であることを特徴とする、前記請求項1に記載の二軸配向ポリエステルフィルム。
- 前記二軸配向ポリエステルフィルムを構成するポリエステル樹脂組成物中のペットボトルをリサイクル使用したポリエステル樹脂の含有率が50質量%以上、100質量%以下であることを特徴とする、請求項1又は2に記載の二軸配向ポリエステルフィルム。
- フィルム1m2当たり1mm以上の欠点数が1.0個未満であることを特徴とする、請求項1~3のいずれかに記載の二軸配向ポリエステルフィルム。
- 前記ペットボトルをリサイクル使用したポリエステル樹脂が少なくとも1度のアルカリ洗浄が施されてなることを特徴とする請求項1~4のいずれかに記載の二軸配向ポリエステルフィルム。
- 前記二軸配向ポリエステルフィルムの前記要件(1)~(3)をすべて満たす面とその
対面の動摩擦係数が0.2以上0.60以下である請求項1~5のいずれかに記載の二軸配向ポリエステルフィルム。 - 前記二軸配向ポリエステルフィルムの前記要件(1)~(3)をすべて満たす面の濡れ張力が50mN/m以上である請求項1~6のいずれかに記載の二軸配向ポリエステルフィルム。
- 前記二軸配向ポリエステルフィルムの外部ヘイズが1.8%以下であり、内部ヘイズが2%以下である請求項1~7のいずれかに記載の二軸配向ポリエステルフィルム。
- 請求項1~8のいずれかに記載の二軸配向ポリエステルフィルムをロール状に巻き取ってなるフィルムロールであって、フィルム長手方向にフィルムロールの表層から巻き芯まで1000m毎にサンプリングした時の面積4×10-12m2あたりの高さ3nm未満の微細突起数、及び面積4×10-12m2あたりの高さ3nm以上の微細突起数のバラつきがいずれも40%以下であることを特徴とする、二軸配向ポリエステルフィルムロール。
(バラつきは、微細突起数の最大値をXmax、最小値をXmin、平均値をXaveとしたときの、下記式[1]で表される。
バラつき(%)=100x(Xmax-Xmin)/Xave・・・[1]) - フィルム長手方向にフィルムロールの表層から巻き芯まで1000m毎にサンプリングした時の算術平均高さSaのバラつきが40%以下であることを特徴とする、請求項9に記載の二軸配向ポリエステルフィルムロール。
(バラつきは、算術平均高さSaの最大値をXmax、最小値をXmin、平均値をXaveとしたときの、下記式[2]で表される。
バラつき(%)=100x(Xmax-Xmin)/Xave・・・[2]) - 二軸配向ポリエステルフィルムの製造方法であって、ポリエステル原料樹脂の溶融押出し工程、及び二軸延伸工程を含んでなり、前記ポリエステル原料樹脂の溶融押出し工程において、ホッパーに上方から前記ペットボトルをリサイクル使用したポリエステル樹脂の原料樹脂チップを供給すると共に、ホッパー内であって押出機直上に出口を有する配管を通じて、安息角が30度以上40度以下である前記粒子を含むポリエステル樹脂組成物の原料樹脂チップを供給して、両チップを混合し、溶融押し出しする工程を有することを特徴とする請求項1~8のいずれかに記載の二軸配向ポリエステルフィルムの製造方法。
- 二軸配向ポリエステルフィルムロールの製造方法であって、ポリエステル原料樹脂の溶融押出し工程、二軸延伸工程、及び二軸延伸後のフィルムをロール状に巻き取る工程を含んでなり、前記ポリエステル原料樹脂の溶融押出し工程において、ホッパーに上方から前記ペットボトルをリサイクル使用したポリエステル樹脂の原料樹脂チップを供給すると共に、ホッパー内であって押出機直上に出口を有する配管を通じて、安息角が30度以上40度以下である前記粒子を含むポリエステル樹脂組成物の原料樹脂チップを供給して、両チップを混合し、溶融押し出しする工程を有することを特徴とする請求項9又は10のいずれかに記載の二軸配向ポリエステルフィルムロールの製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202080085416.1A CN114829466B (zh) | 2019-12-13 | 2020-12-08 | 双轴取向聚酯薄膜和其制造方法 |
EP20898153.0A EP4074489A4 (en) | 2019-12-13 | 2020-12-08 | BIAXIALLY STRETCHED POLYESTER FILM AND PRODUCTION METHOD THEREOF |
JP2021563980A JP7276508B2 (ja) | 2019-12-13 | 2020-12-08 | 二軸配向ポリエステルフィルム及びその製造方法 |
US17/784,393 US20230001619A1 (en) | 2019-12-13 | 2020-12-08 | Biaxially oriented polyester film and production method therefor |
KR1020227022231A KR20220116200A (ko) | 2019-12-13 | 2020-12-08 | 2축 배향 폴리에스테르 필름 및 그 제조 방법 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019225018 | 2019-12-13 | ||
JP2019-225018 | 2019-12-13 | ||
JP2020044267 | 2020-03-13 | ||
JP2020-044267 | 2020-03-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021117736A1 true WO2021117736A1 (ja) | 2021-06-17 |
Family
ID=76329925
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2020/045721 WO2021117736A1 (ja) | 2019-12-13 | 2020-12-08 | 二軸配向ポリエステルフィルム及びその製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20230001619A1 (ja) |
EP (1) | EP4074489A4 (ja) |
JP (2) | JP7276508B2 (ja) |
KR (1) | KR20220116200A (ja) |
