JP2022056851A - Polyester film - Google Patents
Polyester film Download PDFInfo
- Publication number
- JP2022056851A JP2022056851A JP2020164818A JP2020164818A JP2022056851A JP 2022056851 A JP2022056851 A JP 2022056851A JP 2020164818 A JP2020164818 A JP 2020164818A JP 2020164818 A JP2020164818 A JP 2020164818A JP 2022056851 A JP2022056851 A JP 2022056851A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polyester film
- polyester
- resin
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 70
- 238000005482 strain hardening Methods 0.000 claims abstract description 29
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 238000009512 pharmaceutical packaging Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 29
- 239000002184 metal Substances 0.000 abstract description 29
- 239000011888 foil Substances 0.000 abstract description 23
- 239000004952 Polyamide Substances 0.000 abstract description 17
- 229920002647 polyamide Polymers 0.000 abstract description 17
- 239000000565 sealant Substances 0.000 abstract description 14
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 77
- 239000010410 layer Substances 0.000 description 54
- 229920005989 resin Polymers 0.000 description 51
- 239000011347 resin Substances 0.000 description 51
- 239000002245 particle Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 30
- -1 polyethylene terephthalate Polymers 0.000 description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 24
- 229920000728 polyester Polymers 0.000 description 22
- 239000000463 material Substances 0.000 description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 230000035882 stress Effects 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000008151 electrolyte solution Substances 0.000 description 12
- 230000009477 glass transition Effects 0.000 description 12
- 238000010030 laminating Methods 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 229920001155 polypropylene Polymers 0.000 description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000470 constituent Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 239000012790 adhesive layer Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004645 polyester resin Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 230000037303 wrinkles Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000010954 inorganic particle Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011146 organic particle Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 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
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000013213 extrapolation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
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- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
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- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black 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
- 238000005266 casting Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- KHEMNHQQEMAABL-UHFFFAOYSA-J dihydroxy(dioxo)chromium Chemical compound O[Cr](O)(=O)=O.O[Cr](O)(=O)=O KHEMNHQQEMAABL-UHFFFAOYSA-J 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
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- 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
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- 239000004707 linear low-density polyethylene Substances 0.000 description 1
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- 229910003002 lithium salt Inorganic materials 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Images
Abstract
Description
本発明は電池外装用途、医薬包装用途に好適に使用できるポリエステルフィルムに関する。 The present invention relates to a polyester film that can be suitably used for battery exterior applications and pharmaceutical packaging applications.
リチウム電池とは、リチウム２次電池ともいわれ、液状、ゲル状高分子、固体高分子、ポリマー電解質などを持ち、リチウムイオンの移動で電流を発生する電池であって、正極・負極活性物質が高分子からなるものを含むものである。リチウム２次電池の構成としては、正極集電材（アルミ、ニッケル）／正極活性物質層（金属酸化物、カーボンブラック、金属硫化物、電解液、ポリアクリロニトリル等の高分子正極材料）／電解質層（プロピレンカーボネート、エチレンカーボネート、炭酸ジメチル、エチレンメチルカーボネート等のカーボネート系電解液、リチウム塩からなる無機固体電解質、ゲル電解質）／負極活性物質層（リチウム金属、合金、カーボン、電解液、ポリアクリロニトリル等の高分子負極材料）／負極集電材（銅、ニッケル、ステンレス）及びそれらを包装する外装体からなる。近年、リチウム電池はその高い体積効率、重量効率から多岐分野に渡って使用されており、パソコン、携帯端末装置（スマートフォン等）、ビデオカメラ、電気自動車、エネルギー貯蔵用蓄電池、ロボット、衛星等に小型大容量電源として用いられている。 A lithium battery is also called a lithium secondary battery, which has a liquid, gel-like polymer, solid polymer, polymer electrolyte, etc., and generates a current by the movement of lithium ions, and has a high positive electrode / negative electrode active material. It includes those consisting of molecules. The composition of the lithium secondary battery includes a positive electrode current collector (aluminum, nickel) / positive electrode active material layer (metal oxide, carbon black, metal sulfide, electrolytic solution, polymer positive electrode material such as polyacrylonitrile) / electrolyte layer (. Carbonate-based electrolytes such as propylene carbonate, ethylene carbonate, dimethyl carbonate, ethylenemethyl carbonate, inorganic solid electrolytes composed of lithium salts, gel electrolytes) / Negative electrode active material layer (lithium metal, alloys, carbon, electrolytes, polyacrylonitrile, etc.) It consists of a polymer negative electrode material) / negative electrode current collector (copper, nickel, stainless steel) and an exterior body that encloses them. In recent years, lithium batteries have been used in a wide range of fields due to their high volume efficiency and weight efficiency, and are small in size for personal computers, mobile terminal devices (smartphones, etc.), video cameras, electric vehicles, energy storage storage batteries, robots, satellites, etc. It is used as a large-capacity power supply.
リチウム電池の外装体としては、金属をプレス加工して、円筒状または直方体状に容器化した金属製缶が代表的に挙げられる。しかしながら、金属製缶を用いると容器外壁が剛直であるために電池自体の形状が決められてしまい、ハードウエア側を電池に合わせて設計する必要があり、該電池を用いるハードウエアの寸法が電池により決定されてしまうなどデザインに制約ができてしまうという問題がある。そこで、樹脂層／アルミニウム／シーラント層から構成される構成体を角型に絞り成形加工した成形体２つをヒートシールでラミネートした外装体が好まれるようになってきている。構成体において、シーラント層はヒートシール性、アルミニウムはバリア性、樹脂層は深絞り性を担っている。最近では、バッテリー製造工程において、電解液の漏れ等による構成体を構成する樹脂層の劣化に起因した歩留まり低下が問題視されており、樹脂層には深絞り性の付与に加えて、耐電解液性が求められるようになってきている。 A typical example of the exterior body of a lithium battery is a metal can made by pressing a metal into a cylindrical or rectangular parallelepiped container. However, when a metal can is used, the shape of the battery itself is determined because the outer wall of the container is rigid, and it is necessary to design the hardware side according to the battery, and the dimensions of the hardware using the battery are the battery. There is a problem that the design can be restricted, such as being determined by. Therefore, an exterior body obtained by laminating two molded bodies obtained by drawing and molding a body composed of a resin layer / aluminum / sealant layer into a square shape by heat sealing has come to be preferred. In the structure, the sealant layer has a heat-sealing property, aluminum has a barrier property, and the resin layer has a deep drawing property. Recently, in the battery manufacturing process, a decrease in yield due to deterioration of the resin layer constituting the constituent due to leakage of the electrolytic solution or the like has been regarded as a problem. Liquid properties are being required.
これまで、樹脂層として、例えばポリアミドフィルムなどが用いられている（例えば特許文献１参照）。しかしながらポリアミドフィルムは防湿性、電解液に対する安定性が十分ではなく、電池製造工程に電解液が付着した際にポリアミドフィルムが劣化してしまう場合があり、改善が求められていた。また、電池製造工程に電解液が付着した際のポリアミドフィルムの劣化を防ぐためにポリエステルを最外装に設ける構成が提案されており（特許文献２、３参照）成形性は十分であるものの、ポリエステルフィルムとポリアミドを貼り合わせるための工程が余分に必要とされるため、生産性に劣るといった課題があった。
So far, for example, a polyamide film or the like has been used as the resin layer (see, for example, Patent Document 1). However, the polyamide film does not have sufficient moisture resistance and stability with respect to the electrolytic solution, and the polyamide film may deteriorate when the electrolytic solution adheres to the battery manufacturing process, and improvement has been sought. Further, in order to prevent deterioration of the polyamide film when the electrolytic solution adheres to the battery manufacturing process, a configuration in which polyester is provided on the outermost surface has been proposed (see
また、ポリエステルフィルム単体での検討も行われている（例えば特許文献４、５参照）。
Further, studies on a polyester film alone have been conducted (see, for example,
しかしながら、上記ポリエステルフィルムを用いることで、深絞り成形性、耐電解液性は改良されているものの、ポリエステルフィルムとポリアミドフィルムを用いた構成に比べて深絞り成形性は不十分である。本発明は、従来のポリエステルフィルム単体構成よりも更に深絞り成形性を改良したポリエステルフィルムを提供することである。 However, although the deep draw moldability and the electrolytic solution resistance are improved by using the polyester film, the deep draw moldability is insufficient as compared with the configuration using the polyester film and the polyamide film. The present invention is to provide a polyester film having further improved deep draw moldability as compared with the conventional polyester film single structure.
上記課題を解決するため、本発明のポリエステルフィルムは以下の構成とする。
（１）長手方向と幅方向の加工硬化指数がともに１．６以上３．０以下、かつ長手方向と幅方向の加工硬化指数の差が０．５以下であって、固有粘度が０．６６以上０．９５以下、剛直非晶量が２８％以上６０％以下である。
（２）融点が２４８℃以上である。
（３）結晶化度が２５％以上４０％以下である。
（４）長手方向および幅方向の破断伸度がいずれも１００％以上である。
（５）電池外装用に用いられる。
（６）医薬包装用に用いられる。
In order to solve the above problems, the polyester film of the present invention has the following structure.
(1) The work hardening index in both the longitudinal direction and the width direction is 1.6 or more and 3.0 or less, the difference between the work hardening index in the longitudinal direction and the width direction is 0.5 or less, and the intrinsic viscosity is 0.66. It is 0.95 or more and the amount of rigid amorphous is 28% or more and 60% or less.
(2) The melting point is 248 ° C. or higher.
(3) The crystallinity is 25% or more and 40% or less.
(4) The elongation at break in both the longitudinal direction and the width direction is 100% or more.
(5) Used for battery exterior.
(6) Used for pharmaceutical packaging.
本発明のポリエステルフィルムはポリエステル樹脂を用いることにより耐電解液性に優れ、加工硬化指数および固有粘度、剛直非晶量を特定範囲とすることによって、ポリエステルでありながらポリアミドを用いた構成並に深絞り成形性することが可能となり、高容量化対応の電池外装用構成体、様々な形状に対応可能な包装用構成体に好適に使用することができる。 The polyester film of the present invention has excellent electrolytic solution resistance by using a polyester resin, and by setting the processing cure index, the intrinsic viscosity, and the amount of rigid amorphous in a specific range, it is as deep as the configuration using polyamide while being polyester. It can be drawn and formable, and can be suitably used for a battery exterior structure that can be used for high capacity and a packaging structure that can be used for various shapes.
