JP6131112B2 - Styrene flame-retardant resin composition and molded body using the same - Google Patents
Styrene flame-retardant resin composition and molded body using the same Download PDFInfo
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- JP6131112B2 JP6131112B2 JP2013123403A JP2013123403A JP6131112B2 JP 6131112 B2 JP6131112 B2 JP 6131112B2 JP 2013123403 A JP2013123403 A JP 2013123403A JP 2013123403 A JP2013123403 A JP 2013123403A JP 6131112 B2 JP6131112 B2 JP 6131112B2
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- mass
- styrene
- flame retardant
- resin composition
- compound
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- 239000003063 flame retardant Substances 0.000 title claims description 51
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 47
- 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 description 46
- 239000011342 resin composition Substances 0.000 title claims description 29
- -1 brominated phthalimide compound Chemical class 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 239000000454 talc Substances 0.000 claims description 16
- 229910052623 talc Inorganic materials 0.000 claims description 16
- 239000004611 light stabiliser Substances 0.000 claims description 15
- 150000003440 styrenes Chemical class 0.000 claims description 14
- 239000006096 absorbing agent Substances 0.000 claims description 10
- 229920001890 Novodur Polymers 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 229940116351 sebacate Drugs 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 description 2
- BLAWBHWPYNVRFN-UHFFFAOYSA-N 4-[2-(1,3-dioxoisoindol-4-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1NC(=O)C2=C1C=CC=C2CCC1=CC=CC2=C1C(=O)NC2=O BLAWBHWPYNVRFN-UHFFFAOYSA-N 0.000 description 2
- OIPGCJHDZQHXOT-UHFFFAOYSA-N 4-[4-(1,3-dioxoisoindol-4-yl)butyl]isoindole-1,3-dione Chemical compound C(CCCC1=C2C(C(=O)NC2=O)=CC=C1)C1=C2C(C(=O)NC2=O)=CC=C1 OIPGCJHDZQHXOT-UHFFFAOYSA-N 0.000 description 2
- RRZDSQWTGZNJFM-UHFFFAOYSA-N 4-[5-(1,3-dioxoisoindol-4-yl)pentyl]isoindole-1,3-dione Chemical compound O=C1NC(=O)c2c1cccc2CCCCCc1cccc2C(=O)NC(=O)c12 RRZDSQWTGZNJFM-UHFFFAOYSA-N 0.000 description 2
- IJTZNPJNLORUJM-UHFFFAOYSA-N 4-[6-(1,3-dioxoisoindol-4-yl)hexyl]isoindole-1,3-dione Chemical compound O=C1NC(=O)C2=C1C=CC=C2CCCCCCC1=CC=CC2=C1C(=O)NC2=O IJTZNPJNLORUJM-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HYAMCXBBOVHCNL-UHFFFAOYSA-N C(C(C)C1=C2C(C(=O)NC2=O)=CC=C1)C1=C2C(C(=O)NC2=O)=CC=C1 Chemical compound C(C(C)C1=C2C(C(=O)NC2=O)=CC=C1)C1=C2C(C(=O)NC2=O)=CC=C1 HYAMCXBBOVHCNL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000005063 High cis polybutadiene Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadis***e 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 1
- VEAFKIYNHVBNIP-UHFFFAOYSA-N 1,3-Diphenylpropane Chemical compound C=1C=CC=CC=1CCCC1=CC=CC=C1 VEAFKIYNHVBNIP-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 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
- LEGLETKSWODEBL-UHFFFAOYSA-N 2-[[3-(benzotriazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-6-tert-butyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O LEGLETKSWODEBL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-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
- ZITDOJMAOFWSQI-UHFFFAOYSA-N 4-(2,3,4-tribromophenoxy)triazine Chemical compound BrC1=C(Br)C(Br)=CC=C1OC1=CC=NN=N1 ZITDOJMAOFWSQI-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VPICDQPHVNYUMI-UHFFFAOYSA-N 4-[(1,3-dioxoisoindol-4-yl)methyl]isoindole-1,3-dione Chemical compound O=C1NC(=O)C2=C1C=CC=C2CC1=CC=CC2=C1C(=O)NC2=O VPICDQPHVNYUMI-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- DVGPMIRVCZNXMD-UHFFFAOYSA-N 6-phenylhexylbenzene Chemical compound C=1C=CC=CC=1CCCCCCC1=CC=CC=C1 DVGPMIRVCZNXMD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005064 Low cis polybutadiene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 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
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- TUKWPCXMNZAXLO-UHFFFAOYSA-N ethyl 2-nonylsulfanyl-4-oxo-1h-pyrimidine-6-carboxylate Chemical compound CCCCCCCCCSC1=NC(=O)C=C(C(=O)OCC)N1 TUKWPCXMNZAXLO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000001288 lysyl group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Description
本発明は、高度な難燃性（ＵＬ９４ ５Ｖ）及び耐光性を有し、強度と耐熱性の高度なバランスに優れたスチレン系難燃性樹脂組成物に関するものである。 The present invention relates to a styrene-based flame retardant resin composition having high flame resistance (UL94 5V) and light resistance, and having an excellent balance between strength and heat resistance.
ゴム変性スチレン系樹脂は成形性、寸法安定性に優れており、比較的安価であることから広範囲の用途に使用されている。特に難燃性樹脂はワープロ、パーソナルコンピュータ、複写機、プリンター等のＯＡ機器、ＴＶ、ＶＴＲ、オーディオ等の家電製品等を初めとする多岐の分野で使用されている。 Rubber-modified styrenic resins are excellent in moldability and dimensional stability, and are relatively inexpensive, and are used in a wide range of applications. In particular, flame retardant resins are used in various fields including office automation equipment such as word processors, personal computers, copying machines, printers, and home appliances such as TVs, VTRs, and audios.
複写機及びプリンターに使用される外装カバーは、防火エンクロージャとして燃焼あるいは高温物質の飛散や火炎の吹き出しなどを防止する役割を担っている。小型の機器においてはＵＬ９４ Ｖ−１の難燃性能を有する材料であれば使用可能であるが、大型の機器及び固定して使用される機器においては、高度な難燃性（ＵＬ９４ ５Ｖ）が要求される。 An exterior cover used for a copying machine and a printer plays a role as a fireproof enclosure to prevent combustion, scattering of high-temperature substances, blowing of flames, and the like. Small materials can be used as long as they have UL94 V-1 flame retardant materials, but large flame retardants and devices that are used in a fixed manner require high flame resistance (UL94 5V). Is done.
