JP2005082677A - Manufacturing process for polycarbonate resin - Google Patents
Manufacturing process for polycarbonate resin Download PDFInfo
- Publication number
- JP2005082677A JP2005082677A JP2003315229A JP2003315229A JP2005082677A JP 2005082677 A JP2005082677 A JP 2005082677A JP 2003315229 A JP2003315229 A JP 2003315229A JP 2003315229 A JP2003315229 A JP 2003315229A JP 2005082677 A JP2005082677 A JP 2005082677A
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- JP
- Japan
- Prior art keywords
- polycarbonate resin
- bis
- aromatic
- parts
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 34
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 40
- 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 abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 claims description 13
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound 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 10
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000000746 purification Methods 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
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 abstract description 27
- 239000004417 polycarbonate Substances 0.000 abstract description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- -1 amine compound Chemical class 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 150000002989 phenols Chemical class 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 11
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920003002 synthetic resin Polymers 0.000 description 8
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000002952 polymeric resin Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 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
- 239000003963 antioxidant agent Substances 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 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 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- SFDGJDBLYNJMFI-UHFFFAOYSA-N 3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC=NC2=C1 SFDGJDBLYNJMFI-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 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 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000005273 aeration Methods 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000008346 aqueous phase Substances 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
- 238000000748 compression moulding Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 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
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 2
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-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
- 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
- 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
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 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
- 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
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 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
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent 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
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 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
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000001678 irradiating effect Effects 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
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 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
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000013307 optical fiber Substances 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
- 239000012071 phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 238000005476 soldering Methods 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
- 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
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-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
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-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
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-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
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-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
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IFYFNVDTVZKNBZ-UHFFFAOYSA-N tetradecyl 2-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1O IFYFNVDTVZKNBZ-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- HTCCWYQPPPBLQT-UHFFFAOYSA-N triacontyl 2-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1O HTCCWYQPPPBLQT-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
本発明は、ポリカーボネート樹脂の製造方法に関する。さらに詳しくは実質的に酸素不在下でホスゲン化反応及び重合反応を行うことにより、優れた色相のポリカーボネート樹脂を得ることを目的とするポリカーボネート樹脂の製造方法に関する。 The present invention relates to a method for producing a polycarbonate resin. More specifically, the present invention relates to a method for producing a polycarbonate resin which is intended to obtain a polycarbonate resin having an excellent hue by performing a phosgenation reaction and a polymerization reaction substantially in the absence of oxygen.
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が、近年、加工成形品の軽薄短小化が進み、更なる耐熱性、剛性の向上したポリカーボネート樹脂が求められている。 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. 2. Description of the Related Art In recent years, the light and thin size of processed molded articles has progressed, and a polycarbonate resin having further improved heat resistance and rigidity has been demanded.
ポリカーボネート樹脂の耐熱性、剛性を向上するためには、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樹脂が提案されている。中でも、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（例えば特許文献１，２参照）。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ホスゲン化反応及び重合反応中に著しく着色しやすく、したがって成形品の色相が黄色味を帯びるという問題があった。これを解決する手法として、ポリマー溶液に可視光を照射する方法（特許文献３参照）や、ポリマー溶液に金属不活性化剤及び／又は活性水素含有化合物を添加する方法（特許文献４参照）が提案されているが、これらは溶液色や流延法により作成するフィルムの色相を改善することはできても、熱履歴を与えるような成形法（射出成形法、圧縮成形法、溶融押出法など）にて成形体を作成した場合、上記改善法を用いても成形体の色相を改善することはできなかった。 In order to improve the heat resistance and rigidity of the polycarbonate resin, there is generally a method using bisphenols having a bulky structure that is difficult to move, and various polycarbonate resins have been proposed. Among them, a polycarbonate resin having a specific fluorene structure has been proposed (see, for example, Patent Documents 1 and 2). However, the polycarbonate resin having these structures is remarkably easily colored during the phosgenation reaction and the polymerization reaction, and thus there is a problem that the hue of the molded product is yellowish. Methods for solving this include a method of irradiating a polymer solution with visible light (see Patent Document 3) and a method of adding a metal deactivator and / or an active hydrogen-containing compound to the polymer solution (see Patent Document 4). Although proposed, these can improve the color of the film produced by solution color and casting method, but can be used to form a thermal history (injection molding method, compression molding method, melt extrusion method, etc.) ), The hue of the molded body could not be improved even using the above improvement method.
本発明の目的は、優れた耐熱性、剛性を持ち、且つ色相の良好なポリカーボネート樹脂の製造方法を提供することにある。色相が良好であることは、樹脂をレンズ、プリズム及び光ファイバーなどの光路変換部品、リフローハンダ付け部品、光ディスクなどの光学部材に用いる為には好ましい。また、樹脂に任意の色を付与するうえでも好ましい。 An object of the present invention is to provide a method for producing a polycarbonate resin having excellent heat resistance, rigidity and good hue. Good hue is preferable for using the resin for optical path conversion parts such as lenses, prisms and optical fibers, reflow soldering parts, and optical members such as optical disks. Moreover, it is preferable also when giving arbitrary colors to resin.
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、特定の二価フェノールを使用してポリカーボネート共重合体を製造する際、ホスゲン化反応及び重合反応を実質的に酸素不在下で行うことによって、上記目的を達成することを見出し、本発明に到達した。 As a result of intensive research aimed at achieving this object, the present inventor conducted a phosgenation reaction and a polymerization reaction substantially in the absence of oxygen when producing a polycarbonate copolymer using a specific dihydric phenol. As a result, the inventors have found that the above object can be achieved, and have reached the present invention.
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％が下記一般式［１］、 That is, according to the present invention, 5 to 95 mol% of the wholly aromatic dihydroxy component is represented by the following general formula [1],
で表されるジヒドロキシ成分からなるポリカーボネート樹脂の製造方法であって、ホスゲン化反応及び重合反応を実質的に酸素不在下で行うことを特徴とするポリカーボネート樹脂の製造方法が提供される。
A method for producing a polycarbonate resin comprising a dihydroxy component represented by the formula: wherein the phosgenation reaction and the polymerization reaction are carried out substantially in the absence of oxygen.