本発明のポリエステルフィルムは、長手方向と幅方向の加工硬化指数がともに１．６以上３．０以下である。ここで、加工硬化指数とは、後述する評価方法（１１）加工硬化指数、にて定めた引張り試験から得られる伸度５％時の応力および伸度６０％時の応力より算出される値のことである。電池外装に用いられるラミネート材は、最外装フィルム、金属箔、シーラント層を順に積層した構成が代表的であり、最外装フィルムは単層または複合構成で約２５μｍ、金属箔は４０μｍ、シーラント層は８０μｍ程度で構成されているケースが多く、最外装フィルムは最も薄くなっている。本発明者らが鋭意検討したところ、当該構成にて絞り成形を行った際、厚み方向に掛かる応力は、各層の加工硬化状態に応じて中立軸が決定され、厚み方向のどの位置に応力が集中するか決まることを明らかにした。最外装フィルムの加工硬化状態、すなわち加工硬化指数が１．６未満である場合、中立軸は金属箔とシーラント層側に偏り、金属箔に不均一に応力が掛かりやすくなってしまい、その結果、絞り加工における金属箔の破断やピンホールを生じてしまう。このため、本発明のポリエステルフィルムは少なくとも加工硬化指数が１．６以上である必要がある。中立軸が最外装側に偏らないようにする観点から、加工硬化指数は、長手方向、幅方向のいずれの方向においても３．０以下とする必要がある。好ましくは２．０以上２．６以下である。 The polyester film of the present invention has a work hardening index of 1.6 or more and 3.0 or less in both the longitudinal direction and the width direction. Here, the work hardening index is a value calculated from the stress at 5% elongation and the stress at 60% elongation obtained from the tensile test determined by the evaluation method (11) work hardening index described later. That is. The laminate material used for the battery exterior is typically a structure in which the outermost film, the metal foil, and the sealant layer are laminated in this order. In many cases, it is composed of about 80 μm, and the outermost film is the thinnest. As a result of diligent studies by the present inventors, the neutral axis of the stress applied in the thickness direction is determined according to the work hardening state of each layer when drawing molding is performed with the configuration, and the stress is located at which position in the thickness direction. It was revealed that it would be decided whether to concentrate. When the work-hardened state of the outermost film, that is, the work-hardening index is less than 1.6, the neutral axis is biased toward the metal foil and the sealant layer, and the metal foil is likely to be subjected to non-uniform stress, and as a result, the metal foil is likely to be subjected to non-uniform stress. It causes breakage of metal foil and pinholes in drawing. Therefore, the polyester film of the present invention needs to have a work hardening index of at least 1.6 or more. From the viewpoint of preventing the neutral axis from being biased toward the outermost exterior, the work hardening index needs to be 3.0 or less in both the longitudinal direction and the width direction. It is preferably 2.0 or more and 2.6 or less.
ポリエステルフィルムの長手方向と幅方向の加工硬化指数をともに１．６以上３．０以下とするには、フィルム長手方向と幅方向の破断強度を２００ＭＰａ以上にするのが好ましい方法として挙げられる。なお、ここでフィルムの長手方向と幅方向はフィルムの任意の一方向（０°）、該方向から１５°、３０°、４５°、６０°、７５°、９０°、１０５°、１２０°、１３５°、１５０°、１６５°の方向の破断強度を測定し、最も破断強度の高かった方向を幅方向とし、幅方向と直交する方向を長手方向とする。ポリエステルフィルム破断強度を２００ＭＰａ以上とするには高倍率で延伸するとよい。具体的には二軸に延伸するのが最も好ましく、公知の方法で逐次または同時で面積延伸倍率を１１．０倍以上として延伸すると良い。加工硬化指数が１．６未満であると絞り成形性に劣る。また、加工硬化指数は高くなるほど絞り成形時の曲げによる弾性変形が大きくなるため、成形後の反りが大きくなる傾向がある。このため、加工硬化指数は必要とされる反りの程度に応じて最低限に抑えることが重要である。 In order to make the work hardening index in both the longitudinal direction and the width direction of the polyester film 1.6 or more and 3.0 or less, it is preferable to set the breaking strength in the longitudinal direction and the width direction of the film to 200 MPa or more. Here, the longitudinal direction and the width direction of the film are any one direction (0 °) of the film, 15 °, 30 °, 45 °, 60 °, 75 °, 90 °, 105 °, 120 ° from that direction. The breaking strength in the directions of 135 °, 150 °, and 165 ° is measured, the direction having the highest breaking strength is the width direction, and the direction orthogonal to the width direction is the longitudinal direction. In order to increase the breaking strength of the polyester film to 200 MPa or more, it is preferable to stretch the polyester film at a high magnification. Specifically, it is most preferably biaxially stretched, and it is preferable to stretch the area by a known method sequentially or simultaneously with an area stretching ratio of 11.0 times or more. If the work hardening index is less than 1.6, the drawability is inferior. Further, the higher the work hardening index, the larger the elastic deformation due to bending during drawing molding, so that the warpage after molding tends to increase. For this reason, it is important to minimize the work hardening index according to the degree of warpage required.
本発明では面内均一性の観点から長手方向と幅方向の加工硬化指数の差は０．５以下である。長手方向と幅方向の加工硬化指数の差が０．５を超える場合、面内均一性が低く、絞り加工した際に不均一に負荷が掛かり、局部的な変形が起こり絞り成形性に劣ったものとなる。加工硬化指数の差は好ましくは０．３以下が好ましい。 In the present invention, the difference between the work hardening index in the longitudinal direction and the work hardening index in the width direction is 0.5 or less from the viewpoint of in-plane uniformity. When the difference between the work hardening index in the longitudinal direction and the work hardening index in the width direction exceeds 0.5, the in-plane uniformity is low, the load is applied unevenly during drawing, local deformation occurs, and the drawing formability is poor. It becomes a thing. The difference in work hardening index is preferably 0.3 or less.
本発明において、長手方向と幅方向の破断伸度はいずれも１００％以上であることが好ましい。絞り加工における材料の変形挙動の１つは伸長である。フィルムの伸度が大きい程、変形挙動のうち、伸び変形できる要素は大きくなり、絞り加工性は向上する。このため、長手方向と幅方向の破断伸度はいずれも１００％以上であることが好ましい。長手方向と幅方向の破断伸度を１００％以上とするには、いずれの方向の延伸倍率も４．０倍以下であることで調整可能である。延伸倍率が４．０倍を超えた方向がある場合は、加工硬化指数を大きくする上で有利であるものの、当該延伸方向の破断伸度が１００％以下となり、絞り成形性が低下することがある。 In the present invention, the elongation at break in both the longitudinal direction and the width direction is preferably 100% or more. One of the deformation behaviors of a material in drawing is elongation. The larger the elongation of the film, the larger the element that can be stretched and deformed in the deformation behavior, and the drawability is improved. Therefore, it is preferable that the elongation at break in both the longitudinal direction and the width direction is 100% or more. In order to make the breaking elongation in the longitudinal direction and the width direction 100% or more, the stretching ratio in either direction can be adjusted by 4.0 times or less. If there is a direction in which the draw ratio exceeds 4.0 times, it is advantageous in increasing the work hardening index, but the elongation at break in the draw direction becomes 100% or less, and the draw formability may deteriorate. be.
本発明のポリエステルフィルムは、フィルム全体に対する剛直非晶量が２８％以上６０％以下である。ここで、剛直非晶量は後述する（９）剛直非晶量に記載の方法にて測定される値である。剛直非晶量が本範囲であることによって特に顕著な厚み方向に対する特性である突き刺し耐性を得ることができる。電池外装ラミネート材において多く行われている絞り加工は、四隅を金型で固定し、厚み方向に絞る加工である。フィルム全体に対する剛直非晶量を本範囲に制御することによって、前述の絞り加工において、優れた絞り加工特性が発現する。剛直非晶量が６０％を超える場合、非晶成分がフィルムバルク構成の大半を占め、フィルムの寸法安定性が著しく低下する。一方、剛直非晶量が２８％未満である場合、厚み方向に対する特性である突き刺し耐性に劣る。フィルムバルク状態については、使用原料の結晶性に加えて、製膜条件によって決定されるものであり、例えばポリエチレンテレフタレートを用いた場合、剛直非晶量を２８％以上とするには、少なくともフィルムの面配向係数ｆｎを０．１６５以上とすることが重要である。ここで、フィルムの面配向係数は、後述する評価方法（５）ポリエステルフィルムの面配向係数ｆｎに記載の方法にて測定する。フィルムの面配向係数を０．１６５以上とするには、二軸延伸する際の面積延伸倍率を１２．２５倍以上とする方法などが挙げられる。この上で、逐次二軸延伸後の熱処理温度によって剛直非晶を制御することが好ましく、フィルム製膜中に掛かる最も高い温度（熱処理温度）を、２００℃以下とすることが重要である。一方、熱処理温度を２３０℃以上にすることでも樹脂の融解が開始することに起因して、剛直非晶量は増加する傾向を示すが、熱によるフィルムの結晶化を促進させてしまうため、後述する結晶化度が多くなり、フィルムバルク構成として剛直非晶よりも結晶化度が高くなる。このため、熱処理温度は２００℃以下とすることが重要である。フィルムの熱処理温度が２００℃を超え、２３０℃未満である場合、剛直非晶量は２８％未満となることがある。 The polyester film of the present invention has a rigid amorphous amount of 28% or more and 60% or less with respect to the entire film. Here, the amount of rigid amorphous is a value measured by the method described in (9) Amount of rigid amorphous described later. When the amount of rigid amorphous is in this range, it is possible to obtain piercing resistance, which is a characteristic particularly remarkable in the thickness direction. The drawing process that is often performed on battery exterior laminating materials is the process of fixing the four corners with a mold and drawing in the thickness direction. By controlling the amount of rigid amorphous with respect to the entire film within this range, excellent drawing characteristics are exhibited in the above-mentioned drawing. When the amount of rigid amorphous exceeds 60%, the amorphous component occupies most of the film bulk composition, and the dimensional stability of the film is significantly lowered. On the other hand, when the amount of rigid amorphous is less than 28%, the piercing resistance, which is a characteristic in the thickness direction, is inferior. The film bulk state is determined by the film-forming conditions in addition to the crystallinity of the raw material used. For example, when polyethylene terephthalate is used, in order to make the rigid amorphous amount 28% or more, at least the film It is important that the plane orientation coefficient fn is 0.165 or more. Here, the plane orientation coefficient of the film is measured by the method described in the evaluation method (5) plane orientation coefficient fn of the polyester film described later. In order to set the plane orientation coefficient of the film to 0.165 or more, a method of setting the area stretch ratio at the time of biaxial stretching to 12.25 times or more can be mentioned. On this basis, it is preferable to control the rigid amorphous by the heat treatment temperature after the sequential biaxial stretching, and it is important that the highest temperature (heat treatment temperature) applied during film formation is 200 ° C. or lower. On the other hand, even if the heat treatment temperature is set to 230 ° C. or higher, the amount of rigid amorphous tends to increase due to the start of melting of the resin, but it promotes the crystallization of the film due to heat, which will be described later. The degree of crystallinity increases, and the film bulk structure has a higher degree of crystallinity than rigid amorphous. Therefore, it is important that the heat treatment temperature is 200 ° C. or lower. When the heat treatment temperature of the film exceeds 200 ° C. and is lower than 230 ° C., the amount of rigid amorphous may be less than 28%.
本発明のポリエステルフィルムは、結晶化度が２５％以上４０％以下であることが好ましい。結晶化度は延伸による配向結晶化や、熱による結晶化によってフィルムの機械的強度を上昇させることが可能である。結晶化度が２５％未満であるとフィルム面配向が不足し加工硬化指数を本発明の範囲に制御できないことがあり、結晶化度が３５％を超える場合、剛直非晶量を本発明の範囲にすることができなくなることがある。結晶化度を２５％以上４０％以下とするには、例えば、ホモポリエステル樹脂を用い、フィルムの面配向係数を０．１６５以上、０．１７０以下とした上で、熱処理温度を１５０℃以上、２００℃以下とすることで調整可能であるが、他の樹脂を混合しても構わない。 The polyester film of the present invention preferably has a crystallinity of 25% or more and 40% or less. The degree of crystallinity can be increased by orientation crystallization by stretching or crystallization by heat to increase the mechanical strength of the film. If the crystallinity is less than 25%, the film surface orientation may be insufficient and the work hardening index may not be controlled within the range of the present invention. If the crystallinity exceeds 35%, the amount of rigid amorphous shall be within the range of the present invention. May not be possible. To make the crystallinity 25% or more and 40% or less, for example, a homopolyester resin is used, the plane orientation coefficient of the film is 0.165 or more and 0.170 or less, and the heat treatment temperature is 150 ° C. or more. The temperature can be adjusted by setting the temperature to 200 ° C. or lower, but other resins may be mixed.