また外装部材は直接／間接の太陽光あるいは蛍光灯等の人工照明の照射を受けるため、耐光性が要求される。特に大型あるいは固定されて使用される複写機及びプリンターにおいては、小型機と比べて更新頻度が低く使用年数が長くなる傾向が強く、小型機と比べてより高度な耐光性が要求される。 Moreover, since the exterior member is irradiated with direct / indirect sunlight or artificial lighting such as a fluorescent lamp, light resistance is required. In particular, copying machines and printers that are used in a large or fixed manner tend to have a lower update frequency and a longer service life than small machines, and require higher light resistance than small machines.
大型あるいは固定されて使用される機器では、内部機構の大型／複雑化と共に放熱が大きくなるため、小型機と比べてより高度な耐熱性が要求される。更には近年、複写機及びプリンターにおいても、成形品の薄肉化／軽量化が進んでおり、より一層の強度と耐熱性の高度なバランスが求められている。 In a large-sized or fixed device, heat radiation increases as the internal mechanism becomes larger / complex, so that higher heat resistance is required compared to a small machine. Furthermore, in recent years, copying machines and printers are also being made thinner and lighter, and a further balance between strength and heat resistance is required.
従来から、スチレン系樹脂に難燃性を付与するために、種々の難燃剤が提案されている。中でも、安価で物性バランスに優れているハロゲン含有有機化合物が難燃剤として多く使用されている。代表的なものとしては、テトラブロモビスフェノールＡ、デカブロモジフェニルエーテル、デカブロモジフェニルエタン、臭素化トリアジン、臭素化エポキシ、臭素化フタルイミド、又は臭素化エポキシ樹脂のエポキシ基をトリブロモフェノールで封鎖したものが使用される。 Conventionally, various flame retardants have been proposed in order to impart flame retardancy to styrene-based resins. Among them, halogen-containing organic compounds that are inexpensive and excellent in physical property balance are often used as flame retardants. Typical examples include tetrabromobisphenol A, decabromodiphenyl ether, decabromodiphenylethane, brominated triazine, brominated epoxy, brominated phthalimide, or a brominated epoxy resin with the epoxy group blocked with tribromophenol. used.
従来より、上述の難燃性樹脂を得る方法として、ポリハロゲン化ジフェニルアルカンおよびエチレンビステトラブロモフタルイミドを併用する樹脂組成物（特開平１０−２０４２３６号公報）、ポリハロゲン化ジフェニルアルカンを必須成分とし、加えてハロゲン含有芳香族ジオールのエーテル誘導体及びハロゲン化ビスイミドを任意成分として併用する樹脂組成物（特開平１１−２１７４８２号公報、特開平０８−２８３５２５号公報）等が提唱されている。しかしこれらは何れも難燃レベルがＵＬ９４ Ｖ−０であり、大型あるいは固定されて使用される複写機及びプリンターの外装カバーで必要とされる難燃性能（ＵＬ９４ ５Ｖ）を満たしていない。 Conventionally, as a method for obtaining the above-mentioned flame retardant resin, a resin composition using a polyhalogenated diphenylalkane and ethylenebistetrabromophthalimide (Japanese Patent Laid-Open No. 10-204236), and a polyhalogenated diphenylalkane as essential components are used. In addition, resin compositions (JP-A-11-217482, JP-A-08-283525) and the like that use an ether derivative of a halogen-containing aromatic diol and a halogenated bisimide as optional components have been proposed. However, both of them have a flame retardancy level of UL94 V-0, and do not satisfy the flame retardancy (UL94 5V) required for a large-sized or fixedly used copying machine and printer exterior cover.
こうしたことから高度な難燃性（ＵＬ９４ ５Ｖ）及び耐光性を有し、強度と耐熱性の高度なバランスに優れたスチレン系難燃性樹脂組成物が必要とされている。 For these reasons, there is a need for a styrene-based flame retardant resin composition having high flame retardancy (UL94 5V) and light resistance, and having an excellent balance between strength and heat resistance.
本発明は、高度な難燃性（ＵＬ９４ ５Ｖ）及び耐光性を有し、強度と耐熱性の高度なバランスに優れたスチレン系難燃性樹脂組成物に関するものである。 The present invention relates to a styrene-based flame retardant resin composition having high flame resistance (UL94 5V) and light resistance, and having an excellent balance between strength and heat resistance.
本発明者は上記課題について鋭意検討した結果、特定難燃剤を併用し、難燃化助剤、タルク、紫外線吸収剤、安定剤を含む樹脂組成物とすることにより、本発明を完成させた。
１．（Ａ）ゴム変性スチレン系樹脂を１００質量部に対して、（Ｂ）臭素化フタルイミド化合物と（Ｃ）臭素化ジフェニルアルカン化合物の合計量が１０〜２０質量部であり、（Ｂ）臭素化フタルイミド化合物と（Ｃ）臭素化ジフェニルアルカン化合物の比が３０／７０〜９０／１０、（Ｄ）難燃化助剤１〜１０質量部、（Ｅ）タルク１〜１０質量部、（Ｆ）紫外線吸収剤、（Ｇ）光安定剤を含むことを特徴とするスチレン系難燃性樹脂組成物。
２．上記（Ａ）ゴム変性スチレン系樹脂を１００質量部とした時、（Ｆ）紫外線吸収剤と（Ｇ）光安定剤の合計量が０．０１〜２質量部であり、（Ｆ）紫外線吸収剤と（Ｇ）光安定剤の比が１０／９０〜９０／１０である前記１に記載のスチレン系難燃性樹脂組成物。
３．ＵＬ９４における燃焼性が５Ｖを有することを特徴とする前記１及び２のいずれか１項に記載のスチレン系難燃性樹脂組成物。
４.スチレン系難燃性樹脂組成物を成形して得られることを特徴とする前記１〜３のいずれか１項に記載の成形体。
As a result of intensive studies on the above problems, the present inventor has completed the present invention by using a specific flame retardant together to obtain a resin composition containing a flame retardant aid, talc, an ultraviolet absorber, and a stabilizer.
1. (A) 100 parts by mass of the rubber-modified styrene resin, the total amount of (B) brominated phthalimide compound and (C) brominated diphenylalkane compound is 10 to 20 parts by mass, and (B) brominated phthalimide The ratio of the compound to (C) brominated diphenylalkane compound is 30/70 to 90/10, (D) 1 to 10 parts by mass of flame retardant aid, (E) 1 to 10 parts by mass of talc, (F) UV absorption A styrene-based flame retardant resin composition comprising an agent and (G) a light stabilizer.
2. When (A) the rubber-modified styrenic resin is 100 parts by mass, the total amount of (F) UV absorber and (G) light stabilizer is 0.01 to 2 parts by mass, and (F) UV absorber. And (G) the styrene-based flame retardant resin composition as described in 1 above, wherein the ratio of the light stabilizer is 10/90 to 90/10.
3. The styrene flame-retardant resin composition according to any one of 1 and 2 above, wherein the flammability in UL94 is 5V.
4. The molded body according to any one of 1 to 3, which is obtained by molding a styrene-based flame retardant resin composition.
