JP2019108478A - Polyester resin composition and production method thereof - Google Patents
Polyester resin composition and production method thereof Download PDFInfo
- Publication number
- JP2019108478A JP2019108478A JP2017242677A JP2017242677A JP2019108478A JP 2019108478 A JP2019108478 A JP 2019108478A JP 2017242677 A JP2017242677 A JP 2017242677A JP 2017242677 A JP2017242677 A JP 2017242677A JP 2019108478 A JP2019108478 A JP 2019108478A
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- Prior art keywords
- polyester resin
- resin composition
- ppm
- content
- polyester
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 138
- 239000004645 polyester resin Substances 0.000 title claims abstract description 138
- 239000000203 mixture Substances 0.000 title claims abstract description 130
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 46
- 238000006116 polymerization reaction Methods 0.000 claims description 58
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 56
- 238000005886 esterification reaction Methods 0.000 claims description 34
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 30
- -1 polyethylene terephthalate Polymers 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 239000007790 solid phase Substances 0.000 claims description 22
- 229920000728 polyester Polymers 0.000 claims description 20
- 150000002697 manganese compounds Chemical class 0.000 claims description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 14
- 150000002009 diols Chemical class 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 13
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000005809 transesterification reaction Methods 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229920006267 polyester film Polymers 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 36
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 31
- 238000000465 moulding Methods 0.000 abstract description 14
- 238000012545 processing Methods 0.000 abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 149
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 35
- 239000010408 film Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 238000001879 gelation Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 238000010128 melt processing Methods 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 6
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 6
- 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 6
- 239000012788 optical film Substances 0.000 description 6
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000009283 thermal hydrolysis Methods 0.000 description 3
- BCBHDSLDGBIFIX-UHFFFAOYSA-M 4-[(2-hydroxyethoxy)carbonyl]benzoate Chemical compound OCCOC(=O)C1=CC=C(C([O-])=O)C=C1 BCBHDSLDGBIFIX-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 238000000354 decomposition reaction Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- XHYYGJAYKIYARQ-UHFFFAOYSA-M methanesulfonate;tetrabutylazanium Chemical compound CS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC XHYYGJAYKIYARQ-UHFFFAOYSA-M 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000006400 oxidative hydrolysis reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WFUUAJVRMXKBBI-UHFFFAOYSA-N 2-[1-(2-hydroxyethyl)cyclohexyl]ethanol Chemical compound OCCC1(CCO)CCCCC1 WFUUAJVRMXKBBI-UHFFFAOYSA-N 0.000 description 1
- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- BCBHDSLDGBIFIX-UHFFFAOYSA-N 4-[(2-hydroxyethoxy)carbonyl]benzoic acid Chemical compound OCCOC(=O)C1=CC=C(C(O)=O)C=C1 BCBHDSLDGBIFIX-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- 102100037114 Elongin-C Human genes 0.000 description 1
- 101001011859 Homo sapiens Elongin-A Proteins 0.000 description 1
- 101001011846 Homo sapiens Elongin-B Proteins 0.000 description 1
- 101000881731 Homo sapiens Elongin-C Proteins 0.000 description 1
- 101000836005 Homo sapiens S-phase kinase-associated protein 1 Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-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
- XHNSSSBOZPTFJF-UHFFFAOYSA-N [Li].P(O)(O)(O)=O.[Li] Chemical compound [Li].P(O)(O)(O)=O.[Li] XHNSSSBOZPTFJF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 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
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical compound O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ATGAWOHQWWULNK-UHFFFAOYSA-I pentapotassium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ATGAWOHQWWULNK-UHFFFAOYSA-I 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Substances [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、耐熱性や耐加水分解性に優れ、溶融成形や加工工程にて発生するゲル組成物や線状オリゴマー発生量、環状オリゴマー含有量及び増加量が少ないポリエステル樹脂組成物及びその製造方法に関するものである。 The present invention is excellent in heat resistance and hydrolysis resistance, and is a gel composition generated in melt molding and processing steps, a polyester resin composition in which the amount of linear oligomers generated, the amount of cyclic oligomers and the amount of increase are small, and a method of manufacturing the same It is about
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。ポリエステル樹脂の中でも、特にポリエチレンテレフタレート（以降ＰＥＴと記す）は、透明性や加工性に優れていることから、光学用フィルムや離型用フィルムなど高品位性が求められる用途に幅広く使われている。しかしながら、ＰＥＴのモノマー成分や低分子量体（オリゴマー成分）といった線状オリゴマーは、ポリエステル樹脂の分解反応によって発生・増加し、これが成形や加工時に揮発・飛散し、成形品の表面汚れが起こることがある。加えて、この線状オリゴマーの飛散によって工程汚れを引き起こすこともあり、表面汚れや工程汚れによる成形品の品位悪化という問題が起こる。また、溶融成形時にポリエステル樹脂が熱劣化・酸化劣化することでゲル組成物が発生し、口金汚れなどの工程汚染が問題となる。さらにフィルム用途などでは、このゲル組成物がフィルム中にて輝点欠点となり、品質が低下する。近年、光学用フィルムや離型用フィルムなどは品位の要求がますます高くなっており、上記のような表面汚れや工程汚れを引き起こす線状オリゴマーやゲル組成物の発生を抑制するポリエステル樹脂が望まれている。これらの課題に対して、様々な検討がなされている。 Polyester resins are excellent in mechanical properties, thermal properties, chemical resistance, electrical properties and moldability, and are used in various applications. Among polyester resins, polyethylene terephthalate (hereinafter referred to as PET) is widely used for applications requiring high definition such as optical films and release films because it is excellent in transparency and processability. . However, linear oligomers such as PET monomer components and low molecular weight oligomers (oligomer components) are generated and increased by the decomposition reaction of polyester resin, which volatilizes and scatters during molding and processing, and surface staining of molded articles may occur. is there. In addition, the scattering of the linear oligomers may cause process fouling, which causes the problem of deterioration of the quality of molded articles due to surface fouling and process fouling. In addition, when the polyester resin is thermally and oxidatively deteriorated during melt molding, a gel composition is generated, and process contamination such as die contamination becomes a problem. Furthermore, in film applications etc., this gel composition becomes a bright spot defect in the film and the quality is reduced. In recent years, optical films and mold release films are increasingly required to have high quality, and polyester resins that suppress the generation of linear oligomers and gel compositions that cause surface stains and process stains as described above are desired. It is rare. Various studies have been made on these issues.
例えば、特許文献１および２には固相重合及び失活処理を行うことで、ポリエステル樹脂中のオリゴマー含有量および溶融時のオリゴマー再生量を低減させる技術が開示されている。 For example, Patent Documents 1 and 2 disclose techniques for reducing the content of oligomers in a polyester resin and the amount of regenerated oligomers at melting by performing solid-phase polymerization and deactivation treatment.
また特許文献３には、イオン液体をポリエステル中に含有させることで線状オリゴマーの飛散を抑制する技術が開示されている。 Moreover, the technique which suppresses scattering of a linear oligomer is disclosed by patent document 3 by containing an ionic liquid in polyester.
さらに、特許文献４には、金属量とリン量のモル比率を高い範囲に制御し、ゲル組成物を抑制する技術が開示されている。 Furthermore, Patent Document 4 discloses a technique for controlling the gel composition by controlling the molar ratio of the amount of metal and the amount of phosphorus within a high range.
前述した従来の技術のように、固相重合や失活処理では、成形前のポリエステル樹脂に含有される線状オリゴマーや環状オリゴマーを低減させるのみであり、溶融時の熱分解や加水分解という異なる機構により発生・増加する線状オリゴマーには効果がないため、製品の表面汚れや加工工程汚れを防ぐことができなかった。また、線状オリゴマーの飛散を抑制するためにイオン液体を添加した場合や、ゲル抑制のために金属とリンのモル比率を高い範囲にした場合、耐熱性や耐加水分解性が低下してしまうという課題があった。 As in the prior art described above, in solid phase polymerization and deactivation treatment, only linear oligomers and cyclic oligomers contained in the polyester resin before molding are reduced, and thermal decomposition and hydrolysis during melting are different. Since it was ineffective for linear oligomers generated / increased by the mechanism, it was not possible to prevent surface contamination of the product or contamination of the processing process. In addition, when an ionic liquid is added to suppress scattering of linear oligomers, or when the molar ratio of metal to phosphorus is set to a high range for gel suppression, heat resistance and hydrolysis resistance are reduced. There was a problem called.
本発明の目的は、耐熱性や耐加水分解性に優れ、溶融成形や加工工程にて発生するゲル組成物や線状オリゴマー発生量、環状オリゴマー含有量及び増加量が少ないポリエステル樹脂組成物及びその製造方法を提供することにある。 The object of the present invention is to provide a gel composition which is excellent in heat resistance and hydrolysis resistance, a polyester resin composition having a small amount of linear oligomer generation and a small amount of cyclic oligomers, and a small amount of increase in linear oligomers and the like It is in providing a manufacturing method.
上記課題を解決するため、本発明は以下の特徴を有するものである。
（１）下記式（Ｉ）〜（ＩＶ）を満たすことを特徴とするポリエステル樹脂組成物。
線状オリゴマー発生量≦９００ｐｐｍ （Ｉ）
環状オリゴマー含有量≦０．６ｗｔ％ （ＩＩ）
５ｐｐｍ≦Ｍｎ含有量≦４０ｐｐｍ （ＩＩＩ）
４ｐｐｍ≦Ｎａ含有量≦６０ｐｐｍ （ＩＶ）
（２）ジカルボン酸成分またはそのエステル形成誘導体成分と、ジオール成分とをエステル化反応またはエステル交換反応し、次いで溶融重合および固相重合をしてポリエステルを製造するに際して、ポリエステルのＩＶ（固有粘度）が０．４以下の段階で、マンガン化合物を添加し、かつ重縮合反応終了までの段階でリン酸とリン酸アルカリ金属塩を添加し、かつその含有量が下記式（Ｖ）、（ＶＩ）を満たすことを特徴とするポリエステル樹脂組成物の製造方法。
５ｐｐｍ≦Ｍｎ含有量≦４０ｐｐｍ （Ｖ）
４ｐｐｍ≦アルカリ金属元素含有量≦６０ｐｐｍ （ＶＩ）
In order to solve the above-mentioned subject, the present invention has the following features.
(1) A polyester resin composition characterized by satisfying the following formulas (I) to (IV).
Linear oligomer generation amount ≦ 900 ppm (I)
Cyclic oligomer content ≦ 0.6 wt% (II)
5 ppm ≦ Mn content ≦ 40 ppm (III)
4 ppm ≦ Na content ≦ 60 ppm (IV)
(2) IV (intrinsic viscosity) of polyester when esterifying reaction or transesterification reaction of dicarboxylic acid component or ester forming derivative component thereof with diol component, followed by melt polymerization and solid phase polymerization to produce polyester A manganese compound is added at a stage of 0.4 or less, and phosphoric acid and an alkali metal salt of phosphoric acid are added at a stage up to the end of the polycondensation reaction, and the content thereof is represented by the following formulas (V) and (VI) The manufacturing method of the polyester resin composition characterized by satisfy | filling.
5 ppm ≦ Mn content ≦ 40 ppm (V)
4 ppm ≦ alkali metal content ≦ 60 ppm (VI)
本発明によれば、耐熱性や耐加水分解性に優れ、溶融成形や加工工程にて発生するゲル組成物や線状オリゴマー発生量、環状オリゴマー含有量及び増加量が少ないポリエステル樹脂組成物を提供でき、光学フィルムや離型フィルムのような高品位フィルムを提供することが可能となる。 According to the present invention, a gel composition excellent in heat resistance and hydrolysis resistance, and a polyester resin composition having a small amount of linear oligomer generation, a cyclic oligomer content and an increase amount generated in melt molding and processing steps are provided. It is possible to provide a high quality film such as an optical film or a release film.
以下に本発明を詳細に説明する。
本発明に用いられるポリエステル樹脂とは、ジカルボン酸成分とジオール成分を重縮合して得られるポリエステル樹脂を指す。
The present invention will be described in detail below.
The polyester resin used in the present invention refers to a polyester resin obtained by polycondensation of a dicarboxylic acid component and a diol component.
