JP4127119B2 - Production method of polyester resin - Google Patents
Production method of polyester resin Download PDFInfo
- Publication number
- JP4127119B2 JP4127119B2 JP2003148944A JP2003148944A JP4127119B2 JP 4127119 B2 JP4127119 B2 JP 4127119B2 JP 2003148944 A JP2003148944 A JP 2003148944A JP 2003148944 A JP2003148944 A JP 2003148944A JP 4127119 B2 JP4127119 B2 JP 4127119B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- melt
- less
- phase polycondensation
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920001225 polyester resin Polymers 0.000 title claims description 68
- 239000004645 polyester resin Substances 0.000 title claims description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 238000006068 polycondensation reaction Methods 0.000 claims description 169
- 239000007790 solid phase Substances 0.000 claims description 134
- 229920000642 polymer Polymers 0.000 claims description 119
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 81
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 64
- 239000000155 melt Substances 0.000 claims description 47
- 238000006116 polymerization reaction Methods 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 16
- 150000002009 diols Chemical class 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 238000005886 esterification reaction Methods 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000007334 copolymerization reaction Methods 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000005809 transesterification reaction Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims 7
- 238000010791 quenching Methods 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 description 33
- 239000002994 raw material Substances 0.000 description 31
- 238000004458 analytical method Methods 0.000 description 21
- -1 polyethylene terephthalate Polymers 0.000 description 20
- 229920000728 polyester Polymers 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- JHAFEVXNMDQGTR-UHFFFAOYSA-L C(C(=O)[O-])(=O)[O-].[Ge+2] Chemical compound C(C(=O)[O-])(=O)[O-].[Ge+2] JHAFEVXNMDQGTR-UHFFFAOYSA-L 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- GGHTWSNOKADVAG-UHFFFAOYSA-N butan-1-olate germanium(4+) Chemical compound [Ge+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] GGHTWSNOKADVAG-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 2
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 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
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CTCOPPBXAFHGRB-UHFFFAOYSA-N ethanolate;germanium(4+) Chemical compound [Ge+4].CC[O-].CC[O-].CC[O-].CC[O-] CTCOPPBXAFHGRB-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002291 germanium compounds Chemical class 0.000 description 2
- 229940119177 germanium dioxide Drugs 0.000 description 2
- GGQZVHANTCDJCX-UHFFFAOYSA-N germanium;tetrahydrate Chemical compound O.O.O.O.[Ge] GGQZVHANTCDJCX-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 2
- UKGJZDSUJSPAJL-YPUOHESYSA-N (e)-n-[(1r)-1-[3,5-difluoro-4-(methanesulfonamido)phenyl]ethyl]-3-[2-propyl-6-(trifluoromethyl)pyridin-3-yl]prop-2-enamide Chemical compound CCCC1=NC(C(F)(F)F)=CC=C1\C=C\C(=O)N[C@H](C)C1=CC(F)=C(NS(C)(=O)=O)C(F)=C1 UKGJZDSUJSPAJL-YPUOHESYSA-N 0.000 description 1
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- ZVMAGJJPTALGQB-UHFFFAOYSA-N 2-[3-(carboxymethoxy)phenoxy]acetic acid Chemical compound OC(=O)COC1=CC=CC(OCC(O)=O)=C1 ZVMAGJJPTALGQB-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229930183415 Suberin Natural products 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- QUVFJPHBBVJLSA-UHFFFAOYSA-N [Sb].C=C.C=C.C=C.[Sb] Chemical class [Sb].C=C.C=C.C=C.[Sb] QUVFJPHBBVJLSA-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical class [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 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 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- FJTUUPVRIANHEX-UHFFFAOYSA-N butan-1-ol;phosphoric acid Chemical compound CCCCO.OP(O)(O)=O FJTUUPVRIANHEX-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- 150000003606 tin compounds Chemical class 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-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
- 238000000193 wide-angle powder X-ray diffraction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明はポリエステル樹脂の製造方法に関するものである。更に詳しくは、ポリエステルの固相重縮合を極めて高速に実施する方法に関するものである。
【０００２】
【従来の技術】
ポリエステル樹脂、中でもテレフタル酸とエチレングリコールを原料として製造されるポリエチレンテレフタレート（以下ＰＥＴと略すことがある）は数多くの材料および製品、例えば繊維、生地、成形用樹脂および飲料用ボトルなどで幅広く用いられている。
上記用途に必要な成形加工性、機械的特性を引き出すためには、ポリエステル樹脂の重合度を所定のレベルまで上げる必要があり、その方法としてポリエステル原料を溶融重縮合することにより比較的高い粘度を有する重縮合品を得て、引き続き該重縮合品を固相重縮合する方法が工業的に広く用いられている。しかしながら、かかる従来法における固相重縮合は比較的長時間を要するために、より生産性に優れた製造方法が望まれている。
生産性の改良されたポリエステル樹脂の製造方法として、ポリエステル原料モノマーの溶融重縮合で比較的低重合度の溶融重合ポリマーを得て、この溶融重合ポリマーを固相重縮合する方法が提案されている。例えば特表平１０−５１２６０８号公報（WO96/22319）には、溶融重縮合で得られた平均重合度約５から約３５（固有粘度約０．１０から０．３６dl/g）の低重合度溶融重合ポリマーを、結晶子サイズが９nm以上となるように結晶化させてから固相重縮合する方法が開示されている。この方法によれば、重縮合をより高い温度、例えば２３０℃、好適には２４０℃で出発して直接行うことが可能になるとされている。しかしながら、我々の検討によれば、固相重縮合スタート時の重合度が低すぎるためかあるいは結晶が成長して分子の移動を抑制するためか、理由は不明なるも必ずしも満足な固相重縮合速度は得られない。
