JPH0328221A - Aromatic copolyester - Google Patents
Aromatic copolyesterInfo
- Publication number
- JPH0328221A JPH0328221A JP15149490A JP15149490A JPH0328221A JP H0328221 A JPH0328221 A JP H0328221A JP 15149490 A JP15149490 A JP 15149490A JP 15149490 A JP15149490 A JP 15149490A JP H0328221 A JPH0328221 A JP H0328221A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- aromatic
- copolyester
- reaction
- temperature
- 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
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 35
- 125000003118 aryl group Chemical group 0.000 title claims description 53
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000005843 halogen group Chemical group 0.000 claims abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 3
- 239000000155 melt Substances 0.000 abstract description 12
- 125000004429 atom Chemical group 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 59
- 238000006243 chemical reaction Methods 0.000 description 41
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 34
- 238000000034 method Methods 0.000 description 33
- 238000006116 polymerization reaction Methods 0.000 description 26
- 238000002844 melting Methods 0.000 description 25
- 230000008018 melting Effects 0.000 description 25
- -1 etc. Chemical compound 0.000 description 24
- 238000006068 polycondensation reaction Methods 0.000 description 18
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 15
- 239000007790 solid phase Substances 0.000 description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 10
- 150000001491 aromatic compounds Chemical class 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007860 aryl ester derivatives Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 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 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 239000012298 atmosphere Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-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
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000005303 weighing Methods 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
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 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
- 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001137251 Corvidae Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 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 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
- 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
- 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
- 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
- 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
- 239000004301 calcium benzoate Substances 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 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
- DOFDKNLHJKJCMO-UHFFFAOYSA-N diphenyl naphthalene-2,6-dicarboxylate Chemical compound C=1C=C2C=C(C(=O)OC=3C=CC=CC=3)C=CC2=CC=1C(=O)OC1=CC=CC=C1 DOFDKNLHJKJCMO-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
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 235000015108 pies Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、すぐれた耐熱性と透明性を有し、且つ耐湿熱
性の良好な溶融成形品を与える新規な芳香族コポリエス
テルに関するものである．（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℃以上の高温で直接反応させる方法が提案さ
れている（特開昭４６−５５４６号参照）．
また、かかる芳香族ポリエステルの製法として、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
酸とを反応させる方法も提案されている．
しかし、これらの芳香族ポリエステルは、末端力ルボキ
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．耐溶融安定性が劣る
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芳香族
ポリエステルを、溶融或形特に溶融製膜することにより
、耐熱性および耐湿熱性の高く、かつ色調及び透明性の
良好な成形品（特にフィルム》を製造することが困難で
あった．
一方、近年、たとえばテレフタル酸ジフエニルやイソフ
タル酸ジフエニル等とハイドロキノン、，レゾルシン等
のジオキシベンゼンとから溶融重合法で芳香族ポリエス
テルを’ｊｆ！遺し、ついでこの芳香族ポリエステルを
溶融或形する方法が提案された（特開昭５３−５４２５
２号参照〉．しかし、この方法によって得られた芳香族
ポリエステルは暗褐色を示し、本発明者らによって１）
ボリマーが分岐しているためか、以下Ｇこ示したフロー
インデックスが小さく（たとえば約０．６），ここで得
られる芳香族ポリエステルは延仲性に乏しい
２）透明性が良好でない
などの欠点のあることが見出された．
（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：／８融成形が可能な芳香
族コポリエステルを提供しようとするものである．
（課題を解決するための千段）
本発明者は、酸戊分としてイソフタル酸を用ｌｌＸると
共に、ジオール成分として／’ｔイドロキノンおよび４
，４゛−ジオキシビフエニルを併用し、且つ、ハイドロ
キノンと４，４゜−ジオキシビフエニノレとのモル比が
特定の範囲内にある共重合体は、上述の欠点がなく、良
好な成形品となし得ることを見出し、本発明に到達した
．
すなわち、本発明は、実質的に下記［Ｉ］ ［■］およ
び［Ｉ［Ｉ］の楕造単位からなる実質的に線状の芳香族
コポリエステルであって、
ｏ−Ｇｏ −
・・・［１１
該芳香族コポリエステル中の前記［Ｉ］のモル数と［ｎ
］と［Ｉ［Ｉ］との合計モル数が実質的に等しく、前記
［ＩＩ］と［ＩＩ［］の共重合モル比が９＝１〜４：６
であり、且つ分子鎖に結合したハロゲン原子を有しない
、０．６〜２．０の還元粘度（フェノール／テトラクロ
ルエタン−４／６の混合溶媒に溶解し３５℃で測定した
相対粘度より算出）をもつ芳香族コポリエステルである
．
本発明に係る新規な芳香族コポリエステルは、実質上、
インフタル酸を酸成分とし、ハイドロキノンおよび４．
４゛−ジオキシビフエニルをジオール成分とする実質的
に線状の芳香族コポリエステルであって、該芳香族コポ
リエステル中のハイドロキノン戚分と４．４“−ジオキ
シビフエニル成分の共重合モル比は９：１〜４：６の範
囲内にあり、かつ還元粘度にして０．６〜２．０の高い
重合度を有するものである．すなわちこの芳香族コポリ
エステルは下記の繰返し単位Ｔａ）及び（ｂ）を芳香族
コポリエステルを横成する全繰返し単位に対し少くとも
９０モル％以上、好ましくは９５モル％以上含み、（ａ
）と（ｂ）のモル比が９：１〜４：６の範囲内にあるも
のである．
該芳香族コポリエステルにおいて１０モル％以下、特に
５モル％以下の割合で共重合してもよい共重合成分（第
四成分）は、たとえば、テレフタル酸．ナフタレン−２
．６−ジカルボン酸．ナフタレンー２７−ジカルボン酸
，ジフエニルジカルボン酸，ジフェニルエーテルジカル
ボン酸などの芳香族ジカルボン酸ならびにエチレングリ
コール，ネオベンチレングリコール．ビスβ−ヒドロＡ
シエトキシベンゼンなどの脂肪族クリコールなどがある
．かかる本発明の芳香族コボリエスデルを製造する方法
としては、
（八）インフタノレ酸ジアリーノレエステｌレ．ハイド
ロ吉ノンおよび４．４゛−ジオ吉シビフエニルを所定割
合に混合し、重合触媒のイｆ在下に、坐成するヒドロキ
シ芳香族化合物を除去しつつ３５０℃以下の温度で且つ
溶融状態を維持しつつ加熱重縮合せしめ、必要に応じ、
更にこれを囚相重合せしめて還元粘度０．６〜２．０の
ボリマーを形成せしめる方法《以下、Ａ法という》、あ
るいは、
（８）イソフタル酸，ハイドロキノン，４，４゜−ジオ
Ａシビフエニルおよびジアリールカーボネートを所定割
合に混合し、重合触媒の存在下に、坐成ずるヒドロ吉シ
芳香族化合物および二酸化炭素を除去しつつ３５０’Ｃ
以下の温度で■１つ溶融状態を維持しつつ加熱垂縮合せ
しめ、必要に応じ、史にこれを固相重合せしめて還元粘
度０．６〜２．０のボリマーを形成せしめる方法（以下
、Ｂ法という）
が採用される．
上記Ａ法において芳香族コポリエステルを製造する場合
、出発原利は、酸戚分としてはイソフタル酸ジアリール
エステル又はこれと少呈の他の芳香族ジカルボン酸アリ
ールエステルとの混合物が、またジオール成分としては
前記２種のジヒドロキシ芳香族化合物又はこれに少量の
脂肪族グリコールを混合したものが用いられる．
本発明で用いるイソフタル酸ジアリールエスデルの例と
しては、ジフェニルイソフタレ−１・．ジｌ・リルイソ
フタレート．ジ（エチルフェニル）イソフタレート，ジ
（ジメチルフェニル）インフタレー１・．ジ（グロピル
フエニル）インフタルレート，ジ（プチルフエニル）イ
ンフタレート，ジ（オクチルフエニル）インフタレート
．フェニル１−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
エステルなどがあげられる．これと少量併用し得る他の
芳香族ジカルボン酸ジアリールエステルとしては、たと
えばジフエニルデレフタレート．ジフェニルナフタレン
−２．６−ジカルボキシレート．ジフエニルナフタレン
−２．７−ジカルポキシレー１− ，ジフエニルジフエ
ニル−４．４゛−ジカルボキシレート．ジフェニルジフ
ェニルエーテル−４，４゜ジカルボキシレートをあげる
ことができる．本発明では、イソフタル酸成分を主とす
る芳香族ジカルボン欣成分と反応させる芳香族ジオール
成分として、ハイドロキノンと４，４゜−ジオキシビフ
エニルの両名が用いられるが、この両者の割合は上述の
モル比となるように選定される．ハイドロキノン成分と
４，４゜−ジオキシビフエニル成分との共重合比が９：
１〜４：６（特に８二２〜６：４）の範囲内のときは、
生成コポリエステルの融点が適度に低くなり溶融成形性
のすぐれたボリマーとなる．
本発明では、この両者に加え、少量の他のジオールを併
用してもよい．かかるジオールとしては、たとえば上述
