TW202330716A - 聚碳酸酯樹脂組成物及使用其之光學透鏡 - Google Patents
聚碳酸酯樹脂組成物及使用其之光學透鏡 Download PDFInfo
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- TW202330716A TW202330716A TW111145380A TW111145380A TW202330716A TW 202330716 A TW202330716 A TW 202330716A TW 111145380 A TW111145380 A TW 111145380A TW 111145380 A TW111145380 A TW 111145380A TW 202330716 A TW202330716 A TW 202330716A
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- polycarbonate resin
- resin composition
- general formula
- carbons
- constituent unit
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- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 126
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 126
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 230000003287 optical effect Effects 0.000 title claims description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 239000000470 constituent Substances 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 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
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 8
- -1 dihydroxymethyl groups Chemical group 0.000 description 50
- 239000003054 catalyst Substances 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 16
- 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 15
- 238000006243 chemical reaction Methods 0.000 description 14
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 12
- 239000006096 absorbing agent Substances 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 239000011737 fluorine Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000004417 polycarbonate Substances 0.000 description 11
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 230000004075 alteration Effects 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000004650 carbonic acid diesters Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012760 heat stabilizer Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- SFDGJDBLYNJMFI-UHFFFAOYSA-N 3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC=NC2=C1 SFDGJDBLYNJMFI-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 150000004671 saturated fatty acids Chemical class 0.000 description 4
- 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 4
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 3
- 241000208340 Araliaceae Species 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 3
- 235000003140 Panax quinquefolius Nutrition 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 235000008434 ginseng Nutrition 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 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 2
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- 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 2
- 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 2
