JP2024055311A - Polycarbonate resin and molded products made from it - Google Patents
Polycarbonate resin and molded products made from it Download PDFInfo
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- JP2024055311A JP2024055311A JP2022162132A JP2022162132A JP2024055311A JP 2024055311 A JP2024055311 A JP 2024055311A JP 2022162132 A JP2022162132 A JP 2022162132A JP 2022162132 A JP2022162132 A JP 2022162132A JP 2024055311 A JP2024055311 A JP 2024055311A
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- carbon atoms
- polycarbonate resin
- parts
- resin according
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- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 79
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 79
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000007373 indentation Methods 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000003172 aldehyde group Chemical group 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 108
- 239000000243 solution Substances 0.000 description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 34
- 238000003756 stirring Methods 0.000 description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- -1 diol compounds Chemical class 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229920000515 polycarbonate Polymers 0.000 description 10
- 239000004417 polycarbonate Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 7
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 7
- 239000012760 heat stabilizer Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 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 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- MZXNOAWIRQFYDB-UHFFFAOYSA-N 4-(4-hydroxycyclohexyl)cyclohexan-1-ol Chemical compound C1CC(O)CCC1C1CCC(O)CC1 MZXNOAWIRQFYDB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000004650 carbonic acid diesters Chemical class 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 3
- BNNBECJSDDMHFF-UHFFFAOYSA-N 2,2,3,3-tetramethylcyclobutane-1,1-diol Chemical compound CC1(C)CC(O)(O)C1(C)C BNNBECJSDDMHFF-UHFFFAOYSA-N 0.000 description 2
- OKAAOWIRPHWLGF-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)octadecyl propanoate Chemical compound CCCCCCCCCCCCCCCC(CCOC(=O)CC)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 OKAAOWIRPHWLGF-UHFFFAOYSA-N 0.000 description 2
- MPWGZBWDLMDIHO-UHFFFAOYSA-N 3-propylphenol Chemical compound CCCC1=CC=CC(O)=C1 MPWGZBWDLMDIHO-UHFFFAOYSA-N 0.000 description 2
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000012696 Interfacial polycondensation Methods 0.000 description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 2
- 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 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- IBGQHQUOSLYNFC-UHFFFAOYSA-N [1-bis(2,4-ditert-butylphenoxy)phosphanyl-4-phenylcyclohexa-2,4-dien-1-yl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C1(C=CC(=CC1)C=1C=CC=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)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 IBGQHQUOSLYNFC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 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
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-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
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 2
- PXDJXZJSCPSGGI-UHFFFAOYSA-N palmityl palmitate Chemical compound CCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC PXDJXZJSCPSGGI-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- RBKHNGHPZZZJCI-UHFFFAOYSA-N (4-aminophenyl)-phenylmethanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC=C1 RBKHNGHPZZZJCI-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
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- DMBUODUULYCPAK-UHFFFAOYSA-N 1,3-bis(docosanoyloxy)propan-2-yl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCCCCCC DMBUODUULYCPAK-UHFFFAOYSA-N 0.000 description 1
- GNBRZRRANUHHGT-UHFFFAOYSA-N 1-phenylcyclohexa-2,4-dien-1-ol Chemical compound C=1C=CC=CC=1C1(O)CC=CC=C1 GNBRZRRANUHHGT-UHFFFAOYSA-N 0.000 description 1
- ZDSPTFQHKJLGFQ-UHFFFAOYSA-N 10,10-bis(4-hydroxyphenyl)anthracen-9-one Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)C2=CC=CC=C21 ZDSPTFQHKJLGFQ-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical compound CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 description 1
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 description 1
- MAQOZOILPAMFSW-UHFFFAOYSA-N 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=C(CC=3C(=CC=C(C)C=3)O)C=C(C)C=2)O)=C1 MAQOZOILPAMFSW-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- FKOKUHFZNIUSLW-UHFFFAOYSA-N 2-Hydroxypropyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(C)O FKOKUHFZNIUSLW-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- GRYFAKUTFHAPRS-UHFFFAOYSA-N 2-butyl-4-[2-(3-butyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C1=C(O)C(CCCC)=CC(C(C)(C)C=2C=C(CCCC)C(O)=CC=2)=C1 GRYFAKUTFHAPRS-UHFFFAOYSA-N 0.000 description 1
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- IBKKMFMBXQARGV-UHFFFAOYSA-N [3-nonanoyloxy-2,2-bis(nonanoyloxymethyl)propyl] nonanoate Chemical compound CCCCCCCCC(=O)OCC(COC(=O)CCCCCCCC)(COC(=O)CCCCCCCC)COC(=O)CCCCCCCC IBKKMFMBXQARGV-UHFFFAOYSA-N 0.000 description 1
- IQXDUKXUDQPOBC-UHFFFAOYSA-N [3-octadecanoyloxy-2-[[3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propoxy]methyl]-2-(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC IQXDUKXUDQPOBC-UHFFFAOYSA-N 0.000 description 1
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- 238000007542 hardness measurement Methods 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 1
- 229960002479 isosorbide Drugs 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
【課題】耐傷付き性を有し、かつ耐熱性および成形性に優れたポリカーボネート樹脂およびそれからなる成形品を提供する。【解決手段】Ｎ－（４－ベンゾイルフェニル）フェノールフタレイニルビスフェノール、Ｎ－（３－ベンゾイルフェニル）フェノールフタレイニルビスフェノールおよびＮ－（２－ベンゾイルフェニル）フェノールフタレイニルビスフェノールからなる群より選ばれる少なくとも一つの化合物から誘導される繰り返し単位（Ａ）を含み、繰り返し単位（Ａ）の含有割合が全繰り返し単位に対して１０～１００モル％の範囲であるポリカーボネート樹脂とする。【選択図】なし[Problem] To provide a polycarbonate resin having scratch resistance and excellent heat resistance and moldability, and a molded article made from the same. [Solution] The polycarbonate resin contains repeating units (A) derived from at least one compound selected from the group consisting of N-(4-benzoylphenyl)phenolphthaleinyl bisphenol, N-(3-benzoylphenyl)phenolphthaleinyl bisphenol, and N-(2-benzoylphenyl)phenolphthaleinyl bisphenol, and the content of repeating units (A) is in the range of 10 to 100 mol % based on the total repeating units. [Selected Figure] None
Description
本発明は、耐傷付き性、耐熱性および成形性に優れたポリカーボネート樹脂およびそれからなる成形品に関する。 The present invention relates to a polycarbonate resin that has excellent scratch resistance, heat resistance and moldability, and a molded article made from the same.
ポリカーボネート樹脂は、透明性、耐衝撃性、耐熱性、寸法安定性に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、電気・電子機器の筐体、自動車内装・外装部品、建材、家具、楽器、雑貨類などの幅広い分野で使用されている。さらに、無機ガラスと比較し、比重が低く軽量化が可能であり、生産性に優れているため、自動車等の窓用途に使用されている。 Polycarbonate resin has excellent transparency, impact resistance, heat resistance, and dimensional stability, and is therefore used as an engineering plastic in a wide range of fields, including housings for electrical and electronic devices, interior and exterior parts for automobiles, building materials, furniture, musical instruments, and miscellaneous goods. Furthermore, compared to inorganic glass, it has a lower specific gravity, allowing for weight reduction, and is highly manufacturable, so it is used for windows in automobiles, etc.
さらに、ポリカーボネート樹脂を用いたシートやフィルムは、コーティング処理、積層体、表面修飾等の付加的な二次加工を施すことにより、自動車内装の各種表示装置、保護用部品として広く使用されている。 Furthermore, sheets and films made from polycarbonate resins are widely used as various display devices and protective parts for automobile interiors by applying additional secondary processing such as coating, lamination, and surface modification.
しかしながら、コーティング処理を施していないポリカーボネート樹脂は、ＪＩＳ Ｋ５６００－５－４に記載の塗料一般試験方法－第５部：塗膜の機械的性質－第４節：引っかき硬度（鉛筆法）に準拠して測定した鉛筆硬度が２Ｂ程度に過ぎず、塗装レス材料として、表面に傷が付きやすいことが課題といえる。 However, polycarbonate resin that has not been coated has a pencil hardness of only about 2B, as measured in accordance with JIS K5600-5-4, General Test Methods for Paints - Part 5: Mechanical Properties of Coatings - Section 4: Scratch Hardness (Pencil Method), and as a paint-less material, the surface is easily scratched, which is an issue.
そこで、表面硬度の高い共重合ポリカーボネート樹脂（例えば、特許文献１）を用いることが知られている。また、２，２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパンを構成単位とするポリカーボネートやコポリカーボネートとする方法が記載されている（例えば、特許文献２～６）。該ポリカーボネート樹脂は、表面硬度は向上するが、ポリカーボネート樹脂と比べて耐熱性が劣ることが課題である。 It is known to use copolymer polycarbonate resins with high surface hardness (for example, Patent Document 1). In addition, methods have been described in which polycarbonates and copolycarbonates are made using 2,2-bis(4-hydroxy-3-methylphenyl)propane as a structural unit (for example, Patent Documents 2 to 6). Although such polycarbonate resins improve surface hardness, the problem is that they have inferior heat resistance compared to polycarbonate resins.
さらに、特許文献７にはＮ－フェニルフェノールフタレイニルビスフェノールを構成単位とするポリカーボネート樹脂が、電子写真感光体のバインダー樹脂として耐摩耗性に優れる旨記載されている。しかしながら、耐傷付き性を上昇させるために剛直な構造を持つ構成単位を導入するとガラス転移温度が高くなり成形性が低下することから、Ｎ－フェニルフェノールフタレイニルビスフェノールは構成単位として高い比率で導入できないという課題がある。 Furthermore, Patent Document 7 describes that polycarbonate resins containing N-phenylphenolphthaleinylbisphenol as a structural unit have excellent abrasion resistance as binder resins for electrophotographic photoreceptors. However, there is a problem that N-phenylphenolphthaleinylbisphenol cannot be introduced in a high ratio as a structural unit because introducing a structural unit with a rigid structure to increase scratch resistance increases the glass transition temperature and reduces moldability.
そこで、本発明はかかる課題を解決することを目的とするものであって、耐傷付き性、耐熱性および成形性に優れたポリカーボネート樹脂及びそれからなる成形品を提供することを目的とする。 The present invention aims to solve these problems by providing a polycarbonate resin with excellent scratch resistance, heat resistance and moldability, and a molded product made from the same.
本発明が解決しようとする課題は、耐傷付き性を有し、かつ耐熱性および成形性に優れたポリカーボネート樹脂およびそれからなる成形品を提供することにある。 The problem that the present invention aims to solve is to provide a polycarbonate resin that is scratch-resistant and has excellent heat resistance and moldability, and a molded product made from the same.