この製造法を用いることにより該ポリカーボネート樹脂５ｇを塩化メチレン５０ｍｌに遮光状態にて溶解した溶液のｂ値が５．０以下であるポリカーボネート共重合体の製造、提供が可能となる。なお、溶液のｂ値は４．０以下であることがより好ましく、３．５以下が最も好ましい。また、このポリカーボネート共重合体を用いて成形した場合色相の良好な成形品を得ることができる。この成形品のＹＩ値は厚さ２ｍｍの見本板で測定した場合、６．０以下であることが好ましい。なお、このＹＩ値は４．５以下がより好ましく、３．５以下が最も好ましい。ＹＩ値が６．０より大きい場合、色相が悪く、光学成形品として用いることが困難となる。 By using this production method, it is possible to produce and provide a polycarbonate copolymer having a b value of 5.0 or less in a solution obtained by dissolving 5 g of the polycarbonate resin in 50 ml of methylene chloride in a light-shielded state. The b value of the solution is more preferably 4.0 or less, and most preferably 3.5 or less. Moreover, when it shape | molds using this polycarbonate copolymer, a molded article with a favorable hue can be obtained. The YI value of this molded product is preferably 6.0 or less when measured with a sample plate having a thickness of 2 mm. The YI value is more preferably 4.5 or less, and most preferably 3.5 or less. When the YI value is larger than 6.0, the hue is bad and it is difficult to use as an optical molded product.
本発明のポリカーボネート共重合体の製造方法は、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などのカーボネート前駆物質を反応させる方法と同じであるが、ホスゲン化反応および重合反応において実質的に酸素を存在させない事が必要である。 The production method of the polycarbonate copolymer of the present invention is the same as a reaction means known per se for producing a normal aromatic polycarbonate resin, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene. It is necessary that substantially no oxygen is present in the phosgenation reaction and the polymerization reaction.
「実質的に酸素を存在させない」とは、系内の気相および液相に酸素を存在させないことを意味し、例えば気相および液相の酸素濃度が０．５ｐｐｍ以下、好ましくは０．２ｐｐｍ以下、更に好ましくは０．１ｐｐｍ以下であることを意味する。 “Substantially no oxygen” means that no oxygen is present in the gas phase and liquid phase in the system. For example, the oxygen concentration in the gas phase and liquid phase is 0.5 ppm or less, preferably 0.2 ppm. Hereinafter, it means more preferably 0.1 ppm or less.
以下に本発明の目的である、優れた耐熱性、剛性を持ち、且つ色相の良好なポリカーボネート樹脂の製造方法について基本的な手段を簡単に説明する。 The basic means of the method for producing a polycarbonate resin having excellent heat resistance, rigidity and good hue, which is the object of the present invention, will be briefly described below.
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。この時、これらの溶媒は、使用する前に窒素等を吹き込む手法及び還元剤を添加する手法又はその両方の手法で溶媒中の酸素を除いておくことことにより色相の良好なポリカーボネート樹脂の製造が可能となる。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。反応の際にも、窒素を吹き込む手法やハイドロサルファイトのような還元剤を添加することで反応溶液中の酸素を常に除いておくことにより、さらに色相の良好なポリカーボネート樹脂の製造が可能となる。また、反応槽に窒素シール等を施し、酸素の侵入を防止する事も重要である。さらにその後の精製工程も窒素雰囲気下において実施することも色相改善には効果がある。 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. At this time, these solvents can be used to produce a polycarbonate resin having a good hue by removing oxygen in the solvent by blowing nitrogen or the like and / or adding a reducing agent before use. It becomes possible. 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. Even during the reaction, it is possible to produce a polycarbonate resin with a better hue by always removing oxygen in the reaction solution by adding a reducing agent such as a method of blowing nitrogen or hydrosulfite. . It is also important to prevent the invasion of oxygen by applying a nitrogen seal or the like to the reaction tank. Furthermore, the subsequent purification step is also effective in improving the hue by performing it in a nitrogen atmosphere.
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、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン成分を用いる目的の一つである耐熱用材料としての特性が不満足なものとなり好ましくない。 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%, the properties as a heat-resistant material, which is one of the purposes of using the 9,9-bis (4-hydroxy-3-methylphenyl) fluorene component, are unsatisfactory.
前記９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンは、その１０ｇをエタノール５０ｍｌに溶解した溶液を光路長３０ｍｍで測定したｂ値が好ましくは６．０以下、より好ましくは５．５以下であり、さらに好ましくは５．０以下である。ｂ値が上記範囲内であれば、得られるポリカーボネート共重合体から形成される成形体は色相および強度が高く、延伸フィルム特性も良好となり好ましい。 The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene has a b value of preferably 6.0 or less, more preferably 5. measured by measuring a solution of 10 g in 50 ml of ethanol at an optical path length of 30 mm. 5 or less, more preferably 5.0 or less. When the b value is within the above range, a molded product formed from the obtained polycarbonate copolymer has a high hue and strength, and a stretched film property is also preferable.
通常、この９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンはｏ−クレゾールとフルオレノンの反応によって得られる。前記特定のｂ値を有する９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンは、特定の処理を行い不純物を除去することによって得ることができる。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、これに活性白土または活性炭を加えてろ過後、ろ液から結晶化した生成物をろ過して精製された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。かかる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。また、活性炭としては市販されている粉末状または粒状のものが用いられる。 The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is usually obtained by the reaction of o-cresol and fluorenone. The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene having the specific b value can be obtained by performing a specific treatment to remove impurities. Specifically, after the reaction between o-cresol and fluorenone, unreacted o-cresol is distilled off, and the residue is dissolved in an alcohol, ketone, or benzene derivative solvent, and activated clay or activated carbon is added thereto. In addition, after filtration, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene purified by filtering the product crystallized from the filtrate can be obtained. Examples of impurities to be removed include 2,4′-dihydroxy form, 2,2′-dihydroxy form and impurities whose structure is unknown. The alcohol solvent used for such purification is preferably a lower alcohol such as methanol, ethanol, propanol or butanol, and the ketone solvent is preferably a lower aliphatic ketone such as acetone, methyl ethyl ketone, methyl isopropyl ketone or cyclohexanone and a mixture thereof. As the benzene derivative solvent, toluene, xylene, benzene and a mixture thereof are preferable. 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. Further, as the activated carbon, commercially available powdery or granular materials are used.
