JP3643555B2 - Polycarbonate copolymer - Google Patents
Polycarbonate copolymer Download PDFInfo
- Publication number
- JP3643555B2 JP3643555B2 JP2001378482A JP2001378482A JP3643555B2 JP 3643555 B2 JP3643555 B2 JP 3643555B2 JP 2001378482 A JP2001378482 A JP 2001378482A JP 2001378482 A JP2001378482 A JP 2001378482A JP 3643555 B2 JP3643555 B2 JP 3643555B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- bis
- polycarbonate copolymer
- hydroxyphenyl
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000515 polycarbonate Polymers 0.000 title claims description 51
- 239000004417 polycarbonate Substances 0.000 title claims description 51
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 125000003118 aryl group Chemical group 0.000 claims description 36
- 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 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical group C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 claims description 4
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- WJZHBPSXJJQGJO-UHFFFAOYSA-N 4-[2,6-di(propan-2-yl)phenyl]phenol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1C1=CC=C(O)C=C1 WJZHBPSXJJQGJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 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
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- 229920006289 polycarbonate film Polymers 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 83
- 238000000034 method Methods 0.000 description 28
- 239000004973 liquid crystal related substance Substances 0.000 description 27
- -1 aliphatic ketones Chemical class 0.000 description 23
- 229920005668 polycarbonate resin Polymers 0.000 description 20
- 239000004431 polycarbonate resin Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 150000002989 phenols Chemical class 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 150000004650 carbonic acid diesters Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 210000002858 crystal cell Anatomy 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 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
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 2
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- PXDJXZJSCPSGGI-UHFFFAOYSA-N palmityl palmitate Chemical compound CCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC PXDJXZJSCPSGGI-UHFFFAOYSA-N 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 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
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 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
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 1
- WXENKXQUTQFQIP-PLKIVWSFSA-N (2e,4e)-hexa-2,4-dienoic acid;octadecanoic acid Chemical compound C\C=C\C=C\C(O)=O.CCCCCCCCCCCCCCCCCC(O)=O WXENKXQUTQFQIP-PLKIVWSFSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- DMBUODUULYCPAK-UHFFFAOYSA-N 1,3-bis(docosanoyloxy)propan-2-yl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCCCCCC DMBUODUULYCPAK-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 description 1
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- FDIPWBUDOCPIMH-UHFFFAOYSA-N 2-decylphenol Chemical compound CCCCCCCCCCC1=CC=CC=C1O FDIPWBUDOCPIMH-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- OPJWPPVYCOPDCM-UHFFFAOYSA-N 2-ethylhexyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)CCCC OPJWPPVYCOPDCM-UHFFFAOYSA-N 0.000 description 1
- HMWIHOZPGQRZLR-UHFFFAOYSA-N 2-hexadecylphenol Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1O HMWIHOZPGQRZLR-UHFFFAOYSA-N 0.000 description 1
- QEMHBAGGYKJNSS-UHFFFAOYSA-N 2-icosylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O QEMHBAGGYKJNSS-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- JOONSONEBWTBLT-UHFFFAOYSA-N 2-tetradecylphenol Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1O JOONSONEBWTBLT-UHFFFAOYSA-N 0.000 description 1
- OREKREJVUNVFJP-UHFFFAOYSA-N 2-triacontylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O OREKREJVUNVFJP-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 description 1
- UJCYBTZHUJWCMB-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-4-propan-2-ylcyclohexyl]phenol Chemical compound C1CC(C(C)C)CCC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UJCYBTZHUJWCMB-UHFFFAOYSA-N 0.000 description 1
- WCUDAIJOADOKAW-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)pentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCC)C1=CC=C(O)C=C1 WCUDAIJOADOKAW-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
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- NHLHASWXBVULGU-UHFFFAOYSA-N hexadecyl 2-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1O NHLHASWXBVULGU-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、ポリカーボネート共重合体に関する。さらに詳しくは色相が著しく改善された透明性、耐熱性、延伸フィルム特性の良好なポリカーボネート共重合体であり、視野角が広く、無彩色表示の色調が鮮明となる液晶ディスプレー用途に適したポリカーボネート共重合体に関する。
