JP2013001800A - Aromatic polycarbonate resin composition and molded article thereof - Google Patents
Aromatic polycarbonate resin composition and molded article thereof Download PDFInfo
- Publication number
- JP2013001800A JP2013001800A JP2011134203A JP2011134203A JP2013001800A JP 2013001800 A JP2013001800 A JP 2013001800A JP 2011134203 A JP2011134203 A JP 2011134203A JP 2011134203 A JP2011134203 A JP 2011134203A JP 2013001800 A JP2013001800 A JP 2013001800A
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- JP
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- Prior art keywords
- component
- polycarbonate resin
- aromatic polycarbonate
- weight
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- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 71
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 71
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 238000002411 thermogravimetry Methods 0.000 claims abstract description 17
- 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 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 11
- 230000004580 weight loss Effects 0.000 claims abstract description 11
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 4
- 239000004593 Epoxy Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- -1 cyclic carbonate compound Chemical class 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 238000000465 moulding Methods 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 239000000654 additive Substances 0.000 description 14
- 239000000975 dye Substances 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000008188 pellet Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000002989 phenols Chemical class 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 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 7
- 239000000843 powder Substances 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)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 BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000004650 carbonic acid diesters Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 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
- 238000001879 gelation Methods 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012696 Interfacial polycondensation Methods 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004419 Panlite Substances 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000011230 binding agent Substances 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
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000006081 fluorescent whitening agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000001028 reflection method Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LZFOPEXOUVTGJS-ONEGZZNKSA-N trans-sinapyl alcohol Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O LZFOPEXOUVTGJS-ONEGZZNKSA-N 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 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 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 2
- XKMCVHMWMWTINX-UHFFFAOYSA-N (2,3,4-trichlorophenyl) dihydrogen phosphate Chemical compound OP(O)(=O)OC1=CC=C(Cl)C(Cl)=C1Cl XKMCVHMWMWTINX-UHFFFAOYSA-N 0.000 description 1
- 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
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-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
- PHJMLWHPHSYYQI-UHFFFAOYSA-N 1,1-bis(2,6-ditert-butyl-4-ethylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)CC)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)CC)C(C)(C)C PHJMLWHPHSYYQI-UHFFFAOYSA-N 0.000 description 1
- OSZQBLPOQBBXQS-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-(2,4-ditert-butylphenoxy)-5h-benzo[d][1,3,2]benzodioxaphosphocine Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OC2=C(C(C)(C)C)C=C(C(C)(C)C)C=C2CC(C=C(C=C2C(C)(C)C)C(C)(C)C)=C2O1 OSZQBLPOQBBXQS-UHFFFAOYSA-N 0.000 description 1
- MRMCMJOXMLGUFT-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-(2-tert-butyl-4-methylphenoxy)-5h-benzo[d][1,3,2]benzodioxaphosphocine Chemical compound CC(C)(C)C1=CC(C)=CC=C1OP1OC2=C(C(C)(C)C)C=C(C(C)(C)C)C=C2CC(C=C(C=C2C(C)(C)C)C(C)(C)C)=C2O1 MRMCMJOXMLGUFT-UHFFFAOYSA-N 0.000 description 1
- IBABXJRXGSAJLQ-UHFFFAOYSA-N 1,4-bis(2,6-diethyl-4-methylanilino)anthracene-9,10-dione Chemical compound CCC1=CC(C)=CC(CC)=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=C(CC)C=C(C)C=C1CC IBABXJRXGSAJLQ-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- UDFARPRXWMDFQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 UDFARPRXWMDFQU-UHFFFAOYSA-N 0.000 description 1
- GOGVBRWRMAJECZ-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)trisulfanyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(SSSC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 GOGVBRWRMAJECZ-UHFFFAOYSA-N 0.000 description 1
- VMZVBRIIHDRYGK-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VMZVBRIIHDRYGK-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
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- GTLMTHAWEBRMGI-UHFFFAOYSA-N 2-cyclohexyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C2CCCCC2)=C1 GTLMTHAWEBRMGI-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- WYIHUDNDPCJCJL-UHFFFAOYSA-N 2-tert-butyl-6-[1-(3-tert-butyl-2-hydroxy-5-methylphenyl)butyl]-4-methylphenol Chemical compound C=1C(C)=CC(C(C)(C)C)=C(O)C=1C(CCC)C1=CC(C)=CC(C(C)(C)C)=C1O WYIHUDNDPCJCJL-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-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
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
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- AJHKJOCIGPIJFZ-UHFFFAOYSA-N tris(2,6-ditert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1OP(OC=1C(=CC=CC=1C(C)(C)C)C(C)(C)C)OC1=C(C(C)(C)C)C=CC=C1C(C)(C)C AJHKJOCIGPIJFZ-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- QFGXDXGDZKTYFD-UHFFFAOYSA-N tris[2,3-di(propan-2-yl)phenyl] phosphite Chemical compound CC(C)C1=CC=CC(OP(OC=2C(=C(C(C)C)C=CC=2)C(C)C)OC=2C(=C(C(C)C)C=CC=2)C(C)C)=C1C(C)C QFGXDXGDZKTYFD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は芳香族ポリカーボネート樹脂組成物およびその成形品に関する。 The present invention relates to an aromatic polycarbonate resin composition and a molded article thereof.
ポリカーボネート樹脂は、優れた透明性、耐熱性、機械的強度等を有するため電気、機械、自動車、医療用途等に幅広く使用されている。しかしながら、ポリカーボネート樹脂を用いて成形を行う場合、そのゲル化物を起因とした外観不良や、異物由来の外観不良（白モヤ）、繰り返し使用時の色相安定性（リプロ性）が問題となることがある。これらの特性は、近年の成形品の軽量化、薄肉化、低コスト化に伴い要求が高まっている。ポリカーボネート樹脂の成形性を向上させるために種々の添加剤を使用する技術が検討されており、特許文献１には離型剤の酸価、ヨウ素価、金属元素Ｓｎ含有量を規定することにより成形耐熱性低下を抑制する方法が記載されている。しかし、外観不良やリプロ性などの改善については不十分である。また、特許文献２では離型剤の脂肪酸成分の比率、熱安定性、酸価を規定することにより成形耐熱性、離型性をはじめ、内部歪み、割れ耐性などの問題点を改善する方法が提案されているが、特許文献２においてもゲル化物やリプロ性といった問題改善には至っていない。 Polycarbonate resins have excellent transparency, heat resistance, mechanical strength, etc., and are therefore widely used in electrical, mechanical, automotive, medical applications and the like. However, when molding is performed using a polycarbonate resin, the appearance defect caused by the gelled product, the appearance defect due to foreign matters (white haze), and hue stability (reproducibility) during repeated use may become problems. is there. These characteristics are increasing in demand with the recent reduction in weight, thickness and cost of molded products. In order to improve the moldability of the polycarbonate resin, a technique using various additives has been studied. In Patent Document 1, molding is performed by defining the acid value, iodine value, and metal element Sn content of the release agent. A method for suppressing a decrease in heat resistance is described. However, it is insufficient for improving appearance defects and reproducibility. In Patent Document 2, there is a method for improving problems such as internal heat resistance and crack resistance as well as molding heat resistance and releasability by regulating the ratio of fatty acid components, thermal stability, and acid value of the release agent. Although proposed, Patent Document 2 has not yet improved problems such as gelled products and reproducibility.
