JP2005171051A - Optical member and aromatic polycarbonate resin suitable for producing the same - Google Patents
Optical member and aromatic polycarbonate resin suitable for producing the same Download PDFInfo
- Publication number
- JP2005171051A JP2005171051A JP2003411738A JP2003411738A JP2005171051A JP 2005171051 A JP2005171051 A JP 2005171051A JP 2003411738 A JP2003411738 A JP 2003411738A JP 2003411738 A JP2003411738 A JP 2003411738A JP 2005171051 A JP2005171051 A JP 2005171051A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- polycarbonate resin
- optical member
- aromatic polycarbonate
- 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.)
- Pending
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 64
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 52
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 52
- 230000003287 optical effect Effects 0.000 title claims abstract description 32
- 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 32
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 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 abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 5
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 150000002430 hydrocarbons Chemical group 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 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 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 238000002493 microarray Methods 0.000 claims description 2
- 239000013307 optical fiber Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims 1
- 238000005476 soldering Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 9
- 230000006866 deterioration Effects 0.000 abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- -1 (4-hydroxy) Phenyl Chemical group 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- 150000002989 phenols Chemical class 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 10
- 230000007547 defect Effects 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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 239000000047 product 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
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 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 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 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 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- 150000004650 carbonic acid diesters Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 230000007935 neutral effect Effects 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
- 239000012071 phase Substances 0.000 description 4
- 238000005406 washing Methods 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
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 238000002835 absorbance Methods 0.000 description 3
- 230000003078 antioxidant effect 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
- 238000007664 blowing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000748 compression moulding Methods 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
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- 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
- 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
- 230000005540 biological transmission Effects 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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 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
- 239000003480 eluent Substances 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
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- 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
- 239000002244 precipitate Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000000746 purification Methods 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
- 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
- 238000002834 transmittance Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-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
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- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 description 1
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- 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 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
- 238000010992 reflux Methods 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
- 230000000630 rising effect Effects 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 239000007787 solid Substances 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
- 229920003002 synthetic resin Polymers 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
Abstract
Description
本発明は、芳香族ポリカーボネート樹脂より成形されたレンズなどの光学部材に関する。さらに詳しくは、連続成形時に成形品の表面精度の悪化が少なく、優れた耐熱性、剛性を有し、かつ色相が改善された芳香族ポリカーボネート樹脂より形成されたレンズなどの光学部材に関する。 The present invention relates to an optical member such as a lens molded from an aromatic polycarbonate resin. More specifically, the present invention relates to an optical member such as a lens formed from an aromatic polycarbonate resin which has little deterioration in surface accuracy of a molded product during continuous molding, excellent heat resistance and rigidity, and improved hue.
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部材としての用途も多く、レンズ、ミラー等の用途に使用されている。
しかし、熱源に接近して使用するレンズやＬＥＤ用レンズ等の耐熱性の必要な用途には従来のポリカーボネート樹脂では耐熱性に問題があった。
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 member, and is used for applications such as lenses and mirrors.
However, conventional polycarbonate resins have a problem in heat resistance for applications requiring heat resistance such as lenses used close to heat sources and lenses for LEDs.
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。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おり、レンズ用途等にも使用されている。（例えば特許文献１〜３参照）。
しかし、これらの樹脂を使用し、連続成形した場合、成形品の表面精度が悪化し、問題となる場合があるため、これらの問題点を解決する方法が求められている。
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. Among them, a polycarbonate resin having a specific fluorene structure has been proposed and used for lens applications and the like. (For example, see Patent Documents 1 to 3).
However, when these resins are used and continuously molded, the surface accuracy of the molded product may be deteriorated, which may be a problem. Therefore, a method for solving these problems is required.
本発明の目的は、連続成形時に成形品の表面精度の悪化が少なく、優れた耐熱性、剛性を持ち、且つ色相が改善された特定構造の芳香族ポリカーボネート樹脂より形成されたレンズなどの光学部材を提供することにある。 An object of the present invention is to provide an optical member such as a lens made of an aromatic polycarbonate resin having a specific structure that has little deterioration in surface accuracy of a molded product during continuous molding, has excellent heat resistance and rigidity, and has improved hue. Is to provide.
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合成した芳香族ポリカーボネート樹脂に含まれる本文中に定義された方法によって測定されたオリゴマーおよびモノマーの含有率を特定量以下に制御することによって、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 has found that oligomers and monomers measured by the method defined in the text contained in aromatic polycarbonate resins synthesized using specific dihydric phenols. The inventors have found that the above object can be achieved by controlling the content to a specific amount or less, and have reached the present invention.
すなわち、本発明によれば、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 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芳香族ポリカーボネート樹脂であって、本文中に定義された方法によって測定されたオリゴマーおよびモノマーの含有率が０．８％以下であることを特徴とする芳香族ポリカーボネート樹脂より形成されるそれへの入射光線とそれからの出射光線とが、その光路において変化を賦与されるような透明樹脂製光学部材が提供される。
An aromatic polycarbonate resin comprising a dihydroxy component represented by the following formula, wherein the content of oligomers and monomers measured by the method defined in the text is 0.8% or less: A transparent resin optical member is provided in which the incident light beam formed thereon and the light beam emitted therefrom are subjected to a change in the optical path.