本発明者らはこの目的を達成せんとして鋭意研究を重ねた結果、特定の構造を有するポリカ―ボネート樹脂が前記課題を解決できることを見出し本発明に到達した。すなわち、本発明は以下１～１１項の通りである。 As a result of intensive research conducted by the inventors to achieve this objective, they discovered that a polycarbonate resin having a specific structure can solve the above problems, and arrived at the present invention. That is, the present invention is as follows:
１．下記式（１）で表される繰り返し単位（Ａ）を含むポリカーボネート樹脂。 1. A polycarbonate resin containing a repeating unit (A) represented by the following formula (1):
２．前記式（２）のＲ６およびＲ７は水素原子である前項１記載のポリカーボネート樹脂。
３．前記式（１）で表される繰り返し単位（Ａ）がＮ－（４－ベンゾイルフェニル）フェノールフタレイニルビスフェノール、Ｎ－（３－ベンゾイルフェニル）フェノールフタレイニルビスフェノールおよびＮ－（２－ベンゾイルフェニル）フェノールフタレイニルビスフェノールからなる群より選ばれる少なくとも一つの化合物から誘導される繰り返し単位である前項１または２に記載のポリカーボネート樹脂。
４．繰り返し単位（Ａ）の含有割合が全繰り返し単位に対して１０～１００モル％の範囲である前項１～３のいずれかに記載のポリカーボネート樹脂。
５．ガラス転移温度が１２５～３００℃の範囲である前項１～４のいずれかに記載のポリカーボネート樹脂。
６．ＩＳＯ／ＴＳ１９２７８記載のプラスチック－硬さ測定のための計装化マイクロ押込み硬さ試験に準拠して測定された押し込み硬さが１８０～４５０（Ｎ／ｍｍ２）の範囲である前項１～５のいずれかに記載のポリカーボネート樹脂。
７．ＪＩＳ Ｋ５６００－５－４記載のひっかき硬度（鉛筆法）に準拠して測定された鉛筆硬度がＦ以上である前項１～６のいずれかに記載のポリカーボネート樹脂。
８．前項１～７のいずれかに記載のポリカーボネート樹脂を射出成形してなる成形品。
９．前項１～７のいずれかに記載のポリカーボネート樹脂を押出成形してなるシートまたはフィルム。
１０．前項８の成形品を用いた自動車内装部品。
１１．前項９のシートまたはフィルムを用いた自動車内装部品。
2. The polycarbonate resin according to the above item 1, wherein R 6 and R 7 in the formula (2) are hydrogen atoms.
3. The polycarbonate resin according to item 1 or 2 above, wherein the repeating unit (A) represented by formula (1) is a repeating unit derived from at least one compound selected from the group consisting of N-(4-benzoylphenyl)phenolphthaleinyl bisphenol, N-(3-benzoylphenyl)phenolphthaleinyl bisphenol, and N-(2-benzoylphenyl)phenolphthaleinyl bisphenol.
4. The polycarbonate resin according to any one of items 1 to 3 above, wherein the content of the repeating unit (A) is in the range of 10 to 100 mol % based on all repeating units.
5. The polycarbonate resin according to any one of items 1 to 4 above, which has a glass transition temperature in the range of 125 to 300° C.
6. The polycarbonate resin according to any one of items 1 to 5 above, which has an indentation hardness in the range of 180 to 450 (N/mm 2 ) as measured in accordance with the instrumented microindentation hardness test for measuring plastics hardness described in ISO/TS19278.
7. The polycarbonate resin according to any one of items 1 to 6 above, which has a pencil hardness of F or more as measured in accordance with the scratch hardness (pencil method) described in JIS K5600-5-4.
8. A molded article obtained by injection molding the polycarbonate resin according to any one of items 1 to 7 above.
9. A sheet or film obtained by extrusion molding the polycarbonate resin according to any one of items 1 to 7 above.
10. Automobile interior parts using the molded product of the preceding paragraph 8.
11. Automobile interior parts using the sheet or film described in the preceding paragraph 9.
本発明のポリカーボネート樹脂およびそれからなる成形品は、耐傷付き性、耐熱性および成形性に優れているため、自動車内装部品に好適に用いられる。したがって、その奏する産業上の効果は格別である。 The polycarbonate resin of the present invention and the molded products made from it have excellent scratch resistance, heat resistance, and moldability, and are therefore suitable for use in automobile interior parts. Therefore, the industrial effects that they bring about are exceptional.
＜ポリカーボネート樹脂＞
本発明におけるポリカーボネート樹脂は、下記式（１）で表される繰り返し単位（Ａ）を含むポリカーボネート樹脂である。
<Polycarbonate resin>
The polycarbonate resin in the present invention is a polycarbonate resin containing a repeating unit (A) represented by the following formula (1).
Ｒ１、Ｒ２、Ｒ３およびＲ４は、好ましくはＲ１およびＲ３の少なくとも１つが水素原子以外の置換基ならびにＲ２およびＲ４の少なくとも１つが水素原子以外の置換基を有することが好ましく、置換基として好ましくはメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、イソヘキシル基、シクロへキシル基、メトキシ基、フェニル基であり、より好ましくはメチル基、シクロへキシル基、メトキシ基、フェニル基であり、さらに好ましくはメチル基である。Ｒ１およびＲ３の少なくとも１つならびにＲ２およびＲ４の少なくとも１つにおいて、これらの置換基を有することにより、鉛筆硬度が高くなり耐傷つき性に優れるため好ましい。 R 1 , R 2 , R 3 and R 4 are preferably such that at least one of R 1 and R 3 has a substituent other than a hydrogen atom and at least one of R 2 and R 4 has a substituent other than a hydrogen atom, and the substituent is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an n-hexyl group, an isohexyl group, a cyclohexyl group, a methoxy group, or a phenyl group, more preferably a methyl group, a cyclohexyl group, a methoxy group, or a phenyl group, and even more preferably a methyl group. At least one of R 1 and R 3 and at least one of R 2 and R 4 have these substituents, which is preferable because the pencil hardness is increased and the scratch resistance is excellent.
Ｒ５、Ｒ６およびＲ７は、好ましくは水素原子、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、イソヘキシル基、シクロへキシル基、メトキシ基、フェニル基である。Ｒ５は、より好ましくは水素原子、メチル基、シクロへキシル基、メトキシ基、フェニル基であり、さらに好ましくは水素原子、メチル基である。Ｒ６およびＲ７は、より好ましくは水素原子、メチル基であり、さらに好ましくは水素原子である。 R 5 , R 6 and R 7 are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an n-hexyl group, an isohexyl group, a cyclohexyl group, a methoxy group or a phenyl group. R 5 is more preferably a hydrogen atom, a methyl group, a cyclohexyl group, a methoxy group or a phenyl group, and further preferably a hydrogen atom or a methyl group. R 6 and R 7 are more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
ポリカーボネート樹脂における上記式（１）で表される繰り返し単位（Ａ）の含有割合が全繰り返し単位に対して１０～１００モル％が好ましく、より好ましくは１５～１００モル％である。下限以上であると鉛筆硬度が高くなり耐傷つき性に優れるため好ましい。 The content of the repeating unit (A) represented by the above formula (1) in the polycarbonate resin is preferably 10 to 100 mol % relative to the total repeating units, and more preferably 15 to 100 mol %. If it is above the lower limit, the pencil hardness will be high and scratch resistance will be excellent, which is preferable.
かかる繰り返し単位（Ａ）の割合は、ホモポリカーボネート樹脂やポリカーボネート共重合体であっても、異なる組成割合のポリカーボネート樹脂同士の混合（ポリカーボネートブレンド物）により達成されていてもよい。
さらに、繰り返し単位（Ａ）以外の繰り返し単位（Ｂ）を誘導する化合物として、後述する他のジヒドロキシ化合物やジオール化合物が使用できる。
繰り返し単位（Ｂ）の含有割合が全繰り返し単位に対しては９０モル％以下が好ましく、より好ましくは８５モル％以下である。
Such a ratio of the repeating unit (A) may be achieved by a homopolycarbonate resin or a polycarbonate copolymer, or by mixing polycarbonate resins having different composition ratios (polycarbonate blend).
Furthermore, as a compound from which the repeating unit (B) other than the repeating unit (A) can be derived, other dihydroxy compounds and diol compounds, which will be described later, can be used.
The content of the repeating unit (B) is preferably 90 mol % or less, more preferably 85 mol % or less, based on the total repeating units.
＜ポリカーボネート樹脂の製造方法＞
本発明におけるポリカーボネート樹脂は二価フェノール化合物とホスゲン等の炭酸エステル化合物とを反応させることによって製造することができる。
<Production method of polycarbonate resin>
The polycarbonate resin in the present invention can be produced by reacting a dihydric phenol compound with a carbonate compound such as phosgene.
（原料モノマー）
本発明におけるポリカーボネート樹脂に使用される原料モノマーは下記式（５）で表される二価フェノール化合物を含む。
(Raw material monomer)
The raw material monomer used for the polycarbonate resin in the present invention contains a dihydric phenol compound represented by the following formula (5).
上記式（５）で表される二価フェノールとしては、例えばＮ－（４－ベンゾイルフェニル）フェノールフタレイニルビスフェノール（４－ＢｐＰｈＰＰと省略することがある）、Ｎ－（３－ベンゾイルフェニル）フェノールフタレイニルビスフェノール（３－ＢｐＰｈＰＰと省略することがある）、Ｎ－（２－ベンゾイルフェニル）フェノールフタレイニルビスフェノール（２－ＢｐＰｈＰＰと省略することがある）が好適である。これらの二価フェノールは、それぞれ単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 As the dihydric phenol represented by the above formula (5), for example, N-(4-benzoylphenyl)phenolphthaleinyl bisphenol (sometimes abbreviated as 4-BpPhPP), N-(3-benzoylphenyl)phenolphthaleinyl bisphenol (sometimes abbreviated as 3-BpPhPP), and N-(2-benzoylphenyl)phenolphthaleinyl bisphenol (sometimes abbreviated as 2-BpPhPP) are suitable. These dihydric phenols may be used alone or in combination of two or more.
本発明におけるポリカーボネート樹脂に使用される原料モノマーは上記式（５）で表されるモノマーを含み、さらに下記式（７）で表されるモノマーを含んでもよい。 The raw material monomers used for the polycarbonate resin of the present invention include a monomer represented by the above formula (5) and may further include a monomer represented by the following formula (7).