本発明のポリエステルフィルムは、固有粘度が０．６６以上０．９５以下である。ここで固有粘度は後述する（４）固有粘度に記載の方法にて測定される値である。固有粘度が本範囲であることによって分子鎖の絡み合いが上昇し、厚み方向に対する変形、特に突き刺し耐性を得ることができる。固有粘度が０．６６未満であると分子鎖の絡み合いが不足し、充分な絞り加工性を得ることができない。一方、固有粘度が０．９５を超えると溶融製膜時の濾圧が上昇することに起因して吐出量を低くせざるを得なく、生産性に劣る。固有粘度は溶融製膜に使用する原料で調整可能であり、フィルムの固有粘度を高くしたい場合はフィルム製膜時に使用する原料の固有粘度が高くすると良い。分子鎖絡み合い効果と生産性のいずれも考慮すると固有粘度は０．６９以上０．８８以下であることが好ましい。 The polyester film of the present invention has an intrinsic viscosity of 0.66 or more and 0.95 or less. Here, the intrinsic viscosity is a value measured by the method described in (4) Intrinsic viscosity described later. When the intrinsic viscosity is in this range, the entanglement of the molecular chains is increased, and deformation in the thickness direction, particularly piercing resistance can be obtained. If the intrinsic viscosity is less than 0.66, the entanglement of the molecular chains is insufficient, and sufficient drawability cannot be obtained. On the other hand, if the intrinsic viscosity exceeds 0.95, the filtration pressure at the time of melt film formation increases, so that the discharge amount has to be lowered, and the productivity is inferior. The intrinsic viscosity can be adjusted by the raw material used for melt film formation, and if it is desired to increase the intrinsic viscosity of the film, it is preferable to increase the intrinsic viscosity of the raw material used at the time of film film formation. The intrinsic viscosity is preferably 0.69 or more and 0.88 or less in consideration of both the molecular chain entanglement effect and the productivity.
本発明のポリエステルフィルムは、長手方向、幅方向の１５０℃熱収縮率はいずれも３．５％以上１４．０％以下であることが好ましい。本発明のポリエステルフィルムを使用して、加熱を伴う二次加工、例えば溶融した樹脂をフィルムに直接ラミネートする押出ラミネート工程など１５０℃程度の熱が掛かるラミネート工程において、押出しラミネート時のシワを抑制するにあたり、１５０℃熱収縮率は３．５％以上であることが好ましい。一方、ラミネート時に掛かる温度の熱収縮率が１４％を超えるとラミネート時の熱収縮により、フィルムがラミネート時に変形しすぎて不具合を起こすことがある。ラミネート時のシワと熱変形を両立する観点から、本発明のポリエステルフィルムは長手方向および幅方向の１５０℃熱収縮率は１０％以下であることが好ましい。長手方向と幅方向の１５０℃熱収縮率を３．５％以上１４．０％以下とするためには、フィルムの面積倍率を１２．２５倍以上とした上、熱処理温度を１６０℃以上２００℃以下で熱処理することで制御可能である。 The polyester film of the present invention preferably has a heat shrinkage rate of 150 ° C. in both the longitudinal direction and the width direction of 3.5% or more and 14.0% or less. Using the polyester film of the present invention, wrinkles during extrusion laminating are suppressed in secondary processing accompanied by heating, for example, in an extrusion laminating process in which a molten resin is directly laminated to a film, which is subject to heat of about 150 ° C. The heat shrinkage rate at 150 ° C. is preferably 3.5% or more. On the other hand, if the heat shrinkage rate of the temperature applied during laminating exceeds 14%, the film may be deformed too much at the time of laminating due to the heat shrinkage at the time of laminating, which may cause a problem. From the viewpoint of achieving both wrinkles and thermal deformation during laminating, the polyester film of the present invention preferably has a heat shrinkage rate of 150 ° C. in the longitudinal direction and the width direction of 10% or less. In order to reduce the heat shrinkage rate of 150 ° C in the longitudinal and width directions to 3.5% or more and 14.0% or less, the area magnification of the film should be 12.25 times or more and the heat treatment temperature should be 160 ° C or more and 200 ° C or less. It can be controlled by heat treatment below.
本発明のポリエステルフィルムは、示差走査型熱量計から求められる融点（融解吸熱ピーク温度（Ｔｍ））が２４８℃以上であることが好ましい。本発明のポリエステルフィルムを電池用外装材として使用したとき、シーラント層同士をヒートシールすることによって容器化する。このため、ヒートシールの熱によって外装フィルムの溶融を抑制する必要がある。融解吸熱ピーク温度Ｔｍが２４８℃未満であるとヒートシールを行う際の加熱温度を低下する必要があり、ヒートシールによって容器化するまでの所要時間が多くなった結果、量産性に劣ることがある。融解吸熱ピーク温度Ｔｍを２４８℃以上とするにはホモポリエステルを用いることが最も好ましい。なお、加工性の観点からは３２０℃以下であることが好ましい。 The polyester film of the present invention preferably has a melting point (melting endothermic peak temperature (Tm)) obtained from a differential scanning calorimeter of 248 ° C. or higher. When the polyester film of the present invention is used as an exterior material for a battery, the sealant layers are heat-sealed to form a container. Therefore, it is necessary to suppress the melting of the exterior film by the heat of the heat seal. If the melting endothermic peak temperature Tm is less than 248 ° C., it is necessary to lower the heating temperature when performing heat sealing, and as a result of increasing the time required for containerization by heat sealing, mass productivity may be inferior. .. It is most preferable to use homopolyester in order to set the melting endothermic peak temperature Tm to 248 ° C. or higher. From the viewpoint of workability, the temperature is preferably 320 ° C. or lower.
本発明のポリエステルフィルムはポリエステルを主体として構成される。ポリエステルとは主鎖における主要な結合をエステル結合とする高分子化合物の総称である。そして、ポリエステルは、通常ジカルボン酸あるいはその誘導体とジオールあるいはその誘導体を重縮合反応させることによって得ることができ、ポリエステルを主体として構成することで耐電解液性を得ることができる。また、本発明でいう主体として構成する、は対象全体に対して、６０質量％以上１００質量％以下の割合で占めることを指し、ここではポリエステルフィルムに対して占める割合のことをいう。ここで、ジカルボン酸単位（構造単位）あるいはジオール単位（構造単位）とは、重縮合によって除去される部分を除かれた２価の有機基を意味し、以下の一般式で表される。 The polyester film of the present invention is mainly composed of polyester. Polyester is a general term for polymer compounds whose main bond in the main chain is an ester bond. Then, polyester can usually be obtained by polycondensing reaction of a dicarboxylic acid or a derivative thereof with a diol or a derivative thereof, and by constituting the polyester as a main component, electrolytic solution resistance can be obtained. Further, the term "configured as a subject" in the present invention refers to occupying a ratio of 60% by mass or more and 100% by mass or less with respect to the entire object, and here, it means a ratio occupying with respect to a polyester film. Here, the dicarboxylic acid unit (structural unit) or the diol unit (structural unit) means a divalent organic group excluding the portion removed by polycondensation, and is represented by the following general formula.
ジカルボン酸単位（構造単位）： －ＣＯ－Ｒ－ＣＯ－
ジオール単位（構造単位）： －Ｏ－Ｒ’―Ｏ－
（ここで、Ｒ、Ｒ’は二価の有機基。ＲとＲ’は同じであっても異なっていてもよい。）
本発明に用いるポリエステルを与える、ジオールあるいはその誘導体としては、エチレングリコール以外に、１，２－プロパンジオール、１，３－プロパンジオール、１，３－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコールなどの脂肪族ジヒドロキシ化合物、ジエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどのポリオキシアルキレングリコール、１，４－シクロヘキサンジメタノール、スピログリコールなどの脂環族ジヒドロキシ化合物、ビスフェノールＡ、ビスフェノールＳなどの芳香族ジヒドロキシ化合物、並びに、それらの誘導体が挙げられる。
また、本発明に用いるポリエステルを与えるジカルボン酸あるいはその誘導体としては、テレフタル酸以外には、イソフタル酸、フタル酸、２，６－ナフタレンジカルボン酸、ジフェニルジカルボン酸、ジフェニルスルホンジカルボン酸、ジフェノキシエタンジカルボン酸、５－ナトリウムスルホンジカルボン酸などの芳香族ジカルボン酸、シュウ酸、コハク酸、アジピン酸、セバシン酸、ダイマー酸、マレイン酸、フマル酸などの脂肪族ジカルボン酸、１，４－シクロヘキサンジカルボン酸などの脂環族ジカルボン酸、パラオキシ安息香酸などのオキシカルボン酸、並びに、それらの誘導体を挙げることができる。ジカルボン酸の誘導体としてはたとえばテレフタル酸ジメチル、テレフタル酸ジエチル、テレフタル酸２－ヒドロキシエチルメチルエステル、２，６－ナフタレンジカルボン酸ジメチル、イソフタル酸ジメチル、アジピン酸ジメチル、マレイン酸ジエチル、ダイマー酸ジメチルなどのエステル化物を挙げることができる。
Dicarboxylic acid unit (structural unit): -CO-R-CO-
Glycol unit (structural unit): -OR'-O-
(Here, R and R'are divalent organic groups. R and R'may be the same or different.)
Examples of the diol or a derivative thereof that give the polyester used in the present invention include 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,5-pentanediol, and 1, in addition to ethylene glycol. Aliphatic dihydroxy compounds such as 6-hexanediol and neopentyl glycol, polyoxyalkylene glycols such as diethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and alicyclic dihydroxy such as 1,4-cyclohexanedimethanol and spiroglycol. Examples thereof include compounds, aromatic dihydroxy compounds such as bisphenol A and bisphenol S, and derivatives thereof.
In addition to terephthalic acid, the dicarboxylic acid or its derivative that gives the polyester used in the present invention includes isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonicdicarboxylic acid, and diphenoxyetanedicarboxylic acid. Acids, aromatic dicarboxylic acids such as 5-sodium sulfonate dicarboxylic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid, 1,4-cyclohexanedicarboxylic acid, etc. Examples thereof include oxycarboxylic acids such as alicyclic dicarboxylic acids and paraoxybenzoic acids, as well as derivatives thereof. Examples of the derivative of the dicarboxylic acid include dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethylmethyl ester terephthalic acid,
本発明のポリエステルフィルムは、単層構成であっても、２層以上の多層構成であってもよい。多層構成である場合、Ｂ層／Ａ層／Ｂ層のように中心層を基点に対称構成であることが製膜後の反りを抑制する観点から好ましい。製膜後に反りが発生すると、その後の電池製造工程などでハンドリング性が悪化することがある。また、本発明ではＢ／Ａ／Ｂ／Ａ／Ｂといった５層の構成でもよい。多層構成である場合、製膜後の反りの観点からＢ／Ａ／Ｂの３層積層構成が好ましい。本発明では分子配向が異なるＡ層／Ｂ層のような２層構成であると、製膜直後の時点で反りが発生することがある。ただし、本発明の効果を阻害しないのであれば、Ａ／Ｂの２層構成のように非対称構成でもかまわない。
本発明のポリエステルフィルムは、絞り性向上のため、ダイス側接触面の動摩擦係数μｄを０．３以下とすることが好ましい。動摩擦係数を上記範囲とすることによって絞り成形時の変形抵抗が小さくなり加工性が向上する。動摩擦係数を０．３以下とするには特に限定されないが、例えば、平均粒径０．００５μm以上１０μm以下の無機粒子、および／または有機粒子を０．３質量％以上、５質量％以下含有する層を最外層に有することが好ましい。より好ましくは０．５質量％以上３質量％以下である。ただし、粒子を添加し過ぎると複合体の破断伸度を低下させることがある。このため、本発明を阻害しない範囲にて粒子を添加させることが重要である。なお、本発明において粒子として、平均一次粒径として０．００５μｍ以上のものを用いる。ここでいう粒径とは数平均粒径のことを示し、フィルムの断面内において観察される粒子径を意味する。形状が真円でない場合には同面積の真円に変換した値を粒子径とする。ここで、数平均粒径Ｄnは次の（１）～（４）の手順により求めることができる。
（１）まず、ミクロトームを用いて、フィルム断面を厚み方向に潰すことなく切断し、走査型電子顕微鏡を用いて、拡大観察画像を得る。このとき、切断はフィルムＴＤ方向（横方向）と平行方向になるよう行なう。
（２）次いで、該画像中の断面内に観察される各粒子について、その断面積Sを求め、次式にて粒径ｄを求める。
The polyester film of the present invention may have a single-layer structure or a multi-layer structure having two or more layers. In the case of a multi-layer structure, it is preferable to have a symmetrical structure with the central layer as a base point, such as the B layer / A layer / B layer, from the viewpoint of suppressing warpage after film formation. If warpage occurs after film formation, the handleability may deteriorate in the subsequent battery manufacturing process or the like. Further, in the present invention, a five-layer configuration such as B / A / B / A / B may be used. In the case of a multi-layer structure, a B / A / B three-layer laminated structure is preferable from the viewpoint of warpage after film formation. In the present invention, if there is a two-layer structure such as A layer / B layer having different molecular orientations, warpage may occur immediately after film formation. However, an asymmetrical structure such as an A / B two-layer structure may be used as long as the effect of the present invention is not impaired.