本発明では、外観不良が少なく、リプロ性、耐熱性に優れた芳香族ポリカーボネート樹脂およびその成形品を提供することを目的とする。 An object of the present invention is to provide an aromatic polycarbonate resin having few appearance defects and excellent in reproducibility and heat resistance, and a molded product thereof.
本発明は上記課題を解決するために以下の構成を採用する。
１．（Ａ）芳香族ポリカーボネート樹脂（Ａ成分）１００重量部に対し、（Ｂ）ペンタエリスリトールテトラステアレート（Ｂ成分）０．２５〜０．５５重量部、ならびに（Ｃ）リン系安定剤（Ｃ１成分）０．０００５〜１重量部およびヒンダードフェノール系酸化防止剤（Ｃ２成分）０．０００５〜１重量部を配合してなる樹脂組成物であって、該Ａ成分は、Ｆｅ含有量が２００ｐｐｂ以下およびＮａ含有量が１００ｐｐｂ以下であり、該Ｂ成分は、酸価が１．６〜４．０であり、ＴＧＡ（熱重量解析）における５％重量減少温度が３６０℃以上であり、且つＮａイオン濃度が１０ｐｐｍ以下であることを特徴とする芳香族ポリカーボネート樹脂組成物。
２．該Ａ成分は、Ｆｅ含有量とＮａ含有量との合計が２００ｐｐｂ以下である前項１に記載の芳香族ポリカーボネート樹脂組成物。
３．該Ｂ成分は、酸価が２．０〜４．０である前項１に記載の芳香族ポリカーボネート樹脂組成物。
４．該Ｂ成分は、ＴＧＡ（熱重量解析）における５％重量減少温度が３７０℃以上である前項１に記載の芳香族ポリカーボネート樹脂組成物。
５．該Ｂ成分は、Ｎａイオン濃度が５ｐｐｍ以下である前項１に記載の芳香族ポリカーボネート樹脂組成物。
６．該Ｃ１成分および該Ｃ２成分を、Ａ成分１００重量部に対しそれぞれ０．００５〜０．１重量部配合してなる前項１に記載の芳香族ポリカーボネート樹脂組成物。
７．（Ａ）芳香族ポリカーボネート樹脂（Ａ成分）１００重量部に対し、（Ｄ）エポキシ化合物（Ｄ成分）０．００３〜０．１重量部を配合してなる前項１に記載の芳香族ポリカーボネート樹脂組成物。
８．前項１に記載の芳香族ポリカーボネート樹脂からなる成形品。
９．該成形品は、シートまたはフィルムである前項８に記載の成形品。
The present invention adopts the following configuration in order to solve the above problems.
1. (A) 100 parts by weight of aromatic polycarbonate resin (component A), (B) pentaerythritol tetrastearate (component B) 0.25 to 0.55 parts by weight, and (C) phosphorus stabilizer (component C1) ) 0.0005 to 1 part by weight and a hindered phenolic antioxidant (C2 component) 0.0005 to 1 part by weight, wherein the A component has an Fe content of 200 ppb or less And the Na content is 100 ppb or less, the B component has an acid value of 1.6 to 4.0, a 5% weight loss temperature in TGA (thermogravimetric analysis) is 360 ° C. or more, and Na ion An aromatic polycarbonate resin composition having a concentration of 10 ppm or less.
2. 2. The aromatic polycarbonate resin composition according to item 1, wherein the total of the Fe content and the Na content is 200 ppb or less.
3. 2. The aromatic polycarbonate resin composition according to item 1, wherein the component B has an acid value of 2.0 to 4.0.
4). 2. The aromatic polycarbonate resin composition according to item 1, wherein the B component has a 5% weight loss temperature of 370 ° C. or higher in TGA (thermogravimetric analysis).
5. The aromatic polycarbonate resin composition according to item 1, wherein the B component has a Na ion concentration of 5 ppm or less.
6). 2. The aromatic polycarbonate resin composition according to item 1, wherein the C1 component and the C2 component are blended in an amount of 0.005 to 0.1 parts by weight with respect to 100 parts by weight of the component A, respectively.
7). 2. The aromatic polycarbonate resin composition according to item 1 above, wherein 0.003 to 0.1 parts by weight of (D) epoxy compound (D component) is blended with 100 parts by weight of (A) aromatic polycarbonate resin (component A). object.
8). A molded article comprising the aromatic polycarbonate resin according to item 1.
9. 9. The molded article according to item 8, wherein the molded article is a sheet or a film.
本発明によれば、外観不良が少なく、リプロ性、耐熱性に優れた芳香族ポリカーボネート樹脂およびその成形品を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, there can be provided the aromatic polycarbonate resin which has few external appearance defects, and was excellent in repro property and heat resistance, and its molded article.
以下、本発明を詳細に説明する。
［芳香族ポリカーボネート樹脂について］
本発明に用いられる芳香族ポリカーボネート樹脂は二価フェノール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。芳香族ポリカーボネート樹脂はいかなる製造方法によって製造されたものでもよく、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。芳香族ポリカーボネート樹脂は前記二価フェノールまたは二官能性アルコールに加えて、３官能以上の例えば３官能フェノール類の如き多官能フェノール類を重合させた分岐ポリカーボネートであってもよい。更に脂肪族ジカルボン酸や芳香族ジカルボン酸、ポリオルガノシロキサン成分、並びにビニル系単量体を共重合させた共重合ポリカーボネートであってもよい。二価フェノールの代表的な例として２，２−ビス（４−ヒドロキシフェニル）プロパン（通称ビスフェノールＡ）、１，１−ビス（４−ヒドロキシフェニル）エタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジブロモフェニル）プロパン、ビス（４−ヒドロキシフェニル）サルファイド、ビス（４−ヒドロキシフェニル）スルホン等があげられる。好ましい二価フェノールはビス（４−ヒドロキシフェニル）アルカン系であり、特にビスフェノールＡが好ましい。上記二価フェノールは単独で又は二種以上併用して使用することができる。
Hereinafter, the present invention will be described in detail.