【０００３】
一方、USP６２８４８６６号公報には、低温でのヘーズの少ないボトル用の共重合ポリエステルとして、ジカルボン酸成分の共重合量（モル％）とジオール成分の共重合量（モル％）の和が６以上のポリエステルであって固有粘度が０．２５から０．４０dl/gの溶融重合ポリマーを特定条件下で固相重縮合する方法が開示されている。しかしながら、該公報の方法では、固相重縮合を、rotary-vacumn tumble dryerを用いて行っており、高真空状態での固相重縮合であるため、工業的に必ずしも有利ではない。又、我々の検討によれば、共重合成分が多いために溶融重合ポリマーの融点が比較的低く、従って高真空でない場合には、固相重縮合温度を高く設定できないため固相重縮合速度が遅く効率的とはいえない。
【０００４】
【発明が解決しようとする課題】
本発明は、ポリエステルの固相重縮合を極めて高速に実施し、よってポリエステルを生産性良好に製造する方法を提供することを目的とする。更に、本発明は、高真空等の特殊な条件を採用しなくても高速でポリエステルの固相重縮合が可能であり、しかも得られるポリエステル樹脂同士の融着、或いは反応装置へのポリエステル樹脂の付着等の取り扱い性の問題なくポリエステルを生産性良好に製造する方法を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明者は上記課題を解決するため鋭意検討を行った結果、固相重合に供する溶融重合ポリマーの共重合量、固有粘度、見かけ結晶子サイズ、及び固相重縮合温度をコントロールして固相重縮合を行うことにより、上記目的を達成することを見いだし本発明に到達した。
【０００６】
即ち、本発明の要旨はテレフタル酸又はそのエステル形成性誘導体を主成分とするジカルボン酸成分と、エチレングリコールを主成分とするジオール成分とを、エステル化反応或いはエステル交換反応を経て重縮合させることにより製造された溶融重合ポリマーを固相重縮合してポリエステル樹脂を製造する方法に於いて、（１）テレフタル酸成分およびエチレングリコール成分以外の共重合成分量が５．５以下、固有粘度が０．０８ｄｌ／ｇ以上０．５０ｄｌ／ｇ以下、かつ見掛け結晶子サイズが9nm未満の溶融重合ポリマーを得、２）該溶融重合ポリマーの固相重縮合温度への昇温を固相重縮合後のポリエステル樹脂の見掛け結晶サイズが９ｎｍ未満を維持するようにコントロールしつつ行い、（３）該溶融重合ポリマーを、該溶融重合ポリマーのガラス転移温度より１４０℃高い温度以上、融点以下の温度で固相重縮合することにより、見掛け結晶子サイズ9nm未満のポリエステル樹脂を得る、ことを特徴とするポリエステル樹脂の製造方法、に存する。
他の要旨は、テレフタル酸又はそのエステル形成性誘導体を主成分とするジカルボン酸成分と、エチレングリコールを主成分とするジオール成分とを、エステル化反応或いはエステル交換反応を経て重縮合させることにより製造された溶融重合ポリマーを固相重縮合してポリエステル樹脂を製造する方法に於いて、（１）テレフタル酸成分およびエチレングリコール成分以外の共重合成分量が５．５以下、固有粘度が０．０８〜０．５０ｄｌ／ｇ、かつ見掛け結晶子サイズが9nm未満の溶融重合ポリマーを、（２）該溶融重合ポリマーの固相重縮合温度への昇温を固相重縮合後のポリエステル樹脂の見掛け結晶サイズが９ｎｍ未満を維持するようにコントロールしつつ行い、（３）該溶融重合ポリマーの見掛け結晶子サイズを9nm未満に維持した状態で、該溶融重合ポリマーのガラス転移温度より１４０℃高い温度以上、融点以下の温度で固相重縮合する、ことを特徴とするポリエステル樹脂の製造方法、に存する。
【０００７】
【発明の実施の形態】
本発明のポリエステル樹脂の製造方法における溶融重合ポリマーは、テレフタル酸またはそのエステル形成性誘導体を主成分とするジカルボン酸成分と、エチレングリコールを主成分とするジオール成分とを、エステル化反応またはエステル交換反応させた後溶融重縮合反応をさせることにより製造されたエチレンテレフタレート単位を主たる構成繰り返し単位とする溶融重合ポリマーであり、該ポリエステル樹脂のテレフタル酸成分およびエチレングリコール成分以外の共重合成分量が５．５以下であるものをいう。ここで、テレフタル酸成分およびエチレングリコール成分以外の共重合成分量が５．５以下とは、全ジカルボン酸成分に対するテレフタル酸又はそのエステル形成性誘導体以外の成分の量比（モル％）をＡ、全ジオール成分に対するエチレングリコール以外のジオール成分の量比（モル％）をＢとしたとき、Ａ＋Ｂが５．５以下であることを示す。該共重合成分量は、好ましくは４．５以下である。共重合成分量が５．５を越えると、ポリエステル樹脂の融点が低下することとなり、固相重縮合温度に制約が生じるため重縮合速度が遅くなり、又、耐熱性が劣るためポリエステル樹脂の成型時、特に強度、耐熱性を向上させるために延伸、ヒートセットを施す場合、延伸、ヒートセットの効果が十分に発揮されないこととなる。
【０００８】
テレフタル酸のエステル形成性誘導体としては、テレフタル酸ジメチルエステル等テレフタル酸の炭素数１〜４程度のアルキルエステルおよびハロゲン化物などがあげられる。テレフタル酸またはそのエステル形成性誘導体以外のジカルボン酸としては、フタル酸、イソフタル酸、１，３-フェニレンジオキシジ酢酸、４，４’−ジフェニルジカルボン酸、４，４’−ジフェニルエーテルジカルボン酸、４，４’−ジフェニルケトンジカルボン酸、４，４’−ジフェノキシエタンジカルボン酸、４，４’−ジフェニルスルホンジカルボン酸、２，６−ナフタレンジカルボン酸等の芳香族ジカルボン酸；２，６−ナフタレンジカルボン酸ジメチルエステル等の、芳香族ジカルボン酸の炭素数１〜４程度のアルキルエステル、およびハロゲン化物；ヘキサヒドロテレフタル酸等の脂環式ジカルボン酸；コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカンジカルボン酸、ドデカンジカルボン酸等の脂肪族ジカルボン酸；並びに、これらの脂環式ジカルボン酸や脂肪族ジカルボン酸の炭素数１〜４程度のアルキルエステル、およびハロゲン化物等が挙げられる。
【０００９】
エチレングリコール以外のジオールとしては、例えばトリメチレングリコール、テトラメチレングリコール、ヘキサメチレングリコール、デカメチレングリコール、ネオペンチルグリコール、２−エチル−２−ブチル−１，３−プロパンジオール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリテトラメチレンエーテルグリコール等の脂肪族ジオール、１，４−シクロヘキサンジオール、１，４−シクロヘキサンジメチロール、等の脂環式ジオール、及び、キシリレングリコール、等の芳香族ジオール、並びに、２，２−ビス（４’−ヒドロキシフェニル）プロパンのエチレンオキサイド付加物またはプロピレンオキサイド付加物等が挙げられる。
【００１０】
更に、例えば、ステアリルアルコール、ステアリン酸、安息香酸、等の単官能成分、トリメリット酸、トリメシン酸、ピロメリット酸、トリメチロールエタン、トリメチロールプロパン、グリセロール、ペンタエリスリトール等の三官能以上の多官能成分、等の一種または二種以上が、共重合成分として用いられていてもよい。
【００１１】
本発明の溶融重合ポリマーの共重合量が上記範囲であることから、テレフタル酸又はそのエステル形成性誘導体の、全ジカルボン酸成分に対する割合は、９４．５モル％以上が好ましく、更に９６モル％以上が好ましく、一方、エチレングリコールの全ジオール成分に対する割合は９４．５モル％以上が好ましく、更に９６モル％以上が好ましい。
【００１２】
本発明における溶融重合ポリマーは、基本的には、ポリエステル樹脂の慣用の製造方法により製造される。すなわち、前記テレフタル酸またはそのエステル形成性誘導体を主成分とするジカルボン酸とエチレングリコールを主成分とするジオールとを、通常、ジカルボン酸：ジオールを１：１〜１：２（モル比）の割合で使用し、エステル化反応槽で、通常２４０〜２８０℃程度の温度、通常、常圧ないし０．４ＭＰａ程度の加圧下で、攪拌下に１〜１０時間程度でエステル化反応させ、或いは、エステル交換反応触媒の存在下にエステル交換反応させた後、得られたエステル化反応生成物或いはエステル交換反応生成物としてのポリエステル低分子量体を重縮合槽に移送し、重縮合触媒の存在下に、通常２５０〜２９０℃程度の温度、常圧から漸次減圧として最終的に通常１３３３〜１３．３Ｐａ程度の減圧下で、攪拌下に、固有粘度が０．０８〜０．５０dl/gの範囲となる時間、通常、０．５〜５時間程度溶融重縮合させることにより製造される。但し、上記の如く、本発明の溶融重合ポリマーは、テレフタル酸成分およびエチレングリコール成分以外の共重合成分量が５．５以下であることにより、本発明においては、テレフタル酸成分、エチレングリコール成分、及びテレフタル酸成分およびエチレングリコール成分以外の共重合成分を、該共重合成分量が５．５以下で使用する。
上記反応は、連続式、または回分式でなされるが、連続式が好ましい。またエステル化反応槽および重縮合槽はそれぞれ一段としても多段としてもよい。また上述のポリエステル低分子量体を粒体化して溶融重合ポリマーとして固相重縮合にかける場合は溶融重縮合を省略することもできる。
【００１３】
上記エステル化反応においては特に触媒を使用しなくてもよいが必要に応じて、二酸化ゲルマニウム、四酸化ゲルマニウム、水酸化ゲルマニウム、蓚酸ゲルマニウム、ゲルマニウムテトラエトキシド、ゲルマニウムテトラ−ｎ−ブトキシド等のゲルマニウム化合物、三酸化アンチモン、五酸化アンチモン、酢酸アンチモン、アンチモントリスエチレングリコキシド等のアンチモン化合物、チタニウムテトラエトキシド、チタニウムテトラ−ｎ−プロポキシド、チタニウムテトラ−ｉ−プロポキシド、チタニウムテトラ−ｎ−ブトキシド、蓚酸チタン、蓚酸チタンカリウム等のチタン化合物などの公知の触媒を用いることもできる。
【００１４】
エステル交換反応触媒としてはチタン、マグネシウム、カルシウム、マンガン、リチウム、亜鉛などの金属の化合物のうちから一種または複数種が使用される。具体的には、これら金属の有機酸塩、アルコラート、炭酸塩などが挙げられる。なかでも酢酸マグネシウム、酢酸カルシウム、酢酸マンガン、酢酸リチウムなどが好ましく用いられる。エステル交換反応触媒の使用量は、通常、該触媒に由来する金属原子としての含有量が、得られるポリエステル樹脂に対して、通常、１〜２００ppm程度となる量である。
【００１５】
重縮合反応触媒としては二酸化ゲルマニウム、四酸化ゲルマニウム、水酸化ゲルマニウム、蓚酸ゲルマニウム、ゲルマニウムテトラエトキシド、ゲルマニウムテトラ−ｎ−ブトキシド等のゲルマニウム化合物、三酸化アンチモン、五酸化アンチモン、酢酸アンチモン、アンチモントリスエチレングリコキシド等のアンチモン化合物、チタニウムテトラエトキシド、チタニウムテトラ−ｎ−プロポキシド、チタニウムテトラ−ｉ−プロポキシド、チタニウムテトラ−ｎ−ブトキシド、蓚酸チタン、蓚酸チタンカリウム等のチタン化合物、蟻酸コバルト、酢酸コバルト、ステアリン酸コバルト、蓚酸コバルト、炭酸コバルト、臭化コバルト等のコバルト化合物、酢酸錫、蓚酸錫、臭化錫等の錫化合物等が用いられ、これらは単独で、もしくは２種以上併せて使用される。好ましくはゲルマニウ、アンチモン及びチタンから選ばれる少なくとも１種の金属の酸化物、無機酸塩、有機酸塩、アルコラート化合物が使用される。重縮合反応触媒の使用量は、通常、該触媒に由来する金属原子としての含有量が、得られるポリエステル樹脂に対して、通常、１〜５００ppm程度となる量である。