The polyester film of the present invention preferably has a dynamic friction coefficient μd of the contact surface on the die side of 0.3 or less in order to improve drawability. By setting the dynamic friction coefficient within the above range, the deformation resistance during draw forming is reduced and the workability is improved. The dynamic friction coefficient is not particularly limited to 0.3 or less, but for example, it contains 0.3% by mass or more and 5% by mass or less of inorganic particles and / or organic particles having an average particle size of 0.005 μm or more and 10 μm or less. It is preferable to have the layer as the outermost layer. More preferably, it is 0.5% by mass or more and 3% by mass or less. However, adding too much particles may reduce the elongation at break of the complex. Therefore, it is important to add particles within a range that does not interfere with the present invention. In the present invention, particles having an average primary particle size of 0.005 μm or more are used. The particle size here indicates a number average particle size, and means the particle size observed in the cross section of the film. If the shape is not a perfect circle, the value converted into a perfect circle with the same area is used as the particle diameter. Here, the number average particle size Dn can be obtained by the following procedures (1) to (4).
(1) First, a microtome is used to cut a cross section of the film without crushing it in the thickness direction, and a scanning electron microscope is used to obtain a magnified observation image. At this time, cutting is performed so as to be parallel to the film TD direction (horizontal direction).
(2) Next, for each particle observed in the cross section in the image, the cross-sectional area S is obtained, and the particle size d is obtained by the following equation.
ｄ＝２×（Ｓ/π）１/２
（３）得られた粒径ｄと、樹脂粒子の個数ｎを用いて、次式によりＤnを求める。
d = 2 × (S / π) 1/2
(3) Using the obtained particle size d and the number n of resin particles, Dn is obtained by the following equation.
Ｄn＝Σｄ/ｎ
但し、Σｄは観察面内における粒子の粒径の総和、ｎは観察面内の粒子の総数。
（４）上記（１）～（３）を、５箇所場所を変えて実施し、その平均値を粒子の数平均粒径とする。なお、観察点1箇所に付き、２５００μｍ２以上の領域にて上記評価を実施する。
Dn = Σd / n
However, Σd is the total particle size of the particles in the observation surface, and n is the total number of particles in the observation surface.
(4) The above (1) to (3) are carried out at five different locations, and the average value is taken as the number average particle size of the particles. The above evaluation is carried out in a region of 2500 μm 2 or more per observation point.
無機粒子としては、例えば、湿式および乾式シリカ、コロイダルシリカ、ケイ酸アルミ、酸化チタン、炭酸カルシウム、リン酸カルシウム、硫酸バリウム、酸化アルミ、マイカ、カオリン、クレーなどを使用することができる。また、有機粒子としては、スチレン、シリコーン、アクリル酸類、メタクリル酸類、ポリエステル類、ジビニル化合物などを構成成分とする粒子を使用することができる。なかでも、湿式および乾式シリカ、アルミナ、炭酸カルシウムなどの無機粒子およびスチレン、シリコーン、アクリル酸、メタクリル酸、ポリエステル、ジビニルベンゼンなどを構成成分とする粒子を使用することが好ましい。さらに、これらの無機粒子および有機粒子は二種以上を併用してもよい。また、最大表面高さを制御するためにフィルム表面にエンボス加工、サンドブラスト加工といった凹凸加工を施すことも好ましい。 As the inorganic particles, for example, wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, aluminum oxide, mica, kaolin, clay and the like can be used. Further, as the organic particles, particles containing styrene, silicone, acrylic acids, methacrylic acids, polyesters, divinyl compounds and the like as constituents can be used. Among them, it is preferable to use wet and dry silica, inorganic particles such as alumina and calcium carbonate, and particles containing styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like as constituents. Further, two or more kinds of these inorganic particles and organic particles may be used in combination. Further, it is also preferable to perform uneven processing such as embossing and sandblasting on the film surface in order to control the maximum surface height.
本発明のポリエステルフィルムの厚みは、構成体としたときの成形追従性、成形後の反りの観点から、９μｍ以上３０μｍ以下であることが好ましい。最も好ましくは、１２μｍ以上２８μｍ以下である。必要とされる絞り深さに依存するが、９μｍ未満であると成形性に劣ることがあり、３０μｍ以上であると剛性が高くなり成形後に反りが発生することがある。 The thickness of the polyester film of the present invention is preferably 9 μm or more and 30 μm or less from the viewpoint of molding followability when formed into a structure and warpage after molding. Most preferably, it is 12 μm or more and 28 μm or less. Depending on the required drawing depth, if it is less than 9 μm, the moldability may be inferior, and if it is 30 μm or more, the rigidity becomes high and warpage may occur after molding.
本発明に用いられるポリエステルフィルムには接着層との接着性を向上させるために、表面に、コロナ処理、プラズマ処理、オゾン処理、アンカーコート層を設けるなどの表面処理を施すことも好ましい方法として挙げられる。アンカーコート層の形成方法としては、樹脂をフィルム表面に被覆（複合溶融押出法、ホットメルトコート法、水以外の溶媒、水溶性および／または水分散性樹脂からのインライン、オフラインコート法など）する方法が挙げられる。なかでも、配向結晶化が完了する前のフィルムの一方の面に被膜塗剤を塗布し、少なくとも一方向に延伸し、熱処理して、配向結晶化を完了させるインラインコーティング法が均一な被膜形成や生産性の点で好ましい。また、アンカーコート層を設ける場合、樹脂としては、特に限定されるものではないが、たとえば、アクリル系樹脂、ウレタン系樹脂、ポリエステル系樹脂、オレフィン系樹脂、フッ素系樹脂、ビニル系樹脂、塩素系樹脂、スチレン系樹脂、各種グラフト系樹脂、エポキシ系樹脂、シリコーン系樹脂などを使用することができ、これらの樹脂の混合物を使用することもできる。密着性の観点からポリエステル系樹脂、アクリル系樹脂、またはウレタン系樹脂を用いるのが好ましい。ポリエステル系樹脂を水系塗液として用いる場合には、水溶性あるいは水分散性のポリエステル樹脂が用いられるが、このような水溶性化あるいは水分散化のためには、スルホン酸塩基を含む化合物や、カルボン酸塩基を含む化合物を共重合させることが好ましい。またアクリル樹脂を水性塗液として用いる場合には、水に溶解あるいは分散された状態にする必要があり、乳化剤として界面活性剤（例えば、ポリエーテル系化合物などが挙げられるが、限定されるものではない。）を使用する場合がある。また、本発明に用いられるアンカーコート層には、さらに接着性を向上させるために、樹脂に各種の架橋剤を併用することができる。架橋剤樹脂としては、メラミン系、エポキシ系、オキサゾリン系樹脂が一般に用いられる。
本発明のポリエステルフィルムは、各種素材と複合化して使用することができる。例えば金属箔としては、アルミニウム、ステンレス、銅、ニッケル、チタン、錫、銀、金、亜鉛、鉄など目的に応じて使用することができる。中でも、成形性、ガスバリア性、水蒸気バリア性、強度、経済性の観点からアルミニウムを含有する層であることが好ましい。金属箔は、アルミニウム単体であってもよく、銅、亜鉛、マンガン、マグネシウム、シリコン、リチウム、鉄などが添加されたアルミニウム合金であってもよい。金属箔に対してアルミニウムの含有量が９５質量％以上であることが好ましく、純アルミニウム系または、アルミニウム／鉄合金が好ましく用いられる。
As a preferable method, the polyester film used in the present invention is subjected to surface treatment such as corona treatment, plasma treatment, ozone treatment, and an anchor coat layer in order to improve the adhesiveness with the adhesive layer. Be done. As a method for forming the anchor coat layer, a resin is coated on the film surface (composite melt extrusion method, hot melt coat method, solvent other than water, in-line from water-soluble and / or water-dispersible resin, offline coat method, etc.). The method can be mentioned. Among them, an in-line coating method in which a film coating agent is applied to one surface of a film before alignment crystallization is completed, stretched in at least one direction, and heat-treated to complete alignment crystallization is used for uniform film formation. It is preferable in terms of productivity. Further, when the anchor coat layer is provided, the resin is not particularly limited, but for example, an acrylic resin, a urethane resin, a polyester resin, an olefin resin, a fluororesin, a vinyl resin, and a chlorine resin. Resins, styrene resins, various graft resins, epoxy resins, silicone resins and the like can be used, and a mixture of these resins can also be used. From the viewpoint of adhesion, it is preferable to use a polyester resin, an acrylic resin, or a urethane resin. When a polyester resin is used as a water-based coating liquid, a water-soluble or water-dispersible polyester resin is used. For such water-soluble or water-dispersible, a compound containing a sulfonic acid base or a compound containing a sulfonic acid base may be used. It is preferable to copolymerize a compound containing a carboxylic acid base. When the acrylic resin is used as an aqueous coating liquid, it must be in a state of being dissolved or dispersed in water, and examples of the emulsifier include surfactants (for example, polyether compounds), but the emulsifiers are not limited. No.) may be used. Further, in the anchor coat layer used in the present invention, various cross-linking agents can be used in combination with the resin in order to further improve the adhesiveness. As the cross-linking agent resin, a melamine-based resin, an epoxy-based resin, or an oxazoline-based resin is generally used.
The polyester film of the present invention can be used in combination with various materials. For example, as the metal foil, aluminum, stainless steel, copper, nickel, titanium, tin, silver, gold, zinc, iron and the like can be used depending on the purpose. Above all, the layer containing aluminum is preferable from the viewpoint of moldability, gas barrier property, water vapor barrier property, strength, and economy. The metal foil may be aluminum alone, or may be an aluminum alloy to which copper, zinc, manganese, magnesium, silicon, lithium, iron, or the like is added. The content of aluminum is preferably 95% by mass or more with respect to the metal foil, and a pure aluminum-based or aluminum / iron alloy is preferably used.