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[２]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、４，４′−（ｐ−フェニレンジイソプロピリデン）ジフェノール、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。 The other dihydroxy component represented by the above general formula [2] used in the aromatic polycarbonate copolymer of the present invention may be any one that is usually used as a dihydroxy component of an aromatic polycarbonate. For example, hydroquinone, 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- Droxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, α, α'-bis ( 4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, and the like. Among them, bisphenol A, bisphenol Z, bisphenol C, bisphenol E, Bisphenol M is preferred, and bisphenol A is particularly preferred.
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℃における比粘度が０.２〜１．２の範囲が好ましく、０.２５〜１．０の範囲がより好ましく、０.２７〜０．８０の範囲がさらに好ましい。比粘度が上記範囲内であれば成形品、殊にシートの強度が十分強く、溶融粘度および溶液粘度が適当で、取り扱いが容易であり好ましい。 The aromatic polycarbonate copolymer preferably has a specific viscosity at 20 ° C. in a solution of the polymer in methylene chloride in the range of 0.2 to 1.2, more preferably in the range of 0.25 to 1.0. The range of .27 to 0.80 is more preferable. If the specific viscosity is within the above range, the strength of the molded product, particularly the sheet, is sufficiently strong, the melt viscosity and the solution viscosity are appropriate, and handling is easy and preferable.
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。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。 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. In the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as end terminators for molecular weight control, and the resulting aromatic polycarbonate copolymer has monofunctional phenols terminated. Since it is blocked by a group based on, it is superior in thermal stability as compared to those not.
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、下記一般式で表される単官能フェノール類を示すことができる。 Such monofunctional phenols only need to be used as a terminal terminator for aromatic polycarbonate resins, and are generally phenols or lower alkyl-substituted phenols, and monofunctional phenols represented by the following general formula: Can show.
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。 Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.
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。 Further, as other monofunctional phenols, phenols or benzoic acid chlorides having a long chain alkyl group or an aliphatic ester 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].
［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。］
[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 is a divalent aliphatic hydrocarbon group, W 1 is a hydrogen atom, —CO—R 17 , —CO—O—R 18 or R 19 , wherein R 17 , R 18 and R 19 are 1 to 10 carbon atoms, preferably 1 to 5 monovalent aliphatic hydrocarbon groups, 4 to 8 carbon atoms, preferably 5 to 6 monovalent alicyclic hydrocarbon groups or 6 to 15 carbon atoms, respectively. Preferably 6-12 monovalent | monohydric aromatic hydrocarbon group is shown.
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 an 1-5 divalent aliphatic hydrocarbon group, W 2 is a hydrogen atom, C1-10, preferably 1 to 5 monovalent aliphatic hydrocarbon group, having 4 to 8 carbon atoms, Preferably, it represents a monovalent alicyclic hydrocarbon group having 5 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, preferably 6 to 12 carbon atoms. ]
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。 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.
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。 Further, as the substituted phenols of [Ib], compounds 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. Specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.
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。 In the substituted phenols or substituted benzoic acid chlorides represented by the above general formulas [Ia] to [Ig], the position of the substituent is generally preferably the p-position or the o-position, and a mixture of both is preferable.
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。 The monofunctional phenols are desirably introduced into at least 5 mol%, preferably at least 10 mol% of the terminals of the resulting aromatic polycarbonate copolymer, and the monofunctional phenols are used alone. Or you may use it in mixture of 2 or more types.
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。 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.
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。 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.
本発明の芳香族ポリカーボネート共重合体は、そのガラス転移温度が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。 The aromatic polycarbonate copolymer of the present invention has a glass transition temperature of preferably 160 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher.
本発明の芳香族ポリカーボネート樹脂には、離型剤、蛍光増白剤、熱安定剤、酸化防止剤、紫外線吸収剤、着色剤、帯電防止剤、抗菌剤等改質改良剤を適宜添加して用いることができる。 To the aromatic polycarbonate resin of the present invention, a modifying agent such as a mold release agent, a fluorescent brightening agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a coloring agent, an antistatic agent, an antibacterial agent, and the like are appropriately added. Can be used.
本発明において使用される蛍光増白剤は、合成樹脂等の色調を白色あるいは青白色に改善するために用いられるものであれば特に制限はなく、例えばスチルベン系、ベンズイミダゾール系、ナフタルイミド系、ローダミン系、クマリン系、オキサジン系化合物等が挙げられる。 The fluorescent whitening agent used in the present invention is not particularly limited as long as it is used for improving the color tone of a synthetic resin to white or bluish white, for example, stilbene, benzimidazole, naphthalimide, Examples include rhodamine-based, coumarin-based, and oxazine-based compounds.
本発明で用いられる紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤、トリアジン系紫外線吸収剤、ベンゾオキサジン系紫外線吸収剤またはベンゾフェノン系紫外線吸収剤が使用される。 As the ultraviolet absorber used in the present invention, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, a benzoxazine-based ultraviolet absorber, or a benzophenone-based ultraviolet absorber is used.
