JPH03231918A - Production of polyester - Google Patents
Production of polyesterInfo
- Publication number
- JPH03231918A JPH03231918A JP2595590A JP2595590A JPH03231918A JP H03231918 A JPH03231918 A JP H03231918A JP 2595590 A JP2595590 A JP 2595590A JP 2595590 A JP2595590 A JP 2595590A JP H03231918 A JPH03231918 A JP H03231918A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polymerization
- polyester
- diethylene glycol
- anthraquinone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000001045 blue dye Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 claims description 9
- 238000005809 transesterification reaction Methods 0.000 claims description 7
- 150000003609 titanium compounds Chemical class 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000975 dye Substances 0.000 abstract description 7
- 229910052719 titanium Inorganic materials 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 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 abstract description 3
- 150000002148 esters Chemical group 0.000 abstract description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 abstract 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 abstract 1
- 150000004056 anthraquinones Chemical class 0.000 abstract 1
- -1 polyethylene terephthalate Polymers 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 235000013305 food Nutrition 0.000 description 9
- 239000010936 titanium Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 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 4
- 230000000694 effects Effects 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 3
- 150000001869 cobalt compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000243 solution Substances 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 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
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-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
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- OVSGBKZKXUMMHS-VGKOASNMSA-L (z)-4-oxopent-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O OVSGBKZKXUMMHS-VGKOASNMSA-L 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
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- ZLWSWTKSTUPKDY-UHFFFAOYSA-K 16-methylheptadecanoate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)CCCCCCCCCCCCCCC([O-])=O.CC(C)CCCCCCCCCCCCCCC([O-])=O.CC(C)CCCCCCCCCCCCCCC([O-])=O ZLWSWTKSTUPKDY-UHFFFAOYSA-K 0.000 description 1
- UNQWKAVGUZNMJZ-UHFFFAOYSA-N 2,3-dibromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1Br UNQWKAVGUZNMJZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-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 compound O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- 241000219122 Cucurbita Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HIXLYTANKXBHBK-UHFFFAOYSA-H [Ca+2].C(CCC)(=O)[O-].[Ti+4].C(CCC)(=O)[O-].C(CCC)(=O)[O-].C(CCC)(=O)[O-].C(CCC)(=O)[O-].C(CCC)(=O)[O-] Chemical compound [Ca+2].C(CCC)(=O)[O-].[Ti+4].C(CCC)(=O)[O-].C(CCC)(=O)[O-].C(CCC)(=O)[O-].C(CCC)(=O)[O-].C(CCC)(=O)[O-] HIXLYTANKXBHBK-UHFFFAOYSA-H 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JXSVIVRDWWRQRT-UYDOISQJSA-N asiatic acid Chemical compound C1[C@@H](O)[C@H](O)[C@@](C)(CO)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C JXSVIVRDWWRQRT-UYDOISQJSA-N 0.000 description 1
- 229940011658 asiatic acid Drugs 0.000 description 1
- LBGFKBYMNRAMFC-PYSQTNCISA-N asiatic acid Natural products C[C@@H]1CC[C@@]2(CC[C@]3(C)C(=CC[C@@H]4[C@@]5(C)C[C@@H](O)[C@H](O)[C@@](C)(CO)[C@@H]5CC[C@@]34C)[C@]2(C)[C@H]1C)C(=O)O LBGFKBYMNRAMFC-PYSQTNCISA-N 0.000 description 1
- NWCHELUCVWSRRS-UHFFFAOYSA-N atrolactic acid Chemical compound OC(=O)C(O)(C)C1=CC=CC=C1 NWCHELUCVWSRRS-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 235000012745 brilliant blue FCF Nutrition 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 description 1
- 238000005443 coulometric titration Methods 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- MNRCEJBREMEIAP-UHFFFAOYSA-N dihydroxymethyl dihydrogen phosphate Chemical compound OC(O)OP(O)(O)=O MNRCEJBREMEIAP-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CLXOLTFMHAXJST-UHFFFAOYSA-N esculentic acid Natural products C12CC=C3C4CC(C)(C(O)=O)CCC4(C(O)=O)CCC3(C)C1(C)CCC1C2(C)CCC(O)C1(CO)C CLXOLTFMHAXJST-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 210000000554 iris Anatomy 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WIZHEAWZAHMLOR-UHFFFAOYSA-H magnesium butanoate titanium(4+) Chemical compound [Mg+2].C(CCC)(=O)[O-].[Ti+4].C(CCC)(=O)[O-].C(CCC)(=O)[O-].C(CCC)(=O)[O-].C(CCC)(=O)[O-].C(CCC)(=O)[O-] WIZHEAWZAHMLOR-UHFFFAOYSA-H 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- KQJBQMSCFSJABN-UHFFFAOYSA-N octadecan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-] KQJBQMSCFSJABN-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- IBBQVGDGTMTZRA-UHFFFAOYSA-N sodium;2-sulfobenzene-1,3-dicarboxylic acid Chemical compound [Na].OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O IBBQVGDGTMTZRA-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- RGZQGGVFIISIHZ-UHFFFAOYSA-N strontium titanium Chemical compound [Ti].[Sr] RGZQGGVFIISIHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- CYZVXAGZWYPHNJ-UHFFFAOYSA-J tetrapotassium oxalate Chemical compound C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].[K+].[K+].[K+].[K+] CYZVXAGZWYPHNJ-UHFFFAOYSA-J 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野１
本発明はポリエステルの製造法に関し、詳しくは透明性
が良好で且つ材質から充填物への溶出が実質的にない、
食品包装材料に適した色相良好なポリエステルの製造法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a method for producing polyester, and more specifically, a polyester having good transparency and substantially no elution from the material to the filler.