の脂肪族グリコールをあげることができる。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel aromatic copolyester that has excellent heat resistance and transparency and provides melt-molded products with good moist heat resistance. ．． (Prior art) Aromatic polyesters containing isophthalic acid as the main acid component and hydroquinone as the main diol component have been well known.As a method for producing them, isophthalic acid chloride and hydroquinone are used as a high boiling point heating medium. Among them, a method of direct reaction at a high temperature of 270°C or higher has been proposed (see JP-A-46-5546). In addition, as a method for producing such an aromatic polyester, diacetate of a dihydroxy aromatic compound and an aromatic dicarboxylic acid have been proposed. However, these aromatic polyesters have a) poor moist heat resistance, b) probably because they have a large amount of terminal carboxyl groups or because they have halogen atoms bonded to their molecular chains. )Heat-resistant. There are drawbacks such as poor melt stability; C) poor color tone of melt-molded molded products; and d) poor transparency. However, in recent years, it has been difficult to produce molded products (especially films) with high heat resistance and moist heat resistance, as well as good color tone and transparency.On the other hand, in recent years, for example, diphenyl terephthalate, diphenyl isophthalate, etc., and hydroquinone, A method has been proposed in which an aromatic polyester is produced by a melt polymerization method with dioxybenzene such as resorcinol, and then this aromatic polyester is melted or shaped (Japanese Patent Laid-Open No. 53-5425
See issue 2>. However, the aromatic polyester obtained by this method exhibits a dark brown color, and the inventors reported 1)
Perhaps because the polymer is branched, the flow index shown below is small (for example, about 0.6), and the aromatic polyester obtained here has poor ductility.2) It has disadvantages such as poor transparency. Something was discovered. (Problems to be Solved by the Invention) The present invention aims to provide an aromatic copolyester which is free from such drawbacks and is capable of being melt-molded. (A Thousand Steps to Solving the Problem) The present inventor uses isophthalic acid as an acid component, and also uses /'t hydroquinone and 4 as a diol component.
, 4゛-dioxybiphenyl, and the molar ratio of hydroquinone and 4,4゛-dioxybiphenyl is within a specific range. We have discovered that it can be made into a molded product, and have arrived at the present invention. That is, the present invention provides a substantially linear aromatic copolyester consisting essentially of the following elliptical units [I] [■] and [I[I], o-Go - ...[ 11 The number of moles of the above [I] in the aromatic copolyester and [n
] and [I[I] have substantially the same total number of moles, and the copolymerization molar ratio of [II] and [II[] is 9=1 to 4:6
and has no halogen atoms bonded to the molecular chain, and has a reduced viscosity of 0.6 to 2.0 (calculated from the relative viscosity measured at 35°C after dissolving in a mixed solvent of phenol/tetrachloroethane-4/6). ) is an aromatic copolyester. The novel aromatic copolyester according to the present invention essentially comprises:
Inphthalic acid as the acid component, hydroquinone and 4.
A substantially linear aromatic copolyester containing 4'-dioxybiphenyl as a diol component, which is a copolymerization of a hydroquinone relative in the aromatic copolyester and a 4.4"-dioxybiphenyl component. The molar ratio is within the range of 9:1 to 4:6, and the reduced viscosity is 0.6 to 2.0, which is a high degree of polymerization.In other words, this aromatic copolyester has the following repeating unit Ta. ) and (b) at least 90 mol% or more, preferably 95 mol% or more, based on the total repeating units forming the aromatic copolyester, and (a
) and (b) in a molar ratio of 9:1 to 4:6. The copolymer component (fourth component) which may be copolymerized in the aromatic copolyester at a rate of 10 mol% or less, particularly 5 mol% or less, is, for example, terephthalic acid. Naphthalene-2
．． 6-dicarboxylic acid. Aromatic dicarboxylic acids such as naphthalene-27-dicarboxylic acid, diphenyl dicarboxylic acid, and diphenyl ether dicarboxylic acid, as well as ethylene glycol and neobenzene glycol. bis β-hydro A
These include aliphatic glycols such as ethoxybenzene. As a method for producing the aromatic cobolyesdel of the present invention, (8) inftanoleic acid diaryl ester. Hydrokiyone and 4.4'-diokisibiphenyl are mixed in a predetermined ratio, and the molten state is maintained at a temperature of 350°C or less while removing the hydroxy aromatic compound that forms in the presence of a polymerization catalyst. Polycondensate by heating, if necessary,
This is further subjected to prison phase polymerization to form a polymer with a reduced viscosity of 0.6 to 2.0 (hereinafter referred to as method A), or (8) isophthalic acid, hydroquinone, 4,4°-geo-A cibiphenyl and Diaryl carbonates were mixed in a predetermined ratio and heated at 350'C in the presence of a polymerization catalyst while removing the hydrocarbon aromatic compound and carbon dioxide.
A method of heating and condensing while maintaining a molten state at the following temperature, and if necessary, solid-phase polymerizing this to form a polymer with a reduced viscosity of 0.6 to 2.0 (hereinafter referred to as B law) will be adopted. When producing an aromatic copolyester using the above method A, the starting material is isophthalic acid diaryl ester or a mixture of this and a small amount of other aromatic dicarboxylic acid aryl ester as the acid component, and as the diol component. The above two types of dihydroxy aromatic compounds or a mixture thereof with a small amount of aliphatic glycol are used. Examples of diaryl isophthalate used in the present invention include diphenyl isophthalate-1. Di-lylisophthalate. Di(ethylphenyl) isophthalate, di(dimethylphenyl) inphthalate 1. Di(glopylphenyl) inphthalate, di(butylphenyl) inphthalate, di(octylphenyl) inphthalate. Examples include diaryl esters of isophthalic acid with unsubstituted or alkyl-substituted phenols such as phenyl 1-lyl isophthalate. Other aromatic dicarboxylic acid diaryl esters that can be used in small amounts in combination with this include, for example, diphenyl derephthalate. Diphenylnaphthalene-2,6-dicarboxylate. Diphenylnaphthalene-2,7-dicarpoxylate 1-, diphenyldiphenyl-4,4'-dicarboxylate. One example is diphenyl diphenyl ether-4,4° dicarboxylate. In the present invention, both hydroquinone and 4,4°-dioxybiphenyl are used as the aromatic diol component to be reacted with the aromatic dicarbonate component mainly containing the isophthalic acid component, and the ratio of the two is as described above. The molar ratio is selected to be . The copolymerization ratio of hydroquinone component and 4,4°-dioxybiphenyl component is 9:
When it is within the range of 1 to 4:6 (especially 822 to 6:4),
The melting point of the resulting copolyester is moderately low, resulting in a polymer with excellent melt moldability. In the present invention, in addition to these two, small amounts of other diols may be used in combination. Examples of such diols include the aliphatic glycols mentioned above.
