JP6212981B2 - Production method of polyester film - Google Patents
Production method of polyester film Download PDFInfo
- Publication number
- JP6212981B2 JP6212981B2 JP2013132305A JP2013132305A JP6212981B2 JP 6212981 B2 JP6212981 B2 JP 6212981B2 JP 2013132305 A JP2013132305 A JP 2013132305A JP 2013132305 A JP2013132305 A JP 2013132305A JP 6212981 B2 JP6212981 B2 JP 6212981B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- polyester
- resin composition
- film
- ppm
- 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.)
- Expired - Fee Related
Links
- 229920006267 polyester film Polymers 0.000 title claims description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 229920001225 polyester resin Polymers 0.000 claims description 143
- 239000004645 polyester resin Substances 0.000 claims description 143
- 239000000203 mixture Substances 0.000 claims description 94
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 56
- 229910052698 phosphorus Inorganic materials 0.000 claims description 45
- 239000011574 phosphorus Substances 0.000 claims description 45
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 42
- 229920000728 polyester Polymers 0.000 claims description 31
- 229910052783 alkali metal Inorganic materials 0.000 claims description 29
- 150000001340 alkali metals Chemical class 0.000 claims description 29
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 28
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 11
- 238000004898 kneading Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 53
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 46
- 238000000034 method Methods 0.000 description 39
- 238000006460 hydrolysis reaction Methods 0.000 description 29
- 230000007062 hydrolysis Effects 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 21
- 239000004408 titanium dioxide Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- -1 phosphorus compound Chemical class 0.000 description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 13
- 238000006068 polycondensation reaction Methods 0.000 description 13
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000007790 solid phase Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- 238000005809 transesterification reaction Methods 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000004566 building material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000001463 antimony compounds Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000006172 buffering agent Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 150000002291 germanium compounds Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 3
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process 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
- 230000003139 buffering effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012772 electrical insulation material Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000009998 heat setting 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
- 229960002479 isosorbide Drugs 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 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
- 230000000704 physical effect Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical group OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- JJTUDXZGHPGLLC-QWWZWVQMSA-N (3r,6r)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@@H](C)OC1=O JJTUDXZGHPGLLC-QWWZWVQMSA-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
- CEGRHPCDLKAHJD-UHFFFAOYSA-N 1,1,1-propanetricarboxylic acid Chemical compound CCC(C(O)=O)(C(O)=O)C(O)=O CEGRHPCDLKAHJD-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical class CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- VHOJALQDYQKSMT-UHFFFAOYSA-N 2-(4-carboxyphenyl)-9H-fluorene-1-carboxylic acid Chemical class C(=O)(O)C1=CC=C(C=C1)C1=C(C=2CC3=CC=CC=C3C=2C=C1)C(=O)O VHOJALQDYQKSMT-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- RKFNMGWLDGIONW-UHFFFAOYSA-N 3,4,5-trihydroxychromen-2-one Chemical compound O1C(=O)C(O)=C(O)C2=C1C=CC=C2O RKFNMGWLDGIONW-UHFFFAOYSA-N 0.000 description 1
- QLHSZVGLSUHUOI-UHFFFAOYSA-N 3,5,6-trihydroxy-2-phenylchromen-4-one Chemical compound OC=1C(=O)C2=C(O)C(O)=CC=C2OC=1C1=CC=CC=C1 QLHSZVGLSUHUOI-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- SFHBJXIEBWOOFA-UHFFFAOYSA-N 5-methyl-3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OC(C)COC(=O)C2=CC=C1C=C2 SFHBJXIEBWOOFA-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- JJOJFIHJIRWASH-UHFFFAOYSA-N Eicosanedioic acid Natural products OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 1
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- YWMLORGQOFONNT-UHFFFAOYSA-N [3-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1 YWMLORGQOFONNT-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- LBVBDLCCWCJXFA-UHFFFAOYSA-N adamantane-1,2-dicarboxylic acid Chemical compound C1C(C2)CC3CC1C(C(=O)O)C2(C(O)=O)C3 LBVBDLCCWCJXFA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000007933 aliphatic carboxylic acids 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
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- HGMQPWXYDSTESW-UHFFFAOYSA-N anthracene-1,2,3-tricarboxylic acid Chemical compound C1=CC=C2C=C(C(C(O)=O)=C(C(C(=O)O)=C3)C(O)=O)C3=CC2=C1 HGMQPWXYDSTESW-UHFFFAOYSA-N 0.000 description 1
- SLOLMTWBBAFOKJ-UHFFFAOYSA-N anthracene-1,2,3-triol Chemical compound C1=CC=C2C=C(C(O)=C(C(O)=C3)O)C3=CC2=C1 SLOLMTWBBAFOKJ-UHFFFAOYSA-N 0.000 description 1
- FNGGVJIEWDRLFV-UHFFFAOYSA-N anthracene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=CC3=C(C(O)=O)C(C(=O)O)=CC=C3C=C21 FNGGVJIEWDRLFV-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- IHWUGQBRUYYZNM-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-3,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(=O)O)=CC1C2 IHWUGQBRUYYZNM-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- ZNFNDZCXTPWRLQ-UHFFFAOYSA-N butane-1,1,1-tricarboxylic acid Chemical compound CCCC(C(O)=O)(C(O)=O)C(O)=O ZNFNDZCXTPWRLQ-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-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
- 210000004899 c-terminal region Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- MCOFCVVDZHTYIX-UHFFFAOYSA-N ethane-1,1,1-tricarboxylic acid Chemical compound OC(=O)C(C)(C(O)=O)C(O)=O MCOFCVVDZHTYIX-UHFFFAOYSA-N 0.000 description 1
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber 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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- AJDJKHROQJQURF-UHFFFAOYSA-N phenanthrene-1,2-dicarboxylic acid Chemical compound C1=CC=C2C3=CC=C(C(=O)O)C(C(O)=O)=C3C=CC2=C1 AJDJKHROQJQURF-UHFFFAOYSA-N 0.000 description 1
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- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
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Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、耐久性が良好なポリエステルフィルムの製造方法に関する。さらに詳しくはポリエステルフィルムを構成するポリエステル樹脂組成物の生産性を大幅に改善し、耐湿熱環境下における特性維持と生産性を両立可能とするポリエステルフィルムの製造方法に関する。該製造方法により得られたポリエステルフィルムは、特に太陽電池封止用フィルムをはじめ、建築材料、自動車材料等、屋外で使用される用途に有用に用いられる。 The present invention relates to a method for producing a polyester film having good durability. More specifically, the present invention relates to a method for producing a polyester film that greatly improves the productivity of the polyester resin composition constituting the polyester film and makes it possible to maintain both properties and productivity in a moisture and heat resistant environment. The polyester film obtained by the production method is useful for applications that are used outdoors, such as solar cell sealing films, building materials, and automobile materials.
ポリエステル樹脂は機械特性、熱特性、耐薬品性、電気特性、成形性に優れ、様々な用途に用いられている。そのポリエステル樹脂をフィルム化したポリエステルフィルム、中でも二軸配向ポリエステルフィルムは、その機械的特性、電気的特性などから、銅貼り積層板、太陽電池封止フィルム、粘着テープ、フレキシブルプリント基板、メンブレンスイッチ、面状発熱体、もしくはフラットケーブルなどの電気絶縁材料、磁気記録材料や、コンデンサ用材料、包装材料、自動車用材料、建築材料、写真用途、グラフィック用途、感熱転写用途などの各種工業材料として使用されている。 Polyester resins are excellent in mechanical properties, thermal properties, chemical resistance, electrical properties, and moldability, and are used in various applications. The polyester film made from the polyester resin, especially the biaxially oriented polyester film, has its mechanical properties, electrical properties, etc., and has a copper-clad laminate, solar cell sealing film, adhesive tape, flexible printed circuit board, membrane switch, Used as various industrial materials such as sheet heating elements or electrical insulation materials such as flat cables, magnetic recording materials, capacitor materials, packaging materials, automotive materials, building materials, photographic applications, graphic applications, thermal transfer applications, etc. ing.
これらの用途のうち、特に屋外で用いられる電気絶縁材料（例えば太陽電池封止フィルムなど）、自動車用材料、建築材料などでは、長期にわたり過酷な環境下で使用されることが多い。そのような過酷な環境下で長期にわたり使用すると、ポリエステル樹脂は加水分解により分子量が低下し、また、脆化が進行して機械物性などが低下する。そのため、長期にわたり過酷な環境下で使用される場合、或いは湿気のある状態で使用される様な用途では、湿熱に対する耐久性が求められている。たとえば、太陽電池封止用途では太陽電池の耐用年数の向上による発電コストダウンを図るために、ポリエステルフィルムの耐湿熱性向上が求められている。 Among these applications, electrical insulating materials (for example, solar cell sealing films) used outdoors, automotive materials, building materials, and the like are often used in harsh environments for a long period of time. When used in such a harsh environment for a long period of time, the polyester resin has a molecular weight that decreases due to hydrolysis, and the embrittlement progresses, resulting in a decrease in mechanical properties. Therefore, when it is used in a harsh environment for a long period of time or in an application where it is used in a damp state, durability against wet heat is required. For example, in a solar cell sealing application, in order to reduce the power generation cost by improving the service life of the solar cell, it is required to improve the wet heat resistance of the polyester film.
そのため、ポリエステル樹脂の加水分解を抑制すべく様々な検討がなされてきた。例えば、ポリエステル樹脂の重縮合触媒を検討したり（特許文献１）、エポキシ化合物（特許文献２）やポリカルボジイミド（特許文献３）を添加して、ポリエステル樹脂自体の耐湿熱性を向上させる技術が検討されている。また、ポリエステル樹脂に緩衝剤を添加したり（特許文献４）、さらにポリエステル樹脂に３官能成分を導入する事で分子間架橋により耐湿熱性を向上させる方法（特許文献５）が検討されている。 Therefore, various studies have been made to suppress hydrolysis of the polyester resin. For example, a polycondensation catalyst for a polyester resin is studied (Patent Document 1), or an epoxy compound (Patent Document 2) or a polycarbodiimide (Patent Document 3) is added to improve the heat and moisture resistance of the polyester resin itself. Has been. In addition, a method of improving moisture and heat resistance by intermolecular crosslinking by adding a buffering agent to a polyester resin (Patent Document 4) and further introducing a trifunctional component into the polyester resin has been studied (Patent Document 5).
しかしながら、特許文献１の手法では耐加水分解性が不十分であった。特許文献２、３の技術では、フィルム溶融製膜時にゲル化が進行して厚み不良となったり、フィルタ詰まりが発生したり、二軸配向フィルム製造時にフィルム破れが発生しやすく耐加水分解性を向上させるために必要な配向を付与できないといったフィルム製膜プロセスでの問題が発生したり、フィルム中に異物が残り品質不良となったりする問題があった。フィルム中に緩衝剤を含有した特許文献４では、ポリエステル樹脂の耐久性は向上するが、添加した緩衝剤によりポリエステル樹脂の重縮合速度が低下するなど生産性が悪くなる問題や緩衝剤添加設備が必要となるなど従来のポリエステル樹脂生産設備をそのまま使用できないなどの問題があった。さらに、特許文献５のように分子間架橋構造を有した場合は、フィルムの耐加水分解性はさらに向上するが、特許文献４の場合と同様にポリエステル樹脂の生産性低下等の問題があった。また、特許文献４，５に使用される緩衝剤は、添加時に凝集しやすい問題があり、これら凝集物が濾過工程でのフィルタ寿命を縮めたり、濾過しきれずに残存した微小な凝集物が、異物としてフィルム内部に残存するため、外観不良として歩留まりを悪化させてしまう問題もあった。近年コストダウンのための歩留まり向上検討が進む中、フィルムに対する異物欠陥低減に対する要求レベルも益々高くなっており、耐加水分解性の向上に加えて、異物欠陥低減についての改善も求められてきている。 However, the method of Patent Document 1 has insufficient hydrolysis resistance. In the techniques of Patent Documents 2 and 3, gelation progresses during film melting and film formation, resulting in poor thickness, filter clogging, and film breakage during biaxially oriented film production, which is resistant to hydrolysis. There is a problem in the film forming process that the orientation necessary for improvement cannot be imparted, or there is a problem that foreign matter remains in the film, resulting in poor quality. In Patent Document 4 containing a buffering agent in the film, the durability of the polyester resin is improved, but the added buffering agent reduces the polycondensation rate of the polyester resin, resulting in poor productivity and equipment for adding a buffering agent. There has been a problem that conventional polyester resin production facilities cannot be used as they are. Furthermore, when it has an intermolecular cross-linked structure as in Patent Document 5, the hydrolysis resistance of the film is further improved, but there is a problem such as a decrease in productivity of the polyester resin as in Patent Document 4. . In addition, the buffer used in Patent Documents 4 and 5 has a problem of being easily aggregated at the time of addition, and these aggregates shorten the filter life in the filtration process, or the minute aggregates that remain without being filtered, Since it remains inside the film as a foreign substance, there is also a problem that the yield is deteriorated as an appearance defect. In recent years, with the progress of yield improvement for cost reduction proceeding, the level of demand for reducing foreign material defects on films has been increasing, and in addition to improving resistance to hydrolysis, improvements in reducing foreign material defects have been required. .
