JP5267582B2 - Flame retardant polycarbonate resin composition and molded body using the same - Google Patents
Flame retardant polycarbonate resin composition and molded body using the same Download PDFInfo
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- JP5267582B2 JP5267582B2 JP2011010620A JP2011010620A JP5267582B2 JP 5267582 B2 JP5267582 B2 JP 5267582B2 JP 2011010620 A JP2011010620 A JP 2011010620A JP 2011010620 A JP2011010620 A JP 2011010620A JP 5267582 B2 JP5267582 B2 JP 5267582B2
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- polycarbonate resin
- weight
- resin composition
- parts
- flame
- Prior art date
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- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 110
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 110
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000003063 flame retardant Substances 0.000 title claims abstract description 37
- 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 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 239000012765 fibrous filler Substances 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 239000013585 weight reducing agent Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 239000011342 resin composition Substances 0.000 abstract 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 14
- 238000002485 combustion reaction Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- 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 10
- 239000000835 fiber Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 238000004898 kneading Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 150000003460 sulfonic acids Chemical class 0.000 description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000006081 fluorescent whitening agent Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000012756 surface treatment agent Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012784 inorganic fiber Substances 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- BHVOQJHAIJQXNK-UHFFFAOYSA-N 3,4-difluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(F)C(F)=C1 BHVOQJHAIJQXNK-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920006361 Polyflon Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 229960000969 phenyl salicylate Drugs 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- YMZUKGOWUROXET-UHFFFAOYSA-M potassium;2-(trifluoromethyl)benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC=C1C(F)(F)F YMZUKGOWUROXET-UHFFFAOYSA-M 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- POLSVAXEEHDBMJ-UHFFFAOYSA-N (2-hydroxy-4-octadecoxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 POLSVAXEEHDBMJ-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- WZHKDGJSXCTSCK-FNORWQNLSA-N (E)-Hept-3-ene Chemical compound CCC\C=C\CC WZHKDGJSXCTSCK-FNORWQNLSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- PZDAAZQDQJGXSW-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)benzene Chemical group C1=CC(F)=CC=C1C1=CC=C(F)C=C1 PZDAAZQDQJGXSW-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- VDCOTRGOYNBXRU-UHFFFAOYSA-N 2,3-difluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(F)=C1F VDCOTRGOYNBXRU-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- FRUWCRYDUOZXFA-UHFFFAOYSA-M 2,4-difluorobenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C(F)C=C1F FRUWCRYDUOZXFA-UHFFFAOYSA-M 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- AQROEYPMNFCJCK-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-tert-butyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=CC=CC3=N2)=C1O AQROEYPMNFCJCK-UHFFFAOYSA-N 0.000 description 1
- IXSGUIFSMPTAGW-UHFFFAOYSA-N 2-(trifluoromethyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C(F)(F)F IXSGUIFSMPTAGW-UHFFFAOYSA-N 0.000 description 1
- WFYSPVCBIJCZPX-UHFFFAOYSA-N 2-[4-(1,3-benzoxazol-2-yl)naphthalen-1-yl]-1,3-benzoxazole Chemical compound C12=CC=CC=C2C(C=2OC3=CC=CC=C3N=2)=CC=C1C1=NC2=CC=CC=C2O1 WFYSPVCBIJCZPX-UHFFFAOYSA-N 0.000 description 1
- WQPXTXLOSPMDBZ-UHFFFAOYSA-N 2-butyl-3,5-ditert-butyl-4-hydroxy-6-phenylbenzoic acid Chemical group OC1=C(C(C)(C)C)C(CCCC)=C(C(O)=O)C(C=2C=CC=CC=2)=C1C(C)(C)C WQPXTXLOSPMDBZ-UHFFFAOYSA-N 0.000 description 1
- BPPSPQPCYPJYFC-UHFFFAOYSA-N 2-butyl-6-fluoro-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound CCCCC1=CC=CC2(F)OC12 BPPSPQPCYPJYFC-UHFFFAOYSA-N 0.000 description 1
- YTZWQUYIRHGHMJ-UHFFFAOYSA-N 3-(1,2-diamino-2-phenylethenyl)benzene-1,2-disulfonic acid Chemical compound NC(=C(C1=C(C(=CC=C1)S(=O)(=O)O)S(=O)(=O)O)N)C1=CC=CC=C1 YTZWQUYIRHGHMJ-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- MPWGZBWDLMDIHO-UHFFFAOYSA-N 3-propylphenol Chemical compound CCCC1=CC=CC(O)=C1 MPWGZBWDLMDIHO-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 1
- MPIFMUARWKUNQZ-UHFFFAOYSA-N 4-[2-(2-phenylethenyl)phenyl]-2h-benzo[e]benzotriazole Chemical compound C=1C=CC=C(C=2C=3N=NNC=3C3=CC=CC=C3C=2)C=1C=CC1=CC=CC=C1 MPIFMUARWKUNQZ-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
- UDKBLXVYLPCIAZ-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-3,6-di(propan-2-yl)phenyl]phenol Chemical compound C=1C=C(O)C=CC=1C=1C(C(C)C)=CC=C(C(C)C)C=1C1=CC=C(O)C=C1 UDKBLXVYLPCIAZ-UHFFFAOYSA-N 0.000 description 1
- RQTDWDATSAVLOR-UHFFFAOYSA-N 4-[3,5-bis(4-hydroxyphenyl)phenyl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC(C=2C=CC(O)=CC=2)=CC(C=2C=CC(O)=CC=2)=C1 RQTDWDATSAVLOR-UHFFFAOYSA-N 0.000 description 1
- CIEGINNQDIULCT-UHFFFAOYSA-N 4-[4,6-bis(4-hydroxyphenyl)-4,6-dimethylheptan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)CC(C)(C=1C=CC(O)=CC=1)CC(C)(C)C1=CC=C(O)C=C1 CIEGINNQDIULCT-UHFFFAOYSA-N 0.000 description 1
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- PCKPVGOLPKLUHR-UHFFFAOYSA-N OH-Indolxyl Natural products C1=CC=C2C(O)=CNC2=C1 PCKPVGOLPKLUHR-UHFFFAOYSA-N 0.000 description 1
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- VWIUJRUTUZSAAA-UHFFFAOYSA-M [K+].[O-]S(=O)(=O)c1cc(ccc1F)-c1ccc(F)cc1 Chemical compound [K+].[O-]S(=O)(=O)c1cc(ccc1F)-c1ccc(F)cc1 VWIUJRUTUZSAAA-UHFFFAOYSA-M 0.000 description 1
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- 125000003828 azulenyl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
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- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- JYGFTBXVXVMTGB-UHFFFAOYSA-N indolin-2-one Chemical compound C1=CC=C2NC(=O)CC2=C1 JYGFTBXVXVMTGB-UHFFFAOYSA-N 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- SJDACOMXKWHBOW-UHFFFAOYSA-N oxyphenisatine Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2NC1=O SJDACOMXKWHBOW-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 1
- RYDSCANGUMBFRB-UHFFFAOYSA-M potassium;fluoromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)CF RYDSCANGUMBFRB-UHFFFAOYSA-M 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- VYGMKJRCQSPVAI-UHFFFAOYSA-M sodium 2,4-difluorobenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)c1ccc(F)cc1F VYGMKJRCQSPVAI-UHFFFAOYSA-M 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- VJZDBZOTAGNXCT-UHFFFAOYSA-M sodium;2-fluoro-5-(4-fluorophenyl)benzenesulfonate Chemical compound [Na+].C1=C(F)C(S(=O)(=O)[O-])=CC(C=2C=CC(F)=CC=2)=C1 VJZDBZOTAGNXCT-UHFFFAOYSA-M 0.000 description 1
- QTKQPIOWDCRUHR-UHFFFAOYSA-M sodium;fluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)CF QTKQPIOWDCRUHR-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000001721 transfer moulding Methods 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
- 235000011845 white flour Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、難燃性ポリカーボネート樹脂組成物及びこれを含むポリカーボネート樹脂成形体に関する。更に詳しくは、ブロム化合物や燐酸エステルなどの難燃剤を使用せずとも、機械的強度、耐熱性、耐加水分解性(耐湿性)、並びに熱安定性の全てに優れる難燃性ポリカーボネート樹脂組成物、及びこれを含む成形体に関する。 The present invention relates to a flame retardant polycarbonate resin composition and a polycarbonate resin molded body containing the same. More specifically, a flame retardant polycarbonate resin composition having excellent mechanical strength, heat resistance, hydrolysis resistance (moisture resistance), and thermal stability without using a flame retardant such as a bromine compound or a phosphate ester. And a molded body including the same.