本発明のポリエステルフィルムと各種素材とを複合化する方法としては、特に限定されないが、密着性の観点から接着剤からなる接着層を設けて接着させるドライラミネーションが好ましく用いられる。用いる接着剤としては、熱硬化タイプでも熱可塑タイプでも構わないが、熱硬化タイプが好ましい。例えば、ポリウレタン系樹脂、ポリエステル系樹脂、ポリ塩化ビニル系樹脂、スチレン－ブタジエン共重合体、アクリルニトリル－ ブタジエン共重合体、メチルメタアクリレート－ ブタジエン共重合体、クロロプレン、ポリブタジェン等のゴム系樹脂、ポリアクリル酸エステル系樹脂、ポリ塩化ビニリデン系樹脂、ポリブタジエン、あるいはこれらの樹脂のカルボキシル変性物、エポキシ系樹脂、セルロース系誘導体、エチレン酢酸ビニル系共重合体、ポリエチレンオキサイド、アクリル系樹脂、リグニン誘導体等からなる接着剤が挙げられる。ポリエステルフィルムの表面処理面と金属箔との密着性の点からは、ポリウレタン系樹脂、ポリエステル系樹脂からなる接着剤が好ましい。 The method for combining the polyester film of the present invention with various materials is not particularly limited, but dry lamination is preferably used in which an adhesive layer made of an adhesive is provided and adhered from the viewpoint of adhesiveness. The adhesive to be used may be a thermosetting type or a thermoplastic type, but a thermosetting type is preferable. For example, polyurethane resin, polyester resin, polyvinyl chloride resin, styrene-butadiene copolymer, acrylic nitrile-butadiene copolymer, methyl methacrylate-butadiene copolymer, chloroprene, polybutagen and other rubber resins, poly From acrylic acid ester resin, polyvinylidene chloride resin, polybutadiene, or carboxyl modified products of these resins, epoxy resin, cellulose derivative, ethylene vinyl acetate copolymer, polyethylene oxide, acrylic resin, lignin derivative, etc. Adhesives such as From the viewpoint of adhesion between the surface-treated surface of the polyester film and the metal foil, an adhesive made of a polyurethane resin or a polyester resin is preferable.
本発明では、ヒートシール性およびバリア性向上の観点から前記複合体にさらにシーラント層が設けられたポリエステルフィルム／接着層／金属箔／シーラント層の順に配置された構成体として使用することができる。上記構成体を電池外装用として用いることで、耐電解液性、絞り成形性に優れた電池包装材とすることができる。シーラント層としては、例えば、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、線状低密度ポリエチレン、エチレン－ブテン共重合体等のエチレン系樹脂、ホモポリプロピレン、エチレン－プロピレン共重合体、エチレン－プロピレン－ブテン共重合体等のプロピレン系樹脂、メチルペンテン樹脂、環状オレフィン系樹脂等のポリオレフィン樹脂、ポリ塩化ビニル、塩化ビニル単量体と共重合し得るエチレン、プロピレン、酢酸ビニル、塩化アリル、アリルグリシジルエーテル、アクリル酸エステル、メタクリル酸エステル、ビニルエーテル等と塩化ビニルとの共重合体及びこれらの混合物等の塩化ビニル系樹脂が挙げられる。 In the present invention, from the viewpoint of improving the heat-sealing property and the barrier property, the composite can be used as a structure in which a polyester film / an adhesive layer / a metal leaf / a sealant layer in which a sealant layer is further provided is arranged in this order. By using the above structure for the battery exterior, it is possible to obtain a battery packaging material having excellent electrolytic solution resistance and draw moldability. Examples of the sealant layer include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-based resins such as ethylene-butene copolymer, homopolypropylene, ethylene-propylene copolymer, and ethylene-propylene. -Ethylene, propylene, vinyl acetate, allyl chloride, allylglycidyl that can be copolymerized with propylene resins such as butene copolymers, methylpentene resins, polyolefin resins such as cyclic olefin resins, polyvinyl chloride, and vinyl chloride monomers. Examples thereof include a copolymer of vinyl chloride with ether, acrylic acid ester, methacrylic acid ester, vinyl ether and the like, and a vinyl chloride resin such as a mixture thereof.
本発明のポリエステルフィルムは電池外装用に好ましく用いられる。電池外装には、電池性能維持のために、水蒸気の進入を防ぐ水蒸気バリア性、電解液で膨潤しない、および製造工程時の電解液漏れによる最外装が劣化しないなどの耐電解液性、高容量化へのニーズに対応する深絞り成形性が求められる。本発明のポリエステルフィルムを用いることによりポリアミドを用いた構成並に深絞り成形性に優れ、電池外装用途に適用することで工程不具合なく生産性に優れ、かつ高容量化に対応することができる。 The polyester film of the present invention is preferably used for battery exteriors. In order to maintain battery performance, the battery exterior has a water vapor barrier property that prevents the ingress of water vapor, does not swell with the electrolytic solution, and has high electrolytic solution resistance and high capacity such that the outermost exterior does not deteriorate due to electrolytic solution leakage during the manufacturing process. Deep drawability is required to meet the needs for conversion. By using the polyester film of the present invention, it is excellent in deep drawing formability as well as the configuration using polyamide, and by applying it to the battery exterior application, it is excellent in productivity without process trouble and can cope with high capacity.
また、本発明のポリエステルフィルムは、医薬包装用途にも好ましく用いられる。医薬包装は、内容物の劣化を防ぐために、ガスバリア性、水蒸気バリア性が必要であり、印刷を施す仕様に対応できるように印刷適性が求められる。さらに、様々な形状な内容物に対応できるような深絞成形性へのニーズが高まっている。高度なガスバリア性、水蒸気バリア性を達成するためには、金属箔を有していることが好ましいが、金属箔は深絞り成形が困難なため、フィルムを積層させ、フィルムに追従して成形させる必要がある。本発明のポリエステルフィルムを用いることにより、各種素材を積層した複合体の深絞り成形性が良好であり、医薬包装用途に適用することで様々な形状に対応した医薬品に適用することができる。 The polyester film of the present invention is also preferably used for pharmaceutical packaging. Pharmaceutical packaging is required to have gas barrier properties and water vapor barrier properties in order to prevent deterioration of the contents, and printability is required to meet the specifications for printing. Furthermore, there is an increasing need for deep drawability that can handle contents of various shapes. In order to achieve high gas barrier properties and water vapor barrier properties, it is preferable to have a metal foil, but since it is difficult to form a metal foil by deep drawing, the films are laminated and molded following the film. There is a need. By using the polyester film of the present invention, the deep-drawing formability of the composite in which various materials are laminated is good, and it can be applied to pharmaceutical products corresponding to various shapes by being applied to pharmaceutical packaging applications.
本発明のポリエステルフィルム製造方法の概略を例示する。まずポリエステフィルムを製膜する。そのために、上述のポリエステル原料を公知の方法で溶融押出してポリエステルが結晶化しないように１０℃～３５℃程度に調整されたキャスティングドラム上に密着性させてキャストシートを得る。密着方法は静電印加法やエアーナイフ法など公知の方法でよい。次いで、得られたキャストシートを公知の方法で二軸に延伸して配向させる。二軸延伸は逐次二軸、同時二軸、チューブラー法など公知の方法でよい。延伸の際、場合によっては一軸延伸後にアンカーコ－ト層をコーティングしてもよい。ここで、一軸目と二軸目の延伸倍率の積である延伸面積倍率を１２．２５倍以上にすることは少なくともポリエステルフィルム長手方向と幅方向の加工硬化指数平均値を１．６以上にさせる上で重要である。また、同様の理由により延伸温度は樹脂のガラス転移温度以上、ガラス転移温度＋１５℃以下とすることが好ましい。ただし、本発明の効果が得られるのであればこの限りではない。二軸延伸後は寸法安定性などの観点から熱処理を施すことが好ましい。熱処理温度は剛直非晶量を制御する上で重要であり、２００℃以下とすることが重要である。また、寸法安定性の観点から熱処理温度は１５０℃以上であることが好ましい。この際、熱処理時間は１秒～１２０秒以下の範囲で熱処理することが好ましい。熱処理をした後は各種素材との密着性など必要に応じてコロナなどの表面処理をしてポリエステルフィルムを得る。 The outline of the polyester film manufacturing method of this invention is illustrated. First, a polyester film is formed. Therefore, the above-mentioned polyester raw material is melt-extruded by a known method and brought into close contact with a casting drum adjusted to about 10 ° C. to 35 ° C. so that the polyester does not crystallize to obtain a cast sheet. The close contact method may be a known method such as an electrostatic application method or an air knife method. Then, the obtained cast sheet is biaxially stretched and oriented by a known method. Biaxial stretching may be performed by a known method such as sequential biaxial, simultaneous biaxial, or tubular method. At the time of stretching, in some cases, the anchor coat layer may be coated after uniaxial stretching. Here, setting the stretched area ratio, which is the product of the stretch ratios of the first axis and the second axis, to 12.25 times or more makes the average value of the work hardening index in the longitudinal direction and the width direction of the polyester film 1.6 or more. Important above. Further, for the same reason, it is preferable that the stretching temperature is equal to or higher than the glass transition temperature of the resin and lower than the glass transition temperature of + 15 ° C. However, this does not apply as long as the effects of the present invention can be obtained. After biaxial stretching, it is preferable to perform heat treatment from the viewpoint of dimensional stability and the like. The heat treatment temperature is important for controlling the amount of rigid amorphous, and it is important to keep it at 200 ° C. or lower. Further, from the viewpoint of dimensional stability, the heat treatment temperature is preferably 150 ° C. or higher. At this time, the heat treatment time is preferably in the range of 1 second to 120 seconds or less. After the heat treatment, a polyester film is obtained by surface-treating a corona or the like as necessary, such as adhesion to various materials.
（評価方法）
以下の方法でポリエステルフィルム、複合体および構成体の製造、評価を行った。
(Evaluation methods)
Polyester films, complexes and constituents were manufactured and evaluated by the following methods.
（１）ポリエステルの組成
ポリエステル樹脂およびフィルムをヘキサフルオロイソプロパノール（ＨＦＩＰ）に溶解し、１Ｈ－ＮＭＲおよび１３Ｃ－ＮＭＲを用いて各モノマー残基や副生ジエチレングリコールについて含有量を定量した。
(1) Polyester composition The polyester resin and film were dissolved in hexafluoroisopropanol (HFIP), and the contents of each monomer residue and by-product diethylene glycol were quantified using 1 H-NMR and 13 C-NMR.
（２）フィルムの厚み、層厚み
フィルム全体の厚みを測定する際は、ダイヤルゲージを用いて、フィルムを２００ｍｍ×３００ｍｍに切り出し、各々の試料の任意の場所５ヶ所の厚みを測定し、平均して求めた。また、フィルム、複合体および構成体の各層厚みについては、サンプルをエポキシ樹脂に包埋し、フィルム断面をミクロトームで切り出し、該断面を透過型電子顕微鏡（日立製作所製ＴＥＭ Ｈ７１００）で５０００倍の倍率で観察することによって求めた。
(2) Film thickness and layer thickness When measuring the thickness of the entire film, cut out the film to 200 mm x 300 mm using a dial gauge, measure the thickness of each sample at any location, and average it. I asked for it. For the thickness of each layer of the film, composite and constituent, the sample is embedded in epoxy resin, the cross section of the film is cut out with a microtome, and the cross section is magnified by 5000 times with a transmission electron microscope (TEM H7100 manufactured by Hitachi, Ltd.). Obtained by observing in.