[Aromatic polycarbonate resin]
The aromatic polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol and 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. The aromatic polycarbonate resin may be produced by any production method. In the case of interfacial polycondensation, a terminal stopper of monohydric phenols is usually used. The aromatic polycarbonate resin may be a branched polycarbonate obtained by polymerizing polyfunctional phenols such as trifunctional or higher functional phenols in addition to the dihydric phenol or difunctional alcohol. Further, it may be a copolymerized polycarbonate obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a polyorganosiloxane component, and a vinyl monomer. Representative examples of dihydric phenols include 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl). ) Cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) sulfide, Examples thereof include bis (4-hydroxyphenyl) sulfone. A preferred dihydric phenol is a bis (4-hydroxyphenyl) alkane series, and bisphenol A is particularly preferred. The above dihydric phenols can be used alone or in combination of two or more.
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 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. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-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。 For example, a transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating in an inert gas atmosphere to distill the resulting alcohol or phenol. Is called. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification 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、また得られた芳香族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。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、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。 Monofunctional phenols usually used as a terminal terminator can be used. Particularly in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminator for controlling the molecular weight, and the resulting aromatic polycarbonate resin has a terminal monofunctional phenol. Since it is blocked by a group based on, it is superior in thermal stability as compared to those not. Such monofunctional phenols may be used as long as they are used as an end stopper for aromatic polycarbonate resins. Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, and p-cumyl. Phenol and isooctylphenol are mentioned.
芳香族ポリカーボネート樹脂の分子量は粘度平均分子量で表して好ましくは１．０×１０４〜３．５×１０４であり、より好ましくは１．３×１０４〜３．０×１０４であり、さらに好ましくは１．５×１０４〜２．５×１０４である。本発明でいう粘度平均分子量は塩化メチレン１００ｍｌにポリカーボネート樹脂０．７ｇを２０℃で溶解した溶液から求めた比粘度（ηｓｐ）を次式に挿入して求めたものである。
ηｓｐ／ｃ＝［η］＋０．４５×［η］２ｃ（但し［η］は極限粘度）
［η］＝１．２３×１０−４Ｍ０．８３
ｃ＝０．７
The molecular weight of the aromatic polycarbonate resin is preferably 1.0 × 10 4 to 3.5 × 10 4 , more preferably 1.3 × 10 4 to 3.0 × 10 4 , expressed as a viscosity average molecular weight. more preferably 1.5 × 10 4 ~2.5 × 10 4 . The viscosity average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (η sp ) obtained from a solution obtained by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation.
η sp /c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 −4 M 0.83
c = 0.7
本発明で使用される芳香族ポリカーボネート樹脂は、Ｆｅ含有量が２００ｐｐｂ以下およびＮａ含有量が１００ｐｐｂ以下である必要がある。当該量を超える場合、成形耐熱性が低下し、さらにはゲル化物が発生しやすくなるため好ましくない。Ｆｅ含有量は１５０ｐｐｂ以下が好ましく、１００ｐｐｂ以下がより好ましい。Ｎａ含有量は７０ｐｐｂ以下が好ましく、５０ｐｐｂ以下がより好ましい。また、Ｆｅ含有量とＮａ含有量との合計は２００ｐｐｂ以下が好ましく、１５０ｐｐｂ以下がより好ましく、１００ｐｐｂ以下がさらに好ましい。 The aromatic polycarbonate resin used in the present invention needs to have an Fe content of 200 ppb or less and an Na content of 100 ppb or less. When it exceeds the amount, molding heat resistance is lowered, and further, a gelled product is easily generated, which is not preferable. Fe content is preferably 150 ppb or less, and more preferably 100 ppb or less. The Na content is preferably 70 ppb or less, and more preferably 50 ppb or less. Moreover, the total of Fe content and Na content is preferably 200 ppb or less, more preferably 150 ppb or less, and even more preferably 100 ppb or less.
［ペンタエリスリトールテトラステアレートについて］
本発明で使用されるペンタエリスリトールテトラステアレートは、離型性、流動性などの成形性の向上だけでなく、ゲル化物発生の抑制に効果を発揮する。
ペンタエリスリトールテトラステアレートの酸価は、１．６〜４．０であり、２．０〜４．０が好ましく、２．２〜３．８がより好ましく、２．５〜３．５がさらに好ましい。純度は９５重量％以上が好ましく、純度９８重量％以上が特に好ましい。ペンタエリスリトールテトラステアレートの酸価の測定は、公知の方法を用いることができる。
[About pentaerythritol tetrastearate]
The pentaerythritol tetrastearate used in the present invention is effective not only in improving moldability such as releasability and fluidity but also in suppressing the generation of gelled products.
The acid value of pentaerythritol tetrastearate is 1.6 to 4.0, preferably 2.0 to 4.0, more preferably 2.2 to 3.8, and even more preferably 2.5 to 3.5. preferable. The purity is preferably 95% by weight or more, particularly preferably 98% by weight or more. A known method can be used to measure the acid value of pentaerythritol tetrastearate.
また、本発明で使用されるペンタエリスリトールテトラステアレートは、ＴＧＡ（熱重量解析）における５％重量減少温度が３６０℃以上であり、３７０℃以上が好ましい。３６０℃未満の場合、ブリードアウトによる金型汚れや成形品の外観異常の原因となり好ましくない。
さらに、本発明で使用されるペンタエリスリトールテトラステアレートは、Ｎａイオン濃度が１０ｐｐｍ以下であり、５ｐｐｍ以下が好ましく、１ｐｐｍ以下がより好ましい。当該量を超える場合、成形耐熱性が低下し、さらにはゲル化物が発生しやすくなるため好ましくない。
The pentaerythritol tetrastearate used in the present invention has a 5% weight loss temperature in TGA (thermogravimetric analysis) of 360 ° C. or higher, and preferably 370 ° C. or higher. When the temperature is lower than 360 ° C., it is not preferable because it causes mold stains due to bleeding out and abnormal appearance of the molded product.
Furthermore, the pentaerythritol tetrastearate used in the present invention has a Na ion concentration of 10 ppm or less, preferably 5 ppm or less, and more preferably 1 ppm or less. When it exceeds the amount, molding heat resistance is lowered, and further, a gelled product is easily generated, which is not preferable.
ペンタエリスリトールテトラステアレートの配合量は、芳香族ポリカーボネート樹脂１００重量部に対し０．２５〜０．５５重量部の範囲であり、０．３０〜０．５０重量部の範囲が好ましい。かかるペンタエリスリトールテトラステアレートの配合量が０．２５重量部に満たない場合、ゲル化物発生抑制等の所望の効果が得られず、０．５５重量部を超える場合、成形耐熱性に劣り好ましくない。 The blending amount of pentaerythritol tetrastearate is in the range of 0.25 to 0.55 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin, and preferably in the range of 0.30 to 0.50 parts by weight. When the blending amount of such pentaerythritol tetrastearate is less than 0.25 parts by weight, desired effects such as suppression of gelled product generation cannot be obtained, and when it exceeds 0.55 parts by weight, molding heat resistance is inferior, which is not preferable. .