本発明に関わるスチレン系難燃性樹脂組成物は、高度な難燃性（ＵＬ９４ ５Ｖ）及び耐光性を有し、強度と耐熱性の高度なバランスに優れたスチレン系難燃性樹脂組成物である。該スチレン系難燃性樹脂組成物の特性は、特に大型あるいは固定されて使用される複写機及びプリンターに使用される外装カバーに好適であり、その産業上の利用価値は極めて大である。 The styrene-based flame retardant resin composition according to the present invention is a styrene-based flame retardant resin composition having high flame resistance (UL94 5V) and light resistance, and having an excellent balance between strength and heat resistance. is there. The characteristics of the styrene-based flame retardant resin composition are particularly suitable for exterior covers used for copying machines and printers that are used in large or fixed sizes, and have an extremely large industrial utility value.
本発明で用いる（Ａ）ゴム変性スチレン系樹脂は、スチレン系単量体にゴム成分を溶解し、熱重合または過酸化物等の重合開始剤を用いて攪拌下で重合させた物であり、製造プロセスとしてはバッチ重合でも連続重合でも良い。スチレン系単量体としてはｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、２，４−ジメチルスチレン等が挙げられるが、スチレンが最も好適である。これらの単量体を用いて単独重合体としても良いし、２種以上を併用して使用することも出来る。またこれらの単量体と共重合可能なメタクリル酸、メタクリル酸メチル等を用いて共重合体としても良い。ゴム成分としては、ブタジエン、イソプレン等の単独重合体や、ブタジエンと共重合可能なスチレンやメタクリル酸メチル等との共重合体が用いられ、共重合体の分子構造はランダム構造でもブロック構造でも良く、分岐構造を有しても良い。またこうしたゴム変性スチレン系樹脂は、樹脂組成物としてのゴム成分量や衝撃強度、流動性を調節する目的で、ゴム成分を含まないポリスチレン（ＧＰＰＳ）と併用し用いても良い。難燃性樹脂組成物中のゴム状重合体は３〜１２質量％であり、好ましくは４〜１１質量％である。ゴム状重合体の量が３質量％より少ないと強度が低下し、１２質量％より多いと曲げ弾性率が低下するため、好ましくない。なお（Ａ）ゴム変性スチレン系樹脂は、ゴム成分として７０質量％以上が、シス−１、４結合を９０モル％以上の比率で含有するハイシスポリブタジエンゴムを用いたものが好ましい。、１，４−シス結合含量が１０〜４０モル％であるローシスポリブタジエンゴムを用いた場合、離型性が低下するため、好ましくない。 The rubber-modified styrene resin (A) used in the present invention is a product obtained by dissolving a rubber component in a styrene monomer and polymerizing it with stirring using a polymerization initiator such as thermal polymerization or peroxide, The production process may be batch polymerization or continuous polymerization. Examples of the styrenic monomer include o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene and the like, and styrene is most preferable. These monomers may be used as a homopolymer, or two or more types may be used in combination. Moreover, it is good also as a copolymer using methacrylic acid, methyl methacrylate, etc. which can be copolymerized with these monomers. As the rubber component, homopolymers such as butadiene and isoprene, and copolymers with styrene and methyl methacrylate that can be copolymerized with butadiene are used, and the molecular structure of the copolymer may be a random structure or a block structure. , May have a branched structure. Further, such a rubber-modified styrene resin may be used in combination with polystyrene (GPPS) containing no rubber component for the purpose of adjusting the amount of rubber component, impact strength, and fluidity of the resin composition. The rubbery polymer in the flame retardant resin composition is 3 to 12% by mass, preferably 4 to 11% by mass. When the amount of the rubbery polymer is less than 3% by mass, the strength is lowered, and when it is more than 12% by mass, the flexural modulus is lowered, which is not preferable. The (A) rubber-modified styrenic resin preferably uses a high-cis polybutadiene rubber containing 70% by mass or more of a rubber component in a ratio of cis-1,4 bonds of 90 mol% or more. When a low-cis polybutadiene rubber having a 1,4-cis bond content of 10 to 40 mol% is used, it is not preferable because the releasability is lowered.
本発明で使用する（Ｂ）臭素化フタルイミド化合物は、下記に示す（化１）で表される化合物である。 The (B) brominated phthalimide compound used in the present invention is a compound represented by the following (Chemical Formula 1).
（Ｂ）臭素化フタルイミド化合物として、メチレン−ビス−フタルイミド、エチレン−ビス−フタルイミド、プロピレン−ビス−フタルイミド、ブチレン−ビス−フタルイミド、ペンチレン−ビス−フタルイミド、ヘキシレン−ビス−フタルイミド等のジブロモ置換体、トリブロモ置換体、テトラブロモ置換体、ペンタブロモ置換体、ヘキサブロモ置換体、ヘプタブロモ置換体、オクタブロモ置換体が挙げられる。好ましくは、エチレン−ビス−フタルイミド、プロピレン−ビス−フタルイミド、ブチレン−ビス−フタルイミド、ペンチレン−ビス−フタルイミド、ヘキシレン−ビス−フタルイミドのオクタブロモ置換体である。 (B) As brominated phthalimide compounds, dibromo substitution products such as methylene-bis-phthalimide, ethylene-bis-phthalimide, propylene-bis-phthalimide, butylene-bis-phthalimide, pentylene-bis-phthalimide, hexylene-bis-phthalimide, Examples include tribromo-substituted, tetrabromo-substituted, pentabromo-substituted, hexabromo-substituted, heptabromo-substituted, and octabromo-substituted. Preferred are octabromo-substituted products of ethylene-bis-phthalimide, propylene-bis-phthalimide, butylene-bis-phthalimide, pentylene-bis-phthalimide, and hexylene-bis-phthalimide.
本発明で使用する（Ｃ）臭素化ジフェニルアルカン化合物は、下記に示す（化２）で表される化合物である。 The (C) brominated diphenylalkane compound used in the present invention is a compound represented by the following (Chemical Formula 2).
（Ｃ）臭素化ジフェニルアルカン化合物として、ジフェニルメタン、１，２−ジフェニルエタン、１，３−ジフェニルプロパン、１，６−ジフェニルヘキサン等のジブロモ置換体、トリブロモ置換体、テトラブロモ置換体、ペンタブロモ置換体、ヘキサブロモ置換体、ヘプタブロモ置換体、オクタブロモ置換体、ノナブロモ置換体、デカブロモ置換体が挙げられる。好ましくは、ジフェニルアルカンのオクタブロモ置換体、ノナブロモ置換体、デカブロモ置換体であり、特に好ましくはデカブロモジフェニルエタンである。 (C) As brominated diphenylalkane compounds, dibromomethane, 1,2-diphenylethane, 1,3-diphenylpropane, 1,6-diphenylhexane and other dibromo-substituted, tribromo-substituted, tetrabromo-substituted, pentabromo-substituted, Examples include hexabromo-substituted, heptabromo-substituted, octabromo-substituted, nonabromo-substituted, and decabromo-substituted. Preferred are octabromo-substituted, nonabromo-substituted and decabromo-substituted diphenylalkanes, and particularly preferred is decabromodiphenylethane.
