JP2004352807A - Flame-retardant polycarbonate resin composition - Google Patents
Flame-retardant polycarbonate resin composition Download PDFInfo
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- JP2004352807A JP2004352807A JP2003150385A JP2003150385A JP2004352807A JP 2004352807 A JP2004352807 A JP 2004352807A JP 2003150385 A JP2003150385 A JP 2003150385A JP 2003150385 A JP2003150385 A JP 2003150385A JP 2004352807 A JP2004352807 A JP 2004352807A
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- resin composition
- flame
- polycarbonate resin
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- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 40
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 40
- 239000003063 flame retardant Substances 0.000 title claims abstract description 34
- 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 title claims abstract description 31
- 125000003118 aryl group Chemical group 0.000 claims abstract description 44
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 36
- 239000004417 polycarbonate Substances 0.000 claims abstract description 36
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 13
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000011342 resin composition Substances 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 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 description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- PVHOFFUSCYNNNT-UHFFFAOYSA-N 4-[2-(2-methylpentan-3-yl)-6-propan-2-ylphenyl]phenol Chemical compound OC1=CC=C(C=C1)C1=C(C=CC=C1C(C)C)C(CC)C(C)C PVHOFFUSCYNNNT-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 claims 1
- 238000002493 microarray Methods 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 238000005476 soldering Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 9
- 238000011109 contamination Methods 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 33
- -1 phosphate ester Chemical class 0.000 description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000004973 liquid crystal related substance Substances 0.000 description 15
- 150000002989 phenols Chemical class 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 150000003014 phosphoric acid esters Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 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 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-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
- 239000000654 additive Substances 0.000 description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000004650 carbonic acid diesters Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 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
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 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 3
- 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
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- WJZHBPSXJJQGJO-UHFFFAOYSA-N 4-[2,6-di(propan-2-yl)phenyl]phenol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1C1=CC=C(O)C=C1 WJZHBPSXJJQGJO-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001721 carbon Chemical group 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
- 239000004927 clay Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Chemical class 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PXDJXZJSCPSGGI-UHFFFAOYSA-N palmityl palmitate Chemical compound CCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC PXDJXZJSCPSGGI-UHFFFAOYSA-N 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003578 releasing effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 125000001424 substituent group Chemical group 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
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 1
- 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
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- FDIPWBUDOCPIMH-UHFFFAOYSA-N 2-decylphenol Chemical compound CCCCCCCCCCC1=CC=CC=C1O FDIPWBUDOCPIMH-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- OPJWPPVYCOPDCM-UHFFFAOYSA-N 2-ethylhexyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)CCCC OPJWPPVYCOPDCM-UHFFFAOYSA-N 0.000 description 1
- HMWIHOZPGQRZLR-UHFFFAOYSA-N 2-hexadecylphenol Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1O HMWIHOZPGQRZLR-UHFFFAOYSA-N 0.000 description 1
- QEMHBAGGYKJNSS-UHFFFAOYSA-N 2-icosylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O QEMHBAGGYKJNSS-UHFFFAOYSA-N 0.000 description 1
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- JOONSONEBWTBLT-UHFFFAOYSA-N 2-tetradecylphenol Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1O JOONSONEBWTBLT-UHFFFAOYSA-N 0.000 description 1
- OREKREJVUNVFJP-UHFFFAOYSA-N 2-triacontylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O OREKREJVUNVFJP-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
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- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polarising Elements (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、難燃性ポリカーボネート樹脂組成物に関する。さらに詳しくは特定のリン酸エステル系難燃剤を配合した耐熱性の良好な、成形時揮発分が少なく金型汚れのない難燃性ポリカーボネート樹脂組成物に関する。
【０００２】
【従来の技術】
