JP4051549B2 - Polycarbonate resin composition - Google Patents
Polycarbonate resin composition Download PDFInfo
- Publication number
- JP4051549B2 JP4051549B2 JP2002236437A JP2002236437A JP4051549B2 JP 4051549 B2 JP4051549 B2 JP 4051549B2 JP 2002236437 A JP2002236437 A JP 2002236437A JP 2002236437 A JP2002236437 A JP 2002236437A JP 4051549 B2 JP4051549 B2 JP 4051549B2
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate resin
- aromatic
- resin composition
- mol
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000004431 polycarbonate resin Substances 0.000 title claims description 54
- 229920005668 polycarbonate resin Polymers 0.000 title claims description 54
- 239000000203 mixture Substances 0.000 title claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 29
- 230000003287 optical effect Effects 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 19
- 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 18
- 150000001875 compounds Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 12
- 229920000515 polycarbonate Polymers 0.000 description 11
- 239000004417 polycarbonate Substances 0.000 description 11
- -1 oxides Chemical class 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 238000005809 transesterification reaction Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000008188 pellet Substances 0.000 description 7
- 239000004420 Iupilon Substances 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- QYJXDIUNDMRLAO-UHFFFAOYSA-N butyl 4-methylbenzenesulfonate Chemical compound CCCCOS(=O)(=O)C1=CC=C(C)C=C1 QYJXDIUNDMRLAO-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 150000004650 carbonic acid diesters Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000007514 bases Chemical class 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
- 239000000872 buffer Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- GPFJHNSSBHPYJK-UHFFFAOYSA-N (3-methylphenyl) hydrogen carbonate Chemical compound CC1=CC=CC(OC(O)=O)=C1 GPFJHNSSBHPYJK-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
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- KTMNDTPAJZKQPF-UHFFFAOYSA-N 2-tert-butyl-4-[1-(3-tert-butyl-4-hydroxyphenyl)propyl]phenol Chemical compound C=1C=C(O)C(C(C)(C)C)=CC=1C(CC)C1=CC=C(O)C(C(C)(C)C)=C1 KTMNDTPAJZKQPF-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- CKNCVRMXCLUOJI-UHFFFAOYSA-N 3,3'-dibromobisphenol A Chemical compound C=1C=C(O)C(Br)=CC=1C(C)(C)C1=CC=C(O)C(Br)=C1 CKNCVRMXCLUOJI-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
- 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
- RSSGMIIGVQRGDS-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=CC=C1 RSSGMIIGVQRGDS-UHFFFAOYSA-N 0.000 description 1
- OVVCSFQRAXVPGT-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)cyclopentyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCC1 OVVCSFQRAXVPGT-UHFFFAOYSA-N 0.000 description 1
- QHJPJZROUNGTRJ-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)octan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCCCC)C1=CC=C(O)C=C1 QHJPJZROUNGTRJ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- UCVMQZHZWWEPRC-UHFFFAOYSA-L barium(2+);hydrogen carbonate Chemical compound [Ba+2].OC([O-])=O.OC([O-])=O UCVMQZHZWWEPRC-UHFFFAOYSA-L 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- MUCRFDZUHPMASM-UHFFFAOYSA-N bis(2-chlorophenyl) carbonate Chemical compound ClC1=CC=CC=C1OC(=O)OC1=CC=CC=C1Cl MUCRFDZUHPMASM-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- FLLNLJJKHKZKMB-UHFFFAOYSA-N boron;tetramethylazanium Chemical compound [B].C[N+](C)(C)C FLLNLJJKHKZKMB-UHFFFAOYSA-N 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- BLUMOBPWAAOPOY-UHFFFAOYSA-M cesium;benzoate Chemical compound [Cs+].[O-]C(=O)C1=CC=CC=C1 BLUMOBPWAAOPOY-UHFFFAOYSA-M 0.000 description 1
