JP6135791B2 - Method for producing flame retardant foamable styrene resin particles - Google Patents
Method for producing flame retardant foamable styrene resin particles Download PDFInfo
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- JP6135791B2 JP6135791B2 JP2016067843A JP2016067843A JP6135791B2 JP 6135791 B2 JP6135791 B2 JP 6135791B2 JP 2016067843 A JP2016067843 A JP 2016067843A JP 2016067843 A JP2016067843 A JP 2016067843A JP 6135791 B2 JP6135791 B2 JP 6135791B2
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- weight
- retardant
- flame retardant
- parts
- flame
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 142
- 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 129
- 239000002245 particle Substances 0.000 title claims description 80
- 229920005989 resin Polymers 0.000 title claims description 76
- 239000011347 resin Substances 0.000 title claims description 76
- 239000003063 flame retardant Substances 0.000 title claims description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 47
- 239000000203 mixture Substances 0.000 claims description 51
- 239000012760 heat stabilizer Substances 0.000 claims description 45
- -1 brominated bisphenol compound Chemical class 0.000 claims description 41
- 238000005187 foaming Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 11
- 239000003017 thermal stabilizer Substances 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 229920005990 polystyrene resin Polymers 0.000 claims description 6
- 238000002411 thermogravimetry Methods 0.000 claims description 6
- 239000013585 weight reducing agent Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 238000011156 evaluation Methods 0.000 description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 238000000465 moulding Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 8
- 239000007983 Tris buffer Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 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 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 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 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- UKJARPDLRWBRAX-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine Chemical compound C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 UKJARPDLRWBRAX-UHFFFAOYSA-N 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- GRKDVZMVHOLESV-UHFFFAOYSA-N (2,3,4,5,6-pentabromophenyl)methyl prop-2-enoate Chemical compound BrC1=C(Br)C(Br)=C(COC(=O)C=C)C(Br)=C1Br GRKDVZMVHOLESV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- ZJRAAAWYHORFHN-UHFFFAOYSA-N 2-[[2,6-dibromo-4-[2-[3,5-dibromo-4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane Chemical compound C=1C(Br)=C(OCC2OC2)C(Br)=CC=1C(C)(C)C(C=C1Br)=CC(Br)=C1OCC1CO1 ZJRAAAWYHORFHN-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920001890 Novodur Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004794 expanded polystyrene Substances 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 2
- QGMCRJZYVLHHHB-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-4-yl) octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 QGMCRJZYVLHHHB-UHFFFAOYSA-N 0.000 description 1
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 description 1
- OQLRBFNNEQUJPK-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 OQLRBFNNEQUJPK-UHFFFAOYSA-N 0.000 description 1
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical compound BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 description 1
- SVHAMPNLOLKSFU-UHFFFAOYSA-N 1,2,2-trichloroethenylbenzene Chemical compound ClC(Cl)=C(Cl)C1=CC=CC=C1 SVHAMPNLOLKSFU-UHFFFAOYSA-N 0.000 description 1
- JHEUBGXRQQQKCW-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3-dibromopropoxy)benzene Chemical compound BrCC(Br)COC1=C(Br)C(Br)=C(Br)C(Br)=C1Br JHEUBGXRQQQKCW-UHFFFAOYSA-N 0.000 description 1
- PYOIYKRKAHYOKO-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(bromomethyl)benzene Chemical compound BrCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br PYOIYKRKAHYOKO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ORYGKUIDIMIRNN-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2)Br)=C1Br ORYGKUIDIMIRNN-UHFFFAOYSA-N 0.000 description 1
- FJNNYLPBIOZVIQ-UHFFFAOYSA-N 1,2,3-tribromo-4-prop-2-enoxybenzene Chemical compound BrC1=CC=C(OCC=C)C(Br)=C1Br FJNNYLPBIOZVIQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- YUAPUIKGYCAHGM-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromopropoxy)propane Chemical compound BrCC(Br)COCC(Br)CBr YUAPUIKGYCAHGM-UHFFFAOYSA-N 0.000 description 1
- LMLLUTVRELKPNO-UHFFFAOYSA-N 1,2-dibromobicyclo[2.2.1]heptane ethene Chemical compound BrC1C2(CCC(C1)C2)Br.BrC2C1(CCC(C2)C1)Br.C=C LMLLUTVRELKPNO-UHFFFAOYSA-N 0.000 description 1
- KUJHYJBRSXWIFB-UHFFFAOYSA-N 1,3,5-tribromo-2-[1-(2,4,6-tribromophenoxy)ethoxy]benzene Chemical compound BrC=1C=C(Br)C=C(Br)C=1OC(C)OC1=C(Br)C=C(Br)C=C1Br KUJHYJBRSXWIFB-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- PWXTUWQHMIFLKL-UHFFFAOYSA-N 1,3-dibromo-5-[2-(3,5-dibromo-4-prop-2-enoxyphenyl)propan-2-yl]-2-prop-2-enoxybenzene Chemical compound C=1C(Br)=C(OCC=C)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC=C)C(Br)=C1 PWXTUWQHMIFLKL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 1
- FECSFBYOMHWJQG-UHFFFAOYSA-N 1-(4-bromophenyl)pyrrole-2,5-dione Chemical compound C1=CC(Br)=CC=C1N1C(=O)C=CC1=O FECSFBYOMHWJQG-UHFFFAOYSA-N 0.000 description 1
- FOZVXADQAHVUSV-UHFFFAOYSA-N 1-bromo-2-(2-bromoethoxy)ethane Chemical compound BrCCOCCBr FOZVXADQAHVUSV-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- DUKJZYZDOKKAMU-UHFFFAOYSA-N 1-chloronaphthalene-2-carbaldehyde Chemical compound C1=CC=C2C(Cl)=C(C=O)C=CC2=C1 DUKJZYZDOKKAMU-UHFFFAOYSA-N 0.000 description 1
- BAWHYOHVWHQWFQ-UHFFFAOYSA-N 1-naphthalen-1-ylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC2=CC=CC=C12 BAWHYOHVWHQWFQ-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-Tri-t-butyl phenol Natural products CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-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
- 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 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- LVZZNJAPRYIRMT-UHFFFAOYSA-N 2-[1-oxo-1-(2,2,6,6-tetramethylpiperidin-4-yl)oxy-3-(2,2,6,6-tetramethylpiperidin-4-yl)oxycarbonylhexadecan-3-yl]-2-tridecylbutanedioic acid Chemical compound CCCCCCCCCCCCCC(CC(O)=O)(C(CCCCCCCCCCCCC)(CC(OC1CC(C)(C)NC(C)(C)C1)=O)C(OC1CC(C)(C)NC(C)(C)C1)=O)C(O)=O LVZZNJAPRYIRMT-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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- DDBYLRWHHCWVID-UHFFFAOYSA-N 2-ethylbut-1-enylbenzene Chemical compound CCC(CC)=CC1=CC=CC=C1 DDBYLRWHHCWVID-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 description 1
- CEBRPXLXYCFYGU-UHFFFAOYSA-N 3-methylbut-1-enylbenzene Chemical compound CC(C)C=CC1=CC=CC=C1 CEBRPXLXYCFYGU-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
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- SGKKYCDALBXNCG-UHFFFAOYSA-N tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-5-methylphenyl] phosphite Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C(=CC(OP(OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)=C(C=2)C(C)(C)C)C)=C1 SGKKYCDALBXNCG-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、難燃性発泡性スチレン系樹脂粒子の製造方法に関する。 The present invention relates to a method for producing flame-retardant foamable styrene resin particles.
スチレン系発泡成形体は、軽量で緩衝性、断熱性に優れるため住宅用の断熱材、電化製品等の緩衝材、食品の保冷箱等、多くの分野で利用されている。 Styrenic foam moldings are lightweight and excellent in buffering and heat insulating properties, and thus are used in many fields such as heat insulating materials for homes, buffer materials for electrical appliances, and food cold boxes.
しかしながら、スチレン系発泡成形体は燃え易いために、住宅用の断熱材等の難燃性が要求される用途には使用できないという欠点がある。 However, since styrene-based foamed molded products are easily burned, there is a drawback that they cannot be used for applications requiring flame retardancy such as heat insulating materials for houses.
特許文献１には、特定の構造を有する臭素系難燃剤を芳香族ビニルモノマーに溶解し、懸濁重合することによって発泡性スチレン系樹脂粒子を得る製造方法が開示されている。
懸濁重合法は、発泡性スチレン系樹脂粒子の製造方法としては最も一般的ではあるが、大量の排水が発生するため、排水処理のコストがかかる。また、得られた発泡性スチレン系樹脂粒子は粒径分布が広いため、通常、各粒径毎に篩い分けされており、さらなるコストアップとなっているのが現状である。
Patent Document 1 discloses a production method for obtaining expandable styrene resin particles by dissolving a brominated flame retardant having a specific structure in an aromatic vinyl monomer and subjecting it to suspension polymerization.
The suspension polymerization method is the most general method for producing expandable styrene-based resin particles, but a large amount of wastewater is generated, and thus wastewater treatment costs are required. In addition, since the expandable styrene resin particles obtained have a wide particle size distribution, they are usually sieved for each particle size, which further increases the cost.
他方、特許文献１には、上記問題に対して、押出機を用いて、樹脂と難燃剤と発泡剤を混練し、未発泡状態で押し出てペレット化するクエンチ法によっても発泡性スチレン系樹脂粒子中に難燃剤を添加することが可能であるが、難燃剤が分解しやすいという問題があり、高温分解型の難燃剤を使用すると難燃性能が低下すると記載されている。 On the other hand, Patent Document 1 discloses a foaming styrenic resin by a quenching method in which a resin, a flame retardant, and a foaming agent are kneaded using an extruder and extruded into an unfoamed state and pelletized. Although it is possible to add a flame retardant in the particles, there is a problem that the flame retardant is easily decomposed, and it is described that the flame retardant performance is lowered when a high-temperature decomposition type flame retardant is used.