上記式（７）で表される二価フェノールとしては、例えば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－３－メチルフェニル）プロパン；２，２－ビス（４－ヒドロキシ－３－エチルフェニル）プロパン；２，２－ビス（４－ヒドロキシ－３－プロピルフェニル）プロパン；２，２－ビス（４－ヒドロキシ－３－ブチルフェニル）プロパン；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）ブタン；２，２－ビス（４－ヒドロキシフェニル）オクタン；２，２－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）フェニルメタン；２，２－ビス（４－ヒドロキシ－１－メチルフェニル）プロパン；ビス（４－ヒドロキシフェニル）ナフチルメタン；１，１－ビス（４－ヒドロキシ－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；２，２－ビス（４－ヒドロキシ－３，５－テトラメチルフェニル）プロパン；２，２－ビス（４－ヒドロキシ－３－クロロフェニル）プロパン；２，２－ビス（４－ヒドロキシ－３，５－テトラクロロフェニル）プロパン；２，２－ビス（４－ヒドロキシ－３，５－テトラブロモフェニル）プロパンなどのビス（ヒドロキシアリール）アルカン類、４，４’－ジヒドロキシフェニルエーテル；４，４’－ジヒドロキシ－３，３’－ジメチルフェニルエーテルなどのジヒドロキシアリールエーテル類、４，４’－ジヒドロキシジフェニルスルフィド；４，４’－ジヒドロキシ－３，３’－ジメチルジフェニルスルフィドなどのジヒドロキシジアリールスルフィド類、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などのジヒドロキシジアリールスルホキシド類、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などのジヒドロキシジアリールスルホン類、４，４’－ジヒロキシジフェニルなどのジヒドロキシジフェニル類、９，９－ビス（４－ヒドロキシフェニル）フルオレン；９，９－ビス（４－ヒドロキシ－３－メチルフェニル）フルオレンなどのジヒドロキシジアリールフルオレン類、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、１，１－ビス（４－ヒドロキシ－３－メチルフェニル）シクロペンタン、１，１－ビス（４－ヒドロキシ－３－メチルフェニル）シクロヘキサン、１，１－ビス（４－ヒドロキシフェニル）－３，３，５－トリメチルシクロヘキサン、ビス（４－ヒドロキシフェニル）ジフェニルメタン、４，４’－ジヒドロキシベンゾフェノン、４，４’－ジヒドロキシ－３，３’－ジメチルベンゾフェノン、４，４’－ビフェノール、３，３’，５，５’－テトラメチル－４，４’－ビフェニルジオール、３，３’－ジメチル－４，４’－ビフェニルジオール、α、α’－ビス（４－ヒドロキシフェニル）－１，３－ジイソプロピルベンゼン、α、α’－ビス（４－ヒドロキシフェニル）－１，４－ジイソプロピルベンゼンなどが挙げられる。 Examples of the dihydric phenol represented by the above formula (7) include 2,2-bis(4-hydroxyphenyl)propane; 2,2-bis(4-hydroxy-3-methylphenyl)propane; 2,2-bis(4-hydroxy-3-ethylphenyl)propane; 2,2-bis(4-hydroxy-3-propylphenyl)propane; 2,2-bis(4-hydroxy-3-butylphenyl)propane; bis(4-hydroxyphenyl)methane; 1,1-bis(4-hydroxyphenyl)ethane; 2,2-bis(4-hydroxyphenyl)butane; 2,2-bis(4-hydroxyphenyl)octane; 2,2-bis(4-hydroxyphenyl)phenylmethane; 2,2-bis(4-hydroxy-3-methylphenyl)phenylmethane; 2,2-bis(4-hydroxy-1-methylphenyl) bis(hydroxyaryl)alkanes such as 4,4'-dihydroxyphenyl ether; 4,4'-dihydroxy-3,3'-dimethylphenyl ether; 4,4'-dihydroxyaryl ethers such as 4,4'-dihydroxy-3,3'-dimethylphenyl ether; 4,4'-dihydroxydiphenyl sulfide; 4,4'- Dihydroxydiaryl sulfides such as dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone; dihydroxydiaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl, 9,9-bis(4-hydroxyphenyl)fluorene; dihydroxydiarylfluorenes such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclopentane, bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclopentane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxy-3,3'-dimethylbenzophenone, 4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-biphenyldiol, 3,3'-dimethyl-4,4'-biphenyldiol, α,α'-bis(4-hydroxyphenyl)-1,3-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, etc.
これらのなかでも、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－３－メチルフェニル）プロパンまたはα、α’－ビス（４－ヒドロキシフェニル）－１，３－ジイソプロピルベンゼンが好適であり、２，２－ビス（４－ヒドロキシフェニル）プロパン（ＢＰＡと省略することがある）または２，２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパン（ＢＰＣと省略することがある）がさらに好適である。これらの二価フェノールは、それぞれ単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Among these, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane or α,α'-bis(4-hydroxyphenyl)-1,3-diisopropylbenzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane (sometimes abbreviated as BPA) or 2,2-bis(4-hydroxy-3-methylphenyl)propane (sometimes abbreviated as BPC) are more preferred. These dihydric phenols may be used alone or in combination of two or more.
本発明におけるポリカーボネート樹脂は、ポリカーボネート樹脂の特性を損なわない程度に他のジヒドロキシ化合物やジオール化合物を共重合してもよい。 The polycarbonate resin of the present invention may be copolymerized with other dihydroxy compounds or diol compounds to the extent that the properties of the polycarbonate resin are not impaired.
他のジヒドロキシ化合物として、ヒドロキノン、レゾルシノール、オルシノール、２，２－ビス（４－ヒドロキシフェニル）ノルボルネン、１，３－ビス（４－ヒドロキシフェニル）アダマンタン；２，２－ビス（４－ヒドロキシフェニル）アダマンタン；１，３－ビス（４－ヒドロキシフェニル）－５，７－ジメチルアダマンタン、１０，１０－ビス（４－ヒドロキシフェニル）－９－アントロン、１，５－ビス（４－ヒドロキシフェニルチオ）－２，３－ジオキサペンタエンビスフェノキシエタノールフルオレン等が挙げられる。 Other dihydroxy compounds include hydroquinone, resorcinol, orcinol, 2,2-bis(4-hydroxyphenyl)norbornene, 1,3-bis(4-hydroxyphenyl)adamantane; 2,2-bis(4-hydroxyphenyl)adamantane; 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 10,10-bis(4-hydroxyphenyl)-9-anthrone, 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentaene bisphenoxyethanol fluorene, etc.
他のジオール化合物として、イソソルビド：１，４：３，６－ジアンヒドロ－Ｄ－ソルビトール、トリシクロデカンジメタノール（ＴＣＤＤＭ）、４，８－ビス（ヒドロキシメチル）トリシクロデカン、テトラメチルシクロブタンジオール（ＴＭＣＢＤ）、２，２，４，４－テトラメチルシクロブタン－１，３－ジオール、混合異性体、シス／トランス－１，４－シクロヘキサンジメタノール（ＣＨＤＭ）、シス／トランス－１，４－ビス（ヒドロキシメチル）シクロヘキサン、シクロヘクス－１，４－イルエンジメタノール、トランス－１，４－シクロヘキサンジメタノール（ｔＣＨＤＭ）、トランス－１，４－ビス（ヒドロキシメチル）シクロヘキサン、シス－１，４－シクロヘキサンジメタノール（ｃＣＨＤＭ）、シス－１，４－ビス（ヒドロキシメチル）シクロヘキサン、シス－１，２－シクロヘキサンジメタノール、１，１’－ビ（シクロヘキシル）－４，４’－ジオール、スピログリコール、ジシクロヘキシル－４，４’－ジオール、４，４’－ジヒドロキシビシクロヘキシルおよびポリ（エチレングリコール）等が挙げられる。 Other diol compounds include isosorbide:1,4:3,6-dianhydro-D-sorbitol, tricyclodecane dimethanol (TCDDM), 4,8-bis(hydroxymethyl)tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2,2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis/trans-1,4-cyclohexanedimethanol (CHDM), cis/trans-1,4-bis(hydroxymethyl)cyclohexane, cyclohex-1,4-ylenedimethanol. These include trans-1,4-cyclohexanedimethanol (tCHDM), trans-1,4-bis(hydroxymethyl)cyclohexane, cis-1,4-cyclohexanedimethanol (cCHDM), cis-1,4-bis(hydroxymethyl)cyclohexane, cis-1,2-cyclohexanedimethanol, 1,1'-bi(cyclohexyl)-4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexyl, and poly(ethylene glycol).
本発明におけるポリカーボネート樹脂は、前記二価フェノール化合物とカーボネート前駆体とを反応させて得られるものである。反応の方法としては界面重縮合法、溶融エステル交換法、カーボネートプレポリマーの固相エステル交換法、および環状カーボネート化合物の開環重合法などを挙げることができる。界面重縮合の場合は通常一価フェノール類の末端停止剤が使用される。 The polycarbonate resin in the present invention is obtained by reacting the dihydric phenol compound with a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. In the case of interfacial polycondensation, a terminal terminator of a monohydric phenol is usually used.
ポリカーボネート樹脂は、芳香族または脂肪族（脂環式を含む）の二官能性カルボン酸を共重合したポリエステルカーボネートを含む。脂肪族の二官能性のカルボン酸は、α，ω－ジカルボン酸が好ましい。脂肪族の二官能性のカルボン酸としては例えば、セバシン酸（デカン二酸）、ドデカン二酸、テトラデカン二酸、オクタデカン二酸、およびイコサン二酸などの直鎖飽和脂肪族ジカルボン酸、並びにシクロヘキサンジカルボン酸などの脂環式ジカルボン酸が好ましく挙げられる。これらのカルボン酸は、目的を阻害しない範囲で共重合してもよい。また、ポリカーボネート樹脂は、必要に応じてポリオルガノシロキサン単位を含有する構成単位を共重合することもできる。 The polycarbonate resin includes polyester carbonates copolymerized with aromatic or aliphatic (including alicyclic) bifunctional carboxylic acids. The aliphatic bifunctional carboxylic acids are preferably α,ω-dicarboxylic acids. Examples of the aliphatic bifunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane diacid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These carboxylic acids may be copolymerized to the extent that the purpose is not hindered. In addition, the polycarbonate resin may be copolymerized with a structural unit containing a polyorganosiloxane unit, if necessary.
ポリカーボネート樹脂は、必要に応じて三官能以上の多官能性芳香族化合物を含有する構成単位を、共重合し、分岐ポリカーボネートとすることもできる。 If necessary, polycarbonate resins can be copolymerized with structural units containing trifunctional or higher polyfunctional aromatic compounds to form branched polycarbonates.