【００１６】
またエステル化反応またはエステル交換反応、および重縮合反応時には、安定剤としてトリメチルホスフェート、トリエチルホスフェート、トリ−ｎ−ブチルホスフェート、トリオクチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェートなどのリン酸エステル類、トリフェニルホスファイト、トリスドデシルホスファイト、トリスノニルフェニルホスファイトなどの亜リン酸エステル類、メチルアシッドホスフェート、エチルアシッドホスフェート、イソプロピルアシッドホスフェート、ブチルアシッドホスフェート、ジブチルホスフェート、モノブチルホスフェート、ジオクチルホスフェートなどの酸性リン酸エステル、およびリン酸、亜リン酸、次亜リン酸、ポリリン酸などのリン化合物を、またエーテル結合生成抑制剤としてトリエチルアミン、トリ−ｎ−ブチルアミン、ベンジルジメチルアミン等の第三級アミン、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、水酸化トリメチルベンジルアンモニウム等の水酸化第四級アンモニウム、または炭酸リチウム、炭酸ナトリウム、炭酸カリウム、酢酸ナトリウム、酢酸マグネシウム等の塩基性化合物を共存させることができる。
【００１７】
リン化合物の使用量は、リン化合物に由来するリン原子としての含有量が、得られるポリエステル樹脂に対して、通常、１〜２００ppm程度となる量である。尚、上記触媒及び添加剤の中で、特にチタン化合物、マグネシウム化合物、リン化合物を併用することが好ましく、そのときの使用割合としては下記の範囲が挙げられる。
Ｔ ：０．０２〜０．６モル（対ポリエステル樹脂１トン中）
Ｍ ：０．０４〜０．６モル（対ポリエステル樹脂１トン中）
Ｐ ：０．０２〜４モル（対ポリエステル樹脂１トン中）
（但し、Ｔ：チタン原子の総量、Ｍ：マグネシウム原子の総量、Ｐ：リン原子の総量）
又、触媒及び添加剤の好ましい組み合わせ、及び使用割合としては、例えば、 EP1273610-A1 に記載されているものが挙げられる。
溶融重縮合により得られた溶融重合ポリマーは、重縮合槽の底部に設けられた細孔から外部へ噴射し微小粒体としても良いし、重縮合槽の底部に設けられた抜き出し口から空気中又は水中に液滴状粒体として抜き出しても良い。またストランド状に抜き出して、水冷しながらもしくは水冷後、カッターで切断されてペレット状粒体としても良い。更に、得られたペレットを粉砕して更に粒径を細かな粒体としても良い。本発明においては、上で述べたいずれの方法においても、その結晶構造を成長させないためにできるだけ速やかに溶融状態から室温まで冷却することが重要である。具体的には溶融状態からできるだけ早く比熱が高く、温度の低い流体、例えば水と接触させるという方法を挙げることができる。
【００１８】
本発明においては、上記の如くして得られた溶融重合ポリマーを固相重縮合によりポリエステル樹脂を製造するが、冷却によって得られた、固相重縮合に供する溶融重合ポリマーの見かけ結晶子サイズ（ＡＣＳ010）は９ｎｍ未満であり、好ましくは８ｎｍ以下、更に好ましくは７ｎｍ以下である。溶融重合ポリマーの見かけ結晶子サイズが９ｎｍ以上であると固相重縮合速度が遅くなる。尚、溶融重合ポリマーの結晶子サイズは固相重縮合における初期反応速度をできるだけ速く保つという観点から小さい程好ましく、下限は０である。
尚、ここでいう見掛け結晶子サイズとは、結晶構造の大きさを表すパラメータであり、広角Ｘ線回折スペクトル解析より求まる（０１０）反射に関する見掛け結晶子サイズ（ＡＣＳ010）を意味する。
【００１９】
又、本発明の溶融重合ポリマーの固有粘度は、０．０８ｄｌ／ｇ以上０．５０ｄｌ／ｇ以下である。好ましくは、０．１ｄｌ／ｇ以上、更に好ましくは０．１５ｄｌ／ｇ以上、特に好ましくは0.20ｄｌ／ｇ以上であり、一方、０．４５ｄｌ／ｇ以下が好ましく、特に0.40ｄｌ／ｇ以下が好ましい。固有粘度が０．０８ｄｌ／ｇ未満では、引き続き行う固相重縮合での重縮合速度が著しく遅くなり、０．５０ｄｌ／ｇより高いと、その固有粘度まで上昇させるための溶融重縮合装置が高価になる上に、その重合度まで上昇させるための溶融重縮合に時間がかかるため、生産に要する時間が長くなる。
【００２０】
溶融重合ポリマーの見かけ結晶子サイズを上記範囲にコントロールするには、上述のように、溶融状態の溶融重合ポリマーを速やかに冷却すること、即ち、冷却速度をできるだけ速くする方法が挙げられる。該冷却速度は、溶融重合ポリマーの分子量により結晶化速度が異なるので一概に規定できないが、溶融状態から溶融重合ポリマーの結晶化温度以下まで、１０秒以内、好ましくは５秒以内、さらに好ましくは１秒以内に冷却すればよい。又、固有粘度を上記範囲にコントロールするには、重縮合温度、時間、減圧度をコントロールすることにより行われる。 本発明記載の溶融重合ポリマーの固有粘度範囲は、通常用いられる溶融重合ポリマーの粘度範囲より低いためより低温、短時間、弱い減圧度で到達可能であり、副反応が抑えられるため、製品品質が良好であり、又、プロセスが簡略化できるため低コストで製造が可能であるメリットもある。
【００２１】
又、溶融重合ポリマーの酸価は、通常１０から１０００ｍｍｏｌ／ｋｇの範囲であり、環状三量体の含有量は、通常、４０００以上１２０００ｐｐｍ以下の範囲である。
尚、固相重縮合に供される溶融重合ポリマー粒体の平均粒径は１０μｍ以上が好ましく、５０μｍ以上が更に好ましく、特に１００μｍ以上が好ましい。一方、１５００μｍ以下が好ましく、更に１３００μｍ以下が好ましく、１０００μｍ以下が更に好ましく、特に５００μｍ以下が好ましい。平均粒径が１５００μｍを越えると固相重縮合速度が遅くなる傾向があり、また平均粒径が１０μｍ未満であると空中への飛散が起こりやすくなる問題が生じる傾向がある。
【００２２】
上記の如くして得られた、テレフタル酸成分およびエチレングリコール成分以外の共重合成分量が５．５以下、固有粘度が０．０８〜０．５０ｄｌ／ｇ、かつ見かけ結晶子サイズ（ＡＣＳ010）は９ｎｍ未満の溶融重合ポリマーは、引き続き、見かけ結晶子サイズ（ＡＣＳ010）を９ｎｍ未満に保った状態、好ましくはＡＣＳ010が８ｎｍ以下の溶融重合ポリマーを、ＡＣＳ010を８ｎｍ以下に保った状態、更に好ましくは７ｎｍ以下に保った状態で固相重縮合する。尚、固相重縮合をＡＣＳ010を9nm未満に保った状態で行っていることは、固相重縮合後のポリエステルのＡＣＳ010が9nm未満であることにより確認できる。又、ＡＣＳ010を８ｎｍ以下に保った状態で行っていることは、固相重縮合後のポリエステルのＡＣＳ010が８ｎｍ以下であることにより確認できる。
尚、溶融重合ポリマーの固相重縮合温度への昇温条件により、例えば、昇温速度の選定や、例えば１９０℃以下の温度に一定時間保つ等により、固相重縮合温度に到達する昇温過程において、溶融重合ポリマー表面の結晶化が進行することもあるが、適度な結晶化は反応機への付着や、溶融重合ポリマー同士の融着による固相重縮合速度低下が防止できる傾向がある。該昇温過程において、溶融重合ポリマー表面の結晶化を行う場合であっても、引き続き行う固相重縮合速度の低下を極力抑えるため、必要最低限の熱履歴にとどめ、固相重縮合後のポリエステル樹脂の見掛け結晶子サイズが９ｎｍ未満を維持するようにコントロールする。
【００２３】
本発明の固相重縮合温度は、溶融重合ポリマーのガラス転移温度より１４０℃高い温度以上、融点以下である。好ましくは、溶融重合ポリマーのガラス転移温度より１４５℃高い温度以上融点以下の温度であり、更に好ましくは溶融重合ポリマーのガラス転移温度より１５０℃高い温度以上、特に好ましくは１６０℃高い温度以上であり、溶融重合ポリマーの融点以下の温度である。上記範囲で固相重縮合を行うことにより、結晶化の進行を最小限におさえながら効率よく固相重縮合を進めることができる。固相重縮合温度が上記未満では、重縮合速度が遅く、生産性が劣ることとなり、上記範囲を越えると、溶融重合ポリマーの溶融により、該ポリマー同士の融着や該ポリマーが反応機に付着する等の問題が生じ、製品品質或いは生産性に問題を生じる。固相重縮合は、通常、不活性ガス雰囲気下で行われ、必要に応じ溶融重合ポリマー粒体同士が粘着しないように流動等させながら、１０時間程度以下の時間で行われる。尚、ここで言う融点とは、示差走査熱量計を用い、２０℃／分の速度で昇温したときに試料（溶融重合ポリマー）が示す融解ピークのピークトップ温度をさす。
【００２４】
この固相重縮合により、更に高重合度化させ得ると共に、ある程度オリゴマーやアセトアルデヒド等を低減化したものとすることができる。固相重縮合は、１３３３〜１３．３Ｐａ程度の減圧下でも行うことができるが、ある程度規模が大きい工業生産では減圧装置、固相重縮合槽などの設備費用が大きくなり経済的観点からは、常圧付近、特に１００ｋＰａ〜１５０ｋＰａの圧力で行うのが好ましい。
【００２５】
本発明では、上記温度で固相重縮合を行うが、固相重縮合に供する溶融重合ポリマーの固相重縮合温度への昇温は、少なくとも２００℃に到達するまでは１００℃／分以下の速度で温度上昇させることが好ましく、更に好ましくは、少なくとも１８０℃に到達するまでは、１００℃／分以下の速度で温度上昇させることが好ましい。即ち、例えば、ポリエチレンテレフタレートは１８０℃前後での結晶化速度が速いため、急速にこの温度範囲まで到達させると結晶子の成長が急激に進み結晶子サイズが大きくなり、上記本発明の結晶子サイズを維持するのが困難となる傾向があり、その結果、固相重縮合速度が遅くなる。結晶子サイズの増大とともに固相重縮合速度が遅くなる理由としては、結晶サイズが大きくなると非晶部に存在する分子鎖末端の運動が制限され、末端同士が反応しうる距離まで接近する頻度が小さくなるためであることが考えられる。
【００２６】
固相重縮合によって得られるポリエステル樹脂の固有粘度は通常、０．６０ｄｌ／ｇ以上、好ましくは０．６５ｄｌ／ｇ以上、更に好ましくは０．７０ｄｌ／ｇ以上である。又、通常、１．２０ｄｌ／ｇ以下、好ましくは１．１０ｄｌ／ｇ以下、より好ましくは１．００ｄｌ／ｇ以下である。０．６０ｄｌ／ｇ未満の場合、特にブロー成形に用いた場合に肉厚ムラが発生しやすく、１．２０ｄｌ／ｇより大きいと特に射出成形時に金型への樹脂充填量不足による形状異常（ヒケ）が発生しやすい。
【００２７】
また固相重縮合によって得られるポリエステル樹脂中の酸末端濃度は、通常５ｍｍｏｌ／ｋｇ以上１００ｍｍｏｌ／ｋｇ以下であり、同樹脂中に含まれる環状三量体量は通常１５００ｐｐｍ以上８０００ｐｐｍ以下である。
固相重合により得られるポリエステル樹脂の平均粒径は、溶融重合ポリマーの平均粒径に依存し、１０μｍ以上が好ましく、５０μｍ以上が更に好ましく、特に１００μｍ以上が好ましい。一方、１５００μｍ以下が好ましく、更に１３００μｍ以下が好ましく、１０００μｍ以下が更に好ましく、特に５００μｍ以下が好ましい。
尚、固相重縮合によって得られるポリエステル樹脂粒体は、更に必要に応じて顆粒状などの取り扱いやすい形状に造粒してもよい。
【００２８】
【実施例】
以下、実施例により本発明をさらに具体的に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。なお、以下の実施例中「部」とあるのは重量部を意味する。又、本発明における各種物性の測定法は以下に示すとおりである。
【００２９】
（１）見かけ結晶子サイズ（ＡＣＳ010）
