JPH07216079A - Modified aromatic polycarbonate resin and its production - Google Patents
Modified aromatic polycarbonate resin and its productionInfo
- Publication number
- JPH07216079A JPH07216079A JP8640094A JP8640094A JPH07216079A JP H07216079 A JPH07216079 A JP H07216079A JP 8640094 A JP8640094 A JP 8640094A JP 8640094 A JP8640094 A JP 8640094A JP H07216079 A JPH07216079 A JP H07216079A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- polycarbonate resin
- aromatic polycarbonate
- bis
- 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.)
- Granted
Links
- 239000004431 polycarbonate resin Substances 0.000 title claims description 67
- 229920005668 polycarbonate resin Polymers 0.000 title claims description 67
- 125000003118 aryl group Chemical group 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- -1 phenyloxy groups Chemical group 0.000 claims abstract description 44
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 230000003287 optical effect Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 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 30
- 229920000642 polymer Polymers 0.000 description 29
- 238000000034 method Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 21
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 17
- 238000002834 transmittance Methods 0.000 description 17
- 150000002989 phenols Chemical class 0.000 description 16
- 229920000515 polycarbonate Polymers 0.000 description 16
- 239000004417 polycarbonate Substances 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000009477 glass transition Effects 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 238000000862 absorption spectrum Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 10
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 10
- 229940126062 Compound A Drugs 0.000 description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000004419 Panlite Substances 0.000 description 7
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- OKVJCVWFVRATSG-UHFFFAOYSA-N 3-hydroxybenzyl alcohol Chemical compound OCC1=CC=CC(O)=C1 OKVJCVWFVRATSG-UHFFFAOYSA-N 0.000 description 4
- 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 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 3
- IJWIRZQYWANBMP-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-propan-2-ylphenyl)propan-2-yl]-2-propan-2-ylphenol Chemical compound C1=C(O)C(C(C)C)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)C)=C1 IJWIRZQYWANBMP-UHFFFAOYSA-N 0.000 description 3
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 3
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 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 3
- 239000008188 pellet Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- BKTRENAPTCBBFA-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-phenylphenyl)propan-2-yl]-2-phenylphenol Chemical compound C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(C)(C)C(C=1)=CC=C(O)C=1C1=CC=CC=C1 BKTRENAPTCBBFA-UHFFFAOYSA-N 0.000 description 2
- ZJNKCNFBTBFNMO-UHFFFAOYSA-N 4-[3-(4-hydroxyphenyl)-5,7-dimethyl-1-adamantyl]phenol Chemical compound C1C(C)(C2)CC(C3)(C)CC1(C=1C=CC(O)=CC=1)CC23C1=CC=C(O)C=C1 ZJNKCNFBTBFNMO-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 239000002216 antistatic agent 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
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 239000002904 solvent Substances 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
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PYOLJOJPIPCRDP-UHFFFAOYSA-N 1,1,3-trimethylcyclohexane Chemical compound CC1CCCC(C)(C)C1 PYOLJOJPIPCRDP-UHFFFAOYSA-N 0.000 description 1
- 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 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
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-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
- 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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- TWSBXJSZMPALGE-UHFFFAOYSA-N 4-(3,5-dimethyl-1-adamantyl)phenol Chemical compound C1C(C)(C2)CC(C3)CC1(C)CC32C1=CC=C(O)C=C1 TWSBXJSZMPALGE-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phenol Chemical compound C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 description 1
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- MMNLWVVVDFQANH-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-methylphenyl)-1-phenylethyl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C(C)(C=2C=CC=CC=2)C=2C=C(C)C(O)=CC=2)=C1 MMNLWVVVDFQANH-UHFFFAOYSA-N 0.000 description 1
- SVOBELCYOCEECO-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-methylphenyl)cyclohexyl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(CCCCC2)C=2C=C(C)C(O)=CC=2)=C1 SVOBELCYOCEECO-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-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
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-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
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 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
- 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
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000007983 Tris buffer Substances 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
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 239000004566 building material Substances 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
- 150000001721 carbon Chemical group 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- GLOQRSIADGSLRX-UHFFFAOYSA-N decyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCC)OC1=CC=CC=C1 GLOQRSIADGSLRX-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000007865 diluting Methods 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
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 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
- 238000001704 evaporation Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000008204 material by function Substances 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
- AXRSHKZFNKUGQB-UHFFFAOYSA-N octyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC)OC1=CC=CC=C1 AXRSHKZFNKUGQB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 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
- 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 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 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
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000013638 trimer Substances 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
- 239000003039 volatile agent Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、改質芳香族ポリカーボ
ネート樹脂およびその製造法に関する。特に本発明は、
芳香族ポリカーボネート樹脂成形品の優れた透明性およ
び機械的物性を保持しているが、溶融流動性および耐ト
ラッキング性が一層改善された改質芳香族ポリカーボネ
ート樹脂およびその製造法に関する。FIELD OF THE INVENTION The present invention relates to a modified aromatic polycarbonate resin and a method for producing the same. In particular, the present invention is
TECHNICAL FIELD The present invention relates to a modified aromatic polycarbonate resin which has excellent transparency and mechanical properties of an aromatic polycarbonate resin molded article, but has further improved melt flowability and tracking resistance, and a method for producing the same.
【0002】[0002]
【従来の技術】従来、代表的な芳香族ポリカーボネート
樹脂として2,2−ビス(4−ヒドロキシフェニル)プ
ロパン(通称ビスフェノールA)にホスゲンやジフェニ
ルカーボネート等のカーボネート前駆物質を反応させて
得られるものが知られ、工業的に大量に生産されてい
る。かかる芳香族ポリカーボネート樹脂の成形品は透明
性、耐熱性、寸法精度がよい等の優れた性質を有するこ
とから多くの分野に用いられている。また、近年光ディ
スク等の分野で情報記録媒体用基板としても広く用いら
れている。2. Description of the Related Art Conventionally, a typical aromatic polycarbonate resin is one obtained by reacting 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) with a carbonate precursor such as phosgene or diphenyl carbonate. Known and industrially produced in large quantities. Molded products of such aromatic polycarbonate resins have excellent properties such as transparency, heat resistance, and good dimensional accuracy, and are therefore used in many fields. Further, in recent years, it has also been widely used as a substrate for information recording media in the field of optical disks and the like.
【0003】しかしながら、家庭用品、家庭用電気機
器、ビデオ製品、オーディオ製品などの最近の軽薄短小
化の動向を反映して、芳香族ポリカーボネート樹脂も、
いっそう溶融流動性、転写性に優れ、且つ成形サイクル
の短い樹脂の開発が要望されている。また、電気機器の
分野では耐トラッキング性の改善された芳香族ポリカー
ボネート樹脂も求められている。However, aromatic polycarbonate resins have also been reflected in the recent trend of miniaturization of household appliances, household electric appliances, video products, audio products and the like.
There is a demand for the development of a resin that is more excellent in melt flowability and transferability and has a short molding cycle. Further, in the field of electric equipment, aromatic polycarbonate resins having improved tracking resistance are also required.
【0004】芳香族ポリカーボネート樹脂の溶融流動性
を改善する方法として、平均分子量を可能な限り下げる
方法、可塑剤を添加する方法、長鎖脂肪族炭化水素置換
基をポリマー末端に付与する方法およびポリマーブレン
ドによる方法等が提案されている。しかしながら、これ
らの方法ではいずれも物性の低下を招いたり、透明性が
損なわれる等芳香族ポリカーボネート樹脂成形品が有し
ている本来の優れた特性を保持できないという問題があ
る。As a method for improving the melt fluidity of an aromatic polycarbonate resin, a method of lowering the average molecular weight as much as possible, a method of adding a plasticizer, a method of imparting a long chain aliphatic hydrocarbon substituent to a polymer terminal and a polymer A method using blending has been proposed. However, any of these methods has a problem in that the original excellent properties of the aromatic polycarbonate resin molded product, such as deterioration of physical properties and loss of transparency, cannot be maintained.
【0005】[0005]
【発明が解決しようとする課題】本発明の第1の目的
は、芳香族ポリカーボネート樹脂の本来有している透明
性、耐熱性および寸法安定性などの優れた特性を実質的
に損うことなく、溶融流動性の改善された芳香族ポリカ
ーボネート樹脂を提供することにある。SUMMARY OF THE INVENTION A first object of the present invention is to substantially prevent the aromatic polycarbonate resin from having its original excellent properties such as transparency, heat resistance and dimensional stability. Another object of the present invention is to provide an aromatic polycarbonate resin having improved melt fluidity.
【0006】本発明の第2の目的は、芳香族ポリカーボ
ネート樹脂の前記した優れた特性を保持しつつ、電気特
性、殊に耐トラッキング性の改良された芳香族ポリカー
ボネート樹脂を提供することにある。A second object of the present invention is to provide an aromatic polycarbonate resin having improved electric characteristics, especially tracking resistance, while maintaining the above-mentioned excellent characteristics of the aromatic polycarbonate resin.
【0007】本発明の第3の目的は、種々の電気・電子
部品および光学部品の構造材料として優れた特性を有す
る芳香族ポリカーボネート樹脂およびその成形品を提供
することにある。A third object of the present invention is to provide an aromatic polycarbonate resin having excellent properties as a structural material for various electric / electronic parts and optical parts, and a molded product thereof.
【0008】本発明者の他の目的は、前記改質芳香族ポ
リカーボネート樹脂の製造法を提供することにある。Another object of the present inventor is to provide a method for producing the modified aromatic polycarbonate resin.
【0009】[0009]
【課題を解決するための手段】本発明者らの研究によれ
ば、前記本発明の目的は、芳香族ポリカーボネート樹脂
であって、その全末端基の少くとも5モル%は下記一般
式(I)According to the studies made by the present inventors, the object of the present invention is an aromatic polycarbonate resin, of which at least 5 mol% of all the terminal groups has the following general formula (I )
【0010】[0010]
【化4】 [Chemical 4]
【0011】[式中、Xはハロゲン原子または炭素数1
〜10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、Qは[In the formula, X is a halogen atom or has 1 carbon atom.
