JPH0827370A - Aromatic polycarbonate composition - Google Patents
Aromatic polycarbonate compositionInfo
- Publication number
- JPH0827370A JPH0827370A JP6160044A JP16004494A JPH0827370A JP H0827370 A JPH0827370 A JP H0827370A JP 6160044 A JP6160044 A JP 6160044A JP 16004494 A JP16004494 A JP 16004494A JP H0827370 A JPH0827370 A JP H0827370A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polycarbonate
- parts
- polycarbonate composition
- polymer
- composition according
- 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.)
- Granted
Links
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 29
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 230000003287 optical effect Effects 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000004431 polycarbonate resin Substances 0.000 description 10
- 229920005668 polycarbonate resin Polymers 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- -1 alkaline earth metal salts Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000004650 carbonic acid diesters Chemical class 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 3
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- RMTMGXCQEXSWLI-UHFFFAOYSA-N (2-tert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=CC=C1OP(O)O RMTMGXCQEXSWLI-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MXFVKYNQQHVOQP-UHFFFAOYSA-N C(CCCCCCC)P(O)(O)OC1=CC=C(C=C1C(C)(C)C)C(C)(C)C Chemical compound C(CCCCCCC)P(O)(O)OC1=CC=C(C=C1C(C)(C)C)C(C)(C)C MXFVKYNQQHVOQP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- QAEPIAHUOVJOOM-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC QAEPIAHUOVJOOM-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- 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 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 108090000951 RNA polymerase sigma 70 Proteins 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- BQAQHFMZRLEURF-UHFFFAOYSA-N bromo(butyl)phosphane Chemical compound CCCCPBr BQAQHFMZRLEURF-UHFFFAOYSA-N 0.000 description 1
- ZWRWUGGYDBHANL-UHFFFAOYSA-N butyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCC)OC1=CC=CC=C1 ZWRWUGGYDBHANL-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- NJPPTRABUACKFL-UHFFFAOYSA-N decoxy-dihydroxy-diphenyl-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(O)(O)(OCCCCCCCCCC)C1=CC=CC=C1 NJPPTRABUACKFL-UHFFFAOYSA-N 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- NMAKPIATXQEXBT-UHFFFAOYSA-N didecyl phenyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OC1=CC=CC=C1 NMAKPIATXQEXBT-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- HDGDMUNGKHYYEA-UHFFFAOYSA-N dihydroxy-octoxy-diphenyl-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(O)(O)(OCCCCCCCC)C1=CC=CC=C1 HDGDMUNGKHYYEA-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- MKZVQIIAAIPNGH-UHFFFAOYSA-N dioctyl phenyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OC1=CC=CC=C1 MKZVQIIAAIPNGH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000006289 hydroxybenzyl group Chemical group 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 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 1
- 239000013307 optical fiber Substances 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- SMIZARYCGYRDGF-UHFFFAOYSA-N phenyl dipropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC1=CC=CC=C1 SMIZARYCGYRDGF-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 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 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 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
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、芳香族ポリカーボネー
ト組成物に関する。さらに詳しくは2種の芳香族ポリカ
ーボネートより形成される複屈折、成形性の改善された
組成物およびそれからの成形品に関する。FIELD OF THE INVENTION This invention relates to aromatic polycarbonate compositions. More specifically, it relates to a composition having improved birefringence and moldability, which is formed from two kinds of aromatic polycarbonates, and a molded article made from the composition.
【0002】[0002]
【従来の技術】従来、2,2−ビス(4−ヒドロキシフ
ェニル)プロパンにカーボネート前駆体物質を反応させ
て得られるポリカーボネート樹脂は透明性、耐熱性、機
械的特性、寸法安定性が優れているがゆえにエンジニア
リングプラスチックとして多くの分野に広く使用されて
いる。特に透明性に優れることから光学材料としての用
途も多い。2. Description of the Related Art Conventionally, a polycarbonate resin obtained by reacting a carbonate precursor substance with 2,2-bis (4-hydroxyphenyl) propane has excellent transparency, heat resistance, mechanical properties and dimensional stability. Therefore, it is widely used in many fields as engineering plastics. In particular, it has many uses as an optical material because of its excellent transparency.
