JP2000169600A - Polyester film for packaging - Google Patents
Polyester film for packagingInfo
- Publication number
- JP2000169600A JP2000169600A JP34533298A JP34533298A JP2000169600A JP 2000169600 A JP2000169600 A JP 2000169600A JP 34533298 A JP34533298 A JP 34533298A JP 34533298 A JP34533298 A JP 34533298A JP 2000169600 A JP2000169600 A JP 2000169600A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- film
- packaging
- polyester film
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920006267 polyester film Polymers 0.000 title claims description 53
- 238000004806 packaging method and process Methods 0.000 title claims description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 81
- 229920000728 polyester Polymers 0.000 claims abstract description 77
- 239000002184 metal Substances 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000010030 laminating Methods 0.000 claims abstract description 7
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 26
- 230000003197 catalytic effect Effects 0.000 claims description 25
- 238000000465 moulding Methods 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 15
- 238000003475 lamination Methods 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 230000007774 longterm Effects 0.000 abstract description 23
- 239000005022 packaging material Substances 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 11
- 238000010409 ironing Methods 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 23
- 238000003860 storage Methods 0.000 description 21
- 239000010410 layer Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 14
- -1 polyethylene Polymers 0.000 description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005266 casting Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 230000002087 whitening effect Effects 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000007790 scraping Methods 0.000 description 4
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- 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 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009459 flexible packaging Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000005029 tin-free steel Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 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
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000002291 germanium compounds Chemical class 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 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
- 238000007639 printing Methods 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-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
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 102100024693 Death effector domain-containing protein Human genes 0.000 description 1
- 102100037709 Desmocollin-3 Human genes 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 101000830359 Homo sapiens Death effector domain-containing protein Proteins 0.000 description 1
- 101000968042 Homo sapiens Desmocollin-2 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 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
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 101001094026 Synechocystis sp. (strain PCC 6803 / Kazusa) Phasin PhaP Proteins 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 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
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000010951 brass Substances 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
- 239000011575 calcium Substances 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 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
- 238000011088 calibration curve Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- ABXXWVKOBZHNNF-UHFFFAOYSA-N chromium(3+);dioxido(dioxo)chromium Chemical compound [Cr+3].[Cr+3].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O ABXXWVKOBZHNNF-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、包装用ポリエステ
ルフィルムに関するものである。詳しくは内容物に直接
接触する包装材料として使用される際の保存性にすぐれ
るだけでなく、成形加工される用途、ラミネート成形さ
れる用途、特に紙、金属を基材としたラミネート成形用
途、容器に好適な包装用ポリエステルフィルムに関する
ものである。[0001] The present invention relates to a polyester film for packaging. Specifically, it is not only excellent in preservability when used as a packaging material that comes into direct contact with the contents, but also used for molding, lamination, especially paper and metal-based laminate molding, The present invention relates to a polyester film for packaging suitable for a container.
【０００２】[0002]
【従来の技術】従来、包装材料に使用されるポリエステ
ルフィルムは、軟包装の場合にはポリエチレン、ポリプ
ロピレンと接着剤を用いて、または接着剤を使用するこ
となくラミネートされ、シーラント層が直接内容物と接
するために、ポリエステルフィルムと内容物の接触を考
慮することは少なかった。2. Description of the Related Art Conventionally, in the case of flexible packaging, a polyester film used as a packaging material is laminated with polyethylene, polypropylene and an adhesive or without an adhesive, and a sealant layer is directly formed on the contents. In order to make contact, the contact between the polyester film and the contents was rarely considered.
【０００３】しかしながら、近年包装材料が多様化、進
化するにつれポリエステルフィルムと内容物が直接接触
する用途が増え、さらにシェルフライフの増加に伴いポ
リエステルフィルムの品質を改良することが考えられて
きている。However, in recent years, as packaging materials have been diversified and evolved, applications in which the polyester film comes into direct contact with the contents have increased, and it has been considered to improve the quality of the polyester film with an increase in shelf life.
【０００４】特に、内容物が食品、飲料である場合は、
ポリエステルフィルムとの接触により品質の変化が認め
られるケース、例えば飲料や食品の味の変化などは内容
物の商品としての価値を下げることから問題となる場合
がある。[0004] In particular, when the contents are foods and beverages,
A case where a change in quality is recognized due to contact with the polyester film, for example, a change in taste of a beverage or food may be problematic because the value of the content is reduced as a product.
【０００５】包装材料の中で、例えば容器の内面にポリ
エステルフィルムを使用するケースが増加しつつある。
その場合、金属とポリエステルフィルムを接着剤を用い
て、あるいは接着剤を使用せずにラミネートし、成形し
て缶を得ている。[0005] Among packaging materials, for example, cases in which a polyester film is used for the inner surface of a container are increasing.
In this case, a metal and a polyester film are laminated with or without an adhesive and molded to obtain a can.
【０００６】従来、金属缶の缶内面および外面は腐食防
止を目的として、エポキシ系、フェノール系などの各種
熱硬化性樹脂を溶剤に溶解または分散させたものを塗布
し、金属表面を被覆することが広く行われていた。しか
しながら、このような熱硬化性樹脂の被覆方法は塗料の
乾燥に長時間を要し、生産性が低下したり、多量の有機
溶剤による環境汚染など好ましくない問題がある。Conventionally, the inside and outside surfaces of metal cans are coated with a solution of various thermosetting resins such as epoxy or phenol dissolved or dispersed in a solvent for the purpose of corrosion protection, to coat the metal surface. Was widely done. However, such a method of coating the thermosetting resin requires a long time for drying the paint, and has unfavorable problems such as a decrease in productivity and environmental pollution due to a large amount of an organic solvent.
【０００７】これらの問題を解決する方法としては、金
属缶の材料である鋼板、アルミニウム板あるいは該金属
板にメッキなど各種の表面処理を施した金属板にフィル
ムをラミネートする方法がある。そして、フィルムのラ
ミネート金属板を絞り成形やしごき成形加工して金属缶
を製造する場合、フィルムには次のような特性が要求さ
れ、さらに最近では金属缶の内容物への金属触媒成分お
よび金属触媒成分に混じった不純物成分の混入をできる
だけ少なくしたいという要求も強くなりつつある。As a method of solving these problems, there is a method of laminating a film on a steel plate, an aluminum plate, or a metal plate which has been subjected to various surface treatments such as plating, which is a material of a metal can. When a metal can is manufactured by drawing or ironing a laminated metal plate of a film, the film is required to have the following characteristics. More recently, a metal catalyst component and a metal There is also a growing demand for minimizing the contamination of the catalyst components with the impurity components.
【０００８】(1) 金属板へのラミネート性に優れてい
ること。 (2) 金属板との密着性に優れていること。 (3) 成形性に優れ、成形後にピンホールなどの欠陥を
生じないこと。 (4) 金属缶に対する衝撃によって、ポリエステルフィ
ルムが剥離したり、クラック、ピンホールが発生したり
しないこと。 (5) 缶の内容物の風味が、フィルム中の金属成分、低
分子成分によりそこなわれないこと（以下、味特性と記
載する）。さらにその特性が長時間にわたり維持される
こと（長期保存性）。(1) Being excellent in laminating property to a metal plate. (2) Excellent adhesion to the metal plate. (3) It has excellent moldability and does not generate defects such as pinholes after molding. (4) The polyester film shall not peel, crack or pinhole due to impact on the metal can. (5) The flavor of the contents of the can is not impaired by metal components and low molecular components in the film (hereinafter referred to as taste characteristics). Further, its properties are maintained for a long time (long-term storage property).
【０００９】これらの要求の中でも味特性を解決するた
めに多くの提案がなされており、例えば特開平９−２４
１３６１号公報では、触媒金属、リンの含有量を特定の
範囲とすることにより味特性、生産性の両立を図ろうと
している。また、ポリエステル中の低分子成分を低減す
ることについても多くの提案がなされている。Among these demands, many proposals have been made to solve the taste characteristics.
Japanese Patent Publication No. 1361 attempts to achieve both the taste characteristics and the productivity by setting the contents of the catalyst metal and phosphorus in a specific range. Many proposals have also been made for reducing low molecular components in polyester.
【００１０】しかしながら、特公昭３７−６１４２号公
報に記載されるような溶融ポリマーフィルムを静電引加
キャストするために必要な金属、リン量が必要となって
いるため、味特性の確保、特に長期保存性、触媒金属成
分の低減という点では十分とは言えなかった。また、金
属触媒成分および金属触媒成分に混じった不純物成分の
混入をできるだけ少なくするという点でもさらなる改善
が求められてきている。[0010] However, since the amount of metal and phosphorus necessary for electrostatically casting a molten polymer film as described in JP-B-37-6142 is required, it is necessary to secure taste characteristics, especially It was not sufficient in terms of long-term storage properties and reduction of catalytic metal components. Further, further improvement has been demanded in terms of minimizing mixing of the metal catalyst component and the impurity component mixed with the metal catalyst component as much as possible.
【００１１】また、上記の発明では金属板へのラミネー
トは優れているが、紙、不織布、他のポリマーとラミネ
ートすることについては考慮されておらず、他の基材と
の十分な接着性、ラミネート加工、印刷などを行う際の
寸法安定性などは考慮されていなかった。In the above invention, lamination to a metal plate is excellent, but no consideration is given to lamination with paper, nonwoven fabric, or other polymers, and sufficient adhesion to other base materials, No consideration was given to dimensional stability and the like when performing laminating, printing, and the like.
【００１２】[0012]
【発明が解決しようとする課題】本発明の目的は、上記
した従来技術の問題点を解消することにあり、包装材料
として内容物の保護性、特に味特性、長期保存性、触媒
金属成分の低減に優れるとともに、成形、ラミネート加
工を可能とし、特に絞り成形やしごきなどの厳しい成形
加工後も味特性、耐食性に優れる包装用ポリエステルフ
ィルムを提供することにある。また、金属以外のラミネ
ート基材、例えば紙、不織布、他のポリマー層に対して
も優れたラミネート性、接着性、成形性、加工性、内容
物の保護性を有する包装用ポリエステルフィルムを提供
するものである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to protect the contents, especially the taste characteristics, long-term storage properties, and the catalytic metal component as a packaging material. An object of the present invention is to provide a polyester film for packaging which is excellent in reduction, enables molding and lamination, and has excellent taste characteristics and corrosion resistance even after severe molding such as drawing and ironing. Further, the present invention provides a packaging polyester film having excellent laminating properties, adhesive properties, moldability, processability, and content protection properties even with respect to a laminate substrate other than metal, for example, paper, nonwoven fabric, and other polymer layers. Things.
