JPH02242818A - Wholly aromatic polyester and production thereof - Google Patents
Wholly aromatic polyester and production thereofInfo
- Publication number
- JPH02242818A JPH02242818A JP1248890A JP1248890A JPH02242818A JP H02242818 A JPH02242818 A JP H02242818A JP 1248890 A JP1248890 A JP 1248890A JP 1248890 A JP1248890 A JP 1248890A JP H02242818 A JPH02242818 A JP H02242818A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polycondensation
- hydroquinone
- reduced viscosity
- wholly aromatic
- 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
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 53
- 229920000728 polyester Polymers 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 89
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 42
- 238000002844 melting Methods 0.000 claims abstract description 33
- 230000008018 melting Effects 0.000 claims abstract description 33
- -1 diaryl isophthalate Chemical compound 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 125000005843 halogen group Chemical group 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 239000000470 constituent Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 238000006116 polymerization reaction Methods 0.000 claims description 35
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 26
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 16
- 239000007790 solid phase Substances 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 150000001491 aromatic compounds Chemical class 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 6
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 40
- 150000001875 compounds Chemical class 0.000 description 16
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000000155 melt Substances 0.000 description 11
- FHESUNXRPBHDQM-UHFFFAOYSA-N diphenyl benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OC=2C=CC=CC=2)=CC=1C(=O)OC1=CC=CC=C1 FHESUNXRPBHDQM-UHFFFAOYSA-N 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 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 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000007860 aryl ester derivatives Chemical class 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000009998 heat setting Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 3
- 229920006257 Heat-shrinkable film Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 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
- ZGSHFDSKHTZINF-UHFFFAOYSA-N (2-methyl-6-phenylphenyl) hydrogen carbonate Chemical compound CC1=CC=CC(C=2C=CC=CC=2)=C1OC(O)=O ZGSHFDSKHTZINF-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 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
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- RHATVZBALBUXBY-UHFFFAOYSA-N bis(2,3-dimethylphenyl) carbonate Chemical compound CC1=CC=CC(OC(=O)OC=2C(=C(C)C=CC=2)C)=C1C RHATVZBALBUXBY-UHFFFAOYSA-N 0.000 description 1
- VJLJCMIVWQDTFP-UHFFFAOYSA-N bis(2-butylphenyl) benzene-1,3-dicarboxylate Chemical compound CCCCC1=CC=CC=C1OC(=O)C1=CC=CC(C(=O)OC=2C(=CC=CC=2)CCCC)=C1 VJLJCMIVWQDTFP-UHFFFAOYSA-N 0.000 description 1
- FWRXBOKRNGWMDD-UHFFFAOYSA-N bis(2-butylphenyl) carbonate Chemical compound CCCCC1=CC=CC=C1OC(=O)OC1=CC=CC=C1CCCC FWRXBOKRNGWMDD-UHFFFAOYSA-N 0.000 description 1
- BCMNPNDTIQWFJZ-UHFFFAOYSA-N bis(2-ethylphenyl) benzene-1,3-dicarboxylate Chemical compound CCC1=CC=CC=C1OC(=O)C1=CC=CC(C(=O)OC=2C(=CC=CC=2)CC)=C1 BCMNPNDTIQWFJZ-UHFFFAOYSA-N 0.000 description 1
- YAPBIDJHZIYQSK-UHFFFAOYSA-N bis(2-ethylphenyl) carbonate Chemical compound CCC1=CC=CC=C1OC(=O)OC1=CC=CC=C1CC YAPBIDJHZIYQSK-UHFFFAOYSA-N 0.000 description 1
- IVZVDXZDEYZQRJ-UHFFFAOYSA-N bis(2-octylphenyl) carbonate Chemical compound CCCCCCCCC1=CC=CC=C1OC(=O)OC1=CC=CC=C1CCCCCCCC IVZVDXZDEYZQRJ-UHFFFAOYSA-N 0.000 description 1
- NXWNUSGXRSUNBA-UHFFFAOYSA-N bis(2-propylphenyl) carbonate Chemical compound CCCC1=CC=CC=C1OC(=O)OC1=CC=CC=C1CCC NXWNUSGXRSUNBA-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004581 coalescence Methods 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
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- HPGJOUYGWKFYQW-UHFFFAOYSA-N diphenyl benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OC=2C=CC=CC=2)C=CC=1C(=O)OC1=CC=CC=C1 HPGJOUYGWKFYQW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NSETWVJZUWGCKE-UHFFFAOYSA-N propylphosphonic acid Chemical compound CCCP(O)(O)=O NSETWVJZUWGCKE-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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〉
本発明は溶融成形が可能で、且つ溶融成形によってずぐ
れた耐熱性を有する成型品を与える新規な結晶性の共重
合全芳香族ポリエステルならびにその製造法に関する。Detailed Description of the Invention <Industrial Field of Application> The present invention provides a novel crystalline copolymerized wholly aromatic polyester that can be melt-molded and provides a molded product having excellent heat resistance by melt-molding; Regarding its manufacturing method.
〈従来技術〉
従来より、イソフタル酸を主たる酸成分とし、ハイドロ
キノンを主たるジオール成分とする全芳香族ポリエステ
ルはよく知られている。そして、その製造方法として、
イソフタル酸クロライドとハイドロキノンとを高沸点の
熱媒中で２７０ ”Ｃ以上の高温で直接反応させる方法
が提案されている（たとえば、米国特許特許３，１６０
，６０５号、米国特許３．０３６．９９０号、米国特許
３，０３６，９９１号、米国特許３，０３６，９９２号
、米国特許３，１６０，６０３号、米国特許３．１６０
．６０２号参照）。<Prior Art> Fully aromatic polyesters containing isophthalic acid as the main acid component and hydroquinone as the main diol component have been well known. And, as a manufacturing method,
A method has been proposed in which isophthalic acid chloride and hydroquinone are directly reacted in a high boiling point heating medium at a high temperature of 270"C or higher (for example, U.S. Pat. No. 3,160
, 605, U.S. Patent 3.036.990, U.S. Patent 3,036,991, U.S. Patent 3,036,992, U.S. Patent 3,160,603, U.S. Patent 3.160
．． (See No. 602).
また、かかる全芳香族ポリエステルを、ジヒドロキシ芳
香族化合物のジアセテートと芳香族ジカルボン酸とを反
応させて製造する方法も提案されている。Furthermore, a method has been proposed in which such wholly aromatic polyesters are produced by reacting diacetate of a dihydroxy aromatic compound with an aromatic dicarboxylic acid.
しかし、かかる方法によって得られる全芳香族ポリエス
テルは、末端カルボキシル基量が多いためか、または分
子鎖に結合したハロゲン原子を有するためか、
ａ）耐湿熱性が劣る
ｂ）耐熱性、′＃４溶融安定性が劣る
Ｃ）溶融成形した成形品の色調が悪い
ｄ）透明性が劣る
などの欠点があり、そのため上記方法で重合した全芳香
族ポリエステルからは、溶融成形（とくに溶融製膜）に
より耐熱性および耐湿熱性が高く且つ色調及び透明性の
良好な成形品（とくにフィルム）を製造することは困難
であった。However, the wholly aromatic polyester obtained by such a method has a) poor moist heat resistance, b) poor heat resistance, and poor heat resistance due to the large amount of terminal carboxyl groups or the presence of halogen atoms bonded to the molecular chain. There are drawbacks such as poor stability C) poor color tone of melt-molded molded products d) poor transparency; therefore, fully aromatic polyester polymerized by the above method cannot be heat-resistant by melt molding (especially melt film forming). It has been difficult to produce molded products (particularly films) with high heat and humidity resistance, as well as good color tone and transparency.
一方、イソフタル酸成分と２．２゛−ビス（４−ヒドロ
キシフェニル）プロパン（ビスフェノールＡ）成分とか
らなる全芳香族ポリエステルの耐アセトン性を改善する
ため、ハイドロキノンを共重合させた全芳香族ポリエス
テルを提案されているが（特開昭５２−１４６４９６号
）、このポリエステルは実質上非品性であり、ｔｍ維、
フィルム等にしたときの物性が不十分である。On the other hand, in order to improve the acetone resistance of a wholly aromatic polyester consisting of an isophthalic acid component and a 2.2-bis(4-hydroxyphenyl)propane (bisphenol A) component, a wholly aromatic polyester copolymerized with hydroquinone was used. (Japanese Unexamined Patent Publication No. 52-146496), however, this polyester is substantially inferior, and TM fiber,
When made into a film, the physical properties are insufficient.
一方、近年、テレフタル酸、イソフタル酸及びそれらの
アリールエステルよりなる群から選ばれた少なくとも１
種の化合物とハイドロキノン等のジオキシベンゼンとの
反応によって得られる固有粘度０．２〜０．８の結晶性
全芳香族ポリエステルを２８０〜４５０’Ｃの温度で溶
融成形する方法が提案されている（特開昭５３−５４２
５２号）、そして、この特開昭５３−５４２５２号の実
施例では、イソフタル酸ジフェニル０．４モル、ハイド
ロキノン０．２８６モルおよびレゾルシン０．１２２モ
ルとを窒素気流中２８０〜３３０℃で２．５時間加熱し
、次いで減圧下３５０℃で８０分間加熱し、固有粘度０
．４０のポリエステルを製造している。On the other hand, in recent years, at least one compound selected from the group consisting of terephthalic acid, isophthalic acid, and their aryl esters
A method has been proposed in which a crystalline wholly aromatic polyester with an intrinsic viscosity of 0.2 to 0.8 obtained by the reaction of a seed compound with dioxybenzene such as hydroquinone is melt-molded at a temperature of 280 to 450'C. (Unexamined Japanese Patent Publication No. 53-542
52), and in the example of JP-A-53-54252, 0.4 mol of diphenyl isophthalate, 0.286 mol of hydroquinone, and 0.122 mol of resorcin were mixed at 280 to 330°C in a nitrogen stream for 2 hours. Heating for 5 hours, then heating at 350°C under reduced pressure for 80 minutes until the intrinsic viscosity was 0.
．． The company manufactures 40 types of polyester.
しかしながら、本発明者らの研究によれば、上記の如く
生成するポリマーの融点（３２５°Ｃ近辺）よりも高い
温度（この場合約２５℃高い）で重縮合反応を実施した
場合には、実質的に線状であるボッマーは得られず、ま
たここで得られる全芳香族ポリエステルは、１）延伸性
に乏しい１２）透明性が良好でない、３）ポリマーは暗
褐色で色調が不良である、などの欠点を有することが見
出された。However, according to the research conducted by the present inventors, when the polycondensation reaction is carried out at a temperature higher than the melting point (around 325°C) of the polymer produced as described above (in this case, about 25°C higher), the In addition, the wholly aromatic polyester obtained here has 1) poor stretchability, 2) poor transparency, and 3) the polymer is dark brown and has poor color tone. It was found that it has the following drawbacks.
〈発明が解決しようとする課題〉
本発明は、かかる欠点のない耐熱性のすぐれた？８融成
形が可能な結晶性の全芳香族ポリエステル及び該ポリエ
ステルを工業的に製造する方法を提供しようとするもの
である。<Problems to be Solved by the Invention> The present invention provides a heat resistant solution that does not have such drawbacks. The object of the present invention is to provide a crystalline wholly aromatic polyester that can be melt-molded and a method for industrially producing the polyester.