【０００２】
【従来の技術】
従来、ビスフェノールＡにカーボネート前駆物質を反応させて得られるポリカーボネート樹脂は透明性、耐熱性、機械的特性、寸法安定性が優れているがゆえにエンジニアリングプラスチックとして多くの分野に広く使用されている。特に透明性に優れることから光学材料としての用途も多く、近年液晶ディスプレーの液晶基板用フィルムや位相差フィルム用途にも使用されている。しかしながら、通常のビスフェノールＡからのポリカーボネート樹脂より得られるフィルムでは、殊に液晶ディスプレーに用いるフィルムが配向膜形成プロセスや電極形成プロセス等で１８０℃以上の高温処理を要し、その耐熱性が不足するという問題がある。
【０００３】
ポリカーボネート樹脂の耐熱性を向上させるためには、一般的に嵩高い動きにくい構造を有するビスフェノール類を用いる方法があり、種々のポリカーボネートが提案されている。例えば、特開平５−７８４６７号公報では、アダマンタン構造を有するビスフェノールを主として得られるポリカーボネート樹脂が提案され、特開平２−８８６３４号公報では、特定のジヒドロキシジフェニルシクロアルカンをベースとするポリカーボネート樹脂が提案されている。また、特開平１１−１７４４２４号公報、特開平８−１３４１９８号公報および特開平７−５２２７０号公報では、特定のフルオレン構造を有するポリカーボネート樹脂が提案されている。しかしながら、これらの構造を有するポリカーボネート樹脂は耐熱性に優れるものの、色相の点で十分ではなく、また、延伸したフィルムの特性に劣り、位相差フィルムとして使用した際に視野角が狭くなるなどの問題があり、その改善が望まれている。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、殊に液晶ディスプレー用のフィルムとして使用する際に、色相および透明性に優れ、延伸フィルム特性が良好で、視野角が広く無彩色表示の色調が鮮明となる耐熱性に優れたポリカーボネート共重合体を提供することにある。
【０００５】
本発明者はこの目的を達成せんとして鋭意研究を重ねた結果、フィルムの色相の指標となるｂ値に着目し、従来のフルオレン共重合体から得られるポリカーボネート樹脂フィルムに比べて、ポリカーボネート樹脂フィルムのｂ値を低くすることにより、延伸フィルム特性が向上するなどの上記目的を達成することを見出し、本発明に到達した。
【０００６】
【課題を解決するための手段】
すなわち、本発明によれば、全芳香族ジヒドロキシ成分の５〜９５モル％が９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９５〜５モル％が下記一般式［１］
【０００７】
【化２】
［式中、Ｒ1〜Ｒ4は夫々独立して水素原子、炭素原子数１〜９の芳香族基を含んでもよい炭化水素基又はハロゲン原子であり、Ｗは単結合、炭素原子数１〜２０の芳香族基を含んでもよい炭化水素基、Ｏ、Ｓ、ＳＯ、ＳＯ2、ＣＯ又はＣＯＯ基である。］
で表されるジヒドロキシ成分からなり、塩化メチレン溶液での２０℃における極限粘度が０．３５〜１．０の範囲のポリカーボネート共重合体であって、且つ該ポリカーボネート共重合体より形成されるポリカーボネート樹脂フィルムは、０．２ｍｍ厚みにおけるＣ光源で測定したｂ値が１．３以下であることを特徴とするポリカーボネート共重合体が提供される。
【０００９】
本発明の芳香族ポリカーボネート共重合体は、それを構成する芳香族ジヒドロキシ成分として、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンが全芳香族ジヒドロキシ成分の５〜９５モル％、好ましくは１０〜９５モル％、さらに好ましくは３０〜８５モル％である。５モル％未満の場合、本発明の目的である耐熱用材料として不満足な性質となり好ましくない。
【００１０】
本発明の芳香族ポリカーボネート共重合体より形成されるポリカーボネート樹脂フィルムは、ＪＩＳ規格分光光線で昼光照明に相当する標準光であるＣ光源で測定した０．２ｍｍ厚みのポリカーボネート樹脂フィルムのｂ値が１．３以下であり、好ましくは１．０以下であり、より好ましくは０．５以下である。フィルムのｂ値が１．３を越えると、例えば液晶用フィルムとして使用した際に、延伸フィルム特性に劣り、視野角が狭くなったり液晶の白色が不鮮明となり好ましくない。なお、ここでいうポリカーボネート樹脂フィルムは、未延伸フィルムおよび延伸フィルムのどちらも包含するものである。
【００１１】
前記ｂ値が１．３以下であるポリカーボネート樹脂フィルムは、特定の処理を行い不純物を除去した９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンを用いて、芳香族ポリカーボネート共重合体を重合し、この共重合体をフィルム化する方法や、芳香族ポリカーボネート共重合体の重合時に脱酸素処理した反応溶液を用いて重合し、この共重合体をフィルム化する方法などによって得ることができる。使用される９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンは、通常ｏ−クレゾールとフルオレノンの反応によって得られる。
【００１２】
９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン中の不純物を除去する方法として具体的には、ｏ−クレゾールとフルオレノンの反応後に、未反応のｏ−クレゾールを留去した後、残さをアルコール系、ケトン系またはベンゼン誘導体系の溶媒に溶解し、これに活性白土を加えてろ過後、ろ液から結晶化した生成物をろ過して精製する方法が好適である。この方法により９９．５％以上の純度の９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンを得ることができる。除去される不純物としては、２，４′−ジヒドロキシ体、２，２′−ジヒドロキシ体および構造不明の不純物等である。
【００１３】
純度９９．５％以上の９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンを用いることによって、色相の向上したポリカーボネート共重合体を得ることができ、このポリカーボネート共重合体から形成されるポリカーボネート樹脂フィルムは、そのｂ値が１．３以下を達成することができる。通常の方法で得られた９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンを用いると、目的とするｂ値の極めて小さいポリカーボネート樹脂フィルムを得ることはできない。
【００１４】
上記９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンの精製に用いるアルコール系の溶媒としてはメタノール、エタノール、プロパノール、ブタノール等の低級アルコール、ケトン系の溶媒としてはアセトン、メチルエチルケトン、メチルイソプロピルケトン、シクロヘキサノン等の低級脂肪族ケトン類およびこれらの混合物が好ましく、ベンゼン誘導体系の溶媒としてはトルエン、キシレン、ベンゼンおよびこれらの混合物が好ましい。溶媒の使用量はフルオレン化合物が十分に溶解する量であれば足り、通常フルオレン化合物に対して２〜１０倍量程度である。活性白土としては市販されている粉末状または粒状のシリカ−アルミナを主成分とするものが用いられる。
【００１５】
本発明の芳香族ポリカーボネート共重合体において用いられる上記一般式（１）で示される他のジヒドロキシ成分としては、通常芳香族ポリカーボネートのジヒドロキシ成分として使用されているものであればよく、例えばハイドロキノン、レゾルシノール、４，４′−ビフェノール、１，１−ビス（４−ヒドロキシフェニル）エタン（ビスフェノールＥ）、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）、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン（ビスフェノールＣ）、２，２−ビス（４−ヒドロキシフェニル）ブタン、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン（ビスフェノールＺ）、１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン、２，２−ビス（４−ヒドロキシフェニル）ペンタン、α，α′−ビス（４−ヒドロキシフェニル）−ｐ−ジイソプロピルベンゼン、α，α′−ビス（４−ヒドロキシフェニル）−ｍ−ジイソプロピルベンゼン（ビスフェノールＭ）、１，１−ビス（４−ヒドロキシフェニル）−４−イソプロピルシクロヘキサンなどが挙げられ、なかでもビスフェノールＡ、ビスフェノールＺ、ビスフェノールＣ、ビスフェノールＥ、ビスフェノールＭが好ましく、特にビスフェノールＡが好ましい。
【００１６】
本発明の芳香族ポリカーボネート共重合体はそのポリマーを塩化メチレンに溶解した溶液での２０℃における極限粘度が０．３５〜１．０であり、０．５０〜０．８０が好ましく、０．５５〜０．８０がより好ましい。極限粘度が０．３５未満では成形品、殊にフィルムの強度が弱くなり、１．０を越えると溶融粘度および溶液粘度が高くなり、取り扱いが困難になるので好ましくない。
【００１７】
本発明の芳香族ポリカーボネート共重合体は、通常の芳香族ポリカーボネート樹脂を製造するそれ自体公知の反応手段、例えば芳香族ジヒドロキシ成分にホスゲンや炭酸ジエステルなどのカーボネート前駆物質を反応させる方法により製造される。次にこれらの製造方法について基本的な手段を簡単に説明する。
【００１８】
カーボネート前駆物質として、例えばホスゲンを使用する反応では、通常酸結合剤および溶媒の存在下に反応を行う。酸結合剤としては、例えば水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物またはピリジンなどのアミン化合物が用いられる。溶媒としては、例えば塩化メチレン、クロロベンゼンなどのハロゲン化炭化水素が用いられる。また反応促進のために例えば第三級アミンまたは第四級アンモニウム塩などの触媒を用いることもできる。その際、反応温度は通常０〜４０℃であり、反応時間は数分〜５時間である。
【００１９】