［リン系安定剤について］
本発明で使用されるＣ１成分のリン系安定剤としては、特に成形時にポリカーボネート樹脂の劣化を抑制できるものであり、既にポリカーボネート樹脂の熱安定剤として知られたものが使用できる。例えば、ホスファイト系、ホスフェート系、ホスホナイト系の化合物が例示される。
[Phosphorus stabilizer]
As the phosphorus stabilizer of the C1 component used in the present invention, it is possible to suppress deterioration of the polycarbonate resin particularly at the time of molding, and those already known as a heat stabilizer for the polycarbonate resin can be used. For example, phosphite, phosphate and phosphonite compounds are exemplified.
ホスファイト化合物としては、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、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、トリス（ジエチルフェニル）ホスファイト、トリス（ジ−ｉｓｏ−プロピルフェニル）ホスファイト、トリス（ジ−ｎ−ブチルフェニル）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、トリス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）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、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、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、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−エチルフェニル）ペンタエリスリトールジホスファイト、フェニルビスフェノールＡペンタエリスリトールジホスファイト、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、ジシクロヘキシ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。 Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Ite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Examples thereof include bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.
更に他のホスファイト化合物としては二価フェノール類と反応し環状構造を有するものも使用できる。例えば、２，２’−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）（２，４−ジ−ｔｅｒｔ−ブチルフェニル）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）（２−ｔｅｒｔ−ブチル−４−メチルフェニル）ホスファイト、２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェニル）（２−ｔｅｒｔ−ブチル−４−メチルフェニル）ホスファイト、２，２’−エチリデンビス（４−メチル−６−ｔｅｒｔ−ブチルフェニル）（２−ｔｅｒｔ−ブチル−４−メチルフェニル）ホスファイトなどを挙げることができる。 Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.
ホスフェート化合物としては、トリブチルホスフェート、トリメチルホスフェート、トリクレジルホスフェート、トリフェニルホスフェート、トリクロルフェニルホスフェート、トリエチルホスフェート、ジフェニルクレジルホスフェート、ジフェニルモノオルソキセニルホスフェート、トリブトキシエチルホスフェート、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を挙げることができ、好ましくはトリフェニルホスフェート、トリメチルホスフェートである。 Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.
ホスホナイト化合物としては、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，３’−ビフェニレンジホスホナイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−３，３’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−４，３’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−３，３’−ビフェニレンジホスホナイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４−フェニル−フェニルホスホナイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−３−フェニル−フェニルホスホナイト、ビス（２，６−ジ−ｎ−ブチルフェニル）−３−フェニル−フェニルホスホナイト、ビス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−４−フェニル−フェニルホスホナイト、ビス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−３−フェニル−フェニルホスホナイト等があげられ、テトラキス（ジ−ｔｅｒｔ−ブチルフェニル）−ビフェニレンジホスホナイト、ビス（ジ−ｔｅｒｔ−ブチルフェニル）−フェニル−フェニルホスホナイトが好ましく、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−ビフェニレンジホスホナイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−フェニル−フェニルホスホナイトがより好ましい。かかるホスホナイト化合物は上記アルキル基が２以上置換したアリール基を有するホスファイト化合物との併用可能であり好ましい。 Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.
上記リン系安定剤は、１種のみならず２種以上を混合して用いることができる。上記リン系安定剤の中でも、ホスファイト化合物またはホスホナイト化合物が好ましい。殊にトリス（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’−ビフェニレンジホスホナイトおよびビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−フェニル−フェニルホスホナイトが好ましい。 The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable. In particular, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite and bis (2,4-di-) tert-Butylphenyl) -phenyl-phenylphosphonite is preferred.
上記のリン系安定剤の添加量は、Ａ成分１００重量部に対して０．０００５〜１重量部含有されることが必要である。好ましくはＡ成分１００重量部に対して０．００１〜０．５重量部であり、より好ましくは０．００５〜０．１重量部である。リン系安定剤の添加量がＡ成分１００重量部に対して０．０００５重量部未満だと、目的とする芳香族ポリカーボネート樹脂組成物の安定化効果が少なくなり、リン系安定剤の添加量が１重量部を超えると芳香族ポリカーボネート樹脂組成物の着色や成形品の割れ等を引き起こす可能性がある。 The added amount of the phosphorus stabilizer must be 0.0005 to 1 part by weight with respect to 100 parts by weight of component A. Preferably it is 0.001-0.5 weight part with respect to 100 weight part of A component, More preferably, it is 0.005-0.1 weight part. When the addition amount of the phosphorus stabilizer is less than 0.0005 parts by weight with respect to 100 parts by weight of the component A, the stabilization effect of the target aromatic polycarbonate resin composition is reduced, and the addition amount of the phosphorus stabilizer is reduced. If it exceeds 1 part by weight, the aromatic polycarbonate resin composition may be colored or the molded product may be cracked.
［ヒンダードフェノール系酸化防止剤について］
本発明で使用されるＣ２成分のヒンダードフェノール系酸化防止剤としては、特に繰り返し使用時のポリカーボネート樹脂の色抜けを抑制できるものであり、各種樹脂などに適用可能な酸化防止剤が利用できる。例えば、α−トコフェロール、ブチルヒドロキシトルエン、シナピルアルコール、ビタミンＥ、ｎ−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、２−ｔｅｒｔ−ブチル−６−（３’−ｔｅｒｔ−ブチル−５’−メチル−２’−ヒドロキシベンジル）−４−メチルフェニルアクリレート、２，６−ジ−ｔｅｒｔ−ブチル−４−（Ｎ，Ｎ−ジメチルアミノメチル）フェノール、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、２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−メチレンビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレンビス（４−メチル−６−シクロヘキシルフェノール）、２，２’−ジメチレン−ビス（６−α−メチル−ベンジル−ｐ−クレゾール）２，２’−エチリデン−ビス（４，６−ジ−ｔｅｒｔ−ブチルフェノール）、２，２’−ブチリデン−ビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−ブチリデンビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、トリエチレングリコール−Ｎ−ビス−３−（３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート、１，６−へ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］、ビス［２−ｔｅｒｔ−ブチル−４−メチル６−（３−ｔｅｒｔ−ブチル−５−メチル−２−ヒドロキシベンジル）フェニル］テレフタレート、３，９−ビス｛２−［３−（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］−１，１，−ジメチルエチル｝−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、４，４’−チオビス（６−ｔｅｒｔ−ブチル−ｍ−クレゾール）、４，４’−チオビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−チオビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、ビス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）スルフィド、４，４’−ジ−チオビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、４，４’−トリ−チオビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、２，２−チオジエチレンビス−［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］、２，４−ビス（ｎ−オクチルチオ）−６−（４−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−ブチルアニリノ）−１，３，５−トリアジン、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ミド）、Ｎ，Ｎ’−ビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオニル］ヒドラジン、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン、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、トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）イソシアヌレート、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、１，３，５−トリス（４−ｔｅｒｔ−ブチル−３−ヒドロキシ−２，６−ジメチルベンジル）イソシアヌレート、１，３，５−トリス２［３（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ］エチルイソシアヌレート、およびテトラキス［メチレン−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］メタンなどが挙げられ、特に好ましくはテトラキス［メチレン−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］メタンである。上記ヒンダードフェノール系安定剤は、単独でまたは２種以上を組合せて使用することができる。
[About hindered phenolic antioxidants]
As the C2 component hindered phenol antioxidant used in the present invention, it is possible to suppress the color loss of the polycarbonate resin particularly during repeated use, and antioxidants applicable to various resins can be used. For example, α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- ( 3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) ), 4,4′-methylenebis (2,6-di-tert-butylphenol), 2 2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis (4,6-di) -Tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N- Bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], Bis [2-tert-butyl-4-methyl 6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) Phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8, 10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2, 2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4′-di-thiobis (2,6-di-) tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodiethylenebis- [3- (3,5-di-tert Butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, N , N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris (3,5-di-te) t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] Examples thereof include methane, and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane is particularly preferable. The said hindered phenol type stabilizer can be used individually or in combination of 2 or more types.