また、Ｂ法において芳香族コ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前記の芳香族ジカルボン
酸が、またジオール成分としては前記のジヒドロキシ・
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，ジメ
チルフェノール．プロビルフェノール，プチルフェノー
ル，オクチルフェノール，ナフトールなどの非置換もし
くはアルキル置換フェノール、またはナフ１・−ルの如
きモノヒドロキシ芳香族化合物の炭欣エステルである．
このようなジアリールカーボネートの具体的としては、
ジフエニルカーボネート，ジトリルカーボネート．ジ《
エチルフェニル）カーボネート，ジ（ジメチルフェニル
）カーボネート．ジ（プロビルフェニル）カーボネート
．ジ（プチルフェニル）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，フエ
ニルトリルカーボネートなどをあげることができる．上
記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基が１：
Ｉから１ ： １．２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及び４，４゜−ジオキ
シビフエニルのモル数の和が仕込み原料中で９０モル％
以上、好ましくは９５モル％以上になるようにする．
一般に重綿合反応は重縮合触媒のもとて２００℃で始ま
るが、反応速度がおそいので昇温し、反応系内のボリマ
ーの還元粘度が０．０８に達する前は反応系内のボリマ
ーの結晶融点以上で、反応の結果生成するモノしドロキ
シ芳香族化合物を反応系外に除去しつつ重縮合させる．
本発明の芳香族コポリエステルにおいて、重縮合反応温
度は、最終的に芳香族コポリエステルの結晶融点以下で
且つ３５０℃以下、特に３２０〜３３０℃まで高めるの
が好ましい．重合温度が３５０℃よりも高いとボリマー
に分岐が発生しやすくなり、また、得られるコボリヱス
テルの末端力ルボキシル基量が増大する傾向かあるので
、最高温度を３５０″Ｃ又はそれ以下に制御ずべきであ
る．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１コ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。In addition, when producing an aromatic copolyester in Method B, the starting materials are the above-mentioned aromatic dicarboxylic acid as the acid component and the above-mentioned dihydroxy dicarboxylic acid as the diol component.
In addition to each compound used, diaryl carbonate is also used. Here, diaryl carbonate refers to phenol. Cresol. Ethylphenol, dimethylphenol. They are unsubstituted or alkyl-substituted phenols such as propylphenol, butylphenol, octylphenol, naphthol, or carbon esters of monohydroxy aromatic compounds such as naphthol. Specific examples of such diaryl carbonates include:
Diphenyl carbonate, ditolyl carbonate. Ji《
Ethylphenyl) carbonate, di(dimethylphenyl) carbonate. Di(propylphenyl) carbonate. Examples include di(butylphenyl) carbonate, di(octylphenyl) carbonate, dinaphthyl carbonate, and phenyltolyl carbonate. In the case of method A above, the charging ratio of the starting materials is 1:1: hydroxyl groups in the raw materials to aryl ester groups in the raw materials.
I to 1:1.2, and the sum of the moles of diarylisophthalate, hydroquinone and 4,4°-dioxybiphenyl is 90 mol% in the raw materials.
The above should preferably be 95 mol% or more. Polymerization reaction generally starts at 200°C using a polycondensation catalyst, but since the reaction rate is slow, the temperature rises and the polymerization reaction takes place before the reduced viscosity of the polymer in the reaction system reaches 0.08. At temperatures above the crystal melting point, polycondensation is carried out while removing mono-droxy aromatic compounds produced as a result of the reaction from the reaction system. In the aromatic copolyester of the present invention, the polycondensation reaction temperature is preferably raised to a final temperature below the crystalline melting point of the aromatic copolyester and below 350°C, particularly from 320 to 330°C. If the polymerization temperature is higher than 350°C, branching tends to occur in the polymer, and the amount of terminal carboxyl groups in the resulting copolyester tends to increase, so the maximum temperature should be controlled to 350°C or lower. The initial stage of the polycondensation reaction is carried out under atmospheric pressure,
After that, under reduced pressure or by flowing an inert gas, monohydroxy aromatic compounds produced as a result of the reaction and dihydroxy aromatic compounds such as hydro-1 coquinone used in excess as necessary are removed from the reaction system. It is done.
反応系内に生成したボ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Ｘ：７キシ化合物を反応系外に強制的に、好ましく
は減圧下に除去することか好ましい．更に好ましくは上
記大気圧のもとに行なわれる重縮合反Ｌ６は、たとえば
２５０〜２９０’Ｃまでの温度でモノヒドロキシ芳香族
化合物の留出社が理論値の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３２
０〜３５０℃、特に好ましくは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２０＋ｍ＋
ｌＩＱ、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５時間以内に終了する．
また、本発明に係る芳香族コポリエステルの溶融重縮合
において、減圧下または不活性ガスを流し、強制的に反
応の結果生或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う重縮合
反応時間は３時間以内である．
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、た
とえば酢酸マグネシウム．安息香酸カルシウム．酢酸ス
トロンチウム．プロビオン酸バリウム．炭酸ランタン．
酸化セリウム．酢酸マンガン．酢酸；！バルト．酢酸亜
鉛，酸化ゲルマニウム，酢酸第１スズ．酸化鉛．三酸化
アンチモン，三酸１ヒビスマスなどがある．これらの垂
縮合触媒とともに安定剤を併用することか好ましい．好
ましい安定剤の例は従来公知の３価もしくは５価のリン
化合物またはそのエステルである。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, an excess dihydro It is preferable to remove it forcibly, preferably under reduced pressure. More preferably, the polycondensation reaction L6, which is carried out under atmospheric pressure, is continued at a temperature of, for example, 250 to 290'C until the distillation rate of monohydroxy aromatic compounds is 50 to 70% of the theoretical value. ．． After this, the pressure of the reaction system was reduced, and finally 32
While increasing the temperature to 0 to 350°C, preferably 320 to 330°C, the pressure of the reaction system is reduced to 20+m+ within 1 hour.
IQ or lower. Under favorable conditions,
The melt polycondensation reaction is completed within 5 hours. In addition, in the melt polycondensation of the aromatic copolyester according to the present invention, under reduced pressure or by flowing an inert gas, a certain monohydroxy aromatic compound produced as a result of the reaction and, if necessary, an excess of hydroquinone, etc. The polycondensation reaction time, which is carried out while removing the dihydroxy aromatic compound from the reaction system, is within 3 hours. As the polycondensation catalyst, a conventionally known transesterification catalyst is used. Suitable examples of such catalysts include, for example, magnesium acetate. Calcium benzoate. Strontium acetate. Barium probionate. Lanthanum carbonate.