【００１３】[0013]
【課題を解決するための手段】前記した本発明の目的
は、Ｔｉ、Ａｌ、Ｚｒ、Ｓｉから選択される金属元素を
構成成分とする金属化合物を触媒成分として少なくとも
２種類以上含有し、下記式（１）を満足するポリエステ
ルＡを主たる構成成分とすることを特徴とする包装用ポ
リエステルフィルムによって達成することができる。 １≦ＭＡ≦４０ （１） （但し、式中のＭＡはポリエステルＡ中に残存する全触
媒金属元素の中でＴｉ、Ａｌ、Ｚｒ、Ｓｉの合計濃度
（ミリモル％）） 本発明は、鋭意検討の結果、ポリエステル中の金属触媒
成分とその量を限定することにより、金属触媒量を全体
として大幅に低減することができるため、成形加工性、
内容物の保護性に極めて優れることを見出したことに基
づくものであり、特に味特性、長期保存性に優れるだけ
でなく、成形加工にも好適な包装用ポリエステルフィル
ムを提供することを可能にしたものである。SUMMARY OF THE INVENTION The object of the present invention is to contain at least two or more kinds of metal compounds having a metal element selected from Ti, Al, Zr and Si as a catalyst component. It can be achieved by a polyester film for packaging, characterized by using polyester A satisfying (1) as a main component. 1 ≦ MA ≦ 40 (1) (where, MA in the formula is the total concentration (mmol%) of Ti, Al, Zr, and Si among all the catalytic metal elements remaining in the polyester A) As a result, by limiting the amount of the metal catalyst component in the polyester and the amount thereof, the amount of the metal catalyst can be significantly reduced as a whole, so that the molding processability,
Based on the finding that the protection of the contents is extremely excellent, it has become possible to provide a polyester film for packaging which is not only particularly excellent in taste characteristics and long-term storage properties but also suitable for molding. Things.
【００１４】[0014]
【発明の実施の形態】本発明のポリエステルフィルムを
構成するポリエステルとは、主鎖中の主要な結合をエス
テル結合とする高分子の総称であって、通常ジカルボン
酸成分とグリコール成分を重縮合反応させることによっ
て得ることができる。ここでジカルボン酸成分として
は、たとえばテレフタル酸、ナフタレンジカルボン酸、
イソフタル酸、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、フタル酸な
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、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などを挙げることができる。また、
グリコール成分としては、たとえばエチレングリコー
ル、プロパンジオール、ブタンジオール、ペンタンジオ
ール、ヘキサンジオール、ネオペンチルグリコールなど
の脂肪族グリコール、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などのポリ
オキシアルキレングリコール、シクロヘキサンジメタノ
ールなどの脂環族グリコール、ビスフェノールＡ、ビス
フェノールＳなどの芳香族グリコールなどが挙げられ
る。BEST MODE FOR CARRYING OUT THE INVENTION The polyester constituting the polyester film of the present invention is a generic term for polymers having a main bond in the main chain as an ester bond, and is usually a polycondensation reaction of a dicarboxylic acid component and a glycol component. Can be obtained. Here, as the dicarboxylic acid component, for example, terephthalic acid, naphthalenedicarboxylic acid,
Aromatic dicarboxylic acids such as isophthalic acid, diphenyl dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenoxyethane dicarboxylic acid, 5-sodium sulfone dicarboxylic acid, phthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, and maleic Examples thereof include aliphatic dicarboxylic acids such as acid and fumaric acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and oxycarboxylic acids such as p-hydroxybenzoic acid. Also,
Examples of the glycol component include aliphatic glycols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, and neopentyl glycol; polyoxyalkylene glycols such as diethylene glycol, polyethylene glycol, and polypropylene glycol; and fats such as cyclohexanedimethanol. Examples thereof include aromatic glycols, aromatic glycols such as bisphenol A and bisphenol S, and the like.
【００１５】本発明のポリエステルＡの組成は特に限定
されないが、これらのジカルボン酸のうち、テレフタル
酸、ナフタレンジカルボン酸が耐熱性、味特性の点から
好ましく用いられ、ポリエステルを構成する酸成分の８
０モル％以上が、テレフタル酸および／またはナフタレ
ンジカルボン酸であることがさらに好ましく、特に味特
性の厳しい用途ではポリエステルを構成する酸成分の９
５モル％以上が、テレフタル酸および／またはナフタレ
ンジカルボン酸であると長期保存性に優れるので好まし
い。The composition of the polyester A of the present invention is not particularly limited. Of these dicarboxylic acids, terephthalic acid and naphthalenedicarboxylic acid are preferably used from the viewpoint of heat resistance and taste characteristics.
It is more preferable that 0 mol% or more is terephthalic acid and / or naphthalenedicarboxylic acid.
5 mol% or more of terephthalic acid and / or naphthalenedicarboxylic acid is preferable because of excellent long-term storage properties.
【００１６】これらのグリコール成分の中でも、エチレ
ングリコール、プロパンジオール、ブタンジオ−ル、シ
クロヘキサンジメタノ−ルなどが好ましいが、味特性、
長期保存性の厳しい用途では、ポリエステルを構成する
グリコール成分の９５モル％以上がエチレングリコール
であることが好ましい。Among these glycol components, ethylene glycol, propanediol, butanediol, cyclohexanedimethanol, and the like are preferable, but taste characteristics,
In applications in which long-term storage is severe, it is preferable that 95 mol% or more of the glycol component constituting the polyester is ethylene glycol.
【００１７】本発明では、ポリエステルＡの融点は特に
限定されないが、耐熱性、成形性、味特性、長期保存性
の点でポリエステルＡの融点が２００〜２８０℃である
ことが好ましい。特に成形性、接着性を重視する用途で
は融点が２００〜２４５℃であることが好ましい。ま
た、特に耐熱性、味特性、長期保存性の点では融点が２
４６〜２８０℃であることが好ましい。In the present invention, the melting point of the polyester A is not particularly limited, but the melting point of the polyester A is preferably from 200 to 280 ° C. in view of heat resistance, moldability, taste characteristics and long-term storage. In particular, in applications where emphasis is placed on moldability and adhesiveness, the melting point is preferably from 200 to 245 ° C. In addition, the melting point is 2 particularly in terms of heat resistance, taste characteristics, and long-term storage stability.
The temperature is preferably from 46 to 280 ° C.
【００１８】本発明の包装用ポリエステルフィルムは、
成形性、味特性、長期保存性を良好とする上で、Ｔｉ、
Ａｌ、Ｚｒ、Ｓｉから選択される金属元素を構成成分と
する金属化合物を触媒成分として少なくとも２種類以上
含有し、下記式（１）を満足するポリエステルＡを主た
る構成成分とすることが必要である。 １≦ＭＡ≦４０ （１） （但し、式中のＭＡはポリエステルＡ中に残存する全触
媒金属元素の中でＴｉ、Ａｌ、Ｚｒ、Ｓｉの合計濃度
（ミリモル％））The polyester film for packaging of the present invention comprises:
In order to improve moldability, taste characteristics, and long-term storage, Ti,
It is necessary to contain at least two or more kinds of metal compounds having a metal element selected from Al, Zr and Si as a catalyst component as a catalyst component, and to use polyester A satisfying the following formula (1) as a main component. . 1 ≦ MA ≦ 40 (1) (where, MA in the formula is the total concentration (mmol%) of Ti, Al, Zr, and Si among all the catalytic metal elements remaining in the polyester A)
【００１９】触媒の金属化合物の中でも、Ｔｉ／Ｓｉ複
合酸化物、Ｔｉ／Ｓｉ／Ａｌ複合酸化物、Ｔｉ／Ｚｒ複
合酸化物、Ｔｉ／Ｚｒ／Ａｌ複合酸化物などが特に好ま
しい。これらの中でもＴｉ／Ｓｉ複合酸化物が特に好ま
しく、Ｔｉ／Ｓｉのモル比が２０／１〜１／２０が好ま
しく、さらに好ましくはＴｉ／Ｓｉのモル比が１０／１
〜１／１である。Among the metal compounds of the catalyst, Ti / Si composite oxide, Ti / Si / Al composite oxide, Ti / Zr composite oxide, Ti / Zr / Al composite oxide and the like are particularly preferable. Among these, a Ti / Si composite oxide is particularly preferred, the molar ratio of Ti / Si is preferably 20/1 to 1/20, and more preferably the molar ratio of Ti / Si is 10/1.
１／1/1.
【００２０】さらに味特性、長期保存性を極めて良好と
する上では、Ｔｉ、Ａｌ、Ｚｒ、Ｓｉから選択される金
属元素を構成成分とする金属化合物を触媒成分として少
なくとも２種類以上含有し、下記式（２）を満足するポ
リエステルＡを主たる構成成分とすることが好ましい。 １≦ＭＡ＜２０ （２） （但し、式中のＭＡはポリエステルＡ中に残存する全触
媒金属元素の中でＴｉ、Ａｌ、Ｚｒ、Ｓｉの合計濃度
（ミリモル％）） 特に好ましくはＭＡが２ミリモル％以上１８ミリモル％
以下である。In order to further improve taste characteristics and long-term storage stability, at least two types of metal compounds containing metal elements selected from Ti, Al, Zr, and Si as catalyst components are contained as catalyst components. It is preferable that polyester A satisfying the formula (2) is a main component. 1 ≦ MA <20 (2) (where, MA in the formula is the total concentration (mmol%) of Ti, Al, Zr, and Si in all the catalytic metal elements remaining in the polyester A). More than mmol% 18 mmol%
It is as follows.
【００２１】本発明は、特定の元素からなる金属触媒を
用いることで、十分な触媒活性を有するだけでなく触媒
量を低減でき、かつ味特性、長期保存性を極めて良好に
できることを見出したことに基づくものである。According to the present invention, it has been found that by using a metal catalyst comprising a specific element, not only sufficient catalytic activity can be obtained but also the amount of the catalyst can be reduced, and taste characteristics and long-term storage stability can be extremely improved. It is based on.
【００２２】本発明では、味特性、長期保存性を良好と
する上で、ポリエステルＡ中の触媒金属量とリン量が下
記式（３）を満足することがさらに好ましい。In the present invention, in order to improve the taste characteristics and the long-term storage stability, it is more preferable that the amount of the catalyst metal and the amount of phosphorus in the polyester A satisfy the following formula (3).