ポリカーボネート樹脂は優れた機械的性質、熱的性質、電気的性質を有しており、自動車分野、OA機器分野、電気・電子分野、建材分野を始め、幅広い分野で使用されている。近年、OA機器、家電製品等の用途を中心として、合成樹脂材料への難燃化の要望が高まっており、これに応えるために多数の難燃剤が提案されている。 Polycarbonate resins have excellent mechanical properties, thermal properties, and electrical properties, and are used in a wide range of fields including the automotive field, OA equipment field, electrical / electronic field, and building material field. In recent years, there has been an increasing demand for flame retardancy of synthetic resin materials, mainly for applications such as OA equipment and home appliances, and many flame retardants have been proposed to meet this demand.
ポリカーボネート樹脂の難燃化技術としては、当初、主にブロム化合物等を難燃化剤として使用することが行われてきた。しかしブロム化合物による周辺環境への負担増加や、シリンダー、スクリュー、及び金型等の樹脂成形機における腐食問題などから、その使用量低減や代替難燃剤の開発がなされた。そして代替難燃剤として、例えばリン酸エステル系化合物が提案された。しかしこの様な難燃剤を含むポリカーボネート樹脂組成物は、機械的強度や耐熱性が低下するという問題があった。 As a flame retardant technique for polycarbonate resin, it has been used at first to mainly use a bromo compound or the like as a flame retardant. However, due to the increased burden on the surrounding environment due to the bromine compound and the corrosion problem in resin molding machines such as cylinders, screws, and dies, the amount used was reduced and alternative flame retardants were developed. As an alternative flame retardant, for example, phosphate ester compounds have been proposed. However, the polycarbonate resin composition containing such a flame retardant has a problem that mechanical strength and heat resistance are lowered.
一方、臭素化合物やリン酸エステル系化合物を用いない方法として、ポリカーボネート樹脂に炭素数4〜8のパーフルオロアルキルスルホン酸金属塩や第4級アンモニウム塩を用いる方法(特許文献1参照)や、炭素数1〜3のパーフルオロアルキルスルホン酸金属塩を用いる方法が提案されている(特許文献2参照)。しかしこれらの方法でも、得られるポリカーボネート樹脂組成物の難燃性や熱安定性は不十分であった。 On the other hand, as a method not using a bromine compound or a phosphate ester-based compound, a method using a perfluoroalkylsulfonic acid metal salt or quaternary ammonium salt having 4 to 8 carbon atoms in a polycarbonate resin (see Patent Document 1), carbon A method using metal salts of perfluoroalkylsulfonic acid having 1 to 3 has been proposed (see Patent Document 2). However, even with these methods, the flame retardancy and thermal stability of the obtained polycarbonate resin composition were insufficient.
また難燃化剤として、pH5〜9のパーフルオロアルキルスルホン酸の塩水溶液又は水分散液を用いる方法(特許文献3参照)や、アルコール不溶成分含有量を低減したパーフルオロアルキルスルホン酸塩を用いる方法(特許文献4)、そして高フッ素化化合物を用いる方法(特許文献5)、及びイオンクロマトグラフィー法により測定したフッ化物イオンの含有量が重量割合で0.2〜20ppmであるパーフルオロアルキルスルホン酸アルカリ金属塩を用いる方法(特許文献6)などが提案されている。しかし得られるポリカーボネート樹脂組成物の難燃性や、樹脂分子量当の諸物性等は、未だ不十分なままであった。 Further, as a flame retardant, a method using a salt aqueous solution or aqueous dispersion of a perfluoroalkyl sulfonic acid having a pH of 5 to 9 (see Patent Document 3) or a perfluoroalkyl sulfonate having a reduced alcohol-insoluble component content is used. Perfluoroalkyl sulfone having a content of fluoride ion of 0.2 to 20 ppm by weight (Patent Document 4), a method using a highly fluorinated compound (Patent Document 5), and an ion chromatography method A method using an acid alkali metal salt (Patent Document 6) has been proposed. However, the flame retardancy of the obtained polycarbonate resin composition and various physical properties corresponding to the resin molecular weight still remain insufficient.
本発明の目的は、少量の難燃剤の配合により、ポリカーボネート樹脂本来の特性を損なうことなく、且つ難燃性が著しく優れたポリカーボネート樹脂組成物、及びこれを含むポリカーボネート樹脂成形体を提供することにある。 An object of the present invention is to provide a polycarbonate resin composition that is extremely excellent in flame retardancy without impairing the original properties of the polycarbonate resin by blending a small amount of a flame retardant, and a polycarbonate resin molded article including the same. is there.
本発明者は上述した課題を解決するために鋭意検討を重ねた結果、意外にも、特定の、低い割合でフッ素化された炭化水素基を有するスルホン酸金属塩をポリカーボネート樹脂組成物の難燃化剤として用いることで、その使用量が僅かであっても、極めて優れた難燃性を有するポリカーボネート樹脂組成物となるばかりでなく、ポリカーボネート樹脂の特性である機械的強度、耐熱性、耐加水分解性(耐湿性)、並びに熱安定性の全てに優れたものとなることを見出し、本発明を完成させた。
即ち本発明の要旨は、フッ素化率が1%以上50%以下であるアリール基を有するスルホン酸金属塩、ポリテトラフルオロエチレン、及び繊維状充填剤を含み、スルホン酸金属塩の含有量が、ポリカーボネート樹脂100重量部に対して0.001〜1重量部であり、ポリテトラフルオロエチレンの含有量が、ポリカーボネート樹脂100重量部に対して、0.1〜5重量部であり、繊維状充填剤の含有量が、ポリカーボネート樹脂100重量部に対して1〜30重量部であり、かつ、分子量低下((原材料のポリカーボネート樹脂の分子量)−(ポリカーボネート樹脂組成物ペレットの分子量))が2700以下であることを特徴とする難燃性ポリカーボネート樹脂組成物、及びこれを含むポリカーボネート樹脂成形体に存する。
As a result of intensive studies in order to solve the above-mentioned problems, the present inventor surprisingly found that a specific, sulfonic acid metal salt having a hydrocarbon group fluorinated at a low ratio is flame retardant of a polycarbonate resin composition. By using it as an agent, even if the amount used is small, not only becomes a polycarbonate resin composition having extremely excellent flame retardancy, but also the mechanical strength, heat resistance, water resistance, which are the characteristics of the polycarbonate resin. The present invention was completed by finding out that it was excellent in all of decomposability (moisture resistance) and thermal stability.
That aspect of the present invention, the sulfonic acid metal salt fluorination rate has an aryl group is 50% or less than 1%, polytetrafluoroethylene, and saw including a fibrous filler, the content of the sulfonic acid metal salt , 0.001 to 1 part by weight with respect to 100 parts by weight of the polycarbonate resin, and the content of polytetrafluoroethylene is 0.1 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin. The content of the agent is 1 to 30 parts by weight with respect to 100 parts by weight of the polycarbonate resin, and the molecular weight reduction ((molecular weight of the raw material polycarbonate resin) − (molecular weight of the polycarbonate resin composition pellet)) is 2700 or less. It exists in the flame-retardant polycarbonate resin composition characterized by being, and the polycarbonate resin molding containing this.
本発明の難燃性ポリカーボネート樹脂組成物、及びこれを含むポリカーボネート樹脂成形体は、難燃化剤として特定のスルホン酸金属塩を用いることによって、その含有量を低減することが可能となり、周辺環境への負荷を抑えることが可能となった。そして溶融熱安定性に優れるばかりでなく、ポリカーボネート樹脂本来の機械的強度、耐熱性、電気的特性等を保持した、ポリカーボネート樹脂組成物を提供することが出来る。この様な特徴を有することから、本発明のポリカーボネート樹脂組成物は、OA機器分野、電気・電子分野、精密機械分野、建材分野を始め、幅広い用途への使用が期待できる。 The flame-retardant polycarbonate resin composition of the present invention and the polycarbonate resin molded article containing the flame-retardant polycarbonate resin composition can be reduced in content by using a specific sulfonic acid metal salt as a flame retardant, and the surrounding environment. It became possible to suppress the load on the. In addition, it is possible to provide a polycarbonate resin composition that not only has excellent heat stability but also retains the original mechanical strength, heat resistance, electrical characteristics, and the like of the polycarbonate resin. Since it has such characteristics, the polycarbonate resin composition of the present invention can be expected to be used in a wide range of applications including the OA equipment field, the electric / electronic field, the precision machine field, and the building material field.
本発明について、以下具体的に説明する。
本発明に使用されるポリカーボネート樹脂は、従来公知の任意のものを使用することが出来る。本発明では、ポリカーボネート樹脂として、芳香族ポリカーボネート樹脂、脂肪族ポリカーボネート樹脂、芳香族−脂肪族ポリカーボネート樹脂を使用できるが、中でも芳香族ポリカーボネート樹脂が好ましい。
The present invention will be specifically described below.
