TWI698472B - 阻燃性發泡苯乙烯系樹脂組成物及發泡成形體 - Google Patents
阻燃性發泡苯乙烯系樹脂組成物及發泡成形體 Download PDFInfo
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- TWI698472B TWI698472B TW107127578A TW107127578A TWI698472B TW I698472 B TWI698472 B TW I698472B TW 107127578 A TW107127578 A TW 107127578A TW 107127578 A TW107127578 A TW 107127578A TW I698472 B TWI698472 B TW I698472B
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- flame
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- styrene resin
- resin composition
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000003063 flame retardant Substances 0.000 title claims abstract description 68
- 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 67
- 239000011342 resin composition Substances 0.000 title claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011701 zinc Substances 0.000 claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 25
- 239000000194 fatty acid Substances 0.000 claims abstract description 25
- 229930195729 fatty acid Natural products 0.000 claims abstract description 25
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 25
- XUMFBUWGVLTWTH-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromo-2-methylpropoxy)-2-methylpropane Chemical compound BrCC(Br)(C)COCC(C)(Br)CBr XUMFBUWGVLTWTH-UHFFFAOYSA-N 0.000 claims abstract description 17
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 12
- 238000005187 foaming Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 11
- 239000004604 Blowing Agent Substances 0.000 claims description 8
- LXIZRZRTWSDLKK-UHFFFAOYSA-N 1,3-dibromo-5-[2-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]propan-2-yl]-2-(2,3-dibromopropoxy)benzene Chemical compound C=1C(Br)=C(OCC(Br)CBr)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 LXIZRZRTWSDLKK-UHFFFAOYSA-N 0.000 claims description 5
- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 claims description 5
- YUAPUIKGYCAHGM-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromopropoxy)propane Chemical compound BrCC(Br)COCC(Br)CBr YUAPUIKGYCAHGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 claims description 2