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920001651 Cyanoacrylate Polymers 0.000 description 2
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 2
- 240000006927 Foeniculum vulgare Species 0.000 description 2
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 2
- 235000010338 boric acid Nutrition 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 description 2
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 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
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- 239000005304 optical glass Substances 0.000 description 2
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-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
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- ARIWANIATODDMH-UHFFFAOYSA-N rac-1-monolauroylglycerol Chemical compound CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 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 compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- SXJSETSRWNDWPP-UHFFFAOYSA-N (2-hydroxy-4-phenylmethoxyphenyl)-phenylmethanone Chemical compound C=1C=C(C(=O)C=2C=CC=CC=2)C(O)=CC=1OCC1=CC=CC=C1 SXJSETSRWNDWPP-UHFFFAOYSA-N 0.000 description 1
- WXENKXQUTQFQIP-PLKIVWSFSA-N (2e,4e)-hexa-2,4-dienoic acid;octadecanoic acid Chemical compound C\C=C\C=C\C(O)=O.CCCCCCCCCCCCCCCCCC(O)=O WXENKXQUTQFQIP-PLKIVWSFSA-N 0.000 description 1
- GPFJHNSSBHPYJK-UHFFFAOYSA-N (3-methylphenyl) hydrogen carbonate Chemical compound CC1=CC=CC(OC(O)=O)=C1 GPFJHNSSBHPYJK-UHFFFAOYSA-N 0.000 description 1
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- PXDJXZJSCPSGGI-UHFFFAOYSA-N hexadecanoic acid hexadecyl ester Natural products CCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC PXDJXZJSCPSGGI-UHFFFAOYSA-N 0.000 description 1
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- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical compound OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-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
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 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
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229940093625 propylene glycol monostearate Drugs 0.000 description 1
- LKUNXBRZDFMZOK-UHFFFAOYSA-N rac-1-monodecanoylglycerol Chemical compound CCCCCCCCCC(=O)OCC(O)CO LKUNXBRZDFMZOK-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 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
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 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
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- KPHOBSTVDZCCAU-UHFFFAOYSA-N tetracyclo[6.4.0.02,4.05,7]dodeca-1(12),2(4),5(7),8,10-pentaene Chemical group C1=CC=CC2=C3CC3=C(C3)C3=C21 KPHOBSTVDZCCAU-UHFFFAOYSA-N 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 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