This invention relates to a method for producing polyester with good color and suitable for food packaging materials.
［従来の技術］
ポリエステルは物理的材質、化学的材質、透明性にすぐ
れるため、繊維、フィルム、工業用樹脂の他、近年、食
品包装容器としても広く使われている。[Prior Art] Polyester has excellent physical properties, chemical properties, and transparency, so it has been widely used in recent years not only as fibers, films, and industrial resins, but also as food packaging containers.
食品包装容器として、ポリ塩化ビニルの様に可塑剤を使
用することなく、またポリアクリロニトリルの様な有害
なモノマーを残存しないことがら、ポリエチレンテレフ
タレートは食品衛生上すぐれている。そしてガラス並に
透明性を高めるため、触媒はポリマーに溶解性のよいも
のが選ばれている。例えば重合触媒として、繊維、フィ
ルム、工業用樹脂用等に広く用いられている三酸化アン
チモンの代りに三酸化ゲルマニウムが好んで用いられて
いる。As food packaging containers, polyethylene terephthalate is excellent in terms of food hygiene because it does not require the use of plasticizers like polyvinyl chloride and does not leave behind harmful monomers like polyacrylonitrile. In order to make the material as transparent as glass, the catalyst is selected to have good solubility in the polymer. For example, germanium trioxide is preferably used as a polymerization catalyst in place of antimony trioxide, which is widely used for fibers, films, industrial resins, and the like.
また、エステル交換法による場合は、ＥＩ触媒としてカ
ルシウムやマグネシウムよりも、可溶性の有機チタン化
合物が用いられている。Furthermore, in the case of transesterification, a soluble organic titanium compound is used as the EI catalyst rather than calcium or magnesium.
［発明が解決しようとする問題点］
有機チタン化合物はポリマーに対する溶解性がすぐれる
ため、ポリマーの透明性は良好であるが、ポリマーが若
干黄味に着色する上、成形時の熱安定性が低い傾向があ
る。[Problems to be solved by the invention] Since organic titanium compounds have excellent solubility in polymers, the transparency of the polymers is good, but the polymers are slightly yellowish in color and have poor thermal stability during molding. tends to be low.
色相についてはコバルト化合物等の調色剤を使用するこ
とが知られている（例えば特開昭５７１６５４２４号）
ものの、コバルト化合物はポリマーの熱安定性を損う傾
向がある上、酸性食品液等に微量ではあるが溶出する恐
れがある。同様に染料でも銅フタロシアニン系のものは
衛生上問題がある。For hue, it is known to use a toning agent such as a cobalt compound (for example, JP-A-57165424).
However, cobalt compounds tend to impair the thermal stability of polymers, and there is a risk that cobalt compounds may be eluted, albeit in small amounts, into acidic food liquids. Similarly, copper phthalocyanine-based dyes are hygienic.
本発明者らは、安全衛生上問題がなく且つ透明性良好で
成形性に優れ、しかも色相の良好な食品包装用途に供し
得るポリエステルの製造技術を提供するものである。The present inventors provide a technology for producing polyester that is free from health and safety problems, has good transparency, excellent moldability, and has a good hue and can be used for food packaging purposes.
［問題点を解決するための手段］
本発明は、有機チタン化合物をエステル交換触媒又はエ
ステル化触媒とし、テレフタル酸を主たる酸成分、エチ
レングリコールを主たるグリコール成分とするポリエス
テルを製造するに際し、ジエチレングリコールを反応中
に０．９〜２．２重量％副生きせること、及び重合初期
以前の段階でアントラキノン系ブルー染料を０．０５〜
２．Ｏｐｐｍ添加３−
することを特徴とするポリエステルの製造法である。[Means for Solving the Problems] The present invention uses an organic titanium compound as a transesterification catalyst or an esterification catalyst to produce a polyester containing terephthalic acid as the main acid component and ethylene glycol as the main glycol component. The amount of anthraquinone blue dye should be 0.9 to 2.2% by weight during the reaction, and 0.05 to 2.2% by weight should be added to the anthraquinone blue dye before the initial stage of polymerization.