As the polycarbonate resin used in the present invention, any conventionally known polycarbonate resin can be used. In the present invention, an aromatic polycarbonate resin, an aliphatic polycarbonate resin, or an aromatic-aliphatic polycarbonate resin can be used as the polycarbonate resin, and among them, the aromatic polycarbonate resin is preferable.
尚、本発明で用いられるポリカーボネート樹脂とは、ポリカーボネート樹脂単独(ポリカーボネート樹脂単独とは、ポリカーボネート樹脂の1種のみを含む態様に限定されず、例えば、モノマー組成や分子量が互いに異なる複数種のポリカーボネート樹脂を含む態様を含む意味で用いる。)や、ポリカーボネート樹脂と他の熱可塑性樹脂とのアロイ(混合物)の他、例えば、本発明の目的である難燃性を更に高める目的で、シロキサン構造を有するオリゴマーまたはポリマーとの共重合体等の、ポリカーボネート樹脂を主体とする共重合体をも含むものである。 The polycarbonate resin used in the present invention is a polycarbonate resin alone (a polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin. For example, a plurality of types of polycarbonate resins having different monomer compositions and molecular weights are used. In addition to an alloy (mixture) of polycarbonate resin and other thermoplastic resin, for example, it has a siloxane structure for the purpose of further improving the flame retardancy that is the object of the present invention. It also includes a copolymer mainly composed of a polycarbonate resin, such as an oligomer or a copolymer with a polymer.
該アロイや共重合体としては、ポリカーボネート樹脂100重量部に対する他の熱可塑性樹脂(共重合体の場合にはそのブロック部分)の含有量が100重量部以下、中でも70重量部以下更には60重量部以下、特に50重両部以下であることが好ましい。ポリカーボネート樹脂以外の、他の熱可塑性樹脂としては、ポリブチレンテレフタレート、ポリエチレンテレフタレートのようなポリエステル樹脂、ポリアミド樹脂、HIPS樹脂あるいはABS樹脂等のスチレン系樹脂、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂等が挙げられる。中でも熱可塑性ポリエステル樹脂が好ましく、特にポリブチレンテレフタレート樹脂またはポリエチレンテレフタレート樹脂が好ましい。 As the alloy or copolymer, the content of another thermoplastic resin (the block portion in the case of a copolymer) is 100 parts by weight or less, particularly 70 parts by weight or less, and 60 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Part or less, particularly preferably 50 parts or less. Other thermoplastic resins other than polycarbonate resin include polyester resins such as polybutylene terephthalate and polyethylene terephthalate, styrene resins such as polyamide resin, HIPS resin and ABS resin, polyolefin resins such as polyethylene and polypropylene, and the like. . Of these, a thermoplastic polyester resin is preferable, and a polybutylene terephthalate resin or a polyethylene terephthalate resin is particularly preferable.
また、本発明に使用されるポリカーボネート樹脂の製造方法は任意であり、例えばホスゲン法(界面重合法)や、溶融法(エステル交換法)等が挙げられる。具体的には例えば、芳香族ヒドロキシ化合物、またはこれと少量のポリヒドロキシ化合物を、ホスゲンまたは炭酸のジエステルと反応させることによる、分岐していてもよい芳香族ポリカーボネート樹脂の製造方法が挙げられる。さらに、溶融法を用いた場合には、末端基のOH基量を調整した芳香族ポリカーボネート樹脂を製造することが出来る。 Moreover, the manufacturing method of polycarbonate resin used for this invention is arbitrary, For example, the phosgene method (interfacial polymerization method), a melting method (transesterification method), etc. are mentioned. Specific examples include a method for producing an optionally branched aromatic polycarbonate resin by reacting an aromatic hydroxy compound or a small amount of a polyhydroxy compound with phosgene or a diester of carbonic acid. Furthermore, when the melting method is used, an aromatic polycarbonate resin in which the amount of OH groups of terminal groups is adjusted can be produced.
本発明に使用されるポリカーボネート樹脂として、例えば芳香族ポリカーボネート樹脂用いる際、その製造方法としては、芳香族ジヒドロキシ化合物をホスゲンまたは炭酸のジエステルと反応させる方法が挙げられる。 As the polycarbonate resin used in the present invention, for example, when an aromatic polycarbonate resin is used, the production method includes a method of reacting an aromatic dihydroxy compound with phosgene or a carbonic acid diester.
原料の芳香族ジヒドロキシ化合物としては、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)、テトラメチルビスフェノールA、ビス(4−ヒドロキシフェニル)−p−ジイソプロピルベンゼン、ハイドロキノン、レゾルシノール、4,4−ジヒドロキシジフェニルなどが挙げられ、中でもビスフェノールAが好ましい。また、本発明の目的である難燃性を更に高める目的で、上述の芳香族ジヒドロキシ化合物にスルホン酸テトラアルキルホスホニウムが1個以上結合したやシロキサン構造を有する両末端フェノール性OH基含有のポリマーあるいはオリゴマーを使用することができる。 As the raw material aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4 , 4-dihydroxydiphenyl and the like, and among them, bisphenol A is preferable. In addition, for the purpose of further improving the flame retardancy, which is the object of the present invention, a polymer containing both terminal phenolic OH groups having one or more tetraalkylphosphonium sulfonates bonded to the above-mentioned aromatic dihydroxy compound or a siloxane structure or Oligomers can be used.
本発明に使用されるポリカーボネート樹脂の製造方法において、分岐したポリカーボネート樹脂を得るには、例えばフロログルシン、4,6−ジメチル−2,4,6−トリス(4−ヒドロキシフェニル)ヘプテン−2、4,6−ジメチル−2,4,6−トリス(4−ヒドロキシフェニル)ヘプタン、2,6−ジメチル−2,4,6−トリス(4−ヒドロキシフェニル)ヘプテン−3、1,3,5−トリス(4−ヒドロキシフェニル)ベンゼン、1,1,1−トリス(4−ヒドロキシフェニル)エタンなどで示されるポリヒドロキシ化合物、あるいは3,3−ビス(4−ヒドロキシアリール)オキシインドール(=イサチンビスフェノール)、5−クロルイサチン、5,7−ジクロルイサチン、5−臭素イサチンなどを前記芳香族ジヒドロキシ化合物の一部として用いればよく、その使用量は0.01〜10モル%、好ましくは0.1〜2モル%である。 In the method for producing a polycarbonate resin used in the present invention, a branched polycarbonate resin can be obtained by, for example, phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4, 6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3, 1,3,5-tris ( 4-hydroxyphenyl) benzene, a polyhydroxy compound represented by 1,1,1-tris (4-hydroxyphenyl) ethane or the like, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-arouisatin, 5,7-dichloroisatin, 5-bromine isatin and the like as the aromatic dihydroxy It may be used as part of a compound, its amount from 0.01 to 10 mol%, preferably 0.1 to 2 mol%.
またポリカーボネート樹脂の分子量を調節する方法としては、例えば一価芳香族ヒドロキシ化合物を用いる方法が挙げられる。具体的にはm−又はp−メチルフェノール、m−又はp−プロピルフェノール、p−t−ブチルフェノール及びp−長鎖アルキル置換フェノールなどを用いて、分子量を調整すればよい。 Examples of the method for adjusting the molecular weight of the polycarbonate resin include a method using a monovalent aromatic hydroxy compound. Specifically, the molecular weight may be adjusted using m- or p-methylphenol, m- or p-propylphenol, pt-butylphenol, p-long chain alkyl-substituted phenol, or the like.
本発明で用いる芳香族ポリカーボネート樹脂としては、好ましくは、2,2−ビス(4−ヒドロキシフェニル)プロパンから誘導されるポリカーボネート樹脂、または2,2−ビス(4−ヒドロキシフェニル)プロパンと他の芳香族ジヒドロキシ化合物とから誘導されるポリカーボネート共重合体が挙げられる。 The aromatic polycarbonate resin used in the present invention is preferably a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other aromatics. And a polycarbonate copolymer derived from an aromatic dihydroxy compound.
本発明に使用されるポリカーボネート樹脂の分子量は、溶媒としてメチレンクロライドを用い、温度25℃で測定された溶液粘度より換算した粘度平均分子量で表す。この粘度平均分子量が低すぎると機械的強度が不足する場合があり、逆に高すぎても成形性が低下る場合がある。よってその粘度平均分子量は、14000以上、中でも15000以上、特に16000以上であることが好ましく、その上限は30000以下、中でも28000以下、特に26000以下であることが好ましい。 The molecular weight of the polycarbonate resin used in the present invention is represented by a viscosity average molecular weight converted from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. If the viscosity average molecular weight is too low, the mechanical strength may be insufficient. On the other hand, if the viscosity average molecular weight is too high, the moldability may be reduced. Therefore, the viscosity average molecular weight is preferably 14,000 or more, more preferably 15000 or more, particularly preferably 16000 or more, and the upper limit thereof is preferably 30000 or less, particularly 28000 or less, particularly 26000 or less.