本発明におけるジカルボン酸成分としては、芳香族ジカルボン酸、鎖状脂肪族ジカルボン酸、脂環式ジカルボン酸など種々のジカルボン酸成分を用いることができる。その中でも、ポリエステル樹脂組成物の機械的特性、耐熱性、耐加水分解性の観点から、芳香族ジカルボン酸及びそのエステル形成誘導体成分であることが好ましい。特には、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸及びこれらのエステル形成誘導体成分が重合性、機械的特性から好ましい。 As the dicarboxylic acid component in the present invention, various dicarboxylic acid components such as aromatic dicarboxylic acids, linear aliphatic dicarboxylic acids and alicyclic dicarboxylic acids can be used. Among them, from the viewpoints of mechanical properties, heat resistance and hydrolysis resistance of the polyester resin composition, aromatic dicarboxylic acids and ester-forming derivatives thereof are preferable. In particular, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and ester forming derivative components thereof are preferable from the viewpoint of polymerizability and mechanical properties.
本発明におけるジカルボン酸成分としては、芳香族ジカルボン酸、鎖状脂肪族ジカルボン酸、脂環式ジカルボン酸など種々のジカルボン酸成分を用いることができる。その中でも、ポリエステル樹脂組成物の機械的特性、耐熱性、耐加水分解性の観点から、芳香族ジカルボン酸及びそのエステル形成誘導体成分であることが好ましい。特には、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸及びこれらのエステル形成誘導体成分が重合性、機械的特性から好ましい。 As the dicarboxylic acid component in the present invention, various dicarboxylic acid components such as aromatic dicarboxylic acids, linear aliphatic dicarboxylic acids and alicyclic dicarboxylic acids can be used. Among them, from the viewpoints of mechanical properties, heat resistance and hydrolysis resistance of the polyester resin composition, aromatic dicarboxylic acids and ester-forming derivatives thereof are preferable. In particular, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and ester forming derivative components thereof are preferable from the viewpoint of polymerizability and mechanical properties.
本発明におけるジオール成分としては、各種ジオールを用いることができる。例えば、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、ブタンジオール、２−メチル−１，３−プロパンジオール、ヘキサンジオール、ネオペンチルグリコールなどの脂肪族ジオール、脂環式ジオールとしてはシクロヘキサンジメタノール、シクロヘキサンジエタノールなどの各種脂環式ジオールや、ビスフェノールＡ、ビスフェノールＳ、スチレングリコール、９，９−ビス（４−（２−ヒドロキシエトキシ）フェニル）フルオレン、９，９’−ビス（４−ヒドロキシフェニル）フルオレンなどの芳香環式ジオールが例示できる。またジオール以外にもトリメチロールプロパン、ペンタエリスリトールなどの多官能アルコールも用いることができる。 Various diols can be used as the diol component in the present invention. For example, as aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, hexanediol, neopentyl glycol and the like, alicyclic diols Are various alicyclic diols such as cyclohexanedimethanol, cyclohexanediethanol, bisphenol A, bisphenol S, styrene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9'-bis ( Examples include aromatic cyclic diols such as 4-hydroxyphenyl) fluorene. Besides diols, polyfunctional alcohols such as trimethylolpropane and pentaerythritol can also be used.
この中で、反応系外に留出させやすいことから、沸点２３０℃以下のジオールであることが好ましく、低コストであり反応性が高いことから、脂肪族ジオールがより好ましい。さらに、機械的特性の観点からエチレングリコールが特に好ましい。 Among these, diols having a boiling point of 230 ° C. or less are preferable because they are easily distilled out of the reaction system, and aliphatic diols are more preferable because they are low in cost and high in reactivity. Furthermore, ethylene glycol is particularly preferred from the viewpoint of mechanical properties.
なお、本発明の効果の範囲を損なわない程度に、他のジカルボン酸成分やヒドロキシカルボン酸誘導体、ジオール成分が共重合されていてもよい。 In addition, another dicarboxylic acid component, a hydroxycarboxylic acid derivative, and a diol component may be copolymerized to such an extent that the range of the effect of the present invention is not impaired.
本発明のポリエステル樹脂組成物は、線状オリゴマー発生量が９００ｐｐｍ以下であることが必要である。なお、線状オリゴマー発生量は温度２３℃、湿度５０％の環境下に２４時間以上静置したポリエステル樹脂組成物を窒素下、２９０℃で２０分後加熱処理した際の線状オリゴマーの増加量である。通常、ポリエステル樹脂は溶融加工前に乾燥を行い、加水分解の抑制を図っている。線状オリゴマーはポリエステル樹脂の加水分解によっても発生するため、溶融加工前に乾燥しておくことが好ましいが、未乾燥状態のポリエステル樹脂であってもこの線状オリゴマー発生が抑制できれば乾燥工程を省くことができ、大幅なコストダウンとなる。本発明は、ポリエステル樹脂の耐熱性や耐加水分解性を向上させたことで、水分率が高い状態でも線状オリゴマー発生量を飛躍的に低減可能としたものである。 The polyester resin composition of the present invention is required to have a linear oligomer generation amount of 900 ppm or less. The amount of generation of linear oligomers is an increase in the amount of linear oligomers when the polyester resin composition left to stand in an environment of temperature 23 ° C. and humidity 50% for 24 hours or more after heat treatment at 290 ° C. under nitrogen for 20 minutes. It is. In general, polyester resins are dried before melt processing to suppress hydrolysis. Since linear oligomers are also generated by hydrolysis of polyester resins, it is preferable to dry them before melt processing, but even if they are undried polyester resins, the drying process can be omitted if the generation of linear oligomers can be suppressed. It will be possible to reduce costs significantly. In the present invention, the heat resistance and hydrolysis resistance of the polyester resin are improved, so that the generation amount of linear oligomers can be dramatically reduced even in the state of high moisture content.
本発明において、線状オリゴマーとは、ポリエステル樹脂の熱分解や加水分解、酸化分解等の分解反応によって生成するモノマー成分やオリゴマー成分であり、具体的にはポリエステル樹脂を構成するジカルボン酸成分や、ジカルボン酸のカルボキシル基とジオールのヒドロキシル基が反応してできる鎖状の反応物のことを指し、環状３量体のような環状のオリゴマーは含めない。具体的にはジカルボン酸単量体およびグリコール成分とのモノエステル、ジエステルである。この線状オリゴマーは昇華や析出しやすく、溶融成形などの加工工程において、工程汚れや成形体の表面汚れを引き起こすものである。 In the present invention, the linear oligomer is a monomer component or an oligomer component generated by a decomposition reaction such as thermal decomposition, hydrolysis or oxidative decomposition of a polyester resin, specifically, a dicarboxylic acid component constituting the polyester resin, It refers to a chain reaction product formed by the reaction of the carboxyl group of dicarboxylic acid and the hydroxyl group of diol, and does not include cyclic oligomers such as cyclic trimers. Specifically, they are monoesters and diesters with dicarboxylic acid monomers and glycol components. This linear oligomer is easily sublimated or precipitated, and causes process stains and surface stains of the molded product in processing steps such as melt molding.
代表的なポリエステル樹脂であるＰＥＴを例に挙げると、ＴＰＡ（テレフタル酸）、テレフタル酸とエチレングリコールの反応物である、ＭＨＥＴ（モノヒドロキシエチルテレフタレート）およびＢＨＥＴ（ビスヒドロキシエチルテレフタレート）である。これら線状オリゴマーの総量として、発生量が９００ｐｐｍ以下であることが必要であり、好ましくは８００ｐｐｍ以下、より好ましくは７００ｐｐｍ以下である。線状オリゴマーの発生量を上記範囲内とすることで、成形加工時に問題となる、線状オリゴマーに起因した工程汚れや表面汚れの低減を実現することができる。 Taking PET, which is a representative polyester resin, as an example, TPA (terephthalic acid), MHET (monohydroxyethyl terephthalate) and BHET (bishydroxyethyl terephthalate), which are the reaction products of terephthalic acid and ethylene glycol, are mentioned. The total amount of these linear oligomers needs to be 900 ppm or less, preferably 800 ppm or less, more preferably 700 ppm or less. By setting the generation amount of linear oligomers within the above range, it is possible to realize the reduction of process stains and surface stains caused by the linear oligomers, which is a problem during molding processing.
本発明のポリエステル樹脂組成物は、環状オリゴマー含有量が０．６ｗｔ％以下であることが必要であり、好ましくは０．４５ｗｔ％以下である。環状オリゴマーとは、ポリエステル樹脂を構成するジカルボン酸成分とジオール成分とから構成される環状のオリゴマーであり、特に環状３量体が形成されやすい。この環状オリゴマーはフィルムや繊維などの成形体を加熱、または溶剤に曝すなどすると、成形体の表面に析出し、表面欠点や汚れとなり問題となる。本発明のポリエステル樹脂組成物は、固相重合を実施することで環状オリゴマーの含有量を低減させている。 The polyester resin composition of the present invention needs to have a cyclic oligomer content of 0.6 wt% or less, preferably 0.45 wt% or less. The cyclic oligomer is a cyclic oligomer composed of a dicarboxylic acid component and a diol component constituting a polyester resin, and in particular, a cyclic trimer is easily formed. The cyclic oligomer precipitates on the surface of the molded product when the molded product such as a film or a fiber is heated or exposed to a solvent, causing surface defects and contamination, which causes a problem. The polyester resin composition of the present invention reduces the cyclic oligomer content by carrying out solid phase polymerization.
環状オリゴマーの含有量は、固相重合によって低減できるが、ポリエスエル樹脂組成物の溶融成形などの溶融時に再生して増加する。このため、本発明のポリエステル樹脂組成物は、環状オリゴマー増加量が０．３ｗｔ％以下であることが好ましく、より好ましくは０．２５ｗｔ％以下である。なお、環状オリゴマー増加量は窒素下にて３００℃、１５分溶融処理した際の増加量である。環状オリゴマーはポリエステルとの平衡反応によって生成するため、その含有量には飽和量が存在する。したがって、固相重合を実施しない場合の環状オリゴマー増加量は実質０であるが、これは飽和状態であるだけであり、ポリエステル樹脂組成物中の環状オリゴマーは低減しているわけではない。本発明は、固相重合を実施し、環状オリゴマー含有量を低減させたのち、加工工程等の再溶融時に再生する環状オリゴマー増加量を触媒組成を鋭意検討することで抑制したものである。 The content of the cyclic oligomer can be reduced by solid phase polymerization, but is regenerated and increased at the time of melting such as melt molding of the polyester resin composition. Therefore, in the polyester resin composition of the present invention, the amount of cyclic oligomer increase is preferably 0.3 wt% or less, more preferably 0.25 wt% or less. The amount of increase in cyclic oligomers is the amount of increase when melt processing is performed at 300 ° C. for 15 minutes under nitrogen. Since the cyclic oligomer is formed by the equilibrium reaction with the polyester, a saturating amount is present in its content. Therefore, although the increase amount of the cyclic oligomer in the case where the solid phase polymerization is not performed is substantially zero, this is only a saturated state, and the cyclic oligomer in the polyester resin composition is not reduced. In the present invention, after solid phase polymerization is carried out to reduce the content of cyclic oligomers, the amount of cyclic oligomers to be regenerated at the time of remelting such as processing steps is suppressed by intensively examining the catalyst composition.
また、本発明のポリエステル樹脂組成物は、耐加水分解性の指標であるΔＣＯＯＨ／ＣＯＯＨの値が２．０以下であることが好ましい。このΔＣＯＯＨとは、飽和水蒸気下で１５５℃、４時間湿熱処理した際のＣＯＯＨ末端基増加量であり、処理前のＣＯＯＨ末端基量で割ったΔＣＯＯＨ／ＣＯＯＨが少ない値であるほど、耐加水分解性が良好となる。このΔＣＯＯＨ／ＣＯＯＨが２．０以下であることが好ましく、より好ましくは１．９以下である。上記範囲であれば、耐加水分解性は良好であり、加水分解に起因する線状オリゴマーの発生を抑制できる。 In the polyester resin composition of the present invention, the value of ΔCOOH / COOH, which is an index of hydrolysis resistance, is preferably 2.0 or less. This ΔCOOH is the amount of increase in COOH end groups when subjected to wet heat treatment at 155 ° C. for 4 hours under saturated steam, and as the value of ΔCOOH / COOH divided by the amount of COOH end groups before treatment is smaller, hydrolysis resistance The quality is good. The ΔCOOH / COOH is preferably 2.0 or less, more preferably 1.9 or less. If it is the said range, hydrolysis resistance is favorable and can suppress generation | occurrence | production of the linear oligomer resulting from a hydrolysis.