分岐ポリカーボネートに使用される三官能以上の多官能性芳香族化合物としては、４，６－ジメチル－２，４，６－トリス（４－ヒドロキシフェニル）ヘプテン－２、２，４，６－トリメチル－２，４，６－トリス（４－ヒドロキシフェニル）ヘプタン、１，３，５－トリス（４－ヒドロキシフェニル）ベンゼン、１，１，１－トリス（４－ヒドロキシフェニル）エタン、１，１，１－トリス（３，５－ジメチル－４－ヒドロキシフェニル）エタン、２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノール、および４－｛４－［１，１－ビス（４－ヒドロキシフェニル）エチル］ベンゼン｝－α，α－ジメチルベンジルフェノール等のトリスフェノールが好適に例示される。中でも１，１，１－トリス（４－ヒドロキシフェニル）エタンが好ましい。かかる多官能性芳香族化合物から誘導される構成単位は、他の二価フェノール成分からの構成単位との合計１００モル％中、好ましくは０．０３～１．５モル％、より好ましくは０．１～１．２モル％、特に好ましくは０．２～１．０モル％である。 Examples of trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonates include 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and trisphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol. Of these, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The constituent units derived from such polyfunctional aromatic compounds preferably account for 0.03 to 1.5 mol%, more preferably 0.1 to 1.2 mol%, and particularly preferably 0.2 to 1.0 mol%, of a total of 100 mol% including the constituent units from other dihydric phenol components.
また分岐構造単位は、多官能性芳香族化合物から誘導されるだけでなく、溶融エステル交換法による重合反応時に生じる副反応の如き、多官能性芳香族化合物を用いることなく誘導されるものであってもよい。尚、かかる分岐構造の割合については１Ｈ－ＮＭＲ測定により算出することが可能である。 The branched structural unit may be derived not only from a polyfunctional aromatic compound, but also from a side reaction occurring during a polymerization reaction by a melt transesterification method without using a polyfunctional aromatic compound. The proportion of such branched structures can be calculated by 1H -NMR measurement.
カーボネート前駆物質として例えばホスゲンを使用する反応では、通常酸結合剤および溶媒の存在下に反応を行う。酸結合剤としては例えば水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物またはピリジン等のアミン化合物が用いられる。溶媒としては例えば塩化メチレン、クロロベンゼン等のハロゲン化炭化水素が用いられる。また反応促進のために例えば第三級アミンまたは第四級アンモニウム塩等の触媒を用いることもできる。その際、反応温度は通常０～４０℃であり、反応時間は数分～５時間である。 In reactions using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. The acid binder may be, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine. The solvent may be, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene. A catalyst such as a tertiary amine or a quaternary ammonium salt may also be used to promote the reaction. In this case, the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.
カーボネート前駆物質として例えば炭酸ジエステルを用いるエステル交換反応は、不活性ガス雰囲気下所定割合の芳香族ジヒドロキシ成分を炭酸ジエステルと加熱しながら撹拌して、生成するアルコールまたはフェノール類を留出させる方法により行われる。反応温度は生成するアルコールまたはフェノール類の沸点等により異なるが、通常１２０～３００℃の範囲である。反応はその初期から減圧にして生成するアルコールまたはフェノール類を留出させながら反応を完結させる。また反応を促進するために通常エステル交換反応に使用される触媒を使用することもできる。前記エステル交換反応に使用される炭酸ジエステルとしては、例えばジフェニルカーボネート、ジナフチルカーボネート、ビス（ジフェニル）カーボネート、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネート等が挙げられる。これらのうち特にジフェニルカーボネートが好ましい。 The transesterification reaction using, for example, a carbonic acid diester as a carbonate precursor is carried out by heating and stirring a predetermined proportion of aromatic dihydroxy components with a carbonic acid diester under an inert gas atmosphere, and distilling off the resulting alcohol or phenol. The reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is usually in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning and distilling off the resulting alcohol or phenol. In order to promote the reaction, a catalyst usually used in transesterification reactions can also be used. Examples of carbonic acid diesters used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.
末端停止剤として通常使用される単官能フェノール類を使用することができる。殊にカーボネート前駆物質としてホスゲンを使用する反応の場合、単官能フェノール類は末端停止剤として分子量調節のために一般的に使用され、また得られたポリカーボネート樹脂は、末端が単官能フェノール類に基づく基によって封鎖されているので、そうでないものと比べて熱安定性に優れている。前記単官能フェノール類の具体例としては、例えばフェノール、ｍ－メチルフェノール、ｐ－メチルフェノール、ｍ－プロピルフェノール、ｐ－プロピルフェノール、１－フェニルフェノール、２－フェニルフェノール、ｐ－ｔｅｒｔ－ブチルフェノール、ｐ－クミルフェノール、イソオクチルフェノール、ｐ－長鎖アルキルフェノール等が挙げられる。 Monofunctional phenols that are commonly used as end terminators can be used. In particular, in the case of reactions using phosgene as a carbonate precursor, monofunctional phenols are commonly used as end terminators to adjust molecular weight, and the resulting polycarbonate resin has excellent thermal stability compared to those that are not, since the ends are blocked with groups based on monofunctional phenols. Specific examples of the monofunctional phenols include, for example, phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, and p-long-chain alkylphenol.
（その他の成分）
本発明におけるポリカーボネート樹脂には、本発明の目的を損なわない範囲で各種特性を付与するために、各種添加剤を含有させて樹脂組成物としてもよい。添加剤として、離型剤、熱安定剤、紫外線吸収剤、ブルーイング剤、帯電防止剤、難燃剤、熱線遮蔽剤、蛍光染料（蛍光増白剤含む）、顔料、光拡散剤、強化充填剤、他の樹脂やエラストマー等を配することができる。
(Other ingredients)
The polycarbonate resin in the present invention may contain various additives to give various properties to the resin composition within a range that does not impair the object of the present invention. The additives may include a mold release agent, a heat stabilizer, an ultraviolet absorber, a bluing agent, an antistatic agent, a flame retardant, a heat shielding agent, a fluorescent dye (including a fluorescent brightener), a pigment, a light diffusing agent, a reinforcing filler, other resins, elastomers, etc.
離型剤としては、その９０重量％以上がアルコールと脂肪酸のエステルからなるものが好ましい。アルコールと脂肪酸のエステルとしては、具体的には一価アルコールと脂肪酸のエステルや、多価アルコールと脂肪酸との部分エステルあるいは全エステルが挙げられる。具体的に一価アルコールと飽和脂肪酸とエステルとしては、ステアリルステアレート、パルミチルパルミテート、ブチルステアレート、メチルラウレート、イソプロピルパルミテート等が挙げられる。ステアリルステアレートが好ましい。多価アルコールと飽和脂肪酸との部分エステルまたは全エステルとしては、ステアリン酸モノグリセリド、ステアリン酸ジグリセリド、ステアリン酸トリグリセリド、ステアリン酸モノソルビテート、ベヘニン酸モノグリセリド、ペンタエリスリトールモノステアレート、ペンタエリスリトールテトラステアレート、ペンタエリスリトールテトラペラルゴネート、プロピレングリコールモノステアレート、ビフェニルビフェネ－ト、ソルビタンモノステアレート、２－エチルヘキシルステアレート、ジペンタエリスリトールヘキサステアレート等のジペンタエリスルトールの全エステルまたは部分エステル等が挙げられる。これらのエステルのなかでも、ステアリン酸モノグリセリド、ステアリン酸トリグリセリド、ペンタエリスリトールテトラステアレート、ステアリン酸トリグリセリドとステアリルステアレートの混合物が好ましく、ステアリン酸モノグリセリド、ペンタエリスリトールテトラステアレートがより好ましい。 The release agent is preferably one that is composed of 90% by weight or more of an ester of alcohol and fatty acid. Specific examples of the ester of alcohol and fatty acid include ester of monohydric alcohol and fatty acid, and partial or complete ester of polyhydric alcohol and fatty acid. Specific examples of the ester of monohydric alcohol and saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. Stearyl stearate is preferred. Examples of partial or complete esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, and other complete or partial esters of dipentaerythritol. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and mixtures of stearic acid triglyceride and stearyl stearate are preferred, and stearic acid monoglyceride and pentaerythritol tetrastearate are more preferred.
離型剤の配合量としては、ポリカーボネート樹脂１００重量部に対して、０．０５～０．５重量部の範囲が好ましく、０．１～０．４重量部の範囲がより好ましく、０．１２～０．３重量部の範囲がさらに好ましい。 The amount of release agent to be added is preferably in the range of 0.05 to 0.5 parts by weight, more preferably in the range of 0.1 to 0.4 parts by weight, and even more preferably in the range of 0.12 to 0.3 parts by weight, per 100 parts by weight of polycarbonate resin.
熱安定剤としては、リン系熱安定剤、硫黄系熱安定剤およびヒンダードフェノール系熱安定剤が挙げられる。リン系熱安定剤としては、亜リン酸、リン酸、亜ホスホン酸、ホスホン酸およびこれらのエステル等が挙げられる。具体的には、ビス（２，４－ジクミルフェニル）ペンタエリスリトールジホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、トリス（２，６－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸ステアリル、［１，１ービフェニル］－４，４－ジイルビス［ビス（２，４－ジ－ｔｅｒｔ－ブチルフェノキシ）ホスフィン］、３，９－ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノキシ）－２，４，８，１０－テトラオキサー３，９－ジホスファスピロ［５．５］ウンデカンが好ましく、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸ステアリル、３，９－ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ［５．５］ウンデカンがより好ましい。 Examples of heat stabilizers include phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and hindered phenol-based heat stabilizers. Examples of phosphorus-based heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples include bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, [1,1-biphenyl]-4,4-diylbis[bis(2,4-di-tert-butylphenoxy)phosphine], 3,9-bis(2,6-di-tert-butylphenyl)diphosphite, 3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, [1,1-biphenyl]-4,4-diylbis[bis(2,4-di-tert-butylphenoxy)phosphine], 3,9-bis(2,6-di-tert-butylphenyl)diphosphite, 3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, 3,5-di-tert-butyl-4-hydroxyphenyl- ... butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is preferred, and tris(2,4-di-tert-butylphenyl)phosphite, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane are more preferred.
熱安定剤の配合量としては、ポリカーボネート樹脂１００重量部に対して、０．００１～０．５重量部の範囲が好ましく、０．００５～０．４重量部の範囲がより好ましく、０．０１～０．３重量部の範囲がさらに好ましい。 The amount of heat stabilizer to be added is preferably in the range of 0.001 to 0.5 parts by weight, more preferably in the range of 0.005 to 0.4 parts by weight, and even more preferably in the range of 0.01 to 0.3 parts by weight, per 100 parts by weight of polycarbonate resin.