Cerium oxide. Manganese acetate. Acetic acid;! Baltic. Zinc acetate, germanium oxide, stannous acetate. Lead oxide. Examples include antimony trioxide and mono-hibismuth trioxide. It is preferable to use a stabilizer together with these polycondensation catalysts. Examples of preferred stabilizers are conventionally known trivalent or pentavalent phosphorus compounds or esters thereof.
また、上記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ｌ：１がら１：１．０５となるように、更にイ
ソフタル酸．ハイドロキノン及び４，４゜−ジオキシビ
フエニルのモル数の和がジアリールカーボネートを除い
た仕込み原利中で９０モル％以上、好ましくは９５モル
％以上になるようにする．
上記Ｂ法で芳香族コ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（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．そこで上記Ｂ法で芳香族ポリエステルを製造す
る場合には、般には下記の（Ｂ−１）の方法による．（
Ｂ〜１）芳香族ジカルボン酸，ジヒドロキシ芳香族化合
物及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．また、下記の（Ｂ−２＞の方法による
こともできる．
（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
テルを形或させ、ついでジオキシ芳香族化合物を加えて
加熱重縮合させる方法。In addition, in the case of method B, the charging ratio of the starting 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 Furthermore, isophthalic acid. The sum of the moles of hydroquinone and 4,4°-dioxybiphenyl is adjusted to be 90 mol % or more, preferably 95 mol % or more in the starting material excluding diaryl carbonate. When producing an aromatic copolyester using method B above, the diaryl carbonate reacts with the aromatic dicarboxylic acid used (hereinafter referred to as esterification reaction), and the aromatic dicarboxylic acid is converted to an aryl ester with the generation of carbon dioxide gas. Let. Therefore, when producing aromatic polyester by the above method B, the following method (B-1) is generally used. (
B-1) A method of heating and polycondensing a mixture consisting of an aromatic dicarboxylic acid, a dihydroxy aromatic compound, and a diaryl carbonate. Alternatively, the following method (B-2>) can also be used. (B-2) An aromatic dicarboxylic acid and a diaryl carbonate are reacted in advance to form an aryl ester of the aromatic dicarboxylic acid, and then a dioxyaromatic compound is formed. A method of heating and polycondensing by adding
以上、（Ｂ−１）（Ｂ−２）のいずれの方法によるとき
もｆｆｉ縮合反応は、Ａ法と同様な重縮合触媒の存在下
行なわれ、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Ｎシ芳香族化
合物の藍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
戒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．
Ａ法とＢ法の相違点はこのように反応の比較的初１υｌ
の段階に限られ、以後の重縮合反応は両方法とも全く同
様にして行な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１ヒ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．
かくして得られた重合体は、０．１〜０．７の還元粘度
を有するが、更に還元粘度の高められた重合体を望む場
合は、上連の溶融垂合法（Ａ法又はＢ法）により得られ
た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させしめることにより還元粘度の高
い高重合度のボリマーを製造することができる．この固
相重合に供する溶融重合による重合体の還元粘度は、好
ましくは０．１〜０．５である．
固相重合は、芳香族ポリエステルの固相重合において知
られているように、重合体粒子か小さいほど、所望の重
合度まで速やかに到達するため、通常５メッシュより大
きな値をもつ粒径のものについて、好ましくは６〜３０
０メッシュのものについて行なわれる．あまり粒径が小
さいと粉砕や取扱い上の困難が大きくなり、望ましくな
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（たとえばＩＩｍｌＩｌｌｇ以下）で行なわれる
．ｔ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、たとえば溶融重合による還元粘度が約０．１〜０
．１５の重合体から、還元粘度が約０．６〜０．７の重
合体が得られ、また還元粘度が約０，１５〜０．５の重
合体からは還元粘度が０、７〜２．０の重合体が得られ
る．
本発明の芳香族コボリヱステルは、９０当ｉ／１０６ｇ
以下、好ましくは５〜６０当！ｔ／１０６ｇ、より好ま
しくは１０〜５０当量／１０６ ｇの末端力ルボキシル
基を有するものとして提供される．また、本発明の芳香
族コポリエステルは、好ましくは０．６〜２．０、より
好ま゛しくは０．７〜１．５の還元粘度を有するものと
して提供される．木允１明の芳香族コポリエステルは、
さらに分子鎖中に結合したハロゲン原子（たとえば塩素
，臭素など）を実質的に含有しない．分子鎖中に結合し
たハロゲン原子とは、たと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たハロゲン原子（た
とえばハロゲン化ハイドロキノン等の原料に山来するハ
ロゲン原子）などを意味している．
かかるハロゲン原子は、重合体を有機溶媒で抽出すると
か、あるいは重合体の有機溶媒溶液がら沈澱させるとか
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．これに対し、従来法により酸ハ
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％以一Ｌ含有する．
本発明の芳香族コポリエステルは、更に、実質的に線状
である．このような重合体は、たとえばフローインデッ
クスが、すり速度が約５０〜５００ｓｅｃ−１の間にお
いて、平均約０．７〜１、より好ましくは０．７〜０，
９の間の値にある，
上述の如き本発明に係る芳香族コポリエステルは、ｆ！
融成形法によってずぐれた性能のフィルムを与える．
該芳香族コポリエステルは、溶融成形が可能な温度に加
熟され、スリットより好ましくは１００〜１８０℃に加
熱されたドラム上に押出し、フィルムに成形される．成
形時のドラフト率は通常約２〜１０とされる．スリット
としては一般にスリットｒｐ０．５・〜５關のものが用
いられる．
かくして芳香族コポリエステルからなる未延伸フィルム
が得られるが、この未延伸フィルムは透明性が良好で、
２６０℃で１分間熱処理してもその透明性を維持し、強
度保持率は８５％以上で、仲度は３０％以上有し、且つ
寸法変化が１％以下と極めて小さい．また、アセトンな
どの有機溶剤中でも１法変化やａｍ的性質の変化が小さ
い．未延仲フィルムは、ついで一軸延仲または同時的ら
しくは逐次的な二軸延仲を施すことができる．延伸は１
８０〜２８０℃、好ましくは１９０〜２２０℃で行なわ
れる．延伸倍率は、一軸延仲の場合には２〜４倍程度で
あり、二軸延仲の場合にはタテ．ヨ：２各１．７〜３．
５倍程度が好ましい。二軸延仲の場合は、面積倍率を２
．８〜１０倍とするのがよい。延伸フィルムは、ついで
熱固定を施し寸法安定性を改笹することができる．
熟固定はフィルム温度約２５０’Ｃ以上の温度、虹まし
くは重合体の融点より２０℃低い温度以下で、且つ約３
３０℃以下の温度で行なうことができる．悲固定の時間
は１秒以上、好ましくは１０秒〜５分の間で行なうこと
ができる．この熱固定は緊張下実施され、熱固定により
結晶化が進行する．熱固定を受けたフィルムは、ついで
熱収縮処理を受けるのが好ましい．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。As mentioned above, in both methods (B-1) and (B-2), the ffi condensation 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 under atmospheric pressure. Do it. The amount of monooxyaromatic compounds removed from the reaction system at this point is the amount of monooxyaromatic compounds produced in the esterification reaction (the number of moles of diaryl carbonate used at twice the mole of the aromatic dicarboxylic acid used). ) and an amount corresponding to 50 to 70 mol% of the theoretical amount of monooxyaromatic compound to be recovered by the polycondensation reaction as in Method A. The difference between Method A and Method B is that the reaction is relatively initial 1υl.