本発明のポリエステル樹脂組成物は、下記式（ＩＩＩ）で表されるように、マンガン元素を５ｐｐｍ以上４０ｐｐｍ以下含有していることが必要である。 The polyester resin composition of the present invention is required to contain 5 ppm or more and 40 ppm or less of the manganese element as represented by the following formula (III).
５ｐｐｍ≦Ｍｎ含有量≦４０ｐｐｍ （ＩＩＩ）
下限として好ましくは１０ｐｐｍ以上である。また、上限として好ましくは３０ｐｐｍ以下である。上記下限以上とすることで、溶融成形時に発生するゲル組成物を抑制できるため成形体の欠点を抑制できる。また、マンガン元素はフィルム延伸工程などのポリエステル融点以下の比較的低い温度での加熱処理においても触媒活性が高いためにポリエステルの熱分解や酸化分解、加水分解に寄与する。したがって、上記上限以下のマンガン元素量を満たすことで、加工工程における線状オリゴマー発生量や環状オリゴマー増加量を低減することが可能となる。
5 ppm ≦ Mn content ≦ 40 ppm (III)
The lower limit is preferably 10 ppm or more. Also, the upper limit is preferably 30 ppm or less. By setting it as the said minimum or more, since the gel composition which generate | occur | produces at the time of melt molding can be suppressed, the fault of a molded object can be suppressed. The manganese element also contributes to the thermal decomposition, oxidative decomposition, and hydrolysis of the polyester because the catalytic activity is high even in heat treatment at a relatively low temperature below the polyester melting point such as a film stretching step. Therefore, it becomes possible to reduce the linear oligomer generation amount and the cyclic oligomer increase amount in a process process by satisfy | filling the amount of manganese elements below the said upper limit.
また、本発明のポリエステル樹脂組成物は、下記式（ＩＶ）で表されるように、ナトリウム元素を４ｐｐｍ以上６０ｐｐｍ以下含有していることが必要である。 Moreover, the polyester resin composition of this invention needs to contain 4 ppm or more and 60 ppm or less of a sodium element, as represented by following formula (IV).
４ｐｐｍ≦Ｎａ含有量≦６０ｐｐｍ （ＩＶ）
下限として好ましくは１０ｐｐｍ以上である。また上限として好ましくは４０ｐｐｍ以下である。上記範囲とすることで、耐加水分解性が良好となり、加水分解に起因する線状オリゴマー発生を抑制できる。
4 ppm ≦ Na content ≦ 60 ppm (IV)
The lower limit is preferably 10 ppm or more. The upper limit is preferably 40 ppm or less. By setting it as the said range, hydrolysis resistance becomes favorable and it can suppress the linear oligomer generation | occurrence | production resulting from a hydrolysis.
また、本発明のポリエステル樹脂組成物は、リン元素を１７ｐｐｍ以上７０ｐｐｍ以下含有していることが好ましい。下限として好ましくは２０ｐｐｍ以上、より好ましくは２５ｐｐｍ以上である。上限として好ましくは６０ｐｐｍ以下、より好ましくは５０ｐｐｍ以下である。上記範囲とすることで、加工工程における線状オリゴマー発生量や環状オリゴマー増加量を低減できる。 Moreover, it is preferable that the polyester resin composition of this invention contains 17 ppm or more and 70 ppm or less of phosphorus elements. The lower limit is preferably 20 ppm or more, more preferably 25 ppm or more. The upper limit is preferably 60 ppm or less, more preferably 50 ppm or less. By setting it as the said range, the linear oligomer generation amount and the cyclic oligomer increase amount in a process process can be reduced.
さらに、本発明のポリエステル樹脂組成物は、ナトリウム元素とリン元素の含有量のモル比であるＮａ／Ｐが０．３以上１．２以下であることが好ましい。下限として好ましくは０．４以上であり、上限として好ましくは１．０以下である。上記範囲とすることで、耐加水分解性を付与することが可能となり、加工工程における線状オリゴマー発生量を低減できる。 Furthermore, it is preferable that Na / P which is a molar ratio of content of a sodium element and a phosphorus element is 0.3 or more and 1.2 or less of the polyester resin composition of this invention. The lower limit is preferably 0.4 or more, and the upper limit is preferably 1.0 or less. By setting it as the said range, it becomes possible to provide hydrolysis resistance and can reduce the linear oligomer generation amount in a process process.
本発明のポリエステル樹脂組成物は、アンチモン元素含有量が５０ｐｐｍ以上１５０ｐｐｍ以下であることが好ましい。下限として好ましくは８０ｐｐｍ以上であり、上限として好ましくは１２０ｐｐｍ以下である。上記範囲とすることで、重合反応性を損なうことなく、またポリエステル樹脂組成物の溶融成形時に再生する環状オリゴマー増加量を低減させることが可能となる。 The polyester resin composition of the present invention preferably has an antimony content of 50 ppm or more and 150 ppm or less. The lower limit is preferably 80 ppm or more, and the upper limit is preferably 120 ppm or less. By setting it in the above-mentioned range, it is possible to reduce the amount of increase in cyclic oligomers regenerated at the time of melt molding of the polyester resin composition without impairing the polymerization reactivity.
本発明のポリエステル樹脂組成物は、窒素及び硫黄、ハロゲンより選ばれる元素の総含有量が１０ｐｐｍ未満であることが好ましい。より好ましくは５ｐｐｍ未満であり、さらに好ましくは３ｐｐｍ未満である。窒素、硫黄、ハロゲンといった元素を含む化合物はポリエステル中に存在していると熱分解や加水分解を促進する。したがって、含んでいないことが最も好ましい。上記範囲を満たすことで、加工工程における線状オリゴマー発生量を低減できる。 The polyester resin composition of the present invention preferably has a total content of elements selected from nitrogen and sulfur, and less than 10 ppm. More preferably it is less than 5 ppm, still more preferably less than 3 ppm. Compounds containing elements such as nitrogen, sulfur and halogen accelerate thermal decomposition and hydrolysis when they are present in polyester. Therefore, it is most preferable not to contain. By satisfying the above range, the amount of linear oligomers generated in the processing step can be reduced.
また、本発明のポリエステル樹脂組成物は、酸素濃度１％の窒素雰囲気下、３００℃で６時間加熱処理した際のゲル化率が７ｗｔ％以下であることが好ましい。より好ましくは５ｗｔ％以下である。上記範囲とすることで、溶融成形時に発生するゲル組成物を抑制できるため成形体の欠点を抑制できる。 The polyester resin composition of the present invention preferably has a gelation ratio of 7 wt% or less when heat-treated at 300 ° C. for 6 hours in a nitrogen atmosphere with an oxygen concentration of 1%. More preferably, it is 5 wt% or less. By setting it as the said range, since the gel composition which generate | occur | produces at the time of melt molding can be suppressed, the fault of a molded object can be suppressed.
次に、本発明のポリエステル樹脂組成物の製造方法について記載する。 Next, the method for producing the polyester resin composition of the present invention will be described.
本発明のポリエステル樹脂組成物は、ジカルボン酸成分またはそのエステル形成誘導体成分と、ジオール成分とをエステル化反応またはエステル交換反応し、次いで重縮合反応および固相重合をしてポリエステルを製造するに際して、ポリエステルのＩＶ（固有粘度）が０．４以下の段階で、マンガン化合物を添加し、かつ重縮合反応終了までの段階でリン酸とリン酸アルカリ金属塩を添加し、かつその含有量が下記式（Ｖ）、（ＶＩ）を満たすことで得ることができる。 When the polyester resin composition of the present invention is subjected to an esterification reaction or transesterification reaction between a dicarboxylic acid component or its ester-forming derivative component and a diol component, and then a polycondensation reaction and solid phase polymerization to produce a polyester, A manganese compound is added at a stage where the IV (inherent viscosity) of the polyester is 0.4 or less, and phosphoric acid and an alkali metal salt of phosphoric acid are added at a stage up to the end of the polycondensation reaction. It can be obtained by satisfying (V) and (VI).
５ｐｐｍ≦Ｍｎ含有量≦４０ｐｐｍ （Ｖ）
４ｐｐｍ≦アルカリ金属元素含有量≦６０ｐｐｍ （ＶＩ）
本発明のポリエステル樹脂組成物の製造方法において、マンガン化合物はポリエステル樹脂のＩＶ（固有粘度）が０．４以下の段階で添加することが必要である。上記範囲に添加することで、重合反応性が良好となり、またポリエステル樹脂への分散性も良好となるため、透明性が高まる。その中でも、エステル交換反応にてポリエステルオリゴマーを得る場合は、反応をより効率的に進行させるため、エステル交換反応開始時にマンガン化合物を添加することが好ましい。また、エステル化反応にてポリエステルオリゴマーを得る場合には、エステル化反応終了時からポリエステル樹脂のＩＶが０．４以下の段階でマンガン化合物を添加することが好ましく、エステル化反応終了時から、重縮合反応開始までに添加することがより好ましい。エステル化反応は、テレフタル酸などの酸成分による自己触媒反応により、無触媒でも十分に反応は進行し、触媒を含有しているとジオール成分の２量体などの副生成物が増加することから、無触媒で実施し、ポリエステルの粘度が上昇する前に添加することで、耐熱性を損なうことなく、マンガン化合物の分散性が向上し高透明性を発現することが可能となる。
5 ppm ≦ Mn content ≦ 40 ppm (V)
4 ppm ≦ alkali metal content ≦ 60 ppm (VI)
In the method for producing a polyester resin composition of the present invention, the manganese compound needs to be added at a stage where the IV (inherent viscosity) of the polyester resin is 0.4 or less. By being added in the above range, the polymerization reactivity becomes good, and the dispersibility in the polyester resin also becomes good, so the transparency is enhanced. Among them, in the case of obtaining a polyester oligomer by transesterification, in order to allow the reaction to proceed more efficiently, it is preferable to add a manganese compound at the start of transesterification. When a polyester oligomer is obtained by the esterification reaction, it is preferable to add a manganese compound at a stage where the IV of the polyester resin is 0.4 or less from the end of the esterification reaction, and from the end of the esterification reaction It is more preferable to add it by the start of the condensation reaction. The esterification reaction is an autocatalytic reaction with an acid component such as terephthalic acid, so that the reaction proceeds sufficiently even without a catalyst, and if a catalyst is contained, by-products such as a dimer of a diol component increase. Conducting without using a catalyst and adding it before the viscosity of the polyester is increased, the dispersibility of the manganese compound can be improved and high transparency can be exhibited without impairing the heat resistance.
本発明のポリエステル樹脂組成物の製造方法において、マンガン化合物の添加量はポリエステル組成物中でのマンガン元素としての含有量が下記式（Ｖ）を満たすことが必要である。 In the method for producing a polyester resin composition of the present invention, the content of the manganese compound in the polyester composition is required to satisfy the following formula (V) as the amount of the manganese compound added.
５ｐｐｍ≦Ｍｎ含有量≦４０ｐｐｍ （ＶＩＩ）
下限として好ましくは１０ｐｐｍ以上である。また、上限として好ましくは３０ｐｐｍ以下である。上記下限以上とすることで、溶融成形時に発生するゲル組成物を抑制できるため成形体の欠点を抑制できる。また、マンガン元素はフィルム延伸工程などのポリエステル融点以下の比較的低い温度での加熱処理においても触媒活性が高いためにポリエステル樹脂の熱分解や酸化分解、加水分解に寄与する。したがって、上記上限以下のマンガン元素量を満たすことで、加工工程における線状オリゴマー発生量や環状オリゴマー増加量を低減することが可能となる。
5 ppm ≦ Mn content ≦ 40 ppm (VII)
The lower limit is preferably 10 ppm or more. Also, the upper limit is preferably 30 ppm or less. By setting it as the said minimum or more, since the gel composition which generate | occur | produces at the time of melt molding can be suppressed, the fault of a molded object can be suppressed. The manganese element also contributes to thermal decomposition, oxidative decomposition, and hydrolysis of the polyester resin because its catalytic activity is high even in heat treatment at a relatively low temperature below the polyester melting point such as a film stretching step. Therefore, it becomes possible to reduce the linear oligomer generation amount and the cyclic oligomer increase amount in a process process by satisfy | filling the amount of manganese elements below the said upper limit.