（粘度平均分子量）
本発明におけるポリカーボネート樹脂の粘度平均分子量は、好ましくは６，０００～３００，０００の範囲であり、より好ましくは７，０００～２８，０００の範囲であり、さらに好ましくは８，０００～２５，０００の範囲であり、特に好ましくは９，０００～２２，０００の範囲であり、もっとも好ましくは１０，０００～２０，０００の範囲である。上述の範囲内であると、耐傷付き性、耐熱性、成形性に優れ好ましい。
(Viscosity Average Molecular Weight)
The viscosity average molecular weight of the polycarbonate resin in the present invention is preferably in the range of 6,000 to 300,000, more preferably in the range of 7,000 to 28,000, even more preferably in the range of 8,000 to 25,000, particularly preferably in the range of 9,000 to 22,000, and most preferably in the range of 10,000 to 20,000. If it is in the above range, it is preferable because it has excellent scratch resistance, heat resistance, and moldability.
本発明におけるポリカーボネート樹脂の粘度平均分子量は、まず、次式にて算出される比粘度（ηＳＰ）を２０℃で塩化メチレン１００ｍｌに樹脂０．７ｇを溶解した溶液からオストワルド粘度計を用いて求め、
比粘度（ηＳＰ）＝（ｔ－ｔ０）／ｔ０
［ｔ０は塩化メチレンの落下秒数、ｔは試料溶液の落下秒数］
求められた比粘度（ηＳＰ）から次の数式により粘度平均分子量Ｍｖを算出したものである。
ηＳＰ／ｃ＝［η］＋０．４５×［η］２ｃ（但し［η］は極限粘度）
［η］＝１．２３×１０－４Ｍｖ０．８３
ｃ＝０．７
The viscosity average molecular weight of the polycarbonate resin in the present invention is determined by first determining the specific viscosity (η SP ) calculated by the following formula using an Ostwald viscometer from a solution in which 0.7 g of the resin is dissolved in 100 ml of methylene chloride at 20° C.:
Specific viscosity (η SP )=(t−t 0 )/t 0
[ t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls]
The viscosity average molecular weight Mv was calculated from the determined specific viscosity (η SP ) according to the following formula.
η SP /c = [η] + 0.45 × [η] 2 c (where [η] is the intrinsic viscosity)
[η] = 1.23 × 10 −4 Mv 0.83
c=0.7
（ガラス転移温度：Ｔｇ）
本発明におけるポリカーボネート樹脂のガラス転移温度（Ｔｇ）は、好ましくは１２５～３００℃の範囲であり、より好ましくは１３０～２７０℃の範囲であり、さらに好ましくは１３５～２５０℃の範囲であり、特に好ましくは１４０～２４０℃の範囲である。Ｔｇが上記範囲内であると、耐熱性および成形性が良好であり好ましい。ガラス転移温度（Ｔｇ）はティー・エイ・インスツルメント・ジャパン（株）製２９１０型ＤＳＣを使用し、昇温速度２０℃／ｍｉｎにて測定する。
(Glass transition temperature: Tg)
The glass transition temperature (Tg) of the polycarbonate resin in the present invention is preferably in the range of 125 to 300° C., more preferably in the range of 130 to 270° C., even more preferably in the range of 135 to 250° C., and particularly preferably in the range of 140 to 240° C. If the Tg is within the above range, the heat resistance and moldability are good, which is preferable. The glass transition temperature (Tg) is measured using a 2910 DSC manufactured by TA Instruments Japan Ltd. at a heating rate of 20° C./min.
（鉛筆硬度）
本発明におけるポリカーボネート樹脂の鉛筆硬度は、好ましくはＦ以上であり、より好ましくはＨ以上であり、さらに好ましくは２Ｈ以上である。鉛筆硬度とは、特定の鉛筆硬度を有する鉛筆でポリカーボネート樹脂を擦過した場合に擦過しても擦過痕が残らない硬さのことであり、ＪＩＳ Ｋ５６００－５－４記載のひっかき硬度（鉛筆法）に準拠して測定できる塗膜の表面硬度試験に用いる鉛筆硬度を指標とすることが好ましい。鉛筆硬度は、９Ｈ、８Ｈ、７Ｈ、６Ｈ、５Ｈ、４Ｈ、３Ｈ、２Ｈ、Ｈ、Ｆ、ＨＢ、Ｂ、２Ｂ、３Ｂ、４Ｂ、５Ｂ、６Ｂの順で柔らかくなり、最も硬いものが９Ｈ、最も軟らかいものが６Ｂである。
(Pencil hardness)
The pencil hardness of the polycarbonate resin in the present invention is preferably F or more, more preferably H or more, and even more preferably 2H or more. The pencil hardness is a hardness that does not leave a scratch mark when the polycarbonate resin is scratched with a pencil having a specific pencil hardness, and it is preferable to use the pencil hardness used in the surface hardness test of the coating film that can be measured in accordance with the scratch hardness (pencil method) described in JIS K5600-5-4 as an index. The pencil hardness becomes softer in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, and 6B, with the hardest being 9H and the softest being 6B.
（押込み硬さ）
本発明におけるポリカーボネート樹脂のＩＳＯ／ＴＳ１９２７８記載のプラスチック－硬さ測定のための計装化マイクロ押込み硬さ試験に準拠して測定された押込み硬さは、好ましくは１８０～４５０（Ｎ／ｍｍ２）の範囲であり、より好ましくは１９０～４００（Ｎ／ｍｍ２）の範囲であり、さらに好ましくは２００～３５０（Ｎ／ｍｍ２）の範囲である。押込み硬さはＩＳＯ／ＴＳ １９２７８に基づき、ダイナミック超微小硬度計（島津製作所、型式ＤＵＨ－２１０Ｓ）を使用して、樹脂プレートの表面に対して負荷と押しこみ深さの関係をリアルタイムに計測し測定する。
(Indentation hardness)
The indentation hardness of the polycarbonate resin in the present invention, measured in accordance with the instrumented microindentation hardness test for measuring plastic hardness described in ISO/TS 19278, is preferably in the range of 180 to 450 (N/mm 2 ), more preferably in the range of 190 to 400 (N/mm 2 ), and even more preferably in the range of 200 to 350 (N/mm 2 ). The indentation hardness is measured in accordance with ISO/TS 19278 by using a dynamic ultra-microhardness tester (Shimadzu Corporation, model DUH-210S) to measure the relationship between the load and the indentation depth on the surface of the resin plate in real time.
（成形方法および成形品）
本発明におけるポリカーボネート樹脂の成形方法としては、射出成形、押出成形、圧縮成形、溶液キャスト法等、一般のポリカーボネート樹脂の成形法を採用することができる。特に射出成形により成形品を成形する方法や押出成形によりシートまたはフィルムを成形する方法が好ましく採用される。
(Molding method and molded product)
As a method for molding the polycarbonate resin in the present invention, a general method for molding a polycarbonate resin can be used, such as injection molding, extrusion molding, compression molding, solution casting, etc. In particular, a method for molding a molded product by injection molding or a method for molding a sheet or film by extrusion molding is preferably used.
本発明のポリカーボネート樹脂は、耐傷付き性、耐熱性、成形性、透明性に優れているので種々の成形品として利用することができる。殊に耐傷付き性に優れるためコーティング処理を必要とせず、室内照明用ランプレンズ、表示用メーターカバー、メーター文字板、各種スイッチカバー、ディスプレイカバー、ヒートコントロールパネル、インストルメントパネル、センタークラスター、センターパネル、ルームランプレンズ、ヘッドアップディスプレイ等の各種表示装置、保護部品、透光部品などの自動車内装部品に好適に利用できる。 The polycarbonate resin of the present invention has excellent scratch resistance, heat resistance, moldability, and transparency, and can be used as various molded products. In particular, because of its excellent scratch resistance, it does not require coating treatment, and can be suitably used for automobile interior parts such as lamp lenses for interior lighting, display meter covers, meter dials, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, various display devices such as head-up displays, protective parts, and translucent parts.
以下に本発明を実施例によりさらに詳しく説明するが、これらは本発明を限定するものではない。なお、評価は下記の方法に従った。
（１）組成比
日本電子社製 ＪＮＭ－ＡＬ４００のプロトンＮＭＲにて各繰り返し単位を測定し、ポリマー組成比（モル比）を算出した。
The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. The evaluation was performed according to the following methods.
(1) Composition Ratio Each repeating unit was measured by proton NMR using JNM-AL400 manufactured by JEOL Ltd., and the polymer composition ratio (molar ratio) was calculated.
（２）粘度平均分子量
次式にて算出される比粘度（ηＳＰ）を２０℃で塩化メチレン１００ｍｌに試料０．７ｇを溶解した溶液からオストワルド粘度計を用いて求め、
比粘度（ηＳＰ）＝（ｔ－ｔ０）／ｔ０
［ｔ０は塩化メチレンの落下秒数、ｔは試料溶液の落下秒数］
求められた比粘度（ηＳＰ）から次の数式により粘度平均分子量Ｍｖを算出した。
ηＳＰ／ｃ＝［η］＋０．４５×［η］２ｃ （但し［η］は極限粘度）
［η］＝１．２３×１０－４Ｍｖ０．８３
ｃ＝０．７
(2) Viscosity average molecular weight: The specific viscosity (η SP ) calculated by the following formula was determined using an Ostwald viscometer from a solution of 0.7 g of a sample dissolved in 100 ml of methylene chloride at 20° C.
Specific viscosity (η SP )=(t−t 0 )/t 0
[ t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls]
The viscosity average molecular weight Mv was calculated from the determined specific viscosity (η SP ) according to the following formula.
η SP /c = [η] + 0.45 × [η] 2 c (where [η] is the intrinsic viscosity)
[η] = 1.23 × 10 −4 Mv 0.83
c=0.7
（３）ガラス転移温度（Ｔｇ）
試料８ｍｇを用いてティー・エイ・インスツルメント（株）製の熱分析システム ＤＳＣ－２９１０を使用して、ＪＩＳ Ｋ７１２１に準拠して窒素雰囲気下（窒素流量：４０ｍｌ／ｍｉｎ）、昇温速度：２０℃／ｍｉｎの条件下で測定した。
(3) Glass transition temperature (Tg)
Using 8 mg of a sample, a thermal analysis system DSC-2910 manufactured by TA Instruments was used to perform the measurement in accordance with JIS K7121 under the conditions of a nitrogen atmosphere (nitrogen flow rate: 40 ml/min) and a temperature rise rate of 20° C./min.
