JP6099495B2 - Flame retardant melt kneaded material and method for producing polystyrene resin extruded foam using the same - Google Patents
Flame retardant melt kneaded material and method for producing polystyrene resin extruded foam using the same Download PDFInfo
- Publication number
- JP6099495B2 JP6099495B2 JP2013131128A JP2013131128A JP6099495B2 JP 6099495 B2 JP6099495 B2 JP 6099495B2 JP 2013131128 A JP2013131128 A JP 2013131128A JP 2013131128 A JP2013131128 A JP 2013131128A JP 6099495 B2 JP6099495 B2 JP 6099495B2
- Authority
- JP
- Japan
- Prior art keywords
- flame retardant
- melt
- kneaded product
- weight
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003063 flame retardant Substances 0.000 title claims description 188
- 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 181
- 239000006260 foam Substances 0.000 title claims description 112
- 238000004519 manufacturing process Methods 0.000 title claims description 37
- 229920005990 polystyrene resin Polymers 0.000 title description 50
- 239000000463 material Substances 0.000 title description 35
- 239000005062 Polybutadiene Substances 0.000 claims description 65
- 229920002857 polybutadiene Polymers 0.000 claims description 65
- 229920005989 resin Polymers 0.000 claims description 49
- 239000011347 resin Substances 0.000 claims description 49
- 239000004088 foaming agent Substances 0.000 claims description 33
- 239000012760 heat stabilizer Substances 0.000 claims description 31
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- 239000004793 Polystyrene Substances 0.000 claims description 19
- 229920002223 polystyrene Polymers 0.000 claims description 18
- 238000004898 kneading Methods 0.000 claims description 16
- 239000011342 resin composition Substances 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- -1 butane are flammable Natural products 0.000 description 31
- 238000001125 extrusion Methods 0.000 description 30
- 239000000203 mixture Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 238000002845 discoloration Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000005187 foaming Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 238000004383 yellowing Methods 0.000 description 10
- 239000008188 pellet Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 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 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 8
- 229930195734 saturated hydrocarbon Natural products 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 7
- 229910052794 bromium Inorganic materials 0.000 description 7
- 238000010128 melt processing Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 239000003017 thermal stabilizer Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 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 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- FDBMBOYIVUGUSL-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FDBMBOYIVUGUSL-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 206010064127 Solar lentigo Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 230000008569 process Effects 0.000 description 3
- 238000001028 reflection method Methods 0.000 description 3
- 229920006132 styrene block copolymer Polymers 0.000 description 3
- 239000000126 substance Substances 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
- 238000010792 warming Methods 0.000 description 3
- WQJUBZMZVKITBU-UHFFFAOYSA-N (3,4-dimethyl-4-phenylhexan-3-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(CC)C(C)(CC)C1=CC=CC=C1 WQJUBZMZVKITBU-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 206010027146 Melanoderma Diseases 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 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 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 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
- 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 1
- MFFNRVNPBJQZFO-UHFFFAOYSA-N (2,6-dimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(O)=O MFFNRVNPBJQZFO-UHFFFAOYSA-N 0.000 description 1
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 1
- MICYFRBASVQFGY-UHFFFAOYSA-N (3-methyl-5-phenylhex-5-en-3-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(CC)CC(=C)C1=CC=CC=C1 MICYFRBASVQFGY-UHFFFAOYSA-N 0.000 description 1
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 1
- CDOOAUSHHFGWSA-UPHRSURJSA-N (z)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C/C(F)(F)F CDOOAUSHHFGWSA-UPHRSURJSA-N 0.000 description 1
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 description 1
- NWHNXXMYEICZAT-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidin-4-ol Chemical compound CN1C(C)(C)CC(O)CC1(C)C NWHNXXMYEICZAT-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
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-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
- 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
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-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
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-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
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-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
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-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
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- HUUJFOGLCYMPCS-UHFFFAOYSA-N C(C)(C)(C)C(CC(C(O[P])OC1=CC=CC=C1)CC)CCC(C)(C)C Chemical compound C(C)(C)(C)C(CC(C(O[P])OC1=CC=CC=C1)CC)CCC(C)(C)C HUUJFOGLCYMPCS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000579895 Chlorostilbon Species 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- QAEPIAHUOVJOOM-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC QAEPIAHUOVJOOM-UHFFFAOYSA-N 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- JZFBUVFLQQQFRN-UHFFFAOYSA-N [11,15-ditert-butyl-2-[3,3-di(tridecyl)hexadecyl]-4,13-dimethyl-2-tridecyl-7,9-dioxa-8-phosphatricyclo[8.2.2.23,6]hexadeca-1(12),3(16),4,6(15),10,13-hexaen-8-yl] dihydrogen phosphite Chemical compound CCCCCCCCCCCCCC1(C2=CC(=C(C=C2C)OP(OC3=C(C=C1C(=C3)C)C(C)(C)C)OP(O)O)C(C)(C)C)CCC(CCCCCCCCCCCCC)(CCCCCCCCCCCCC)CCCCCCCCCCCCC JZFBUVFLQQQFRN-UHFFFAOYSA-N 0.000 description 1
- UFGYQQVAMKUVNS-UHFFFAOYSA-N [2,3-di(nonyl)phenyl] (4-nonylphenyl) hydrogen phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(O)OC1=CC=CC(CCCCCCCCC)=C1CCCCCCCCC UFGYQQVAMKUVNS-UHFFFAOYSA-N 0.000 description 1
- YNUDZCVMRZTAOJ-UHFFFAOYSA-N [4-(4-dihydroxyphosphanylphenyl)phenyl]phosphonous acid Chemical compound C1=CC(P(O)O)=CC=C1C1=CC=C(P(O)O)C=C1 YNUDZCVMRZTAOJ-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- APOXBWCRUPJDAC-UHFFFAOYSA-N bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C APOXBWCRUPJDAC-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 229940077445 dimethyl ether Drugs 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 239000010976 emerald Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 239000004795 extruded polystyrene foam Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 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
- 239000000314 lubricant Substances 0.000 description 1
- 125000003588 lysine group Chemical group [H]N([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920006249 styrenic copolymer Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、新規な難燃剤溶融混練物及び該難燃剤溶融混練物を難燃剤として用いるポリスチレン系樹脂押出発泡体の製造方法に関し、詳しくは、製造時の熱安定性に優れ、かつ、生産性、製造安定性にも優れた新規な難燃剤溶融混練物、及びこれを難燃剤として用いた難燃性に優れると共にリサイクル性に優れるポリスチレン系樹脂押出発泡体の製造方法に関する。 The present invention relates to a novel flame retardant melt-kneaded product and a method for producing a polystyrene resin extruded foam using the flame retardant melt-kneaded product as a flame retardant, and more specifically, excellent thermal stability during production and productivity. The present invention also relates to a novel flame retardant melt-kneaded product excellent in production stability, and a method for producing a polystyrene resin extruded foam having excellent flame retardancy and excellent recyclability using this as a flame retardant.
従来、ポリスチレン系樹脂材料に気泡調整剤を加え、押出機で加熱混練し、次いで物理発泡剤を該押出機中に圧入し更に混練し、これらの溶融混合物を高圧域から低圧域（通常は大気中）に押し出し、ポリスチレン系樹脂発泡体（以下、押出発泡体又は発泡体ともいう。）を得る方法が知られている。 Conventionally, an air conditioner is added to a polystyrene-based resin material, heated and kneaded by an extruder, and then a physical foaming agent is pressed into the extruder and further kneaded, and the molten mixture is changed from a high pressure range to a low pressure range (usually atmospheric) And a method of obtaining a polystyrene resin foam (hereinafter also referred to as an extruded foam or a foam) is known.
前記押出発泡体を建築用の断熱材として使用するには、例えば、ＪＩＳ Ａ９５１１（２００６Ｒ）記載の押出ポリスチレンフォーム保温板の燃焼性規格を満足することが要求される。そのために、該押出発泡体中には難燃剤が添加されており、該難燃剤としては、ヘキサブロモシクロドデカン（以下、ＨＢＣＤという。）が広く使用されてきた。ＨＢＣＤは、汎用性があり、比較的少量の添加で難燃効果が得られる優れた難燃剤である。
しかし、ＨＢＣＤに対しては化審法やＲＥＡＣＨによる規制の動きがあり、規制対象物質に指定された場合を想定し、ＨＢＣＤ難燃剤を使用しない難燃剤代替押出発泡体製造技術の開発が求められている。
In order to use the extruded foam as a heat insulating material for construction, for example, it is required to satisfy the flammability standard of an extruded polystyrene foam heat insulating plate described in JIS A9511 (2006R). For this purpose, a flame retardant is added to the extruded foam, and hexabromocyclododecane (hereinafter referred to as HBCD) has been widely used as the flame retardant. HBCD is an excellent flame retardant that is versatile and can provide a flame retardant effect with a relatively small amount of addition.
However, there is a movement of regulation by the Chemical Substances Control Law and REACH for HBCD, and it is required to develop a flame retardant alternative extrusion foam manufacturing technology that does not use HBCD flame retardant assuming that it is designated as a regulated substance. ing.
一方、前記押出発泡体の製造方法における発泡剤としては、従来、ジクロロジフルオロメタン等の塩化フッ化炭化水素（以下、ＣＦＣという。）が広く使用されてきたが、オゾンホール拡大の問題との関連性が疑われているＣＦＣは使用が控えられ、オゾン破壊係数の小さい水素原子含有塩化フッ化炭化水素（以下、ＨＣＦＣという。）やオゾン破壊係数が０（ゼロ）の水素原子含有フッ化炭化水素（以下、ＨＦＣという。）がＣＦＣの代わりに用いられるようになった。また更に、地球温暖化の観点からＨＣＦＣやＨＦＣに代わり、オゾン破壊係数が０（ゼロ）であるとともに、地球温暖化係数も小さいイソブタンやイソペンタン等の飽和炭化水素が用いられるようになった。 On the other hand, chlorofluorocarbons (hereinafter referred to as CFC), such as dichlorodifluoromethane, have been widely used as a foaming agent in the process for producing extruded foams. CFCs that are suspected of being refractory are refrained from use, and hydrogen atom-containing fluorinated fluorinated hydrocarbons (hereinafter referred to as HCFC) with a low ozone depletion potential and hydrogen atom-containing fluorinated hydrocarbons with an ozone depletion potential of 0 (zero) (Hereinafter referred to as HFC) has been used instead of CFC. Furthermore, from the viewpoint of global warming, saturated hydrocarbons such as isobutane and isopentane having an ozone depletion coefficient of 0 (zero) and a small global warming coefficient have been used instead of HCFC and HFC.