【００２３】−２０≦ＭＡ−ＰＡ≦２０ （３） （但し、式中のＭＡはポリエステルＡ中に残存する全触
媒金属元素の中でＴｉ、Ａｌ、Ｚｒ、Ｓｉの合計触媒金
属元素の濃度（ミリモル％）、ＰＡはポリエステルＡ中
に残存するリン元素の濃度（ミリモル％）を示す。） 特に好ましくは、ポリエステルＡ中の触媒金属量とリン
量が下記式（４）を満足することが望ましい。-20 ≦ MA−PA ≦ 20 (3) (where, MA in the formula is the concentration of the total catalytic metal element of Ti, Al, Zr, and Si among all the catalytic metal elements remaining in the polyester A ( (Millimol%), PA indicates the concentration (millimol%) of the phosphorus element remaining in the polyester A.) Particularly preferably, the amount of the catalyst metal and the amount of phosphorus in the polyester A should satisfy the following formula (4). .
【００２４】−１０≦ＭＡ−ＰＡ≦１０ （４） （但し、式中のＭＡはポリエステルＡ中に残存する全触
媒金属元素の中でＴｉ、Ａｌ、Ｚｒ、Ｓｉの合計触媒金
属元素の濃度（ミリモル％）、ＰＡはポリエステルＡ中
に残存するリン元素の濃度（ミリモル％）を示す。） 本発明のポリエステルを製造する際の触媒としては、式
（１）を満たすことが必要であるが、特性を損ねない範
囲でアルカリ土類金属化合物、マンガン化合物、コバル
ト化合物、アンチモン化合物、ゲルマニウム化合物など
も併用して使用できる。-10 ≦ MA−PA ≦ 10 (4) (where, MA in the formula is the concentration of the total catalytic metal element of Ti, Al, Zr, and Si among all the catalytic metal elements remaining in the polyester A ( And the PA represents the concentration (mmol%) of the phosphorus element remaining in the polyester A.) As a catalyst for producing the polyester of the present invention, it is necessary to satisfy the formula (1). Alkaline earth metal compounds, manganese compounds, cobalt compounds, antimony compounds, germanium compounds and the like can be used in combination as long as the properties are not impaired.
【００２５】例えば触媒としてＴｉ／Ｓｉ複合酸化物触
媒を添加する場合には、テレフタル酸成分とエチレング
リコール成分をＴｉ／Ｓｉ複合酸化物の存在下でエステ
ル交換またはエステル化反応させ、リン化合物を添加
し、引き続き高温、減圧下で一定のジエチレングリコー
ル含有量になるまで重縮合反応させ、特定の触媒金属
量、リン量を有するポリエステルを得る方法などが好ま
しく採用される。For example, when a Ti / Si composite oxide catalyst is added as a catalyst, a terephthalic acid component and an ethylene glycol component are transesterified or esterified in the presence of the Ti / Si composite oxide, and a phosphorus compound is added. Then, a method in which a polycondensation reaction is continuously performed at a high temperature under reduced pressure until the content of diethylene glycol reaches a certain value to obtain a polyester having a specific catalytic metal content and a specific phosphorus content is preferably employed.
【００２６】熱安定剤として添加されるリン化合物は特
に限定されないが、リン酸、亜リン酸などが好ましい。The phosphorus compound added as a heat stabilizer is not particularly limited, but phosphoric acid and phosphorous acid are preferred.
【００２７】一方、ポリエステルＡには味特性を損ねな
い範囲でアルカリ金属を添加しても良く、アルカリ金属
元素の総量としては２０ｐｐｍ以下が好ましく、さらに
好ましくは１０ｐｐｍ以下、特に好ましくは８ｐｐｍ以
下である。特に本発明のポリエステルとして融点が２４
６〜２８０℃のポリエステルを使用する場合は、耐熱性
に優れるため１〜２０ｐｐｍ以下でアルカリ金属元素を
含有しても良い。On the other hand, an alkali metal may be added to polyester A as long as taste characteristics are not impaired, and the total amount of alkali metal elements is preferably 20 ppm or less, more preferably 10 ppm or less, and particularly preferably 8 ppm or less. . Particularly, the polyester of the present invention has a melting point of 24.
When a polyester at 6 to 280 ° C is used, an alkali metal element may be contained at 1 to 20 ppm or less because of excellent heat resistance.
【００２８】さらに、本発明において容器や軟包装の印
刷、製袋加工などの製造工程、内容物充填工程での熱処
理後の長期保存性を良好とし、基材との密着性を良好と
する点で、フィルム中のカルボン酸濃度が下記式（５）
を満足することが好ましい。 ３０≦Ｃ≦４５ （５） （但し、式中のＣはフィルム中のカルボン酸濃度（当量
／トン）を示す。） さらに好ましくは３０〜４２当量／トンである。Furthermore, in the present invention, the long-term storage stability after heat treatment in the manufacturing process such as printing of containers and flexible packaging, bag making process, and the filling process of the contents is improved, and the adhesion to the base material is improved. And the carboxylic acid concentration in the film is represented by the following formula (5)
Is preferably satisfied. 30 ≦ C ≦ 45 (5) (where C in the formula represents the carboxylic acid concentration (equivalent / ton) in the film.) More preferably, it is 30 to 42 equivalent / ton.
【００２９】本発明の包装用ポリエステルフィルムは、
成形加工性、フィルムの強度の点で面配向係数が０．０
６〜０．１７であることが好ましく、特に紙、金属板な
どの基材とラミネートして使用する用途では面配向係数
が０．０６〜０．１５が好ましく、さらに好ましくは
０．０６〜０．１４である。ここで、面配向係数とは、
フィルムの長手方向屈折率をｎＭＤ、フィルムの幅方向
屈折率をｎＴＤ、フィルムの厚さ方向屈折率をｎＺＤと
した際に、面配向係数Ｆｎ＝（ｎＭＤ＋ｎＴＤ）／２−
ｎＺＤで表される。The polyester film for packaging of the present invention comprises:
The plane orientation coefficient is 0.0 in terms of moldability and film strength.
The surface orientation coefficient is preferably from 0.06 to 0.15, more preferably from 0.06 to 0.15, and particularly preferably from 0.06 to 0.15 in applications where the surface orientation coefficient is used by lamination with a substrate such as paper or a metal plate. .14. Here, the plane orientation coefficient is
When the refractive index in the longitudinal direction of the film is nMD, the refractive index in the width direction of the film is nTD, and the refractive index in the thickness direction of the film is nZD, the plane orientation coefficient Fn = (nMD + nTD) / 2−2
It is represented by nZD.
【００３０】さらに、成形性、耐熱性、耐経時性の点で
は厚さ方向屈折率ｎＺＤが１．５以上であることが好ま
しい。特に、好ましくは１．５１〜１．５５であると成
形性、耐経時性を両立する上で望ましい。Further, in terms of moldability, heat resistance and aging resistance, it is preferable that the refractive index in the thickness direction nZD is 1.5 or more. In particular, it is preferably 1.51 to 1.55 in order to achieve both moldability and aging resistance.
【００３１】また、包装用フィルムとしての加工性、ハ
ンドリングの点で、粒子を含有していることが好まし
く、粒子径、添加量は特に限定されないが、成形加工時
の滑り性、ラミネート時の接着性の点で平均粒子径が３
μｍ以下の粒子を０．０１〜１重量％含有していること
が好ましい。特に好ましくは０．０３〜０．５重量％で
ある。Further, it is preferable that particles are contained from the viewpoint of processability and handling as a packaging film, and the particle diameter and the amount of addition are not particularly limited. Average particle size of 3
It is preferred that the particles contain particles having a particle size of not more than 0.01 μm. Particularly preferably, it is 0.03 to 0.5% by weight.
【００３２】本発明で使用される無機粒子としては特に
限定されないが、具体的には湿式および乾式シリカ、コ
ロイダルシリカ、ケイ酸アルミニウム、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、アル
ミナ、マイカ、カオリン、クレ−等が挙げられ、表面形
成性の点からケイ酸アルミニウム、コロイダルシリカ等
が好ましい。The inorganic particles used in the present invention are not particularly limited, but specific examples thereof include wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, and kaolin. , Clay and the like, and aluminum silicate, colloidal silica and the like are preferable from the viewpoint of surface forming properties.
【００３３】また、本発明で使用できる有機粒子として
は、様々な有機高分子粒子を用いることができるが、そ
の種類としては、少なくとも一部がポリエステルに対し
不溶の粒子であればいかなる組成の粒子でもかまわな
い。また、このような粒子の素材としては、ポリイミ
ド、ポリアミドイミド、ポリメチルメタクリレート、ホ
ルムアルデヒド樹脂、フェノール樹脂、架橋ポリスチレ
ン、シリコーン樹脂およびこれらの混合、共重合樹脂な
どの種々のものを使用することができるが、耐熱性が高
く、かつ粒度分布の均一な粒子が得られやすいビニル系
架橋高分子粒子が特に好ましい。As the organic particles that can be used in the present invention, various organic polymer particles can be used, and the type of the particles is not particularly limited as long as at least a part of the particles is insoluble in the polyester. But it doesn't matter. Further, as a material of such particles, various materials such as polyimide, polyamide imide, polymethyl methacrylate, formaldehyde resin, phenol resin, cross-linked polystyrene, silicone resin and a mixture thereof, a copolymer resin, and the like can be used. However, vinyl crosslinked polymer particles having high heat resistance and easy to obtain particles having a uniform particle size distribution are particularly preferable.
【００３４】本発明におけるポリエステルは、好ましく
はジエチレングリコール成分量が０．０１〜５モル％、
さらに好ましくは０．０１〜３モル％であることが包装
材料におけるレトルト処理、熱処理などの多くの熱履歴
を受けても優れた内容物の保護性、味特性を維持する上
で望ましい。The polyester in the present invention preferably has a diethylene glycol content of 0.01 to 5 mol%,
More preferably, the content is 0.01 to 3 mol% in order to maintain excellent protective properties and taste characteristics of the contents even when subjected to many heat histories such as retort treatment and heat treatment of the packaging material.
【００３５】また、味特性を良好にする上で、フィルム
中のアセトアルデヒドの含有量を好ましくは１５ｐｐｍ
以下、さらに好ましくは１０ｐｐｍ以下とすることが望
ましい。アセトアルデヒドの含有量が１５ｐｐｍを越え
ると味特性に劣ることがある。フィルム中のアセトアル
デヒドの含有量を１５ｐｐｍ以下にする方法は特に限定
されるものではないが、たとえばポリエステルを重縮合
反応などで製造する際の熱分解によって生じるアセトア
ルデヒドを除去するため、ポリエステルを減圧下もしく
は不活性ガス雰囲気下でポリエステルの融点以下の温度
で熱処理する方法、好ましくはポリエステルを減圧下あ
るいは不活性ガス雰囲気下において１５５℃以上融点以
下の温度で固相重合する方法、ベント式押出機を使用し
て溶融押出する方法、高分子を溶融押出する際に押出温
度を融点＋２５℃以内、好ましくは融点＋２０℃以内で
短時間で押し出す方法、また二軸延伸製膜時に熱処理を
行う方法を挙げることができる。In order to improve the taste characteristics, the content of acetaldehyde in the film is preferably 15 ppm.