上記のヒンダードフェノール系安定剤の添加量は、Ａ成分１００重量部に対して０．０００５〜１重量部含有されることが必要である。好ましくはＡ成分１００重量部に対して０．００１〜０．５重量部であり、より好ましくは０．００５〜０．１重量部である。ヒンダードフェノール系安定剤の添加量がＡ成分１００重量部に対して０．０００５重量部未満だと、目的とする芳香族ポリカーボネート樹脂組成物の色相安定化効果が少なくなり、１重量部を超えると芳香族ポリカーボネート樹脂組成物の着色や成形品の割れ等を引き起こす可能性がある。 The added amount of the hindered phenol stabilizer is required to be 0.0005 to 1 part by weight with respect to 100 parts by weight of the component A. Preferably it is 0.001-0.5 weight part with respect to 100 weight part of A component, More preferably, it is 0.005-0.1 weight part. If the amount of the hindered phenol stabilizer added is less than 0.0005 parts by weight with respect to 100 parts by weight of the component A, the hue stabilizing effect of the target aromatic polycarbonate resin composition is reduced, and the amount exceeds 1 part by weight. And coloring of the aromatic polycarbonate resin composition and cracking of the molded product may occur.
［エポキシ化合物について］
本発明で好適に使用されるＤ成分のエポキシ化合物は、良好な耐沸水性を付与するという目的や、金型腐食を抑制するという目的に対しては、基本的にエポキシ官能基を有するもの全てが適用できる。例えば、３，４ーエポキシシクロヘキシルメチルー３’，４’ーエポキシシクロヘキシルカルボキシレート、２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロセキサン付加物、メチルメタクリレートとグリシジルメタクリレートの共重合体、スチレンとグリシジルメタクリレートの共重合体等が挙げられる。
[About epoxy compounds]
For the purpose of imparting good boiling water resistance and the purpose of suppressing mold corrosion, the D component epoxy compound suitably used in the present invention is basically all those having an epoxy functional group. Is applicable. For example, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 1,2-epoxy-4- (2-oxiranyl) cyclosoxane of 2,2-bis (hydroxymethyl) -1-butanol Examples thereof include an adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, and a copolymer of styrene and glycidyl methacrylate.
上記のエポキシ化合物の添加量としては、Ａ成分１００重量部に対して０．００３〜０．１重量部が好ましい。より好ましくはＡ成分１００重量部に対して０．００４〜０．０５重量部であり、さらに好ましくは０．００５〜０．０３重量部である。エポキシ化合物の添加量が０．００３重量部以上であると、耐沸水性の改善効果が十分であり、また本発明の芳香族ポリカーボネート樹脂組成物を成形する際の金型腐食の抑制効果が十分である。エポキシ化合物の添加量が０．１重量部以下であると芳香族ポリカーボネート樹脂組成物の耐熱性が良好であり、結果として成形品の着色を引き起こす等の問題が抑制される。 As addition amount of said epoxy compound, 0.003-0.1 weight part is preferable with respect to 100 weight part of A components. More preferably, it is 0.004-0.05 weight part with respect to 100 weight part of A component, More preferably, it is 0.005-0.03 weight part. When the added amount of the epoxy compound is 0.003 parts by weight or more, the boiling water resistance improving effect is sufficient, and the mold corrosion inhibiting effect when molding the aromatic polycarbonate resin composition of the present invention is sufficient. It is. When the addition amount of the epoxy compound is 0.1 parts by weight or less, the heat resistance of the aromatic polycarbonate resin composition is good, and as a result, problems such as causing coloring of the molded product are suppressed.
［その他の添加剤について］
本発明の芳香族ポリカーボネート樹脂組成物は、更にブルーイング剤を芳香族ポリカーボネート樹脂組成物中０．０５〜３ｐｐｍ（重量割合）含むことが好ましい。芳香族ポリカーボネート樹脂成形品の黄色味を消し、自然な透明感を付与するために有効である。
[Other additives]
The aromatic polycarbonate resin composition of the present invention preferably further contains 0.05 to 3 ppm (weight ratio) of a bluing agent in the aromatic polycarbonate resin composition. This is effective for eliminating the yellowness of the aromatic polycarbonate resin molded product and imparting a natural transparency.
ここでブルーイング剤とは、橙色ないし黄色の光線を吸収することにより青色ないし紫色を呈する着色剤をいい、特に染料が好ましい。ブルーイング剤の配合により本発明のポリカーボネート樹脂組成物は、更に良好な色相を達成する。ここで重要な点はかかるブルーイング剤の配合量である。樹脂組成物中、ブルーイング剤が０．０５ｐｐｍ未満では色相の改善効果が不十分な場合がある一方、３ｐｐｍを超える場合には光線透過率が低下し適当ではない。より好ましいブルーイング剤の配合量は樹脂組成物中０．２〜２．５ｐｐｍ、更に好ましくは０．３〜２ｐｐｍの範囲である。 Here, the bluing agent refers to a colorant that exhibits a blue or purple color by absorbing light of orange or yellow color, and a dye is particularly preferable. By blending the bluing agent, the polycarbonate resin composition of the present invention achieves a better hue. The important point here is the blending amount of the bluing agent. In the resin composition, if the bluing agent is less than 0.05 ppm, the hue improving effect may be insufficient. On the other hand, if it exceeds 3 ppm, the light transmittance is not suitable. A more preferable blending amount of the bluing agent is 0.2 to 2.5 ppm, more preferably 0.3 to 2 ppm in the resin composition.