ベンゾトリアゾール系紫外線吸収剤としては、例えば２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’−（３，４，５，６−テトラヒドロフタルイミドメチル）−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔｅｒｔ−オクチルフェニル）ベンゾトリアゾール、２−（３’−ｔｅｒｔ−ブチル−５’−メチル−２’−ヒドロキシフェニル）−５−クロロベンゾトリアゾール、２，２’−メチレンビス（４−（１，１，３，３−テトラメチルブチル）−６−（２Ｈ−ベンゾトリアゾール−２−イル）フェノール）、２−（２’−ヒドロキシ−３’，５’−ビス（α，α−ジメチルベンジル）フェニル）−２Ｈ−ベンゾトリアゾール、２−（３’，５’−ジ−ｔｅｒｔ−アミル−２’−ヒドロキシフェニル）ベンゾトリアゾール、５−トリフルオロメチル−２−（２−ヒドロキシ−３−（４−メトキシ−α−クミル）−５−ｔｅｒｔ−ブチルフェニル）−２Ｈ−ベンゾトリアゾール等が挙げられる。 Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′-(3,4,5,6-tetrahydrophthalimidomethyl). ) -5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) ) Benzotriazole, 2- (3'-tert-butyl-5'-methyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis (4- (1,1,3,3- Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3 ', 5'-bi) (Α, α-dimethylbenzyl) phenyl) -2H-benzotriazole, 2- (3 ′, 5′-di-tert-amyl-2′-hydroxyphenyl) benzotriazole, 5-trifluoromethyl-2- (2 -Hydroxy-3- (4-methoxy-α-cumyl) -5-tert-butylphenyl) -2H-benzotriazole and the like.
なかでも２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’−（３，４，５，６−テトラヒドロフタルイミドメチル）−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔｅｒｔ−オクチルフェニル）ベンゾトリアゾール、２−（３’−ｔｅｒｔ−ブチル−５’−メチル−２’−ヒドロキシフェニル）−５−クロロベンゾトリアゾールが好ましく、更に２−（２’−ヒドロキシ−５’−ｔｅｒｔ−オクチルフェニル）ベンゾトリアゾールが好ましい。 Among them, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′-(3,4,5,6-tetrahydrophthalimidomethyl) -5′-methylphenyl) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3 '-Tert-butyl-5'-methyl-2'-hydroxyphenyl) -5-chlorobenzotriazole is preferred, and 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole is more preferred.
トリアジン系の紫外線吸収剤としては、ヒドロキシフェニルトリアジン系の例えば商品名チヌビン４００（チバスペシャルティーケミカル社製）が好ましい。 As the triazine-based ultraviolet absorber, hydroxyphenyltriazine-based, for example, trade name Tinuvin 400 (manufactured by Ciba Specialty Chemicals) is preferable.
ベンゾオキサジン系の紫外線吸収剤としては、２−メチル−３，１−ベンゾオキサジン−４−オン、２−ブチル−３，１−ベンゾオキサジン−４−オン、２−フェニル−３，１−ベンゾオキサジン−４−オン、２−（１−又は２−ナフチル）−３，１−ベンゾオキサジン−４−オン、２−（４−ビフェニル）−３，１−ベンゾオキサジン−４−オン、２，２’−ビス（３，１−ベンゾオキサジン−４−オン）、２，２’−ｐ−フェニレンビス（３，１−ベンゾオキサジン−４−オン、２，２’−ｍ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）、２，２’−（４，４’−ジフェニレン）ビス（３，１−ベンゾオキサジン−４−オン）、２，２’−（２，６又は１，５−ナフタレン）ビス（３，１−ベンゾオキサジン−４−オン）、１，３，５−トリス（３，１−ベンゾオキサジン−４−オン−２−イル）ベンゼンなどが挙げられるが、中でも２，２’−ｐ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）が好ましい。 Examples of the benzoxazine-based ultraviolet absorber include 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazine-4-one, 2-phenyl-3,1-benzoxazine -4-one, 2- (1- or 2-naphthyl) -3,1-benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzoxazin-4-one, 2,2 ′ -Bis (3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (3,1-benzoxazin-4-one, 2,2'-m-phenylenebis (3,1- Benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6 or 1,5-naphthalene) ) Bis (3,1-benzoxazin-4-one) 1,3,5-tris (3,1-benzoxazin-4-on-2-yl) benzene and the like, among others, 2,2′-p-phenylenebis (3,1-benzoxazine-4- ON) is preferred.
ベンゾフェノン系紫外線吸収剤としては、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−２’−カルボキシベンゾフェノン、２，４−ジヒドロキシベンゾフェノン、２，２’−ジヒドロキシ−４−メトキシベンゾフェノン等が挙げられ、なかでも２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノンが好ましい。これらの紫外線吸収剤は単独で用いても、二種以上併用してもよい。 Examples of the benzophenone ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and the like can be mentioned, among which 2-hydroxy-4-n-octoxybenzophenone is preferable. These ultraviolet absorbers may be used alone or in combination of two or more.
これらの紫外線吸収剤は、ポリカーボネート樹脂と紫外線吸収剤との合計量を１００重量％として０．０１〜５重量％であり、好ましくは０．０２〜３重量％であり、特に好ましくは０．０５〜２重量％である。０．０１重量％未満では紫外線吸収性能が不十分で、５重量％を超えると樹脂の色相が悪化することがあるので好ましくない。 These ultraviolet absorbers are 0.01 to 5% by weight, preferably 0.02 to 3% by weight, particularly preferably 0.05, based on 100% by weight of the total amount of the polycarbonate resin and the ultraviolet absorber. ~ 2% by weight. If it is less than 0.01% by weight, the ultraviolet absorption performance is insufficient, and if it exceeds 5% by weight, the hue of the resin may be deteriorated.