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 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
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
依據本發明時,可提供一種聚碳酸酯樹脂組成物,其係包含來自下述通式(i)表示之單體的構成單位(A),及來自下述通式(ii)表示之單體的構成單位(B)的聚碳酸酯樹脂組成物,前述構成單位(A)與前述構成單位(B)以質量比計,構成單位(A):構成單位(B)=91:9~99:1。
(通式(i)中,R表示氫原子、或碳數1~4之烷基)
(通式(ii)中,R
1、R
2、R
3及R
4各自獨立地表示氫原子等,Y
1及Y
2各自獨立地表示碳數1~4之伸烷基)。
Description
本發明係關於新穎聚碳酸酯樹脂組成物,及藉由其所形成的光學透鏡者。
作為於照相機、底片一體型照相機、攝影機等之各種照相機之光學系所使用之光學元件的材料,使用如光學玻璃或光學用透明樹脂。光學玻璃因耐熱性或透明性、尺寸安定性、耐藥品性等優異,故存在於具有各種折射率(nD)或阿貝數(νD)之多種類的材料,但具有材料成本高,成形加工性差,及生產性低的問題。特別是加工使用於像差校正之非球面透鏡時,因需要極高度之技術與高成本,故成為實用上極大障礙。
另一方面,光學用透明樹脂,其中由熱塑性透明樹脂所構成之光學透鏡,可藉由射出成形來大量生產,而且具有非球面透鏡製造也容易的優點,故現在作為照相機用透鏡用途使用。例如,例示如由雙酚A所構成之聚碳酸酯、聚苯乙烯、聚-4-甲基戊烯、聚甲基丙烯酸甲酯或非晶質聚烯烴等。
然而,光學用透明樹脂作為光學透鏡使用時,除了折射率或阿貝數外,亦要求透明性、耐熱性、低雙折射性,故有因樹脂之特性平衡而限定了使用場所之弱點。例如,聚苯乙烯為耐熱性低且雙折射大,聚-4-甲基戊烯為耐熱性低,聚甲基丙烯酸甲酯為玻璃轉移溫度低、耐熱性低且折射率小,故使用區域受到限,由雙酚A所構成之聚碳酸酯因具有雙折射大等的弱點,故使用場所受到限制。
光學單元之光學設計中,已知藉由組合使用阿貝數互為相異之複數透鏡,而修正色收差的方法。例如,組合比較高阿貝數之環烯烴樹脂製之透鏡與由低阿貝數之雙酚A所構成之聚碳酸酯樹脂製之透鏡來修正色收差。然而,環烯烴樹脂與聚碳酸酯樹脂之間具有吸水膨脹率之差,在組合兩者透鏡而形成透鏡單元時,在智慧型手機等之使用環境,經吸水後時發生透鏡之大小差異。由於此一膨脹率差而使透鏡之性能受損。
專利文獻1~3中記載包含氧化羥基二甲橋萘(perhydroxy dimethanonaphthalene)骨架之聚碳酸酯共聚物,但由於二羥基甲基之位置皆為2,3位,故強度較弱,而不適合光學透鏡用途。
專利文獻4係對於高折射率且低阿貝數之聚碳酸酯樹脂,提供吸水膨脹率之差為小之高阿貝數之樹脂為目的,揭示以十氫-1,4:5,8-二甲橋萘二醇(D-NDM)作為原料之聚碳酸酯樹脂。但期望進一步之光學特性之改善。又,專利文獻5中揭示色相(YI)或霧度(Hz)不會降低,且具有低雙折射率、中折射率、且中阿貝數之聚碳酸酯樹脂組成物,但是期望進一步之光學特性之改善。
[先前技術文獻]
[專利文獻]
[專利文獻1] 日本特開平5-70584號公報
[專利文獻2] 日本特開平2-69520號公報
[專利文獻3] 日本特開平5-341124號公報
[專利文獻4] 國際公開第2016/052370A1
[專利文獻5] 國際公開第2018/181157A1
[發明所欲解決之課題]
本發明所欲解決之課題係提供光彈性模數低,具有中折射率、且中阿貝數的聚碳酸酯樹脂組成物及由此樹脂組成物所形成之光學透鏡。
[用以解決課題之手段]
以往,摻合低折射率材料與高折射率材料時,有透過率降低的課題。但是本發明人等為了解決前述課題而精心檢討的結果,發現以特定比包含特定結構之構成單位(A)與特定結構之構成單位(B)時,可得到光彈性模數低,具有中折射率且中阿貝數的聚碳酸酯樹脂組成物,遂達成本發明。
亦即,上述課題可藉由以下所示之聚碳酸酯樹脂組成物、使用其之光學透鏡解決。
<1> 一種聚碳酸酯樹脂組成物,其係包含來自下述通式(i)表示之單體的構成單位(A),及來自下述通式(ii)表示之單體的構成單位(B)的聚碳酸酯樹脂組成物,
前述構成單位(A)與前述構成單位(B)以質量比計,構成單位(A):構成單位(B)=91:9~99:1,
(通式(i)中,R表示氫原子、或碳數1~4之烷基)
(通式(ii)中,R
1、R
2、R
3及R
4各自獨立地表示氫原子、碳數1~20之烷基、碳數1~20之烷氧基、碳數5~20之環烷基、碳數5~20之環烷氧基、碳數6~20之芳基或碳數6~20之芳氧基,Y
1及Y
2各自獨立地表示碳數1~4之伸烷基)。
<2> 如上述<1>之聚碳酸酯樹脂組成物,其包含具有前述構成單位(A)之聚碳酸酯樹脂(A)與具有前述構成單位(B)之聚碳酸酯樹脂(B)的樹脂混合物。
<3> 如上述<1>或<2>之聚碳酸酯樹脂組成物,其中前述通式(ii)中,R
1及R
2各自獨立地表示氫原子或苯基,R
3及R
4表示氫原子。
<4> 如上述<1>~<3>中任一項之聚碳酸酯樹脂組成物,其中前述通式(i)中之R表示氫原子。
<5> 如上述<1>~<4>中任一項之聚碳酸酯樹脂組成物,其中前述聚碳酸酯樹脂組成物之光彈性模數為11.0~ 12.0(×10
-12m
2/N)。
<6> 如上述<1>~<5>中任一項之聚碳酸酯樹脂組成物,其中前述聚碳酸酯樹脂組成物之阿貝數(Abbe Number)為46~55。
<7> 如上述<1>~<6>中任一項之聚碳酸酯樹脂組成物,其中前述聚碳酸酯樹脂組成物之折射率(nD)為1.533~ 1.547。
<8> 如上述<1>~<7>中任一項之聚碳酸酯樹脂組成物,其中前述聚碳酸酯樹脂組成物之Tg為132~135℃。
<9> 一種光學透鏡,其包含如上述<1>~<8>之聚碳酸酯樹脂組成物。
[發明效果]
藉由本發明可提供光彈性模數低,具有中折射率、且中阿貝數的聚碳酸酯樹脂組成物及使用此樹脂組成物的光學透鏡。
[實施發明之形態]
以下,詳細說明本實施發明之形態,但本發明並非受此所限定者,在不超出其要旨之範圍,可予以各種的變形。
本發明之聚碳酸酯樹脂組成物,其係包含來自下述通式(i)表示之單體的構成單位(A),及來自下述通式(ii)表示之單體的構成單位(B),