従来、ビスフェノールＡにカーボネート前駆物質を反応させて得られるポリカーボネート樹脂は透明性、耐熱性、機械的特性、寸法安定性が優れているがゆえにエンジニアリングプラスチックとして多くの分野に広く使用されている。特に透明性に優れることから光学材料としての用途も多く、自動車ランプレンズ、照明グローブ、各種光学レンズ、クレージング用途等に使用されている。また、近年液晶ディスプレーの液晶基板用フィルムや位相差フィルム用途にも使用されている。しかしながら、ポリカーボネート樹脂は自己消火性ではあるが、より難燃性が必要とされる用途には、従来よりハロゲン化合物、リン化合物、スルホン酸金属塩などの難燃剤を配合した難燃組成物が使われてきた。ハロゲン化合物の添加は燃焼時の有毒ガスの問題や金型腐食の問題から、近年ではノンハロゲン化が望まれている。リン酸エステル系の難燃剤には、モノマータイプでは揮発性、金型汚染性の問題があり、この改善がなされてきた（例えば特許文献１〜４参照）。しかしながら、未だ十分ではない。
【０００３】
また、殊に熱源に近い位置で用いられる光学部品や液晶ディスプレーに用いるフィルムでは配向膜形成プロセスや電極形成プロセス等で１８０℃以上の高温処理を必要とするため、通常のビスフェノールＡからのポリカーボネート樹脂ではその耐熱性が不足するという問題がある。
【０００４】
ポリカーボネート樹脂の耐熱性を向上するためには、一般的に嵩高い動きにくい構造を有するビスフェノール類を用いる方法があり、種々のポリカーボネートが提案されている。中でも、特定のフルオレン構造を有するポリカーボネート樹脂が提案されている（例えば特許文献５，６参照）。しかしながら、これらの構造を有するポリカーボネート樹脂は耐熱性に優れるものの難燃性が十分ではなく、電気・電子部品用途に用いる場合には問題があった。
【０００５】
【特許文献１】
特開平７−３０４９４３号公報
【特許文献２】
特開平８−１２８１１号公報
【特許文献３】
特開平８−２５３６６６号公報
【特許文献４】
特開平８−３２５４４９号公報
【特許文献５】
特開平１１−１７４４２４号公報
【特許文献６】
特開平８−１３４１９８号公報
【０００６】
【発明が解決しようとする課題】
本発明の目的は、難燃性に優れ、揮発性も少なく、耐金型汚染性にも優れた耐熱性の良好な難燃性芳香族ポリカーボネート樹脂組成物を提供することにある。
【０００７】
本発明者はこの目的を達成せんとして鋭意研究を重ねた結果、特定の二価フェノールを使用することにより得られた芳香族ポリカーボネート共重合体を主成分とする組成物に特定の有機リン系難燃剤を配合することによって、耐熱性の良好な、優れた難燃性ポリカーボネート樹脂組成物が得られることを見出し、本発明に到達した。
【０００８】
【課題を解決するための手段】
すなわち、本発明によれば、全芳香族ジヒドロキシ成分の５〜９５モル％が９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９５〜５モル％が下記一般式［１］
【０００９】
【化３】
［式中、Ｒ１〜Ｒ４は夫々独立して水素原子、炭素原子数１〜９の芳香族基を含んでもよい炭化水素基又はハロゲンであり、Ｗは単結合、炭素原子数１〜２０の芳香族基を含んでもよい炭化水素基、Ｏ、Ｓ、ＳＯ、ＳＯ２、ＣＯ又はＣＯＯ基である。］
で表されるジヒドロキシ成分からなるポリカーボネート共重合体を主成分とする熱可塑性樹脂組成物に、一般式［２］
【００１１】
【化４】
［式中、Ｒ５〜Ｒ８は１価の芳香族基または脂肪族基、Ｘは２価の芳香族基、ｎは１〜１５を示す］で表される縮合リン酸エステルをポリカーボネート組成物に対して０．１〜２０重量％配合してなる難燃性ポリカーボネート樹脂組成物が提供される。
【００１３】
本発明の難燃性ポリカーボネート樹脂組成物を構成する芳香族ポリカーボネート共重合体は、それを構成する芳香族ジヒドロキシ成分として、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンが全芳香族ジヒドロキシ成分の５〜９５モル％、好ましくは１０〜９５モル％、さらに好ましくは３０〜８５モル％である。５モル％未満の場合、本発明の目的である耐熱用材料として不満足な性質となり好ましくない。
【００１４】
前記９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンは、その１０ｇをエタノール５０ｍｌに溶解した溶液を光路長３０ｍｍで測定したｂ値が好ましくは６．０以下、より好ましくは５．５以下であり、さらに好ましくは５．０以下である。ｂ値が上記範囲内であれば、得られるポリカーボネート共重合体から形成されるフィルムは色相および耐侯性に優れ、また、フィルム強度が高く、延伸フィルム特性が良好となり好ましい。
【００１５】
通常、この９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンはｏ−クレゾールとフルオレノンの反応によって得られる。前記特定のｂ値を有する９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンは、特定の処理を行い不純物を除去することによって得ることができる。具体的には、ｏ−クレゾールとフルオレノンの反応後に、未反応のｏ−クレゾールを留去した後、残さをアルコール系、ケトン系またはベンゼン誘導体系の溶媒に溶解し、これに活性白土または活性炭を加えてろ過後、ろ液から結晶化した生成物をろ過して精製された９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンを得ることができる。除去される不純物としては、２，４′−ジヒドロキシ体、２，２′−ジヒドロキシ体および構造不明の不純物等である。かかる精製に用いるアルコール系の溶媒としてはメタノール、エタノール、プロパノール、ブタノール等の低級アルコール、ケトン系の溶媒としてはアセトン、メチルエチルケトン、メチルイソプロピルケトン、シクロヘキサノン等の低級脂肪族ケトン類およびこれらの混合物が好ましく、ベンゼン誘導体系の溶媒としてはトルエン、キシレン、ベンゼンおよびこれらの混合物が好ましい。溶媒の使用量はフルオレン化合物が十分に溶解する量であれば足り、通常フルオレン化合物に対して２〜１０倍量程度である。活性白土としては市販されている粉末状または粒状のシリカ−アルミナを主成分とするものが用いられる。また、活性炭としては市販されている粉末状または粒状のものが用いられる。
【００１６】
本発明の難燃性ポリカーボネート樹脂組成物を構成する芳香族ポリカーボネート共重合体において用いられる前記一般式［１］で示される他のジヒドロキシ成分としては、通常芳香族ポリカーボネートのジヒドロキシ成分として使用されているものであればよく、例えばハイドロキノン、レゾルシノール、４，４′−ビフェノール、１，１−ビス（４−ヒドロキシフェニル）エタン（ビスフェノールＥ）、２，２−ビス（４−ヒドロキシフェニル）プロパン（ビスフェノールＡ）、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン（ビスフェノールＣ）、２，２−ビス（４−ヒドロキシフェニル）ブタン、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン（ビスフェノールＺ）、１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン、２，２−ビス（４−ヒドロキシフェニル）ペンタン、４，４′−（ｐ−フェニレンジイソプロピリデン）ジフェノール、α，α′−ビス（４−ヒドロキシフェニル）−ｍ−ジイソプロピルベンゼン（ビスフェノールＭ）、１，１−ビス（４−ヒドロキシフェニル）−４−イソプロピルシクロヘキサンなどが挙げられ、なかでもビスフェノールＡ、ビスフェノールＺ、ビスフェノールＣ、ビスフェノールＥ、ビスフェノールＭが好ましく、特にビスフェノールＡが好ましい。
【００１７】
該芳香族ポリカーボネート共重合体はそのポリマーを塩化メチレンに溶解した溶液での２０℃における比粘度が０．２〜１．２の範囲が好ましく、０．２５〜１．０の範囲がより好ましく、０．２７〜０．８０の範囲がさらに好ましい。比粘度が上記範囲内であれば成形品、殊にフィルムの強度が十分強く、溶融粘度および溶液粘度が適当で、取り扱いが容易であり好ましい。
【００１８】
本発明の難燃性ポリカーボネート樹脂組成物を構成する芳香族ポリカーボネート共重合体は、通常の芳香族ポリカーボネート樹脂を製造するそれ自体公知の反応手段、例えば芳香族ジヒドロキシ成分にホスゲンや炭酸ジエステルなどのカーボネート前駆物質を反応させる方法により製造される。次にこれらの製造方法について基本的な手段を簡単に説明する。
【００１９】
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、水酸化カリウムなどのアルカリ金属水酸化物またはピリジンなど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、クロロベンゼンなど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など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。
【００２０】
カーボネート前駆物質として炭酸ジエステルを用いるエステル交換反応は、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などにより異なるが、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。
【００２１】
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などが挙げられる。これらのうち特にジフェニルカーボネートが好ましい。
【００２２】
本発明の難燃性ポリカーボネート樹脂組成物を構成する芳香族ポリカーボネート共重合体は、その重合反応において、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、また得られた芳香族ポリカーボネート共重合体は、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。
【００２３】
かかる単官能フェノール類としては、芳香族ポリカーボネート樹脂の末端停止剤として使用されるものであればよく、一般にはフェノール或いは低級アルキル置換フェノールであって、下記一般式で表される単官能フェノール類を示すことができる。
【００２４】
【化５】
［式中、Ａは水素原子、炭素数１〜９の直鎖または分岐のアルキル基あるいはアリールアルキル基であり、ｒは１〜５、好ましくは１〜３の整数である。］
【００２６】
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、ｐ−ｔｅｒｔ−ブチルフェノール、ｐ−クミルフェノールおよびイソオクチルフェノールが挙げられる。
【００２７】
また、他の単官能フェノール類としては、長鎖のアルキル基或いは脂肪族エステル基を置換基として有するフェノール類または安息香酸クロライド類、もしくは長鎖のアルキルカルボン酸クロライド類を使用することができ、これらを用いて芳香族ポリカーボネート共重合体の末端を封鎖すると、これらは末端停止剤または分子量調節剤として機能するのみならず、樹脂の溶融流動性が改良され、成形加工が容易となるばかりでなく、物性も改良される。特に樹脂の吸水率を低くする効果があり、好ましく使用される。これらは下記一般式［Ｉ−ａ］〜［Ｉ−ｈ］で表される。
【００２８】
【化６】
【化７】
【化８】
【化９】
【化１０】
【化１１】
【化１２】
【化１３】
［前記一般式［Ｉ−ａ］〜［Ｉ−ｈ］中、Ｘは−Ｒ−Ｏ−、−Ｒ−ＣＯ−Ｏ−または−Ｒ−Ｏ−ＣＯ−である、ここでＲは単結合または炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、Ｔは単結合または上記Ｘと同様の結合を示し、ｎは１０〜５０の整数を示す。
Ｑはハロゲン原子または炭素数１〜１０、好ましくは１〜５の一価の脂肪族炭化水素基を示し、ｐは０〜４の整数を示し、Ｙは炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、Ｗ１は水素原子、−ＣＯ−Ｒ１７、−ＣＯ−Ｏ−Ｒ１８またはＲ１９である、ここでＲ１７、Ｒ１８およびＲ１９は、それぞれ炭素数１〜１０、好ましくは１〜５の一価の脂肪族炭化水素基、炭素数４〜８、好ましくは５〜６の一価の脂環族炭化水素基または炭素数６〜１５、好ましくは６〜１２の一価の芳香族炭化水素基を示す。