（４）鉛筆硬度
得られたポリカーボネート樹脂を熱プレス成形機（（神藤金属工業所（株）製 圧縮成形機：ＳＦＶ－１０、真空ポンプユニット：ＧＸＤ－３６０）でプレス成形し、厚さ約３ｍｍの円盤状の樹脂プレートを得た。プレス成形条件は、金型温度１５０～３５０℃、１次圧：１ＭＰａ（３０秒）、２次圧：１．５ＭＰａ（１２分）とした。この樹脂プレートを用いてＪＩＳ Ｋ５６００－５－４記載のひっかき硬度（鉛筆法）に基づき、雰囲気温度２３℃の恒温室内で樹脂プレートの表面に対して鉛筆を４５度の角度を保ちつつ７５０ｇの荷重をかけた状態で線を引き、表面状態を目視にて評価した。
荷重：７５０ｇ
測定速度：５０ｍｍ／ｍｉｎ
測定距離：７ｍｍ
鉛筆：三菱鉛筆製Ｈｉ―ｕｎｉ
(4) Pencil Hardness The obtained polycarbonate resin was press molded with a hot press molding machine (manufactured by Shinto Metal Industries Co., Ltd., compression molding machine: SFV-10, vacuum pump unit: GXD-360) to obtain a disk-shaped resin plate with a thickness of about 3 mm. The press molding conditions were a mold temperature of 150 to 350 ° C., a primary pressure of 1 MPa (30 seconds), and a secondary pressure of 1.5 MPa (12 minutes). Using this resin plate, a line was drawn with a pencil at an angle of 45 degrees to the surface of the resin plate in a constant temperature room at an atmospheric temperature of 23 ° C., with a load of 750 g applied, based on the scratch hardness (pencil method) described in JIS K5600-5-4, and the surface condition was evaluated visually.
Load: 750g
Measurement speed: 50 mm/min
Measurement distance: 7 mm
Pencil: Mitsubishi Pencil Hi-uni
（５）押込み硬さ（Ｈｉｔ）
得られたポリカーボネート樹脂を熱プレス成形機（（神藤金属工業所（株）製 圧縮成形機：ＳＦＶ－１０、真空ポンプユニット：ＧＸＤ－３６０）でプレス成形し、厚さ約３ｍｍの円盤状の樹脂プレートを得た。プレス成形条件は、金型温度１５０～３５０℃、１次圧：１ＭＰａ（３０秒）、２次圧：１．５ＭＰａ（１２分）とした。この樹脂プレートを用いてＩＳＯ／ＴＳ１９２７８記載のプラスチック－硬さ測定のための計装化マイクロ押込み硬さ試験に基づき、ダイナミック超微小硬度計（島津製作所、型式ＤＵＨ－２１０Ｓ）を使用して、樹脂プレートの表面に対して、負荷と押しこみ深さの関係をリアルタイムに計測し、押し込み硬さ（Ｎ／ｍｍ２）を測定した。
（測定条件）
測定圧子：バーコビッチ圧子（ダイヤモンド製）
試験力：５００ｍＮ
最小試験力：４．９ｍＮ
負荷／除荷時間：３０ｓｅｃ
負荷保持時間：４０ｓｅｃ
除荷保持時間：０ｓｅｃ
試験回数：５
（押し込み硬さ算出方法）
押し込み硬さ（Ｈｉｔ）は、半永久的な変形あるいは損傷に関する抵抗を測定したものである。押し込み硬さは以下の式で算出される。
Ｈｉｔ＝Ｆｍａｘ／Ａｐ
Ｆｍａｘ：最大試験力
Ａｐ：圧子と試験片が接している投影面積
Ａｐ＝２３．９６×ｈｃ
２（三角錐圧子（１１５°）の場合）
ｈｃ＝ｈｍａｘ－ε（ｈｍａｘ－ｈｒ）
ε＝３／４（三角錐の場合）
ｈｒ：試験力―深さ曲線のＦｍａｘにおける除荷曲線の接線が深さ軸と交わる切片
（高速液体クロマトグラフィー（ＨＰＬＣ））
日立製高速液体クロマトグラフィーＣｈｒｏｍａｓｔｅｒを用いて下表の測定条件で測定した。特に断らない限り％はＨＰＬＣにおける溶媒を除いて補正した面積百分率値である。
(5) Indentation hardness (Hit)
The obtained polycarbonate resin was press molded using a hot press molding machine (Shinto Metal Industries Co., Ltd., compression molding machine: SFV-10, vacuum pump unit: GXD-360) to obtain a disk-shaped resin plate with a thickness of approximately 3 mm. The press molding conditions were a mold temperature of 150 to 350°C, a primary pressure of 1 MPa (30 seconds), and a secondary pressure of 1.5 MPa (12 minutes). Using this resin plate, the relationship between the load and the indentation depth on the surface of the resin plate was measured in real time using a dynamic ultra-microhardness meter (Shimadzu Corporation, model DUH-210S) based on the instrumented microindentation hardness test for plastic hardness measurement described in ISO/TS19278, and the indentation hardness (N/ mm2 ) was measured.
(Measurement condition)
Measurement indenter: Berkovich indenter (made of diamond)
Test force: 500 mN
Minimum test force: 4.9 mN
Loading/unloading time: 30 sec
Load holding time: 40 sec
Unloading holding time: 0 sec
Number of tests: 5
(Method of calculating indentation hardness)
Indentation hardness (Hit) is a measure of the resistance to semi-permanent deformation or damage. Indentation hardness is calculated by the following formula:
Hit = F max / A p
F max : Maximum test force A p : Projected area where the indenter and the test piece are in contact A p = 23.96 × h c 2 (in the case of a triangular pyramidal indenter (115°))
hc = hmax - ε (hmax - hr )
ε = 3/4 (in the case of a triangular pyramid)
hr : Intercept of the tangent of the unloading curve at Fmax of the test force-depth curve intersects with the depth axis (high performance liquid chromatography (HPLC))
Measurements were performed using a Hitachi high performance liquid chromatograph Chromaster under the measurement conditions in the table below. Unless otherwise specified, % is an area percentage value corrected by excluding the solvent in HPLC.
［参考例１］Ｎ－（４－ベンゾイルフェニル）フェノールフタレイニルビスフェノール（４－ＢｐＰｈＰＰ）の合成
４－アミノベンゾフェノン１１１ｇ（５６３．１ミリモル）を１３０℃以上で加熱溶融し、３６％濃塩酸２１ｍＬ（２４３．５ミリモル）を滴下した。その後、フェノールフタレイン２５ｇ（７８．５ミリモル）を加えて反応液が１６０±５℃になるよう加熱しながら水を留去した。反応の進行具合はＨＰＬＣで追跡し、原料のフェノールフタレインがほぼ消失するまで撹拌を続けた。反応終了後、得られた反応液にＤＭＦを加えて加熱撹拌していたところ結晶が析出したため、結晶を濾過したのち、濾液に酢酸エチルを加えて分液水洗した。その後、酢酸エチル／ヘキサン（ｖ／ｖ＝１／１）の溶離液を用いてシリカゲルカラムで精製し目的物を含む薄黄色の粗結晶を２１．４ｇ、粗収率５５％で得た。更にトルエン／ヘキサンで再結晶したのち目的物であるＮ－（４－ベンゾイルフェニル）フェノールフタレイニルビスフェノール（４－ＢｐＰｈＰＰ）の白色結晶を１６ｇ、収率４０％で得た。得られた４－ＢｐＰｈＰＰをプロトンＮＭＲ（重溶媒：（ＣＤ３）２ＳＯ）により分析し目的物であることを確認した（図１）。また、ＨＰＬＣを測定したところ、純度は９９．５％であった。
Reference Example 1: Synthesis of N-(4-benzoylphenyl)phenolphthaleinyl bisphenol (4-BpPhPP) 111 g (563.1 mmol) of 4-aminobenzophenone was heated and melted at 130° C. or higher, and 21 mL (243.5 mmol) of 36% concentrated hydrochloric acid was added dropwise. Then, 25 g (78.5 mmol) of phenolphthalein was added, and water was distilled off while heating the reaction solution to 160±5° C. The progress of the reaction was monitored by HPLC, and stirring was continued until the raw material phenolphthalein was almost completely consumed. After the reaction was completed, DMF was added to the obtained reaction solution and the mixture was heated and stirred, and crystals were precipitated. The crystals were filtered, and then ethyl acetate was added to the filtrate and separated and washed with water. Then, the mixture was purified on a silica gel column using an eluent of ethyl acetate/hexane (v/v=1/1), and 21.4 g of pale yellow crude crystals containing the target product were obtained in a crude yield of 55%. After further recrystallization from toluene/hexane, 16 g of white crystals of the target product, N-(4-benzoylphenyl)phenolphthaleinyl bisphenol (4-BpPhPP), was obtained in a yield of 40%. The resulting 4-BpPhPP was analyzed by proton NMR (heavy solvent: (CD 3 ) 2 SO) and confirmed to be the target product (Figure 1). In addition, HPLC analysis revealed that the purity was 99.5%.
［実施例１］
温度計、撹拌機、還流冷却器付き反応器にイオン交換水５２．８９質量部、２５％水酸化ナトリウム水溶液３０．１６質量部を入れ、ジオールとして参考例１で得られたＮ－（４－ベンゾイルフェニル）フェノールフタレイニルビスフェノール（４－ＢｐＰｈＰＰ）２７．５８質量部およびハイドロサルファイト０．０５５質量部を溶解した後、塩化メチレン６１．２６質量部を加え、撹拌下１６～２４℃でホスゲン７．３０質量部を７０分かけて吹き込んだ。その後、２５％水酸化ナトリウム水溶液４．４４質量部、ｐ－ｔｅｒｔ－ブチルフェノール０．２６６質量部を塩化メチレン２．６６質量部に溶解した溶液を加え攪拌して乳化状態とした。かかる攪拌下、反応液が２８℃の状態で０．０１４質量部のトリエチルアミンを加えて温度２６～３１℃において１時間撹拌を続けて反応を終了した。反応終了後有機相を分離し、塩化メチレンで希釈し、イオン交換水で水洗を繰り返し、洗浄液が中性になったところで塩酸を加えた。その後、イオン交換水で繰り返し洗浄し水相の導電率がイオン交換水とほぼ同じになるまで水洗を繰り返し、ポリカーボネートの塩化メチレン溶液を得た。次いで、得られた塩化メチレン溶液を５０～８０℃に保った温水中に滴下し、溶媒を蒸発除去し、フレーク状の固形物を得た。得られた固形物をろ過し、１２０℃で２４時間乾燥し、白色フレーク状のポリカーボネート樹脂を得た。得られたポリカーボネート樹脂を用いて、前記の方法で各種評価を実施しその結果を表２に示した。
[Example 1]
A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 52.89 parts by mass of ion-exchanged water and 30.16 parts by mass of a 25% aqueous sodium hydroxide solution, and 27.58 parts by mass of N-(4-benzoylphenyl)phenolphthaleinylbisphenol (4-BpPhPP) obtained in Reference Example 1 as a diol and 0.055 parts by mass of hydrosulfite were dissolved therein, and then 61.26 parts by mass of methylene chloride was added, and 7.30 parts by mass of phosgene was blown in over 70 minutes at 16 to 24 ° C. under stirring. Thereafter, a solution in which 4.44 parts by mass of a 25% aqueous sodium hydroxide solution and 0.266 parts by mass of p-tert-butylphenol were dissolved in 2.66 parts by mass of methylene chloride was added and stirred to form an emulsion. Under such stirring, 0.014 parts by mass of triethylamine was added when the reaction solution was at 28 ° C., and the reaction was terminated by continuing stirring at a temperature of 26 to 31 ° C. for 1 hour. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washing liquid became neutral, hydrochloric acid was added. After that, the mixture was repeatedly washed with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, and a methylene chloride solution of polycarbonate was obtained. Next, the obtained methylene chloride solution was dropped into warm water kept at 50 to 80°C, and the solvent was evaporated and removed to obtain a flaky solid. The obtained solid was filtered and dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin. Using the obtained polycarbonate resin, various evaluations were carried out by the above-mentioned methods, and the results are shown in Table 2.