- OZHJEQVYCBTHJT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-methylbenzene Chemical compound CC1=C(Br)C(Br)=C(Br)C(Br)=C1Br OZHJEQVYCBTHJT-UHFFFAOYSA-N 0.000 claims 1
- ANENLORAJJKWAA-UHFFFAOYSA-N 4-bromoisoindole-1,3-dione Chemical compound BrC1=CC=CC2=C1C(=O)NC2=O ANENLORAJJKWAA-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 claims 1
- 239000004088 foaming agent Substances 0.000 abstract description 7
- 239000006260 foam Substances 0.000 description 20
- -1 tris(2,3-dibromopropyl) isocyanuric acid Ester Chemical class 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000003017 thermal stabilizer Substances 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002667 nucleating agent Substances 0.000 description 4
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000010097 foam moulding Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 229940098697 zinc laurate Drugs 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- WFGSFFHEXNRKCS-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane;3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propanoic acid Chemical compound C=COCCOC=C.CC1=CC(CCC(O)=O)=C(O)C(C(C)(C)C)=C1.CC1=CC(CCC(O)=O)=C(O)C(C(C)(C)C)=C1 WFGSFFHEXNRKCS-UHFFFAOYSA-N 0.000 description 1
- CWZVMVIHYSYLSI-UHFFFAOYSA-N 1,3-dibromo-5-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]sulfonyl-2-(2,3-dibromopropoxy)benzene Chemical compound C1=C(Br)C(OCC(Br)CBr)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 CWZVMVIHYSYLSI-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 description 1
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-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
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- WDYYJEFALNLPOT-UHFFFAOYSA-N 2,2,6,6-tetramethyl-4-phenylmethoxypiperidine Chemical compound C1C(C)(C)NC(C)(C)CC1OCC1=CC=CC=C1 WDYYJEFALNLPOT-UHFFFAOYSA-N 0.000 description 1