本発明では、ブルーイング剤を用いてもよく、かかるブルーイング剤としては、例えばバイエル（株）製のマクロレックスバイオレット、三菱化学（株）製のダイアレジンバイオレット、ダイアレジンブルー、サンド（株）製のテラゾールブルー等が挙げられ、最も好適なものとしてマクロレックスバイオレットが挙げられる。これらのブルーイング剤は好ましくは０．１〜３ｐｐｍ、より好ましくは０．３〜１．５ｐｐｍ、最も好ましくは０．３〜１．２ｐｐｍの濃度で芳香族ポリカーボネート樹脂中に配合される。 In the present invention, a bluing agent may be used. Examples of such a bluing agent include Macrolex Violet manufactured by Bayer Co., Ltd., Dialresin Violet manufactured by Mitsubishi Chemical Co., Ltd., Dial Resin Blue, Sand Co., Ltd. Terazole blue and the like are available, and the most suitable is macrolex violet. These bluing agents are preferably incorporated into the aromatic polycarbonate resin at a concentration of 0.1 to 3 ppm, more preferably 0.3 to 1.5 ppm, and most preferably 0.3 to 1.2 ppm.
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。 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.
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 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
［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。
[Wherein, R 5 to R 16 are each independently a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl. Represents an alkyl group having 1 to 20 carbon atoms such as octadecyl, an aryl group having 6 to 15 carbon atoms such as phenyl, tolyl and naphthyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl and phenethyl; In the case where two alkyl groups are present, 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:
上記（１）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。 Examples of the phosphorus compound represented by the formula (1) 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.
上記（２）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（３）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（４）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。 Examples of the phosphorus compound represented by the formula (2) include tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like (3 ) The phosphorus compound represented by the formula includes tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite, and the compound represented by the formula (4) Examples thereof include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
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。 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.
本発明の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。 To the polycarbonate copolymer of the present invention, 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.
さらに本発明の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。 Furthermore, a higher fatty acid ester of a monohydric or polyhydric alcohol can be added to the aromatic polycarbonate copolymer of the present invention as necessary.
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。 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. .
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。 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.
本発明の芳香族ポリカーボネート共重合体には、さらに滑剤、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。 In the aromatic polycarbonate copolymer of the present invention, additives such as lubricants and fillers, other polycarbonate resins, and other thermoplastic resins may be added in a small amount within a range not impairing the object of the present invention.
本発明の芳香族ポリカーボネート樹脂組成物から成形品を得る方法としては、射出成形、押出成形、圧縮成形、射出圧縮成形、ブロー成形等が用いられ、フィルムやシート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、例えば溶融押出し法、カレンダー法等が挙げられる。 As a method for obtaining a molded product from the aromatic polycarbonate resin composition of the present invention, injection molding, extrusion molding, compression molding, injection compression molding, blow molding or the like is used. A method that is excellent in uniformity and that does not cause optical defects such as gels, brats, fish eyes, and scratches is preferred, and examples thereof include a melt extrusion method and a calendar method.
かかる方法により製造された成形品は色相が良好であり、その上耐熱性、剛性が高いため、ソリが少なく、色調の優れた光学成形品に好適に用いられる。 A molded product produced by such a method has a good hue, and also has high heat resistance and rigidity. Therefore, the molded product is suitably used for an optical molded product with little warpage and excellent color tone.
本発明の製造方法によれば、優れた耐熱性、剛性を持ち、且つ色相の良好なポリカーボネート樹脂の製造、及び提供することが可能となる。色相が良好であることは、樹脂をレンズ、プリズム及び光ファイバーなどの光路変換部品、リフローハンダ付け部品、光ディスクなどの光学部材に用いる為には好ましい。また、樹脂に任意の色を付与するうえでも好ましい。従って本発明がもたらす工業的効果は格別である。 According to the production method of the present invention, it is possible to produce and provide a polycarbonate resin having excellent heat resistance, rigidity and good hue. Good hue is preferable for using the resin for optical path conversion parts such as lenses, prisms and optical fibers, reflow soldering parts, and optical members such as optical disks. Moreover, it is preferable also when giving arbitrary colors to resin. Therefore, the industrial effect brought about by the present invention is exceptional.
以下に実施例を挙げて本発明をさらに説明する。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）比粘度：ポリマー０．７ｇを塩化メチレン１００ｍｌに溶解し２０℃の温度で測定した。
（２）ガラス転移温度（Ｔｇ）：ティー・エイ・インスツルメント・ジャパン（株）社製２９１０型ＤＳＣを使用し、昇温速度２０℃／ｍｉｎにて測定した。
（３）ＢＣＦモノマー溶液ｂ値：試料１０ｇを５０ｍｌのエタノールに溶解し光路長３０ｍｍの試料管にて日本電色（株）色差計３００Ａを用いて測定した。
（４）ポリマー溶液ｂ値：ポリカーボネート共重合体５ｇを塩化メチレン５０ｍｌに遮光状態にて溶解し、光路長３０ｍｍの試料管にて日本電色（株）色差計３００Ａを用いて測定した。
（５）成形品ＹＩ値：ＪＳＷ（株）製Ｎ−２０Ｃ射出成形機を用いて、表１に示すシリンダ温度及び金型温度にて、厚さ２ｍｍの見本板を射出成形により作成した。この見本板の黄色度（ＹＩ）を日本電色（株）製分光色彩計ＳＥ−２０００（光源：Ｃ／２）を用いて測定した。
The following examples further illustrate the present invention. The part in an Example is a weight part and% is weight%. The evaluation was based on the following method.
(1) Specific viscosity: 0.7 g of polymer was dissolved in 100 ml of methylene chloride and measured at a temperature of 20 ° C.
(2) Glass transition temperature (Tg): Measured at a heating rate of 20 ° C./min using a 2910 type DSC manufactured by TA Instruments Japan Co., Ltd.
(3) BCF monomer solution b value: 10 g of a sample was dissolved in 50 ml of ethanol and measured with a color difference meter 300A by Nippon Denshoku Co., Ltd. in a sample tube having an optical path length of 30 mm.
(4) Polymer solution b value: 5 g of the polycarbonate copolymer was dissolved in 50 ml of methylene chloride in a light-shielded state, and measured using a Nippon Denshoku Co., Ltd. color difference meter 300A in a sample tube having an optical path length of 30 mm.