前述構成單位(A)與前述構成單位(B)以質量比計,構成單位(A):構成單位(B)=91:9~99:1,較佳為構成單位(A):構成單位(B)=91:9~97:3,更佳為構成單位(A):構成單位(B)=92:8~96:4。
通式(i)中,R表示氫原子、或碳數1~4之烷基,較佳為表示氫原子、甲基、或乙基,特佳為表示氫原子)
通式(ii)中,R
1、R
2、R
3及R
4各自獨立地表示氫原子、碳數1~20之烷基、碳數1~20之烷氧基、碳數5~20之環烷基、碳數5~20之環烷氧基、碳數6~20之芳基或碳數6~20之芳氧基。R
1及R
2較佳為表示氫原子、甲基、或苯基,更佳為表示氫原子或苯基。R
3及R
4較佳為表示氫原子。Y
1及Y
2各自獨立地表示碳數1~4之伸烷基,較佳為表示伸乙基、或伸丙基,更佳為表示伸乙基。
本發明係以91:9~99:1質量比計,包含構成單位(A):構成單位(B)時,可為具有構成單位(A)之聚碳酸酯樹脂(A)與具有構成單位(B)之聚碳酸酯樹脂(B)之樹脂混合物的態樣,或相同樹脂中含有構成單位(A)與構成單位(B)之共聚樹脂的態樣,但是更佳為前者之樹脂混合物的態樣。
以下,詳細地說明更佳之態樣的樹脂混合物。
<聚碳酸酯樹脂(A)>
本發明之較佳之態樣中的聚碳酸酯樹脂(A)具有下述通式(1)表示之構成單位(A)。
通式(1)中,R係與前述通式(i)中者同義。
前述通式(1)表示之構成單位(A),例如由前述通式(i)表示之二羥基化合物所衍生之構成單位。例如,由十氫-1、4:5、8-二甲橋萘二酚(以下有時稱為「D-NDM」)所衍生的構成單位。
構成單位(A)較佳為下述通式(M)表示之
-CH
2O-基鍵結於6位之異構物(2,6位之異構物),與下述通式(N)表示之-CH
2O-基鍵結於7位之異構物(2,7位之異構物)的混合物。計樹脂之強度、拉伸伸度、成形體之外觀等之樹脂物性的觀點,以質量比計,2,6位之異構物:2,7位之異構物=1.0:99.0~99.0:1.0為佳,2,6位之異構物:2,7位之異構物=20:80~80:20為較佳,2,6位之異構物:2,7位之異構物=50:50~80:20為特佳。本發明中,以不包含2,3位之異構物為佳。
(通式(M)中,R表示氫原子、或碳數1~4之烷基)
(通式(N)中,R表示氫原子、或碳數1~4之烷基)
前述通式(M)表示之構成單位,例如由下述通式(O)表示之二羥基化合物所衍生之構成單位,前述通式(N)表示之構成單位,例如由下述通式(P)表示之二羥基化合物所衍生之構成單位。
(通式(O)中,R表示氫原子、或碳數1~4之烷基)
(通式(P)中,R表示氫原子、或碳數1~4之烷基)
前述通式(i)、(M)、(N)、(O)及(P)中,R較佳為皆相同,就流通性的觀點,R為氫原子較佳。
本發明之聚碳酸酯樹脂(A)具有上述通式(1)表示之構成單位(A),但在不損及本發明之效果範圍內,亦可包含其他構成單位。本發明之聚碳酸酯樹脂(A)中所佔之構成單位(A)之比例,較佳為70質量%以上,更佳為100質量%。
本發明之聚碳酸酯樹脂(A)可包含之其他構成單位係指使通式(1)以外之二醇化合物與碳酸二酯反應而得的構成單位,作為通式(1)以外之二醇化合物,可列舉例如,雙酚A、雙酚AP、雙酚AF、雙酚B、雙酚BP、雙酚C、雙酚E、雙酚F、雙酚G、雙酚M、雙酚S、雙酚P、雙酚PH、雙酚TMC、雙酚Z等。
<聚碳酸酯樹脂(B)>
本發明之較佳之態樣中之聚碳酸酯樹脂(B),具有下述通式(2)表示之構成單位(B)。
通式(2)中,R
1、R
2、R
3、R
4、Y
1及Y
2係與前述通式(ii)中者同義。
前述通式(2)表示之構成單位(B),例如由前述通式(ii)表示之二羥基化合物所衍生之構成單位。
前述通式(ii)表示之茀系二醇化合物之具體例,可列舉例如9,9-雙(4-羥基苯基)茀、9,9-雙(4-羥基-3-甲基苯基)茀、9,9-雙(4-羥基-3-tert-丁基苯基)茀、9,9-雙(4-羥基-3-異丙基苯基)茀、9,9-雙(4-羥基-3-環己基苯基)茀、9,9-雙(4-羥基-3-苯基苯基)茀、9,9-雙(4-(2-羥基乙氧基)苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-甲基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-tert-丁基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-異丙基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-環己基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-苯基苯基)茀等。此等之中,較佳為9,9-雙(4-(2-羥基乙氧基)苯基)茀(BPEF)、9,9-雙(4-(2-羥基乙氧基)-3-苯基苯基)茀(BPPEF),及9,9-雙(4-(2-羥基乙氧基)-3-甲基苯基)茀(BPMEF),更佳為9,9-雙(4-(2-羥基乙氧基)苯基)茀(BPEF),及9,9-雙(4-(2-羥基乙氧基)-3-苯基苯基)茀(BPPEF)。
本發明中之聚碳酸酯樹脂(B)具有上述通式(2)表示之構成單位(B),但是在不損及本發明之效果的範圍內,也可含有其他之構成單位。本發明之聚碳酸酯樹脂(B)中所佔之上述通式(2)表示之構成單位(B)之比例,較佳為70質量%以上,更佳為100質量%。
本發明中之聚碳酸酯樹脂(B)可含有其他之構成單位係指通式(ii)以外之二醇化合物與碳酸二酯反應所得之構成單位,通式(ii)以外之二醇化合物,可列舉例如雙酚A、雙酚AP、雙酚AF、雙酚B、雙酚BP、雙酚C、雙酚E、雙酚F、雙酚G、雙酚M、雙酚S、雙酚P、雙酚PH、雙酚TMC、雙酚Z等。
<聚碳酸酯樹脂組成物>
本發明之較佳之態樣的聚碳酸酯樹脂組成物,包含具有上述通式(1)表示之構成單位(A)的聚碳酸酯樹脂(A),及具有上述通式(2)表示之構成單位(B)的聚碳酸酯樹脂(B)。
本發明之聚碳酸酯樹脂組成物,在不損及本發明之效果的範圍內,也可含有其他之樹脂。本發明之聚碳酸酯樹脂組成物中所佔之上述聚碳酸酯樹脂(A)及聚碳酸酯樹脂(B)之合計之比例,較佳為70質量%以上,更佳為100質量%。
本發明之聚碳酸酯樹脂組成物係前述聚碳酸酯樹脂(A)與前述聚碳酸酯樹脂(B)之混合比,以質量比計,為91:9~99:1,較佳為91:9~97:3,更佳為92:8~96:4。