Below, it is more desirable to make it 10 ppm or less. If the content of acetaldehyde exceeds 15 ppm, the taste characteristics may be poor. The method for reducing the content of acetaldehyde in the film to 15 ppm or less is not particularly limited. For example, in order to remove acetaldehyde generated by thermal decomposition during production of a polyester by a polycondensation reaction or the like, the polyester is reduced under reduced pressure or A method in which heat treatment is performed at a temperature lower than the melting point of the polyester in an inert gas atmosphere, preferably a method in which the polyester is subjected to solid-state polymerization at a temperature of 155 ° C. or higher and a temperature lower than the melting point under reduced pressure or an inert gas atmosphere, And a method of extruding a polymer at a melting point within + 25 ° C, preferably within a melting point + 20 ° C in a short time when melt-extruding a polymer, and a method of performing heat treatment during biaxial stretching film formation. Can be.
【００３６】また、ポリエステルの固有粘度は特に限定
されないが、０．５〜１．３であることが好ましく、特
に耐熱性、耐経時性が要求される用途では固有粘度が
０．６〜１．１であることが好ましい。特に成形性が重
視される用途では、ポリエステルＡを主たる構成成分と
するフィルムの少なくとも片面に下記式（６）を満足す
るポリエステルＢを積層すると、成形性が特に良好とな
るので好ましい。 ＭＢ≧ＭＡ （６） （但し、式中のＭＢはポリエステルＢ中に残存する全触
媒金属元素の濃度（ミリモル％） さらに好ましくはＭＢ−ＭＡが５ミリモル％以上２００
ミリモル％以下であり、特に好ましくは１０ミリモル％
以上１００ミリモル％以下である。The intrinsic viscosity of the polyester is not particularly limited, but is preferably 0.5 to 1.3, and particularly when the heat resistance and the aging resistance are required, the intrinsic viscosity is 0.6 to 1. It is preferably 1. In particular, in applications where emphasis is placed on moldability, it is preferable to laminate polyester B satisfying the following formula (6) on at least one surface of a film containing polyester A as a main component, since moldability is particularly improved. MB ≧ MA (6) (where, MB in the formula is the concentration (mmol%) of all the catalytic metal elements remaining in the polyester B).
Mmol% or less, particularly preferably 10 mmol%.
Not less than 100 mmol%.
【００３７】積層フィルムの場合、ポリエステルＢの厚
みは特に限定されないが、ポリエステルフィルムの全体
厚みの１〜９０％であることが好ましく、味特性、長期
保存性を重視する場合、ポリエステルフィルムの全体厚
みの１〜５０％であること好ましい。さらにポリエステ
ルＢの厚みはポリエステルフィルムの全体厚みの５〜４
０％であることが好ましく、特に好ましくは５〜２０％
である。In the case of a laminated film, the thickness of the polyester B is not particularly limited, but is preferably 1 to 90% of the total thickness of the polyester film. Is preferably 1 to 50%. Further, the thickness of the polyester B is 5 to 4 times the total thickness of the polyester film.
It is preferably 0%, particularly preferably 5 to 20%
It is.
【００３８】本発明のフイルムの厚さは、金属にラミネ
ートした後の成形性、耐熱性、被覆性、およびラミネー
トした軟包装材料、容器では耐熱性、腰、強度の点で１
〜１０００μｍであることが好ましく、さらに好ましく
は５〜２００μｍである。特に軟包装、容器として幅広
くて使用する際には８〜１００μｍである。The thickness of the film of the present invention is 1 in terms of moldability, heat resistance, covering property after lamination to metal, and heat resistance, waist and strength for laminated soft packaging materials and containers.
The thickness is preferably from 1000 to 1000 μm, and more preferably from 5 to 200 μm. In particular, when used widely as a soft package or a container, the thickness is 8 to 100 μm.
【００３９】本発明におけるフィルムの製造方法として
は、特に限定されないが例えばポリエステルを必要に応
じて乾燥した後、公知の溶融押出機に供給し、スリット
状のダイからシート状に押出し、静電印加、水膜を設け
たキャスト法、キャスティングドラムの温度を増加させ
て粘着させる方法などの方式によりキャスティングドラ
ムに密着させ冷却固化し未延伸フィルムを得る方法があ
る。The method for producing a film in the present invention is not particularly limited. For example, after drying polyester as required, it is supplied to a known melt extruder, extruded into a sheet from a slit die, and subjected to electrostatic application. There is a method in which an unstretched film is obtained by bringing the film into close contact with the casting drum and cooling and solidifying the film by a method such as a casting method provided with a water film or a method of increasing the temperature of the casting drum to adhere the film.
【００４０】また、該未延伸フィルムをフイルムの長手
方向及び幅方向に延伸、熱処理し、目的とする厚さ方向
屈折率を有するフィルムを得る方法は、耐熱性、耐経時
性の点で特に好ましい。フィルムの品質の点でテンター
方式による方法が好ましく、長手方向に延伸した後、幅
方向に延伸する逐次二軸延伸方式、長手方向、幅方向を
ほぼ同時に延伸していく同時二軸延伸方式が望ましい。
中でもリニアモーター方式による同時二軸延伸方式は成
形性を良好にする上で特に好ましい。倍率としては、そ
れぞれの方向に１．５〜１０．０倍、好ましくは２．０
〜６．０倍である。長手方向、幅方向の延伸倍率はどち
らを大きくしてもよく、同一としてもよい。また、延伸
速度は１０００〜２０００００％／分であることが望ま
しく、延伸温度はポリエステルのガラス転移温度〜ガラ
ス転移温度＋８０℃であれば任意の温度とすることがで
きるが、ガラス転移温度＋２０〜６０℃が好ましい。The method of stretching and heat-treating the unstretched film in the longitudinal and width directions of the film to obtain a film having a desired refractive index in the thickness direction is particularly preferable in view of heat resistance and aging resistance. . From the viewpoint of film quality, a method using a tenter method is preferable, and after stretching in the longitudinal direction, a sequential biaxial stretching method in which the film is stretched in the width direction and a simultaneous biaxial stretching method in which the film is stretched almost simultaneously in the longitudinal direction and the width direction are desirable. .
Among them, a simultaneous biaxial stretching method using a linear motor method is particularly preferable in terms of improving moldability. The magnification is 1.5 to 10.0 times in each direction, preferably 2.0 times.
It is up to 6.0 times. Either the stretching ratio in the longitudinal direction or the stretching ratio in the width direction may be increased, and may be the same. The stretching speed is desirably 1000 to 200,000% / minute, and the stretching temperature can be any temperature as long as it is between the glass transition temperature of the polyester and the glass transition temperature + 80 ° C. C is preferred.
【００４１】更に、この後にフイルムの熱処理を行う
が、この熱処理はオ−ブン中、加熱されたロ−ル上等、
従来公知の任意の方法で行なうことができる。熱処理温
度は６０〜２５０℃の任意の温度とすることができる
が、好ましくは１５０〜２４０℃である。また熱処理時
間は任意とすることができるが、０．１〜６０秒間が好
ましく、さらに好ましくは１〜２０秒間である。Further, after this, the film is subjected to a heat treatment which is performed in an oven, on a heated roll, or the like.
It can be performed by any conventionally known method. The heat treatment temperature can be any temperature from 60 to 250 ° C, but is preferably from 150 to 240 ° C. The heat treatment time can be arbitrarily set, but is preferably 0.1 to 60 seconds, and more preferably 1 to 20 seconds.
【００４２】熱処理は、フィルムをその長手方向および
／または幅方向に弛緩させつつ行ってもよい。さらに、
再延伸を各方向に対して１回以上行ってもよく、その後
熱処理を行ってもよい。The heat treatment may be performed while relaxing the film in the longitudinal direction and / or the width direction. further,
Re-stretching may be performed once or more in each direction, and then heat treatment may be performed.
【００４３】また、フィルム表面にコロナ放電処理など
の表面処理を施すことにより、接着性をさらに向上させ
ることは、特性を向上させる上で好ましい。その際、Ｅ
値としては好ましくは５〜５０、さらに好ましくは１０
〜４５である。ここで、Ｅ値とは、コロナ放電処理強度
であり、印加電圧（Ｖｐ）、印加電流（Ｉｐ）、処理速
度（Ｓ）、処理幅（Ｗｔ）の関数であり、Ｅ＝Ｖｐ×Ｉ
ｐ／Ｓ×Ｗｔで表される。It is preferable to further improve the adhesiveness by subjecting the film surface to a surface treatment such as a corona discharge treatment in order to improve the characteristics. At that time, E
The value is preferably 5 to 50, more preferably 10
~ 45. Here, the E value is the intensity of the corona discharge treatment, and is a function of the applied voltage (Vp), the applied current (Ip), the treatment speed (S), and the treatment width (Wt), and E = Vp × I
It is represented by p / S × Wt.
【００４４】本発明のフィルムには、各種コーティング
を施してもよく、その塗布化合物、方法、厚みは、本発
明の効果を損なわない範囲であれば特に限定されない。The film of the present invention may be coated with various coatings, and the coating compound, method, and thickness are not particularly limited as long as the effects of the present invention are not impaired.
【００４５】本発明の包装用ポリエステルフィルムは、
包装材料用途に用いられるものであり、その用途は包装
用途であれば特に限定されないが、アルミ蒸着用途、金
属酸化物蒸着用途、ポリエステルシーラント用途、ポリ
エステルラミネートによる軟包装、容器などが挙げられ
る。中でも折り曲げ成形、絞り成形、しごき成形などの
成形加工用途に使用されることが好ましく、さらには基
材とのラミネート後に成形加工される用途であることが
より好ましい。The packaging polyester film of the present invention comprises:
It is used for packaging materials, and the application is not particularly limited as long as it is a packaging application, and examples thereof include aluminum deposition applications, metal oxide deposition applications, polyester sealant applications, flexible packaging with polyester laminate, containers, and the like. Above all, it is preferably used for a forming process such as bending, drawing, and ironing, and more preferably a forming process after lamination with a substrate.