(5) Molded product YI value: Using a N-20C injection molding machine manufactured by JSW, a sample plate having a thickness of 2 mm was prepared by injection molding at the cylinder temperature and the mold temperature shown in Table 1. The yellowness (YI) of this sample plate was measured using a spectrocolorimeter SE-2000 (light source: C / 2) manufactured by Nippon Denshoku Co., Ltd.
［実施例１］
温度計、撹拌機、ベント付き反応器にイオン交換水２１５４０部、４８％水酸化ナトリウム水溶液４９３０部を入れ、窒素で３０分間バブリングを行った後、エタノール溶液でのｂ値が３．０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“ＢＣＦ”と略称することがある）３２３１部、２，２−ビス（４−ヒドロキシフェニル）プロパン（以下“ＢＰＡ”と略称することがある）１９４９部およびハイドロサルファイト１５部を溶解し、塩化メチレン１４５３０部を加えた後、窒素気流下、撹拌しながら１５〜２５℃でホスゲン２２００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１１５．４部および４８％水酸化ナトリウム水溶液７０５部を加え、乳化後、トリエチルアミン５．９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、窒素気流下にて水洗した後、塩酸酸性にして水洗し、水相の導電率がイオン交換水とほぼ同じになったところで、ニーダーにて塩化メチレンを蒸発して、ＢＣＦとＢＰＡの比がモル比で５０：５０の比粘度が０.２８２、Ｔｇが１９５℃である白色のポリマー５４６０部を得た（収率９５％）。
[Example 1]
In a thermometer, stirrer, and vented reactor, 21540 parts of ion-exchanged water and 4930 parts of 48% aqueous sodium hydroxide solution were bubbled with nitrogen for 30 minutes, and the b value in an ethanol solution was 3.0. , 9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) 3231 parts, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “BPA”) 1949 parts and 15 parts of hydrosulfite were dissolved, 14530 parts of methylene chloride was added, and 2200 parts of phosgene was blown in at a temperature of 15 to 25 ° C. for 60 minutes with stirring under a nitrogen stream. After completion of phosgene blowing, 115.4 parts of p-tert-butylphenol and 705 parts of 48% aqueous sodium hydroxide solution were added. After emulsification, 5.9 parts of triethylamine was added and stirred at 28-33 ° C. for 1 hour to complete the reaction. did. After completion of the reaction, the product was diluted with methylene chloride, washed with water in a nitrogen stream, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, The methylene chloride was evaporated to obtain 5460 parts of a white polymer having a BCF to BPA ratio of 50:50, a specific viscosity of 0.282, and a Tg of 195 ° C. (yield 95%).
このポリカーボネート樹脂粉粒体に、トリス（２,４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト０．０５０％、オクタデシル−３−（３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネートを０.０１０％、ペンタエリスリトールテトラステアレートを０．０３０％加えて、ベント付きφ３０ｍｍ単軸押出機を用いてペレット化し、これを用いて成形品を作成した。評価結果を表１に示す。 Tris (2,4-di-tert-butylphenyl) phosphite 0.050% and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate were added to the polycarbonate resin granules. 0.010% and 0.030% of pentaerythritol tetrastearate were added and pelletized using a vented φ30 mm single screw extruder, and a molded product was prepared using this. The evaluation results are shown in Table 1.
［実施例２］
実施例１のＢＣＦの使用量を１２９２部、ＢＰＡの使用量を３１１８部、ｐ−ｔｅｒｔ−ブチルフェノールの使用量を１０２．６部とする以外は実施例１と同様にしてＢＣＦとＢＰＡの比がモル比で２０：８０である白色のポリマー４７７０部（収率９６％）を得た。このポリマーの比粘度は０．３７０、Ｔｇは１７０℃であった。このポリマー樹脂粉粒体を実施例１と同様にしてペレット化し、これを用いて成形品を作成した。結果を表１に示す。
[Example 2]
The ratio of BCF to BPA is the same as in Example 1 except that the amount of BCF used in Example 1 is 1292 parts, the amount of BPA used is 3118 parts, and the amount of p-tert-butylphenol used is 102.6 parts. 4770 parts (yield 96%) of a white polymer having a molar ratio of 20:80 were obtained. This polymer had a specific viscosity of 0.370 and a Tg of 170 ° C. This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this. The results are shown in Table 1.
［実施例３］
実施例１のＢＣＦの使用量を４５２３部、ＢＰＡの使用量を１１６９部、ｐ−ｔｅｒｔ−ブチルフェノールの使用量を１２８．２部とする以外は実施例１と同様にしてＢＣＦとＢＰＡの比がモル比で７０：３０であるポリマー５８４０部（収率９３％）を得た。この白色のポリマーの比粘度は０．２５８、Ｔｇは２１３℃であった。このポリマー樹脂粉粒体を実施例１と同様にしてペレット化し、これを用いて成形品を作成した。結果を表１に示す。
[Example 3]
The ratio of BCF to BPA is the same as in Example 1 except that the amount of BCF used in Example 1 is 4523 parts, the amount of BPA used is 1169 parts, and the amount of p-tert-butylphenol used is 128.2 parts. 5840 parts (yield 93%) of polymer with a molar ratio of 70:30 were obtained. The white polymer had a specific viscosity of 0.258 and Tg of 213 ° C. This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this. The results are shown in Table 1.
［実施例４］
実施例１のハイドロサルファイトの使用量を５０部とする以外は実施例１と同様にしてＢＣＦとＢＰＡの比がモル比で５０：５０である白色のポリマー５６５０部（収率９８％）を得た。このポリマーの比粘度は０．２８０、Ｔｇは１９５℃であった。このポリマー樹脂粉粒体を実施例１と同様にしてペレット化し、これを用いて成形品を作成した。結果を表１に示す。
[Example 4]
5650 parts of white polymer (yield 98%) having a molar ratio of BCF to BPA of 50:50 in the same manner as in Example 1 except that the amount of hydrosulfite used in Example 1 was 50 parts. Obtained. This polymer had a specific viscosity of 0.280 and a Tg of 195 ° C. This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this. The results are shown in Table 1.