マンガン化合物は、特に限定しないが、酢酸マンガン、硝酸マンガン、硫酸マンガン、塩化マンガンなどが挙げられ、溶解性及び触媒活性の点から酢酸マンガンが好ましい。 The manganese compound is not particularly limited, and manganese acetate, manganese nitrate, manganese sulfate, manganese chloride and the like can be mentioned, and manganese acetate is preferable in terms of solubility and catalytic activity.
また、添加する際の形態は粉体、スラリー、溶液のいずれでもよく、分散性の点から、溶液として添加することが好ましい。この時の溶媒は、ポリエステル樹脂組成物のジオール成分と同一にすることが好ましく、ポリエチレンテレフタレートの場合はエチレングリコールを用いることが特に好ましい。 The form of addition may be any of powder, slurry, and solution, and from the viewpoint of dispersibility, it is preferable to add as a solution. It is preferable to make the solvent at this time the same as the diol component of the polyester resin composition, and in the case of polyethylene terephthalate, it is particularly preferable to use ethylene glycol.
本発明のポリエステル樹脂組成物の製造方法において、重縮合反応が終了するまでの段階で、リン酸とリン酸アルカリ金属塩を添加することが必要である。リン酸とリン酸アルカリ金属塩の添加時期として、より好ましくは、エステル交換反応及びエステル化反応終了後から重縮合反応開始までの間である。上記範囲に添加することで、重縮合反応を遅延させることなく、効果的にポリエステル樹脂に熱安定性と耐加水分解性を付与することができる。 In the method for producing a polyester resin composition of the present invention, it is necessary to add phosphoric acid and an alkali metal phosphate in the stage until the polycondensation reaction is completed. More preferably, it is from the end of the ester exchange reaction and the esterification reaction to the start of the polycondensation reaction as the addition time of the phosphoric acid and the phosphoric acid alkali metal salt. By adding to the above range, it is possible to effectively impart thermal stability and hydrolysis resistance to the polyester resin without delaying the polycondensation reaction.
リン酸の添加量には特に制限を設けないが、添加量の下限としては、リン元素として２５ｐｐｍ以上であることが好ましく、より好ましくは４５ｐｐｍ以上である。添加量の上限としては、２００ｐｐｍ以下であることが好ましく、より好ましくは１５０ｐｐｍ以下である。上記範囲にすることで、重合の遅延を起こすことがなく、ポリエステル樹脂組成物の熱安定性を良好にすることができ、結果として加工工程における線状オリゴマー発生量や環状オリゴマー増加量を低減することができる。なお、リン酸は通常の場合、水溶液として入手できるため、前記添加量は水溶液の濃度から換算したリン酸成分正味の添加量である。 The addition amount of phosphoric acid is not particularly limited, but the lower limit of the addition amount is preferably 25 ppm or more as phosphorus element, more preferably 45 ppm or more. The upper limit of the addition amount is preferably 200 ppm or less, more preferably 150 ppm or less. By setting it in the above range, the thermal stability of the polyester resin composition can be improved without delaying the polymerization, and as a result, the amount of linear oligomers generated and the amount of cyclic oligomers increased in the processing step can be reduced. be able to. Since phosphoric acid is usually obtained as an aqueous solution, the addition amount is the net addition amount of the phosphoric acid component converted from the concentration of the aqueous solution.
リン酸アルカリ金属塩の添加量は、ポリエステル組成物中でのアルカリ金属元素としての含有量が４ｐｐｍ以上６０ｐｐｍ以下とすることが必要である。下限としてより好ましくは１０ｐｐｍ以上である。また上限として好ましくは４０ｐｐｍ以下である。上記範囲とすることで、耐加水分解性が良好となり、加水分解に起因する線状オリゴマー発生を抑制できる。 The addition amount of the alkali metal phosphate is required to be 4 ppm or more and 60 ppm or less as the alkali metal element in the polyester composition. More preferably, the lower limit is 10 ppm or more. The upper limit is preferably 40 ppm or less. By setting it as the said range, hydrolysis resistance becomes favorable and it can suppress the linear oligomer generation | occurrence | production resulting from a hydrolysis.
リン酸アルカリ金属塩としては、リン酸二水素ナトリウム、リン酸水素二ナトリウム、リン酸三ナトリウム、リン酸二水素カリウム、リン酸水素二カリウム、リン酸三カリウム、リン酸二水素リチウム、リン酸水素二リチウム、リン酸三リチウムが挙げられる。耐加水分解性の点から、ナトリウム塩であることが好ましく、リン酸二水素ナトリウムが特に好ましい。また、複数のリン酸アルカリ金属塩を併用しても構わない。 As an alkali metal phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium triphosphate, lithium dihydrogen phosphate, phosphoric acid Dilithium hydrogen and trilithium phosphate are mentioned. From the viewpoint of hydrolysis resistance, sodium salts are preferred, and sodium dihydrogen phosphate is particularly preferred. Further, a plurality of alkali metal phosphates may be used in combination.
また、添加する際の形態は粉体、スラリー、溶液のいずれでもよく、分散性の点から、溶液として添加することが好ましい。この時の溶媒は、ポリエステル樹脂組成物のジオール成分と同一にすることが好ましく、ポリエチレンテレフタレートの場合はエチレングリコールを用いることが特に好ましい。 The form of addition may be any of powder, slurry, and solution, and from the viewpoint of dispersibility, it is preferable to add as a solution. It is preferable to make the solvent at this time the same as the diol component of the polyester resin composition, and in the case of polyethylene terephthalate, it is particularly preferable to use ethylene glycol.
さらに、リン酸とリン酸アルカリ金属塩の溶液を混合し添加することが好ましい。リン酸とリン酸アルカリ金属塩を混合し、緩衝溶液として添加することで、より良好な耐加水分解性が発現し、加工工程における線状オリゴマー発生量を低減することが可能となる。 Furthermore, it is preferable to mix and add a solution of phosphoric acid and a phosphoric acid alkali metal salt. By mixing phosphoric acid and a phosphoric acid alkali metal salt and adding them as a buffer solution, better hydrolysis resistance is expressed, and it becomes possible to reduce the amount of linear oligomers generated in the processing step.
また、上記アルカリ金属元素の添加量を満たす範囲で、リン酸アルカリ金属塩以外のアルカリ金属化合物を併用しても構わない。具体的には、リチウム、ナトリウム、カリウムの水酸化物、酢酸塩、炭酸塩、硝酸塩、塩化物などが挙げられる。この中でも、水酸化カリウムを併用することで、線状オリゴマー発生量を増加させることなく、静電印加製膜に必要なポリエステル樹脂の溶融比抵抗を小さくすることができ、成形性が向上する。 In addition, alkali metal compounds other than the alkali metal phosphate may be used in combination as long as the addition amount of the alkali metal element is satisfied. Specifically, lithium, sodium, potassium hydroxide, acetate, carbonate, nitrate, chloride and the like can be mentioned. Among these, by using potassium hydroxide in combination, the melting specific resistance of the polyester resin necessary for electrostatic application film forming can be reduced without increasing the linear oligomer generation amount, and the formability is improved.
本発明のポリエステル樹脂組成物の製造方法において、エステル化反応を経て実施する場合、エステル化反応後から、リン酸アルカリ金属塩を添加するまでの間に、エチレングリコールなどグリコール成分の追加添加を実施することが好ましい。より好ましくは、マンガン化合物添加後から、リン酸アルカリ金属塩を添加するまでの間である。エステル化反応にて得られるポリエステル樹脂組成物の低分子量体は、エステル交換反応で得られる低分子量体よりも重合度が高いためにリン酸アルカリ金属塩が分散しにくく、異物化が起こりやすい。したがって、エチレングリコールなどグリコール成分を追加添加し、解重合によって重合度を低下させておくことで異物化を抑制できる。この時、マンガン化合物が存在しているとより効率的に解重合できる。 In the method for producing a polyester resin composition of the present invention, when carrying out via an esterification reaction, additional addition of a glycol component such as ethylene glycol is carried out after the esterification reaction until the addition of an alkali metal salt of phosphoric acid. It is preferable to do. More preferably, it is from the addition of the manganese compound to the addition of the alkali metal phosphate. The low molecular weight polymer of the polyester resin composition obtained by the esterification reaction has a higher degree of polymerization than the low molecular weight polymer obtained by the transesterification reaction, so that the alkali metal phosphate is difficult to disperse and foreign matter is likely to occur. Therefore, foreign matter formation can be suppressed by additionally adding a glycol component such as ethylene glycol and reducing the degree of polymerization by depolymerization. At this time, when a manganese compound is present, depolymerization can be performed more efficiently.
この追加添加するエチレングリコールなどグリコール成分は、全酸成分に対し０．０５倍モル以上０．５倍モル以下であることが好ましい。より好ましくは０．１倍モル以上０．３倍モル以下である。上記範囲とすることで、重合系内の温度降下による重合時間の遅延を起こすことなく、リン酸アルカリ金属塩の異物化を抑制できる。 It is preferable that the glycol component such as ethylene glycol to be additionally added is 0.05-fold mol or more and 0.5-fold mol or less with respect to the total acid component. More preferably, it is 0.1 times mole or more and 0.3 times mole or less. By setting it as the said range, foreign material formation of the alkali metal phosphate can be suppressed, without causing the delay of the superposition | polymerization time by the temperature fall in a superposition | polymerization system.
本発明のポリエステル樹脂組成物の製造に用いられるその他触媒は公知のエステル交換触媒、重縮合触媒、助触媒を用いることができる。例えば、重合触媒としてはアンチモン化合物、ゲルマニウム化合物、チタン化合物、アルミニウム化合物が挙げられるが、これらに限定されるものではない。また、エステル交換触媒及び助触媒としては、マンガン化合物、マグネシウム化合物、カルシウム化合物、コバルト化合物、亜鉛化合物、リチウム化合物、ナトリウム化合物、カリウム化合物などが挙げられるが、これらに限定されるものではない。 As other catalysts used for producing the polyester resin composition of the present invention, known ester exchange catalysts, polycondensation catalysts and cocatalysts can be used. For example, as a polymerization catalyst, although an antimony compound, a germanium compound, a titanium compound, and an aluminum compound are mentioned, it is not limited to these. In addition, as the transesterification catalyst and the co-catalyst, manganese compounds, magnesium compounds, calcium compounds, cobalt compounds, zinc compounds, lithium compounds, sodium compounds, potassium compounds and the like can be mentioned, but it is not limited thereto.
また本発明のポリエステル樹脂組成物の製造方法において、固相重合を実施することが必要である。固相重合を実施することで、ポリエステル樹脂組成物中の環状オリゴマーおよび線状オリゴマーを低減させることができる。固相重合の条件は、特に限定しないが、ポリエステル樹脂組成物の融点−３０℃以下、融点−６０℃以上の温度にて実施することが好ましく、真空度は４０Ｐａ以下であることが好ましい。固相重合時間は、目的とするポリエステル樹脂組成物の環状オリゴマー含有量やＩＶなどにより、適宜設定されるが、３時間以上、２０時間以下とすることが生産タイムサイクルより好ましい。 Moreover, in the method for producing a polyester resin composition of the present invention, it is necessary to carry out solid phase polymerization. By performing solid phase polymerization, cyclic oligomers and linear oligomers in the polyester resin composition can be reduced. The conditions for solid phase polymerization are not particularly limited, but it is preferable to carry out at a temperature of melting point -30 ° C or less and melting point -60 ° C or more of the polyester resin composition, and the vacuum degree is preferably 40Pa or less. The solid phase polymerization time is appropriately set depending on the cyclic oligomer content of the target polyester resin composition, IV and the like, but it is more preferable than the production time cycle to be 3 hours or more and 20 hours or less.