10 represents a monovalent aliphatic hydrocarbon group, P represents an integer of 0 to 4, and Q represents
【0012】[0012]
【化5】 [Chemical 5]
【0013】を示す。ここでYは炭素数1〜10の二価
の脂肪族炭化水素基を示し、W1 は水素原子、−C(=
O)R1 、−C(=O)OR2 またはR3 であり、ここ
でR1、R2 およびR3 は、それぞれ炭素数1〜10の
一価の脂肪族炭化水素基、炭素数4〜8の一価の脂環族
炭化水素基または炭素数6〜15の一価の芳香族炭化水
素基を示す。mは4〜20の整数を示し、nは1〜10
0の整数を示す。]で表される少なくとも一種の置換フ
ェニルオキシ基を含有していることを特徴とする改質芳
香族ポリカーボネート樹脂によって達成されることが見
出された。Is shown. Here, Y represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, W 1 is a hydrogen atom, and -C (=
O) R 1, -C (= O) a OR 2 or R 3, wherein R 1, R 2 and R 3 are aliphatic hydrocarbon groups having 1 to 10 carbon atoms, respectively mono-, carbon atoms 4 A monovalent alicyclic hydrocarbon group having 8 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms is shown. m represents an integer of 4 to 20, n is 1 to 10
Indicates an integer of 0. ] It was found to be achieved by a modified aromatic polycarbonate resin containing at least one substituted phenyloxy group represented by
【0014】従来知られている芳香族ポリカーボネート
樹脂は、その末端基に、通常フェニルオキシ基またはア
ルキル基置換フェニルオキシ基を有しているものが殆ん
どである。このような末端基を重合体中に付与すること
は、重合度の調整や耐熱性の向上に寄与している。とこ
ろが、本発明においては、全末端の少なくとも5モル%
好ましくは7〜90モル%を前記式(I)で表される特
定構造の置換フェニルオキシ基とすることにより、芳香
族ポリカーボネート樹脂の透明性、耐熱性および寸法安
定性などの優れた特性を損うことなく、溶融流動性がよ
くなり加工が容易となるばかりでなく、電気特性が改善
された。Most of the conventionally known aromatic polycarbonate resins usually have a phenyloxy group or an alkyl group-substituted phenyloxy group at the terminal group. Providing such a terminal group in the polymer contributes to the adjustment of the degree of polymerization and the improvement of heat resistance. However, in the present invention, at least 5 mol% of all terminals
Preferably, 7 to 90 mol% of the substituted phenyloxy group having the specific structure represented by the formula (I) impairs excellent properties such as transparency, heat resistance and dimensional stability of the aromatic polycarbonate resin. In addition to improving the melt fluidity and facilitating the processing, the electrical characteristics were improved.
【0015】前記一般式(I)で表される置換フェニル
オキシ基は、Qで示されるアルキレンエステル基を有す
る残基がフェニルオキシ基に置換されている構造を有し
ている点に特徴を有している。The substituted phenyloxy group represented by the general formula (I) is characterized in that it has a structure in which a residue having an alkylene ester group represented by Q is substituted with a phenyloxy group. is doing.
【0016】以下、本発明についてさらに詳細に説明す
る。本発明において末端基を前記一般式(I)で表され
る置換フェニルオキシ基で置換されるべき構造の芳香族
ポリカーボネート樹脂は、それ自体従来知られているか
或いは工業的に生産されている重合体であることができ
る。すなわち、本発明の芳香族ポリカーボネート樹脂の
骨格は、二価フェノールとカーボネート前駆体との反応
によって得られた重合体であることができる。The present invention will be described in more detail below. The aromatic polycarbonate resin having a structure in which the terminal group of the present invention is to be substituted with the substituted phenyloxy group represented by the general formula (I) is a polymer which has been known per se or is industrially produced. Can be That is, the skeleton of the aromatic polycarbonate resin of the present invention can be a polymer obtained by the reaction of a dihydric phenol and a carbonate precursor.
【0017】芳香族ポリカーボネート樹脂の製造に使用
される二価フェノールとしては、単環および二環の二価
フェノールが挙げられ、単環の二価フェノールの具体例
としてはハイドロキノン、レゾルシンがあり、また二環
の二価フェノールの具体例としては下記一般式(III )
で表される化合物がある。Examples of the divalent phenol used in the production of the aromatic polycarbonate resin include monocyclic and bicyclic dihydric phenols, and specific examples of the monocyclic divalent phenol include hydroquinone and resorcin. Specific examples of the bicyclic dihydric phenol include the following general formula (III)
There is a compound represented by.
【0018】[0018]
【化6】 [Chemical 6]
【0019】前記式(III )中、R4 、R5 、R6 およ
びR7 は互いに同一もしくは異なり、水素原子、ハロゲ
ン原子、炭素数1〜6の脂肪族炭化水素基または炭素数
6〜12の芳香族炭化水素基を示す。Aは単結合、−O
−、−S−、−SO2 −、炭素数1〜6のアルキレン
基、炭素数2〜6のアルキリデン基、炭素数6〜10の
シクロアルキレン基、炭素数6〜10のシクロアルキリ
デン基またはフェニル置換の炭素数2〜6のアルキリデ
ン基を示す。In the above formula (III), R 4 , R 5 , R 6 and R 7 are the same or different from each other and represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms or 6 to 12 carbon atoms. Is an aromatic hydrocarbon group of. A is a single bond, -O
-, - S -, - SO 2 -, an alkylene group having 1 to 6 carbon atoms, an alkylidene group having 2 to 6 carbon atoms, cycloalkylene group having 6 to 10 carbon atoms, a cycloalkylidene group or a phenyl having 6 to 10 carbon atoms The substituted alkylidene group having 2 to 6 carbon atoms is shown.
【0020】芳香族ポリカーボネート樹脂を形成する前
記二価フェノールの具体例としては例えばハイドロキノ
ン、レゾルシン、4,4′−ジヒドロキシジフェニル、
ビス(4−ヒドロキシフェニル)メタン、1,1−ビス
(4−ヒドロキシフェニル)エタン、2,2−ビス(4
−ヒドロキシフェニル)プロパン(通称ビスフェノール
A)、2,2−ビス(3−メチル−4−ヒドロキシフェ
ニル)プロパン、1,1−ビス(4−ヒドロキシフェニ
ル)シクロヘキサン、2,2−ビス(3−フェニル−4
−ヒドロキシフェニル)プロパン、2,2−ビス(3−
イソプロピル−4−ヒドロキシフェニル)プロパン、
2,2−ビス(4−ヒドロキシフェニル)ブタン、2,
2−ビス(3,5−ジメチル−4−ヒドロキシフェニ
ル)プロパン、2,2−ビス(3,5−ジブロモ−4−
ヒドロキシフェニル)プロパン、4,4′−ジヒドロキ
シジフェニルスルホン、4,4′−ジヒドロキシジフェ
ニルスルホキシド、4,4′−ジヒドロキシジフェニル
スルフィド、3,3′−ジメチル−4,4′−ジヒドロ
キシジフェニルスルフィド、4,4′−ジヒドロキシジ
フェニルオキシド、9,9−ビス(4−ヒドロキシフェ
ニル)フルオレン、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および
1,3−ビス(4−ヒドロキシフェニル)−5,7−ジ
メチルアダマンタン等が挙げられる。Specific examples of the dihydric phenol forming the aromatic polycarbonate resin include hydroquinone, resorcin, 4,4'-dihydroxydiphenyl,
Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-phenyl) -4
-Hydroxyphenyl) propane, 2,2-bis (3-
Isopropyl-4-hydroxyphenyl) propane,
2,2-bis (4-hydroxyphenyl) butane, 2,
2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-)
Hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 4, 4'-dihydroxydiphenyl oxide, 9,9-bis (4-hydroxyphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 1,3-bis (4-hydroxy) Phenyl) -5,7-dimethyl adamantane and the like can be mentioned.
【0021】これら二価フェノール化合物のうち、ビス
フェノールA、2,2−ビス(3−メチル−4−ヒドロ
キシフェニル)プロパン、1,1−ビス(4−ヒドロキ
シフェニル)シクロヘキサン、2,2−ビス(3−フェ
ニル−4−ヒドロキシフェニル)プロパン、2,2−ビ
ス(3−イソプロピル−4−ヒドロキシフェニル)プロ
パン、2,2−ビス(4−ヒドロキシフェニル)ブタ
ン、9,9−ビス(4−ヒドロキシフェニル)フルオレ
ン、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および1,3−ビス
(4−ヒドロキシフェニル)−5,7−ジメチルアダマ
ンタンが好ましい。Among these dihydric phenol compounds, bisphenol A, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis ( 3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 9,9-bis (4-hydroxy) Phenyl) fluorene, 1,1-bis (4-hydroxyphenyl) -3,
3,5-Trimethylcyclohexane and 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane are preferred.
【0022】さらに、これら二価フェノールのうち、実
用性および物性の点からビスフェノールA、1,1−ビ
ス(4−ヒドロキシフェニル)シクロヘキサン、9,9
−ビス(4−ヒドロキシフェニル)フルオレン、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および1,3−ビス(4−ヒドロ
キシフェニル)−5,7−ジメチルアダマンタンが好ま
しい。これらは単独でまたは二種以上を組合わせて用い
てもよい。また、少量の三官能化合物を分岐剤として用
いても、脂肪族二官能性化合物を少量併用してもよい。
とりわけ本発明の芳香族ポリカーボネートは、ビスフェ
ノールAを使用して得られた樹脂が特に有用である。Further, among these dihydric phenols, bisphenol A, 1,1-bis (4-hydroxyphenyl) cyclohexane, 9,9, from the viewpoint of practicality and physical properties.
-Bis (4-hydroxyphenyl) fluorene, 1,1
-Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane are preferred. These may be used alone or in combination of two or more. Also, a small amount of a trifunctional compound may be used as a branching agent, or a small amount of an aliphatic bifunctional compound may be used in combination.
Particularly, for the aromatic polycarbonate of the present invention, a resin obtained by using bisphenol A is particularly useful.
【0023】芳香族ポリカーボネート樹脂は、前記二価
フェノールとカーボネート前駆体との反応により製造す
ることができる。その際使用されるカーボネート前駆物
質としては例えばホスゲン、ホスゲンダイマー、ホスゲ
ントリマー、上記二価フェノール類のビスクロロホーメ
ート等が挙げられ、なかでもホスゲンが好ましい。The aromatic polycarbonate resin can be produced by reacting the dihydric phenol with the carbonate precursor. Examples of the carbonate precursor used at that time include phosgene, phosgene dimer, phosgene trimer, and bischloroformate of the above dihydric phenols. Among them, phosgene is preferable.