本発明の目的は、かかる従来技術の問題点に鑑み、高温高湿下条件での耐久性の維持と、ポリエステル樹脂およびフィルムの生産性ならびに品質向上とが両立可能な、ポリエステルフィルムの製造方法を提供することである。 In view of the problems of the prior art, an object of the present invention is to provide a method for producing a polyester film capable of maintaining durability under conditions of high temperature and high humidity, and improving the productivity and quality of polyester resin and film. Is to provide.
本発明は、かかる課題を解決するために、次のような手段を用いるものである。
（１）．ポリエステル樹脂組成物Ａを溶融押出しし、シート状に成型した後に長手方向と幅方向の二軸に延伸する工程を有するポリエステルフィルムの製造方法であって、前記ポリエステル樹脂組成物Ａ中に、アルカリ金属元素含有量ＷＡが１６５ｐｐｍ以上８５０ｐｐｍ以下、リン元素含有量ＷＰが３３０ｐｐｍ以上２０００ｐｐｍ以下であるポリエステル樹脂組成物αをポリエステル樹脂組成物Ａに対して５質量％以上５０質量％以下含有する事を特徴とするポリエステルフィルムの製造方法。
（２）．前記ポリエステル樹脂組成物αが、固有粘度（ＩＶ）が０．７０以上１．００以下のポリエステル樹脂組成物に、リン酸およびリン酸アルカリ金属塩を含む溶液またはスラリーを添加した後溶融混練して得られたものであり、かつ、前記溶液またはスラリーにおけるリン酸とリン酸アルカリ金属塩を合計した濃度が３．０質量％以下である事を特徴とする、（１）．に記載のポリエステルフィルムの製造方法。
（３）．前記リン酸およびリン酸アルカリ金属塩を含む溶液またはスラリーが、固有粘度（ＩＶ）が０．７０以上１．００以下のポリエステル樹脂組成物に対して、リン酸アルカリ金属塩を７．０モル／ｔを越えて３０．０モル／ｔ以下、リン酸を３．５モル／ｔを越えて３５．０モル／ｔ以下となるように添加する事を特徴とする、（２）．に記載のポリエステルフィルムの製造方法。
（４）．（１）．〜（３）．のいずれかの方法により製造された二軸配向ポリエステルフィルムであって、ポリエステルフィルムを構成するポリエステル樹脂組成物中のアルカリ金属元素含有量ＷＡｆが２０ｐｐｍ以上１５０ｐｐｍ以下、リン元素含有量ＷＰｆが４０ｐｐｍ以上５００ｐｐｍ以下、ＷＡｆ／ＷＰｆが０．３以上０．７以下である二軸配向ポリエステルフィルム。
（５）．ポリエステルフィルムを構成するポリエステル樹脂組成物中に、マンガン元素を１００ｐｐｍ以上３００ｐｐｍ以下含有する（４）．に記載の二軸配向ポリエステルフィルム。
（６）．ポリエステルフィルムを構成するポリエステル樹脂の末端カルボキシル基量が２５当量／ｔ以下である（４）．または（５）．に記載の二軸配向ポリエステルフィルム。
The present invention uses the following means in order to solve this problem.
(1). A method for producing a polyester film comprising a step of melt-extruding a polyester resin composition A and forming it into a sheet shape and then stretching it in two directions of a longitudinal direction and a width direction, wherein the polyester resin composition A contains an alkali metal The polyester resin composition α having an element content WA of 165 ppm or more and 850 ppm or less and a phosphorus element content WP of 330 ppm or more and 2000 ppm or less is contained in an amount of 5 mass% or more and 50 mass% or less with respect to the polyester resin composition A. A method for producing a polyester film.
(2). The polyester resin composition α is melt-kneaded after adding a solution or slurry containing phosphoric acid and an alkali metal phosphate to a polyester resin composition having an intrinsic viscosity (IV) of 0.70 or more and 1.00 or less. (1). It is obtained, and the total concentration of phosphoric acid and alkali metal phosphate in the solution or slurry is 3.0% by mass or less. The manufacturing method of the polyester film of description.
(3). The solution or slurry containing the phosphoric acid and the alkali metal phosphate contains 7.0 mol / liter of the alkali metal phosphate with respect to the polyester resin composition having an intrinsic viscosity (IV) of 0.70 to 1.00. (2), wherein t is more than 30.0 mol / t and phosphoric acid is added more than 3.5 mol / t to 35.0 mol / t. The manufacturing method of the polyester film of description.
(4). (1). To (3). A biaxially oriented polyester film produced by any of the methods described above, wherein the alkali metal element content WAf in the polyester resin composition constituting the polyester film is 20 ppm or more and 150 ppm or less, and the phosphorus element content WPf is 40 ppm or more and 500 ppm. Hereinafter, biaxially oriented polyester film having WAf / WPf of 0.3 or more and 0.7 or less.
(5). The polyester resin composition constituting the polyester film contains 100 ppm to 300 ppm of manganese element (4). 2. A biaxially oriented polyester film described in 1.
(6). The amount of terminal carboxyl groups of the polyester resin constituting the polyester film is 25 equivalents / t or less (4). Or (5). 2. A biaxially oriented polyester film described in 1.
本発明によれば、高温高湿下での耐久性とポリエステル樹脂およびフィルムの生産性を両立することができ、かつ異物欠陥が少ないポリエステルフィルムを提供することができる。かかるポリエステルフィルムは、太陽電池封止シート、銅貼り積層板、粘着テープ、フレキシブルプリント基板、メンブレンスイッチ、面状発熱体、もしくはフラットケーブルなどの電気絶縁材料、コンデンサ用材料、自動車用材料、建築材料を初めとした耐久性が重視されるような用途に好適に使用することができる。 ADVANTAGE OF THE INVENTION According to this invention, durability under high temperature high humidity and productivity of a polyester resin and a film can be made compatible, and the polyester film with few foreign material defects can be provided. Such a polyester film is a solar cell encapsulating sheet, a copper-clad laminate, an adhesive tape, a flexible printed circuit board, a membrane switch, a planar heating element, a flat cable, or other electrically insulating material, capacitor material, automotive material, building material. Can be suitably used for applications where durability is important.
本発明において、ポリエステル樹脂組成物Ａを溶融押出しし、シート状に成型した後に長手方向と幅方向の二軸に延伸する事が必要である。ポリエステルフィルムは二軸方向に延伸することで、分子が配向し広角Ｘ線回折で二軸配向のパターンを示す所謂二軸配向ポリエステルフィルムとなる。その結果として機械的な特性が向上したり、耐久性（耐湿熱性）が向上する。一般的なポリエステルフィルムは結晶性ポリエステルから構成され、フィルム中にはポリエステルの結晶部と非晶部が存在する。また、かかる結晶性ポリエステルを二軸延伸して得られるポリエステルフィルム中には、配向によりポリエステルが結晶化した部分（以下、配向結晶化部とする）と非晶部が存在する。ここで、非晶部は、結晶部、配向結晶部に比べて密度が低く、平均の分子間距離が大きい状態にあると考えられる。ポリエステルフィルムが湿熱雰囲気下に曝された場合、水分（水蒸気）は、密度の低いこの非晶部の分子間を通って内部に進入し、非晶部を可塑化させ分子の運動性を高め、ポリエステルの耐加水分解を促進させる。フィルムの配向を高め、非晶部の分子運動を抑制することで、分子内部への水分（水蒸気）の進入を抑制し、耐湿熱性（耐加水分解性）を高めることができると考えられる。 In the present invention, the polyester resin composition A needs to be melt-extruded and formed into a sheet shape and then stretched biaxially in the longitudinal direction and the width direction. The polyester film becomes a so-called biaxially oriented polyester film that is oriented in the biaxial direction, and in which the molecules are oriented and show a biaxially oriented pattern by wide-angle X-ray diffraction. As a result, mechanical properties are improved and durability (wet heat resistance) is improved. A general polyester film is composed of crystalline polyester, and there are crystalline and amorphous parts of the polyester in the film. Moreover, in the polyester film obtained by biaxially stretching such crystalline polyester, there are a portion where the polyester is crystallized by orientation (hereinafter referred to as an orientation crystallized portion) and an amorphous portion. Here, the amorphous part is considered to be in a state where the density is lower than that of the crystal part and the oriented crystal part and the average intermolecular distance is large. When the polyester film is exposed to a moist heat atmosphere, moisture (water vapor) enters the interior through the molecules of the amorphous part having a low density, plasticizes the amorphous part, and increases the mobility of the molecule. Promotes hydrolysis resistance of polyester. By increasing the orientation of the film and suppressing the molecular motion of the amorphous part, it is considered that moisture (water vapor) can be prevented from entering the inside of the molecule and the heat and humidity resistance (hydrolysis resistance) can be improved.
本発明の長手方向、幅方向の延伸方法としては、ロール間の速度差を利用するロール延伸方式や、幅方向の両端をクリップで把持し、向かい合うあるいは隣り合うクリップ間の間隔を広げる延伸方式や、圧縮空気を送り込みエアーの圧力で延伸するインフレーション方式など公知の方法を用いることができる。また、延伸の順番についても、長手方向延伸後に幅方向延伸を施しても、逆に幅方向延伸後に長手方向延伸を施しても良い。さらに長手方向と幅方向を同時に延伸する方法を用いても良い。一般的には、フィルム配向の制御のしやすさ延伸の均一性、あるいは設備制約の少なさなどの観点から、長手方向にはロール間の周速差を用いて延伸するロール延伸方式を、幅方向にはオーブン中で両端を把持したクリップの向かい合うクリップ間の距離を広げることで延伸するテンター方式を用いることが好ましい。 As the stretching method in the longitudinal direction and the width direction of the present invention, a roll stretching method that uses a speed difference between rolls, a stretching method that grips both ends in the width direction with clips, and widens the interval between facing or adjacent clips, A known method such as an inflation method in which compressed air is fed and stretched by the pressure of air can be used. Moreover, also about the order of extending | stretching, you may give width direction extending | stretching after longitudinal direction extending | stretching, and conversely may perform longitudinal direction extending | stretching after width direction extending | stretching. Furthermore, you may use the method of extending | stretching a longitudinal direction and the width direction simultaneously. In general, from the standpoint of ease of control of film orientation, uniformity of stretching, and few equipment restrictions, a roll stretching method that stretches using a circumferential speed difference between rolls in the longitudinal direction is used. For the direction, it is preferable to use a tenter system that extends by extending the distance between the clips facing each other in the oven.
本発明において、長手方向延伸時の倍率が３．０〜４．５倍、その時のフィルム温度がポリエステル樹脂のガラス転移温度をＴｇとした場合Ｔｇ以上Ｔｇ＋４０℃以下である事が好ましく、さらに、延伸時のフィルム温度がＴｇ＋１０℃以上Ｔｇ＋３０℃以下である事が好ましい。また、幅方向延伸時の倍率が３．５〜４．５倍、その時のフィルム温度がＴｇ以上Ｔｇ＋４０℃以下が好ましく、さらにはＴｇ＋１０℃以上Ｔｇ＋３０℃以下である事が好ましい。 In the present invention, the stretching ratio in the longitudinal direction is 3.0 to 4.5 times, and the film temperature at that time is preferably Tg or more and Tg + 40 ° C. or less when the glass transition temperature of the polyester resin is Tg. The film temperature is preferably Tg + 10 ° C. or higher and Tg + 30 ° C. or lower. Further, the magnification during stretching in the width direction is 3.5 to 4.5 times, and the film temperature at that time is preferably Tg or more and Tg + 40 ° C. or less, more preferably Tg + 10 ° C. or more and Tg + 30 ° C. or less.
本発明においては、長手方向・幅方向の二軸方向に延伸した後に、ポリエステル樹脂の融点をＴｍとした場合、Ｔｍ−８０℃以上Ｔｍ−２０℃以下の温度にて２秒間以上熱固定処理を施すことが、フィルムの結晶化を進め、結果として熱寸法安定性や耐薬品性などの特性が向上するため好ましい。熱固定温度については、更にはＴｍ−６０℃以上Ｔｍ−３０℃以下が好ましい。 In the present invention, when the melting point of the polyester resin is Tm after stretching in the biaxial direction of the longitudinal direction and the width direction, the heat setting treatment is performed for 2 seconds or more at a temperature of Tm-80 ° C. or more and Tm-20 ° C. or less. It is preferable to apply it because the crystallization of the film proceeds and as a result, characteristics such as thermal dimensional stability and chemical resistance are improved. About heat setting temperature, Tm-60 degreeC or more and Tm-30 degrees C or less are still more preferable.