押出クエンチ法における上記問題に対して、特許文献２では、スチレン系樹脂、不透熱性粒子、臭素含有量７０％以上の臭素系難燃剤および発泡剤を押出機に供給して、水中でペレット化する発泡性スチレン系樹脂粒子の製造方法が開示されている。
しかしながら、臭素系難燃剤としてヘキサブロモシクロドデカン（以下、ＨＢＣＤ）等が挙げられているが、ＨＢＣＤは、近年、難分解性であり、且つ、土壌等の環境及び人体等の生態への蓄積性が高いことがわかってきたため、使用を制限される可能性が高まってきているという問題がある。
In order to solve the above problem in the extrusion quench method, in Patent Document 2, a styrene resin, heat-impermeable particles, a brominated flame retardant having a bromine content of 70% or more, and a blowing agent are supplied to an extruder and pelletized in water. A process for producing expandable styrene resin particles is disclosed.
However, hexabromocyclododecane (hereinafter referred to as HBCD) is mentioned as a brominated flame retardant, but HBCD has recently been indegradable and has an accumulation property in the environment such as soil and in the ecology of the human body. However, there is a problem that the possibility of being restricted is increasing.
従って、低コストで発泡性スチレン系樹脂粒子が製造可能なクエンチ法において、難燃性能が低下することなく、押出機での溶融混練中に分解せず、さらには環境適合性にも優れた難燃剤を使用した発泡性スチレン系樹脂粒子の製造方法は提案されていないのが現状である。 Therefore, in the quench method that can produce expandable styrene resin particles at a low cost, flame retardancy is not degraded, it does not decompose during melt kneading in an extruder, and it is also difficult to be environmentally friendly. The present condition is that the manufacturing method of the expandable styrene resin particle which uses a flame retardant is not proposed.
本発明は、上記のような問題に鑑みて、難燃性能が低下することなく、押出機での溶融混練中に分解せず、さらには、環境適合性にも優れた難燃剤を使用してなる難燃性発泡性スチレン系樹脂粒子の製造方法を提供することにある。 In view of the above problems, the present invention uses a flame retardant that does not degrade during the melt-kneading in an extruder without lowering the flame retardant performance, and further has excellent environmental compatibility. It is providing the manufacturing method of the flame-retardant foaming styrene-type resin particle which becomes.
本発明者は、上記課題を解決すべく鋭意検討を行った結果、スチレン系樹脂、臭素系難燃剤と熱安定剤の混合物、および発泡剤を押出機に供給し、押出機内で溶融混練された溶融樹脂を押出機先端に取り付けた小孔を多数有するダイスより循環水で満たされたカッターチャンバー内に押し出し、押し出し直後からダイスと接する回転カッターにより溶融樹脂をカットする難燃性発泡性スチレン系樹脂粒子の製造方法にあって、特定の熱重量分析における１重量％減少温度を有する臭素系難燃剤と熱安定剤との混合物および、炭化水素系発泡剤を特定量使用することによって、押出機での溶融混練中に分解されず、難燃性能を低下させることなく、さらには環境適合性にも優れた難燃剤を使用できる難燃性発泡性スチレン系樹脂粒子が得られることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventor supplied a styrene resin, a mixture of a brominated flame retardant and a heat stabilizer, and a foaming agent to the extruder, and was melt-kneaded in the extruder. A flame-retardant foaming styrene resin that extrudes the molten resin into a cutter chamber filled with circulating water from a die having a large number of small holes attached to the tip of the extruder and cuts the molten resin immediately after extrusion with a rotary cutter that contacts the die. In a method for producing particles, by using a specific amount of a mixture of a brominated flame retardant having a 1% by weight reduction temperature in a specific thermogravimetric analysis and a thermal stabilizer and a hydrocarbon-based blowing agent, Flame retardant expandable styrene resin particles that are not decomposed during melting and kneading, can be used without lowering the flame retardant performance, and can also use a flame retardant having excellent environmental compatibility Heading the door, leading to the present invention.
すなわち、本発明は、
［１］ スチレン系樹脂１００重量部に対して、臭素系難燃剤と安定剤との混合物０．５重量部以上１５重量部以下、および発泡剤３重量部以上１０重量部以下を押出機に供給し、
押出機内で溶融混練された溶融樹脂を、押出機先端に取り付けた小孔を多数有するダイスを通じて、循環水で満たされたカッターチャンバー内に押し出し、
押し出し直後から、ダイスと接する回転カッターにより溶融樹脂をカットする難燃性発泡性スチレン系樹脂粒子の製造方法であって、
臭素系難燃剤および熱安定剤の混合物の、熱重量分析における１％重量減少温度が、該臭素系難燃剤単体の１％重量減少温度に対して２℃以上高い温度であり、
発泡剤が、炭素数３以上６以下の炭化水素の少なくとも１種であることを特徴とする、難燃性発泡性スチレン系樹脂粒子の製造方法、
［２］ 臭素系難燃剤と安定剤との混合物中の熱安定剤の添加量が、前記臭素系難燃剤１００重量部に対して、０．１重量部以上１０重量部以下であることを特徴とする、［１］記載の難燃性発泡性スチレン系樹脂粒子の製造方法、
［３］ 前記臭素系難燃剤が臭素化ビスフェノール系化合物であることを特徴とする、［１］または［２］記載の難燃性発泡性スチレン系樹脂粒子の製造方法。
［４］ 前記熱安定剤が、ヒンダードアミン化合物、リン系化合物よりなる群から選ばれる少なくとも１種以上の熱安定剤であることを特徴とする、［１］〜［３］のいずれかに記載の難燃性発泡性スチレン系樹脂粒子の製造方法。
［５］ スチレン系樹脂１００重量部に対して、臭素系難燃剤および熱安定剤の混合物のスチレン樹脂系マスターバッチ２重量部以上３５重量部以下を供給し、かつ、
該マスターバッチが、５０重量％以上７０重量％以下のスチレン系樹脂および、３０重量％以上５０重量％以下の臭素系難燃剤と熱安定剤の混合物からなる（両者の合計量は１００重量％）であることを特徴とする、［１］〜［４］のいずれかに記載の難燃性発泡性スチレン系樹脂粒子の製造方法、
［６］ ［１］〜［５］に記載のいずれかの製造方法によって得られる難燃性発泡性ポリスチレン系樹脂粒子を予備発泡することを特徴とする、難燃性ポリスチレン系樹脂発泡粒子の製造方法、および
［７］ ［６］記載の製造方法によって得られる難燃性ポリスチレン系発泡粒子を型内成形することを特徴とする、難燃性ポリスチレン系発泡成形体の製造方法
に関する。
That is, the present invention
[1] Supplying 0.5 to 15 parts by weight of a mixture of a brominated flame retardant and a stabilizer and 3 to 10 parts by weight of a foaming agent to an extruder with respect to 100 parts by weight of a styrene resin And
The molten resin melt-kneaded in the extruder is extruded into a cutter chamber filled with circulating water through a die having a large number of small holes attached to the tip of the extruder,
Immediately after extrusion, a method for producing flame-retardant foamable styrene resin particles that cuts molten resin with a rotary cutter in contact with a die,
The 1% weight loss temperature in the thermogravimetric analysis of the mixture of brominated flame retardant and thermal stabilizer is a temperature higher by 2 ° C. or more than the 1% weight decreased temperature of the brominated flame retardant alone,
The method for producing flame-retardant foaming styrene resin particles, wherein the foaming agent is at least one kind of hydrocarbon having 3 to 6 carbon atoms,
[2] The addition amount of the heat stabilizer in the mixture of brominated flame retardant and stabilizer is 0.1 to 10 parts by weight with respect to 100 parts by weight of the brominated flame retardant. And [1] a method for producing a flame-retardant foamable styrene resin particle,
[3] The method for producing flame-retardant expandable styrene resin particles according to [1] or [2], wherein the brominated flame retardant is a brominated bisphenol compound.
[4] The heat stabilizer according to any one of [1] to [3], wherein the heat stabilizer is at least one heat stabilizer selected from the group consisting of a hindered amine compound and a phosphorus compound. A method for producing flame-retardant foamable styrene resin particles.
[5] With respect to 100 parts by weight of the styrene resin, 2 parts by weight or more and 35 parts by weight or less of a styrene resin masterbatch of a mixture of a brominated flame retardant and a heat stabilizer are supplied, and
The master batch is composed of 50% by weight or more and 70% by weight or less of a styrene resin and 30% by weight or more and 50% by weight or less of a mixture of a brominated flame retardant and a heat stabilizer (the total amount of both is 100% by weight). The method for producing flame-retardant foamable styrene resin particles according to any one of [1] to [4],
[6] Production of flame-retardant polystyrene-based resin expanded particles, wherein the flame-retardant expanded polystyrene-based resin particles obtained by any one of the production methods according to [1] to [5] are pre-expanded. The present invention relates to a method and a method for producing a flame-retardant polystyrene-based foam-molded product, wherein the flame-retardant polystyrene-based foamed particles obtained by the production method according to [7] [6] are molded in a mold.
本発明の製造方法に従えば、押出機での溶融混練中に分解されず、難燃性能が低下することなく、さらには環境適合性にも優れた難燃剤を用いた難燃性発泡性スチレン系樹脂粒子の製造方法を提供することができる。 According to the production method of the present invention, flame retardant foaming styrene using a flame retardant that is not decomposed during melt kneading in an extruder, does not deteriorate flame retardant performance, and is also excellent in environmental compatibility. A method for producing a resin particle can be provided.
以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明の難燃性発泡性スチレン系樹脂粒子の製造方法は、スチレン系樹脂、臭素系難燃剤と熱安定剤との混合物、および発泡剤を押出機に供給し、押出機内で溶融混練された溶融樹脂を押出機先端に取り付けた小孔を多数有するダイスより循環水で満たされたカッターチャンバー内に押し出し、押し出し直後からダイスと接する回転カッターにより溶融樹脂をカットする難燃性発泡性スチレン系樹脂粒子の製造方法であって、特定の１重量％減少温度を示す臭素系難燃剤と熱安定剤との混合物および、炭化水素系発泡剤を特定量使用することを特徴とする製造方法である。 The method for producing the flame-retardant foamable styrene resin particles of the present invention was obtained by supplying a styrene resin, a mixture of a brominated flame retardant and a heat stabilizer, and a foaming agent to the extruder, and melt-kneading in the extruder. A flame-retardant foaming styrene resin that extrudes the molten resin into a cutter chamber filled with circulating water from a die having a large number of small holes attached to the tip of the extruder and cuts the molten resin immediately after extrusion with a rotary cutter that contacts the die. A method for producing particles, characterized in that a specific amount of a mixture of a brominated flame retardant and a thermal stabilizer exhibiting a specific 1% by weight reduction temperature and a hydrocarbon-based blowing agent is used.