- VKCMZEUOQWUNAR-UHFFFAOYSA-N 2,2-bis(2,4-ditert-butyl-6-methylphenyl)ethyl dihydrogen phosphite Chemical compound CC1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1C(COP(O)O)C1=C(C)C=C(C(C)(C)C)C=C1C(C)(C)C VKCMZEUOQWUNAR-UHFFFAOYSA-N 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- PNZLJNVUTPFUIE-UHFFFAOYSA-N 2,3-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]propyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)OC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 PNZLJNVUTPFUIE-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- TVWGHFVGFWIHFN-UHFFFAOYSA-N 2-hexadecan-2-yl-4,6-dimethylphenol Chemical compound CCCCCCCCCCCCCCC(C)C1=CC(C)=CC(C)=C1O TVWGHFVGFWIHFN-UHFFFAOYSA-N 0.000 description 1
- YAQDPWONDFRAHF-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-ylperoxy)pentane Chemical compound CCCC(C)(C)OOC(C)(C)CCC YAQDPWONDFRAHF-UHFFFAOYSA-N 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- FJDLQLIRZFKEKJ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanamide Chemical compound CC(C)(C)C1=CC(CCC(N)=O)=CC(C(C)(C)C)=C1O FJDLQLIRZFKEKJ-UHFFFAOYSA-N 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 239000000779 smoke Substances 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- 229940012185 zinc palmitate Drugs 0.000 description 1
- 229940057977 zinc stearate Drugs 0.000 description 1
- 229940006174 zinc valerate Drugs 0.000 description 1
- ODNJVAVDJKOYFK-GRVYQHKQSA-L zinc;(9z,12z)-octadeca-9,12-dienoate Chemical compound [Zn+2].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O ODNJVAVDJKOYFK-GRVYQHKQSA-L 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- FRZSCIVUSFMNBX-UHFFFAOYSA-L zinc;12-hydroxyoctadecanoate Chemical compound [Zn+2].CCCCCCC(O)CCCCCCCCCCC([O-])=O.CCCCCCC(O)CCCCCCCCCCC([O-])=O FRZSCIVUSFMNBX-UHFFFAOYSA-L 0.000 description 1
- WDHVIZKSFZNHJB-UHFFFAOYSA-L zinc;butanoate Chemical compound [Zn+2].CCCC([O-])=O.CCCC([O-])=O WDHVIZKSFZNHJB-UHFFFAOYSA-L 0.000 description 1
- NVKSAUAQUPYOPO-UHFFFAOYSA-L zinc;decanoate Chemical compound [Zn+2].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O NVKSAUAQUPYOPO-UHFFFAOYSA-L 0.000 description 1
- IJQXGKBNDNQWAT-UHFFFAOYSA-L zinc;docosanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O IJQXGKBNDNQWAT-UHFFFAOYSA-L 0.000 description 1