2. This is a method for producing polyester characterized by adding Oppm.
本発明において「ポリエステル」とはテレフタル酸を主
たる酸成分とし、エチレングリコールを主たるグリコー
ルとするポリエチレンテレフタレートである。ここに「
主たる」とは９５モル％以上を言い、５モル％未満のテ
レフタル酸、エチレングリコール、ジエチレングリコー
ル以外の第３成分を含有することが出来る。In the present invention, "polyester" refers to polyethylene terephthalate containing terephthalic acid as the main acid component and ethylene glycol as the main glycol. Here"
"Main" means 95 mol% or more, and can contain less than 5 mol% of a third component other than terephthalic acid, ethylene glycol, and diethylene glycol.
共重合可能な第３成分としてはテレフタル酸。The third copolymerizable component is terephthalic acid.
エチレングリコール、ジエチレングリコール以外のジカ
ルボン酸及びジオール又はオキシ酸がある。There are dicarboxylic acids and diols or oxyacids other than ethylene glycol and diethylene glycol.
具体的には、芳香族ジカルボン酸、たとえば、イソフタ
ル酸、ナフタレンジカルボン酸、ジフェニルジカルボン
酸、ジフェニルエーテルジカルボン酸、ジフェニルスル
ホンジカルボン酸、ジフェニルケトンジカルボン酸、ナ
トリウム−スルホイソフタル酸、ジブロモテレフタル酸
など；脂環族シカフレボン酸、たとえば、デカリンジカ
ルボン酸。Specifically, aromatic dicarboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ketone dicarboxylic acid, sodium-sulfoisophthalic acid, dibromoterephthalic acid, etc.; Group cicaflebonic acids, for example decalindicarboxylic acid.
ヘキサヒドロテレフタル酸など；脂肪族ジカルボ４−
ン酸、たとえばマロン酸、コハク酸、アジピン酸などが
例示される。またグリコール成分としては、脂肪族ジオ
ール、たとえばトリメチレングリコール、テ１〜ラメチ
レングリコール、ヘキサメチレングリコールなど；芳香
族ジオール、たとえばビトロノン、カテコール、ナフタ
レンジオール、レゾルシン、 ４．４’ −ジヒドロ
キシ−ジフェニル−スルホン、ビスフェノールＡ ［２
，２’ −ビス（４ヒドロキシフエニル）プロパン］、
テトラブロモビスフェノールＡ、ビスヒドロキシエトキ
シビスフェノールＡなど；脂環族ジオール、たとえばシ
クロヘキサンジオールなど：脂肪族オキシカルボン酸、
たとえばグリコール酸、ヒドロアクリル酸。Examples include hexahydroterephthalic acid and the like; aliphatic dicarboxylic acids such as malonic acid, succinic acid, and adipic acid. Glycol components include aliphatic diols such as trimethylene glycol, 1-ramethylene glycol, hexamethylene glycol, etc.; aromatic diols such as vitronone, catechol, naphthalene diol, resorcinol, 4,4'-dihydroxy-diphenyl- Sulfone, bisphenol A [2
,2'-bis(4hydroxyphenyl)propane],
Tetrabromobisphenol A, bishydroxyethoxybisphenol A, etc.; Alicyclic diols, such as cyclohexanediol; Aliphatic oxycarboxylic acids,
For example, glycolic acid, hydroacrylic acid.
３−オキシプロピオン酸など：脂環族オキシカルボン酸
、たとえばアジアチン酸、キノバ酸など；芳香族オキシ
カルボン酸、たとえばサリチル酸。3-oxypropionic acid, etc.; alicyclic oxycarboxylic acids, such as asiatic acid, quinobic acid, etc.; aromatic oxycarboxylic acids, such as salicylic acid.
ｍ−オキシ安息香酸、ｐ−オキシ安息香酸、マンデル酸
、アトロラクチン酸などを挙げることができる。Examples include m-oxybenzoic acid, p-oxybenzoic acid, mandelic acid, atrolactic acid, and the like.
さらにポリエステルが実質的に線上である範囲内で３価
以上の多官能化合物、たとえばグリセリン、トリメチロ
ールプロパン、ペンタエリスリトール、トリメリット酸
、トリメシン酸、ビロメリトット酸、トリカルバリル酸
、没食子酸などを共重合してもよく、要すれば単官能化
合物、たとえば０−ベンゾイル安息香酸、ナフトエ酸な
どを添加してもよい。Furthermore, a polyfunctional compound of trivalent or higher valence, such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, trimesic acid, biromellitotic acid, tricarballylic acid, gallic acid, etc., is copolymerized within the range where the polyester is substantially linear. If necessary, a monofunctional compound such as 0-benzoylbenzoic acid or naphthoic acid may be added.
本発明のポリエステルは、エステル化又はエステル変換
触媒として有機チタン化合物を用いる。The polyester of the present invention uses an organic titanium compound as an esterification or ester conversion catalyst.