【0003】しかしながら、かかるポリカーボネート樹
脂はベンゼン環の光学異方性から光弾性定数が大きく、
従って成形品の複屈折が大きい欠点があり、この改善が
求められている。またより溶融流動性に優れた転写性の
良い、成形サイクルの短い樹脂が求められている。However, such a polycarbonate resin has a large photoelastic constant due to the optical anisotropy of the benzene ring,
Therefore, there is a defect that the birefringence of the molded product is large, and this improvement is required. There is also a demand for a resin having a better melt flowability and a good transfer property and a short molding cycle.
【0004】一方、特開平2−88634号公報には、
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より得られる芳香族ポリカー
ボネート樹脂が開示されており、このポリマーが低複屈
折性で耐熱性が良好なことも知られているが、溶融流動
性が悪く、良好な成形品が得られ難い。On the other hand, Japanese Patent Laid-Open No. 2-88634 discloses that
1,1-bis (4-hydroxyphenyl) -3,3,5-
An aromatic polycarbonate resin obtained from trimethylcyclohexane is disclosed, and it is also known that this polymer has low birefringence and good heat resistance, but melt flowability is poor and it is difficult to obtain a good molded product. .
【0005】[0005]
【発明が解決しようとする課題】本発明の目的は、光学
用材料に適したポリカーボネートの優れた透明性、機械
物性を保持しつつ斜め入射複屈折、成形性、反り等を向
上した芳香族ポリカーボネート組成物を提供することに
ある。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、2種の特定の芳香族ポリカーボネートを特
定割合で混合した組成物が光学用材料として好適である
ことを見出し、本発明に到達した。SUMMARY OF THE INVENTION An object of the present invention is to improve the oblique incidence birefringence, moldability, warpage, etc. of an aromatic polycarbonate while maintaining the excellent transparency and mechanical properties of the polycarbonate suitable for optical materials. To provide a composition. The present inventor has conducted intensive studies to achieve this object and, as a result, found that a composition obtained by mixing two kinds of specific aromatic polycarbonates in a specific ratio was suitable as an optical material, and arrived at the present invention. .
【0006】[0006]
【課題を解決するための手段】すなわち本発明によれ
ば、下記一般式[I]That is, according to the present invention, the following general formula [I]
【0007】[0007]
【化3】 Embedded image
【0008】で表される繰返し単位[I]よりなる芳香
族ポリカーボネート(PC−I)および下記一般式[I
I]An aromatic polycarbonate (PC-I) comprising a repeating unit [I] represented by the following general formula [I]
I]
【0009】[0009]
【化4】 [Chemical 4]
【0010】で表される繰返し単位[II]よりなる芳
香族ポリカーボネート(PC−II)より実質的にな
り、前記芳香族ポリカーボネート(PC−I)と前記芳
香族ポリカーボネート(PC−II)の割合が重量比で
80:20〜30:70の範囲である芳香族ポリカーボ
ネート組成物が提供される。It substantially consists of an aromatic polycarbonate (PC-II) consisting of the repeating unit [II] represented by the following formula, and the ratio of the aromatic polycarbonate (PC-I) and the aromatic polycarbonate (PC-II) is There is provided an aromatic polycarbonate composition having a weight ratio in the range of 80:20 to 30:70.
【0011】本発明の芳香族ポリカーボネート樹脂組成
物を形成するPC−IおよびPC−IIの製造に用いる
4,4'−(m−フェニレンジイソプロピリデン)ジフェ
ノールおよび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はその合成時に
副生する不純物を極力除去した99.0%以上の高純度
のものが好ましい。本発明の組成物を形成するPC−I
は80〜30重量%であり、PC−IIは20〜70重
量%である。PC−Iは75〜35重量%、PC−II
は25〜65重量%が好ましい。PC−Iが80重量%
より多く、PC−IIが20重量%より少なくなると得
られた樹脂の光弾性定数が大きくなりかつガラス転移点
も低くなるので好ましくない。またPC−Iが30重量
%より少なく、PC−IIが70重量%より多くなると
得られた樹脂の溶融流動性が悪く成形不良を生じ、光学
的に良好な成形品が得られ難くなる。4,4 '-(m-Phenylenediisopropylidene) diphenol and 1,1-bis (4-) used in the production of PC-I and PC-II forming the aromatic polycarbonate resin composition of the present invention. Hydroxyphenyl)
-3,3,5-Trimethylcyclohexane preferably has a high purity of 99.0% or more in which impurities by-produced during the synthesis are removed as much as possible. PC-I forming compositions of the present invention
Is 80 to 30% by weight, and PC-II is 20 to 70% by weight. PC-I is 75-35% by weight, PC-II
Is preferably 25 to 65% by weight. 80% by weight of PC-I
If the amount of PC-II is more than 20% by weight, the photoelastic constant of the obtained resin becomes large and the glass transition point becomes low, which is not preferable. If PC-I is less than 30% by weight and PC-II is more than 70% by weight, the melt flowability of the obtained resin is poor and molding failure occurs, making it difficult to obtain an optically good molded product.