本発明において、ポリエステル樹脂組成物Ａが、アルカリ金属元素含有量ＷＡ１６５ｐｐｍ以上８５０ｐｐｍ以下、リン元素含有量ＷＰが３３０ｐｐｍ以上２０００ｐｐｍ以下であるポリエステル樹脂組成物αをポリエステル樹脂組成物Ａに対して５質量％以上５０質量％以下含有する必要がある。本発明において、ポリエステルフィルムを構成するポリエステル樹脂組成物に含有するアルカリ金属元素量ＷＡｆとリン元素量ＷＰｆはそれぞれ、ＷＡｆが２０ｐｐｍ以上１５０ｐｐｍ以下、ＷＰｆが４０ｐｐｍ以上５００ｐｐｍであることが好ましい。さらに好ましくはＷＡｆが４０ｐｐｍ以上１００ｐｐｍ以下、ＷＰｆが１００ｐｐｍ以上３００ｐｐｍの範囲である。ポリエステルフィルムを構成するポリエステル樹脂組成物に含有するアルカリ金属元素量ＷＡｆとリン元素量ＷＰｆを上記の範囲に調整することで、リン元素とアルカリ金属元素の相互作用により、ポリエステルフィルム中に含まれる重合触媒残渣が分解反応触媒として働く事を抑制し、その結果、熱や水蒸気によるポリエステル分子鎖の分解反応速度を低下させることができると考えられる。しかしながら、リン元素やアルカリ金属元素をポリエステル樹脂の重合工程中に添加した場合は、重縮合時の触媒活性も低下させるため、ポリエスエル樹脂の生産性が悪化する問題がある。本発明の製造方法においては、生産性のネックとなっているリン元素ならびにアルカリ金属元素をポリエステル樹脂に添加する方法として、それらを高濃度に含有するポリエステル樹脂組成物αを通常のポリエステル樹脂と混合して使用することで、耐久性に優れるポリエステルの生産性を改善し製造コストを低減するものである。よって、ポリエステル樹脂組成物Ａ中にはＷＡ１６５ｐｐｍ以上８５０ｐｐｍ以下、ＷＰが３３０ｐｐｍ以上２０００ｐｐｍ以下のポリエスエル樹脂組成物αをポリエステル樹脂組成物Ａに対して５質量％以上５０質量％以下含有することが必要で有り、ＷＡが１６５ｐｐｍ未満であったり、ＷＰが３３０ｐｐｍ未満である場合は、耐湿熱性が低下する。一方、ＷＡが８５０ｐｐｍを超えたり、ＷＰが２０００ｐｐｍを超える場合は樹脂組成物αそのものの生産性が大きく低下したり、リン元素起因の異物が添加時や溶融押出し時に発生し外観を損なう。なお、好ましい範囲としてはＷＡが２００ｐｐｍ以上５００ｐｐｍ以下、ＷＰが５００ｐｐｍ以上１２５０ｐｐｍ以下である。また、ポリエステル樹脂組成物Ａ中におけるポリエステル樹脂組成物αの含有量が５質量％未満である場合は、耐湿熱性が低下する。５０質量％を超える場合は、相対的に生産性が悪いリン元素とアルカリ金属元素を多量に含有するポリエステル樹脂組成物αの混率が高くなることで、ポリエスエルフィルムの生産性が悪化したり、ポリエステル樹脂組成物Ａを溶融押出しする工程において、リン元素由来の異物が発生する。 In the present invention, the polyester resin composition A has an alkali metal element content WA of 165 ppm or more and 850 ppm or less, and a phosphorus element content WP of 330 ppm or more and 2000 ppm or less of 5% by mass with respect to the polyester resin composition A. It is necessary to contain more than 50 mass%. In the present invention, it is preferable that the amount of alkali metal element WAf and the amount of phosphorus element WPf contained in the polyester resin composition constituting the polyester film are WAf of 20 ppm to 150 ppm and WPf of 40 ppm to 500 ppm, respectively. More preferably, WAf is in the range of 40 ppm to 100 ppm, and WPf is in the range of 100 ppm to 300 ppm. Polymerization contained in the polyester film by the interaction of the phosphorus element and the alkali metal element by adjusting the alkali metal element amount WAf and the phosphorus element amount WPf contained in the polyester resin composition constituting the polyester film to the above ranges. It is considered that the catalyst residue can be prevented from acting as a decomposition reaction catalyst, and as a result, the decomposition reaction rate of the polyester molecular chain by heat or water vapor can be reduced. However, when a phosphorus element or an alkali metal element is added during the polymerization process of the polyester resin, the catalytic activity at the time of polycondensation is also lowered, and there is a problem that the productivity of the polyester resin deteriorates. In the production method of the present invention, as a method of adding phosphorus element and alkali metal element, which are bottlenecks in productivity, to a polyester resin, a polyester resin composition α containing them in a high concentration is mixed with a normal polyester resin. Therefore, the productivity of polyester having excellent durability is improved and the production cost is reduced. Therefore, it is necessary that the polyester resin composition A contains the polyester resin composition α having a WA of 165 ppm or more and 850 ppm or less and a WP of 330 ppm or more and 2000 ppm or less with respect to the polyester resin composition A of 5 mass% or more and 50 mass% or less. Yes, when the WA is less than 165 ppm or the WP is less than 330 ppm, the heat and moisture resistance is lowered. On the other hand, when WA exceeds 850 ppm or WP exceeds 2000 ppm, the productivity of the resin composition α itself is greatly reduced, or foreign matters derived from phosphorus elements are generated at the time of addition or melt extrusion, thereby impairing the appearance. In addition, as a preferable range, WA is 200 ppm or more and 500 ppm or less, and WP is 500 ppm or more and 1250 ppm or less. Moreover, when the content of the polyester resin composition α in the polyester resin composition A is less than 5% by mass, the heat-and-moisture resistance decreases. If it exceeds 50% by mass, the polyester film composition α containing a large amount of phosphorus element and alkali metal element with relatively poor productivity is increased, and the productivity of the polyester film deteriorates. In the step of melt-extruding the polyester resin composition A, foreign matters derived from phosphorus elements are generated.
本発明において、ポリエステル樹脂組成物αは、固有粘度（ＩＶ）が０．７０以上１．００以下のポリエステル樹脂組成物に、リン酸アルカリ金属塩を７．０モル／ｔを超えて３０．０モル／ｔ以下、リン酸を３．５モル／ｔを超えて３５．０モル／ｔ以下添加して得られる事が耐湿熱性（耐加水分解性）の観点から好ましい。リン酸アルカリ金属塩はポリエステル中で乖離してイオン性を示すため、加水分解反応の触媒として作用するプロトンを中和する事ができる。さらに、リン酸が添加されることで、リン酸アルカリ金属塩との緩衝作用により、たとえばｐＨなどの環境変化や、ポリエスエル分子鎖の加水分解によって生じた酸末端や塩基性末端を中和する作用が向上し、より安定した耐湿熱性を発現することが可能となる。この結果、加水分解反応を抑制し耐湿熱性を向上することが可能となる。緩衝作用を示すリン酸アルカリ金属塩の具体例としては、下記化学式（Ｉ）で示される化合物が挙げられるが、ポリエステル樹脂の重合反応性や、溶融成形時の耐熱性、耐湿熱性の観点から、リン酸二水素カリウム、リン酸二水素ナトリウムが特に好ましい例としてあげ挙げられる。
ＰＯｘＨｙＭｚ ・・・化学式（Ｉ）
（ここで、ｘは２〜４の整数、ｙは１または２、ｚは１または２であり、Ｍはアルカリ金属である）。
In the present invention, the polyester resin composition α is added to a polyester resin composition having an intrinsic viscosity (IV) of 0.70 or more and 1.00 or less to an alkali metal phosphate salt of more than 7.0 mol / t to 30.0. It is preferable from a viewpoint of heat-and-moisture resistance (hydrolysis resistance) that it is obtained by adding mol / t or less and phosphoric acid exceeding 3.5 mol / t and 35.0 mol / t or less. Since alkali metal phosphates dissociate in polyester and show ionicity, protons that act as a catalyst for hydrolysis reaction can be neutralized. Furthermore, by adding phosphoric acid, it acts to neutralize acid ends and basic ends caused by environmental changes such as pH and hydrolysis of polyester molecular chains by buffering with alkali metal phosphate. As a result, more stable moisture and heat resistance can be achieved. As a result, it is possible to suppress the hydrolysis reaction and improve the heat and moisture resistance. Specific examples of the alkali metal phosphate having a buffering action include compounds represented by the following chemical formula (I), from the viewpoint of polymerization reactivity of the polyester resin, heat resistance during melt molding, and heat and humidity resistance. Particularly preferred examples include potassium dihydrogen phosphate and sodium dihydrogen phosphate.
POxHyMz: Chemical formula (I)
(Where x is an integer from 2 to 4, y is 1 or 2, z is 1 or 2, and M is an alkali metal).
リン酸アルカリ金属塩の添加量が７．０モル／ｔ以下であったり、リン酸の添加量が３.５モル／ｔ以下である場合は、十分な耐湿熱性が得られない場合があり、リン酸アルカリ金属塩の添加量が３０．０モル／ｔを超えたり、リン酸の添加量が３５.０モル／ｔを超える場合は、生産性が悪化する他、リン元素起因の異物が増加したり、過剰なアルカリ金属により分解反応が促進される場合がある。リン酸アルカリ金属塩およびリン酸の添加量の好ましい範囲は８．０モル／ｔ以上２０．０モル／ｔ以下である。 When the addition amount of the alkali metal phosphate is 7.0 mol / t or less, or when the addition amount of phosphoric acid is 3.5 mol / t or less, sufficient moisture and heat resistance may not be obtained. When the addition amount of alkali metal phosphate exceeds 30.0 mol / t or the addition amount of phosphoric acid exceeds 35.0 mol / t, the productivity deteriorates and the foreign matter caused by phosphorus element increases. Or an excessive alkali metal may accelerate the decomposition reaction. A preferable range of the addition amount of the alkali metal phosphate and phosphoric acid is 8.0 mol / t or more and 20.0 mol / t or less.
アルカリ金属元素およびリン元素を含有する化合物はポリエステルの重合時に添加する方法と、重合完了後に後添加する方法があるが、上述したように、重合時にリン元素およびアルカリ金属元素含有化合物を添加すると、高濃度にリン元素およびアルカリ金属元素含有化合物を添加することで、重縮合反応速度が極端に低下する。そのため、本発明においては、ポリエステル樹脂重合完了後に後添加する方法が好ましい。ただし、後添加する方法を用いる場合においては、固有粘度（ＩＶ）が０.７０以上１.００以下のポリエステル樹脂組成物と、リン酸とリン酸アルカリ金属塩を含む溶液またはスラリーを添加した後溶融混練し、かつ、前記溶液またはスラリーにおけるリン酸とリン酸アルカリ金属塩を合計した濃度が３．０質量％以下とする方法を用いると、ポリエステル樹脂中への均一分散性を高め、添加時のリン元素起因の異物発生を抑制し、さらにポリエステル樹脂組成物αのＩＶを適度な範囲に制御できるため好ましい。ポリエステル樹脂組成物のＩＶが０.７未満である場合は、溶融混練後のポリエステル樹脂組成物αのＩＶが低くなりすぎ、フィルムの耐湿熱性が悪化したり、フィルムの生産性が低下する場合がある。またポリエステル樹脂組成物のＩＶが１.０を超える場合は、溶融混練性が悪化する場合がある。リン酸アルカリ金属塩とリン酸を含む溶液またはスラリーの濃度が３.０質量％を超える場合は、添加時にリン化合物同士が反応することで、リン元素起因の異物を発生させる場合がある。なお、溶液またはスラリー濃度の下限は特には限定されないが、生産性やポリエステル樹脂組成物αのＩＶ維持の観点から０.５質量％が実質的な下限値となる。また、前記溶液に使用する溶媒については、ポリエステル樹脂中に含有されるグリコール成分を用いる事が好ましく、一般的にはエチレングリコールやジエチレングリコールを使用することが、混練性や生産性の観点から好ましい。さらに、リン酸アルカリ金属塩とリン酸を含む溶液またはスラリーは一度に添加するのではなく、複数回に分けて添加する方法が分散性を向上させ、リン起因の異物抑制の点で好ましい。 A compound containing an alkali metal element and a phosphorus element has a method of adding at the time of polymerization of the polyester and a method of adding it after the completion of the polymerization, as described above, when adding a phosphorus element and an alkali metal element-containing compound at the time of polymerization, By adding the phosphorus element and alkali metal element-containing compound at a high concentration, the polycondensation reaction rate is extremely reduced. Therefore, in this invention, the method of post-adding after completion | finish of polyester resin polymerization is preferable. However, in the case of using the post-addition method, after adding a polyester resin composition having an intrinsic viscosity (IV) of 0.70 or more and 1.00 or less and a solution or slurry containing phosphoric acid and an alkali metal phosphate. When the method of melt kneading and using the method in which the total concentration of phosphoric acid and alkali metal phosphate in the solution or slurry is 3.0% by mass or less is used, the uniform dispersibility in the polyester resin is improved and added. This is preferable because the generation of foreign matter due to the phosphorus element can be suppressed and the IV of the polyester resin composition α can be controlled within an appropriate range. When the IV of the polyester resin composition is less than 0.7, the IV of the polyester resin composition α after melt-kneading becomes too low, and the heat and moisture resistance of the film may deteriorate, or the productivity of the film may decrease. is there. Moreover, when IV of a polyester resin composition exceeds 1.0, melt-kneading property may deteriorate. When the concentration of the solution or slurry containing the alkali metal phosphate and phosphoric acid exceeds 3.0% by mass, the phosphorus compounds may react with each other at the time of addition to generate foreign elements due to the phosphorus element. The lower limit of the solution or slurry concentration is not particularly limited, but 0.5% by mass is a substantial lower limit from the viewpoint of productivity and maintaining IV of the polyester resin composition α. Moreover, about the solvent used for the said solution, it is preferable to use the glycol component contained in a polyester resin, and generally using ethylene glycol and diethylene glycol is preferable from a kneadability and productivity viewpoint. Further, a solution or slurry containing an alkali metal phosphate and phosphoric acid is not added at once, but a method of adding the solution or a plurality of times in a plurality of times is preferable in terms of improving the dispersibility and suppressing foreign matters caused by phosphorus.