有機チタン化合物としては例えば、テトラブチルチタネ
ート、テトライソプロピルチタネート。Examples of organic titanium compounds include tetrabutyl titanate and tetraisopropyl titanate.
テトラ（２−エチルヘキシル）ヂタネート、テトラステ
アリルチタネート、ジイソプロポキシビス（アセチルア
セトナート）チタン、ジーｎ−ブ１〜キシビス（トリエ
タノールアミナート）チタン。Tetra(2-ethylhexyl) ditanate, tetrastearyl titanate, diisopropoxybis(acetylacetonato)titanium, di-n-b1-xybis(triethanolaminate)titanium.
トリブチルモノアセチルチタネート、トリイソプロピル
モノアセチルチタネート、ジヒドロキシビス（ラフター
ト）チタン、チタニウムイソブロボキシオクチレングリ
コレート、イソプロポキシチタントリイソステアレート
、テトラ安息香酸チタネート、トリメリット酸チタン、
酢酸チタン、チタンメチレートマグネシウム、チタンブ
チレートマグネシウム、チタンオクチレートマグネシウ
ム。Tributyl monoacetyl titanate, triisopropyl monoacetyl titanate, dihydroxybis(raftate) titanium, titanium isobroboxyoctylene glycolate, isopropoxytitanium triisostearate, tetrabenzoic acid titanate, titanium trimellitate,
Titanium acetate, magnesium titanium methylate, magnesium titanium butyrate, magnesium titanium octylate.
チタンブチレートカルシウム、チタンエチレートストロ
ンチウム、テトラブチルチタネートと無水トリメリット
酸との反応生成物、及びこれらの部分加水分解物；シュ
ウ酸チタン、ジオキザラートヂタン＜ｍ＞酸カリウム、
ジオキザラートヂタン（ＩＩＩ）酸アンモニシウム、オ
キソジオキザラートチタン（ＩＶ）酸水素、オキソジオ
キザラートチタン（ＩＶ）酸ナトリウム、オキソジオキ
ザラートヂタン（ＩＶ）酸バリウム、トリオキザラート
（ＩＶ）酸カルシウム及びこれらの水和物等をあげるこ
とができる。これらのうち、熱安定性、加水分解安定性
、ポリマーへの溶解性等の点から、酢酸チタン、トリメ
リット酸チタンが好ましい。Calcium titanium butyrate, strontium titanium ethylate, reaction products of tetrabutyl titanate and trimellitic anhydride, and partial hydrolysates thereof; titanium oxalate, potassium dioxalate ditanate,
Ammonium dioxalatoditanate (III), oxodioxalate titanate (IV) hydrogen, sodium oxodioxalate titanate (IV), barium oxodioxalate titanate (IV), trioxalate (IV) ) acid calcium and their hydrates. Among these, titanium acetate and titanium trimellitate are preferred in terms of thermal stability, hydrolytic stability, solubility in polymers, and the like.
使用量としではチタン原子として５〜２０１１１１ｍ程
度が好ましい。The amount used is preferably about 5 to 201111 m in terms of titanium atoms.
本発明において、ポリエステルの反応中に、ジエチレン
グリコールを０，９〜２．２重量％副生させ７−
る。ポリエステル製造時、ポリマー中残存率が０．９〜
２．２重量％となる様にジエチレングリコールを添加し
てはならない。添加すると微量であるが未反応のジエチ
レングリコールが残存し、衛生上問題がある。従って、
ジエチレングリコールは反応中に共重合される様な形で
副生させる必要がある。具体的な方法としては、例えば
（１）重合初期に高温常圧保持時間を通常より長目にと
る。In the present invention, 0.9 to 2.2% by weight of diethylene glycol is produced as a by-product during the polyester reaction. When producing polyester, the residual rate in the polymer is 0.9~
Do not add diethylene glycol to 2.2% by weight. When added, a small amount of unreacted diethylene glycol remains, which poses a hygiene problem. Therefore,
Diethylene glycol must be produced as a by-product in such a way that it can be copolymerized during the reaction. As a specific method, for example, (1) the holding time at high temperature and normal pressure is set longer than usual in the initial stage of polymerization.
（２） エステル化又はエステル交換反応終了後、リ
ン系安定剤を添加した状態で保持する。(2) After the esterification or transesterification reaction is completed, the phosphorus stabilizer is added and maintained.
（３） 重合触媒（特にゲルマニウム化合物の場合）
の添加時期をエステル化又はエステル交換反応終了以前
とする。(3) Polymerization catalyst (especially for germanium compounds)
The timing of addition is before the completion of the esterification or transesterification reaction.
等が例示される。etc. are exemplified.