更にポリカーボネート樹脂としては、バージン原料だけでなく、使用済みの製品から再生されたポリカーボネート樹脂、いわゆるマテリアルリサイクルされたポリカーボネート樹脂の使用も可能である。使用済みの製品としては、光学ディスクなどの光記録媒体、導光板、自動車窓ガラスや自動車ヘッドランプレンズ、風防などの車両透明部材、水ボトルなどの容器、メガネレンズ、防音壁やガラス窓、波板などの建築部材などが好ましく挙げられる。また、再生ポリカーボネート樹脂としては、製品の不適合品、スプルー、またはランナーなどから得られた粉砕品またはそれらを溶融して得たペレットなども使用可能である。 Further, as the polycarbonate resin, it is possible to use not only virgin raw materials but also polycarbonate resins regenerated from used products, so-called material-recycled polycarbonate resins. Used products include optical recording media such as optical disks, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, glasses lenses, soundproof walls and glass windows, waves A building member such as a plate is preferred. In addition, as the recycled polycarbonate resin, non-conforming product, pulverized product obtained from sprue or runner or pellets obtained by melting them can be used.
本発明の特徴は、難燃剤として、フッ素化率が50%以下である炭化水素基を有するスルホン酸金属塩を含むことにある(以下、「フッ素化率が50%以下である炭化水素基を有するスルホン酸金属塩」を「部分フッ素化スルホン酸金属塩」と略記することがある。)。ここで「フッ素化率」とは、炭化水素基上の水素原子の数をA、フッ素原子の数をBとした際に、B/(A+B)で表される。
フッ素化率は50%以下であればよいが、一般的には1%以上、中でも5%以上、更には10%以上、特に20%以上であることが好ましく、その上限は49%、中でも48%以下、特に45%以下であることが好ましい。
A feature of the present invention is that it includes a sulfonic acid metal salt having a hydrocarbon group having a fluorination rate of 50% or less as a flame retardant (hereinafter referred to as a “hydrocarbon group having a fluorination rate of 50% or less. The sulfonic acid metal salt having “may be abbreviated as“ partially fluorinated sulfonic acid metal salt ”. Here, the “fluorination rate” is represented by B / (A + B), where A is the number of hydrogen atoms on the hydrocarbon group and B is the number of fluorine atoms.
The fluorination rate may be 50% or less, but is generally 1% or more, preferably 5% or more, more preferably 10% or more, and particularly preferably 20% or more, and the upper limit is 49%, especially 48 % Or less, and particularly preferably 45% or less.
本発明に使用される該部分フッ素化スルホン酸金属塩としては、その難燃効果や溶融熱安定性の観点から、アルカリ(土類)金属塩、又はアンモニウム塩であることが好ましい。
アルカリ金属としてはリチウム、ナトリウム、カリウム、ルビジウム、セシウム等が、またアルカリ土類金属としてはベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウムが挙げられ、中でもリチウム、ナトリウム、カリウムが好ましい。
The partially fluorinated sulfonic acid metal salt used in the present invention is preferably an alkali (earth) metal salt or an ammonium salt from the viewpoint of flame retardancy and melt heat stability.
Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium. Of these, lithium, sodium, and potassium are preferable.
本発明に使用される、部分フッ素化スルホン酸金属塩における炭化水素基としては、環状、又は直鎖状で分岐鎖を有していてもよい、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリレン基等の脂肪族炭化水素基;単環式又は縮合環式の、置換基を有していてもよいフェニル基、ナフチル基、アズレニル基等の芳香族炭化水素基が挙げられる。
これら炭化水素基を構成する炭素数は、適宜選択して決定すればよいが、通常、脂肪族炭化水素基の場合には1〜12、芳香族炭化水素基の場合には6〜14である。脂肪族炭化水素基としては、直鎖状で分枝鎖を有していてもよいものが好ましく、更には炭素数1〜12のアルキル基であることが好ましい。具体的にはメチル基、エチル基、n−プロピル基、n−ブチル基、iso−プロピル基、iso−ブチル基、sec−ブチル基、t−ブチル基等の低級アルキル基であることが好ましい。
As the hydrocarbon group in the partially fluorinated sulfonic acid metal salt used in the present invention, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, which may be cyclic or linear and have a branched chain, Aliphatic hydrocarbon groups such as arylene groups; monocyclic or condensed cyclic aromatic hydrocarbon groups such as phenyl, naphthyl and azulenyl groups which may have a substituent.
The number of carbon atoms constituting these hydrocarbon groups may be appropriately selected and determined, but is usually 1 to 12 for an aliphatic hydrocarbon group and 6 to 14 for an aromatic hydrocarbon group. . The aliphatic hydrocarbon group is preferably a straight chain which may have a branched chain, and more preferably an alkyl group having 1 to 12 carbon atoms. Specifically, a lower alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-propyl group, an iso-butyl group, a sec-butyl group, or a t-butyl group is preferable.
また芳香族炭化水素基としては、炭素数6〜12の置換されていてもよいアリール基が好ましく、具体的には例えばフェニル基;トリメチルフェニル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ニトロフェニル基、メトキシフェニル基、ビフェニル基等の置換フェニル基;クレジル基;(o−、m−、p−)トリル基;(2,3−、2,4−、2,5−、2,6−、3,4−、3,5−)キシリル基;メシチル基;ナフチル基等が挙げられる。中でもフェニル、ビフェニル基、キシリル基が好ましい。 The aromatic hydrocarbon group is preferably an aryl group having 6 to 12 carbon atoms which may be substituted. Specifically, for example, a phenyl group; a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, Substituted phenyl group such as nitrophenyl group, methoxyphenyl group, biphenyl group; cresyl group; (o-, m-, p-) tolyl group; (2,3-, 2,4-, 2,5-, 2, 6-, 3,4-, 3,5-) xylyl group; mesityl group; naphthyl group and the like. Of these, phenyl, biphenyl and xylyl are preferred.
これらの中でも、炭化水素基としては芳香族炭化水素基であることが好ましく、中でもフェニル基、アルキルフェニル基、ビフェニル基であることが好ましい。これらのうち、芳香環を構成する炭素原子に結合している水素原子がフッ素原子に置換されていても、また置換基上を構成する炭素原子に結合している水素原子がフッ素原子に置換されていてもよいが、アルキルフェニル基の場合にはアルキル基上の水素原子がフッ素原子に置換されていることが好ましい。
尚、本発明に使用される部分フッ素化スルホン酸金属塩においては、これを構成する炭化水素基において2個以上のアリール基を有する場合には、これらは単結合で直接結合していても、また−O−結合、−SO2−結合、−S−結合等により結合されていてもよい。
Among these, as the hydrocarbon group, an aromatic hydrocarbon group is preferable, and among them, a phenyl group, an alkylphenyl group, and a biphenyl group are preferable. Among these, even if the hydrogen atom bonded to the carbon atom constituting the aromatic ring is substituted with a fluorine atom, the hydrogen atom bonded to the carbon atom constituting the substituent is substituted with a fluorine atom. However, in the case of an alkylphenyl group, it is preferable that a hydrogen atom on the alkyl group is substituted with a fluorine atom.
In addition, in the partially fluorinated sulfonic acid metal salt used in the present invention, when the hydrocarbon group constituting this has two or more aryl groups, these may be directly bonded by a single bond, Further, they may be bonded by an —O— bond, —SO 2 — bond, —S— bond or the like.