カーボネート前駆物質として炭酸ジエステルを用いるエステル交換反応は、不活性ガス雰囲気下所定割合の芳香族ジヒドロキシ成分を炭酸ジエステルと加熱しながら撹拌して、生成するアルコールまたはフェノール類を留出させる方法により行われる。反応温度は生成するアルコールまたはフェノール類の沸点などにより異なるが、通常１２０〜３００℃の範囲である。反応はその初期から減圧にして生成するアルコールまたはフェノール類を留出させながら反応を完結させる。また反応を促進するために通常エステル交換反応に使用される触媒を使用することもできる。前記エステル交換反応に使用される炭酸ジエステルとしては、例えばジフェニルカーボネート、ジナフチルカーボネート、ビス（ジフェニル）カーボネート、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネートなどが挙げられる。これらのうち特にジフェニルカーボネートが好ましい。
【００２０】
本発明の芳香族ポリカーボネート共重合体は、その重合反応において、末端停止剤として通常使用される単官能フェノール類を使用することができる。殊にカーボネート前駆物質としてホスゲンを使用する反応の場合、単官能フェノール類は末端停止剤として分子量調節のために一般的に使用され、また得られた芳香族ポリカーボネート共重合体は、末端が単官能フェノール類に基づく基によって封鎖されているので、そうでないものと比べて熱安定性に優れている。
【００２１】
かかる単官能フェノール類としては、芳香族ポリカーボネート樹脂の末端停止剤として使用されるものであればよく、一般にはフェノール或いは低級アルキル置換フェノールであって、下記一般式（２）で表される単官能フェノール類を示すことができる。
【００２２】
【化３】
［式中、Ａは水素原子、炭素数１〜９の直鎖または分岐のアルキル基あるいはアリールアルキル基であり、ｒは１〜５、好ましくは１〜３の整数である。］
前記単官能フェノール類の具体例としては、例えばフェノール、ｐ−ｔｅｒｔ−ブチルフェノール、ｐ−クミルフェノールおよびイソオクチルフェノールが挙げられる。
【００２４】
また、他の単官能フェノール類としては、長鎖のアルキル基或いは脂肪族ポリエステル基を置換基として有するフェノール類または安息香酸クロライド類、もしくは長鎖のアルキルカルボン酸クロライド類を使用することができ、これらを用いて芳香族ポリカーボネート共重合体の末端を封鎖すると、これらは末端停止剤または分子量調節剤として機能するのみならず、樹脂の溶融流動性が改良され、成形加工が容易となるばかりでなく、物性も改良される。特に樹脂の吸水率を低くする効果があり、好ましく使用される。これらは下記一般式［Ｉ−ａ］〜［Ｉ−ｈ］で表される。
【００２５】
【化４】
【化５】
【化６】
【化７】
【化８】
【化９】
【化１０】
【化１１】
［前記一般式［Ｉ−ａ］〜［Ｉ−ｈ］中、Ｘは−Ｒ−Ｏ−、−Ｒ−ＣＯ−Ｏ−または−Ｒ−Ｏ−ＣＯ−である、ここでＲは単結合または炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、Ｔは単結合または上記Ｘと同様の結合を示し、ｎは１０〜５０の整数を示す。
Ｑはハロゲン原子または炭素数１〜１０、好ましくは１〜５の一価の脂肪族炭化水素基を示し、ｐは０〜４の整数を示し、Ｙは炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、Ｗ1は水素原子、−ＣＯ−Ｒ17、−ＣＯ−Ｏ−Ｒ18またはＲ19である、ここでＲ17、Ｒ18およびＲ19は、それぞれ炭素数１〜１０、好ましくは１〜５の一価の脂肪族炭化水素基、炭素数４〜８、好ましくは５〜６の一価の脂環族炭化水素基または炭素数６〜１５、好ましくは６〜１２の一価の芳香族炭化水素基を示す。
ａは４〜２０、好ましくは５〜１０の整数を示し、ｍは１〜１００、好ましくは３〜６０、特に好ましくは４〜５０の整数を示し、Ｚは単結合または炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、Ｗ2は水素原子、炭素数１〜１０、好ましくは１〜５の一価の脂肪族炭化水素基、炭素数４〜８、好ましくは５〜６の一価の脂環族炭化水素基または炭素数６〜１５、好ましくは６〜１２の一価の芳香族炭化水素基を示す。］
これらのうち好ましいのは、［Ｉ−ａ］および［Ｉ−ｂ］の置換フェノール類である。この［Ｉ−ａ］の置換フェノール類としては、ｎが１０〜３０、特に１０〜２６のものが好ましく、その具体例としては、例えばデシルフェノール、ドデシルフェノール、テトラデシルフェノール、ヘキサデシルフェノール、オクタデシルフェノール、エイコシルフェノール、ドコシルフェノールおよびトリアコンチルフェノールなどを挙げることができる。
【００３４】
また、［Ｉ−ｂ］の置換フェノール類としてはＸが−Ｒ−ＣＯ−Ｏ−であり、Ｒが単結合である化合物が適当であり、ｎが１０〜３０、特に１０〜２６のものが好適であって、その具体例としては、例えばヒドロキシ安息香酸デシル、ヒドロキシ安息香酸ドデシル、ヒドロキシ安息香酸テトラデシル、ヒドロキシ安息香酸ヘキサデシル、ヒドロキシ安息香酸エイコシル、ヒドロキシ安息香酸ドコシルおよびヒドロキシ安息香酸トリアコンチルが挙げられる。
【００３５】
前記一般式［Ｉ−ａ］〜［Ｉ−ｇ］で示される置換フェノール類または置換安息香酸クロライドにおいて置換基の位置は、ｐ位またはｏ位が一般的に好ましく、その両者の混合物が好ましい。
【００３６】
前記単官能フェノール類は、得られた芳香族ポリカーボネート共重合体の全末端に対して少なくとも５モル％、好ましくは少なくとも１０モル％末端に導入されることが望ましく、また単官能フェノール類は単独でもしくは２種以上混合して使用してもよい。
【００３７】
また、本発明の芳香族ポリカーボネート共重合体において、９,９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンが、全芳香族ヒドロキシ成分の６０モル％以上である場合は、樹脂の流動性が低下することがあり、そのため前記一般式［Ｉ−ａ］〜［Ｉ−ｇ］で示される置換フェノール類または置換安息香酸クロライド類を末端停止剤として使用することが好ましい。
【００３８】
本発明の芳香族ポリカーボネート共重合体は、本発明の趣旨を損なわない範囲で、芳香族ジカルボン酸、例えばテレフタル酸、イソフタル酸、ナフタレンジカルボン酸あるいはその誘導体を共重合したポリエステルカーボネートであってもよい。また少量の３官能化合物を共重合した分岐ポリカーボネートであってもよい。
【００３９】
本発明の芳香族ポリカーボネート共重合体は、そのガラス転移点が１６０℃以上が好ましく、１８０℃以上がより好ましく、２００℃以上がさらに好ましい。また、ガラス転移点は２５０℃以下が好ましく、２４０℃以下がより好ましく、２３０℃以下がさらに好ましい。
【００４０】
本発明において、前記芳香族ポリカーボネート共重合体に必要に応じて、リン酸、亜リン酸、ホスホン酸、亜ホスホン酸およびこれらのエステルよりなる群から選択された少なくとも１種のリン化合物を配合することができる。かかるリン化合物の配合量は、該芳香族ポリカーボネート共重合体に対して０.０００１〜０.０５重量％が好ましく、０.０００５〜０.０２重量％がより好ましく、０.００１〜０.０１重量％が特に好ましい。このリン化合物を配合することにより、かかる芳香族ポリカーボネート共重合体の熱安定性が向上し、成形時における分子量の低下や色相の悪化が防止される。
【００４１】
かかるリン化合物としては、リン酸、亜リン酸、ホスホン酸、亜ホスホン酸およびこれらのエステルよりなる群から選択される少なくとも１種のリン化合物であり、好ましくは下記一般式
【００４２】
【化１２】
【化１３】
【化１４】
【化１５】
［式中、Ｒ5〜Ｒ16は、それぞれ独立して、水素原子、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ドデシル、ヘキサデシル、オクタデシルなどの炭素数１〜２０のアルキル基、フェニル、トリル、ナフチルなどの炭素数６〜１５のアリール基またはベンジル、フェネチルなどの炭素数７〜１８のアラルキル基を表し、また１つの化合物中に２つのアルキル基が存在する場合は、その２つのアルキル基は互いに結合して環を形成していてもよい。］
よりなる群から選択された少なくとも１種のリン化合物である。
【００４７】
上記（３）式で示されるリン化合物としては、例えばトリフェニルホスファイト、トリスノニルフェニルホスファイト、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジデシルモノフェニルホスファイト、ジオクチルモノフェニルホスファイト、ジイソプロピルモノフェニルホスファイト、モノブチルジフェニルホスファイト、モノデシルジフェニルホスファイト、モノオクチルジフェニルホスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、２，２−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）オクチルホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイトなどが挙げられる。
【００４８】
上記（４）式で示されるリン化合物としては、例えばトリブチルホスフェート、トリメチルホスフェート、トリフェニルホスフェート、トリエチルホスフェート、ジフェニルモノオルソキセニルホスフェート、ジブチルホスフェート、ジオクチルホスフェート、ジイソプロピルホスフェートなどが挙げられ、上記（５）式で示されるリン化合物としては、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４−ジフェニレンホスホナイトなどが挙げられ、また上記（６）式で示される化合物としては、ベンゼンホスホン酸ジメチル、ベンゼンホスホン酸ジエチル、ベンゼンホスホン酸ジプロピルなどが挙げられる。
【００４９】
これらのリン化合物のなかで、トリスノニルフェニルホスファイト、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４−ジフェニレンホスホナイトが好ましく使用される。
【００５０】
前記ポリカーボネート共重合体には、酸化防止の目的で通常知られた酸化防止剤を添加することができる。その例としてはフェノール系酸化防止剤を示すことができ、具体的には例えばトリエチレングリコール−ビス［３−（３−ｔｅｒｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］、１，６−ヘキサンジオール−ビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、ペンタエリスリトール−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、Ｎ，Ｎ−ヘキサメチレンビス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシ−ヒドロシンナマイド）、３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシ−ベンジルホスホネート−ジエチルエステル、トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、３，９−ビス｛１，１−ジメチル−２−［β−（３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］エチル｝−２，４，８，１０−テトラオキサスピロ（５，５）ウンデカン等が挙げられる。これら酸化防止剤の好ましい添加量の範囲はポリカーボネート共重合体に対して０．０００１〜０．０５重量％である。