［実施例２］
温度計、撹拌機、還流冷却器付き反応器にイオン交換水４０．６５質量部、２５％水酸化ナトリウム水溶液２３．１８質量部を入れ、ジオールとして参考例１で得られたＮ－（４－ベンゾイルフェニル）フェノールフタレイニルビスフェノール（４－ＢｐＰｈＰＰ）７．４２質量部、２，２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパン（ＢＰＣ）７．０９質量部およびハイドロサルファイト０．０２９質量部を溶解した後、塩化メチレン４７．０８質量部を加え、撹拌下１６～２４℃でホスゲン５．６１質量部を７０分かけて吹き込んだ。その後、２５％水酸化ナトリウム水溶液３．４１質量部、ｐ－ｔｅｒｔ－ブチルフェノール０．２０５質量部を塩化メチレン２．０５質量部に溶解した溶液を加え攪拌して乳化状態とした。かかる攪拌下、反応液が２８℃の状態で０．０１１質量部のトリエチルアミンを加えて温度２６～３１℃において１時間撹拌を続けて反応を終了した。反応終了後有機相を分離し、塩化メチレンで希釈し、イオン交換水で水洗を繰り返し、洗浄液が中性になったところで塩酸を加えた。その後、イオン交換水で繰り返し洗浄し水相の導電率がイオン交換水とほぼ同じになるまで水洗を繰り返し、ポリカーボネートの塩化メチレン溶液を得た。次いで、得られた塩化メチレン溶液を５０～８０℃に保った温水中に滴下し、溶媒を蒸発除去し、フレーク状の固形物を得た。得られた固形物をろ過し、１２０℃で２４時間乾燥し、白色フレーク状のポリカーボネート樹脂を得た。得られたポリカーボネート樹脂を用いて、前記の方法で各種評価を実施しその結果を表２に示した。
[Example 2]
A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 40.65 parts by mass of ion-exchanged water and 23.18 parts by mass of a 25% aqueous sodium hydroxide solution, and 7.42 parts by mass of N-(4-benzoylphenyl)phenolphthaleinylbisphenol (4-BpPhPP) obtained in Reference Example 1 as a diol, 7.09 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC), and 0.029 parts by mass of hydrosulfite were dissolved therein, and then 47.08 parts by mass of methylene chloride was added, and 5.61 parts by mass of phosgene was blown in over 70 minutes at 16 to 24° C. with stirring. Thereafter, a solution in which 3.41 parts by mass of a 25% aqueous sodium hydroxide solution and 0.205 parts by mass of p-tert-butylphenol were dissolved in 2.05 parts by mass of methylene chloride was added and stirred to form an emulsified state. Under such stirring, 0.011 parts by mass of triethylamine was added while the reaction solution was at 28°C, and the reaction was terminated by continuing stirring at a temperature of 26 to 31°C for 1 hour. After the reaction was terminated, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water, and when the washing solution became neutral, hydrochloric acid was added. Thereafter, the mixture was repeatedly washed with ion-exchanged water until the conductivity of the aqueous phase was almost the same as that of the ion-exchanged water, and a methylene chloride solution of polycarbonate was obtained. Next, the obtained methylene chloride solution was dropped into warm water kept at 50 to 80°C, and the solvent was evaporated and removed, and a flaky solid was obtained. The obtained solid was filtered and dried at 120°C for 24 hours, and a white flaky polycarbonate resin was obtained. Using the obtained polycarbonate resin, various evaluations were performed by the above-mentioned methods, and the results are shown in Table 2.
［実施例３］
温度計、撹拌機、還流冷却器付き反応器にイオン交換水５２．８９質量部、２５％水酸化ナトリウム水溶液３０．１６質量部を入れ、ジオールとして参考例１で得られたＮ－（４－ベンゾイルフェニル）フェノールフタレイニルビスフェノール（４－ＢｐＰｈＰＰ）５．５２質量部、２，２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパン（ＢＰＣ）１１．３５質量部およびハイドロサルファイト０．０３４質量部を溶解した後、塩化メチレン６１．２６質量部を加え、撹拌下１６～２４℃でホスゲン７．３０質量部を７０分かけて吹き込んだ。その後、２５％水酸化ナトリウム水溶液３．４１質量部、ｐ－ｔｅｒｔ－ブチルフェノール０．２６６質量部を塩化メチレン２．６６質量部に溶解した溶液を加え攪拌して乳化状態とした。かかる攪拌下、反応液が２８℃の状態で０．０１４質量部のトリエチルアミンを加えて温度２６～３１℃において１時間撹拌を続けて反応を終了した。反応終了後有機相を分離し、塩化メチレンで希釈し、イオン交換水で水洗を繰り返し、洗浄液が中性になったところで塩酸を加えた。その後、イオン交換水で繰り返し洗浄し水相の導電率がイオン交換水とほぼ同じになるまで水洗を繰り返し、ポリカーボネートの塩化メチレン溶液を得た。次いで、得られた塩化メチレン溶液を５０～８０℃に保った温水中に滴下し、溶媒を蒸発除去し、フレーク状の固形物を得た。得られた固形物をろ過し、１２０℃で２４時間乾燥し、白色フレーク状のポリカーボネート樹脂を得た。得られたポリカーボネート樹脂を用いて、前記の方法で各種評価を実施しその結果を表２に示した。
[Example 3]
A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 52.89 parts by mass of ion-exchanged water and 30.16 parts by mass of a 25% aqueous sodium hydroxide solution, and 5.52 parts by mass of N-(4-benzoylphenyl)phenolphthaleinylbisphenol (4-BpPhPP) obtained in Reference Example 1 as a diol, 11.35 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC), and 0.034 parts by mass of hydrosulfite were dissolved therein, and then 61.26 parts by mass of methylene chloride was added, and 7.30 parts by mass of phosgene was blown in over 70 minutes at 16 to 24° C. with stirring. Thereafter, a solution in which 3.41 parts by mass of a 25% aqueous sodium hydroxide solution and 0.266 parts by mass of p-tert-butylphenol were dissolved in 2.66 parts by mass of methylene chloride was added and stirred to form an emulsified state. Under such stirring, 0.014 parts by mass of triethylamine was added while the reaction solution was at 28°C, and the reaction was terminated by continuing stirring at a temperature of 26 to 31°C for 1 hour. After the reaction was terminated, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water, and when the washing solution became neutral, hydrochloric acid was added. Thereafter, the solution was repeatedly washed with ion-exchanged water until the conductivity of the aqueous phase was almost the same as that of the ion-exchanged water, and a methylene chloride solution of polycarbonate was obtained. Next, the obtained methylene chloride solution was dropped into warm water kept at 50 to 80°C, and the solvent was evaporated and removed, and a flaky solid was obtained. The obtained solid was filtered and dried at 120°C for 24 hours, and a white flaky polycarbonate resin was obtained. Using the obtained polycarbonate resin, various evaluations were performed by the above-mentioned methods, and the results are shown in Table 2.
［実施例４］
温度計、撹拌機、還流冷却器付き反応器にイオン交換水５１．５９質量部、２５％水酸化ナトリウム水溶液２９．４２質量部を入れ、ジオールとして参考例１で得られたＮ－（４－ベンゾイルフェニル）フェノールフタレイニルビスフェノール（４－ＢｐＰｈＰＰ）５．３８質量部、２，２－ビス（４－ヒドロキシフェニル）プロパン（ＢＰＡ）９．８６質量部およびハイドロサルファイト０．０３０質量部を溶解した後、塩化メチレン５９．７５質量部を加え、撹拌下１６～２４℃でホスゲン７．１２質量部を７０分かけて吹き込んだ。その後、２５％水酸化ナトリウム水溶液４．３３質量部、ｐ－ｔｅｒｔ－ブチルフェノール０．２６０質量部を塩化メチレン２．６０質量部に溶解した溶液を加え攪拌して乳化状態とした。かかる攪拌下、反応液が２８℃の状態で０．０１４質量部のトリエチルアミンを加えて温度２６～３１℃において１時間撹拌を続けて反応を終了した。反応終了後有機相を分離し、塩化メチレンで希釈し、イオン交換水で水洗を繰り返し、洗浄液が中性になったところで塩酸を加えた。その後、イオン交換水で繰り返し洗浄し水相の導電率がイオン交換水とほぼ同じになるまで水洗を繰り返し、ポリカーボネートの塩化メチレン溶液を得た。次いで、得られた塩化メチレン溶液を５０～８０℃に保った温水中に滴下し、溶媒を蒸発除去し、フレーク状の固形物を得た。得られた固形物をろ過し、１２０℃で２４時間乾燥し、白色フレーク状のポリカーボネート樹脂を得た。得られたポリカーボネート樹脂を用いて、前記の方法で各種評価を実施しその結果を表２に示した。
[Example 4]
A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 51.59 parts by mass of ion-exchanged water and 29.42 parts by mass of a 25% aqueous sodium hydroxide solution, and 5.38 parts by mass of N-(4-benzoylphenyl)phenolphthaleinylbisphenol (4-BpPhPP) obtained in Reference Example 1 as a diol, 9.86 parts by mass of 2,2-bis(4-hydroxyphenyl)propane (BPA), and 0.030 parts by mass of hydrosulfite were dissolved therein, and then 59.75 parts by mass of methylene chloride was added, and 7.12 parts by mass of phosgene was blown in over 70 minutes at 16 to 24° C. with stirring. Thereafter, a solution in which 4.33 parts by mass of a 25% aqueous sodium hydroxide solution and 0.260 parts by mass of p-tert-butylphenol were dissolved in 2.60 parts by mass of methylene chloride was added and stirred to form an emulsified state. Under such stirring, 0.014 parts by mass of triethylamine was added while the reaction solution was at 28°C, and the reaction was terminated by continuing stirring at a temperature of 26 to 31°C for 1 hour. After the reaction was terminated, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water, and when the washing solution became neutral, hydrochloric acid was added. Thereafter, the solution was repeatedly washed with ion-exchanged water until the conductivity of the aqueous phase was almost the same as that of the ion-exchanged water, and a methylene chloride solution of polycarbonate was obtained. Next, the obtained methylene chloride solution was dropped into warm water kept at 50 to 80°C, and the solvent was evaporated and removed, and a flaky solid was obtained. The obtained solid was filtered and dried at 120°C for 24 hours, and a white flaky polycarbonate resin was obtained. Using the obtained polycarbonate resin, various evaluations were performed by the above-mentioned methods, and the results are shown in Table 2.