ジエチレングリコールの副生共重合量は、ポリエステル
に対して０．９〜２．２重量％である。０．９重量％未
満では溶融成形温度を高くする必要があり、熱分解を起
し易い。成形温度を高めない場合には、溶融時、高粘度
で剪断発熱が起こり、肖り８−
くポリマーが劣化する。２．２重量％を超えると、成形
温度は下げられるが、エーテル結合が主鎖に入りすぎ、
これによってポリマーが熱的に不安定となる。０．９〜
２．２重量％の範囲にある限り、熱安定性と流動性のバ
ランスがとれ、良好な成形品が得られる。The amount of diethylene glycol copolymerized as a by-product is 0.9 to 2.2% by weight based on the polyester. If it is less than 0.9% by weight, it is necessary to increase the melt molding temperature and thermal decomposition is likely to occur. If the molding temperature is not raised, the high viscosity will cause shear heat generation during melting, which will cause the polymer to deteriorate. If it exceeds 2.2% by weight, the molding temperature can be lowered, but too many ether bonds enter the main chain,
This makes the polymer thermally unstable. 0.9～
As long as the content is within the range of 2.2% by weight, thermal stability and fluidity are well balanced and good molded products can be obtained.
本発明において、更に重合初期以前にアントラキノン系
ブルー染料を０，０５〜２．０ｐｐｍ添加する。In the present invention, 0.05 to 2.0 ppm of anthraquinone blue dye is further added before the initial stage of polymerization.
コバルトや銅フタロシアニン系ブルー染料は酸性食品液
やアルコール食品液で溶出し、食品衛生上不適当である
。アントラキノン系ブルー染料では、上記０．０５〜２
．Ｏｏｐｍの範囲では、酸、アルコール、オイル等疑似
食品液で溶出テストを行なっても、極めて感度のよい紫
外分光光度計ですら、検知せず、実質的に溶出しない。Cobalt and copper phthalocyanine-based blue dyes dissolve in acidic and alcoholic food liquids, making them unsuitable for food hygiene. For anthraquinone blue dyes, the above 0.05 to 2
．． In the Oopm range, even if an elution test is performed with a simulated food liquid such as acid, alcohol, or oil, even an extremely sensitive ultraviolet spectrophotometer will not detect it, and virtually no elution will occur.
アントラキノン系ブルー染料の添加時期は、重合初期以
前、特に内温が２６０℃以下の時点が好ましい。重合中
期以降、後期に添加すると、調色の効果が小さいばかり
か、異物が発生する場合がある。The anthraquinone blue dye is preferably added before the initial stage of polymerization, especially when the internal temperature is 260° C. or lower. If added at the middle or late stage of polymerization, not only the toning effect will be small but also foreign matter may be generated.
アントラキノン系ブルー染料の添加量は０．０５〜２．
０ｐｐｍである。０．Ｏ５ｐｐｍ未満では調色の効果が
少なく、２．Ｏｐｐｍを超えると青味が強すぎ、チタン
触媒によってベースの黄味が強いと緑色がかることもあ
る。The amount of anthraquinone blue dye added is 0.05 to 2.
It is 0 ppm. 0. If O is less than 5 ppm, the toning effect is small; 2. If it exceeds Oppm, the blue tint will be too strong, and if the base has a strong yellow tint due to the titanium catalyst, it may take on a green tint.
アントラキノン系ブルー染料としては、特に１．４−ビ
ス（メチルフェニルアミノ）アントラキノン−３−スル
ホン酸が好ましい。本発明の範囲内で初めて透明且つ色
相良好なポリマーが得られる。As the anthraquinone blue dye, 1,4-bis(methylphenylamino)anthraquinone-3-sulfonic acid is particularly preferred. Polymers that are transparent and have good color can be obtained for the first time within the scope of the present invention.
本発明においては、必要に応じて他の添加剤、たとえば
着色剤、抗酸化剤、紫外線吸収剤、帯電防止剤、Ｎ燃剤
などを使用してもよいが、食品衛生上、できる限り何も
添加しない方がよい。In the present invention, other additives such as colorants, antioxidants, ultraviolet absorbers, antistatic agents, N reagents, etc. may be used as necessary, but from the viewpoint of food hygiene, as little as possible is added. It's better not to.
［実施例］
以下実施例により、本発明を補説する。なお、実施例中
「部」は、重量部を意味する。又、実施例中で用いた特
性の測定法を以下に示す。[Example] The present invention will be explained below with reference to Examples. In addition, "parts" in the examples mean parts by weight. In addition, methods for measuring characteristics used in the examples are shown below.
１）固有粘度：［η］
フェノール／テトラクロロエタン（重量比６０／４０）
の混合溶媒を用い、３５℃で測定した溶液粘度から算出
した。1) Intrinsic viscosity: [η] Phenol/tetrachloroethane (weight ratio 60/40)
It was calculated from the solution viscosity measured at 35°C using a mixed solvent of
２）ポリマー色相：Ｌ、ａ、ｂ
ポリマーを１４０℃×１時間熱処理し、ハンター式カラ
ーマシンで測定した。2) Polymer hue: L, a, b The polymer was heat treated at 140°C for 1 hour and measured using a Hunter color machine.