本発明において、ポリエステルフィルムを構成するポリエステル樹脂組成物中のアルカリ金属元素含有量ＷＡｆとリン元素含有量ＷＰｆの比ＷＡｆ／ＷＰｆが０．３以上０．７以下となるように調整することが好ましい。この範囲に含有量を調整することで、ポリエステルフィルムの加水分解抑制効果が維持しながら、耐熱安定性を付与することができる。また、リン化合物としてリン酸アルカリ金属塩とリン酸を併用すると、加水分解抑制効果をさらに高めることが可能となるため特に好ましい。 In the present invention, the ratio WAf / WPf of the alkali metal element content WAf and the phosphorus element content WPf in the polyester resin composition constituting the polyester film is preferably adjusted to be 0.3 or more and 0.7 or less. . By adjusting the content within this range, heat resistance stability can be imparted while maintaining the hydrolysis inhibiting effect of the polyester film. In addition, it is particularly preferable to use an alkali metal phosphate and phosphoric acid together as the phosphorus compound because the hydrolysis inhibiting effect can be further enhanced.
本発明において、ポリエステルフィルムを構成するポリエステル樹脂組成物中に、リン酸アルカリ金属塩を１．０モル／ｔ以上５．０モル／ｔ以下、リン酸を０．５モル／ｔを超えて７．５モル／ｔ以下となるように、ポリエステル樹脂組成物αの含有量を調整することが、耐湿熱性、生産性ならびに外観（異物抑制）の観点から好ましい。なお、リン酸アルカリ金属塩ならびにリン酸含有量の好ましい範囲としては、それぞれ１．５モル／ｔ以上３．０モル／ｔ以下、２．０モル／ｔ以上４．０モル／ｔ以下である。 In the present invention, in the polyester resin composition constituting the polyester film, the alkali metal phosphate is from 1.0 mol / t to 5.0 mol / t and the phosphoric acid is from 0.5 mol / t to 7 mol / t. It is preferable to adjust the content of the polyester resin composition α so as to be 5 mol / t or less from the viewpoints of heat and humidity resistance, productivity, and appearance (foreign matter suppression). In addition, as a preferable range of alkali metal phosphate and phosphoric acid content, they are 1.5 mol / t or more and 3.0 mol / t or less, respectively 2.0 mol / t or more and 4.0 mol / t or less. .
本発明において、ポリエステルフィルムを構成するポリエステル樹脂中の末端カルボキシル基量が２５当量／ｔ以下である事が好ましく、２０当量／ｔ以下である事がさらに好ましい。末端のプロトンを反応触媒として加水分解反応が進むため、ポリエステルフィルムを構成するポリエステル樹脂の末端カルボキシル基量が少ないほど耐加水分解性が向上すると考えられる。ただし、この場合は、ポリエステル樹脂の末端カルボキシル基量を減少させるために固相重合時間を長くするなどの処理が必要となるため、生産性は悪化する方向となる。本発明のアルカリ金属元素ならびにリン元素を高濃度に含有可能な樹脂組成物αを用いその混率を調整することで、それぞれの使用方法や目標コストに適合した耐湿熱性（加水分解性）を有するフィルムを効率よく生産することが可能となる。 In this invention, it is preferable that the terminal carboxyl group amount in the polyester resin which comprises a polyester film is 25 equivalent / t or less, and it is further more preferable that it is 20 equivalent / t or less. Since the hydrolysis reaction proceeds using the terminal proton as a reaction catalyst, it is considered that the hydrolysis resistance improves as the amount of the terminal carboxyl group of the polyester resin constituting the polyester film decreases. However, in this case, since a treatment such as increasing the solid phase polymerization time is required in order to reduce the amount of terminal carboxyl groups of the polyester resin, productivity tends to deteriorate. A film having moisture and heat resistance (hydrolysis) suitable for each method of use and target cost by adjusting the mixing ratio using the resin composition α that can contain alkali metal element and phosphorus element in high concentration of the present invention. Can be produced efficiently.
本発明のポリエステルフィルムにおいては、フィルム中における長径１００μｍ以上のリン元素を含有する異物が６ヶ／１０００ｃｍ２以下であることが好ましく、さらに好ましくは３ヶ／１０００ｃｍ２以下である。異物量が６ヶ／１０００ｃｍ２を超えると用途などにより外観の悪化が問題となる場合がある。なお、リン元素を含有する異物を低減する方法は上述した通りである。 In the polyester film of the present invention, the number of foreign substances containing a phosphorus element having a major axis of 100 μm or more in the film is preferably 6/1000 cm 2 or less, more preferably 3/1000 cm 2 or less. If the amount of foreign matter exceeds 6 pcs / 1000 cm 2 , deterioration of the appearance may be a problem depending on the application. In addition, the method of reducing the foreign material containing a phosphorus element is as above-mentioned.
本発明のポリエステル樹脂の重縮合触媒としては、従来のアンチモン化合物、ゲルマニウム化合物、チタン化合物を用いることができる。アンチモン化合物および／またはゲルマニウム化合物を用いる場合は、そのアンチモン元素、ゲルマニウム元素の和として５０ｐｐｍ〜５００ｐｐｍであることが重縮合反応性、固相重合反応性の点から好ましく、さらには５０〜３００ｐｐｍであることが耐熱性、耐加水分解性の点から好ましい。５００ｐｐｍを超えると重縮合反応性、固相重合反応性は向上するものの、再溶融時の分解反応も促進されるため、カルボンキシル末端基が増加し、耐熱性、耐加水分解性が低下する原因となることがある。好適に使用されるアンチモン化合物、ゲルマニウム化合物としては、五酸化アンチモン、三酸化アンチモン、二酸化ゲルマニウムを挙げることができ、それぞれ目的に応じて使い分けることができる。例えば、色調が最も良好となるのはゲルマニウム化合物であり、固相重合反応性が良好となるのはアンチモン化合物である。環境面を配慮し、非アンチモン系で製造する場合には、チタン触媒が重縮合反応や固相重合の反応性が良好となる点で好ましい。さらに、マンガン化合物を１００〜３００ｐｐｍの範囲で添加すると耐加水分解性が良好となるため好ましい。これはマンガンは水和エネルギーが高く、ポリエステルフィルム中の水との親和性が低いため、加水分解反応が進行しにくくなるためと考えられる。１００ｐｐｍ未満の場合は、加水分解抑制効果が不十分となり、３００ｐｐｍを越えると逆に耐加水分解性が悪化する傾向が見られる。 As the polycondensation catalyst for the polyester resin of the present invention, conventional antimony compounds, germanium compounds, and titanium compounds can be used. When using an antimony compound and / or a germanium compound, the sum of the antimony element and germanium element is preferably 50 ppm to 500 ppm from the viewpoint of polycondensation reactivity and solid phase polymerization reactivity, and more preferably 50 to 300 ppm. Is preferable from the viewpoint of heat resistance and hydrolysis resistance. If it exceeds 500 ppm, the polycondensation reactivity and solid-phase polymerization reactivity will improve, but the decomposition reaction during remelting will also be accelerated, leading to an increase in carboxyxyl end groups and a decrease in heat resistance and hydrolysis resistance. It may become. Examples of the antimony compound and the germanium compound that are preferably used include antimony pentoxide, antimony trioxide, and germanium dioxide, which can be used according to the purpose. For example, the germanium compound has the best color tone, and the antimony compound has the best solid-phase polymerization reactivity. In consideration of the environment, when producing non-antimony system, a titanium catalyst is preferable in that the reactivity of polycondensation reaction or solid phase polymerization is improved. Furthermore, it is preferable to add a manganese compound in the range of 100 to 300 ppm because hydrolysis resistance is improved. This is presumably because manganese has high hydration energy and low affinity with water in the polyester film, so that the hydrolysis reaction does not proceed easily. When it is less than 100 ppm, the hydrolysis inhibiting effect is insufficient, and when it exceeds 300 ppm, the hydrolysis resistance tends to deteriorate.
本発明において、ポリエステルフィルムを構成するポリエステル樹脂の固有粘度（ＩＶ）は０．６５以上０．８０以下となるように調整する事が好ましい。ＩＶが０．６５未満である場合は、分子鎖が短く耐湿熱環境下での分子運動性が高まり易かったり、末端部分が増える事で耐加水分解性が悪化しやすい。また０．８０を越える場合は、粘度が高くなりすぎるため、フィルム製膜時に破断が増えるなど生産性が悪化したり、厚みムラが悪化したりする事がある。固有粘度（ＩＶ）は、ポリエステル樹脂製造時に固相重合を行うと、前述の末端カルボキシル基量を低下させ、かつ固有粘度（ＩＶ）を上記の範囲に調整する事が容易となるため好ましい。なお、ポリエステル樹脂を溶融製膜する際の溶融状態において、残存する水分による加水分解や熱分解が進行するため、フィルム原料として用いるポリエステル樹脂の固有粘度（ＩＶ）は、フィルムを構成するポリエステル樹脂におけるＩＶの目標値よりも高くすることが好ましい。ただし、フィルム原料のポリエステル樹脂の固有粘度（ＩＶ）を上げるためには、ポリエステル樹脂製造時の固相重合の時間を長くしたり、触媒添加量を増やす必要があり、ポリエステル樹脂の着色や特性の悪化につながる場合がある。そのため、フィルム原料のポリエステル樹脂の固有粘度（ＩＶ）は、フィルムを構成するポリエステル樹脂におけるＩＶの目標値よりも高くするとしても、その差は小さい方が好ましい。フィルム原料のポリエステル樹脂の固有粘度（ＩＶ）は、フィルムを構成するポリエステル樹脂におけるＩＶの目標値よりも０．０５〜０．１５高くすることが好ましい。ポリエステル樹脂をフィルムに溶融押出製膜する前に、ポリエステル樹脂を減圧下にて加熱する等の方法にてあらかじめポリエステル樹脂中の水分量を５０ｐｐｍ以下とする事や、フィルムに溶融押出製膜する時のポリエステル樹脂の温度をポリエステル樹脂の融点（Ｔｍ）＋３０℃以下として、さらに押出機先端から口金までの樹脂の溶融時間を５分未満、さらには３分未満とする事によって、ポリエステル樹脂の溶融製膜時の加水分解や熱分解を抑制して固有粘度（ＩＶ）の低下を少なくし、安定して耐加水分解性の良いポリエステルフィルムを得る事が可能となる。 In this invention, it is preferable to adjust so that the intrinsic viscosity (IV) of the polyester resin which comprises a polyester film may be 0.65-0.80. When IV is less than 0.65, the molecular mobility is short and the molecular mobility in a heat-and-moisture resistant environment is likely to increase, and the hydrolysis resistance tends to deteriorate due to an increase in the terminal portion. On the other hand, when it exceeds 0.80, the viscosity becomes too high, so that the productivity may be deteriorated such as an increase in breakage during film formation, and the thickness unevenness may be deteriorated. Intrinsic viscosity (IV) is preferable when solid phase polymerization is performed at the time of producing a polyester resin because the amount of the terminal carboxyl group is reduced and the intrinsic viscosity (IV) can be easily adjusted to the above range. In addition, in the melted state when the polyester resin is melt-formed, hydrolysis and thermal decomposition with residual water proceed, so the intrinsic viscosity (IV) of the polyester resin used as the film raw material is the polyester resin constituting the film. It is preferable to make it higher than the target value of IV. However, in order to increase the intrinsic viscosity (IV) of the polyester resin of the film raw material, it is necessary to lengthen the solid phase polymerization time during the production of the polyester resin or increase the amount of the catalyst added. It may lead to deterioration. Therefore, even if the intrinsic viscosity (IV) of the polyester resin of the film raw material is higher than the target value of IV in the polyester resin constituting the film, the difference is preferably small. It is preferable that the intrinsic viscosity (IV) of the polyester resin of the film raw material is 0.05 to 0.15 higher than the target value of IV in the polyester resin constituting the film. Before the polyester resin is melt-extruded and formed into a film, when the polyester resin is made to have a moisture content of 50 ppm or less in advance, such as by heating the polyester resin under reduced pressure, or when the film is melt-extruded into a film The temperature of the polyester resin is set to the melting point of the polyester resin (Tm) + 30 ° C. or less, and the melting time of the resin from the extruder tip to the die is set to less than 5 minutes, and further to less than 3 minutes. It is possible to obtain a polyester film having good hydrolysis resistance stably by suppressing hydrolysis and thermal decomposition during filming to reduce the decrease in intrinsic viscosity (IV).
本発明のポリエステル組成物Ａを構成するポリエステル樹脂はジカルボン酸構成成分とジオール構成成分を有してなるポリエステルである。なお、本明細書内において、構成成分とはポリエステルを加水分解することで得ることが可能な最小単位のことを示す。 The polyester resin constituting the polyester composition A of the present invention is a polyester having a dicarboxylic acid component and a diol component. In addition, in this specification, a structural component shows the minimum unit which can be obtained by hydrolyzing polyester.