（３）ポリエステルフィルムの長手方向と幅方向
本発明では、フィルムの任意の一方向（０°）、該方向から１５°、３０°、４５°、６０°、７５°、９０°、１０５°、１２０°、１３５°、１５０°、１６５°の方向の破断強度を測定し、最も破断強度の高かった方向を幅方向とし、幅方向と直交する方向を長手方向とした。なお、破断強度は（８）ポリエステルフィルムの破断強度に示した方法により得ることができる。
(3) Longitudinal and Width Direction of Polyester Film In the present invention, any one direction (0 °) of the film, 15 °, 30 °, 45 °, 60 °, 75 °, 90 °, 105 °, from that direction. The breaking strengths in the directions of 120 °, 135 °, 150 °, and 165 ° were measured, and the direction having the highest breaking strength was defined as the width direction, and the direction orthogonal to the width direction was defined as the longitudinal direction. The breaking strength can be obtained by the method shown in (8) Breaking strength of the polyester film.
（４）固有粘度
本発明のポリエステルフィルムをオルトクロロフェノール中、２５℃でオストワルド粘度計を用いて溶液粘度を測定し、当該溶液粘度から算出した。固有粘度の単位は［ｄｌ／ｇ］で示される。なお、ｎ数は３とし、その平均値を採用した。
(4) Intrinsic Viscosity The polyester film of the present invention was measured for solution viscosity in orthochlorophenol at 25 ° C. using an Ostwald viscometer and calculated from the solution viscosity. The unit of intrinsic viscosity is indicated by [dl / g]. The number of n was set to 3, and the average value was adopted.
（５）ポリエステルフィルムの面配向係数ｆｎ
アッベ屈折率計を用いて面配向係数を測定する層（以下、測定層とする）をガラス面に密着させ、次いでナトリウムＤ線を光源として、ａ方向、ｂ方向、厚み方向の屈折率（Ｎｘ、Ｎｙ、Ｎｚ）を測定し、下記式より測定層の面配向係数ｆｎを求めた。
・面配向係数ｆｎ＝（Ｎｘ+Ｎｙ）／２－Ｎｚ
（６）破断伸度
フィルムおよび複合体を長手方向および幅方向に長さ１５０ｍｍ×幅１０ｍｍの矩形に切り出しサンプルとした。２５℃、６３％Ｒｈの条件下で、引張試験機（オリエンテック（株）製フィルム強伸度自動測定装置“テンシロンＡＭＦ／ＲＴＡ－１００”）を用いてクロスヘッドスピード３００ｍｍ／分、幅１０ｍｍ、試料長５０ｍｍとしてフィルムの長手方向、幅方向について、引張試験を行い、破断した際の伸度を読み取った値を破断伸度とする。測定は５回行い、その平均を用いた。
(5) Surface orientation coefficient fn of polyester film
A layer for measuring the plane orientation coefficient using an Abbe refractive index meter (hereinafter referred to as a measuring layer) is brought into close contact with the glass surface, and then the refractive index (Nx) in the a-direction, b-direction, and thickness direction using sodium D-ray as a light source. , Ny, Nz), and the plane orientation coefficient fn of the measurement layer was obtained from the following formula.
-Surface orientation coefficient fn = (Nx + Ny) /2-Nz
(6) The breaking elongation film and the composite were cut into a rectangle having a length of 150 mm and a width of 10 mm in the longitudinal direction and the width direction and used as a sample. Crosshead speed 300 mm / min, width 10 mm, using a tensile tester (Orientec Co., Ltd. automatic film strength elongation measuring device "Tencilon AMF / RTA-100") under the conditions of 25 ° C. and 63% Rh. A tensile test is performed in the longitudinal direction and the width direction of the film with a sample length of 50 mm, and the value obtained by reading the elongation at the time of breaking is defined as the breaking elongation. The measurement was performed 5 times and the average was used.
（７）結晶化度
ＪＩＳ Ｋ７１２２ （１９９９年）に準じて、セイコー電子工業（株）製示差走査熱量測定装置ロボットＤＳＣ－ＲＤＣ２２０を、データ解析には“ディスクセッション”ＳＳＣ／５２００を用いて、フィルムサンプル５ｍｇをアルミニウム製受け皿上で室温から３００°まで昇温速度２０℃／分で昇温し、３００℃で５分間保持した。そのとき、測定によって得られた吸熱ピーク熱量ΔＨｍ、冷結晶化熱量ΔＨｃ、完全結晶ＰＥＴの融解熱量ΔＨｍ０（１４０．１Ｊ／ｇ）より、下記式によって算出した。
結晶化度（％）＝（ΔＨｍ－ΔＨｃ）／ΔＨｍ０ｘ１００
（８）剛直非晶量
剛直非晶量は、測定によって得られた可動非晶量、結晶化度より、以下の計算式にて算出した。
剛直非晶量（％）＝１００－（可動非晶量＋結晶化度）。
ポリエチレンテレフタレート完全非晶物の比熱差理論値＝０．４０５２Ｊ／（ｇ℃）
また、本発明ではポリエチレンテレフタレートの完全非晶物の比熱差理論値を参照した。
(7) Crystallinity According to JIS K7122 (1999), a differential scanning calorimetry robot DSC-RDC220 manufactured by Seiko Electronics Inc. is used, and a "disk session" SSC / 5200 is used for data analysis. 5 mg of the sample was heated from room temperature to 300 ° on an aluminum saucer at a heating rate of 20 ° C./min and held at 300 ° C. for 5 minutes. At that time, it was calculated by the following formula from the endothermic peak heat amount ΔHm, the cold crystallization heat amount ΔHc, and the melting heat amount ΔHm0 (140.1 J / g) of the perfect crystal PET obtained by the measurement.
Crystallinity (%) = (ΔHm-ΔHc) / ΔHm0x100
(8) Rigid amorphous amount The rigid amorphous amount was calculated by the following formula from the movable amorphous amount and the crystallinity obtained by the measurement.
Rigid amorphous amount (%) = 100- (movable amorphous amount + crystallinity).
Theoretical value of specific heat difference of polyethylene terephthalate completely amorphous material = 0.4052J / (g ℃)
Further, in the present invention, the theoretical value of the specific heat difference of the completely amorphous material of polyethylene terephthalate was referred to.
尚、可動非晶量は以下の通り測定した。
ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製温度変調ＤＳＣを用い、試料５ｍｇを窒素雰囲気下、０℃から１５０℃まで２℃／ｍｉｎの昇温速度、温度変調振幅±１℃、温度変調周期６０秒で測定した。測定によって得られたガラス転移温度での比熱差を求め、以下の式より算出した。
可動非晶量（％）＝（比熱差）／（ポリエステル完全非晶物の比熱差理論値）×１００
ポリエチレンテレフタレート完全非晶物の比熱差理論値＝０．４０５２Ｊ／（ｇ℃）
また、本発明ではポリエチレンテレフタレートユニットが７０モル％以上であるものについては、ポリエチレンテレフタレートの完全非晶物の比熱差理論値を参照した。
The amount of movable amorphous was measured as follows.
Using a temperature-modulated DSC manufactured by TA Instruments, 5 mg of a sample was measured under a nitrogen atmosphere at a temperature rise rate of 2 ° C./min from 0 ° C. to 150 ° C., a temperature modulation amplitude of ± 1 ° C., and a temperature modulation cycle of 60 seconds. The specific heat difference at the glass transition temperature obtained by the measurement was obtained and calculated from the following formula.
Movable amorphous amount (%) = (specific heat difference) / (theoretical value of specific heat difference of polyester complete amorphous) × 100
Theoretical value of specific heat difference of polyethylene terephthalate completely amorphous material = 0.4052J / (g ℃)
Further, in the present invention, for the polyethylene terephthalate unit having a content of 70 mol% or more, the theoretical value of the specific heat difference of the completely amorphous material of polyethylene terephthalate was referred to.
（９）ガラス転移温度Ｔｇ、融点（融解吸熱ピーク温度Ｔｍ）
ＪＩＳ７１２２（１９９９）に準拠し、示差走査熱量計（セイコーインスツル製ＥＸＳＴＡＲ ＤＳＣ６２２０）を用いて、窒素雰囲気中で３ｍｇの樹脂を３０℃から３００℃まで２０℃／ｍｉｎの条件で昇温する。次いで、３００℃で５分保持した後、４０℃／ｍｉｎの条件で３０℃まで降温する。さらに、３０℃で５分保持した後、３０℃から３００℃まで２０℃／ｍｉｎの条件で昇温する。この昇温時に得られるガラス転移温度を下記式（ｉ）により算出した。
ガラス転移温度＝（補外ガラス転移開始温度＋補外ガラス転移終了温度）／２・・・（ｉ）
ここで補外ガラス転移開始温度は、低温側のベースラインを高温側に延長した直線と、ガラス転移の階段状変化部分の曲線の勾配が最大になるような点で引いた接線との交点の温度とする。補外ガラス転移終了温度は、高温側のベースラインを低温側に延長した直線と、ガラス転移の階段状変化部分の曲線の勾配が最大になるような点で引いた接線との交点の温度とする。また、樹脂の結晶融解に伴う吸熱ピークのピークトップを融点（融解吸熱ピーク温度Ｔｍ）とした。
(9) Glass transition temperature Tg, melting point (melting endothermic peak temperature Tm)
In accordance with JIS7122 (1999), a differential scanning calorimeter (EXSTAR DSC6220 manufactured by Seiko Instruments Inc.) is used to raise the temperature of 3 mg of the resin from 30 ° C. to 300 ° C. at 20 ° C./min in a nitrogen atmosphere. Then, after holding at 300 ° C. for 5 minutes, the temperature is lowered to 30 ° C. under the condition of 40 ° C./min. Further, after holding at 30 ° C. for 5 minutes, the temperature is raised from 30 ° C. to 300 ° C. under the condition of 20 ° C./min. The glass transition temperature obtained at the time of this temperature rise was calculated by the following formula (i).
Glass transition temperature = (extrapolation glass transition start temperature + extrapolation glass transition end temperature) / 2 ... (i)
Here, the outer glass transition start temperature is the intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the curve of the stepped change part of the glass transition is maximized. Let it be the temperature. The outer glass transition end temperature is the temperature of the intersection of the straight line extending the baseline on the high temperature side to the low temperature side and the tangent line drawn at the point where the slope of the curve of the stepped change part of the glass transition is maximized. do. Further, the peak top of the endothermic peak accompanying the melting of the crystal of the resin was defined as the melting point (melting endothermic peak temperature Tm).
（１０）加工硬化指数
フィルムを長手方向および幅方向に長さ１５０ｍｍ×幅１０ｍｍの矩形に切り出しサンプルとした。２５℃、６３％Ｒｈの条件下で、引張試験機（オリエンテック（株）製フィルム強伸度自動測定装置“テンシロンＡＭＦ／ＲＴＡ－１００”）を用いてクロスヘッドスピード３００ｍｍ／分、幅１０ｍｍ、試料長５０ｍｍとしてフィルムの長手方向、幅方向について、引張試験を行い、初期長をＬ０（ｍｍ）、５％伸長時の長さをＬ１（ｍｍ）、５％伸長時の公称応力をＰ１（ＭＰａ）、６０％伸長時の長さをＬ２（ｍｍ）、６０％伸長時の公称応力をＰ２（ＭＰａ）としたとき、５％伸長時の真ひずみを（１）式、６０％伸長時の真ひずみを（２）式、５％伸長時の真応力を（３）式、６０％伸長時の真応力（４）式よりそれぞれ得られた値とする。（１）～（４）から得られた値より、Ｘ軸を真ひずみ、Ｙ軸を真応力としたときに成す式から得られる傾きを加工硬化指数とした。これを長手方向、幅方向につき、それぞれ５回ずつ測定したときの平均値を用いた。
(10) Work Hardening Index The film was cut into a rectangle having a length of 150 mm and a width of 10 mm in the longitudinal direction and the width direction as a sample. Cross head speed 300 mm / min, width 10 mm, using a tensile tester (Orientec Co., Ltd. automatic film strength elongation measuring device "Tencilon AMF / RTA-100") under the conditions of 25 ° C. and 63% Rh. Tensile tests were performed in the longitudinal and width directions of the film with a sample length of 50 mm, and the initial length was L 0 (mm), the length at 5% elongation was L 1 (mm), and the nominal stress at 5% elongation was P. When 1 (MPa), the length at 60% elongation is L 2 (mm), and the nominal stress at 60% elongation is P 2 (MPa), the true strain at 5% elongation is Eq. (1), 60. The true strain at the time of% elongation is the value obtained from the equation (2), the true stress at the time of 5% elongation is the value obtained from the equation (3), and the true stress at the time of 60% elongation is the value obtained from the equation (4). From the values obtained from (1) to (4), the slope obtained from the equation when the X-axis is true strain and the Y-axis is true stress is defined as the work hardening index. The average value when this was measured 5 times in each of the longitudinal direction and the width direction was used.