【００４６】特に好ましくは、ラミネート基材が紙、不
織布、金属から選択される基材であることが望ましい。
紙、金属との間には特性を大きく損ねない範囲で接着剤
などが用いられていても良いが、接着剤を介さずに熱に
より直接ポリエステルフィルムを接着させることが好ま
しい。紙／ポリエステルフィルム、不織布／ポリエステ
ルフィルム、金属／ポリエステルフィルムから形成され
る包装材料は、例えば容器の中で味特性、長期保存性の
低下の原因となるポリエステルフィルムを薄膜化するこ
とができるので好ましい。Particularly preferably, the laminate substrate is a substrate selected from paper, nonwoven fabric and metal.
An adhesive or the like may be used between paper and metal as long as the properties are not significantly impaired, but it is preferable to directly bond the polyester film by heat without using an adhesive. A packaging material formed of paper / polyester film, nonwoven fabric / polyester film, or metal / polyester film is preferable because, for example, a polyester film which causes a decrease in taste characteristics and long-term storage properties can be reduced in a container. .
【００４７】その場合、特にラミネート基材が金属であ
ることが、バリア性、十分な加熱を施せるという点で好
ましく、内容物の保護性が一段と向上するので好まし
い。In this case, it is particularly preferable that the laminate substrate is made of a metal in terms of barrier properties and sufficient heating, and is more preferable because the protection of the contents is further improved.
【００４８】これらの用途の中でも、特に飲料、食品を
内容物とする成形容器に使用することが好ましい。Among these uses, it is particularly preferable to use them in molded containers containing beverages and foods as contents.
【００４９】本発明において用いられる金属板は、特に
限定されないが、成形性の点で鉄、アルミニウムから選
択される材料を主体とする金属板が好ましい。The metal plate used in the present invention is not particularly limited, but is preferably a metal plate mainly composed of a material selected from iron and aluminum in view of formability.
【００５０】さらに、鉄を素材とする金属板の場合、そ
の表面に接着性や耐腐食性を改良する無機酸化物被膜
層、例えばクロム酸処理、リン酸処理、クロム酸／リン
酸処理、電解クロム酸処理、クロメート処理、クロムク
ロメート処理などで代表される化成処理被覆層を設けて
もよい。特に金属クロム換算値でクロムとして５〜２０
０ｍｇ／ｍ2 のクロム水和酸化物が好ましく、さらに、
展延性金属メッキ層、例えばニッケル、スズ、亜鉛、ア
ルミニウム、砲金、真ちゅうなどを設けてもよい。スズ
メッキの場合１〜２０ｍｇ／ｍ2 、ニッケルの場合１０
０〜１０００ｍｇ／ｍ2 のメッキ量を有するものが好ま
しい。さらにクロムメッキを施しても良い。Further, in the case of a metal plate made of iron, an inorganic oxide coating layer for improving adhesion and corrosion resistance on the surface thereof, for example, chromic acid treatment, phosphoric acid treatment, chromic acid / phosphoric acid treatment, electrolytic treatment A chemical conversion coating layer represented by chromic acid treatment, chromate treatment, chromium chromate treatment, or the like may be provided. Especially 5 to 20 as chromium in terms of metal chromium
0 mg / m 2 chromium hydrated oxide is preferred,
A malleable metal plating layer, for example, nickel, tin, zinc, aluminum, gunmetal, brass, etc. may be provided. 1-20 mg / m 2 for tin plating, 10 for nickel
Those having a plating amount of 0 to 1000 mg / m 2 are preferred. Further, chrome plating may be applied.
【００５１】本発明に使用される紙は特に限定されない
が、パルプの含有率が９０％以上であることが好まし
く、再生紙を使用しても良い。The paper used in the present invention is not particularly limited, but the pulp content is preferably 90% or more, and recycled paper may be used.
【００５２】成形後にフィルム厚みが下記式（７）を満
足する容器となることを特徴とする包装材料に使用され
る用途が好ましい。 ０．１≦ＴＦ／ＴＩ≦０．９ （７） （但し、ＴＦは成形後の容器の中でフィルム厚みが最も
薄い部分のフィルム厚み（μｍ）、ＴＩは成形後の容器
の中でフィルム厚みが最も厚い部分のフィルム厚み（μ
ｍ）） さらに好ましくは、成形後にフィルム厚みが下記式
（８）を満足する容器となる用途に使用することが本発
明のポリエステルフィルムのパフォーマンスを最大限に
発現する上で望ましい。 ０．１≦ＴＦ／ＴＩ≦０．６ （８） （但し、ＴＦは成形後の容器の中でフィルム厚みが最も
薄い部分のフィルム厚み（μｍ）、ＴＩは成形後の容器
の中でフィルム厚みが最も厚い部分のフィルム厚み（μ
ｍ））It is preferable to use the composition as a packaging material characterized in that a container having a film thickness satisfying the following formula (7) after molding is obtained. 0.1 ≦ TF / TI ≦ 0.9 (7) (where TF is the film thickness (μm) of the thinnest part in the molded container, and TI is the film thickness in the molded container. Is the thickest part of the film thickness (μ
m)) More preferably, it is desirable to use the polyester film of the present invention for use as a container whose film thickness satisfies the following formula (8) after molding in order to maximize the performance of the polyester film of the present invention. 0.1 ≦ TF / TI ≦ 0.6 (8) (where TF is the film thickness (μm) of the thinnest part in the molded container, and TI is the film thickness in the molded container. Is the thickest part of the film thickness (μ
m))
【００５３】[0053]
【実施例】以下、実施例によって本発明を詳細に説明す
る。なお、特性は以下の方法により測定、評価した。The present invention will be described below in detail with reference to examples. The characteristics were measured and evaluated by the following methods.
【００５４】（１）アルカリ金属量 フィルムをオルソクロロフェノールに溶解し、０．５規
定塩酸溶液で抽出し、原子吸光分析で求めた。なお、積
層フィルムの場合は、各層を削り取るなどして、分離し
て求めた。(1) Amount of alkali metal The film was dissolved in orthochlorophenol, extracted with a 0.5 N hydrochloric acid solution, and determined by atomic absorption analysis. In the case of a laminated film, each layer was separated and obtained by scraping off each layer.
【００５５】（２）触媒金属元素量、リン元素量 フィルムを融点＋２０℃に加熱して溶融させ、円形ディ
スクを作成し、蛍光Ｘ線分析により、触媒金属元素量、
リン元素量を求めた。なお、量の決定の際にはあらかじ
め各金属元素の添加量を変更したサンプルから求めた蛍
光Ｘ線での検量線を使用した。フィルム中の粒子による
金属成分は、該成分を除去して求めた。なお、粒子を除
去する方法としては、例えばフィルムを８０〜１００℃
に熱したオルソクロロフェノールに溶解させ、遠心分離
操作を行い、粒子を取り除き、溶液中のポリマーを析出
した後に上記の蛍光Ｘ線分析を行う方法がある。なお、
積層フィルムの場合は、各層を削り取るなどして、分離
して求めた。(2) Catalytic metal element amount, phosphorus element amount The film was heated to a melting point of + 20 ° C. and melted to form a circular disk, and the amount of the catalytic metal element was determined by X-ray fluorescence analysis.
The phosphorus element amount was determined. In determining the amount, a calibration curve of X-ray fluorescence obtained from a sample in which the amount of each metal element added was changed in advance was used. The metal component due to the particles in the film was determined by removing the component. In addition, as a method of removing particles, for example, a film is heated at 80 to 100 ° C.
A method of dissolving the polymer in orthochlorophenol heated to a temperature above, performing a centrifugal separation operation, removing particles, and precipitating the polymer in the solution, and then performing the above-mentioned fluorescent X-ray analysis is known. In addition,
In the case of a laminated film, each layer was separated and obtained by scraping off each layer.
【００５６】（３）ポリエステルの固有粘度 ポリエステルをオルソクロロフェノ−ルに溶解し、２５
℃において測定した。(3) Intrinsic Viscosity of Polyester Polyester is dissolved in orthochlorophenol,
Measured in ° C.
【００５７】（４）フィルムの面配向係数 ナトリウムＤ線（波長５８９ｎｍ）を光源として、アッ
ベ屈折計を用いて、フィルムの長手方向屈折率ｎＭＤ、
フィルムの幅方向屈折率ｎＴＤ、フィルムの厚さ方向屈
折率ｎＺＤを求め、面配向係数Ｆｎ＝（ｎＭＤ＋ｎＴ
Ｄ）／２−ｎＺＤを求めた。なお、Ｂ／Ａ／Ｂ積層フィ
ルムの場合は、Ｂ層を削り取り求めた。(4) Surface Orientation Coefficient of Film Using the Abbe refractometer with sodium D line (wavelength 589 nm) as a light source, the longitudinal refractive index nMD of the film,
The refractive index nTD in the width direction of the film and the refractive index nZD in the thickness direction of the film are obtained, and the plane orientation coefficient Fn = (nMD + nT
D) / 2-nZD was determined. In the case of the B / A / B laminated film, the B layer was scraped off.
【００５８】（５）平均粒子径、添加量 フィルム断面を切断し超薄切片を作成し、透過型電子顕
微鏡を用いて倍率５０００〜２００００倍程度で写真撮
影を５０枚撮影し、ポリエステル中に分散した各粒子の
円相当径を測定し、平均粒子径を求めた。粒子添加量は
ポリエステル成分を溶解させ、粒子成分のみを遠心分離
させるなどして求めた。(5) Average particle diameter and amount of addition A cross section of the film was cut to form an ultrathin section, and 50 photographs were taken with a transmission electron microscope at a magnification of about 5,000 to 20,000, and dispersed in polyester. The equivalent circle diameter of each of the obtained particles was measured, and the average particle diameter was determined. The amount of added particles was determined by dissolving the polyester component and centrifuging only the particle component.
【００５９】（６）ポリエステルのカルボキシル末端基
量 ポリエステルをｏ−クレゾール／クロロホルム（重量比
７／３）に１００℃、２０分の条件で溶解し、アルカリ
で電位差滴定を行ない求めた。なお、積層フィルムの場
合は、各層を削り取るなどして、分離して求めた。(6) Carboxyl end group content of polyester The polyester was dissolved in o-cresol / chloroform (weight ratio: 7/3) at 100 ° C. for 20 minutes, and potentiometric titration was performed with alkali. In the case of a laminated film, each layer was separated and obtained by scraping off each layer.
【００６０】（７）ポリエステルの融点 ポリエステルを溶融後急冷し、示差走査熱量計（パーキ
ン・エルマー社製ＤＳＣ２型）により、１０℃／分の昇
温速度で測定し、融解ピークから融点を求めた。なお、
積層フィルムの場合は、各層を削り取るなどして、分離
して求めた。(7) Melting point of polyester The polyester was melted, rapidly cooled, and measured at a heating rate of 10 ° C./min by a differential scanning calorimeter (DSC2, manufactured by Perkin-Elmer Co.), and the melting point was determined from the melting peak. . In addition,
In the case of a laminated film, each layer was separated and obtained by scraping off each layer.