く課題を解決する手段〉
本発明者らの研究によれば、イソフタル酸成分とハイド
ロキノン成分に特定の第３成分を特定量共重合した末端
カルボキシル基含量の少ない全芳香族ポリエステルは、
結晶性を損うことなく前述の欠点が改善されることが見
い出された。According to the research of the present inventors, a wholly aromatic polyester with a low content of terminal carboxyl groups, which is obtained by copolymerizing an isophthalic acid component and a hydroquinone component with a specific amount of a specific third component,
It has been found that the aforementioned drawbacks can be improved without impairing crystallinity.
本発明は、かかる知見に基づきなされたものであり、本
発明に係る全芳香族ポリエステルは、ポリマー構成単位
が下記式［Ｉ］ ［ＩＩ］および［Ｉ［［］からなる
実質的に線状の全芳香族ポリエステルであって、
−ｏｃ−■−ｃｏ−・・・・・・［Ｉ］−〇（ン０−
・・ ［Ｉ［］
−ｏ （ｙｘ ％ ｏ−・・・・・・［、ＩＩｒ］［式
［■コ中のＸは一〇−、−ＣＯ−またはメチル、エチル
、プロピルもしくはフェニルであるか、またはＲ，Ｒ’
およびそれらが結合している炭素原子が一緒になってシ
クロヘキサン環を形成しているものを指す、Ｒ１Ｒ′は
互いに同一でも相異っていてもよい、コ該全芳香族ポリ
エステルにおける前記式［Ｉ］と［ＩＩ］のモル数の和
が９５〜８５モル％の範囲内にあり、９０当量／１０６
ｆ以下の末端カルボキシル基と、少くとも０．６の還
元粘度（フェノール／テトラクロロエタン＝４／６の混
合溶剤中３５°Ｃで測定した相対粘度より算出）を有し
、且つ分子鎖に結合したハロゲン原子を実質的に含まな
いことを特徴とするものである。The present invention has been made based on this knowledge, and the wholly aromatic polyester according to the present invention has substantially linear polymer constituent units consisting of the following formulas [I] [II] and [I[[]. A wholly aromatic polyester, -oc-■-co-...[I]-〇(n0-
... [I[] -o (yx % o-...[, IIr] [Formula , or R, R'
and the carbon atoms to which they are bonded together form a cyclohexane ring, R1R' may be the same or different, and the above formula [I ] and [II] is within the range of 95 to 85 mol%, and 90 equivalents/106
has a terminal carboxyl group of not more than It is characterized by substantially no halogen atoms.
本発明の全芳香族ポリエステルは、前述の如くイソフタ
ル酸から誘導される前記式［Ｉ］の構造単位と、ハイド
ロキノンから誘導される前記式［１］の構造単位とから
主としてなり、且つ前記式［１１［］で表わされる構造
単位を共重合成分として含有するコポリエステルであり
、ここでコポリエステル中の主成分であるイソフタル酸
成分とハイドロキノン成分の合計の全成分（全酸成分と
全ジオール成分の和）に対する割合は、８５〜９５モル
％、好ましくは８７〜９３モル％の範囲内である。As described above, the wholly aromatic polyester of the present invention mainly consists of the structural unit of the formula [I] derived from isophthalic acid and the structural unit of the formula [1] derived from hydroquinone, and also comprises the structural unit of the formula [1] derived from hydroquinone. It is a copolyester containing structural units represented by (sum) is within the range of 85 to 95 mol%, preferably 87 to 93 mol%.
本発明において共重合成分（第三成分）となる構造単位
は、前記式（ａ）で表わされる２価の芳香族基をもつジ
オキシ芳香族化合物から誘導されるものである。In the present invention, the structural unit serving as the copolymerization component (third component) is derived from a dioxyaromatic compound having a divalent aromatic group represented by the above formula (a).
前記式（ａ）の芳香族基をもつジオキシ芳香族化合物の
好適な例は、２，２−ビス（４−ヒドロキシフェニル）
プロパン、２．２−ビス（４〜ヒドロキシフエニル）ブ
タン、ビス（４−ヒドロキシフェニル）メタン、１−フ
ェニル−１，１−ビス（４−ヒドロキシフェニル）エタ
ン、ビスフェニル−ビス（４−ヒドロキシフェニル）メ
タン、１，１−ビス（４−ヒドロキシフェニル）シクロ
ヘキサン。A preferred example of the dioxyaromatic compound having an aromatic group of formula (a) is 2,2-bis(4-hydroxyphenyl).
Propane, 2,2-bis(4-hydroxyphenyl)butane, bis(4-hydroxyphenyl)methane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, bisphenyl-bis(4-hydroxyphenyl) phenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane.
ジ（４−ヒドロキシフェニル）エーテル、ジ（４−ヒド
ロキシフェニル）ケトンなどであり、これらの中でも２
，２−ビス（４−ヒドロキシフェニル）プロパン、ジ（
４−ヒドロキシフェニル）エーテルが特に好ましい。di(4-hydroxyphenyl) ether, di(4-hydroxyphenyl) ketone, etc. Among these, 2
, 2-bis(4-hydroxyphenyl)propane, di(
Particularly preferred is 4-hydroxyphenyl)ether.
かかる本発明の全芳香族ポリエステルは、次の（＾）ま
たは（Ｂ）の方法によって製造される。The wholly aromatic polyester of the present invention is produced by the following method (^) or (B).
（＾）イソフタル酸ジアリールエステル１ハイドロキノ
ン及び
［ただし、Ｘは前記と同じ］
で表わされるジヒドロキシ芳香族化合物の１種又は２種
以上を所定割合に混合した混合物を、生成するヒドロキ
シ芳香族化合物を除去しつつ、そして反応系内に形成さ
れた重合体の還元粘度が０．１５に到達したのちは少く
とも該重合体の結晶融点より低い温度で且つ溶融状態を
維持しつつ重縮合触媒の存在下に加熱重縮合せしめるか
、またはここで得られた低重合体を更に固相重合させる
方法（以下Ａ法と呼ぶ）、
（Ｂ）イソフタル酸、ハイドロキノンおよびジアリール
カーボネートならびに前述の式（ａ）で表わされるジヒ
ドロキシ芳香族化合物からなる所定割合の混合物を、生
成するヒドロキシ芳香族化合物および二酸化炭素を除去
しつつ、反応系内に形成された重合体の還元粘度が０．
１５に到達したのちは少くとも該重合体の結晶融点より
低い温度で且つ溶融状態を維持しつつ重縮合触媒の存在
下に加熱重縮合せしめるか、またはここで得られた低重
合体を更に固相重合させる方法（以下Ｂ法と呼ぶ）、
前記Ａ法によって全芳香族ポリエステルを製造する場合
、出発原料は、酸成分としてイソフタル酸ジアリールエ
ステルが用いられる。(^) Isophthalic acid diaryl ester 1 A mixture of one or more dihydroxy aromatic compounds represented by hydroquinone and [where X is the same as above] in a predetermined ratio is removed to remove the generated hydroxy aromatic compound. and after the reduced viscosity of the polymer formed in the reaction system reaches 0.15, it is heated at least at a temperature lower than the crystalline melting point of the polymer and while maintaining the molten state in the presence of a polycondensation catalyst. (B) Isophthalic acid, hydroquinone, diaryl carbonate and the above-mentioned compound represented by formula (a). While removing the produced hydroxy aromatic compound and carbon dioxide, the reduced viscosity of the polymer formed in the reaction system is reduced to 0.
After reaching 15, heat polycondensation is carried out in the presence of a polycondensation catalyst while maintaining the molten state at least at a temperature lower than the crystalline melting point of the polymer, or the obtained low polymer is further solidified. Phase polymerization method (hereinafter referred to as method B) When producing a wholly aromatic polyester using method A, the starting material is an isophthalic acid diaryl ester as an acid component.
このようなりアリールエステルの例は、ジフェニルイソ
フタレート、ジトリルイソフタレート。Examples of such aryl esters are diphenyl isophthalate, ditolylisophthalate.
ジ（エチルフェニル）イソフタレート、ジ（ジメチルフ
ェニル）イソフタレート、ジ（プロピルフェニル）イン
フタレート、ジ（ブチルフェニル）イソフタレート、ジ
（オクチルフェニル）イソフタレート、フェニルトリル
イソフタレートの如きイソフタル酸の非置換またはアル
キル置換フェノールとのジアリールエステルなどを挙げ
ることができる。また、ジヒドロキシ化合物としては、
ハイドロキノンおよび前記のジヒドロキシ芳香族化合物
が用いられる。Non-isophthalic acids such as di(ethylphenyl)isophthalate, di(dimethylphenyl)isophthalate, di(propylphenyl)inphthalate, di(butylphenyl)isophthalate, di(octylphenyl)isophthalate, phenyltolyl isophthalate. Examples include diaryl esters with substituted or alkyl-substituted phenols. In addition, as a dihydroxy compound,
Hydroquinone and the dihydroxy aromatic compounds mentioned above are used.
また前記Ｂ法によって全芳香族ポリエステルを製造する
場合、出発原料は、酸成分としてはイソフタル酸がまた
ジオール成分としてはハイドロキノンおよび前記のジヒ
ドロキシ芳香族化合物がそれぞれ用いられるほかに、ジ
アリールカーボネートが用いられる。ここでジアリール
カーボネートとはフェノール、クレゾール、エチルフェ
ノール。In addition, when producing a wholly aromatic polyester by the method B, the starting materials include isophthalic acid as the acid component, hydroquinone and the above-mentioned dihydroxy aromatic compound as the diol component, and diaryl carbonate. . Here, diaryl carbonate refers to phenol, cresol, and ethylphenol.
ジメチルフェノール、プロピルフェノール、ブチルフェ
ノール、オクチルフェノール、ナフトールなどの非置換
またはアルキル置換フェノール、またはナフトールの如
きモノヒドロキシ芳香族化合物の炭酸エステルである。Carbonic esters of unsubstituted or alkyl-substituted phenols such as dimethylphenol, propylphenol, butylphenol, octylphenol, naphthol, or monohydroxy aromatic compounds such as naphthol.
このようなジアリールカーボネートの具体例としては、
ジフェニルカーボネート、ジトリルカーボネート、ジ（
エチルフェニル）カーボネート。Specific examples of such diaryl carbonates include:
diphenyl carbonate, ditolyl carbonate, di(
ethylphenyl) carbonate.
ジ（ジメチルフェニル）カーボネート、ジ（プロピルフ
ェニル）カーボネート、ジ（ブチルフェニル）カーボネ
ート、ジ（オクチルフェニル）カーボネート、ジナフチ
ルカーボネート、フェニルトリルカーボネートなどが挙
げられる。Examples include di(dimethylphenyl) carbonate, di(propylphenyl) carbonate, di(butylphenyl) carbonate, di(octylphenyl) carbonate, dinaphthyl carbonate, phenyltolyl carbonate, and the like.