【００５１】
さらに前記芳香族ポリカーボネート共重合体には、必要に応じて一価または多価アルコールの高級脂肪酸エステルを加えることもできる。
【００５２】
かかる高級脂肪酸エステルとしては、炭素原子数１〜２０の一価または多価アルコールと炭素原子数１０〜３０の飽和脂肪酸との部分エステルまたは全エステルであるのが好ましい。また、かかる一価または多価アルコールと飽和脂肪酸との部分エステルまたは全エステルとしては、ステアリン酸モノグリセリド、ステアリン酸モノソルビテート、ベヘニン酸モノグリセリド、ペンタエリスリトールモノステアレート、ペンタエリスリトールテトラステアレート、プロピレングリコールモノステアレート、ステアリルステアレート、パルミチルパルミテート、ブチルステアレート、メチルラウレート、イソプロピルパルミテート、２−エチルヘキシルステアレートなどが挙げられ、なかでもステアリン酸モノグリセリド、ペンタエリスリトールテトラステアレートが好ましく用いられる。
【００５３】
かかるアルコールと高級脂肪酸とのエステルの配合量は、該芳香族ポリカーボネート共重合体に対して０.０１〜２重量％が好ましく、０.０１５〜０.５重量％がより好ましく、０.０２〜０.２重量％がさらに好ましい。配合量がこの範囲内であれば離型性に優れ、また離型剤がマイグレートし金属表面に付着することもなく好ましい。
【００５４】
前記芳香族ポリカーボネート共重合体には、さらに光安定剤、着色剤、帯電防止剤、滑剤、充填剤などの添加剤や他のポリカーボネート樹脂、他の熱可塑性樹脂を本発明の目的を損なわない範囲で少割合添加することもできる。
【００５５】
前記芳香族ポリカーボネート共重合体からフィルムを製造する方法としては、厚みの均一性に優れ、ゲル、ブツ、フィッシュアイ、スクラッチ等の光学欠点の生じない方法が好ましく、例えば溶剤キャスト法、溶融押出し法、カレンダー法等が挙げられる。なかでも、本発明のポリカーボネート共重合体より形成されるポリカーボネート樹脂フィルムが好適に使用される光学用途は高度な均一性を要求されるために、溶液からのキャスティング法が好ましく採用される。キャスティング法は、一般にはダイから溶液を押出すキャスティング法、ドクターナイフ法等が好ましく用いられる。溶媒としては、例えば塩化メチレン、ジオキソラン、トルエン、ジオキサン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等の有機溶媒が好ましい。これらは一種でもよいし、二種以上の混合溶媒でもよい。液晶ディスプレー用フィルムは厚膜であり、溶液濃度は１５重量％以上、好適には２０重量％以上の高濃度溶液が好ましく用いられる。
【００５６】
芳香族ポリカーボネート樹脂フィルムの膜厚は用途に応じて選択すればよいが、５０〜５００μｍの範囲が好ましく、８０〜３００μｍの範囲がより好ましく用いられる。この範囲内では、位相差フィルムにおいて屈折率異方性に基づく充分なリターデーションが得られ、また液晶基板用フィルム（プラセル基板）では充分に腰のある（剛直な）フィルムが得られ、また、製膜が容易であり好ましい。さらに、位相差フィルムにおいて延伸により精度良く目的のリターデーションが得られやすく好ましい。
【００５７】
かかる方法により製造されたフィルムを位相差フィルムとして用いるためには、最適な複屈折特性を有するよう少なくとも一軸方向に延伸配向して位相差フィルムにする。一軸延伸方法としてはテンター法による横一軸延伸、ロール間による縦一軸延伸、ロール間圧延法等の任意の方法を用いることができる。延伸温度は用いる樹脂のガラス転移温度（Ｔｇ）−５０℃以上、Ｔｇ＋２０℃以下が好ましく、Ｔｇ−３０℃以上、Ｔｇ＋１０℃以下がより好ましい。かかる範囲の温度で延伸することにより、ポリマー分子の運動が凍結されることなく均一配向が容易になり好ましく、また、ポリマーの分子運動が適度であり、延伸による配向の緩和が起り難く、所望した配向度が得られ易く配向抑制が容易になり好ましい。
【００５８】
また、延伸倍率は目的とするフィルムのリターデーションの大きさに応じて適宜選択すればよい。この値は、延伸温度、膜厚にも依存する。一般に厚膜では延伸倍率は小さくともよく、薄膜では大きくとる必要が有る。ＳＴＮ型液晶ディスプレーに用いる位相差板のリターデーションの値は、一般には１００〜１２００ｎｍであり、好ましくは１５０〜６５０ｎｍの範囲が用いられる。更にリターデーションの振れ幅は１０％以下が好ましく、５％以下が特に好ましい。リターデーションの振れ幅が大きくなりすぎると色補償の偏差が生じ、色むらになりやすい。
【００５９】
位相差フィルムはバリヤー層およびインジウム、酸化スズをターゲットとした液晶用透明電極を形成した後、偏向板に積層して複合偏向板として好ましく用いられる。この複合偏向板は、通常の偏向板の光学軸と位相差フィルムの光学軸を４０〜５０度の範囲で単層または複層張り合わせることにより形成できる。この複合偏向板は耐熱耐久性に優れ、リターデーションの経時変化が少ない等の優れた特徴を有する。
【００６０】
また、延伸フィルム特性の一つにフィルム面内方向の屈折率ｎxとｎyの平均値と厚み方向の屈折率ｎzの差の絶対値とフィルム厚みｔ（ｎｍ）の積で規定されるＫ値＝｜（ｎx＋ｎy）／２−ｎz｜×ｔがあり、Ｋ値が大きくなると液晶表示素子として用いた場合に表示が浮いて見える等視野角が狭くなるため、この値は好ましくは８０ｎｍ以下、より好ましくは７５ｎｍ以下に押さえるのが好ましい。
【００６１】
また、液晶セルの片面または両面に偏向板を配置した液晶表示パネルは、視面側の偏向板と液晶セルの間に前記位相差フィルムを配することにより、液晶の複屈折による着色を解消した白黒表示の液晶表示パネルを形成することができ、更に白黒表示用液晶パネルにカラーマスクを被せＲＧＢの３色を発色させることによりフルカラーの液晶表示パネルを形成することができる。
【００６２】
本発明のポリカーボネート共重合体より形成されるポリカーボネート樹脂フィルムは、耐熱性、強度、色相に優れ、延伸フィルム特性が良好であり、このフィルムの両面にガスバリヤー膜、耐溶剤膜を付けたり、透明導電膜や偏光板と共に液晶基板用フィルム（プラセル基板）または位相差フィルム等の液晶ディスプレー用フィルムとして、特に位相差フィルム用途として好適に用いられ、具体的には、ポケベル、携帯電話、ハンディーターミナル、種々の表示素子等に有利に使用することができる。
【００６３】
【実施例】
以下に実施例を挙げて本発明をさらに説明する。なお、実施例中の部は重量部であり、％は重量％である。なお、評価は下記の方法によった。
（１）モノマー純度：試料１０ｍｇを１０ｍｌのアセトニトリルに溶解し東ソー（株）ＴＳＫ−ＧＥＬ ＯＤＳ−８０ＴＭカラムを用いて、アセトニトリル／水＝６／４の溶媒にて波長２５４ｎｍでＨＰＬＣ分析して求めた。
（２）極限粘度：ポリマーを塩化メチレンに溶解し２０℃の温度で測定した。
（３）ガラス転移点（Ｔｇ）：デュポン社製９１０型ＤＳＣにより測定した。
（４）フィルムのｂ値：実施例で得られた厚み０．２ｍｍのフィルムを、Ｃ光源により日立Ｕ−３０００分光光度計を用いて測定した。
（５）全光線透過率：ＡＳＴＭ Ｄ−１００３に準拠して日本電色（株）シグマ８０により測定した。
（６）Ｋ値：王子製紙（株）製ＫＯＢＲＡ２１ＡＤＨを用いて５５０ｎｍの波長で、延伸方向、直角方向、厚み方向の屈折率を測定して求めた。
【００６４】
［実施例１］
温度計、撹拌機、還流冷却器付き反応器にイオン交換水１５２４００部、２５％水酸化ナトリウム水溶液８４３２０部を入れ、ＨＰＬＣ分析で純度９９．８％の９,９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン（以下“ビスクレゾールフルオレン”と略称することがある）３４８４８部、２，２−ビス（４−ヒドロキシフェニル）プロパン９００８部（以下“ビスフェノールＡ”と略称することがある）およびハイドロサルファイト８８部を溶解した後、塩化メチレン１７８４００部を加えた後撹拌下１５〜２５℃でホスゲン１８２４８部を６０分を要して吹き込んだ。ホスゲン吹き込み終了後、ｐ−ｔｅｒｔ−ブチルフェノール１７７．８部を塩化メチレン２６４０部に溶解した溶液および２５％水酸化ナトリウム水溶液１０５６０部を加え、乳化後、トリエチルアミン３２部を加えて２８〜３３℃で１時間撹拌して反応を終了した。反応終了後、生成物を塩化メチレンで希釈して水洗したのち塩酸酸性にして水洗し、水相の導電率がイオン交換水と殆ど同じになったところで、塩化メチレン相を濃縮、脱水してポリカーボネート濃度が２０％の溶液を得た。この溶液から溶媒を除去して得たポリカーボネートはビスクレゾールフルオレンとビスフェノールＡとの構成単位の比がモル比で７０：３０であった（ポリマー収率９７％）。また、このポリマーの極限粘度は０.６７４、Ｔｇは２２６℃であった。
【００６５】
このポリカーボネート溶液を２０℃でＴダイより移動しているステンレス板上に流延し、徐々に温度を上げながら塩化メチレンを蒸発し、ステンレス板より剥離して更に加熱して塩化メチレンを除去して２００μｍの厚みのフィルムを得た。キャスティング製膜性は良好で、このフィルムのｂ値は０．５、全光線透過率は９０％であった。このフィルムをテンター法により２２６℃で延伸倍率２．０に一軸延伸した。この延伸フィルムのＫ値は７１と好ましい値を示した。この一軸延伸したフィルムにバリヤー層および液晶用透明電極をスパッタリングした後、粘着剤を用いて偏向板の片面に光学軸が４５度になるように接着して複合偏向板を得た。次いでこのものをＳＴＮ液晶表示装置の液晶セルと上部偏向板の間に貼り合わせて用いたところ、視野角が広く、背景色が白、表示色が黒のコントラストのよい白黒表示が得られた。また、この上部にカラーフィルターを被せ、ＲＧＢのセルを白黒のグレー濃度で発色表示させることにより、鮮明なフルカラー表示が得られた。
【００６６】
［実施例２］