本発明の成形品には、オリゴマーおよびモノマー含有率が０．８％以下、好ましくは０．７％以下、特に好ましくは０．６％以下である芳香族ポリカーボネート樹脂が好適に使用される。オリゴマーおよびモノマー含有率が０．７％、殊に０．８％を越えると、連続成形時に成形品の表面精度が悪化するので望ましくなく、表面精度の悪化はオリゴマーおよびモノマーの含有率が多くなる程顕著になる傾向がある。 オリゴマーおよびモノマーは、前記した含有率以下であればよく、その値を満足する限り、少割合含有されているのが好ましい。０.１％以上、好ましくは０.１５％以上の少割合の含有率でオリゴマーおよびモノマーが存在すると、それ以下のものと比べて溶融流動性が向上し、表面精度が良化する。そのため、特に好ましくはオリゴマーおよびモノマー含有率は０．１５〜０．６％の範囲である。なお、このオリゴマーおよびモノマー含有率の値は下記方法により測定された値である。すなわち、東ソー（株）製、ＴＳＫｇｅｌＧ２０００ＨＸＬとＧ３０００ＨＸＬカラム各１本づつ直列に繋いで溶離液としてクロロホルムを用い、流量０.７ｍｌ／分で安定化した後、該ポリカーボネート樹脂のクロロホルム溶液を注入する方法を用い、それにより得られた波長２５４ｎｍの光源で検出したＧＰＣチャートのリテンションタイムが１９分以降のピーク面積の合計の全ピーク面積に対する割合をオリゴマーおよびモノマー含有率とした。 For the molded article of the present invention, an aromatic polycarbonate resin having an oligomer and monomer content of 0.8% or less, preferably 0.7% or less, particularly preferably 0.6% or less is suitably used. If the oligomer and monomer content exceeds 0.7%, especially 0.8%, the surface accuracy of the molded product deteriorates during continuous molding, which is undesirable. The deterioration in surface accuracy increases the content of oligomers and monomers. There is a tendency to become more prominent. The oligomer and the monomer may be contained in a small proportion as long as the content is less than the above-described content, and as long as the value is satisfied. When the oligomer and the monomer are present in a small content of 0.1% or more, preferably 0.15% or more, the melt fluidity is improved and the surface accuracy is improved as compared with the content less than that. Therefore, the oligomer and monomer content is particularly preferably in the range of 0.15 to 0.6%. In addition, the value of this oligomer and monomer content rate is the value measured by the following method. That is, a method in which a TSKgel G2000HXL column and a G3000HXL column, manufactured by Tosoh Corporation, are connected in series one by one with chloroform as an eluent, stabilized at a flow rate of 0.7 ml / min, and then injected with a chloroform solution of the polycarbonate resin. The ratio of the total peak area with a retention time of 19 minutes or later for the retention time of the GPC chart detected with the light source having a wavelength of 254 nm obtained thereby was defined as the oligomer and monomer content.
本発明の芳香族ポリカーボネート樹脂は、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。 In the aromatic polycarbonate resin of the present invention, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene as an aromatic dihydroxy component constituting the aromatic polycarbonate resin is preferably 5-95 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.
本発明の芳香族ポリカーボネート樹脂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 resin 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-hydroxy) Phenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydride) Xylphenyl) -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, etc., among which bisphenol A, bisphenol Z, bisphenol C, bisphenol E, bisphenol M And bisphenol A is particularly preferable.
本発明の芳香族ポリカーボネート樹脂は、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。 The aromatic polycarbonate resin of the present invention is produced by a reaction means known per se for producing an ordinary aromatic polycarbonate resin, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. Next, basic means for these manufacturing methods will be briefly described.
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。ただし、本発明の芳香族ポリカーボネート樹脂を作成するためには、反応工程、精製工程および造粒工程において下記の方法が好ましく採用される。 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. 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. However, in order to prepare the aromatic polycarbonate resin of the present invention, the following methods are preferably employed in the reaction step, the purification step and the granulation step.
かかる反応工程においてはホスゲン仕込み終了後の反応液を、水相に含まれるモノマーの含有量が特定量以下になるまで撹拌した後に、末端停止剤および触媒を加えることが好ましい。このホスゲン仕込み終了後の反応液はそのまま撹拌を継続しても、一度静置して水相と有機相に分離した後に再度撹拌してもよい。また末端停止剤および触媒を加えるのは、水相を紫外分光光度計にて光路長１ｃｍで測定した２９０〜２９５ｎｍにおける吸光度の値が１．０以下になってからが好ましい。 In such a reaction step, it is preferable to add a terminal terminator and a catalyst after stirring the reaction solution after the completion of phosgene charging until the content of the monomer contained in the aqueous phase is a specific amount or less. The reaction solution after completion of the phosgene charge may be continuously stirred, or may be allowed to stand once and separated into an aqueous phase and an organic phase, and then stirred again. Further, the end terminator and the catalyst are preferably added after the absorbance value at 290 to 295 nm of the aqueous phase measured with an ultraviolet spectrophotometer at an optical path length of 1 cm becomes 1.0 or less.