Ａ法による場合、出発原料の仕込み割合は、原料中のア
リールエステル基に対し、原料中のヒドロキシル基が１
＝１から１：Ｌ２となるように、またジアリールイソフ
タレートとハイドロキノンのモル数の和が仕込み原料中
で８５〜９５モル％、好ましくは８７〜９３モル％にな
るようにする。In the case of method A, the charging ratio of the starting materials is such that hydroxyl groups in the raw materials are 1 to aryl ester groups in the raw materials.
= 1 to 1:L2, and the sum of the moles of diarylisophthalate and hydroquinone is 85 to 95 mol%, preferably 87 to 93 mol%, in the raw materials.
ここで、上記モル数が８５モル％より少いとポリマーの
結晶性が低下し、また９５モル％より多いとホモポリマ
ーの欠点が実質上改善され難い。Here, if the number of moles is less than 85 mol%, the crystallinity of the polymer will decrease, and if it is more than 95 mol%, it will be difficult to substantially improve the defects of the homopolymer.
一般に重縮合反応は、重縮合触媒のもとて２００°Ｃで
始まるが、反応速度が遅いので昇温し、反応系内のポリ
マーの還元粘度が０．０８に達する前は反応系内のポリ
マーの結晶融点以上で反応の結果生成するモノヒドロキ
シ芳香族化合物を反応系外に除去しつつ重縮合させる。Generally, the polycondensation reaction starts at 200°C using a polycondensation catalyst, but since the reaction rate is slow, the temperature rises, and before the reduced viscosity of the polymer in the reaction system reaches 0.08, the polymer in the reaction system Polycondensation is carried out while removing the monohydroxy aromatic compound produced as a result of the reaction from the reaction system at a temperature higher than the crystal melting point of .
本発明における全芳香族ポリエステルの重縮合方法の特
徴の１つは、少くとら該全芳香族ポリエステルの還元粘
度が０．１５に到達した後は、重縮合反応温度を反応系
内に生成したポリマーの結晶融点以下に保ち且つポリマ
ーを溶融状態に保ち重縮合させる点にある。One of the characteristics of the polycondensation method of wholly aromatic polyester in the present invention is that after the reduced viscosity of the wholly aromatic polyester reaches 0.15, the polycondensation reaction temperature is lowered to the polymer produced in the reaction system. The point is to maintain the temperature below the crystalline melting point of the polymer and to keep the polymer in a molten state for polycondensation.
このような重縮合方法が可能である理由は、多分本発明
の全芳香族ポリエステルの結晶化の速度が融点以下で遅
いことによると思われる。この結晶化速度はポリマー組
成に依存し、したがってこのようなポリマーの融点以下
での＠縮合が続けられる時間も組成に依存する。The reason why such a polycondensation method is possible is probably that the rate of crystallization of the wholly aromatic polyester of the present invention is slow below its melting point. The rate of crystallization is dependent on the polymer composition, and therefore the time that condensation continues below the melting point of such polymers also depends on the composition.
本発明の溶融縮合によって還元粘度が０．６〜０．８の
ポリマーを得ることもできる６本発明において重縮合反
応温度は最終的に好ましくは３２０〜３３０℃まで高め
られる０重縮合反応の初期は大気圧のもとで行なわれる
が、その後は減圧下または不活性ガスを流し、強制的に
反応の結果生成するモノヒドロキシ芳香族化合物および
必要に応じて過剰に用いたハイドロキノンなどのジヒド
ロキシ芳香族化合物を反応系外に除去しつつ行なわれる
。It is also possible to obtain a polymer with a reduced viscosity of 0.6 to 0.8 by the melt condensation of the present invention.6 In the present invention, the polycondensation reaction temperature is finally preferably increased to 320 to 330°C.0 The initial stage of the polycondensation reaction The reaction is carried out under atmospheric pressure, but then under reduced pressure or by flowing an inert gas, the monohydroxy aromatic compounds produced as a result of the reaction and dihydroxy aromatic compounds such as hydroquinone, which are used in excess if necessary, are removed. This is carried out while removing the compound from the reaction system.
反応系内に生成したポリマーの還元粘度が約０．１に達
する前に、反応の結果生成するモノヒドロキシ化合物お
よび必要に応じて過剰に用いたハイドロキノンなどのジ
ヒドロキシ化合物を反応系外に強制的に、例えば減圧下
に、除去することが好ましい、上記大気圧のもとに行な
われる重縮合反応は、たとえば２５０〜２９０℃までの
温度でモノヒドロキシ芳香族化合物の留出量が理論値の
５０〜７０％になるまで続けられる。この後反応系の圧
力は減圧され、最終的に３２０〜３３０℃になるまで昇
温しつつ、１時間以内に反応系の圧力は２０ｍｍＨＱま
たはそれ以下にされる。好適な条件下では、溶融重縮合
反応は６時間以内に終了する。Before the reduced viscosity of the polymer produced in the reaction system reaches approximately 0.1, the monohydroxy compound produced as a result of the reaction and, if necessary, the dihydroxy compound such as hydroquinone used in excess, are forced out of the reaction system. For example, the polycondensation reaction carried out under atmospheric pressure, which is preferably removed under reduced pressure, can be carried out at a temperature of, for example, 250 to 290°C, and the distillation amount of the monohydroxy aromatic compound is 50 to 50% of the theoretical value. Continue until it reaches 70%. After this, the pressure of the reaction system is reduced, and while the temperature is finally raised to 320 to 330°C, the pressure of the reaction system is reduced to 20 mmHQ or less within 1 hour. Under suitable conditions, the melt polycondensation reaction is complete within 6 hours.
また本発明における全芳香族ポリエステルの溶融ｆｆｉ
縮合において、減圧下または不活性ガスを流し、強制的
に反応の結果生成するモノヒドロキシ芳香族化合物およ
び必要に応じて過剰に用いたハイドロキノンなどのジヒ
ドロキシ芳香族化合物を反応系外に除去しつつ行う重縮
合反応時間は３時間以内である。Furthermore, the melt ffi of the wholly aromatic polyester in the present invention
Condensation is carried out under reduced pressure or by flowing an inert gas while forcibly removing monohydroxy aromatic compounds produced as a result of the reaction and, if necessary, dihydroxy aromatic compounds such as hydroquinone used in excess, from the reaction system. The polycondensation reaction time is within 3 hours.
本発明において重縮合触媒としては従来公知のエステル
交換触媒が用いられる。このような触媒のうち好適なも
のの例は、カルシウム、マグネシウム、ストロンチウム
、バリウム、ランタン セリウム、マンガン、コバルト
、亜鉛、ゲルマニウム、スズ、釦アンチモン１ビスマス
などの金属を含む化合物である。In the present invention, a conventionally known transesterification catalyst is used as the polycondensation catalyst. Examples of suitable such catalysts are compounds containing metals such as calcium, magnesium, strontium, barium, lanthanum cerium, manganese, cobalt, zinc, germanium, tin, antimony, and bismuth.
これら重縮合触媒とともに、安定剤を使用することが好
ましい、好ましい安定剤としては、３価又は５価のリン
化合物またはそのエステル類で、たとえば亜すン酸、リ
ン酸、フェニルホスホン酸。It is preferable to use a stabilizer together with these polycondensation catalysts. Preferred stabilizers include trivalent or pentavalent phosphorus compounds or esters thereof, such as stunrous acid, phosphoric acid, and phenylphosphonic acid.
メチルホスホン酸、エチルホスホン酸、プロピルホスホ
ン酸、ブチルホスホン酸、ベンジルホスホン酸、トリメ
チルホスファイト、トリメチルホスフェート、トリエチ
ルホスフェート、トリブチルホスフェート、トリフェニ
ルホスファイト、トリフェニルホスフェート、ジエチル
フェニルホスボネート、ジメチル（メチル）ホスホネー
ト、ジメチル（エチル）ホスホネート、ジメチル（ベン
ジル）ホスホネートなどをあげることができる。Methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, benzylphosphonic acid, trimethyl phosphite, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphite, triphenyl phosphate, diethylphenyl phosphonate, dimethyl (methyl) Examples include phosphonate, dimethyl (ethyl) phosphonate, dimethyl (benzyl) phosphonate, and the like.
このような安定剤は、ポリマーの溶融安定性や色調を改
良し、ある場合には重縮合触媒を不活性化する。触媒を
不活性化する場合には、安定剤は重縮合反応後に加える
ことが好ましく、アンチモン又はゲルマニウムを含む重
縮合触媒を用いる場合には安定剤は２Ｉ！縮合反応の最
初から加えることができる。Such stabilizers improve the melt stability and color of the polymer, and in some cases deactivate the polycondensation catalyst. When inactivating the catalyst, the stabilizer is preferably added after the polycondensation reaction, and when using a polycondensation catalyst containing antimony or germanium, the stabilizer is 2I! It can be added from the beginning of the condensation reaction.
また、前記Ｂ法による場合には、出発原料の仕込み割合
は、原料中のカルボキシル基に対して原料中のヒドロキ
シル基が１：１から１ ：’１．２となるように、また
原料中のカルボキシル基に対して原料中のジアリールカ
ーボネートが１：１から１：１．０５となるように、更
にイソフタル酸とハイドロキノンのモル数の和がジアリ
ールカーボネートを除いた仕込み原料中で８５〜９５モ
ル％、好ましくは８７〜９３モル％になるようにする。In addition, in the case of method B, the charging ratio of the starting raw materials is such that the ratio of hydroxyl groups in the raw materials to carboxyl groups in the raw materials is 1:1 to 1:1.2, and The ratio of diaryl carbonate in the raw material to the carboxyl group is 1:1 to 1:1.05, and the sum of the moles of isophthalic acid and hydroquinone is 85 to 95 mol% in the raw material excluding diaryl carbonate. , preferably 87 to 93 mol%.
Ｂ法で全芳香族ポリエステルを製造する場合、ジアリー
ルカーボネートは用いた芳香族ジカルボン酸と反応しく
以下エステル化反応と呼ぶ）、炭酸ガスの発生をともな
って芳香族ジカルボン酸をアリールエステルに変換させ
る。When producing a fully aromatic polyester using Method B, the diaryl carbonate reacts with the aromatic dicarboxylic acid used (hereinafter referred to as an esterification reaction), generating carbon dioxide gas and converting the aromatic dicarboxylic acid into an aryl ester.
そこでＢ法で全芳香族ポリエステルを製造するる場合に
は、一般には下記の（Ｂ−１）の方法によるが、下記（
Ｂ−２）の方法によることもできる。Therefore, when producing a wholly aromatic polyester using Method B, generally the method (B-1) below is used, but the method (B-1) below is generally used.
It is also possible to use method B-2).
（Ｂ−１） 芳香族ジカルボン酸、ハイドロキノンを
含むジヒドロキシ芳香族化合物類およびジアリールカー
ボネートからなる混合物を加熱重縮合させる方法。(B-1) A method of heating and polycondensing a mixture consisting of an aromatic dicarboxylic acid, a dihydroxy aromatic compound containing hydroquinone, and a diaryl carbonate.