試料の広角Ｘ線散乱スペクトルを測定し、（０１０）面からの回折角θ、回折ピークの半値幅β０１０、Ｘ線の波長λ、常数Ｋ（１と仮定）を下記式（１）に代入することにより算出した。
広角ｘ線粉末回折で平均結晶子サイズを測定したが、測定方法または手順は下記の通りである。
［試料調製］
ポリエステル試料を凍結粉砕した後、該試料を、片面に厚み８μｍのポリイミドフィルムを貼った約１ｍｍ厚みのドーナツ型の金属製スペーサー中に入れ、ポリイミドを貼っていない面より軽く押し固め、厚さ約１ｍｍの測定試料とした。
［測定条件］
Ｘ線発生装置：リガク（株）URTRAX18 [40kV, 250mA]
ターゲット：ＣｕＫα、
検出器：シンチレーションカウンター
測定法：対称透過法
コリメーター：１ｍｍφ
受光スリット：１°
スキャンモード：２θ＝５〜３５°を０．０５°／ステップでスキャンした。各ステップでの積算時間は５秒／ステップとした。
［ＡＣＳ010の算出］
ａ．サンプルの回折プロファイルから、測定に用いたポリイミドフィルムの散乱を差し引く。
ｂ．測定によって得られたデータにローレンツ補正を行う。
ｃ．２θ＝１５°−１９°領域のバックグラウンド散乱分として２θ＝１５．００°から２θ＝１ ９．００°へと伸びる直線を仮定して、差し引く。
ｄ．１５−１９°領域の重なりをガウス分布を仮定して（０１０）、（０１１）の２つのピークに 分離し（０１０）ピークの位置、半値幅、高さを求め式１に代入しＡＣＳ010を算出する。Ｋは１ ．０と仮定した。
なお、λはＸ線の波長［Å］、β010は（０１０）ピークの半値幅［ｒａｄ］、θ010は（０１０）ピークの回折角［ｒａｄ］である。
【００３０】
【数１】
（２）ガラス転移温度（Ｔｇ）
セイコー電子社製示差走査熱量計ＤＳＣ２２０Ｃを用い、３００℃まで試料を加熱した後１０分間保持し、セルよりサンプルパンを取り出し液体窒素中でサンプルパンを急冷した後、再びセルに戻し２０℃／分の速度で昇温することにより測定した。
【００３２】
（３）固有粘度（ＩＶ）
ａ．凍結粉砕した樹脂試料０．２５ｇを、フェノール／テトラクロロエタン（重量比１／１）の混合溶媒に、濃度（ｃ）を１．０ｇ／ｄｌとして、１４０℃で３０分間で溶解させた後、ウベローデ型毛細粘度管を用いて、３０℃で、溶媒との相対粘度（ηrel ）を測定した。
ｂ．この相対粘度（ηrel ）−１から求めた比粘度（ηsp）と濃度（ｃ）との比（ηsp／ｃ）を求めた。
ｃ．同じく濃度（ｃ）を０．５ｇ／ｄｌ、０．２ｇ／ｄｌ、０．１ｇ／ｄｌとしたときについてもそれぞれの比（ηsp／ｃ）を求めた。
ｄ．これらの値より、濃度（ｃ）を０に外挿したときの比（ηsp／ｃ）を固有粘度〔η〕（ｄｌ／ｇ）として求めた。
（４）平均粒径
JISＫ００６９に記載の方法により積算分布曲線を作成し、積算百分率が５０％になるときの値を平均粒径とした。
【００３３】
（５）共重合成分量
試料をトリフルオロ酢酸に溶解させた溶液について、核磁気共鳴装置（日本電子社「ＪＮＭ−ＥＸ２７０型」）を用いて、１Ｈ−ＮＭＲを測定して各ピークを帰属し、ピークの積分値から、全カルボン酸成分に対するテレフタル酸又はそのエステル形成性誘導体以外のジカルボン酸成分のモル％（Ａ）、及び、全ジオール成分に対するエチレングリコール以外のジオール成分のモル％（Ｂ）を算出し、その和（Ａ＋Ｂ）を算出した。
（６）融着有無
溶融重合ポリマーの固相重縮合後、室温まで冷却し、金属板からポリエステル樹脂を回収する際の剥がれ易さを◎○×で表１に示した。
◎：ポリエステル樹脂の金属板への付着は少なく、容易に剥離できた
○：ポリエステル樹脂の金属板への付着が認められたが、容易に剥離できた
×：ポリエステルが金属板に強固に付着しており、剥がれにくかった
【００３４】
実施例１
テレフタル酸およびエチレングリコールを、テレフタル酸１３．０部とエチレングリコール５．８２部となる様にスラリー調製槽に連続的に供給し、スラリーを調製した。該スラリーを第１段のエステル化反応槽へ連続的に供給し、略常圧下２６０℃で連続的にエステル化反応を行い、エステル反応率８４％のビス（２−ヒドロキシエチル）テレフタレート及びその低重合体を調製した。反応物を第２段のエステル化反応槽に連続的に供給し、略常圧下２５５℃で連続して反応を行い、エステル反応率９５％のビス（２−ヒドロキシエチル）テレフタレートおよびその低重合体を得た。
【００３５】
更に、反応物を第１段の重縮合反応槽に連続的に供給し、正リン酸０．０１１部及び三酸化二アンチモン０．０３８部を連続的に上記反応物に加え、２〜４ｋＰａの減圧下２８０℃で、滞留時間約１時間で連続的に反応を行い、次いで、第１段の重縮合反応槽の反応物を第２段の重縮合反応槽に連続的に供給し２００〜４００Ｐａの減圧下２８０℃で、滞留時間約１時間で連続的に重縮合反応を行った。
【００３６】
得られた重縮合反応物をストランドとして連続的に水中に抜き出し、ペレット化した。このときペレットは透明で実質結晶化を起こしていなかった。得られたペレットを回転式ミルにより粉砕し、粉砕品（固相重縮合原料である溶融重合ポリマー）を得た。固相重縮合原料（溶融重合ポリマー）の分析結果を表１の固相重縮合原料欄に示す。
続いて粉砕品１ｇを、３０ｃｍ四方の金属板上に均一に広げ、オーブン中５０Ｌ／分の窒素流通下、静置状態で１２０℃で２時間保持した後、１７０℃まで３０分かけて昇温し、１７０℃で２時間保持した。さらに２５０℃まで１０分で昇温し２５０℃で１０分保持し固相重縮合を行った。その後、２５０℃から室温まで冷却したが、冷却は窒素の供給を継続したままヒーターのスイッチを切ることにより行った。オーブン内温度が２５０℃から２００℃まで下がるのに要した時間は２５分であった。得られたポリマーの分析結果を表１の製品欄に示す。
【００３７】
実施例２
正リン酸および三酸化二アンチモンのかわりに、エチルアシッドホスフェート０．０００１３５部、酢酸マグネシウム４水塩０．０００７９４部及びテトラブトキシチタン０．００２１３部を第１段の重縮合反応槽に連続的に供給した以外は実施例１と同様にして粉砕品（固相重縮合原料（溶融重合ポリマー））を得た。固相重縮合原料（溶融重合ポリマー）の分析結果を表１の固相重縮合原料欄に示す。引き続き表１記載の固相重縮合温度、固相重縮合時間とした以外は実施例１と同様にして固相重縮合を行った。得られたポリマーの分析結果を表１の製品欄に示す。
実施例３
テトラブトキシチタンの量を０．００３２４部とした以外は実施例２と同様にして粉砕品（固相重縮合原料（溶融重合ポリマー））を得た。固相重縮合原料（溶融重合ポリマー）の分析結果を表１の固相重縮合原料欄に示す。引き続き表１記載の固相重縮合温度、固相重縮合時間とした以外は実施例１と同様にして固相重縮合を行った。得られたポリマーの分析結果を表１の製品欄に示す。
実施例４
イソフタル酸０．３４部とテレフタル酸１２．７部とをテレフタル酸１３部の代わりとしてスラリー調製槽に連続的に供給した以外は実施例３と同様にして粉砕品（固相重縮合原料（溶融重合ポリマー））を得た。固相重縮合原料（溶融重合ポリマー）の分析結果を表１の固相重縮合原料欄に示す。引き続き表１記載の固相重縮合温度、固相重縮合時間とした以外は実施例１と同様にして固相重縮合を行った。得られたポリマーの分析結果を表１の製品欄に示す。
実施例５
２８０℃、２００〜４００Ｐａの減圧下での重縮合反応時間を延長した点と、粉砕に凍結粉砕機を用いた以外は実施例３と同様にして粉砕品（固相重縮合原料（溶融重合ポリマー））を得た。固相重縮合原料（溶融重合ポリマー）の分析結果を表１の固相重縮合原料欄に示す。引き続き表１記載の固相重縮合温度、固相重縮合時間とした以外は実施例１と同様にして固相重縮合を行った。得られたポリマーの分析結果を表１の製品欄に示す。
実施例６
回転式ミルでの粉砕時間を短縮した以外は実施例３と同様にして粉砕品（固相重縮合原料（溶融重合ポリマー））を得た。固相重縮合原料（溶融重合ポリマー）の分析結果を表１の固相重縮合原料欄に示す。引き続き表１記載の固相重縮合温度、固相重縮合時間とした以外は実施例１と同様にして固相重縮合を行った。得られたポリマーの分析結果を表１の製品欄に示す。
実施例７
実施例３で得られた粉砕品（固相重縮合原料（溶融重合ポリマー））１ｇを、３０ｃｍ四方の金属板上に均一に広げ、オーブン中５０Ｌ／分の窒素流通下、静置状態で１２０℃で２時間保持した後、１７０℃まで３０分かけて昇温し、１７０℃で３０分間保持した。いったん室温まで冷却し、回収した粉砕品を固相重縮合原料（溶融重合ポリマー）として用い、実施例１と同様にして固相重縮合を行った。得られたポリマーの分析結果を表１の製品欄に示す。
【００３８】
比較例１
実施例１と同様にしてエステル化反応及び重縮合反応を行った。
重縮合反応物約５０ｇを、重縮合槽底部に取り付けたノズルから１８０℃±１０℃に保ったホットプレート上に、ホットプレート表面からの高さが２mm以下となるように抜き出し、５分保持し結晶化させた。得られた結晶化物をコーヒーミルにより粉砕し、粉砕品（固相重縮合原料（溶融重合ポリマー））を得た。固相重縮合原料（溶融重合ポリマー）の分析結果を表１の固相重縮合原料欄に示す。
【００３９】
続いて、粉砕品について、実施例１と同様にして固相重縮合を行った。得られたポリマーの分析結果を表１の製品欄に示す。
実施例１と同じ固相重縮合時間で、得られたポリマーの固有粘度が低いことから、重縮合速度が遅いことが分かる。
比較例２
実施例２と同様にしてエステル化反応及び重縮合反応を行った後、得られた重縮合反応物について、比較例１と同様に処理して粉砕品（固相重縮合原料（溶融重合ポマー））を得た。固相重縮合原料（溶融重合ポリマー）の分析結果を表１の固相重縮合原料欄に示す。
【００４０】
続いて、粉砕品について、実施例１と同様にして固相重縮合を行った。得られたポリマーの分析結果を表１の製品欄に示す。
実施例２と同じ固相重縮合時間で、得られたポリマーの固有粘度が低いことから、重縮合速度が遅いことが分かる。
比較例３
イソフタル酸０．７３部とテレフタル酸１２．３部とをテレフタル酸１３部の代わりとしてスラリー調製槽に連続的に供給した以外は実施例３と同様にして粉砕品（固相重縮合原料（溶融重合ポリマー））を得た。固相重縮合原料（溶融重合ポリマー）の分析結果を表１の固相重縮合原料欄に示す。引き続き表１記載の固相重縮合温度、固相重縮合時間とした以外は実施例１と同様にして固相重縮合を行った。得られたポリマーの分析結果を表１の製品欄に示す。
比較例４
実施例３によって得られた粉砕品（固相重縮合原料（溶融重合ポリマー））を用い、表１記載の固相重縮合温度、固相重縮合時間とした以外は実施例１と同様にして固相重縮合を行った。得られたポリマーの分析結果を表１の製品欄に示す。
【００４１】
【表１】
【発明の効果】
本発明の方法によれば、固相重縮合速度が速く、極めて高速に高分子量のポリエステル樹脂を得ることができる。
又、本発明の方法によれば、高真空等の特殊な条件を採用しなくても高速でポリエステルの固相重縮合が可能であり、しかも得られるポリエステル樹脂同士の融着、或いは反応装置へのポリエステル樹脂の付着等の取り扱い性の問題がないため、ポリエステルを工業的有利に、生産性良好に製造できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a polyester resin. More specifically, the present invention relates to a method for carrying out solid phase polycondensation of polyester at an extremely high speed.