かかる精製工程においては反応液から水相を除去した後、再度アルカリ水溶液にて水洗することが好ましい。この場合のアルカリ水溶液はｐＨ１２〜１４が好ましい。 In such a purification step, it is preferable that the aqueous phase is removed from the reaction solution and then washed again with an aqueous alkaline solution. In this case, the alkaline aqueous solution is preferably pH 12-14.
かかる造粒工程においては水洗工程で精製された有機相に、貧溶媒または非溶媒を加えることによりポリマーを沈殿させるか、または温水に有機相を滴下し溶媒を除去するなどの他の方法で得られたポリマー固形物から、貧溶媒または非溶媒で抽出することにより低分子量物を除去することが好ましい。かかる貧溶媒または非溶媒にはメタノール、エタノール、イソプロパノール、アセトン、メチルエチルケトン、ヘキサン、ヘプタンなどが好ましい。これらは単独で用いても二種以上混合して用いてもよい。 In such a granulation step, the polymer is precipitated by adding a poor solvent or a non-solvent to the organic phase purified in the water washing step, or obtained by another method such as dropping the organic phase into warm water to remove the solvent. It is preferable to remove low molecular weight substances from the resulting polymer solid by extraction with a poor solvent or a non-solvent. As such a poor solvent or non-solvent, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, hexane, heptane and the like are preferable. These may be used alone or in combination of two or more.
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。 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.
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。 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.
本発明の芳香族ポリカーボネート樹脂は、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樹脂は、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 resin of the present invention, monofunctional phenols which 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 controlling the molecular weight, and the resulting aromatic polycarbonate resin has a terminal monofunctional phenol. Since it is blocked by a group based on, it is superior in thermal stability 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樹脂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 end of an aromatic polycarbonate resin, they not only function as a terminal terminator or molecular weight regulator, but also improve the melt fluidity of the resin and facilitate molding, as well as physical properties. Will also be 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樹脂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 total terminal of the obtained aromatic polycarbonate resin. You may mix and use seeds or more.
また、本発明の芳香族ポリカーボネート樹脂において、９,９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンが、全芳香族ジヒドロキシ成分の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。 In the aromatic polycarbonate resin of the present invention, when 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is 60 mol% or more of the total aromatic dihydroxy component, the fluidity of the resin is lowered. 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樹脂は、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 resin 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、例えばスチルべン系、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。蛍光増白剤の配合量は、本発明の芳香族ポリカーボネート樹脂１００重量部に対して、０．０００５〜０．１重量部、好ましくは０．００１〜０．０５重量部、さらに好ましくは０．００５〜０．０２重量部である。配合量が０．０００５重量部より少ないと、十分な色調の改良効果が得られず、０．１重量部を超えると、かえって色調のムラが生じて好ましくない。また、コスト高にもなる。 The fluorescent brightener 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 , Rhodamine-based, coumarin-based, and oxazine-based compounds. The compounding amount of the optical brightener is 0.0005 to 0.1 parts by weight, preferably 0.001 to 0.05 parts by weight, and more preferably 0.000 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin of the present invention. 005 to 0.02 parts by weight. If the blending amount is less than 0.0005 parts by weight, a sufficient effect of improving the color tone cannot be obtained. In addition, the cost is increased.
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、芳香族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, based on the total amount of the aromatic polycarbonate resin and the ultraviolet absorber as 100% by weight. 0.05 to 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 blended in an aromatic polycarbonate resin 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樹脂に必要に応じて、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樹脂に対して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樹脂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 resin may contain at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof. it can. 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% by weight based on the aromatic polycarbonate resin. Is particularly preferred. By blending this phosphorus compound, the thermal stability of the aromatic polycarbonate resin 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
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。
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.
本発明の芳香族ポリカーボネート樹脂には、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芳香族ポリカーボネート樹脂に対して０．０００１〜０．０５重量％である。 To the aromatic polycarbonate resin 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 the preferable addition amount of these antioxidants is 0.0001 to 0.05% by weight with respect to the aromatic polycarbonate resin.
さらに本発明の芳香族ポリカーボネート樹脂には、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, higher fatty acid esters of mono- or polyhydric alcohols can be added to the aromatic polycarbonate resin 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樹脂に対して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 the ester of alcohol and higher fatty acid is preferably 0.01 to 2% by weight, more preferably 0.015 to 0.5% by weight, and 0.02 to 0.02% by weight based on the aromatic polycarbonate resin. 2% by weight is more preferred. 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樹脂には、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 resin of the present invention, additives such as lubricants and fillers, other polycarbonate resins, and other thermoplastic resins may be added in a small proportion 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は、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。 In the aromatic polycarbonate resin of the present invention, the specific viscosity at 20 ° C. in a solution dissolved in methylene chloride is preferably in the range of 0.2 to 1.2, more preferably in the range of 0.25 to 1.0, and A 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樹脂は、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 resin 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.