【0024】二価フェノールとカーボネート前駆物質か
ら芳香族ポリカーボネート樹脂を製造するには、芳香族
ポリカーボネート樹脂の製造に用いる通常の方法、例え
ば二価フェノールにホスゲン等のカーボネート前駆物質
を反応させる方法を用いることにより製造される。二価
フェノールとホスゲンとの反応では、通常酸結合剤及び
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、水酸化カリウム等のアルカリ金属水酸
化物、ピリジン等が用いられる。溶媒としては例えば塩
化メチレン、クロロベンゼン等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、第四級アンモニウム塩等の触媒を用いることができ
る。反応温度は通常0〜40℃、反応時間は数分〜5時
間、反応中の pH は通常10以上に保つのが好ましい。To produce an aromatic polycarbonate resin from a dihydric phenol and a carbonate precursor, a conventional method used for producing an aromatic polycarbonate resin, for example, a method of reacting a dihydric phenol with a carbonate precursor such as phosgene is used. It is manufactured by The reaction between the dihydric phenol and phosgene is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine and the like are used. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. A catalyst such as a tertiary amine or a quaternary ammonium salt can be used to accelerate the reaction. The reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is usually preferably kept at 10 or higher.
【0025】本発明の改質芳香族ポリカーボネート樹脂
は、前記芳香族ポリカーボネート樹脂の製造において、
前記一般式(I)の置換フェニルオキシ基が末端基に結
合するように、単官能性のフェノール化合物を、二価フ
ェノール化合物およびカーボネート前駆体と共に反応系
に存在させればよい。The modified aromatic polycarbonate resin of the present invention comprises
The monofunctional phenol compound may be present in the reaction system together with the dihydric phenol compound and the carbonate precursor so that the substituted phenyloxy group of the general formula (I) is bonded to the terminal group.
【0026】すなわち、前記一般式(I)の末端基を形
成させるために使用される代表的化合物は下記一般式
(II)で表される置換フェノール化合物である。That is, a typical compound used for forming the terminal group of the general formula (I) is a substituted phenol compound represented by the following general formula (II).
【0027】[0027]
【化7】 [Chemical 7]
【0028】[式中、X、PおよびQは前記一般式
(I)における定義と同じ意味を有する]前記一般式
(II)で表される置換フェノール化合物はフェノール性
水酸基を一個有する単官能性化合物であり、芳香族ポリ
カーボネート樹脂の製造に添加されると、末端停止剤と
して作用し、末端に結合する。本発明の改質芳香族ポリ
カーボネート樹脂を得るために、前記一般式(II)で表
される置換フェノール化合物を使用すると共に他の単官
能性フェノール化合物を併用することができる。この他
の単官能性フェノール化合物は下記一般式(IV)で表す
ことができる。[Wherein X, P and Q have the same meanings as defined in the general formula (I)] The substituted phenol compound represented by the general formula (II) is a monofunctional compound having one phenolic hydroxyl group. A compound that, when added to the production of aromatic polycarbonate resins, acts as a terminating agent and binds to the ends. In order to obtain the modified aromatic polycarbonate resin of the present invention, the substituted phenol compound represented by the general formula (II) can be used together with another monofunctional phenol compound. Other monofunctional phenol compounds can be represented by the following general formula (IV).
【0029】[0029]
【化8】 [Chemical 8]
【0030】[式中、X´はハロゲン原子または炭素数
1〜10の脂肪族炭化水素基を示し、p´は0〜5の整
数を示す][In the formula, X'represents a halogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and p'represents an integer of 0 to 5]
【0031】前記一般式(IV)で表される単官能性フェ
ノール化合物の具体例としては、フェノール、p−te
rt−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を挙げることができる。Specific examples of the monofunctional phenol compound represented by the general formula (IV) include phenol and p-te.
Mention may be made of rt-butylphenol, p-cumylphenol and isooctylphenol.
【0032】本発明の改質芳香族ポリカーボネート樹脂
を製造する際に、前記一般式(II)で表される置換フェ
ノール化合物の使用量またはそれと前記一般式(IV)で
表される単官能性フェノール化合物との使用量並びに割
合は、ポリカーボネート樹脂の種類、末端基の種類、重
合度および所望する特性などによって決められる。In producing the modified aromatic polycarbonate resin of the present invention, the amount of the substituted phenol compound represented by the general formula (II) or the monofunctional phenol represented by the general formula (IV) is used. The amount and ratio of the compound used are determined by the type of polycarbonate resin, the type of end groups, the degree of polymerization and the desired properties.
【0033】前記したように、本発明の改質芳香族ポリ
カーボネート樹脂は、その全末端基の少なくとも5モル
%好ましくは7〜90モル%特に好ましくは10〜80
モル%は、前記一般式(I )で表される置換フェニルオ
キシ基を含有している。この一般式(I)で表される置
換フェニルオキシ基は前記一般式(II)で表される置換
フェノール化合物を使用することによって、ポリマーの
末端基に導入される。As described above, the modified aromatic polycarbonate resin of the present invention has at least 5 mol%, preferably 7 to 90 mol%, and particularly preferably 10 to 80 mol% of all the terminal groups.
Mol% contains the substituted phenyloxy group represented by the general formula (I). The substituted phenyloxy group represented by the general formula (I) is introduced into the terminal group of the polymer by using the substituted phenol compound represented by the general formula (II).
【0034】本発明の改質芳香族ポリカーボネート樹脂
は、前記一般式(I)で表される置換フェニルオキシ基
を前記割合で末端に含有しているが、その他の末端基は
特に制限されるわけではない。しかし、他の末端基は前
記一般式(IV)の単官能性フェノール化合物に基づく末
端基であるのが好ましい。The modified aromatic polycarbonate resin of the present invention contains the substituted phenyloxy group represented by the general formula (I) at the terminal in the above proportion, but the other terminal groups are not particularly limited. is not. However, the other end groups are preferably those based on the monofunctional phenolic compounds of the general formula (IV).
【0035】本発明の改質芳香族ポリカーボネート樹脂
を製造する最も簡単な方法は、芳香族ポリカーボネート
樹脂の重合中に前記一般式(II)で表される置換フェノ
ール化合物を原料と共に添加する方法である。しかし本
発明の改質芳香族ポリカーボネート樹脂は、必ずしも前
記式(II)の化合物を重合原料中に添加する方法によっ
て得る必要はなく、他の化合物を添加し得られた芳香族
ポリカーボネート樹脂にさらに反応性の化合物を付与し
て、結果的に前記式(I)で表される置換フェニルオキ
シ基を末端基として含有する方法であればよい。また重
合原料中に前記式(II)で表される化合物を添加し得ら
れた改質芳香族ポリカーボネート樹脂に、さらに反応性
の化合物を添加し、前記式(I)で表される置換フェニ
ルオキシ基の範ちゅうに含まれる他の末端基に変換する
こともできる。このように、一旦改質芳香族ポリカーボ
ネート樹脂を製造した後に後処理によって目的とする末
端基を付与することもできる(以下これらの方法を“後
処理法”と称することがある)。The simplest method for producing the modified aromatic polycarbonate resin of the present invention is to add the substituted phenol compound represented by the general formula (II) together with the raw materials during the polymerization of the aromatic polycarbonate resin. . However, the modified aromatic polycarbonate resin of the present invention does not necessarily have to be obtained by the method of adding the compound of the formula (II) to the polymerization raw material, and further reacts with the aromatic polycarbonate resin obtained by adding another compound. A compound having a volatile compound and resultingly containing the substituted phenyloxy group represented by the formula (I) as an end group may be used. Further, a reactive compound is added to the modified aromatic polycarbonate resin obtained by adding the compound represented by the formula (II) to the polymerization raw material, and the substituted phenyloxy compound represented by the formula (I) is added. It is also possible to convert to other end groups included in the group of groups. As described above, after the modified aromatic polycarbonate resin is once produced, the target terminal group can be imparted by post-treatment (these methods may be referred to as “post-treatment methods” hereinafter).
【0036】このような方法の例としては、前記一般式
(II)においてW1 が水素原子である化合物を使用して
その化合物を末端基に有する改質芳香族ポリカーボネー
ト樹脂を得、次いで、前記式(II)の化合物の末端のア
ルコール性水酸基をカルボン酸エステル{−C(=O)
R1 }或いは炭酸エステル{−C(=O)OR2 }の形
で封鎖する方法である。これら封鎖のためには前記改質
芳香族ポリカーボネート樹脂にカルボン酸クロライド或
いはクロロ蟻酸エステルを反応させればよい。その際使
用されるカルボン酸クロライドとしては式ClCOR1 で
表される化合物であり、ここでR1 は前記式(I)およ
び(II)の定義で示したとおり、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の脂環族炭化水素基または炭素数6〜1
5好ましくは6〜12の芳香族炭化水素基を示す。また
クロロ蟻酸エステルは式ClCOOR2 で表される化合物
であり、ここでR2 は前記R1 で説明した炭化水素基か
ら選ばれる。As an example of such a method, a compound in which W 1 is a hydrogen atom in the general formula (II) is used to obtain a modified aromatic polycarbonate resin having the compound as an end group. The terminal alcoholic hydroxyl group of the compound of formula (II) is converted to a carboxylic acid ester {-C (= O)
This is a method of blocking in the form of R 1 } or carbonic acid ester {-C (= O) OR 2 }. In order to block them, the modified aromatic polycarbonate resin may be reacted with carboxylic acid chloride or chloroformate. The carboxylic acid chloride used at this time is a compound represented by the formula ClCOR 1 , wherein R 1 has 1 to 10 carbon atoms, preferably 1 as defined in the above formulas (I) and (II). To 5 monovalent aliphatic hydrocarbon groups, 4 to 8 carbon atoms, preferably 5 to 6 alicyclic hydrocarbon groups or 6 to 1 carbon atoms
5 preferably represents 6 to 12 aromatic hydrocarbon groups. The chloroformic acid ester is a compound represented by the formula ClCOOR 2 , in which R 2 is selected from the hydrocarbon groups described for R 1 .