（Ｂ−２） 芳香族ジカルボン酸とジアリールカーボ
ネートを予め反応させて芳香族ジカルボン酸のアリール
エステルを形成させ、次いでハイドロキノンを含むジオ
キシ芳香族化合物類を加え加熱重縮合させる方法。(B-2) A method in which an aromatic dicarboxylic acid and a diaryl carbonate are reacted in advance to form an aryl ester of an aromatic dicarboxylic acid, and then a dioxyaromatic compound containing hydroquinone is added and subjected to heating polycondensation.
以上いずれの方法によるときも重縮合反応はＡ法と同様
な重縮合触媒の存在下で行なう、また重縮合反応初期は
大気圧のもとに行なう、この時点で反応系外に除去され
るモノオキシ芳香族化合物の量はエステル化反応におい
て生成するモノオキシ芳香族化合物の量（使用した芳香
族ジカルボン酸の２倍モルで使用したジアリールカーボ
ネートのモル数にほぼ等しい）と、Ａ法におけると同様
重縮合反応によって生成するモノオキシ芳香族化合物の
理論量の５０〜７０モル％に相当する量の和である。In any of the above methods, the polycondensation reaction is carried out in the presence of the same polycondensation catalyst as in Method A, and the initial stage of the polycondensation reaction is carried out under atmospheric pressure. The amount of aromatic compound is determined by the amount of monooxyaromatic compound produced in the esterification reaction (approximately equal to the number of moles of diaryl carbonate used at twice the mole of the aromatic dicarboxylic acid used), and the amount of the monooxyaromatic compound produced in the esterification reaction. This is the sum of amounts corresponding to 50 to 70 mol% of the theoretical amount of monooxyaromatic compounds produced by the reaction.
Ａ法とＢ法の相違点は、このように反応の比較的初期の
段階に限られ、以後の重縮合反応は両方法とも全く同様
にして行わせることができる。すなわち、Ｂ法において
も上記大気圧下での反応のあとは、重縮合反応温度を上
昇させつつ、また重縮合反応の結果生成するモノオキシ
芳香族化合物および必要に応じて過剰に用いた芳香族ジ
オキシ化合物を反応系外に強制的に除去しつつ重縮合反
応が行なわれる。The difference between Method A and Method B is thus limited to the relatively early stage of the reaction, and the subsequent polycondensation reaction can be carried out in exactly the same manner in both methods. That is, in Method B, after the above reaction under atmospheric pressure, the polycondensation reaction temperature is raised, and the monooxyaromatic compound produced as a result of the polycondensation reaction and the aromatic dioxygen compound used in excess as necessary are The polycondensation reaction is carried out while the compound is forcibly removed from the reaction system.
上記の通り、Ａ法およびＢ法によれば還元粘度が０，２
〜０．８の重合体を製造することができる。As mentioned above, according to methods A and B, the reduced viscosity is 0.2
~0.8 polymers can be produced.
かくして得られた重合体よりも還元粘度の高い重合体は
、溶融重合法により得られた前記重合体をそれ自体公知
の方法で減圧下または不活性気体を通じつつ固相重合せ
しめることにより製造することができる。A polymer having a higher reduced viscosity than the polymer thus obtained can be produced by subjecting the polymer obtained by a melt polymerization method to solid phase polymerization under reduced pressure or while passing an inert gas by a method known per se. I can do it.
この固相重合に供する重合体の還元粘度は好ましくは０
．２以上、特に好ましくは０゜２５〜０．６である。The reduced viscosity of the polymer subjected to this solid phase polymerization is preferably 0.
．． 2 or more, particularly preferably 0°25 to 0.6.
本発明の上記溶融重合法において、重合体が約０．６以
上の還元粘度を有する場合には、改善された性質を示す
フィルムを与える重合体として評価され、る、そのなめ
、還元粘度が約０．６以上の重合体は、更に固相重合す
る必要はないが、還元粘度が０．６より小さい重合体は
固相重合して更に還元粘度を高めることが必要である。In the melt polymerization method of the present invention, if the polymer has a reduced viscosity of about 0.6 or more, it is evaluated as a polymer that provides a film exhibiting improved properties; Polymers with a reduced viscosity of 0.6 or more do not need to be further solid-phase polymerized, but polymers with a reduced viscosity of less than 0.6 need to be solid-phase polymerized to further increase the reduced viscosity.
固相重合は、全芳香族ポリエステルの固相重合おいて知
られているように重合体粒子が小さいほど所望の重合度
まで速やかに到達するため、６〜３００メツシユの粒度
で行うのが好ましい、固相重合は、約２３０℃以上で且
つ通常粒子同士が凝集しないような温度、好ましくは約
２５０〜３００℃の温度で不活性ガス雰囲気中常圧〜減
圧下、好ましくは減圧下例えば１關ＨΩで行われる。The solid phase polymerization is preferably carried out at a particle size of 6 to 300 meshes, since the smaller the polymer particles, the faster the desired degree of polymerization is reached, as is known in the solid phase polymerization of wholly aromatic polyesters. The solid phase polymerization is carried out at a temperature of about 230° C. or higher and at a temperature such that the particles do not agglomerate, preferably about 250 to 300° C., in an inert gas atmosphere under normal pressure to reduced pressure, preferably reduced pressure, e.g. 1 HΩ. It will be done.
上記固相重合法によれば還元粘度がより高められた重合
体、例えば還元粘度が約０．２〜０．６の重合体から還
元粘度が約０．８〜１．５の重合体が得られ、また還元
粘度が約０．６〜０．８の重合体から還元粘度が１．５
〜２．０の重合体が得られる。According to the solid phase polymerization method described above, a polymer with a reduced viscosity of about 0.8 to 1.5 can be obtained from a polymer with a reduced viscosity of about 0.2 to 0.6. and a reduced viscosity of 1.5 from a polymer with a reduced viscosity of about 0.6 to 0.8.
~2.0 polymer is obtained.
かかる方法により、全芳香族ポリエステルは、９０当藍
／ｉｏｅ を以下、好ましくは約５〜約７０当量／１０
６ 、、より好ましくは約１０〜約５０当量／１０６ｇ
の末端カルボキシル基を有するものとして提供される。By such a method, the wholly aromatic polyester can be prepared in a range of 90 equivalents/ioe or less, preferably from about 5 to about 70 equivalents/10
6, more preferably about 10 to about 50 equivalents/106g
It is provided as having a terminal carboxyl group.
また本発明の全芳香族ポリエステルは、０．６以上好ま
しくは０．６〜２．Ｏｌより好ましくは約０．７〜約１
．５の還元粘度を有するものとして提供される。Further, the wholly aromatic polyester of the present invention has a molecular weight of 0.6 or more, preferably 0.6 to 2. More preferably about 0.7 to about 1
．． It is provided as having a reduced viscosity of 5.
本発明の全芳香族ポリエステルは、さらに分子鎖中に結
合したハロゲン原子（例えば塩素、臭素など）を実質的
に有さない０分子鎖中に結合したハロゲン原子とは、例
えば、分子鎖末端のハロゲン原子（たとえば酸クロライ
ドの形態にあるハロゲン原子）、あるいは分子鎖の芳香
環に結合しなハロゲン原子（たとえばハロゲン化ハイド
ロキノン等の原料に由来するハロゲン原子）などを意味
している。かかるハロゲン原子は重合体の有機溶媒溶で
抽出するとか、あるいは重合体の有機溶奴液から再沈さ
せるとかの方法によっても重合体中にハロゲン原子が含
まれることによって証明できる。The wholly aromatic polyester of the present invention further has no halogen atoms (e.g., chlorine, bromine, etc.) bonded in the molecular chain.Halogen atoms bonded in the molecular chain are, for example, It means a halogen atom (for example, a halogen atom in the form of an acid chloride), or a halogen atom that is not bonded to an aromatic ring in a molecular chain (for example, a halogen atom derived from a raw material such as halogenated hydroquinone). Such halogen atoms can be verified by the presence of halogen atoms in the polymer by extracting the polymer from a solution in an organic solvent or by reprecipitating the polymer from an organic solution.
本発明の方法によらず、例えば酸ハロゲン化物を原料と
して製造した重合体中には、ハロゲン原子を約０．３重
量％以上含有する。Regardless of the method of the present invention, for example, a polymer produced using an acid halide as a raw material contains halogen atoms in an amount of about 0.3% by weight or more.
更に、本発明の全芳香族ポリエステルは、実質的に線状
である。このような重合体は例えばフローインデックス
が、すり速度約５０〜約５００ ｓ ｅ ｃ ’の間に
おいて、平均的０．７〜約１、好ましくは０．１５〜０
．９０の間の値にある。Furthermore, the fully aromatic polyesters of the present invention are substantially linear. Such polymers, for example, have a flow index on average of 0.7 to about 1, preferably 0.15 to 0, at a slip rate of about 50 to about 500 sec'.
．． The value is between 90 and 90.
これに対し、従来技術、例えば特開昭５３−５４２５２
号に開示された生成する重合体の結晶融点より高い温度
で重縮合する方法で得られた重合体は、フローインデッ
クスが約０．６程度の値を示す（Ｐｏｌｙｌａｒ Ｅｎ
ｇｉｎｅｅｒｉｎｇ ａｎｄ ５ｃｉｅｎｃｅ 、 Ｈ
ｉｄ−Ｈａｙ Ｖｏ！ １９゜随６４６２〜４６７頁、
特に４６３頁（１９７９）参照）。On the other hand, conventional techniques such as JP-A-53-54252
Polymers obtained by the method of polycondensation at a temperature higher than the crystal melting point of the resulting polymer disclosed in the above issue exhibit a flow index of approximately 0.6 (Polylar En
gineering and 5science, H
id-Hey Vo! 19゜Episode 6462-467,
(See especially p. 463 (1979)).
〈発明の効果〉
本発明の全芳香族ポリエステルは、良好な結晶性を有し
、耐湿熱性、耐熱性、耐溶融安定性がすぐれており、容
易に溶融成形することができる。<Effects of the Invention> The wholly aromatic polyester of the present invention has good crystallinity, excellent moist heat resistance, heat resistance, and melt stability, and can be easily melt-molded.
特に溶融成形および延伸・熱処理によってすぐれた透明
性１色調及び機械的性能のフィルムを与えるという利点
がある。In particular, it has the advantage of providing a film with excellent transparency, one color tone, and mechanical performance by melt molding and stretching/heat treatment.
例えば、本発明の全芳香族ポリエステルは、溶融成形が
可能な温度に加熱されスリットより押出し、フィルムに
成形される。ここで溶融成形が可能な温度は、通常は融
点より約５℃高い温度から約５０℃高い温度との間であ
って且つ約４００’Ｃ以下の温度である。成形時のドラ
フト率は約２〜１０とされる。押出し用のスリットとし
てはスリット中０．５〜５１ｗ１Ｉのものが用いられる
。For example, the wholly aromatic polyester of the present invention is heated to a temperature that allows melt molding, extruded through a slit, and molded into a film. The temperature at which melt molding can be performed is usually between about 5° C. and about 50° C. higher than the melting point, and about 400° C. or less. The draft rate during molding is approximately 2 to 10. As the slit for extrusion, a slit with a diameter of 0.5 to 51w1I is used.