- WLZGEDNSZCPRCJ-UHFFFAOYSA-M cesium;octadecanoate Chemical compound [Cs+].CCCCCCCCCCCCCCCCCC([O-])=O WLZGEDNSZCPRCJ-UHFFFAOYSA-M 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical compound C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- TYJOJLOWRIQYQM-UHFFFAOYSA-L disodium;phenyl phosphate Chemical compound [Na+].[Na+].[O-]P([O-])(=O)OC1=CC=CC=C1 TYJOJLOWRIQYQM-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940031993 lithium benzoate Drugs 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- JGIZKLDQCIOYLH-UHFFFAOYSA-L magnesium;phenyl phosphate Chemical compound [Mg+2].[O-]P([O-])(=O)OC1=CC=CC=C1 JGIZKLDQCIOYLH-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- WJMMDJOFTZAHHS-UHFFFAOYSA-L strontium;carbonic acid;carbonate Chemical compound [Sr+2].OC([O-])=O.OC([O-])=O WJMMDJOFTZAHHS-UHFFFAOYSA-L 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、高い屈折率および逆分散値、低い光弾性定数を有し、耐衝撃性、耐熱性、色相に優れた透明なポリカーボネート樹脂組成物に関する。このポリカーボネート樹脂組成物は各種プラスチックレンズ、プリズム、光ディスク基板などのプラスチック光学材料に好適に利用できるものである。
【０００２】
【従来の技術】
ポリカーボネート樹脂は、耐衝撃性等の機械的特性に優れ、しかも耐熱性、透明性等にも優れていることから、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、透明性に優れていることから光学材料としての用途も多い。例えば、光学材料として各種プラスチックレンズ、プリズム、光ディスク基板などに利用されている。
【０００３】
しかし、芳香族ジヒドロキシ化合物からなるポリカーボネート樹脂は、光弾性定数が大きく、溶融流動性が比較的悪いために成形品の複屈折が大きくなり、また屈折率は１．５８と高いもののアッベ数が３０と低いため、広く光記録材料や光学レンズ等の用途に用いられるには十分な性能を有していないという欠点がある。
【０００４】
これらの欠点を改良する方法として、芳香族−脂肪族共重合ポリカーボネート樹脂（特開昭６４−６６２３４号、特開平１１−１６５４２６号）が提案されている。これらの芳香族−脂肪族共重合ポリカーボネート樹脂は、優れた耐衝撃性、耐熱性を有し、その上、光弾性定数が低く、屈折率と分散特性のバランスが良いことから、広く光学材料として用いることが可能である。
【０００５】
しかし、これらの芳香族−脂肪族共重合ポリカーボネート樹脂を成形品として用いる際に、環境応力割れの問題が生じる。すなわち成形品が成形の際の残留歪のため、あるいは長期間にわたる外部からうける歪のためクラックが生じ、場合によっては破断にいたることもある。さらに水やオイル、有機溶媒などが存在する環境ではクラックの発生が著しく加速されることが知られている。
【０００６】
【発明が解決しようとする課題】
本発明は、上記のような従来技術に伴う問題点を解決しようとするものであり、良好な機械物性と優れた耐衝撃性を有し、且つ高い耐熱性、屈折率およびアッベ数を有し、さらに優れた耐クラック性を持つポリカーボネート樹脂組成物並びに該ポリカーボネート樹脂組成物を成形して得られる光学材料を提供することを目的としている。
【０００７】
【課題を解決するためのするため手段】
本発明者らは、上記の目的を達成する為に鋭意検討した結果、本発明に到達した。すなわち、本発明は、下記一般式（１）、式（２）および式（３）で表される構成単位からなる芳香族ー脂肪族共重合ポリカーボネート樹脂（Ａ）と、下記式（１）で表される構成単位からなる芳香族ポリカーボネート樹脂（Ｂ）とからなるポリカーボネート樹脂組成物に関するものである。
【０００８】
【化６】
【０００９】
【化７】
【００１０】
【化８】
【化９】
【発明の実施の形態】
以下、本発明のポリカーボネート樹脂組成物に関して具体的に説明する。
【００１３】
本発明で用いる芳香族−脂肪族共重合ポリカーボネート樹脂（Ａ）は、ランダム、ブロック或いは交互共重合体等を含むものであり、上記式（２）で表される脂肪族ジヒドロキシ化合物から誘導される構成単位のモル分率が、３０％以上であることが好ましく、さらに好ましくは、４０％以上である。３０％より低いと、光弾性定数、アッベ数等の光学特性の改善効果が小さくなる。また、脂肪族−芳香族共重合ポリカーボネート樹脂（Ａ）の数平均分子量は、１０，０００〜１００，０００であることが好ましく、さらに好ましくは１０，０００〜４０，０００である。
【００１４】
芳香族−脂肪族共重合ポリカーボネート樹脂（Ａ）は、一般のポリカーボネート樹脂の製造方法として公知の方法で製造することができ、特にエステル交換法により製造することができる。炭酸ジエステルを使用するエステル交換反応では、公知の溶融重縮合法により重合を行うことができる。すなわち、下記（５）式で表される芳香族ジヒドロキシ化合物、下記（６）式で表されるトリシクロ（５．２．１．０2.6）デカンジメタノール、下記（７）式で表されるスピログリコール、炭酸ジエステル及び触媒を用いて、加熱下に常圧または減圧下に副生物を除去しながら溶融重縮合を行うものである。反応は一般には二段階以上の多段工程で実施される。
【００１５】
【化１０】
【００１６】
【化１１】
【００１７】
【化１２】
【化１３】
上記式（5）で表される芳香族ジヒドロキシ化合物として、具体的にはビス（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、2,2-ビス（4-ヒドロキシフェニル）ブタン、2,2-ビス（4-ヒドロキシフェニル）オクタン、ビス（4-ヒドロキシフェニル）フェニルメタン、2,2-ビス（4-ヒドロキシ-3- メチルフェニル）プロパン、1,1-ビス（4-ヒドロキシ-3- ｔ- ブチルフェニル）プロパン、2,2-ビス（4-ヒドロキシ-3- ブロモフェニル）プロパン、1,1-ビス（4-ヒドロキシフェニル）シクロペンタン、1,1-ビス（4-ヒドロキシフェニル）シクロヘキサン、4,4'- ジヒドロキシジフェニルエーテル、4,4'- ジヒドロキシ-3,3'-ジメチルフェニルエーテル、4,4'- ジヒドロキシフェニルスルフィド、4,4'- ジヒドロキシ-3,3'-ジメチルジフェニルスルフィド、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-3,3'-ジメチル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ホン、4,4'- ジヒドロキシ-3,3'-ジメチルジフェニルスルホン等が挙げられる。これらのうちで、特に1,1-ビス（4-ヒドロキシフェニル）シクロヘキサンが好ましい。
【００２０】
本発明に関わるポリカーボネートの製造方法では、エステル交換反応で用いられる炭酸ジエステルとしては、ジフェニルカーボネート、ジトリールカーボネート、ビス（クロロフェニル）カーボネート、ｍ−クレジルカーボネート、ジナフチルカーボネート、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、ジシクロヘキシルカーボネート等が上げられる。これらの中でも特にジフェニルカーボネートが好ましい。また、着色原因ともなるジフェニルカーボネート中の塩素含有量は、２０ppm以下であることが好ましい。より好ましくは、１０ppm以下である。ジフェニルカーボネートは、芳香族ジヒドロキシ化合物と脂肪族ジヒドロキシ化合物の合計１モルに対して０．９７〜１．２モルの量で用いられることが好ましく、特に好ましくは０．９９〜１．１０モルの量である。
【００２１】