- XWHCUISQLSVNCW-UHFFFAOYSA-L zinc;heptanoate Chemical compound [Zn+2].CCCCCCC([O-])=O.CCCCCCC([O-])=O XWHCUISQLSVNCW-UHFFFAOYSA-L 0.000 description 1
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 description 1
- PKJOUIVGCFHFTK-UHFFFAOYSA-L zinc;hexanoate Chemical compound [Zn+2].CCCCCC([O-])=O.CCCCCC([O-])=O PKJOUIVGCFHFTK-UHFFFAOYSA-L 0.000 description 1
- PVLBCXWFQZZIGP-UHFFFAOYSA-L zinc;nonanoate Chemical compound [Zn+2].CCCCCCCCC([O-])=O.CCCCCCCCC([O-])=O PVLBCXWFQZZIGP-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- BUDAIZWUWHWZPQ-UHFFFAOYSA-L zinc;pentanoate Chemical compound [Zn+2].CCCCC([O-])=O.CCCCC([O-])=O BUDAIZWUWHWZPQ-UHFFFAOYSA-L 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
- LVLIEOIPDYPFNY-UHFFFAOYSA-L zinc;tetracosanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCC([O-])=O LVLIEOIPDYPFNY-UHFFFAOYSA-L 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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Abstract
本發明提供一種以含溴阻燃劑的少量的添加量而具有高阻燃性與熱穩定性且可再循環的阻燃性發泡苯乙烯系樹脂組成物。一種阻燃性發泡苯乙烯系樹脂組成物,其包含苯乙烯系樹脂(A)、阻燃劑(B)、脂肪酸鋅(C)、熱穩定劑(D)及發泡劑(F),所述阻燃劑(B)包含四溴雙酚A-雙(2,3-二溴-2-甲基丙醚)(B1)、及(B1)以外的含溴阻燃劑(B2)。
Description
本發明是有關於一種藉由在擠出機內進行熔融並將發泡劑壓入至熔融物中進行擠出而成形為發泡體的阻燃性發泡苯乙烯系樹脂組成物。
苯乙烯系樹脂發泡體由於為輕量,因此可在家電製品、建材等的隔熱用途、填土工法等土木用途等多種領域中使用。
苯乙烯系樹脂僅由碳與氫構成,具有一旦著火則產生黑煙並劇烈燃燒的性質。因此,需要根據用途添加阻燃劑進行阻燃化。例如,關於作為隔熱材使用的擠出發泡聚苯乙烯成形體,必須通過日本工業標準(Japanese Industrial Standards,JIS)A 9511的燃燒試驗。另外,根據消防法,將氧指數未滿26.0的合成樹脂發泡體設為指定可燃物,明顯地限制超過20 m3
的發泡體的貯藏、搬運及轉移,事實上沒有市場性。
至今為止利用擠出法的苯乙烯系樹脂發泡體的阻燃化一直使用可以較少的添加量而獲得所需的阻燃效果的六溴環十二烷(hexabromocyclododecane,HBCD)。然而,HBCD存在有害性的擔心,在日本禁止使用,在其他國家亦逐漸置換成其他阻燃劑。
提出了於擠出發泡苯乙烯系樹脂發泡體中使用其他溴系阻燃劑來代替HBCD,其中之一有四溴雙酚A-雙(2,3-二溴-2-甲基丙醚)。其具有與HBCD匹敵的阻燃效果,但熱穩定性低。因此,為了達成氧指數為26.0以上的阻燃性,本申請人提出了藉由利用四溴雙酚A-雙(2,3-二溴丙醚)等對四溴雙酚A-雙(2,3-二溴-2-甲基丙醚)(B1)的一部分進行置換,與單獨使用(B1)的情況相比而防止以分子量下降率為代表的樹脂的劣化。於其他專利文獻中亦提出了於苯乙烯系樹脂的擠出發泡體中使用所述阻燃劑混合物。 [現有技術文獻] [專利文獻]
[專利文獻1]日本專利特開2010-275528號公報 [專利文獻2]日本專利特開2012-107227號公報 [專利文獻3]日本專利特開2012-136674號公報 [專利文獻4]日本專利特開2012-136675號公報
[發明所欲解決之課題] 藉由於苯乙烯系樹脂擠出發泡體的阻燃化中併用所述阻燃劑,可以相同的添加量獲得與(B1)單獨達成的阻燃性匹敵、且熱穩定性得到改善的發泡體,但期望進一步提高著色及分子量下降率所代表的熱穩定性。進而,亦期望探究一種可以與阻燃劑(B1)單獨為相同水準的添加量而達成同等的阻燃效果且可進一步提高穩定性的阻燃劑。本發明的課題在於滿足該些要求。 [解決課題之手段]