The subsequent polycondensation reactions 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, if necessary, an The polycondensation reaction is carried out while the aromatic dioxy compounds present are forcibly removed from the reaction system. The thus obtained polymer has a reduced viscosity of 0.1 to 0.7, but if a polymer with an even higher reduced viscosity is desired, it can be prepared by the Kamiren melt tanning method (method A or method B). A polymer with a high reduced viscosity and a high degree of polymerization can be produced by solid-phase polymerizing the obtained polymer by a method known per se under reduced pressure or while passing an inert gas. The reduced viscosity of the melt polymerized polymer subjected to this solid phase polymerization is preferably 0.1 to 0.5. In solid phase polymerization, as is known in the solid phase polymerization of aromatic polyester, the smaller the polymer particles, the faster the desired degree of polymerization is reached. , preferably 6 to 30
This is done for objects with 0 mesh. If the particle size is too small, it becomes difficult to crush and handle, which is not desirable. The solid phase polymerization is carried out at a temperature of about 230°C or higher and at a temperature at which particles do not aggregate with each other, preferably about 250 to 300°C.
The reaction is carried out at a temperature of 1,000 ml in an inert gas atmosphere at normal pressure to reduced pressure, preferably under reduced pressure (for example, less than IImlIllg). According to the solid phase polymerization method described in t, a polymer with a higher reduced viscosity, for example, a reduced viscosity obtained by melt polymerization of about 0.1 to 0.
．． From the polymer No. 15, a polymer with a reduced viscosity of about 0.6 to 0.7 is obtained, and from the polymer with a reduced viscosity of about 0.15 to 0.5, a reduced viscosity of about 0.7 to 2. 0 polymer is obtained. The aromatic cobolyester of the present invention is 90 equivalent i/106 g
Below, preferably 5 to 60! t/106 g, more preferably 10 to 50 equivalents/106 g. Further, the aromatic copolyester of the present invention is provided as having a reduced viscosity of preferably 0.6 to 2.0, more preferably 0.7 to 1.5. Mu Yun's aromatic copolyester is
Furthermore, it does not substantially contain halogen atoms (for example, chlorine, bromine, etc.) bonded in the molecular chain. A halogen atom bonded in a molecular chain is, for example, a halogen atom at the end of a molecular chain (for example, a halogen atom in the form of an acid chloride).
, or a halogen atom bonded to an aromatic ring in a molecular chain (for example, a halogen atom found in raw materials such as halogenated hydroquinone). Such halogen atoms can be verified by the presence of halogen atoms in the polymer by extracting the polymer with an organic solvent or by precipitating a solution of the polymer in an organic solvent. On the other hand, polymers produced by conventional methods using acid halides as raw materials contain halogen atoms of about 0.3% by weight or more. The aromatic copolyesters of the present invention are further substantially linear. Such a polymer has, for example, a flow index of about 0.7 to 1, more preferably 0.7 to 0, on average at a slip rate of about 50 to 500 sec-1.
The aromatic copolyester according to the invention as described above has a value between f!
The melt forming process provides films with superior performance. The aromatic copolyester is cured to a temperature that allows melt molding, and extruded onto a drum heated to preferably 100 to 180°C through slits to form a film. The draft rate during molding is usually about 2 to 10. Generally, a slit with a slit rp of 0.5 to 5 is used. In this way, an unstretched film made of aromatic copolyester is obtained, and this unstretched film has good transparency.
It maintains its transparency even after heat treatment at 260°C for 1 minute, has a strength retention rate of 85% or more, a consistency of 30% or more, and has an extremely small dimensional change of 1% or less. In addition, even in organic solvents such as acetone, there is little change in one method or change in am-like properties. The unrolled film can then be subjected to uniaxial stretching or simultaneous or sequential biaxial stretching. Stretching is 1
It is carried out at a temperature of 80 to 280°C, preferably 190 to 220°C. The stretching magnification is approximately 2 to 4 times in the case of uniaxially drawn medium, and the stretching ratio is about 2 to 4 times in the case of biaxially drawn medium. Yo: 2 each 1.7~3.
About 5 times is preferable. In the case of biaxial extension, increase the area magnification by 2.
．． It is preferable to increase the amount by 8 to 10 times. The stretched film can then be heat set to improve its dimensional stability. Ripe fixation is performed at a film temperature of about 250°C or higher, or at a temperature lower than 20°C below the melting point of the polymer, and at a temperature of about 30°C or less.
It can be carried out at temperatures below 30°C. The period of stabilization can be 1 second or more, preferably 10 seconds to 5 minutes. This heat fixation is performed under tension, and crystallization progresses due to heat fixation. Preferably, 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.
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℃低い温度以下で、且つ３２０℃以下の温度
、好ましくは約２００℃と熱固定温度より１０゛Ｃ以上
低い温度との間の温度、特に約２２０℃と熱固定温度よ
り１０℃以上低い温度との間の温度で行つ。The heat shrinking treatment is carried out at a film temperature of about 200°C or above and below a temperature of 20°C below the melting point of the polymer, and below 320°C, preferably between about 200°C and a temperature at least 10°C below the heat setting temperature. The temperature is preferably between about 220° C. and at least 10° C. below the heat setting temperature.
（発明の効果）
かくして本発明によれば、分岐が少なく、末端力ルボキ
シル基量が約９０当Ｊｉ／１０’ｇ以下、特に５〜６０
当ｉ／１０６ｇで、且つ還元粘度が０．６〜０．２、好
ましくは０．７〜１．５であって、実質的にハロゲンを
含まない芳香族コボリヱステルが提供される．
本発明に係る芳香族；１ポリエステルは、末延仲でも耐
熱性の良好なポリエステルシ一トまたはフィルムを与え
、またこのシートまたはフィルムは耐湿熱性もすぐれ、
工業的に有用なものである。(Effects of the Invention) Thus, according to the present invention, there is little branching, and the amount of terminal carboxyl groups is about 90 equivalent Ji/10'g or less, particularly 5 to 60
Provided is an aromatic cobolyester having a reduced viscosity of 0.6 to 0.2, preferably 0.7 to 1.5, and substantially halogen-free. The aromatic;
It is industrially useful.