本発明のポリカーボネート樹脂の色相、すなわち２ｍｍ厚みの成形片を透過法で測定したｂ値は、３．０以下が好ましく、２．０以下がより好ましく、１．５以下が最も好ましい。 The hue of the polycarbonate resin of the present invention, that is, the b value measured by a transmission method of a 2 mm-thick molded piece, is preferably 3.0 or less, more preferably 2.0 or less, and most preferably 1.5 or less.
本発明における光学部材とは、光学機器用の部品となる光学素子であるレンズ，プリズムの類や、導光板，光導波路などを指す。具体的には、レンズとしては二つの球面もしくは非球面の屈折表面を持ち、光を透過させうるものを指し、これを満たすものであれば特に限定されるものではないが、例えば、球面レンズ，非球面レンズ，フレネルレンズ，マイクロアレーレンズ等の種類が挙げられる。 The optical member in the present invention refers to lenses, prisms, light guide plates, optical waveguides, and the like, which are optical elements that are components for optical equipment. Specifically, the lens has two spherical or aspherical refractive surfaces and can transmit light, and is not particularly limited as long as it satisfies this. For example, a spherical lens, Examples include aspherical lenses, Fresnel lenses, and microarray lenses.
また、プリズムとしては、少なくとも平行でなく、ある角度で構成された研磨面を二つ以上持つ成形体を指し、これを満たすものであれば特に限定されるものではないが、例を挙げるとすれば、直角プリズム，ポロプリズム，アミシプリズム，五角プリズム，ドーブレッスプリズム，ヘンゾルトプリズム，スプレングープリズム，メーラプリズム，ウォラストンプリズム，傾斜プリズム，アッベプリズムなどが挙げられる。 In addition, the prism refers to a molded body having two or more polished surfaces that are not parallel but at an angle, and is not particularly limited as long as it satisfies this, but an example is given. For example, right-angle prisms, poro prisms, amic prisms, pentagonal prisms, doubless prisms, Hensolt prisms, Sprenggo prisms, mailer prisms, Wollaston prisms, tilted prisms, and Abbe prisms.
本発明における芳香族ポリカーボネート共重合体から形成される光学部材は、例えば射出成形法、圧縮成形法、射出圧縮成形法、押出成形法、溶液キャスティング法など任意の方法により成形される。成形の容易性やコストの面から特には射出成形法あるいは射出圧縮成形法により成形されることが好ましい。 The optical member formed from the aromatic polycarbonate copolymer in the present invention is molded by an arbitrary method such as an injection molding method, a compression molding method, an injection compression molding method, an extrusion molding method, or a solution casting method. In view of ease of molding and cost, it is particularly preferable to mold by an injection molding method or an injection compression molding method.
かかる方法により製造されたレンズ等の光学部材は、光透過性が高く、その上表面精度が良好であり、耐熱性、剛性が高く、かつ色相が改善されているため電子電気機器等に好適に用いられる。 An optical member such as a lens manufactured by such a method has a high light transmittance, a good surface accuracy, a high heat resistance, a high rigidity, and an improved hue. Used.
本発明の芳香族ポリカーボネート樹脂は、それより形成される光学部材は光透過性が高く、表面精度が良好であり、優れた耐熱性と剛性を有しており、且つ色相が良好であるため、レンズ、プリズム、光ファイバ、光学フィルム、液晶ディスプレー、液晶テレビのバックライト方式の光拡散板またはスキャナーに用いられている導光板等の光学部材に好適であり、本発明がもたらす工業的効果は格別である。 In the aromatic polycarbonate resin of the present invention, the optical member formed therefrom has high light transmittance, good surface accuracy, excellent heat resistance and rigidity, and good hue, It is suitable for optical members such as lenses, prisms, optical fibers, optical films, liquid crystal displays, backlight type light diffusing plates of liquid crystal televisions, or light guide plates used in scanners, and the industrial effects brought about by the present invention are exceptional. It is.
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る。なお、評価は下記の方法によった。
（１）オリゴマーおよびモノマー含有率：東ソー製ＧＰＣカラムＴＳＫｇｅｌＧ２０００ＨＸＬとＴＳＫｇｅｌＧ３０００ＨＸＬを用い、溶離液としてクロロホルムを流量０.７ｍｌ／分で流しながら試料５０ｍｇをクロロホルム５ｍｌに溶解した溶液を２０μｌ注入する方法を用い、それにより得られた波長２５４ｎｍの光源で検出したＧＰＣチャートのリテンションタイムが１９分以降のオリゴマー成分のピーク面積の全ピーク面積に対する割合を含有率（％）とした。
（２）ガラス転移温度（Ｔｇ）：デュポン社製９１０型ＤＳＣ測定装置にて、４０ｍＬ／分の窒素気流下、２０℃／分の昇温条件で測定し求めた。
（３）粘度平均分子量（Ｍｖ）：ポリカーボネート樹脂０．７ｇを塩化メチレン１００ｍＬに溶解し２０℃で測定した比粘度（ηｓｐ）を次式に挿入し、ビスフェノールＡより得られるポリカーボネート樹脂の極限粘度に換算して求めた。
ηｓｐ／ｃ＝［η］＋０．４５×［η］２ｃ
［η］＝１．２３×１０−４Ｍ０．８３
（但し［η］は極限粘度、ｃ＝０．７）
（４）成形片ｂ値：厚み２ｍｍの成形片を日本電色（株）色差計ＳＥ２０００を用いて透過法で測定し、２０枚の測定値の平均値を成形片ｂ値とした。
（５）成形不良率：ポリカーボネート樹脂を１２０℃、４時間乾燥後、ＪＳＷ（株）製Ｎ−２０Ｃ射出成形機を用いてシリンダー温度３２０〜３５０℃、金型温度１１５〜１４０℃にて外径２．０ｍｍ、中心厚０．８ｍｍ、焦点距離２．０ｍｍの平凸レンズを連続５，０００ショット射出成形し、４，９０１ショットから５，０００ショットまでの１００ショット分のレンズを微分顕微鏡を用いて検査し、不良個数率を％で求めた。なお、レンズ表面の凹み不良およびレンズ表面への付着物の有無などの表面形状異常のあるものを不良とした。
The following examples further illustrate the present invention. The part in an Example is a weight part. The evaluation was based on the following method.