[0002]
[Prior art]
Polyester resins, especially polyethylene terephthalate (hereinafter sometimes abbreviated as PET) manufactured from terephthalic acid and ethylene glycol, are widely used in many materials and products such as fibers, fabrics, molding resins and beverage bottles. ing.
In order to bring out the moldability and mechanical properties necessary for the above applications, it is necessary to increase the degree of polymerization of the polyester resin to a predetermined level. A method of obtaining a polycondensation product having the same and subsequently subjecting the polycondensation product to solid phase polycondensation is widely used industrially. However, since solid phase polycondensation in such a conventional method requires a relatively long time, a production method with higher productivity is desired.
As a method for producing a polyester resin with improved productivity, a method has been proposed in which a melt polymerization polymer having a relatively low polymerization degree is obtained by melt polycondensation of a polyester raw material monomer, and this melt polymerization polymer is subjected to solid phase polycondensation. . For example, JP-T-10-512608 (WO96 / 22319) discloses a low degree of polymerization having an average degree of polymerization of about 5 to about 35 (inherent viscosity of about 0.10 to 0.36 dl / g) obtained by melt polycondensation. A method is disclosed in which a melt-polymerized polymer is crystallized to have a crystallite size of 9 nm or more and then subjected to solid phase polycondensation. According to this method, it is said that the polycondensation can be carried out directly starting at a higher temperature, for example 230 ° C., preferably 240 ° C. However, according to our study, the degree of polymerization at the start of solid-phase polycondensation is too low, or because the crystal grows and suppresses the movement of molecules, but the reason is unknown, but it is not always satisfactory. Speed cannot be obtained.
[0003]
On the other hand, in US Pat. No. 6,284,866, as a copolyester for a bottle having a low haze at a low temperature, the sum of the copolymerization amount (mol%) of a dicarboxylic acid component and the copolymerization amount (mol%) of a diol component is 6 or more. A method for solid-phase polycondensation of a melt polymerized polymer having an intrinsic viscosity of 0.25 to 0.40 dl / g under specific conditions is disclosed. However, in the method of this publication, solid-phase polycondensation is performed using a rotary-vacumn tumble dryer and is not necessarily industrially advantageous because of solid-phase polycondensation in a high vacuum state. According to our study, the melting point of the melt-polymerized polymer is relatively low due to the large amount of copolymerization components. Therefore, if the vacuum is not high, the solid-phase polycondensation temperature cannot be set high, and the solid-phase polycondensation rate is low. Not slow and efficient.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for carrying out solid-phase polycondensation of polyester at extremely high speed, and thus producing polyester with good productivity. Furthermore, the present invention is capable of solid-phase polycondensation of polyester at a high speed without adopting special conditions such as high vacuum, and furthermore, fusion of the obtained polyester resins or the polyester resin to the reaction apparatus. It is an object of the present invention to provide a method for producing a polyester with good productivity without problems of handling such as adhesion.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor has controlled the amount of copolymerization, intrinsic viscosity, apparent crystallite size, and solid-phase polycondensation temperature of the melt-polymerized polymer to be used for solid-phase polymerization. It has been found that the above object can be achieved by performing polycondensation, and the present invention has been achieved.
[0006]
That is, the gist of the present invention is to polycondense a dicarboxylic acid component mainly composed of terephthalic acid or an ester-forming derivative thereof and a diol component mainly composed of ethylene glycol through an esterification reaction or a transesterification reaction. In the method of producing a polyester resin by solid-phase polycondensation of the melt polymerized polymer produced by the following steps: (1) The amount of copolymer components other than the terephthalic acid component and the ethylene glycol component is 5.5 or less, and the intrinsic viscosity is 0. 0.08 dl / g or more and 0.50 dl / g or less, and a melt-polymerized polymer having an apparent crystallite size of less than 9 nm is obtained. 2) The temperature of the melt polymerized polymer is raised to the solid phase polycondensation temperature while controlling the apparent crystal size of the polyester resin after the solid phase polycondensation to be less than 9 nm, (3) A polyester resin having an apparent crystallite size of less than 9 nm is obtained by solid-phase polycondensation of the melt polymerized polymer at a temperature of 140 ° C. higher than the glass transition temperature of the melt polymerized polymer and lower than the melting point. A method for producing a polyester resin.
Another gist is produced by polycondensing a dicarboxylic acid component mainly composed of terephthalic acid or an ester-forming derivative thereof and a diol component mainly composed of ethylene glycol through an esterification reaction or a transesterification reaction. In the method for producing a polyester resin by solid-phase polycondensation of the melt-polymerized polymer, (1) the amount of copolymer components other than the terephthalic acid component and the ethylene glycol component is 5.5 or less, and the intrinsic viscosity is 0.08. A melt-polymerized polymer having an apparent crystallite size of less than 9 nm (2) to 0.50 dl / g The temperature of the melt polymerized polymer is raised to the solid phase polycondensation temperature while controlling the apparent crystal size of the polyester resin after the solid phase polycondensation to be less than 9 nm, (3) Polyester characterized by solid-phase polycondensation at a temperature not lower than the melting point and not higher than 140 ° C. above the glass transition temperature of the melt-polymerized polymer while maintaining the apparent crystallite size of the melt-polymerized polymer below 9 nm. Resin manufacturing method.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the method for producing a polyester resin according to the present invention, the melt polymerized polymer comprises a dicarboxylic acid component containing terephthalic acid or an ester-forming derivative thereof as a main component and a diol component containing ethylene glycol as a main component. It is a melt polymerized polymer having ethylene terephthalate units produced by a melt polycondensation reaction as a main constituent repeating unit, and the amount of copolymer components other than the terephthalic acid component and ethylene glycol component of the polyester resin is 5 .5 or less. Here, the amount of the copolymer component other than the terephthalic acid component and the ethylene glycol component is 5.5 or less means that the amount ratio (mol%) of the component other than terephthalic acid or its ester-forming derivative to the total dicarboxylic acid component is A, When the amount ratio (mol%) of diol components other than ethylene glycol to all diol components is B, A + B is 5.5 or less. The amount of the copolymer component is preferably 4.5 or less. If the amount of the copolymerization component exceeds 5.5, the melting point of the polyester resin is lowered, the solid phase polycondensation temperature is restricted, the polycondensation rate is slow, and the heat resistance is inferior, so the polyester resin is molded. In particular, when stretching and heat setting are performed to improve strength and heat resistance, the effects of stretching and heat setting are not sufficiently exhibited.
[0008]
Examples of the ester-forming derivative of terephthalic acid include alkyl esters and halides of terephthalic acid having about 1 to 4 carbon atoms such as dimethyl terephthalate. Dicarboxylic acids other than terephthalic acid or its ester-forming derivatives include phthalic acid, isophthalic acid, 1,3-phenylenedioxydiacetic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4 , 4′-diphenylketone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and other aromatic dicarboxylic acids; 2,6-naphthalenedicarboxylic acid C1-C4 alkyl esters of aromatic dicarboxylic acids such as dimethyl esters and halides; Alicyclic dicarboxylic acids such as hexahydroterephthalic acid; Succinic acid, glutaric acid, adipic acid, pimelic acid, suberin Acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecane Aliphatic dicarboxylic acids such as carboxylic acids; and alkyl esters having about 1 to 4 carbon atoms in the alicyclic dicarboxylic acid or aliphatic dicarboxylic acids, and halides.
[0009]
Examples of diols other than ethylene glycol include trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, diethylene glycol, triethylene glycol, Aliphatic diols such as polyethylene glycol and polytetramethylene ether glycol, alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethylol, and aromatic diols such as xylylene glycol, and Examples include ethylene oxide adducts or propylene oxide adducts of 2,2-bis (4′-hydroxyphenyl) propane.
[0010]
Furthermore, for example, monofunctional components such as stearyl alcohol, stearic acid, benzoic acid, etc., trifunctional or more polyfunctional such as trimellitic acid, trimesic acid, pyromellitic acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol One type or two or more types of components may be used as a copolymerization component.
[0011]
Since the copolymerization amount of the melt polymerization polymer of the present invention is in the above range, the ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid component is preferably 94.5 mol% or more, and more preferably 96 mol% or more. On the other hand, the ratio of ethylene glycol to all diol components is preferably 94.5 mol% or more, more preferably 96 mol% or more.
[0012]
The melt polymerized polymer in the present invention is basically produced by a conventional production method for polyester resins. That is, the dicarboxylic acid containing terephthalic acid or its ester-forming derivative as the main component and the diol containing ethylene glycol as the main component, usually in a ratio of dicarboxylic acid: diol of 1: 1 to 1: 2 (molar ratio). In an esterification reaction tank, usually at a temperature of about 240 to 280 ° C., usually under normal pressure to about 0.4 MPa, and under stirring for about 1 to 10 hours, or After the ester exchange reaction in the presence of the exchange reaction catalyst, the resulting esterification reaction product or the polyester low molecular weight product as the ester exchange reaction product is transferred to a polycondensation tank, and in the presence of the polycondensation catalyst, The viscosity is usually about 250 to 290 ° C. and gradually reduced from normal pressure to about 1333 to 13.3 Pa. 0.50 dl / g range to become time, usually prepared by melt polycondensation of about 0.5 to 5 hours. However, as described above, the melt polymerization polymer of the present invention has a copolymer component amount other than the terephthalic acid component and the ethylene glycol component of 5.5 or less, so in the present invention, the terephthalic acid component, the ethylene glycol component, In addition, a copolymer component other than the terephthalic acid component and the ethylene glycol component is used at an amount of the copolymer component of 5.5 or less.
The above reaction is carried out continuously or batchwise, but is preferably continuous. Each of the esterification reaction tank and the polycondensation tank may be one stage or multistage. Further, when the above polyester low molecular weight material is granulated and subjected to solid phase polycondensation as a melt polymerization polymer, the melt polycondensation can be omitted.