本発明に使用される、部分フッ素化スルホン酸金属塩の具体例としては、モノフルオロメタンスルホン酸カリウム塩、モノフルオロメタンスルホン酸ナトリウム塩、2,4−ジフルオロベンゼンスルホン酸ナトリウム塩、2,4−ジフルオロベンゼンスルホン酸カリウム塩、3,4−ジフルオロベンゼンスルホン酸ナトリウム塩、3,4−ジフルオロベンゼンスルホン酸カリウム塩、2−トリフルオロメチルベンゼンスルホン酸ナトリウム塩、2−トリフルオロメチルベンゼンスルホン酸カリウム塩、4,4’−ジフルオロビフェニル−3−スルホン酸ナトリウム塩、4,4’−ジフルオロビフェニル−3−スルホン酸カリウム塩、4,4’−ジフルオロジフェニルスルフィド−3−スルホン酸ナトリウム塩、4,4’−ジフルオロジフェニルスルフィド−3−スルホン酸カリウム塩、テトラフルオロジフェニルエーテルジスルホン酸ジナトリウム塩、テトラフルオロジフェニルエーテルジスルホン酸ジカリウム塩、ポリ(2−フルオロ−6−ブチルフェニレンオキシド)ポリスルホン酸リチウム塩等が挙げられる。これらの中でも特に、2,4−ジフルオロベンゼンスルホン酸カリウム塩、2−トリフルオロメチルベンゼンスルホン酸カリウム塩が好ましい。 Specific examples of the partially fluorinated sulfonic acid metal salt used in the present invention include monofluoromethanesulfonic acid potassium salt, monofluoromethanesulfonic acid sodium salt, 2,4-difluorobenzenesulfonic acid sodium salt, 2,4 -Potassium difluorobenzenesulfonate, sodium salt of 3,4-difluorobenzenesulfonate, potassium salt of 3,4-difluorobenzenesulfonate, sodium salt of 2-trifluoromethylbenzenesulfonate, potassium 2-trifluoromethylbenzenesulfonate Salt, 4,4′-difluorobiphenyl-3-sulfonic acid sodium salt, 4,4′-difluorobiphenyl-3-sulfonic acid potassium salt, 4,4′-difluorodiphenyl sulfide-3-sulfonic acid sodium salt, 4, 4'-difluorodipheny Sulfide-3-sulfonic acid potassium salt, tetrafluoro ether disulfonic acid disodium salt, tetrafluoro ether disulfonic acid dipotassium salt, poly (2-fluoro-6-butylphenylene oxide) polysulfonate lithium salts, and the like. Among these, 2,4-difluorobenzenesulfonic acid potassium salt and 2-trifluoromethylbenzenesulfonic acid potassium salt are preferable.
本発明の難燃性ポリカーボネート樹脂組成物における、部分フッ素化スルホン酸金属塩の含有量は、少なすぎると難燃効果が不充分となり、逆に多すぎても含有量の増加に見合う効果の向上が期待できない。よってその含有量は、ポリカーボネート樹脂100重量部に対して0.001重量部以上、中でも0.01重量部以上、更には0.02重量部以上であることが好ましい。またその上限は、ポリカーボネート樹脂100重量部に対して1重量部以下、中でも0.6重量部以下、更には0.3重量部以下であることが好ましい。 In the flame retardant polycarbonate resin composition of the present invention, if the content of the partially fluorinated sulfonic acid metal salt is too small, the flame retardant effect is insufficient, and conversely, if the content is too large, the effect is commensurate with the increase in content. I can not expect. Therefore, the content is preferably 0.001 part by weight or more, more preferably 0.01 part by weight or more, and further preferably 0.02 part by weight or more with respect to 100 parts by weight of the polycarbonate resin. The upper limit thereof is preferably 1 part by weight or less, more preferably 0.6 parts by weight or less, and further preferably 0.3 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin.
本発明においては、上述したフッ素化率が50%以下である炭化水素基を有するスルホン酸金属塩の他に、更に必要に応じて、燃焼時の滴下防止剤、無機フィラー、無機繊維、蛍光増白剤、衝撃改良剤、蛍光増白剤、熱安定剤、酸化防止剤、紫外線吸収剤、顔料、染料、滑剤、その他の難燃剤、離型剤、摺動性改良剤等の添加剤を、単独又は適宜選択して組み合わせて含有させてもよい。特に、本発明の組成物が光線反射板として使用される場合には、要求される光反射特性及び耐候性を改良するため、蛍光増白剤や紫外線吸収剤を添加することが好ましい。 In the present invention, in addition to the sulfonic acid metal salt having a hydrocarbon group having a fluorination rate of 50% or less as described above, an anti-dripping agent during combustion, an inorganic filler, an inorganic fiber, a fluorescent enhancement agent, as necessary. Additives such as whitening agents, impact modifiers, fluorescent brighteners, thermal stabilizers, antioxidants, UV absorbers, pigments, dyes, lubricants, other flame retardants, mold release agents, slidability improvers, You may make it contain individually or suitably selected and combined. In particular, when the composition of the present invention is used as a light reflector, it is preferable to add a fluorescent whitening agent or an ultraviolet absorber in order to improve required light reflection characteristics and weather resistance.
燃焼時の滴下防止剤としては、従来公知の任意のものを使用できるが、中でもポリテトラフルオロオレフィン樹脂を配合することが好ましい。具体的には、フィブリル形成能を有するポリテトラフルオロエチレン樹脂が挙げられ、中でもポリカーボネート樹脂中に容易に分散し、かつポリカーボネート樹脂同士を結合して繊維状構造を作る傾向を示すものが好ましい。フィブリル形成能を有するポリテトラフルオロエチレン樹脂は、種々市販されており、容易に入手することができる。 As a dripping preventive agent at the time of combustion, any conventionally known one can be used, and among them, it is preferable to blend a polytetrafluoroolefin resin. Specific examples include polytetrafluoroethylene resins having a fibril-forming ability, and among them, those that readily disperse in a polycarbonate resin and tend to form a fibrous structure by bonding the polycarbonate resins together are preferable. Various polytetrafluoroethylene resins having fibril-forming ability are commercially available and can be easily obtained.
具体的には例えば、テフロン(登録商標)6J(三井・デュポンフロロケミカル社製)、ポリフロン(ダイキン化学工業社製)が挙げられる。またポリテトラフルオロエチレンの水性分散液の市販品として、テフロン(登録商標)30J(三井デュポンフロロケミカル社製)、フルオンD−1(ダイキン化学工業社製)等が挙げられる。更にビニル系単量体を重合してなる多層構造を有するポリテトラフルオロエチレン重合体も使用することができ、具体的にはメタブレンA−3800(三菱レイヨン社製)が挙げられる。 Specific examples include Teflon (registered trademark) 6J (Mitsui / DuPont Fluorochemicals) and Polyflon (Daikin Chemical Industries). Examples of commercially available aqueous dispersions of polytetrafluoroethylene include Teflon (registered trademark) 30J (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), Fluon D-1 (manufactured by Daikin Chemical Industries, Ltd.), and the like. Furthermore, a polytetrafluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used, and specific examples include Methrene A-3800 (manufactured by Mitsubishi Rayon Co., Ltd.).
ポリテトラフルオロエチレンの含有量が少なすぎると、添加量に見合う難燃性の発現が不十分であり、逆に多すぎても、ポリカーボネート樹脂成形品の外観や機械的強度が低下するばあいがある。よって本発明の難燃性ポリカーボネート樹脂組成物におけるポリテトラフルオロオレフィン樹脂の含有量は、ポリカーボネート樹脂100重量部に対して、0.1重量部以上、5重量部以下、中でも2重量部以下であることが好ましい。 If the content of polytetrafluoroethylene is too small, the expression of flame retardancy commensurate with the amount added will be insufficient, and conversely, if the content is too large, the appearance and mechanical strength of the polycarbonate resin molded product may decrease. is there. Therefore, the content of the polytetrafluoroolefin resin in the flame retardant polycarbonate resin composition of the present invention is 0.1 parts by weight or more and 5 parts by weight or less, especially 2 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. It is preferable.
本発明の難燃性ポリカーボネート樹脂組成物やこれを含む樹脂成形体を、光線反射板等の用途に使用する場合には、本発明のポリカーボネート樹脂組成物に、無機フィラーとして酸化チタンを含有させることが好ましい。本発明に使用される酸化チタンとしては、従来公知の任意のものを使用できる。酸化チタンの粒子径は、小さすぎると遮光性及び光反射率が不充分となる場合があり、逆に大きすぎても、成形品表面の肌荒れを生じたり、衝撃強度が低下する場合がある。よって酸化チタンの粒子径は通常、0.05μm以上、中でも0.1μm以上、特に0.15μm以上であることが好ましく、その上限は0.5μm以下、中でも0.35μm以下である。 When using the flame-retardant polycarbonate resin composition of the present invention or a resin molded body containing the same for applications such as a light reflector, the polycarbonate resin composition of the present invention contains titanium oxide as an inorganic filler. Is preferred. Any conventionally known titanium oxide can be used as the titanium oxide used in the present invention. If the particle size of the titanium oxide is too small, the light shielding property and the light reflectance may be insufficient. Conversely, if the particle size is too large, the surface of the molded product may be roughened or the impact strength may be reduced. Therefore, the particle diameter of titanium oxide is usually 0.05 μm or more, preferably 0.1 μm or more, and particularly preferably 0.15 μm or more, and the upper limit is 0.5 μm or less, especially 0.35 μm or less.