５％伸長時の真ひずみ＝Ｌｎ（Ｌ１／Ｌ０）・・・（１）
６０％伸長時の真ひずみ＝Ｌｎ（Ｌ２／Ｌ１）・・・（２）
５％伸長時の真応力＝Ｐ１（１＋Ｌｎ（Ｌ１／Ｌ０））・・・（３）
６０％伸長時の真応力＝Ｐ２（１＋Ｌｎ（Ｌ２／Ｌ１））・・・（４）
※Ｌｎ：自然対数
（１１）ポリエステルフィルム幅方向、長手方向の１５０℃熱収縮率
フィルムを長手方向および幅方向に長さ１５０ｍｍ×幅１０ｍｍの矩形に切り出しサンプルとした。サンプルに１００ｍｍの間隔で標線を描き、３ｇの錘を吊して１５０℃に加熱した熱風オーブン内に３０分間設置し加熱処理を行った。熱処理後の標線間距離を測定し、加熱前後の標線間距離の変化から熱収縮率を算出し、熱収縮率とした。測定は長手方向および幅方向に５サンプル実施して平均値で評価を行った。
True strain at 5% elongation = Ln (L 1 / L 0 ) ... (1)
True strain at 60% elongation = Ln (L 2 / L 1 ) ... (2)
True stress at 5% elongation = P 1 (1 + Ln (L 1 / L 0 )) ... (3)
True stress at 60% elongation = P 2 (1 + Ln (L 2 / L 1 )) ... (4)
* Ln: Natural logarithm (11) Polyester film A heat shrinkage film at 150 ° C. in the width direction and the longitudinal direction was cut into a rectangle having a length of 150 mm and a width of 10 mm in the longitudinal direction and the width direction as a sample. Marked lines were drawn on the sample at intervals of 100 mm, and a 3 g weight was hung and placed in a hot air oven heated to 150 ° C. for 30 minutes for heat treatment. The distance between the marked lines after the heat treatment was measured, and the heat shrinkage rate was calculated from the change in the distance between the marked lines before and after heating, and used as the heat shrinkage rate. Five samples were measured in the longitudinal direction and the width direction, and the average value was used for evaluation.
（１２）ポリエステルフィルムの動摩擦係数
東洋精機（株）製スリップテスターを用いて、ＪＩＳ－Ｋ７１２５（１９９９年）に準じて、フィルムの両面を重ねて摩擦させた時の初期の立ち上がり後の抵抗値の安定領域を測定し、動摩擦係数μｄとした。サンプルは、幅８０ｍｍ、長さ２００ｍｍの長方形とし、長方形の長手方向となるようにロールから３セット（６枚）切り出した。３回測定を行い、平均値を求めた。
(12) Dynamic friction coefficient of polyester film The resistance value after the initial rise when both sides of the film are rubbed on top of each other according to JIS-K7125 (1999) using a slip tester manufactured by Toyo Seiki Co., Ltd. The stable region was measured and the dynamic friction coefficient was μd. The sample was a rectangle having a width of 80 mm and a length of 200 mm, and 3 sets (6 sheets) were cut out from the roll so as to be in the longitudinal direction of the rectangle. The measurement was performed three times, and the average value was calculated.
（１３）絞り成形性
（ａ）構成体の作成方法
構成体は本発明のポリエステルフィルムまたはポリアミドフィルム（ここでは興人製ボニールＲＸ２５μｍを用いた）と金属箔とを接着層を介して接着させることで得る。また、接着層を構成する接着剤としてウレタン系接着剤である東洋インキ製“ＡＤ５０２”を主剤、同社のＣＡＴ１０Ｌを架橋剤として用いＡＤ５０２、ＣＡＴ１０Ｌ、酢酸エチルを１５：１．５：２５の質量比となるように混合した塗剤をドライラミネート法にて、５ｇ／ｍ２となるように均一にポリエステルフィルムまたはポリアミドフィルムの表面処理を施した面に塗布し、金属箔の化成処理を施していない面とポリエステルフィルムまたはポリアミドフィルム接着剤塗布面とを８０℃に加熱したロールに０．５ＭＰａで押し付けながら加熱圧着し、巻き取った。その後、６０℃で７日間エージング処理を施し、構成体を得た。
(13) Drawing formability (a) Method for creating a constituent The constituent is a polyester film or polyamide film of the present invention (here, Kohjin Bonil RX 25 μm is used) and a metal foil are adhered to each other via an adhesive layer. Get in. Further, as the adhesive constituting the adhesive layer, "AD502" manufactured by Toyo Ink Co., Ltd., which is a urethane adhesive, is used as a main agent, and CAT10L of the same company is used as a cross-linking agent, and AD502, CAT10L, and ethyl acetate have a mass ratio of 15: 1.5: 25. The coating material mixed so as to be applied is uniformly applied to the surface-treated surface of the polyester film or the polyamide film so as to be 5 g / m 2 by the dry laminating method, and the metal foil is not chemically treated. The surface and the polyester film or polyamide film adhesive-coated surface were heat-bonded to a roll heated to 80 ° C. at 0.5 MPa and wound up. Then, it was subjected to aging treatment at 60 ° C. for 7 days to obtain a constituent.
（ｂ）複合体の作成方法
（ａ）で作成した構成体金属箔の上に、シーラント層としてマレイン酸変性ポリプロピレン樹脂とポリプロピレンとを共押出しした２層共押出しフィルム（マレイン酸変性ポリプロピレン樹脂層：２０μｍ、ポリプロピレン樹脂層：６０μｍ）を、マレイン酸変性ポリプロピレン樹脂層が化成処理を施した金属箔側と接着するようにし、ラミネーターを用いて実施例、比較例に記載の複合体と金属箔側とを加熱圧着（１５０℃、０．３ＭＰａ、２ｍ／ｍｉｎ）させることで、ポリエステルフィルムまたはポリアミドフィルム／接着層／金属箔／シーラント層となる構成体を作成した。
(B) A two-layer co-extruded film (maleic acid-modified polypropylene resin layer:) in which maleic acid-modified polypropylene resin and polypropylene are co-extruded as a sealant layer on the constituent metal foil prepared in (a). 20 μm, polypropylene resin layer: 60 μm) so that the maleic acid-modified polypropylene resin layer adheres to the metal foil side subjected to the chemical conversion treatment, and a laminator is used to attach the composite and the metal foil side described in Examples and Comparative Examples. Was heat-bonded (150 ° C., 0.3 MPa, 2 m / min) to prepare a composition to be a polypropylene film or a polyamide film / adhesive layer / metal foil / sealant layer.
（ｂ）で得られた構成体を、１００ｍｍ×１００ｍｍ大に切り出し、５０ｍｍ×３０ｍｍの矩形状の雄型（構成体と接触する面と側面が成す角のＲ：２ｍｍ、図１）とこの雄型とのクリアランスが０．５ｍｍの雌型（構成体と接触する面と側面が成す角のＲ：２ｍｍ、図１）からなる金型を用いて、雄型側にシーラント側がくるように雌型上に構成体をセットし、プレス成形（加圧：０．１ＭＰａ、ワンショット１０秒、）を行い、下記の基準で評価を行った。尚、深絞り成形後にラミネート材にピンホールや破れが発生した場合を深絞り成形ができなかった、とした。
Ｓ：ポリアミド構成よりも１ｍｍ以上深絞り成形ができた。
Ａ：ポリアミド構成と同等の深絞り成形ができた
Ｂ：Ａ評価よりも１ｍｍ以内低い範囲で絞り深さが成形できた。
Ｃ：Ｂ評価よりも１ｍｍ以内低い範囲で絞り深さが成形できた。
Ｄ：Ｃ評価よりも深絞り成形に劣っていた。
The structure obtained in (b) was cut into a size of 100 mm × 100 mm, and a 50 mm × 30 mm rectangular male die (R: 2 mm of the angle formed by the surface and the side surface in contact with the structure, FIG. 1) and this male. Using a female mold with a clearance of 0.5 mm from the mold (R: 2 mm at the angle formed by the surface and side surface in contact with the structure, Fig. 1), use a female mold so that the sealant side comes to the male mold side. The structure was set on the top, press molding (pressurization: 0.1 MPa, one shot 10 seconds) was performed, and evaluation was performed according to the following criteria. It was determined that deep drawing could not be performed when pinholes or tears occurred in the laminated material after deep drawing.
S: Deep drawing was possible by 1 mm or more than the polyamide composition.
A: Deep drawing equivalent to the polyamide composition was possible. B: The drawing depth could be formed within 1 mm lower than the A evaluation.
The drawing depth could be formed within 1 mm lower than the C: B evaluation.
D: It was inferior to C evaluation in deep drawing.
（１４）押出ラミネート時のシワ
（１３）絞り成形性（ｂ）複合体の作成方法に記載の方法にて得られた複合体から切り出した任意６００００ｍｍ２外観を目視し、以下の通り判定を行った。
○：フィルム全体にシワが見られなかった。
△：５ｍｍ以上のシワが見られた。
(14) Wrinkles during extrusion laminating (13) Stretchability (b) Arbitrary 60,000 mm 2 cut out from the complex obtained by the method described in the method for producing a complex The appearance is visually inspected and the judgment is made as follows. rice field.
◯: No wrinkles were seen on the entire film.
Δ: Wrinkles of 5 mm or more were observed.
（ポリエステルフィルムの製造）
製膜に供したポリエステルフィルムを構成する樹脂は主原料、副原料、粒子マスターを各実施例、各比較例につき表１に記載の種類、割合で混合した。また、各実施例および各比較例に用いた主原料、副原料、粒子マスターは以下のように準備した。
・ポリエステルＡ
ジカルボン酸成分としてテレフタル酸成分が１００モル％、グリコール成分としてエチレングリコール成分が１００モル％であるポリエチレンテレフタレート樹脂（固有粘度０．７２）。
・ポリエステルＢ
ジカルボン酸成分としてテレフタル酸成分が１００モル％、グリコール成分としてエチレングリコール成分が１００モル％であるポリエチレンテレフタレート樹脂（固有粘度０．８２）。
・ポリエステルＣ
ジカルボン酸成分としてテレフタル酸成分が１００モル％、グリコール成分としてエチレングリコール成分が１００モル％であるポリエチレンテレフタレート樹脂（固有粘度０．９２）。
・ポリエステルＤ
ジカルボン酸成分としてテレフタル酸成分が１００モル％、グリコール成分として１－４，ブタンジオール成分が１００モル％であるポリブチレンテレフタレート樹脂（固有粘度１．２）。
・ポリエステルＥ
ジカルボン酸成分としてテレフタル酸成分が１００モル％、グリコール成分としてエチレングリコール成分が１００モル％であるポリエチレンテレフタレート樹脂（固有粘度０．６５）。
・粒子マスターＡ
ポリエステルＡ中に平均粒子径１．２μｍの凝集シリカ粒子を粒子濃度２質量％で含有したポリエチレンテレフタレート粒子マスター。
・粒子マスターＢ
ポリエステルＤ中に平均粒子径１．２μｍの凝集シリカ粒子を粒子濃度２質量％で含有したポリブチレンテレフタレート粒子マスター。
(Manufacturing of polyester film)
As the resin constituting the polyester film used for film formation, the main raw material, the auxiliary raw material, and the particle master were mixed in the types and ratios shown in Table 1 for each Example and each Comparative Example. In addition, the main raw material, auxiliary raw material, and particle master used in each Example and each Comparative Example were prepared as follows.