[0013]
In the esterification reaction, it is not necessary to use a catalyst, but if necessary, germanium compounds such as germanium dioxide, germanium tetroxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, germanium tetra-n-butoxide, etc. Antimony compounds such as antimony trioxide, antimony pentoxide, antimony acetate, antimontris ethylene glycoloxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetra-i-propoxide, titanium tetra-n-butoxide, Known catalysts such as titanium compounds such as titanium oxalate and potassium potassium oxalate can also be used.
[0014]
As the transesterification reaction catalyst, one or more kinds of compounds of metals such as titanium, magnesium, calcium, manganese, lithium and zinc are used. Specific examples include organic acid salts, alcoholates, and carbonates of these metals. Of these, magnesium acetate, calcium acetate, manganese acetate, lithium acetate and the like are preferably used. The amount of the transesterification reaction catalyst is usually such that the content as a metal atom derived from the catalyst is usually about 1 to 200 ppm with respect to the obtained polyester resin.
[0015]
Germanium compounds such as germanium dioxide, germanium tetroxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, germanium tetra-n-butoxide, antimony trioxide, antimony pentoxide, antimony acetate, antimony trisethylene Antimony compounds such as glycoloxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetra-i-propoxide, titanium tetra-n-butoxide, titanium compounds such as titanium oxalate and potassium titanium oxalate, cobalt formate, acetic acid Cobalt compounds such as cobalt, cobalt stearate, cobalt oxalate, cobalt carbonate, and cobalt bromide, and tin compounds such as tin acetate, tin oxalate, and tin bromide are used. It is used in conjunction with above. Preferably, an oxide, inorganic acid salt, organic acid salt or alcoholate compound of at least one metal selected from germanium, antimony and titanium is used. The use amount of the polycondensation reaction catalyst is usually such that the content as a metal atom derived from the catalyst is usually about 1 to 500 ppm with respect to the obtained polyester resin.
[0016]
Further, during esterification reaction or transesterification reaction, and polycondensation reaction, phosphate esters such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate as stabilizers, Phosphites such as triphenyl phosphite, trisdodecyl phosphite, trisnonylphenyl phosphite, methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate, dioctyl phosphate Acid phosphate esters and phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, and ether bond formation Tertiary amines such as triethylamine, tri-n-butylamine, benzyldimethylamine, quaternary ammonium hydroxides such as tetraethylammonium hydroxide, tetran-butylammonium hydroxide, trimethylbenzylammonium hydroxide, or carbonic acid Basic compounds such as lithium, sodium carbonate, potassium carbonate, sodium acetate and magnesium acetate can coexist.
[0017]
The amount of the phosphorus compound used is such that the content as the phosphorus atom derived from the phosphorus compound is usually about 1 to 200 ppm with respect to the obtained polyester resin. In addition, it is preferable to use together a titanium compound, a magnesium compound, and a phosphorus compound especially in the said catalyst and additive, and the following range is mentioned as a usage rate at that time.
T: 0.02 to 0.6 mol (in 1 ton of polyester resin)
M: 0.04 to 0.6 mol (in 1 ton of polyester resin)
P: 0.02 to 4 mol (in 1 ton of polyester resin)
(However, T: total amount of titanium atoms, M: total amount of magnesium atoms, P: total amount of phosphorus atoms)
In addition, examples of preferable combinations and usage ratios of the catalyst and the additive include those described in EP1273610-A1.
The melt polymerized polymer obtained by melt polycondensation may be sprayed to the outside from the pores provided at the bottom of the polycondensation tank to form fine particles, or in the air from the outlet provided at the bottom of the polycondensation tank. Alternatively, it may be extracted as droplets in water. Alternatively, it may be extracted into a strand shape and cut with a cutter while cooling with water or after cooling with water to form pellets. Furthermore, the obtained pellets may be pulverized to form particles with a finer particle size. In the present invention, in any of the methods described above, it is important to cool the molten structure to room temperature as quickly as possible in order not to grow the crystal structure. Specifically, a method in which the specific heat is increased as soon as possible from the molten state and is brought into contact with a fluid having a low temperature, such as water, can be mentioned.
[0018]
In the present invention, a polyester resin is produced by solid-phase polycondensation of the melt-polymerized polymer obtained as described above, but the apparent crystallite size of the melt-polymerized polymer used for solid-phase polycondensation obtained by cooling ( ACS 010 ) Is less than 9 nm, preferably 8 nm or less, more preferably 7 nm or less. When the apparent crystallite size of the melt-polymerized polymer is 9 nm or more, the solid phase polycondensation rate becomes slow. The crystallite size of the melt polymerized polymer is preferably as small as possible from the viewpoint of keeping the initial reaction rate in solid phase polycondensation as fast as possible, and the lower limit is 0.
The apparent crystallite size referred to here is a parameter representing the size of the crystal structure, and is obtained from analysis of a wide-angle X-ray diffraction spectrum (010) Apparent crystallite size (ACS) relating to reflection. 010 ).
[0019]
In addition, the intrinsic viscosity of the melt polymerization polymer of the present invention is 0.08 dl / g or more and 0.50 dl / g or less. Preferably, it is 0.1 dl / g or more, more preferably 0.15 dl / g or more, particularly preferably 0.20 dl / g or more, while 0.45 dl / g or less is preferable, and 0.40 dl / g or less is particularly preferable. . When the intrinsic viscosity is less than 0.08 dl / g, the polycondensation rate in the subsequent solid-phase polycondensation is remarkably slow. When it is higher than 0.50 dl / g, the melt polycondensation apparatus for increasing the intrinsic viscosity is expensive. In addition, since the melt polycondensation for increasing the degree of polymerization takes time, the time required for production becomes longer.
[0020]
In order to control the apparent crystallite size of the melt-polymerized polymer within the above range, as described above, there is a method of rapidly cooling the melt-polymerized polymer in a molten state, that is, a method of increasing the cooling rate as much as possible. The cooling rate cannot be generally specified because the crystallization rate varies depending on the molecular weight of the melt-polymerized polymer, but it is within 10 seconds, preferably within 5 seconds, more preferably 1 from the molten state to the crystallization temperature of the melt-polymerized polymer. Cool in less than a second. The intrinsic viscosity is controlled within the above range by controlling the polycondensation temperature, time and degree of vacuum. Since the intrinsic viscosity range of the melt polymerized polymer described in the present invention is lower than the viscosity range of a commonly used melt polymerized polymer, it can be reached at a lower temperature, a shorter time, and a lower degree of vacuum, and side reactions are suppressed, so that the product quality is improved. There is also a merit that it is good and can be manufactured at low cost because the process can be simplified.
[0021]
Further, the acid value of the melt polymerization polymer is usually in the range of 10 to 1000 mmol / kg, and the content of the cyclic trimer is usually in the range of 4000 to 12000 ppm.
The average particle size of the melt-polymerized polymer particles subjected to solid phase polycondensation is preferably 10 μm or more, more preferably 50 μm or more, and particularly preferably 100 μm or more. On the other hand, it is preferably 1500 μm or less, more preferably 1300 μm or less, still more preferably 1000 μm or less, and particularly preferably 500 μm or less. When the average particle size exceeds 1500 μm, the solid phase polycondensation rate tends to be slow, and when the average particle size is less than 10 μm, there is a tendency that scattering into the air tends to occur.
[0022]
The amount of copolymer components other than the terephthalic acid component and ethylene glycol component obtained as described above is 5.5 or less, the intrinsic viscosity is 0.08 to 0.50 dl / g, and the apparent crystallite size (ACS) 010 ) Less than 9 nm melt polymerized polymer continues to have an apparent crystallite size (ACS) 010 ) Kept below 9 nm, preferably ACS 010 A melt polymerized polymer having a particle size of 8 nm or less is converted to ACS. 010 Is solid-phase polycondensed in a state where is kept at 8 nm or less, more preferably 7 nm or less. In addition, solid phase polycondensation is performed using ACS. 010 Is carried out in a state where it is kept below 9 nm, the ACS of the polyester after solid-phase polycondensation 010 Can be confirmed by being less than 9 nm. ACS 010 Is performed in a state in which the polyester is maintained at 8 nm or less, the ACS of the polyester after solid-phase polycondensation 010 Can be confirmed by being 8 nm or less.
Depending on the temperature rise condition to the solid phase polycondensation temperature of the melt polymerized polymer, for example, the temperature rise to reach the solid phase polycondensation temperature by selecting the rate of temperature rise or keeping the temperature at 190 ° C. or lower for a certain time, for example. In the process, the crystallization of the surface of the melt polymerization polymer may proceed, but moderate crystallization tends to prevent the adhesion to the reactor and the decrease in the solid phase polycondensation rate due to the fusion of the melt polymerization polymers. . Even when crystallization is performed on the surface of the melt-polymerized polymer in the temperature rising process, in order to suppress the subsequent decrease in the solid-phase polycondensation rate as much as possible, the heat history is kept to the minimum necessary, Control is made so that the apparent crystallite size of the polyester resin is kept below 9 nm.
[0023]
The solid phase polycondensation temperature of the present invention is at least 140 ° C. higher than the glass transition temperature of the melt polymerized polymer and below the melting point. Preferably, the temperature is 145 ° C. higher than the glass transition temperature of the melt polymerization polymer and not higher than the melting point, more preferably 150 ° C. higher than the glass transition temperature of the melt polymerization polymer, particularly preferably 160 ° C. higher than the temperature. The temperature is below the melting point of the melt polymerization polymer. By performing solid phase polycondensation within the above range, solid phase polycondensation can be efficiently advanced while minimizing the progress of crystallization. If the solid-phase polycondensation temperature is less than the above, the polycondensation rate will be slow and the productivity will be inferior. If the above range is exceeded, the melt-polymerized polymer will melt and the polymer will adhere to the reactor. Problems occur, resulting in problems in product quality or productivity. The solid phase polycondensation is usually carried out in an inert gas atmosphere, and is carried out for about 10 hours or less while flowing so that the melt-polymerized polymer particles do not stick together if necessary. The melting point here refers to the peak top temperature of the melting peak exhibited by the sample (melt polymerized polymer) when the temperature is raised at a rate of 20 ° C./min using a differential scanning calorimeter.
[0024]
By this solid phase polycondensation, the degree of polymerization can be further increased, and oligomers, acetaldehyde and the like can be reduced to some extent. Solid phase polycondensation can be carried out under reduced pressure of about 1333 to 13.3 Pa. However, in industrial production that is large to some extent, equipment costs such as a pressure reducing device and a solid phase polycondensation tank increase, and from an economical viewpoint, It is preferable to carry out at around normal pressure, particularly at a pressure of 100 kPa to 150 kPa.