しかし、ブタンなどの飽和炭化水素は可燃性であることから、ポリスチレン系樹脂押出発泡体に十分な難燃性を付与するためには、ＨＦＣ等の不燃性発泡剤を用いて製造する場合よりも多くの難燃剤を添加しなければならなくなった。多量の難燃剤が添加されると、押出発泡の安定性が著しく損なわれたり、得られた発泡板の物性が損なわれたりするという問題が新たに発生した。 However, since saturated hydrocarbons such as butane are flammable, in order to impart sufficient flame retardancy to polystyrene-based resin extruded foams, compared to the case of using non-flammable foaming agents such as HFC. Many flame retardants had to be added. When a large amount of a flame retardant is added, there is a new problem that stability of extrusion foaming is remarkably impaired or physical properties of the obtained foamed plate are impaired.
上記の状況において、ＨＢＣＤ以外の優れた難燃剤を用いたポリスチレン系樹脂押出発泡体の検討がなされてきた。例えば、特許文献１に代表される臭素化ブタジエン−スチレン共重合体などの臭素化ポリブタジエンタイプのものが提案されている。 In the above situation, a polystyrene resin extruded foam using an excellent flame retardant other than HBCD has been studied. For example, a brominated polybutadiene type such as a brominated butadiene-styrene copolymer represented by Patent Document 1 has been proposed.
また、この臭素化ポリブタジエン系難燃剤の熱安定性を改善するために、臭素化ブタジエンホモポリマー又は臭素化スチレン／ブタジエンブロックコポリマーにアルキルホスファイト及び／又はエポキシ化合物を含有させた難燃剤を用いる方法も提案されている（例えば特許文献２）。 In order to improve the thermal stability of the brominated polybutadiene-based flame retardant, a method using a flame retardant in which a brominated butadiene homopolymer or a brominated styrene / butadiene block copolymer contains an alkyl phosphite and / or an epoxy compound is used. Has also been proposed (for example, Patent Document 2).
しかしながら、特許文献１の臭素化ポリブタジエン系難燃剤は、発泡体に優れた難燃性を付与することができるものであるが、押出加工時の熱安定性に劣り、それに起因して発泡体に黒点の発生や変色が生じるといった問題点があった。 However, the brominated polybutadiene-based flame retardant of Patent Document 1 can impart excellent flame retardancy to the foam, but is inferior in thermal stability at the time of extrusion processing. There was a problem that black spots were generated or discolored.
また、特許文献２においては、上記臭素化ポリブタジエン系難燃剤とアルキルホスファイト及び／又はエポキシ化合物等の熱安定剤とを併用したことから、特許文献１の難燃剤に比べ押出加工時の熱安定性が若干改善される。 Moreover, in patent document 2, since the said brominated polybutadiene type flame retardant and heat stabilizers, such as an alkyl phosphite and / or an epoxy compound, were used together, compared with the flame retardant of patent document 1, the thermal stability at the time of extrusion processing The characteristics are slightly improved.
しかし、特許文献２の難燃剤は、臭素化ポリブタジエン系難燃剤と熱安定剤であるアルキルホスファイトやエポキシ化合物とのドライブレンドにより調製されているので、継続的に安定した状態で押出発泡体を製造することが難しかった。
また、このドライブレンド法では前記各成分が均一に混合されていないため、添加した熱安定剤の機能が十分に発揮されないため、臭素化ポリブタジエン系難燃剤の熱安定性がそれほど改善されず、加熱により黒点や変色が発生する場合があった。そのため、特許文献２の難燃剤を用いてポリスチレン系樹脂発泡体を製造した場合には、押出時の熱安定性は若干改善されるものの、押出発泡時の黒点の発生や基材樹脂であるポリスチレン系樹脂の分解による分子量の低下や黄変を抑えきることは困難であった。
However, since the flame retardant of Patent Document 2 is prepared by a dry blend of a brominated polybutadiene flame retardant and a heat stabilizer alkyl phosphite or an epoxy compound, the extruded foam is continuously stabilized. It was difficult to manufacture.
In addition, in the dry blend method, since the respective components are not uniformly mixed, the function of the added heat stabilizer is not sufficiently exhibited, so the thermal stability of the brominated polybutadiene flame retardant is not improved so much, and heating is performed. In some cases, black spots or discoloration may occur. Therefore, when a polystyrene resin foam is produced using the flame retardant of Patent Document 2, although the thermal stability during extrusion is slightly improved, the generation of black spots during extrusion foaming and polystyrene as the base resin It was difficult to suppress the decrease in molecular weight and yellowing due to the decomposition of the resin.
このため、臭素化ポリブタジエン系難燃剤を用いて、黒点の発生や変色がなく、かつ難燃性に優れるポリスチレン系樹脂押出発泡体の製造方法の開発研究が強く望まれていたが、未だそのような提案がなされていないのが現状である。 For this reason, there has been a strong demand for research and development of a method for producing extruded polystyrene-based foams that are free of black spots or discoloration and have excellent flame resistance using brominated polybutadiene flame retardants. The current situation is that no proposal has been made.
本発明は前記従来技術の実状に鑑み、ポリスチレン系樹脂発泡体を製造する際などに、押出発泡時に黒点が発生することを防ぎ、かつ押出時における基材樹脂であるポリスチレン系樹脂の分解による分子量の低下や黄変を抑制でき、押出発泡体に高度な難燃性を付与することができる新規な難燃剤溶融混練物及び該難燃剤溶融混練物を用いたポリスチレン系樹脂押出発泡体の製造方法を提供することを、その課題とするものである。 In view of the state of the prior art, the present invention prevents the generation of black spots during extrusion foaming when producing a polystyrene resin foam, and has a molecular weight due to decomposition of the polystyrene resin as a base resin during extrusion. Flame retardant melt-kneaded product that can suppress deterioration and yellowing of the resin, and can impart high flame retardancy to the extruded foam, and a method for producing a polystyrene-based resin extruded foam using the flame retardant melt-kneaded product The issue is to provide
本発明によれば、以下に示す、難燃剤溶融混練物、及び該難燃剤溶融混練物を難燃剤として用いたポリスチレン系樹脂押出発泡体の製造方法が提供される。
＜１＞臭素化ポリブタジエン系難燃剤、ポリ−１，４−ジイソプロピルベンゼン及び熱安定剤の溶融混練物であって、該熱安定剤の配合量が該臭素化ポリブタジエン系難燃剤１００重量部に対して５〜３５重量部であり、該溶融混練物のＪＩＳ Ｋ７２１０：１９９０の条件Ｈにおけるメルトフローレイトが２〜３０ｇ／１０分であることを特徴とする難燃剤溶融混練物。
＜２＞ポリ−１，４−ジイソプロピルベンゼンの配合量が、臭素化ポリブタジエン系難燃剤１００重量部に対して２〜１５重量部であることを特徴とする＜１＞に記載の難燃剤溶融混練物。
＜３＞熱安定剤が、エポキシ樹脂系熱安定剤、ホスファイト系熱安定剤、フェノール系熱安定剤及びヒンダードアミン系熱安定剤から選択される１種以上であることを特徴とする＜１＞又は＜２＞に記載の難燃剤溶融混練物。
＜４＞難燃剤溶融混練物が、さらに芳香族リン酸エステルを含み、該芳香族リン酸エステルの配合量が、臭素化ブタジエン系共重合体１００重量部に対して、０．５〜５重量部であることを特徴とする＜１＞〜＜３＞のいずれかに記載の難燃剤溶融混練物。
＜５＞ポリスチレン系樹脂、＜１＞〜＜４＞のいずれかに記載の難燃剤溶融混練物及び物理発泡剤を混練してなる発泡性溶融樹脂組成物を押出して発泡体を得ることを特徴とするポリスチレン系樹脂押出発泡体の製造方法。
According to the present invention, the following flame retardant melt-kneaded product and a method for producing a polystyrene resin extruded foam using the flame retardant melt-kneaded product as a flame retardant are provided.
<1> A melt-kneaded product of a brominated polybutadiene flame retardant, poly-1,4-diisopropylbenzene and a heat stabilizer, the blending amount of the heat stabilizer being 100 parts by weight of the brominated polybutadiene flame retardant 5 to 35 parts by weight of a flame retardant melt kneaded product, characterized in that the melt kneaded product has a melt flow rate of 2 to 30 g / 10 min under JIS K7210: 1990 condition H.
<2> The flame retardant melt kneading according to <1>, wherein the blending amount of poly-1,4-diisopropylbenzene is 2 to 15 parts by weight with respect to 100 parts by weight of brominated polybutadiene flame retardant object.
<3> The heat stabilizer is one or more selected from an epoxy resin heat stabilizer, a phosphite heat stabilizer, a phenol heat stabilizer, and a hindered amine heat stabilizer <1> Or the flame retardant melt kneaded material as described in <2> .
<4> The flame retardant melt-kneaded product further contains an aromatic phosphate ester, and the blending amount of the aromatic phosphate ester is 0.5 to 5 weights with respect to 100 parts by weight of the brominated butadiene copolymer. The flame retardant melt-kneaded product according to any one of <1> to < 3 >, wherein
< 5 > Polystyrene resin, a foamable molten resin composition obtained by kneading the flame retardant melt kneaded material according to any one of <1> to < 4 > and a physical foaming agent to obtain a foam. A method for producing a polystyrene resin extruded foam.