実施例１のビスクレゾールフルオレンの使用量を２９７６０部、ビスフェノールＡの使用量を１２０００部とする以外は実施例１と同様にして、ビスクレゾールフルオレンとビスフェノールＡとの構成単位の比がモル比で６０：４０であるポリマー２０％溶液を得た（ポリマー収率９８％）。このポリマーの極限粘度は０.７０７、Ｔｇは２１７℃であった。このポリカーボネート溶液を実施例１と同様の方法により２００μｍの厚みのフィルムを得た。キャスティング製膜性は良好で、このフィルムのｂ値は０．５、全光線透過率は９０％であった。このフィルムをテンター法により２１７℃で延伸倍率２．０に一軸延伸した。この延伸フィルムのＫ値は７２と好ましい値を示した。このフィルムを実施例１と同様の方法で液晶表示させたところ、視野角の広い鮮明なフルカラー表示が得られた。
【００６７】
［比較例１］
実施例１と同様の反応器を用いて、ＨＰＬＣ純度が９９．０％のビスクレゾールフルオレンを用いる以外は実施例１と同様にして２０％のポリカーボネート溶液（ポリマー収率９８％）を得た。このポリマーの極限粘度は０．６７２、Ｔｇは２２５℃であった。このポリカーボネート溶液を実施例１と同様の方法により２００μｍの厚みのフィルムを得た。このフィルムのｂ値は２．１、全光線透過率は８８％であった。このフィルムをテンター法により２２５℃で延伸倍率２．０に一軸延伸したところ、Ｋ値は８５とやや大きくなった。このフィルムを実施例１と同様の方法で液晶表示をさせたところ、視野角が狭くなり、白表示がやや黄色味を帯び、色相補償が不十分で色ズレが生じ、やや赤みがかった色調になった。またカラー表示には色ズレや滲み等があり鮮明なフルカラー表示はできなかった。
【００６８】
［比較例２］
実施例１のｐ−ｔｅｒｔ−ブチルフェノールを４９．４部使用する以外は実施例１と同様にして２０％のポリカーボネート溶液（ポリマー収率９８％）を得た。このものの極限粘度は１．１３３と高く、溶液粘度が高く、キャスティング製膜性が悪く、良好なフィルムは得られなかった。
【００６９】
【発明の効果】
本発明のポリカーボネート共重合体は、色相、透明性、耐熱性に優れ、延伸フィルム特性が良好であり、このポリカーボネート共重合体より形成されたフィルムを殊にプラセル基板、位相差フィルム等の液晶ディスプレー用のフィルムとして使用すると、視野角が広く、無彩色表示の色調が鮮明となり、これらの用途に好適に用いられる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polycarbonate copolymer. More specifically, it is a polycarbonate copolymer with significantly improved hue, excellent transparency, heat resistance, and stretched film characteristics. It has a wide viewing angle and is suitable for liquid crystal display applications with clear achromatic colors. It relates to a polymer.
[0002]
[Prior art]
Conventionally, polycarbonate resins obtained by reacting bisphenol A with a carbonate precursor have been widely used in many fields as engineering plastics because of their excellent transparency, heat resistance, mechanical properties, and dimensional stability. Since it is particularly excellent in transparency, it has many uses as an optical material, and in recent years, it is also used for liquid crystal substrate films and retardation films for liquid crystal displays. However, in the film obtained from the polycarbonate resin from ordinary bisphenol A, the film used for the liquid crystal display particularly requires high-temperature treatment of 180 ° C. or more in the alignment film forming process or the electrode forming process, and the heat resistance is insufficient. There is a problem.
[0003]
In order to improve the heat resistance of the polycarbonate resin, there is generally a method using bisphenols having a bulky structure that is difficult to move, and various polycarbonates have been proposed. For example, JP-A-5-78467 proposes a polycarbonate resin mainly obtained from bisphenol having an adamantane structure, and JP-A-2-88634 proposes a polycarbonate resin based on a specific dihydroxydiphenylcycloalkane. ing. In addition, JP-A-11-174424, JP-A-8-134198, and JP-A-7-52270 propose a polycarbonate resin having a specific fluorene structure. However, although polycarbonate resins having these structures are excellent in heat resistance, they are not sufficient in terms of hue, are inferior in properties of stretched films, and have problems such as narrowing the viewing angle when used as retardation films. There is a need for improvement.
[0004]
[Problems to be solved by the invention]
The object of the present invention is, particularly when used as a film for a liquid crystal display, excellent in hue and transparency, excellent in stretched film characteristics, wide viewing angle, and excellent heat resistance that makes the color tone of achromatic display clear. Another object is to provide a polycarbonate copolymer.
[0005]
As a result of intensive research aimed at achieving this object, the present inventor has focused on the b value, which is an index of the hue of the film, and compared with a polycarbonate resin film obtained from a conventional fluorene copolymer, The inventors have found that by reducing the b value, the above-mentioned object such as improved stretched film characteristics can be achieved, and the present invention has been achieved.
[0006]
[Means for Solving the Problems]
That is, according to the present invention, 5 to 95 mol% of the wholly aromatic dihydroxy component is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 95 to 5 mol% is the following general formula [1].
[0007]
[Chemical formula 2]
[Wherein R 1 ~ R Four Each independently represents a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms, and W may contain a single bond or an aromatic group having 1 to 20 carbon atoms. Hydrocarbon group, O, S, SO, SO 2 , CO or COO groups. ]
A polycarbonate copolymer having a limiting viscosity in a methylene chloride solution at 20 ° C. in the range of 0.35 to 1.0, and formed from the polycarbonate copolymer A polycarbonate copolymer is provided in which the film has a b value measured with a C light source at a thickness of 0.2 mm of 1.3 or less.