【００６１】（８）成形性−１（絞り、しごき性） １００ｍ／分で加熱されたＴＦＳ（ティンフリースチー
ル）鋼板（厚さ０．２ｍｍ）にフィルムを両面ラミネー
ト後、６０℃の温水にて冷却した後、絞り、しごき成形
機で成形した。なお、ここでＴＦＳの温度は、フィルム
の面配向係数が熱ラミネートした後に、０．０３〜０．
０４になるように行った。ラミネート前のフィルムの面
配向係数が０のフィルムは、融点＋５℃の温度で熱ラミ
ネートした。その後、ラミネート金属板をリダクション
率４５％（成形前のラミネート金属板厚みをＹ１（ｍ
ｍ）、成形後のラミネート金属板の最も薄い部分の厚み
をＹ２（ｍｍ）とした際にリダクション率＝（Ｙ１−Ｙ
２）／Ｙ１×１００で定義される）で成形し、缶を得
た。缶にイオン交換水を充填し１週間後にフィルムの様
子を調べて、下記のように判定した。(8) Formability-1 (drawing and ironing properties) After laminating a film on both sides of a TFS (tin-free steel) steel plate (thickness 0.2 mm) heated at 100 m / min, it was heated with hot water at 60 ° C. After cooling, it was formed by drawing and ironing. Here, the temperature of TFS is set to 0.03 to 0.
04. A film having a plane orientation coefficient of 0 before lamination was thermally laminated at a temperature of melting point + 5 ° C. Thereafter, the reduction rate of the laminated metal sheet was reduced to 45% (the thickness of the laminated metal sheet before molding was changed to Y1 (m
m), when the thickness of the thinnest portion of the laminated metal sheet after molding is Y2 (mm), the reduction rate = (Y1-Y
2) / Y1 × 100) to obtain a can. One week after filling the can with ion-exchanged water, the state of the film was examined and judged as follows.
【００６２】なお、製缶後に金属を塩酸で溶解し、フィ
ルムのみを取りだし、各部位のフィルム厚みを測定し、
フィルム厚みの最も薄い部分と、最も厚い部分のフィル
ム厚みをそれぞれＴＦ（μｍ）、ＴＩ（μｍ）とした。 ◎：フィルムに白化、亀裂がない。 ○：フィルムにやや白化が見られるが、亀裂はない。 △：フィルムに白化が見られるが、亀裂はない。 ×：フィルムに白化、亀裂が見られる。After the can was made, the metal was dissolved with hydrochloric acid, only the film was taken out, and the film thickness of each part was measured.
The film thicknesses of the thinnest part and the thickest part were defined as TF (μm) and TI (μm), respectively. A: There is no whitening or crack in the film. ：: The film was slightly whitened, but no crack was found. C: Whitening is observed in the film, but no crack. ×: Whitening and cracks are observed in the film.
【００６３】（９）成形性−２（折り曲げ性） 紙にポリエステルフィルムを両面熱ラミネート（ラミネ
ート後に面配向係数０．０２〜０．０３となるように）
し、折り曲げ成形して容器を作成した。なお、ラミネー
ト前のフィルムの面配向係数が０のフィルムは、融点＋
５℃の温度で熱ラミネートした。その後、折り曲げ加工
を行い、飲料パックを作成した。紙パックにイオン交換
水を充填し１週間後にパックの紙部分を取り除き、折り
曲げ部のフィルムを下記のように判定した。 ◎：フィルムに白化、亀裂がない。 ○：フィルムにやや白化が見られるが、亀裂はない。 △：フィルムに白化が見られるが、亀裂はない。 ×：フィルムに白化、亀裂が見られる。(9) Formability-2 (Bendability) A polyester film is heat-laminated on both sides with paper (so that the plane orientation coefficient becomes 0.02 to 0.03 after lamination).
Then, it was bent and formed to make a container. The film having a plane orientation coefficient of 0 before lamination has a melting point +
Thermal lamination was performed at a temperature of 5 ° C. After that, bending was performed to prepare a beverage pack. The paper pack was filled with ion-exchanged water, and one week later, the paper portion of the pack was removed, and the film at the bent portion was determined as follows. A: There is no whitening or crack in the film. ：: The film was slightly whitened, but no crack was found. C: Whitening is observed in the film, but no crack. ×: Whitening and cracks are observed in the film.
【００６４】（１０）味特性 ポリエステルフィルムが内面側にラミネートされた金属
容器に、イオン交換水を充填し、巻き締めを行い密封
し、１２５℃×２０分熱処理後に、４０℃で１週間保存
した。開封後に、比較用のイオン交換水と比較して５０
人のパネラーで下記の判定を行った。 ◎：味、透明度の変化を認めた人数が３人以下 ○：味、透明度の変化を認めた人数が４人〜６人 △：味、透明度の変化を認めた人数が７人〜９人 ×：味、透明度の変化を認めた人数が１０人以上(10) Taste characteristics A metal container having a polyester film laminated on its inner surface was filled with ion-exchanged water, tightly wound and sealed, and heat-treated at 125 ° C for 20 minutes, and then stored at 40 ° C for 1 week. . After opening, compare with ion exchange water for comparison 50
The following judgment was made by a human panelist. ：: 3 or less persons who recognized changes in taste and transparency ○: 4 to 6 persons who recognized changes in taste and transparency △: 7 to 9 persons who recognized changes in taste and transparency × : More than 10 people who recognized changes in taste and transparency
【００６５】（１１）長期保存性 ポリエステルフィルムが内面側にラミネートされた金属
容器に、イオン交換水を充填し、巻き締めを行い密封
し、１２５℃×２０分熱処理後に４０℃で２ヶ月間保存
し、５０人のパネラーで下記の判定を行った。 ◎：味、透明度の変化を認めた人数が３人以下 ○：味、透明度の変化を認めた人数が４人〜６人 △：味、透明度の変化を認めた人数が７人〜９人 ×：味、透明度の変化を認めた人数が１０人以上(11) Long-term storage properties A metal container having a polyester film laminated on the inner surface is filled with ion-exchanged water, tightly wound and sealed, and stored at 40 ° C for 2 months after heat treatment at 125 ° C for 20 minutes. Then, the following judgment was made by 50 panelists. ：: 3 or less persons who recognized changes in taste and transparency ○: 4 to 6 persons who recognized changes in taste and transparency △: 7 to 9 persons who recognized changes in taste and transparency × : More than 10 people who recognized changes in taste and transparency
【００６６】実施例１〜６ 表１、２に示す構成成分、金属量、リン量で構成される
ポリエステルを用いてフィルムを製膜した。Examples 1 to 6 Films were formed using polyesters having the components, metal amounts and phosphorus amounts shown in Tables 1 and 2.
【００６７】実施例１ではＴｉ／Ｚｒ（モル比９／１）
複合酸化物触媒、リン酸および粒子としてケイ酸アルミ
粒子（平均径１μｍ）を用いてポリエステルを重合し、
１６０℃で充分に真空乾燥し、２８０℃で溶融押出し
て、キャスティングドラムのキャスト直前の表面温度を
上昇させ、テープ上の電極で静電印加させながら、キャ
スト上で急冷固化し、未延伸フィルムを得た。In Example 1, Ti / Zr (molar ratio 9/1)
Polyester is polymerized using a composite oxide catalyst, phosphoric acid and aluminum silicate particles (average diameter 1 μm) as particles,
Full vacuum drying at 160 ° C, melt extrusion at 280 ° C, raising the surface temperature of the casting drum immediately before casting, quenching and solidifying on the cast while applying static electricity with electrodes on the tape, and unstretched film Obtained.
【００６８】この未延伸フィルムを、リニアモーター方
式の同時二軸延伸機で、温度１００℃にて同時二軸延伸
（縦横ともに延伸倍率２．７倍、延伸速度２９００％／
分）し、１９１℃にて、弛緩３％、４秒間熱処理し、３
０μｍのフィルムを得た。味特性、長期保存性に特に優
れる結果を得た。The unstretched film was simultaneously biaxially stretched at a temperature of 100 ° C. with a simultaneous biaxial stretching machine of a linear motor type (stretching ratio 2.7 times in both length and width, stretching speed 2900% /
Min), and heat-treated at 191 ° C. for 3% relaxation for 4 seconds.
A 0 μm film was obtained. The results were particularly excellent in taste characteristics and long-term storage stability.
【００６９】実施例２では、Ｔｉ／Ｓｉ複合酸化物触
媒、リン酸を用いて、炭酸カルシウム粒子を配合させた
共重合ＰＥＴを重合した。１６０℃で充分に真空乾燥
し、２８０℃で溶融押出して、キャスティングドラムの
表面に水膜を形成させてテープ上の電極で静電印加させ
ながら、キャスト上で急冷固化し、未延伸フィルムを得
た。得られた未延伸フィルムをテンター方式の逐次二軸
延伸機で製膜した。その際の条件は、縦延伸温度９６
℃、縦延伸倍率３．０倍、横延伸温度１１１℃、横延伸
倍率３．０倍、熱処理温度１７６℃、弛緩３％である。
得られたフィルム特性を表１に示す。成形性は特に優れ
ていたが、実施例１より長期保存性がやや低下した。In Example 2, copolymerized PET containing calcium carbonate particles was polymerized using a Ti / Si composite oxide catalyst and phosphoric acid. Full vacuum drying at 160 ° C and melt extrusion at 280 ° C to form a water film on the surface of the casting drum and quench and solidify on the cast while applying static electricity with electrodes on the tape to obtain an unstretched film Was. The obtained unstretched film was formed with a tenter-type sequential biaxial stretching machine. The condition at that time is that the longitudinal stretching temperature is 96.
° C, longitudinal stretching ratio 3.0 times, transverse stretching temperature 111 ° C, transverse stretching ratio 3.0 times, heat treatment temperature 176 ° C, relaxation 3%.
Table 1 shows the obtained film properties. The moldability was particularly excellent, but the long-term storage stability was slightly lower than in Example 1.
【００７０】実施例３では、ポリエステル、触媒を変更
し実施例２と同様にして製膜を行いフィルムを得た。表
１に示すように良好な結果を得たが、触媒量が多いた
め、やや味特性が低下した。In Example 3, a film was formed in the same manner as in Example 2 except that the polyester and the catalyst were changed. As shown in Table 1, good results were obtained, but due to the large amount of catalyst, taste characteristics were slightly lowered.