本発明に使用される酸化チタンの製造方法は、塩素法、硫酸法等の、従来公知の任意の製造方法によって得られたものを使用できる。中でも白度が優れていることから、塩素法で製造されたものが好ましい。また酸化チタンの結晶形態も、ルチル型、アナターゼ型のいずれも用いることが出来、特に制限はないが、中でも白度、光線反射率、及び耐候性の点で優れていることから、ルチル型の酸化チタンが好ましい。 As a method for producing titanium oxide used in the present invention, one obtained by any conventionally known production method such as chlorine method or sulfuric acid method can be used. Of these, those produced by the chlorine method are preferred because of their excellent whiteness. The crystal form of titanium oxide can be either rutile type or anatase type, and is not particularly limited, but is particularly excellent in terms of whiteness, light reflectance, and weather resistance. Titanium oxide is preferred.
また本発明に使用される酸化チタンは、分散性向上等を目的として、シリカ、アルミナ、ジルコニア等の無機酸化物による表面処理がなされていてもよい。但し、無機酸化物により表面処理された酸化チタンを用いると、その表面に存在する吸着水によって、難燃性ポリカーボネート樹脂組成物やこれを含む樹脂成形品の外観性低下や燃焼時のドリッピング等を生ずる場合がある。よって本発明に使用される酸化チタンとしては、表面処理剤として、吸水性の低いアルミナ、ジルコニア等を用いるか、表面処理に用いる無機酸化物の量を低減するか、もしくは表面処理がなされていないものを用いることが好ましい。 The titanium oxide used in the present invention may be subjected to a surface treatment with an inorganic oxide such as silica, alumina, zirconia, etc. for the purpose of improving dispersibility. However, when titanium oxide surface-treated with an inorganic oxide is used, the adsorbed water present on the surface causes a deterioration in the appearance of the flame-retardant polycarbonate resin composition or a resin molded product containing the same, dripping during combustion, etc. May occur. Therefore, as titanium oxide used in the present invention, alumina, zirconia or the like having low water absorption is used as a surface treatment agent, the amount of inorganic oxide used for surface treatment is reduced, or surface treatment is not performed. It is preferable to use one.
また本発明に使用される酸化チタンは、有機化合物により表面処理されているものが好ましい。表面処理に用いる有機化合物としては、有機シラン化合物や有機シロキサン化合物が好ましく、特にアルコキシ基、エポキシ基、アミノ基、又はSi−H結合を有する有機シラン化合物や、有機シリコーン化合物が好ましい。具体的には例えば、ハイドロジェンポリシロキサン(Si−H結合を有するシリコーン化合物)が挙げられる。この様な有機化合物の使用量としては、酸化チタンに対して1重量部以上、中でも1.5重量部以上であることが好ましく、その上限は5重量%以下、中でも3重量%であることが好ましい。 Further, the titanium oxide used in the present invention is preferably surface-treated with an organic compound. As the organic compound used for the surface treatment, an organic silane compound or an organic siloxane compound is preferable, and an organic silane compound or an organic silicone compound having an alkoxy group, an epoxy group, an amino group, or a Si—H bond is particularly preferable. Specific examples include hydrogen polysiloxane (silicone compound having a Si—H bond). The amount of such an organic compound used is preferably 1 part by weight or more, more preferably 1.5 parts by weight or more with respect to titanium oxide, and the upper limit thereof is 5% by weight or less, especially 3% by weight. preferable.
本発明のポリカーボネート樹脂組成物における酸化チタンの含有量(表面処理剤の量を含む)は適宜選択して決定すればよいが、少なすぎると光線反射性が不十分となり、逆に多すぎても樹脂成形品とした際の機械的強度が低下する場合がある。よって酸化チタンの含有量は、ポリカーボネート樹脂100重量部に対して5重量部以上、中でも7重量部以上、特に10重量部以上であることが好ましく、その上限は50重量部以下、中でも30重量部以下、特に25重量部以下であることが好ましい。 The content of titanium oxide (including the amount of the surface treatment agent) in the polycarbonate resin composition of the present invention may be selected and determined as appropriate. However, if the amount is too small, the light reflectivity becomes insufficient. In some cases, the mechanical strength of the resin molded product is lowered. Accordingly, the content of titanium oxide is preferably 5 parts by weight or more, more preferably 7 parts by weight or more, and particularly preferably 10 parts by weight or more with respect to 100 parts by weight of the polycarbonate resin, and the upper limit is 50 parts by weight or less, especially 30 parts by weight. Hereinafter, it is particularly preferably 25 parts by weight or less.
本発明には、繊維状充填材を用いることが出来る。繊維状充填材としては例えば、ガラス繊維、カーボン繊維、シリカ・アルミナ繊維、ジルコニア繊維、ホウ素繊維、窒化ホウ素繊維、窒化ケイ素チタン酸カリウム繊維、金属繊維等の無機繊維、芳香族ポリアミド繊維、フッ素樹脂繊維等の各種有機合成繊維等が挙げられ、これらを単独又は二種以上を任意の割合で組み合わせて使用できる。中でも無機繊維を用いることが好ましく、特にガラス繊維が好ましい。 In the present invention, a fibrous filler can be used. Examples of fibrous fillers include glass fibers, carbon fibers, silica / alumina fibers, zirconia fibers, boron fibers, boron nitride fibers, silicon nitride potassium titanate fibers, metal fibers and other inorganic fibers, aromatic polyamide fibers, and fluorine resins. Various organic synthetic fibers such as fibers can be used, and these can be used alone or in combination of two or more at any ratio. Among these, inorganic fibers are preferably used, and glass fibers are particularly preferable.
繊維状充填材の平均繊維径は特に制限されず、適宜選択して決定すればよいが、通常、1μm以上、中でも3μm以上、特に5μm以上であることが好ましく、その上限は100μm以下、中でも50μm以下、更には30μm以下、特に20μm以下であることが好ましい。また平均繊維長も特に限定されず、適宜選択して決定すればよいが、通常、0.1mm以上であることが好ましく、その上限は20mm以下、特に10mm以下であることが好ましい。 The average fiber diameter of the fibrous filler is not particularly limited and may be appropriately selected and determined. Usually, it is preferably 1 μm or more, more preferably 3 μm or more, particularly preferably 5 μm or more, and the upper limit is 100 μm or less, especially 50 μm. Hereinafter, it is further preferably 30 μm or less, particularly preferably 20 μm or less. Also, the average fiber length is not particularly limited and may be appropriately selected and determined. Usually, it is preferably 0.1 mm or more, and the upper limit thereof is preferably 20 mm or less, particularly preferably 10 mm or less.
繊維状充填材としては、樹脂成分との界面密着性を向上させるために、収束剤又は表面処理剤(例えば、エポキシ系化合物、アクリル系化合物等)、イソシアネート系化合物、シラン系化合物、チタネート系化合物等の官能性化合物により表面処理されていることが好ましい。この表面処理は、ポリカーボネート樹脂等との混合、混練前に予め行われていても、または混合、混練中に表面処理剤を添加して行ってもよい。 As a fibrous filler, in order to improve the interfacial adhesion with the resin component, a sizing agent or a surface treatment agent (for example, epoxy compound, acrylic compound, etc.), isocyanate compound, silane compound, titanate compound It is preferable that the surface is treated with a functional compound such as This surface treatment may be performed in advance before mixing and kneading with a polycarbonate resin or the like, or may be performed by adding a surface treatment agent during mixing and kneading.
本発明における繊維状充填材の含有量は、少なすぎてもその充填効果が小さく、逆に多すぎても難燃性ポリカーボネート樹脂成形体の外観が低下する場合がある。よってその含有量は、本発明に用いるポリカーボネート樹脂100重量部に対して、1重量部以上、30重量部以下であることが好ましい。 If the content of the fibrous filler in the present invention is too small, the filling effect is small. Conversely, if the content is too large, the appearance of the flame-retardant polycarbonate resin molded product may be deteriorated. Therefore, the content is preferably 1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin used in the present invention.
本発明に使用される蛍光増白剤は、樹脂成形体を明るく見せるため、成形体に加えられる染・顔料であり、成形体の黄色味を消し、明るさを増加させる添加剤である。この点では、ブルーイング剤と似ているが、ブルーイング剤が黄色光を除去するのに対して、蛍光増白剤は紫外線を吸収し、そのエネルギーを可視部青紫色の光線に変えて放射する点で異なっている。 The fluorescent whitening agent used in the present invention is a dye / pigment added to the molded body to make the resin molded body appear brighter, and is an additive that eliminates the yellowness of the molded body and increases the brightness. In this respect, it is similar to the bluing agent, but the bluing agent removes yellow light, whereas the fluorescent whitening agent absorbs ultraviolet light and changes its energy into a visible violet light. Is different.