為了解決所述課題的本發明提供 一種阻燃性發泡苯乙烯系樹脂組成物,其包含苯乙烯系樹脂(A)、阻燃劑(B)、脂肪酸鋅(C)、熱穩定劑(D)及發泡劑(F),所述阻燃劑(B)包含四溴雙酚A-雙(2,3-二溴-2-甲基丙醚)(B1)、及(B1)以外的含溴阻燃劑(B2)。 一種發泡成形體,其是對所述阻燃性發泡苯乙烯系樹脂組成物進行擠出發泡成形而獲得。 [發明的效果]
即便於在作為苯乙烯系樹脂的擠出發泡體的阻燃劑而添加時併用四溴雙酚A-雙(2,3-二溴-2-甲基丙醚)(B1)、及(B1)以外的含溴阻燃劑(B2)而未達到所需的阻燃性水準的情況下,亦可藉由含有脂肪酸鋅(C)及熱穩定劑(D)而達成所需的阻燃性水準,同時以不會對再循環帶來阻礙的程度改善發泡體的著色及樹脂的分子量下降所代表的熱穩定性。
本發明的(A)苯乙烯系樹脂例如為苯乙烯的均聚物;苯乙烯與鄰甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、2,4-二甲基苯乙烯、乙基苯乙烯、對第三丁基苯乙烯、α-甲基苯乙烯、α-甲基-對甲基苯乙烯、1,1-二苯基乙烯、對(N,N-二乙基胺基乙基)苯乙烯、對(N,N-二乙基胺基甲基)苯乙烯等的共聚物;進而其混合物,較佳為含有50重量%以上的苯乙烯單量體者、典型而言為聚苯乙烯。
進而,亦可於所述苯乙烯系樹脂中調配橡膠狀聚合物。作為橡膠狀聚合物,例如可列舉:聚丁二烯、聚異戊二烯、苯乙烯-丁二烯共聚物、苯乙烯-異戊二烯共聚物、丙烯腈-丁二烯共聚物、苯乙烯-異丁烯-丁二烯系共聚物、丁二烯-(甲基)丙烯酸酯共聚物、苯乙烯-丁二烯嵌段共聚物、苯乙烯-異戊二烯嵌段共聚物、丁基橡膠、乙烯-α-烯烴系共聚物(乙烯-丙烯橡膠)、乙烯-α-烯烴-多烯共聚物(乙烯-丙烯-二烯橡膠)、矽酮橡膠、丙烯酸系橡膠、氫化二烯系橡膠(氫化苯乙烯-丁二烯嵌段共聚物、氫化丁二烯系聚合物等)等。該些橡膠狀聚合物可單獨或混合使用兩種以上。其使用量於單量體成分中較佳為30重量%以下,進而佳為20重量%以下。
本發明中,作為阻燃劑(B),含有四溴雙酚A-雙(2,3-二溴-2-甲基丙醚)(B1)、及(B1)以外的含溴阻燃劑(B2)。(B1)以外的含溴阻燃劑(B2)的具體例包含四溴雙酚A-雙(2,3-二溴丙醚)、三(2,3-二溴丙基)異三聚氰酸酯、四溴雙酚S-雙(2,3-二溴丙醚)、四溴雙酚F-雙(2,3-二溴丙醚)、四溴雙酚A、六溴苯、五溴甲苯、聚溴二苯醚、聚溴二苯基乙烷、雙聚溴苯氧基乙烷、三(三溴苯氧基)三嗪、聚溴苯基茚滿、丙烯酸聚五溴苄酯、乙烯雙四溴鄰苯二甲醯亞胺、三(三溴新戊基)磷酸酯、溴化環氧樹脂寡聚物。阻燃劑(B2)亦可組合使用兩種以上。作為阻燃劑(B2),就阻燃性及熱穩定性更優異的方面而言,較佳為使用四溴雙酚A-雙(2,3-二溴丙醚)、三(2,3-二溴丙基)異三聚氰酸酯或三(三溴苯氧基)三嗪。另外,阻燃劑(B)亦可進而含有磷酸三苯酯、磷酸三甲苯酯、磷酸三二甲苯酯等磷酸酯、或矽酮、氫氧化鎂等水合金屬化合物等。
阻燃劑(B1)與阻燃劑(B2)的合計量相對於每100重量份的苯乙烯系樹脂而言為1重量份~10重量份,較佳為1重量份~6重量份。混合物中的阻燃劑(B1)與阻燃劑(B2)的比以重量基準計為1/99~40/60,較佳為2/98~30/70,更佳為3/97~20/80,藉由含有比例為所述範圍內,可達成高阻燃性與熱穩定性。
本發明的特徵為於利用阻燃劑(B1)與阻燃劑(B2)對苯乙烯系樹脂擠出發泡體進行阻燃化時,使用脂肪酸鋅(C)及熱穩定劑(D)。藉此,阻燃性與熱穩定性變得優異。
作為脂肪酸鋅(C),例如可列舉:乙酸鋅、丙酸鋅、丁酸鋅、戊酸鋅、己酸鋅、庚酸鋅、辛酸鋅、壬酸鋅、癸酸鋅、月桂酸鋅、肉豆蔻酸鋅、棕櫚酸鋅、硬脂酸鋅、二十酸鋅、二十二酸鋅及二十四酸鋅等飽和脂肪酸鋅;棕櫚油酸鋅、油酸鋅、亞麻油酸鋅及次亞麻油酸鋅等不飽和脂肪酸鋅等。該些中,就對苯乙烯系樹脂的分散性更優異的方面而言,較佳為飽和脂肪酸鋅。另外,就阻燃性及熱穩定性更優異的方面而言,較佳為碳數8~30的脂肪酸鋅,更佳為碳數12~24的脂肪酸鋅,進而佳為碳數16~20的脂肪酸鋅。
作為熱穩定劑(D),例如可列舉:亞磷酸酯化合物、硫醚化合物、受阻酚化合物、受阻胺化合物、有機錫化合物、磷酸酯及水滑石等。
作為亞磷酸酯化合物,例如可列舉:三(2,4-二-第三丁基苯基)亞磷酸酯、雙(2,4-二-第三丁基苯基)季戊四醇二亞磷酸酯、亞磷酸雙[2,4-雙(1,1-二甲基乙基)-6-甲基苯基]乙酯、四(2,4-二-第三丁基苯基)[1,1-聯苯基]-4,4'-二基雙膦酸酯、雙(壬基苯基)季戊四醇二亞磷酸酯、雙硬脂基季戊四醇二亞磷酸酯、雙(2,6-二-第三丁基-4-甲基苯基)季戊四醇二亞磷酸酯、2,2'-亞甲基雙(4,6-二-第三丁基-1-苯氧基)(2-乙基己氧基)磷、四(十三烷基)-4,4'-亞丁基-雙(2-第三丁基-5-甲基苯基)二亞磷酸酯、六-十三烷基-1,1,3-三(3-第三丁基-6-甲基-4-氧基苯基)-3-甲基丙烷三亞磷酸酯、單(二壬基苯基)單-對壬基苯基亞磷酸酯、三(單壬基苯基)亞磷酸酯、四烷基(C=12~16)-4,4'-異亞丙基-(雙苯基)二亞磷酸酯、亞磷酸單或二苯基單或二烷基(或烷氧基烷基,C=8~13)酯、二苯基異癸基亞磷酸酯、三癸基亞磷酸酯、三苯基亞磷酸酯等。