【００７１】実施例４では、実施例１と同様にして製膜
を行ったが、表２に示すように良好な結果を得た。In Example 4, a film was formed in the same manner as in Example 1, but good results were obtained as shown in Table 2.
【００７２】実施例５では、表２に示すようにリン量が
やや多くなったため、成形性、味特性が低下した。In Example 5, as shown in Table 2, the amount of phosphorus was slightly increased, so that moldability and taste characteristics were reduced.
【００７３】実施例６では、表２に示すようにリン量が
少なくなり、味特性がやや低下し、さらにカルボン酸濃
度が少ないため、成形性がやや低下した。実施例７〜９
では、ポリエステルＢを使用し、製膜条件を変更し逐次
二軸延伸機で積層フィルムを製膜した（表３）。In Example 6, as shown in Table 2, the phosphorus content was small, the taste characteristics were slightly lowered, and the carboxylic acid concentration was low, so that the moldability was slightly lowered. Examples 7 to 9
Then, a laminated film was formed using a sequential biaxial stretching machine while changing the film forming conditions using polyester B (Table 3).
【００７４】実施例７は、Ａ／Ｂ２層積層フィルム、実
施例８、９では、Ｂ／Ａ／Ｂ３層積層フィルムを製膜
し、Ｂ層をラミネート基材に接する方とした。In Example 7, an A / B two-layer laminated film was produced. In Examples 8 and 9, a B / A / B three-layer laminated film was produced, and the B layer was brought into contact with the laminated substrate.
【００７５】実施例７、８では、逐次二軸延伸方式で、
縦延伸温度１００℃、縦延伸倍率２．９倍、横延伸温度
１２０℃、横延伸倍率３．０倍とし、熱処理温度を１９
０℃に変更してＡ層が表３に示す面配向係数となるフィ
ルムを製膜した。得られたフィルムは特に特性が良好で
あった。In Examples 7 and 8, the sequential biaxial stretching method was used.
The longitudinal stretching temperature was 100 ° C, the longitudinal stretching ratio was 2.9 times, the transverse stretching temperature was 120 ° C, the transverse stretching ratio was 3.0 times, and the heat treatment temperature was 19
The temperature was changed to 0 ° C., and a film in which the layer A had the plane orientation coefficient shown in Table 3 was formed. The obtained film had particularly good properties.
【００７６】実施例９では実施例３と同様にして製膜を
行ったが、ポリエステルＢの触媒量が少なく、成形性が
やや低下したが味特性が良好となった。In Example 9, a film was formed in the same manner as in Example 3. However, the amount of the catalyst of polyester B was small, and the moldability was slightly lowered, but the taste characteristics were good.
【００７７】比較例１〜３ 触媒金属種、量、リン量を変更して表４の面配向係数が
得られるようにしてフィルムを製膜した。得られたフィ
ルム特性を表４に示す。比較例１では触媒量が多く、面
配向係数が高いため、成形性、味特性、長期保存性とも
に悪化した。比較例２は、共重合量が多く、触媒成分が
異なるため味特性、長期保存性が特に悪化した。比較例
３では触媒量が多く、リン量が少ないため、成形性、味
特性、長期保存性が低下した。Comparative Examples 1 to 3 Films were formed by changing the kind of catalyst metal, the amount and the amount of phosphorus so as to obtain the plane orientation coefficient shown in Table 4. Table 4 shows the obtained film properties. In Comparative Example 1, since the amount of the catalyst was large and the plane orientation coefficient was high, all of the moldability, taste characteristics, and long-term storage stability were deteriorated. In Comparative Example 2, since the copolymerization amount was large and the catalyst components were different, taste characteristics and long-term storage properties were particularly deteriorated. In Comparative Example 3, since the amount of the catalyst was large and the amount of phosphorus was small, moldability, taste characteristics, and long-term storability were reduced.
【００７８】本発明のポリエステルフィルムを用いたも
のは、成形性、味特性、長期保存性に優れる結果となっ
た。The one using the polyester film of the present invention was excellent in moldability, taste characteristics and long-term storage.
【００７９】[0079]
【表１】 [Table 1]
【００８０】[0080]
【表２】 [Table 2]
【００８１】[0081]
【表３】 [Table 3]
【００８２】[0082]
【表４】 [Table 4]
【００８３】なお、表中の記号は次の通りである（数値
は酸、グリコール成分のモル％）。 ＴＰＡ：テレフタル酸 ＩＰＡ：イソフタル酸 ＥＧ：エチレングリコール ＤＥＧ：ジエチレングリコール ＮＤＣ：ナフタレンジカルボン酸 ＮＰＧ：ネオペンチルグリコール ＭＡ：ポリエステルＡ中に残存する全触媒金属元素の中
でＴｉ、Ａｌ、Ｚｒ、Ｓｉの合計濃度（ミリモル％） ＰＡ：ポリエステルＡ中に残存するリン元素の濃度（ミ
リモル％） ＭＢ：ポリエステルＢ中に残存する全触媒金属元素の合
計濃度（ミリモル％） ＰＢ：ポリエステルＢ中に残存するリン元素の濃度（ミ
リモル％） Ｔｉ／Ｓｉ：Ti/Si複合酸化物 Ｔｉ：チタン化合物 Ｇｅ：ゲルマニウム化合物 Ｃａ：カルシウム化合物The symbols in the table are as follows (numerical values are mol% of acid and glycol components). TPA: Terephthalic acid IPA: Isophthalic acid EG: Ethylene glycol DEG: Diethylene glycol NDC: Naphthalenedicarboxylic acid NPG: Neopentyl glycol MA: Total concentration of Ti, Al, Zr, and Si among all catalytic metal elements remaining in polyester A (Mmol%) PA: Concentration of phosphorus element remaining in polyester A (mmol%) MB: Total concentration of all catalytic metal elements remaining in polyester B (mmol%) PB: Phosphorus element remaining in polyester B Concentration (mmol%) Ti / Si: Ti / Si composite oxide Ti: titanium compound Ge: germanium compound Ca: calcium compound
【００８４】[0084]
【発明の効果】本発明の包装用ポリエステルフィルム
は、成形性、耐熱性、味特性、長期保存性に優れてお
り、包装材料、中でも成形加工、ラミネート成形加工、
紙、金属を基材としたラミネート成形加工、容器に好適
に使用することができる。Industrial Applicability The polyester film for packaging of the present invention is excellent in moldability, heat resistance, taste characteristics and long-term storage property, and is used for packaging materials, especially molding, lamination molding, and the like.
It can be suitably used for lamination molding processing and containers using paper and metal as a base material.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｃ０８Ｇ 63/84 Ｃ０８Ｇ 63/84 63/85 63/85 Ｆターム(参考） 4F071 AA45 AA46 AA80 AA84 AF38 AF45 AH04 BA01 BB06 BB08 BC01 BC12 BC17 4F100 AB10A AB10H AB11A AB11H AB12A AB12H AK41A AK41B AK41C BA02 BA03 BA04 BA06 BA07 BA10B BA10C BA13 DA01 DE01A DG10D DG15D EH17 EJ38 GB15 JA04A JA20A JC00 JJ03 JL01 YY00A 4J002 CF031 CF041 CF051 CF061 CF071 CF081 CF141 CF181 GF00 GG02 4J029 AA03 AB05 AB07 AC01 AC02 AD02 AD06 AD10 AE03 BA02 BA03 BA05 BA08 BA10 BB13A BD06A BF09 BF25 BH02 CA01 CA02 CA06 CB04A CB05A CB06A CB10A CC05A CD03 CF15 CH02 CH06 DB13 EB05A GA13 GA14 HA01 HB01 HB02 JA091 JA093 JA123 JA203 JA281 JA283 JA293 JC483 JC583 JE053 JE093 JE143 JE182 JE213 JE223 JF013 JF143 JF163 JF221 JF321 JF331 KB04 KB05 KE02 KE03 KE05 KH08Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) // C08G 63/84 C08G 63/84 63/85 63/85 F term (reference) 4F071 AA45 AA46 AA80 AA84 AF38 AF45 AH04 BA01 BB06 BB08 BC01 BC12 BC17 4F100 AB10A AB10H AB11A AB11H AB12A AB12H AK41A AK41B AK41C BA02 BA03 BA04 BA06 BA07 BA10B BA10C BA13 DA01 DE01A DG10D DG15D EH17 EJ38 GB15 JA04A JA20A CF1 J01 CF1 CF01 J01 CF3 AB07 AC01 AC02 AD02 AD06 AD10 AE03 BA02 BA03 BA05 BA08 BA10 BB13A BD06A BF09 BF25 BH02 CA01 CA02 CA06 CB04A CB05A CB06A CB10A CC05A CD03 CF15 CH02 CH06 DB13 EB05A GA13 GA13 HA01 HB01 HB02 JA093E JA3 JAJA3E JA3 JA3 JE223 JF013 JF143 JF163 JF221 JF321 JF331 KB04 KB05 KE02 KE03 KE05 KH08
Claims (19)
属元素を構成成分とする金属化合物を触媒成分として少
なくとも２種類以上含有し、下記式（１）を満足するポ
リエステルＡを主たる構成成分とすることを特徴とする
包装用ポリエステルフィルム。 １≦ＭＡ≦４０ （１） （但し、式中のＭＡはポリエステルＡ中に残存する全触
媒金属元素の中でＴｉ、Ａｌ、Ｚｒ、Ｓｉの合計濃度
（ミリモル％））1. A polyester A containing at least two kinds of metal compounds having a metal element selected from Ti, Al, Zr, and Si as a catalyst component and satisfying the following formula (1): A polyester film for packaging characterized by the following. 1 ≦ MA ≦ 40 (1) (where, MA in the formula is the total concentration (mmol%) of Ti, Al, Zr, and Si among all the catalytic metal elements remaining in the polyester A)
主たる構成成分とする請求項１に記載の包装用ポリエス
テルフィルム。 １≦ＭＡ＜２０ （２） （但し、式中のＭＡはポリエステルＡ中に残存する全触
媒金属元素の中でＴｉ、Ａｌ、Ｚｒ、Ｓｉの合計濃度
（ミリモル％））2. The polyester film for packaging according to claim 1, wherein the polyester A satisfies the following formula (2) as a main component. 1 ≦ MA <20 (2) (where, MA in the formula is the total concentration (mmol%) of Ti, Al, Zr, and Si among all the catalytic metal elements remaining in the polyester A)
量が下記式（３）を満足する請求項１または請求項２に
記載の包装用ポリエステルフィルム。 −２０≦ＭＡ−ＰＡ≦２０ （３） （但し、式中のＭＡはポリエステルＡ中に残存する全触
媒金属元素の中でＴｉ、Ａｌ、Ｚｒ、Ｓｉの合計触媒金
属元素の濃度（ミリモル％）、ＰＡはポリエステルＡ中
に残存するリン元素の濃度（ミリモル％）を示す。）3. The polyester film for packaging according to claim 1, wherein the amount of the catalytic metal element and the amount of phosphorus in the polyester A satisfy the following formula (3). −20 ≦ MA−PA ≦ 20 (3) (where, MA in the formula is the concentration of the total catalytic metal element of Ti, Al, Zr, and Si among all the catalytic metal elements remaining in the polyester A (mmol%) , PA indicates the concentration (mmol%) of the phosphorus element remaining in the polyester A.)