さらに、本発明のポリエステル樹脂組成物の製造方法において、失活処理を実施しても構わない。失活処理とは、ポリエステル樹脂組成物中に残存している重縮合触媒を不活性化する工程であり、実施することでポリエステル樹脂組成物を再溶融した際の環状オリゴマー増加量を低減できる。失活処理は、水やリン化合物、アンモニア化合物など種々の溶液中にポリエステル樹脂組成物を常温または加熱下にて接触させる処理にて実施することが可能である。リン化合物としては、リン酸トリメチル、リン酸トリエチル、リン酸トリブチル、リン酸トリフェニル、リン酸ジメチル、リン酸ジフェニル、リン酸メチル、リン酸エチルなどのリン酸エステル類、またリン酸やポリリン酸のようなリン化合物の水溶液や溶液などが挙げられ、これに限定されない。また、アンモニア化合物としては、トリエチルアミン、水酸化テトラエチルアンモニウム、水酸化テトラ−ｎ−ブチルアンモニウムなどが挙げられる。処理温度は、２０℃以上１２０℃以下が好ましく、より好ましくは４０℃以上１００℃以下、５０℃以上１００℃以下がさらに好ましい。処理時間は、３０分以上２４時間以下であることが好ましく、より好ましくは１時間以上１２時間以下である。 Furthermore, in the method for producing a polyester resin composition of the present invention, a deactivation treatment may be carried out. The deactivation treatment is a step of deactivating the polycondensation catalyst remaining in the polyester resin composition, and by carrying out the treatment, it is possible to reduce the amount of increase in cyclic oligomers when the polyester resin composition is remelted. The deactivation treatment can be carried out by bringing the polyester resin composition into contact with water, a phosphorus compound, an ammonia compound or the like at various temperatures or under heating. The phosphorus compounds include phosphoric acid such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, dimethyl phosphate, diphenyl phosphate, methyl phosphate and ethyl phosphate, and phosphoric acid and polyphosphoric acid These include aqueous solutions and solutions of phosphorus compounds such as, but not limited thereto. Further, as the ammonia compound, triethylamine, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide and the like can be mentioned. The treatment temperature is preferably 20 ° C. or more and 120 ° C. or less, more preferably 40 ° C. or more and 100 ° C. or less, and further preferably 50 ° C. or more and 100 ° C. or less. The treatment time is preferably 30 minutes or more and 24 hours or less, more preferably 1 hour or more and 12 hours or less.
本発明のポリエステル樹脂組成物は、本発明の効果を損なわない範囲で、末端封鎖剤、酸化防止剤、紫外線吸収剤、難燃剤、蛍光増白剤、艶消剤、可塑剤もしくは消泡剤またはその他の添加剤等を必要に応じて配合しても良い。 The polyester resin composition of the present invention is an end blocking agent, an antioxidant, an ultraviolet light absorber, a flame retardant, a brightening agent, a matting agent, a plasticizer or an antifoaming agent, as long as the effects of the present invention are not impaired. Other additives and the like may be blended as necessary.
以下、本発明におけるポリエステル樹脂組成物の製造方法の具体例を挙げるが、これに制限されない。 Hereinafter, although the specific example of the manufacturing method of the polyester resin composition in this invention is given, it is not restrict | limited to this.
２５５℃にて溶解したビスヒドロキシエチルテレフタレートが仕込まれたエステル化反応器に、テレフタル酸とエチレングリコール（テレフタル酸に対し１．１５倍モル）のスラリーをスネークポンプにて徐々に添加し、エステル化反応を進行させる。反応系内の温度は２４５〜２５５℃になるようにコントロールし、反応率が９５％に到達した段階でエステル化反応を終了とする。 A slurry of terephthalic acid and ethylene glycol (1.15 moles per 1 mole of terephthalic acid) was gradually added to the esterification reactor charged with bishydroxyethyl terephthalate dissolved at 255 ° C using a snake pump to effect esterification. Let the reaction proceed. The temperature in the reaction system is controlled to be 245 to 255 ° C., and the esterification reaction is terminated when the reaction rate reaches 95%.
こうして得られた２５５℃のエステル化反応物を重合装置に移送し、マンガン化合物、重縮合触媒を添加する。その後、エチレングリコールを追加添加し、リン酸、リン酸アルカリ金属塩を添加する。これらの操作の際は、エステル化物が固化しないように、反応系内の温度を２４０〜２５５℃に保つことが好ましい。 The thus obtained esterification reaction product at 255 ° C. is transferred to a polymerization apparatus, and a manganese compound and a polycondensation catalyst are added. Thereafter, ethylene glycol is additionally added, and phosphoric acid and phosphoric acid alkali metal salts are added. During these operations, it is preferable to maintain the temperature in the reaction system at 240 to 255 ° C. so that the esterified product does not solidify.
その後、重合装置内の温度を２９０℃まで徐々に昇温しながら、重合装置内の圧力を常圧から１３３Ｐａ以下まで徐々に減圧してエチレングリコールを留出させる。所定の撹拌トルクに到達した段階で反応を終了とし、反応系内を窒素ガスで常圧にし、溶融ポリマーを冷水中にストランド状に吐出、カッティングし、ペレット状ポリマーを得る。 Thereafter, while the temperature in the polymerization apparatus is gradually raised to 290 ° C., the pressure in the polymerization apparatus is gradually reduced from normal pressure to 133 Pa or less to distill ethylene glycol off. The reaction is terminated when a predetermined stirring torque is reached, the pressure in the reaction system is brought to normal pressure with nitrogen gas, and the molten polymer is discharged in cold water into strands and cut to obtain a pellet-like polymer.
この得られたペレット状ポリマーを１６０℃で６時間乾燥、結晶化させ、真空度４０Ｐａ、２２０℃にて８時間固相重合を実施し、ポリエステル樹脂組成物を得た。 The obtained pellet-like polymer was dried at 160 ° C. for 6 hours for crystallization, and solid phase polymerization was carried out at 220 ° C. for 8 hours under vacuum of 40 Pa to obtain a polyester resin composition.
本発明のポリエステル樹脂組成物は、耐熱性や耐加水分解性に優れ、溶融成形や加工工程にて発生するゲル組成物や線状オリゴマー発生量、環状オリゴマー量が少ない。したがって、フィルム、繊維、成形体など各種用途に好適に用いることができ、特に本発明のポリエステルフィルムは高透明性の求められる光学フィルムや離型フィルムなどの高品位フィルムに用いることが可能である。 The polyester resin composition of the present invention is excellent in heat resistance and hydrolysis resistance, and the gel composition generated in the melt molding and processing steps, the amount of linear oligomers generated and the amount of cyclic oligomers are small. Therefore, it can be used suitably for various uses, such as a film, a fiber, and a molded object, and it is possible to use especially the polyester film of this invention for high quality films, such as an optical film and release film for which high transparency is required. .
フィルムとしては、本発明のポリエステル樹脂組成物から構成される単膜フィルムでも本発明のポリエステル樹脂組成物を少なくとも１層有する積層フィルムでもよい。特に積層フィルムの場合は、本発明のポリエステル樹脂組成物からなる層を少なくとも片表面に有する積層フィルムが好ましい。本発明のポリエステル樹脂組成物からなる層がフィルム表面に存在する場合、フィルム表面からの線状オリゴマー揮発などが抑制されるため、線状オリゴマー欠点の発生を効果的に抑制できる。 The film may be a single film film composed of the polyester resin composition of the present invention or a laminated film having at least one layer of the polyester resin composition of the present invention. In particular, in the case of a laminated film, a laminated film having a layer of the polyester resin composition of the present invention on at least one surface is preferred. When the layer consisting of the polyester resin composition of the present invention is present on the film surface, the linear oligomer volatilization from the film surface is suppressed, so that the generation of the linear oligomer defect can be effectively suppressed.
以下実施例を挙げて、本発明をさらに詳細に説明する。なお、実施例中の物性値は以下の方法で測定した。以下記載する方法は、本発明のポリエステル樹脂組成物単成分の場合の測定方法を記載しているが、積層フィルムなどのように複数樹脂からなる成形体の場合、各層の樹脂を削り出すなどして単離し、分析を行う。 The present invention will be described in more detail with reference to the following examples. In addition, the physical-property value in an Example was measured by the following method. The method described below describes the measurement method in the case of the polyester resin composition single component of the present invention, but in the case of a molded product composed of a plurality of resins such as a laminated film, the resin of each layer is scraped etc. Isolate and analyze.
（１）ポリエステル樹脂組成物の固有粘度（ＩＶ）
ｏ−クロロフェノール溶媒を用い、２５℃で測定した。
(1) Intrinsic viscosity of polyester resin composition (IV)
It measured at 25 degreeC using the o-chlorophenol solvent.
（２）ポリエステル樹脂組成物のＣＯＯＨ末端基量
Ｍａｕｒｉｃｅの方法によって測定した。（文献 Ｍ．Ｊ．Ｍａｕｒｉｃｅ，Ｆ．Ｈｕｉｚｉｎｇａ，Ａｎａｌ．Ｃｈｅｍ．Ａｃｔａ、２２、３６３（１９６０）） 。
(2) Measured by the method of COOH end group amount Maurice of polyester resin composition. (Reference M. J. Maurice, F. Huizinga, Anal. Chem. Acta, 22, 363 (1960)).
（３）ポリエステル樹脂組成物のマンガン及びリン、アルカリ金属元素含有量
原子吸光法（（株）日立製作所製：偏光ゼーマン原子吸光光度型１８０−８０、フレーム：アセチレン空気）にて定量を行った。
(3) Manganese and phosphorus of the polyester resin composition, alkali metal content: Determination by atomic absorption spectrometry (manufactured by Hitachi, Ltd .: polarized Zeeman atomic absorption type 180-80, frame: acetylene air).
（４）ポリエステル樹脂組成物の窒素元素含有量
ポリエステル樹脂組成物を凍結粉砕し、室温で３時間減圧乾燥した。その後、ＩＣＰ発光分光分析法（三菱化学（株）製ＮＤ−１００型）にて定量を行った。
(4) Elemental nitrogen content of polyester resin composition The polyester resin composition was freeze-ground and dried under reduced pressure at room temperature for 3 hours. Then, it quantified by ICP emission spectrometry (ND-100 type | mold by Mitsubishi Chemical Co., Ltd. product).
（５）ポリエステル樹脂組成物の硫黄、ハロゲン元素含有量
ポリエステル樹脂組成物を凍結粉砕し、室温で３時間減圧乾燥した。その後、燃焼イオンクロマトグラフ（東亜ＤＫＫ（株）製ＩＣＡ２０００）により定量を行った。この時、５ｐｐｍ未満は検出下限以下（ＮＤ）とした。
(5) Sulfur and Halogen Element Content of Polyester Resin Composition The polyester resin composition was freeze-ground and dried under reduced pressure for 3 hours at room temperature. Thereafter, quantification was carried out using a combustion ion chromatograph (ICA2000 manufactured by Toa DKK Co., Ltd.). At this time, less than 5 ppm was below the lower limit of detection (ND).
（６）ポリエステル樹脂組成物のゲル化率
ポリステル樹脂組成物を凍結粉砕機（Ｓｐｒｅｘ ＣｅｒｔｉＰｅｒｐ社製）にて粉砕し、容量５０ｍｌのステンレスビーカーに０．５ｇ秤量した。真空乾燥機を用いて、５０℃で２時間真空乾燥した後、酸素／窒素濃度１％ガス流通下（流量０．５Ｌ／分）、３００℃で６時間加熱処理を行った。これを、２０ｍｌのｏ−クロロフェノールで、１６０℃で１時間溶解し、放冷した。この溶液を、ガラスフィルター（柴田科学（株）製、３ＧＰ４０）を使用してろ過し、ジクロロメタンにてガラスフィルターを洗浄した。ガラスフィルターを１３０℃で２時間乾燥し、ろ過前後のろ過器の重量の増加分より、ポリエステル重量（０．５ｇ）に対する重量分率を求め、ゲル化率（％）とした。
(6) Gelation Rate of Polyester Resin Composition The polyester resin composition was pulverized by a freeze pulverizer (manufactured by Sprex CertiPerp), and weighed 0.5 g into a stainless beaker having a volume of 50 ml. After vacuum drying at 50 ° C. for 2 hours using a vacuum dryer, heat treatment was performed at 300 ° C. for 6 hours under oxygen / nitrogen concentration 1% gas flow (flow rate 0.5 L / min). This was dissolved in 20 ml of o-chlorophenol at 160 ° C. for 1 hour and allowed to cool. This solution was filtered using a glass filter (3 GP 40, manufactured by Shibata Scientific Co., Ltd.), and the glass filter was washed with dichloromethane. The glass filter was dried at 130 ° C. for 2 hours, and the weight fraction relative to the polyester weight (0.5 g) was determined from the increase in the weight of the filter before and after filtration to obtain the gelation ratio (%).