作為硫醚化合物,例如可列舉:3,3'-硫代二丙酸二月桂酯、3,3'-硫代二丙酸二肉豆蔻酯、3,3'-硫代二丙酸二硬脂酯、季戊四醇四(3-月桂基硫代丙酸酯)、3,3'-硫代二丙酸二-十三烷基酯、2-巰基苯并咪唑等。
作為受阻酚化合物,例如可列舉:1,6-己二醇-雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、三乙二醇-雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯]、甘油三[3-(3,5-二-第三丁基-4-羥基苯基)-丙酸酯]、季戊四醇四[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、十八烷基-3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯、硫代二乙烯雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、N,N'-己烷-1,6-二基雙[3-(3,5-二-第三丁基-4-羥基苯基)丙醯胺]、2,4-二甲基-6-(1-甲基十五烷基)苯酚、二乙基[[3,5-雙(1,1-二甲基乙基)-4-羥基苯基]甲基]磷酸酯、二乙基雙[[3,5-雙(1,1-二甲基乙基)-4-羥基苯基]甲基]磷酸鈣、3,3',3'',5,5',5''-六-第三丁基-a,a',a''-(均三甲苯-2,4,6-三基)三-對甲酚、4,6-雙(辛基硫代甲基)-鄰甲酚、乙烯雙(氧乙烯)雙[3-(5-第三丁基-4-羥基-間甲苯基)丙酸酯]、六亞甲基雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、1,3,5-三(3,5-二-第三丁基-4-羥基苄基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1,3,5-三[(4-第三丁基-3-羥基-2,6-二甲苯基)甲基]-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、2,6-二-第三丁基-4-(4,6-雙(辛基硫代)-1,3,5-三嗪-2-基胺基)苯酚等。
受阻胺化合物的例子包含4-苯甲醯氧基-2,2,6,6-四甲基哌啶、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)-2-(3,5-二-第三丁基-4-羥基苄基-2-正丁基丙二酸酯)、四(2,2,6,6-四甲基-4-哌啶基-1,2,3,4-丁烷四羧酸酯)、四(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯等。
有機錫化合物的例子包含二月桂酸二辛基錫、順丁烯二酸二辛基錫,磷酸酯的例子包含磷酸三苯酯、磷酸三甲苯酯、磷酸三二甲苯酯等。
就阻燃性及熱穩定性更優異的方面而言,熱穩定劑(D)較佳為亞磷酸酯化合物。
脂肪酸鋅(C)相對於每100重量份的苯乙烯系樹脂(A)而言較佳為使用0.0005重量份~0.05重量份,更佳為使用0.001重量份~0.03重量份。藉由以所述比例使用脂肪酸鋅(C),阻燃性及熱穩定性變得更優異。
脂肪酸鋅(C)相對於每合計量100重量份的阻燃劑(B1)與阻燃劑(B2)而言較佳為使用0.01重量份~3重量份,更佳為使用0.02重量份~2重量份,進而佳為使用0.03重量份~1重量份。藉由以所述比例使用脂肪酸鋅(C),阻燃性及熱穩定性變得更優異。
脂肪酸鋅(C)相對於每100重量份的四溴雙酚A-雙(2,3-二溴-2-甲基丙醚)(B1)而言較佳為使用0.025重量份~300重量份,更佳為使用0.1重量份~66重量份。藉由以所述比例使用脂肪酸鋅(C),阻燃性及熱穩定性變得更優異。
脂肪酸鋅(C)相對於每100重量份的(B1)以外的含溴阻燃劑(B2)而言較佳為使用0.01重量份~5重量份,更佳為使用0.03重量份~2.5重量份。藉由以所述比例使用脂肪酸鋅(C),阻燃性及熱穩定性變得更優異。
熱穩定劑(D)相對於每100重量份的苯乙烯系樹脂(A)而言較佳為使用0.005重量份~0.2重量份,更佳為使用0.01重量份~0.1重量份,進而佳為使用0.02重量份~0.08重量份。藉由以所述比例使用熱穩定劑(D),阻燃性及熱穩定性變得更優異。