此外,本發明之聚碳酸酯樹脂組成物中,較佳為添加抗氧化劑、脫模劑、加工安定劑、紫外線吸收劑、流動性改質劑、結晶核劑、強化劑、染料、抗靜電劑或抗菌劑等。
作為抗氧化劑,可列舉受阻酚系抗氧化劑、亞磷酸酯系抗氧化劑、三乙二醇-雙[3-(3-tert-丁基-5-甲基-4-羥基苯基)丙酸酯]、1,6-已二醇-雙[3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯]、季戊四醇-肆[3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯]、十八烷基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯、1,3,5-三甲基-2,4,6-參(3,5-二-tert-丁基-4-羥基苄基)苯、N,N-六亞甲基雙(3,5-二-tert-丁基-4-羥基-氫桂皮醯胺(hydrocinnamide))、3,5-二-tert-丁基-4-羥基-苄基膦酸酯-二乙基酯、參(3,5-二-tert-丁基-4-羥基苄基)異三聚氰酸酯及3,9-雙{1,1-二甲基-2-[β-(3-tert-丁基-4-羥基-5-甲基苯基)丙醯氧基]乙基}-2,4,8,10-四氧雜螺(5,5)十一烷等。此等之中,較佳為受阻酚系抗氧化劑及亞磷酸酯系抗氧化劑。聚碳酸酯樹脂組成物中之抗氧化劑之含量係相對於聚碳酸酯樹脂(A)及(B)之合計100質量份,較佳為0.001~0.3質量份。
作為脫模劑,較佳為其90質量%以上為醇與脂肪酸之酯所構成者。醇與脂肪酸之酯,具體例,可列舉一價醇與脂肪酸之酯或多元醇與脂肪酸之部分酯或全酯。上述一價醇與脂肪酸之酯,較佳為碳原子數1~20之一價醇與碳原子數10~30之飽和脂肪酸之酯。又,多元醇與脂肪酸之部分酯或全酯,較佳為碳原子數1~25之多元醇與碳原子數10~30之飽和脂肪酸之部分酯或全酯。
具體而言,一價醇與飽和脂肪酸之酯,可列舉十八烷基硬脂酸酯、十六烷基棕櫚酸酯、丁基硬脂酸酯、甲基月桂酸酯、異丙基棕櫚酸酯等。作為多元醇與飽和脂肪酸之部分酯或全酯,可列舉硬脂酸單甘油酯、硬脂酸二甘油酯、硬脂酸三甘油酯、硬脂酸單山梨酸酯、二十二酸單甘油酯、癸酸單甘油酯、月桂酸單甘油酯、季戊四醇單硬脂酸酯、季戊四醇四硬脂酸酯、季戊四醇四壬酸甲酯(Pelargonate)、丙二醇單硬脂酸酯、聯苯基雙酚酯(phenate)、山梨糖醇酐單硬脂酸酯、2-乙基己基硬脂酸酯、二季戊四醇六硬脂酸酯等之二季戊四醇之全酯或部分酯等。此等之中,特佳為硬脂酸單甘油酯及月桂酸單甘油酯。此等脫模劑之含量,相對於聚碳酸酯樹脂(A)及(B)之合計100重量份,較佳為0.005~2.0重量份之範圍,更佳為0.01~0.6重量份之範圍,又更佳為0.02~0.5重量份之範圍。
作為加工安定劑,可列舉磷系加工熱安定劑、硫系加工熱安定劑等。作為磷系加工熱安定劑,可列舉亞磷酸、磷酸、亞膦酸、膦酸及此等之酯等。具體而言,可列舉三苯基亞磷酸酯、參(壬基苯基)亞磷酸酯、三(2,4-二-tert-丁基苯基)亞磷酸酯、參(2,6-二-tert-丁基苯基)亞磷酸酯、十三烷基亞磷酸酯、三辛基亞磷酸酯、參十八烷基亞磷酸酯、二癸基單苯基亞磷酸酯、二辛基單苯基亞磷酸酯、二異丙基單苯基亞磷酸酯、單丁基二苯基亞磷酸酯、單癸基二苯基亞磷酸酯、單辛基二苯基亞磷酸酯、雙(2,6-二-tert-丁基-4-甲基苯基)季戊四醇二亞磷酸酯、2,2-亞甲基雙(4,6-二-tert-丁基苯基)辛基亞磷酸酯、雙(壬基苯基)季戊四醇二亞磷酸酯、雙(2,4-二枯基苯基)季戊四醇二亞磷酸酯、雙(2,4-二-tert-丁基苯基)季戊四醇二亞磷酸酯、二十八烷基季戊四醇二亞磷酸酯、三丁基磷酸酯、三乙基磷酸酯、三甲基磷酸酯、三苯基磷酸酯、磷酸二苯基單鄰聯苯酯(diphenylmonoorthoxenyl phosphate)、二丁基磷酸酯、二辛基磷酸酯、二異丙基磷酸酯、苯膦酸二甲基、苯膦酸二乙基、苯膦酸二丙基、四(2,4-二-t-丁基苯基)-4,4’-亞聯苯基二亞膦酸酯、四(2,4-二-t-丁基苯基)-4,3’-亞聯苯基二亞膦酸酯、四(2,4-二-t-丁基苯基)-3,3’-亞聯苯基二亞膦酸酯、雙(2,4-二-tert-丁基苯基)-4-苯基-苯基亞膦酸酯及雙(2,4-二-tert-丁基苯基)-3-苯基-苯基亞膦酸酯等。此等之中,更佳為雙(2,6-二-tert-丁基-4-甲基苯基)季戊四醇二亞磷酸酯。聚碳酸酯樹脂組成物中之磷系加工熱安定劑之含量,相對於聚碳酸酯樹脂(A)及(B)之合計100質量份,較佳為0.001~0.2質量份。
作為硫系加工熱安定劑,可舉出如季戊四醇-肆(3-月桂基硫代丙酸酯)、季戊四醇-肆(3-肉豆蔻基硫代丙酸酯)、季戊四醇-肆(3-硬脂醯基硫代丙酸酯)、二月桂基-3,3’-硫代二丙酸酯、二肉豆蔻基-3,3’-硫代二丙酸酯、二硬脂醯基-3,3’-硫代二丙酸酯等。聚碳酸酯樹脂組成物中之硫系加工熱安定劑之含量係相對於聚碳酸酯樹脂(A)及(B)之合計100質量份,較佳為0.001~0.2質量份為佳。
作為紫外線吸收劑,較佳為選自由苯並三唑系紫外線吸收劑、二苯甲酮系紫外線吸收劑、三嗪系紫外線吸收劑、環狀亞胺基酯系紫外線吸收劑及氰基丙烯酸酯系紫外線吸收劑所成群之至少1種的紫外線吸收劑。亦即,以下所舉出之紫外線吸收劑,皆可單獨使用,亦可組合2種以上使用。
苯並三唑系紫外線吸收劑,可列舉2-(2-羥基-5-甲基苯基)苯並三唑、2-(2-羥基-5-tert-辛基苯基)苯並三唑、2-(2-羥基-3,5-二枯基苯基)苯基苯並三唑、2-(2-羥基-3-tert-丁基-5-甲基苯基)-5-氯苯並三唑、2,2’-亞甲基雙[4-(1,1,3,3-四甲基丁基)-6-(2N-苯並三唑-2-基)酚]、2-(2-羥基-3,5-二-tert-丁基苯基)苯並三唑、2-(2-羥基-3,5-二-tert-丁基苯基)-5-氯苯並三唑、2-(2-羥基-3,5-二-tert-戊基苯基)苯並三唑、2-(2-羥基-5-tert-辛基苯基)苯並三唑、2-(2-羥基-5-tert-丁基苯基)苯並三唑、2-(2-羥基-4-辛氧基苯基)苯並三唑、2,2’-亞甲基雙(4-枯基-6-苯並三唑苯基)、2,2’-p-伸苯基雙(1,3-苯並噁嗪-4-酮)、2-[2-羥基-3-(3,4,5,6-四氫酞醯亞胺甲基)-5-甲基苯基]苯並三唑等。