ａは４〜２０、好ましくは５〜１０の整数を示し、ｍは１〜１００、好ましくは３〜６０、特に好ましくは４〜５０の整数を示し、Ｚは単結合または炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、Ｗ２は水素原子、炭素数１〜１０、好ましくは１〜５の一価の脂肪族炭化水素基、炭素数４〜８、好ましくは５〜６の一価の脂環族炭化水素基または炭素数６〜１５、好ましくは６〜１２の一価の芳香族炭化水素基を示す。］
【００３７】
これらのうち好ましいのは、［Ｉ−ａ］および［Ｉ−ｂ］の置換フェノール類である。この［Ｉ−ａ］の置換フェノール類としては、ｎが１０〜３０、特に１０〜２６のものが好ましく、その具体例としては、例えばデシルフェノール、ドデシルフェノール、テトラデシルフェノール、ヘキサデシルフェノール、オクタデシルフェノール、エイコシルフェノール、ドコシルフェノールおよびトリアコンチルフェノールなどを挙げることができる。
【００３８】
また、［Ｉ−ｂ］の置換フェノール類としてはＸが−Ｒ−ＣＯ−Ｏ−であり、Ｒが単結合である化合物が適当であり、ｎが１０〜３０、特に１０〜２６のものが好適であって、その具体例としては、例えばヒドロキシ安息香酸デシル、ヒドロキシ安息香酸ドデシル、ヒドロキシ安息香酸テトラデシル、ヒドロキシ安息香酸ヘキサデシル、ヒドロキシ安息香酸エイコシル、ヒドロキシ安息香酸ドコシルおよびヒドロキシ安息香酸トリアコンチルが挙げられる。
【００３９】
前記一般式［Ｉ−ａ］〜［Ｉ−ｇ］で示される置換フェノール類または置換安息香酸クロライドにおいて置換基の位置は、ｐ位またはｏ位が一般的に好ましく、その両者の混合物が好ましい。
【００４０】
前記単官能フェノール類は、得られた芳香族ポリカーボネート共重合体の全末端に対して少なくとも５モル％、好ましくは少なくとも１０モル％末端に導入されることが望ましく、また単官能フェノール類は単独でもしくは２種以上混合して使用してもよい。
【００４１】
また、本発明の芳香族ポリカーボネート共重合体において、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンが、全芳香族ヒドロキシ成分の６０モル％以上である場合は、樹脂の流動性が低下することがあり、そのため前記一般式［Ｉ−ａ］〜［Ｉ−ｇ］で示される置換フェノール類または置換安息香酸クロライド類を末端停止剤として使用することが好ましい。
【００４２】
本発明の芳香族ポリカーボネート共重合体は、本発明の趣旨を損なわない範囲で、芳香族ジカルボン酸、例えばテレフタル酸、イソフタル酸、ナフタレンジカルボン酸あるいはその誘導体を共重合したポリエステルカーボネートであってもよい。また少量の３官能化合物を共重合した分岐ポリカーボネートであってもよい。
【００４３】
本発明の難燃性ポリカーボネート樹脂組成物を構成する芳香族ポリカーボネート共重合体は、そのガラス転移点が１６０℃以上が好ましく、１８０℃以上がより好ましく、２００℃以上がさらに好ましい。
【００４４】
本発明で難燃剤として用いられる縮合リン酸エステルは、前記一般式［２］で示されるものである。好ましくはＲ５〜Ｒ８が芳香環でＸがフェニレンプロピリデンフェニレン残基のものである。かかるビスフェノールＡジフェニルエーテル系縮合リン酸エステルはリン含量が高いため難燃性が良好であり、揮発性もなく、金型汚染性もない。また耐加水分解性も良好であるため、それを含む樹脂も長期の品質保持性にも優れる。ｎは１〜１５、好ましくは１〜５である。また、これらは異なる２種以上の縮合リン酸エステルを混合して用いてもよい。これらの縮合リン酸エステルは全組成物重量に対して０．１〜２０重量％、好ましくは１〜１５重量％、より好ましくは３〜１０重量％配合される。
【００４５】
さらに、難燃性を高めるために、補助難燃剤として炭素原子数６〜３０の芳香族スルホン酸塩又は炭素原子数３〜３０のフッ素置換してもよい脂肪族スルホン酸塩又は炭素原子数８〜３０の脂肪族硫酸エステル塩を配合しても良い。これらの補助難燃剤は全組成物重量に対して０．００１〜１重量％、好ましくは０．０１〜０．５重量％、より好ましくは０．０３〜０．１重量％配合される。
【００４６】
本発明の難燃性ポリカーボネート樹脂組成物は、燃焼時のドリップを防止するためにドリップ防止剤を含むことが好ましい。中でもフィブリル形成能を有する含フッ素ポリマーが好ましく、テトラフルオロエチレン系ポリマーが好ましい。その混合割合は、全組成物重量に対して０．０１〜５重量％、好ましくは０．１〜１．５重量％である。
【００４７】
本発明では、ブルーイング剤を用いてもよく、かかるブルーイング剤としては、例えばバイエル（株）製のマクロレックスバイオレット、三菱化学（株）製のダイアレジンバイオレット、ダイアレジンブルー、サンド（株）製のテラゾールブルー等が挙げられ、最も好適なものとしてマクロレックスバイオレットが挙げられる。これらのブルーイング剤は好ましくは０．１〜３ｐｐｍ、より好ましくは０．３〜１．５ｐｐｍ、最も好ましくは０．３〜１．２ｐｐｍの濃度で芳香族ポリカーボネート樹脂中に配合される。
【００４８】
本発明の難燃性ポリカーボネート樹脂組成物には必要に応じて、リン酸、亜リン酸、ホスホン酸、亜ホスホン酸およびこれらのエステルよりなる群から選択された少なくとも１種のリン化合物を配合することができる。かかるリン化合物の配合量は、該組成物に対して０．０００１〜０．０５重量％が好ましく、０．０００５〜０．０２重量％がより好ましく、０．００１〜０．０１重量％が特に好ましい。このリン化合物を配合することにより、該組成物の熱安定性が向上し、成形時における分子量の低下や色相の悪化が防止される。
【００４９】
かかるリン化合物としては、リン酸、亜リン酸、ホスホン酸、亜ホスホン酸およびこれらのエステルよりなる群から選択される少なくとも１種のリン化合物であり、好ましくは下記一般式
【００５０】
【化１４】
【化１５】
【化１６】
【化１７】
［式中、Ｒ５〜Ｒ１６は、それぞれ独立して、水素原子、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ドデシル、ヘキサデシル、オクタデシルなどの炭素数１〜２０のアルキル基、フェニル、トリル、ナフチルなどの炭素数６〜１５のアリール基またはベンジル、フェネチルなどの炭素数７〜１８のアラルキル基を表し、また１つの化合物中に２つのアルキル基が存在する場合は、その２つのアルキル基は互いに結合して環を形成していてもよい。］
よりなる群から選択された少なくとも１種のリン化合物である。
【００５５】
上記（１）式で示されるリン化合物としては、例えばトリフェニルホスファイト、トリスノニルフェニルホスファイト、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジデシルモノフェニルホスファイト、ジオクチルモノフェニルホスファイト、ジイソプロピルモノフェニルホスファイト、モノブチルジフェニルホスファイト、モノデシルジフェニルホスファイト、モノオクチルジフェニルホスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、２，２−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）オクチルホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイトなどが挙げられる。
【００５６】
上記（２）式で示されるリン化合物としては、例えばトリブチルホスフェート、トリメチルホスフェート、トリフェニルホスフェート、トリエチルホスフェート、ジフェニルモノオルソキセニルホスフェート、ジブチルホスフェート、ジオクチルホスフェート、ジイソプロピルホスフェートなどが挙げられ、上記（３）式で示されるリン化合物としては、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４−ジフェニレンホスホナイトなどが挙げられ、また上記（４）式で示される化合物としては、ベンゼンホスホン酸ジメチル、ベンゼンホスホン酸ジエチル、ベンゼンホスホン酸ジプロピルなどが挙げられる。
【００５７】
これらのリン化合物のなかで、トリスノニルフェニルホスファイト、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４−ジフェニレンホスホナイトが好ましく使用される。
【００５８】
本発明の難燃性ポリカーボネート樹脂組成物には、酸化防止の目的で通常知られた酸化防止剤を添加することができる。その例としてはフェノール系酸化防止剤を示すことができ、具体的には例えばトリエチレングリコール−ビス［３−（３−ｔｅｒｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］、１，６−ヘキサンジオール−ビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、ペンタエリスリトール−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、Ｎ，Ｎ−ヘキサメチレンビス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシ−ヒドロシンナマイド）、３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシ−ベンジルホスホネート−ジエチルエステル、トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、３，９−ビス｛１，１−ジメチル−２−［β−（３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］エチル｝−２，４，８，１０−テトラオキサスピロ（５，５）ウンデカン等が挙げられる。これら酸化防止剤の好ましい添加量の範囲は該組成物に対して０．０００１〜０．０５重量％である。
【００５９】
さらに本発明の難燃性ポリカーボネート樹脂組成物には、必要に応じて一価または多価アルコールの高級脂肪酸エステルを加えることもできる。
【００６０】
かかる高級脂肪酸エステルとしては、炭素原子数１〜２０の一価または多価アルコールと炭素原子数１０〜３０の飽和脂肪酸との部分エステルまたは全エステルであるのが好ましい。また、かかる一価または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、プロピレングリコールモノステアレート、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、２−エチルヘキシルステアレートなどが挙げられ、なかでも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好ましく用いられる。
【００６１】
かかるアルコールと高級脂肪酸とのエステルの配合量は、該芳香族ポリカーボネート共重合体に対して０．０１〜２重量％が好ましく、０．０１５〜０．５重量％がより好ましく、０．０２〜０．２重量％がさらに好ましい。配合量がこの範囲内であれば離型性に優れ、また離型剤がマイグレートし金属表面に付着することもなく好ましい。
【００６２】
本発明の難燃性ポリカーボネート樹脂組成物には、さらにＵＶ吸収剤、着色剤、帯電防止剤、滑剤、充填剤などの添加剤や他のポリカーボネート樹脂、他の熱可塑性樹脂を本発明の目的を損なわない範囲で少割合添加することもできる。
【００６３】
本発明の難燃性ポリカーボネート樹脂組成物を製造するには、任意の方法が採用される。例えば前記芳香族ポリカーボネート樹脂に各種添加剤を加え、Ｖ型ブレンダー、ヘンシェルミキサー、メカノケミカル装置、押出混合機などの予備混合手段を用いて十分に混合した後、場合により押出造粒機やブリケッティングマシーン等により造粒を行い、その後ベント式２軸ルーダーに代表される溶融混練機で押し出しペレット化する方法が挙げられる。また、各成分をそれぞれ独立にベント式２軸押出機に供給する方法や、各成分の一部を予備混合した後、残りの成分と独立に溶融混練機に供給する方法なども挙げられる。また、添加剤のマスターバッチを作製した後混合する方法も用いられる。