本発明に係る新規な難燃剤溶融混練物は、臭素化ポリブタジエン系難燃剤を含む難燃剤と熱安定剤との溶融混練物であることから、該溶融混練物を難燃剤として押出機に供給して押出発泡体を製造することにより、熱安定剤が臭素化ポリブタジエン系難燃剤に対して効果的に作用して押出加工温度において臭素化ポリブタジエン系難燃剤を安定化させ、黒点の発生や変色を抑制、防止することができ、かつ、燃焼時には臭素化ポリブタジエン系難燃剤が効果的に分解して高度な難燃性を押出発泡体に付与することができる。さらに、この難燃剤溶融混練物は、ポリ−１，４−ジイソプロピルベンゼンを含有することにより、その流動性が向上し、そのメルトフローレートが特定範囲にあることから、溶融混練時に適度な流動性を示し、低い加工温度でも、安定して臭素化ポリブタジエン系難燃剤と熱安定剤とが溶融混練されているので、押出発泡体を製造する過程では、より確実に黒点の発生や変色を抑制、防止することができ、さらに、ポリ−１，４−ジイソプロピルベンゼンは、臭素化ポリブタジエン系難燃剤の有する優れた難燃性を更に向上させる難燃助剤としても機能することから、本発明に係る難燃剤溶融混練物はさらに高度な難燃性を有するものである。
したがって、本発明の難燃剤溶融混練物を用いると、たとえ臭素化ポリブタジエン系難燃剤の配合量が少量であっても、高度な難燃性及び十分な酸素指数を有する発泡体を得ることができ、しかも基材樹脂であるポリスチレン系樹脂の着色が抑制され、再生原料としても使用可能な、ポリスチレン系樹脂押出発泡体が得られる。
Since the novel flame retardant melt kneaded product according to the present invention is a melt kneaded product of a flame retardant containing a brominated polybutadiene flame retardant and a thermal stabilizer, the melt kneaded product is supplied to the extruder as a flame retardant. By producing extruded foam, the thermal stabilizer effectively acts on the brominated polybutadiene flame retardant, stabilizes the brominated polybutadiene flame retardant at the extrusion processing temperature, and generates black spots and discoloration. The brominated polybutadiene flame retardant can be effectively decomposed at the time of combustion and can impart high flame retardancy to the extruded foam. Furthermore, since this flame retardant melt-kneaded material contains poly-1,4-diisopropylbenzene, its fluidity is improved and its melt flow rate is in a specific range. Since the brominated polybutadiene flame retardant and heat stabilizer are melted and kneaded stably even at low processing temperatures, in the process of producing extruded foam, the generation and discoloration of black spots are more reliably suppressed. Furthermore, since poly-1,4-diisopropylbenzene also functions as a flame retardant aid that further improves the excellent flame retardancy of brominated polybutadiene flame retardants, it relates to the present invention. The flame retardant melt-kneaded product has higher flame retardancy.
Therefore, when the flame retardant melt-kneaded product of the present invention is used, a foam having high flame retardancy and a sufficient oxygen index can be obtained even if the blending amount of the brominated polybutadiene flame retardant is small. Moreover, coloring of the polystyrene resin as the base resin is suppressed, and a polystyrene resin extruded foam that can be used as a recycled material is obtained.
また、本発明のポリスチレン系樹脂押出発泡体の製造方法は、上記難燃剤溶融混練物とポリスチレン系樹脂を任意の割合で押出機に供給し、さらに発泡剤と混練して押出発泡させることにより、難燃性に優れ、かつ黒点、黄変に代表される外観の不具合のない良好な発泡体を得ることができる。
また、該難燃剤溶融混練物を用いて製造された押出発泡体や、その端材・スクラップを加熱溶融しリサイクル原料として再利用する際にもリサイクル原料の分子量の低下や黄変が抑制でき、かつ黒点の発生を抑制できる効果を有する。
In addition, the method for producing a polystyrene resin extruded foam of the present invention is to supply the above flame retardant melt-kneaded product and polystyrene resin to an extruder at an arbitrary ratio, and further knead with a foaming agent to cause extrusion foaming. It is possible to obtain a good foam having excellent flame retardancy and having no defects in appearance typified by black spots and yellowing.
In addition, the extrusion foam produced using the flame retardant melt-kneaded product, and when the end material and scrap are heated and melted and reused as a recycled material, reduction in molecular weight and yellowing of the recycled material can be suppressed, In addition, it has the effect of suppressing the occurrence of black spots.
以下、本発明の難燃剤溶融混練物について詳細に説明する。
本発明の難燃剤溶融混練物は、臭素化ポリブタジエン系難燃剤、ポリ−１，４−ジイソプロピルベンゼン及び熱安定剤の溶融混練物であって、該溶融混練物のＪＩＳ Ｋ７２１０：１９９０の条件Ｈにおけるメルトフローレイトが２〜３０ｇ／１０分であることを特徴としている。
Hereinafter, the flame retardant melt kneaded product of the present invention will be described in detail.
The flame retardant melt-kneaded product of the present invention is a melt-kneaded product of brominated polybutadiene-based flame retardant, poly-1,4-diisopropylbenzene and a heat stabilizer, and the melt-kneaded product is subjected to the condition H of JIS K7210: 1990. The melt flow rate is 2 to 30 g / 10 min.
上記したように、臭素化ポリブタジエン系難燃剤は、ポリスチレンなどの熱可塑性樹脂の難燃剤として用いる場合に、優れた難燃性付与効果を示すものである。しかしながら、溶融加工時の熱安定性に劣るため、溶融加工条件によっては重合体から臭素が遊離しやすく、この臭素の遊離により難燃性付与効果を低下させる恐れや熱可塑性樹脂を分解させる恐れがある。さらに、臭素化ポリブタジエン系難燃剤はポリマーであるため、臭素の遊離によって該重合体中で炭素−炭素不飽和結合が形成されると、該重合体自体又は熱可塑性樹脂が着色される恐れや、不飽和結合の架橋により臭素化ポリブタジエン系難燃剤のゲル化や黒点の発生の原因となり得るといった種々の問題点があった。 As described above, the brominated polybutadiene-based flame retardant exhibits an excellent flame retardancy imparting effect when used as a flame retardant for thermoplastic resins such as polystyrene. However, because of poor thermal stability during melt processing, bromine tends to be liberated from the polymer depending on the melt processing conditions, and the liberation of bromine may reduce the effect of imparting flame retardancy and may cause decomposition of the thermoplastic resin. is there. Furthermore, since the brominated polybutadiene flame retardant is a polymer, if a carbon-carbon unsaturated bond is formed in the polymer by liberation of bromine, the polymer itself or the thermoplastic resin may be colored, There have been various problems such as cross-linking of unsaturated bonds that can cause gelation and black spots of brominated polybutadiene flame retardants.
一般に、溶融加工時に臭素の遊離を抑制するためには、熱安定剤を配合する方法が考えられるが、単にドライブレンド法により熱安定剤を臭素化ポリブタジエン系難燃剤に配合しただけでは、変色や黒点の発生を十分に抑制することができなかった。 In general, in order to suppress the liberation of bromine at the time of melt processing, a method of blending a heat stabilizer is conceivable. However, if the heat stabilizer is simply blended with a brominated polybutadiene flame retardant by a dry blend method, discoloration or The generation of sunspots could not be sufficiently suppressed.
本発明者等は、かかる問題点を解消するために、まず、押出発泡体の製造時に、臭素化ポリブタジエン系難燃剤と熱安定剤をドライブレンド法ではなく、臭素化ポリブタジエン系難燃剤に熱安定剤を配合し、これらを溶融混練して難燃剤溶融混練物として、押出発泡体の基材樹脂に配合することを試みた。具体的には、臭素化ポリブタジエン系難燃剤が黒点化せず、かつ著しく変色しない加工温度条件で臭素化ポリブタジエン系難燃剤と熱安定剤とを溶融混練して難燃剤溶融混練物を難燃剤として用いて、ポリスチレン系樹脂を基材樹脂とする押出発泡体を製造したところ、効果的に黒点の発生や押出発泡体の変色を抑制できることが判明した。 In order to eliminate such problems, the present inventors firstly stabilized the brominated polybutadiene flame retardant and the thermal stabilizer in the brominated polybutadiene flame retardant instead of the dry blend method during the production of the extruded foam. An agent was blended, and these were melted and kneaded, and an attempt was made to blend them into a base resin of an extruded foam as a flame retardant melt kneaded product. Specifically, the brominated polybutadiene-based flame retardant does not become black spots and melts and kneads the brominated polybutadiene-based flame retardant and the heat stabilizer under processing temperature conditions that do not significantly change color, and the flame retardant melt-kneaded product serves as a flame retardant. When an extruded foam using a polystyrene resin as a base resin was produced, it was found that generation of black spots and discoloration of the extruded foam can be effectively suppressed.
一方、黒点の発生及び変色をより効果的に抑制するという観点からは、臭素化ポリブタジエン系難燃剤と熱安定剤との溶融加工温度は、押出可能な温度範囲においてより低い温度とすることが好ましいが、低温で、具体的には押出時の樹脂温度が１９０℃以下となるように溶融混練を試みたところ、難燃剤溶融混練物を得ることは可能であったが、臭素化ポリブタジエン系難燃剤の流動性が著しく悪く、混練物の吐出量を上げると押出機の負荷が高まり、さらには混練物の樹脂温度が上昇してしまい、効率良くかつ安定的に所望の溶融混練物が得られないことを知見した。そこで、更に検討を進めた結果、ポリ−１，４−ジイソプロピルベンゼンを配合して溶融混練加工すると、意外にも、溶融加工温度を低くしても容易かつ安定的に製造することが可能であり、しかもそれ自体に黒点の発生や変色が抑制された難燃剤溶融混練物が得られることを知見した。更には、この新規な難燃剤溶融混練物は、ポリスチレン系樹脂発泡体を製造する際に、押出発泡時に黒点が発生することを防ぎ、かつ押出時における基材樹脂であるポリスチレン系樹脂の分解による分子量の低下や黄変をより効果的に抑制できることを知見した。本発明はこれらの知見に基づいてなされたものである。 On the other hand, from the viewpoint of more effectively suppressing the occurrence and discoloration of black spots, the melt processing temperature of the brominated polybutadiene flame retardant and the thermal stabilizer is preferably set to a lower temperature in the extrudable temperature range. However, when melt kneading was attempted so that the resin temperature during extrusion was 190 ° C. or lower at a low temperature, it was possible to obtain a flame retardant melt kneaded product, but brominated polybutadiene flame retardant The flowability of the kneaded product is remarkably poor, and when the discharge amount of the kneaded product is increased, the load on the extruder increases and the resin temperature of the kneaded product increases, and the desired melt-kneaded product cannot be obtained efficiently and stably. I found out. Therefore, as a result of further investigation, when poly-1,4-diisopropylbenzene is blended and melt-kneaded, surprisingly, even if the melt processing temperature is lowered, it can be easily and stably produced. Moreover, it has been found that a flame retardant melt kneaded product in which the occurrence of black spots and discoloration are suppressed can be obtained. Furthermore, this novel flame retardant melt kneaded product prevents the generation of black spots during extrusion foaming during the production of polystyrene resin foam and is due to the decomposition of the polystyrene resin as the base resin during extrusion. It was found that molecular weight reduction and yellowing can be more effectively suppressed. The present invention has been made based on these findings.