また、本発明の芳香族コポリエステルは透明性と耐熱性
を要求されるボトル，パイ１等にも使用できる．
（実施ｒＩＡ）
以下、実施例により本発明方法について詳述するが、そ
の前に測定法について記述する．くサンプルの調整〉
ａ） Ｍ元粘度（ηＳＯ／Ｃ ）およびカルボキシル基
１ （ ［ＣＯＯＩ＋］ ”Ｊ測定用サンプル：本発明
方法によるボリマーは結晶性であり、固相重合のような
長時間の熱処理を受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
相重合したボリマーのηｓｐ／ｃおよび［ＣＯＯＩＩ］
の測定に際しては、ボリマーを予め１５０℃で乾燥し、
ついでこのボリマー約１ｇを直径１間、長さ５ＩＩｌｌ
のノズルを備えた断面積１−のシリンダーに充填し、つ
いでボ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た
． 溶融押出し成形した未延仲フィルム，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ηＳＤ／ Ｃおよび［ＣＯＯＨ］測定用
サンプルとした．
ｂ）融点測定用サンプル：
ボリマーの融点の測定に際しては、ポリマ−を予め２０
０℃で１時間然処理したもの用いた．く還元粘度〈ηｓ
ｐ／ｃ ）の測定〉
サンプル１２０＃を１０ｍｌ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（董量比−４：６）に溶かし、３５゜Ｃ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．
［Ａ−Ｂ］ｘ５
ボリマー量（ｇ）
０．５
くカルボキシル基量（ ［ＣＯＯＩ＋］ ）の定量〉サ
ンプル１００ ｍｇを１０ｍｌ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：テトラク口ルエ
タン（重量比＝４：６）に溶かし、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、下記式を用いて［
ＣＯＯＩ＋ ］を算出した．
くボリマー融点の測定〉
示差熱分析装置（理学電機８０７５０１型）を用いて、
１０℃／分の昇温速度で常法によりそのピーク位置より
融点を求めた．
くフローインデックスの測定〉
ボリマー約１ｇを直径ＩＩｕｌ、長さ５曲のノズルを備
えた断面積１−のシリンダーに充填し、ついでボリマー
の溶融押出し可能な温度で種々の加圧下に溶融押出し、
フローインデックスを求めた．
くハロゲンの定量〉
Ｘ線スペク１〜口メーター アンセンブリＫＧ−Ｘ（理
学電機》を用い、螢光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．
く強度、仲度およびヤング率の測定〉
強度、仲度およびヤング率は、巾５關、長さ６０一ｍの
フィルムを２５℃、湿度６５％の雰囲気のもとチャンク
間距離２０關でつかみ、毎分１００％（２０ｍｍ＋／分
）の引張り速度仲張させて求めた。Furthermore, the aromatic copolyester of the present invention can be used for bottles, pies, etc. that require transparency and heat resistance. (Implementation rIA) Hereinafter, the method of the present invention will be explained in detail with reference to Examples, but before that, the measurement method will be described. Preparation of sample> a) M original viscosity (ηSO/C) and carboxyl group 1 ([COOI+] Sample for J measurement: The polymer produced by the method of the present invention is crystalline and cannot be subjected to long-term heat treatment such as solid state polymerization. The obtained product is difficult to dissolve in a mixed solvent of phenol and tetrachloroethane.Therefore, the ηsp/c and [COOII] of the solid phase polymerized polymer were determined.
When measuring, the polymer was dried at 150°C in advance,
Next, about 1 g of this polymer was placed into a tube with a diameter of 1 inch and a length of 5 IIll.
The polymer is then heated to a temperature above its melting point (380°C in the example).
After heating and melting for 2 minutes, the sample was extruded and used as the sample for the above measurement. Melt-extruded unrolled film and stretched film. The heat-set films and heat-shrinked films were used as samples for ηSD/C and [COOH] measurements. b) Sample for melting point measurement: When measuring the melting point of a polymer, prepare the polymer at 20%
The samples were treated at 0°C for 1 hour and then used. Reduced viscosity〈ηs
Measurement of p/c) Sample 120# was dissolved in 10 ml of a mixed solvent of phenol and tetrachloroethane (phenol:tetrachloroethane (volume ratio -4:6), and measured at 35°C using an Ostwald viscometer. The relative viscosity (η') was measured, and ηsp/c was calculated using the following formula. [A-B] was dissolved in 10 ml of a mixed solvent of phenol and tetrachloroethane (phenol:tetrachloroethane (weight ratio = 4:6), and titrated using a 0.1N solution of caustic soda in benzyl alcohol using bromcresol green as an indicator. , using the following formula [
COOI+] was calculated. Measurement of melting point of polymer> Using a differential thermal analyzer (Rigaku Denki model 807501),
The melting point was determined from the peak position using a conventional method at a heating rate of 10°C/min. Measurement of Flow Index> Approximately 1 g of the polymer was filled into a cylinder with a diameter of IIul and a cross-sectional area of 1 - equipped with a nozzle with a length of 5 turns, and then melt-extruded under various pressures at a temperature at which the polymer could be melt-extruded.
The flow index was calculated. Quantitative determination of halogen> X-ray spec 1 to halogen meter assembly KG-X (Rigaku Denki) was used for quantitative determination using the fluorescent X-ray method. Measurement of strength, density and Young's modulus The strength, density and Young's modulus were determined by measuring the strength, density and Young's modulus of a film with a width of 5 cm and a length of 60 m at 25°C and humidity. It was determined by gripping the chunks at a distance of 20 mm in an atmosphere of 65% and tensioning at a tensile rate of 100% per minute (20 mm+/min).
く透明性〉
ボリマーの透明性は、厚さ３００μの未延仲フィルムを
サンプルとして用い、フィルム面に垂直に波長７００ｍ
μの可視光を照射し、その透過率を測定して評価した．
以下、実施例中、単に「部」とあるところは「重量部」
を表わす。Transparency〉 The transparency of the polymer is determined by using an unrolled film with a thickness of 300μ as a sample, and applying a wavelength of 700m perpendicular to the film surface.
It was evaluated by irradiating it with visible light of μ and measuring its transmittance. In the examples below, "parts" simply means "parts by weight."
represents.
実施例１
ジフエニルイソフタレート１９０．８０部．ハイドロキ
ノン５５． ４４部， ４．４’−ジオ′キシビフエニ
ル２１．２６部．二酸化アンチモン０． ０７０部およ
びトリフェニルホスフエート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６５部（理論値の約
５８％）を留出させた（反応系内の生成物のηＳＥＩ／
Ｃと融点はそれぞれ０．０８， ２８５゜Ｃであった）
．ついで、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２０１ｌ
＋ｎｌｌ（１、反応温度を３３０℃とし（この際反応系
内のポリマーのηｓｐ／’ｃと融点はそれぞれ０． １
６，３６０℃であった）この条件下で３０分間重量を続
けた．得られたボリマーのηＳＯ／ Ｃと融点は、それ
ぞれ０．５０， ３６０℃であった．
ここで溶融重縮合を停止し、ボリマーを冷却後１２〜２
０メッシュに粉砕し、０．２ｍＨｉ；ｌの減圧下２５０
℃で２時間、更に０．２ｍＨＱの減圧下２９０℃で１２
時間固相垂合を行なった．得られたボリマーはηｓｐ／
ｃ ＝０．９８、［ＣＯＯＩ＋］ ＝２６当量／１０”
ｇおよび融点＝３６５゜Ｃであった．また、３８０℃
で求めたこのボリマーのフローインデックスは０．７５
であった．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４５．０５部， ４．４’−ジオキシビフエニル４
１．０１部．三酸化アンチモン０． １０５部及びトリ
フェニルホスフエート０．０９８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７３部（理論値
の約６５％）を留出させた（反応系内の生成物のηｓｐ
／ ｃは０、０８であった）．ついで、反応系の圧力を
徐々に減圧にするのとともに反応温度を上げ始め、約１
時間を要して圧力を２０ｎｓ＋ｔｌＪ、反応温度を３３
０℃とし（この際反応系内のボリマーのηｓｐ／ ｃと
融点はそれぞれ０．１５３，５５℃であった）、この条
件下で更に３０時間重量を続けた．得られたボリマーの
ηＳｐ／ ｃと融点は、それぞれ０．４５， ３５５℃
であった．ここで溶融重合を停止し、ボリマーを冷却後
１２〜５０メッシュに粉砕し、０．０５ａｌＩＨｇの減
圧下２５０℃で２時間、更に０．０５一〇（ｌの減圧下
２９０℃で１０時間固相重合を行なった．得られたボリ
マーはηＳＯ／ｃ＝１．０２、［ ＣＯＯＨ ］は２０
当４１／１０６ ｇおよび融点は３６５℃であった．ま
た、３８０゜Ｃ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。Example 1 190.80 parts of diphenyl isophthalate. Hydroquinone 55. 44 parts, 4.4'-dio'oxybiphenyl 21.26 parts. Antimony dioxide 0. 070 parts and 0.070 parts of triphenyl phosphate. 098 parts were charged into a polymerization reactor equipped with a stirrer and heated at 250 to 290°C for 2 hours, and 65 parts of phenol (approximately 58% of the theoretical value) produced as a result of the reaction was distilled out (products in the reaction system ηSEI/
C and melting point were 0.08 and 285°C, respectively)
．． 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 201 liters.