【0037】かくして得られる改質芳香族ポリカーボネ
ート樹脂の分子量は、あまりに低いと脆くて実用性がな
くなるので、ポリマー0.7g を塩化メチレン100ml
に溶解し、20℃で測定した溶液の比粘度が0.165
以上のものが成形品としての優れた特性を与える。好ま
しい比粘度は0.229〜0.559、特に好ましい比
粘度は0.264〜0.451の範囲である。If the molecular weight of the modified aromatic polycarbonate resin thus obtained is too low, it becomes brittle and unpractical, so 0.7 g of the polymer is added to 100 ml of methylene chloride.
And the specific viscosity of the solution measured at 20 ° C. is 0.165
The above gives excellent properties as a molded article. A preferable specific viscosity is 0.229 to 0.559, and a particularly preferable specific viscosity is 0.264 to 0.451.
【0038】本発明の改質芳香族ポリカーボネート樹脂
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。
なお本発明の改質芳香族ポリカーボネート樹脂には、必
要に応じて熱安定剤、酸化防止剤、光安定剤、着色剤、
帯電防止剤、滑剤、離型剤等の添加剤、ガラス繊維、ガ
ラスビーズ、カーボン繊維、金属繊維、タルク、シリカ
等の無機充填剤を加えることができる。また、他のポリ
カーボネート樹脂または他の熱可塑性樹脂をブレンドし
て用いることもできる。The modified aromatic polycarbonate resin 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.
The modified aromatic polycarbonate resin of the present invention, if necessary, a heat stabilizer, an antioxidant, a light stabilizer, a colorant,
Additives such as antistatic agents, lubricants and release agents, and inorganic fillers such as glass fibers, glass beads, carbon fibers, metal fibers, talc and silica can be added. Further, other polycarbonate resins or other thermoplastic resins may be blended and used.
【0039】本発明による改質芳香族ポリカーボネート
樹脂は、芳香族ポリカーボネート樹脂の本来の優れた透
明性、耐熱性および機械的物性を保持したままで溶融流
動性が著しく改善され、低温ハイサイクル成形にも適用
でき、更に耐トラッキング性も著しく改善されている。The modified aromatic polycarbonate resin according to the present invention has remarkably improved melt flowability while maintaining the original excellent transparency, heat resistance and mechanical properties of the aromatic polycarbonate resin, and is suitable for low temperature high cycle molding. Can be applied, and the tracking resistance is significantly improved.
【0040】また、改質芳香族ポリカーボネート樹脂を
得るための二価フェノールとして、2,2−ビス(3−
メチル−4−ヒドロキシフェニル)プロパン、1,1−
ビス(3−メチル−4−ヒドロキシフェニル)シクロヘ
キサン、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(3−メチル−4−ヒ
ドロキシフェニル)−1−フェニルエタン、2,2−ビ
ス(3−フェニル−4−ヒドロキシフェニル)プロパ
ン、4,4′−ジヒドロキシテトラフェニルメタン、
2,2−ビス(4−ヒドロキシフェニル)ブタン、9,
9−ビス(4−ヒドロキシフェニル)フルオレン、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(3−イソプロ
ピル−4−ヒドロキシフェニル)プロパン、および1,
3−ビス(4−ヒドロキシフェニル)−5,7−ジメチ
ルアダマンタンから選ばれた少なくとも一種を使用した
ものは、光学的特性が優れ、殊に複屈折率が小さいので
その樹脂を成形したものは低複屈折性の用途に適してい
る。かくしてこの樹脂を使用した成形品は、光学部品の
構造材料や機能材料用途、特に液晶ユニットのフラット
パネル、光カード、光ディスク、光ファイバー、コネク
ター、各種レンズ、プリズム、フィルムおよび光導波路
に適している。Further, as a dihydric phenol for obtaining a modified aromatic polycarbonate resin, 2,2-bis (3-
Methyl-4-hydroxyphenyl) propane, 1,1-
Bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1
-Phenylethane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1-phenylethane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 4,4'-dihydroxytetraphenyl methane,
2,2-bis (4-hydroxyphenyl) butane, 9,
9-bis (4-hydroxyphenyl) fluorene, 1,
1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, and 1,
The one using at least one selected from 3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane has excellent optical characteristics, and in particular, the birefringence is small. Suitable for birefringent applications. Thus, a molded product using this resin is suitable for structural materials and functional materials of optical parts, particularly for flat panels of liquid crystal units, optical cards, optical disks, optical fibers, connectors, various lenses, prisms, films and optical waveguides.
【0041】さらに本発明の改質芳香族ポリカーボネー
ト樹脂が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を二価フェノー
ルとして使用して得られたものは、他の樹脂よりも一層
耐熱性および光弾性定数が優れており、そのためランプ
用レンズとして使用するのが望ましくまたその樹脂を基
板として使用した光学情報記録媒体としても利用でき
る。Further, the modified aromatic polycarbonate resin of the present invention is 1,1-bis (4-hydroxyphenyl)-
The product obtained by using 3,3,5-trimethylcyclohexane as a dihydric phenol has more excellent heat resistance and photoelastic constant than other resins, and therefore, it is desirable to use it as a lens for a lamp. It can also be used as an optical information recording medium using the resin as a substrate.
【0042】特に光学情報記録媒体の基板として使用す
るためには、比粘度および下記定数Nが下記式(a)お
よび(b)を満足するものが好適である。 0.23≦ηSP≦0.37 (a) 30≦N≦60 (b) [上記式中ηSPは改質芳香族ポリカーボネート樹脂の
比粘度を示し、Nは改質芳香族ポリカーボネート樹脂中
の二価フェノール単位および一般式(I)で表される置
換フェニルオキシ基におけるエステル単位{−C(=
O)(CH2 )m O−}の合計モル数に対する該エステ
ル単位の割合(%)を示す]Particularly, for use as a substrate of an optical information recording medium, it is preferable that the specific viscosity and the following constant N satisfy the following expressions (a) and (b). 0.23 ≤ ηSP ≤ 0.37 (a) 30 ≤ N ≤ 60 (b) [wherein ηSP represents the specific viscosity of the modified aromatic polycarbonate resin, and N is the divalent value in the modified aromatic polycarbonate resin. Ester unit in the substituted phenyloxy group represented by the phenol unit and general formula (I) {-C (=
O) (CH 2 ) m O-} shows the ratio (%) of the ester unit to the total number of moles]
【0043】さらに本発明の改質芳香族ポリカーボネー
ト樹脂をガラス系充填剤と、両者屈折率の差を一定範囲
に調整して混合すると、透明性が改良され且つ優れた物
性を有する樹脂組成物が得られることがわかった。Furthermore, when the modified aromatic polycarbonate resin of the present invention is mixed with a glass-based filler while adjusting the difference in refractive index between the glass-based filler and the glass filler, the resin composition having improved transparency and excellent physical properties is obtained. It turned out to be obtained.
【0044】すなわち、本発明によれば、改質芳香族ポ
リカーボネート樹脂40〜95重量%および該改質芳香
族ポリカーボネート樹脂との屈折率の差が0.01以下
であるガラス系充填剤60〜5重量%よりなる樹脂組成
物およびそれからの成形品が提供される。That is, according to the present invention, 40 to 95% by weight of the modified aromatic polycarbonate resin and the glass-based fillers 60 to 5 having a difference in the refractive index with the modified aromatic polycarbonate resin of 0.01 or less. There is provided a resin composition consisting of wt% and a molded article made thereof.
【0045】かかる樹脂組成物に配合されるガラス系充
填剤は、改質芳香族ポリカーボネート樹脂との屈折率の
差が0.01以下、好ましくは0.005以下である。
屈折率の差が0.01越えると透明性が低下するように
なる。その形状は例えば繊維状、粉粒状、フレーク状、
板状等通常熱可塑性樹脂に適用可能な任意の形状のもの
であり、繊維状のものにあっては径3〜25μm 程度が
好ましく、成形品中の繊維長は0.02〜0.5mm程度
が好ましい。また、ガラス系充填剤には、樹脂との親和
性を向上させる目的でシランカップリング剤等の表面処
理を施したり、取扱性を向上させる目的でエポキシ樹
脂、アクリル系樹脂、ウレタン系樹脂等で集束処理を施
してもよい。ガラス系充填剤の添加割合は5〜60重量
%、好ましくは10〜55重量%である。5重量%未満
では、十分なガラス補強効果が得られ難く、60重量%
より多くなると成形性が低下するので適当でない。The glass-based filler compounded in such a resin composition has a difference in refractive index from the modified aromatic polycarbonate resin of 0.01 or less, preferably 0.005 or less.
If the difference in refractive index exceeds 0.01, the transparency will decrease. Its shape is, for example, fibrous, powdery, flaky,
It is an arbitrary shape that can be applied to a thermoplastic resin such as a plate, and a fibrous shape preferably has a diameter of about 3 to 25 μm, and the fiber length in a molded product is about 0.02 to 0.5 mm. Is preferred. Further, the glass-based filler may be surface-treated with a silane coupling agent or the like for the purpose of improving the affinity with the resin, or may be an epoxy resin, an acrylic resin, a urethane-based resin or the like for the purpose of improving the handleability. Focusing processing may be performed. The addition ratio of the glass-based filler is 5 to 60% by weight, preferably 10 to 55% by weight. If it is less than 5% by weight, it is difficult to obtain a sufficient glass reinforcing effect, and 60% by weight.
If the amount is larger, the moldability is lowered, so that it is not suitable.
【0046】前記樹脂組成物を製造するには任意の方法
が採用される。例えば改質芳香族ポリカーボネート樹脂
およびガラス系充填剤をタンブラー、スーパーミキサ
ー、ナウターミキサー等を用いてドライブレンドした後
押出機によりペレット化する方法、改質芳香族ポリカー
ボネート樹脂および他の添加剤を予め混合した後、ガラ
ス繊維と共に押出してペレット化する方法等いずれでも
よい。また、この樹脂組成物は例えば射出成形法、圧縮
成形法、押出成形法等任意の方法で成形品とすることが
できる。Any method may be used to produce the resin composition. For example, a method of dry blending a modified aromatic polycarbonate resin and a glass-based filler using a tumbler, a super mixer, a Nauta mixer, etc., and then pelletizing the mixture, a modified aromatic polycarbonate resin and other additives in advance. After mixing, any method such as extrusion with glass fibers and pelletization may be used. The resin composition can be formed into a molded product by any method such as an injection molding method, a compression molding method and an extrusion molding method.