【００６４】
本発明の縮合リン酸エステルは、縮合度によっては液状または水飴状となる。従って押出機への供給に液注または液添装置を使用する方法が採用される。そのため、本発明で使用される押出機は、押出方向に対して、上流側と下流側に２つ以上の原料供給口を持つものが好ましく、その場合、縮合リン酸エステルの添加は、最も下流側の原料供給口から供給することが熱履歴を少なくする点で好ましい。また、かかる縮合リン酸エステルの添加は、押出機のバレルに設けたフィード口から、ギアポンプ等の公知の液体運搬装置で押出機内の吐出圧以上の圧力で供給する。その際粘度を下げるために通常５０〜１００℃に加熱する。１００℃以上では長期間には、該リン酸エステルの揮発、劣化、分解を引き起こす場合があるので好ましくない。
【００６５】
本発明の芳香族ポリカーボネート樹脂組成物から成形品を得る方法としては、射出成形、押し出し成形、ブロー成形等が用いられ、フィルムやシートを製造する方法としては、厚みの均一性に優れ、ゲル、ブツ、フィッシュアイ、スクラッチ等の光学欠点の生じない方法が好ましく、例えば溶剤キャスト法、溶融押出し法、カレンダー法等が挙げられる。
【００６６】
かかる方法により製造された成形品は各種グレージング用途、自動車ランプレンズ、ランプカバー、光学レンズ、ＯＨＰシート、銘板、表示灯等に用いられる。またかかる方法により製造されたフィルムはフラットパネルディスプレイ基板用途としてプラセル基板や位相差フィルムとして好適に用いられる。プラセル基板は未延伸で用いるが位相差フィルムとして用いるためには、最適な複屈折特性を有するよう少なくとも一軸方向に延伸配向して位相差フィルムにする。
【００６７】
一軸延伸方法としてはテンター法による横一軸延伸、ロール間による縦一軸延伸、ロール間圧延法等の任意の方法を用いることができる。延伸温度は用いる樹脂のガラス転移温度をＴｇとして、Ｔｇ−５０℃以上、Ｔｇ＋２０℃以下が好ましく、Ｔｇ−３０℃以上、Ｔｇ＋１０℃以下がより好ましい。かかる範囲の温度で延伸することにより、ポリマー分子の運動が凍結されることなく均一配向が容易になり好ましく、また、ポリマーの分子運動が適度であり、延伸による配向の緩和が起り難く、所望した配向度が得られ易く配向抑制が容易になり好ましい。
【００６８】
また、延伸倍率は目的とするフィルムのリターデーションの大きさに応じて適宜選択すればよい。この値は、延伸温度、膜厚にも依存する。一般に厚膜では延伸倍率は小さくともよく、薄膜では大きくとる必要が有る。ＳＴＮ型液晶ディスプレーに用いる位相差板のリターデーションの値は、一般には４００〜６５０ｎｍの範囲が用いられる。更にリターデーションの振れ幅は１０％以下が好ましく、５％以下が特に好ましい。リターデーションの振れ幅が大きくなりすぎると色補償の偏差が生じ、色むらになりやすい。
【００６９】
位相差フィルムはバリヤー層およびインジウム、酸化スズをターゲットとした液晶用透明電極を形成した後、偏向板に積層して複合偏向板として好ましく用いられる。この複合偏向板は、通常の偏向板の光学軸と位相差フィルムの光学軸を４０〜５０度の範囲で単層または複層張り合わせることにより形成できる。この複合偏向板は耐熱耐久性に優れ、リターデーションの経時変化が少ない等の優れた特徴を有する。
【００７０】
また、延伸フィルム特性の一つにフィルム面内方向の屈折率ｎｘとｎｙの平均値と厚み方向の屈折率ｎｚの差の絶対値とフィルム厚みｔ（ｎｍ）の積で規定されるＫ値＝｜（ｎｘ＋ｎｙ）／２−ｎｚ｜×ｔがあり、Ｋ値が大きくなると液晶表示素子として用いた場合に表示が浮いて見える等視野角が狭くなるため、この値は１２０ｎｍ以下に押さえるのが好ましい。
【００７１】
また、液晶セルの片面または両面に偏向板を配置した液晶表示パネルは、視面側の偏向板と液晶セルの間に前記位相差フィルムを配することにより、液晶の複屈折による着色を解消した白黒表示の液晶表示パネルを形成することができ、更に白黒表示用液晶パネルにカラーマスクを被せＲＧＢの３色を発色させることによりフルカラーの液晶表示パネルを形成することができる。
【００７２】
本発明の難燃性ポリカーボネート樹脂組成物から形成されたフィルムは、フィルム強度に優れ、耐熱性、色相も良好であり、例えばかかる芳香族ポリカーボネート樹脂組成物を塩化メチレン、ジオキソラン、トルエン、ジオキサン等の有機溶媒に溶解し、キャスティングフィルムを成形して、このフィルムの両面にガスバリヤー膜、耐溶剤膜を付けたり、透明導電膜や偏光板と共に液晶基板用フィルム（プラセル基板）または位相差フィルム等の液晶ディスプレー用フィルムとして好適に用いられ、具体的には、ポケベル、携帯電話、ハンディーターミナル、種々の表示素子等に有利に使用することができる。
【００７３】
【実施例】
以下に実施例を挙げて本発明をさらに説明する。実施例中の部は重量部であり、％は重量％である。なお、評価は下記の方法によった。
（１）比粘度：ポリマー０．７ｇを塩化メチレン１００ｍｌに溶解し２０℃の温度で測定した。
（２）ガラス転移点（Ｔｇ）：デュポン社製９１０型ＤＳＣにより測定した。
（３）モノマー溶液のｂ値：試料１０ｇを５０ｍｌのエタノールに溶解し光路長３０ｍｍの試料管にて日本電色（株）色差計３００Ａを用いて測定した。
（４）難燃性：ＵＬ９４Ｖに準拠して厚み１．６ｍｍにおける燃焼試験を実施した。
（５）金型汚染性：ファナック（株）製Ｔ−１５０Ｄ射出成形機を用いて縦１００ｍｍ×横１５０ｍｍ×高さ１５ｍｍの箱型成形品を、射出圧力８００ｋｇ／ｃｍ２でほぼ良好な成形品が得られるシリンダー温度および金型温度７０℃で連続成形し、１００ショット毎に金型表面の付着物の有無を確認し、付着物が発生したショット数をカウントした。
（６）耐熱性：１８０±１℃に温度調節された熱風循環式オーブンに上記箱型成形品を入れ、２４時間放置後の成形品に変形が見られるか否かを目視チェックした。変形があった場合は×、変形がない場合は○とした。
【００７４】
［合成例１］
温度計、撹拌機、還流冷却器付き反応器にイオン交換水２４６２３部、４８％水酸化ナトリウム水溶液４１５３部を入れ、エタノール溶液でのｂ値が３．０の９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン（以下“ビスクレゾールフルオレン”と略称することがある）１９３６．９部、２，２−ビス（４−ヒドロキシフェニル）プロパン（以下“ビスフェノールＡ”と略称することがある）２７２６部およびハイドロサルファイト８部を溶解した後、塩化メチレン１８１８８部を加えた後撹拌下１５〜２５℃でホスゲン１９９４部を６０分を要して吹き込んだ。ホスゲン吹き込み終了後、ｐ−ｔｅｒｔ−ブチルフェノール１０２．５部を塩化メチレン３３０部に溶解した溶液および４８％水酸化ナトリウム水溶液６９２．１部を加え、乳化後、トリエチルアミン５．８部を加えて２８〜３３℃で１時間撹拌して反応を終了した。反応終了後、生成物を塩化メチレンで希釈して水洗したのち塩酸酸性にして水洗し、水相の導電率がイオン交換水と殆ど同じになったところで、塩化メチレン相を濃縮、脱水してポリカーボネート濃度が２０％の溶液を得た。この溶液から溶媒を除去して得たポリカーボネートはビスクレゾールフルオレンとビスフェノールＡとの構成単位の比がモル比で３０：７０であった（ポリマー収率９７％）。またこのポリマーの比粘度は０．３３７、Ｔｇは１９０℃であった。このポリマーをポリカーボネートＡとする。
【００７５】
［合成例２］
合成例１のビスクレゾールフルオレンの使用量を３１７１．４部、ビスフェノールＡの使用量を１９１３部とする以外は合成例１と同様にしてビスクレゾールフルオレンとビスフェノールＡの比がモル比で５０：５０であるポリマー５３００部（収率９６％）を得た。このポリマーの比粘度は０．３２０、Ｔｇは２０５℃であった。このポリマーをポリカーボネートＢとする。
【００７６】
［合成例３］
合成例１と同様の装置にイオン交換水３５３１５部、４８％水酸化ナトリウム３９２０部を入れ、α，α’−ビス（４−ヒドロキシフェニル）−ｍ−ジイソプロピルベンゼン（ビスフェノールＭと略称）２９５４．９部、ビスクレゾールフルオレン３２２８．１部およびハイドロサルファイト１４部を溶解した後、塩化メチレン１２７７５部を加え、攪拌下１５〜２０℃でホスゲン１９４６部を４５分を要して吹き込んだ。ホスゲン吹き込み終了後、ｐ−ｔｅｒｔ−ブチルフェノール１０８．５部と４８％水酸化ナトリウム水溶液７１０．５部を加え乳化後、トリエチルアミン４．５５部を加えて、２８〜３３℃で１時間攪拌して反応を終了した。このものを実施例１と同様に処理してビスフェノールＭとビスクレゾールフルオレン構成単位のモル比が５０：５０であるポリマーを得た（収率９８％）。このものの比粘度は０．２５０、Ｔｇは１８０℃であった。このポリマーをポリカーボネートＣとする。
【００７７】
［合成例４］
合成例１のビスクレゾールフルオレンを使用せず、ビスフェノールＡを３８９４．２部用いた以外は、合成例１と同様にして、ビスフェノールＡホモポリカーボネートを得た（収率９９％）。このものの比粘度は０．３６５、Ｔｇは１４８℃であった。このポリマーをポリカーボネートＤとする。
【００７８】
［実施例１］
合成例１で得たポリカーボネートＡ１００部に、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト０．０５部、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート０．０１部、ペンタエリスリトールテトラステアレート０．０３部加えて、ベント付き２軸押出機の第１供給口に定量供給機にて供給した。一方縮合リン酸エステル（大八化学工業（株）製「ＣＲ−７４１」）は８０℃に加熱した状態で液注装置（富士テクノ工業（株）製ＨＹＭ−ＪＳ−０８）を用いてシリンダー途中の第３供給口（第２供給口とベント排気口との間に位置）から、それぞれ所定の割合になるよう押出機に定量供給した。シリンダー温度２７０〜３００℃でペレット化した後、ＪＳＷ（株）製Ｎ−２０Ｃ射出成形機を用いてＵＬ９４Ｖの厚み１．６ｍｍの試験片に射出成形し、ＵＬ９４Ｖに準拠して評価した。また、金型汚染性も評価した。結果を表１．に示す。
【００７９】
［実施例２］
実施例１のポリカーボネートをポリカーボネートＢとした以外は実施例１と同様にして試験片を得、同様にテストした結果を表１．に示す。
【００８０】
［実施例３］
実施例１のポリカーボネートをポリカーボネートＣとした以外は実施例１と同様にしてテストした結果を表１．に示す。
【００８１】
［実施例４］
実施例１のポリカーボネートＡにポリテトラフルオロエチレン（ダイキン工業（株）製Ｆ２０１Ｌ）を０．３部加えた以外は実施例１と同様にしてテストをした結果を表１．に示す。
【００８２】
［比較例１］
実施例１の縮合リン酸エステルをトリフェニルホスフェート（大八化学（株）製ＴＰＰ）に変えた以外は実施例１と同様の方法でテストをした結果を表１．に示す。
【００８３】
［比較例２］
実施例２の縮合リン酸エステルを上記トリフェニルホスフェートとした以外は実施例２と同様の方法でテストをした結果を表１．に示す。
【００８４】
［比較例３］
実施例１のポリカーボネートをポリカーボネートＤとした以外は実施例１と同様の方法でテストをした結果を表１．に示す。
【００８５】
【表１】
【発明の効果】
本発明の耐熱性の良好な、耐金型汚染性にも優れた難燃性ポリカーボネート樹脂組成物は、耐熱性の要求される電気・電子用途、光学用途の各種成形品、シート、フィルム等に好適に用いられる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a flame retardant polycarbonate resin composition. More specifically, the present invention relates to a flame-retardant polycarbonate resin composition containing a specific phosphate ester-based flame retardant, having good heat resistance, having a small amount of volatile matter during molding and free from mold contamination.