(1) Oligomer and monomer content: Using a method of injecting 20 μl of a solution in which 50 mg of a sample was dissolved in 5 ml of chloroform while flowing chloroform at a flow rate of 0.7 ml / min as an eluent, using Tosoh GPC columns TSKgel G2000HXL and TSKgel G3000HXL. The ratio of the peak area of the oligomer component with a retention time of 19 minutes or later with respect to the total peak area of the GPC chart detected with the light source having a wavelength of 254 nm obtained as a content rate (%).
(2) Glass transition temperature (Tg): Measured by a DuPont 910 type DSC measuring apparatus under a nitrogen stream of 40 mL / min under a temperature rising condition of 20 ° C./min.
(3) Viscosity average molecular weight (Mv): The intrinsic viscosity of polycarbonate resin obtained from bisphenol A by dissolving 0.7 g of polycarbonate resin in 100 mL of methylene chloride and inserting the specific viscosity (η sp ) measured at 20 ° C. into the following equation: It was calculated in terms of
η sp /c=[η]+0.45×[η] 2 c
[Η] = 1.23 × 10 −4 M 0.83
([Η] is intrinsic viscosity, c = 0.7)
(4) Molded piece b value: A molded piece having a thickness of 2 mm was measured by a transmission method using Nippon Denshoku Co., Ltd. color difference meter SE2000, and an average value of 20 measured values was defined as a molded piece b value.
(5) Molding failure rate: After drying polycarbonate resin at 120 ° C for 4 hours, using a JSW N-20C injection molding machine at a cylinder temperature of 320 to 350 ° C and a mold temperature of 115 to 140 ° C, the outer diameter A plano-convex lens having a thickness of 2.0 mm, a center thickness of 0.8 mm, and a focal length of 2.0 mm is injection-molded continuously, and a lens for 100 shots from 4,901 shots to 5,000 shots is obtained using a differential microscope. Inspected, and the defective number rate was determined in%. In addition, the thing with surface shape abnormality, such as a dent defect on a lens surface and the presence or absence of the deposit | attachment to a lens surface, was made into the defect.
［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２２１４８部、４８％
水酸化ナトリウム水溶液４１０９部を入れ、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）１１６５部、２，２−ビス（４−ヒドロキシフェニル）プロパン（以下“ビスフェノールＡ”と略称することがある）２８００部およびハイドロサルファイト１３部を溶解した後、塩化メチレン１５６７０部を加えた後撹拌下１５〜２５℃でホスゲン１８１５部を６０分を要して吹き込んだ。ホスゲン吹き込み終了後撹拌を継続し、水相を紫外分光光度計にて光路長１ｃｍで測定した２９０〜２９５ｎｍにおける吸光度が１．０以下であることを確認し、ｐ−ｔｅｒｔ−ブチルフェノール９２部を塩化メチレン３３０部に溶解した溶液および４８％水酸化ナトリウム水溶液６３３部を加え、乳化後、トリエチルアミン５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有機相を除去した後、ｐＨ１３．０の水酸化ナトリウム水溶液にて水洗し、その後中性になるまでイオン交換水で水洗し、塩酸酸性後、水相が再びほぼ中性になるまで洗浄を繰り返した。続いて、塩化メチレン相を濃縮してポリカーボネート濃度１０％の溶液を得、これに３倍量のイソプロパノールを加え、重合物を沈殿させた。沈殿物を濾過後、乾燥機にて乾燥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２０：８０であるポリマーを得た。このポリマーのオリゴマーおよびモノマー含有率は０．２５％であった。このポリマーにチバスペシャリティケミカルズ社製「Ｉｒｇａｆｏｓ１６８」を０．１重量％添加し、３０φ単軸押出機を用いて３００℃で押し出し、ペレット化した。ガラス転移温度（Ｔｇ）は１６５℃、粘度平均分子量（Ｍｖ）は１８，５００であった。このペレットを１２０℃、４時間乾燥後、５０×９０×２ｍｍの試験片に射出成形した。このもののｂ値は０．９であった。さらに、このペレットを用い、ＪＳＷ（株）製Ｎ−２０Ｃ射出成形機を使用して外径２．０ｍｍ、中心厚０．８ｍｍ、焦点距離２．０ｍｍの平凸レンズを連続５，０００ショット射出成形した。４，９０１ショットから５，０００ショットまでの１００ショット分のレンズの不良率は２％であった。結果を表１に示す。
[Example 1]
Reactor with thermometer, stirrer, reflux condenser and ion exchange water 22148 parts, 48%