+nll (1, the reaction temperature was 330°C (at this time, the ηsp/'c and melting point of the polymer in the reaction system were each 0.1
The weighing was continued under these conditions for 30 minutes (6,360°C). The ηSO/C and melting point of the obtained polymer were 0.50 and 360°C, respectively. At this point, the melt polycondensation was stopped, and after cooling the polymer,
Grind to 0 mesh, 250 ml under reduced pressure of 0.2 mHi;
℃ for 2 hours, and then at 290℃ under a reduced pressure of 0.2 mHQ for 12 hours.
Time-solid phase merging was performed. The obtained polymer is ηsp/
c = 0.98, [COOI+] = 26 equivalents/10”
g and melting point = 365°C. Also, 380℃
The flow index of this polymerer calculated by is 0.75
Met. Example 2 190.80 parts of diphenyl isophthalate. Hydroquinone 45.05 parts, 4.4'-dioxybiphenyl 4
1.01 part. Antimony trioxide 0. 105 parts of triphenyl phosphate 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 under a nitrogen atmosphere, resulting in 73 parts of phenol (approximately 65% of the theoretical value) produced as a result of the reaction. was distilled out (ηsp of the product in the reaction system
/c was 0.08). Next, the pressure of the reaction system was gradually reduced and the reaction temperature started to increase until about 1
It takes time to increase the pressure to 20 ns + tlJ and the reaction temperature to 33
The temperature was set at 0°C (at this time, the η sp/c and melting point of the polymer in the reaction system were 0.153 and 55°C, respectively), and weighing was continued under these conditions for an additional 30 hours. The ηSp/c and melting point of the obtained polymer were 0.45 and 355°C, respectively.
Met. At this point, the melt polymerization was stopped, and the polymer was cooled and ground to 12 to 50 mesh, solidified at 250°C for 2 hours under a reduced pressure of 0.05 alIHg, and then for 10 hours at 290°C under a reduced pressure of 0.05 lHg. Polymerization was carried out.The obtained polymer had ηSO/c=1.02 and [COOH] of 20
The weight was 41/106 g and the melting point was 365°C. Further, the flow index of this polymer determined at 380°C was 0.75.
実施…１３
ジフェニルイソフタレート１９０．８０部．ハイドロキ
ノン３８．１２部，４，４゜−ジオキシビフエニル５２
． ７３部および酢酸第１スズ０． ０８８部を撹拌機
付き重合反応器に仕込み、窒素雰囲気下、２５０〜２９
０゜Ｃに２時間加熱し、反応の結果生或ずるフェノール
６８部（理論値の約６０％）を留出させたく反応系内の
生成物のηｓｐ／ ｃは０． ０７であった）。Implementation...13 Diphenylisophthalate 190.80 parts. Hydroquinone 38.12 parts, 4,4°-dioxybiphenyl 52
．． 73 parts and 0.0 parts stannous acetate. 088 parts was charged into a polymerization reactor equipped with a stirrer, and under a nitrogen atmosphere, 250 to 29
It was heated to 0°C for 2 hours to distill off 68 parts of phenol (approximately 60% of the theoretical value) produced as a result of the reaction.The ηsp/c of the product in the reaction system was 0. 07).
ついで、反応系の圧力を徐々に減圧にするのとともに反
応温度を上げ始め、約１時間を要して圧力を２０ａｍＨ
ｇ、反応温度を３４０℃とした（この際、反応系内のボ
リマーのηｓｐ／ｃと融点はそれぞれ０．１９， ３６
５℃であった）．
ここで溶融重合を停止し、ボリマーを冷却後１２〜５０
メッシュに粉砕し、２５０℃、０．１＋ｗ＋ｔｌｑの減
『下で２時間、更に０．１關１１！＋の減圧下２９０゜
Ｃで８時間固相重合を行なった．得られたボリマーはη
Ｓｐ／ｃ ＝０．９０、［ ＣＯＯＨ］ ＝ １５当量
７１０” ．および融点は３６５℃であった．また、３
８０℃で求めたこのボリマーのフローインデックスは０
．７７であった．実施例４
実施例１〜３において得たボリマーをそれぞれ３８０゜
Ｃの温度でエクストルーダー中で溶融し、スリ７ トＦ
１３ １，５ ｉｉ＋ノＴダイより１００゜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３００μｍの未延伸フィル
ムを得た．これら未延仲フイルムは気泡を含まず透明な
ものであった．各フィルムのボリマー性能を表１に、ａ
械的性能および透明性を表２に示す．
なお、各未延伸フィルムはアセトン中で２４時間放置し
たが、寸法変化は１％以下で、且つ強度，仲度．ヤング
率共にほとんど変化がみとめられなかった．
表 １
表 ２
実施例５
実施例４によって得た未延仲フィルムを切断後１５０℃
で２４時間乾燥後直径１關、長さ５關のノズルを備えた
断面積１ａａのシリンダーに充填し、３８０℃で５分間
溶融した後３０ｋｇ／一の加圧下で押出した．糸状で得
られたボリマーのηｓｏ／ｃ？：測定し、この溶融操作
前後のηＳＤ／ Ｃの変化より本発明の芳香族コポリエ
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 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 amH.
g, the reaction temperature was 340°C (at this time, the ηsp/c and melting point of the polymer in the reaction system were 0.19 and 36, respectively).
). After stopping the melt polymerization and cooling the polymer,
Grind into a mesh, 250℃, 0.1+w+tlq reduction for 2 hours, then 0.1 x 11! Solid phase polymerization was carried out at 290°C under + vacuum for 8 hours. The obtained polymer is η
Sp/c = 0.90, [COOH] = 15 equivalents 710''. and melting point was 365°C. Also, 3
The flow index of this polymer, determined at 80°C, is 0.
．． It was 77. Example 4 The polymers obtained in Examples 1 to 3 were each melted in an extruder at a temperature of 380° C.
It was extruded from a 13 1,5 ii + T die onto a casting drum heated to 100°C to obtain an unstretched film with a light brown color and a thickness of about 300 μm, which had good smoothness and transparency. These unfinished films were transparent and did not contain air bubbles. The polymer performance of each film is shown in Table 1, a
The mechanical performance and transparency are shown in Table 2. Each unstretched film was left in acetone for 24 hours, but the dimensional change was less than 1%, and the strength and consistency were . Almost no change was observed in both Young's modulus. Table 1 Table 2 Example 5 The unrolled intermediate film obtained in Example 4 was cut at 150°C.
After drying for 24 hours, the mixture was filled into a cylinder with a cross-sectional area of 1 aa equipped with a nozzle with a diameter of 1 mm and a length of 5 mm, melted at 380°C for 5 minutes, and then extruded under a pressure of 30 kg/cm. ηso/c of the polymer obtained in the form of threads? : The melt stability of the aromatic copolyester of the present invention was evaluated from the change in ηSD/C before and after the melting operation (hereinafter referred to as test A).
.
また、湿熱安定性は実施例４によって得た未延伸フィル
ムを水と共にガラス管に入れ、ガラス管を溶封後１２０
℃のオートクレープ中で２４時間保持して後、未延仲フ
ィルムのηｓｐ／ ｃを測定し、この湿熱処理操作の前
後のηｓｐ／ｃの変化より温熱安定性を評価した（以下
テストＢとする）．その結果は表３に示す。In addition, the wet heat stability was determined by putting the unstretched film obtained in Example 4 into a glass tube with water, and after melting and sealing the glass tube.