ブルーイング剤としては代表例として、バイエル（株）製のマクロレックスバイオレットＢおよびマクロレックスブルーＲＲや、クラリアントジャパン（株）製のポリシンスレンブルーＲＬＳなどが挙げられる。 Representative examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer Co., Ltd., and Polysynthrene Blue RLS manufactured by Clariant Japan Co., Ltd.
本発明の芳香族ポリカーボネート樹脂組成物には、発明の目的を損なわない範囲で上記ブルーイング剤以外にも各種の染顔料を使用することができる。特に透明性を維持する点から、染料が好適である。好ましい染料としてはペリレン系染料、クマリン系染料、チオインジゴ系染料、アンスラキノン系染料、チオキサントン系染料、紺青等のフェロシアン化物、ペリノン系染料、キノリン系染料、キナクリドン系染料、ジオキサジン系染料、イソインドリノン系染料、およびフタロシアニン系染料などを挙げることができる。更にビスベンゾオキサゾリル−スチルベン誘導体、ビスベンゾオキサゾリル−ナフタレン誘導体、ビスベンゾオキサゾリル−チオフェン誘導体、およびクマリン誘導体などの蛍光増白剤を使用することができる。これら染料および蛍光増白剤の使用量は、芳香族ポリカーボネート樹脂１００重量部あたり、０．０００１〜１重量部が好ましく、０．０００５〜０．５重量部がより好ましい。 In the aromatic polycarbonate resin composition of the present invention, various dyes and pigments can be used in addition to the bluing agent as long as the object of the invention is not impaired. In particular, a dye is preferable from the viewpoint of maintaining transparency. Preferred dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindo Examples thereof include linone dyes and phthalocyanine dyes. Furthermore, fluorescent whitening agents such as bisbenzoxazolyl-stilbene derivatives, bisbenzoxazolyl-naphthalene derivatives, bisbenzoxazolyl-thiophene derivatives, and coumarin derivatives can be used. The amount of these dyes and fluorescent whitening agent used is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight per 100 parts by weight of the aromatic polycarbonate resin.
本発明においては、本発明の目的を損なわない範囲で、前記以外の樹脂添加剤、例えば、紫外線吸収剤、難燃剤、帯電防止剤、滑剤、可塑剤などを配合してもよい。
本発明の芳香族ポリカーボネート樹脂組成物は、本発明の効果を損なわない範囲において、他の樹脂を含んでいてもよい。他の樹脂としては、例えば、ポリアミド樹脂；ポリイミド樹脂；ポリエーテルイミド樹脂；ポリウレタン樹脂；ポリフェニレンエーテル樹脂；ポリフェニレンスルフィド樹脂；ポリスルホン樹脂；ポリエチレン、ポリプロピレン等のポリオレフィン樹脂；ポリスチレン、アクリロニトリル−スチレン共重合体などのスチレン系樹脂；ポリメタクリレート樹脂、フェノール樹脂、エポキシ樹脂などが挙げられる。上記の他樹脂の配合量は、芳香族ポリカーボネート樹脂１００重量部に対し、通常４０重量部以下、好ましくは３０重量部以下である。
In the present invention, resin additives other than those described above, for example, ultraviolet absorbers, flame retardants, antistatic agents, lubricants, plasticizers, and the like may be blended within the range not impairing the object of the present invention.
The aromatic polycarbonate resin composition of the present invention may contain other resins as long as the effects of the present invention are not impaired. Other resins include, for example, polyamide resins; polyimide resins; polyetherimide resins; polyurethane resins; polyphenylene ether resins; polyphenylene sulfide resins; polysulfone resins; polyolefin resins such as polyethylene and polypropylene; Styrenic resin of polymethacrylate resin, phenol resin, epoxy resin, etc. are mentioned. The compounding amount of the other resin is usually 40 parts by weight or less, preferably 30 parts by weight or less, with respect to 100 parts by weight of the aromatic polycarbonate resin.
［芳香族ポリカーボネート樹脂組成物の成形方法等について］
本発明で使用される芳香族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、Ａ〜Ｃ成分並びに任意に他の添加剤を、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充分に混合した後、必要に応じて押出造粒器やブリケッティングマシーンなどによりかかる予備混合物の造粒を行い、その後ベント式二軸押出機に代表される溶融混練機で溶融混練し、ペレタイザーによりペレット化する方法が挙げられる。
[Method for molding aromatic polycarbonate resin composition, etc.]
Arbitrary methods are employ | adopted in order to manufacture the aromatic polycarbonate resin composition used by this invention. For example, the components A to C and optionally other additives are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer, and then extruded as necessary. There is a method of granulating such a premixed mixture using a vessel or a briquetting machine, then melt-kneading with a melt-kneader represented by a vent type twin screw extruder, and pelletizing with a pelletizer.
Ａ〜Ｃ成分およびその他の添加剤とのブレンドにあたっては、一段階で実施してもよいが、二段階以上に分けて実施してもよい。二段階に分けて実施する方法には、例えば、配合予定の芳香族ポリカーボネート樹脂パウダーやペレットの一部と添加剤とをブレンドした後、つまり、添加剤を芳香族ポリカーボネート樹脂パウダーで希釈して添加剤のマスターバッチとした後、これを用いて最終的なブレンドを行う方法がある。 The blending with the components A to C and other additives may be performed in one stage, but may be performed in two or more stages. For example, after blending a part of the aromatic polycarbonate resin powder or pellets to be blended with the additive, the additive is diluted with the aromatic polycarbonate resin powder and added. There is a method in which a final blend is carried out using a master batch of the agent.
例えば、一段階でブレンドする方法においては、各所定量の各添加剤を予め混合したものを芳香族ポリカーボネート樹脂パウダーやペレットとブレンドする方法、また、各所定量の各添加剤を各々別個に計量し、芳香族ポリカーボネート樹脂パウダーやペレットに順次添加後ブレンドする方法等を採用することができる。リン系化合物以外の添加剤の配合にあたっては、かかる添加剤を押出機に直接添加、注入する方法をとることができる。その場合、各添加剤を加熱融解後注入することも可能である。 For example, in the method of blending in one step, a method in which each predetermined amount of each additive is premixed with an aromatic polycarbonate resin powder or pellets, and each predetermined amount of each additive is weighed separately, For example, a method of sequentially adding to an aromatic polycarbonate resin powder or pellet and then blending can be employed. In blending additives other than phosphorus compounds, such additives can be directly added and injected into an extruder. In that case, it is also possible to inject each additive after heating and melting.