（Ｂ）臭素化フタルイミド化合物及び（Ｃ）臭素化ジフェニルアルカン化合物は、その合計量として１０〜２０質量部用いるのが必須であり、好ましくは１２〜１８質量部である。（Ｂ）臭素化フタルイミド化合物と（Ｃ）臭素化ジフェニルアルカン化合物の比率は、３０／７０〜９０／１０、好ましくは５０／５０〜９０／１０、より好ましくは６０／４０〜９０/１０の範囲である。（Ｂ）臭素化フタルイミド化合物と（Ｃ）臭素化ジフェニルアルカン化合物の合計量が１０質量部より少ないと難燃性が確保できず、２０質量部より多いとシャルピー衝撃強度が低下する。（Ｂ）臭素化フタルイミド化合物と（Ｃ）臭素化ジフェニルアルカン化合物の比率が３０／７０より小さいと耐光性が悪化し、９０／１０より大きいとシャルピー強度が低下する。 It is essential to use (B) brominated phthalimide compound and (C) brominated diphenylalkane compound in a total amount of 10 to 20 parts by mass, preferably 12 to 18 parts by mass. The ratio of (B) brominated phthalimide compound to (C) brominated diphenylalkane compound is in the range of 30/70 to 90/10, preferably 50/50 to 90/10, more preferably 60/40 to 90/10. It is. When the total amount of (B) brominated phthalimide compound and (C) brominated diphenylalkane compound is less than 10 parts by mass, flame retardancy cannot be ensured, and when it exceeds 20 parts by mass, Charpy impact strength decreases. When the ratio of (B) brominated phthalimide compound and (C) brominated diphenylalkane compound is smaller than 30/70, the light resistance is deteriorated, and when it is larger than 90/10, the Charpy strength is decreased.
本発明では（Ｂ）及び（Ｃ）の臭素系難燃剤と共に（Ｄ）難燃化助剤を用いる。難燃化助剤とは難燃剤の難燃効果を更に高める働きをするものであり、例えば酸化アンチモンとして三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、アンチモン酸ソーダ等、ホウ素系化合物としてホウ酸亜鉛、メタホウ酸バリウム、無水ホウ酸亜鉛、無水ホウ酸等、スズ系化合物として酸化第二スズ、スズ酸亜鉛、ヒドロキシスズ酸亜鉛等、モリブデン系化合物として酸化モリブデン、モリブデン酸アンモニウム等、ジルコニウム系化合物として酸化ジルコニウム、水酸化ジルコニウム等、また亜鉛系化合物として硫化亜鉛等が挙げられる。好ましくは三酸化アンチモンである。 In the present invention, the flame retardant aid (D) is used together with the brominated flame retardants (B) and (C). The flame retardant aid functions to further enhance the flame retardant effect of the flame retardant, such as antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, boric acid as a boron compound, etc. Zinc, barium metaborate, anhydrous zinc borate, anhydrous boric acid, etc., tin compounds such as stannic oxide, zinc stannate, zinc hydroxystannate, etc., molybdenum compounds such as molybdenum oxide, ammonium molybdate, zirconium compounds, etc. Zirconium oxide, zirconium hydroxide, etc., and zinc-based compounds include zinc sulfide. Antimony trioxide is preferred.
（Ｄ）難燃化助剤は１〜１０質量部用いるのが必須であり、好ましくは２〜８質量部である。難燃化助剤が１質量部より少ないと難燃性が確保できず、１０質量部より多いとシャルピー衝撃強度が低下する。 (D) It is essential to use 1 to 10 parts by mass of the flame retardant aid, and preferably 2 to 8 parts by mass. When the amount of the flame retardant aid is less than 1 part by mass, flame retardancy cannot be ensured, and when it is more than 10 parts by mass, the Charpy impact strength is lowered.
無機化合物としては（Ｅ）タルクを使用する。（Ｅ）タルクの添加量は１〜１０質量部であり、好ましくは１〜８質量部である。タルクが１質量部より少ないと難燃性が確保できず、タルクが１０質量部より多いとシャルピー衝撃強度が低下する。 As the inorganic compound, (E) talc is used. (E) The amount of talc added is 1 to 10 parts by mass, preferably 1 to 8 parts by mass. If the talc content is less than 1 part by mass, flame retardancy cannot be ensured, and if the talc content is greater than 10 parts by mass, the Charpy impact strength decreases.
（Ｆ）紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、サリシレート系紫外線吸収剤、シアノアクリレート系紫外線吸収剤、ニッケル錯塩紫外線吸収剤等が挙げられる。好ましいのはベンゾトリアゾール系紫外線吸収剤である。 Examples of (F) UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, and nickel complex UV absorbers. Preferred is a benzotriazole ultraviolet absorber.
ベンゾトリアゾール系紫外線吸収剤としては、市販されているものを適用できる。例えば、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−（３−ｔ−ブチル−５−メチル−２−ヒドロキシフェニル）−５−クロロ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−５’−ｔ−オクチルフェニル）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）−５−クロロ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）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−アミノフェニル）ベンゾトリアゾール、２−｛２’−ヒドロキシ−３’−（３’’，４’’，５’’，６’’−テトラヒドロフタルイミドメチル）−５’−メチルフェニル｝ベンゾトリアゾール、２，２’−メチレンビス｛４−（１，１，３，３−テトラメチルブチル）−６−（２Ｈ−ベンゾトリアゾール−２−イル）フェノール｝、６−（２−ベンゾトリアゾリル）−４−ｔ−オクチル−６’−ｔ−ブチル−４’−メチル−２，２’−メチレンビスフェノール等が挙げられる。これらは単独で用いてもよく２種以上を組み合わせて用いてもよい。特に２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾールが好ましい。 A commercially available product can be applied as the benzotriazole ultraviolet absorber. For example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2′- Hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t- Butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy) -3 ′, 5′-di-t-aminophenyl) benzotriazole, 2- {2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthal Imidomethyl) -5′-methylphenyl} benzotriazole, 2,2′-methylenebis {4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol}, Examples include 6- (2-benzotriazolyl) -4-t-octyl-6′-t-butyl-4′-methyl-2,2′-methylenebisphenol. These may be used alone or in combination of two or more. 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole is particularly preferable.