[0002]
[Prior art]
Conventionally, polycarbonate resins obtained by reacting bisphenol A with a carbonate precursor have been widely used in many fields as engineering plastics because of their excellent transparency, heat resistance, mechanical properties, and dimensional stability. In particular, it has many uses as an optical material because of its excellent transparency, and is used for automotive lamp lenses, lighting gloves, various optical lenses, crazing applications, and the like. In recent years, it has also been used for liquid crystal substrate films and retardation films for liquid crystal displays. However, for applications where polycarbonate resin is self-extinguishing but requires more flame retardancy, a flame retardant composition containing a flame retardant such as a halogen compound, a phosphorus compound, or a metal salt of sulfonic acid has conventionally been used. I have been. In recent years, the addition of halogen compounds has been desired to be non-halogenated due to the problem of toxic gas during combustion and the problem of mold corrosion. Phosphate ester-based flame retardants have problems of volatility and mold contamination in the monomer type, and such improvements have been made (for example, see Patent Documents 1 to 4). However, it is not enough.
[0003]
Further, in particular, in the case of a film used for an optical component or a liquid crystal display used near a heat source, a high temperature treatment of 180 ° C. or more is required in an alignment film forming process, an electrode forming process, and the like. However, there is a problem that the heat resistance is insufficient.
[0004]
In order to improve the heat resistance of the polycarbonate resin, there is generally a method using a bisphenol having a bulky and hard-moving structure, and various polycarbonates have been proposed. Among them, polycarbonate resins having a specific fluorene structure have been proposed (for example, see Patent Documents 5 and 6). However, although polycarbonate resins having these structures are excellent in heat resistance, they do not have sufficient flame retardancy, and have a problem when used for electric / electronic parts.
[0005]
[Patent Document 1]
JP-A-7-304943 [Patent Document 2]
JP-A-8-12811 [Patent Document 3]
JP-A-8-253666 [Patent Document 4]
JP-A-8-325449 [Patent Document 5]
JP-A-11-174424 [Patent Document 6]
JP-A-8-134198 [0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a flame-retardant aromatic polycarbonate resin composition having excellent flame retardancy, low volatility, and excellent mold heat resistance and excellent heat resistance.
[0007]
The present inventors have conducted intensive studies to achieve this object, and as a result, have found that a composition containing an aromatic polycarbonate copolymer as a main component obtained by using a specific dihydric phenol has a specific organic phosphorus-based difficulty. The inventor has found that by adding a flame retardant, an excellent flame-retardant polycarbonate resin composition having good heat resistance can be obtained, and the present invention has been achieved.
[0008]
[Means for Solving the Problems]
That is, according to the present invention, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene accounts for 5 to 95 mol% of the wholly aromatic dihydroxy component, and 95 to 5 mol% of the following general formula [1]:
[0009]
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[Wherein, R 1 to R 4 are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms or halogen, W is a single bond, 1 to 20 carbon atoms. And O, S, SO, SO 2 , CO and COO groups which may contain an aromatic group. ]
A thermoplastic resin composition comprising a polycarbonate copolymer comprising a dihydroxy component represented by the following formula:
[0011]
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[Wherein, R 5 to R 8 are a monovalent aromatic group or an aliphatic group, X is a divalent aromatic group, and n is from 1 to 15]. And a flame retardant polycarbonate resin composition which is blended in an amount of 0.1 to 20% by weight based on the weight of the composition.
[0013]
The aromatic polycarbonate copolymer constituting the flame-retardant polycarbonate resin composition of the present invention has 9,9-bis (4-hydroxy-3-methylphenyl) fluorene as the aromatic dihydroxy component constituting the aromatic polycarbonate copolymer. It is from 5 to 95 mol%, preferably from 10 to 95 mol%, more preferably from 30 to 85 mol% of the group III dihydroxy component. If the amount is less than 5 mol%, unsatisfactory properties as a heat-resistant material, which is the object of the present invention, are not preferred.
[0014]
The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene has a b value of preferably 6.0 or less, more preferably 5.0, when a solution obtained by dissolving 10 g of the same in 50 ml of ethanol is measured at an optical path length of 30 mm. 5 or less, more preferably 5.0 or less. When the b value is within the above range, a film formed from the obtained polycarbonate copolymer is excellent in hue and weather resistance, and has high film strength and good stretched film characteristics, which is preferable.