・ Polyester A
A polyethylene terephthalate resin having 100 mol% of terephthalic acid component as a dicarboxylic acid component and 100 mol% of ethylene glycol component as a glycol component (intrinsic viscosity 0.72).
・ Polyester B
A polyethylene terephthalate resin (intrinsic viscosity 0.82) having 100 mol% of terephthalic acid component as a dicarboxylic acid component and 100 mol% of ethylene glycol component as a glycol component.
・ Polyester C
A polyethylene terephthalate resin having 100 mol% of terephthalic acid component as a dicarboxylic acid component and 100 mol% of ethylene glycol component as a glycol component (intrinsic viscosity 0.92).
・ Polyester D
A polybutylene terephthalate resin (intrinsic viscosity 1.2) in which the dicarboxylic acid component is 100 mol% terephthalic acid component and the glycol component is 1-4, butanediol component is 100 mol%.
・ Polyester E
A polyethylene terephthalate resin (intrinsic viscosity 0.65) containing 100 mol% of terephthalic acid component as a dicarboxylic acid component and 100 mol% of ethylene glycol component as a glycol component.
・ Particle Master A
A polyethylene terephthalate particle master containing aggregated silica particles having an average particle diameter of 1.2 μm in polyester A at a particle concentration of 2% by mass.
・ Particle Master B
A polybutylene terephthalate particle master containing aggregated silica particles having an average particle diameter of 1.2 μm in polyester D at a particle concentration of 2% by mass.
（塗剤Ａ）実施例１～１１、比較例１～３
・メチルメタクリレート／エチルアクリレート／アクリル酸／Ｎ－メチロールアクリルアミド＝６３／３５／１／１質量％の共重合組成から成るアクリル樹脂： ３．００質量％
・メラミン架橋剤： ０．７５質量％
・コロイダルシリカ粒子（平均粒径：８０ｎｍ）： ０．１５質量％
・ヘキサノール： ０．２６質量％
・ブチルセロソルブ： ０．１８質量％
・水： ９５．６６質量％
（金属箔）
本発明で使用した金属箔は以下のもの用いた。
・金属箔Ａ
金属箔の両面に化成処理としてクロム酸クロメート処理を施した厚さが４０μｍの日本製箔製アルミニウム“８０２１”。
(Coating A) Examples 1 to 11 and Comparative Examples 1 to 3
Acrylic resin having a copolymer composition of methyl methacrylate / ethyl acrylate / acrylic acid / N-methylolacrylamide = 63/35/1 / 1% by mass: 3.00% by mass.
-Melamine cross-linking agent: 0.75% by mass
-Coloidal silica particles (average particle size: 80 nm): 0.15% by mass
-Hexanol: 0.26% by mass
-Butyl cellosolve: 0.18% by mass
-Water: 95.66% by mass
(Metal leaf)
The following metal foils were used in the present invention.
・ Metal leaf A
Aluminum "8021" made in Japan with a thickness of 40 μm, in which both sides of the metal foil are subjected to chromic acid chromate treatment as a chemical conversion treatment.
（実施例１～１２、比較例１～２）
押出機を用い、表１に記載のポリエステル種、粒子マスターをそれぞれ真空乾燥機にて１８０℃４時間乾燥し、水分を十分に除去した後、表１に記載のとおり押出機に主原料および副原料、粒子マスターを投入し、２８０℃にて溶融した。次いで押出機から溶融押出された樹脂を、口金から吐出された樹脂を２５℃に冷却されたキャストドラム上に冷却固化して未延伸シートを得た。その際、Ｔダイのリップと冷却ドラム間の距離は３５ｍｍに設定し、直径０．１ｍｍのワイヤー状電極を使用して１４ｋＶの電圧で静電印加させ、冷却ドラムに密着をさせた。また、未延伸シートの冷却ドラムの通過速度は２５ｍ／分、未延伸シートの冷却ドラムとの接触長さは、２．５ｍとした。
(Examples 1 to 12, Comparative Examples 1 to 2)
Using an extruder, the polyester seeds and particle masters shown in Table 1 are each dried at 180 ° C. for 4 hours in a vacuum dryer to sufficiently remove water, and then the main raw material and auxiliary materials are added to the extruder as shown in Table 1. The raw material and the particle master were added and melted at 280 ° C. Next, the resin melt-extruded from the extruder was cooled and solidified on a cast drum in which the resin discharged from the mouthpiece was cooled to 25 ° C. to obtain an unstretched sheet. At that time, the distance between the lip of the T-die and the cooling drum was set to 35 mm, and electrostatically applied at a voltage of 14 kV using a wire-shaped electrode having a diameter of 0.1 mm to bring the T-die into close contact with the cooling drum. The passing speed of the cooling drum of the unstretched sheet was 25 m / min, and the contact length of the unstretched sheet with the cooling drum was 2.5 m.
続いて、該未延伸シートを表２に記載した温度に加熱したロール群で予熱した後、表２に記載した温度に制御した加熱ロールを用いて長手方向（縦方向）にそれぞれ表２に示した倍率に延伸し、２５℃の温度のロール群で冷却して一軸延伸フィルムを得た。 Subsequently, the unstretched sheet is preheated with a roll group heated to the temperature shown in Table 2, and then shown in Table 2 in the longitudinal direction (longitudinal direction) using a heating roll controlled to the temperature shown in Table 2. The film was stretched to a different magnification and cooled with a roll group having a temperature of 25 ° C. to obtain a uniaxially stretched film.
この一軸延伸フィルムに空気中でコロナ放電処理を施し、その処理面にアンカーコート層として塗剤Ａを超音波分散させながら混合し、＃４メタリングバーにてキャストと接着した面に均一に塗布して表面処理を施した。次いで、一軸延伸フィルムの両端をクリップで把持しながらテンター内を表２に記載の温度に制御した予熱ゾーンに導き、引き続き連続的に表２に記載した温度に保たれた加熱ゾーンで長手方向に直角な方向（幅方向）にそれぞれ表２に示した倍率に延伸した。さらに引き続いて、テンター内の熱処理ゾーンで表２に示す熱処理温度にて２０秒間の熱処理を施し、さらに表２に示す弛緩温度で表２示す弛緩率にて弛緩処理を行った。次いで、均一に徐冷し、表１に示す厚さのポリエステルフィルムを得た。ポリエステルフィルムの特性は表３に示したとおりである。 This uniaxially stretched film is subjected to corona discharge treatment in air, and the coating material A is mixed while being ultrasonically dispersed as an anchor coat layer on the treated surface, and uniformly applied to the surface adhered to the cast with a # 4 metering bar. And surface treatment was applied. Next, while grasping both ends of the uniaxially stretched film with clips, the inside of the tenter is guided to a preheating zone controlled to the temperature shown in Table 2, and then continuously in the heating zone kept at the temperature shown in Table 2 in the longitudinal direction. It was stretched in the perpendicular direction (width direction) to the magnification shown in Table 2, respectively. Further, subsequently, the heat treatment was performed in the heat treatment zone in the tenter at the heat treatment temperature shown in Table 2 for 20 seconds, and further, the relaxation treatment was performed at the relaxation temperature shown in Table 2 at the relaxation rate shown in Table 2. Then, it was cooled slowly to obtain a polyester film having the thickness shown in Table 1. The characteristics of the polyester film are as shown in Table 3.
得られたポリエステルフィルムの表面処理面側と金属箔Ａが接着するようにドライラミネート法によって、ウレタン系接着剤である東洋インキ製“ＡＤ５０２”ＡＤ５０２、ＣＡＴ１０Ｌ、酢酸エチルを２５：１５：２の比率となるように混合した塗剤を接着層として用いて張り合わせた。ここで、接着剤塗布量は固形分としてポリエステルフィルム表面処理面側に５ｇ／ｍ２とし、張り合わせ後に６０℃、１４４時間のエージング処理をして複合体を得た。複合体の特性は表３に示したとおりである。 By a dry laminating method so that the surface-treated surface side of the obtained polyester film and the metal leaf A adhere to each other, a urethane-based adhesive "AD502" AD502, CAT10L, and ethyl acetate are mixed in a ratio of 25:15: 2. The coating materials mixed so as to be as an adhesive layer were used and bonded together. Here, the amount of the adhesive applied was 5 g / m 2 on the surface-treated surface side of the polyester film as a solid content, and after laminating, aging treatment was performed at 60 ° C. for 144 hours to obtain a composite. The characteristics of the complex are as shown in Table 3.
得られた複合体の金属箔Ａ上に、シーラントとしてマレイン酸変性ポリプロピレン樹脂とポリプロピレンとを共押出しした２層共押出しフィルム（マレイン酸変性ポリプロピレン樹脂層：２０μｍ、ポリプロピレン樹脂層：６０μｍ）を、マレイン酸変性ポリプロピレン樹脂層が金属箔側に位置するようにし、ラミネーターを用いて加熱圧着（１６０℃、０．３ＭＰａ、２ｍ／ｍｉｎ）させることで積層させ、ポリエステルフィルム／接着層／アルミニウム箔／シーラントとなる構成体を作成した。得られた構成体の評価をした結果は表３に示したとおりであり、実施例１～１２については絞り成形性に優れていることが確認できた。 A two-layer co-extruded film (maleic acid-modified polypropylene resin layer: 20 μm, polypropylene resin layer: 60 μm) in which maleic acid-modified polypropylene resin and polypropylene are co-extruded as a sealant is placed on the metal foil A of the obtained composite. The acid-modified polypropylene resin layer is located on the metal foil side, and is laminated by heat-pressing (160 ° C, 0.3 MPa, 2 m / min) using a laminator to form a polyester film / adhesive layer / aluminum foil / sealant. I created a structure that consists of. The results of evaluation of the obtained constituents are as shown in Table 3, and it was confirmed that Examples 1 to 12 were excellent in draw moldability.
本発明のポリエステルフィルムは加工硬化指数、固有粘度、剛直非晶量を特定範囲とすることでポリアミドを用いた構成同等以上の絞り成形性を発現し、高容量化対応の電池外装用構成体、様々な形状に対応可能な医薬包装用構成体に好適に使用することができる。 The polyester film of the present invention exhibits work hardening index, intrinsic viscosity, and squeeze formability equal to or higher than the composition using polyamide by setting the specific ranges of the work hardening index, the intrinsic viscosity, and the amount of rigid amorphous. It can be suitably used for a pharmaceutical packaging structure that can be used in various shapes.
１ 構成体
２ 雄型金型
３ 雌型金型
４ 成形体
1
Claims (6)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020164818A JP2022056851A (en) | 2020-09-30 | 2020-09-30 | Polyester film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020164818A JP2022056851A (en) | 2020-09-30 | 2020-09-30 | Polyester film |
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| JP2022056851A true JP2022056851A (en) | 2022-04-11 |
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