本発明に関わるポリカーボネートの製造方法において、エステル交換反応で用いられる触媒としては、塩基性化合物が用いられる。このような塩基性化合物としては、特にアルカリ金属および／またはアルカリ土類化合物、含窒素化合物等があげられる。
【００２２】
このような化合物としては、アルカリ金属およびアルカリ土類化合物等の有機酸、無機塩類、酸化物、水酸化物、水素化物あるいはアルコキシド、４級アンモニウムヒドロキシドおよびそれらの塩、アミン類等が好ましく用いられ、これらの化合物は単独もしくは組み合わせて用いることができる。
【００２３】
このようなアルカリ金属化合物としては、具体的には、水酸化ナトリウム、水酸化カリウム、水酸化セシウム、水酸化リチウム、炭酸水素ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、炭酸リチウム、酢酸ナトリウム、酢酸カリウム、酢酸セシウム、酢酸リチウム、ステアリン酸ナトリウム、ステアリン酸カリウム、ステアリン酸セシウム、ステアリン酸リチウム、水素化ホウ素ナトリウム、フェニル化ホウ素ナトリウム、安息香酸ナトリウム、安息香酸カリウム、安息香酸セシウム、安息香酸リチウム、リン酸水素２ナトリウム、リン酸水素２カリウム、リン酸水素２リチウム、フェニルリン酸２ナトリウム、ビスフェノールＡの２ナトリウム塩、２カリウム塩、２セシウム塩、２リチウム塩、フェノールのナトリウム塩、カリウム塩、セシウム塩、リチウム塩等が用いられる。
【００２４】
また、アルカリ土類金属化合物としては、具体的には、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム、炭酸水素マグネシウム、炭酸水素カルシウム、炭酸水素ストロンチウム、炭酸水素バリウム、酢酸マグネシウム、酢酸カルシウム、酢酸ストロンチウム、酢酸バリウム、ステアリン酸マグネシウム、ステアリン酸カルシウム、安息香酸カルシウム、フェニルリン酸マグネシウム等が用いられる。
【００２５】
また、含窒素化合物としては、具体的には、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、トリメチルベンジルアンモニウムヒドロキシド等のアルキル、アリール、アルアリール基などを有するアンモニウムヒドロキシド類、トリエチルアミン、ジメチルベンジルアミン、トリフェニルアミン等の３級アミン類、ジエチルアミン、ジブチルアミン等の２級アミン類、プロピルアミン、ブチルアミン等の１級アミン類、２−メチルイミダゾール、２−フェニルイミダゾール等のイミダゾール類、あるいは、アンモニア、テトラメチルアンモニウムボロハイドライド、テトラブチルアンモニウムテトラフェニルボレート、テトラフェニルアンモニウムテトラフェニルボレート等の塩基性塩等が用いられる。
【００２６】
これらの触媒は、芳香族ジヒドロキシ化合物と脂肪族ジヒドロキシ化合物との合計１モルに対して、１０-9〜１０-3モルの量で、好ましくは１０-7〜１０-5モルの量で用いられる。
【００２７】
本発明に関わるエステル交換反応は、公知の溶融重縮合法により行うことができる。すなわち、前記の原料、および触媒を用いて、加熱下に常圧または減圧下にエステル交換反応により副生物を除去しながら溶融重縮合を行うものである。反応は、一般には二段以上の多段工程で実施される。
【００２８】
具体的には、第一段目の反応を１２０〜２６０℃、好ましくは１８０〜２４０℃の温度で０〜５時間、好ましくは０．５〜３時間反応させる。次いで反応系の減圧度を上げながら反応温度を高めて芳香族ジヒドロキシ化合物と脂肪族ジヒドロキシ化合物と炭酸ジエステルとの反応を行い、最終的には１ｍｍＨｇ以下の減圧下、２００〜３００℃の温度で重縮合反応を行う。このような反応は、連続式で行っても良くまたバッチ式で行っても良い。上記の反応を行うに際して用いられる反応装置は、槽型であっても押出機型であってもパドル翼、格子翼、メガネ翼等、表面更新性の優れた撹拌翼を備えた横型装置であってもよい。
【００２９】
本発明で使用する芳香族ポリカーボネート樹脂（Ｂ）として、芳香族ポリカーボネート樹脂のいずれも使用できるが、特にビスフェノールＡから得られるポリカーボネートが好ましい。芳香族ポリカーボネート樹脂（Ｂ）の数平均分子量は、１０，０００〜３５，０００であることが好ましく、さらに好ましくは１５，０００〜３０，０００である。分子量が１０，０００以下であれば、耐衝撃性が十分でなく、また３５，０００以上であれば溶融粘度が高くなりすぎ、射出成形上の問題を生じ好ましくない。また、芳香族ポリカーボネート樹脂（Ｂ）の構成単位と、芳香族−脂肪族共重合ポリカーボネート樹脂（Ａ）中の芳香族化合物から誘導される構成単位の構造は同一でも異なっていても良い。製造は、エステル交換法、界面重合法など公知の重合方法で製造できるものであり、方法は問わない。
【００３０】
さらに、本発明のポリカーボネート樹脂には、熱安定性、および加水分解安定性を保持するために、触媒を除去または失活させることが好ましい。一般的には、公知の酸性物質の添加によるアルカリ金属あるいはアルカリ土類金属等のエステル交換触媒の失活を行う方法が好適に実施される。これらの物質としては、具体的には、ｐ−トルエンスルホン酸のごとき芳香族スルホン酸、パラトルエンスルホン酸ブチル等の芳香族スルホン酸エステル類、ステアリン酸クロライド、酪酸クロライド、塩化ベンゾイル、トルエンスルホン酸クロライドのような有機ハロゲン化物、ジメチル硫酸のごときアルキル硫酸塩、塩化ベンジルのごとき有機ハロゲン化物、ホウ酸、リン酸等の無機酸等が好適に用いられる。この触媒失活剤の添加は、芳香族ポリカーボネート樹脂（Ｂ）を溶融混合する時点で添加しても良いし、その前に添加しても良いし、その後に添加しても良い。
【００３１】
触媒失活後、ポリマー中の低沸点化合物を０．１〜１ｍｍＨｇの圧力、２００〜３００℃の温度で脱揮除去する工程を設けても良く、このためにはパドル翼、格子翼、メガネ翼等を備えた横型あるいは薄膜蒸発器が好適に用いられる。
【００３２】
なお、本発明に於いて、上記熱安定化剤、加水分解安定化剤の他に、酸化防止剤、顔料、染料、強化剤や充填剤、紫外線吸収剤、滑剤、離型剤、結晶核剤、可塑剤、流動性改良材、帯電防止剤等を添加することができる。また、さらに樹脂の特性を改良する目的で他のポリカーボネート樹脂、あるいは熱可塑性樹脂をブレンドして用いることもできる。
【００３３】
本発明のポリカーボネート樹脂組成物では、芳香族−脂肪族共重合ポリカーボネート樹脂（Ａ）と芳香族ポリカーボネート樹脂（Ｂ）の混合割合を重量比で５：９５〜９５：５とするのが好ましい。ポリカーボネート樹脂組成物中の芳香族ポリカーボネート樹脂（Ｂ）の混合割合が５重量％以下であると、芳香族ポリカーボネート樹脂の耐衝撃性、耐熱性等の特徴が十分組成物に反映されず添加の意味が薄れる。一方、芳香族ポリカーボネート樹脂（Ｂ）の混合割合が９５重量％以上であると、本来の目的である光弾性定数、アッベ数等の改善効果を十分得られない。この範囲であれば、芳香族−脂肪族共重合ポリカーボネート樹脂（Ａ）の物性を鑑みて適宜芳香族ポリカーボネート樹脂（Ｂ）の添加量を決定して、所望の物性を持つポリカーボネート樹脂組成物を得ることができる。さらに、本発明のポリカーボネート樹脂組成物中の芳香族化合物から誘導される構成単位と脂肪族化合物から誘導される構成単位のモル比（芳香族構成単位／脂肪族構成単位）は、１０／９０〜９０／１０が好ましく、さらに好ましくは２０／８０〜８０／２０である。芳香族化合物から誘導される構成単位と脂肪族化合物から誘導される構成単位のモル比（芳香族構成単位／脂肪族構成単位）が１０／９０より低いと、耐熱性が劣るものとなる。また、９０／１０より高いと光弾性定数、吸水率などが高くなり、さらに屈折率と分散値のバランスが悪くなる。 また、本発明における式（１０）成分は１モル％以上４モル％以下であることが望ましい。４モル％以上添加するとアッベ数及び耐衝撃性が著しく低下し好ましくない。１モル％以下では添加の効果があまりない。
【００３４】
芳香族−脂肪族共重合ポリカーボネート樹脂（Ａ）と芳香族ポリカーボネート樹脂（Ｂ）との混合法としては、ポリマーアロイあるいはポリマーブレンドを製造する方法として公知の、機械的混合、共通溶媒に溶解してからの凍結乾燥あるいはスプレー乾燥、微粒子混合等を用いることができる。経済的な観点からは機械的混合法が最も優れており、代表的な機械的混合法を挙げれば、二軸スクリュー押出し機、単軸スクリュー押出し機、ロール混練、インターナルミキサー等を用いた溶融混合法を挙げることができる。
【００３５】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明は、以下の実施例に何らの制限を受けるものではない。
【００３６】