（Ｇ）光安定剤としてはヒンダードアミン系光安定剤が好ましく、市販されているものを適用できる。例えば、ビス（２，２，６，６−テトラメチル−４−ペピリジル）セバケート、ビス（１−オクチロキシ−２，２，６，６−テトラメチル−４−ペピリジル）セバケート、コハク酸ジメチルと１−（２−ヒドロキシエチル）−４−ヒドロキシ−２，２，６，６−テトラメチルペピリジンとの重縮合物、ポリ［｛６−（１，１，３，３−テトラメチルブチル）アミノ−１，３，５−トリアジン−２，４−ジイル｝｛（２，２，６，６−テトラメチル−４−ペピリジル）イミノ｝ヘキサメチレン｛（２，２，６，６−テトラメチル−４−ペピリジル）イミノ｝］、Ｎ，Ｎ’−ビス（３−アミノプロピル）エチレンジアミンと２，４−ビス［Ｎ−ブチル−Ｎ−（１，２，２，６，６−ペンタメチル−４−ペピリジル）アミノ］−６−クロロ−１，３，５−トリアジンとの縮合物、１，２，３，４−テトラ（２，２，６，６−テトラメチル−４−ペピリジル）−ブタンテトラカルボキシレート、１，４−ビス（２，２，６，６−テトラメチル−４−ペピリジル）−２，３−ブタンジオン、トリス−（２，２，６，６−テトラメチル−４−ペピリジル）トリメリテート、１，２，２，６，６−ペンタメチル−４−ペピリジル−ｎ−オクトエート、１，２，２，６，６−ペンタメチル−４−ペピリジルステアレート、４−ヒドロキシ−１，２，２，６，６−ペンタメチルペピリジン、ビス（１，２，２，６，６−ペンタメチル−４−ペピリジニル）セバケート、２−（３，５−ｔ−ブチル−４−ヒドロキシベンジル）−２−ｎ−ブチルマロン酸ビス（１，２，２，６，６−ペンタメチル−４−ペピリジル）等が挙げられる。これらは単独で用いてもよく２種以上を組み合わせて用いてもよい。特にビス（２，２，６，６-テトラメチル−４−ピペリジル）セパケートが好ましい。 (G) A hindered amine light stabilizer is preferable as the light stabilizer, and commercially available ones can be applied. For example, bis (2,2,6,6-tetramethyl-4-pepyridyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-pepyridyl) sebacate, dimethyl succinate and 1- Polycondensate with (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpepyridine, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1 , 3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-pepyridyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-pepyridyl) ) Imino}], N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-pepyridyl) amino] -6-chloro-1,3 Condensate with 5-triazine, 1,2,3,4-tetra (2,2,6,6-tetramethyl-4-pepyridyl) -butanetetracarboxylate, 1,4-bis (2,2,6 , 6-tetramethyl-4-pepyridyl) -2,3-butanedione, tris- (2,2,6,6-tetramethyl-4-pepyridyl) trimellitate, 1,2,2,6,6-pentamethyl-4 -Pepyridyl-n-octoate, 1,2,2,6,6-pentamethyl-4-pepyridyl stearate, 4-hydroxy-1,2,2,6,6-pentamethylpepyridine, bis (1,2 , 2,6,6-pentamethyl-4-pepyridinyl) sebacate, bis (1,2,2,6,6) 2- (3,5-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate -Pentamethyl-4-pe Lysyl), and the like. These may be used alone or in combination of two or more. Bis (2,2,6,6-tetramethyl-4-piperidyl) separate is particularly preferable.
（Ｆ）紫外線吸収剤及び（Ｇ）光安定剤は、その合計量として０．０１〜２質量部であり、好ましくは０．１〜１．５質量部である。紫外線吸収剤及び光安定剤の比率は、１０／９０〜９０／１０の範囲であり、好ましくは２０／８０〜８０／２０の範囲である。紫外線吸収剤及び光安定剤が０．０１質量部より少ないと耐光性が悪化し、２質量部より多いと耐熱性が低下する。 (F) A ultraviolet absorber and (G) light stabilizer are 0.01-2 mass parts as the total amount, Preferably it is 0.1-1.5 mass parts. The ratio of the ultraviolet absorber and the light stabilizer is in the range of 10/90 to 90/10, preferably in the range of 20/80 to 80/20. When the amount of the ultraviolet absorber and the light stabilizer is less than 0.01 parts by mass, the light resistance is deteriorated, and when the amount is more than 2 parts by mass, the heat resistance is decreased.
本発明のスチレン系難燃性樹脂組成物には、本発明の要旨を超えない範囲で各種添加物、例えば染顔料、着色防止剤、滑剤、酸化防止剤、老化防止剤、帯電防止剤、充填剤、相溶化剤、滴下防止剤等の公知の添加剤、酸化チタンやカーボンブラックなどの着色剤、エラストマー成分（ＳＢＳや水添ＳＢＳ）などの改質剤を添加できる。これらの添加方法は特に限定される訳では無く、公知の方法例えば、使用する（Ａ）ゴム変性スチレン系樹脂の重合開始前、重合途中の反応液に対して、または重合終了後、及び（Ｂ）臭素化フタルイミド化合物、（Ｃ）臭素化ジフェニルアルカン化合物、（Ｄ）難燃化助剤、（Ｅ）タルク、（Ｆ）紫外線吸収剤、（Ｇ）光安定剤を配合する際、更には、押出機や成形機においても添加することができる。 The styrene-based flame retardant resin composition of the present invention has various additives within a range not exceeding the gist of the present invention, such as dyes and pigments, coloring agents, lubricants, antioxidants, anti-aging agents, antistatic agents, and filling. Known additives such as additives, compatibilizers, anti-dripping agents, colorants such as titanium oxide and carbon black, and modifiers such as elastomer components (SBS and hydrogenated SBS) can be added. These addition methods are not particularly limited, and known methods such as (A) the rubber-modified styrenic resin to be used before the start of polymerization, with respect to the reaction solution in the middle of polymerization, or after the completion of polymerization, and (B When blending a) brominated phthalimide compound, (C) brominated diphenylalkane compound, (D) flame retardant aid, (E) talc, (F) ultraviolet absorber, (G) light stabilizer, It can also be added in an extruder or a molding machine.