（７）ポリエステル樹脂組成物の耐加水分解性評価（ΔＣＯＯＨ／ＣＯＯＨ）
ポリエステル樹脂組成物を飽和水蒸気下、１５５℃で４時間湿熱処理し、処理前後のＣＯＯＨ末端基量を測定することで、ＣＯＯＨ末端基増加量（ΔＣＯＯＨ＝処理後ＣＯＯＨ−処理前ＣＯＯＨ）を算出した。このΔＣＯＯＨの値を処理前のＣＯＯＨ末端基量で割ることで耐加水分解性を評価した。
なお、処理装置は次の加熱処理装置を使用した。
ＰＲＥＳＳＥＲ ＣＯＯＫＥＲ ３０６ＳＩＩＩ（ＨＩＲＡＹＡＭＡ製作所（株）製） 。
(7) Evaluation of hydrolysis resistance of polyester resin composition (ΔCOOH / COOH)
The polyester resin composition was subjected to wet heat treatment under saturated steam at 155 ° C. for 4 hours, and the amount of COOH end group increase (ΔCOOH = post-treatment COOH-pre-treatment COOH) was calculated by measuring the COOH end group weight before and after treatment. . The hydrolysis resistance was evaluated by dividing the value of ΔCOOH by the amount of COOH end group before treatment.
The following heat treatment apparatus was used as the treatment apparatus.
PRESSER COOKER 306 SIII (manufactured by HIRAYAMA Manufacturing Co., Ltd.).
（８）ポリエステル樹脂組成物の線状オリゴマー発生量
温度２３℃、湿度５０％の環境下に２４時間以上静置したポリエステル樹脂組成物（水分率２５００ｐｐｍ）を０．１ｇ計量し、封管内を窒素雰囲気下とし、２９０℃で２０分溶融処理を行った。溶融処理した封管内の試料を２ｍＬのＨＦＩＰ（ヘキサフルオロ−２−プロパノール）／クロロホルム＝１／１（体積）混合溶液で溶解させた後、ビーカーに移し、クロロホルム３ｍＬを添加し、さらにメタノール４０ｍＬを徐々に加えた。その後、ペーパーフィルター（ＡＤＶＡＮＴＥＣ製Ｎｏ．２）でろ過して得られた溶液を濃縮乾固させて得られた残渣にＤＭＦ（Ｎ，Ｎ−ジメチルホルムアミド）０．５ｍＬを加えて溶解・分散させ、エタノールを加えて５ｍＬに定容した。孔径０．４５μｍのＰＴＦＥメンブレンフィルターでろ過した溶液を試料溶液とした。得られた試料溶液を、ＬＣ／ＵＶで分析することにより、溶融処理後のポリエステル樹脂組成物中の線状オリゴマー（ＴＰＡ、ＭＨＥＴ、ＢＨＥＴ）の含有量を測定した。この時、溶融処理前後の線状オリゴマー含有量の差（溶融処理後含有量−溶融処理前含有量）を算出することで、線状オリゴマー発生量を求めた。
(8) Linear Oligomer Generation Amount of Polyester Resin Composition Measure 0.1 g of the polyester resin composition (water content 2500 ppm) which was allowed to stand for 24 hours or more under the environment of temperature 23 ° C. and humidity 50%. Under the atmosphere, melting was performed at 290 ° C. for 20 minutes. After dissolving the sample in the melt-treated sealed tube with 2 mL of HFIP (hexafluoro-2-propanol) / chloroform = 1/1 (volume) mixed solution, transfer to a beaker, add 3 mL of chloroform, and further add 40 mL of methanol I added it gradually. Then, 0.5 mL of DMF (N, N-dimethylformamide) is added to the residue obtained by concentrating and drying the solution obtained by filtering through a paper filter (No. 2 made by ADVANTEC), and then dissolved and dispersed, Ethanol was added to make up to 5 mL. The solution filtered through a PTFE membrane filter with a pore size of 0.45 μm was used as a sample solution. The content of linear oligomers (TPA, MHET, BHET) in the polyester resin composition after melt processing was measured by analyzing the obtained sample solution by LC / UV. At this time, the amount of generation of linear oligomers was determined by calculating the difference between the content of linear oligomers before and after melt processing (content after melt processing-content before melt processing).
（９）環状オリゴマー含有量
オルトクロロフェノールを溶媒とし、液体クロマトグラフにて測定した。
(9) Cyclic oligomer content It measured by the liquid chromatograph using orthochlorophenol as a solvent.
装置：島津ＬＣ−１０ＡＤｖｐ
カラム：ＹＭＣ−Ｐａｃｋ ＯＤＳ−Ａ １５０×４．６ｍｍ Ｓ−５μｍ
カラム温度：４０℃
流量：１．３ｍｌ／ｍｉｎ
検出器：２４０ｎｍ
溶離液：Ａ液純水３５％ Ｂ液メタノール７５％ 。
Device: Shimadzu LC-10 ADvp
Column: YMC-Pack ODS-A 150 × 4.6 mm S-5 μm
Column temperature: 40 ° C
Flow rate: 1.3 ml / min
Detector: 240 nm
Eluent: liquid A pure water 35% liquid B methanol 75%.
（１０）環状オリゴマー増加量
ポリエステル樹脂組成物８ｇを１５０℃で８時間真空乾燥を行った。乾燥したポリエステル樹脂組成物を窒素雰囲気下、３００℃で１５分溶融処理を行った。この溶融処理後ポリマーの環状オリゴマー含有量を前記（９）と同様に測定し、溶融処理前後を比較することで環状オリゴマー増加量を算出した。
(10) Cyclic Oligomer Increasing Amount 8 g of the polyester resin composition was vacuum dried at 150 ° C. for 8 hours. The dried polyester resin composition was subjected to a melting treatment at 300 ° C. for 15 minutes in a nitrogen atmosphere. The cyclic oligomer content of the polymer after melt processing was measured in the same manner as in (9) above, and the increase in cyclic oligomer was calculated by comparing before and after melt processing.
（実施例１）
２５５℃にて溶解したビスヒドロキシエチルテレフタレート１０５重量部が仕込まれたエステル化反応器に、テレフタル酸８６重量部とエチレングリコール３７重量部（テレフタル酸に対し１．１５倍モル）からなるスラリーを徐々に添加し、エステル化反応を進行させた。反応系内の温度は２４５〜２５５℃になるようにコントロールし、反応率が９５％に到達した段階でエステル化反応を終了とした。
Example 1
A slurry consisting of 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times the molar amount of terephthalic acid) was gradually added to an esterification reactor charged with 105 parts by weight of bishydroxyethyl terephthalate dissolved at 255 ° C. The esterification reaction was allowed to proceed. The temperature in the reaction system was controlled to be 245 to 255 ° C., and the esterification reaction was ended when the reaction rate reached 95%.
こうして得られた２５５℃のエステル化反応物１０５重量部（ＰＥＴ１００重量部相当）を重合装置に移送し、酢酸マンガン４水和物０．０１重量部のエチレングリコール溶液（マンガン元素として２３ｐｐｍ）、三酸化二アンチモン０．０１２重量部のエチレングリコールスラリーを添加した。その後、エチレングリコール５重量部（テレフタル成分対比０．１５倍モル）を追加添加して解重合を進め、次いでリン酸０．００６重量部とリン酸２水素ナトリウム２水和物０．００９５重量部（ナトリウム元素として１４ｐｐｍ）の混合エチレングリコール溶液を添加した。 105 parts by weight (equivalent to 100 parts by weight of PET) of the esterification reaction product at 255 ° C. thus obtained is transferred to a polymerization apparatus, and an ethylene glycol solution (23 ppm as manganese element) of 0.01 parts by weight of manganese acetate tetrahydrate An ethylene glycol slurry of 0.012 parts by weight of diantimony oxide was added. Thereafter, 5 parts by weight of ethylene glycol (0.15 times the molar amount of the terephthal component) is further added to proceed with depolymerization, and then 0.006 parts by weight of phosphoric acid and 0.0095 parts by weight of sodium dihydrogen phosphate dihydrate A mixed ethylene glycol solution (14 ppm as sodium element) was added.
その後、重合装置内温度を徐々に２９０℃まで昇温しながら、重合装置内圧力を常圧から１３３Ｐａ以下まで徐々に減圧してエチレングリコールを留出させた。固有粘度０．５５相当の溶融粘度に到達した時点で、反応を終了とし、反応系内を窒素ガスにて常圧にし、重合装置下部より冷水中にストランド状に吐出、カッティングし、ペレット状ポリマーを得た。得られたペレット状ポリマーを１６０℃で６時間乾燥、結晶化させ、真空度４０Ｐａ、２２０℃にて８時間固相重合を実施し、ポリエステル樹脂組成物を得た。得られたポリエステル樹脂組成物の特性を表１に示す。 Thereafter, while the temperature in the polymerization apparatus was gradually raised to 290 ° C., the pressure in the polymerization apparatus was gradually reduced from atmospheric pressure to 133 Pa or less to distill ethylene glycol. When reaching a melt viscosity equivalent to an intrinsic viscosity of 0.55, the reaction is terminated, the inside of the reaction system is brought to normal pressure with nitrogen gas, and it is discharged in cold water from the lower part of the polymerization apparatus into strands and cut. I got The obtained pellet-like polymer was dried at 160 ° C. for 6 hours for crystallization, and solid phase polymerization was carried out at 220 ° C. for 8 hours under vacuum of 40 Pa to obtain a polyester resin composition. The properties of the obtained polyester resin composition are shown in Table 1.
実施例１で得られたポリエステル樹脂組成物は、ゲル化率および耐加水分解性が良好であり、線状オリゴマー発生量、環状オリゴマー含有量及び増加量も少ないことから、光学フィルムや離型フィルムに好適な物性を有していた。 The polyester resin composition obtained in Example 1 has good gelation rate and hydrolysis resistance, and the amount of linear oligomers generated, the content of cyclic oligomers and the amount of increase are also small, so an optical film or a release film is obtained. Physical properties suitable for
（実施例２〜５、比較例１〜３）
マンガン化合物及びリン酸の添加量を表１の通りに変更した以外は、実施例１と同様の方法でポリエステル樹脂組成物を得た。得られたポリエステル樹脂組成物の特性を表１に示す。
(Examples 2-5, comparative examples 1-3)
A polyester resin composition was obtained in the same manner as in Example 1, except that the amounts of the manganese compound and phosphoric acid added were changed as shown in Table 1. The properties of the obtained polyester resin composition are shown in Table 1.
実施例２〜５にて得られたポリエステル樹脂組成物は、ゲル化率および耐加水分解性が良好であり、線状オリゴマー発生量、環状オリゴマー含有量及び増加量も少ないことから、光学フィルムや離型フィルムに好適な物性を有していた。 The polyester resin compositions obtained in Examples 2 to 5 have good gelation rate and hydrolysis resistance, and the amount of linear oligomers generated, the content of cyclic oligomers and the amount of increase are also small. It had physical properties suitable for the release film.
比較例１で得られたポリエステル樹脂組成物は、マンガン化合物を添加していないため、ゲル化率・ΔＣＯＯＨ／ＣＯＯＨが増加した。 In the polyester resin composition obtained in Comparative Example 1, the gelation ratio .DELTA.COOH / COOH increased because the manganese compound was not added.
比較例２、３で得られたポリエステル樹脂組成物は、マンガン化合物の添加量が多いため、ΔＣＯＯＨ／ＣＯＯＨ及び線状オリゴマー発生量、環状オリゴマー増加量が増加した。 Since the polyester resin compositions obtained in Comparative Examples 2 and 3 contained a large amount of the manganese compound, the ΔCOOH / COOH, the linear oligomer generation amount, and the cyclic oligomer increase amount increased.
（比較例４）
固相重合を実施しない以外は、実施例１と同様の方法でポリエステル樹脂組成物を得た。得られたポリエステル樹脂組成物の特性を表１に示す。
(Comparative example 4)
A polyester resin composition was obtained in the same manner as in Example 1 except that solid phase polymerization was not performed. The properties of the obtained polyester resin composition are shown in Table 1.
比較例４にて得られたポリエステル樹脂組成物は、固相重合を実施していないため、環状オリゴマー含有量が増加した。 In the polyester resin composition obtained in Comparative Example 4, since the solid phase polymerization was not performed, the cyclic oligomer content increased.