かくして得られた未延伸フィルムは透明性が良好で、１
００℃の清水中で処理してもその透明性を維持し、且つ
寸法変化が極めて小さい。The unstretched film thus obtained had good transparency and 1
Even when treated in clear water at 00°C, it maintains its transparency and shows extremely small dimensional changes.
未延伸フィルムは、次いで一軸又は二軸延伸する。延伸
は好ましくは１８０〜２８０℃、より好ましくは１９０
〜２２０℃で行なわれる。延伸は、−軸延伸の場合には
延伸方向の屈折率が約１．６２以上となるまで、二軸延
伸の場合には延伸方向の屈折率がいずれも約１．６２以
上、好ましくは１．６４以上となるまで行なわれる。こ
のような屈折率を与える延伸倍率は、−軸延伸の場合に
は２〜４倍程度であり、二軸延伸の場合には縦方向（Ｍ
Ｄ＞、横方向（ＴＤそれぞれ１．７〜３．５倍程度であ
る。二軸延伸の場合は、面積倍率が２．８〜１０＠とす
るのがよい。The unstretched film is then uniaxially or biaxially stretched. Stretching is preferably carried out at 180-280°C, more preferably at 190°C.
Performed at ~220°C. In the case of -axial stretching, the stretching is carried out until the refractive index in the stretching direction becomes approximately 1.62 or more, and in the case of biaxial stretching, the refractive index in the stretching direction is approximately 1.62 or more, preferably 1. This process continues until the number reaches 64 or more. The stretching ratio that gives such a refractive index is about 2 to 4 times in the case of -axial stretching, and in the longitudinal direction (M
D>, the transverse direction (TD is about 1.7 to 3.5 times, respectively. In the case of biaxial stretching, the area magnification is preferably 2.8 to 10 @.
二軸延伸は逐次二軸延伸によるかまたは同時二軸延伸の
いずれでもよい。The biaxial stretching may be either sequential biaxial stretching or simultaneous biaxial stretching.
延伸フィルムは熱固定により結晶化度を高め寸法安定性
を改善することがてきる。熱固定はフィルム温度約２５
０℃以上の温度、好ましくは重合体の融点より２０℃低
い温度以下で且つ約３３０℃以下の温度で行なうことが
できる。熱固定の時間は１０秒〜５分の間が好ましい、
この熱固定は緊張下で実施され、これにより結晶化が進
行する。Stretched films can be heat-set to increase crystallinity and improve dimensional stability. Heat fixing is done at a film temperature of approximately 25
It can be carried out at temperatures above 0°C, preferably below 20°C below the melting point of the polymer and below about 330°C. The heat setting time is preferably between 10 seconds and 5 minutes.
This heat fixation is carried out under tension, which promotes crystallization.
熱固定したフィルムは、ついで熱収縮処理を施すのが好
ましい。この処理によって熱収縮率の小さい耐熱性の良
好なフィルムが得られる。熱収縮処理はフィルム温度約
２００℃以上重合体の融点より２０°Ｃ低い温度以下で
且つ３２０℃以下の温度、好ましくは約２００’Ｃと熱
固定温度より１０℃以上低い温度との間の温度で行うこ
とができる。この熱収縮処理は緊張下（制限収縮下）ま
たは無緊張下のいずれの条件下で行うこともできる。熱
収縮の割合は、熱収縮処理に付す熱固定されたフィルム
の最大収縮率に依存して変えることが望ましく、特に熱
固定されたフィルムを熱固定温度における最大収縮率約
３０％以下のものとして製造し、そして熱収縮処理にお
いて熱固定温度における残余の収縮率が約５％以下、好
ましくは約２％以下、特に約１％以下となるようにする
のが望ましい。It is preferable that the heat-set film is then subjected to a heat-shrinking treatment. By this treatment, a film with low heat shrinkage and good heat resistance can be obtained. The heat shrinking treatment is carried out at a film temperature of about 200°C or more, but not more than 20°C lower than the melting point of the polymer, and not more than 320°C, preferably at a temperature between about 200'C and a temperature 10°C or more lower than the heat setting temperature. It can be done with This heat shrinking treatment can be carried out either under tension (limited shrinkage) or under no tension. The rate of heat shrinkage is preferably changed depending on the maximum shrinkage rate of the heat-set film subjected to the heat-shrinking treatment, and in particular, the heat-set film should have a maximum shrinkage rate of about 30% or less at the heat-setting temperature. It is desirable that the residual shrinkage at the heat setting temperature be less than about 5%, preferably less than about 2%, especially less than about 1% during the manufacturing and heat shrinking treatment.
このように延伸されたフィルム、あるいは延伸熱固定さ
れたフィルムおよび更に熱収縮処理されたフィルムは、
いずれも２５℃における縦、横のヤフグ率が約１５０
ｋｇ ／ ｒｎ＋ ２以上、強度が約１０踵／閣２以上
であり、更に２５℃における伸度は約２０％以上、であ
る。Films stretched in this way, or stretched and heat-set films, and films further heat-shrinked are
Both have vertical and horizontal yafugu ratios of approximately 150 at 25°C.
kg/rn+ 2 or more, the strength is about 10 heel/height 2 or more, and the elongation at 25°C is about 20% or more.
また、熱固定されたフィルムおよび熱収縮処理されたフ
ィルムは、２６０℃において１分間無緊張下で加熱した
のち、２５℃で測定したときの伸度が約２０％以上であ
り、瞬時耐熱性にすぐれている。In addition, heat-set films and heat-shrinkable films have an elongation of approximately 20% or more when measured at 25°C after being heated at 260°C for 1 minute without tension, and have instantaneous heat resistance. It is excellent.
また本発明の全芳香族ポリエステルからの未延伸フィル
ムおよび熱収縮処理されたフィルムは２６０℃で１分間
無緊張下で加熱した際の熱収縮率が５％以下である。Further, the unstretched film and the heat-shrinkable film made of the wholly aromatic polyester of the present invention have a heat shrinkage rate of 5% or less when heated at 260° C. for 1 minute without tension.
このように熱固定されたフィルムおよび熱収縮処理され
たフィルムは平均の線膨張係数が約８×１ Ｇ４Ｏ／
ａｍ ／ ’Ｃ以下であり、寸法安定性にもすぐれてい
る。The heat-set film and the heat-shrinkable film have an average coefficient of linear expansion of approximately 8×1 G4O/
am/'C or less, and has excellent dimensional stability.
また、このフィルムは、吸水率が約０．５％程度と小さ
く、またトリクレンの如き有機溶剤に対しても耐溶剤性
がすぐれている。Further, this film has a low water absorption rate of about 0.5%, and also has excellent solvent resistance to organic solvents such as trichlene.
そして、本発明の全芳香族ポリエステルから溶融成形に
より得られたフィルムは該全芳香族ポリエステルが異物
を含まず（該全芳香族ポリエステルを製造する本発明の
重縮合法によれば重縮合時に重合体に溶解しない異物の
生成がないため）、また溶融安定性にすぐれているため
、極めてすぐれた透明性を有するのみならず異物を含ま
ず表面が平滑である。The film obtained by melt molding from the wholly aromatic polyester of the present invention is such that the wholly aromatic polyester does not contain any foreign matter (according to the polycondensation method of the present invention for producing the wholly aromatic polyester, polymerization occurs during polycondensation). Because there is no generation of foreign matter that does not dissolve during coalescence), and because it has excellent melting stability, it not only has extremely excellent transparency but also has a smooth surface free of foreign matter.
したがって、このフィルムは、そのすぐれた耐熱性を利
用して、たとえば金属蒸着用フィルム。Therefore, this film can be used as a film for metal deposition, for example, by taking advantage of its excellent heat resistance.
フレキシブルプリント配線用フィルム、電気絶縁用フィ
ルムなどに用いることができる。It can be used for flexible printed wiring films, electrical insulation films, etc.
〈実施例〉
以下実施例により本発明について詳述するが、その前に
ポリマー特性の測定法および測定用サンプルの調製につ
いて説明する。<Example> The present invention will be described in detail with reference to Examples below, but before that, a method for measuring polymer properties and preparation of samples for measurement will be explained.
本発明におけるポリマーは結晶性であり、固相重合のよ
うな長時間の熱処理をうけたものはフェノールとテトラ
クロルエタンの混合溶剤には溶解が困難である。そこで
固相重合したポリマーのｒｚ ｓｐ／ ｃおよび［ＣＯ
ＯＨ］の測定に際しては、ポリマーを予め１５０℃で乾
燥し、ついでこのポリマー約ＩＩｒを直径ｌＩｍ、長さ
５市のノズルを備えた断面積１−のシリンダーに充填し
、ついでポリマーを融点以上の温度（実施例では３８０
℃）で２分間加熱溶融後押出し、上記測定用サンプルと
してた。The polymer used in the present invention is crystalline, and those that have been subjected to long-term heat treatment such as solid phase polymerization are difficult to dissolve in a mixed solvent of phenol and tetrachloroethane. There, the rz sp/c and [CO
For the measurement of OH], the polymer was dried in advance at 150°C, then about IIr of this polymer was filled into a cylinder with a cross-sectional area of 1 - equipped with a nozzle with a diameter of lIm and a length of 5 cm, and then the polymer was heated to a temperature above the melting point. Temperature (380 in the example)
℃) for 2 minutes and then extruded to obtain the sample for the above measurement.
溶融押出し成形した未延伸フィルム、延伸フィルム、熱
固定されたフィルムおよび熱収縮させたフィルムなどは
、そのままηｓｐ／ ｃおよび［ＣＯＯＨ］測定用サン
プルとした。Melt-extruded unstretched films, stretched films, heat-set films, heat-shrinked films, and the like were used as samples for measuring ηsp/c and [COOH].
（０］ −゛ ノズルの−。。(0) -゛ -.
本発明におけるポリマーの融点の測定に際してはポリマ
ーを予め２００℃で１時間熱処理したものを用いた。When measuring the melting point of a polymer in the present invention, a polymer that had been heat-treated in advance at 200° C. for 1 hour was used.
（１４還−ＦＳｃ の・」
サンプル１２０■を１０ｍ１のフェノールとテトラクロ
ルエタンとの混合溶剤（フェノール：テトラクロルエタ
ン（重量比）＝４：６）に溶解し、３５℃でオストワル
ドの粘度計を用いて相対粘度（η「）を測定し、下記式
によりηｓｐ／ｃを算出した。(14-reduced-FSc) Sample 120 was dissolved in 10 ml of a mixed solvent of phenol and tetrachloroethane (phenol:tetrachloroethane (weight ratio) = 4:6), and an Ostwald viscometer was measured at 35°C. The relative viscosity (η'') was measured using the following formula, and ηsp/c was calculated using the following formula.