[0009]
The aromatic polycarbonate copolymer of the present invention has 9,9-bis (4-hydroxy-3-methylphenyl) fluorene as an aromatic dihydroxy component constituting it, 5 to 95 mol% of the total aromatic dihydroxy component, Preferably it is 10-95 mol%, More preferably, it is 30-85 mol%. If it is less than 5 mol%, it is not preferable because it is an unsatisfactory property as a heat-resistant material which is the object of the present invention.
[0010]
The polycarbonate resin film formed from the aromatic polycarbonate copolymer of the present invention has a b value of a 0.2 mm-thick polycarbonate resin film measured with a C light source, which is standard light equivalent to daylight illumination with JIS standard spectral rays. 1.3 or less, preferably 1.0 or less, more preferably 0.5 or less. When the b value of the film exceeds 1.3, for example, when used as a liquid crystal film, the stretched film characteristics are inferior, the viewing angle becomes narrow, and the liquid crystal white color becomes unclear, which is not preferable. In addition, the polycarbonate resin film here includes both an unstretched film and a stretched film.
[0011]
The polycarbonate resin film whose b value is 1.3 or less is an aromatic polycarbonate copolymer using 9,9-bis (4-hydroxy-3-methylphenyl) fluorene obtained by removing impurities by performing a specific treatment. Can be obtained by a method of polymerizing the copolymer and forming a film of the copolymer, a method of polymerizing using a reaction solution deoxidized during the polymerization of the aromatic polycarbonate copolymer, and forming a film of the copolymer. it can. The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene used is usually obtained by the reaction of o-cresol and fluorenone.
[0012]
Specifically, as a method for removing impurities in 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, after the reaction of o-cresol and fluorenone, unreacted o-cresol was distilled off, A method is preferred in which the residue is dissolved in an alcohol-based, ketone-based or benzene derivative-based solvent, activated clay is added thereto and filtered, and then the product crystallized from the filtrate is filtered and purified. By this method, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene having a purity of 99.5% or more can be obtained. Examples of impurities to be removed include 2,4′-dihydroxy form, 2,2′-dihydroxy form and impurities whose structure is unknown.
[0013]
By using 9,9-bis (4-hydroxy-3-methylphenyl) fluorene having a purity of 99.5% or more, a polycarbonate copolymer with improved hue can be obtained, and the polycarbonate copolymer is formed from this polycarbonate copolymer. The polycarbonate resin film can achieve a b value of 1.3 or less. When 9,9-bis (4-hydroxy-3-methylphenyl) fluorene obtained by a usual method is used, a target polycarbonate resin film having a very small b value cannot be obtained.
[0014]
Alcohol solvents used for the purification of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene are lower alcohols such as methanol, ethanol, propanol and butanol, and ketone solvents are acetone, methyl ethyl ketone and methyl. Lower aliphatic ketones such as isopropyl ketone and cyclohexanone and mixtures thereof are preferred, and toluene, xylene, benzene and mixtures thereof are preferred as solvents for benzene derivatives. The amount of the solvent used is sufficient if the fluorene compound is sufficiently dissolved, and is usually about 2 to 10 times the amount of the fluorene compound. As the activated clay, a commercially available powdery or granular silica-alumina main component is used.
[0015]
Other dihydroxy components represented by the above general formula (1) used in the aromatic polycarbonate copolymer of the present invention may be those usually used as the dihydroxy component of the aromatic polycarbonate, such as hydroquinone and resorcinol. 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane (bisphenol E), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4- Hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4 Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, α, α'-bis (4-Hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, etc. are mentioned, among them bisphenol A, bisphenol Z, bisphenol C, bisphenol E Bisphenol M is preferred, and bisphenol A is particularly preferred.
[0016]
The aromatic polycarbonate copolymer of the present invention has an intrinsic viscosity at 20 ° C. in a solution of the polymer in methylene chloride of 0.35 to 1.0, preferably 0.50 to 0.80, 0.55 -0.80 is more preferable. If the intrinsic viscosity is less than 0.35, the strength of the molded article, particularly the film, becomes weak, and if it exceeds 1.0, the melt viscosity and the solution viscosity become high and handling becomes difficult.
[0017]
The aromatic polycarbonate copolymer of the present invention is produced by a reaction means known per se for producing an ordinary aromatic polycarbonate resin, for example, a method in which an aromatic dihydroxy component is reacted with a carbonate precursor such as phosgene or carbonic acid diester. . Next, basic means for these manufacturing methods will be briefly described.
[0018]
In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours.
[0019]
The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.
[0020]
In the aromatic polycarbonate copolymer of the present invention, monofunctional phenols that are usually used as a terminal terminator can be used in the polymerization reaction. Particularly in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminator for molecular weight control, and the resulting aromatic polycarbonate copolymer has a monofunctional end. Since it is blocked by a group based on phenols, it is superior in thermal stability compared to other groups.
[0021]
Such monofunctional phenols may be those used as an end stopper for aromatic polycarbonate resins, and are generally phenols or lower alkyl-substituted phenols, which are monofunctional compounds represented by the following general formula (2). Phenols can be indicated.
[0022]
[Chemical 3]
[Wherein, A is a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms or an arylalkyl group, and r is an integer of 1 to 5, preferably 1 to 3. ]
Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.
[0024]
Further, as other monofunctional phenols, phenols or benzoic acid chlorides having a long chain alkyl group or an aliphatic polyester group as a substituent, or long chain alkyl carboxylic acid chlorides can be used, When these are used to block the ends of the aromatic polycarbonate copolymers, they not only function as end terminators or molecular weight regulators, but also improve the melt fluidity of the resin and facilitate molding processes. The physical properties are also improved. In particular, it has the effect of reducing the water absorption rate of the resin and is preferably used. These are represented by the following general formulas [Ia] to [Ih].
[0025]
[Formula 4]
[Chemical formula 5]
[Chemical 6]
[Chemical 7]
[Chemical 8]
[Chemical 9]
[Chemical Formula 10]
Embedded image
[In the general formulas [Ia] to [Ih], X represents —RO—, —R—CO—O—, or —R—O—CO—, wherein R represents a single bond or A divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, T represents a single bond or a bond similar to the above X, and n represents an integer of 10 to 50.
Q represents a halogen atom or a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, p represents an integer of 0 to 4, Y represents 1 to 10 carbon atoms, preferably 1 to 1 carbon atoms. 5 represents a divalent aliphatic hydrocarbon group, W 1 Is a hydrogen atom, -CO-R 17 , -CO-O-R 18 Or R 19 Where R 17 , R 18 And R 19 Are each a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 8 carbon atoms, preferably 5 to 6 carbon atoms, or 6 to 6 carbon atoms. 15 represents a monovalent aromatic hydrocarbon group, preferably 6-12.
a represents an integer of 4 to 20, preferably 5 to 10, m represents an integer of 1 to 100, preferably 3 to 60, particularly preferably 4 to 50, and Z represents a single bond or a carbon number of 1 to 10, Preferably it represents a divalent aliphatic hydrocarbon group of 1 to 5, W 2 Is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 8 carbon atoms, preferably 5 to 6 carbon atoms, or 6 carbon atoms. -15, preferably 6-12 monovalent aromatic hydrocarbon groups. ]
Of these, the substituted phenols of [Ia] and [Ib] are preferable. As the substituted phenols of [Ia], those having n of 10 to 30, particularly 10 to 26 are preferable. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, and octadecyl. Phenol, eicosylphenol, docosylphenol and triacontylphenol can be mentioned.
[0034]
Further, as the substituted phenols of [Ib], those in which X is —R—CO—O— and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26 are suitable. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.
[0035]
In the substituted phenols or substituted benzoic acid chlorides represented by the general formulas [Ia] to [Ig], the position of the substituent is generally preferably p-position or o-position, and a mixture of both is preferable.
[0036]
The monofunctional phenols are desirably introduced into at least 5 mol%, preferably at least 10 mol% of the terminals of the obtained aromatic polycarbonate copolymer, and the monofunctional phenols are used alone. Or you may use it in mixture of 2 or more types.