4109 parts of an aqueous sodium hydroxide solution was added, 1165 parts of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “biscresol fluorene”), 2,2-bis (4- 2800 parts of hydroxyphenyl) propane (hereinafter may be abbreviated as “bisphenol A”) and 13 parts of hydrosulfite were dissolved, 15670 parts of methylene chloride was added, and then 1815 parts of phosgene was added at 15 to 25 ° C. with stirring. It took a minute to blow. Stirring was continued after the completion of phosgene blowing, and the water phase was measured with an ultraviolet spectrophotometer at an optical path length of 1 cm to confirm that the absorbance at 290 to 295 nm was 1.0 or less, and 92 parts of p-tert-butylphenol was chlorinated. A solution dissolved in 330 parts of methylene and 633 parts of a 48% aqueous sodium hydroxide solution were added, and after emulsification, 5 parts of triethylamine was added and stirred at 28 to 33 ° C. for 1 hour to complete the reaction. After completion of the reaction, the product was diluted with methylene chloride to remove the organic phase, then washed with an aqueous sodium hydroxide solution having a pH of 13.0, then washed with ion-exchanged water until neutral, acidified with hydrochloric acid, The washing was repeated until the aqueous phase was almost neutral again. Subsequently, the methylene chloride phase was concentrated to obtain a solution having a polycarbonate concentration of 10%, and 3 times the amount of isopropanol was added thereto to precipitate a polymer. The precipitate was filtered and then dried in a drier to obtain a polymer having a molar ratio of biscresol fluorene to bisphenol A of 20:80. The oligomer and monomer content of this polymer was 0.25%. 0.1% by weight of “Irgafos 168” manufactured by Ciba Specialty Chemicals was added to this polymer and extruded at 300 ° C. using a 30φ single-screw extruder to be pelletized. The glass transition temperature (Tg) was 165 ° C., and the viscosity average molecular weight (Mv) was 18,500. The pellets were dried at 120 ° C. for 4 hours, and then injection molded into 50 × 90 × 2 mm test pieces. The b value of this was 0.9. Further, using this pellet, a plano-convex lens having an outer diameter of 2.0 mm, a center thickness of 0.8 mm, and a focal length of 2.0 mm is continuously injected by 5,000 shots using an N-20C injection molding machine manufactured by JSW. did. The lens defect rate for 100 shots from 4,901 shots to 5,000 shots was 2%. The results are shown in Table 1.
［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３０５８部、ビスフェノールＡの使用量を１８４５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の比がモル比で５０：５０であるポリマーを得た。このポリマーのオリゴマーおよびモノマー含有率は０．３２％であった。このポリマーにチバスペシャリティケミカルズ社製「Ｉｒｇａｆｏｓ１６８」を０．１重量％添加し、３０φ単軸押出機を用いて３００℃で押し出し、ペレット化した。ガラス転移温度（Ｔｇ）は１９７℃、粘度平均分子量（Ｍｖ）は１５，５００であった。実施例１と同様に測定した試験片のｂ値は１．５であった。さらに、実施例１と同様にレンズを連続製造し、同様に不良率を求めたところ、不良率は３％であった。結果を表１に示す。
[Example 2]
The ratio of biscresol fluorene to bisphenol A is 50:50 in the same manner as in Example 1 except that the amount of biscresol fluorene used in Example 1 is 3058 parts and the amount of bisphenol A used is 1845 parts. A polymer was obtained. The oligomer and monomer content of this polymer was 0.32%. 0.1% by weight of “Irgafos 168” manufactured by Ciba Specialty Chemicals was added to this polymer and extruded at 300 ° C. using a 30φ single-screw extruder to be pelletized. The glass transition temperature (Tg) was 197 ° C., and the viscosity average molecular weight (Mv) was 15,500. The b value of the test piece measured in the same manner as in Example 1 was 1.5. Further, when lenses were continuously manufactured in the same manner as in Example 1 and the defect rate was determined in the same manner, the defect rate was 3%. The results are shown in Table 1.