CN (1) | CN114829466B (ja) |
TW (1) | TW202132085A (ja) |
WO (1) | WO2021117736A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023157930A1 (ja) * | 2022-02-17 | 2023-08-24 | 東洋紡株式会社 | ポリアミドフィルムロール |
WO2023157730A1 (ja) * | 2022-02-16 | 2023-08-24 | 東洋紡株式会社 | 二軸配向ポリエステルフィルム |
WO2023157729A1 (ja) * | 2022-02-16 | 2023-08-24 | 東洋紡株式会社 | 二軸配向ポリエステルフィルム |
WO2023157731A1 (ja) * | 2022-02-16 | 2023-08-24 | 東洋紡株式会社 | 二軸配向ポリエステルフィルム |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20220379589A1 (en) * | 2019-11-20 | 2022-12-01 | Toyobo Co., Ltd. | Laminated film |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10119172A (ja) | 1996-08-27 | 1998-05-12 | Toray Ind Inc | 蒸着2軸配向ポリエステルフイルム |
JPH1110725A (ja) | 1997-06-27 | 1999-01-19 | Toray Ind Inc | 透明蒸着用ポリエステルフィルム |
JP4834923B2 (ja) | 2001-06-18 | 2011-12-14 | 東レ株式会社 | 蒸着用ポリエステルフィルム及び蒸着ポリエステルフィルム |
JP2013047317A (ja) * | 2011-02-15 | 2013-03-07 | Fujifilm Corp | 2軸延伸ポリエステルフィルム及びその製造方法、太陽電池用バックシート、並びに太陽電池モジュール |
JP2013155385A (ja) * | 2013-05-20 | 2013-08-15 | Toyobo Co Ltd | 二軸延伸ポリエステルフィルム |
JP2014065282A (ja) | 2012-09-27 | 2014-04-17 | Toyobo Co Ltd | Petボトル再生原料を使用した二軸配向ポリエステルフィルム |
JP2014080594A (ja) * | 2012-09-27 | 2014-05-08 | Toyobo Co Ltd | ポリエステルフィルム |
WO2018062145A1 (ja) * | 2016-09-28 | 2018-04-05 | 東洋紡株式会社 | 白色熱収縮性ポリエステル系フィルムロール |
WO2020203106A1 (ja) * | 2019-03-29 | 2020-10-08 | 東洋紡株式会社 | ポリエステルフィルム及びその製造方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1600625A (ja) | 1968-05-18 | 1970-07-27 | ||
JP2671333B2 (ja) * | 1987-12-01 | 1997-10-29 | 東レ株式会社 | 二軸配向ポリエステルフィルム |
JP3956452B2 (ja) * | 1997-11-19 | 2007-08-08 | 東レ株式会社 | ラミネート用二軸延伸ポリエステルフィルム |
DE10251675A1 (de) * | 2002-11-07 | 2004-05-19 | Mitsubishi Polyester Film Gmbh | Verfahren zur Herstellung einer Thermoplastfolie unter Verwendung von Kunststoffflaschen-Recyclat |
JP2007156132A (ja) * | 2005-12-06 | 2007-06-21 | Sumitomo Chemical Co Ltd | 防眩フィルム及び画像表示装置 |
JP2011184617A (ja) * | 2010-03-10 | 2011-09-22 | Toray Ind Inc | 二軸配向ポリエステルフィルム |
CN104603186B (zh) * | 2012-09-27 | 2016-08-24 | 东洋纺株式会社 | 聚酯薄膜 |
JP2017082053A (ja) * | 2015-10-26 | 2017-05-18 | 東レ株式会社 | 二軸配向ポリエステルフィルム。 |
CN106142794A (zh) * | 2016-06-29 | 2016-11-23 | 安徽国风塑业股份有限公司 | 一种电子胶带用双向拉伸聚酯薄膜的制备方法及其薄膜 |
CN110494476A (zh) * | 2017-03-28 | 2019-11-22 | 东洋纺株式会社 | 双轴取向聚酯薄膜和其制造方法 |
-
2020
- 2020-12-08 JP JP2021563980A patent/JP7276508B2/ja active Active
- 2020-12-08 CN CN202080085416.1A patent/CN114829466B/zh active Active
- 2020-12-08 US US17/784,393 patent/US20230001619A1/en active Pending
- 2020-12-08 KR KR1020227022231A patent/KR20220116200A/ko unknown
- 2020-12-08 EP EP20898153.0A patent/EP4074489A4/en active Pending
- 2020-12-08 WO PCT/JP2020/045721 patent/WO2021117736A1/ja unknown
- 2020-12-10 TW TW109143580A patent/TW202132085A/zh unknown
-
2023