【0012】本発明の芳香族ポリカーボネート樹脂組成
物を形成するそれぞれの樹脂は通常の芳香族ポリカーボ
ネート樹脂を製造する際に用いる公知の方法、例えば二
価フェノールにホスゲンや炭酸ジエステル等のカーボネ
ート前駆物質を反応させる方法により製造される。Each of the resins forming the aromatic polycarbonate resin composition of the present invention is a known method used for producing an ordinary aromatic polycarbonate resin, for example, dihydric phenol is mixed with a carbonate precursor such as phosgene or carbonic acid diester. It is produced by a reaction method.
【0013】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、通常酸結合剤の水溶液に上記二
価フェノールを溶解し、有機溶媒の存在下に反応させ
る。酸結合剤としては例えば水酸化ナトリウム、水酸化
カリウム等のアルカリ金属水酸化物が用いられ、有機溶
媒としては例えば塩化メチレン、クロロベンゼン等のハ
ロゲン化炭化水素が用いられる。反応温度は通常0〜4
0℃であり、反応時間は数分〜5時間である。In a reaction using, for example, phosgene as a carbonate precursor, the above dihydric phenol is usually dissolved in an aqueous solution of an acid binder and the reaction is carried out in the presence of an organic solvent. An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used as the acid binder, and a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used as the organic solvent. Reaction temperature is usually 0-4
It is 0 ° C., and the reaction time is several minutes to 5 hours.
【0014】また、反応を促進させるために触媒を用い
てもよく、触媒としては例えばトリエチルアミン、テト
ラ−n−ブチルアンモニウムブロマイド、テトラ−n−
ブチルホスホニウムブロマイドのような三級アミン、四
級アンモニウム化合物、四級ホスホニウム化合物等が挙
げられる。更に、必要に応じハイドロサルファイトのよ
うな酸化防止剤を加えることもできる。A catalyst may be used to accelerate the reaction, and examples of the catalyst include triethylamine, tetra-n-butylammonium bromide and tetra-n-.
Examples include tertiary amines such as butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds. Further, if necessary, an antioxidant such as hydrosulfite can be added.
【0015】さらに末端停止剤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、イソオクチルフェノール等の単官能フェノール
類を用いる。また溶融流動性をさらに向上するためには
炭素原子数10〜50のアルキルフェノールを全末端停
止剤の少なくとも5モル%以上用いると良い。その際用
いられる炭素原子数10〜50のアルキルフェノールの
アルキル基の置換位置は通常水酸基のオルソ位またはパ
ラ位のものが用いられ、中でもオルソ位とパラ位の混合
物が好ましく用いられる。Further, as the terminal terminator, for example, monofunctional phenols such as phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol are used. Further, in order to further improve the melt fluidity, it is advisable to use an alkylphenol having 10 to 50 carbon atoms in an amount of at least 5 mol% of the total end-stopping agent. The substitution position of the alkyl group of the alkylphenol having 10 to 50 carbon atoms used at that time is usually the ortho position or para position of the hydroxyl group, and among them, the mixture of the ortho position and the para position is preferably used.
【0016】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では、不活性ガス雰囲気下
所定割合の上記二価フェノールを炭酸ジエステルと加熱
しながら攪拌して生成するアルコールまたはフェノール
を留出させることで行われる。反応温度は生成するアル
コールまたはフェノールの沸点等により異なるが、通常
120〜300℃の範囲である。反応後期には系を減圧
にして生成するアルコールまたはフェノールの留出を容
易にさせて反応を完結させる。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
等が挙げられる。このらのうち特にジフェニルカーボネ
ートが好ましい。The transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by distilling alcohol or phenol produced by stirring the dihydric phenol in a predetermined ratio with the carbonic acid diester in an inert gas atmosphere while heating. Be seen. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, etc., but is usually in the range of 120 to 300 ° C. In the latter stage of the reaction, the system is depressurized to facilitate the distillation of the produced alcohol or phenol to complete the reaction. Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable.