本発明の難燃性発泡性スチレン系樹脂粒子に用いられるスチレン系樹脂としては、スチレン単独重合体のみならず、本発明の効果を損なわない範囲で、スチレンと共重合可能な他の単量体またはその誘導体が共重合されていてもよい。 As the styrene resin used in the flame-retardant foamable styrene resin particles of the present invention, not only a styrene homopolymer but also other monomers copolymerizable with styrene as long as the effects of the present invention are not impaired. Alternatively, a derivative thereof may be copolymerized.
スチレンと共重合しやすい他の単量体またはその誘導体としては、例えば、メチルスチレン、ジメチルスチレン、エチルスチレン、ジエチルスチレン、イソプロピルスチレン、ブロモスチレン、ジブロモスチレン、トリブロモスチレン、クロロスチレン、ジクロロスチレン、トリクロロスチレンなどのスチレン誘導体、ジビニルベンゼンなどの多官能性ビニル化合物、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチルなどの（メタ）アクリル酸エステル化合物、（メタ）アクリロニトリルなどのシアン化ビニル化合物、ブダジエンなどのジエン系化合物またはその誘導体、無水マレイン酸、無水イタコン酸などの不飽和カルボン酸無水物、Ｎ−メチルマレイミド、Ｎ−ブチルマレイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−フェニルマレイミド、Ｎ−４−ジフェニルマレイミド、Ｎ−２−クロロフェニルマレイミド、Ｎ−４−ブロモフェニルマレイミド、Ｎ−１−ナフチルマレイミドなどのＮ−アルキル置換マレイミド化合物などがあげられる。これらは単独で使用してもよく、２種以上を混合して使用してもよい。 Examples of other monomers that are easily copolymerized with styrene or derivatives thereof include, for example, methylstyrene, dimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, bromostyrene, dibromostyrene, tribromostyrene, chlorostyrene, dichlorostyrene, Cyanation of styrene derivatives such as trichlorostyrene, polyfunctional vinyl compounds such as divinylbenzene, (meth) acrylate compounds such as methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, and (meth) acrylonitrile Vinyl compounds, diene compounds such as budadiene or derivatives thereof, unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, N-methylmaleimide, N-butylmaleimide, N-cyclohexyl Reimido, N- phenylmaleimide, N-4-diphenyl maleimide, N-2-chlorophenyl maleimide, N-4-bromophenyl maleimide, etc. N- alkyl-substituted maleimide compounds such as N-1- naphthyl maleimide. These may be used alone or in combination of two or more.
本発明に用いられるスチレン系樹脂は、前記スチレン系単量体又は誘導体の単独重合体又は共重合体に限られず、前記スチレン系単量体又は誘導体の単独重合体又は共重合体と、前記他の単量体又は誘導体の単独重合体又は共重合体とのブレンド物であってもよく、ジエン系ゴム強化ポリスチレンやアクリル系ゴム強化ポリスチレン、ポリフェニレンエーテル系樹脂をブレンドすることもできる。 The styrenic resin used in the present invention is not limited to the homopolymer or copolymer of the styrenic monomer or derivative, but the homopolymer or copolymer of the styrenic monomer or derivative, and the other It may be a blend with a monomer or derivative homopolymer or copolymer, and a diene rubber reinforced polystyrene, an acrylic rubber reinforced polystyrene, or a polyphenylene ether resin can also be blended.
本発明においては、臭素系難燃剤と熱安定剤との混合物とすることにより、熱重量分析における１重量％減少温度を、臭素系難燃剤単体の１重量％減少温度より高くすることができ、押出機内での溶融混練中に臭素系難燃剤が分解することがないため、良好な難燃性能のスチレン系発泡成形体を得ることができる。 In the present invention, by using a mixture of a brominated flame retardant and a thermal stabilizer, the 1 wt% reduction temperature in thermogravimetric analysis can be made higher than the 1 wt% reduction temperature of the brominated flame retardant alone, Since the brominated flame retardant does not decompose during melt-kneading in the extruder, a styrene-based foam molded article having good flame retardant performance can be obtained.
臭素系難燃剤と熱安定剤との混合物の１重量％減少温度は、該臭素系難燃剤単体の１重量％減少温度に対して、２℃以上高いことが好ましく、５℃以上がより好ましく、１０℃以上がさらに好ましい。
ここで、熱重量分析における１重量％減少温度は、熱重量分析装置［（株）島津製作所製、ＤＴＧ−６０Ａ］を用いて、秤量された５ｍｇの試料を、１０℃／ｍｉｎの昇温速度で３０℃から３５０℃まで加熱して測定した値である。
The 1% by weight reduction temperature of the mixture of brominated flame retardant and heat stabilizer is preferably 2 ° C. or more higher than the 1% by weight reduction temperature of the brominated flame retardant alone, more preferably 5 ° C. or more, 10 degreeC or more is further more preferable.
Here, the 1% by weight reduction temperature in thermogravimetric analysis was measured using a thermogravimetric analyzer [manufactured by Shimadzu Corporation, DTG-60A], and a 5 mg sample weighed at a rate of temperature increase of 10 ° C./min. It is the value measured by heating from 30 ° C to 350 ° C.
本発明の製造方法で用いられる臭素系難燃剤としては、例えば、テトラブロモビスフェノールＡ、テトラブロモビスフェノールＡジアリルエーテル、テトラブロモビスフェノールＡジメタリルエーテル、テトラブロモビスフェノールＡジグリシジルエーテル、テトラブロモビスフェノールＡジグリシジルエーテルのトリブロモフェノール付加物、
テトラブロモビスフェノールＡビス（２，３−ジブロモプロピルエーテル）、テトラブロモビスフェノールＡビス（２−ブロモエチルエーテル）、テトラブロモビスフェノールＡビス（２，３−ジブロモ−２−メチルプロピルエーテル）、テトラブロモビスフェノールＳビス（２，３−ジブロモプロピルエーテル）、テトラブロモビスフェノールＳ、などの臭素化ビスフェノール系化合物あるいはその誘導体、
ヘキサブロモベンゼン、ペンタブロモトルエン、エチレンビスペンタブロモジフェニル、デカブロモジフェニルエーテル、オクタブロモジフェニルエーテル、ペンタブロモベンジルブロマイド、ビス（２，４，６ートリブロモフェノキシ）エタン、テトラブロモ無水フタル酸、オクタブロモトリメチルフェニルインダン、ペンタブロモベンジルアクリレート、トリブロモフェニルアリルエーテル、２，３−ジブロモプロピルペンタブロモフェニルエーテルなどの臭素化芳香族化合物あるいはその誘導体、
モノ（２，３−ジブロモプロピル）イソシアヌレート、ジ（２，３−ジブロモプロピルイソシアヌレート）、トリス（２，３−ジブロモプロピル）イソシアヌレート、モノ（２，３，４−トリブロモブチル）イソシアヌレート、ジ（２，３，４−トリブロモブチル）イソシアヌレート、トリス（２，３，４−トリブロモブチル）イソシアヌレートなどの臭素化イソシアヌレート
あるいはエチレンビステトラブロモフタルイミド、エチレンビスジブロモノルボルナンジカルボキシイミド、２，４，６−トリス（２，４，６−トリブロモフェノキシ）１，３，５−トリアジンなどの臭素および窒素原子含有化合物、
テトラブロモビスフェノールＡポリカーボネートオリゴマー、テトラブロモビスフェノールＡジグリシジルエーテルとブロモ化ビスフェノール付加物エポキシオリゴマーなどの臭素化ビスフェノール類誘導体オリゴマー、
ペンタブロモベンジルアクリレートポリマーなどの臭素化アクリル樹脂、
トリス（トリブロモネオペンチル）ホスフェート、トリス（ブロモフェニル）ホスフェートなどの臭素および燐原子含有化合物、
臭化アンモニウムなどの臭素化無機化合物、などが挙げられる。
これらの化合物は、単独または２種以上を混合して使用できる。
Examples of the brominated flame retardant used in the production method of the present invention include tetrabromobisphenol A, tetrabromobisphenol A diallyl ether, tetrabromobisphenol A dimethallyl ether, tetrabromobisphenol A diglycidyl ether, and tetrabromobisphenol A diester. Tribromophenol adduct of glycidyl ether,
Tetrabromobisphenol A bis (2,3-dibromopropyl ether), tetrabromobisphenol A bis (2-bromoethyl ether), tetrabromobisphenol A bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol Brominated bisphenol compounds such as S bis (2,3-dibromopropyl ether) and tetrabromobisphenol S or derivatives thereof,
Hexabromobenzene, pentabromotoluene, ethylenebispentabromodiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, pentabromobenzyl bromide, bis (2,4,6-tribromophenoxy) ethane, tetrabromophthalic anhydride, octabromotrimethylphenyl Brominated aromatic compounds such as indane, pentabromobenzyl acrylate, tribromophenyl allyl ether, 2,3-dibromopropyl pentabromophenyl ether or derivatives thereof,
Mono (2,3-dibromopropyl) isocyanurate, di (2,3-dibromopropylisocyanurate), tris (2,3-dibromopropyl) isocyanurate, mono (2,3,4-tribromobutyl) isocyanurate Brominated isocyanurates such as di (2,3,4-tribromobutyl) isocyanurate, tris (2,3,4-tribromobutyl) isocyanurate, ethylene bistetrabromophthalimide, ethylene bisdibromonorbornane dicarboximide Bromine and nitrogen atom-containing compounds such as 2,4,6-tris (2,4,6-tribromophenoxy) 1,3,5-triazine,
Brominated bisphenol derivatives oligomers such as tetrabromobisphenol A polycarbonate oligomer, tetrabromobisphenol A diglycidyl ether and brominated bisphenol adduct epoxy oligomer,
Brominated acrylic resins such as pentabromobenzyl acrylate polymer,
Bromine and phosphorus atom-containing compounds such as tris (tribromoneopentyl) phosphate, tris (bromophenyl) phosphate,
Brominated inorganic compounds such as ammonium bromide.