[0025]
In the present invention, solid phase polycondensation is carried out at the above temperature. The temperature of the melt polymerization polymer subjected to solid phase polycondensation to the solid phase polycondensation temperature is 100 ° C./min or less until at least 200 ° C. is reached. The temperature is preferably increased at a rate, and more preferably at a rate of 100 ° C./min or less until at least 180 ° C. is reached. That is, for example, since polyethylene terephthalate has a high crystallization rate at around 180 ° C., when it reaches this temperature range rapidly, the crystallite grows rapidly and the crystallite size increases. Tends to be difficult to maintain, resulting in a slow solid phase polycondensation rate. The reason why the solid-phase polycondensation rate decreases as the crystallite size increases is that the movement of the molecular chain ends present in the amorphous part is limited when the crystal size is increased, and the frequency at which the ends approach each other can react. It is conceivable that it is small.
[0026]
The intrinsic viscosity of the polyester resin obtained by solid phase polycondensation is usually 0.60 dl / g or more, preferably 0.65 dl / g or more, more preferably 0.70 dl / g or more. Moreover, it is 1.20 dl / g or less normally, Preferably it is 1.10 dl / g or less, More preferably, it is 1.00 dl / g or less. If it is less than 0.60 dl / g, unevenness in thickness is likely to occur, particularly when used for blow molding, and 1.20 dl / g. Greater than In particular, shape abnormalities (sinks) are likely to occur due to insufficient resin filling in the mold during injection molding.
[0027]
The acid terminal concentration in the polyester resin obtained by solid phase polycondensation is usually 5 mmol / kg or more and 100 mmol / kg or less, and the amount of cyclic trimer contained in the resin is usually 1500 ppm or more and 8000 ppm or less.
The average particle size of the polyester resin obtained by solid phase polymerization depends on the average particle size of the melt polymerized polymer, preferably 10 μm or more, more preferably 50 μm or more, and particularly preferably 100 μm or more. On the other hand, it is preferably 1500 μm or less, more preferably 1300 μm or less, still more preferably 1000 μm or less, and particularly preferably 500 μm or less.
The polyester resin granules obtained by solid-phase polycondensation may be further granulated into a shape that is easy to handle, such as granules, if necessary.
[0028]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, “parts” means parts by weight. The measuring methods for various physical properties in the present invention are as follows.
[0029]
(1) Apparent crystallite size (ACS 010 )
The wide-angle X-ray scattering spectrum of the sample is measured, and the diffraction angle θ from the (010) plane, the half-value width β010 of the diffraction peak, the wavelength λ of the X-ray, and the constant K (assuming 1) are substituted into the following formula (1). Was calculated.
The average crystallite size was measured by wide-angle x-ray powder diffraction, and the measurement method or procedure is as follows.
[Sample preparation]
After freeze-pulverizing the polyester sample, the sample was put in a doughnut-shaped metal spacer having a thickness of about 1 mm with a polyimide film having a thickness of 8 μm on one side, and lightly pressed and hardened from the surface to which no polyimide was applied. A measurement sample of 1 mm was used.
[Measurement condition]
X-ray generator: Rigaku Corporation URTRAX18 [40kV, 250mA]
Target: CuKα,
Detector: Scintillation counter
Measurement method: Symmetric transmission method
Collimator: 1mmφ
Receiving slit: 1 °
Scan mode: 2θ = 5-35 ° was scanned at 0.05 ° / step. The integration time at each step was 5 seconds / step.
[ACS 010 Calculation]
a. The scattering of the polyimide film used for the measurement is subtracted from the diffraction profile of the sample.
b. Lorentz correction is performed on the data obtained by the measurement.
c. Assuming a straight line extending from 2θ = 15.00 ° to 2θ = 19.00 ° as the background scattering in the region of 2θ = 15 ° -19 °, it is subtracted.
d. The overlap of the 15-19 ° region is separated into two peaks (010) and (011) assuming a Gaussian distribution. (010) The peak position, half width, and height are calculated and substituted into Equation 1. 010 Is calculated. K is 1. 0 was assumed.
Here, λ is the X-ray wavelength [Å], β010 is the half-width [rad] of the (010) peak, and θ010 is the diffraction angle [rad] of the (010) peak.
[0030]
[Expression 1]
(2) Glass transition temperature (Tg)
Using a differential scanning calorimeter DSC220C manufactured by Seiko Electronics Co., Ltd., the sample was heated to 300 ° C. and held for 10 minutes. The sample pan was taken out of the cell, rapidly cooled in liquid nitrogen, returned to the cell, and returned to the cell at 20 ° C./min. It measured by heating up at the speed | rate.
[0032]
(3) Intrinsic viscosity (IV)
a. After 0.25 g of the freeze-pulverized resin sample was dissolved in a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1) at a concentration (c) of 1.0 g / dl at 140 ° C. for 30 minutes, Ubbelohde The relative viscosity (ηrel) with the solvent was measured at 30 ° C. using a type capillary viscosity tube.
b. The ratio (ηsp / c) between the specific viscosity (ηsp) and the concentration (c) determined from this relative viscosity (ηrel) -1 was determined.
c. Similarly, the respective ratios (ηsp / c) were determined when the concentration (c) was 0.5 g / dl, 0.2 g / dl, and 0.1 g / dl.
d. From these values, the ratio (ηsp / c) when the concentration (c) was extrapolated to 0 was determined as the intrinsic viscosity [η] (dl / g).
(4) Average particle size
A cumulative distribution curve was created by the method described in JISK0069, and the value when the cumulative percentage was 50% was defined as the average particle diameter.
[0033]
(5) Copolymerization component amount
About the solution which melt | dissolved the sample in the trifluoroacetic acid, 1H-NMR was measured using a nuclear magnetic resonance apparatus (JEOL Co., Ltd. "JNM-EX270 type | mold"), each peak was assigned, From the integrated value of a peak, Calculate the mol% (A) of the dicarboxylic acid component other than terephthalic acid or its ester-forming derivative with respect to the total carboxylic acid component, and the mol% (B) of the diol component other than ethylene glycol with respect to the total diol component. A + B) was calculated.
(6) Fusion presence / absence
After solid-phase polycondensation of the melt-polymerized polymer, it is cooled to room temperature, and the ease of peeling when recovering the polyester resin from the metal plate is shown in Table 1 as ○.
A: The polyester resin is less attached to the metal plate and can be easily peeled off.
○: Adhesion of the polyester resin to the metal plate was observed, but it was easily peeled off
X: The polyester was firmly attached to the metal plate and was difficult to peel off
[0034]
Example 1
A slurry was prepared by continuously supplying terephthalic acid and ethylene glycol to a slurry preparation tank so that 13.0 parts of terephthalic acid and 5.82 parts of ethylene glycol were obtained. The slurry was continuously supplied to the first stage esterification reaction tank, and the esterification reaction was continuously carried out at approximately normal pressure at 260 ° C., and bis (2-hydroxyethyl) terephthalate having an ester reaction rate of 84% and its low A polymer was prepared. Bis (2-hydroxyethyl) terephthalate having low ester reaction rate of 95% and its low polymer are continuously fed to the second stage esterification reaction tank and reacted at 255 ° C. under normal pressure. Got.
[0035]
Further, the reaction product was continuously supplied to the first stage polycondensation reaction tank, 0.011 part of orthophosphoric acid and 0.038 part of diantimony trioxide were continuously added to the reaction product, and 2-4 kPa The reaction is continuously performed at 280 ° C. under reduced pressure at a residence time of about 1 hour, and then the reaction product in the first stage polycondensation reaction tank is continuously supplied to the second stage polycondensation reaction tank to 200 to 400 Pa. The polycondensation reaction was carried out continuously under reduced pressure at 280 ° C. for a residence time of about 1 hour.
[0036]
The resulting polycondensation reaction product was continuously extracted into water as a strand and pelletized. At this time, the pellets were transparent and did not cause substantial crystallization. The obtained pellets were pulverized by a rotary mill to obtain a pulverized product (melt polymerized polymer as a solid phase polycondensation raw material). The analysis results of the solid phase polycondensation raw material (melt polymerized polymer) are shown in the solid phase polycondensation raw material column of Table 1.
Subsequently, 1 g of the pulverized product was spread evenly on a 30 cm square metal plate, held at 120 ° C. for 2 hours under a nitrogen flow of 50 L / min in an oven, and then heated to 170 ° C. over 30 minutes. And kept at 170 ° C. for 2 hours. Further, the temperature was raised to 250 ° C. over 10 minutes and held at 250 ° C. for 10 minutes to carry out solid phase polycondensation. Thereafter, cooling from 250 ° C. to room temperature was performed by switching off the heater while continuing to supply nitrogen. The time required for the oven temperature to drop from 250 ° C. to 200 ° C. was 25 minutes. The analysis results of the obtained polymer are shown in the product column of Table 1.
[0037]
Example 2
Instead of orthophosphoric acid and diantimony trioxide, 0.000135 parts of ethyl acid phosphate, 0.000794 parts of magnesium acetate tetrahydrate and 0.00213 parts of tetrabutoxytitanium are continuously added to the first stage polycondensation reaction tank. A pulverized product (solid phase polycondensation raw material (melt polymerized polymer)) was obtained in the same manner as in Example 1 except that it was supplied. The analysis results of the solid phase polycondensation raw material (melt polymerized polymer) are shown in the solid phase polycondensation raw material column of Table 1. Subsequently, solid phase polycondensation was carried out in the same manner as in Example 1 except that the solid phase polycondensation temperature and the solid phase polycondensation time shown in Table 1 were used. The analysis results of the obtained polymer are shown in the product column of Table 1.
Example 3
A pulverized product (solid phase polycondensation raw material (melt polymerized polymer)) was obtained in the same manner as in Example 2 except that the amount of tetrabutoxytitanium was 0.00324 part. The analysis results of the solid phase polycondensation raw material (melt polymerized polymer) are shown in the solid phase polycondensation raw material column of Table 1. Subsequently, solid phase polycondensation was carried out in the same manner as in Example 1 except that the solid phase polycondensation temperature and the solid phase polycondensation time shown in Table 1 were used. The analysis results of the obtained polymer are shown in the product column of Table 1.
Example 4
A pulverized product (solid phase polycondensation raw material (melted) was prepared in the same manner as in Example 3 except that 0.34 parts of isophthalic acid and 12.7 parts of terephthalic acid were continuously supplied to the slurry preparation tank instead of 13 parts of terephthalic acid. Polymerized polymer)) was obtained. The analysis results of the solid phase polycondensation raw material (melt polymerized polymer) are shown in the solid phase polycondensation raw material column of Table 1. Subsequently, solid phase polycondensation was carried out in the same manner as in Example 1 except that the solid phase polycondensation temperature and the solid phase polycondensation time shown in Table 1 were used. The analysis results of the obtained polymer are shown in the product column of Table 1.