二苯甲酮系紫外線吸收劑,可列舉2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-辛氧基二苯甲酮、2-羥基-4-苄氧基二苯甲酮、2-羥基-4-甲氧基-5-亞碸二苯甲酮、2-羥基-4-甲氧基-5-亞碸三水合物二苯甲酮、2,2’-二羥基-4-甲氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基-5-鈉亞碸二苯甲酮、雙(5-苯甲醯基-4-羥基-2-甲氧基苯基)甲烷、2-羥基-4-n-十二烷氧基二苯甲酮、2-羥基-4-甲氧基-2’-羧基二苯甲酮等。
三嗪系紫外線吸收劑,可列舉2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[(己基)氧基]-苯酚、2-(4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-[(辛基)氧基]-苯酚等。
環狀亞胺基酯系紫外線吸收劑,可列舉2,2’-雙(3,1-苯並噁嗪-4-酮)、2,2’-p-伸苯基雙(3,1-苯並噁嗪-4-酮)、2,2’-m-伸苯基雙(3,1-苯並噁嗪-4-酮)、2,2’-(4,4’-二伸苯基)雙(3,1-苯並噁嗪-4-酮)、2,2’-(2,6-萘)雙(3,1-苯並噁嗪-4-酮)、2,2’-(1,5-萘)雙(3,1-苯並噁嗪-4-酮)、2,2’-(2-甲基-p-伸苯基)雙(3,1-苯並噁嗪-4-酮)、2,2’-(2-硝基-p-伸苯基)雙(3,1-苯並噁嗪-4-酮)及2,2’-(2-氯-p-伸苯基)雙(3,1-苯並噁嗪-4-酮)等。
氰基丙烯酸酯系紫外線吸收劑,可列舉1,3-雙-[(2’-氰基-3’,3’-二苯基丙烯醯基)氧基]-2,2-雙[(2-氰基-3,3-二苯基丙烯醯基)氧基]甲基)丙烷、及1,3-雙-[(2-氰基-3,3-二苯基丙烯醯基)氧基]苯等。
紫外線吸收劑之含量係相對於聚碳酸酯樹脂(A)及(B)之合計100質量份,較佳為0.01~3.0質量份,更佳為0.02~1.0質量份,又更佳為0.05~0.8質量份。在此調配量之範圍時,依據用途,對於聚碳酸酯樹脂組成物,可賦予充分的耐候性。
聚碳酸酯樹脂組成物中,製造時生成之苯酚或未反應殘存之碳酸二酯以雜質形態存在。聚碳酸酯樹脂組成物中之苯酚含量,較佳為0.1~3000ppm,更佳為0.1~ 2000ppm,又更佳為1~1000ppm、1~800ppm、1~500ppm、或1~300ppm。又,聚碳酸酯樹脂組成物中之碳酸二酯含量,較佳為0.1~1000ppm,更佳為0.1~500ppm,特佳為1~ 100ppm。藉由調節聚碳酸酯樹脂組成物中所含有之苯酚及碳酸二酯之量,可得到具有依據目的之物性的樹脂。苯酚及碳酸二酯之含量之調節,可藉由變更聚縮合之條件或裝置,適宜進行。又,也可藉由聚縮合後之擠壓步驟之條件調節。
苯酚或碳酸二酯之含量高於上述範圍時,會生成所取得之樹脂成形體之強度降低,或臭氣產生等的問題。另一方面,苯酚或碳酸二酯之含量低於上述範圍時,有樹脂熔融時之可塑性降之疑慮。
<聚碳酸酯樹脂組成物之製造方法>
本發明之聚碳酸酯樹脂組成物之製造方法,無特別限制,藉由例如(1)混合聚碳酸酯樹脂(A)與聚碳酸酯樹脂(B)之各自之固體,藉由混練機進行混練的方法,(2)對熔融狀態之聚碳酸酯樹脂(A)添加固體聚碳酸酯樹脂(B)並進行混練的方法,(3)對熔融狀態之聚碳酸酯樹脂(B)添加固體聚碳酸酯樹脂(A)進行混練的方法,(4)混合熔融狀態之聚碳酸酯樹脂(A)與熔融狀態之聚碳酸酯樹脂(B)進行混練的方法之任一方法也可製造。
混練可為連續式、分批式之任一者。混練機若為連續式時較佳為擠壓機,若分批式適宜使用小型混合擠壓機(Labo Plastomill),及捏合機。
本發明之聚碳酸酯樹脂(A)係將通式(i)所示之二羥基化合物及碳酸二酯作為原料,可藉由熔融聚縮合法製造。通式(i)所示之二羥基化合物中,存在有羥基甲基為2,6位之異構物及2,7位之異構物的混合物。此等異構物在質量比計為2,6位之異構物:2,7位之異構物=0.1:99.9 ~99.9:0.1。就樹脂之強度、拉伸伸度、成形體之外觀等之樹脂物性的觀點,較佳為2,6位之異構物:2,7位之異構物=1.0:99.0~99.0:1.0,更佳為2,6位之異構物:2,7位之異構物=20:80~80:20,特佳為2,6位之異構物:2,7位之異構物=50:50~80:20。本發明中,較佳為不包含2,3位之異構物。此外,亦可併用其他之二醇化合物。此反應中,作為聚縮合觸媒為鹼性化合物觸媒、酯交換觸媒或由其兩者所構成之混合觸媒的存在下進行製造。
又,本發明之聚碳酸酯樹脂(B),可將通式(B)所示之二羥基化合物及碳酸二酯作為原料,藉由熔融聚縮合法進行製造。
作為碳酸二酯,可舉出如碳酸二苯酯、碳酸二甲苯酯、碳酸雙(氯苯基)酯、碳酸m-甲苯酚酯、碳酸二甲酯、碳酸二乙酯、碳酸二丁酯、碳酸二環己酯等。該等之中,從反應性與純度之觀點,特別係以碳酸二苯酯為佳。碳酸二酯係相對於二醇成分1莫耳,較佳為0.97~1.20莫耳之比率使用,更佳為0.98~1.10莫耳之比率。藉由調整此莫耳比率來控制聚碳酸酯樹脂之分子量。
作為鹼性化合物觸媒,可舉出如鹼金屬化合物、鹼土金屬化合物,及含氮化合物等。
作為鹼金屬化合物,可舉出例如鹼金屬之有機酸鹽、無機鹽、氧化物、氫氧化物、氫化物或烷氧化物等。具體而言,可使用如氫氧化鈉、氫氧化鉀、氫氧化銫、氫氧化鋰、碳酸氫鈉、碳酸鈉、碳酸鉀、碳酸銫、碳酸鋰、乙酸鈉、乙酸鉀、乙酸銫、乙酸鋰、硬脂酸鈉、硬脂酸鉀、硬脂酸銫、硬脂酸鋰、氫化硼鈉、苯基化硼鈉、安息香酸鈉、安息香酸鉀、安息香酸銫、安息香酸鋰、磷酸氫二鈉、磷酸氫二鉀、磷酸氫二鋰、苯基磷酸二鈉、雙酚A之二鈉鹽、二鉀鹽、二銫鹽、二鋰鹽、苯酚之鈉鹽、鉀鹽、銫鹽、鋰鹽等。從觸媒效果、價格、流通量、對樹脂色相之影響等的觀點,較佳為碳酸鈉,及碳酸氫鈉。
作為鹼土金屬化合物,可舉出例如鹼土金屬化合物之有機酸鹽、無機鹽、氧化物、氫氧化物、氫化物或烷氧化物等。具體而言,可使用如氫氧化鎂、氫氧化鈣、氫氧化鍶、氫氧化鋇、碳酸氫鎂、碳酸氫鈣、碳酸氫鍶、碳酸氫鋇、碳酸鎂、碳酸鈣、碳酸鍶、碳酸鋇、乙酸鎂、乙酸鈣、乙酸鍶、乙酸鋇、硬脂酸鎂、硬脂酸鈣、安息香酸鈣、苯基磷酸鎂等。
作為含氮化合物,可舉出例如氫氧化四級銨及該等之鹽、胺類等。具體而言,可使用如氫氧化四甲銨、氫氧化四乙銨、氫氧化四丙銨、氫氧化四丁銨、氫氧化三甲基苄基銨等之具有烷基、芳基等之氫氧化四級銨類、三乙基胺、二甲基苄基胺、三苯基胺等之三級胺類、二乙基胺、二丁基胺等之二級胺類、丙基胺、丁基胺等之一級胺類、2-甲基咪唑、2-苯基咪唑、苯並咪唑等之咪唑類,或氨、硼氫化四甲銨、硼氫化四丁銨、四丁基四苯基硼酸銨、四苯基四苯基硼酸銨等之鹼或鹼性鹽等。
作為酯交換觸媒,較佳為使用鋅、錫、鋯、鉛之鹽,此等可單獨使用或組合使用。又,亦可組合使用上述鹼金屬化合物或鹼土金屬化合物。