These compounds can be used individually or in mixture of 2 or more types.
これら臭素系難燃剤のうちでも、難燃性に優れる点から、臭素化ビスフェノール系化合物が好ましい。 Among these brominated flame retardants, a brominated bisphenol compound is preferable from the viewpoint of excellent flame retardancy.
本発明で用いられる熱安定剤としては、例えば、トリエチレングリコール−ビス［３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］、１，６−ヘキサンジオール−ビス｛３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート｝、２，４−ビス−（ｎ−オクチルチオ）−６−（４−ヒドロキシ−３，５−ジ−ｔ−ブチルアニリノ）−１，３，５−トリアジン、ペンタエリスリチル−テトラキス［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］、オクタデシル−３−（３，５−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ベンジルホスフェート−ジエチルエステル、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレイトなどのヒンダードフェノール系化合物、２，２，６，６−テトラメチル−４−ピペリジルステアレート、１，２，２，６，６−ペンタメチル−４−ピペリジルステアレート、２，２，６，６−テトラメチル−４−ピペリジルベンゾエート、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、ビス（２−（トリス（２，２，６，６−テトラメチルピペリジルオキシカルボニル）ブチルカルボニルオキシ）−１，１−ジメチルエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン、ビス（２−（トリス（１，２，２，６，６−ペンタメチルピペリジルオキシカルボニル）ブチルカルボニルオキシ）−１，１−ジメチルエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン、ビス（２，２，６，６−テトラメチル−４−ピペリジル）・ジ（トリデシル）−１，２，３，４−ブタンテトラカルボキシレート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）・ジ（トリデシル）−１，２，３，４−ブタンテトラカルボキシレート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）−２−ブチル−２−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）マロネート、１−（２−ヒドロキシエチル）−２，２，６，６−テトラメチル−４−ピペリジノール／コハク酸ジエチル重縮合物、１，６−ビス（２，２，６，６−テトラメチル−４−ピペリジルアミノ）ヘキサン／ジブロモエタン重縮合物、１，６−ビス（２，２，６，６−テトラメチル−４−ピペリジルアミノ）ヘキサン／２，４−ジクロロ−６−モルホリノ−ｓ−トリアジン重縮合物、１，６−ビス（２，２，６，６−テトラメチル−４−ピペリジルアミノ）ヘキサン／２，４−ジクロロ−６−ｔ−オクチルアミノ−ｓ−トリアジン重縮合物、テトラキス（２，２，６，６−テトラメチルピペリジルオキシカルボニル）ブタン、テトラキス（１，２，２，６，６−ペンタメチルピペリジルオキシカルボニル）ブタン、１，５，８，１２−テトラキス〔２，４−ビス（Ｎ−ブチル−Ｎ−（２，２，６，６−テトラメチル−４−ピペリジル）アミノ）−ｓ−トリアジン−６−イル〕−１，５，８，１２−テトラアザドデカン、１，５，８，１２−テトラキス〔２，４−ビス（Ｎ−ブチル−Ｎ−（１，２，２，６，６−ペンタメチル−４−ピペリジル）アミノ）−ｓ−トリアジン−６−イル〕−１，５，８，１２−テトラアザドデカン、１，６，１１−トリス〔２，４−ビス（Ｎ−ブチル−Ｎ−（２，２，６，６−テトラメチル−４−ピペリジル）アミノ）−ｓ−トリアジン−６−イル〕アミノウンデカン１，６，１１−トリス〔２，４−ビス（Ｎ−ブチル−Ｎ−（１，２，２，６，６−ペンタメチル−４−ピペリジル）アミノ）−ｓ−トリアジン−６−イル〕アミノウンデカンなどのヒンダードアミン化合物、トリスノニルフェニルホスファイト、トリス〔２−ｔ−ブチル−４−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニルチオ）−５−メチルフェニル〕ホスファイト、トリデシルホスファイト、オクチルジフェニルホスファイト、ジ（デシル）モノフェニルホスファイト、ジ（トリデシル）ペンタエリスリトールジホスファイト、ジ（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４−ジーｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジーｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４，６−トリーｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４−ジクミルフェニル）ペンタエリスリトールジホスファイト、テトラ（トリデシル）イソプロピリデンジフェノールジホスファイト、テトラ（トリデシル）−４，４’−ｎ−ブチリデンビス（２−ｔ−ブチル−５−メチルフェノール）ジホスファイト、ヘキサ（トリデシル）−１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタントリホスファイト、テトラキス（２，４−ジーｔ−ブチルフェニル）ビフェニレンジホスホナイト、９，１０−ジハイドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキサイド、２，２’−メチレンビス（４，６−ｔ−ブチルフェニル）−２−エチルヘキシルホスファイト、２，２’−メチレンビス（４，６−ｔ−ブチルフェニル）−オクタデシルホスファイト、２，２’−エチリデンビス（４，６−ジ−ｔ−ブチルフェニル）フルオロホスファイト、トリス（２−〔（２，４，８，１０−テトラキスーｔ−ブチルジベンゾ〔ｄ，ｆ〕〔１，３，２〕ジオキサホスフェピン−６−イル）オキシ〕エチル）アミン、２−エチル−２−ブチルプロピレングリコールと２，４，６−トリ−ｔ−ブチルフェノールのホスファイトなどのリン系化合物、２，２，４−トリメチル−１，２−ジヒドロキノリン重合体、アルキル化ジフェニルアミン、オクチル化ジフェニルアミン、４，４’−ビス（α，α−ジメチルベンジル）ジフェニルアミンなどのアミン系化合物、３，３−チオビスプロピオン酸ジオデシルエステル、３，３’−チオビスプロピオン酸ジオクタデシルエステルなどの硫黄系化合物などが挙げられる。
これらの化合物は、単独または２種以上を混合して使用できる。
Examples of the heat stabilizer used in the present invention include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis {3. -(3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-t-butyl-4- Hydroxyphenyl) propionate, 3,5-di-tert-butyl-4-hydroxy-benzyl phosphate-diethyl ester, 1,3,5-trimethyl-2,4, Hindered phenol compounds such as tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate; 2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2- (tris (2,2,6 , 6-Tetramethylpiperidyloxycarbonyl) butylcarbonyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] un Can, bis (2- (tris (1,2,2,6,6-pentamethylpiperidyloxycarbonyl) butylcarbonyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [ 5.5] undecane, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2, 6,6-pentamethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- Butyl-2- (3,5-di-t-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate Polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetra Methyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-t-octylamino-s-triazine polycondensate, tetrakis (2,2,6,6-tetramethylpiperidyloxycarbonyl) butane, tetrakis (1,2,2,6,6- Pentamethylpiperidyloxycarbonyl) butane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s − Riazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6, 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-) N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane 1,6,11-tris [2,4-bis (N-butyl-N Hindered amine compounds such as (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, trisnonylphenyl phosphite, tris [2-t-butyl- 4- (3-t-butyl 4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di ( Nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) ) -4,4′-n-butylidenebis (2-t-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-t-) Butylphenyl) butanetriphosphite, tetrakis (2,4-di-t-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2 ′ -Methylenebis (4,6-t-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-t-butylphenyl) -octadecyl phosphite, 2,2'-ethylidenebis (4 6-di-t-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis-t-butyldibenzo [D, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-t-butylphenol Phosphorous compounds such as phosphite, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, alkylated diphenylamine, octylated diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, etc. Examples thereof include sulfur compounds such as amine compounds, 3,3-thiobispropionic acid didecyl ester, and 3,3′-thiobispropionic acid dioctadecyl ester.
These compounds can be used individually or in mixture of 2 or more types.
これら熱安定剤のうちでも、難燃剤の熱安定性付与に優れる点から、ヒンダードアミン化合物、リン系化合物が好ましい。 Among these heat stabilizers, a hindered amine compound and a phosphorus compound are preferable because they are excellent in imparting the thermal stability of the flame retardant.
本発明の製造方法における臭素系難燃剤と熱安定剤との混合物中での熱安定剤の添加量は、前記臭素系難燃剤１００重量部に対して、０．１重量部以上１０重量部以下であることが好ましく、０．３重量部以上８重量部以下であることがより好ましく、０．５重量部以上６重量部以下であることがさらに好ましい。
臭素系難燃剤と熱安定剤との混合物中での熱安定剤の添加量を０．１重量部以上１０重量部以下とすることによって、難燃性能を低下させることなく、難燃剤の熱安定性を飛躍的に向上させることができる。
The addition amount of the heat stabilizer in the mixture of the brominated flame retardant and the thermal stabilizer in the production method of the present invention is 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the brominated flame retardant. It is preferable that it is 0.3 to 8 parts by weight, more preferably 0.5 to 6 parts by weight.
Thermal stability of the flame retardant without deteriorating the flame retardant performance by adding the amount of the thermal stabilizer in the mixture of the brominated flame retardant and the thermal stabilizer to 0.1 parts by weight or more and 10 parts by weight or less. The sex can be improved dramatically.
本発明の製造方法における臭素系難燃剤と熱安定剤との混合物の添加量は、スチレン系樹脂１００重量部に対して、０．５重量部以上１５重量部以下であることが好ましく、０．７重量部以上１２重量部以下であることがより好ましく、１．０重量部以上１０重量部以下であることがさらに好ましい。
臭素系難燃剤と熱安定剤との混合物の添加量を０．５重量部以上１５重量部以下にすることによって、スチレン系発泡成形体とした際に良好な難燃性が得られる。
The addition amount of the mixture of brominated flame retardant and heat stabilizer in the production method of the present invention is preferably 0.5 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the styrene resin. It is more preferably 7 parts by weight or more and 12 parts by weight or less, and further preferably 1.0 part by weight or more and 10 parts by weight or less.