一般的にはクマリン系、ナフトトリアゾリルスチルベン系、ベンズオキサゾール系、ベンズイミダゾール系、およびジアミノスチルベン−ジスルホネート系などの蛍光増白剤が使用される。市販品としては、ハッコールPSR(ハッコールケミカル社製)、HOSTALUX KCB(ヘキスト社製)、WHITEFLOUR PSN CONC(住友化学社製)等が使用される。本発明における蛍光増白剤の含有量は、ポリカーボネート樹脂100重量部に対して0.005重量部以上、0.1重量部以下の範囲が好ましい。 In general, fluorescent whitening agents such as coumarin, naphthotriazolyl stilbene, benzoxazole, benzimidazole, and diaminostilbene-disulfonate are used. As a commercially available product, HACKOL PSR (manufactured by HACKOL CHEMICAL), HOSTALUX KCB (manufactured by Hoechst), WHITEFLOUR PSN CONC (manufactured by Sumitomo Chemical) and the like are used. The content of the optical brightener in the present invention is preferably in the range of 0.005 parts by weight to 0.1 parts by weight with respect to 100 parts by weight of the polycarbonate resin.
本発明に使用される紫外線吸収剤としては、ベンゾフェノン系、ベンゾトリアゾール系、サリチル酸フェニル系、ヒンダードアミン系等が挙げられる。紫外線吸収剤を配合することにより耐候性を向上させることができる。
ベンゾフェノン系紫外線吸収剤としては、2,4−ジヒドロキシ−ベンゾフェノン、2−ヒドロキシ−4−メトキシ−ベンゾフェノン、2−ヒドロキシ−4−n−オクトキシ−ベンゾフェノン、2−ヒドロキシ−4−ドデシロキシ−ベンゾフェノン、2−ヒドロキシ−4−オクタデシロキシ−ベンゾフェノン、2,2’−ジヒドロキシ−4−メトキシ−ベンゾフェノン、2,2’−ジヒドロキシ−4,4’−ジメトキシ−ベンゾフェノン、2,2’,4,4’−テトラヒドロキシ−ベンゾフェノン等が挙げられる。
Examples of the ultraviolet absorber used in the present invention include benzophenone, benzotriazole, phenyl salicylate, and hindered amine. Weather resistance can be improved by blending an ultraviolet absorber.
Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2- Hydroxy-4-octadecyloxy-benzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone, 2,2 ′, 4,4′-tetra And hydroxy-benzophenone.
ベンゾトリアゾール系紫外線吸収剤としては、2−(2’−ヒドロキシ−5−メチルフェニル)ベンゾトリアゾール、2−(2’−ヒドロキシ−3’,5’−ジ−t−ブチルフェニル)ベンゾトリアゾール、2−(2’−ヒドロキシ−3’−t−ブチル−5’−メチルフェニル)ベンゾトリアゾール等が挙げられる。 Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole and the like.
サリチル酸フェニル系紫外線吸収剤としては、フェニルサルチレート、2−4−ジターシャリーブチルフェニル−3,5−ジ−t−ブチル−4−ヒドロキシベンゾエート等が挙げられる。ヒンダードアミン系紫外線吸収剤としては、ビス(2,2,6,6−テトラメチルピペリジン−4−イル)セバケート等が挙げられる。 Examples of the phenyl salicylate UV absorber include phenylsulcylate, 2-4-ditertiary butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like. Examples of hindered amine ultraviolet absorbers include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
紫外線吸収剤としては、上記以外に紫外線の保有するエネルギーを、分子内で振動エネルギーに変換し、その振動エネルギーを、熱エネルギー等として放出する機能を有する化合物が含まれる。さらに、酸化防止剤あるいは着色剤等との併用で効果を発現するもの、あるいはクエンチャーと呼ばれる、光エネルギー変換剤的に作用する光安定剤等も併用することができる。 In addition to the above, the ultraviolet absorber includes a compound having a function of converting the energy held by ultraviolet rays into vibrational energy in the molecule and releasing the vibrational energy as thermal energy or the like. Furthermore, those that exhibit an effect when used in combination with an antioxidant, a colorant, or the like, or a light stabilizer that acts as a light energy conversion agent, called a quencher, can be used in combination.
本発明における紫外線吸収剤の含有量は、少なすぎると樹脂成形品の耐侯性が不十分となり、逆に多すぎても樹脂成形体の黄味が強くなり調色性が低下したり、またブリードアウトが生ずる場合がある。よってその含有量は、ポリカーボネート樹脂100重量部に対して0.01重量部以上、中でも0.05重量部以上、特に0.1重量部以上であることが好ましく、その上限は2重量部以下、中でも1.8重量部以下、特に1.5重量部以下であることが好ましい。 If the content of the ultraviolet absorber in the present invention is too small, the weather resistance of the resin molded product will be insufficient. Conversely, if it is too much, the yellowness of the resin molded product will become strong and the toning property will be lowered, Out may occur. Therefore, the content is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, and particularly preferably 0.1 parts by weight or more with respect to 100 parts by weight of the polycarbonate resin, and the upper limit is 2 parts by weight or less. Of these, 1.8 parts by weight or less, particularly 1.5 parts by weight or less is preferable.
本発明の難燃性ポリカーボネート樹脂組成物の製造方法は任意であり、従来公知の製造方法を使用できる。例えば、ポリカーボネート樹脂と、部分フッ素化スルホン酸金属塩、さらに必要により配合される他の添加剤や繊維状充填材等を一括混合し、溶融混練する方法や、これらのうち繊維状充填材以外を予め混合し、溶融混練した後に、これに繊維状充填材を添加し更に溶融混練する製造方法等が挙げられる。 The manufacturing method of the flame-retardant polycarbonate resin composition of this invention is arbitrary, and a conventionally well-known manufacturing method can be used. For example, polycarbonate resin, partially fluorinated sulfonic acid metal salt, and other additives and fibrous fillers that are blended if necessary, and a method of kneading and melting and kneading, and of these, except for fibrous fillers Examples include a production method in which after mixing and melt-kneading in advance, a fibrous filler is added thereto and further melt-kneading.
各成分を混合、混練する方法としては、例えばリボンブレンダー、ヘンシェルミキサー、バンバリーミキサー、ドラムタンブラー、単軸または二軸スクリュー押出機、コニーダーなど、従来公知の任意のものを使用できる。また混合、混練温度は特に制限されないが、通常240〜320℃の範囲で適宜選択して決定すればよい。 As a method of mixing and kneading each component, for example, any conventionally known one such as a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single or twin screw extruder, and a kneader can be used. The mixing and kneading temperatures are not particularly limited, but may be appropriately selected and determined usually in the range of 240 to 320 ° C.
本発明の難燃性ポリカーボネート樹脂組成物は、各種成形体の成形材料として使用できる。適用できる成形方法は、熱可塑性樹脂の成形に適用できる方法をそのまま適用することができ、射出成形法、押出成形法、中空成形法、回転成形法、圧縮成形法、差圧成形法、トランスファー成形法などが挙げられる。
本発明の成形体は、難燃性である上、機械的強度、耐熱性、熱安定性などが優れているので、自動車分野、OA機器分野、電気・電子分野、建材分野をはじめ、その他の広い分野において極めて有用である。
The flame-retardant polycarbonate resin composition of the present invention can be used as a molding material for various molded products. As the applicable molding method, a method applicable to the molding of a thermoplastic resin can be applied as it is, an injection molding method, an extrusion molding method, a hollow molding method, a rotational molding method, a compression molding method, a differential pressure molding method, a transfer molding. Law.
The molded product of the present invention is flame retardant and has excellent mechanical strength, heat resistance, thermal stability, etc., so that it can be used in the automotive field, OA equipment field, electrical / electronic field, building material field, and other fields. It is extremely useful in a wide field.
以下、本発明を実施例及び比較例により更に詳細に説明するが、本発明はその要旨を超えない限り、以下の例に限定されるものではない。尚、以下の例において使用した原材料は次の通りである。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following examples, unless the summary is exceeded. The raw materials used in the following examples are as follows.
・ポリカーボネート樹脂(PC−1):「ポリ−4,4−イソプロピリデンジフェニルカーボネート、ユーピロン(登録商標)S−3000、三菱エンジニアリングプラスチックス社製、粘度平均分子量21000。」
・金属塩1:「2−トリフルオロメチルベンゼンスルホン酸カリウム」、フッ素化率43%。
・金属塩2:「2,4−ジフルオロベンゼンスルホン酸カリウム」、フッ素化率40%。・金属塩3:「4,4’−ジフルオロビフェニルスルホン酸カリウム」、フッ素化率22%。
・金属塩4:「パーフルオロブタンスルホン酸カリウム」、フッ素化率100%。
・安定剤:「アデカスタブ2112 旭電化工業社製」
・ポリテトラフルオロエチレン(PTFE):「ポリフロンF−201L ダイキン社製」
・オリゴマー:「カーボネートオリゴマーAL−071 三菱ガス化学社製」
・酸化チタン:「メチルハイドロジェンポリシロキサン表面処理酸化チタンPC−5 レジノカラー社製。」
・GF:「ガラスファイバー FT−737 旭ファイバー社製」
・離型剤:「ポリエチレンワックス PE520 日本油脂社製」
Polycarbonate resin (PC-1): “Poly-4,4-isopropylidenediphenyl carbonate, Iupilon (registered trademark) S-3000, manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 21000.”