本発明において、臭素系難燃剤として用いる前記臭素化ポリブタジエン系難燃剤それ自体は従来公知のものであり、たとえば特許文献１や２で開示されるものがそのまま使用できる。
一般に、難燃剤として使用される臭素化ポリブタジエン系難燃剤は、ポリブタジエン換算で、重量平均分子量１.０×１０３〜２．０×１０５程度、好ましくは２．０×１０３〜１．０×１０５、より好ましくは５．０×１０３〜１．０×１０５、さらに好ましくは５．０×１０４〜１．０×１０５のブタジエン系重合体を臭素化することにより製造される。
In the present invention, the brominated polybutadiene flame retardant itself used as a brominated flame retardant is a conventionally known one. For example, those disclosed in Patent Documents 1 and 2 can be used as they are.
In general, a brominated polybutadiene flame retardant used as a flame retardant is approximately 1.0 × 10 3 to 2.0 × 10 5 , preferably 2.0 × 10 3 to 1.0 in terms of polybutadiene. It is produced by brominating a butadiene-based polymer of × 10 5 , more preferably 5.0 × 10 3 to 1.0 × 10 5 , and even more preferably 5.0 × 10 4 to 1.0 × 10 5. The
臭素化ポリブタジエン系難燃剤をポリスチレン系樹脂の難燃剤として用いる場合、ポリスチレン系樹脂との相溶性を考慮すると、臭素化ポリブタジエン系難燃剤は、スチレン系単量体成分単位を含むブロック共重合体、ランダム共重合体又はグラフト共重合体であることが好ましく（以下、これらを併せて臭素化ブタジエン−スチレン共重合体ともいう。）、ポリスチレン系重合体ブロックと臭素化ポリブタジエンブロックとのブロック共重合体であることがより好ましい。
また、スチレン系単量体としては、スチレン、臭素化スチレン、塩素化スチレン、２−メチルスチレン、４−メチルスチレン、２，４−ジメチルスチレン、α−メチルスチレンなどが例示でき、これこれらの中でも、スチレン、４−メチルスチレン、α−メチルスチレン又はこれらの混合物が好ましく、より好ましくはスチレンである。
When using brominated polybutadiene flame retardant as a flame retardant for polystyrene resin, considering compatibility with polystyrene resin, brominated polybutadiene flame retardant is a block copolymer containing a styrene monomer component unit, It is preferably a random copolymer or a graft copolymer (hereinafter also referred to as a brominated butadiene-styrene copolymer), and a block copolymer of a polystyrene polymer block and a brominated polybutadiene block. It is more preferable that
Examples of styrene monomers include styrene, brominated styrene, chlorinated styrene, 2-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, α-methylstyrene, and the like. , Styrene, 4-methylstyrene, α-methylstyrene, or a mixture thereof, more preferably styrene.
難燃性付与効果の観点から、臭素化ポリブタジエン系難燃剤中の臭素含有率は、６０重量％以上であることが好ましく、より好ましくは６３重量％以上である。なお、上記臭素含有率は、ＪＩＳ Ｋ７３９２：２００９に基づき求めることができる。 From the viewpoint of imparting flame retardancy, the bromine content in the brominated polybutadiene-based flame retardant is preferably 60% by weight or more, and more preferably 63% by weight or more. The bromine content can be determined based on JIS K7392: 2009.
臭素化ポリブタジエン系難燃剤の重量平均分子量は、ポリスチレン換算で、好ましくは１．０×１０５〜２.０×１０５程度であり、その２００℃、剪断速度１００ｓｅｃ−１における溶融粘度は、４０００〜８０００Ｐａ・ｓ程度である。 The weight average molecular weight of the brominated polybutadiene-based flame retardant is preferably about 1.0 × 10 5 to 2.0 × 10 5 in terms of polystyrene, and the melt viscosity at 200 ° C. and a shear rate of 100 sec −1 is 4000. About 8000 Pa · s.
一般に、代表的な臭素化ポリブタジエン系難燃剤である臭素化ブタジエン−スチレンブロック共重合体は下記一般式で表すことができる。 In general, a brominated butadiene-styrene block copolymer which is a typical brominated polybutadiene-based flame retardant can be represented by the following general formula.
（式中、Ｘ、Ｙ及びＺは、正の整数である。）
(In the formula, X, Y and Z are positive integers.)
このような臭素化ブタジエン−スチレンブロック共重合体は、たとえばブタジエン−スチレンブロック共重合体を臭素化することにより製造される。
本発明で好ましく用いられるポリスチレン−臭素化ポリブタジエン共重合体としては、Ｃｈｅｍｔｕｒａ社のＥｍｅｒａｌｄ３０００、ＩＣＬ−ＩＰ社のＦＲ１２２Ｐなどの市販品を挙げられる。
Such a brominated butadiene-styrene block copolymer is produced, for example, by brominating a butadiene-styrene block copolymer.
Examples of the polystyrene-brominated polybutadiene copolymer preferably used in the present invention include commercially available products such as Emerald 3000 from Chemtura and FR122P from ICL-IP.
本発明において、臭素化ポリブタジエン系難燃剤及び熱安定剤と共に、ポリ−１，４−ジイソプロピルベンゼンを用いる。 In the present invention, poly-1,4-diisopropylbenzene is used together with a brominated polybutadiene flame retardant and a heat stabilizer.
このポリ−１，４−ジイソプロピルベンゼンが下記の構造式で表され、それ自体公知の化合物である。
（ｎは繰り返し単位である）
This poly-1,4-diisopropylbenzene is represented by the following structural formula and is a known compound per se.
(N is a repeating unit)
このポリ−１，４−ジイソプロピルベンゼンは、臭素化ポリブタジエン系難燃剤を可塑化し、臭素化ポリブタジエン系難燃剤の流動性を高める。
このため、臭素化ポリブタジエン系難燃剤にポリ−１，４−ジイソプロピルベンゼンを配合させると、溶融加工時に臭素化ポリブタジエン系難燃剤の粘度を低下させるので、押出機の負荷が軽減され、溶融加工温度が低い条件においても、安定的に黒点や変色のない難燃剤溶融混練物を簡便に製造することができる。
This poly-1,4-diisopropylbenzene plasticizes the brominated polybutadiene flame retardant and enhances the fluidity of the brominated polybutadiene flame retardant.
For this reason, when poly-1,4-diisopropylbenzene is added to the brominated polybutadiene flame retardant, the viscosity of the brominated polybutadiene flame retardant is reduced during melt processing, so the load on the extruder is reduced and the melt processing temperature is reduced. Even under low conditions, a flame retardant melt kneaded product having no black spots or discoloration can be easily and stably produced.
また、上記ポリ−１，４−ジイソプロピルベンゼンは、臭素化ポリブタジエン系難燃剤の有する優れた難燃性を更に向上させる難燃助剤としても機能することから、本発明に係る難燃剤溶融混練物はさらに高度な難燃性を有するものである。
したがって、本発明の難燃剤溶融混練物を用いると、たとえ臭素化ポリブタジエン系難燃剤の配合量が少量であっても、高度な難燃性及び十分な酸素指数を有する発泡体を得ることができ、しかも基材樹脂であるポリスチレン系樹脂の着色が抑制され、再生原料としても使用可能な、ポリスチレン系樹脂押出発泡体が得られる。
The poly-1,4-diisopropylbenzene also functions as a flame retardant aid that further improves the excellent flame retardant properties of the brominated polybutadiene flame retardant, so that the flame retardant melt kneaded product according to the present invention Has a higher degree of flame retardancy.
Therefore, when the flame retardant melt-kneaded product of the present invention is used, a foam having high flame retardancy and a sufficient oxygen index can be obtained even if the blending amount of the brominated polybutadiene flame retardant is small. Moreover, coloring of the polystyrene resin as the base resin is suppressed, and a polystyrene resin extruded foam that can be used as a recycled material is obtained.
ポリ−１，４−ジイソプロピルベンゼンの配合量は、特に制約はないが、臭素化ポリブタジエン系難燃剤１００重量部に対して２〜１５重量部、好ましくは３〜１２重量部である。
配合量が上記範囲内であると、難燃剤溶融混練物のＭＦＲを所望の範囲に調整しやくすく、さらに該難燃剤溶融混練物は優れた難燃性付与効果を示し、好ましい結果を与える。
The blending amount of poly-1,4-diisopropylbenzene is not particularly limited, but is 2 to 15 parts by weight, preferably 3 to 12 parts by weight with respect to 100 parts by weight of the brominated polybutadiene flame retardant.
When the blending amount is within the above range, it is easy to adjust the MFR of the flame retardant melt-kneaded product to a desired range, and the flame retardant melt-kneaded product exhibits an excellent flame retardancy imparting effect and gives a preferable result.
本発明の難燃剤溶融混練物には、更に熱安定剤が配合される。
熱安定剤としては、エポキシ樹脂系安定剤、ホスファイト系安定剤、フェノール系安定剤及びヒンダードアミン系安定剤から選ばれる一種以上のものが挙げられる。
これらの熱安定剤の総配合量は、臭素化ポリブタジエン系難燃剤１００重量部に対して、５〜３０重量部とすることが好ましく、より好ましくは１０〜２５重量部である。
A heat stabilizer is further blended in the flame retardant melt kneaded product of the present invention.
Examples of the thermal stabilizer include one or more selected from an epoxy resin stabilizer, a phosphite stabilizer, a phenol stabilizer, and a hindered amine stabilizer.
The total amount of these heat stabilizers is preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight with respect to 100 parts by weight of the brominated polybutadiene flame retardant.
エポキシ樹脂系安定剤としては、ノボラック型またはビスフェノール型が好ましい。ビスフェノール型エポキシ系化合物としては、特に臭素化ビスフェノールＡ型エポキシ化合物、所謂臭素化エポキシ化合物が好ましい。 The epoxy resin stabilizer is preferably a novolak type or a bisphenol type. As the bisphenol type epoxy compound, a brominated bisphenol A type epoxy compound, that is, a so-called brominated epoxy compound is particularly preferable.