本発明に係わるスチレン系難燃性樹脂組成物を得る方法は、特に限定される訳では無く公知の混合技術を適用することが出来る。例えば、ミキサー型混合機、Ｖ型他ブレンダー、及びタンブラー型混合機等の混合装置であらかじめ混合しておいた混合物を、バンバリー型ミキサー、ニーダー、ロール、単軸押出機、特殊単軸押出機、及び二軸押出機等で溶融混練することが挙げられる。各原材料の添加方法としては、（Ａ）ゴム変性スチレン系樹脂及び（Ｂ）臭素化フタルイミド化合物、（Ｃ）臭素化ジフェニルアルカン化合物、（Ｄ）難燃化助剤、（Ｅ）タルク、（Ｆ）紫外線吸収剤、（Ｇ）光安定剤、及び必要に応じて他の添加剤を直接上記のような混練機に投入し、更に、押出機等の溶融混練装置の途中から添加剤を別途に添加して樹脂組成物を得てもよいし、本発明の趣旨を超えない範囲で予め樹脂等と（Ｂ）臭素化フタルイミド化合物、（Ｃ）臭素化ジフェニルアルカン化合物、（Ｄ）難燃化助剤等を混練してペレット状にしたマスターバッチを作製し、このマスターバッチと（Ａ）ゴム変性スチレン系樹脂を混練機に投入する方法でもよい。 The method for obtaining the styrene-based flame retardant resin composition according to the present invention is not particularly limited, and a known mixing technique can be applied. For example, a mixture previously mixed with a mixing apparatus such as a mixer-type mixer, V-type blender, and tumbler-type mixer is used as a Banbury mixer, kneader, roll, single-screw extruder, special single-screw extruder, And melt-kneading with a twin screw extruder or the like. Methods for adding each raw material include (A) rubber-modified styrene resin and (B) brominated phthalimide compound, (C) brominated diphenylalkane compound, (D) flame retardant aid, (E) talc, (F ) Ultraviolet absorber, (G) Light stabilizer, and other additives as required, are directly charged into the kneader as described above, and the additives are added separately from the middle of the melt kneader such as an extruder. It may be added to obtain a resin composition, or within a range not exceeding the gist of the present invention, resin and the like in advance (B) brominated phthalimide compound, (C) brominated diphenylalkane compound, (D) flame retardant aid The master batch which knead | mixed the agent etc. into the pellet form is produced, and the method of throwing this master batch and (A) rubber-modified styrene resin into a kneading machine may be used.
本発明のスチレン系難燃性樹脂組成物から成形品を得る成形法には特に制限は無いが、好ましいのは射出成形であり、特に複写機及びプリンターの外装カバーには射出成形が好適である。 There is no particular limitation on the molding method for obtaining a molded product from the styrene-based flame retardant resin composition of the present invention, but injection molding is preferable, and injection molding is particularly suitable for an outer cover of a copying machine and a printer. .
以下実施例により詳細を説明するが、本発明はこれに限定されるものではない。 Hereinafter, details will be described by way of examples, but the present invention is not limited thereto.
（Ａ）ゴム変性スチレン系樹脂：実施例及び比較例で使用した（Ａ）ゴム変性スチレン系樹脂は、それぞれ以下の組成である。ゴム状重合体にシス１、４結合を９０モル％以上の比率で含有するハイシスポリブタジエンゴムを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂の組成は、マトリックス部分の還元粘度が０．７６ｄｌ／ｇであり、ゴム状重合体の含有量が９．１質量％であり、ゴム状重合体のゲル含有量が２６質量％であり、及びゴム状重合体の体積平均粒子径２．８μｍである。ここで言う還元粘度、ゴム状重合体の質量％、ゴム状重合体のゲル含有量の質量％、ゴム状重合体の体積平均粒子径は以下の方法で測定した。 (A) Rubber-modified styrene resin: The rubber-modified styrene resin (A) used in Examples and Comparative Examples has the following composition. This is a rubber-modified styrene resin using a high-cis polybutadiene rubber containing cis 1,4 bonds in a ratio of 90 mol% or more in the rubber-like polymer. The composition of this rubber-modified styrene resin has a reduced viscosity of 0.76 dl / g in the matrix portion, a rubber-like polymer content of 9.1% by mass, and a rubber-like polymer gel content of 26%. The volume average particle diameter of the rubber-like polymer is 2.8 μm. The reduced viscosity, the mass% of the rubber-like polymer, the mass% of the gel content of the rubber-like polymer, and the volume average particle diameter of the rubber-like polymer as measured herein were measured by the following methods.
還元粘度（ηsp／Ｃ）の測定：ゴム変性スチレン系樹脂１ｇにメチルエチルケトン１７.５ｍｌとアセトン１７.５ｍｌの混合溶媒を加え、温度２５℃で２時間振とう溶解した後、遠心分離で不溶分を沈降させ、デカンテーションにより上澄み液を取り出し、２５０ｍｌのメタノールを加えて樹脂分を析出させ、不溶分を濾過乾燥する。同操作で得られた樹脂分をトルエンに溶解してポリマー濃度０．４％（質量／体積）の試料溶液を作成した。この試料溶液、及び純トルエンを３０℃の恒温でウベローデ型粘度計により溶液流下秒数を測定して、下式にて算出した。
ηsp／Ｃ＝（ｔ1／ｔ0−１）／Ｃ
ｔ0：純トルエン流下秒数
ｔ１：試料溶液流下秒数
Ｃ ：ポリマー濃度
Measurement of reduced viscosity (ηsp / C): 1 g of rubber-modified styrene resin is mixed with 17.5 ml of methyl ethyl ketone and 17.5 ml of acetone, dissolved by shaking at a temperature of 25 ° C. for 2 hours, and then insoluble by centrifugation. The mixture is allowed to settle, the supernatant is removed by decantation, 250 ml of methanol is added to precipitate the resin component, and the insoluble component is filtered and dried. The resin component obtained by the same operation was dissolved in toluene to prepare a sample solution having a polymer concentration of 0.4% (mass / volume). The sample solution and pure toluene were measured at a constant temperature of 30 ° C. using a Ubbelohde viscometer, and the number of seconds during which the solution flowed was measured.
ηsp / C = (t1 / t0-1) / C
t0: Pure toluene flow down seconds
t1: Sample solution flow down seconds
C: Polymer concentration
ゴム状重合体含有量の測定：該スチレン系難燃性樹脂組成物をクロロホルムに溶解させ、一定量の一塩化ヨウ素／氷酢酸溶液を加え暗所に約３０分放置後、１５質量％のヨウ化カリウム溶液と純水５０ｍｌを加え、過剰の一塩化ヨウ素を０．１Ｎチオ硫酸ナトリウム溶液で滴定し、付加した一塩化ヨウ素量から算出した。 Measurement of rubbery polymer content: The styrenic flame retardant resin composition was dissolved in chloroform, a certain amount of iodine monochloride / glacial acetic acid solution was added and left in the dark for about 30 minutes, and then 15% by mass of iodine. Potassium iodide solution and 50 ml of pure water were added, and excess iodine monochloride was titrated with 0.1N sodium thiosulfate solution, and calculated from the amount of iodine monochloride added.