［比較例１］
温度計、撹拌機、還流冷却器付き反応器にイオン交換水６８．７７質量部、２５％水酸化ナトリウム水溶液４１．１５質量部を入れ、ジオールとしてＮ－フェニルフェノールフタレイニルビスフェノール（ＰＰＰ－ＢＰ；オージー社製）５．７８質量部、２，２－ビス（４－ヒドロキシフェニル）プロパン（ＢＰＡ）１３．２８質量部およびハイドロサルファイト０．０３８質量部を溶解した後、塩化メチレン８１．１９質量部を加え、撹拌下１６～２４℃でホスゲン９．８２質量部を７０分かけて吹き込んだ。その後、２５％水酸化ナトリウム水溶液５．８８質量部、ｐ－ｔｅｒｔ－ブチルフェノール０．３５３質量部を塩化メチレン３．５３質量部に溶解した溶液を加え攪拌して乳化状態とした。かかる攪拌下、反応液が２８℃の状態で０．０１９質量部のトリエチルアミンを加えて温度２６～３１℃において１時間撹拌を続けて反応を終了した。反応終了後有機相を分離し、塩化メチレンで希釈し、イオン交換水で水洗を繰り返し、洗浄液が中性になったところで塩酸を加えた。その後、イオン交換水で繰り返し洗浄し水相の導電率がイオン交換水とほぼ同じになるまで水洗を繰り返し、ポリカーボネートの塩化メチレン溶液を得た。次いで、得られた塩化メチレン溶液を５０～８０℃に保った温水中に滴下し、溶媒を蒸発除去し、フレーク状の固形物を得た。得られた固形物をろ過し、１２０℃で２４時間乾燥し、白色フレーク状の比較例１のポリカーボネート樹脂を得た。得られたポリカーボネート樹脂を用いて、前記の方法で各種評価を実施しその結果を表２に示した。
[Comparative Example 1]
A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 68.77 parts by mass of ion-exchanged water and 41.15 parts by mass of a 25% aqueous sodium hydroxide solution, and 5.78 parts by mass of N-phenylphenolphthaleinyl bisphenol (PPP-BP; manufactured by OG Co., Ltd.) as a diol, 13.28 parts by mass of 2,2-bis(4-hydroxyphenyl)propane (BPA) and 0.038 parts by mass of hydrosulfite were dissolved therein, and then 81.19 parts by mass of methylene chloride was added, and 9.82 parts by mass of phosgene was blown in over 70 minutes at 16 to 24 ° C. under stirring. Thereafter, 5.88 parts by mass of a 25% aqueous sodium hydroxide solution and a solution in which 0.353 parts by mass of p-tert-butylphenol was dissolved in 3.53 parts by mass of methylene chloride were added and stirred to form an emulsion. Under such stirring, 0.019 parts by mass of triethylamine was added when the reaction solution was at 28 ° C., and the reaction was terminated by continuing stirring at a temperature of 26 to 31 ° C. for 1 hour. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washing liquid became neutral, hydrochloric acid was added. After that, washing with ion-exchanged water was repeated until the conductivity of the aqueous phase was almost the same as that of the ion-exchanged water, and a methylene chloride solution of polycarbonate was obtained. Next, the obtained methylene chloride solution was dropped into warm water kept at 50 to 80°C, and the solvent was evaporated and removed to obtain a flaky solid. The obtained solid was filtered and dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin of Comparative Example 1. Using the obtained polycarbonate resin, various evaluations were performed by the above-mentioned methods, and the results are shown in Table 2.
［比較例２］
温度計、撹拌機、還流冷却器付き反応器にイオン交換水１０６６３部、２５％水酸化ナトリウム水溶液６０１５部を入れ、二価フェノールとしてＢＰＣ２９２１部、およびハイドロサルファイト５．８４部を溶解した後、塩化メチレン１２５８８部を加え、撹拌下１６～２４℃でホスゲン１５００部を７０分要して吹き込んだ。その後、２５％水酸化ナトリウム水溶液９１１部、トリエチルアミン０．５８部を加え、ｐ－ｔｅｒｔ－ブチルフェノール５１．２６部を塩化メチレン２７７部に溶解した溶液を加え、攪拌させて乳化状態とした。かかる攪拌下、反応液が２８℃の状態でトリエチルアミン２．３０部を加えた後、温度２６～３１℃において１時間撹拌を続けたところで反応を終了した。反応終了後有機相を分離し、塩化メチレンで希釈してイオン交換水で水洗を繰り返し、洗浄液が中性になったところで塩酸酸性水にて水洗した。その後、イオン交換水で繰り返し洗浄し水相の導電率がイオン交換水と殆ど同じになったところで温水を張ったニーダーに投入して、攪拌しながら溶媒を蒸発させ、樹脂のパウダーを得た。脱水後、熱風循環式乾燥機により１００℃で１２時間乾燥し、白色パウダー状の比較例２のポリカーボネート樹脂を得た。得られたポリカーボネート樹脂を用いて、前記の方法で各種評価を実施しその結果を表２に示した。
[Comparative Example 2]
A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 10663 parts of ion-exchanged water and 6015 parts of 25% aqueous sodium hydroxide solution, and 2921 parts of BPC as a dihydric phenol and 5.84 parts of hydrosulfite were dissolved therein. Then, 12588 parts of methylene chloride were added, and 1500 parts of phosgene were blown in over 70 minutes at 16 to 24 ° C. under stirring. Then, 911 parts of 25% aqueous sodium hydroxide solution and 0.58 parts of triethylamine were added, and a solution in which 51.26 parts of p-tert-butylphenol were dissolved in 277 parts of methylene chloride was added, and the mixture was stirred to form an emulsified state. Under such stirring, 2.30 parts of triethylamine were added when the reaction solution was at 28 ° C., and the reaction was terminated when stirring was continued for 1 hour at a temperature of 26 to 31 ° C. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washing solution became neutral, it was washed with hydrochloric acid acid water. After that, it was repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was put into a kneader filled with warm water, and the solvent was evaporated while stirring to obtain a resin powder. After dehydration, it was dried at 100°C for 12 hours in a hot air circulation dryer to obtain a white powder-like polycarbonate resin of Comparative Example 2. Using the obtained polycarbonate resin, various evaluations were performed using the above-mentioned methods, and the results are shown in Table 2.
［比較例３］
温度計、撹拌機、還流冷却器付き反応器にイオン交換水１４８７６部、２５％水酸化ナトリウム水溶液６６１２部を入れ、二価フェノールとしてＢＰＡ３１４０部、ハイドロサルファイト６．２８部を溶解した後、塩化メチレン１４０５０部を加え、撹拌下１６～２４℃でホスゲン１５００部を７０分要して吹き込んだ。その後、２５％水酸化ナトリウム水溶液１１０２部を加え、さらにｐ－ｔｅｒｔ－ブチルフェノール８８．８４部を塩化メチレン２５１部に溶解した溶液を加え、攪拌させて乳化状態とした。かかる攪拌下、反応液が２８℃の状態でトリエチルアミン２．７８部を加えた後、温度２６～３１℃において１時間撹拌を続けたところで反応を終了した。反応終了後有機相を分離し、塩化メチレンで希釈してイオン交換水で水洗を繰り返し、洗浄液が中性になったところで塩酸酸性水にて水洗した。その後、イオン交換水で繰り返し洗浄し水相の導電率がイオン交換水と殆ど同じになったところで温水を張ったニーダーに投入して、攪拌しながら溶媒を蒸発させ、ポリカーボネート樹脂のパウダーを得た。脱水後、熱風循環式乾燥機により１００℃で１２時間乾燥し、白色パウダー状の比較例３のポリカーボネート樹脂を得た。得られたポリカーボネート樹脂を用いて、前記の方法で各種評価を実施しその結果を表２に示した。
[Comparative Example 3]
A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 14876 parts of ion-exchanged water and 6612 parts of a 25% aqueous sodium hydroxide solution, and 3140 parts of BPA and 6.28 parts of hydrosulfite were dissolved as dihydric phenols. Then, 14050 parts of methylene chloride were added, and 1500 parts of phosgene were blown in at 16 to 24 ° C. for 70 minutes while stirring. Thereafter, 1102 parts of a 25% aqueous sodium hydroxide solution were added, and a solution in which 88.84 parts of p-tert-butylphenol was dissolved in 251 parts of methylene chloride was added and stirred to form an emulsified state. Under such stirring, 2.78 parts of triethylamine was added when the reaction solution was at 28 ° C., and the reaction was terminated when stirring was continued for 1 hour at a temperature of 26 to 31 ° C. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washing solution became neutral, it was washed with hydrochloric acid acid water. After that, it was repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was put into a kneader filled with warm water, and the solvent was evaporated while stirring to obtain a polycarbonate resin powder. After dehydration, it was dried at 100°C for 12 hours in a hot air circulation dryer to obtain a white powder-like polycarbonate resin of Comparative Example 3. Using the obtained polycarbonate resin, various evaluations were performed using the above-mentioned methods, and the results are shown in Table 2.
本発明のポリカーボネート樹脂は、耐傷付き性、耐熱性および成形性に優れるため、コーティング処理を必要とせず、室内照明用ランプレンズ、表示用メーターカバー、メーター文字板、各種スイッチカバー、ディスプレイカバー、ヒートコントロールパネル、インストルメントパネル、センタークラスター、センターパネル、ルームランプレンズ、ヘッドアップディスプレイ等の各種表示装置、保護部品、透光部品などの自動車内装部品に利用できる。 The polycarbonate resin of the present invention has excellent scratch resistance, heat resistance and moldability, so it does not require coating treatment and can be used for automobile interior parts such as lamp lenses for interior lighting, display meter covers, meter dials, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, various display devices such as head-up displays, protective parts, and translucent parts.
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