かかるポリエステルを構成するジカルボン酸構成成分としては、マロン酸、コハク酸、グルタル酸、アジピン酸、スベリン酸、セバシン酸、ドデカンジオン酸、ダイマー酸、エイコサンジオン酸、ピメリン酸、アゼライン酸、メチルマロン酸、エチルマロン酸等の脂肪族ジカルボン酸類、アダマンタンジカルボン酸、ノルボルネンジカルボン酸、イソソルビド、シクロヘキサンジカルボン酸、デカリンジカルボン酸、などの脂環族ジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、１，４−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、１，８−ナフタレンジカルボン酸、４，４’−ジフェニルジカルボン酸、４，４’−ジフェニルエーテルジカルボン酸、５−ナトリウムスルホイソフタル酸、フェニルエンダンジカルボン酸、アントラセンジカルボン酸、フェナントレンジカルボン酸、９，９’−ビス（４−カルボキシフェニル）フルオレン酸等芳香族ジカルボン酸などのジカルボン酸、もしくはそのエステル誘導体が挙げられるがこれらに限定されない。また、上述のカルボン酸構成成分のカルボキシ末端に、ｌ-ラクチド、ｄ−ラクチド、ヒドロキシ安息香酸などのオキシ酸類、およびその誘導体や、オキシ酸類が複数個連なったもの等を付加させたものも好適に用いられる。また、これらは単独で用いても、必要に応じて、複数種類用いても構わない。 Examples of the dicarboxylic acid component constituting the polyester include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalon. Aliphatic dicarboxylic acids such as acid, ethylmalonic acid and the like, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexanedicarboxylic acid, decalin dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4 -Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, 5-sodium Sulfoiso Examples include dicarboxylic acids such as taric acid, phenylendanedicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, aromatic dicarboxylic acid such as 9,9′-bis (4-carboxyphenyl) fluorenic acid, or ester derivatives thereof. It is not limited. Also suitable are those obtained by adding oxyacids such as l-lactide, d-lactide, hydroxybenzoic acid, and derivatives thereof, or a combination of a plurality of oxyacids to the carboxy terminus of the carboxylic acid component. Used for. Moreover, these may be used independently or may be used in multiple types as needed.
また、かかるポリエステルを構成するジオール構成成分としては、エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，４−ブタンジオール、１，２−ブタンジオール、１，３−ブタンジオール等の脂肪族ジオール類、シクロヘキサンジメタノール、スピログリコール、イソソルビドなどの脂環式ジオール類、ビスフェノールＡ、１，３―ベンゼンジメタノール，１，４−ベンセンジメタノール、９，９’−ビス（４−ヒドロキシフェニル）フルオレン、芳香族ジオール類等のジオール、上述のジオールが複数個連なったものなどが例としてあげられるがこれらに限定されない。また、これらは単独で用いても、必要に応じて、複数種類用いても構わない。 Examples of the diol component constituting the polyester include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol. Aliphatic diols such as cyclohexanedimethanol, spiroglycol and isosorbide, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9′-bis (4 -Hydroxyphenyl) fluorene, diols such as aromatic diols, and a series of a plurality of the above-mentioned diols are exemplified, but the invention is not limited thereto. Moreover, these may be used independently or may be used in multiple types as needed.
また、本発明のポリエステル樹脂組成物Ａ中には、カルボン酸成分と水酸基成分の合計が３以上である構成成分や、エポキシ系化合物やカルボジイミド系化合物、オキサゾリン系化合物など末端カルボキシル基の封止剤を本発明の効果を損なわない程度に含有することが可能である。カルボン酸成分と水酸基成分の合計が３以上である構成成分の例としては、三官能の芳香族カルボン酸構成成分としては、トリメシン酸、トリメリット酸、ピロメリット酸、ナフタレントリカルボン酸、アントラセントリカルボン酸等が、三官能の脂肪族カルボン酸構成成分として、メタントリカルボン酸、エタントリカルボン酸、プロパントリカルボン酸、ブタントリカルボン酸等が挙げられ、水酸基数が３以上の構成成分の例としては、トリヒドロキシベンゼン、トリヒドロキシナフタレン、トリヒドロキシアントラセン、トリヒドロキシカルコン、トリヒドロキシフラボン、トリヒドロキシクマリン等が挙げられる。ただし上記、カルボン酸成分と水酸基成分の合計が３以上である構成成分や末端封止剤を添加すると、ポリエステル樹脂の分子鎖同士を架橋した３次元構造を形成しやすく、結果としてフィルムの延伸性を悪化させたり、ゲル化物によるフィルム中の異物量が増加するため、極力使用しない方が好ましい。 In the polyester resin composition A of the present invention, a terminal carboxyl group sealing agent such as a component having a total of 3 or more carboxylic acid components and hydroxyl components, an epoxy compound, a carbodiimide compound, an oxazoline compound, etc. It is possible to contain to the extent which does not impair the effect of this invention. Examples of components having a total of three or more carboxylic acid components and hydroxyl components include trifunctional aromatic carboxylic acid components such as trimesic acid, trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, anthracentricarboxylic acid Examples of the trifunctional aliphatic carboxylic acid component include methanetricarboxylic acid, ethanetricarboxylic acid, propanetricarboxylic acid, and butanetricarboxylic acid. Examples of the component having 3 or more hydroxyl groups include trihydroxybenzene. , Trihydroxynaphthalene, trihydroxyanthracene, trihydroxychalcone, trihydroxyflavone, trihydroxycoumarin and the like. However, when a component having a total of 3 or more of the carboxylic acid component and the hydroxyl component or a terminal blocking agent is added, a three-dimensional structure in which the molecular chains of the polyester resin are cross-linked is easily formed, and as a result, the stretchability of the film It is preferable not to use as much as possible, because the amount of foreign matter in the film due to the gelled product increases.
また、本発明のポリエステル樹脂組成物Ａにおいて、ポリエステル中の全ジカルボン酸構成成分中の芳香族ジカルボン酸構成成分の割合は、９０モル％以上１００モル％以下が好ましい。より好ましくは９５モル％以上１００モル％が好ましい。更に好ましくは９８モル％以上１００モル％以下、特に好ましくは９９モル％以上１００モル％以下、最も好ましくは１００モル％、すなわちジカルボン酸構成成分全てが芳香族ジカルボン酸構成成分であるのがよい。９０モル％に満たないと、耐湿熱性、耐熱性が低下したりする場合がある。本発明のポリエステルフィルムにおいて、ポリエステル中の全ジカルボン酸構成成分中の芳香族ジカルボン酸構成成分の割合を９０モル％以上１００モル％以下とすることで、耐湿熱性、耐熱性を両立することが可能となる。 Moreover, in the polyester resin composition A of this invention, 90 mol% or more and 100 mol% or less of the ratio of the aromatic dicarboxylic acid structural component in all the dicarboxylic acid structural components in polyester are preferable. More preferably, it is 95 mol% or more and 100 mol%. More preferably, it is 98 mol% or more and 100 mol% or less, particularly preferably 99 mol% or more and 100 mol% or less, and most preferably 100 mol%, that is, all dicarboxylic acid components should be aromatic dicarboxylic acid components. If it is less than 90 mol%, the heat and moisture resistance and heat resistance may decrease. In the polyester film of the present invention, by making the ratio of the aromatic dicarboxylic acid constituent component in the total dicarboxylic acid constituent component in the polyester 90 mol% or more and 100 mol% or less, it is possible to achieve both heat and moisture resistance and heat resistance. It becomes.
本発明のポリエステル樹脂組成物Ａにおいて、ポリエステルが主として構成される、ジカルボン酸構成成分とジオール構成成分からなる主たる繰り返し単位は、エチレンテレフタレート、エチレン−２，６−ナフタレンジカルボキシレート、プロピレンテレフタレート、ブチレンテレフタレート、１，４−シクロヘキシレンジメチレンテレフタレート、エチレン−２，６−ナフタレンジカルボキシレートおよびこれら混合物をからなるものが好適に用いられる。なお、ここでいう主たる繰り返し単位とは、上記繰り返し単位の合計が全繰り返し単位の７０モル％以上、より好ましくは８０モル％以上、更に好ましくは９０モル％以上である。さらには低コストで、より容易に重合が可能で、かつ耐熱性に優れるという点で、エチレンテレフタレートが主たる構成成分であることが好ましい。 In the polyester resin composition A of the present invention, the main repeating unit comprising a dicarboxylic acid component and a diol component, which are mainly composed of polyester, is ethylene terephthalate, ethylene-2,6-naphthalenedicarboxylate, propylene terephthalate, butylene. Those composed of terephthalate, 1,4-cyclohexylenedimethylene terephthalate, ethylene-2,6-naphthalenedicarboxylate and mixtures thereof are preferably used. The main repeating unit as used herein means that the total of the above repeating units is 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more of all repeating units. Furthermore, it is preferable that ethylene terephthalate is a main constituent in terms of low cost, easy polymerization, and excellent heat resistance.
更に、本発明のポリエステル樹脂組成物Ａには、各種添加剤、例えば、酸化防止剤、耐熱安定剤、耐候安定剤、紫外線吸収剤、有機の易滑剤、顔料、染料、有機または無機の微粒子、充填剤、帯電防止剤、核剤、架橋剤などがその特性を悪化させない程度に添加されていてもよい。特に、紫外線カット能を付与するにはポリエステルフィルム中に隠蔽性が高い二酸化チタンなどの無機粒子や紫外線吸収剤を含有させるのが好ましく、特に二酸化チタンはその隠蔽性および反射率の高さから、太陽電池封止フィルムとして使用した場合、内部の配線を見えにくくしたり、背面側の封止フィルムとして使用した場合は、発電に利用されなかった光を反射することで発電効率向上に寄与する事が出来るため好ましい。 Further, the polyester resin composition A of the present invention includes various additives such as antioxidants, heat stabilizers, weathering stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, Fillers, antistatic agents, nucleating agents, crosslinking agents, and the like may be added to such an extent that the properties are not deteriorated. In particular, it is preferable to contain inorganic particles such as titanium dioxide having a high concealment property or an ultraviolet absorber in the polyester film in order to impart ultraviolet cut ability, and in particular, titanium dioxide has a high concealability and high reflectance. When used as a solar cell sealing film, the internal wiring is less visible, or when used as a back side sealing film, it contributes to improving power generation efficiency by reflecting light that was not used for power generation. Is preferable.
二酸化チタンとしては、アナターゼ型及びルチル型の結晶構造を有する二酸化チタンが存在するが、アナターゼ型と比較してルチル型の方が結晶構造が密であるため屈折率が高い。そのため本発明にて使用される二酸化チタンは、高い反射作用による隠蔽効果を得ることができるという観点から、ルチル型二酸化チタンが好ましい。 Titanium dioxide includes titanium dioxide having anatase and rutile crystal structures, but the rutile type has a higher refractive index because the crystal structure is denser than the anatase type. Therefore, the titanium dioxide used in the present invention is preferably rutile titanium dioxide from the viewpoint that a concealing effect due to high reflection action can be obtained.
二酸化チタン粒子の製造方法としては、主に硫酸法と塩素法が挙げられる。硫酸法プロセスではイルメナイト鉱を濃硫酸に溶解し、鉄分を硫酸鉄として分離した後、この溶液を加水分解することでチタンを水酸化物としてとして沈殿分離する。次いでこの水酸化物を高温のロータリーキールン等で焼くことで、二酸化チタンを得ることができる。一方塩素法プロセスでは、ルチル鉱を原料とし、約１，０００℃の高温で塩素ガスとカーボンに反応させ、四塩化チタンを生成させた後に、四塩化チタンを分離し、高速に噴射しながら酸化することで二酸化チタンを得ることができる。塩素法プロセスで生成された二酸化チタンは、硫酸法プロセスと比較して、気体だけが関与する気相反応で合成されることから、バナジウム、鉄、マンガンといった不純物が少なく、高純度な二酸化チタンを得ることができ、特に好ましい。 As a production method of the titanium dioxide particles, mainly a sulfuric acid method and a chlorine method are exemplified. In the sulfuric acid process, ilmenite ore is dissolved in concentrated sulfuric acid, iron is separated as iron sulfate, and the solution is hydrolyzed to precipitate and separate titanium as a hydroxide. Next, titanium dioxide can be obtained by baking this hydroxide with a high-temperature rotary keeln or the like. On the other hand, in the chlorine process, rutile ore is used as a raw material and reacted with chlorine gas and carbon at a high temperature of about 1,000 ° C. to produce titanium tetrachloride. Then, titanium tetrachloride is separated and oxidized while being injected at high speed. By doing so, titanium dioxide can be obtained. Compared to the sulfuric acid process, titanium dioxide produced by the chlorine process is synthesized by a gas phase reaction involving only gas, so there are few impurities such as vanadium, iron, and manganese, and high purity titanium dioxide is used. It can be obtained and is particularly preferred.
本発明で使用される二酸化チタンは、二酸化チタンの光触媒活性を抑制するため、あるいはポリエステル樹脂中での分散性を向上させるために、表面処理が行われていることが好ましい。光触媒活性を抑制するためには、例えば表面をシリカ、アルミナなどの無機酸化物で被覆処理する方法が挙げられる。また、分散性向上のためには、例えば、シロキサン化合物やポリオールなどで表面処理をする方法が挙げられる。 The titanium dioxide used in the present invention is preferably surface-treated in order to suppress the photocatalytic activity of titanium dioxide or to improve the dispersibility in the polyester resin. In order to suppress the photocatalytic activity, for example, a method of coating the surface with an inorganic oxide such as silica or alumina can be mentioned. In order to improve dispersibility, for example, a method of surface treatment with a siloxane compound or a polyol can be used.