- 2023-04-19 JP JP2023068679A patent/JP2023103252A/ja active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10119172A (ja) | 1996-08-27 | 1998-05-12 | Toray Ind Inc | 蒸着2軸配向ポリエステルフイルム |
JPH1110725A (ja) | 1997-06-27 | 1999-01-19 | Toray Ind Inc | 透明蒸着用ポリエステルフィルム |
JP4834923B2 (ja) | 2001-06-18 | 2011-12-14 | 東レ株式会社 | 蒸着用ポリエステルフィルム及び蒸着ポリエステルフィルム |
JP2013047317A (ja) * | 2011-02-15 | 2013-03-07 | Fujifilm Corp | 2軸延伸ポリエステルフィルム及びその製造方法、太陽電池用バックシート、並びに太陽電池モジュール |
JP2014065282A (ja) | 2012-09-27 | 2014-04-17 | Toyobo Co Ltd | Petボトル再生原料を使用した二軸配向ポリエステルフィルム |
JP2014080594A (ja) * | 2012-09-27 | 2014-05-08 | Toyobo Co Ltd | ポリエステルフィルム |
JP2013155385A (ja) * | 2013-05-20 | 2013-08-15 | Toyobo Co Ltd | 二軸延伸ポリエステルフィルム |
WO2018062145A1 (ja) * | 2016-09-28 | 2018-04-05 | 東洋紡株式会社 | 白色熱収縮性ポリエステル系フィルムロール |
WO2020203106A1 (ja) * | 2019-03-29 | 2020-10-08 | 東洋紡株式会社 | ポリエステルフィルム及びその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP4074489A4 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023157730A1 (ja) * | 2022-02-16 | 2023-08-24 | 東洋紡株式会社 | 二軸配向ポリエステルフィルム |
WO2023157729A1 (ja) * | 2022-02-16 | 2023-08-24 | 東洋紡株式会社 | 二軸配向ポリエステルフィルム |
WO2023157731A1 (ja) * | 2022-02-16 | 2023-08-24 | 東洋紡株式会社 | 二軸配向ポリエステルフィルム |
WO2023157930A1 (ja) * | 2022-02-17 | 2023-08-24 | 東洋紡株式会社 | ポリアミドフィルムロール |
Also Published As
Publication number | Publication date |
---|---|
JPWO2021117736A1 (ja) | 2021-06-17 |
CN114829466A (zh) | 2022-07-29 |
EP4074489A4 (en) | 2024-01-10 |
JP2023103252A (ja) | 2023-07-26 |
EP4074489A1 (en) | 2022-10-19 |
KR20220116200A (ko) | 2022-08-22 |
CN114829466B (zh) | 2023-06-23 |
JP7276508B2 (ja) | 2023-05-18 |
TW202132085A (zh) | 2021-09-01 |
US20230001619A1 (en) | 2023-01-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2021117736A1 (ja) | 二軸配向ポリエステルフィルム及びその製造方法 | |
WO2022049998A1 (ja) | 二軸配向ポリエステルフィルムロール及びその製造方法 | |
WO2020203106A1 (ja) | ポリエステルフィルム及びその製造方法 | |
WO2021019965A1 (ja) | 二軸配向ポリエステルフィルム | |
WO2022168702A1 (ja) | 二軸配向ポリエステルフィルム及びその製造方法 | |
EP4289599A1 (en) | Biaxially oriented polyester film and production method therefor | |
WO2020203105A1 (ja) | ポリエステルフィルム及びその製造方法 | |
EP4393698A1 (en) | Laminated film | |
JP7514434B2 (ja) | 二軸配向ポリエステルフィルム、積層体、および包装容器 | |
JP7514433B2 (ja) | 二軸配向ポリエステルフィルム、積層体、および包装容器 | |
JP7514438B2 (ja) | 二軸配向ポリエステルフィルム、積層体、および包装容器 | |
JP7216353B1 (ja) | 二軸配向ポリエステルフィルム、積層体、および包装容器 | |
WO2024024952A1 (ja) | 二軸配向ポリエステルフィルム、積層体、および包装容器 | |
WO2024024941A1 (ja) | 二軸配向ポリエステルフィルム、積層体、および包装容器 | |
WO2024024947A1 (ja) | 二軸配向ポリエステルフィルム、積層体、および包装容器 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20898153 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2021563980 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20227022231 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2020898153 Country of ref document: EP Effective date: 20220713 |