η「−１
ηｓｐ／ｃ＝
０．５
（ニ） カルボキシル基量 Ｃ０ＯＨのサンプル１００
■を１０ｍ１のフェノールとテトラクロルエタンとの混
合溶剤（フェノール：テトラクロルエタン（重量比）＝
４：６）に溶解し、ブロムクレゾールグリーンを指示薬
として０．１規定の苛性ソーダのベンジルアルコール溶
液を用いて滴定し、下記式を用い［Ｃ０ＯＨ］を算出し
た。η"-1 ηsp/c= 0.5 (d) Carboxyl group amount C0OH sample 100
■ is a mixed solvent of 10ml of phenol and tetrachloroethane (phenol:tetrachloroethane (weight ratio) =
4:6) and titrated with a 0.1 N benzyl alcohol solution of caustic soda using bromcresol green as an indicator, and [C0OH] was calculated using the following formula.
［Ｃ０ＯＨ］ ＝
［Ａ−Ｂ］Ｘｆ
ｘ１０２ （当量／１０６＋ｒ）
ポリマー量（ｒ）
サンプルを示差熱分析装置（理学電機８０７５Ｄ１型）
を用いて１０℃／分の速度で昇温して常法によりそのピ
ーク位置より融点を求めた。[C0OH] = [A-B]
The temperature was raised at a rate of 10° C./min using a 10° C./min, and the melting point was determined from the peak position using a conventional method.
（Ｎ フローインデックスの・、
ポリマー約１ｇを直径１■、長さ５ｒＩｍ３のノズルを
備えた断面積１１のシリンダーに充填し、次いでポリマ
ーの溶融押出し可能な温度で種々の加圧下に溶融押出し
、下記式よりすり応力（τ）とすり速度（γ）を求め
Ｐ
τ＝ （ｄｙｎｅ／ ｃｄ ）Ｌ
Ｑ
γ＝ （ｓｅｃ’）
πＲ３
次に、τ、γおよびフローインデックス（ｎ）の下記関
係式中の
τ／γｎ＝一定
ｎの値を ｌｏｇγを横軸に、 ｌｏｇτを縦軸とする
グラフの直線の勾配として求めた。(with a flow index of N), approximately 1 g of polymer was filled into a cylinder with a cross-sectional area of 11 equipped with a nozzle with a diameter of 1 mm and a length of 5 rIm3, and then melt-extruded under various pressures at a temperature at which the polymer could be melt-extruded, as described below. Calculate the slip stress (τ) and slip velocity (γ) from the equations P τ= (dyne/cd)L Q γ= (sec') πR3 Next, calculate the following relational expression of τ, γ, and flow index (n). The value of τ/γn=constant n was determined as the slope of a straight line in a graph with logγ on the horizontal axis and logτ on the vertical axis.
（ト） 乙ニーｏ二之−≦ヒニ！２！）ヒー１１
Ｘ線スペクトロメーターアンセンブリ ＫＧ−Ｘ（理学
電機）を用い蛍光Ｘ線法により定量した。検量線は試料
にｐ−ハロゲン置換安息香酸（ハロゲン原子が塩素の場
合ｐ−クロル安息香酸）を添加し作成した。(G) Otsunie ojino-≦Hini! 2! ) Hee 11
Quantification was performed by fluorescent X-ray method using X-ray spectrometer assembly KG-X (Rigaku Denki). A calibration curve was created by adding p-halogen-substituted benzoic acid (p-chlorobenzoic acid when the halogen atom is chlorine) to the sample.
以下、実施例を述べるが、例中単に「部」とあるは「重
量部」を表わす。Examples will be described below, and in the examples, "parts" simply means "parts by weight."
実施例１
ジフェニルイソフタレート１９０．８０部、ハイドロキ
ノン５５．４４部、２．２−ビス（４−ヒドロキシフェ
ニル）プロパン２８．７３部、三酸化アンチモン０．０
７０部及びトリフェニルホスフェート０．０９８ 部を
撹拌機付き重合反応器に仕込み、２５０〜２９０℃に２
時間加熱し、反応の結果生成するフェノール６．８部（
理論値の約６０％）を留出させた（反応系内の生成物の
還元粘度と融点はそれぞれ０．０８゜２８０℃である）
。Example 1 190.80 parts of diphenyl isophthalate, 55.44 parts of hydroquinone, 28.73 parts of 2,2-bis(4-hydroxyphenyl)propane, 0.0 parts of antimony trioxide
70 parts and 0.098 parts of triphenyl phosphate were placed in a polymerization reactor equipped with a stirrer, and heated to 250 to 290°C for 2 hours.
6.8 parts of phenol produced as a result of the reaction.
(approximately 60% of the theoretical value) was distilled out (reduced viscosity and melting point of the product in the reaction system are 0.08° and 280°C, respectively).
.
次いで反応系の圧力を徐々に減圧にするのと一緒に反応
温度を上げ始め、約１時間を要して圧力を２０部ｍＨ！
Ｊ、反応温度を３３０’Ｃとしくこの際反応系内のポリ
マーの還元粘度と融点はそれぞれ０．１５゜３５０℃で
ある）、この条件下で３０分間、更に圧力２ ｍ＋ｎ
ＨＱとして１５分間重合を続けた。得られたポリマーの
還元粘度と融点はそれぞれ０．６０．３６０℃であった
。Next, the pressure of the reaction system was gradually reduced and the reaction temperature began to increase, and it took about 1 hour to raise the pressure to 20 parts mH!
J, the reaction temperature was 330'C, and the reduced viscosity and melting point of the polymer in the reaction system were 0.15° and 350°C, respectively), and under these conditions for 30 minutes, and at a pressure of 2 m+n.
Polymerization continued for 15 minutes as HQ. The reduced viscosity and melting point of the obtained polymer were 0.60.360°C, respectively.
ここで溶融重縮合を停止し、ポリマーを冷却後１２〜２
０メツシユに粉砕し、０．２＋ｎ＋）［（ｌの減圧下２
５０℃で２時間、更に０．２闇ＨＱの減圧下２９０℃で
１５時間固相重合を行った。得られたポリマーの還元粘
度は０．９０．［Ｃ０ＯＨ］は２５当量／ ｌ Ｑ ６
ｇ。After stopping the melt polycondensation and cooling the polymer,
Grind to 0 mesh, 0.2+n+)[(2 under reduced pressure of 1
Solid phase polymerization was carried out at 50°C for 2 hours and then at 290°C under reduced pressure of 0.2 HQ for 15 hours. The reduced viscosity of the obtained polymer was 0.90. [C0OH] is 25 equivalents/l Q 6
g.
融点は３５５℃であった。また３８０℃で求めたこのポ
リマーのフローインデックスは０．７８であった。The melting point was 355°C. Further, the flow index of this polymer determined at 380°C was 0.78.
実施例２
ジフェニルイソフタレート１９０．８０部、ハイドロキ
ノン５８．９１部、２，２−ビス（４−しドロキシフェ
ニル）プロパン２１．５５部、三酸化アンチモン０．１
０５部及びトリフェニルホスフェート０．０４２部を用
い２關Ｈ１ｌｌでの重合は行なわず、２０ ＋ｍ Ｈｇ
における重合時間を１５分と変えた以外は、実施例１と
同様にして溶融重合を行った。Example 2 190.80 parts of diphenyl isophthalate, 58.91 parts of hydroquinone, 21.55 parts of 2,2-bis(4-droxyphenyl)propane, 0.1 parts of antimony trioxide
Polymerization was carried out using 0.05 parts of triphenyl phosphate and 0.042 parts of triphenyl phosphate at 20 + m Hg.
Melt polymerization was carried out in the same manner as in Example 1, except that the polymerization time was changed to 15 minutes.
得られたポリマーの還元粘度と融点はそれぞれ０．３０
．３７０℃であった。The reduced viscosity and melting point of the obtained polymer were each 0.30.
．． The temperature was 370°C.
ここで得られたポリマーは１２〜５０メツシユに粉砕し
、２５０℃０．２庫トｒ ｏの減圧下で２時間、更に０
．２ＩｌｌＩＨｇの減圧下２８０℃で３０時間固相重合
を行った。ここで得られたポリマーは、還元粘度０．８
８゜［Ｃ００Ｈ］２８当量／１０”ｔ、融点３７０’Ｃ
であった。また３８０℃で求めたこのポリマーのフロー
インデックスは０．７７であった。The obtained polymer was pulverized into 12 to 50 meshes and heated at 250°C under reduced pressure at 0.2°C for 2 hours.
．． Solid phase polymerization was carried out at 280° C. for 30 hours under a reduced pressure of 2IllIHg. The polymer obtained here has a reduced viscosity of 0.8
8゜[C00H]28 equivalents/10"t, melting point 370'C
Met. The flow index of this polymer determined at 380°C was 0.77.
実施例３
ジフェニルイソフタレート１９０．８０部、ハイドロキ
ノン５５．４４部、ビス（４−しドロキシフェニル）エ
ーテル２５．４５部、三酸化アンチモン０．０７０部お
よびトリフェニルホスフェート０．０５５部を撹拌機付
き重合反応器に仕込み、窒素雰囲気下２５０〜２９０℃
に２．５時間加熱し、反応の結果生成するフェノール５
６部（理論値の約５０％）留出させた（反応系内の生成
物の還元粘度は０．０７である。）次いで反応系の圧力
を徐々に減圧するのと一緒に反応温度を上げ始め、約１
時間を要して圧力を２０ｍｍＨＱ、反応温度を３３０℃
としくこの際反応系内のポリマーの還元粘度と融点はそ
れぞれ０．１４゜３５０℃である）、この条件下で更に
１５分間重合を続けた。得られたポリマーの還元粘度と
融点は、それぞれ０．４１．３５５℃であった。Example 3 190.80 parts of diphenyl isophthalate, 55.44 parts of hydroquinone, 25.45 parts of bis(4-droxyphenyl)ether, 0.070 parts of antimony trioxide and 0.055 parts of triphenyl phosphate were mixed in a stirrer. Pour into a polymerization reactor and heat at 250 to 290℃ under nitrogen atmosphere.
The phenol 5 produced as a result of the reaction is heated for 2.5 hours.
6 parts (approximately 50% of the theoretical value) were distilled off (the reduced viscosity of the product in the reaction system is 0.07).Then, the pressure in the reaction system was gradually reduced and the reaction temperature was increased. Start, about 1
It takes time to increase the pressure to 20mmHQ and the reaction temperature to 330℃.
At this time, the reduced viscosity and melting point of the polymer in the reaction system were 0.14°C and 350°C, respectively), and the polymerization was continued for an additional 15 minutes under these conditions. The reduced viscosity and melting point of the obtained polymer were 0.41.355°C, respectively.
ここで溶融重合を停止し、ポリマーを冷却後１５〜２０
メツシユに粉砕し、２５０℃、 ０．０２ｍｍ Ｈ（ｌ
の減圧下で１時間、更に２９０℃、 ０．０２ｍ＋ＨＯ
の減圧下３２時間固相重合を行った。得られたポリマー
は、還元粘度１．０５．［Ｃ００Ｈ］２５当Ｊｉ／１０
６ｇ、融点３６０℃であった。ｔた３８０℃で求めたこ
のポリマーのフローインデックスは０．７５であった。After stopping the melt polymerization and cooling the polymer,
Grind into mesh, heat at 250℃, 0.02mm H(l
1 hour under reduced pressure of 290℃, 0.02m+HO
Solid phase polymerization was carried out under reduced pressure for 32 hours. The obtained polymer had a reduced viscosity of 1.05. [C00H] 25 points Ji/10
6g, melting point 360°C. The flow index of this polymer determined at 380° C. was 0.75.