When the addition amount of the mixture of the brominated flame retardant and the heat stabilizer is 0.5 parts by weight or more and 15 parts by weight or less, good flame retardancy can be obtained when a styrene foam molded article is obtained.
本発明の製造方法においては、臭素系難燃剤と熱安定剤の混合物は、そのままスチレン系樹脂に練り込むこともできるが、通常は、分散性等を考慮して、スチレン系樹脂とのマスターバッチを作り、該マスターバッチとスチレン系樹脂を溶融混練することが好ましい。 In the production method of the present invention, the mixture of the brominated flame retardant and the heat stabilizer can be kneaded into the styrene resin as it is, but usually a master batch with the styrene resin in consideration of dispersibility and the like. It is preferable to melt and knead the master batch and the styrene resin.
本発明の製造方法におけるマスターバッチとしては、スチレン系樹脂５０重量％以上７０重量％以下および、臭素系難燃剤と熱安定剤との混合物３０重量％以上５０重量％以下である（両者の合計量は１００重量％）ことが好ましく、スチレン系樹脂５５重量％以上６５重量％以下および、臭素系難燃剤と熱安定剤との混合物３５重量％以上４５重量％以下であることがより好ましい。
マスターバッチ中での臭素系難燃剤と熱安定剤との混合物の比率を３０重量％以上５０重量％以下にすることにより、臭素系難燃剤と熱安定剤との混合物の分散性が優れるため、低い添加量で優れた難燃性を得ることができる。
The master batch in the production method of the present invention includes 50% by weight or more and 70% by weight or less of a styrene resin and 30% by weight or more and 50% by weight or less of a mixture of a brominated flame retardant and a heat stabilizer (the total amount of both). Is preferably 100% by weight, more preferably 55% by weight to 65% by weight of a styrene resin and 35% by weight to 45% by weight of a mixture of a brominated flame retardant and a heat stabilizer.
By making the ratio of the mixture of brominated flame retardant and heat stabilizer in the masterbatch 30 wt% or more and 50 wt% or less, the dispersibility of the mixture of brominated flame retardant and heat stabilizer is excellent, Excellent flame retardancy can be obtained with a low addition amount.
本発明の製造方法において、臭素系難燃剤と熱安定剤の混合物のマスターバッチを添加する場合には、該マスターバッチの添加量は、スチレン系樹脂１００重量部に対して、２重量部以上３５重量部以下が好ましく、５重量部以上２５重量部以下がより好ましい。 In the production method of the present invention, when a master batch of a mixture of a brominated flame retardant and a heat stabilizer is added, the added amount of the master batch is 2 parts by weight or more to 35 parts by weight with respect to 100 parts by weight of the styrene resin. The weight is preferably 5 parts by weight or less and more preferably 5 parts by weight or more and 25 parts by weight or less.
本発明の製造方法では、発泡剤として炭素数３以上６以下の炭化水素を使用することにより、良好な発泡性、成形性を発現させることができる。 In the manufacturing method of this invention, favorable foamability and moldability can be expressed by using C3-C6 hydrocarbon as a foaming agent.
本発明で用いられる炭素数３以上６以下の炭化水素としては、例えば、プロパン、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタン、シクロペンタン、ネオペンタン等が挙げられる。これらの発泡剤は単独または２種以上を混合して使用できる。
これらのうちでも、発泡成形体として十分使用可能は発泡倍率に発泡可能な点から、炭素数４または５の炭化水素が好ましい。
Examples of the hydrocarbon having 3 to 6 carbon atoms used in the present invention include propane, normal butane, isobutane, normal pentane, isopentane, cyclopentane, neopentane and the like. These foaming agents can be used alone or in admixture of two or more.
Among these, hydrocarbons having 4 or 5 carbon atoms are preferable from the viewpoint that they can be sufficiently used as foamed molded articles and can be foamed at a foaming ratio.
本発明の製造方法における発泡剤の添加量は、スチレン系樹脂１００重量部に対して、３重量部以上１０重量部以下であることが好ましく、４重量部以上９重量部以下であることがより好ましく、５重量部以上８重量以下であることがさらに好ましい。発泡剤の添加量を３重量部以上１０重量部以下にすることにより、発泡成形体として十分使用可能な発泡倍率に発泡可能である。 The addition amount of the foaming agent in the production method of the present invention is preferably 3 parts by weight or more and 10 parts by weight or less, more preferably 4 parts by weight or more and 9 parts by weight or less with respect to 100 parts by weight of the styrene resin. Preferably, it is 5 parts by weight or more and 8 parts by weight or less. By setting the addition amount of the foaming agent to 3 parts by weight or more and 10 parts by weight or less, foaming can be performed at a foaming ratio that can be sufficiently used as a foamed molded article.
本発明の製造方法においては、発泡セルの均一化、細孔化を目的として、タルク、シリカ、カオリン、ゼオライト、マイカ、アルミナなどの無機粒子、炭酸または重炭酸塩、カルボン酸のアルカリ金属塩などの塩を添加してもよいが、これらに限定されるものではない。 In the production method of the present invention, inorganic particles such as talc, silica, kaolin, zeolite, mica, and alumina, carbonic acid or bicarbonate, alkali metal salt of carboxylic acid, etc. for the purpose of homogenizing and making pores in the foam cell However, it is not limited to these.
本発明の製造方法においては、本発明の効果を損なわない範囲で、帯電防止剤、輻射抑制剤、紫外線吸収剤、防カビ剤、抗菌剤、消臭剤、芳香剤、着色剤、等の各種添加剤を添加してもよい。
さらに、発泡助剤として、可塑剤、トルエン、エチルベンゼン、キシレン、シクロヘキサン等を添加してもよい。
In the production method of the present invention, various types such as an antistatic agent, a radiation inhibitor, an ultraviolet absorber, an antifungal agent, an antibacterial agent, a deodorant, a fragrance, a colorant, etc., are within the range not impairing the effects of the present invention. Additives may be added.
Further, a plasticizer, toluene, ethylbenzene, xylene, cyclohexane or the like may be added as a foaming aid.
本発明の製造方法において用いられる押出機としては、例えば、単軸押出機、二軸押出機、または、第一押出機と第二押出機が直列に連結されるタンデム式押出（例えば、単軸―単軸タンデム押出機、二軸―単軸タンデム押出機）、等が挙げられる他、第二押出機の代わりにスタティックミキサーを１つあるいは２つ以上を直列に連結した押出機等も使用可能である。 Examples of the extruder used in the production method of the present invention include a single-screw extruder, a twin-screw extruder, or a tandem extruder in which a first extruder and a second extruder are connected in series (for example, a single-screw extruder). -Single-screw tandem extruder, twin-screw-single-screw tandem extruder), etc. In addition to the second extruder, an extruder with one or more static mixers connected in series can also be used. It is.
本発明の製造方法における押出機の溶融部でのシリンダ温度は、スチレン系樹脂が溶融する温度であればよく、１５０℃以上２５０℃以下であることが好ましく、１７０℃以上２３０℃以下であることがより好ましい。押出機先端の温度は１７０℃以下が好ましい。
タンデム押出機を用いる場合は、第１押出機のシリンダ温度は、１５０℃以上２５０℃以下であることが好ましく、さらに好ましくは１７０℃以上２３０℃以下であり、第２押出機の温度は１７０℃以下が好ましい。
The cylinder temperature in the melting part of the extruder in the production method of the present invention may be a temperature at which the styrene resin melts, and is preferably 150 ° C. or higher and 250 ° C. or lower, and is 170 ° C. or higher and 230 ° C. or lower. Is more preferable. The temperature at the tip of the extruder is preferably 170 ° C or lower.
When using a tandem extruder, the cylinder temperature of the first extruder is preferably 150 ° C. or higher and 250 ° C. or lower, more preferably 170 ° C. or higher and 230 ° C. or lower, and the temperature of the second extruder is 170 ° C. The following is preferred.
本発明の製造方法においては、押出機の先端には、小孔を多数有するダイスが取り付けられている。 In the production method of the present invention, a die having a large number of small holes is attached to the tip of the extruder.
ダイスにおける小孔の直径は、０．２ｍｍ以上１．５ｍｍ以下であることが好ましく、０．３ｍｍ以上１．０ｍｍ以下であることがより好ましい。小孔の直径を０．２ｍｍ以上１．５ｍｍ以下にすることにより、発泡成形性に優れた粒径の難燃性発泡性スチレン系樹脂粒子を安定的に製造することができる。 The diameter of the small hole in the die is preferably 0.2 mm or more and 1.5 mm or less, and more preferably 0.3 mm or more and 1.0 mm or less. By setting the diameter of the small holes to 0.2 mm or more and 1.5 mm or less, flame-retardant foaming styrene resin particles having a particle diameter excellent in foam moldability can be stably produced.
ダイスの温度は２３０℃以上３００℃以下が好ましく、２４０℃以上２８０℃以下であることがより好ましい。ダイスの温度を２３０℃以上３００℃以下にすることにより、小孔の目詰まりがなく安定的に粒径のそろった難燃性発泡性スチレン系樹脂粒子が得られる。 The temperature of the die is preferably 230 ° C. or higher and 300 ° C. or lower, and more preferably 240 ° C. or higher and 280 ° C. or lower. By setting the temperature of the die to 230 ° C. or more and 300 ° C. or less, flame-retardant foaming styrene resin particles having a uniform particle size without clogging of small holes can be obtained.
本発明の製造方法においては、押出機内で溶融混練された溶融樹脂を、押出機先端に取り付けたダイスを通じて、循環水で満たされたカッターチャンバー内に押し出し、押し出し直後から、ダイスと接する回転カッターにより溶融樹脂を切断する。 In the production method of the present invention, the molten resin melt-kneaded in the extruder is extruded into a cutter chamber filled with circulating water through a die attached to the tip of the extruder, and immediately after extrusion, by a rotary cutter in contact with the die. Cut the molten resin.