また、実施例において物性値は以下の方法で測定した。
MI：２４０℃、５．００ｋｇの荷重で測定した。
Ｔｇ：示差走査熱量分析計にて測定した。
屈折率：ＪＩＳ Ｋ ７１０５に従いアッベ屈折計にて測定した。
アッベ数：アッベ屈折計にて測定し、計算して求めた。
落錘衝撃強度：１００mmφ×３mmの円板を、射出成形機により成形し、恒温槽を備えた計装化落錘衝撃試験機（ＣＨＡＳＴ社製、ＦＲＡＣＴＶＩＳ）で、先端２０Ｒの計装化落錘を７ｍ/secで衝突させ、破壊エネルギーを計測した。
耐クラック性：５０ｍｍ×３ｍｍの円板を溶融プレス成形により成形し、万能引っ張り試験機島津製作書製オートグラフにより三点曲げ試験を行なった。試験の手順を以下に示す手順で行なった。下部支点間距離24ｍｍ、上部支店R５ｍｍである。
円板の両面にサラダオイル（豊年キャノーラ油）を塗布する。
1分後に50℃に保った恒温槽中の試験治具にのせる。
10分後に2mm/minでクロスヘッドの移動を開始する。
変位が０．８ｍmに達した後２分間その位置に静止した。
クロスヘッド静止後2分間で応力が減少する割合を応力緩和とし、耐クラック性の指標とした。応力の減少は、目視で確認すると降伏によるものではなく、クラックの発生に対応している。値が小さいほどクラックの発生が少なく耐クラック性が高いことになる。
【００３７】
実施例１
実質的に酸素の存在しない窒素ガス雰囲気下、１３０℃に保温された混合槽にジフェニルカーボネートと２，２−ビス（４−ヒドロキシフェニル）プロパン（以下ＢＰＺと略す）とスピログリコール（以下ＳＰＧと略す）とを一定比率（ジフェニルカーボネート／ＢＰＺ／ＳＰＧ（モル比）＝４．２９１／１．００／０．１６６）になるように、１３０℃に保温されたジフェニルカーボネートの液体を混合槽に送液し、撹拌開始後ＢＰＺ（粉末）を混合槽に投入した。ＢＰＺ投入時に炭酸水素ナトリウム（触媒、ＢＰＺ１００重量部に対し０．００００５４重量部）をＢＰＺと混合しながら添加した。混合槽の内部温度が１５５℃に維持されるように加熱を開始し、内温が１５５℃に達してから１時間後、内部温度を１５分で１３０℃まで低下させ、１３０℃に保温されたバッファー槽に送液した。第１竪型攪拌重合槽（反応条件：１３．３ｋＰａ、２０５℃、攪拌速度１６０rpm）での原料モル比（ジフェニルカーボネート／（ＢＰＺ＋ＴＣＤＤＭ））が１．０１となるように、バッファー槽のジフェニルカーボネートとＢＰＺの溶融混合物を１２．１４kg/hの流量で、第１重合槽に連続的に供給し、また、同時にＴＣＤＤＭ（トリシクロ（５．２．１．０2.6）デカンジメタノール）を、２６.６２kg/hの流量で連続的に供給した。また２液を供給する際、各々０．６μｍの金属フィルターを通過させた後、第１槽に供給した。第１重合槽での平均滞留時間が６０分となるように槽底部のポリマー排出ラインに設けられたバルブ開度を制御しつつ液面レベルを一定に保った。槽底より排出された重合液（プレポリマー）は、引き続き第２、第３、第４の竪型重合槽並びに第５の横型重合槽（日立製作所製 メガネ翼重合機（商品名））に逐次連続供給された。平均滞留時間は第２〜第４の竪型重合槽が各６０分、第５横型重合槽は９０分となるように液面レベルを制御し、また同時に副生するフェノールの留去も行った。
第２〜第５重合槽各槽の重合条件はそれぞれ、第２重合槽（２２０℃、２０００Ｐａ、攪拌速度１６０rpm）、第３重合槽（２３０℃、４０Ｐａ、攪拌速度６０rpm）、第４重合槽（２４０℃、４０Ｐａ、攪拌速度２０rpm）、第５横型重合槽（２４５℃、４０Ｐａ、攪拌速度５rpm）とした。
第５横型重合槽より排出されたポリマーは溶融状態のまま連続的に３ベント式２軸押出機（４６mm２軸押出機 神戸製鋼所製）に導入され、樹脂供給口の最も近いベント口の手前で後述する添加剤をマスターバッチの形態で樹脂に対し０．５kg/hの供給速度でサイドフィードコンパクターにより供給し、その後混錬およびベントでの脱気後、さらに４０ｍｍφ単軸押出機（Ｌ／Ｄ＝２８）で加熱溶融した芳香族ポリカーボネート樹脂（ビスフェノールＡタイプのポリカーボネート；数平均分子量Mn=30,000 ）[ 三菱ガス化学（株）製ユーピロンＥ-2000]を２軸押出機に７．６kg/hで供給し、混練脱気した後、１０μｍの樹脂フィルターを通し、その後水冷ペレット化した。
マスターバッチの組成は、ユーピロンＳ−３０００（三菱ガス化学製ポリカーボネート）の粉末状のものをベースとし、ｐ−トルエンスルホン酸ブチル（東京化成工業製；以下ｐＴＳＢ）の添加量が炭酸水素ナトリウムの中和当量の９倍量［２７μmol/mol（ＢＰＺとＴＣＤＤＭの合計モルに対して）］、及び樹脂の合計量１００重量部に対して、５，７−ジ−ｔ−ブチル−３−（３，４−ジメチルフェニル）−３Ｈ−ベンゾフラン−２−オン（ＨＰ−１３６；チバスペシャリティケミカルズ製）が３００ｐｐｍ、２，２−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイト（旭電化工業製 ＨＰ−１０）が５００ｐｐｍとなるように調製した。評価結果を表１に示す。
【００３８】
実施例２
ＢＰＺ３０３０ｋｇ（１１．３モル）、ＴＣＤＤＭ６６４８ｇ（３３．９モル）、スピログリコール５７２．７ｇ（１．３５モル）、ジフェニルカーボネート１０３７９ｇ（４８．４５モル）、炭酸水素ナトリウム０．０１１３g（１．３５×１０-4モル）を、撹拌機および留出装置付きの５０リットル反応釜に入れ、窒素雰囲気下２００℃に加熱し、３０分間撹拌した。その後、減圧度を１３．３ｋＰａに調整すると同時に、２４０℃まで昇温し副生するフェノールを留去しながらエステル交換反応を行った。ほぼフェノールの留出が終了した時点で真空度をさらに上げ、１ｍｍＨｇ以下の条件でさらに２時間撹拌を行い、反応終了後、反応器内に窒素を吹き込み常圧に戻し、芳香族−脂肪族ポリカーボネートを取り出した。この芳香族−脂肪族ポリカーボネート樹脂１００重量部に対して、芳香族ポリカーボネート樹脂（ビスフェノールＡタイプのポリカーボネート；数平均分子量Mn=30,000 ）[ 三菱ガス化学（株）製ユーピロンＥ-2000] を５０．５重量部の割合で混合し、触媒失活剤として、ｐ−トルエンスルホン酸ブチル０．０８ｇ、酸化防止剤としてｎ−オクタデシル−３−（３, ５ −ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート０．６６ｇおよびトリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト０．６６ｇを配合して二軸押出し機を用いて溶融混練し、樹脂ペレットを得た。このペレットを評価し、得られた結果を表１に示す。
【００３９】
実施例３
ＢＰＺ２１７４ｋｇ（８．１モル）、ＴＣＤＤＭ４７７０ｇ（２４．３モル）、スピログリコール４１０．７ｇ（１．３５モル）、ビスフェノールＡ３０６１ｇ（１３．４１モル）、ジフェニルカーボネート１０５０６ｇ（４９．０４モル）、炭酸水素ナトリウム０．０１１３g（１．３５×１０-4モル）を、撹拌機および留出装置付きの５０リットル反応釜に入れ、実施例２同様重合反応を行なった。この芳香族−脂肪族ポリカーボネート樹脂１００重量部に対して、芳香族ポリカーボネート樹脂（ビスフェノールＡタイプのポリカーボネート；数平均分子量Mn=30,100 ）[ 三菱ガス化学（株）製ユーピロンＥ-2000] を３０．０重量部の割合で混合し、触媒失活剤として、ｐ−トルエンスルホン酸ブチル０．０８ｇ、酸化防止剤としてｎ−オクタデシル−３−（３, ，５, −ジ−ｔ−ブチル−４, −ヒドロキシフェニル）プロピオネート０．６６ｇおよびトリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト０．６６ｇを配合して二軸押出し機を用いて溶融混練し、樹脂ペレットを得た。このペレットを評価し、得られた結果を表１に示す。
【００４０】
比較例１
芳香族ポリカーボネート樹脂（ビスフェノールＡタイプのポリカーボネート；数平均分子量Mn=22,000 ）[ 三菱ガス化学（株）製ユーピロンS-3000]のペレットを評価し、得られた結果を表１に示す。
【００４１】
比較例２
ＢＰＺ４８５９．１ｋｇ（1８．１モル）、ＴＣＤＤＭ５３３１．１ｇ（２７．２モル）、ジフェニルカーボネート１０１２４ｇ（４７．２５モル）、炭酸水素ナトリウム０．０１１３g（１．３５×１０-4モル）を、撹拌機および留出装置付きの５０リットル反応釜に入れ、実施例２同様重合反応を行なった。この芳香族−脂肪族ポリカーボネート樹脂１００重量部に対して、芳香族ポリカーボネート樹脂（ビスフェノールＡタイプのポリカーボネート；数平均分子量Mn=30,100 ）[ 三菱ガス化学（株）製ユーピロンＥ-2000] を３０．０重量部の割合で混合し、触媒失活剤として、ｐ−トルエンスルホン酸ブチル０．０８ｇ、酸化防止剤としてｎ−オクタデシル−３−（３，５−ジ−ｔ−ブチル−４, −ヒドロキシフェニル）プロピオネート０．６６ｇおよびトリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト０．６６ｇを配合して二軸押出し機を用いて溶融混練し、樹脂ペレットを得た。このペレットを評価し、得られた結果を表１に示す。