【0047】また前記樹脂組成物には、必要により各種
熱安定剤および酸化防止剤を加えることができる。熱安
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−te
rt−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およびテトラキス(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、モノエステルが挙げられ、これらは単独で使用して
も、二種以上併用してもよい。一方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)イソシアヌレートおよび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)ウンデカン等のフェノール系酸化防止剤が挙げられ
る。If necessary, various heat stabilizers and antioxidants can be added to the resin composition. Examples of the heat stabilizer include triphenylphosphite, trisnonylphenylphosphite, tris (2,4-di-).
tert-butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite,
Dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-te
rt-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 and tetrakis (2,2
4-di-tert-butylphenyl) -4,4-diphenylenephosphonite and other phosphorous acid triesters, diesters, and monoesters may be used. These may be used alone or in combination of two or more. Good. On the other hand, examples of the antioxidant include 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-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {1,1-
Dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5
5) Examples include phenolic antioxidants such as undecane.
【0048】前記熱安定剤および酸化防止剤の添加量
は、改質芳香族ポリカーボネート樹脂に対して0.00
005〜0.05重量%の範囲が適当である。また必要
により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、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、部分エステル等が挙げられ、その好ましい添加量は
0.001〜0.2重量%程度である。さらに光安定
剤、着色剤、帯電防止剤、滑剤等の添加剤を加えること
もでき、他のポリカーボネート樹脂や他の熱可塑性樹脂
をブレンドすることもできる。The amount of the heat stabilizer and antioxidant added is 0.00 based on the modified aromatic polycarbonate resin.
A range of 005 to 0.05% by weight is suitable. If desired, higher fatty acid esters of polyhydric alcohols may be added, and preferred fatty acid esters include saturated aliphatic monocarboxylic acids having 8 to 22 carbon atoms and glycols,
Examples thereof include total esters and partial esters with glycerol and pentaerythritol, and the preferable addition amount thereof is about 0.001 to 0.2% by weight. Further, additives such as a light stabilizer, a colorant, an antistatic agent and a lubricant can be added, and another polycarbonate resin or another thermoplastic resin can be blended.
【0049】前記ガラス系充填剤含有樹脂組成物は透明
性が改善されているので自動車部品、建材分野、電気電
子部品等の分野の成形品として極めて好適に用いられ
る。Since the resin composition containing a glass-based filler has improved transparency, it is very suitably used as a molded article in the fields of automobile parts, building materials, electric / electronic parts and the like.
【0050】[0050]
【実施例】以下に実施例をあげて本発明を更に説明す
る。なお、実施例中の部及び%は重量部及び重量%であ
り、評価は下記の方法によった。 (a) 比粘度はポリマー0.7g を塩化メチレン100ml
に溶解し、20℃で測定した。 (b) ガラス転移温度はデュポンDSC 910を用いて測定
した。 (c) 全光線透過率は日本電色製シグマ80を用いて測定
した。 (d) 溶融流動性(MFR)は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測定し
た。測定温度は280℃とし荷重は2.16kgとした。 (e) アイゾット衝撃強度はJIS K 7110に準拠して測
定した(厚み1/8インチ、ノッチ付き)。 (f) 耐トラッキング性はIEC 112に準拠して測定し
た。EXAMPLES The present invention will be further described with reference to the following examples. The parts and% in the examples are parts by weight and% by weight, and the evaluation was performed by the following method. (a) Specific viscosity is 0.7 g of polymer and 100 ml of methylene chloride.
And was measured at 20 ° C. (b) The glass transition temperature was measured using DuPont DSC 910. (c) The total light transmittance was measured using Sigma 80 manufactured by Nippon Denshoku. (d) Melt fluidity (MFR) was measured according to JIS K 7210 using a semi-auto melt indexer manufactured by Toyo Seiki. The measurement temperature was 280 ° C. and the load was 2.16 kg. (e) Izod impact strength was measured according to JIS K 7110 (thickness 1/8 inch, with notch). (f) Tracking resistance was measured according to IEC 112.
【0051】[参考例1](置換フェノ−ル化合物の合
成) 乾燥した温度計、撹拌機および還流冷却器付き反応器に
m−ヒドロキシベンジルアルコール248部およびテト
ライソプロピルチタネート0.02部を入れて窒素気流
中で145℃に加熱し、この温度でテトライソプロピル
チタネート0.08部を配合したε−カプロラクトン1
140部を70分を要して添加した。この添加中に温度
は徐々に180℃に上昇した。さらに120分間170
℃で攪拌を続けて反応を終了した。得られた反応生成物
の水酸基価は75.8mg KOH/g、酸価は2.3mg KOH
/g 、収率は殆ど定量的であった。この反応生成物のNM
Rのチャートを図1に示した。このNMR のチャートから
も反応生成物がフェノール末端ポリε−カプロラクトン
(n=5)であることが判る。以下、この反応生成物を
“置換フェノ−ル化合物A”と略称する。すなわちこの
反応生成物は下記構造を有する。Reference Example 1 (Synthesis of Substituted Phenol Compound) 248 parts of m-hydroxybenzyl alcohol and 0.02 part of tetraisopropyl titanate were put into a reactor equipped with a dry thermometer, stirrer and reflux condenser. Ε-caprolactone 1 which was heated to 145 ° C. in a nitrogen stream, and 0.08 parts of tetraisopropyl titanate was added at this temperature.
140 parts were added over 70 minutes. The temperature gradually increased to 180 ° C during this addition. 170 for an additional 120 minutes
The reaction was completed by continuing stirring at ℃. The reaction product obtained had a hydroxyl value of 75.8 mg KOH / g and an acid value of 2.3 mg KOH.
/ G, the yield was almost quantitative. NM of this reaction product
The R chart is shown in FIG. From this NMR chart, it can be seen that the reaction product is phenol-terminated poly ε-caprolactone (n = 5). Hereinafter, this reaction product is abbreviated as "substituted phenol compound A". That is, this reaction product has the following structure.
【0052】[0052]
【化9】 [Chemical 9]
【0053】ここでε−カプロラクトンの重合度部分の
n=5は平均値を表すものとする(以下同じ)。Here, n = 5 in the degree of polymerization of ε-caprolactone represents an average value (the same applies hereinafter).
【0054】なお、前記反応生成物の酸価および水酸基
価は日本薬局法油脂試験法に準拠して測定し、NMR の測
定は重クロロホルム溶液を使用して行なった。The acid value and the hydroxyl value of the reaction product were measured according to the Japanese Pharmacopoeia method for fats and oils, and NMR was measured using a heavy chloroform solution.
【0055】[参考例2]m−ヒドロキシベンジルアル
コールの使用量を62部とする以外は参考例1と同様に
反応させた。得られた反応生成物の水酸基価は24.3
mg KOH/g 、酸価は1.0mg KOH/g であった。収率は
殆ど定量的であった。この反応生成物のNMR チャートを
図2に示した。このNMR チャートからも反応生成物がフ
ェノール末端ポリε−カプロラクトン(n=20)であ
ることが判る。以下この反応生成物を“置換フェノール
化合物B”と略称する。[Reference Example 2] The reaction was carried out in the same manner as in Reference Example 1 except that the amount of m-hydroxybenzyl alcohol used was 62 parts. The obtained reaction product has a hydroxyl value of 24.3.
The mg value was 1.0 mg KOH / g and the acid value was 1.0 mg KOH / g. The yield was almost quantitative. The NMR chart of this reaction product is shown in FIG. From this NMR chart, it can be seen that the reaction product is phenol-terminated poly ε-caprolactone (n = 20). Hereinafter, this reaction product is abbreviated as "substituted phenol compound B".
【0056】[実施例1]温度計、攪拌機、ホスゲン吹
込管および還流冷却器付き反応槽にイオン交換水495
4部及び48%水酸化ナトリウム水溶液347.7部を
仕込み、これにビスフェノールA955.9部およびハ
イドロサルファイト0.95部を溶解した後、塩化メチ
レン3049.5部を加え、撹拌下15〜20℃でホス
ゲン456.3部を60分を要して吹込んだ。ホスゲン
吹込み終了後置換フェノール化合物A)165.8部を
塩化メチレン400部に溶解して加え、更に48%水酸
化ナトリウム水溶液174.9部およびビスフェノール
A93.3部を加えて乳化させた後、トリエチルアミン
3部を加え、28〜33℃で約2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、水
洗した後塩酸酸性にして水洗し、水相の導電率がイオン
交換水と殆ど同じになったところで塩化メチレンを蒸発
させて無色の改質ポリカーボネート1130部(収率9
2%)を得た。このポリマーのカプロラクトン部分の割
合は IR 吸収スペクトル分析で12.3%、比粘度は
0.390、ガラス転移温度は104℃、MFR は28 g
/10分、全光線透過率は89%、アイゾット衝撃強度
は41kg・cm/cmであった。[Example 1] Ion-exchanged water 495 was added to a reaction tank equipped with a thermometer, a stirrer, a phosgene blow-in tube and a reflux condenser.
4 parts and 347.7 parts of a 48% sodium hydroxide aqueous solution were charged, 955.9 parts of bisphenol A and 0.95 parts of hydrosulfite were dissolved therein, methylene chloride 3049.5 parts was added, and the mixture was stirred for 15 to 20 parts. 456.3 parts of phosgene were bubbled in at 0 ° C. over a period of 60 minutes. After the completion of blowing phosgene, 165.8 parts of the substituted phenol compound A) was dissolved in 400 parts of methylene chloride and added, and 174.9 parts of a 48% sodium hydroxide aqueous solution and 93.3 parts of bisphenol A were added and emulsified. Triethylamine (3 parts) was added, and the reaction was completed by stirring at 28 to 33 ° C for about 2 hours. 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 give colorless modified polycarbonate 1130. Parts (yield 9
2%) was obtained. The proportion of caprolactone moiety in this polymer was 12.3% by IR absorption spectrum analysis, the specific viscosity was 0.390, the glass transition temperature was 104 ° C, and the MFR was 28 g.
/ 10 minutes, the total light transmittance was 89%, and the Izod impact strength was 41 kg · cm / cm.
【0057】[実施例2]実施例1で用いた反応槽にイ
オン交換水4206.2部および48%水酸化ナトリウ
ム水溶液295.2部を仕込み、これにビスフェノール
A811.7部およびハイドロサルファイト2.4部を
溶解した後、塩化メチレン2589.4部を加え、実施
例1と同様の条件でホスゲン387.5部を吹込んだ。
ホスゲン吹込み終了後置換フェノール化合物B487.