【0017】重合速度を速めるために重合触媒を使用す
ることもでき、重合触媒としては水酸化ナトリウムや水
酸化カリウム等のアルカリ金属及びアルカリ土類金属の
水酸化物類、ホウ素やアルミニウムの水酸化物のアルカ
リ金属塩、アルカリ土類金属塩、第4級アンモニウム塩
類、アルカリ金属及びアルカリ土類金属のアルコキシド
類、アルカリ金属及びアルカリ土類金属の有機酸塩類、
亜鉛化合物類、ホウ素化合物類、ケイ素化合物類、ゲル
マニウム化合物類、有機スズ化合物類、鉛化合物類、ア
ンチモン化合物類、マンガン化合物類、チタン化合物
類、ジルコニウム化合物類等の通常エステル化反応、エ
ステル交換反応に使用される触媒を使用することができ
る。触媒は1種だけを用いても2種以上を組合わせて用
いてもよい。これらの触媒の使用量は原料の二価フェノ
ールに対し0.0001〜1重量%、好ましくは0.00
05〜0.5重量%の範囲で選ばれる。A polymerization catalyst can also be used to accelerate the polymerization rate. As the polymerization catalyst, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide and potassium hydroxide, and hydroxides of boron and aluminum can be used. Alkaline metal salts, alkaline earth metal salts, quaternary ammonium salts, alkali metal and alkaline earth metal alkoxides, alkali metal and alkaline earth metal organic acid salts,
Ordinary esterification reaction, transesterification reaction of zinc compounds, boron compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, etc. The catalyst used for can be used. The catalyst may be used alone or in combination of two or more kinds. The amount of these catalysts used is 0.0001 to 1% by weight, preferably 0.000, based on the starting dihydric phenol.
It is selected in the range of 05 to 0.5% by weight.
【0018】かくして得られるPC−IおよびPC−I
Iのポリマーはいずれもポリマー0.7gを100ml
の塩化メチレンに溶解し、20℃で測定した比粘度が
0.2〜0.4の範囲のものが好ましく、0.25〜0.3
5の範囲のものがさらに好ましい。比粘度が0.2未満
では成形品が脆くなり、一方、0.4より高くなると溶
融流動性が悪く、成形不良を生じ、光学的に良好な成形
品が得られ難くなる。PC-I and PC-I thus obtained
Polymer I is 0.7 ml of polymer in 100 ml.
Of methylene chloride, the specific viscosity of which is measured at 20 ° C. is preferably in the range of 0.2 to 0.4, and 0.25 to 0.3.
The range of 5 is more preferable. If the specific viscosity is less than 0.2, the molded product becomes brittle, while if it is higher than 0.4, the melt flowability is poor and molding defects occur, making it difficult to obtain an optically good molded product.
【0019】本発明の芳香族ポリカーボネート樹脂組成
物は、例えば射出成形法、圧縮成形法、押出成形法、溶
液キャスティング法等任意の方法で成形することができ
る。The aromatic polycarbonate resin composition of the present invention can be molded by any method such as an injection molding method, a compression molding method, an extrusion molding method and a solution casting method.
【0020】なお、本発明の芳香族ポリカーボネート樹
脂組成物には、必要に応じてりん系の熱安定剤、フェノ
ール系の酸化防止剤等を加えることができる。りん系の
安定剤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
デシルホスファィト、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、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等の亜りん酸のトリエステ
ル、ジエステル、モノエステルでありこれらは単独で使
用してもまたは2種以上を併用してもよい。添加量とし
ては0.0001〜0.05重量%が好ましい。The aromatic polycarbonate resin composition of the present invention may optionally contain a phosphorus-based heat stabilizer, a phenol-based antioxidant and the like. Examples of phosphorus-based stabilizers include triphenylphosphite, trisnonylphenylphosphite, and tris (2,4-di-).
(tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl Diphenylphosphite, monooctyldiphenylphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,
6-di-tert-butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-diphenyl) -Tert-butylphenyl) -4,4
-Triesters, diesters, and monoesters of phosphorous acid such as diphenylenephosphonite, which may be used alone or in combination of two or more kinds. The amount added is preferably 0.0001 to 0.05% by weight.