本発明での二酸化チタンの粒径は、０．１μｍ〜０．５μｍであることが好ましい。二酸化チタンの光反射能力が最大発揮される波長は、二酸化チタン粒径の約２倍の波長であるため、二酸化チタンの粒径が上記の範囲であると可視光線領域の反射効率が高くなるため、例えば太陽電池の封止フィルムとして用いられた場合は、発電効率が向上し好ましい。二酸化チタンの粒径は０．２μｍ〜０．４μｍであることが特に好ましい。二酸化チタンの粒径が０．１μｍ未満となると、二酸化チタン粒子が凝集しやすく、分散が難しい傾向があり、また０．５μｍを越えると可視光線領域の反射効率が落ちる傾向がある。なお、ここで言う二酸化チタン粒子の平均粒径とは、積層フィルムを灰化処理をした後に、走査型電子顕微鏡（ＳＥＭ）にて２０，０００倍の倍率で観察し、観察された粒子５０ヶの数平均粒径を求めた値である。 The particle diameter of titanium dioxide in the present invention is preferably 0.1 μm to 0.5 μm. The wavelength at which the light reflection ability of titanium dioxide is maximized is about twice the wavelength of the titanium dioxide particle size, and if the titanium dioxide particle size is in the above range, the reflection efficiency in the visible light region is increased. For example, when used as a sealing film for solar cells, the power generation efficiency is improved, which is preferable. The particle size of titanium dioxide is particularly preferably 0.2 μm to 0.4 μm. When the particle diameter of titanium dioxide is less than 0.1 μm, the titanium dioxide particles tend to aggregate and tend to be difficult to disperse, and when it exceeds 0.5 μm, the reflection efficiency in the visible light region tends to decrease. The average particle diameter of the titanium dioxide particles referred to here means that the laminated film was incinerated and then observed with a scanning electron microscope (SEM) at a magnification of 20,000 times. The number average particle diameter was obtained.
本発明の製造方法にて製造されるポリエステルフィルムの厚みは１０μｍ以上５００μｍ以下が好ましく、２０μｍ以上３００μｍ以下がより好ましい。更に好ましくは、２５μｍ以上２００μｍ以下である。厚みが１０μｍ未満の場合、フィルムの耐湿熱性が低下しすぎる場合がある。一方、５００μｍより厚い場合は、フィルム延伸工程で破れやすくなる等、耐湿熱性と生産性の両立が難しくなる傾向がある。 The thickness of the polyester film produced by the production method of the present invention is preferably from 10 μm to 500 μm, more preferably from 20 μm to 300 μm. More preferably, they are 25 micrometers or more and 200 micrometers or less. When thickness is less than 10 micrometers, the heat-and-moisture resistance of a film may fall too much. On the other hand, when it is thicker than 500 μm, it tends to be difficult to achieve both heat resistance and productivity, such as being easily broken in the film stretching process.
［物性の測定法］
以下、実施例により本発明の構成、効果をさらに具体的に説明する。なお、本発明は下記実施例に限定されるものではない。各実施例の記述に先立ち、各種物性の測定方法を記載する。
[Measurement method of physical properties]
Hereinafter, the configuration and effects of the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the following Example. Prior to describing each example, a method for measuring various physical properties will be described.
（１）アルカリ金属元素含有量
原子吸光分析法（日立製作所製：偏光ゼーマン原子吸光光度計１８０−８０。フレーム：アセチレン−空気）にて定量を行った。
(1) Alkali metal element content Quantification was performed by atomic absorption spectrometry (manufactured by Hitachi, Ltd .: polarized Zeeman atomic absorption photometer 180-80, frame: acetylene-air).
（２）リン元素およびマンガン元素含有量
（株）リガク社製波長分散型蛍光Ｘ線分析装置（型番：ＺＳＸ１００ｅ）を用いて測定した。
(2) Content of phosphorus element and manganese element It was measured using a wavelength dispersive X-ray fluorescence spectrometer (model number: ZSX100e) manufactured by Rigaku Corporation.
（３）固有粘度（ＩＶ）
オルトクロロフェノール１００ｍＬにポリエステル樹脂又はポリエステルフィルムを溶解させ（溶液濃度Ｃ＝１．２ｇ／ｍＬ）、その溶液の２５℃での粘度をオストワルド粘度計を用いて測定した。また、同様に溶媒の粘度を測定した。得られた溶液粘度、溶媒粘度を用いて、下記式（Ｃ）により、［η］を算出し、得られた値でもって固有粘度（ＩＶ）とした。
ηｓｐ／Ｃ＝［η］＋Ｋ［η］２・Ｃ ・・・式（Ｃ）
（ここで、ηｓｐ＝（溶液粘度／溶媒粘度）―１、Ｋはハギンス定数（０．３４３とする）
である。）。なお、ポリエステル樹脂を溶解させた溶液中に不溶物がある場合は、溶液を濾過して濾物の質量測定を行い、濾物の質量を測定試料質量から差し引いた値を測定試料質量として測定する。
(3) Intrinsic viscosity (IV)
A polyester resin or a polyester film was dissolved in 100 mL of orthochlorophenol (solution concentration C = 1.2 g / mL), and the viscosity of the solution at 25 ° C. was measured using an Ostwald viscometer. Similarly, the viscosity of the solvent was measured. Using the obtained solution viscosity and solvent viscosity, [η] was calculated by the following formula (C), and the obtained value was used as the intrinsic viscosity (IV).
ηsp / C = [η] + K [η] 2 · C Formula (C)
(Where ηsp = (solution viscosity / solvent viscosity) −1, K is a Huggins constant (assuming 0.343)
It is. ). In addition, when there is an insoluble matter in the solution in which the polyester resin is dissolved, the solution is filtered and the mass of the filtrate is measured, and the value obtained by subtracting the mass of the filtrate from the mass of the measurement sample is measured as the measurement sample mass. .
（４）末端カルボキシル基量
Ｍａｕｌｉｃｅの方法（文献 Ｍ．Ｊ．Ｍａｕｌｉｃｅ，Ｆ．Ｈｕｉｚｉｎｇａ．Ａｎａｌ．Ｃｈｉｍ．Ａｃｔａ，２２ ３６３（１９６０））に準じて、以下の方法にて測定した。
ポリエステル樹脂またはポリエステルフィルム２ｇをｏ−クレゾール／クロロホルム（質量比７／３）５０ｍＬに温度８０℃にて溶解し、０．０５ＮのＫＯＨ／メタノール溶液によって滴定し、末端カルボキシル基濃度を測定し、当量／ポリエステル１ｔの値で示した。なお、滴定時の指示薬はフェノールレッドを用いて、黄緑色から淡紅色に変化したところを滴定の終点とした。なお、ポリエステル組成物を溶解させた溶液中に不溶物がある場合は、溶液を濾過して濾物の質量測定を行い、濾物の質量を測定試料質量から差し引いた値を測定試料質量として測定する。
(4) Terminal carboxyl group amount It was measured by the following method according to the method of Malice (reference MJ Mauleice, F. Huizinga. Anal. Chim. Acta, 22 363 (1960)).
2 g of a polyester resin or polyester film was dissolved in 50 mL of o-cresol / chloroform (mass ratio 7/3) at a temperature of 80 ° C., titrated with a 0.05 N KOH / methanol solution, the terminal carboxyl group concentration was measured, / Indicated by the value of polyester 1t. In addition, the indicator at the time of titration used phenol red, and the place where it changed from yellowish green to light red was set as the end point of titration. If there is insoluble matter in the solution in which the polyester composition is dissolved, the solution is filtered and the mass of the filtrate is measured, and the value obtained by subtracting the mass of the filtrate from the mass of the measurement sample is measured as the measurement sample mass. To do.
（５）リン元素を含有する異物数
三波長蛍光灯を光源としてフィルムを透過光および反射光にて１０００ｃｍ２を検査し観察された異物をマーキングして試料を採取した。なお、この時にフィルム位置での光量が１０００ルクスとなるように光源とフィルム間距離を調整した。得られた異物試料について光学顕微鏡（倍率１００倍）にて観察して異物のサイズが最も大きくなる方向で測定し異物の長径とした。また、異物試料を走査型電子顕微鏡（ＳＥＭ）Ｓ−４３００Ａ形（（株）日立製作所製）にエネルギー分散型Ｘ線分析装置（ＥＤＸ）ＥＭＡＸ−７０００（（株）堀場製作所製）を付属させた装置を用いて異物部分の元素分析を行い、リン元素の含有有無を測定し、長径１００μｍ以上のリン元素を含有する異物の個数をカウントした。なお、評価は以下の基準にて実施した。Ｂ以上が合格である。
(5) Number of foreign substances containing phosphorus element Using a three-wavelength fluorescent lamp as a light source, 1000 cm 2 was inspected with transmitted light and reflected light through the film, and the observed foreign substances were marked to collect samples. At this time, the distance between the light source and the film was adjusted so that the amount of light at the film position was 1000 lux. The obtained foreign material sample was observed with an optical microscope (magnification 100 times) and measured in the direction in which the size of the foreign material was the largest, and was taken as the long diameter of the foreign material. In addition, an energy dispersive X-ray analyzer (EDX) EMAX-7000 (manufactured by Horiba, Ltd.) was attached to a scanning electron microscope (SEM) S-4300A (manufactured by Hitachi, Ltd.) as a foreign material sample. Elemental analysis of the foreign matter portion was performed using an apparatus, the presence or absence of phosphorus element was measured, and the number of foreign matters containing phosphorus element having a major axis of 100 μm or more was counted. The evaluation was performed according to the following criteria. B or higher is acceptable.
Ｓ：１ヶ／１０００ｃｍ２以下
Ａ：１ヶ／１０００ｃｍ２を超えて３ヶ／１０００ｃｍ２以下
Ｂ：３ヶ／１０００ｃｍ２を超えて６ヶ／１０００ｃｍ２以下
Ｃ：６ヶ／１０００ｃｍ２を超える。
S: 1 month / 1000 cm 2 or less A: 1 month / 1000 cm 2 to more than 3 months / 1000 cm 2 or less B: more than 3 months / 1000 cm 2 6 months / 1000 cm 2 or less C: more than 6 months / 1000 cm 2.
（６）耐湿熱性評価（伸度保持率）
中間ロールの中央部のロールと最端部ロール、それぞれのロールの幅方向中央部からフィルムを切り出し、（７）項にて測定した超音波伝導速度の最大値の方向と最小値の方向が長さ方向となるように、各方向それぞれ幅１０ｍｍ、長さ２５０ｍｍの短冊状に切り出した伸度測定用試料を準備した。切り出した試料を高度加速寿命試験装置ＥＨＳ−２２１（エスペック社製）にて、温度１２１℃、湿度１００ＲＨ％の環境下にて６０時間処理を実施した。上記処理前および処理後のフィルムの伸度をテンシロンを用いて、原長（チャック間距離）１００ｍｍ、引っ張り速度２００ｍｍ／分の条件にて測定した。なお、伸度についてはそれぞれＮ＝５で測定した平均値とした。得られたフィルム伸度について処理後の伸度を処理前の伸度で除した値を耐湿熱評価における伸度保持率とした。なお、評価は以下の基準にて実施した。Ｂ以上が合格である。
(6) Evaluation of wet heat resistance (elongation retention)
Cut the film from the center roll and endmost roll of the middle roll, and the width direction center of each roll, and the direction of the maximum value and the minimum value of the ultrasonic conduction velocity measured in (7) are long. A sample for measuring elongation was cut out in a strip shape with a width of 10 mm and a length of 250 mm in each direction so as to be in the horizontal direction. The cut sample was processed for 60 hours in an environment with a temperature of 121 ° C. and a humidity of 100 RH% using an advanced accelerated life test apparatus EHS-221 (manufactured by Espec). The elongation of the film before and after the treatment was measured using Tensilon under conditions of an original length (distance between chucks) of 100 mm and a pulling speed of 200 mm / min. In addition, about the elongation, it was set as the average value measured by N = 5, respectively. About the obtained film elongation, the value which remove | divided the elongation after a process by the elongation before a process was made into the elongation retention in wet heat resistance evaluation. The evaluation was performed according to the following criteria. B or higher is acceptable.
Ｓ：伸度保持率が７０％以上。 S: Elongation retention is 70% or more.
Ａ：伸度保持率が６０％以上、７０％未満。 A: The elongation retention is 60% or more and less than 70%.
Ｂ：伸度保持率が５０％以上、６０％未満。 B: The elongation retention is 50% or more and less than 60%.
Ｃ：伸度保持率が５０％未満。 C: Elongation retention is less than 50%.