8部を塩化メチレン800部に溶解して加え、更に48
%水酸化ナトリウム水溶液148.5部およびビスフェ
ノールA79.2部を加え、以下実施例1と同様にして
改質ポリカーボネート1321.4部(収率95%)を
得た。このポリマーのカプロラクトン部分の割合は IR
吸収スペクトル分析で34.3%、比粘度は0.35
5、ガラス転移温度は35.4℃であった。このポリマ
ーにガラスファイバーチョップドストランド[日東紡
(株)製3 PE-455 FB ]を20%ドライブレンド
し、押出機によりペレット状に押出した後3mm厚みの角
板に射出成形した。このものの耐トラッキング性は20
0V で100滴以上であった。Example 2 The reaction tank used in Example 1 was charged with 4206.2 parts of ion-exchanged water and 295.2 parts of a 48% aqueous sodium hydroxide solution, and 811.7 parts of bisphenol A and hydrosulfite 2 were charged therein. After dissolving .4 parts, 2589.4 parts of methylene chloride were added, and 387.5 parts of phosgene was blown in under the same conditions as in Example 1.
After completion of blowing phosgene, substituted phenol compound B487.
Dissolve 8 parts in 800 parts of methylene chloride and add
% Aqueous sodium hydroxide solution (148.5 parts) and bisphenol A (79.2 parts) were added to obtain 1321.4 parts (yield 95%) of modified polycarbonate in the same manner as in Example 1. The percentage of caprolactone moiety in this polymer is IR
34.3% by absorption spectrum analysis, specific viscosity 0.35
5. The glass transition temperature was 35.4 ° C. 20% of this polymer was dry blended with glass fiber chopped strand [3 PE-455 FB manufactured by Nitto Boseki Co., Ltd.], extruded into pellets by an extruder, and injection-molded into a square plate having a thickness of 3 mm. The tracking resistance of this product is 20
More than 100 drops at 0V.
【0058】[実施例3]比粘度0.405のビスフェ
ノールAポリカーボネート[帝人化成(株)製パンライ
ト L−1225 W]100部に実施例1で得た改質ポリ
カーボネート68.5部を混合し、押出機により250
℃で押出してペレット化した。このもののカプロラクト
ン部分の割合は IR 吸収スペクトル分析で5%、MFR は
17 g/10分、全光線透過率は89%、衝撃強度は8
6kg・cm/cmであった。Example 3 68.5 parts of the modified polycarbonate obtained in Example 1 was mixed with 100 parts of bisphenol A polycarbonate [Panlite L-1225 W manufactured by Teijin Chemicals Ltd.] having a specific viscosity of 0.405. 250 depending on extruder
It was extruded at 0 ° C and pelletized. The proportion of caprolactone portion of this product was 5% by IR absorption spectrum analysis, MFR was 17 g / 10 min, total light transmittance was 89%, and impact strength was 8
It was 6 kg · cm / cm.
【0059】[実施例4]比粘度0.405のビスフェ
ノールAポリカーボネート[帝人化成(株)製パンライ
ト L−1225 W]100部に実施例2で得た改質ポリ
カーボネート17.1部を混合し、押出機により250
℃で押出してペレット化した。このもののカプロラクト
ン部分の割合は IR 吸収スペクトル分析で5%、MFR は
18 g/10分、全光線透過率は89%、衝撃強度は8
5kg・cm/cmであった。Example 4 100 parts of bisphenol A polycarbonate [Panlite L-1225 W manufactured by Teijin Chemicals Ltd.] having a specific viscosity of 0.405 was mixed with 17.1 parts of the modified polycarbonate obtained in Example 2. 250 depending on extruder
It was extruded at 0 ° C and pelletized. The ratio of caprolactone portion of this product was 5% by IR absorption spectrum analysis, MFR was 18 g / 10 min, total light transmittance was 89%, and impact strength was 8
It was 5 kg · cm / cm.
【0060】[実施例5]比粘度0.405のビスフェ
ノールAポリカーボネート[帝人化成(株)製パンライ
ト L−1225 W]100部に実施例2で得た改質ポリ
カーボネート41.2部を混合し、押出機により230
℃で押出してペレット化した。このもののカプロラクト
ン部分の割合は IR 吸収スペクトル分析で10%、MFR
は25 g/10分、全光線透過率は89%、衝撃強度は
45kg・cm/cmであった。Example 5 100 parts of a bisphenol A polycarbonate having a specific viscosity of 0.405 [Panlite L-1225 W manufactured by Teijin Chemicals Ltd.] was mixed with 41.2 parts of the modified polycarbonate obtained in Example 2. 230 by extruder
It was extruded at 0 ° C and pelletized. The ratio of caprolactone portion of this product was 10% by IR absorption spectrum analysis, MFR
Was 25 g / 10 minutes, the total light transmittance was 89%, and the impact strength was 45 kg · cm / cm.
【0061】[比較例1]比粘度0.405のビスフェ
ノールAポリカーボネート[帝人化成(株)製パンライ
ト L−1225 W]を押出機により270℃で押出して
ペレット化した。このものの MFRは11 g/10分、全
光線透過率は90%、衝撃強度は95kg・cm/cmであっ
た。このポリマーに実施例2と同様にガラスファイバー
チョップドストランドを20%ドライブレンドして耐ト
ラッキング性を評価したところ200V で40〜90滴
とバラツキが大きかった。Comparative Example 1 Bisphenol A polycarbonate [Panlite L-1225W manufactured by Teijin Kasei Co., Ltd.] having a specific viscosity of 0.405 was extruded at 270 ° C. by an extruder to be pelletized. This product had an MFR of 11 g / 10 minutes, a total light transmittance of 90%, and an impact strength of 95 kg · cm / cm. When 20% of the glass fiber chopped strands were dry blended with this polymer in the same manner as in Example 2 and the tracking resistance was evaluated, there was a large variation of 40 to 90 drops at 200V.
【0062】[比較例2]比粘度0.405のビスフェ
ノールAポリカーボネート[帝人化成(株)製パンライ
ト L−1225 W]に市販のポリカプロラクトン[ダイ
セル(株)製 PLACCEL H−1、数平均分子量1000
0)を5%ドライブレンドし、押出機により260℃で
押出してペレット化した。このものの見かけの粘度平均
分子量は22000、比粘度は0.400、MFR は13
g/10分、全光線透過率は88%、衝撃強度は9kg・
cm/cmであった。Comparative Example 2 Bisphenol A polycarbonate having a specific viscosity of 0.405 [Panlite L-1225 W manufactured by Teijin Chemicals Ltd.] and commercially available polycaprolactone [PLACCEL H-1 manufactured by Daicel Corp., number average molecular weight] 1000
0) was 5% dry blended and extruded by an extruder at 260 ° C. to form pellets. This product has an apparent viscosity average molecular weight of 22,000, a specific viscosity of 0.400 and an MFR of 13
g / 10 minutes, total light transmittance 88%, impact strength 9 kg
It was cm / cm.
【0063】[実施例6]実施例1で用いた反応槽に純
水17800部および48.5%水酸化ナトリウム水溶
液3732部を仕込み、これに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3131部を溶解した後、塩化メチレン11110
部を加え、撹拌下20℃でホスゲン1200部を約40
分を要して吹込んだ。ホスゲン吹込み終了後内温を30
℃に上げ、置換フェノール化合物A420.6部を加え
て乳化させた後、トリエチルアミン3.5部を加え、約
2時間撹拌して反応を終了した。反応終了後有機相を分
離し、塩化メチレンで希釈して水洗した後塩酸で中和
し、水洗を繰返して水相の導電率が純水と殆ど等しくな
ったところで有機相を分離し、塩化メチレンを蒸発させ
ながら粉砕して無色の改質ポリカーボネート3794.
5部(収率99.5%)を得た。このポリマーの比粘度
は0.339、ガラス転移温度は175℃、MFR は2.
0 g/10分であった。このポリマーにトリス(ノニル
フェニル)ホスファイトを0.03%、イルガノックス
1076を0.05%及びステアリン酸モノグリセリド
を0.2%加え、280℃で溶融押出してペレット化し
た後、40mmφ、1mm厚みの試験片に射出成形した。こ
の試験片の全光線透過率は89%であった。Example 6 The reaction tank used in Example 1 was charged with 17800 parts of pure water and 3732 parts of a 48.5% sodium hydroxide aqueous solution, and 1,1-bis (4-hydroxyphenyl) -3 was added thereto. , 3,5-Trimethylcyclohexane 3131 parts were dissolved and then methylene chloride 11110
Parts and add about 40 parts of phosgene 1200 parts under stirring at 20 ° C.
It took minutes to blow. After finishing blowing phosgene, the internal temperature is 30
After the temperature was raised to 0 ° C., 420.6 parts of the substituted phenol compound A was added and emulsified, 3.5 parts of triethylamine was added and stirred for about 2 hours to complete the reaction. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, neutralized with hydrochloric acid, and repeatedly washed with water. When the conductivity of the aqueous phase becomes almost equal to that of pure water, the organic phase is separated, and methylene chloride is added. Of colorless modified polycarbonate 3794.
5 parts (yield 99.5%) were obtained. This polymer has a specific viscosity of 0.339, a glass transition temperature of 175 ° C. and an MFR of 2.
It was 0 g / 10 minutes. 0.03% of tris (nonylphenyl) phosphite, 0.05% of Irganox 1076 and 0.2% of stearic acid monoglyceride were added to this polymer, and the mixture was melt extruded at 280 ° C. and pelletized, then 40 mmφ, 1 mm thick Was injection-molded into a test piece. The total light transmittance of this test piece was 89%.
【0064】[実施例7]置換フェノール化合物Aの使
用量を350.5部にし、更に p−tert−ブチルフェノ
ールを15.2部用いる以外は実施例6と同様にして改
質ポリカーボネート3721部(収率99%)を得た。
このポリマーの比粘度は0.293、ガラス転移温度は
176℃、MFR は2.5 g/10分であった。このポリ
マーに実施例6と同様の添加剤を加えて実施例6と同様
に成形して評価したところ全光線透過率は89%であっ
た。Example 7 3721 parts of modified polycarbonate were obtained in the same manner as in Example 6 except that the amount of the substituted phenol compound A used was 350.5 parts and 15.2 parts of p-tert-butylphenol was used. Rate 99%) was obtained.