リン酸アルカリ金属塩の添加量を表２の通りに変更した以外は、実施例１と同様の方法でポリエステル樹脂組成物を得た。得られたポリエステル樹脂組成物の特性を表２に示す。
実施例６〜９で得られたポリエステル樹脂組成物は、ゲル化率および耐加水分解性が良好であり、線状オリゴマー発生量、環状オリゴマー含有量及び増加量も少ないことから、光学フィルムや離型フィルムに好適な物性を有していた。
A polyester resin composition was obtained in the same manner as in Example 1 except that the addition amount of the alkali metal phosphate was changed as shown in Table 2. The properties of the obtained polyester resin composition are shown in Table 2.
The polyester resin compositions obtained in Examples 6 to 9 have good gelation rate and hydrolysis resistance, and the amount of generation of linear oligomers, the content of cyclic oligomers and the amount of increase are also small. It had physical properties suitable for the mold film.
比較例５で得られたポリエステル樹脂組成物は、リン酸アルカリ金属塩を添加していないため、ΔＣＯＯＨ／ＣＯＯＨ及び線状オリゴマー発生量が増加した。 Since the polyester resin composition obtained in Comparative Example 5 did not contain an alkaline metal salt of phosphoric acid, ΔCOOH / COOH and the amount of linear oligomers generated increased.
比較例６で得られたポリエステル樹脂組成物は、リン酸アルカリ金属塩の添加量が多いため、ΔＣＯＯＨ／ＣＯＯＨ及び線状オリゴマー発生量が増加した。 Since the polyester resin composition obtained in Comparative Example 6 had a large amount of addition of the alkali metal phosphate, the ΔCOOH / COOH and the amount of linear oligomers generated increased.
リン酸の添加量を表３の通りに変更した以外は、実施例１と同様の方法でポリエステル樹脂組成物を得た。得られたポリエステル樹脂組成物の特性を表３に示す。
実施例１０〜１２で得られたポリエステル樹脂組成物は、ゲル化率および耐加水分解性が良好であり、線状オリゴマー発生量、環状オリゴマー含有量及び増加量も少ないことから、光学フィルムや離型フィルムに好適な物性を有していた。
A polyester resin composition was obtained in the same manner as in Example 1 except that the addition amount of phosphoric acid was changed as shown in Table 3. The properties of the obtained polyester resin composition are shown in Table 3.
The polyester resin compositions obtained in Examples 10 to 12 have good gelation rate and hydrolysis resistance, and the amount of generation of linear oligomers, the content of cyclic oligomers and the amount of increase are also small. It had physical properties suitable for the mold film.
比較例７にて得られたポリエステル樹脂組成物は、リン酸を添加していないため、ΔＣＯＯＨ／ＣＯＯＨ及び線状オリゴマー発生量、環状オリゴマー増加量が増加した。 In the polyester resin composition obtained in Comparative Example 7, since no phosphoric acid was added, ΔCOOH / COOH, the amount of linear oligomer generation, and the amount of cyclic oligomer increase were increased.
２５５℃にて溶解したビスヒドロキシエチルテレフタレート１０５重量部が仕込まれたエステル化反応器に、テレフタル酸８６重量部とエチレングリコール３７重量部（テレフタル酸に対し１．１５倍モル）からなるスラリーを徐々に添加し、エステル化反応を進行させた。反応系内の温度は２４５〜２５５℃になるようにコントロールし、反応率が９５％に到達した段階でエステル化反応を終了とした。
A slurry consisting of 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times the molar amount of terephthalic acid) was gradually added to an esterification reactor charged with 105 parts by weight of bishydroxyethyl terephthalate dissolved at 255 ° C. The esterification reaction was allowed to proceed. The temperature in the reaction system was controlled to be 245 to 255 ° C., and the esterification reaction was ended when the reaction rate reached 95%.
こうして得られた２５５℃のエステル化反応物１０５重量部（ＰＥＴ１００重量部相当）を重合装置に移送し、酢酸マンガン４水和物０．０１重量部のエチレングリコール溶液（マンガン元素として２３ｐｐｍ）、三酸化二アンチモン０．０１２重量部のエチレングリコールスラリー、水酸化カリウム０．０００８重量部のエチレングリコール溶液を添加した。その後、エチレングリコール５重量部（テレフタル成分対比０．１５倍モル）を追加添加して解重合を進め、次いでリン酸０．００６重量部とリン酸２水素ナトリウム２水和物０．００９５重量部（ナトリウム元素として１４ｐｐｍ）の混合エチレングリコール溶液を添加した。 105 parts by weight (equivalent to 100 parts by weight of PET) of the esterification reaction product at 255 ° C. thus obtained is transferred to a polymerization apparatus, and an ethylene glycol solution (23 ppm as manganese element) of 0.01 parts by weight of manganese acetate tetrahydrate An ethylene glycol slurry of 0.012 parts by weight of diantimony oxide and an ethylene glycol solution of 0.0008 parts by weight of potassium hydroxide were added. Thereafter, 5 parts by weight of ethylene glycol (0.15 times the molar amount of the terephthal component) is further added to proceed with depolymerization, and then 0.006 parts by weight of phosphoric acid and 0.0095 parts by weight of sodium dihydrogen phosphate dihydrate A mixed ethylene glycol solution (14 ppm as sodium element) was added.
その後、重合装置内温度を徐々に２９０℃まで昇温しながら、重合装置内圧力を常圧から１３３Ｐａ以下まで徐々に減圧してエチレングリコールを留出させた。固有粘度０．６２相当の溶融粘度に到達した時点で、反応を終了とし、反応系内を窒素ガスにて常圧にし、重合装置下部より冷水中にストランド状に吐出、カッティングし、ペレット状ポリマーを得た。得られたペレット状ポリマーを１６０℃で６時間乾燥、結晶化させ、真空度４０Ｐａ、２２０℃にて８時間固相重合を実施し、ポリエステル樹脂組成物を得た。得られたポリエステル樹脂組成物の特性を表４に示す。 Thereafter, while the temperature in the polymerization apparatus was gradually raised to 290 ° C., the pressure in the polymerization apparatus was gradually reduced from atmospheric pressure to 133 Pa or less to distill ethylene glycol. When reaching a melt viscosity equivalent to an intrinsic viscosity of 0.62, the reaction is terminated, the inside of the reaction system is brought to normal pressure with nitrogen gas, and it is discharged in cold water from the lower part of the polymerization apparatus into strands and cut. I got The obtained pellet-like polymer was dried at 160 ° C. for 6 hours for crystallization, and solid phase polymerization was carried out at 220 ° C. for 8 hours under vacuum of 40 Pa to obtain a polyester resin composition. The properties of the obtained polyester resin composition are shown in Table 4.
実施例１３で得られたポリエステル樹脂組成物は、ゲル化率および耐加水分解性が良好であり、線状オリゴマー発生量、環状オリゴマー含有量及び増加量も少ないことから、光学フィルムや離型フィルムに好適な物性を有していた。 The polyester resin composition obtained in Example 13 has good gelation rate and hydrolysis resistance, and the amount of linear oligomers generated, the content of cyclic oligomers and the amount of increase are also small, so an optical film or a release film is obtained. Physical properties suitable for
（実施例１４）
テレフタル酸ジメチル１０１．０重量部、エチレングリコール６４．６重量部（ジカルボン酸成分の２倍モル）の割合でそれぞれ計量し、エステル交換反応装置に仕込んだ。内容物を１５０℃で溶解した後、酢酸マンガン４水和物０．０１８重量部のエチレングリコール溶液（マンガン元素として４０ｐｐｍ）、三酸化二アンチモンを０．０１２重量部のエチレングリコールスラリー添加し撹拌した。２４０℃まで昇温しながらメタノールを留出させ、所定量のメタノールが留出した後、リン酸０．００６重量部とリン酸２水素ナトリウム２水和物０．００９５重量部（ナトリウム元素として１４ｐｐｍ）の混合エチレングリコール溶液を添加し、エステル交換反応を終了した。
(Example 14)
101.0 parts by weight of dimethyl terephthalate and 64.6 parts by weight of ethylene glycol (twice the molar amount of the dicarboxylic acid component) were respectively weighed and charged in a transesterification reactor. After dissolving the contents at 150 ° C, an ethylene glycol solution of 0.018 parts by weight of manganese acetate tetrahydrate (40 ppm as manganese element), 0.012 parts by weight of ethylene glycol slurry of diantimony trioxide was added and stirred. . Methanol is distilled while raising the temperature to 240 ° C., and a predetermined amount of methanol is distilled, and then 0.006 parts by weight of phosphoric acid and 0.0095 parts by weight of sodium dihydrogen phosphate dihydrate (14 ppm as a sodium element) The mixed ethylene glycol solution of) was added to complete the transesterification reaction.
その後、反応物を重合装置に移送し、次いで重合装置内温度を徐々に２９０℃まで昇温しながら、重合装置内圧力を常圧から１３３Ｐａ以下まで徐々に減圧してエチレングリコールを留出させた。固有粘度０．６２相当の溶融粘度に到達した時点で、反応を終了とし、反応系内を窒素ガスにて常圧にし、重合装置下部より冷水中にストランド状に吐出、カッティングし、ペレット状ポリマーを得た。得られたペレット状ポリマーを１６０℃で６時間乾燥、結晶化させ、真空度４０Ｐａ、２２０℃にて８時間固相重合を実施し、ポリエステル樹脂組成物を得た。得られたポリエステル樹脂組成物の特性を表４に示す。 Thereafter, the reaction product was transferred to the polymerization apparatus, and then while the temperature in the polymerization apparatus was gradually raised to 290 ° C., the pressure in the polymerization apparatus was gradually reduced from normal pressure to 133 Pa or less to distill ethylene glycol . When reaching a melt viscosity equivalent to an intrinsic viscosity of 0.62, the reaction is terminated, the inside of the reaction system is brought to normal pressure with nitrogen gas, and it is discharged in cold water from the lower part of the polymerization apparatus into strands and cut. I got The obtained pellet-like polymer was dried at 160 ° C. for 6 hours for crystallization, and solid phase polymerization was carried out at 220 ° C. for 8 hours under vacuum of 40 Pa to obtain a polyester resin composition. The properties of the obtained polyester resin composition are shown in Table 4.
実施例１４で得られたポリエステル樹脂組成物は、ゲル化率および耐加水分解性が良好であり、線状オリゴマー発生量、環状オリゴマー含有量及び増加量も少ないことから、光学フィルムや離型フィルムに好適な物性を有していた。 The polyester resin composition obtained in Example 14 is excellent in gelation rate and hydrolysis resistance, and the generation amount of linear oligomers, the content of cyclic oligomers and the amount of increase are also small. Physical properties suitable for
（比較例８）
２５５℃にて溶解したビスヒドロキシエチルテレフタレート１０５重量部が仕込まれたエステル化反応器に、テレフタル酸８６重量部とエチレングリコール３７重量部（テレフタル酸に対し１．１５倍モル）からなるスラリーを徐々に添加し、エステル化反応を進行させた。反応系内の温度は２４５〜２５５℃になるようにコントロールし、反応率が９５％に到達した段階でエステル化反応を終了とした。
(Comparative example 8)
A slurry consisting of 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times the molar amount of terephthalic acid) was gradually added to an esterification reactor charged with 105 parts by weight of bishydroxyethyl terephthalate dissolved at 255 ° C. The esterification reaction was allowed to proceed. The temperature in the reaction system was controlled to be 245 to 255 ° C., and the esterification reaction was ended when the reaction rate reached 95%.
こうして得られた２５５℃のエステル化反応物１０５重量部（ＰＥＴ１００重量部相当）を重合装置に移送し、酢酸マンガン４水和物０．０２重量部のエチレングリコール溶液（マンガン元素として４５ｐｐｍ）、三酸化二アンチモン０．０１２重量部のエチレングリコールスラリーを添加した。その後、エチレングリコール５重量部（テレフタル成分対比０．１５倍モル）を追加添加して解重合を進め、次いでリン酸０．００６重量部とリン酸２水素ナトリウム２水和物０．０１１重量部（ナトリウム元素として１６ｐｐｍ）の混合エチレングリコール溶液を添加した。その後、テトラブチルアンモニウムブロミド０．１重量部を添加した。 105 parts by weight (equivalent to 100 parts by weight of PET) of the esterification reaction product at 255 ° C. thus obtained is transferred to a polymerization apparatus, and an ethylene glycol solution (45 ppm as manganese element) of 0.02 parts by weight of manganese acetate tetrahydrate An ethylene glycol slurry of 0.012 parts by weight of diantimony oxide was added. Thereafter, 5 parts by weight of ethylene glycol (0.15 times the molar amount of the terephthal component) is further added to proceed with depolymerization, and then 0.006 parts by weight of phosphoric acid and 0.011 parts by weight of sodium dihydrogen phosphate dihydrate A mixed ethylene glycol solution (16 ppm as sodium element) was added. Thereafter, 0.1 parts by weight of tetrabutylammonium bromide was added.