Metal salt 1: “2-trifluoromethylbenzene potassium sulfonate”, fluorination rate 43%.
Metal salt 2: “Potassium 2,4-difluorobenzenesulfonate”, fluorination rate 40%. Metal salt 3: “4,4′-difluorobiphenylsulfonic acid potassium salt”, fluorination rate 22%.
Metal salt 4: “Potassium perfluorobutanesulfonate”, fluorination rate 100%.
・ Stabilizer: “ADK STAB 2112 manufactured by Asahi Denka Kogyo Co., Ltd.”
・ Polytetrafluoroethylene (PTFE): “Polyflon F-201L made by Daikin”
・ Oligomer: “Carbonate oligomer AL-071 manufactured by Mitsubishi Gas Chemical Company”
Titanium oxide: “Methyl hydrogen polysiloxane surface-treated titanium oxide PC-5 manufactured by Resino Color Co., Ltd.”
・ GF: “Glass Fiber FT-737 Asahi Fiber Co., Ltd.”
・ Release agent: “polyethylene wax PE520 manufactured by NOF Corporation
(実施例1)
ポリカーボネート樹脂100重量部に対して、金属塩1を0.0784部、安定剤0.03重量部を添加し、ヘンシェルミキサーにて900回転にて10分攪拌した後、取り出してさらにPTFEを0.3重量部添加し、タンブラーにて10分間混合した。得られた混合物をシリンダー温度300℃の二軸押出機にて押し出しペレット化した。得られたペレットを射出成形機にて、シリンダー温度280℃、金型温度80℃の条件下にて1.6mmのUL−94燃焼試験片を成形した。射出成形サイクルは40秒とした。得られた燃焼試験片にて垂直燃焼試験を実施した。
Example 1
0.0784 parts of metal salt 1 and 0.03 parts by weight of stabilizer are added to 100 parts by weight of the polycarbonate resin, and the mixture is stirred for 10 minutes at 900 rpm with a Henschel mixer, and then taken out and PTFE is further added to a concentration of 0.1. 3 parts by weight was added and mixed with a tumbler for 10 minutes. The obtained mixture was extruded and pelletized by a twin screw extruder having a cylinder temperature of 300 ° C. A 1.6 mm UL-94 combustion test piece was molded from the obtained pellets with an injection molding machine under conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. The injection molding cycle was 40 seconds. A vertical combustion test was performed on the obtained combustion test piece.
また、本発明のポリカーボネート樹脂組成物における熱安定性を測定すべく、上述の射出成形サイクルを延長して180秒とし、より熱履歴の掛かる滞留成形品を成形し、その分子量を測定した。尚、射出成形サイクル以外の製造条件は、上述と同様の条件とした。
結果を表−1に示す。
Further, in order to measure the thermal stability of the polycarbonate resin composition of the present invention, the above-described injection molding cycle was extended to 180 seconds, a staying molded product with more heat history was molded, and the molecular weight was measured. The manufacturing conditions other than the injection molding cycle were the same as described above.
The results are shown in Table-1.
(実施例2〜4、比較例1)
表1に示す処方にて、実施例1と同様に試験片を作成し、評価した。結果を表1に示す。
(Examples 2 to 4, Comparative Example 1)
Test pieces were prepared and evaluated in the same manner as in Example 1 with the formulation shown in Table 1. The results are shown in Table 1.
(実施例5)
ポリカーボネート樹脂100重量部に対して、金属塩1を0.127部を添加し、ヘンシェルミキサーにて900回転にて10分攪拌した後、取り出してさらにPTFEを0.3重量部、オリゴマー14.5重量部、離型剤0.5重量部を添加しタンブラーにて9分間混合した。その後、GFを添加し1分間混合した。
(Example 5)
0.127 parts of metal salt 1 is added to 100 parts by weight of the polycarbonate resin, stirred for 10 minutes at 900 rpm with a Henschel mixer, then taken out and further 0.3 parts by weight of PTFE, oligomer 14.5 Part by weight and 0.5 part by weight of release agent were added and mixed for 9 minutes with a tumbler. Then, GF was added and mixed for 1 minute.
その混合物を300℃のシリンダー温度の単軸押出機にて押し出してペレット化した。
そのペレットを射出成形機にて280℃のシリンダー温度、80℃の金型温度にて1.6mmのUL−94燃焼試験片を成形した。射出成形サイクルは40秒とした。燃焼試験片にて垂直燃焼試験を実施した。結果を表2に示す。
The mixture was extruded into a pellet by a single screw extruder having a cylinder temperature of 300 ° C.
The pellets were molded into 1.6 mm UL-94 combustion test pieces at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using an injection molding machine. The injection molding cycle was 40 seconds. A vertical combustion test was performed on the combustion test piece. The results are shown in Table 2.
(実施例6、7、比較例2)
実施例5と同様の方法にて表2の処方にて評価を実施した。結果を表2に示す。
(Examples 6 and 7, Comparative Example 2)
Evaluation was carried out according to the formulation shown in Table 2 in the same manner as in Example 5. The results are shown in Table 2.
(実施例8、9、比較例3)
酸化チタン14.5重量部を更に添加した以外は実施例5と同様に行い、評価した。結果を表2に示す。
(Examples 8 and 9, Comparative Example 3)
Evaluation was performed in the same manner as in Example 5 except that 14.5 parts by weight of titanium oxide was further added. The results are shown in Table 2.
実施例1〜4と比較例1とを比較すると、本発明のポリカーボネート樹脂組成物、及びこれを含む樹脂成形体は、難燃剤の含有量が少なくても、より短い燃焼時間での燃焼試験1.6mmでV−0を達成できるという、所望の難燃性を確保できることが判る。
また一般的に滞留成形を行うと、難燃剤等の分解によりポリカーボネート樹脂が分解され、分子量の大幅な低下が問題となる場合があるが、本発明においては難燃剤の含有量を抑えることで、ポリカーボネート樹脂ペレットの分子量及び滞留成形品の分子量低下も抑制でき、ポリカーボネート樹脂としての特性を保持でき、優れた性質を有するものであることが判る。
Comparing Examples 1 to 4 and Comparative Example 1, the polycarbonate resin composition of the present invention and the resin molded body containing the same showed the combustion test 1 in a shorter combustion time even when the content of the flame retardant was small. It can be seen that the desired flame retardancy that V-0 can be achieved at .6 mm can be ensured.
In general, when the retention molding is performed, the polycarbonate resin is decomposed by decomposition of the flame retardant and the like, and there may be a problem of a significant decrease in molecular weight, but in the present invention, by suppressing the content of the flame retardant, It can be seen that the molecular weight of the polycarbonate resin pellet and the molecular weight of the staying molded product can be suppressed, the characteristics as the polycarbonate resin can be maintained, and the resin has excellent properties.
一方、ガラス繊維を添加したポリカーボネート樹脂組成物である実施例5〜7と比較例2とを比較しても、また酸化チタンを添加したポリカーボネート樹脂組成物である実施例8、9と比較例3とを比較しても、本発明のポリカーボネート樹脂組成物、及びこれを含む樹脂成形体は、より短い燃焼時間での燃焼試験1.6mmでV−0を達成できるという、所望の難燃性を確保できることが判る。そして難燃剤の含有量を抑えることで、ポリカーボネート樹脂ペレットの分子量低下が抑制できることから、ポリカーボネート樹脂としての特性を保持でき、優れた性質を有するものであることが判る。 On the other hand, when Examples 5-7, which are polycarbonate resin compositions to which glass fibers were added, were compared with Comparative Example 2, Examples 8 and 9 and Comparative Example 3, which were polycarbonate resin compositions to which titanium oxide was added. Even if the polycarbonate resin composition of the present invention and the resin molded body including the same are compared with each other, the desired flame retardancy that V-0 can be achieved with a combustion test of 1.6 mm with a shorter combustion time is obtained. It can be seen that it can be secured. And since the molecular weight fall of a polycarbonate resin pellet can be suppressed by suppressing content of a flame retardant, the characteristic as polycarbonate resin can be hold | maintained and it turns out that it has the outstanding property.
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