The specific viscosity of this polymer was 0.293, the glass transition temperature was 176 ° C., and the MFR was 2.5 g / 10 minutes. When the same additives as in Example 6 were added to this polymer and molding was carried out in the same manner as in Example 6 and evaluated, the total light transmittance was 89%.
【0065】[実施例8]置換フェノール化合物Aの使
用量を350.5部にし、更に p−tert−ブチルフェノ
ールを30.3部用いる以外は実施例6と同様にして改
質ポリカーボネート3736部(収率99%)を得た。
このポリマーの比粘度は0.253、ガラス転移温度は
173℃、MFR は4.0 g/10分であった。このポリ
マーに実施例6と同様の添加剤を加えて実施例6と同様
に成形して評価したところ全光線透過率は90%であっ
た。Example 8 3736 parts of modified polycarbonate (acquisition yield) in the same manner as in Example 6 except that the amount of substituted phenol compound A used was 350.5 parts and p-tert-butylphenol was 30.3 parts. Rate 99%) was obtained.
The polymer had a specific viscosity of 0.253, a glass transition temperature of 173 ° C., and an MFR of 4.0 g / 10 minutes. When the same additives as in Example 6 were added to this polymer and molding was performed in the same manner as in Example 6 and evaluated, the total light transmittance was 90%.
【0066】[実施例9]置換フェノール化合物Aの使
用量を210.3部にし、更に p−tert−ブチルフェノ
ールを45.5部用いる以外は実施例6と同様にして改
質ポリカーボネート3593.9部(収率98.5%)
を得た。このポリマーの比粘度は0.290、ガラス転
移温度は180℃、MFR は2.0 g/10分であった。
このポリマーに実施例6と同様の添加剤を加えて実施例
6と同様に成形して評価したところ全光線透過率は90
%であった。Example 9 Modified polycarbonate 3593.9 parts in the same manner as in Example 6 except that the amount of the substituted phenol compound A used was 210.3 parts, and p-tert-butylphenol was 45.5 parts. (Yield 98.5%)
Got The specific viscosity of this polymer was 0.290, the glass transition temperature was 180 ° C., and the MFR was 2.0 g / 10 minutes.
When the same additives as in Example 6 were added to this polymer and molding was carried out in the same manner as in Example 6 and evaluated, the total light transmittance was 90.
%Met.
【0067】[比較例3]置換フェノール化合物Aに代
えて p−tert−ブチルフェノールを90.9部用いる以
外は実施例6と同様にしてポリマー3469.7部(収
率99.6%)を得た。このポリマーの比粘度は0.2
48、ガラス転移温度は227℃、MFR は0.3 g/1
0分と溶融流動性が悪かった。このポリマーを用いて実
施例6と同様に成形したところ、成形片にヤケが生じ、
全光線透過率は83%と低くなった。[Comparative Example 3] Polymer 3469.7 parts (yield 99.6%) was obtained in the same manner as in Example 6 except that 90.9 parts of p-tert-butylphenol was used in place of the substituted phenol compound A. It was The specific viscosity of this polymer is 0.2
48, glass transition temperature 227 ° C, MFR 0.3 g / 1
The melt flowability was poor at 0 minutes. When molding was carried out in the same manner as in Example 6 using this polymer, the molded piece was burned,
The total light transmittance was as low as 83%.
【0068】[実施例10]実施例1で用いた反応槽に
イオン交換水4954部および48%水酸化ナトリウム
水溶液347.7部を仕込み、これにビスフェノールA
955.9部およびハイドロサルファイト0.95部を
溶解した後塩化メチレン3049.5部を加え、撹拌下
15〜20℃でホスゲン456.3部を60分を要して
吹込んだ。ホスゲン吹込み終了後置換フェノール化合物
A165.8部を塩化メチレン400部に溶解して加
え、更に48%水酸化ナトリウム水溶液174.9部お
よびビスフェノールA93.3部を加えて乳化させた
後、トリエチルアミン3部を加えて28〜33℃で約1
時間撹拌して反応を終了した。反応終了後生成物を塩化
メチレンで希釈して水洗した後塩酸酸性にして水洗し、
水相の導電率がイオン交換水と殆ど同じになったところ
で塩化メチレン相を分離し、乾燥した無水硫酸ナトリウ
ムで脱水した後塩化ベンゾイル50.4部を加え、更に
ピリジン28.5部を加え、約1時間撹拌して反応を終
了した。反応を終了後濾過してピリジンの塩酸塩を除去
した後塩酸酸性にして水洗し、水相の導電率がイオン交
換水と殆ど同じになったところで塩化メチレンを蒸発さ
せて無色の改質ポリカーボネート1165.2部(収率
93%)を得た。このポリマ−の末端 OH 基は IR 吸収
スペクトル分析で殆ど検出されず、比粘度は0.39
4、ガラス転移温度は105℃、MFR は26 g/10
分、全光線透過率は89%、衝撃強度は45kg・cm/cm
であった。Example 10 The reaction tank used in Example 1 was charged with 4954 parts of ion-exchanged water and 347.7 parts of a 48% sodium hydroxide aqueous solution, and bisphenol A was added thereto.
After 955.9 parts and 0.95 parts of hydrosulfite were dissolved, 3049.5 parts of methylene chloride was added, and 456.3 parts of phosgene was blown in at 15 to 20 ° C. for 60 minutes while stirring. After the completion of phosgene blowing, 165.8 parts of the substituted phenol compound A was dissolved in 400 parts of methylene chloride and added, and 174.9 parts of a 48% aqueous sodium hydroxide solution and 93.3 parts of bisphenol A were added to emulsify the product, and then triethylamine 3 was added. Add 1 part at 28-33 ℃
The reaction was completed by stirring for a period of time. After the reaction was completed, 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 the ion-exchanged water, the methylene chloride phase was separated, dehydrated with dry anhydrous sodium sulfate, 50.4 parts of benzoyl chloride was added, and 28.5 parts of pyridine was further added. The reaction was completed by stirring for about 1 hour. After the completion of the reaction, the pyridine hydrochloride is removed by filtration and then acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water, methylene chloride is evaporated to give colorless modified polycarbonate 1165. .2 parts (yield 93%) was obtained. The terminal OH group of this polymer was hardly detected by IR absorption spectrum analysis, and the specific viscosity was 0.39.
4. Glass transition temperature is 105 ℃, MFR is 26 g / 10
Min, total light transmittance is 89%, impact strength is 45 kg · cm / cm
Met.
【0069】[実施例11]実施例1で用いた反応槽に
イオン交換水4206.2部および48%水酸化ナトリ
ウム水溶液295.2部を仕込み、これにビスフェノー
ルA811.7部およびハイドロサルファイト2.4部
を溶解した後、塩化メチレン2589.4部を加え、実
施例1と同様の条件でホスゲン387.5部を吹込ん
だ。ホスゲン吹込み終了後置換フェノール化合物Bのア
ルコール末端をアセチル化したもの496.3部を塩化
メチレン800部に溶解して添加し、更に48%水酸化
ナトリウム水溶液148.5部およびビスフェノールA
79.2部を加えて乳化させた後、トリエチルアミン3
部を加えて28〜33℃で約1時間撹拌して反応を終了
した。反応終了後実施例1と同様に精製して改質ポリカ
ーボネート1315.2部(収率94%)を得た。この
ポリマーの末端 OH 基は IR 吸収スペクトル分析で殆ど
検出されず、比粘度は0.360、ガラス転移温度は3
7℃であった。このポリマーにガラスファイバーチョッ
プドストランド[日東紡(株)製3 PE-455 FB ]を
20%ドライブレンドし、押出機によりペレット状に押
出した後3mm厚みの角板に射出成形した。このものの耐
トラッキング性は200V で100滴以上であった。Example 11 The reaction tank used in Example 1 was charged with 4206.2 parts of ion-exchanged water and 295.2 parts of a 48% sodium hydroxide aqueous solution, and 811.7 parts of bisphenol A and hydrosulfite 2 were charged therein. After dissolving .4 parts, 2589.4 parts of methylene chloride were added, and 387.5 parts of phosgene was blown in under the same conditions as in Example 1. After the completion of blowing phosgene, 496.3 parts of the substituted phenol compound B in which the alcohol terminal was acetylated was dissolved in 800 parts of methylene chloride and added, and further, 148.5 parts of a 48% sodium hydroxide aqueous solution and bisphenol A were added.
After 79.2 parts were added and emulsified, triethylamine 3 was added.
The mixture was added and stirred at 28 to 33 ° C. for about 1 hour to complete the reaction. After the completion of the reaction, purification was carried out in the same manner as in Example 1 to obtain 1315.2 parts (yield 94%) of modified polycarbonate. The terminal OH groups of this polymer were hardly detected by IR absorption spectroscopy, the specific viscosity was 0.360 and the glass transition temperature was 3
It was 7 ° C. 20% of this polymer was dry blended with glass fiber chopped strand [3 PE-455 FB manufactured by Nitto Boseki Co., Ltd.], extruded into pellets by an extruder, and injection-molded into a square plate having a thickness of 3 mm. The tracking resistance of this product was 100 drops or more at 200V.
【0070】[実施例12]比粘度0.405のビスフ
ェノールAポリカーボネート[帝人化成(株)製パンラ
イト L−1225 W]100部に実施例10で得た改質
ポリカーボネート69.8部を混合し、押出機により2
50℃で押出してペレット化した。このもののカプロラ
クトン部分の割合は IR 吸収スペクトル分析で5%、MF
R は15 g/10分、全光線透過率は89%、衝撃強度
は84kg・cm/cmであった。Example 12 100 parts of a bisphenol A polycarbonate having a specific viscosity of 0.405 [Panlite L-1225 W manufactured by Teijin Chemicals Ltd.] was mixed with 69.8 parts of the modified polycarbonate obtained in Example 10. , By extruder 2
It was extruded at 50 ° C. and pelletized. The ratio of the caprolactone portion of this product was 5% by IR absorption spectrum analysis, MF
R was 15 g / 10 minutes, total light transmittance was 89%, and impact strength was 84 kg · cm / cm.