その後、重合装置内温度を徐々に２９０℃まで昇温しながら、重合装置内圧力を常圧から１３３Ｐａ以下まで徐々に減圧してエチレングリコールを留出させた。固有粘度０．６２相当の溶融粘度に到達した時点で、反応を終了とし、反応系内を窒素ガスにて常圧にし、重合装置下部より冷水中にストランド状に吐出、カッティングし、ペレット状ポリマーを得た。得られたペレット状ポリマーを１６０℃で６時間乾燥、結晶化させ、真空度４０Ｐａ、２２０℃にて８時間固相重合を実施し、ポリエステル樹脂組成物を得た。得られたポリエステル樹脂組成物の特性を表４に示す。 Thereafter, while the temperature in the polymerization apparatus was gradually raised to 290 ° C., the pressure in the polymerization apparatus was gradually reduced from atmospheric pressure to 133 Pa or less to distill ethylene glycol. When reaching a melt viscosity equivalent to an intrinsic viscosity of 0.62, the reaction is terminated, the inside of the reaction system is brought to normal pressure with nitrogen gas, and it is discharged in cold water from the lower part of the polymerization apparatus into strands and cut. I got The obtained pellet-like polymer was dried at 160 ° C. for 6 hours for crystallization, and solid phase polymerization was carried out at 220 ° C. for 8 hours under vacuum of 40 Pa to obtain a polyester resin composition. The properties of the obtained polyester resin composition are shown in Table 4.
比較例８で得られたポリエステル樹脂組成物は、マンガン元素及び窒素元素、ハロゲン元素を多量に含有していることから、ΔＣＯＯＨ／ＣＯＯＨ及び線状オリゴマー発生量が増加した。 Since the polyester resin composition obtained in Comparative Example 8 contained a large amount of manganese element, nitrogen element and halogen element, ΔCOOH / COOH and linear oligomer generation amount increased.
（比較例９）
２５５℃にて溶解したビスヒドロキシエチルテレフタレート１０５重量部が仕込まれたエステル化反応器に、テレフタル酸８６重量部とエチレングリコール３７重量部（テレフタル酸に対し１．１５倍モル）からなるスラリーを徐々に添加し、エステル化反応を進行させた。反応系内の温度は２４５〜２５５℃になるようにコントロールし、反応率が９５％に到達した段階でエステル化反応を終了とした。
(Comparative example 9)
A slurry consisting of 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times the molar amount of terephthalic acid) was gradually added to an esterification reactor charged with 105 parts by weight of bishydroxyethyl terephthalate dissolved at 255 ° C. The esterification reaction was allowed to proceed. The temperature in the reaction system was controlled to be 245 to 255 ° C., and the esterification reaction was ended when the reaction rate reached 95%.
こうして得られた２５５℃のエステル化反応物１０５重量部（ＰＥＴ１００重量部相当）を重合装置に移送し、酢酸マンガン４水和物０．０２重量部のエチレングリコール溶液（マンガン元素として４５ｐｐｍ）、三酸化二アンチモン０．０１２重量部のエチレングリコールスラリーを添加した。その後、エチレングリコール５重量部（テレフタル成分対比０．１５倍モル）を追加添加して解重合を進め、次いでリン酸０．００６重量部とリン酸２水素ナトリウム２水和物０．０１１重量部（ナトリウム元素として１６ｐｐｍ）の混合エチレングリコール溶液を添加した。その後、テトラブチルアンモニウムメタンスルホネート０．１重量部を添加した。 105 parts by weight (equivalent to 100 parts by weight of PET) of the esterification reaction product at 255 ° C. thus obtained is transferred to a polymerization apparatus, and an ethylene glycol solution (45 ppm as manganese element) of 0.02 parts by weight of manganese acetate tetrahydrate An ethylene glycol slurry of 0.012 parts by weight of diantimony oxide was added. Thereafter, 5 parts by weight of ethylene glycol (0.15 times the molar amount of the terephthal component) is further added to proceed with depolymerization, and then 0.006 parts by weight of phosphoric acid and 0.011 parts by weight of sodium dihydrogen phosphate dihydrate A mixed ethylene glycol solution (16 ppm as sodium element) was added. Thereafter, 0.1 parts by weight of tetrabutylammonium methanesulfonate was added.
その後、重合装置内温度を徐々に２９０℃まで昇温しながら、重合装置内圧力を常圧から１３３Ｐａ以下まで徐々に減圧してエチレングリコールを留出させた。固有粘度０．６２相当の溶融粘度に到達した時点で、反応を終了とし、反応系内を窒素ガスにて常圧にし、重合装置下部より冷水中にストランド状に吐出、カッティングし、ペレット状ポリマーを得た。得られたペレット状ポリマーを１６０℃で６時間乾燥、結晶化させ、真空度４０Ｐａ、２２０℃にて８時間固相重合を実施し、ポリエステル樹脂組成物を得た。得られたポリエステル樹脂組成物の特性を表４に示す。 Thereafter, while the temperature in the polymerization apparatus was gradually raised to 290 ° C., the pressure in the polymerization apparatus was gradually reduced from atmospheric pressure to 133 Pa or less to distill ethylene glycol. When reaching a melt viscosity equivalent to an intrinsic viscosity of 0.62, the reaction is terminated, the inside of the reaction system is brought to normal pressure with nitrogen gas, and it is discharged in cold water from the lower part of the polymerization apparatus into strands and cut. I got The obtained pellet-like polymer was dried at 160 ° C. for 6 hours for crystallization, and solid phase polymerization was carried out at 220 ° C. for 8 hours under vacuum of 40 Pa to obtain a polyester resin composition. The properties of the obtained polyester resin composition are shown in Table 4.
比較例９で得られたポリエステル樹脂組成物は、マンガン元素及び窒素元素、硫黄元素を多量に含有していることから、ΔＣＯＯＨ／ＣＯＯＨ及び線状オリゴマー発生量が増加した。 Since the polyester resin composition obtained in Comparative Example 9 contained a large amount of manganese element, nitrogen element and sulfur element, ΔCOOH / COOH and linear oligomer generation amount increased.
（比較例１０）
２５５℃にて溶解したビスヒドロキシエチルテレフタレート１０５重量部が仕込まれたエステル化反応器に、テレフタル酸８６重量部とエチレングリコール３７重量部（テレフタル酸に対し１．１５倍モル）からなるスラリーを徐々に添加し、エステル化反応を進行させた。反応系内の温度は２４５〜２５５℃になるようにコントロールし、反応率が９５％に到達した段階でエステル化反応を終了とした。
(Comparative example 10)
A slurry consisting of 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times the molar amount of terephthalic acid) was gradually added to an esterification reactor charged with 105 parts by weight of bishydroxyethyl terephthalate dissolved at 255 ° C. The esterification reaction was allowed to proceed. The temperature in the reaction system was controlled to be 245 to 255 ° C., and the esterification reaction was ended when the reaction rate reached 95%.
こうして得られた２５５℃のエステル化反応物１０５重量部（ＰＥＴ１００重量部相当）を重合装置に移送し、酢酸マンガン４水和物０．０１重量部のエチレングリコール溶液（マンガン元素として２３ｐｐｍ）、三酸化二アンチモン０．０１２重量部のエチレングリコールスラリーを添加した。その後、エチレングリコール５重量部（テレフタル成分対比０．１５倍モル）を追加添加して解重合を進め、次いでリン酸０．００６重量部とリン酸２水素ナトリウム２水和物０．００９５重量部（ナトリウム元素として１４ｐｐｍ）の混合エチレングリコール溶液を添加した。その後、テトラブチルアンモニウムメタンスルホネート０．１重量部を添加した。 105 parts by weight (equivalent to 100 parts by weight of PET) of the esterification reaction product at 255 ° C. thus obtained is transferred to a polymerization apparatus, and an ethylene glycol solution (23 ppm as manganese element) of 0.01 parts by weight of manganese acetate tetrahydrate An ethylene glycol slurry of 0.012 parts by weight of diantimony oxide was added. Thereafter, 5 parts by weight of ethylene glycol (0.15 times the molar amount of the terephthal component) is further added to proceed with depolymerization, and then 0.006 parts by weight of phosphoric acid and 0.0095 parts by weight of sodium dihydrogen phosphate dihydrate A mixed ethylene glycol solution (14 ppm as sodium element) was added. Thereafter, 0.1 parts by weight of tetrabutylammonium methanesulfonate was added.
その後、重合装置内温度を徐々に２９０℃まで昇温しながら、重合装置内圧力を常圧から１３３Ｐａ以下まで徐々に減圧してエチレングリコールを留出させた。固有粘度０．６２相当の溶融粘度に到達した時点で、反応を終了とし、反応系内を窒素ガスにて常圧にし、重合装置下部より冷水中にストランド状に吐出、カッティングし、ペレット状ポリマーを得た。得られたペレット状ポリマーを１６０℃で６時間乾燥、結晶化させ、真空度４０Ｐａ、２２０℃にて８時間固相重合を実施し、ポリエステル樹脂組成物を得た。得られたポリエステル樹脂組成物の特性を表４に示す。
比較例１０で得られたポリエステル樹脂組成物は、窒素元素及び硫黄元素を多量に含有していることから、ΔＣＯＯＨ／ＣＯＯＨ及び線状オリゴマー発生量が増加した。
Thereafter, while the temperature in the polymerization apparatus was gradually raised to 290 ° C., the pressure in the polymerization apparatus was gradually reduced from atmospheric pressure to 133 Pa or less to distill ethylene glycol. When reaching a melt viscosity equivalent to an intrinsic viscosity of 0.62, the reaction is terminated, the inside of the reaction system is brought to normal pressure with nitrogen gas, and it is discharged in cold water from the lower part of the polymerization apparatus into strands and cut. I got The obtained pellet-like polymer was dried at 160 ° C. for 6 hours for crystallization, and solid phase polymerization was carried out at 220 ° C. for 8 hours under vacuum of 40 Pa to obtain a polyester resin composition. The properties of the obtained polyester resin composition are shown in Table 4.
Since the polyester resin composition obtained in Comparative Example 10 contained a large amount of nitrogen and sulfur elements, the amount of ΔCOOH / COOH and the amount of linear oligomers increased.
Claims (10)
線状オリゴマー発生量≦９００ｐｐｍ （Ｉ）
環状オリゴマー含有量≦０．６ｗｔ％ （ＩＩ）
５ｐｐｍ≦Ｍｎ含有量≦４０ｐｐｍ （ＩＩＩ）
４ｐｐｍ≦Ｎａ含有量≦６０ｐｐｍ （ＩＶ） The polyester resin composition characterized by satisfy | filling following formula (I)-(IV).
Linear oligomer generation amount ≦ 900 ppm (I)
Cyclic oligomer content ≦ 0.6 wt% (II)
5 ppm ≦ Mn content ≦ 40 ppm (III)
4 ppm ≦ Na content ≦ 60 ppm (IV)
５ｐｐｍ≦Ｍｎ含有量≦４０ｐｐｍ （Ｖ）
４ｐｐｍ≦アルカリ金属元素含有量≦６０ｐｐｍ （ＶＩ） When the dicarboxylic acid component or the ester-forming derivative component thereof and the diol component are subjected to esterification reaction or transesterification reaction, and then melt polymerization and solid phase polymerization to produce a polyester, the IV (inherent viscosity) of the polyester is 0. Manganese compound is added at 4 or less stages, phosphoric acid and alkali metal phosphate are added at the stage until completion of polycondensation reaction, and the content satisfies the following formulas (V) and (VI) The manufacturing method of the polyester resin composition characterized by the above.
5 ppm ≦ Mn content ≦ 40 ppm (V)
4 ppm ≦ alkali metal content ≦ 60 ppm (VI)
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