【００４２】
【発明の効果】
本発明ポリカーボネート樹脂は、ポリカーボネートの優れた耐衝撃性、耐熱性等の特性を維持しながら、屈折率、分散のバランスおよび光弾性定数などが改善されたものであり、各種レンズ、プリズム、光ディスク基板などのプラスチック光学材料用として好適に利用できる。
【００４３】
【表１】
BACKGROUND OF THE INVENTION
The present invention relates to a transparent polycarbonate resin composition having a high refractive index, a reverse dispersion value, a low photoelastic constant, and excellent in impact resistance, heat resistance, and hue. This polycarbonate resin composition can be suitably used for plastic optical materials such as various plastic lenses, prisms, and optical disk substrates.
[0002]
[Prior art]
Polycarbonate resins are widely used in many fields as engineering plastics because they are excellent in mechanical properties such as impact resistance, and are also excellent in heat resistance and transparency. In particular, it has many uses as an optical material because of its excellent transparency. For example, it is used as an optical material for various plastic lenses, prisms, optical disk substrates and the like.
[0003]
However, a polycarbonate resin made of an aromatic dihydroxy compound has a large photoelastic constant and a relatively poor melt fluidity, so that the birefringence of the molded product is large and the Abbe number is 30 although the refractive index is as high as 1.58. Therefore, there is a drawback in that it does not have sufficient performance to be widely used in applications such as optical recording materials and optical lenses.
[0004]
As a method for improving these disadvantages, aromatic-aliphatic copolymer polycarbonate resins (JP-A Nos. 64-66234 and 11-165426) have been proposed. These aromatic-aliphatic copolymer polycarbonate resins have excellent impact resistance, heat resistance, low photoelastic constant, and good balance between refractive index and dispersion characteristics. It is possible to use.
[0005]
However, when these aromatic-aliphatic copolymer polycarbonate resins are used as molded articles, there is a problem of environmental stress cracking. That is, a crack is generated due to a residual strain at the time of molding or a strain that is externally applied for a long period of time. Furthermore, it is known that the generation of cracks is remarkably accelerated in an environment where water, oil, organic solvent and the like are present.
[0006]
[Problems to be solved by the invention]
The present invention is to solve the problems associated with the prior art as described above, has good mechanical properties and excellent impact resistance, and has high heat resistance, refractive index and Abbe number. Another object of the present invention is to provide a polycarbonate resin composition having further excellent crack resistance and an optical material obtained by molding the polycarbonate resin composition.
[0007]
[Means for solving the problems]
The inventors of the present invention have arrived at the present invention as a result of intensive studies to achieve the above-mentioned object. That is, the present invention includes an aromatic-aliphatic copolymer polycarbonate resin (A) composed of structural units represented by the following general formula (1), formula (2) and formula (3), and the following formula (1): The present invention relates to a polycarbonate resin composition comprising an aromatic polycarbonate resin (B) comprising the structural units represented.
[0008]
[Chemical 6]
[0009]
[Chemical 7]
[0010]
[Chemical 8]
[Chemical 9]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the polycarbonate resin composition of the present invention will be specifically described.