循環水の温度は、３０℃以上８０℃以下が好ましく、さらに好ましくは４０℃以上７０℃以下である。循環水の温度を３０℃以上８０℃以下にすることにより、カット直後から粒子が冷却され、粒子同士の膠着を防ぐことができる。 The temperature of the circulating water is preferably 30 ° C. or higher and 80 ° C. or lower, more preferably 40 ° C. or higher and 70 ° C. or lower. By setting the temperature of the circulating water to 30 ° C. or more and 80 ° C. or less, the particles are cooled immediately after cutting, and the particles can be prevented from sticking together.
カッターチャンバー内の水圧は、０．４ＭＰａ以上２．０ＭＰａ以下であることが好ましく、０．５ＭＰａ以上１．８ＭＰａ以下であることがより好ましい。カッターチャンバー内の水圧を０．４ＭＰａ以上２．０ＭＰａ以下にすることにより、難燃性発泡性スチレン系樹脂粒子の内部に気泡が発生せず、予備発泡した際に、均一美麗なセルが発現する。 The water pressure in the cutter chamber is preferably 0.4 MPa or more and 2.0 MPa or less, and more preferably 0.5 MPa or more and 1.8 MPa or less. By setting the water pressure in the cutter chamber to 0.4 MPa or more and 2.0 MPa or less, air bubbles are not generated inside the flame-retardant foamable styrene resin particles, and uniform and beautiful cells appear when pre-foamed. .
本発明における難燃性スチレン系発泡粒子は、本発明の製造方法により得られる難燃性発泡性スチレン系樹脂粒子を、水蒸気や熱風、高周波等によって発泡させる方法が適用できるが、発泡スチロール用予備発泡機を用いる方法が最も簡便で一般的である。 The flame-retardant styrene-based expanded particles in the present invention can be applied by a method of foaming the flame-retardant expanded styrene-based resin particles obtained by the production method of the present invention with water vapor, hot air, high frequency, etc. The method using a machine is the simplest and most common.
本発明における難燃性スチレン系発泡粒子の発泡倍率は、２０倍以上１００倍以下であることが好ましく、３０倍以上７０倍以下であることがより好ましい。難燃性スチレン系発泡粒子の発泡倍率が前記範囲であれば、軽量で、優れた緩衝性、断熱性を有する難燃性スチレン系発泡成形体が得られる。 The expansion ratio of the flame-retardant styrene-based expanded particles in the present invention is preferably from 20 times to 100 times, and more preferably from 30 times to 70 times. When the expansion ratio of the flame-retardant styrene-based expanded particles is within the above range, a flame-retardant styrene-based expanded molded article having a light weight and excellent buffering properties and heat insulating properties can be obtained.
本発明における難燃性スチレン系発泡成形体は、難燃性スチレン系発泡粒子を発泡スチロールや発泡ポリエチレン、発泡ポリプロピレン等の成形に用いる成形機によって型内成形する方法が最も簡便で一般的である。 The flame-retardant styrene-based foam-molded article in the present invention is most simply and generally formed by in-mold molding of flame-retardant styrene-based foam particles using a molding machine used for molding foamed polystyrene, foamed polyethylene, foamed polypropylene, or the like.
以下、実施例によって本発明を詳細に説明するが、本発明は、これらの実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples at all.
なお、実施例および比較例の評価は、下記の方法で行った。 In addition, evaluation of the Example and the comparative example was performed by the following method.
（１）臭素系難燃剤および、臭素系難燃剤と熱安定剤の混合物の熱重量分析：
試料５ｍｇを測りとり、示差熱・熱重量同時測定装置［（株）島津製作所製、ＤＴＧ−６０Ａ］を用いて、１０℃／ｍｉｎの昇温速度で３０℃から３５０℃まで加熱して、１％重量減少温度を測定した。
(1) Thermogravimetric analysis of brominated flame retardants and mixtures of brominated flame retardants and thermal stabilizers:
A sample of 5 mg was weighed and heated from 30 ° C. to 350 ° C. at a rate of temperature increase of 10 ° C./min using a differential thermal / thermogravimetric simultaneous measurement device [manufactured by Shimadzu Corporation, DTG-60A]. The% weight loss temperature was measured.
（２）発泡倍率の測定方法
得られた発泡粒子を、内容積２０００ｃｍ３のポリエチレン製カップに擦切り一杯量り取り、重量を測定し、風袋重量を差引いて発泡粒子の重量を求めた。
発泡倍率は、発泡粒子の重量と見かけ体積（２０００ｃｍ３）から、下記の式により求めた。
発泡倍率＝見かけ体積（２０００ｃｍ３）／発泡粒子の重量（ｇ）
(2) Method for measuring foaming ratio The obtained foamed particles were scraped into a polyethylene cup having an internal volume of 2000 cm 3 and weighed and measured, and the weight of the foamed particles was determined by subtracting the tare weight.
The expansion ratio was determined by the following formula from the weight of the expanded particles and the apparent volume (2000 cm 3 ).
Expansion ratio = apparent volume (2000 cm 3 ) / weight of expanded particles (g)
（３）成形性の評価方法
後述する成形条件にて型内成形を行い、以下の基準で目視にて評価した。
○：ヒケ、メルト、収縮等なく、良好な発泡成形体が得られた。
×：ヒケ、メルト、収縮等が発生し、良好な発泡成形体が得られなかった。
(3) Formability evaluation method In-mold molding was performed under the molding conditions described later, and visual evaluation was performed according to the following criteria.
○: There was no sink, melt, shrinkage, etc., and a good foamed molded article was obtained.
X: Sink, melt, shrinkage, etc. occurred, and a good foamed molded article could not be obtained.
（４）難燃性の評価方法１
得られた発泡成形体に対して、ＪＩＳ Ａ ９５１１（発泡プラスチック保温材）測定方法Ａに準じた評価を行った。
○：消火時間が３秒以内。
×：消火時間が３秒を超える或いは消火しなかった。
(4) Flame retardant evaluation method 1
The obtained foamed molded product was evaluated according to JIS A 9511 (foamed plastic heat insulating material) measuring method A.
○: Fire extinguishing time is within 3 seconds.
X: Fire extinguishing time exceeded 3 seconds or did not extinguish.
（５）難燃性の評価方法２
得られた発泡成形体に対して、ＪＩＳ Ｋ ７２０１に準じた評価を行った。酸素指数が２６．０以上の場合、難燃性を有すると判定した。
(5) Flame retardant evaluation method 2
The obtained foamed molded product was evaluated according to JIS K7201. When the oxygen index was 26.0 or more, it was determined to have flame retardancy.
実施例および比較例で使用した、臭素系難燃剤および、臭素系難燃剤と熱安定剤の混合物の種類、その１％重量減少温度を、表１にまとめた。 Table 1 summarizes the types of brominated flame retardants used in Examples and Comparative Examples, types of mixtures of brominated flame retardants and thermal stabilizers, and 1% weight loss temperature thereof.
（実施例１）
［樹脂粒子の作製］
ポリスチレン樹脂［ＰＳジャパン（株）製、商品名：Ｇ９４０１］１００重量部に対して、臭素系難燃剤と熱安定剤の混合物（ｂ−１）を１．５重量部をブレンダーに投入して、１０分間ブレンドして、樹脂組成物を得た。
得られた樹脂組成物を口径６５ｍｍの単軸押出機（第一押出機）と口径９０ｍｍの単軸押出機（第二押出機）を直列に連結したタンデム型二段押出機へ供給し、口径６５ｍｍ押出機の設定温度２２０℃にて溶融混練した。口径６５ｍｍ押出機（第一押出機）の途中から、ポリスチレン樹脂１００重量部に対してイソペンタン７重量部を圧入した。その後、２３０℃に設定された継続管を通じて、口径９０ｍｍ押出機（第二押出機）に供給した。口径９０ｍｍ押出機（第二押出機）にて樹脂温度を１６７℃まで溶融樹脂を冷却した後、２７５℃に設定したダイスを通して水中に押し出し、ダイスに接する回転カッターにて溶融樹脂を切断、冷却固化させて、難燃性発泡性スチレン系樹脂粒子を得た。
［発泡性樹脂粒子の作製］
得られた難燃性発泡性スチレン系樹脂粒子を、予備発泡機［大開工業株式会社製、ＢＨＰ−３００］に投入し、０．０８ＭＰａの水蒸気を予備発泡機に導入して発泡させ、発泡倍率５１倍の難燃性スチレン系発泡粒子を得た。
［発泡成形体の作製］
得られた難燃性スチレン系発泡粒子を、発泡スチロール用成形機［ダイセン工業株式会社製、ＫＲ−５７］に取り付けた型内成形用金型（４４５ｍｍ×２９５ｍｍ×２５ｍｍ）内に充填して、０．０６ＭＰａの水蒸気を導入し、外観美麗な直方体状の難燃性スチレン系発泡成形体を得た。
得られた難燃性スチレン系発泡成形体から難燃性試験サンプルを切り出し、難燃性試験を行った結果、３秒以内に消火し、且つ、酸素指数は２６．５であった。
結果を、表２にまとめた。
Example 1
[Production of resin particles]
With respect to 100 parts by weight of polystyrene resin [manufactured by PS Japan Co., Ltd., trade name: G9401], 1.5 parts by weight of a mixture of a brominated flame retardant and a heat stabilizer (b-1) was put into a blender, The resin composition was obtained by blending for 10 minutes.
The obtained resin composition is supplied to a tandem type two-stage extruder in which a single screw extruder (first extruder) having a diameter of 65 mm and a single screw extruder (second extruder) having a diameter of 90 mm are connected in series. Melt kneading was performed at a set temperature of 220 ° C. in a 65 mm extruder. 7 parts by weight of isopentane was press-fitted into 100 parts by weight of polystyrene resin from the middle of a 65 mm diameter extruder (first extruder). Then, it supplied to the 90-mm-diameter extruder (2nd extruder) through the continuation pipe | tube set to 230 degreeC. After the molten resin is cooled to 167 ° C with a 90 mm diameter extruder (second extruder), it is extruded into water through a die set at 275 ° C, and the molten resin is cut with a rotary cutter in contact with the die and cooled and solidified. Thus, flame-retardant foamable styrene resin particles were obtained.