【0021】フェノール系酸化防止剤としては例えばト
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。好ましい添
加量の範囲は0.0001〜0.05%である。Examples of phenolic antioxidants include triethylene glycol-bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate) and 1,6-hexanediol-bis (3- ( Three,
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-hydroxy-)
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 Examples include 10,10-tetraoxaspiro (5,5) undecane and the like. The preferred range of addition is 0.0001 to 0.05%.
【0022】また必要に応じて多価アルコールの高級脂
肪酸エステルを加える事もできる。好ましい脂肪酸エス
テルとしては炭素原子数8〜22の飽和脂肪族モノカル
ボン酸とグリコール類、グリセロール、ペンタエリスリ
トール等との全エステル、部分エステルで、好ましい添
加量は0.001〜0.5重量%である。また光安定剤、
着色剤、帯電防止剤、滑剤等の添加剤を透明性を損なわ
ない範囲で加えることができる。また他のポリカーボネ
ート樹脂、あるいは熱可塑性樹脂を少割合ブレンドして
用いることもできる。If desired, higher fatty acid esters of polyhydric alcohols may be added. The preferred fatty acid ester is a total ester or a partial ester of a saturated aliphatic monocarboxylic acid having 8 to 22 carbon atoms and glycols, glycerol, pentaerythritol, etc., and the preferable addition amount is 0.001 to 0.5% by weight. is there. Also a light stabilizer,
Additives such as colorants, antistatic agents and lubricants can be added within a range that does not impair transparency. Other polycarbonate resins or thermoplastic resins may be blended in a small proportion and used.
【0023】また本発明の芳香族ポリカーボネート樹脂
に含まれる塩素(Cl)は1.0ppm以下が好まし
い。また平均径0.5μm以上の異物は10000個/
g以下が好ましい。The chlorine (Cl) contained in the aromatic polycarbonate resin of the present invention is preferably 1.0 ppm or less. In addition, 10000 foreign matter with an average diameter of 0.5 μm or more
It is preferably g or less.
【0024】本発明の芳香族ポリカーボネート組成物
は、複屈折性および成形性に特に優れているので種々の
成形品として利用することができる。殊に光学ディス
ク、光学レンズ、液晶パネル、光カード、シート、フィ
ルム、光ファイバー、コネクター、蒸着プラスチック反
射鏡、ディスプレー等の光学部品の構造材料または機能
材料用途に適した光学用成形品として有利に使用するこ
とができる。これらのうち、光ディスク用基板として特
に有利に使用することができる。Since the aromatic polycarbonate composition of the present invention is particularly excellent in birefringence and moldability, it can be used as various molded products. Particularly, it is advantageously used as an optical molded product suitable for structural materials or functional material applications of optical components such as optical discs, optical lenses, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic reflectors, and displays. can do. Of these, it can be used particularly advantageously as a substrate for optical disks.
【0025】[0025]
【実施例】以下に実施例を挙げて本発明をさらに説明す
る。なお合成例および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。比粘度; ポリマー0.7gを100mlの塩化メチレン
に溶解し20℃の温度で測定した。ガラス転移点(Tg); デュポン社製910型DSCに
より測定した。流動性(MFR); JIS K−7210に準拠して、
東洋精機製セミオートメルトインデクサーを用いて、2
80℃、荷重2.16kgで10分間に流出したポリマ
ー量(g)で示した。全光線透過率; ASTM D−1003に準拠して日本
電色シグマ80を用いて測定した。光弾性定数; 理研計器(株)製の光弾性測定装置PA−
150により測定した。斜め入射複屈折位相差; オーク製エリプソメータADR
−200B自動複屈折測定装置を用い、入射角30度で
測定した。反り; 80℃、85%RHの恒温恒湿機中に光ディスク
を1000時間放置した後、小野測器製LM−1200
光ディスク検査装置を用いて基板の反りを測定した。The present invention will be further described with reference to the following examples. In the synthesis examples and examples, parts are parts by weight and% is% by weight. The evaluation was based on the following method. Specific viscosity: 0.7 g of the polymer was dissolved in 100 ml of methylene chloride and measured at a temperature of 20 ° C. Glass transition point (Tg); measured by DuPont Model 910 DSC. Fluidity (MFR): In accordance with JIS K-7210,
Using a semi-auto melt indexer manufactured by Toyo Seiki, 2
The amount of polymer (g) flowed out at 80 ° C. under a load of 2.16 kg for 10 minutes was shown. Total light transmittance: Measured using Nippon Denshoku Sigma 80 in accordance with ASTM D-1003. Photoelastic constant; photoelasticity measuring device PA manufactured by Riken Keiki Co., Ltd.