[0013]
The aromatic-aliphatic copolymer polycarbonate resin (A) used in the present invention contains a random, block or alternating copolymer, and is derived from an aliphatic dihydroxy compound represented by the above formula (2). The molar fraction of the structural unit is preferably 30% or more, and more preferably 40% or more. If it is lower than 30%, the effect of improving the optical properties such as the photoelastic constant and Abbe number becomes small. The number average molecular weight of the aliphatic-aromatic copolymer polycarbonate resin (A) is preferably 10,000 to 100,000, more preferably 10,000 to 40,000.
[0014]
The aromatic-aliphatic copolymer polycarbonate resin (A) can be produced by a known method as a production method of a general polycarbonate resin, and in particular, can be produced by a transesterification method. In the transesterification reaction using a carbonic acid diester, polymerization can be carried out by a known melt polycondensation method. That is, an aromatic dihydroxy compound represented by the following formula (5), tricyclo (5.2.1.0 2.6 ) decanedimethanol represented by the following formula (6), spiro represented by the following formula (7) Using polyglycol, carbonic acid diester and catalyst, melt polycondensation is carried out while removing by-products under normal pressure or reduced pressure under heating. The reaction is generally carried out in a multistage process of two or more stages.
[0015]
[Chemical Formula 10]
[0016]
Embedded image
[0017]
Embedded image
Embedded image
Specific examples of the aromatic dihydroxy compound represented by the above formula (5) include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxy). Phenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy- 3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis (4 -Hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxy Phenyl sulfide, 4,4'-dihydride Roxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'- And dihydroxy-3,3′-dimethyldiphenylsulfone. Of these, 1,1-bis (4-hydroxyphenyl) cyclohexane is particularly preferred.
[0020]
In the polycarbonate production method according to the present invention, as the carbonic acid diester used in the transesterification reaction, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, Examples include dibutyl carbonate and dicyclohexyl carbonate. Of these, diphenyl carbonate is particularly preferred. Moreover, it is preferable that the chlorine content in the diphenyl carbonate which also causes coloring is 20 ppm or less. More preferably, it is 10 ppm or less. Diphenyl carbonate is preferably used in an amount of 0.97 to 1.2 mol, particularly preferably 0.99 to 1.10 mol, based on 1 mol of the total of the aromatic dihydroxy compound and the aliphatic dihydroxy compound. It is.
[0021]
In the polycarbonate production method according to the present invention, a basic compound is used as the catalyst used in the transesterification reaction. Examples of such basic compounds include alkali metal and / or alkaline earth compounds and nitrogen-containing compounds.
[0022]
As such compounds, organic acids such as alkali metals and alkaline earth compounds, inorganic salts, oxides, hydroxides, hydrides or alkoxides, quaternary ammonium hydroxides and salts thereof, amines, etc. are preferably used. These compounds can be used alone or in combination.
[0023]
Specific examples of such alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, acetic acid. Potassium, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, Disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium salt of phenol, Potassium salt, cesium salt, lithium salt or the like is used.
[0024]
Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium acetate, Calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate and the like are used.
[0025]
Specific examples of nitrogen-containing compounds include alkyl, aryl, and aryl groups such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Ammonium hydroxides having trimethylamine, dimethylbenzylamine, tertiary amines such as triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole, Imidazoles such as 2-phenylimidazole, or ammonia, tetramethylammonium borohydride, tetrabutylammonium tetraphenylborate, Basic salts such as tiger phenyl tetraphenylborate is used.
[0026]
These catalysts are used in an amount of 10 −9 to 10 −3 mol, preferably 10 −7 to 10 −5 mol, with respect to a total of 1 mol of the aromatic dihydroxy compound and the aliphatic dihydroxy compound. .
[0027]
The transesterification reaction according to the present invention can be carried out by a known melt polycondensation method. That is, melt polycondensation is carried out using the above-mentioned raw materials and catalyst while removing by-products by a transesterification reaction under heating at normal pressure or under reduced pressure. The reaction is generally carried out in a multistage process of two or more stages.
[0028]
Specifically, the reaction at the first stage is allowed to react at a temperature of 120 to 260 ° C, preferably 180 to 240 ° C for 0 to 5 hours, preferably 0.5 to 3 hours. Next, the reaction temperature is raised while raising the pressure reduction degree of the reaction system to react the aromatic dihydroxy compound, the aliphatic dihydroxy compound and the carbonic acid diester. Finally, the reaction is carried out at a temperature of 200 to 300 ° C. under a reduced pressure of 1 mmHg or less. Perform a condensation reaction. Such a reaction may be carried out continuously or batchwise. The reaction apparatus used for carrying out the above reaction is a horizontal apparatus equipped with a stirring blade having excellent surface renewability, such as a paddle blade, a lattice blade, and a glasses blade, regardless of whether it is a tank type or an extruder type. May be.
[0029]
Although any of the aromatic polycarbonate resins can be used as the aromatic polycarbonate resin (B) used in the present invention, a polycarbonate obtained from bisphenol A is particularly preferable. The number average molecular weight of the aromatic polycarbonate resin (B) is preferably 10,000 to 35,000, and more preferably 15,000 to 30,000. If the molecular weight is 10,000 or less, the impact resistance is not sufficient, and if it is 35,000 or more, the melt viscosity becomes too high, causing problems in injection molding. Moreover, the structure of the structural unit derived from the aromatic compound in the aromatic polycarbonate resin (A) and the structural unit of the aromatic polycarbonate resin (B) may be the same or different. The production can be carried out by a known polymerization method such as transesterification or interfacial polymerization, and the method is not limited.
[0030]
Furthermore, in the polycarbonate resin of the present invention, it is preferable to remove or deactivate the catalyst in order to maintain thermal stability and hydrolysis stability. In general, a method of deactivating a transesterification catalyst such as an alkali metal or an alkaline earth metal by adding a known acidic substance is preferably carried out. Specific examples of these substances include aromatic sulfonic acid esters such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl paratoluenesulfonate, stearic acid chloride, butyric acid chloride, benzoyl chloride, and toluenesulfonic acid. Organic halides such as chloride, alkyl sulfates such as dimethyl sulfate, organic halides such as benzyl chloride, and inorganic acids such as boric acid and phosphoric acid are preferably used. The catalyst deactivator may be added when the aromatic polycarbonate resin (B) is melt-mixed, may be added before, or may be added thereafter.
[0031]
After deactivation of the catalyst, a step of devolatilizing and removing low-boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 300 ° C. may be provided. A horizontal type or thin film evaporator equipped with the above is preferably used.
[0032]
In the present invention, in addition to the above heat stabilizer and hydrolysis stabilizer, antioxidants, pigments, dyes, reinforcing agents and fillers, ultraviolet absorbers, lubricants, mold release agents, crystal nucleating agents. Plasticizers, fluidity improvers, antistatic agents, and the like can be added. Further, for the purpose of improving the properties of the resin, other polycarbonate resins or thermoplastic resins can be blended and used.