After being held in an autoclave at ℃ for 24 hours, the ηsp/c of the unrolled film was measured, and the thermal stability was evaluated from the change in ηsp/c before and after this moist heat treatment operation (hereinafter referred to as test B). ). The results are shown in Table 3.
表 ３
実施例１０
イソフタル酸９９．６０部．ハイドロキノン５５．４４
部、４，４゜−ジオキシビフェニル２１．２６部．ジフ
ェニルカーボネート１２８．４０部及び三酸化アンチモ
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３時間加熱し、反応の結果
生成するフェノール１２４部（使用したジフエニルカー
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鼠の６０％との和に相当する
）を留出させたく反応系内の生成物のηＳｐ／’Ｃと融
点はそれぞれ０．０８， ２９０ ’Ｃであった）．
ついで、反応系に窒素を導入しつつ、反応系のの圧力を
徐々に減圧にするのとともに反応温度を上げ始め、約１
時間を要して圧力を２０ｎｍｌｌｌｊ、反応温度を３３
０℃とし、この条件下で更に３０分間重合させた．得ら
れたのボリマーのηｓｐ／ ｃと融点は０．４７， ３
６０℃であった．
ここで溶融重合を停止し、ボリマーを冷却後１５〜２４
メッシュに粉砕し、２５０゜Ｃ ．． ０． ０ １ｒ
ｖｎｔｌｇの減圧下で１時間、ついで２９０℃、０．０
２１ｕＩｔｌｇの減圧下で１３時間固相重合させた．
このようにして得られたボリマーは、ηｓｐ／ ｃＯ．
９６、［ＣＯＯＩ＋］ ＝２４当ｆｆｉ／１０６ｉｒ，
融点＝ ３６０゜Ｃであった．また、このボリマーの３
８０ ’Ｃにおけるフローインデックスは０．７６であ
った．また、このポリマーからハロゲンは検出されなか
った．このボリマーは実施例１のボリマーと同様フィル
ムに溶融成形できることが確められた．また、このボリ
マーを３８０゜Ｃ″ｉ′直径０．３ｎ＋Ｉ＋のノズルよ
り押出して１００ｒｎ／分で巻取って得られた繊維は、
強度１ｒ／ｄｅ、仲度７０％であった．このＩＩｍ維も
、フィルムの場合と同様、耐湿熱性がすぐれていた．Table 3 Example 10 Isophthalic acid 99.60 parts. Hydroquinone 55.44
parts, 21.26 parts of 4,4°-dioxybiphenyl. 128.40 parts of diphenyl carbonate and 0.105 parts of antimony trioxide were placed in a polymerization reactor equipped with a stirrer and heated at 250 to 290°C for 3 hours under a nitrogen atmosphere. ηSp/'C and melting point of the product in the reaction system are respectively 0.08, 290'C). Next, while introducing nitrogen into the reaction system, the pressure of the reaction system was gradually reduced and the reaction temperature began to increase until about 1
It took time to increase the pressure to 20nmlllj and the reaction temperature to 33%.
The temperature was set to 0°C, and polymerization was continued for an additional 30 minutes under these conditions. The obtained polymer has ηsp/c and melting point of 0.47.3
The temperature was 60℃. After stopping the melt polymerization and cooling the polymer,
Grind into mesh and heat at 250°C. ．． 0. 0 1r
vntlg vacuum for 1 hour, then 290°C, 0.0
Solid phase polymerization was carried out for 13 hours under a reduced pressure of 21 uItlg. The polymer thus obtained has a ηsp/cO.
96, [COOI+] =24offfi/106ir,
The melting point was 360°C. Also, 3 of this polymer
The flow index at 80'C was 0.76. Furthermore, no halogen was detected in this polymer. It was confirmed that this polymer, like the polymer of Example 1, could be melt-formed into a film. In addition, the fiber obtained by extruding this polymerer through a nozzle with a diameter of 0.3n+I+ at 380°C″i′ and winding it at 100rn/min is as follows:
The strength was 1r/de and the density was 70%. Like the film, this IIm fiber also had excellent moisture and heat resistance.
Claims (1)
単位からなる実質的に線状の芳香族コポリエステルであ
って、 ▲数式、化学式、表等があります▼ ▲数式、化学式、表等があります▼ ▲数式、化学式、表等があります▼ 該芳香族コポリエステル中の前記［ I ］のモル数と［
II］と［III］との合計モル数が実質的に等しく、前記
［II］と［III］の共重合モル比が９：１〜４：６であ
り、且つ分子鎖に結合したハロゲン原子を有しない、０
．６〜２．０の還元粘度（フェノール／テトラクロルエ
タン＝４／６の混合溶媒に溶解し３５℃で測定した相対
粘度より算出）をもつ芳香族コポリエステル。(1) A substantially linear aromatic copolyester consisting essentially of the following structural units [I], [II] and [III], ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas, chemical formulas , tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The number of moles of [I] above in the aromatic copolyester and [
The total number of moles of [II] and [III] is substantially equal, the copolymerization molar ratio of [II] and [III] is 9:1 to 4:6, and the halogen atoms bonded to the molecular chain are do not have, 0
．． An aromatic copolyester having a reduced viscosity of 6 to 2.0 (calculated from the relative viscosity measured at 35°C after being dissolved in a mixed solvent of phenol/tetrachloroethane = 4/6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15149490A JPH0328221A (en) | 1990-06-12 | 1990-06-12 | Aromatic copolyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15149490A JPH0328221A (en) | 1990-06-12 | 1990-06-12 | Aromatic copolyester |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14473481A Division JPS5847019A (en) | 1981-09-16 | 1981-09-16 | Copolyester and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0328221A true JPH0328221A (en) | 1991-02-06 |
Family
ID=15519727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15149490A Pending JPH0328221A (en) | 1990-06-12 | 1990-06-12 | Aromatic copolyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0328221A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04372647A (en) * | 1991-06-20 | 1992-12-25 | Teijin Ltd | Resin composition |
| JPH055024A (en) * | 1990-08-22 | 1993-01-14 | Teijin Ltd | Crystalline wholly aromatic polyester production thereof, resin composition using the same and molded article the resin |
| US5216109A (en) * | 1990-08-22 | 1993-06-01 | Teijin Limited | Crystalline wholly aromatic polyester, process for its production, resin composition containing it, and articles from the resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4921440A (en) * | 1972-06-19 | 1974-02-25 | ||
| JPS5629684A (en) * | 1979-08-14 | 1981-03-25 | Mitsui Toatsu Chem Inc | Production of hydrogen |
-
1990
- 1990-06-12 JP JP15149490A patent/JPH0328221A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4921440A (en) * | 1972-06-19 | 1974-02-25 | ||
| JPS5629684A (en) * | 1979-08-14 | 1981-03-25 | Mitsui Toatsu Chem Inc | Production of hydrogen |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH055024A (en) * | 1990-08-22 | 1993-01-14 | Teijin Ltd | Crystalline wholly aromatic polyester production thereof, resin composition using the same and molded article the resin |
| US5216109A (en) * | 1990-08-22 | 1993-06-01 | Teijin Limited | Crystalline wholly aromatic polyester, process for its production, resin composition containing it, and articles from the resin composition |
| JPH04372647A (en) * | 1991-06-20 | 1992-12-25 | Teijin Ltd | Resin composition |
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