［実施例５］
実施例１と同様の装置にイオン交換水３２３２０部、４８％水酸化ナトリウム４３２０部を入れ、窒素で３０分間バブリングを行った後、ＢＣＦ２８２８部、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（以下“ＢＰＭ”と略称することがある）２５８９部およびハイドロサルファイト１３部を溶解し、塩化メチレン１２７２０部を加えた後、窒素気流下、撹拌しながら１５〜２０℃でホスゲン２０００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１１２．２部と４８％水酸化ナトリウム水溶液６１７部を加え乳化後、トリエチルアミン３．８部を加えて、２８〜３３℃で１時間攪拌して反応を終了した。このものを実施例１と同様に処理してＢＣＦとＢＰＭ構成単位のモル比が５０：５０である白色のポリマー５４５０を得た（収率９２％）。このポリマーの比粘度は０．２８５、Ｔｇは１７８℃であった。このポリマー樹脂粉粒体を実施例１と同様にしてペレット化し、これを用いて成形品を作成した。結果を表１に示す。
[Example 5]
32320 parts of ion-exchanged water and 4320 parts of 48% sodium hydroxide were put in the same apparatus as in Example 1, and after bubbling with nitrogen for 30 minutes, 2828 parts of BCF, α, α′-bis (4-hydroxyphenyl)- 2589 parts of m-diisopropylbenzene (hereinafter sometimes abbreviated as “BPM”) and 13 parts of hydrosulfite are dissolved, 12720 parts of methylene chloride are added, and phosgene is added at 15 to 20 ° C. with stirring under a nitrogen stream. 2000 parts were blown in 60 minutes. After completion of phosgene blowing, 112.2 parts of p-tert-butylphenol and 617 parts of 48% aqueous sodium hydroxide solution were added to emulsify, and 3.8 parts of triethylamine was added, followed by stirring at 28 to 33 ° C. for 1 hour to complete the reaction. did. This was treated in the same manner as in Example 1 to obtain a white polymer 5450 having a molar ratio of BCF to BPM constitutional unit of 50:50 (yield 92%). This polymer had a specific viscosity of 0.285 and a Tg of 178 ° C. This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this. The results are shown in Table 1.
［比較例１］
実施例１と同様の装置にイオン交換水２１５４０部、４８％水酸化ナトリウム水溶液４９３０部を入れ、窒素でのバブリングは行わず、エタノール溶液でのｂ値が３．０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“ＢＣＦ”と略称することがある）３２３１部、２，２−ビス（４−ヒドロキシフェニル）プロパン（以下“ＢＰＡ”と略称することがある）１９４９部およびハイドロサルファイト１５部を溶解し、塩化メチレン１４５３０部を加えた後、窒素通気は行わず、撹拌しながら１５〜２５℃でホスゲン２２００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１１５．４部および４８％水酸化ナトリウム水溶液７０５部を加え、乳化後、トリエチルアミン５．９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、窒素通気は行わない状態で水洗した後、塩酸酸性にして水洗し、水相の導電率がイオン交換水とほぼ同じになったところで、ニーダーにて塩化メチレンを蒸発して、ＢＣＦとＢＰＡの比がモル比で５０：５０の比粘度が０.２７８、Ｔｇが１９５℃である黄白色のポリマー５２９０部を得た（収率９０％）。このポリマー樹脂粉粒体を実施例１と同様にしてペレット化し、これを用いて成形品を作成した。結果を表１に示す。
[Comparative Example 1]
In the same apparatus as in Example 1, 21540 parts of ion-exchanged water and 4930 parts of 48% sodium hydroxide aqueous solution were added, and bubbling with nitrogen was not performed. 4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as “BCF”) 3231 parts, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “BPA”) 1949 And 15 parts of hydrosulfite were dissolved, 14530 parts of methylene chloride was added, and nitrogen aeration was not performed, but 2200 parts of phosgene was blown in at 15 to 25 ° C. for 60 minutes with stirring. After completion of phosgene blowing, 115.4 parts of p-tert-butylphenol and 705 parts of 48% aqueous sodium hydroxide solution were added. After emulsification, 5.9 parts of triethylamine was added and stirred at 28-33 ° C. for 1 hour to complete the reaction. did. After completion of the reaction, the product was diluted with methylene chloride, washed with water without nitrogen aeration, then acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, a kneader was used. To obtain 5290 parts of a yellowish white polymer having a BCF to BPA molar ratio of 50:50, a specific viscosity of 0.278, and a Tg of 195 ° C. (90% yield). . This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this. The results are shown in Table 1.
［比較例２］
比較例１にて作成したポリカーボネート樹脂の塩化メチレン溶液に４００Ｗの高圧水銀灯（（株）日立ライティング製）（主波長３５０〜５００ｎｍ）を１時間照射し、溶液の黄色味が退色した後、ニーダーにて塩化メチレンを蒸発して、ＢＣＦとＢＰＡの比がモル比で５０：５０の比粘度が０.２７８、Ｔｇが１９５℃である白色のポリマーを得た。このポリマー樹脂粉粒体を実施例１と同様にしてペレット化し、これを用いて成形品を作成した。結果を表１に示す。
[Comparative Example 2]
After irradiating the methylene chloride solution of the polycarbonate resin prepared in Comparative Example 1 with a 400 W high-pressure mercury lamp (manufactured by Hitachi Lighting Co., Ltd.) (main wavelength: 350 to 500 nm) for 1 hour, The methylene chloride was evaporated to obtain a white polymer having a molar ratio of BCF to BPA of 50:50, a specific viscosity of 0.278, and a Tg of 195 ° C. This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this. The results are shown in Table 1.