実施例４
実施例１〜３において得たポリマーをそれぞれ３８０℃
でエクストルーダー中で溶融し、スリット巾１．５市、
ランド長１０ＩｌＩＩのＴダイよりｉｏｏ’ｃに加熱さ
れたキャスティングドラム上に押出し、平滑性、透明性
共に良好で淡褐色の厚さ約３００μの未延伸フィルムを
得た。ここで得られた未延伸フィルムはいずれもハロゲ
ン含量が１０ｐｐ１未満であった。これらのフィルムを
２００℃で縦方向（機械軸方向、ＭＤ）に２，０〜２．
５＠に延伸し、次いで同温度で横方向（機械軸方向と直
角な方向、ＴＤ）に同じ倍率に延伸することによって二
軸延伸フィルムを得た。さらにこの延伸フィルムを２８
５℃で１０秒間定長で熱固定し、さらに２７０℃で２０
秒間収縮させ、高強度・高ヤング率のフィルムを得な。Example 4 The polymers obtained in Examples 1 to 3 were heated at 380°C.
Melt in an extruder with a slit width of 1.5 cm,
It was extruded from a T-die with a land length of 10IlII onto a casting drum heated to IOO'C to obtain an unstretched film with a light brown color and a thickness of about 300μ with good smoothness and transparency. All of the unstretched films obtained here had a halogen content of less than 10 pp1. These films were heated at 200°C in the longitudinal direction (mechanical axis direction, MD) by 2.0 to 2.
A biaxially stretched film was obtained by stretching the film at the same temperature and then at the same temperature in the transverse direction (direction perpendicular to the machine axis direction, TD) at the same magnification. Furthermore, this stretched film was
Heat set at 5℃ for 10 seconds at a fixed length, then further heat set at 270℃ for 20 seconds.
Shrink for seconds to obtain a film with high strength and high Young's modulus.
次に、上述の未延伸フィルムを、切断ｔ＆１５０℃で２
４時間乾燥後直径ｌ ｃｍ 、長さ５ＩｗＩのノズルを
備えた断面積１−のシリンダーに充填し、３８０℃５分
間溶融後３０ｋｇ／−の加圧下で押出し、糸状で得られ
るポリマーの還元粘度を測定し、この溶融操作前後の還
元粘度の変化より本発明の全芳香族ポリエステルの溶融
安定性を評価した（以下テストＡとする）。Next, the above-mentioned unstretched film was cut at t & 2 at 150°C.
After drying for 4 hours, it was filled into a cylinder with a cross section of 1 - equipped with a nozzle with a diameter of 1 cm and a length of 5 IwI, melted at 380°C for 5 minutes, and then extruded under a pressure of 30 kg/- to determine the reduced viscosity of the polymer obtained in the form of threads. The melt stability of the wholly aromatic polyester of the present invention was evaluated based on the change in reduced viscosity before and after the melting operation (hereinafter referred to as Test A).
また各未延伸フィルムを、水と共にガラス管に入れ、ガ
ラス管を溶封後１２０℃のオートクレーブ中で２４時間
保持して後未延伸フィルムの還元粘度を測定し、この湿
熱処理操作の前後の還元粘度の変化より温熱安定性を評
価した（以下テストＢとする）。In addition, each unstretched film was placed in a glass tube with water, and the glass tube was melt-sealed and kept in an autoclave at 120°C for 24 hours.The reduced viscosity of the unstretched film was then measured. The thermal stability was evaluated from the change in viscosity (hereinafter referred to as test B).
その結果を表１に示す。The results are shown in Table 1.
実施例５
イソフタル酸９９．６０部、ハイドロキノン５５．４４
部、２．２−ビス（４−ヒドロキシフェニル）プロパン
２８．７３部、ジフェニルカーボネー）１２８．４０部
及び三酸化アンチモンｏ、ｉｏｓ部を゛撹拌機付き重合
反応器に仕込み、窒素雰囲気下２５０〜２９０℃に３時
間加熱し、反応の結果生成するフェノール１２４部（Ｏ
１！用したジフェニルカーボネートのモル数と重合体を
形成するためのエステル交換反応により生成する理論量
の６０％との和に相当する）留出させたく反応系内の生
成物の還元粘度と融点はそれぞれ０．０８．２７５℃で
ある）。Example 5 99.60 parts of isophthalic acid, 55.44 parts of hydroquinone
28.73 parts of 2-bis(4-hydroxyphenyl)propane, 128.40 parts of diphenyl carbonate) and 128.40 parts of antimony trioxide (O, IOS) were charged into a polymerization reactor equipped with a stirrer, and 250 parts of 2.2-bis(4-hydroxyphenyl)propane was charged under a nitrogen atmosphere. Heated to ~290°C for 3 hours to remove 124 parts of phenol (O
1! The reduced viscosity and melting point of the product in the reaction system to be distilled are the same as the sum of the number of moles of diphenyl carbonate used and 60% of the theoretical amount produced by the transesterification reaction to form the polymer. 0.08.275°C).
次いで反応系に窒素を導入しつつ反応系の圧力を徐々に
減圧するのと一緒に反応温度を上げ始め、約１時間を要
して圧力を２０部ｍＨｇ、反応温度を３３０℃とし、こ
の条件下で更に３０分間重合させた。Next, while introducing nitrogen into the reaction system, the pressure of the reaction system was gradually reduced, and at the same time, the reaction temperature began to increase, and it took about 1 hour to bring the pressure to 20 parts mHg and the reaction temperature to 330°C, and under these conditions. Polymerization was continued for an additional 30 minutes at a lower temperature.
得られたポリマーの還元粘度と融点は、それぞれ０．４
５．３５５℃であった。The reduced viscosity and melting point of the obtained polymer were each 0.4.
It was 5.355°C.
ここで溶融重合を停止し、ポリマーを冷却後１５〜２４
メツシユに粉砕し、２５０℃、 ０．０１ｍ＋ＨＩＪの
減圧下で１時間さらに２９０℃、 ０．０２市Ｈｇの減
圧下２０時間固相重合させた。After stopping the melt polymerization and cooling the polymer,
The mixture was pulverized into a mesh and subjected to solid phase polymerization at 250° C. for 1 hour under a reduced pressure of 0.01 m+HIJ, and then for 20 hours at 290° C. under a reduced pressure of 0.02 city Hg.
このようにして得られたポリマーは還元粘度０．９１．
［Ｃ００Ｈ１２３当量／ １Ｑ６ ｔ、融点３５５
℃であった。またこのポリマーの３８０℃におけるフロ
ーインデックスは０．７７であった。The polymer thus obtained had a reduced viscosity of 0.91.
[C00H123 equivalent/1Q6 t, melting point 355
It was ℃. Further, the flow index of this polymer at 380°C was 0.77.
このポリマーは実施例１のポリマーと同様フィルムに溶
融成形できることが確認された。It was confirmed that this polymer, like the polymer of Example 1, could be melt-formed into a film.
実施例６〜８
次の１）〜３）の原料を用いて全芳香族ポリエステルを
製造した。Examples 6 to 8 Whole aromatic polyesters were manufactured using the following raw materials 1) to 3).
１）ジフェニルイソフタレート１７１．７２部、ジフェ
ニルテレフタレート１９．０８部、ハイドロキノン６２
．３７部および２．２−ビス（４−ヒドロキシフェニル
）プロパン１４．３６部を用いる（実施例６）、
２）ジフェニルイソフタレート１９０．８０部１ハイド
ロキノン５５．４４部及びビス（４−ヒドロキシフェニ
ル）ゲトン２６．９６部を用いる（実施例７）、３）ジ
フェニルイソフタレート１９０．８０部、ハイドロキノ
ン５５．４４部及び１，１−ビス（４−ヒドロキシフェ
ニル）シクロヘキサン３３．７７部を用いる（実施例８
）、
それぞれ、上記原料およびトリフェニルホスフェート０
．０９８部、三酸化アンチモン０．１０５部を撹拌機付
き重合反応器に仕込み、窒素雰囲気下２５０〜２９０℃
に２時間加熱し、反応の結果生成するフェノール７０部
（理論値の約６２％）留出させた。1) 171.72 parts of diphenyl isophthalate, 19.08 parts of diphenyl terephthalate, 62 parts of hydroquinone
．． using 37 parts of 2.2-bis(4-hydroxyphenyl)propane (Example 6); 2) 190.80 parts of diphenyl isophthalate; 55.44 parts of hydroquinone and bis(4-hydroxyphenyl); Using 26.96 parts of getone (Example 7), 3) Using 190.80 parts of diphenyl isophthalate, 55.44 parts of hydroquinone and 33.77 parts of 1,1-bis(4-hydroxyphenyl)cyclohexane (Example 7) 8
), respectively, the above raw materials and triphenyl phosphate 0
．． 098 parts of antimony trioxide and 0.105 parts of antimony trioxide were charged into a polymerization reactor equipped with a stirrer, and heated at 250 to 290°C under a nitrogen atmosphere.
The mixture was heated for 2 hours to distill off 70 parts of phenol (approximately 62% of the theoretical value) produced as a result of the reaction.
（反応系内の生成物の還元粘度は０．０８であった）。(The reduced viscosity of the product in the reaction system was 0.08).
次いで反応系の圧力を徐々に減圧するのと一緒に反応温
度を上げ始め、約１時間を要して圧力を２０ｍ＋Ｈｇ、
反応温度を３２０°Ｃとしくこの際反応系内のポリマー
の還元粘度と融点はそれぞれ０．１５゜３５０℃である
）、この条件下で更に１８分間重合を続けた。得られた
ポリマーの還元粘度と融点はそれぞれ０．３０．３７０
℃であった。Next, the pressure of the reaction system was gradually reduced and the reaction temperature started to increase, and it took about 1 hour to increase the pressure to 20m+Hg.
The reaction temperature was set at 320°C (at this time, the reduced viscosity and melting point of the polymer in the reaction system were 0.15° and 350°C, respectively), and polymerization was continued for an additional 18 minutes under these conditions. The reduced viscosity and melting point of the obtained polymer were 0.30.370, respectively.
It was ℃.
ここで溶融重合を停止し、ポリマーを冷却後１２〜５０
メツシユに粉砕し、０．０５部ｍＨ！Ｊの減圧下で２５
０℃で２時間、更に０．０５市Ｈ１ｌｌの減圧下２９０
℃で２８時間固相重合を行った。得られた各ポリマーを
製膜し、ＭＤ、ＴＤ両方向に各２．０倍（実施例６．８
）又は各２．２倍（実施例７）に逐次二軸延伸し、２８
５℃で定長で熱固定し、更に２７０℃で収縮させてフィ
ルムを得た。得られたフィルムの特性を測定した結果を
表２に示す。After stopping the melt polymerization and cooling the polymer,
Grind into mesh, 0.05 part mH! 25 under reduced pressure of J
2 hours at 0°C, and further under reduced pressure of 0.05 ml H290
Solid phase polymerization was carried out at ℃ for 28 hours. Each of the obtained polymers was formed into a film, and the film was 2.0 times larger in both MD and TD directions (Example 6.8
) or 2.2 times each (Example 7), sequentially biaxially stretched, 28
The film was heat-set at a constant length at 5°C and further shrunk at 270°C to obtain a film. Table 2 shows the results of measuring the properties of the obtained film.