作為酯交換觸媒,具體而言,可使用如乙酸鋅、安息香酸鋅、2-乙基己酸鋅、氯化錫(II)、氯化錫(IV)、乙酸錫(II)、乙酸錫(IV)、二丁基錫二月桂酸酯、氧化二丁基錫、二甲氧基化二丁基錫、乙醯基丙酮酸鋯、氧乙酸鋯、四丁氧基化鋯、乙酸鉛(II)、乙酸鉛(IV)等。
此等觸媒係相對於二醇化合物之合計1莫耳,較佳為使用1×10
-9~1×10
-3莫耳之比率,較佳為使用1×10
-7~1×10
-4莫耳之比率。
熔融聚縮合法係使用前述原料及觸媒,在加熱下常壓或減壓下藉由酯交換反應,邊去除副產物邊進行熔融聚縮合者。反應一般以二段以上之多段步驟來實施。
具體而言,使第一段之反應以120~260℃,較佳為180~240℃之溫度反應0.1~5小時,較佳為反應0.5~ 3小時。其次,提高反應系統之減壓度,並同時提高反應溫度,進行二醇化合物與碳酸二酯之反應,最後在1mmHg以下的減壓下,以200~350℃之溫度進行0.05~2小時聚縮合反應。此種反應可以連續式來進行,亦可以分批式來進行。進行前述反應時所使用之反應裝置可為裝備有錨型攪拌葉、MAXBLEND攪拌葉、螺旋帶型攪拌葉等縱型,也可為裝備有漿葉、格子葉、眼鏡葉等之橫型,亦可為裝備有螺桿之擠壓機型,又,以在考量到聚合物之黏度,較佳為使用適宜組合此等之反應裝置。
本發明之聚碳酸酯樹脂(A)及聚碳酸酯樹脂(B)之製造方法中,在聚合反應結束後,為了保持熱安定性及水解安定性,亦可去除觸媒或使其失活。一般而言,適宜實施進行添加公知之酸性物質所成之觸媒失活的方法。作為此等物質,具體而言,可適宜使用如安息香酸丁基等之酯類、p-甲苯磺酸等之芳香族磺酸類、p-甲苯磺酸丁酯、p-甲苯磺酸己酯等之芳香族磺酸酯類、亞磷酸、磷酸、膦酸等之磷酸類、亞磷酸三苯酯、亞磷酸單苯酯、亞磷酸二苯酯、亞磷酸二乙酯、亞磷酸二n-丙酯、亞磷酸二n-丁酯、亞磷酸二n-己酯、亞磷酸二辛酯、亞磷酸單辛酯等之亞磷酸酯類、磷酸三苯基磷酸二苯酯、磷酸單苯酯、磷酸二丁酯、磷酸二辛酯、磷酸單辛酯等之磷酸酯類、二苯膦酸、二辛基膦酸、二丁基膦酸等之膦酸類、苯基膦酸二乙酯等之膦酸酯類、三苯基膦、雙(二苯基膦基)乙烷等之膦類、硼酸、苯基硼酸等之硼酸類、十二烷基苯磺酸四丁基鏻鹽等之芳香族磺酸鹽類、硬脂酸氯、氯化苄醯基、p-甲苯磺酸氯等之有機鹵化物、二甲基硫酸等之烷基硫酸、氯化苄基等之有機鹵化物等。從失活效果、樹脂之色相及安定性的觀點,較佳為使用p-甲苯磺酸丁酯。又,此等失活劑係相對於觸媒量,較佳為使用0.01~50倍莫耳,更佳為使用0.3~20倍莫耳。相對於觸媒量,若少於0.01倍莫耳時,失活效果變得不充分而不佳。又,相對於觸媒量,若多於50倍莫耳時,因耐熱性降低,且成形體容易著色,故不佳。
在觸媒失活後,亦可設置使聚合物中之低沸點化合物在0.1~1mmHg之壓力、200~350℃之溫度下揮脫發去除之步驟,因此,而適宜使用具備有漿葉、格子葉、眼鏡葉等表面更新能力優異之攪拌葉的橫型裝置,或薄膜蒸發器。
本發明之聚碳酸酯樹脂組成物,盡量減少異物含量較理想,適宜實施熔融原料之過濾、觸媒液之過濾。過濾器之篩目係以5μm以下為佳,更佳為1μm以下。並且,適宜實施生成之樹脂之藉由聚合物過濾器之過濾。聚合物過濾器之篩目以100μm以下為佳,更佳為30μm以下。又,採收樹脂顆粒的步驟當然必須在低塵環境中,以等級1000以下為佳,較佳為等級100以下。
<聚碳酸酯樹脂組成物之物性>
本發明之聚碳酸酯樹脂組成物之較佳的玻璃轉移溫度(Tg)為132~135℃,更佳為132~133℃。
本發明之聚碳酸酯樹脂組成物,成形後以JIS-K-7142的方法進行測定的折射率,較佳為1.533~ 1.547,更佳為1.535~1.542。
本發明之聚碳酸酯樹脂組成物,成形後以JIS-K-7142的方法進行測定的阿貝數,較佳為46~55,更佳為48~53。
本發明之聚碳酸酯樹脂組成物係成形所得之厚度0.1mm之鑄膜(cast film)進行測定的光彈性模數,較佳為11.0~12.0(×10
-12m
2/N),更佳為11.0~11.5(×10
-12m
2/N)。
本發明之聚碳酸酯樹脂組成物之較佳之聚苯乙烯換算重量平均分子量(Mw)為20,000~70,000。更佳之聚苯乙烯換算重量平均分子量(Mw)為25,000~65,000,特佳之聚苯乙烯換算重量平均分子量(Mw)為30,000~ 60,000。Mw小於20,000時,光學透鏡變脆,故不佳。Mw為大於70,000時,熔融黏度變高,故製造後之樹脂取出變得困難,此外,流動性變差,在熔融狀態下不易射出成形,故不佳。
就耐黃變性、安定性(耐熱、耐候等)的觀點,最終顆粒(含有添加劑之聚碳酸酯樹脂組成物)所含有之十氫-1、4:5、8-二甲橋萘二酚(D-NDM),較佳為30ppm以下,又更佳為20ppm以下。
<光學透鏡>
本發明之光學透鏡,可藉由射出成形機或射出壓縮成形機,將上述本發明之聚碳酸酯樹脂組成物射出成形為透鏡形狀而得。射出成形之成形條件無特別限定,但是成形溫度,較佳為180~280℃。又,射出壓力較佳為50~1700 kg/cm
2。
為了盡量避免異物混入於光學透鏡,因此成形環境亦必須為低塵環境,較佳為等級1000以下,較佳為等級100以下。
本發明之光學透鏡,在因應需要,適宜實施在非球面透鏡之形狀下使用。非球面透鏡,由於1片透鏡可將球面像差作成實質為零,故並不需以複數球面透鏡之組合來去除球面像差(Spherical aberration),而能使輕量化及降低生產成本降低。因此,在光學透鏡之中尤其是以非球面透鏡作為照相機透鏡使用。非球面透鏡之像散(astigmatism),較佳為0~15mλ,較佳為0~10mλ。
本發明之光學透鏡的厚度,因應用途可設定為廣大範圍,無特別限制,較佳為0.01~30mm,較佳為0.1~15mm。本發明之光學透鏡之表面,因應需要可設有抗反射層或稱為硬塗層等的塗覆層。抗反射層可為單層亦可為多層,可為有機物亦可為無機物,但較佳為無機物。具體而言,可列舉氧化矽、氧化鋁、氧化鋯、氧化鈦、氧化鈰、氧化鎂、氟化鎂等之氧化物或氟化物。此等之中,較佳者為氧化矽、氧化鋯,更佳者為氧化矽與氧化鋯之組合。又,關於抗反射層,其為單層/多層之組合,及該等之成分、厚度之組合等皆無特別限定,較佳為2層構成或3層構成,特佳為3層構成。又,作為該抗反射層全體,以光學透鏡之厚度之0.00017~3.3%為佳,具體如0.05~3μm,特佳係以成為1~2μm之厚度來形成即可。
[實施例]
以下依據實施例說明本發明,但本發明不受此等實施例所任何限制者。又,實施例中之測量值使用以下之方法或裝置進行測量。