以下、実施例を挙げて詳細に説明するが、本発明はその趣旨を超えない限り、何らこれに限定されるものではない。なお実施例、比較例中の性能評価は下記の方法に従った。 Hereinafter, although an example is given and explained in detail, the present invention is not limited to this unless it exceeds the purpose. In addition, the performance evaluation in an Example and a comparative example followed the following method.
（１）酸価
ＪＩＳ Ｋ ００７０に準拠して中和滴定法により酸価（ＫＯＨｍｇ／ｇ）を求めた。
(1) Acid value The acid value (KOHmg / g) was calculated | required by the neutralization titration method based on JISK0070.
（２）熱重量測定による５％重量減少温度
ＴＡ−ｉｎｓｔｒｕｍｅｎｔｓ社製のＨｉ−Ｒｅｓ ＴＧＡ２９５０ Ｔｈｅｒｍｏｇｒａｖｉｍｅｔｒｉｃ Ａｎａｌｙｚｅｒを使用し、Ｎ２雰囲気下において２０℃／ｍｉｎで昇温させ、試料の減量が仕込み重量の５重量％となった時の温度をＴＧＡ５％重量減少温度として測定した。
(2) 5% weight reduction temperature by thermogravimetry Using Hi-Res TGA2950 Thermographic Analyzer manufactured by TA-instruments, the temperature was raised at 20 ° C./min in an N 2 atmosphere, and the weight loss of the sample was 5 of the charged weight. The temperature at which the weight percentage was reached was measured as the TGA 5% weight loss temperature.
（３）ペンタエリスリトールテトラステアレート中のＮａイオン量
イオンクロマトグラフによってペンタエリスリトールテトラステアレートのＮａイオン濃度を求めた。
(3) Na ion amount in pentaerythritol tetrastearate The Na ion concentration of pentaerythritol tetrastearate was determined by ion chromatography.
（４）芳香族ポリカーボネート樹脂中のＦｅおよびＮａ量
ＩＣＰ発光分光分析にて芳香族ポリカーボネート樹脂中のＦｅおよびＮａの含有量を求めた。
(4) Amounts of Fe and Na in the aromatic polycarbonate resin The contents of Fe and Na in the aromatic polycarbonate resin were determined by ICP emission spectroscopic analysis.
（５）ゲル化率
芳香族ポリカーボネート樹脂組成物からなる粉粒体（ペレット）５，０００ｍｇをアルミ箔上にて温度３００℃および空気中の条件において６時間加熱した後、ジクロロメタンに溶解し、孔径１０μｍのＰＴＦＥ製メンブランフィルターを通して濾過した際にフィルター上に捕集されるゲル化物の重量測定し、下記式によりゲル化率を求めた。
ゲル化率（％）＝（ゲル化物重量／試料重量）×１００
(5) Gelation rate After 5,000 mg of a granular material (pellet) made of an aromatic polycarbonate resin composition was heated on an aluminum foil for 6 hours at a temperature of 300 ° C. and in air, it was dissolved in dichloromethane and the pore size was reduced. When filtered through a 10 μm PTFE membrane filter, the weight of the gelled product collected on the filter was measured, and the gelation rate was determined by the following formula.
Gelation rate (%) = (weight of gelled product / weight of sample) × 100
（６）成形耐熱性
各実施例で得られたペレットを最大型締め力が８５Ｔｏｎの射出成形機にて、シリンダー温度３５０℃、金型温度８０℃の条件で、成形サイクル６０秒で成形して「滞留前の成形板」（縦９０ｍｍ×横５０ｍｍ×厚み２ｍｍ）を得た。さらに、該射出成形機のシリンダー中に樹脂を１０分間滞留させた後に成形して、「滞留後の成形板」（縦９０ｍｍ×横５０ｍｍ×厚み２ｍｍ）を得た。滞留前後の成形板の色相（Ｌ、ａ、ｂ）を、日本電色（株）製ＳＥ−２０００を用いてＣ光源反射法で測定し、下記式により色差ΔＥを求めた。ΔＥが大きいほど成形耐熱性に劣ることを示す。
ΔＥ＝｛（Ｌ−Ｌ’）２＋（ａ−ａ’）２＋（ｂ−ｂ’）２｝１／２
「滞留前の成形板」の色相：Ｌ、ａ、ｂ
「滞留後の成形板」の色相：Ｌ’、ａ’、ｂ’
(6) Molding heat resistance The pellets obtained in each example were molded in a molding cycle of 60 seconds on an injection molding machine with a maximum clamping force of 85 Ton and a cylinder temperature of 350 ° C and a mold temperature of 80 ° C. A “molded plate before residence” (length 90 mm × width 50 mm × thickness 2 mm) was obtained. Further, the resin was retained in the cylinder of the injection molding machine for 10 minutes and then molded to obtain a “molded plate after retention” (length 90 mm × width 50 mm × thickness 2 mm). The hue (L, a, b) of the molded plate before and after the residence was measured by the C light source reflection method using SE-2000 manufactured by Nippon Denshoku Co., Ltd., and the color difference ΔE was determined by the following formula. A larger ΔE indicates inferior molding heat resistance.
ΔE = {(L−L ′) 2 + (aa ′) 2 + (b−b ′) 2 } 1/2
Hue of “molded plate before stay”: L, a, b
Hue of “molded plate after residence”: L ′, a ′, b ′
（７）リプロ性
各実施例で得られたバージンペレットを３０ｍｍ径の単軸押出機にて２回リペレットした。得られたペレットの黄色度（ｂ）を日本電色（株）製ＳＥ−２０００を用いてＣ光源反射法で測定し、バージンペレットと２回リペレットの変色の度合い△ｂを求めた。△ｂが小さいほど色相の変化が小さく良好である。
Δｂ＝ｂ’−ｂ
「バージンペレットの色相」：ｂ
「２回リペレットの色相」：ｂ’
(7) Reproducibility Virgin pellets obtained in each example were re-pelleted twice with a 30 mm diameter single screw extruder. The yellowness (b) of the obtained pellet was measured by a C light source reflection method using SE-2000 manufactured by Nippon Denshoku Co., Ltd., and the degree of discoloration Δb between the virgin pellet and the twice repellet was determined. The smaller the Δb, the better the change in hue.
Δb = b′−b
"Virgin pellet hue": b
"Twice repellet hue": b '
（８）白モヤ発生率
各実施例で得られたペレットを１２０℃で５時間乾燥した後、住友重機社製射出成形機ＳＧ−１５０によりシリンダー温度３００℃、金型温度１１０℃の条件で、成形板（縦１５０ｍｍ×横１５０ｍｍ×厚み３ｍｍ）を作成した。ＨＩＤランプを該成形板（縦１５０ｍｍ×横１５０ｍｍ×厚み３ｍｍ）に照射し、成形板５０枚中に観察される白モヤ発生枚数から白モヤ発生率（％）を算出した。
(8) White haze generation rate After drying the pellets obtained in each example at 120 ° C for 5 hours, the injection molding machine SG-150 manufactured by Sumitomo Heavy Industries Co., Ltd. was used at a cylinder temperature of 300 ° C and a mold temperature of 110 ° C. A molded plate (length 150 mm × width 150 mm × thickness 3 mm) was prepared. The molding plate (length 150 mm × width 150 mm × thickness 3 mm) was irradiated with an HID lamp, and the white haze generation rate (%) was calculated from the number of white haze generation observed in 50 sheets of the molding plate.