It was measured by 150. Oblique incidence birefringence phase difference; oak ellipsometer ADR
The measurement was performed at an incident angle of 30 degrees using a -200B automatic birefringence measuring device. Warp: After leaving the optical disk in a thermo-hygrostat at 80 ° C. and 85% RH for 1000 hours, LM-1200 manufactured by Ono Sokki Co., Ltd.
The warp of the substrate was measured using an optical disc inspection device.
【0026】合成例1(PC−Iの合成) 温度計、攪拌機、還流冷却器付き反応器にイオン交換水
1023部と48%カセイソーダ水溶液67.5部を入
れ、4,4'−(m−フェニレンジイソプロピリデン)ジ
フェノール95.9部およびハイドロサルファイト0.2
部を溶解し、塩化メチレン702.2部を加え、攪拌下
15〜25℃でホスゲン35.7部を40分を要して吹
き込み反応せしめた。ホスゲン吹き込み終了後、p−t
ert−ブチルフェノール1.66部および48%カセ
イソーダ水溶液17.2部を加えて乳化後、トリエチル
アミン0.1部を加えて28〜33℃で約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
で希釈して水洗したのち塩酸酸性にして水洗し、水相の
導電率がイオン交換水と殆ど同じになったところで塩化
メチレンを蒸発してポリマー98部を得た(収率95
%)。このポリマーの比粘度は0.275、Tgは98
℃であった。Synthesis Example 1 (Synthesis of PC-I) 1023 parts of ion-exchanged water and 67.5 parts of 48% caustic soda aqueous solution were placed in a reactor equipped with a thermometer, a stirrer and a reflux condenser, and 4,4 '-(m- Phenylene diisopropylidene) diphenol 95.9 parts and hydrosulfite 0.2
70 parts of methylene chloride was added thereto, and 35.7 parts of phosgene was blown thereinto under stirring at 15 to 25 ° C. for 40 minutes to cause a reaction. After the completion of blowing phosgene, pt
After the addition of 1.66 parts of ert-butylphenol and 17.2 parts of a 48% aqueous sodium hydroxide solution to emulsify the mixture, 0.1 part of triethylamine was added and stirred at 28 to 33 ° C. for about 1 hour to complete the reaction. After completion of the reaction, the product was diluted with methylene chloride, washed with water, 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, methylene chloride was evaporated to obtain 98 parts of a polymer. (Yield 95
%). This polymer has a specific viscosity of 0.275 and a Tg of 98.
° C.
【0027】合成例2(PC−IIの合成) 合成例1と同様の装置にイオン交換水1137.3部、
48%カセイソーダ水溶液238.5部を入れ、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200.1部およびハイドロサルファ
イト0.2部を溶解した後、塩化メチレン709.9部を
加えて、攪拌下15〜25℃でホスゲン83.1部を4
0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5.8部を加え乳化後、
トリエチルアミン0.2部を加えて合成例1と同様にし
てポリマー208.2部を得た(収率96%)。このポ
リマーの比粘度は0.258、Tgは226℃であっ
た。Synthesis Example 2 (Synthesis of PC-II) In the same apparatus as in Synthesis Example 1, 1137.3 parts of ion-exchanged water,
Add 238.5 parts of 48% caustic soda solution, 1,1-
After dissolving 20.1 parts of bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 0.2 parts of hydrosulfite, 709.9 parts of methylene chloride was added, and the mixture was stirred at 15 to 25 ° C. 83.1 parts of phosgene 4
It took 0 minutes to blow. After finishing blowing phosgene, p
After adding 5.8 parts of -tert-butylphenol and emulsifying,
Triethylamine (0.2 part) was added to obtain 208.2 parts of a polymer in the same manner as in Synthesis Example 1 (yield 96%). The polymer had a specific viscosity of 0.258 and a Tg of 226 ° C.