[0015]
Usually, this 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is obtained by the reaction of o-cresol and fluorenone. 9,9-bis (4-hydroxy-3-methylphenyl) fluorene having the specific b value can be obtained by performing a specific treatment to remove impurities. Specifically, after the reaction of o-cresol and fluorenone, unreacted o-cresol is distilled off, and the residue is dissolved in an alcohol-based, ketone-based or benzene derivative-based solvent, and activated clay or activated carbon is added thereto. In addition, after filtration, the product crystallized from the filtrate is filtered to obtain purified 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. The impurities to be removed include a 2,4'-dihydroxy compound, a 2,2'-dihydroxy compound, and an impurity of unknown structure. As alcohol solvents used for such purification, lower alcohols such as methanol, ethanol, propanol and butanol are preferable, and as ketone solvents lower acetone ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and cyclohexanone and mixtures thereof are preferable. As the benzene derivative-based solvent, toluene, xylene, benzene and a mixture thereof are preferable. The amount of the solvent to be used is sufficient as long as the fluorene compound is sufficiently dissolved, and is usually about 2 to 10 times the amount of the fluorene compound. As the activated clay, commercially available powdered or granular silica-alumina having a main component is used. As the activated carbon, commercially available powdered or granular activated carbon is used.
[0016]
The other dihydroxy component represented by the general formula [1] used in the aromatic polycarbonate copolymer constituting the flame-retardant polycarbonate resin composition of the present invention is generally used as a dihydroxy component of an aromatic polycarbonate. Any substance can be used, for example, hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane (bisphenol E), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) ), 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1- Phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohex (Bisphenol Z), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4 ′-(p-phenylenediene Isopropylidene) diphenol, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane and the like. However, bisphenol A, bisphenol Z, bisphenol C, bisphenol E, and bisphenol M are preferred, and bisphenol A is particularly preferred.
[0017]
The aromatic polycarbonate copolymer has a specific viscosity at 20 ° C. of a solution in which the polymer is dissolved in methylene chloride, preferably in the range of 0.2 to 1.2, more preferably in the range of 0.25 to 1.0, The range of 0.27 to 0.80 is more preferable. When the specific viscosity is within the above range, the strength of the molded product, particularly the film, is sufficiently strong, the melt viscosity and the solution viscosity are appropriate, and the handling is easy, which is preferable.
[0018]
The aromatic polycarbonate copolymer constituting the flame-retardant polycarbonate resin composition of the present invention is a reaction means known per se for producing a normal aromatic polycarbonate resin, for example, a carbonate such as phosgene or carbonate diester in an aromatic dihydroxy component. It is manufactured by a method of reacting a precursor. Next, basic means of these manufacturing methods will be briefly described.
[0019]
In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.
[0020]
The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which a predetermined ratio of an aromatic dihydroxy component is stirred with a carbonic acid diester while heating under an inert gas atmosphere to distill off the alcohol or phenol to be produced. . The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, and is usually in the range of 120 to 300 ° C. The reaction is completed under reduced pressure from the beginning while distilling off alcohol or phenols produced.
[0021]
Further, a catalyst usually used in a transesterification reaction to promote the reaction can be used. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferred.
[0022]
As the aromatic polycarbonate copolymer constituting the flame-retardant polycarbonate resin composition of the present invention, monofunctional phenols which are usually used as a terminal stopper in the polymerization reaction can be used. Particularly in the case of the reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminating agent for controlling the molecular weight, and the obtained aromatic polycarbonate copolymer has a monofunctional terminal. Since it is blocked by a group based on phenols, it has better heat stability than that which is not.
[0023]
The monofunctional phenol may be any one used as a terminal terminator of an aromatic polycarbonate resin, and is generally a phenol or a lower alkyl-substituted phenol, and is a monofunctional phenol represented by the following general formula. Can be shown.
[0024]
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[In the formula, A is a hydrogen atom, a linear or branched alkyl group or an arylalkyl group having 1 to 9 carbon atoms, and r is an integer of 1 to 5, preferably 1 to 3. ]
[0026]
Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.
[0027]
Further, as other monofunctional phenols, phenols or benzoic acid chlorides having a long-chain alkyl group or an aliphatic ester group as a substituent, or long-chain alkyl carboxylic acid chlorides can be used. When these compounds are used to block the ends of the aromatic polycarbonate copolymer, they not only function as a terminal terminator or a molecular weight regulator, but also improve the melt fluidity of the resin and facilitate molding and processing. Also, the physical properties are improved. Particularly, it has an effect of lowering the water absorption of the resin, and is preferably used. These are represented by the following general formulas [Ia] to [Ih].
[0028]
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[In the above general formulas [Ia] to [Ih], X is -RO-, -R-CO-O- or -RO-CO-, wherein R is a single bond or Represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, T represents a single bond or a bond similar to the above X, and n represents an integer of 10 to 50.
Q represents a halogen atom or a monovalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, p represents an integer of 0 to 4, and Y represents 1 to 10 carbon atoms, preferably 1 to 5 represents a divalent aliphatic hydrocarbon group, wherein W 1 is a hydrogen atom, —CO—R 17 , —CO—O—R 18 or R 19 , wherein R 17 , R 18 and R 19 are C 1-10, preferably C 1-5 monovalent aliphatic hydrocarbon group, C 4-8, preferably C 5-6 monovalent alicyclic hydrocarbon group or C 6-15, It preferably represents 6 to 12 monovalent aromatic hydrocarbon groups.
a represents an integer of 4 to 20, preferably 5 to 10, m represents an integer of 1 to 100, preferably 3 to 60, and particularly preferably 4 to 50; Z represents a single bond or 1 to 10 carbon atoms; It preferably represents a divalent aliphatic hydrocarbon group of 1 to 5, W 2 represents a hydrogen atom, a carbon atom of 1 to 10, preferably a monovalent aliphatic hydrocarbon group of 1 to 5, a carbon number of 4 to 8, It preferably represents a monovalent alicyclic hydrocarbon group having 5 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, preferably 6 to 12 carbon atoms. ]
[0037]
Of these, preferred are the substituted phenols [Ia] and [Ib]. As the substituted phenols of [Ia], those having n of 10 to 30, especially 10 to 26 are preferable, and specific examples thereof include, for example, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecyl Phenol, eicosylphenol, docosylphenol and triacontylphenol can be mentioned.
[0038]
Further, as the substituted phenols of [Ib], compounds in which X is -R-CO-O- and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26 are preferable. Suitable and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and tricontyl hydroxybenzoate.
[0039]
In the substituted phenols or substituted benzoyl chlorides represented by the general formulas [Ia] to [Ig], the position of the substituent is generally preferably the p-position or the o-position, and a mixture of both is preferable.
[0040]
The monofunctional phenols are desirably introduced at least 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained aromatic polycarbonate copolymer, and the monofunctional phenols are used alone. Alternatively, two or more kinds may be used in combination.
[0041]
In the aromatic polycarbonate copolymer of the present invention, when 9,9-bis (4-hydroxy-3-methylphenyl) fluorene accounts for 60 mol% or more of the total aromatic hydroxy component, the fluidity of the resin is reduced. Therefore, it is preferable to use substituted phenols or substituted benzoyl chlorides represented by the above general formulas [Ia] to [Ig] as a terminal stopper.
[0042]
The aromatic polycarbonate copolymer of the present invention may be a polyester carbonate obtained by copolymerizing an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the spirit of the present invention is not impaired. . Alternatively, a branched polycarbonate obtained by copolymerizing a small amount of a trifunctional compound may be used.
[0043]
The glass transition point of the aromatic polycarbonate copolymer constituting the flame-retardant polycarbonate resin composition of the present invention is preferably 160 ° C. or higher, more preferably 180 ° C. or higher, even more preferably 200 ° C. or higher.
[0044]
The condensed phosphoric acid ester used as a flame retardant in the present invention is represented by the general formula [2]. Preferably, R 5 to R 8 are aromatic rings and X is a phenylenepropylidenephenylene residue. The bisphenol A diphenyl ether-based condensed phosphoric acid ester has a high phosphorus content and therefore has good flame retardancy, no volatility, and no mold contamination. Further, since the resin has good hydrolysis resistance, the resin containing the same is also excellent in long-term quality retention. n is 1 to 15, preferably 1 to 5. These may be used as a mixture of two or more different condensed phosphoric esters. These condensed phosphoric acid esters are added in an amount of 0.1 to 20% by weight, preferably 1 to 15% by weight, more preferably 3 to 10% by weight based on the total weight of the composition.
[0045]
Further, in order to enhance the flame retardancy, an aromatic sulfonate having 6 to 30 carbon atoms or an aliphatic sulfonate which may be substituted with fluorine having 3 to 30 carbon atoms or an 8 carbon atom is used as an auxiliary flame retardant. Up to 30 aliphatic sulfates may be blended. These auxiliary flame retardants are added in an amount of 0.001 to 1% by weight, preferably 0.01 to 0.5% by weight, more preferably 0.03 to 0.1% by weight based on the total weight of the composition.