[Production of expandable resin particles]
The obtained flame-retardant foaming styrene resin particles are put into a pre-foaming machine [BHP-300, manufactured by Daikai Kogyo Co., Ltd.], and 0.08 MPa of water vapor is introduced into the pre-foaming machine to cause foaming. A 51-fold flame-retardant styrene-based expanded particle was obtained.
[Production of foamed molded product]
The obtained flame-retardant styrene-based expanded particles were filled into an in-mold molding die (445 mm × 295 mm × 25 mm) attached to an expanded polystyrene molding machine [manufactured by Daisen Kogyo Co., Ltd., KR-57]. 0.06 MPa water vapor was introduced to obtain a cuboid flame-retardant styrene-based foam molded article having a beautiful appearance.
A flame retardant test sample was cut out from the obtained flame retardant styrene-based foam molded product and subjected to a flame retardant test. As a result, the fire was extinguished within 3 seconds, and the oxygen index was 26.5.
The results are summarized in Table 2.
（実施例２）
臭素系難燃剤と熱安定剤の混合物（ｂ−１）の添加量を１０重量部に変更したこと以外は、実施例１と同様の操作を行った。
発泡倍率５２倍の発泡粒子を得て、外観美麗な成形体を得た。難燃性の評価の結果、３秒以内に消火し、且つ、酸素指数は２９．２であった。
結果を、表２にまとめた。
(Example 2)
The same operation as in Example 1 was performed except that the addition amount of the mixture (b-1) of the brominated flame retardant and the heat stabilizer was changed to 10 parts by weight.
Foamed particles having an expansion ratio of 52 times were obtained, and a molded article having a beautiful appearance was obtained. As a result of the evaluation of flame retardancy, the fire was extinguished within 3 seconds and the oxygen index was 29.2.
The results are summarized in Table 2.
（実施例３）
臭素系難燃剤と熱安定剤の混合物として（ｂ−２）を用いたこと以外は、実施例１と同様の操作を行った。
発泡倍率５２倍の発泡粒子を得て、外観美麗な成形体を得た。難燃性の評価の結果、３秒以内に消火し、且つ、酸素指数は２６．９であった。
結果を、表２にまとめた。
(Example 3)
The same operation as in Example 1 was performed except that (b-2) was used as a mixture of a brominated flame retardant and a heat stabilizer.
Foamed particles having an expansion ratio of 52 times were obtained, and a molded article having a beautiful appearance was obtained. As a result of the evaluation of flame retardancy, the fire was extinguished within 3 seconds and the oxygen index was 26.9.
The results are summarized in Table 2.
（実施例４）
臭素系難燃剤と熱安定剤との混合物として（ｂ−２）を用いたこと以外は、実施例２と同様の操作を行った。
発泡倍率５１倍の発泡粒子を得て、外観美麗な成形体を得た。難燃性の評価の結果、３秒以内に消火し、且つ、酸素指数は２９．６であった。
結果を、表２にまとめた。
Example 4
The same operation as in Example 2 was performed except that (b-2) was used as a mixture of a brominated flame retardant and a heat stabilizer.
Foamed particles having an expansion ratio of 51 times were obtained, and a molded article having a beautiful appearance was obtained. As a result of the evaluation of flame retardancy, the fire was extinguished within 3 seconds and the oxygen index was 29.6.
The results are summarized in Table 2.
（実施例５）
臭素系難燃剤と熱安定剤の混合物として（ｃ−１）を用いたこと以外は、実施例１と同様の操作を行った。
発泡倍率５２倍の発泡粒子を得て、外観美麗な成形体を得た。難燃性の評価の結果、３秒以内に消火し、且つ、酸素指数は２６．２であった。
結果を、表２にまとめた。
(Example 5)
The same operation as in Example 1 was performed except that (c-1) was used as a mixture of a brominated flame retardant and a heat stabilizer.
Foamed particles having an expansion ratio of 52 times were obtained, and a molded article having a beautiful appearance was obtained. As a result of the evaluation of flame retardancy, the fire was extinguished within 3 seconds and the oxygen index was 26.2.
The results are summarized in Table 2.
（実施例６）
臭素系難燃剤と熱安定剤の混合物として（ｃ−１）を用いたこと以外は、実施例２と同様の操作を行った。
発泡倍率５０倍の発泡粒子を得て、外観美麗な成形体を得た。難燃性の評価の結果、３秒以内に消火し、且つ、酸素指数は２８．１であった。
結果を、表２にまとめた。
(Example 6)
The same operation as Example 2 was performed except having used (c-1) as a mixture of a brominated flame retardant and a heat stabilizer.
Foamed particles having an expansion ratio of 50 times were obtained to obtain a molded article having a beautiful appearance. As a result of the evaluation of flame retardancy, the fire was extinguished within 3 seconds and the oxygen index was 28.1.
The results are summarized in Table 2.
（実施例７）
臭素系難燃剤と熱安定剤の混合物として（ｃ−２）を用いたこと以外は、実施例１と同様の操作を行った。
発泡倍率５０倍の発泡粒子を得て、外観美麗な成形体を得た。難燃性の評価の結果、３秒以内に消火し、且つ、酸素指数は２７．０であった。
結果を、表２にまとめた。
(Example 7)
The same operation as Example 1 was performed except having used (c-2) as a mixture of a brominated flame retardant and a heat stabilizer.
Foamed particles having an expansion ratio of 50 times were obtained to obtain a molded article having a beautiful appearance. As a result of the evaluation of flame retardancy, the fire was extinguished within 3 seconds and the oxygen index was 27.0.
The results are summarized in Table 2.
（実施例８）
臭素系難燃剤と熱安定剤の混合物として（ｃ−２）を用いたこと以外は、実施例２と同様の操作を行った。
発泡倍率４９倍の発泡粒子を得て、外観美麗な成形体を得た。難燃性の評価の結果、３秒以内に消火し、且つ、酸素指数は２９．３であった。
結果を、表２にまとめた。
(Example 8)
The same operation as in Example 2 was performed except that (c-2) was used as a mixture of a brominated flame retardant and a heat stabilizer.
Expanded particles having an expansion ratio of 49 times were obtained, and a molded article having a beautiful appearance was obtained. As a result of the evaluation of flame retardancy, the fire was extinguished within 3 seconds and the oxygen index was 29.3.
The results are summarized in Table 2.
（実施例９）
臭素系難燃剤と熱安定剤の混合物として（ｄ−１）を用いたこと以外は、実施例１と同様の操作を行った。
発泡倍率５２倍の発泡粒子を得て、外観美麗な成形体を得た。難燃性の評価の結果、３秒以内に消火し、且つ、酸素指数は２７．１であった。
結果を、表２にまとめた。
Example 9
The same operation as Example 1 was performed except having used (d-1) as a mixture of a brominated flame retardant and a heat stabilizer.
Foamed particles having an expansion ratio of 52 times were obtained, and a molded article having a beautiful appearance was obtained. As a result of the evaluation of flame retardancy, the fire was extinguished within 3 seconds and the oxygen index was 27.1.
The results are summarized in Table 2.
（実施例１０）
臭素系難燃剤と熱安定剤の混合物として（ｄ−１）を用いたこと以外は、実施例２と同様の操作を行った。
発泡倍率５２倍の発泡粒子を得て、外観美麗な成形体を得た。難燃性の評価の結果、３秒以内に消火し、且つ、酸素指数は３０．８であった。
結果を、表２にまとめた。
(Example 10)
The same operation as in Example 2 was performed except that (d-1) was used as a mixture of a brominated flame retardant and a heat stabilizer.
Foamed particles having an expansion ratio of 52 times were obtained, and a molded article having a beautiful appearance was obtained. As a result of the evaluation of flame retardancy, the fire was extinguished within 3 seconds and the oxygen index was 30.8.
The results are summarized in Table 2.
（実施例１１）
スチレン系樹脂６０重量％および、臭素系難燃剤と熱安定剤の混合物（ｄ−１）４０重量％からなるマスターバッチを、 を用いて、
スチレン系樹脂６０重量％および、臭素系難燃剤と熱安定剤の混合物（ｄ−１）４０重量％からなるマスターバッチを、ポリスチレン樹脂１００重量部に対し１０重量部としたこと以外は、実施例１と同様の操作を行った。
発泡倍率５０倍の発泡粒子を得て、外観美麗な成形体を得た。難燃性の評価の結果、３秒以内に消火し、且つ、酸素指数は３１．２であった。
結果を、表２にまとめた。
(Example 11)
A master batch composed of 60% by weight of a styrene resin and 40% by weight of a mixture of a brominated flame retardant and a heat stabilizer (d-1) was used,
Except that the master batch consisting of 60% by weight of styrene resin and 40% by weight of the mixture of brominated flame retardant and heat stabilizer (d-1) was 10 parts by weight with respect to 100 parts by weight of polystyrene resin. The same operation as 1 was performed.
Foamed particles having an expansion ratio of 50 times were obtained to obtain a molded article having a beautiful appearance. As a result of the evaluation of flame retardancy, the fire was extinguished within 3 seconds, and the oxygen index was 31.2.
The results are summarized in Table 2.
（実施例１２）
イソペンタンの添加量を３．５重量部に変更したこと以外は、実施例１１と同様の操作を行った。
発泡倍率３３倍の発泡粒子を得て、外観美麗な成形体を得た。難燃性の評価の結果、３秒以内に消火し、且つ、酸素指数は２９．２であった。
結果を表２にまとめた。
(Example 12)
The same operation as in Example 11 was performed except that the addition amount of isopentane was changed to 3.5 parts by weight.
Foamed particles having an expansion ratio of 33 times were obtained, and a molded article having a beautiful appearance was obtained. As a result of the evaluation of flame retardancy, the fire was extinguished within 3 seconds and the oxygen index was 29.2.