ホスファイト系安定剤としては、例えば、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、ビス（２，６−ジ−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−ジ−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、テトラ（トリデシル）−４，４’−ブチリデン−ビス（２−ｔ−ブチル−５−メチルフェニル）ジホスファイト、ビス［２，４−ビス（１，１−ジメチルエチル）−６−メチルフェニル］エチルエステル亜リン酸、テトラキス（２，４，−ジ−ｔ−ブチルフェニル）［１，１−ビフェニル］−４，４’−ジイルビスホスフォナイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ビスステアリルペンタエリスリトールジホスファイト、２，２’−メチレンビス（４，６−ジ−ｔ−ブチル−１−フェニルオキシ）（２−エチルヘキシルオキシ）ホスホラス、モノ（ジノニルフェニル）モノ−ｐ−ノニルフェニルホスファイト、トリス（モノノニルフェニル）ホスファイト、テトラアルキル（Ｃ＝１２〜１６）−４，４’−イソプロピリデン−（ビスフェニル）ジホスファイト、ヘキサトリデシル−１，１，３−トリス（３−ｔ−ブチル−６−メチル−４オキシフェニル）−３−メチルプロパントリホスファイト、ジフェニルイソデシルホスファイト、トリデシルホスファイトなどがあげられる。これらは、単独または２種以上を組み合わせて用いてもよい。これらのうちでも、押出安定性の点から、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイトまたはビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジホスファイトが好ましい。 Examples of the phosphite stabilizer include tris (2,4-di-t-butylphenyl) phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, bis ( 2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) -4,4′-butylidene-bis (2-tert-butyl-5-methylphenyl) diphosphite, bis [2,4- Bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetrakis (2,4, -di-t-butylphenyl) [1,1-biphenyl] -4,4′-diylbis Phosphonite, bis (nonylphenyl) pentaerythritol diphosphite, bisstearyl pentaerythritol diphosphite, 2,2 -Methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, mono (dinonylphenyl) mono-p-nonylphenyl phosphite, tris (monononylphenyl) phosphite, Tetraalkyl (C = 12-16) -4,4′-isopropylidene- (bisphenyl) diphosphite, hexatridecyl-1,1,3-tris (3-t-butyl-6-methyl-4oxyphenyl) Examples include -3-methylpropane triphosphite, diphenylisodecyl phosphite, and tridecyl phosphite. You may use these individually or in combination of 2 or more types. Among these, from the viewpoint of extrusion stability, tris (2,4-di-t-butylphenyl) phosphite or bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite is used. preferable.
フェノール系安定剤としては、例えば、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、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］、テトラキス−［メチレン−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］メタン、２，２−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、１，６−ヘキサンジオール−ビス［３−（３，５−ジ−ｔ−ブチル−４−ドロキシフェニル）プロピオネート］、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］等が挙げられる。
これらは、単独または２種以上を組み合わせて用いてもよい。これらの中でも、押出安定性、難燃性の点から、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］が好ましい。
Examples of the phenol-based stabilizer include 2,6-di-t-butyl-p-cresol, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], tetrakis -[Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2,2-methylenebis (4-methyl-6-t-butylphenol), 1,6-hexanediol- Bis [3- (3,5-di-tert-butyl-4-droxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like Can be mentioned.
You may use these individually or in combination of 2 or more types. Among these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is preferable from the viewpoint of extrusion stability and flame retardancy.
ヒンダードアミン系化合物としては、例えば、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン、４−ヒドロキシ−１，２，２，６，６−ペンタメチルピペリジン、または４−ヒドロキシ−１−オクチルオキシ−２，２，６，６−テトラメチルピペリジンの脂肪族または芳香族カルボン酸エステル、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジニル）−２−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−２−ｎ−ブチルマロネート、ビス（２，２，６，６−テトラメチル−４−ピペリジニル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジニル）セバケート、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン、テトラキス（２，２，６，６−テトラメチル−４−ピペリジニル）−１，２，３，４−ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジニル）−１，２，３，４−ブタンテトラカルボキシレートなどがあげられる。これらは、単独または２種以上を組み合わせて用いてもよい。これらのうちでも、難燃性に関して消炎を早める効果、および押出発泡体の耐熱性を低下させない点から、テトラキス（２，２，６，６−テトラメチル−４−ピペリジニル）−１，２，３，４−ブタンテトラカルボキシラート、又はビス（２，２，６，６−テトラメチル−４−ピペリジニル）セバケートが好ましい。 Examples of hindered amine compounds include 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, or 4-hydroxy-1-octyl. Aliphatic or aromatic carboxylic acid ester of oxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) -2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6- Pentamethyl-4-piperidinyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, tetrakis (2,2,6,6-tetramethyl-4-pi Lysinyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl) -1,2,3,4-butanetetracarboxylate It is done. You may use these individually or in combination of 2 or more types. Among these, tetrakis (2,2,6,6-tetramethyl-4-piperidinyl) -1,2,3 is effective because it accelerates the extinction of flame retardancy and does not decrease the heat resistance of the extruded foam. , 4-butanetetracarboxylate or bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate is preferred.
本発明の難燃剤溶融混練物は、上記したように、臭素化ポリブタジエン系難燃剤、ポリ−１，４−ジイソプロピルベンゼン及び熱安定剤を必須成分とするが、ＪＩＳ Ｋ７２１０：１９９０の条件Ｈ（２００℃、５ｋｇ荷重）におけるメルトフローレイト（ＭＦＲ）は２〜３０ｇ／１０分の範囲、好ましくは５〜３０ｇ／１０分、更に好ましくは５〜２０ｇ／１０分であるように調製されている。 As described above, the flame retardant melt-kneaded material of the present invention contains a brominated polybutadiene flame retardant, poly-1,4-diisopropylbenzene, and a heat stabilizer as essential components. However, the condition H (200 of JIS K7210: 1990) The melt flow rate (MFR) at 5 ° C. and 5 kg load is adjusted to be in the range of 2 to 30 g / 10 minutes, preferably 5 to 30 g / 10 minutes, and more preferably 5 to 20 g / 10 minutes.
難燃剤溶融混練物のＭＦＲが２〜３０ｇ／１０分となるようにポリ−１，４−ジイソプロピルベンゼンを臭素化ポリブタジエン系難燃剤に配合して溶融混練することにより、溶融混練物中に黒点が発生することや溶融混練物自体が変色することを抑制しつつ、該溶融混練物を高吐出量で効率よく、かつ安定して製造することができる。さらに、該難燃剤溶融混練物をポリスチレンなどの熱可塑性樹脂に難燃剤として添加して押出加工することにより、熱可塑性樹脂に高い難燃性を付与することができると共に、臭素化ポリブタジエン系難燃剤中への熱安定剤の分散性が向上しているためか、その押出加工時の加熱下においても、黒点の発生や熱可塑性樹脂の変色を効果的に抑制できる。 By blending poly-1,4-diisopropylbenzene with a brominated polybutadiene-based flame retardant so that the MFR of the flame retardant melt-kneaded product is 2 to 30 g / 10 minutes, a black spot is formed in the melt-kneaded product. It is possible to efficiently and stably produce the melt-kneaded product with a high discharge amount while suppressing the occurrence and discoloration of the melt-kneaded product itself. Furthermore, by adding the flame retardant melt-kneaded product as a flame retardant to a thermoplastic resin such as polystyrene and extruding it, the thermoplastic resin can be imparted with high flame retardancy, and a brominated polybutadiene flame retardant Probably because of the improved dispersibility of the heat stabilizer therein, the generation of black spots and the discoloration of the thermoplastic resin can be effectively suppressed even under heating during the extrusion process.
本発明の難燃剤溶融物は、臭素化ポリブタジエン系難燃剤、ポリ−１，４−ジイソプロピルベンゼン及び熱安定剤とを含む混合物を押出機やミキサー等に投入し、溶融混練させることにより作製される。
溶融混練時の温度は、臭素化ポリブタジエン系難燃剤からの臭素の遊離を効果的に抑制するためには溶融混練時の樹脂温度は低いほど好ましく、概ね１９０℃以下、好ましくは１８５℃以下とする。一方、上記観点からは、溶融混練時の樹脂温度の下限は特に制限されることはないが、臭素化ポリブタジエン系難燃剤と熱安定剤、さらにはポリ−１，４−ジイソプロピルベンゼンとを安定して溶融混練するためには概ね１４０℃以上とすることが好ましく、１５０℃以上とすることが好ましい。
また、難燃剤溶融混練物は、計量性、取扱の容易性等から押出機からストランド状に押出した後、カットしてペレット化しておくことが好ましい。
The flame retardant melt of the present invention is prepared by charging a mixture containing a brominated polybutadiene-based flame retardant, poly-1,4-diisopropylbenzene and a heat stabilizer into an extruder or a mixer, and melt-kneading the mixture. .
The temperature at the time of melt-kneading is preferably as low as the resin temperature at the time of melt-kneading in order to effectively suppress the liberation of bromine from the brominated polybutadiene flame retardant, and is generally 190 ° C. or less, preferably 185 ° C. or less. . On the other hand, from the above viewpoint, the lower limit of the resin temperature at the time of melt-kneading is not particularly limited. However, the brominated polybutadiene flame retardant and the thermal stabilizer, and further, poly-1,4-diisopropylbenzene are stabilized. In order to melt and knead, it is preferably about 140 ° C. or higher, preferably 150 ° C. or higher.
The flame retardant melt-kneaded product is preferably cut into a pellet after being extruded in a strand form from an extruder from the standpoint of meterability and ease of handling.
本発明の難燃剤溶融混練物には、流動性向上剤として、更に芳香族リン酸エステルを含有させておくことが好ましい。
芳香族リン酸エステルを含有させることにより、ポリ−１，４−ジイソプロピルベンゼンと芳香族リン酸エステルとの相乗効果により、少量の含有量で臭素化ブタジエン系難燃剤を含む難燃剤溶融混練物の流動性を効果的に向上させることができる。
The flame retardant melt-kneaded product of the present invention preferably further contains an aromatic phosphate as a fluidity improver.
By containing an aromatic phosphate ester, a flame retardant melt-kneaded material containing a brominated butadiene flame retardant with a small amount of content due to a synergistic effect of poly-1,4-diisopropylbenzene and aromatic phosphate ester. The fluidity can be effectively improved.