[0033]
In the polycarbonate resin composition of the present invention, the mixing ratio of the aromatic-aliphatic copolymer polycarbonate resin (A) and the aromatic polycarbonate resin (B) is preferably 5:95 to 95: 5 by weight ratio. When the mixing ratio of the aromatic polycarbonate resin (B) in the polycarbonate resin composition is 5% by weight or less, the characteristics such as impact resistance and heat resistance of the aromatic polycarbonate resin are not sufficiently reflected in the composition, meaning of addition Fades. On the other hand, when the mixing ratio of the aromatic polycarbonate resin (B) is 95% by weight or more, it is not possible to sufficiently obtain the original effects such as improvement of the photoelastic constant and Abbe number. If it is this range, the addition amount of aromatic polycarbonate resin (B) will be determined suitably in view of the physical property of aromatic-aliphatic copolymer polycarbonate resin (A), and the polycarbonate resin composition which has a desired physical property will be obtained. be able to. Further, the molar ratio of the structural unit derived from the aromatic compound and the structural unit derived from the aliphatic compound (aromatic structural unit / aliphatic structural unit) in the polycarbonate resin composition of the present invention is 10/90 to 90/10 is preferable, and more preferably 20/80 to 80/20. When the molar ratio of the structural unit derived from the aromatic compound to the structural unit derived from the aliphatic compound (aromatic structural unit / aliphatic structural unit) is lower than 10/90, the heat resistance is inferior. On the other hand, if it is higher than 90/10, the photoelastic constant, the water absorption rate and the like are increased, and the balance between the refractive index and the dispersion value is further deteriorated. Further, the component of the formula (10) in the present invention is desirably 1 mol% or more and 4 mol% or less. Addition of 4 mol% or more is not preferable because the Abbe number and impact resistance are remarkably lowered. If it is 1 mol% or less, the effect of addition is not so much.
[0034]
As a mixing method of the aromatic-aliphatic copolymer polycarbonate resin (A) and the aromatic polycarbonate resin (B), known as a method for producing a polymer alloy or a polymer blend, it is dissolved in a common solvent. Freeze drying or spray drying, fine particle mixing, etc. can be used. From an economic point of view, the mechanical mixing method is the most excellent. Typical mechanical mixing methods include twin screw extruder, single screw extruder, roll kneading, melting using an internal mixer, etc. A mixing method can be mentioned.
[0035]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention does not receive a restriction | limiting at all to a following example.
[0036]
In the examples, physical property values were measured by the following methods.
MI: Measured at 240 ° C. and a load of 5.00 kg.
Tg: Measured with a differential scanning calorimeter.
Refractive index: Measured with an Abbe refractometer according to JIS K 7105.
Abbe number: Measured by Abbe refractometer and calculated.
Drop weight impact strength: 100mmφ × 3mm disc was molded with an injection molding machine and instrumented drop weight impact tester (CHACT, FRACTVIS) equipped with a thermostatic chamber. Was collided at 7 m / sec, and the fracture energy was measured.
Crack resistance: A 50 mm × 3 mm disk was molded by melt press molding, and a three-point bending test was performed using an autograph made by Shimadzu Corporation, a universal tensile testing machine. The test procedure was as follows. The distance between the lower fulcrums is 24 mm, and the upper branch R is 5 mm.
Apply salad oil (billionaire canola oil) on both sides of the disc.
After 1 minute, place it on a test jig in a thermostatic chamber maintained at 50 ° C.
Start moving the crosshead at 2 mm / min after 10 minutes.
It stopped at that position for 2 minutes after the displacement reached 0.8 mm.
The rate at which the stress decreased in 2 minutes after the crosshead was stopped was defined as stress relaxation and used as an index of crack resistance. The decrease in stress is not due to yield when visually confirmed, but corresponds to the occurrence of cracks. The smaller the value, the less cracking occurs and the higher the crack resistance.
[0037]
Example 1
Diphenyl carbonate, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as BPZ) and spiroglycol (hereinafter abbreviated as SPG) are placed in a mixing tank kept at 130 ° C. in a nitrogen gas atmosphere substantially free of oxygen. ) And a diphenyl carbonate liquid kept at 130 ° C. so that it becomes a certain ratio (diphenyl carbonate / BPZ / SPG (molar ratio) = 4.291 / 1.00 / 0.166). Then, after stirring was started, BPZ (powder) was charged into the mixing tank. Sodium hydrogen carbonate (catalyst, 0.000054 parts by weight with respect to 100 parts by weight of BPZ) was added while mixing with BPZ when BPZ was charged. Heating was started so that the internal temperature of the mixing tank was maintained at 155 ° C., and 1 hour after the internal temperature reached 155 ° C., the internal temperature was reduced to 130 ° C. in 15 minutes and kept at 130 ° C. The solution was sent to the buffer tank. Diphenyl carbonate in the buffer tank was adjusted so that the raw material molar ratio (diphenyl carbonate / (BPZ + TCDDM)) in the first vertical stirring polymerization tank (reaction conditions: 13.3 kPa, 205 ° C., stirring speed 160 rpm) was 1.01. A molten mixture of BPZ was continuously fed to the first polymerization tank at a flow rate of 12.14 kg / h, and at the same time, TCDDM (tricyclo (5.2.1.0 2.6 ) decanedimethanol) was added to 26.62 kg. It was continuously supplied at a flow rate of / h. Moreover, when supplying 2 liquids, after passing each 0.6 micrometer metal filter, it supplied to the 1st tank. The liquid level was kept constant while controlling the valve opening degree provided in the polymer discharge line at the bottom of the tank so that the average residence time in the first polymerization tank was 60 minutes. The polymerization liquid (prepolymer) discharged from the tank bottom continues to the second, third, and fourth vertical polymerization tanks and the fifth horizontal polymerization tank (Hitachi Glasses Blade Polymerizer (trade name)) successively. Continuously supplied. The liquid surface level was controlled so that the average residence time was 60 minutes for each of the second to fourth vertical polymerization tanks and 90 minutes for the fifth horizontal polymerization tank, and at the same time, by-product phenol was distilled off. .
The polymerization conditions for the second to fifth polymerization tanks were the second polymerization tank (220 ° C., 2000 Pa, stirring speed 160 rpm), the third polymerization tank (230 ° C., 40 Pa, stirring speed 60 rpm), the fourth polymerization tank ( 240 ° C., 40 Pa, stirring speed 20 rpm), and a fifth horizontal polymerization tank (245 ° C., 40 Pa, stirring speed 5 rpm).
The polymer discharged from the 5th horizontal polymerization tank was continuously introduced into a 3 vent type twin screw extruder (46 mm twin screw extruder manufactured by Kobe Steel) in a molten state, just before the vent port closest to the resin supply port. Additives to be described later in the form of a masterbatch are supplied to the resin at a supply rate of 0.5 kg / h by a side feed compactor, and after further kneading and venting, 40 mmφ single screw extruder (L / D = 28) Aromatic polycarbonate resin (bisphenol A type polycarbonate; number average molecular weight Mn = 30,000) [Mitsubishi Gas Chemical Co., Ltd. Iupilon E-2000] was loaded into a twin screw extruder at 7.6 kg / h. After being supplied and kneaded and degassed, it was passed through a 10 μm resin filter and then pelletized with water.