The results are summarized in Table 2.
（比較例１）
臭素系難燃剤と熱安定剤の混合物（ｂ−１）の代わりに、臭素系難燃剤単体をポリスチレン樹脂１００重量部に対して１．５５重量部用いたこと以外は、実施例１と同様の操作を行った。
得られた難燃性発泡性スチレン系樹脂粒子は、難燃剤の熱分解によるものと思われるが、茶色に変色していた。発泡倍率５２倍の発泡粒子が得られた。しかしながら、成形体は、茶色に変色しており、かつ、成形体表面に多数のメルトがあり、外観の悪い成形体となった。難燃性評価の結果、３秒以内に消火し、且つ、酸素指数は２６．８と合格であった。
結果を、表３にまとめた。
(Comparative Example 1)
Instead of the brominated flame retardant and heat stabilizer mixture (b-1), the same procedure as in Example 1 was used except that 1.55 parts by weight of the brominated flame retardant alone was used with respect to 100 parts by weight of the polystyrene resin. The operation was performed.
The obtained flame-retardant foaming styrene resin particles were discolored to brown, although it was probably due to thermal decomposition of the flame retardant. Expanded particles having an expansion ratio of 52 times were obtained. However, the molded body was discolored brown, and there were many melts on the surface of the molded body, resulting in a molded body with a poor appearance. As a result of the flame retardancy evaluation, the fire was extinguished within 3 seconds, and the oxygen index was 26.8.
The results are summarized in Table 3.
（比較例２）
臭素系難燃剤と熱安定剤の混合物（ｂ−１）の添加量を０．３重量部に変更したこと以外は、実施例１と同様の操作を行った。
発泡倍率５１倍の発泡粒子を得て、外観美麗な成形体を得た。難燃性の評価の結果、３秒以内に消火せず、また、酸素指数は２１．３と不合格であった。結果を表３にまとめた。
(Comparative Example 2)
The same operation as in Example 1 was performed except that the addition amount of the mixture (b-1) of the brominated flame retardant and the heat stabilizer was changed to 0.3 parts by weight.
Foamed particles having an expansion ratio of 51 times were obtained, and a molded article having a beautiful appearance was obtained. As a result of the evaluation of flame retardancy, the fire was not extinguished within 3 seconds, and the oxygen index was 21.3, which was unacceptable. The results are summarized in Table 3.
（比較例３）
臭素系難燃剤と熱安定剤の混合物（ｂ−１）の添加量を２０重量部に変更したこと以外は、実施例１と同様にした。発泡倍率４９倍の発泡粒子が得られた。
しかしながら、成形時に収縮してしまい、外観美麗な成形体を得ることはできず、その後の評価を断念した。
結果を表３にまとめた。
(Comparative Example 3)
The same procedure as in Example 1 was conducted except that the addition amount of the mixture (b-1) of brominated flame retardant and heat stabilizer was changed to 20 parts by weight. Expanded particles having an expansion ratio of 49 times were obtained.
However, it contracted during molding, and a molded article with a beautiful appearance could not be obtained, and the subsequent evaluation was abandoned.
The results are summarized in Table 3.
（比較例４）
臭素系難燃剤と熱安定剤の混合物（ｂ−２）の添加量を２０重量部に変更した以外は、実施例３と同様の操作を行った。
発泡倍率５０倍の発泡粒子を得た。しかしながら、成形時に収縮してしまい、外観美麗な成形体を得ることはできず、その後の評価を断念した。
結果を表３にまとめた。
(Comparative Example 4)
The same operation as in Example 3 was performed, except that the addition amount of the mixture (b-2) of the brominated flame retardant and the heat stabilizer was changed to 20 parts by weight.
Expanded particles having an expansion ratio of 50 times were obtained. However, it contracted during molding, and a molded article with a beautiful appearance could not be obtained, and the subsequent evaluation was abandoned.
The results are summarized in Table 3.
（比較例５）
臭素系難燃剤と熱安定剤との混合物として（ｂ−３）を用いたこと以外は、実施例２と同様の操作を行った。
発泡倍率５２倍の発泡粒子が得られた。しかしながら、成形体は若干茶色に変色しており、且つ成形体表面にいくつかのメルトがあり、外観の悪い成形体となった。難燃性評価の結果、３秒以内に消化し、且つ酸素指数は２７．８となった。
結果を表２にまとめた。
(Comparative Example 5)
The same operation as in Example 2 was performed except that (b-3) was used as a mixture of a brominated flame retardant and a heat stabilizer.
Expanded particles having an expansion ratio of 52 times were obtained. However, the molded product was slightly browned, and there were some melts on the surface of the molded product, resulting in a molded product with a poor appearance. As a result of flame retardant evaluation, digestion was made within 3 seconds, and the oxygen index was 27.8.
The results are summarized in Table 2.
（比較例６）
臭素系難燃剤と熱安定剤の混合物（ｃ−１）の添加量を２０重量部に変更した以外は、実施例５と同様の操作を行った。発泡倍率５１倍の発泡粒子を得た。しかしながら、成形時に収縮してしまい、外観美麗な成形体を得ることはできず、その後の評価を断念した。結果を表３にまとめた。
(Comparative Example 6)
The same operation as in Example 5 was performed except that the addition amount of the mixture (c-1) of the brominated flame retardant and the heat stabilizer was changed to 20 parts by weight. Expanded particles having an expansion ratio of 51 times were obtained. However, it contracted during molding, and a molded article with a beautiful appearance could not be obtained, and the subsequent evaluation was abandoned. The results are summarized in Table 3.
（比較例７）
臭素系難燃剤と熱安定剤の混合物（ｃ−２）の添加量を２０重量部に変更した以外は、実施例７と同様の操作を行った。
発泡倍率５１倍の発泡粒子を得た。しかしながら、成形時に収縮してしまい、外観美麗な成形体を得ることはできず、その後の評価を断念した。
結果を表３にまとめた。
(Comparative Example 7)
The same operation as in Example 7 was performed except that the addition amount of the mixture of the brominated flame retardant and the heat stabilizer (c-2) was changed to 20 parts by weight.
Expanded particles having an expansion ratio of 51 times were obtained. However, it contracted during molding, and a molded article with a beautiful appearance could not be obtained, and the subsequent evaluation was abandoned.
The results are summarized in Table 3.
（比較例８）
臭素系難燃剤と熱安定剤の混合物（ｄ−１）の添加量を２０重量部に変更した以外は、実施例９と同様の操作を行った。
発泡倍率５１倍の発泡粒子を得た。しかしながら、成形時に収縮してしまい、外観美麗な成形体を得ることはできず、その後の評価を断念した。
結果を表３にまとめた。
(Comparative Example 8)
The same operation as in Example 9 was performed except that the addition amount of the mixture of the brominated flame retardant and the heat stabilizer (d-1) was changed to 20 parts by weight.
Expanded particles having an expansion ratio of 51 times were obtained. However, it contracted during molding, and a molded article with a beautiful appearance could not be obtained, and the subsequent evaluation was abandoned.
The results are summarized in Table 3.
（比較例９）
イソペンタンの添加量を２．０重量部に変更したこと以外は、実施例１１と同様の操作を行った。
発泡倍率１５倍の発泡粒子を得た。しかしながら、成形時に収縮してしまい、外観美麗な成形体を得ることはできず、その後の評価を断念した。
結果を表３にまとめた。
(Comparative Example 9)
The same operation as in Example 11 was performed except that the amount of isopentane added was changed to 2.0 parts by weight.
Expanded particles having an expansion ratio of 15 were obtained. However, it contracted during molding, and a molded article with a beautiful appearance could not be obtained, and the subsequent evaluation was abandoned.
The results are summarized in Table 3.
Claims (7)
押出機内で溶融混練された溶融樹脂を、押出機先端に取り付けた小孔を多数有するダイスを通じて、循環水で満たされたカッターチャンバー内に押し出し、
押し出し直後から、ダイスと接する回転カッターにより溶融樹脂を切断する難燃性発泡性スチレン系樹脂粒子の製造方法であって、
臭素系難燃剤と熱安定剤との混合物の、熱重量分析における１％重量減少温度が、該臭素系難燃剤単体の１％重量減少温度に対して２℃以上高い温度であり、
発泡剤が、炭素数３以上６以下の炭化水素の少なくとも１種であることを特徴とする、難燃性発泡性スチレン系樹脂粒子の製造方法。 A mixture of a brominated flame retardant and a thermal stabilizer of 0.5 to 15 parts by weight and a foaming agent of 3 to 10 parts by weight with respect to 100 parts by weight of a styrene resin is supplied to the extruder.
The molten resin melt-kneaded in the extruder is extruded into a cutter chamber filled with circulating water through a die having a large number of small holes attached to the tip of the extruder,
Immediately after extrusion, a method for producing flame retardant foamable styrene resin particles in which a molten resin is cut by a rotary cutter in contact with a die,
The 1% weight reduction temperature in the thermogravimetric analysis of the mixture of brominated flame retardant and thermal stabilizer is a temperature higher by 2 ° C. or more than the 1% weight decreased temperature of the brominated flame retardant alone,
The method for producing flame-retardant foaming styrene resin particles, wherein the foaming agent is at least one kind of hydrocarbon having 3 to 6 carbon atoms.
該マスターバッチが、５０重量％以上７０重量％以下のスチレン系樹脂および、３０重量％以上５０重量％以下の臭素系難燃剤と熱安定剤の混合物からなる（両者の合計量は１００重量％）であることを特徴とする、請求項１〜４のいずれかに記載の難燃性発泡性スチレン系樹脂粒子の製造方法。 Supplying 2 to 35 parts by weight of a styrene resin masterbatch of a mixture of a brominated flame retardant and a heat stabilizer to 100 parts by weight of a styrene resin; and
The master batch is composed of 50% by weight or more and 70% by weight or less of a styrene resin and 30% by weight or more and 50% by weight or less of a mixture of a brominated flame retardant and a heat stabilizer (the total amount of both is 100% by weight). The method for producing flame-retardant foamable styrene resin particles according to any one of claims 1 to 4, wherein
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