芳香族リン酸エステルの具体例としては、トリフェニルホスフェート（ＴＰＰ）、トリクレジルホスフェート（ＴＣＰ）、トリキシリルホスフェート、オクチルジフェニルホスフェート、クレジルジフェニルホスフェート、１，３−フェニレンビス（ジフェニルホスフェート）、１，３−フェニレンビス（ジ−２，６−キシレニルホスフェート）等が挙げられる。
これらの中でも、取扱い性や、効果の発現性がより顕著なことから、トリフェニルホスフェート（ＴＰＰ）などの芳香族リン酸エステルが好ましい。
Specific examples of the aromatic phosphate ester include triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, 1,3-phenylenebis (diphenyl phosphate), 1,3-phenylenebis (di-2,6-xylenyl phosphate) and the like.
Among these, aromatic phosphate esters such as triphenyl phosphate (TPP) are preferable because handleability and effect expression are more remarkable.
上記臭素化ポリブタジエン系難燃剤に対する芳香族リン酸エステルの配合量は、溶融混練物の流動性を向上させる機能が発揮され、かつ難燃性付与効果を阻害しない範囲であれば特に制約はないが、流動性向上剤が上記臭素化ポリブタジエン系難燃剤１００重量部に対して０．５〜５重量部配合されていることが好ましく、更に１〜４重量部配合されていることがより好ましい。 The blending amount of the aromatic phosphate with respect to the brominated polybutadiene-based flame retardant is not particularly limited as long as the function of improving the fluidity of the melt-kneaded product is exhibited and the effect of imparting flame retardancy is not impaired. The fluidity improver is preferably added in an amount of 0.5 to 5 parts by weight, more preferably 1 to 4 parts by weight, based on 100 parts by weight of the brominated polybutadiene flame retardant.
前記臭素化ポリブタジエン系難燃剤のほかに、本発明の目的、効果を妨げない範囲において、他の難燃剤を混合して使用することができる。他の難燃剤として、例えば、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−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−Ｆ−ビス（２，３−ジブロモ−２−メチルプロピルエーテル）)に代表される２，３−ジブロモ−２−メチルプロピル基を有する有機化合物、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−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−Ｆ−ビス（２，３−ジブロモプロピルエーテル）、トリス（２，３−ジブロモプロピル）イソシアヌレートおよびトリス（２，３−ジブロモプロピル）シアヌレートに代表される２，３−ジブロモプロピル基を有する有機化合物、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）イソシアヌレートに代表される臭素化イソシアヌレート、クレジルジ２，６−キシレニルホスフェート、三酸化アンチモン、五酸化二アンチモン、硫酸アンモニウム、スズ酸亜鉛、シアヌル酸、ペンタブロモトルエン、イソシアヌル酸、トリアリルイソシアヌレート、メラミンシアヌレート、メラミン、メラム、メレム等の窒素含有環状化合物、シリコーン系化合物、酸化ホウ素、ホウ酸亜鉛、硫化亜鉛などの無機化合物等が挙げられる。これらの化合物は単独又は２種以上を混合して使用できる。 In addition to the brominated polybutadiene-based flame retardant, other flame retardants can be mixed and used within a range not hindering the object and effects of the present invention. Other flame retardants include, for example, tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol-S-bis (2,3-dibromo-2-methylpropyl ether), An organic compound having a 2,3-dibromo-2-methylpropyl group represented by tetrabromobisphenol-F-bis (2,3-dibromo-2-methylpropyl ether)), tetrabromobisphenol-A-bis (2 , 3-dibromopropyl ether), tetrabromobisphenol-S-bis (2,3-dibromopropyl ether), tetrabromobisphenol-F-bis (2,3-dibromopropyl ether), tris (2,3-dibromopropyl) ) Isocyanurate and tris (2,3-dibromopropyl) silane Organic compounds having a 2,3-dibromopropyl group typified by annulate, mono (2,3,4-tribromobutyl) isocyanurate, di (2,3,4-tribromobutyl) isocyanurate, tris (2 , 3,4-tribromobutyl) isocyanurate, brominated isocyanurate, cresyl di 2,6-xylenyl phosphate, antimony trioxide, antimony pentoxide, ammonium sulfate, zinc stannate, cyanuric acid, pentabromo Examples thereof include nitrogen-containing cyclic compounds such as toluene, isocyanuric acid, triallyl isocyanurate, melamine cyanurate, melamine, melam, and melem, silicone compounds, inorganic compounds such as boron oxide, zinc borate, and zinc sulfide. These compounds can be used alone or in admixture of two or more.
さらに、上記難燃剤溶融混練物には、本発明の目的、効果を妨げない範囲において、ポリスチレン系樹脂やポリエチレン系樹脂、ポリプロピレン系樹脂、ポリエステル系樹脂などの熱可塑性樹脂を配合することができる。その配合量は、上記溶融混練物中に２０重量％以下とすることが好ましく、より好ましくは１０重量％、さらに好ましくは５重量％である。また、着色剤を配合しても良い。 Furthermore, a thermoplastic resin such as a polystyrene resin, a polyethylene resin, a polypropylene resin, or a polyester resin can be blended with the flame retardant melt-kneaded material within a range that does not interfere with the object and effect of the present invention. The blending amount is preferably 20% by weight or less in the melt-kneaded product, more preferably 10% by weight, and still more preferably 5% by weight. Moreover, you may mix | blend a coloring agent.
つぎに、本発明のポリスチレン系樹脂押出発泡体の製造方法について詳細に説明する。
本発明のポリスチレン系樹脂押出発泡体の製造方法は、ポリスチレン系樹脂と上記難燃剤溶融混練物と発泡剤を混練して得られる発泡性溶融樹脂組成物を押出して押出発泡体を製造する方法が採用される。
Below, the manufacturing method of the polystyrene-type resin extrusion foam of this invention is demonstrated in detail.
The method for producing a polystyrene resin extruded foam of the present invention is a method for producing an extruded foam by extruding a foamable molten resin composition obtained by kneading a polystyrene resin, the flame retardant melt-kneaded product and a foaming agent. Adopted.
具体例としては、ポリスチレン系樹脂、難燃剤溶融混練物、必要に応じて気泡調整剤やその他の添加剤を押出機に供給して、加熱、混練し、更に発泡剤を該押出機中に圧入し、混練して得られた発泡性ポリスチレン系樹脂溶融組成物を、例えば、フラットダイを通して高圧の押出機内より低圧域（通常は大気中）に押出して、発泡させると共に、該ダイの出口に配置された成形型〔平行あるいは入口から出口に向かって緩やかに拡大するよう設置された上下２枚のポリテトラフルオロエチレン樹脂等からなる板で構成されるもの（以下、ガイダーとも言う。）〕や成形ロール等の成形具を通過させることによって板状に成形し、板状のポリスチレン系樹脂押出発泡体（以下、単に押出発泡体ともいう。）を製造する方法が挙げられる。 Specific examples include polystyrene resin, flame retardant melt-kneaded product, and if necessary, supply of a bubble regulator and other additives to the extruder, heating and kneading, and press-fitting a foaming agent into the extruder. Then, the expandable polystyrene resin melt composition obtained by kneading is extruded through a flat die into a low pressure region (usually in the atmosphere) from the inside of a high pressure extruder and foamed, and disposed at the outlet of the die. Molded molds (comprised of plates made of two or more upper and lower polytetrafluoroethylene resins installed in parallel or gently so as to gradually expand from the entrance to the exit (hereinafter also referred to as guiders)) or molding A method of forming a plate-like polystyrene-based resin extruded foam (hereinafter also simply referred to as an extruded foam) by forming a plate by passing through a forming tool such as a roll can be mentioned.
本発明方法は上記板状押出発泡体の製造方法に限定されるものではなく、サーキュラーダイから押出された筒状の発泡体をシート状に切り開いて又は筒状の発泡体の内面を融着させてシート状押出発泡体とする方法、ストランド状に押出された発泡体を粒子状に切断して粒子状の押出発泡体とする方法、また、発泡剤を含む発泡性溶融樹脂組成物を水中に押出すなどして急冷して（発泡させない）粒子状に切断し、その後、発泡剤を含む発泡性樹脂粒子をスチームなどの加熱媒体により加熱することにより発泡させ粒子状の発泡体とする方法に適用できることはもちろんである。 The method of the present invention is not limited to the above-described method for producing a plate-like extruded foam, and the tubular foam extruded from a circular die is cut into a sheet or the inner surface of the tubular foam is fused. A sheet-like extruded foam, a strand-extruded foam cut into particles, and a particulate extruded foam, or a foamable molten resin composition containing a foaming agent in water A method in which the resin is rapidly cooled by extrusion or the like (not foamed) and cut into particles, and then the foamed resin particles containing the foaming agent are heated by a heating medium such as steam to form a particulate foam. Of course, it can be applied.
本発明の製造方法においては、難燃剤として上述した特定の難燃剤溶融混練物を用いる以外の基本的な製造方法は、従来公知の押出発泡体の製造方法を利用できる。 In the production method of the present invention, a conventionally known production method of an extruded foam can be used as a basic production method other than using the specific flame retardant melt-kneaded material described above as a flame retardant.
本発明において押出機に供給されるポリスチレン系樹脂としては、例えばポリスチレンやスチレンを主成分とするスチレン−アクリル酸共重合体、スチレン−アクリル酸メチル共重合体、スチレン−アクリル酸エチル共重合体、スチレン−メタクリル酸共重合体、スチレン−メタクリル酸メチル共重合体、スチレン−メタクリル酸エチル共重合体、スチレン−無水マレイン酸共重合体、スチレン−ポリフェニレンエーテル共重合体、スチレン−アクリロニトリル共重合体、アクリロニトリル−ブタジエン−スチレン共重合体、スチレン−メチルスチレン共重合体、スチレン−ジメチルスチレン共重合体、スチレン−エチルスチレン共重合体、スチレン−ジエチルスチレン共重合体等が挙げられる。上記スチレン系共重合体におけるスチレン単位成分含有量は５０モル％以上が好ましく、特に好ましくは８０モル％以上である。 Examples of the polystyrene-based resin supplied to the extruder in the present invention include styrene-acrylic acid copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer mainly containing polystyrene or styrene, Styrene-methacrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-polyphenylene ether copolymer, styrene-acrylonitrile copolymer, Examples include acrylonitrile-butadiene-styrene copolymer, styrene-methylstyrene copolymer, styrene-dimethylstyrene copolymer, styrene-ethylstyrene copolymer, and styrene-diethylstyrene copolymer. The styrene unit component content in the styrenic copolymer is preferably 50 mol% or more, particularly preferably 80 mol% or more.