【0028】合成例3(PC−IIの合成) 合成例2のp−tert−ブチルフェノールの代わりに
炭素原子数20のアルキルフェノール(オルソ置換体7
0%とパラ置換体30%の混合物)14.5部を用いる
以外は合成例2と同様にしてポリマー217.5部を得
た(収率94%)。このものの比粘度は0.272、T
gは182℃であった。Synthesis Example 3 (Synthesis of PC-II) Instead of p-tert-butylphenol of Synthesis Example 2, an alkylphenol having 20 carbon atoms (ortho-substituted compound 7)
217.5 parts of polymer was obtained in the same manner as in Synthesis Example 2 except that 14.5 parts of a mixture of 0% and 30% of para-substituted product was used (yield 94%). The specific viscosity of this product is 0.272, T
The g was 182 ° C.
【0029】実施例1 合成例1で合成したポリカーボネート70部、合成例2
で合成したポリカーボネート30部、トリス(2,4−
ジ−tert−ブチルフェニル)ホスファイト0.00
5部、トリメチルホスフェート0.005部、ステアリ
ン酸モノグリセライド0.045部を塩化メチレンに均
一に溶解した後、塩化メチレンを蒸発してポリマー組成
物を得た。このものを250℃で溶融押出ししてペレッ
ト化した。このもののTgは132℃、MFRは80g
/10分であった。このものを住友重機製DISK5M
lllを用いて120mmφ、1.2mm厚みのディス
ク基板に射出成形した。このものの全光線透過率は89
%、光弾性定数は41×10 -13cm2/dyn、斜め入
射複屈折位相差は20nm、反りは0.2mmであっ
た。Example 1 70 parts of the polycarbonate synthesized in Synthesis Example 1, Synthesis Example 2
Polycarbonate synthesized in 30 parts, Tris (2,4-
Di-tert-butylphenyl) phosphite 0.00
5 parts, trimethyl phosphate 0.005 parts, steari
Add 0.045 parts of acid monoglyceride to methylene chloride.
After dissolving in one, evaporate the methylene chloride and polymer composition
I got a thing. This is melt extruded at 250 ° C and pelletized.
Turned into This product has a Tg of 132 ° C and an MFR of 80g.
/ 10 minutes. Sumitomo Heavy Industries DISK5M
120mmφ, 1.2mm thick disc
It was injection molded on the substrate. The total light transmittance of this product is 89
%, The photoelastic constant is 41 × 10 -13cm2/ Dyn, diagonally inserted
The birefringence phase difference is 20 nm and the warpage is 0.2 mm.
Was.
【0030】実施例2 合成例1で合成したポリマー40部、合成例3で合成し
たポリマー60部を実施例1と同様の添加剤組成で実施
例1と同様にしてペレット化した。このもののTgは1
49℃、MFRは53g/10分であった。このものを
実施例1と同様にしてディスク基板を成形し評価したと
ころ、全光線透過率は89%、光弾性定数は37×10
-13cm2/dyn、斜め入射複屈折位相差は23nm、
反りは0.2mmであった。Example 2 40 parts of the polymer synthesized in Synthesis Example 1 and 60 parts of the polymer synthesized in Synthesis Example 3 were pelletized in the same manner as in Example 1 with the same additive composition as in Example 1. This product has a Tg of 1
At 49 ° C., MFR was 53 g / 10 minutes. When a disk substrate was molded and evaluated in the same manner as in Example 1, the total light transmittance was 89% and the photoelastic constant was 37 × 10.
-13 cm 2 / dyn, oblique incidence birefringence phase difference 23 nm,
The warp was 0.2 mm.
【0031】比較例1 通常のビスフェノールAポリカーボネート(帝人化成製
パンライトAD−5503)を実施例1と同様のディス
ク基板に成形し実施例1と同様にして評価したところ全
光線透過率は89%、光弾性定数は82×10-13cm2
/dyn、斜め入射複屈折位相差は68nm、反りは
0.3mmであった。Comparative Example 1 A normal bisphenol A polycarbonate (Panlite AD-5503 manufactured by Teijin Chemicals Ltd.) was molded on the same disk substrate as in Example 1 and evaluated in the same manner as in Example 1. The total light transmittance was 89%. , The photoelastic constant is 82 × 10 -13 cm 2
/ Dyn, the oblique incidence birefringence phase difference was 68 nm, and the warpage was 0.3 mm.