The composition of the masterbatch is based on the powdery form of Iupilon S-3000 (Mitsubishi Gas Chemical Polycarbonate), and the amount of p-toluenesulfonic acid butyl (Tokyo Chemical Industry; hereinafter referred to as pTSB) added in sodium bicarbonate. 9 times the sum equivalent [27 μmol / mol (based on the total moles of BPZ and TCDDM)] and 100 parts by weight of the total amount of resin, 5,7-di-t-butyl-3- (3 4-dimethylphenyl) -3H-benzofuran-2-one (HP-136; manufactured by Ciba Specialty Chemicals) is 300 ppm, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (Asahi Denka Kogyo) Preparation of HP-10) was 500 ppm. The evaluation results are shown in Table 1.
[0038]
Example 2
3030 kg (11.3 mol) of BPZ, 6648 g (33.9 mol) of TCDDM, 572.7 g (1.35 mol) of spiroglycol, 10379 g (48.45 mol) of diphenyl carbonate, 0.0113 g of sodium hydrogencarbonate (1.35 × 10 6) -4 mol) was placed in a 50 liter reaction kettle equipped with a stirrer and a distillation apparatus, heated to 200 ° C. under a nitrogen atmosphere, and stirred for 30 minutes. Thereafter, the degree of vacuum was adjusted to 13.3 kPa, and at the same time, the temperature was raised to 240 ° C., and transesterification was carried out while distilling off by-product phenol. When the distillation of phenol is almost completed, the degree of vacuum is further increased and stirring is further performed for 2 hours under conditions of 1 mmHg or less. After the reaction is completed, nitrogen is blown into the reactor to return to normal pressure, and the aromatic-aliphatic polycarbonate is obtained. Was taken out. The aromatic polycarbonate resin (bisphenol A type polycarbonate; number average molecular weight Mn = 30,000) [Iupilon E-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd.] is 50.5 with respect to 100 parts by weight of the aromatic-aliphatic polycarbonate resin. Mixing by weight, 0.08 g of butyl p-toluenesulfonate as catalyst deactivator, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) as antioxidant 0.66 g of propionate and 0.66 g of tris (2,4-di-t-butylphenyl) phosphite were blended and melt kneaded using a twin screw extruder to obtain resin pellets. The pellets were evaluated and the results obtained are shown in Table 1.
[0039]
Example 3
BPZ 2174 kg (8.1 mol), TCDDM 4770 g (24.3 mol), spiroglycol 410.7 g (1.35 mol), bisphenol A 3061 g (13.41 mol), diphenyl carbonate 10506 g (49.04 mol), sodium hydrogen carbonate 0.0113 g (1.35 × 10 −4 mol) was placed in a 50 liter reaction kettle equipped with a stirrer and a distillation apparatus, and the polymerization reaction was carried out in the same manner as in Example 2. For 100 parts by weight of this aromatic-aliphatic polycarbonate resin, 30.0 aromatic polycarbonate resin (bisphenol A type polycarbonate; number average molecular weight Mn = 30,100) [Iupilon E-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd.] Mixing in a part by weight, 0.08 g of butyl p-toluenesulfonate as a catalyst deactivator and n-octadecyl-3- (3,, 5, -di-t-butyl-4, − as an antioxidant Hydroxyphenyl) propionate (0.66 g) and tris (2,4-di-t-butylphenyl) phosphite (0.66 g) were blended and melt-kneaded using a twin screw extruder to obtain resin pellets. The pellets were evaluated and the results obtained are shown in Table 1.
[0040]
Comparative Example 1
The pellets of aromatic polycarbonate resin (bisphenol A type polycarbonate; number average molecular weight Mn = 22,000) [Iupilon S-3000 manufactured by Mitsubishi Gas Chemical Co., Ltd.] were evaluated, and the obtained results are shown in Table 1.
[0041]
Comparative Example 2
BPZ4859.1 kg (18.1 mol), TCDDM 5331.1 g (27.2 mol), diphenyl carbonate 10124 g (47.25 mol), sodium hydrogen carbonate 0.0113 g (1.35 × 10 −4 mol) were added to a stirrer. And it put into the 50 liter reaction kettle with a distillation apparatus, and performed the polymerization reaction like Example 2. FIG. For 100 parts by weight of this aromatic-aliphatic polycarbonate resin, 30.0 aromatic polycarbonate resin (bisphenol A type polycarbonate; number average molecular weight Mn = 30,100) [Iupilon E-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd.] Mixing by weight, 0.08 g of butyl p-toluenesulfonate as catalyst deactivator, n-octadecyl-3- (3,5-di-t-butyl-4, -hydroxyphenyl as antioxidant ) 0.66 g of propionate and 0.66 g of tris (2,4-di-t-butylphenyl) phosphite were blended and melt-kneaded using a twin screw extruder to obtain resin pellets. The pellets were evaluated and the results obtained are shown in Table 1.
[0042]
【The invention's effect】
The polycarbonate resin of the present invention has improved refractive index, dispersion balance and photoelastic constant while maintaining the excellent impact resistance, heat resistance and other characteristics of polycarbonate. Various lenses, prisms, optical disk substrates It can utilize suitably for plastic optical materials, such as.
[0043]
[Table 1]
Claims (4)
【０００１】A plastic lens having a refractive index of 1.54 to 1.60 and an Abbe number of 35 to 50, formed from the polycarbonate resin composition according to claim 1.
[0001]
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| EP1947131A4 (en) * | 2005-11-10 | 2010-10-27 | Teijin Chemicals Ltd | OPTICAL DEVICE AND ACHROMATIC LENS |
| JP4521022B2 (en) * | 2006-10-18 | 2010-08-11 | 出光興産株式会社 | Polycarbonate copolymer, molded body, optical material, and electrophotographic photoreceptor |
| KR101256333B1 (en) | 2006-10-18 | 2013-04-18 | 이데미쓰 고산 가부시키가이샤 | Polycarbonate copolymer, method for producing the same, molded body, optical material, and electrophotographic photosensitive body |
| JP2011126970A (en) * | 2009-12-16 | 2011-06-30 | Mitsubishi Chemicals Corp | Polycarbonate resin and surface impact resistant member obtained therefrom |
| JP6079843B2 (en) * | 2015-09-07 | 2017-02-15 | 三菱化学株式会社 | Polycarbonate resin composition and molded product |
| JP2017149922A (en) * | 2016-02-19 | 2017-08-31 | 宇部興産株式会社 | Polycarbonate polyol |
| EP4421108A3 (en) * | 2020-08-13 | 2024-11-06 | Mitsubishi Gas Chemical Company, Inc. | Thermoplastic resin composition for optical material, molded article, compounding agent, method for producing thermoplastic resin composition, and method for improving transmissivity |
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