Example 5
A pulverized product (solid phase polycondensation raw material (melt polymerized polymer) was obtained in the same manner as in Example 3 except that the polycondensation reaction time was extended at 280 ° C. under a reduced pressure of 200 to 400 Pa and a freeze pulverizer was used for pulverization. )). The analysis results of the solid phase polycondensation raw material (melt polymerized polymer) are shown in the solid phase polycondensation raw material column of Table 1. Subsequently, solid phase polycondensation was carried out in the same manner as in Example 1 except that the solid phase polycondensation temperature and the solid phase polycondensation time shown in Table 1 were used. The analysis results of the obtained polymer are shown in the product column of Table 1.
Example 6
A pulverized product (solid phase polycondensation raw material (melt polymerized polymer)) was obtained in the same manner as in Example 3 except that the pulverization time in the rotary mill was shortened. The analysis results of the solid phase polycondensation raw material (melt polymerized polymer) are shown in the solid phase polycondensation raw material column of Table 1. Subsequently, solid phase polycondensation was carried out in the same manner as in Example 1 except that the solid phase polycondensation temperature and the solid phase polycondensation time shown in Table 1 were used. The analysis results of the obtained polymer are shown in the product column of Table 1.
Example 7
1 g of the pulverized product obtained in Example 3 (solid phase polycondensation raw material (melt polymerized polymer)) is spread evenly on a 30 cm square metal plate, and 120 g in a stationary state under a nitrogen flow of 50 L / min in an oven. After holding at 0 ° C. for 2 hours, the temperature was raised to 170 ° C. over 30 minutes and held at 170 ° C. for 30 minutes. Once cooled to room temperature, the recovered pulverized product was used as a solid phase polycondensation raw material (melt polymerized polymer), and solid phase polycondensation was carried out in the same manner as in Example 1. The analysis results of the obtained polymer are shown in the product column of Table 1.
[0038]
Comparative Example 1
An esterification reaction and a polycondensation reaction were carried out in the same manner as in Example 1.
About 50 g of the polycondensation reaction product is extracted on a hot plate maintained at 180 ° C. ± 10 ° C. from a nozzle attached to the bottom of the polycondensation tank so that the height from the surface of the hot plate is 2 mm or less and held for 5 minutes. Crystallized. The obtained crystallized product was pulverized with a coffee mill to obtain a pulverized product (solid phase polycondensation raw material (melt polymerization polymer)). The analysis results of the solid phase polycondensation raw material (melt polymerized polymer) are shown in the solid phase polycondensation raw material column of Table 1.
[0039]
Subsequently, the pulverized product was subjected to solid phase polycondensation in the same manner as in Example 1. The analysis results of the obtained polymer are shown in the product column of Table 1.
Implementation The same solid phase polycondensation time as in Example 1 shows that the resulting polymer has a low intrinsic viscosity, indicating that the polycondensation rate is slow.
Comparative Example 2
After performing esterification reaction and polycondensation reaction in the same manner as in Example 2, the obtained polycondensation reaction product was treated in the same manner as in Comparative Example 1 to give a pulverized product (solid phase polycondensation raw material (melt polymerization pomer)) ) The analysis results of the solid phase polycondensation raw material (melt polymerized polymer) are shown in the solid phase polycondensation raw material column of Table 1.
[0040]
Subsequently, the pulverized product was subjected to solid phase polycondensation in the same manner as in Example 1. The analysis results of the obtained polymer are shown in the product column of Table 1.
Implementation The same solid phase polycondensation time as in Example 2 indicates that the resulting polymer has a low intrinsic viscosity, indicating that the polycondensation rate is slow.
Comparative Example 3
A pulverized product (solid phase polycondensation raw material (melting) was prepared in the same manner as in Example 3 except that 0.73 parts of isophthalic acid and 12.3 parts of terephthalic acid were continuously supplied to the slurry preparation tank instead of 13 parts of terephthalic acid. Polymerized polymer)) was obtained. The analysis results of the solid phase polycondensation raw material (melt polymerized polymer) are shown in the solid phase polycondensation raw material column of Table 1. Subsequently, solid phase polycondensation was carried out in the same manner as in Example 1 except that the solid phase polycondensation temperature and the solid phase polycondensation time shown in Table 1 were used. The analysis results of the obtained polymer are shown in the product column of Table 1.
Comparative Example 4
Except for using the pulverized product obtained in Example 3 (solid phase polycondensation raw material (melt polymerized polymer)) and setting the solid phase polycondensation temperature and solid phase polycondensation time described in Table 1, the same procedure as in Example 1 was performed. Solid phase polycondensation was performed. The analysis results of the obtained polymer are shown in the product column of Table 1.
[0041]
[Table 1]
【The invention's effect】
According to the method of the present invention, a solid phase polycondensation rate is high, and a high molecular weight polyester resin can be obtained at a very high speed.
Further, according to the method of the present invention, it is possible to perform solid-phase polycondensation of polyester at high speed without adopting special conditions such as high vacuum, and to the fusion of the obtained polyester resins, or to a reaction apparatus. Since there is no problem of handling properties such as adhesion of the polyester resin, polyester can be produced industrially advantageously and with good productivity.
Claims (22)
（１）テレフタル酸成分およびエチレングリコール成分以外の共重合成分量が５．５以下、固有粘度が０．０８ｄｌ／ｇ以上０．５０ｄｌ／ｇ以下、かつ見掛け結晶子サイズが９ｎｍ未満の溶融重合ポリマーを得、
（２）該溶融重合ポリマーの固相重縮合温度への昇温を固相重縮合後のポリエステル樹脂の見掛け結晶子サイズが９ｎｍ未満を維持するようにコントロールしつつ行い、
（３）該溶融重合ポリマーを、該溶融重合ポリマーのガラス転移温度より１４０℃高い温度以上、融点以下の温度で固相重縮合することにより、見掛け結晶子サイズ９ｎｍ未満のポリエステル樹脂を得る、
ことを特徴とするポリエステル樹脂の製造方法。A melt-polymerized polymer produced by polycondensing a dicarboxylic acid component containing terephthalic acid or an ester-forming derivative thereof as a main component with a diol component containing ethylene glycol as a main component via an esterification reaction or a transesterification reaction. In the method of producing a polyester resin by solid phase polycondensation,
(1) A melt-polymerized polymer having an amount of copolymerization component other than terephthalic acid component and ethylene glycol component of 5.5 or less, an intrinsic viscosity of 0.08 dl / g or more and 0.50 dl / g or less, and an apparent crystallite size of less than 9 nm And
(2) Performing the temperature rise to the solid phase polycondensation temperature of the melt polymerization polymer while controlling the apparent crystallite size of the polyester resin after solid phase polycondensation to be less than 9 nm,
(3) Polyester resin having an apparent crystallite size of less than 9 nm is obtained by solid-phase polycondensation of the melt polymerized polymer at a temperature of 140 ° C. higher than the glass transition temperature of the melt polymerized polymer and below the melting point.
A method for producing a polyester resin.
（１）テレフタル酸成分およびエチレングリコール成分以外の共重合成分量が５．５以下、固有粘度が０．０８ｄｌ／ｇ以上０．５０ｄｌ／ｇ以下、かつ見掛け結晶子サイズが９ｎｍ未満の溶融重合ポリマーを、
（２）該溶融重合ポリマーの固相重縮合温度への昇温を固相重縮合後のポリエステル樹脂の見掛け結晶子サイズが９ｎｍ未満を維持するようにコントロールしつつ行い、
（３）該溶融重合ポリマーの見掛け結晶子サイズを９ｎｍ未満に維持した状態で、該溶融重合ポリマーのガラス転移温度より１４０℃高い温度以上、融点以下の温度で固相重縮合する、
ことを特徴とするポリエステル樹脂の製造方法。A melt-polymerized polymer produced by polycondensing a dicarboxylic acid component containing terephthalic acid or an ester-forming derivative thereof as a main component with a diol component containing ethylene glycol as a main component via an esterification reaction or a transesterification reaction. In the method of producing a polyester resin by solid phase polycondensation,
(1) A melt-polymerized polymer having an amount of copolymerization component other than terephthalic acid component and ethylene glycol component of 5.5 or less, an intrinsic viscosity of 0.08 dl / g or more and 0.50 dl / g or less, and an apparent crystallite size of less than 9 nm The
(2) Performing the temperature rise to the solid phase polycondensation temperature of the melt polymerization polymer while controlling the apparent crystallite size of the polyester resin after solid phase polycondensation to be less than 9 nm,
(3) Solid state polycondensation at a temperature not lower than the melting point and not lower than 140 ° C. above the glass transition temperature of the melt polymerization polymer in a state where the apparent crystallite size of the melt polymerization polymer is maintained below 9 nm.
A method for producing a polyester resin.
（１）溶融重合により、テレフタル酸成分及びエチレングリコール成分以外の共重合成分量が５．５以下で、固有粘度が０．２０ｄｌ／ｇ以上で０．５０ｄｌ／ｇ以下の液状の溶融重合ポリマーを生成させ、
（２）該溶融重合ポリマーを急冷して、見掛け結晶子サイズが９ｎｍ未満の固体状の溶融重合ポリマーとし、
（３）該固体状の溶融重合ポリマーを、平均粒径１５００μｍ以下にして、
（４）該溶融重合ポリマーの固相重縮合温度への昇温を固相重縮合後のポリエステル樹脂の見掛け結晶子サイズが９ｎｍ未満を維持するようにコントロールしつつ行い、
（５）そのガラス転移点よりも１４０℃以上高くてかつ融点以下の温度で、固有粘度が０．６０ｄｌ／ｇ以上となるまで固相重縮合する、ことを特徴とするポリエステル樹脂の製造方法。A melt-polymerized polymer produced by polycondensing a dicarboxylic acid component containing terephthalic acid or an ester-forming derivative thereof as a main component with a diol component containing ethylene glycol as a main component via an esterification reaction or a transesterification reaction. In the method for producing a polyester resin by solid phase polycondensation,
(1) By melt polymerization, a liquid melt polymerization polymer having a copolymer component amount other than terephthalic acid component and ethylene glycol component of 5.5 or less and an intrinsic viscosity of 0.20 dl / g or more and 0.50 dl / g or less. Generated,
(2) The melt polymerized polymer is rapidly cooled to form a solid melt polymerized polymer having an apparent crystallite size of less than 9 nm ,
(3) The solid melt polymerization polymer is made to have an average particle size of 1500 μm or less,
(4) The temperature of the melt-polymerized polymer is raised to a solid phase polycondensation temperature while controlling the apparent crystallite size of the polyester resin after the solid phase polycondensation to be less than 9 nm,
(5) A method for producing a polyester resin, characterized in that solid-phase polycondensation is carried out at a temperature higher than the glass transition point by 140 ° C. or higher and below the melting point until the intrinsic viscosity becomes 0.60 dl / g or higher.
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