［実施例３］
実施例１のビスクレゾールフルオレンの使用量を４０６５部、ビスフェノールＡの使用量を１０５１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の比がモル比で７０：３０であるポリマーを得た。このポリマーのオリゴマーおよびモノマー含有率は０．３５％であった。このポリマーにチバスペシャリティケミカルズ社製「Ｉｒｇａｆｏｓ１６８」を０．１重量％添加し、３０φ単軸押出機を用いて３００℃で押し出し、ペレット化した。ガラス転移温度（Ｔｇ）は１９７℃、粘度平均分子量（Ｍｖ）は１３，０００であった。実施例１と同様に測定した試験片のｂ値は２．５であった。さらに、実施例１と同様にレンズを連続製造し、同様に不良率を求めたところ、不良率は４％であった。結果を表１に示す。
[Example 3]
The ratio of biscresol fluorene to bisphenol A is 70:30 in molar ratio as in Example 1 except that the amount of biscresol fluorene used in Example 1 is 4065 parts and the amount of bisphenol A used is 1051 parts. A polymer was obtained. The oligomer and monomer content of this polymer was 0.35%. 0.1% by weight of “Irgafos 168” manufactured by Ciba Specialty Chemicals was added to this polymer and extruded at 300 ° C. using a 30φ single-screw extruder to be pelletized. The glass transition temperature (Tg) was 197 ° C., and the viscosity average molecular weight (Mv) was 13,000. The b value of the test piece measured in the same manner as in Example 1 was 2.5. Further, when lenses were continuously manufactured in the same manner as in Example 1 and the defect rate was determined in the same manner, the defect rate was 4%. The results are shown in Table 1.
［実施例４］
実施例１と同様の装置にイオン交換水３５３１５部、４８％水酸化ナトリウム３９２０部を入れ、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と略称）２９５５部、ビスクレゾールフルオレン３２２８部およびハイドロサルファイト１４部を溶解した後、塩化メチレン１２７７５部を加え、攪拌下１５〜２０℃でホスゲン１９４６部を４５分を要して吹き込んだ。ホスゲン吹き込み終了後撹拌を継続し、水相を紫外分光光度計にて光路長１ｃｍで測定した２９０〜２９５ｎｍにおける吸光度が１．０以下であることを確認し、ｐ−ｔｅｒｔ−ブチルフェノール１０９部を塩化メチレン３３０部に溶解した溶液および４８％水酸化ナトリウム水溶液７１１部を加え、乳化後、トリエチルアミン４．５５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有機相を除去した後、ｐＨ１３．０の水酸化ナトリウム水溶液にて水洗し、その後中性になるまでイオン交換水で水洗し、塩酸酸性後、水相が再びほぼ中性になるまで洗浄を繰り返した。続いて、塩化メチレン相を濃縮してポリカーボネート濃度１０％の溶液を得、これに３倍量のイソプロパノールを加え、重合物を沈殿させた。沈殿物を濾過後、乾燥機にて乾燥してビスフェノールＭとビスクレゾールフルオレン構成単位のモル比が５０：５０であるポリマーを得た。このポリマーのオリゴマーおよびモノマー含有率は０．４０％であった。このポリマーにチバスペシャリティケミカルズ社製「Ｉｒｇａｆｏｓ１６８」を０．１重量％添加し、３０φ単軸押出機を用いて３００℃で押し出し、ペレット化した。ガラス転移温度（Ｔｇ）は１８０℃、粘度平均分子量（Ｍｖ）は１３，２００であった。実施例１と同様に測定した試験片のｂ値は２．６であった。さらに、実施例１と同様にレンズを連続製造し、同様に不良率を求めたところ、不良率は２％であった。結果を表１に示す。
[Example 4]
Ion exchange water 35315 parts, 48% sodium hydroxide 3920 parts were put in the same apparatus as in Example 1, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene (abbreviated as bisphenol M) 2955 parts, After dissolving 3228 parts of biscresol fluorene and 14 parts of hydrosulfite, 12775 parts of methylene chloride was added, and 1946 parts of phosgene was blown in at 45 ° C. with stirring for 15 minutes. Stirring was continued after the completion of phosgene blowing, and the water phase was measured with an ultraviolet spectrophotometer at an optical path length of 1 cm to confirm that the absorbance at 290 to 295 nm was 1.0 or less, and 109 parts of p-tert-butylphenol was chlorinated. A solution dissolved in 330 parts of methylene and 711 parts of a 48% aqueous sodium hydroxide solution were added. After emulsification, 4.55 parts of triethylamine was added and stirred at 28 to 33 ° C. for 1 hour to complete the reaction. After completion of the reaction, the product was diluted with methylene chloride to remove the organic phase, then washed with an aqueous sodium hydroxide solution having a pH of 13.0, then washed with ion-exchanged water until neutral, acidified with hydrochloric acid, The washing was repeated until the aqueous phase was almost neutral again. Subsequently, the methylene chloride phase was concentrated to obtain a solution having a polycarbonate concentration of 10%, and 3 times the amount of isopropanol was added thereto to precipitate a polymer. The precipitate was filtered and then dried in a drier to obtain a polymer having a molar ratio of bisphenol M and biscresol fluorene units of 50:50. The oligomer and monomer content of this polymer was 0.40%. 0.1% by weight of “Irgafos 168” manufactured by Ciba Specialty Chemicals was added to this polymer and extruded at 300 ° C. using a 30φ single-screw extruder to be pelletized. The glass transition temperature (Tg) was 180 ° C., and the viscosity average molecular weight (Mv) was 13,200. The b value of the test piece measured in the same manner as in Example 1 was 2.6. Further, when lenses were continuously manufactured in the same manner as in Example 1 and the defect rate was determined in the same manner, the defect rate was 2%. The results are shown in Table 1.