熱穩定劑(D)相對於每合計量100重量份的阻燃劑(B1)與阻燃劑(B2)而言較佳為使用0.1重量份~10重量份,更佳為使用0.3重量份~5重量份,進而佳為使用0.5重量份~3重量份。藉由以所述比例使用熱穩定劑(D),阻燃性及熱穩定性變得更優異。
熱穩定劑(D)相對於每100重量份的阻燃劑(B)四溴雙酚A-雙(2,3-二溴-2-甲基丙醚)(B1)而言較佳為使用0.2重量份~2000重量份,更佳為使用2重量份~67重量份。藉由以所述比例使用熱穩定劑(D),阻燃性及熱穩定性變得更優異。
熱穩定劑(D)相對於每100重量份的(B1)以外的含溴阻燃劑(B2)而言較佳為使用0.05重量份~33重量份,更佳為使用0.3重量份~6.3重量份。藉由以所述比例使用熱穩定劑(D),阻燃性及熱穩定性變得更優異。
熱穩定劑(D)相對於每100重量份的脂肪酸鋅(C)而言較佳為使用16重量份~20000重量份,更佳為使用50重量份~10000重量份。藉由以所述比例使用脂肪酸鋅(C)及熱穩定劑(D),阻燃性及熱穩定性變得更優異。
溴系阻燃劑的阻燃效果已知可藉由自由基產生劑(E1)或酞菁金屬錯合物(E2)等阻燃增強劑(E)而增強。所述自由基產生劑(E1)的例子為過氧化異丙苯、氫過氧化異丙苯、過氧化二-第三丁基、過氧化二-第三己基、2,5-二甲基-2,5-二(第三丁基過氧化)-己炔-3、過氧化二枯基、2,3-二甲基-2,3-二苯基丁烷等,酞菁金屬錯合物(E2)的例子為酞菁鐵、酞菁錳、酞菁鈷等。較佳為過氧化二枯基、2,3-二甲基-2,3-二苯基丁烷及酞菁鐵。
本發明的阻燃性發泡苯乙烯系樹脂組成物較佳為擠出發泡用途。藉由用於擠出發泡用途,阻燃性及熱穩定性變得更優異。
本發明的阻燃性發泡苯乙烯系樹脂組成物可藉由擠出發泡法形成為發泡成形體。於擠出發泡法的情況下,將阻燃劑(B)、脂肪酸鋅(C)及其他添加劑與苯乙烯系樹脂(A)在擠出機內熔融混合,在壓入發泡劑(F)後,自擠出機模口擠出至大氣中,藉此進行發泡成形。
此處,作為發泡劑(F),例如可列舉:丙烷、丁烷、異丁烷、戊烷、環戊烷、己烷、環己烷、1-氯-1,1-二氟乙烷、單氯二氟甲烷、單氯-1,2,2,2-四氟乙烷、1,1-二氟乙烷、1,1,1,2-四氟乙烷、1,1,3,3,3-五氟丙烷、二氯甲烷、1,2-二氯乙烷、二甲醚、二乙醚、乙基甲醚等揮發性有機發泡劑;水、氮氣、二氧化碳氣體等無機發泡劑;偶氮化合物等化學發泡劑等。該些可單獨或併用使用兩種以上。發泡劑的調配量根據所需的發泡體的性能或成形方法而改變,因此並無限定,但較佳為相對於苯乙烯系樹脂(A)100重量份而為0.01莫耳~0.5莫耳,更佳為0.05莫耳~0.3莫耳。
另外,於製造本發明的阻燃性苯乙烯系樹脂發泡成形體時,除了發泡劑(F)以外,亦可進一步調配發泡成核劑(G)。作為所述發泡成核劑,例如可列舉:滑石、膨潤土、高嶺土、雲母、二氧化矽、黏土、矽藻土等。於使用發泡成核劑的情況下,使用量相對於苯乙烯系樹脂(A)100重量份而較佳為0.01重量份~20重量份,更佳為0.1重量份~10重量份。
另外,於本發明的阻燃性發泡苯乙烯系樹脂組成物中,可於無損本發明的效果的範圍內,調配光穩定劑、紫外線吸收劑、紫外線穩定劑、重金屬鈍化劑、耐衝擊改良劑、著色劑、潤滑劑、防垂滴劑(Anti-Dripping Agents)、結晶成核劑、抗靜電劑、相容劑等公知的樹脂添加劑。 [實施例]
以下關於實施例及比較例,對本發明進行具體說明,但本發明並不限定於此。
實施例及比較例中使用的原料為如下所述。 ·苯乙烯系樹脂(A) (A-1)GP-PS:PSJ聚苯乙烯G9305(日本PS(股)製造) ·阻燃劑(B) (B1)四溴雙酚A-雙(2,3-二溴-2-甲基丙醚):商品名派羅格德(Pyroguard)SR-130(第一工業製藥(股)製造) (B2-1)四溴雙酚A-雙(2,3-二溴丙醚):商品名派羅格德(Pyroguard)SR720N(第一工業製藥(股)製造) (B2-2)三(2,3-二溴丙基)異三聚氰酸酯:商品名派羅格德(Pyroguard)SR-750(第一工業製藥(股)製造) (B2-3)三(三溴苯氧基)三嗪:商品名派羅格德(Pyroguard)SR245(第一工業製藥(股)製造) (B2-4)溴化環氧基寡聚物:商品名YDB-406(新日鐵住金化學(股)製造) (B2-5)六溴環十二烷:商品名派羅格德(Pyroguard)SR-103(第一工業製藥(股)製造)(比較例用) (B3)磷酸三苯酯:商品名TPP(大八化學工業(股)製造) ·脂肪酸鋅(C) (C-1)硬脂酸鋅:商品名Zn-St(日東化成工業(股)製造) (C-2)12-羥基硬脂酸鋅:商品名ZS-6(日東化成工業(股)製造) (C-3)月桂酸鋅:商品名ZS-3(日東化成工業(股)製造) ·熱穩定劑(D) (D-1)雙(2,6-二-第三丁基-4-甲基苯基)季戊四醇二磷酸酯:商品名艾迪科斯塔普(Adk stab)PEP-36(艾迪科(ADEKA)(股)製造) (D-2)三(2,4-二-第三丁基苯基)亞磷酸酯:商品名艾迪科斯塔普(Adk