1)折射率(nD):對於將所得之聚碳酸酯樹脂組成物成形所得之厚度0.1mm的鑄膜,使用阿貝式折射計,以JIS-K-7142的方法進行測定。
2)阿貝數(νd):對於將所得之聚碳酸酯樹脂組成物成形所得之厚度0.1mm的鑄膜,使用阿貝式折射計,以JIS-K-7142的方法在23℃下測定波長486nm、589nm及656nm之折射率,同時使用下述式,算出阿貝數。
νd=(nD-1)/(nF-nC)
nD:波長589nm下之折射率
nC:波長656nm下之折射率
nF:波長486nm下之折射率
3)玻璃轉移溫度(Tg):藉由示差熱掃描熱量計(DSC),測定玻璃轉移溫度(Tg)。特定條件如下述。
裝置:股份公司Hitachi High-Tech Science DSC7000X
樣品量:5mg
環境:氮氣環境下
昇溫條件:10℃/分鐘
4)光彈性模數:對於將所得之聚碳酸酯樹脂組成物成形所得之厚度0.1mm的鑄膜,使用橢圓測厚儀,測定對於波長633nm下之荷重變化之雙折射之變化而算出。
橢圓測厚儀:日本分光股份公司製M-220
[合成例1]
將作為原料之下述結構式表示之十氫-1,4;5,8-二甲橋萘二酚(D-NDM)20000g(89.97莫耳)、二苯基碳酸酯(DPC)19425g(90.68莫耳),及0.10莫耳/公升之碳酸氫鈉水溶液10.8ml(1.08×10
-3莫耳,亦即,相對於二羥基化合物之合計1莫耳,為1.2×10
-5莫耳)置入附攪拌機及餾出裝置之50公升反應器中,在氮環境760Torr之下,花費1小時,加熱至215℃,進行攪拌。然後,花費10分鐘,將減壓度調整為150Torr,在215℃、150Torr的條件下,保持20分鐘,進行酯交換反應。此外,在37.5℃/hr之速度,昇溫至240℃,在240℃、150Torr保持10分鐘。然後,花費10分鐘,調整至120Torr,在240℃、120T orr下保持70分鐘。然後,花費10分鐘調整為100Torr,在240℃、100Torr下保持10分鐘。進一步,花費40分鐘,成為1Torr以下,在240℃、1Torr以下的條件下,攪拌10分鐘進行聚合反應。反應終了後,對反應器內加壓吹入氮,將生成之聚碳酸酯樹脂(D-NDM-PC)邊造粒邊取出。
[合成例2]
除了將D-NDM取代為下述結構式表示之9,9-雙(4-(2-羥基乙氧基)苯基)茀(BPEF)39455g(89.97莫耳)外,與合成例1同樣得到聚碳酸酯樹脂(BPEF-PC)。
(實施例1)
在混合有合成例1所得之聚碳酸酯樹脂(D-NDM-PC) 2881g(D-NDM單體單元換算為13.0莫耳)與合成例2所得之聚碳酸酯樹脂(BPEF-PC)119g(BPEF單體單元換算為0.27莫耳)者中添加受阻酚系抗氧化劑(股份公司ADEKA製 AО-60)3.0g,亞磷酸酯系抗氧化劑(股份公司ADEKA製 PEP-36)0.9及作為脫模劑之丙三醇單硬脂酸酯(理研vitamin股份公司製 S-100A)7.2g,使用二軸擠壓機(芝浦機械股份公司製TEM-18SS),在樹脂溫度260℃,螺桿旋轉數200rpm,進行混練、顆粒化,得到聚碳酸酯樹脂組成物。所得之聚碳酸酯樹脂組成物之物性示於表1。
(實施例2、比較例1~3)
除了使用表1所示之聚碳酸酯樹脂(D-NDM-PC及/或BPEF-PC)取代實施例1使用之聚碳酸酯樹脂外,與實施例1相同得到聚碳酸酯樹脂組成物。所得之聚碳酸酯樹脂組成物之物性示於表1。
(比較例4)
除了使用作為原料之BPEF 585g(1.33莫耳)、下述結構式表示之三環癸烷二甲醇(TCDDM)5189g(26.44莫耳)、DPC 5996g(27.99莫耳),及0.10莫耳/公升之碳酸氫鈉水溶液10.8ml(1.08×10
-3莫耳,亦即,相對於二羥基化合物之合計1莫耳,為1.2×10
-5莫耳)外,與合成例1同樣,得到聚碳酸酯樹脂(BPEF-TCDDM-PC)。除了使用上述得到之聚碳酸酯樹脂(BPEF-TCDDM-PC)3000g取代實施例1使用之聚碳酸酯樹脂外,與實施例1相同得到聚碳酸酯樹脂組成物。所得之聚碳酸酯樹脂組成物之物性示於表1。
[產業上之可利用性]
本發明之聚碳酸酯樹脂組成物,適用於智慧型手機、DSC、車載等之相機用透鏡。此外,藉由使用本發明之聚碳酸酯樹脂組成物,可期待可使用於望遠鏡等之透鏡單元之薄型化。
Claims (9)
- 一種聚碳酸酯樹脂組成物,其係包含來自下述通式(i)表示之單體的構成單位(A),及來自下述通式(ii)表示之單體的構成單位(B)的聚碳酸酯樹脂組成物, 前述構成單位(A)與前述構成單位(B)以質量比計,構成單位(A):構成單位(B)=91:9~99:1, (通式(i)中,R表示氫原子、或碳數1~4之烷基) (通式(ii)中,R 1、R 2、R 3及R 4各自獨立地表示氫原子、碳數1~20之烷基、碳數1~20之烷氧基、碳數5~20之環烷基、碳數5~20之環烷氧基、碳數6~20之芳基或碳數6~20之芳氧基,Y 1及Y 2各自獨立地表示碳數1~4之伸烷基)。
- 如請求項1之聚碳酸酯樹脂組成物,其包含具有前述構成單位(A)之聚碳酸酯樹脂(A)與具有前述構成單位(B)之聚碳酸酯樹脂(B)的樹脂混合物。
- 如請求項1或2之聚碳酸酯樹脂組成物,其中前述通式(ii)中,R 1及R 2各自獨立地表示氫原子或苯基,R 3及R 4表示氫原子。
- 如請求項1~3中任一項之聚碳酸酯樹脂組成物,其中前述通式(i)中之R表示氫原子。
- 如請求項1~4中任一項之聚碳酸酯樹脂組成物,其中前述聚碳酸酯樹脂組成物之光彈性模數為11.0 ~12.0(×10 -12m 2/N)。
- 請求項1~5中任一項之聚碳酸酯樹脂組成物,其中前述聚碳酸酯樹脂組成物之阿貝數(Abbe Number)為46~55。
- 如請求項1~6中任一項之聚碳酸酯樹脂組成物,其中前述聚碳酸酯樹脂組成物之折射率(nD)為1.533~1.547。
- 如請求項1~7中任一項之聚碳酸酯樹脂組成物,其中前述聚碳酸酯樹脂組成物之Tg為132~135℃。
- 一種光學透鏡,其包含如請求項1~8中任一項之聚碳酸酯樹脂組成物。
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KR102478201B1 (ko) * | 2017-03-31 | 2022-12-15 | 미츠비시 가스 가가쿠 가부시키가이샤 | 폴리카보네이트 수지 조성물 및 그것을 사용한 광학 렌즈 |
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