[0037]
Further, in the aromatic polycarbonate copolymer of the present invention, when 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is 60 mol% or more of the total aromatic hydroxy component, the fluidity of the resin Therefore, it is preferable to use the substituted phenols or substituted benzoic acid chlorides represented by the above general formulas [Ia] to [Ig] as a terminal terminator.
[0038]
The aromatic polycarbonate copolymer of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the gist of the present invention is not impaired. . Moreover, the branched polycarbonate which copolymerized a small amount of trifunctional compounds may be sufficient.
[0039]
The aromatic polycarbonate copolymer of the present invention has a glass transition point of preferably 160 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. The glass transition point is preferably 250 ° C. or lower, more preferably 240 ° C. or lower, and further preferably 230 ° C. or lower.
[0040]
In the present invention, if necessary, the aromatic polycarbonate copolymer is blended with at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof. be able to. The amount of the phosphorus compound is preferably 0.0001 to 0.05% by weight, more preferably 0.0005 to 0.02% by weight, and 0.001 to 0.01 based on the aromatic polycarbonate copolymer. Weight percent is particularly preferred. By blending this phosphorus compound, the thermal stability of the aromatic polycarbonate copolymer is improved, and a decrease in molecular weight and a deterioration in hue during molding are prevented.
[0041]
The phosphorus compound is at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, and esters thereof, preferably the following general formula
[0042]
Embedded image
Embedded image
Embedded image
Embedded image
[Wherein R Five ~ R 16 Are each independently a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, etc. An alkyl group having 6 to 15 carbon atoms such as phenyl, tolyl or naphthyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl or phenethyl, and when two alkyl groups are present in one compound The two alkyl groups may be bonded to each other to form a ring. ]
At least one phosphorus compound selected from the group consisting of:
[0047]
Examples of the phosphorus compound represented by the above formula (3) include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, and trioctyl phosphite. , Trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentae Sri diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, and distearyl pentaerythritol phosphite.
[0048]
Examples of the phosphorus compound represented by the formula (4) include tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like (5 ) The phosphorus compound represented by the formula includes tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite, and the compound represented by the formula (6) Examples thereof include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
[0049]
Among these phosphorus compounds, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylene Phosphonite is preferably used.
[0050]
To the polycarbonate copolymer, an antioxidant generally known for the purpose of antioxidant can be added. Examples thereof include phenolic antioxidants. Specifically, for example, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6 -Hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl -4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4- Loxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3.9 -Bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5 5) Undecane etc. are mentioned. The range of preferable addition amount of these antioxidants is 0.0001 to 0.05% by weight with respect to the polycarbonate copolymer.
[0051]
Furthermore, a higher fatty acid ester of a monohydric or polyhydric alcohol can be added to the aromatic polycarbonate copolymer as necessary.
[0052]
The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Further, partial esters or total esters of such monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, propylene glycol. Examples thereof include monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate, among which stearic acid monoglyceride and pentaerythritol tetrastearate are preferably used. .
[0053]
The amount of ester of such alcohol and higher fatty acid is preferably 0.01 to 2% by weight, more preferably 0.015 to 0.5% by weight, more preferably 0.02 to 0.5% by weight based on the aromatic polycarbonate copolymer. More preferred is 0.2% by weight. If the blending amount is within this range, it is preferable that the release property is excellent and the release agent does not migrate and adhere to the metal surface.
[0054]
The aromatic polycarbonate copolymer further includes additives such as light stabilizers, colorants, antistatic agents, lubricants, fillers, other polycarbonate resins, and other thermoplastic resins within a range that does not impair the purpose of the present invention. Can also be added in small proportions.
[0055]
As a method for producing a film from the aromatic polycarbonate copolymer, a method excellent in thickness uniformity and free from optical defects such as gel, butts, fish eyes, and scratches is preferable. For example, a solvent casting method, a melt extrusion method, and the like. And calendar method. Especially, since the optical use for which the polycarbonate resin film formed from the polycarbonate copolymer of this invention is used suitably requires high uniformity, the casting method from a solution is employ | adopted preferably. As the casting method, generally, a casting method in which a solution is extruded from a die, a doctor knife method, or the like is preferably used. As the solvent, for example, organic solvents such as methylene chloride, dioxolane, toluene, dioxane, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are preferable. These may be one kind or a mixed solvent of two or more kinds. The liquid crystal display film is a thick film, and a high concentration solution having a solution concentration of 15% by weight or more, preferably 20% by weight or more is preferably used.
[0056]
Although the film thickness of an aromatic polycarbonate resin film may be selected according to a use, the range of 50-500 micrometers is preferable and the range of 80-300 micrometers is used more preferable. Within this range, sufficient retardation based on refractive index anisotropy is obtained in the retardation film, and a sufficiently stiff (rigid) film is obtained in the liquid crystal substrate film (placel substrate). Film formation is easy and preferable. Furthermore, the retardation film is preferred because the desired retardation can be obtained with good precision by stretching.
[0057]
In order to use a film produced by such a method as a retardation film, the film is stretched and oriented in at least a uniaxial direction so as to have an optimal birefringence characteristic to obtain a retardation film. As a uniaxial stretching method, an arbitrary method such as a lateral uniaxial stretching by a tenter method, a longitudinal uniaxial stretching between rolls, or an inter-roll rolling method can be used. The stretching temperature is preferably a glass transition temperature (Tg) of the resin to be used of −50 ° C. or higher and Tg + 20 ° C. or lower, more preferably Tg−30 ° C. or higher and Tg + 10 ° C. or lower. By stretching at a temperature in such a range, it is preferable that uniform orientation is facilitated without freezing the movement of the polymer molecules, and that the molecular motion of the polymer is moderate and the orientation is not easily relaxed by stretching. It is preferable because the degree of orientation can be easily obtained and the orientation can be easily suppressed.
[0058]
Further, the draw ratio may be appropriately selected according to the target retardation of the film. This value also depends on the stretching temperature and the film thickness. In general, the stretch ratio may be small for a thick film, and large for a thin film. The retardation value of the retardation plate used in the STN type liquid crystal display is generally 100 to 1200 nm, preferably 150 to 650 nm. Furthermore, the fluctuation width of the retardation is preferably 10% or less, particularly preferably 5% or less. When the fluctuation width of the retardation becomes too large, a deviation in color compensation occurs and color unevenness is likely to occur.
[0059]
The retardation film is preferably used as a composite deflecting plate after forming a barrier layer and a transparent electrode for liquid crystal targeting indium and tin oxide, and then laminating on the deflecting plate. This composite deflecting plate can be formed by laminating a single layer or multiple layers of an optical axis of a normal deflecting plate and an optical axis of a retardation film in the range of 40 to 50 degrees. This composite deflection plate has excellent characteristics such as excellent heat resistance and little change in retardation with time.
[0060]
One of the stretched film characteristics is a K value defined by the product of the average value of the refractive indices nx and ny in the in-plane direction of the film and the refractive index nz in the thickness direction and the film thickness t (nm) = | (Nx + ny) / 2−nz | × t. When the K value is increased, the viewing angle becomes narrower when the display is used as a liquid crystal display element. Therefore, this value is preferably 80 nm or less. Is preferably suppressed to 75 nm or less.
[0061]
In addition, a liquid crystal display panel in which a deflector is disposed on one or both sides of a liquid crystal cell eliminates coloring due to birefringence of the liquid crystal by arranging the retardation film between the deflector on the viewing surface side and the liquid crystal cell. A monochrome display liquid crystal display panel can be formed. Further, a full color liquid crystal display panel can be formed by covering the monochrome display liquid crystal panel with a color mask to develop three colors of RGB.
[0062]
The polycarbonate resin film formed from the polycarbonate copolymer of the present invention is excellent in heat resistance, strength and hue, and has good stretched film properties. A gas barrier film and a solvent-resistant film are attached to both sides of this film, or transparent. It is suitably used as a liquid crystal display film such as a liquid crystal substrate film (placel substrate) or a retardation film together with a conductive film and a polarizing plate, particularly as a retardation film application. Specifically, a pager, a mobile phone, a handy terminal, It can be advantageously used for various display elements.