３）ポリマー中ジエチレングリコール濃度＝ＤＥポリマ
ーをヒドラジン分解し、ガスクロマトグラフィーによっ
て定量した。3) Diethylene glycol concentration in polymer = DE The polymer was decomposed with hydrazine and determined by gas chromatography.
４）ヘーズ：
３オンスの射出成形機（来遊機械製、ｌＳ−６０３型）
を囲い、シリンダー温度２７０℃、射出圧力３Ｑ１ｇ
／ ｃｉ 、成形サイクル３５秒、金型温度２０〜３０
℃の条件で、１００＃＋×１００ＩＩＩＩＲ×２１１１
＃Ｉの平板を射出成形する。4) Haze: 3 oz injection molding machine (Raiyu Kikai, model 1S-603)
cylinder temperature 270℃, injection pressure 3Q1g
/ci, molding cycle 35 seconds, mold temperature 20-30
Under the conditions of ℃, 100#+×100IIIR×2111
Injection mold a #I flat plate.
この平板を積分球式温度計を用い、ヘーズを測定する。The haze of this flat plate is measured using an integrating sphere thermometer.
５）アセトアルデヒド： ３オンスの射出成型機（東芝機械株式会社製。5) Acetaldehyde: 3oz injection molding machine (manufactured by Toshiba Machine Co., Ltd.).
ｌ５−６０Ｂ型）により、外形２８ＩｌｌＩ＋＋、長さ
１６０ａ＋ｍ。15-60B type), external size 28IllI++, length 160a+m.
１１ −
肉厚２．５Ｉ！Ｉ１．重１３８ｇのプリフォームをシリ
ンダー温度２７５℃、射出圧力３０Ｋｇ／ｃｄ、成型サ
イクル３５秒、射出金型及びコア温度を２０〜３０℃の
条件で成型した。11 - Wall thickness 2.5I! I1. A preform weighing 138 g was molded under conditions of a cylinder temperature of 275°C, an injection pressure of 30 kg/cd, a molding cycle of 35 seconds, and an injection mold and core temperature of 20 to 30°C.
このプリフォームの口部をサンプリングし、冷凍粉砕、
セラニーズ法によりガスクロマトグラフィーを用いてア
セトアルデヒド（ＡＡと略記する）を定量した。The mouth of this preform was sampled, frozen and crushed.
Acetaldehyde (abbreviated as AA) was quantified using gas chromatography according to the Celanese method.
６）材質試験：
上記プリフォームを加熱し、ブロー延伸して１リボトル
を作成した。このボトルの胴部（肉厚的０．３．）をサ
ンプリングし、浴比１／ １００で４％酢酸中９５℃×
３０分で抽出後、ＩＣＰにて溶出金属を定量した。6) Material test: The above preform was heated and blow-stretched to create a 1-rebottle. The body of this bottle (wall thickness: 0.3 mm) was sampled and heated at 95°C in 4% acetic acid at a bath ratio of 1/100.
After extraction for 30 minutes, the eluted metals were quantified by ICP.
７）染料の抽出試験（ＵＶ、Ｎ、Ｓ）：前記１ρブロー
ボトルの胴部をサンプリングし、クロロホルムで室温２
０分間超音波にて抽出した。これを３回くり返して抽出
液を集め、１０倍に濃縮して紫外分光光度計にて５８０
ｎｍ 、 ６２５ｎｍ（ｉ、４−ジ（メチルフェニル
アミノ）アンド１２−
ワキノン−３〜スルホン酸の吸光波長）の吸光度を測定
した。7) Dye extraction test (UV, N, S): The body of the 1ρ blow bottle was sampled and heated with chloroform at room temperature 2.
Extraction was performed using ultrasound for 0 minutes. Repeat this three times to collect the extract, concentrate it 10 times, and measure it with an ultraviolet spectrophotometer at 580
The absorbance at 625 nm (i,4-di(methylphenylamino)and-12-waquinone-3-sulfonic acid absorption wavelength) was measured.
またクロロホルム抽出液を乾固後、残渣をメタノールに
溶解、電量滴定にて窒素とイオウを定量した。After drying the chloroform extract, the residue was dissolved in methanol, and nitrogen and sulfur were determined by coulometric titration.