[参考例１] ポリエステル樹脂組成物１の調製
第一工程として、テレフタル酸ジメチル１００質量部とエチレングリコール３８．５質量部を窒素雰囲気下、温度２６０℃にて混合した。その後温度を２２５℃へ降下させ、酢酸マンガン４水和物０．０６８質量部、三酸化アンチモン０．０２９質量部を添加後攪拌しながら、更にエチレングリコール１７質量部を２時間かけて徐々に添加しながらメタノールを留出させ、エステル交換反応を終了した。第二工程として、エステル交換反応終了後、反応系内のポリエステルの温度を２２５℃とし、リン酸０．００５質量部（０．５モル／ｔ相当）を添加した。引き続き重縮合反応を最終到達温度２８５℃、圧力１３Ｐａの減圧下で４時間実施し、固有粘度０．７０、末端カルボキシル基量２５当量／ｔのポリエステル樹脂組成物１を得た。得られた樹脂組成物の特性を表１に示す。
Reference Example 1 Preparation of Polyester Resin Composition 1 As a first step, 100 parts by mass of dimethyl terephthalate and 38.5 parts by mass of ethylene glycol were mixed at a temperature of 260 ° C. in a nitrogen atmosphere. Thereafter, the temperature was lowered to 225 ° C., 0.068 parts by mass of manganese acetate tetrahydrate and 0.029 parts by mass of antimony trioxide were added, and then 17 parts by mass of ethylene glycol was gradually added over 2 hours while stirring. While distilling off methanol, the transesterification reaction was completed. As the second step, after the transesterification reaction, the temperature of the polyester in the reaction system was 225 ° C., and 0.005 part by mass of phosphoric acid (corresponding to 0.5 mol / t) was added. Subsequently, a polycondensation reaction was carried out under a reduced pressure of 285 ° C. and a pressure of 13 Pa for 4 hours to obtain a polyester resin composition 1 having an intrinsic viscosity of 0.70 and a terminal carboxyl group amount of 25 equivalents / t. The properties of the obtained resin composition are shown in Table 1.
[参考例２] ポリエステル樹脂組成物２〜４の調製
第一工程として、テレフタル酸ジメチル１００質量部とエチレングリコール３８．５質量部を窒素雰囲気下、温度２６０℃にて混合した。その後温度を２２５℃へ降下させ、酢酸マンガン４水和物０．０６８質量部、三酸化アンチモン０．０２９質量部を添加後攪拌しながら、更にエチレングリコール１７質量部を２時間かけて徐々に添加しながらメタノールを留出させ、エステル交換反応を終了した。第二工程として、エステル交換反応終了後、反応系内のポリエステルの温度を２２５℃とし、リン酸０．００５質量部（０．５モル／ｔ相当）を添加した。引き続き重縮合反応を最終到達温度２８５℃、圧力１３Ｐａの減圧下で３時間実施し、固有粘度０．５４、末端カルボキシル基量１９当量／ｔのポリエステルを得た。さらに、第三工程として、得られたポリエチレンテレフタレートを１６０℃で６時間乾燥、結晶化させたのち、圧力６５Ｐａの減圧条件下にて２２０℃にて、固相重合反応を表１に示す時間実施し、ポリエステル樹脂組成物２〜４を得た。得られた樹脂組成物の特性を表１に示す。
[Reference Example 2] Preparation of polyester resin compositions 2 to 4 As a first step, 100 parts by mass of dimethyl terephthalate and 38.5 parts by mass of ethylene glycol were mixed at a temperature of 260 ° C under a nitrogen atmosphere. Thereafter, the temperature was lowered to 225 ° C., 0.068 parts by mass of manganese acetate tetrahydrate and 0.029 parts by mass of antimony trioxide were added, and then 17 parts by mass of ethylene glycol was gradually added over 2 hours while stirring. While distilling off methanol, the transesterification reaction was completed. As the second step, after the transesterification reaction, the temperature of the polyester in the reaction system was 225 ° C., and 0.005 part by mass of phosphoric acid (corresponding to 0.5 mol / t) was added. Subsequently, a polycondensation reaction was carried out under a reduced pressure of 285 ° C. and a pressure of 13 Pa for 3 hours to obtain a polyester having an intrinsic viscosity of 0.54 and a terminal carboxyl group amount of 19 equivalents / t. Furthermore, as a third step, the obtained polyethylene terephthalate was dried and crystallized at 160 ° C. for 6 hours, and then subjected to solid-phase polymerization reaction at 220 ° C. under a reduced pressure of 65 Pa for the time shown in Table 1. Then, polyester resin compositions 2 to 4 were obtained. The properties of the obtained resin composition are shown in Table 1.
[参考例３] ポリエステル樹脂組成物５の調製
第一工程として、テレフタル酸ジメチル１００質量部とエチレングリコール３８．５質量部を窒素雰囲気下、温度２６０℃にて混合した。その後温度を２２５℃へ降下させ、酢酸マンガン４水和物０．０６８質量部、三酸化アンチモン０．０２９質量部を添加後攪拌しながら、更にエチレングリコール１７質量部を２時間かけて徐々に添加しながらメタノールを留出させ、エステル交換反応を終了した。第二工程として、エステル交換反応終了後、反応系内のポリエステルの温度を２２５℃とし、リン酸０．００５質量部（０．５モル／ｔ相当）を添加した。引き続き重縮合反応を最終到達温度２８５℃、圧力１３Ｐａの減圧下で４時間実施し、固有粘度０．７０、末端カルボキシル基量３０当量／ｔのポリエステルを得た。さらに、第三工程として、得られたポリエチレンテレフタレートを１６０℃で６時間乾燥、結晶化させたのち、圧力６５Ｐａの減圧条件下にて２２５℃にて２０時間固相重合反応を実施し、固有粘度（ＩＶ）１．００、末端カルボキシル基量９．５当量／ｔのポリエステル樹脂組成物５を得た。得られた樹脂の特性を表１に示す。
Reference Example 3 Preparation of Polyester Resin Composition 5 As a first step, 100 parts by mass of dimethyl terephthalate and 38.5 parts by mass of ethylene glycol were mixed at a temperature of 260 ° C. in a nitrogen atmosphere. Thereafter, the temperature was lowered to 225 ° C., 0.068 parts by mass of manganese acetate tetrahydrate and 0.029 parts by mass of antimony trioxide were added, and then 17 parts by mass of ethylene glycol was gradually added over 2 hours while stirring. While distilling off methanol, the transesterification reaction was completed. As the second step, after the transesterification reaction, the temperature of the polyester in the reaction system was 225 ° C., and 0.005 part by mass of phosphoric acid (corresponding to 0.5 mol / t) was added. Subsequently, a polycondensation reaction was carried out under a reduced pressure of 285 ° C. and a pressure of 13 Pa for 4 hours to obtain a polyester having an intrinsic viscosity of 0.70 and a terminal carboxyl group amount of 30 equivalents / t. Furthermore, as a third step, the obtained polyethylene terephthalate was dried and crystallized at 160 ° C. for 6 hours, and then subjected to a solid-state polymerization reaction at 225 ° C. for 20 hours under a reduced pressure of 65 Pa to obtain an intrinsic viscosity. (IV) A polyester resin composition 5 having 1.00 and a terminal carboxyl group amount of 9.5 equivalent / t was obtained. The properties of the obtained resin are shown in Table 1.
[参考例４] ポリエステル樹脂組成物６の調製
第一工程として、テレフタル酸ジメチル１００質量部とエチレングリコール３８．５質量部を窒素雰囲気下、温度２６０℃にて混合した。その後温度を２２５℃へ降下させ、三酸化アンチモン０．０２９質量部を添加後攪拌しながら、更にエチレングリコール１７質量部を２時間かけて徐々に添加しながらメタノールを留出させ、エステル交換反応を終了した。第二工程として、エステル交換反応終了後、反応系内のポリエステルの温度を２２５℃とし、リン酸０．００５質量部（０．５モル／ｔ相当）を添加した。引き続き重縮合反応を最終到達温度２８５℃、圧力１３Ｐａの減圧下で３時間実施し、固有粘度０．５４、末端カルボキシル基量１９当量／ｔのポリエステルを得た。さらに、第三工程として、得られたポリエチレンテレフタレートを１６０℃で６時間乾燥、結晶化させたのち、圧力６５Ｐａの減圧条件下にて２２０℃にて、固相重合反応を１２時間実施し、ポリエステル樹脂組成物６を得た。得られた樹脂組成物の特性を表１に示す。
Reference Example 4 Preparation of Polyester Resin Composition 6 As the first step, 100 parts by mass of dimethyl terephthalate and 38.5 parts by mass of ethylene glycol were mixed at a temperature of 260 ° C. in a nitrogen atmosphere. Thereafter, the temperature was lowered to 225 ° C., 0.029 parts by mass of antimony trioxide was added and then stirred, and methanol was distilled off while gradually adding 17 parts by mass of ethylene glycol over 2 hours to carry out a transesterification reaction. finished. As the second step, after the transesterification reaction, the temperature of the polyester in the reaction system was 225 ° C., and 0.005 part by mass of phosphoric acid (corresponding to 0.5 mol / t) was added. Subsequently, a polycondensation reaction was carried out under a reduced pressure of 285 ° C. and a pressure of 13 Pa for 3 hours to obtain a polyester having an intrinsic viscosity of 0.54 and a terminal carboxyl group amount of 19 equivalents / t. Furthermore, as a third step, the obtained polyethylene terephthalate was dried and crystallized at 160 ° C. for 6 hours, and then subjected to a solid phase polymerization reaction at 220 ° C. under a reduced pressure of 65 Pa for 12 hours. A resin composition 6 was obtained. The properties of the obtained resin composition are shown in Table 1.
[参考例５] ポリエステル樹脂組成物７の調製
第一工程として、テレフタル酸ジメチル１００質量部とエチレングリコール３８．５質量部を窒素雰囲気下、温度２６０℃にて混合した。その後温度を２２５℃へ降下させ、三酸化アンチモン０．０２９質量部を添加後攪拌しながら、更にエチレングリコール１７質量部を２時間かけて徐々に添加しながらメタノールを留出させ、エステル交換反応を終了した。第二工程として、エステル交換反応終了後、反応系内のポリエステルの温度を２２５℃とし、リン酸０．０２０質量部（２．０モル／ｔ相当）とリン酸二水素ナトリウム２水和物０．０３１質量部（２．０モル／ｔ相当）をエチレングリコール１．７質量部に溶解したエチレングリコール溶液を添加した。引き続き重縮合反応を最終到達温度２８５℃、圧力１３Ｐａの減圧下で４時間実施し、固有粘度０．５４、末端カルボキシル基量１７当量／ｔのポリエステルを得た。さらに、第三工程として、得られたポリエチレンテレフタレートを１６０℃で６時間乾燥、結晶化させたのち、圧力６５Ｐａの減圧条件下にて２２０℃、１６時間の固相重合を行い、固有粘度（ＩＶ）０．８２、末端カルボキシル基量９．７当量／ｔのポリエステル樹脂組成物６を得た。得られた樹脂組成物の特性を表１に示す。
Reference Example 5 Preparation of Polyester Resin Composition 7 As the first step, 100 parts by mass of dimethyl terephthalate and 38.5 parts by mass of ethylene glycol were mixed at a temperature of 260 ° C. in a nitrogen atmosphere. Thereafter, the temperature was lowered to 225 ° C., 0.029 parts by mass of antimony trioxide was added and then stirred, and methanol was distilled off while gradually adding 17 parts by mass of ethylene glycol over 2 hours to carry out a transesterification reaction. finished. As the second step, after completion of the transesterification reaction, the temperature of the polyester in the reaction system is set to 225 ° C., 0.020 parts by mass of phosphoric acid (corresponding to 2.0 mol / t) and sodium dihydrogen phosphate dihydrate 0 An ethylene glycol solution in which 0.031 parts by mass (equivalent to 2.0 mol / t) was dissolved in 1.7 parts by mass of ethylene glycol was added. Subsequently, the polycondensation reaction was carried out for 4 hours under a reduced pressure of 285 ° C. and a pressure of 13 Pa to obtain a polyester having an intrinsic viscosity of 0.54 and a terminal carboxyl group content of 17 equivalents / t. Further, as a third step, the obtained polyethylene terephthalate was dried and crystallized at 160 ° C. for 6 hours, and then subjected to solid phase polymerization at 220 ° C. for 16 hours under a reduced pressure of 65 Pa to obtain an intrinsic viscosity (IV ) 0.82 and a polyester resin composition 6 having a terminal carboxyl group amount of 9.7 equivalent / t was obtained. The properties of the obtained resin composition are shown in Table 1.
[参考例６] ポリエステル樹脂組成物α１の調製
参考例２で得られたポリエステル樹脂組成物４を２軸押出機に投入した。リン酸二水素ナトリウム２水和物７．５モル／ｔとリン酸７．０モル／ｔとエチレングリコールとの混合物（リン化合物の濃度２．０質量％）を、ポリエステル樹脂組成物投入直後（ポリエステル樹脂組成物の溶融前）とポリエステル樹脂組成物溶融後の２回に分けて半量ずつ２軸押出機内に投入し、温度２９０℃にて余剰なエチレングリコールをベント口から排出しながら溶融混練を行い、ポリエステル樹脂組成物α１を得た。得られたポリエステル樹脂組成物の特性を表２に示す。
[Reference Example 6] Preparation of polyester resin composition α1 The polyester resin composition 4 obtained in Reference Example 2 was charged into a twin-screw extruder. A mixture of sodium dihydrogen phosphate dihydrate 7.5 mol / t, phosphoric acid 7.0 mol / t and ethylene glycol (phosphorus compound concentration 2.0 mass%) was added immediately after the polyester resin composition was charged ( Before the polyester resin composition is melted) and after the polyester resin composition is melted, it is poured into the twin screw extruder in half and melt kneading while discharging excess ethylene glycol from the vent port at a temperature of 290 ° C. The polyester resin composition α1 was obtained. Table 2 shows the characteristics of the obtained polyester resin composition.