[0046]
The flame-retardant polycarbonate resin composition of the present invention preferably contains an anti-drip agent for preventing drip during combustion. Among them, a fluoropolymer having a fibril-forming ability is preferable, and a tetrafluoroethylene-based polymer is preferable. The mixing ratio is from 0.01 to 5% by weight, preferably from 0.1 to 1.5% by weight, based on the total weight of the composition.
[0047]
In the present invention, a bluing agent may be used. Examples of the bluing agent include Macrolex Violet manufactured by Bayer Corp., Diaresin Violet manufactured by Mitsubishi Chemical Corporation, Diaresin Blue, and Sandoz Co., Ltd. And terazole blue, and Macrox Violet as the most preferable one. These bluing agents are preferably incorporated into the aromatic polycarbonate resin at a concentration of 0.1 to 3 ppm, more preferably 0.3 to 1.5 ppm, most preferably 0.3 to 1.2 ppm.
[0048]
The flame-retardant polycarbonate resin composition of the present invention optionally contains at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof. be able to. The amount of the phosphorus compound is preferably 0.0001 to 0.05% by weight, more preferably 0.0005 to 0.02% by weight, and particularly preferably 0.001 to 0.01% by weight based on the composition. preferable. The incorporation of this phosphorus compound improves the thermal stability of the composition, and prevents a decrease in molecular weight and hue during molding.
[0049]
Such a phosphorus compound is at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof, and is preferably represented by the following general formula:
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[Wherein, R 5 to R 16 each independently represent a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl Represents an alkyl group having 1 to 20 carbon atoms such as octadecyl, an aryl group having 6 to 15 carbon atoms such as phenyl, tolyl or naphthyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl and phenethyl. When two alkyl groups are present, the two alkyl groups may be bonded to each other to form a ring. ]
At least one phosphorus compound selected from the group consisting of:
[0055]
Examples of the phosphorus compound represented by the above formula (1) include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, and trioctyl phosphite. , Trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentae Sri diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, and distearyl pentaerythritol phosphite.
[0056]
Examples of the phosphorus compound represented by the formula (2) include tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like. Examples of the phosphorus compound represented by the formula) include tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite, and the compound represented by the formula (4) includes: Examples thereof include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
[0057]
Among these phosphorus compounds, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylene Phosphonite is preferably used.
[0058]
The flame-retardant polycarbonate resin composition of the present invention may contain an antioxidant generally known for the purpose of preventing oxidation. Examples thereof include phenolic antioxidants, and specifically, for example, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6 -Hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl -4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-h) Roxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3,9 -Bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5, 5) Undecane and the like. The preferable range of the addition amount of these antioxidants is 0.0001 to 0.05% by weight based on the composition.
[0059]
Further, a higher fatty acid ester of a monohydric or polyhydric alcohol can be added to the flame retardant polycarbonate resin composition of the present invention, if necessary.
[0060]
The higher fatty acid ester is preferably a partial ester or a whole ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Examples of the partial or total ester of a monohydric or polyhydric alcohol with a saturated fatty acid include monoglyceride stearate, monosorbitate stearate, monoglyceride behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, and propylene glycol. Monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate, and the like, among which stearic acid monoglyceride and pentaerythritol tetrastearate are preferably used .
[0061]
The amount of the ester of the alcohol and the higher fatty acid is preferably 0.01 to 2% by weight, more preferably 0.015 to 0.5% by weight, more preferably 0.02 to 0.5% by weight based on the aromatic polycarbonate copolymer. 0.2% by weight is more preferred. When the compounding amount is within this range, the releasing property is excellent, and the releasing agent is preferable because it does not migrate and adhere to the metal surface.
[0062]
The flame-retardant polycarbonate resin composition of the present invention further comprises additives such as UV absorbers, colorants, antistatic agents, lubricants, fillers and other polycarbonate resins, and other thermoplastic resins for the purpose of the present invention. A small proportion can be added within a range not to impair.
[0063]
To produce the flame-retardant polycarbonate resin composition of the present invention, any method is employed. For example, after adding various additives to the aromatic polycarbonate resin and sufficiently mixing them using a pre-mixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, and an extruder, optionally, an extrusion granulator or a briquette is used. There is a method in which granulation is performed with a tinting machine or the like, and then extruded into a pellet using a melt kneader represented by a vented twin-screw ruder. In addition, a method in which each component is independently supplied to a vent-type twin-screw extruder, a method in which a part of each component is preliminarily mixed, and then the remaining components are supplied to a melt kneader independently, and the like are also included. A method of preparing a master batch of additives and then mixing them is also used.
[0064]
The condensed phosphoric acid ester of the present invention becomes liquid or syrup-like depending on the degree of condensation. Therefore, a method of using a liquid injection or liquid addition device for supply to the extruder is adopted. Therefore, the extruder used in the present invention preferably has two or more raw material supply ports on the upstream side and the downstream side with respect to the extrusion direction. In this case, the addition of the condensed phosphoric acid ester is most downstream. Supplying from the raw material supply port on the side is preferable in that the heat history is reduced. The addition of the condensed phosphoric acid ester is supplied from a feed port provided in the barrel of the extruder by a known liquid conveying device such as a gear pump at a pressure higher than the discharge pressure in the extruder. At that time, it is usually heated to 50 to 100 ° C. in order to reduce the viscosity. If the temperature is higher than 100 ° C., the phosphoric acid ester may be volatilized, deteriorated or decomposed for a long time, which is not preferable.
[0065]
As a method for obtaining a molded article from the aromatic polycarbonate resin composition of the present invention, injection molding, extrusion molding, blow molding and the like are used, and as a method for producing a film or sheet, excellent uniformity of thickness, gel, A method that does not cause optical defects such as spots, fish eyes, and scratches is preferable, and examples thereof include a solvent casting method, a melt extrusion method, and a calendering method.
[0066]
Molded articles produced by such a method are used for various glazing applications, automotive lamp lenses, lamp covers, optical lenses, OHP sheets, nameplates, indicating lights, and the like. Further, the film produced by such a method is suitably used as a placell substrate or a retardation film for flat panel display substrates. Although the placell substrate is used in an unstretched state, in order to use it as a retardation film, it is stretched and oriented in at least one axial direction so as to have optimal birefringence characteristics, thereby forming a retardation film.
[0067]
As the uniaxial stretching method, an arbitrary method such as a horizontal uniaxial stretching by a tenter method, a vertical uniaxial stretching between rolls, and a roll-to-roll rolling method can be used. The stretching temperature is preferably Tg−50 ° C. or higher and Tg + 20 ° C. or lower, more preferably Tg−30 ° C. or higher and Tg + 10 ° C. or lower, where Tg is the glass transition temperature of the resin used. Stretching at a temperature in such a range facilitates uniform orientation without freezing the movement of the polymer molecules, and is preferable.Also, the molecular movement of the polymer is moderate, and the relaxation of the orientation by stretching hardly occurs. It is preferable because the degree of orientation can be easily obtained and the orientation can be easily suppressed.
[0068]
The stretching ratio may be appropriately selected according to the desired retardation of the film. This value also depends on the stretching temperature and the film thickness. In general, the stretching ratio may be small for a thick film, and large for a thin film. The retardation value of the retardation plate used for the STN type liquid crystal display is generally in the range of 400 to 650 nm. Further, the amplitude of the retardation is preferably 10% or less, particularly preferably 5% or less. If the fluctuation width of the retardation is too large, a deviation in color compensation occurs, and color unevenness tends to occur.
[0069]
The retardation film is preferably used as a composite deflecting plate by forming a barrier layer and a transparent electrode for liquid crystal targeting indium and tin oxide, and then laminating it on a deflecting plate. This composite deflecting plate can be formed by laminating the optical axis of the ordinary deflecting plate and the optical axis of the retardation film in a single layer or multiple layers in the range of 40 to 50 degrees. This composite deflecting plate has excellent characteristics such as excellent heat resistance and durability, and little change in retardation with time.
[0070]
One of the characteristics of the stretched film is a K value defined by the product of the absolute value of the difference between the average value of the refractive indices nx and ny in the film plane direction and the refractive index nz in the thickness direction and the film thickness t (nm) = | (Nx + ny) / 2-nz | × t, and when the K value is large, the viewing angle is narrowed such that the display appears to be floating when used as a liquid crystal display element. Therefore, this value is preferably suppressed to 120 nm or less. .
[0071]
In addition, the liquid crystal display panel in which the deflecting plate is disposed on one or both sides of the liquid crystal cell has eliminated coloring due to birefringence of the liquid crystal by disposing the retardation film between the deflecting plate on the viewing side and the liquid crystal cell. A monochrome liquid crystal display panel can be formed. Further, a full-color liquid crystal display panel can be formed by covering the monochrome liquid crystal panel with a color mask and emitting three colors of RGB.