実施例１〜３．比較例１〜３
ジメチレンテレフタレート１７００部、エチレングリコ
ール１１００部、酢酸チタンのエチレングリコール溶液
（Ｔｉ としＴ １．０ｗｔ％）を１．５部（Ｔｉとし
て８ｐｐｍ）エステル交換反応槽に仕込み、１７０〜２
３５℃でエステル交換反応を行った。留出物が出なくな
った時点で酸化ゲルマニウム０．３部、ジヒドロキシメ
チルホスフェートのエチレングリコール溶液（Ｐとして
５．５ｗｔ％）を１．７部添加し、重合反応槽に移した
。ここで１，４−ジ（メチルフェニルアミノ）アントラ
キノン−３−スルホン酸を所定量添加し、２６０〜２７
０℃で約１５分間常圧反応せしめ、その後、２８０℃で
高真空下（数ｓ ８９以上の高真空）にて約３時間反応
を行った。その後重合反応槽より常法によって大量の流
水中に抜きだし、［η］ ０．５３のストランド型の
チップを得た。Examples 1-3. Comparative Examples 1 to 3 1,700 parts of dimethylene terephthalate, 1,100 parts of ethylene glycol, and 1.5 parts (8 ppm of Ti) of an ethylene glycol solution of titanium acetate (Ti and T 1.0 wt%) were charged into a transesterification reaction tank, 2
The transesterification reaction was carried out at 35°C. When no more distillate was produced, 0.3 parts of germanium oxide and 1.7 parts of an ethylene glycol solution of dihydroxymethyl phosphate (5.5 wt% as P) were added, and the mixture was transferred to a polymerization reaction tank. Here, a predetermined amount of 1,4-di(methylphenylamino)anthraquinone-3-sulfonic acid was added, and 260 to 27
The reaction was carried out at normal pressure at 0°C for about 15 minutes, and then at 280°C under high vacuum (high vacuum of several seconds or more) for about 3 hours. Thereafter, it was extracted from the polymerization reaction tank into a large amount of running water by a conventional method to obtain a strand-shaped chip with [η] of 0.53.
このチップを１５０℃で２時間熱処理した後、０．５ｍ
Ｈｇの高真空下、２３０℃で１５時間同相重合を行った
。その処理したチップの［η］は０．７６で共重合ジエ
チレングリコールは実施例１．同２゜比較例１及び同２
ではいずれも１．４ｗｔ％、また実施例３及び比較例３
では１．５ｗｔ％であった。このポリマー及び成形した
１ｆｌボトルの性能は第１表の通りであった。After heat treating this chip at 150℃ for 2 hours, 0.5m
In-phase polymerization was carried out at 230° C. for 15 hours under a high vacuum of Hg. The [η] of the treated chips was 0.76, and the copolymerized diethylene glycol of Example 1. Comparative Example 1 and Comparative Example 2
In both cases, 1.4 wt%, and Example 3 and Comparative Example 3
It was 1.5 wt%. The performance of this polymer and the molded 1 fl bottle were as shown in Table 1.
第
１
表
染料添加量が多いとｂ値は下がるがＬ値の低下も大きく
透明性が劣り、色相は悪化する。また緑色を若干呈する
ようになる（比較例３）。Table 1: When the amount of dye added is large, the b value decreases, but the L value also decreases greatly, resulting in poor transparency and poor hue. In addition, it becomes slightly green (Comparative Example 3).
０．０１ ｐｐｍでは色相改善効果は殆どないく比較例
１５−
２）。At 0.01 ppm, there was almost no hue improvement effect in Comparative Example 15-2).
なおいずれもヘーズ、ＡＡは極めて少なく、また材質テ
ストで染料の溶出は認められなかった。In both cases, haze and AA were extremely low, and no dye elution was observed in material tests.
比較例４〜８
実施例１において、染料を集合末期に添加したもの（比
較例４）、常圧重合反応時間（ＮＨ＞を０分、３０分と
したもの（比較例５，６）、又、染料１，４−ジ（メチ
ルフェニルアミノ）アントラキノン−３−スルホン酸の
代りに銅フタロシアニンブルー１゜Ｏｐｐｍを用いたも
の（比較例７）、酢酸コバルト（コバルトとして２１）
Ｉ）ｌ）を用いたちのく比較例８）を第２表に示した。Comparative Examples 4 to 8 In Example 1, the dye was added at the final stage of aggregation (Comparative Example 4), the normal pressure polymerization reaction time (NH> was set to 0 minutes, 30 minutes (Comparative Examples 5 and 6), , using copper phthalocyanine blue 1° Oppm instead of dye 1,4-di(methylphenylamino)anthraquinone-3-sulfonic acid (Comparative Example 7), cobalt acetate (21 as cobalt)
I) Comparative Example 8) using l) is shown in Table 2.
１６− 蕾 〇 ＠ヨ ｃＬｏｏｏ優０ 劃 籐 瓢 菖 〇 台ヨ ｃＬｏｏｏｏｚ 徂 ； の 台ヨ Ｃ″優ｏｏｏ。16- bud 〇 @Yo cLooo Yu0 Harvest rattan gourd irises 〇 Taiwan cLoooooz Next ; of Taiwan C″Yuoooo.