表１における記号表記の各成分は下記の通りである。
（Ａ成分）
Ａ−１：ビスフェノールＡとホスゲンから界面重合法により製造された粘度平均分子量２２，５００、Ｆｅ含有量：５０ｐｐｂ、Ｎａ含有量：３０ｐｐｂの芳香族ポリカーボネート樹脂パウダー（帝人化成（株）製：パンライトＬ−１２２５ＷＰ）
Ａ−２：ビスフェノールＡとホスゲンから界面重合法により製造された粘度平均分子量２２，５００、Ｆｅ含有量：２１０ｐｐｂ、Ｎａ含有量：２０ｐｐｂの芳香族ポリカーボネート樹脂パウダー（帝人化成（株）製：パンライトＬ−１２２５ＷＰ）
（Ｂ成分）
Ｂ−１：酸価：３．１、ＴＧＡ５％重量減少温度：３７８℃、Ｎａイオン濃度：０．５ｐｐｍであるぺンタエリスリトールテトラステアレート（日油（株）製：ユニスターＨ−４７６）
Ｂ−２：酸価：１０．０、ＴＧＡ５％重量減少温度：３２２℃、Ｎａイオン濃度：２７．０ｐｐｍであるぺンタエリスリトールテトラステアレート（理研ビタミン（株）製：ＥＷ−４００）
Ｂ−３：酸価：１．０、ＴＧＡ５％重量減少温度：３８２℃、Ｎａイオン濃度：１３．４ｐｐｍであるぺンタエリスリトールテトラステアレート（エメリー オレオケミカルズ（株）製：ロキシオールＶＰＧ８６１）
（Ｃ成分）
Ｃ−１：リン系安定剤（主成分テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、クラリアントジャパン（株）製：ホスタノックスＰ−ＥＰＱ）
Ｃ−２：ヒンダードフェノール系酸化防止剤（テトラキス［メチレン−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］メタン、バスフジャパン（株）製 イルガノックス１０１０）
（Ｄ成分）
Ｄ−１：スチレンとグリシジルメタクリレートの共重合体（日油（株）製：マープルーフＧ−０２５０ＳＰ）
（その他添加剤）
ブルーイング剤（バイエル（株）製：マクロレックスバイオレットＢ）
Each component of the symbol notation in Table 1 is as follows.
(A component)
A-1: Aromatic polycarbonate resin powder having viscosity average molecular weight of 22,500, Fe content: 50 ppb, Na content: 30 ppb manufactured by interfacial polymerization from bisphenol A and phosgene (manufactured by Teijin Chemicals Ltd .: Panlite) L-1225WP)
A-2: Aromatic polycarbonate resin powder with viscosity average molecular weight of 22,500, Fe content: 210 ppb, Na content: 20 ppb produced from bisphenol A and phosgene by interfacial polymerization method (manufactured by Teijin Chemicals Ltd .: Panlite) L-1225WP)
(B component)
B-1: Pentaerythritol tetrastearate having an acid value of 3.1, a TGA 5% weight loss temperature of 378 ° C., and an Na ion concentration of 0.5 ppm (manufactured by NOF Corporation: Unistar H-476)
B-2: Pentaerythritol tetrastearate having an acid value of 10.0, a TGA 5% weight loss temperature of 322 ° C., and an Na ion concentration of 27.0 ppm (manufactured by Riken Vitamin Co., Ltd .: EW-400)
B-3: Pentaerythritol tetrastearate having an acid value of 1.0, a TGA 5% weight loss temperature of 382 ° C., and an Na ion concentration of 13.4 ppm (manufactured by Emery Oleochemicals: Roxyol VPG861)
(C component)
C-1: Phosphorus stabilizer (main component tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, manufactured by Clariant Japan KK: Hostanox P-EPQ)
C-2: hindered phenol antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane, irganox 1010 manufactured by Basf Japan Co., Ltd.)
(D component)
D-1: Copolymer of styrene and glycidyl methacrylate (manufactured by NOF Corporation: Marproof G-0250SP)
(Other additives)
Blueing agent (manufactured by Bayer Co., Ltd .: Macrolex Violet B)
［実施例１〜９、比較例１〜１０］
ビスフェノールＡとホスゲンから界面縮重合法により製造された芳香族ポリカーボネート樹脂パウダー１００重量部に、表１記載の各種添加剤を各配合量で、ブレンダーにて混合した。スクリュー径３０ｍｍのベント付単軸押出機により、シリンダー温度２８０℃で溶融混練し、ストランドカットによりペレットを作成した。
下表１から明らかなように、本発明の芳香族ポリカーボネート樹脂組成物は、成形耐熱性、リプロ性に優れ、ゲル化物や白モヤの発生が抑制されたことが分かる。
[Examples 1 to 9, Comparative Examples 1 to 10]
Various additives shown in Table 1 were mixed in blenders in various amounts in 100 parts by weight of aromatic polycarbonate resin powder produced from bisphenol A and phosgene by the interfacial condensation polymerization method. The mixture was melt-kneaded at a cylinder temperature of 280 ° C. using a vented single screw extruder with a screw diameter of 30 mm, and pellets were prepared by strand cutting.
As is clear from Table 1 below, it can be seen that the aromatic polycarbonate resin composition of the present invention is excellent in molding heat resistance and reproducibility, and the generation of gelled products and white haze is suppressed.
本発明の芳香族ポリカーボネート樹脂組成物から形成された成形品は、特にシートやフィルムの成形品として有用である。 The molded article formed from the aromatic polycarbonate resin composition of the present invention is particularly useful as a molded article for sheets and films.
Claims (9)
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| JP2014231581A (en) * | 2013-05-30 | 2014-12-11 | 住化スタイロンポリカーボネート株式会社 | Polycarbonate resin composition |
| WO2024048485A1 (en) * | 2022-09-01 | 2024-03-07 | 三菱瓦斯化学株式会社 | Method for producing polycarbonate resin molded product |
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| WO2010024363A1 (en) * | 2008-08-26 | 2010-03-04 | 帝人化成株式会社 | Method for manufacturing molded article |
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| WO2024048485A1 (en) * | 2022-09-01 | 2024-03-07 | 三菱瓦斯化学株式会社 | Method for producing polycarbonate resin molded product |
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