[参考例７] ポリエステル樹脂組成物α２〜１７、β１〜２の調製
表２に示すポリエステル樹脂ならびにリン酸アルカリ金属塩、リン酸を用いた以外は参考例６と同様の方法でポリエステル樹脂組成物を得た。なお、ポリエステル樹脂組成物α５では、リン酸アルカリ金属塩・リン酸・エチレングリコール混合物を、ポリエステル樹脂投入直後（溶融前）に一括添加し、またポリエステル樹脂組成物α１４においては、溶融混練温度を３００℃に変更した。得られたポリエステル樹脂組成物の特性を表２に示す。
[Reference Example 7] Preparation of polyester resin compositions α2-17, β1-2 Polyester resin composition in the same manner as in Reference Example 6 except that the polyester resin shown in Table 2 and alkali metal phosphate and phosphoric acid were used. Got. In the polyester resin composition α5, the alkali metal phosphate / phosphoric acid / ethylene glycol mixture is added all at once after the polyester resin is added (before melting). In the polyester resin composition α14, the melt-kneading temperature is 300. Changed to ° C. Table 2 shows the characteristics of the obtained polyester resin composition.
[参考例８] 二酸化珪素含有ポリエステル樹脂組成物の調製
参考例２で得られた９５質量部のポリエステル樹脂組成物４に、平均粒径３μｍの二酸化珪素粒子５質量部を２軸押出機にて２９０℃にて混練し、二酸化珪素含有ポリエステル樹脂組成物を得た。
Reference Example 8 Preparation of Silicon Dioxide-Containing Polyester Resin Composition 95 parts by mass of the polyester resin composition 4 obtained in Reference Example 2 and 5 parts by mass of silicon dioxide particles having an average particle diameter of 3 μm were obtained with a twin screw extruder. The mixture was kneaded at 290 ° C. to obtain a silicon dioxide-containing polyester resin composition.
[実施例１]
参考例に従って調製した２５質量部のポリエステル樹脂組成物α１と７４質量部のポリエステル樹脂組成物１と１質量部の二酸化珪素含有ポリエステル樹脂組成物との混合物を圧力１ｋＰａの減圧条件下、温度１７０℃で４時間乾燥した後、押出機に供給し２８５℃で溶融押出を行った。
ステンレス鋼繊維を焼結圧縮した平均目開き６０μｍのフィルターで濾過した後、Ｔ字型口金よりシート状に押し出し、静電印加キャスト法を用いて表面温度２０℃の鏡面キャスティングドラムに巻き付けて冷却固化せしめた。この未延伸フィルムを予熱ロールにて８５℃に予熱後、上下方向からラジエーションヒーターを用いて１００℃まで加熱しつつロール間の周速差を利用して長手方向に３．５倍延伸し、引き続き冷却ロールにて２５℃まで冷却し、一軸配向（一軸延伸）フィルムとした。
[Example 1]
A mixture of 25 parts by mass of the polyester resin composition α1, 74 parts by mass of the polyester resin composition 1 and 1 part by mass of a silicon dioxide-containing polyester resin composition prepared according to the reference example was subjected to a pressure of 1 kPa and a temperature of 170 ° C. After drying for 4 hours, the mixture was supplied to an extruder and melt-extruded at 285 ° C.
After filtering with stainless steel fiber sintered and compressed through a filter with an average opening of 60 μm, it is extruded into a sheet form from a T-shaped die, wound around a mirror casting drum having a surface temperature of 20 ° C. using an electrostatic application casting method, and cooled and solidified. I was damned. After preheating this unstretched film to 85 ° C. with a preheating roll, it is stretched 3.5 times in the longitudinal direction using the peripheral speed difference between the rolls while heating to 100 ° C. using a radiation heater from the top and bottom, It cooled to 25 degreeC with the cooling roll, and was set as the uniaxially oriented (uniaxial stretching) film.
次いで、一軸配向（一軸延伸）フィルムをクリップで把持してオーブン中にて１００℃の熱風にて予熱し、引き続き連続的に延伸工程において１２０℃熱風で加熱しながら幅方向に３．８倍延伸した。得られた二軸配向（二軸延伸）フィルムを熱処理工程に導き、２１５℃の熱風にて１０秒間熱処理を行った。熱処理工程を経たフィルムを２１５℃から１００℃まで冷却しながら５％の弛緩処理を施し、続けて８０℃まで冷却した。次いで、フィルムをオーブンより引き出し、幅方向両端部を除去した後に巻き取り、厚さ１２５μｍのポリエステルフィルムを得た。得られたポリエステルフィルムの特性を表４−１に示す。高い耐湿熱性（伸度保持率）を有し、リン起因の異物が非常に少なく、かつ特に重合時間が短縮された生産性にも優れたポリエステルフィルムであった。 Next, a uniaxially oriented (uniaxially stretched) film is gripped with a clip, preheated with hot air of 100 ° C. in an oven, and continuously stretched 3.8 times in the width direction while continuously heated with 120 ° C. hot air in a stretching process. did. The obtained biaxially oriented (biaxially stretched) film was introduced into a heat treatment step, and was heat treated with hot air at 215 ° C. for 10 seconds. The film subjected to the heat treatment step was subjected to a relaxation treatment of 5% while being cooled from 215 ° C. to 100 ° C., and subsequently cooled to 80 ° C. Next, the film was drawn out from the oven, and both ends in the width direction were removed and wound up to obtain a polyester film having a thickness of 125 μm. Properties of the obtained polyester film are shown in Table 4-1. It was a polyester film having high wet heat resistance (elongation retention), very little foreign matter due to phosphorus, and excellent productivity especially with a shortened polymerization time.
[実施例２〜２０、参考例２１〜２２、比較例１〜６]
ポリエステル樹脂組成物Ａを表３−１、表３−２に示した構成とした以外は実施例１と同様にして二軸配向ポリエステルフィルムを得た。得られたフィルムの特性を表４−１、表４−２に示す。
[Examples 2 to 20 , Reference Examples 21 to 22 , Comparative Examples 1 to 6]
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the polyester resin composition A was configured as shown in Tables 3-1 and 3-2. The characteristics of the obtained film are shown in Tables 4-1 and 4-2.
[結果の考察]
アルカリ金属元素含有量ＷＡが１６５ｐｐｍ以上８５０ｐｐｍ以下、リン元素含有量ＷＰが３３０ｐｐｍ以上２０００ｐｐｍ以下であるポリエステル樹脂組成物αを５質量％以上５０質量％以下含有したポリエステル樹脂組成物Ａを用いることで、生産性が良好でありながら、高い耐湿熱性の維持およびリン起因の異物発生を抑制可能な、優れた特性のポリエステルフィルムを得ることができた。
[Consideration of results]
By using the polyester resin composition A containing 5% by mass to 50% by mass of the polyester resin composition α having an alkali metal element content WA of 165 ppm to 850 ppm and a phosphorus element content WP of 330 ppm to 2000 ppm, It was possible to obtain a polyester film having excellent characteristics capable of maintaining high moisture and heat resistance and suppressing the generation of foreign matters due to phosphorus while having good productivity.
また、ポリエステル樹脂組成物αの製造方法としては、固有粘度（ＩＶ）が０．７０以上１．００以下のポリエステル樹脂とリン酸とリン酸アルカリ金属塩を合計した濃度が３．０質量％以下の溶液またはスラリーを溶融混練することで、リン起因の異物発生を抑制しながら、高濃度にリン化合物を含有したポリエステル樹脂組成物を得ることができた。 Moreover, as a manufacturing method of the polyester resin composition α, the total concentration of the polyester resin having an intrinsic viscosity (IV) of 0.70 or more and 1.00 or less, phosphoric acid, and alkali metal phosphate is 3.0% by mass or less. By melt-kneading this solution or slurry, it was possible to obtain a polyester resin composition containing a phosphorus compound at a high concentration while suppressing the generation of foreign matters due to phosphorus.
さらに、ポリエステルフィルムを構成するポリエステル樹脂組成物中に、アルカリ金属元素含有量ＷＡｆが２０ｐｐｍ以上１５０ｐｐｍ以下、リン元素含有量ＷＰｆが４０ｐｐｍ以上５００ｐｐｍ以下、ＷＡｆ／ＷＰｆが０．３以上０．８以下に、アルカリ金属元素とリン元素の含有量を調製する事で、高い耐湿熱性とリン起因の異物低減の両立を高いレベルで両立させることが可能となるため好ましく、さらには、マンガン化合物をマンガン元素量として１００ｐｐｍ以上３００ｐｐｍ以下含有する事で耐湿熱性をより高めることが可能となる（実施例２と実施例１５との比較）。特に、耐湿熱性を向上させるためには、フィルム中の末端カルボキシル基を２５当量／ｔ以下とすることが好ましい。ただし、この場合は、ポリエステル樹脂中の末端カルボキシル基量を減少させるために固相重合時間を長くするなどの処理が必要となるため、生産性は悪化する方向となるが、本発明のアルカリ金属元素ならびにリン元素を高濃度に含有可能な樹脂組成物αを用い、その混率を調整することで、それぞれの使用方法に適合した耐湿熱性（加水分解性）を有するフィルムを効率よく生産することが可能となる。 Further, in the polyester resin composition constituting the polyester film, the alkali metal element content WAf is 20 ppm or more and 150 ppm or less, the phosphorus element content WPf is 40 ppm or more and 500 ppm or less, and WAf / WPf is 0.3 or more and 0.8 or less. By adjusting the content of alkali metal element and phosphorus element, it is possible to achieve both high moisture and heat resistance and reduction of foreign matters caused by phosphorus at a high level. As a result, it becomes possible to further improve the heat and moisture resistance (Comparison between Example 2 and Example 15). In particular, in order to improve wet heat resistance, the terminal carboxyl group in the film is preferably 25 equivalent / t or less. However, in this case, since it is necessary to increase the solid phase polymerization time in order to reduce the amount of terminal carboxyl groups in the polyester resin, the productivity tends to deteriorate, but the alkali metal of the present invention It is possible to efficiently produce a film having heat and humidity resistance (hydrolysis) suitable for each method of use by adjusting the mixing ratio by using a resin composition α that can contain a high concentration of elements and phosphorus elements. It becomes possible.
一方、ポリエステル樹脂組成物Ａ中にアルカリ金属元素を全く含まなかったり（比較例１）また、ポリエステル樹脂組成物Ａ中に含まれるリン元素、アルカリ金属元素を含有するポリエステル樹脂組成物において、リン元素、アルカリ金属元素量が規定量より少なかったり（比較例２）、さらにポリエステル樹脂組成物αの混率が少なかった場合（比較例４）については、耐湿熱性（耐加水分解性）に劣るものであった。また、ポリエステル樹脂組成物Ａ中に含まれるリン元素、アルカリ金属元素を含有するポリエステル樹脂組成物において、リン元素、アルカリ金属元素量が規定量より多かったり（比較例３）、ポリエステル樹脂組成物αの混率が多かった場合（比較例５）はリン元素を含む異物量が増加した。さらに、リン元素およびアルカリ金属元素を含有するポリエステル樹脂の比率が大きい比較例５や比較例７については生産性に劣る問題があった。 On the other hand, the polyester resin composition A does not contain any alkali metal element (Comparative Example 1). Also, in the polyester resin composition containing the phosphorus element and alkali metal element contained in the polyester resin composition A, the phosphorus element In the case where the amount of the alkali metal element is less than the prescribed amount (Comparative Example 2) and the mixing ratio of the polyester resin composition α is small (Comparative Example 4), the heat and moisture resistance (hydrolysis resistance) is poor. It was. Further, in the polyester resin composition containing the phosphorus element and alkali metal element contained in the polyester resin composition A, the amount of phosphorus element and alkali metal element is larger than the prescribed amount (Comparative Example 3), the polyester resin composition α When the mixing ratio was high (Comparative Example 5), the amount of foreign matter containing phosphorus element increased. Furthermore, Comparative Example 5 and Comparative Example 7 in which the ratio of the polyester resin containing a phosphorus element and an alkali metal element is large have a problem of poor productivity.
本発明の製造方法によって、高温高湿下での耐久性に優れた内部欠陥が少ないポリエステルフィルムを生産性よく得ることができる。本発明の製造方法により得られるポリエステルフィルムは、高温高湿下での耐久性に優れるため、太陽電池封止シート、銅貼り積層板、粘着テープ、フレキシブルプリント基板、メンブレンスイッチ、面状発熱体、もしくはフラットケーブルなどの電気絶縁材料、コンデンサ用材料、自動車用材料、建築材料を初めとした耐久性が重視されるような用途に好適に使用することができる By the production method of the present invention, a polyester film having excellent durability under high temperature and high humidity and having few internal defects can be obtained with high productivity. Since the polyester film obtained by the production method of the present invention is excellent in durability under high temperature and high humidity, a solar cell sealing sheet, a copper-clad laminate, an adhesive tape, a flexible printed circuit board, a membrane switch, a planar heating element, Or it can be suitably used for applications where durability is important, including electrical insulation materials such as flat cables, capacitor materials, automotive materials, and building materials.
Claims (5)
Method for producing a port re ester film according to claim 1 terminal carboxyl group of the polyester resin constituting the polyester film is not more than 25 eq / t.
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