昨
劃
く
く
七
五
笹
ト■三トド
□−，４８９
０−〇〇ロ
アントラキノン系でも重合末期に添加したものは色相改
善効果が少ない上、微量溶出する。ＤＥＧが少ないとボ
トルの透明性が低下し、又剪断発熱のためか、ＡＡが高
目となる。逆にＤＥＧが多すぎると熱分解のため、色相
が悪化し、ＡＡも高い。他の調色剤では金属が極微量で
はあるが検出される。Even in the case of 489 0-〇〇 loanthraquinone, added at the final stage of polymerization has little hue-improving effect and elutes in small amounts. When DEG is low, the transparency of the bottle decreases, and AA becomes high, probably due to shear heat generation. On the other hand, if there is too much DEG, the hue will deteriorate due to thermal decomposition and the AA will also be high. In other toning agents, metals are detected, albeit in very small amounts.
Claims (1)
媒とし、テレフタル酸を主たる酸成分、エチレングリコ
ールを主たるグリコール成分とするポリエステルを製造
するに際し、ジエチレングリコールを反応中に０．９〜
２．２重量％副生させること、及び重合初期以前の段階
で、アントラキノン系ブルー染料を０．０５〜２．０ｐ
ｐｍ添加することを特徴とするポリエステルの製造法。When producing a polyester containing terephthalic acid as the main acid component and ethylene glycol as the main glycol component using an organic titanium compound as a transesterification or esterification catalyst, diethylene glycol is added during the reaction from 0.9 to
By producing 2.2% by weight of anthraquinone blue dye and adding 0.05 to 2.0p of anthraquinone blue dye at a stage before the initial stage of polymerization.
A method for producing polyester, characterized by adding pm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2595590A JPH03231918A (en) | 1990-02-07 | 1990-02-07 | Production of polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2595590A JPH03231918A (en) | 1990-02-07 | 1990-02-07 | Production of polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03231918A true JPH03231918A (en) | 1991-10-15 |
Family
ID=12180180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2595590A Pending JPH03231918A (en) | 1990-02-07 | 1990-02-07 | Production of polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03231918A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1153953A4 (en) * | 1998-10-23 | 2002-12-04 | Toyo Boseki | Polymerization catalyst for polyester production, polyester, and process for producing polyester |
| JP2006152139A (en) * | 2004-11-30 | 2006-06-15 | Teijin Fibers Ltd | Polyester composition and molded product formed out of the same |
| US7132383B2 (en) | 2000-09-12 | 2006-11-07 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
| US7144614B2 (en) | 2001-02-23 | 2006-12-05 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using the same, and process for producing polyester |
| US7199212B2 (en) | 2000-01-05 | 2007-04-03 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyesters, polyesters produced with the same and process for producing polyesters |
| US7208565B1 (en) | 1999-08-24 | 2007-04-24 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyesters, polyester produced with the same, and process for production of polyester |
| JP2011012200A (en) * | 2009-07-03 | 2011-01-20 | Toray Ind Inc | Copolyester and method for producing the same |
| JP2011026438A (en) * | 2009-07-24 | 2011-02-10 | Teijin Fibers Ltd | Method for producing polyethylene terephthalate |
| JP2012503067A (en) * | 2008-09-18 | 2012-02-02 | グルポ、ペトロテメックス、ソシエダッド、アノニマ、デ、カピタル、バリアブレ | Polyester melt phase composition with improved thermal oxidative stability, process for its production, and method of use thereof |
-
1990
- 1990-02-07 JP JP2595590A patent/JPH03231918A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1153953A4 (en) * | 1998-10-23 | 2002-12-04 | Toyo Boseki | Polymerization catalyst for polyester production, polyester, and process for producing polyester |
| US7501373B1 (en) * | 1998-10-23 | 2009-03-10 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyester production, polyester, and process for producing polyester |
| US7208565B1 (en) | 1999-08-24 | 2007-04-24 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyesters, polyester produced with the same, and process for production of polyester |
| US8293862B2 (en) | 1999-08-24 | 2012-10-23 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using the same, and a process for producing polyester |
| US7199212B2 (en) | 2000-01-05 | 2007-04-03 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyesters, polyesters produced with the same and process for producing polyesters |
| US7132383B2 (en) | 2000-09-12 | 2006-11-07 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
| US7144614B2 (en) | 2001-02-23 | 2006-12-05 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using the same, and process for producing polyester |
| JP2006152139A (en) * | 2004-11-30 | 2006-06-15 | Teijin Fibers Ltd | Polyester composition and molded product formed out of the same |
| JP2012503067A (en) * | 2008-09-18 | 2012-02-02 | グルポ、ペトロテメックス、ソシエダッド、アノニマ、デ、カピタル、バリアブレ | Polyester melt phase composition with improved thermal oxidative stability, process for its production, and method of use thereof |
| JP2011012200A (en) * | 2009-07-03 | 2011-01-20 | Toray Ind Inc | Copolyester and method for producing the same |
| JP2011026438A (en) * | 2009-07-24 | 2011-02-10 | Teijin Fibers Ltd | Method for producing polyethylene terephthalate |
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