[0063]
【Example】
The following examples further illustrate the present invention. In addition, the part in an Example is a weight part and% is weight%. The evaluation was based on the following method.
(1) Monomer purity: 10 mg of sample was dissolved in 10 ml of acetonitrile, and HPLC analysis was performed at a wavelength of 254 nm with a solvent of acetonitrile / water = 6/4 using a Tosoh Corporation TSK-GEL ODS-80TM column. .
(2) Intrinsic viscosity: The polymer was dissolved in methylene chloride and measured at a temperature of 20 ° C.
(3) Glass transition point (Tg): measured by DuPont 910 DSC.
(4) b value of the film: The film having a thickness of 0.2 mm obtained in the examples was measured with a C light source using a Hitachi U-3000 spectrophotometer.
(5) Total light transmittance: Measured by Nippon Denshoku Sigma 80 in accordance with ASTM D-1003.
(6) K value: It was determined by measuring the refractive index in the stretching direction, the right-angle direction, and the thickness direction at a wavelength of 550 nm using KOBRA 21ADH manufactured by Oji Paper Co., Ltd.
[0064]
[Example 1]
In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 152400 parts of ion-exchanged water and 84320 parts of 25% aqueous sodium hydroxide solution were added, and 9,9-bis (4-hydroxy-3 having a purity of 99.8% by HPLC analysis. -Methylphenyl) fluorene (hereinafter sometimes abbreviated as “biscresol fluorene”) 34848 parts, 2,2-bis (4-hydroxyphenyl) propane 9008 parts (hereinafter sometimes abbreviated as “bisphenol A”) and After dissolving 88 parts of hydrosulfite, 178400 parts of methylene chloride was added, and 18248 parts of phosgene was blown in at a temperature of 15 to 25 ° C. with stirring for 60 minutes. After completion of the phosgene blowing, a solution obtained by dissolving 177.8 parts of p-tert-butylphenol in 2640 parts of methylene chloride and 10560 parts of 25% aqueous sodium hydroxide solution were added. After emulsification, 32 parts of triethylamine was added and the mixture was heated at 28 to 33 ° C. The reaction was terminated by stirring for a period of time. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, the methylene chloride phase is concentrated and dehydrated to remove polycarbonate. A solution with a concentration of 20% was obtained. The polycarbonate obtained by removing the solvent from this solution had a molar ratio of biscresol fluorene to bisphenol A of 70:30 (polymer yield 97%). This polymer had an intrinsic viscosity of 0.674 and a Tg of 226 ° C.
[0065]
This polycarbonate solution is cast on a stainless steel plate moving from a T die at 20 ° C., and methylene chloride is evaporated while gradually raising the temperature. The methylene chloride is peeled off from the stainless steel plate and further heated to remove methylene chloride. A film having a thickness of 200 μm was obtained. Casting film-forming property was good. The b value of this film was 0.5, and the total light transmittance was 90%. This film was uniaxially stretched at a stretching ratio of 2.0 at 226 ° C. by a tenter method. The stretched film had a preferred K value of 71. A barrier layer and a transparent electrode for liquid crystal were sputtered on this uniaxially stretched film, and then adhered to one side of the deflecting plate with an adhesive so that the optical axis was 45 degrees to obtain a composite deflecting plate. This was then used by being bonded between the liquid crystal cell of the STN liquid crystal display device and the upper deflection plate, and a black and white display with a wide viewing angle, a white background color, and a black display color was obtained. Moreover, a clear full color display was obtained by covering the upper portion with a color filter and displaying the RGB cells in black and white gray density.
[0066]
[Example 2]
In the same manner as in Example 1 except that the amount of biscresol fluorene used in Example 1 is 29760 parts and the amount of bisphenol A used is 12000 parts, the ratio of the structural units of biscresol fluorene and bisphenol A is in molar ratio. A 20% polymer solution 60:40 was obtained (polymer yield 98%). This polymer had an intrinsic viscosity of 0.707 and a Tg of 217 ° C. A 200 μm thick film was obtained from this polycarbonate solution in the same manner as in Example 1. Casting film-forming property was good. The b value of this film was 0.5, and the total light transmittance was 90%. This film was uniaxially stretched at a stretching ratio of 2.0 at 217 ° C. by the tenter method. The stretched film had a preferred K value of 72. When this film was subjected to liquid crystal display in the same manner as in Example 1, a clear full color display with a wide viewing angle was obtained.
[0067]
[Comparative Example 1]
Using the same reactor as in Example 1, a 20% polycarbonate solution (polymer yield: 98%) was obtained in the same manner as in Example 1 except that biscresol fluorene having an HPLC purity of 99.0% was used. This polymer had an intrinsic viscosity of 0.672 and a Tg of 225 ° C. A 200 μm thick film was obtained from this polycarbonate solution in the same manner as in Example 1. The b value of this film was 2.1, and the total light transmittance was 88%. When this film was uniaxially stretched at 225 ° C. and a draw ratio of 2.0 by the tenter method, the K value was slightly increased to 85. When this film was subjected to liquid crystal display in the same manner as in Example 1, the viewing angle was narrowed, the white display was slightly yellowish, the hue was not compensated sufficiently, and color misregistration occurred, resulting in a slightly reddish color tone. It was. Further, the color display has a color shift and bleeding, and a clear full color display could not be performed.
[0068]
[Comparative Example 2]
A 20% polycarbonate solution (polymer yield 98%) was obtained in the same manner as in Example 1 except that 49.4 parts of p-tert-butylphenol of Example 1 was used. The intrinsic viscosity of this product was as high as 1.133, the solution viscosity was high, the casting film-forming property was poor, and a good film could not be obtained.
[0069]
【The invention's effect】
The polycarbonate copolymer of the present invention is excellent in hue, transparency and heat resistance, and has good stretched film properties. A film formed from this polycarbonate copolymer is used for a liquid crystal display such as a plastic substrate and a retardation film. When used as a film, the viewing angle is wide and the color tone of achromatic display becomes clear, and it is suitably used for these applications.
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| JP2001378482A JP3643555B2 (en) | 2001-12-12 | 2001-12-12 | Polycarbonate copolymer |
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| JP2004099754A (en) * | 2002-09-10 | 2004-04-02 | Teijin Ltd | Optical film |
| JP2005060628A (en) * | 2003-08-20 | 2005-03-10 | Teijin Chem Ltd | Polycarbonate resin having excellent reflow resistance |
| WO2007074892A1 (en) * | 2005-12-26 | 2007-07-05 | Teijin Limited | Transparent film |
| FR3056458B1 (en) | 2016-09-23 | 2019-04-12 | Reydel Automotive Bv | SHUTTER COMPONENT DEVICE FOR AERATION PIPE |
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| JPH06145331A (en) * | 1992-11-02 | 1994-05-24 | Teijin Chem Ltd | Production of aromatic polycarbonate |
| JP3475972B2 (en) * | 1994-11-14 | 2003-12-10 | 三菱瓦斯化学株式会社 | Polycarbonate resin for wet molding |
| JPH1045655A (en) * | 1996-07-30 | 1998-02-17 | Taoka Chem Co Ltd | Production of fluorene derivative |
| JPH1045656A (en) * | 1996-07-30 | 1998-02-17 | Taoka Chem Co Ltd | Production of fluorene derivative |
| JPH1135815A (en) * | 1997-07-15 | 1999-02-09 | Teijin Chem Ltd | Polycarbonate composition |
| JPH1180529A (en) * | 1997-09-10 | 1999-03-26 | Teijin Chem Ltd | Flame-retardant polycarbonate composition |
| JPH11174424A (en) * | 1997-12-11 | 1999-07-02 | Teijin Ltd | Substrate for liquid crystal display panel |
| KR100602815B1 (en) * | 1998-10-30 | 2006-07-19 | 데이진 가부시키가이샤 | Phase difference film and optical device using it |
| JP2000347170A (en) * | 1999-06-09 | 2000-12-15 | Teijin Ltd | Substrate for liquid crystal display panel |
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