上記ポリスチレン系樹脂としては、本発明の目的、効果が達成される範囲内において、その他の重合体を混合したものであってもよい。その他の重合体としては、ポリエステル樹脂、ポリエチレン系樹脂（エチレン単独重合体及びエチレン単位成分含有量が５０モル％以上のエチレン共重合体の群から選択される１種、或いは２種以上の混合物）、ポリプロピレン系樹脂（プロピレン単独重合体及びプロピレン単位成分含有量が５０モル％以上のプロピレン共重合体の群から選択される１種、或いは２種以上の混合物）、ポリフェニレンエーテル樹脂、スチレン−ブタジエン−スチレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体、スチレン−ブタジエン−スチレンブロック共重合体水添物、スチレン−イソプレン−スチレンブロック共重合体水添物、スチレン−エチレン共重合体等が挙げられ、これらの他の重合体は、ポリスチレン系樹脂中で５０重量％未満となるように、好ましくは３０重量％以下となるように、更に好ましくは１０重量％以下となるように、目的に応じて混合することができる。 As said polystyrene-type resin, what mixed the other polymer may be sufficient in the range in which the objective of this invention and an effect are achieved. Other polymers include polyester resins and polyethylene resins (one or a mixture of two or more selected from the group consisting of ethylene homopolymers and ethylene copolymers having an ethylene unit component content of 50 mol% or more). , Polypropylene resins (one or a mixture of two or more selected from the group of propylene homopolymers and propylene copolymers having a propylene unit component content of 50 mol% or more), polyphenylene ether resins, styrene-butadiene- Styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer hydrogenated product, styrene-isoprene-styrene block copolymer hydrogenated product, styrene-ethylene copolymer, etc. These other polymers are listed in polystyrene resins. As it will be less than an amount%, preferably such that 30 wt% or less, more preferably such that 10 wt% or less, can be mixed according to the purpose.
本発明においては、炭素数３〜５の飽和炭化水素（Ａ）と以下に示す他の発泡剤（Ｂ）とを含有する複合発泡剤を用いることが、背景技術に記載した観点から好ましい。 In this invention, it is preferable from the viewpoint described in background art to use the composite foaming agent containing C3-C5 saturated hydrocarbon (A) and the other foaming agent (B) shown below.
前記炭素数３〜５の飽和炭化水素（Ａ）としては、プロパン、ｎ−ブタン、ｉ−ブタン、ｎ−ペンタン、ｉ−ペンタン、シクロペンタン、ネオペンタンなどが挙げられる。
上記の飽和炭化水素（Ａ）は、単独又は２種以上混合して使用することができる。
前記飽和炭化水素（Ａ）の中では、発泡性の点からプロパン、ｎ−ブタン、ｉ−ブタンあるいはこれらの混合物が好ましい。また、発泡体の断熱性能の点からｎ−ブタン、ｉ−ブタンあるいはこれらの混合物が好ましく、特に好ましくはｉ−ブタンである。
Examples of the saturated hydrocarbon having 3 to 5 carbon atoms (A) include propane, n-butane, i-butane, n-pentane, i-pentane, cyclopentane, neopentane and the like.
Said saturated hydrocarbon (A) can be used individually or in mixture of 2 or more types.
Among the saturated hydrocarbons (A), propane, n-butane, i-butane or a mixture thereof is preferable from the viewpoint of foamability. Moreover, n-butane, i-butane or a mixture thereof is preferable from the viewpoint of the heat insulating performance of the foam, and i-butane is particularly preferable.
他の発泡剤（Ｂ）としては、有機系物理発泡剤、及び無機系物理発泡剤を用いることができる。
前記有機系物理発泡剤としては、例えば、ジメチルエーテル、ジエチルエーテル、エチルメチルエーテル、ジ−ｎ−ブチルエーテル、ジイソプロピルエーテルなどのエーテル類、メタノール、エタノール、プロピルアルコール、ｉ−プロピルアルコール、ブチルアルコール、ｉ−ブチルアルコール、ｔ−ブチルアルコールなどのアルコール類、蟻酸メチル、蟻酸エチル、蟻酸プロピル、蟻酸ブチルなどの蟻酸エステル類、塩化メチル、塩化エチルなどの塩化アルキル類などが挙げられる。また、オゾン破壊係数が０、かつ地球温暖化係数の小さいトランス−１，３，３，３−テトラフルオロプロペン、シス−１，３，３，３−テトラフルオロプロペン、１，１，１，２−テトラフルオロプロペンなどのフッ化不飽和炭化水素を用いることもできる。
前記無機系物理発泡剤としては、例えば水、二酸化炭素、窒素などが挙げられる。
上記の他の発泡剤（Ｂ）は、単独又は２種以上混合して使用することができる。
As another foaming agent (B), an organic physical foaming agent and an inorganic physical foaming agent can be used.
Examples of the organic physical foaming agent include ethers such as dimethyl ether, diethyl ether, ethyl methyl ether, di-n-butyl ether, diisopropyl ether, methanol, ethanol, propyl alcohol, i-propyl alcohol, butyl alcohol, i- Examples include alcohols such as butyl alcohol and t-butyl alcohol, formic acid esters such as methyl formate, ethyl formate, propyl formate, and butyl formate, and alkyl chlorides such as methyl chloride and ethyl chloride. In addition, trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene, 1,1,1,2 having a low ozone depletion coefficient and a low global warming potential Fluorinated unsaturated hydrocarbons such as tetrafluoropropene can also be used.
Examples of the inorganic physical foaming agent include water, carbon dioxide, nitrogen and the like.
Said other foaming agent (B) can be used individually or in mixture of 2 or more types.
前記他の発泡剤（Ｂ）の中では、発泡性、発泡体成形性などの点からは、塩化メチル、塩化エチル、ジメチルエーテル、ジエチルエーテル、エチルメチルエーテル、メタノール、エタノール、水、二酸化炭素が好ましい。 Among the other foaming agents (B), methyl chloride, ethyl chloride, dimethyl ether, diethyl ether, ethyl methyl ether, methanol, ethanol, water, and carbon dioxide are preferable from the viewpoint of foamability and foam moldability. .
水、二酸化炭素は、他の発泡剤と比べて、ポリスチレン系樹脂に対する可塑化効果が低いため、水、二酸化炭素を発泡剤として使用すると、押出時の圧力が高くなる傾向にある。一方、臭素化ポリブタジエン系難燃剤も、これまで難燃剤として使用されてきたＨＢＣＤに比べるとやはり可塑化効果が低く、押出時の圧力が高くなりやすいため、押出発泡体を製造することがさらに難しくなる。本発明の難燃剤溶融混練物は、臭素化ポリブタジエン系難燃剤を含むが特定のＭＦＲを示す流動性に優れるものである。そのため、上記発泡剤（Ｂ）が水及び／又は二酸化炭素を含む場合であっても、本発明の溶融混練物を難燃剤として配合することにより、ＨＢＣＤ使用時と同様な条件で、かつ安定して押出発泡体を製造することができる。 Since water and carbon dioxide have a lower plasticizing effect on the polystyrene-based resin than other foaming agents, when water or carbon dioxide is used as the foaming agent, the pressure during extrusion tends to increase. On the other hand, brominated polybutadiene flame retardants also have a lower plasticizing effect than HBCD that has been used as a flame retardant so far, and the pressure during extrusion tends to be high, making it more difficult to produce extruded foams. Become. The flame retardant melt-kneaded product of the present invention contains a brominated polybutadiene flame retardant, but is excellent in fluidity showing a specific MFR. Therefore, even when the foaming agent (B) contains water and / or carbon dioxide, by blending the melt-kneaded product of the present invention as a flame retardant, it is stable under the same conditions as when using HBCD. Thus, an extruded foam can be produced.
前記複合発泡剤においては、飽和炭化水素（Ａ）の配合割合が１０〜８０モル％であり、他の発泡剤（Ｂ）の配合割合が９０〜２０モル％〔但し、発泡剤（Ａ）と発泡剤（Ｂ）との合計量は１００モル％〕であることが好ましい。配合割合がこの範囲内の混合発泡剤を使用することにより、安全かつ安定的に高発泡倍率の押出発泡体の製造することができるようになると共に断熱性、難燃性に優れた押出発泡体を製造する上で好ましい。かかる観点から、飽和炭化水素（Ａ）３０〜７０モル％と他の発泡剤（Ｂ）７０〜３０モル％〔但し、発泡剤（Ａ）と発泡剤（Ｂ）との合計量は１００モル％〕とを含有する複合発泡剤がより好ましい。 In the composite foaming agent, the blending ratio of the saturated hydrocarbon (A) is 10 to 80 mol%, and the blending ratio of the other foaming agent (B) is 90 to 20 mol% [provided that the foaming agent (A) and The total amount with the foaming agent (B) is preferably 100 mol%]. By using a mixed foaming agent having a blending ratio within this range, an extruded foam having a high expansion ratio can be produced safely and stably, and at the same time, an extruded foam excellent in heat insulation and flame retardancy. Is preferable in manufacturing. From this point of view, saturated hydrocarbon (A) 30-70 mol% and other blowing agent (B) 70-30 mol% [however, the total amount of blowing agent (A) and blowing agent (B) is 100 mol% And a composite foaming agent containing
本発明における発泡剤の添加量は、発泡性溶融樹脂組成物１ｋｇ中に、０．５〜２．５モルとなるように添加することが好ましく、０．８〜２．０モルがより好ましい。 In the present invention, the amount of the foaming agent added is preferably 0.5 to 2.5 mol, more preferably 0.8 to 2.0 mol, in 1 kg of the foamable molten resin composition.
本発明においては、このように予め作製した前記難燃剤溶融混練物を難燃剤とし、これをポリスチレン系樹脂に任意の割合で混合し押出機に供給し、さらに発泡剤を供給してこれらを混練して押出発泡させることで、難燃性に優れ、かつ黒点、黄変に代表される外観の不具合のない良好な発泡体を得ることができる。
また、該難燃剤溶融混練物を用いることで、製造された押出発泡体や、その端材・スクラップを加熱溶融しリサイクル原料として再利用する際にもリサイクル原料の分子量の低下や黄変を抑制することができる。
In the present invention, the flame retardant melt kneaded material prepared in advance as described above is used as a flame retardant, and this is mixed with polystyrene resin at an arbitrary ratio, supplied to an extruder, and further supplied with a foaming agent to knead them. By extruding and foaming, it is possible to obtain a good foam that is excellent in flame retardancy and has no defects in appearance typified by black spots and yellowing.