【0071】[実施例13]比粘度0.405のビスフ
ェノールAポリカーボネート[帝人化成(株)製パンラ
イト L−1225 W]100部に実施例11で得た改質
ポリカーボネート17.2部を混合し、押出機により2
50℃で押出してペレット化した。このもののカプロラ
クトン部分の割合は IR 吸収スペクトル分析で5%、MF
R は19 g/10分、全光線透過率は89%、衝撃強度
は81kg・cm/cmであった。[Example 13] 100 parts of bisphenol A polycarbonate [Panlite L-1225 W manufactured by Teijin Chemicals Ltd.] having a specific viscosity of 0.405 was mixed with 17.2 parts of the modified polycarbonate obtained in Example 11. , By extruder 2
It was extruded at 50 ° C. and pelletized. The ratio of the caprolactone portion of this product was 5% by IR absorption spectrum analysis, MF
R was 19 g / 10 minutes, total light transmittance was 89%, and impact strength was 81 kg · cm / cm.
【0072】[実施例14]実施例1で用いた反応槽に
純水17800部および48.5%水酸化ナトリウム水
溶液3732部を仕込み、これに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3131部を溶解した後塩化メチレン11110
部を加え、撹拌下20℃でホスゲン1200部を約40
分を要して吹込んだ。ホスゲン吹込み終了後内温を30
℃に上げ、置換フェノール化合物A420.6部を加え
て乳化させた後、トリエチルアミン3.5部を加え、約
1時間撹拌して反応を終了し、反応終了後有機相を分離
し、塩化メチレンで希釈して水洗した後、塩酸で中和
し、水洗を繰返して水相の導電率が純水と略等しくなっ
たところで有機相を分離し、乾燥した無水硫酸ナトリウ
ムで脱水した後クロロ蟻酸フェニル123.3部を加
え、更にピリジン62.5部を加えて約1時間撹拌して
反応を終了した。反応終了後濾過してピリジンの塩酸塩
を除去し、水洗した後塩酸酸性にして水洗を繰返し、水
相の導電率が純水と略等しくなったところで塩化メチレ
ンを蒸発させながら粉砕して無色の改質ポリカーボネー
ト3730.8部(収率96%)を得た。このポリマー
の末端 OH 基は IR 吸収スペクトル分析で殆ど検出され
ず、比粘度は0.341、ガラス転移温度は177℃、
MFR は3.0 g/10分であった。このポリマーにトリ
ス(ノニルフェニル)ホスファイトを0.03%、イル
ガノックス1076を0.05%及びステアリン酸モノ
グリセリドを0.2%加えて280℃で溶融押出してペ
レット化した後40mmφ、1mm厚みの試験片に射出成形
した。この試験片の全光線透過率は89%であった。Example 14 The reactor used in Example 1 was charged with 17800 parts of pure water and 3732 parts of a 48.5% aqueous sodium hydroxide solution, and 1,1-bis (4-hydroxyphenyl) -3 was added thereto. , 3,5-Trimethylcyclohexane 3131 parts were dissolved and then methylene chloride 11110
Parts and add about 40 parts of phosgene 1200 parts at 20 ° C. with stirring.
It took minutes to blow. After finishing blowing phosgene, the internal temperature is 30
After the temperature was raised to ℃, emulsified by adding 420.6 parts of the substituted phenol compound A, 3.5 parts of triethylamine was added, the reaction was completed by stirring for about 1 hour, and after the reaction was completed, the organic phase was separated and washed with methylene chloride. After diluting and washing with water, it was neutralized with hydrochloric acid, and the washing with water was repeated. When the conductivity of the aqueous phase became almost equal to that of pure water, the organic phase was separated, dehydrated with dry anhydrous sodium sulfate, and then phenyl chloroformate 123 .3 parts was added, and 62.5 parts of pyridine was further added and stirred for about 1 hour to complete the reaction. After the completion of the reaction, the pyridine hydrochloride is removed by filtration, washed with water, acidified with hydrochloric acid, and repeatedly washed with water. When the conductivity of the aqueous phase becomes substantially equal to that of pure water, pulverization is performed by evaporating methylene chloride to give a colorless solution. 3730.8 parts (yield 96%) of modified polycarbonate was obtained. The terminal OH groups of this polymer were hardly detected by IR absorption spectrum analysis, the specific viscosity was 0.341, the glass transition temperature was 177 ° C,
The MFR was 3.0 g / 10 minutes. To this polymer, 0.03% of tris (nonylphenyl) phosphite, 0.05% of Irganox 1076 and 0.2% of stearic acid monoglyceride were added, melt-extruded at 280 ° C. and pelletized, and then 40 mmφ, 1 mm thick. The test piece was injection molded. The total light transmittance of this test piece was 89%.
【0073】[実施例15]置換フェノール化合物A1
65.8部の代りに置換フェノール化合物B60.4部
および p−tert−ブチルフェノール33.9部を用いる
以外は実施例1と同様にして改質ポリカーボネート10
91.5部(収率97%)を得た。このポリマーのカプ
ロラクトン部分の割合は IR 吸収スペクトル分析で5.
2%、比粘度は0.316、ガラス転移温度は115
℃、MFR は38 g/10分、全光線透過率は89%、衝
撃強度は32kg・cm/cmであった。Example 15 Substituted Phenolic Compound A1
Modified polycarbonate 10 in the same manner as in Example 1 except that 60.4 parts of the substituted phenol compound B and 33.9 parts of p-tert-butylphenol were used instead of 65.8 parts.
91.5 parts (97% yield) were obtained. The ratio of the caprolactone portion of this polymer was determined by IR absorption spectrum analysis to be 5.
2%, specific viscosity 0.316, glass transition temperature 115
C., MFR was 38 g / 10 minutes, total light transmittance was 89%, and impact strength was 32 kg.cm/cm.
【0074】[0074]
【発明の効果】本発明による改質芳香族ポリカーボネー
ト樹脂は、本来の優れた透明性、機械的物性を保持した
ままで溶融流動性が著しく改善され、低温ハイサイクル
成形にも適用でき、更に耐トラッキング性も著しく改善
されており、本発明の奏する効果は格別なものである。The modified aromatic polycarbonate resin according to the present invention has remarkably improved melt fluidity while maintaining the original excellent transparency and mechanical properties, and can be applied to low temperature high cycle molding as well. The tracking property has also been remarkably improved, and the effect of the present invention is exceptional.
Claims (4)
その全末端基の少くとも5モル%は下記一般式(I) 【化1】 [式中、Xはハロゲン原子または炭素数1〜10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、
Qは 【化2】 を示す。ここでYは炭素数1〜10の二価の脂肪族炭化
水素基を示し、W1 は水素原子、−C(=O)R1 、−
C(=O)OR2 またはR3 であり、ここでR1、R2
およびR3 は、それぞれ炭素数1〜10の一価の脂肪族
炭化水素基、炭素数4〜8の一価の脂環族炭化水素基ま
たは炭素数6〜15の一価の芳香族炭化水素基を示す。
mは4〜20の整数を示し、nは1〜100の整数を示
す。]で表される少なくとも一種の置換フェニルオキシ
基を含有していることを特徴とする改質芳香族ポリカー
ボネート樹脂。1. An aromatic polycarbonate resin, comprising:
At least 5 mol% of all the terminal groups have the following general formula (I): [In the formula, X represents a halogen atom or a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, P represents an integer of 0 to 4, and
Q is [Chemical formula 2] Indicates. Where Y represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, W 1 is a hydrogen atom, -C (= O) R 1 , -
C (= O) OR 2 or R 3 , where R 1 , R 2
And R 3 are each a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms. Indicates a group.
m shows the integer of 4-20, n shows the integer of 1-100. ] The modified aromatic polycarbonate resin characterized by containing at least 1 type of substituted phenyloxy group represented by these.
族ポリカーボネート樹脂。2. The modified aromatic polycarbonate resin according to claim 1, which is melt-moldable.
請求項1記載の改質芳香族ポリカーボネート樹脂。3. The modified aromatic polycarbonate resin according to claim 1, having a specific viscosity of at least 0.165.
体の反応により芳香族ポリカーボネート樹脂を製造する
方法において、該反応を下記一般式(II) 【化3】 [式中、X、PおよびQは前記一般式(I)における定
義と同じ意味を有する]で表される置換フェノール化合
物の存在下に行なうことを特徴とする請求項1記載の改
質芳香族ポリカーボネート樹脂の製造法。4. A method for producing an aromatic polycarbonate resin by the reaction of a dihydric phenol and a carbonate precursor, the reaction comprising the following general formula (II): The modified aromatic compound according to claim 1, which is carried out in the presence of a substituted phenol compound represented by the formula: wherein X, P and Q have the same meaning as defined in the general formula (I). Manufacturing method of polycarbonate resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP06086400A JP3100828B2 (en) | 1993-04-27 | 1994-04-25 | Modified aromatic polycarbonate resin and production method thereof |
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10108393 | 1993-04-27 | ||
JP23485393 | 1993-09-21 | ||
JP5-305230 | 1993-12-06 | ||
JP5-101083 | 1993-12-06 | ||
JP30523093 | 1993-12-06 | ||
JP5-234853 | 1993-12-06 | ||
JP06086400A JP3100828B2 (en) | 1993-04-27 | 1994-04-25 | Modified aromatic polycarbonate resin and production method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07216079A true JPH07216079A (en) | 1995-08-15 |
JP3100828B2 JP3100828B2 (en) | 2000-10-23 |
Family
ID=27467255
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP06086400A Expired - Fee Related JP3100828B2 (en) | 1993-04-27 | 1994-04-25 | Modified aromatic polycarbonate resin and production method thereof |
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JP (1) | JP3100828B2 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9282796B2 (en) | 2010-05-19 | 2016-03-15 | Johnson & Johnson Vision Care, Inc. | UV radiation control for disinfecting of ophthalmic lenses |
US20110284773A1 (en) | 2010-05-19 | 2011-11-24 | Pugh Randall B | Germicidal bulb disinfection base for ophthalmic lenses |
US20110284764A1 (en) | 2010-05-19 | 2011-11-24 | Pugh Randall B | Ophthalmic lens disinfecting base |
US8969830B2 (en) * | 2010-12-07 | 2015-03-03 | Johnson & Johnson Vision Care, Inc. | Ophthalmic lens disinfecting base unit with programmable and communication elements |
-
1994
- 1994-04-25 JP JP06086400A patent/JP3100828B2/en not_active Expired - Fee Related
Also Published As
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JP3100828B2 (en) | 2000-10-23 |
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