【0032】比較例2 合成例1で合成したポリマー90部、合成例2で合成し
たポリマー10部とした以外は実施例1と同様にしてペ
レットおよびディスク基板を得た。このもののTgは1
10℃と低く、光弾性定数は46×10-13cm2/dy
n、斜め入射複屈折位相差は35nmと大きかった。Comparative Example 2 A pellet and a disk substrate were obtained in the same manner as in Example 1 except that 90 parts of the polymer synthesized in Synthesis Example 1 and 10 parts of the polymer synthesized in Synthesis Example 2 were used. This product has a Tg of 1
Low as 10 ° C, photoelastic constant 46 × 10 -13 cm 2 / dy
n, the birefringent phase difference of oblique incidence was as large as 35 nm.
【0033】比較例3 合成例1で合成したポリマー10部、合成例2で合成し
たポリマー90部とした以外は実施例1と同様にしてペ
レット化した。このもののTgは219℃と高くMFR
は測定不可能で良好な成形品は得られなかった。Comparative Example 3 Pelletization was carried out in the same manner as in Example 1 except that 10 parts of the polymer synthesized in Synthesis Example 1 and 90 parts of the polymer synthesized in Synthesis Example 2 were used. This product has a high Tg of 219 ° C and an MFR of
Was not measurable and a good molded product could not be obtained.
【0034】[0034]
【発明の効果】本発明の芳香族ポリカーボネート組成物
は、低複屈折で溶融流動性が良くかつ透明性にも優れる
ので、光学ディスク、光学レンズ、光カード等の各種光
学用成形品として好適に用いられる。EFFECT OF THE INVENTION The aromatic polycarbonate composition of the present invention has low birefringence, good melt fluidity, and excellent transparency, and is therefore suitable for various optical molded articles such as optical discs, optical lenses and optical cards. Used.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 G11B 7/24 526 H 7215−5D ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location G11B 7/24 526 H 7215-5D
Claims (7)
ネート(PC−I)および下記一般式[II] 【化2】 で表される繰返し単位[II]よりなる芳香族ポリカー
ボネート(PC−II)より実質的になり、前記芳香族
ポリカーボネート(PC−I)と前記芳香族ポリカーボ
ネート(PC−II)の割合が重量比で80:20〜3
0:70の範囲である芳香族ポリカーボネート組成物。1. The following general formula [I]: And an aromatic polycarbonate (PC-I) comprising a repeating unit [I] represented by the following general formula [II] Which is substantially composed of an aromatic polycarbonate (PC-II) composed of a repeating unit [II] represented by: and the ratio of the aromatic polycarbonate (PC-I) and the aromatic polycarbonate (PC-II) is a weight ratio. 80: 20-3
Aromatic polycarbonate composition in the range of 0:70.
は、それぞれそのポリマー0.7gを100mlの塩化
メチレンに溶解した20℃における溶液の比粘度が0.
2〜0.4である請求項1記載の芳香族ポリカーボネー
ト組成物。2. The polymers of PC-I and PC-II each have a specific viscosity of a solution of 0.7 g of the polymer dissolved in 100 ml of methylene chloride at 20.degree.
The aromatic polycarbonate composition according to claim 1, which is 2 to 0.4.
重量%および/またはフェノール系酸化防止剤0.00
01〜0.05重量%を含有する請求項1記載の芳香族
ポリカーボネート組成物。3. A phosphorus-based heat stabilizer 0.0001 to 0.05
% By weight and / or phenolic antioxidant 0.00
The aromatic polycarbonate composition according to claim 1, which comprises 01 to 0.05% by weight.
炭素数10〜50のアルキルフェニルオキシ基を、全末
端当り少なくとも5モル%以上有する請求項1記載の芳
香族ポリカーボネート組成物。4. The aromatic polycarbonate composition according to claim 1, wherein the polymer of PC-I has an alkylphenyloxy group having 10 to 50 carbon atoms as an end group in an amount of at least 5 mol% or more based on all the ends.
て炭素数10〜50のアルキルフェニルオキシ基を、全
末端当り少なくとも5モル%以上有する請求項1記載の
芳香族ポリカーボネート組成物。5. The aromatic polycarbonate composition according to claim 1, wherein the PC-II polymer has an alkylphenyloxy group having 10 to 50 carbon atoms as an end group in an amount of at least 5 mol% or more per all ends.
組成物より形成された光学用材料。6. An optical material formed from the aromatic polycarbonate composition according to claim 1.
組成物より形成された光ディスク用基板。7. A substrate for an optical disc formed from the aromatic polycarbonate composition according to claim 1.
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JP3830983B2 JP3830983B2 (en) | 2006-10-11 |
Family
ID=15706717
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