［比較例１］
実施例１において、ホスゲン吹き込み終了後撹拌をすぐに停止した以外は実施例１と同様にしてペレットを得た。得られたペレットを用いて実施例１と同様に評価した結果を表１に示す。
[Comparative Example 1]
In Example 1, pellets were obtained in the same manner as in Example 1 except that the stirring was stopped immediately after the completion of phosgene blowing. Table 1 shows the results of evaluation in the same manner as in Example 1 using the obtained pellets.
［比較例２］
実施例２において、反応終了後、生成物を塩化メチレンで希釈して有機相を除去した後、ｐＨ１３．０の水酸化ナトリウム水溶液にて水洗しなかった以外は実施例２と同様にしてペレットを得た。得られたペレットを用いて実施例１と同様に評価した結果を表１に示す。
[Comparative Example 2]
In Example 2, after completion of the reaction, the product was diluted with methylene chloride to remove the organic phase, and then the pellet was prepared in the same manner as in Example 2 except that it was not washed with an aqueous sodium hydroxide solution having a pH of 13.0. Obtained. Table 1 shows the results of evaluation in the same manner as in Example 1 using the obtained pellets.
［比較例３］
実施例３において、有機相を水洗した後、イソプロパノールでポリマーを沈殿させずに、温水中に濃縮した有機相を滴下すること以外は実施例３と同様にしてペレットを得た。得られたペレットを用いて実施例１と同様に評価した結果を表１に示す。
[Comparative Example 3]
In Example 3, after washing the organic phase with water, pellets were obtained in the same manner as in Example 3 except that the organic phase concentrated in warm water was dropped without precipitating the polymer with isopropanol. Table 1 shows the results of evaluation in the same manner as in Example 1 using the obtained pellets.
Claims (6)
芳香族ジヒドロキシ成分の５〜９５モル％が下記一般式［１］、
９５〜５モル％が下記一般式［２］
で表されるジヒドロキシ成分からなる芳香族ポリカーボネート樹脂であって、本文中に定義された方法によって測定されたオリゴマーおよびモノマーの含有率が０．８％以下である芳香族ポリカーボネート樹脂であることを特徴とする光学部材。 It is an optical member made of a transparent resin such that the incident light beam and the outgoing light beam from the incident light beam are changed in the optical path.
5 to 95 mol% of the aromatic dihydroxy component is represented by the following general formula [1],
95-5 mol% is the following general formula [2]
An aromatic polycarbonate resin having a content of oligomers and monomers of 0.8% or less measured by the method defined in the text. An optical member.
９５〜５モル％が下記一般式［２］
で表されるジヒドロキシ成分からなる芳香族ポリカーボネート樹脂であって、本文中に定義された方法によって測定されたオリゴマーおよびモノマーの含有率が０．８％以下であることを特徴とする芳香族ポリカーボネート樹脂。 5 to 95 mol% of the aromatic dihydroxy component is represented by the following general formula [1],
95-5 mol% is the following general formula [2]
An aromatic polycarbonate resin comprising a dihydroxy component represented by the following formula, wherein the content of oligomers and monomers measured by the method defined in the text is 0.8% or less: .
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| JP2003411738A JP2005171051A (en) | 2003-12-10 | 2003-12-10 | Optical member and aromatic polycarbonate resin suitable for producing the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006119383A (en) * | 2004-10-21 | 2006-05-11 | Osaka Gas Co Ltd | Infrared absorbing filter and infrared absorbing panel |
| WO2007063724A1 (en) * | 2005-11-30 | 2007-06-07 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition for light diffusion plate and light diffusion plate |
| US20120007200A1 (en) * | 2009-04-09 | 2012-01-12 | Cheil Industries Inc. | Image Sensor and Method for Manufacturing the Same |
| DE112010003497T5 (en) | 2009-08-31 | 2012-09-20 | Sumitomo Electric Industries, Ltd. | Clear resin molded article and process for its production |
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2003
- 2003-12-10 JP JP2003411738A patent/JP2005171051A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006119383A (en) * | 2004-10-21 | 2006-05-11 | Osaka Gas Co Ltd | Infrared absorbing filter and infrared absorbing panel |
| JP4514577B2 (en) * | 2004-10-21 | 2010-07-28 | 大阪瓦斯株式会社 | Infrared absorption filter and infrared absorption panel |
| WO2007063724A1 (en) * | 2005-11-30 | 2007-06-07 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition for light diffusion plate and light diffusion plate |
| US20120007200A1 (en) * | 2009-04-09 | 2012-01-12 | Cheil Industries Inc. | Image Sensor and Method for Manufacturing the Same |
| US8502334B2 (en) * | 2009-04-09 | 2013-08-06 | Cheil Industries Inc. | Image sensor and method for manufacturing the same |
| DE112010003497T5 (en) | 2009-08-31 | 2012-09-20 | Sumitomo Electric Industries, Ltd. | Clear resin molded article and process for its production |
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