量が下記式（４）を満足する請求項３に記載の包装用ポ
リエステルフィルム。 −１０≦ＭＡ−ＰＡ≦１０ （４） （但し、式中のＭＡはポリエステルＡ中に残存する全触
媒金属元素の中でＴｉ、Ａｌ、Ｚｒ、Ｓｉの合計触媒金
属元素の濃度（ミリモル％）、ＰＡはポリエステルＡ中
に残存するリン元素の濃度（ミリモル％）を示す。）4. The packaging polyester film according to claim 3, wherein the amount of the catalytic metal element and the amount of phosphorus in the polyester A satisfy the following formula (4). −10 ≦ MA−PA ≦ 10 (4) (where, MA in the formula is the concentration (mmol%) of the total catalytic metal element of Ti, Al, Zr and Si among all the catalytic metal elements remaining in the polyester A) , PA indicates the concentration (mmol%) of the phosphorus element remaining in the polyester A.)
粒子を０．０１〜１重量％含有するものである請求項１
〜４のいずれかに記載の包装用ポリエステルフィルム。5. The polyester A contains 0.01 to 1% by weight of particles having an average particle diameter of 3 μm or less.
5. The packaging polyester film according to any one of items 1 to 4.
である請求項１〜５のいずれかに記載の包装用ポリエス
テルフィルム。6. Polyester A has a melting point of 200 to 280 ° C.
The polyester film for packaging according to any one of claims 1 to 5, which is:
である請求項６に記載の包装用ポリエステルフィルム。7. Polyester A has a melting point of 200 to 245 ° C.
The polyester film for packaging according to claim 6, which is:
である請求項６に記載の包装用ポリエステルフィルム。8. The polyester A has a melting point of 246 to 280 ° C.
The polyester film for packaging according to claim 6, which is:
（５）を満足する請求項１〜８のいずれかに記載の包装
用ポリエステルフィルム。 ３０≦Ｃ≦４５ （５） （但し、式中のＣはフィルム中のカルボン酸濃度（当量
／トン）を示す。）9. The polyester film for packaging according to claim 1, wherein the carboxylic acid concentration in the film satisfies the following formula (5). 30 ≦ C ≦ 45 (5) (where C in the formula indicates the carboxylic acid concentration (equivalent / ton) in the film.)
請求項１〜９のいずれかに記載の包装用ポリエステルフ
ィルム。10. The polyester film for packaging according to claim 1, which has a plane orientation coefficient of 0.06 to 0.14.
モル％以上が、テレフタル酸および／またはナフタレン
ジカルボン酸である請求項１〜１０のいずれかに記載の
包装用ポリエステルフィルム。11. An acid component constituting the polyester A of 95.
The polyester film for packaging according to any one of claims 1 to 10, wherein at least mol% is terephthalic acid and / or naphthalenedicarboxylic acid.
分の９５モル％以上が、エチレングリコールである請求
項１〜１１のいずれかに記載の包装用ポリエステルフィ
ルム。12. The packaging polyester film according to claim 1, wherein 95% by mole or more of the glycol component constituting the polyester A is ethylene glycol.
エステルフィルムの少なくとも片面に下記式（６）を満
足するポリエステルＢを積層してなる包装用ポリエステ
ルフィルム。 ＭＢ≧ＭＡ （６） （但し、式中のＭＢはポリエステルＢ中に残存する全触
媒金属元素の濃度（ミリモル％）13. A polyester film for packaging obtained by laminating polyester B satisfying the following formula (6) on at least one surface of the polyester film according to claim 1. MB ≧ MA (6) (where MB is the concentration of all catalytic metal elements remaining in polyester B (mmol%)
１〜１３のいずれかに記載の包装用ポリエステルフィル
ム。14. The polyester film for packaging according to any one of claims 1 to 13, which is molded.
４に記載の包装用ポリエステルフィルム。15. The method according to claim 1, wherein the molding is performed after lamination.
5. The polyester film for packaging according to 4.
れる材料である請求項１５に記載の包装用ポリエステル
フィルム。16. The packaging polyester film according to claim 15, wherein the laminate substrate is a material selected from paper and nonwoven fabric.
に記載の包装用ポリエステルフィルム。17. The laminate substrate according to claim 15, wherein the laminate substrate is a metal.
The polyester film for packaging according to 1.
満足する容器となる請求項１〜１７のいずれかに記載の
成形用ポリエステルフィルム。 ０．１≦ＴＦ／ＴＩ≦０．９ （７） （但し、ＴＦは成形後の容器の中でフィルム厚みが最も
薄い部分のフィルム厚み（μｍ）、ＴＩは成形後の容器
の中でフィルム厚みが最も厚い部分のフィルム厚み（μ
ｍ））18. The polyester film for molding according to claim 1, which becomes a container having a film thickness satisfying the following formula (7) after molding. 0.1 ≦ TF / TI ≦ 0.9 (7) (where TF is the film thickness (μm) of the thinnest part in the molded container, and TI is the film thickness in the molded container. Is the thickest part of the film thickness (μ
m))
満足する容器となる請求項１８に記載の成形用ポリエス
テルフィルム。 ０．１≦ＴＦ／ＴＩ≦０．６ （８） （但し、ＴＦは成形後の容器の中でフィルム厚みが最も
薄い部分のフィルム厚み（μｍ）、ＴＩは成形後の容器
の中でフィルム厚みが最も厚い部分のフィルム厚み（μ
ｍ））19. The polyester film for molding according to claim 18, which becomes a container having a film thickness satisfying the following formula (8) after molding. 0.1 ≦ TF / TI ≦ 0.6 (8) (where TF is the film thickness (μm) of the thinnest part in the molded container, and TI is the film thickness in the molded container. Is the thickest part of the film thickness (μ
m))
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34533298A JP4159154B2 (en) | 1998-12-04 | 1998-12-04 | Polyester film for packaging |
| CNB998014427A CN1150274C (en) | 1998-10-26 | 1999-10-20 | Polyester composition, method for producing same, and polyester film |
| EP99949330A EP1043362A4 (en) | 1998-10-26 | 1999-10-20 | Polyester composition, method for producing the same and polyester film |
| PCT/JP1999/005797 WO2000024827A1 (en) | 1998-10-26 | 1999-10-20 | Polyester composition, method for producing the same and polyester film |
| ID20001437A ID27680A (en) | 1998-10-26 | 1999-10-20 | POLYESTER COMPOSITION, PRODUCTION METHODS OF IT AND POLYESTER FILM |
| KR1020007004151A KR20010015777A (en) | 1998-10-26 | 1999-10-20 | Polyester composition, method of fabrication thereof and polyester film |
| MYPI99004596A MY117547A (en) | 1998-10-26 | 1999-10-25 | Polyester composition and film, and production method |
| US09/589,587 US6365659B1 (en) | 1998-10-26 | 2000-06-08 | Polyester composition and film, and production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34533298A JP4159154B2 (en) | 1998-12-04 | 1998-12-04 | Polyester film for packaging |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000169600A true JP2000169600A (en) | 2000-06-20 |
| JP4159154B2 JP4159154B2 (en) | 2008-10-01 |
Family
ID=38857900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34533298A Expired - Fee Related JP4159154B2 (en) | 1998-10-26 | 1998-12-04 | Polyester film for packaging |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4159154B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002194185A (en) * | 2000-12-22 | 2002-07-10 | Toray Ind Inc | Polyester film for molding |
| US7323537B2 (en) | 2003-06-03 | 2008-01-29 | Mitsubishi Chemical Corporation | Catalyst for production of polyester, process for producing polyester using it and titanium-containing polyethylene terephthalate |
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| JP5575671B2 (en) | 2010-01-18 | 2014-08-20 | 富士フイルム株式会社 | Polyester resin polymerization method, polyester resin composition and polyester film |
| JP5750226B2 (en) | 2010-01-18 | 2015-07-15 | 富士フイルム株式会社 | Film for solar cell backsheet and manufacturing method thereof |
| JP5734569B2 (en) | 2010-01-18 | 2015-06-17 | 富士フイルム株式会社 | SOLAR CELL BACK SHEET, MANUFACTURING METHOD THEREOF, AND SOLAR CELL MODULE |
| JP2011165967A (en) | 2010-02-10 | 2011-08-25 | Fujifilm Corp | Solar cell backsheet and solar cell module |
| JP5623938B2 (en) | 2010-03-25 | 2014-11-12 | 富士フイルム株式会社 | Solar cell backsheet |
| JP2012017456A (en) | 2010-06-11 | 2012-01-26 | Fujifilm Corp | Polyester film and method for producing the same, back sheet for solar cell, and solar cell module |
| US20120048348A1 (en) | 2010-08-26 | 2012-03-01 | Fujifilm Corporation | Solar cell protective sheet and its production method, backsheet for solar cell, and solar cell module |
| CN103201851A (en) | 2010-11-12 | 2013-07-10 | 富士胶片株式会社 | Back sheet for solar cells and process for production thereof, and solar cell module |
| JP5753110B2 (en) | 2012-02-03 | 2015-07-22 | 富士フイルム株式会社 | Back surface protection sheet for solar cell module and solar cell module |
| JP6200131B2 (en) | 2012-03-28 | 2017-09-20 | 富士フイルム株式会社 | Polymer sheet, back surface protection sheet for solar cell, and solar cell module |
| JP5852626B2 (en) | 2012-11-06 | 2016-02-03 | 富士フイルム株式会社 | Ketene imine compound, polyester film, back sheet for solar cell module and solar cell module |
-
1998
- 1998-12-04 JP JP34533298A patent/JP4159154B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002194185A (en) * | 2000-12-22 | 2002-07-10 | Toray Ind Inc | Polyester film for molding |
| US7323537B2 (en) | 2003-06-03 | 2008-01-29 | Mitsubishi Chemical Corporation | Catalyst for production of polyester, process for producing polyester using it and titanium-containing polyethylene terephthalate |
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|---|---|
| JP4159154B2 (en) | 2008-10-01 |
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