ゲル含有量の測定：ゴム変性スチレン系樹脂をトルエンに３．３％（質量／体積）の割合で加え、温度２５℃で４０分振とう溶解した後、遠心分離（回転数１００００〜１４０００ｒｐｍ、分離時間３０分）で不溶分（ゲル分）を沈降させ、デカンテーションにより上澄み液を除去してゲルを得た。次に、この膨潤ゲルを温度１００℃で２時間予備乾燥した後、温度１２０℃の真空乾燥機で１時間乾燥した。デシケータで常温まで冷却し精秤し下式にて算出した。
ゲル分率（％）＝[（ｍ１−ｍ０）／Ｓ]×１００
ｍ０：遠心沈降管質量
ｍ１：乾燥ゲル＋遠心沈降管質量
Ｓ：試料樹脂質量
Measurement of gel content: rubber-modified styrene resin was added to toluene at a ratio of 3.3% (mass / volume), dissolved by shaking at a temperature of 25 ° C. for 40 minutes, and then centrifuged (revolution speed: 10,000 to 14000 rpm, separation) The insoluble content (gel content) was allowed to settle at 30 minutes, and the supernatant was removed by decantation to obtain a gel. Next, this swollen gel was preliminarily dried at a temperature of 100 ° C. for 2 hours, and then dried by a vacuum dryer at a temperature of 120 ° C. for 1 hour. It cooled to normal temperature with the desiccator, weighed precisely, and computed with the following formula.
Gel fraction (%) = [(m1-m0) / S] × 100
m0: centrifugal sedimentation tube mass
m1: Dry gel + centrifugal sedimentation tube mass
S: Sample resin mass
ゴム状重合体の体積平均粒子径の測定：ゴム変性スチレン系樹脂をジメチルホルムアミドに完全に溶解させ、レーザー回析方式粒度分布装置にて測定した。 Measurement of volume average particle diameter of rubber-like polymer: A rubber-modified styrene resin was completely dissolved in dimethylformamide and measured with a laser diffraction particle size distribution apparatus.
（Ｂ）臭素化フタルイミド化合物：商品名SAYTEX ＢＴ−９３（アルベマール日本社製）を使用した。 (B) Brominated phthalimide compound: Trade name SAYTEX BT-93 (manufactured by Albemarle Japan) was used.
（Ｃ）臭素化ジフェニルアルカン化合物：商品名SAYTEX ８０１０（アルベマール日本社製）を使用した。 (C) Brominated diphenylalkane compound: Trade name SAYTEX 8010 (manufactured by Albemarle Japan) was used.
難燃剤の比較例としてトリブロモフェノキシトリアジン：商品名ＳＲ２４５（第一工業製薬社製）を使用した。 As a comparative example of the flame retardant, tribromophenoxytriazine: trade name SR245 (Daiichi Kogyo Seiyaku Co., Ltd.) was used.
（Ｄ）難燃化助剤：三酸化アンチモン商品名ＡＴ−３ＣＮ（鈴裕化学社製）を使用した。 (D) Flame retardant aid: Antimony trioxide trade name AT-3CN (manufactured by Suzuhiro Chemical Co., Ltd.) was used.
（Ｅ）タルク：商品名ＫＰタルク（富士タルク社製）を使用した。 (E) Talc: The brand name KP talc (manufactured by Fuji Talc) was used.
（Ｆ）紫外線吸収剤：２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾール商品名ＪＦ−７９（城北化学社製）を使用した。 (F) Ultraviolet absorber: 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole trade name JF-79 (manufactured by Johoku Chemical Co., Ltd.) was used.
（Ｇ）光安定剤：ビス（２，２，６，６-テトラメチル−４−ピペリジル）セパケート商品名ＪＦ−９０（城北化学社製）を使用した。 (G) Light stabilizer: Bis (2,2,6,6-tetramethyl-4-piperidyl) sepacate product name JF-90 (manufactured by Johoku Chemical Co., Ltd.) was used.
[樹脂組成物の調製] [Preparation of resin composition]
表１〜４に記載した質量部の（Ａ）ゴム変性スチレン系樹脂、（Ｂ）臭素化フタルイミド化合物、（Ｃ）臭素化ジフェニルアルカン化合物、（Ｄ）難燃化助剤、（Ｅ）タルク（Ｆ）紫外線吸収剤、（Ｇ）光安定剤を秤量し、ヘンシェルミキサー（三井三池化工（株）製、ＦＭ２０Ｂ）で混合し、得られた混合物をスクリューフィーダ付き二軸押出機（日本製鋼所（株）製、ＴＥＭ２６ＳＳ）で混練して樹脂組成物のペレットを製造した。 (A) rubber-modified styrenic resin, (B) brominated phthalimide compound, (C) brominated diphenylalkane compound, (D) flame retardant aid, (E) talc ( F) Ultraviolet absorber and (G) light stabilizer were weighed and mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd., FM20B), and the resulting mixture was twin screw extruder with a screw feeder (Nippon Steel Works ( The resin composition pellets were kneaded with TEM26SS).
なお、予備混合時にカルシウムステアレート、ミネラルオイル、ポリテトラフルオロエチレン、フェノール系酸化防止剤｛オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート｝、ポリエチレンワックス、スチレン−ブタジエン−スチレンブロック共重合体及び酸化チタンも同時添加した。 In addition, calcium stearate, mineral oil, polytetrafluoroethylene, phenolic antioxidant {octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, polyethylene wax, styrene during premixing -Butadiene-styrene block copolymer and titanium oxide were also added simultaneously.
押出し条件
シリンダー設定温度：２００℃(搬送部位)〜２４０℃(混練部位)
スクリュー回転数：３００ｒｐｍ
押出速度：３０ｋｇ／ｈ
Extrusion conditions Cylinder set temperature: 200 ° C. (conveying part) to 240 ° C. (kneading part)
Screw rotation speed: 300rpm
Extrusion speed: 30kg / h
[機械物性測定用試験片の成形]
得られたペレットを温度７０℃×３時間で加熱乾燥後、射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）にて、ＪＩＳ Ｋ ７１３９に記載のＡ型試験片（ダンベル）を成形した。この際、シリンダー温度２０５℃、金型温度４５℃とした。
[Molding specimens for measuring mechanical properties]
The obtained pellets were dried by heating at a temperature of 70 ° C. for 3 hours, and then an A-type test piece (dumbbell) described in JIS K 7139 was molded by an injection molding machine (manufactured by Nippon Steel Works, Ltd., J100E-P). did. At this time, the cylinder temperature was 205 ° C. and the mold temperature was 45 ° C.
[シャルピー衝撃強さ]
上記ダンベル片の中央部より切り出し、切削でノッチ（タイプＡ、ｒ＝０．２５ｍｍ）を入れた試験片を用いて、ＪＩＳ Ｋ ７１１１−１に基づき測定を行った。強度が８kJ／ｍ２未満だと成形品の強度が不十分であり、８ＫJ／ｍ２以上を合格とした。
[Charpy impact strength]
Measurement was performed based on JIS K 7111-1, using a test piece cut out from the center of the dumbbell piece and cut into a notch (type A, r = 0.25 mm). When the strength is less than 8 kJ / m 2, the strength of the molded product is insufficient, and 8 KJ / m 2 or more is regarded as acceptable.