比較例
比較のため、ジフェニルイソフタレートとハイドロキノ
ンとの合計が８０モル％となるように、ジフェニルイソ
フタレート１９０．８部、ハイドロキノン４２．９部、
２．２−ビス（４−ｂドロキシフェニル）プロパン５４
．７部、二酸化アンチモン０．０７０部及びトリフェニ
ルホスフェート０．０９８部を撹拌機付き重合反応器に
仕込み、２５０〜２９０℃に２時間加熱し、反応の結果
生成するフェノールを留出させた。Comparative Example For comparison, 190.8 parts of diphenyl isophthalate, 42.9 parts of hydroquinone,
2.2-bis(4-b droxyphenyl)propane 54
．． 7 parts of antimony dioxide, 0.070 parts of antimony dioxide, and 0.098 parts of triphenyl phosphate were placed in a polymerization reactor equipped with a stirrer, and heated at 250 to 290°C for 2 hours to distill off the phenol produced as a result of the reaction.
次いで反応系の圧力を徐々に減圧にするのと一緒に反応
温度を上げ始め、約１時間を要して圧力を２０ｎｍＨＯ
１反応温度を３３０℃として３０分間、更に圧力を約１
ｍＨＱとして４５分間重合をつづけた。Next, the pressure of the reaction system was gradually reduced and the reaction temperature started to increase, and it took about 1 hour to reduce the pressure to 20 nm HO.
1 The reaction temperature was set at 330°C for 30 minutes, and the pressure was increased to about 1
Polymerization was continued for 45 minutes at mHQ.
得られたポリマーのη５０／ＣＯ，９７で非晶透明であ
り、熱処理−しても結晶化しなかった。The resulting polymer had a η50/CO of 97 and was amorphous and transparent, and did not crystallize even after heat treatment.
次に該ポリマーを実施例４と同じ条件で溶融押出し、未
延伸フィルムを得た。該未延伸フィルムの物性は下記衣
３の通りであった・、このフィルムは２００℃で延伸す
るとフローしてしまい表３に示した物性は殆んど向上し
なかった。Next, the polymer was melt-extruded under the same conditions as in Example 4 to obtain an unstretched film. The physical properties of the unstretched film were as shown in Figure 3 below. This film flowed when stretched at 200°C, and the physical properties shown in Table 3 were hardly improved.
Claims (1)
III］で表わされる単位からなる実質的に線状の共重合
全芳香族ポリエステルであつて、▲数式、化学式、表等
があります▼・・・・・・［ I ］ ▲数式、化学式、表等があります▼・・・・・・［II］ ▲数式、化学式、表等があります▼・・・・・・［III
］ ［なお、式［III］中のＸは−Ｏ−、−ＣＯ−または▲
数式、化学式、表等があります▼であり、Ｒ、Ｒ′は、
それぞれ水素原子またはメチル、エチル、プロピルもし
くはフェニルであるか、またはＲ、Ｒ′およびそれらが
結合している炭素原子が一緒になつてシクロヘキサン環
を形成しているものであり、これらは同一でも相異って
もよい。］該全芳香族ポリエステルにおける前記式［
I ］と［II］で表わされる単位のモル数の和が９５〜８
５モル％の範囲内にあり、９０当量／１０＾６ｇ以下の
末端カルボキシル基と、少くとも０．６の還元粘度（フ
ェノール／テトラクロロエタン＝４／６の混合溶剤中３
５℃で測定した相対粘度より算出）とを有し、且つ分子
鎖に結合したハロゲン原子を実質的に含まないことを特
徴とする全芳香族ポリエステル。 ２、イソフタル酸ジアリールエステルおよびハイドロキ
ノンならびに下記式（ａ）で表わされるジヒドロキシ芳
香族化合物 ▲数式、化学式、表等があります▼・・・・・・（ａ） ［ただし、式（ａ）中のＸは前記と同じ］ の少くとも１種を、イソフタル酸ジアリールエステルお
よびハイドロキノンの合計量が全反応成分の９５〜８５
モル％となるように仕込んで重縮合せしめることからな
り、且つ、その際、反応系内に形成された重合体の還元
粘度が０．１５に到達したのちは少くとも該重合体の結
晶融点より低い温度で且つ溶融状態を維持しつつ重縮合
触媒の存在下に加熱重縮合せしめ、更に必要に応じて固
相重合せしめて、末端カルボキシル基量９０当量／１０
＾６ｇ以下で、かつ還元粘度（フェノール／テトラクロ
ロエタン＝４／６の混合溶剤中３５℃で測定した相対粘
度より算出）０．６以上のポリマーとすることを特徴と
する全芳香族ポリエステルの製造法。 ３、イソフタル酸、ハイドロキノンおよびジアリルカー
ボネートならびに下記式（ａ）で表わされるジヒドロキ
シ芳香族化合物 ▲数式、化学式、表等があります▼・・・・・・（ａ） ［ただし、式（ａ）中のＸは前記と同じ］ の少くとも１種を、イソフタル酸およびハイドロキノン
の合計量がジアリルカーボネートを除いた全反応成分の
９５〜８５モル％となるように仕込んで重縮合せしめる
ことから成り、且つ、その際反応系内に形成された重合
体の還元粘度が０．１５に到達したのちは少くとも該重
合体の結晶融点より低い温度で且つ溶融状態を維持しつ
つ重縮合触媒の存在下に加熱重縮合せしめ、更に必要に
応じて固相重合せしめて、末端カルボキシル基量９０当
量／１０＾６ｇ以下で、かつ還元粘度（フェノール／テ
トラクロロエタン＝４／６の混合溶剤３５℃で測定した
相対粘度より算出）０．６以上のポリマーとすることを
特徴とする全芳香族ポリエステルの製造法。[Claims] 1. The polymer constituent units have the following formulas [I], [II] and [
A substantially linear copolymerized wholly aromatic polyester consisting of units represented by ▲Mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I] ▲Mathematical formulas, chemical formulas, tables, etc. There are▼・・・・・・［II］ ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・［III
] [In addition, X in formula [III] is -O-, -CO- or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, and R and R' are
Each is a hydrogen atom or methyl, ethyl, propyl, or phenyl, or R, R' and the carbon atoms to which they are bonded together form a cyclohexane ring, and these may be the same or different. May be different. ] The above formula in the wholly aromatic polyester [
The sum of the number of moles of units represented by [I] and [II] is 95 to 8
5 mol %, a terminal carboxyl group of not more than 90 equivalents/10^6 g, and a reduced viscosity of at least 0.6 (in a mixed solvent of phenol/tetrachloroethane = 4/6).
A wholly aromatic polyester having a relative viscosity (calculated from a relative viscosity measured at 5° C.) and substantially free of halogen atoms bonded to its molecular chains. 2. Isophthalic acid diaryl ester, hydroquinone, and dihydroxy aromatic compound represented by the following formula (a) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼・・・・・・(a) [However, X in formula (a) is the same as above] and the total amount of isophthalic acid diaryl ester and hydroquinone is 95 to 85 of the total reaction components.
% by mole and polycondensation, and at that time, after the reduced viscosity of the polymer formed in the reaction system reaches 0.15, it is at least higher than the crystalline melting point of the polymer. Polycondensation is carried out by heating in the presence of a polycondensation catalyst at a low temperature while maintaining a molten state, and if necessary, solid phase polymerization is carried out to obtain a terminal carboxyl group weight of 90 equivalents/10
Production of a wholly aromatic polyester characterized by a polymer having a weight of ^6g or less and a reduced viscosity (calculated from the relative viscosity measured at 35°C in a mixed solvent of phenol/tetrachloroethane = 4/6) of 0.6 or more. Law. 3. Isophthalic acid, hydroquinone, diallyl carbonate, and dihydroxy aromatic compounds represented by the following formula (a) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼・・・・・・(a) [However, in formula (a) X is the same as above] is charged and polycondensed such that the total amount of isophthalic acid and hydroquinone is 95 to 85 mol% of the total reaction components excluding diallyl carbonate, and At this time, after the reduced viscosity of the polymer formed in the reaction system reaches 0.15, it is heated in the presence of a polycondensation catalyst at a temperature at least lower than the crystalline melting point of the polymer and while maintaining the molten state. Polycondensation is performed, and if necessary, solid phase polymerization is performed to achieve a terminal carboxyl group weight of 90 equivalents/10^6 g or less, and a reduced viscosity (relative viscosity measured at 35°C in a mixed solvent of phenol/tetrachloroethane = 4/6). (calculated from) 0.6 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1248890A JPH02242818A (en) | 1981-09-01 | 1990-01-24 | Wholly aromatic polyester and production thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13608081A JPH0231096B2 (en) | 1981-09-01 | 1981-09-01 | ZENHOKOZOKUHORIESUTERUOYOBISONOSEIZOHO |
| JP1248890A JPH02242818A (en) | 1981-09-01 | 1990-01-24 | Wholly aromatic polyester and production thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13608081A Division JPH0231096B2 (en) | 1981-09-01 | 1981-09-01 | ZENHOKOZOKUHORIESUTERUOYOBISONOSEIZOHO |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02242818A true JPH02242818A (en) | 1990-09-27 |
Family
ID=26348122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1248890A Pending JPH02242818A (en) | 1981-09-01 | 1990-01-24 | Wholly aromatic polyester and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02242818A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100773646B1 (en) * | 2000-09-22 | 2007-11-05 | 폴리플라스틱스 가부시키가이샤 | Wholly aromatic polyester and polyester resin composition |
| JP2010083986A (en) * | 2008-09-30 | 2010-04-15 | Unitika Ltd | Polyarylate and method for producing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5278999A (en) * | 1975-12-26 | 1977-07-02 | Teijin Ltd | Production of polyesters |
| JPS5324234A (en) * | 1976-08-19 | 1978-03-06 | Yamura Shinkoseisakusho Kk | Optical reading kanji printer |
| JPS5335796A (en) * | 1976-09-16 | 1978-04-03 | Teijin Ltd | Preparation of polyester |
-
1990
- 1990-01-24 JP JP1248890A patent/JPH02242818A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5278999A (en) * | 1975-12-26 | 1977-07-02 | Teijin Ltd | Production of polyesters |
| JPS5324234A (en) * | 1976-08-19 | 1978-03-06 | Yamura Shinkoseisakusho Kk | Optical reading kanji printer |
| JPS5335796A (en) * | 1976-09-16 | 1978-04-03 | Teijin Ltd | Preparation of polyester |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100773646B1 (en) * | 2000-09-22 | 2007-11-05 | 폴리플라스틱스 가부시키가이샤 | Wholly aromatic polyester and polyester resin composition |
| JP2010083986A (en) * | 2008-09-30 | 2010-04-15 | Unitika Ltd | Polyarylate and method for producing the same |
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