[0072]
The film formed from the flame-retardant polycarbonate resin composition of the present invention has excellent film strength, heat resistance, and good hue.For example, such an aromatic polycarbonate resin composition can be prepared using methylene chloride, dioxolan, toluene, dioxane, or the like. It is dissolved in an organic solvent to form a casting film, and a gas barrier film and a solvent-resistant film are attached to both sides of this film, or a film for a liquid crystal substrate (placell substrate) or a retardation film together with a transparent conductive film or a polarizing plate. It is suitably used as a liquid crystal display film, and more specifically, can be advantageously used in pagers, mobile phones, handy terminals, various display devices, and the like.
[0073]
【Example】
Hereinafter, the present invention will be further described with reference to examples. Parts in Examples are parts by weight, and% is% by weight. In addition, evaluation was based on the following method.
(1) Specific viscosity: 0.7 g of a polymer was dissolved in 100 ml of methylene chloride and measured at a temperature of 20 ° C.
(2) Glass transition point (Tg): measured by DuPont 910 DSC.
(3) b value of the monomer solution: 10 g of a sample was dissolved in 50 ml of ethanol, and measured using a color difference meter 300A of Nippon Denshoku Co., Ltd. in a sample tube having an optical path length of 30 mm.
(4) Flame retardancy: A combustion test was conducted at a thickness of 1.6 mm in accordance with UL94V.
(5) Mold Contamination: Using a T-150D injection molding machine manufactured by FANUC CORPORATION, a box-shaped molded product having a length of 100 mm, a width of 150 mm, and a height of 15 mm is almost excellent at an injection pressure of 800 kg / cm 2. Was continuously formed at a cylinder temperature and a mold temperature of 70 ° C., and the presence or absence of deposits on the mold surface was checked every 100 shots, and the number of shots in which deposits occurred was counted.
(6) Heat resistance: The box-shaped molded product was placed in a hot-air circulating oven whose temperature was adjusted to 180 ± 1 ° C., and the molded product after standing for 24 hours was visually checked for any deformation. When there was deformation, it was evaluated as x, and when there was no deformation, it was evaluated as ○.
[0074]
[Synthesis Example 1]
In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 24623 parts of ion-exchanged water and 4153 parts of a 48% aqueous sodium hydroxide solution were added, and 9,9-bis (4-hydroxy) having a b value of 3.0 in an ethanol solution was used. 1936.9 parts of -3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “biscresol fluorene”) and 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes abbreviated as “bisphenol A”) After dissolving 2726 parts and 8 parts of hydrosulfite, 18188 parts of methylene chloride were added, and 1994 parts of phosgene was blown in at 60 ° C. for 60 minutes at 15 to 25 ° C. with stirring. After completion of the phosgene blowing, a solution prepared by dissolving 102.5 parts of p-tert-butylphenol in 330 parts of methylene chloride and 692.1 parts of a 48% aqueous sodium hydroxide solution were added. After emulsification, 5.8 parts of triethylamine was added to add 28 to 48%. The reaction was completed by stirring at 33 ° C. for 1 hour. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and washed with water.When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, the methylene chloride phase was concentrated and dehydrated to give polycarbonate. A solution with a concentration of 20% was obtained. The polycarbonate obtained by removing the solvent from this solution had a molar ratio of the structural units of biscresol fluorene and bisphenol A of 30:70 (polymer yield: 97%). The polymer had a specific viscosity of 0.337 and a Tg of 190 ° C. This polymer is referred to as polycarbonate A.
[0075]
[Synthesis Example 2]
The ratio of biscresol fluorene to bisphenol A was 50:50 in molar ratio in the same manner as in Synthesis Example 1 except that the amount of biscresol fluorene used in Synthesis Example 1 was 3171.4 parts and the amount of bisphenol A used was 1913 parts. 5300 parts (yield: 96%) of the polymer was obtained. The specific viscosity of this polymer was 0.320 and the Tg was 205 ° C. This polymer is referred to as polycarbonate B.
[0076]
[Synthesis Example 3]
35315 parts of ion-exchanged water and 3920 parts of 48% sodium hydroxide were placed in the same apparatus as in Synthesis Example 1, and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene (abbreviated as bisphenol M) 2954.9. After dissolving 3228.1 parts of biscresol fluorene and 14 parts of hydrosulfite, 12775 parts of methylene chloride were added, and 1946 parts of phosgene was blown in at 45 to 20 ° C for 45 minutes while stirring. After the injection of phosgene was completed, 108.5 parts of p-tert-butylphenol and 710.5 parts of a 48% aqueous sodium hydroxide solution were added and emulsified, and 4.55 parts of triethylamine was added. The mixture was stirred at 28 to 33 ° C for 1 hour and reacted. Finished. This was treated in the same manner as in Example 1 to obtain a polymer having a molar ratio of bisphenol M to biscresol fluorene constituting unit of 50:50 (yield 98%). This had a specific viscosity of 0.250 and a Tg of 180 ° C. This polymer is referred to as polycarbonate C.
[0077]
[Synthesis Example 4]
Bisphenol A homopolycarbonate was obtained in the same manner as in Synthesis Example 1 except that 3894.2 parts of bisphenol A was used without using biscresol fluorene of Synthesis Example 1. Its specific viscosity was 0.365 and Tg was 148 ° C. This polymer is referred to as polycarbonate D.
[0078]
[Example 1]
To 100 parts of the polycarbonate A obtained in Synthesis Example 1, 0.05 parts of tris (2,4-di-tert-butylphenyl) phosphite and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) were added. ) 0.01 parts of propionate and 0.03 parts of pentaerythritol tetrastearate were added, and the mixture was supplied to a first supply port of a vented twin-screw extruder by a constant-rate supply machine. On the other hand, the condensed phosphoric acid ester (“CR-741” manufactured by Daihachi Chemical Industry Co., Ltd.) is heated to 80 ° C. while using a liquid injection device (HYM-JS-08 manufactured by Fuji Techno Kogyo Co., Ltd.). From the third supply port (located between the second supply port and the vent exhaust port) to the extruder at a predetermined ratio. After pelletizing at a cylinder temperature of 270 to 300 ° C., a UL94V 1.6 mm thick test piece was injection molded using an N-20C injection molding machine manufactured by JSW Corporation, and evaluated according to UL94V. The mold contamination was also evaluated. Table 1 shows the results. Shown in
[0079]
[Example 2]
A test piece was obtained in the same manner as in Example 1 except that the polycarbonate in Example 1 was changed to Polycarbonate B. Shown in
[0080]
[Example 3]
Table 1 shows the results of a test performed in the same manner as in Example 1 except that the polycarbonate in Example 1 was changed to Polycarbonate C. Shown in
[0081]
[Example 4]
Table 1 shows the results of a test performed in the same manner as in Example 1 except that 0.3 parts of polytetrafluoroethylene (F201L manufactured by Daikin Industries, Ltd.) was added to the polycarbonate A of Example 1. Shown in
[0082]
[Comparative Example 1]
Table 1 shows the results of tests performed in the same manner as in Example 1 except that the condensed phosphoric acid ester of Example 1 was changed to triphenyl phosphate (TPP manufactured by Daihachi Chemical Co., Ltd.). Shown in
[0083]
[Comparative Example 2]
Table 1 shows the results of a test performed in the same manner as in Example 2 except that the condensed phosphoric ester of Example 2 was changed to the above triphenyl phosphate. Shown in
[0084]
[Comparative Example 3]
Table 1 shows the results of a test performed in the same manner as in Example 1 except that the polycarbonate in Example 1 was changed to Polycarbonate D. Shown in
[0085]
[Table 1]
【The invention's effect】
The flame-retardant polycarbonate resin composition having good heat resistance of the present invention and excellent mold contamination resistance can be used for various molded articles, sheets, films, etc. for electric / electronic and optical applications where heat resistance is required. It is preferably used.
Claims (8)
で表されるジヒドロキシ成分からなるポリカーボネート共重合体を主成分とする熱可塑性樹脂組成物に、一般式［２］
A thermoplastic resin composition comprising a polycarbonate copolymer comprising a dihydroxy component represented by the following formula:
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| JP2018080300A (en) * | 2016-11-18 | 2018-05-24 | 帝人株式会社 | Flame-retardant polycarbonate resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010520361A (en) * | 2007-03-07 | 2010-06-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Flame retardant polycarbonate composition |
| JP2018080300A (en) * | 2016-11-18 | 2018-05-24 | 帝人株式会社 | Flame-retardant polycarbonate resin composition |
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