[耐光性]
耐光性の評価用試験片は、射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）にて、８０×５０×２ｍｍの試験片を成形した。この際、シリンダー温度１９０℃、金型温度３０℃とした。アトラス社製キセノンウエザーメータＣｉ４０００を用い、ＡＳＴＭ Ｄ ４４５９に基づき、照射強度０．３Ｗ／ｍ２、ブラックパネル温度５５℃、湿度５０％ＲＨで３００時間照射後のテストピースの色相差ΔＥ＊abを日本電色工業社製Σ８０で測定し、未暴露サンプルとの差で表した。ΔＥ＊abが３より大きいと長期使用時の色相変化が顕著となるため、ΔＥ＊abが３以下を合格とした。
[Light resistance]
The test piece for evaluation of light resistance was formed as an 80 × 50 × 2 mm test piece using an injection molding machine (manufactured by Nippon Steel Works, Ltd., J100E-P). At this time, the cylinder temperature was 190 ° C. and the mold temperature was 30 ° C. Using Atlas Xenon Weather Meter Ci4000, based on ASTM D 4459, the test piece hue difference ΔE * ab after irradiation for 300 hours at an irradiation intensity of 0.3 W / m 2, a black panel temperature of 55 ° C. and a humidity of 50% RH in Japan It was measured with Σ80 manufactured by Denshoku Industries Co., Ltd. and expressed as the difference from the unexposed sample. If ΔE * ab is greater than 3, the hue change during long-term use becomes significant. Therefore, ΔE * ab is 3 or less.
[燃焼性]
燃焼性の評価用試験片は、射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）にて、１２７×１２.７×２．０ｍｍの燃焼用試験片を成形した。米国アンダーライターズ・ラボラトリーズ社のサブジェクト９４号の垂直燃焼試験方法（ＵＬ９４）に基づき、燃焼試験を行った。この試験法で５Ｖの評価となった場合を合格とし、５Ｖに満たなかった場合を不合格とした。
[Combustion quality]
The test piece for evaluation of combustibility was formed as a 127 × 12.7 × 2.0 mm combustion test piece using an injection molding machine (manufactured by Nippon Steel Works, J100E-P). A combustion test was performed based on the vertical combustion test method (UL94) of Subject 94 of US Underwriters Laboratories. The case where it was evaluated as 5V by this test method was accepted, and the case where it was less than 5V was rejected.
（Ａ）ゴム変性スチレン系樹脂、（Ｂ）臭素化フタルイミド化合物、（Ｃ）臭素化ジフェニルアルカン化合物、（Ｄ）難燃化助剤、（Ｅ）タルク（Ｆ）紫外線吸収剤、（Ｇ）光安定剤の各配合量と共に評価結果を表１〜４に示す。 (A) rubber-modified styrene resin, (B) brominated phthalimide compound, (C) brominated diphenylalkane compound, (D) flame retardant aid, (E) talc (F) ultraviolet absorber, (G) light The evaluation results are shown in Tables 1 to 4 together with the blending amounts of the stabilizers.
（各実施例・比較例について）
実施例１〜６は本発明のスチレン系難燃性樹脂組成物であり、本願発明の組成及び規定量を満たすことにより、ＵＬ９４ ５Ｖを満たし、シャルピー衝撃強さ、荷重たわみ温度、及び、耐光性が高度なバランスを有していることがわかる。
(About each example and comparative example)
Examples 1 to 6 are styrene-based flame retardant resin compositions of the present invention, satisfying UL94 5V by satisfying the composition and specified amount of the present invention, Charpy impact strength, deflection temperature under load, and light resistance It can be seen that has a high balance.
しかし本発明の規定を満足しない比較例１〜９で得られたスチレン系難燃性樹脂組成物では、何れかに優れることはあっても、その全てに優れていることはないことがわかる。 However, it can be seen that the styrene-based flame retardant resin compositions obtained in Comparative Examples 1 to 9 that do not satisfy the provisions of the present invention are excellent in any one, but not all.
例えば（Ｂ）臭素化フタルイミド化合物と（Ｃ）臭素化ジフェニルアルカン化合物の比が規定量から外れると比較例１に示すように燃焼性、耐光性が不足する。（Ｂ）臭素化フタルイミド化合物単独で５Ｖ燃焼性を満たすまで難燃剤を加えると比較例２に示すようにシャルピー衝撃強さが不足する。（Ｃ）臭素化ジフェニルアルカン化合物単独で５Ｖ燃焼性を満たすまで難燃剤を加えると比較例１０に示すように耐光性及びシャルピー衝撃強さが不足する。（Ｃ）臭素化ジフェニルアルカン化合物の代わりに他の難燃剤化合物を使用すると比較例３に示すように難燃性及びシャルピー衝撃強さが不足する。（Ｂ）臭素化フタルイミド化合物及び（Ｃ）臭素化ジフェニルアルカン化合物、（Ｄ）難燃化助剤、あるいは（Ｅ）タルクの量が少ないと比較例４、６、８に示すように難燃性が不足する。（Ｂ）臭素化フタルイミド化合物及び（Ｃ）臭素化ジフェニルアルカン化合物の量が多いと比較例５に示すようにシャルピー衝撃強さが不足する。（Ｄ）難燃化助剤、あるいは（Ｅ）タルクの量が多いと比較例７、９に示すようにシャルピー衝撃強さが不足し、難燃性もグローイング発生のためNGとなる。 For example, if the ratio of (B) brominated phthalimide compound and (C) brominated diphenylalkane compound deviates from the specified amount, as shown in Comparative Example 1, combustibility and light resistance are insufficient. (B) When a flame retardant is added until the brominated phthalimide compound alone satisfies 5 V flammability, the Charpy impact strength is insufficient as shown in Comparative Example 2. (C) When a flame retardant is added until the brominated diphenylalkane compound alone satisfies 5 V flammability, light resistance and Charpy impact strength are insufficient as shown in Comparative Example 10. (C) If another flame retardant compound is used instead of the brominated diphenylalkane compound, the flame retardancy and Charpy impact strength are insufficient as shown in Comparative Example 3. When the amount of (B) brominated phthalimide compound and (C) brominated diphenylalkane compound, (D) flame retardant assistant, or (E) talc is small, the flame retardancy is as shown in Comparative Examples 4, 6, and 8. Is lacking. When the amount of (B) brominated phthalimide compound and (C) brominated diphenylalkane compound is large, the Charpy impact strength is insufficient as shown in Comparative Example 5. If the amount of (D) flame retardant aid or (E) talc is large, the Charpy impact strength is insufficient as shown in Comparative Examples 7 and 9, and the flame retardancy is NG due to the occurrence of glowing.
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