stab)2112(艾迪科(ADEKA)(股)製造) (D-3)雙硬脂基季戊四醇二亞磷酸酯:商品名艾迪科斯塔普(Adk stab)PEP-8(艾迪科(ADEKA)(股)製造) (D-4)季戊四醇四[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]:商品名易璐諾斯(IRGANOX)1010(巴斯夫(BASF)公司製造) ·阻燃增強劑(E) (E-1)2,3-二甲基-2,3-二苯基丁烷:娜芙莫(Nofmer)BC-90(日油(股)製造) ·發泡劑(F) (F-1)異丁烷 (F-2)二甲醚 ·發泡成核劑(G) (G-1)滑石MS(日本滑石工業(股)製造)
<試驗片製作方法> (擠出發泡成形體) 在由口徑65 mm串聯連接於口徑90 mm的兩段式擠出機的口徑65 mm的擠出機中投入除了發泡劑(F)以外的表1及表2中記載的原料,加熱至200℃而進行熔融、塑化、混煉,藉此製成苯乙烯系樹脂組成物。繼而,在65 mm擠出機前端(與口徑90 mm的擠出機的模口相反的一側)利用其他線路壓入規定量的發泡劑,在口徑90 mm的擠出機中將樹脂溫度冷卻至120℃,由在口徑90 mm擠出機的前端設置的厚度方向2.5 mm、寬度方向45 mm的長方形剖面的模唇(die lip)向大氣中擠出,藉此獲得長方體狀的苯乙烯系樹脂的擠出發泡成形體。
再者,發泡成形體的評價藉由下述方法進行。 <阻燃性> 根據JIS K-7201測定氧指數。 ○:氧指數為26以上。 ×:氧指數未滿26。
<分子量下降率> 藉由凝膠滲透層析法(Gel Permeation Chromatography,GPC)分析來測定發泡成形前的苯乙烯系樹脂與阻燃性苯乙烯系樹脂發泡成形體的分子量,計算出聚苯乙烯系樹脂的成形前後的重量平均分子量(Mw)的下降率(%)。
<熱穩定性> 將試驗過程中的擠出發泡成形體用切割機切片製成板材,在利用雙軸輥進行壓縮後,利用粉碎機進行粗碎。將粗碎物投入至實驗室混料擠出機(Labo Plastomill)中,在200℃下進行熔融混煉後立刻取出,利用冷卻壓力機成形為3.2 mm厚的板狀。利用220℃的熱壓力機對所得的板狀成形品進行40分鐘加熱後,利用冷卻壓力機進行冷卻,而製成耐熱試驗樣品。使用日本電色工業(股)製造的分光色彩計SD6000,求出以標準白板為基準的耐熱試驗樣品的ΔE。ΔE越小,表示耐熱性越高。
將實施例及比較例的樹脂組成物的調配與試驗結果示於表1~表3中。表中的成分的數值為重量份。
根據表1及表2明確般,實施例1~實施例19的擠出發泡體滿足阻燃性、分子量下降率及耐熱性中的任一項目。另一方面,如表3所示可知,比較例1~比較例2及比較例5~比較例8的擠出發泡體不滿足阻燃性,比較例3的擠出發泡體不滿足分子量下降率及耐熱性。再者,比較例4及比較例9中苯乙烯系樹脂組成物變為黑色,而無法獲得發泡成形體。
無
Claims (7)
- 一種阻燃性發泡苯乙烯系樹脂組成物,其為擠出發泡用途,且包含苯乙烯系樹脂(A)、阻燃劑(B)、脂肪酸鋅(C)、熱穩定劑(D)及發泡劑(F),所述阻燃劑(B)包含四溴雙酚A-雙(2,3-二溴-2-甲基丙醚)(B1)及(B1)以外的含溴阻燃劑(B2)。
- 如申請專利範圍第1項所述的阻燃性發泡苯乙烯系樹脂組成物,其中四溴雙酚A-雙(2,3-二溴-2-甲基丙醚)(B1)與(B1)以外的含溴阻燃劑(B2)的比以重量基準計為1/99~40/60。
- 如申請專利範圍第1項或第2項所述的阻燃性發泡苯乙烯系樹脂組成物,其中相對於脂肪酸鋅(C)100質量份而言,含有16質量份~20000質量份的熱穩定劑(D)。
- 如申請專利範圍第1項或第2項所述的阻燃性發泡苯乙烯系樹脂組成物,其中相對於四溴雙酚A-雙(2,3-二溴-2-甲基丙醚)(B1)100質量份而言,包含0.025質量份~300質量份的脂肪酸鋅(C)。
- 如申請專利範圍第1項或第2項所述的阻燃性發泡苯乙烯系樹脂組成物,其中相對於(B1)以外的含溴阻燃劑(B2)100質量份而言,含有0.01質量份~5質量份的脂肪酸鋅(C)。
- 如申請專利範圍第1項或第2項所述的阻燃性發泡苯乙烯系樹脂組成物,其中(B1)以外的含溴阻燃劑(B2)為選自四溴雙酚A-雙(2,3-二溴丙醚)、三(2,3-二溴丙基)異三聚氰酸酯、四 溴雙酚S-雙(2,3-二溴丙醚)、四溴雙酚F-雙(2,3-二溴丙醚)、四溴雙酚A、六溴苯、五溴甲苯、聚溴二苯醚、聚溴二苯基乙烷、雙聚溴苯氧基乙烷、三(三溴苯氧基)三嗪、聚溴苯基茚滿、丙烯酸聚五溴苄酯、乙烯雙四溴鄰苯二甲醯亞胺、三(三溴新戊基)磷酸酯、溴化環氧樹脂寡聚物中的至少一種。
- 一種發泡成形體,其是對如申請專利範圍第1項至第6項中任一項所述的阻燃性發泡苯乙烯系樹脂組成物進行擠出發泡成形而獲得。
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