［比較例３］
実施例１と同様の装置にイオン交換水３２３２０部、４８％水酸化ナトリウム４３２０部を入れ、窒素でのバブリングは行わず、ＢＣＦ２８２８部、ＢＰＭ２５８９部およびハイドロサルファイト１３部を溶解し、塩化メチレン１２７２０部を加えた後、窒素通気は行わず、撹拌しながら１５〜２０℃でホスゲン２０００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１１２．２部と４８％水酸化ナトリウム水溶液６１７部を加え乳化後、トリエチルアミン３．８部を加えて、２８〜３３℃で１時間攪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、窒素通気は行わない状態で水洗した後、塩酸酸性にして水洗し、水相の導電率がイオン交換水とほぼ同じになったところに、ニーダーにて塩化メチレンを蒸発して、ＢＣＦとＢＰＭ構成単位のモル比が５０：５０である黄白色のポリマー５４４０部を得た。このポリマーを塩化メチレン２１７６０部に再度溶解し、これにメタノール２７２部を加え攪拌し、溶液の黄色味が退色した後、ニーダーにて塩化メチレンを蒸発して、白色のポリマー５０３０部を得た（収率８５％）。このポリマーの比粘度は０．２８７、Ｔｇは１７８℃であった。このポリマー樹脂粉粒体を実施例１と同様にしてペレット化し、これを用いて成形品を作成した。結果を表１に示す。
[Comparative Example 3]
32320 parts of ion-exchanged water and 4320 parts of 48% sodium hydroxide were placed in the same apparatus as in Example 1, and bubbling with nitrogen was not performed, but 2828 parts of BCF, 2589 parts of BPM and 13 parts of hydrosulfite were dissolved, and methylene chloride 12720 After adding a part, nitrogen aeration was not performed but 2000 parts of phosgene was blown in for 15 minutes at 15 to 20 ° C. with stirring. After completion of phosgene blowing, 112.2 parts of p-tert-butylphenol and 617 parts of 48% aqueous sodium hydroxide solution were added to emulsify, and 3.8 parts of triethylamine was added, followed by stirring at 28 to 33 ° C. for 1 hour to complete the reaction. did. After completion of the reaction, the product was diluted with methylene chloride, washed with water without carrying out nitrogen bubbling, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, The methylene chloride was evaporated with a kneader to obtain 5440 parts of a yellowish white polymer having a molar ratio of BCF to BPM constitutional unit of 50:50. This polymer was dissolved again in 21760 parts of methylene chloride, and 272 parts of methanol was added thereto and stirred. After the yellow color of the solution faded, the methylene chloride was evaporated with a kneader to obtain 5030 parts of a white polymer ( Yield 85%). This polymer had a specific viscosity of 0.287 and a Tg of 178 ° C. This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this. The results are shown in Table 1.
Claims (7)
で表されるジヒドロキシ成分からなるポリカーボネート樹脂の製造方法であって、ホスゲン化反応及び重合反応を実質的に酸素不在下で行うことを特徴とするポリカーボネート樹脂の製造方法。 5 to 95 mol% of the total aromatic dihydroxy component is represented by the following general formula [1],
A process for producing a polycarbonate resin comprising a dihydroxy component represented by formula (1), wherein the phosgenation reaction and the polymerization reaction are carried out substantially in the absence of oxygen.
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| JP2003315229A JP2005082677A (en) | 2003-09-08 | 2003-09-08 | Manufacturing process for polycarbonate resin |
| TW92131783A TWI315320B (en) | 2002-11-14 | 2003-11-13 | Polycarbonate copolymer, resin composition and molded article |
| AU2003280769A AU2003280769B2 (en) | 2002-11-14 | 2003-11-13 | Polycarbonate copolymer, resin composition, and molded article |
| EP20030772737 EP1566396B1 (en) | 2002-11-14 | 2003-11-13 | Polycarbonate copolymer, resin composition, and molded article |
| CA 2505969 CA2505969C (en) | 2002-11-14 | 2003-11-13 | Polycarbonate copolymer, resin composition, and molded article |
| KR1020057008566A KR100956048B1 (en) | 2002-11-14 | 2003-11-13 | Polycarbonate copolymer, resin composition, and molded article |
| US10/534,706 US7244804B2 (en) | 2002-11-14 | 2003-11-13 | Polycarbonate copolymer, resin composition, and molded article |
| PCT/JP2003/014458 WO2004044033A1 (en) | 2002-11-14 | 2003-11-13 | Polycarbonate copolymer, resin composition, and molded article |
| DE60333218T DE60333218D1 (en) | 2002-11-14 | 2003-11-13 | POLYCARBONATE COPOLYMER, RESIN COMPOSITION AND FORM BODY |
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| WO2008050669A1 (en) | 2006-10-18 | 2008-05-02 | Idemitsu Kosan Co., Ltd. | Polycarbonate copolymer, method for producing the same, molded body, optical material, and electrophotographic photosensitive body |
| WO2017159727A1 (en) * | 2016-03-15 | 2017-09-21 | 出光興産株式会社 | Polycarbonate resin, method for producing polycarbonate resin, coating liquid, electrophotographic photoreceptor, and electrophotography device |
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| WO2008050669A1 (en) | 2006-10-18 | 2008-05-02 | Idemitsu Kosan Co., Ltd. | Polycarbonate copolymer, method for producing the same, molded body, optical material, and electrophotographic photosensitive body |
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| WO2017159727A1 (en) * | 2016-03-15 | 2017-09-21 | 出光興産株式会社 | Polycarbonate resin, method for producing polycarbonate resin, coating liquid, electrophotographic photoreceptor, and electrophotography device |
| CN108779238A (en) * | 2016-03-15 | 2018-11-09 | 出光兴产株式会社 | Polycarbonate resin, method for producing polycarbonate resin, coating liquid, electrophotographic photoreceptor, and electrophotographic apparatus |
| US10787541B2 (en) | 2016-03-15 | 2020-09-29 | Idemitsu Kosan Co., Ltd. | Polycarbonate resin, method for producing polycarbonate resin, coating liquid, electrophotographic photoreceptor, and electrophotography device |
| CN108779238B (en) * | 2016-03-15 | 2021-10-29 | 出光兴产株式会社 | Polycarbonate resin, method for producing polycarbonate resin, coating liquid, electrophotographic photoreceptor, and electrophotographic apparatus |
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