In addition, by using the flame retardant melt-kneaded product, even when the manufactured extruded foam and its scraps and scrap are heated and melted and reused as a recycled material, the molecular weight and yellowing of the recycled material are suppressed. can do.
難燃剤溶融混練物の添加量は、所望の難燃性により適宜調整されるものであるが、押出発泡板にＪＩＳ Ａ９５１１の燃焼規格を満足するような高度な難燃性を付与するという観点からは、臭素化ポリブタジエン系難燃剤を含む難燃剤の配合量が押出機に投入されるポリスチレン系樹脂１００重量部に対し１〜１０重量部となるようにすることが好ましく、より好ましくは１．５〜７重量部である。さらに、上記範囲内であれば、難燃性に優れると共に、良好なリサイクル性を有する押出発泡体をより容易に製造可能となる。 The addition amount of the flame retardant melt-kneaded product is appropriately adjusted depending on the desired flame retardancy, but from the viewpoint of imparting high flame retardancy that satisfies the combustion standard of JIS A9511 to the extruded foamed plate. Is preferably 1 to 10 parts by weight, more preferably 1.5 parts by weight based on 100 parts by weight of the polystyrene resin to be introduced into the extruder. ~ 7 parts by weight. Furthermore, if it is in the said range, while being excellent in a flame retardance, it becomes possible to manufacture the extrusion foam which has favorable recyclability more easily.
本発明においては、上記難燃剤とともに、さらにジフェニルアルカン、ジフェニルアルケンから選ばれる少なくとも１種の添加剤を配合することで、得られる発泡体の酸素指数を向上させることができる。該添加剤は上記難燃剤１００重量部に対して、１〜２０重量部配合されることが好ましく、２〜１５重量部配合されることがより好ましい。 In this invention, the oxygen index of the foam obtained can be improved by mix | blending at least 1 sort (s) of additive chosen from diphenyl alkane and diphenyl alkene with the said flame retardant. The additive is preferably added in an amount of 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the flame retardant.
前記ジフェニルアルカンとしては具体的には、２，３−ジメチル−２，３−ジフェニルブタン、２，３−ジエチル−２，３−ジフェニルブタン、３，４−ジメチル−３，４−ジフェニルヘキサン、３，４−ジエチル−３，４−ジフェニルヘキサンが挙げられる。ジフェニルアルケンは具体的には、例えば、２，４−ジフェニル−４−メチル−１−ペンテン、２，４−ジフェニル−４−エチル−１−ペンテンが例示される。 Specific examples of the diphenylalkane include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, , 4-diethyl-3,4-diphenylhexane. Specific examples of the diphenylalkene include 2,4-diphenyl-4-methyl-1-pentene and 2,4-diphenyl-4-ethyl-1-pentene.
本発明の製造方法において、発泡性溶融樹脂組成物には、押出発泡体の平均気泡径を調整するために気泡調整剤を添加することができる。気泡調整剤としては、タルク、カオリン、マイカ、シリカ、炭酸カルシウム、硫酸バリウム、酸化チタン、クレー、酸化アルミニウム、ベントナイト、ケイソウ土等の無機物が例示される。また、本発明において該気泡調整剤は２種以上組合せて用いることもできる。前記各種の気泡調整剤の中で、得られる発泡体の気泡径の調整が容易で気泡径を小さくし易い等の理由でタルクが好適に用いられ、特に、粒子径の細かい平均粒径（光透過遠心沈降法による５０％粒径）が０．５〜７５μｍのタルクが好ましい。 In the production method of the present invention, a foam regulator can be added to the foamable molten resin composition in order to adjust the average cell diameter of the extruded foam. Examples of the air conditioner include inorganic substances such as talc, kaolin, mica, silica, calcium carbonate, barium sulfate, titanium oxide, clay, aluminum oxide, bentonite, and diatomaceous earth. Further, in the present invention, two or more kinds of the air bubble adjusting agents can be used in combination. Among the various bubble regulators, talc is preferably used because it is easy to adjust the bubble diameter of the foam obtained and to easily reduce the bubble diameter. In particular, the average particle diameter (light Talc having a 50% particle size (permeation centrifugal sedimentation method) of 0.5 to 75 μm is preferred.
該気泡調整剤の添加量は、ポリスチレン系樹脂１００重量部に対して０．０１〜７．５重量部、更に０．１〜５重量部の割合で添加されることが好ましい。 The amount of the air bubble regulator added is preferably 0.01 to 7.5 parts by weight and more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polystyrene resin.
本発明の製造方法においては、前記気泡調整剤、難燃剤以外にも、本発明の目的、効果を妨げない範囲において、グラファイト、ハイドロタルサイト、カーボンブラックやアルミニウム等の断熱性向上剤、着色剤、充填剤、滑剤等の各種添加剤を適宜添加することができる。尚、上記気泡調整剤等の各種添加剤は、ポリスチレン系樹脂などの熱可塑性樹脂を基材とするマスターバッチとして添加しても良い。 In the production method of the present invention, in addition to the above-mentioned bubble regulator and flame retardant, a heat insulation improver such as graphite, hydrotalcite, carbon black and aluminum, and a colorant, as long as the object and effect of the present invention are not hindered. Various additives such as fillers and lubricants can be appropriately added. In addition, you may add various additives, such as the said bubble regulator, as a masterbatch which uses thermoplastic resins, such as a polystyrene-type resin, as a base material.
本発明により得られる押出発泡体の密度は、優れた断熱性と機械的強度の観点から、２０〜６０ｋｇ／ｍ３、更に２２〜５０ｋｇ／ｍ３であることが好ましく、厚みは、５〜１５０ｍｍ、更に１５〜１００ｍｍであることが好ましい。 The density of the extruded foam obtained by the present invention is preferably 20 to 60 kg / m 3 , more preferably 22 to 50 kg / m 3 from the viewpoint of excellent heat insulation and mechanical strength, and the thickness is 5 to 150 mm. Furthermore, it is preferable that it is 15-100 mm.
本発明の方法によって製造されるポリスチレン系樹脂押出発泡体において、厚み方向の平均気泡径は、より高い断熱性を有する発泡体とする上で０．８ｍｍ以下、更に０．５ｍｍ以下であることが好ましい。尚、該気泡径が小さすぎる場合は、厚みが厚く、低見掛け密度の板状の押出発泡体を得ること自体が難しい。かかる観点から、厚み方向の平均気泡径は０．０５ｍｍ以上、更に０．０６ｍｍ以上、特に０．０７ｍｍ以上であることが好ましい。 In the polystyrene resin extruded foam produced by the method of the present invention, the average cell diameter in the thickness direction is 0.8 mm or less, and more preferably 0.5 mm or less in order to obtain a foam having higher heat insulating properties. preferable. When the bubble diameter is too small, it is difficult to obtain a plate-like extruded foam having a large thickness and a low apparent density. From this viewpoint, the average cell diameter in the thickness direction is preferably 0.05 mm or more, more preferably 0.06 mm or more, and particularly preferably 0.07 mm or more.
上記厚み方向の平均気泡径の測定方法は次のとおりである。まず、押出発泡体を幅方向に３等分し、分割した各測定用サンプルの幅方向中央部付近の幅方向垂直断面（押出発泡体の押出方向と直交する垂直断面）の顕微鏡拡大写真を得る。次いで、該拡大写真上において発泡体の厚み方向に沿って押出発泡体の全厚みに亘る直線を引き、その直線と交差する気泡の数を計数し、直線の長さ（当然のことながら、この長さは拡大写真上の直線の長さではなく、写真の拡大率を考慮した直線の長さを指す。）を計数された気泡の数で割ることによって、各直線上に存在する気泡の平均径Ｔｎ（直線の長さ／該直線と交差する気泡の数）を求め、求められた３箇所の平均径Ｔｎの算術平均値を厚み方向の平均気泡径Ｔ（ｍｍ）とする。なお、押出発泡体の全厚みが１枚の顕微鏡拡大写真に納まらない場合には、数枚に分けて撮影すればよい。 The method for measuring the average cell diameter in the thickness direction is as follows. First, the extruded foam is divided into three equal parts in the width direction, and a microscopic enlarged photograph of the widthwise vertical cross section (vertical cross section perpendicular to the extrusion direction of the extruded foam) of each divided measurement sample is obtained. . Next, on the enlarged photograph, a straight line is drawn over the entire thickness of the extruded foam along the thickness direction of the foam, and the number of bubbles crossing the straight line is counted. The length is not the length of the straight line on the enlarged photo, but the length of the straight line taking into account the magnification of the photo.) Dividing by the number of bubbles counted, the average of the bubbles present on each straight line The diameter Tn (the length of the straight line / the number of bubbles intersecting with the straight line) is determined, and the arithmetic average value of the three average diameters Tn thus determined is defined as the average bubble diameter T (mm) in the thickness direction. In addition, what is necessary is just to divide | segment and image | photograph several sheets, when the whole thickness of an extrusion foam does not fit in one microscope enlarged photograph.
本発明においては、前記押出発泡体を加熱融解して得られる再生ポリスチレン系樹脂組成物を、バージン原料のポリスチレン系樹脂、難燃性溶融混練物と共に押出機中にて加熱、混練し、更に発泡剤を該押出機中に圧入して添加し、混練して得られる発泡性溶融樹脂組成物を押出発泡することにより、押出発泡体を製造することができる。本発明の押出発泡体は、前記難燃性溶融混練物を難燃剤として用いて製造されたものであり、押出時加工時の熱安定性に優れているものであることから、その再生原料（再生ポリスチレン系樹脂組成物）は回収時における分子量低下、黄変の程度、黒点の発生が少ないものである。従って、該回収原料を用いることにより、前記押出発泡体を低コストで製造することができる。 In the present invention, the recycled polystyrene resin composition obtained by heating and melting the extruded foam is heated and kneaded in an extruder together with a virgin raw material polystyrene resin and a flame-retardant melt-kneaded product, and further foamed. An extruded foam can be produced by extrusion-foaming a foamable molten resin composition obtained by press-fitting and adding an agent into the extruder and kneading. The extruded foam of the present invention is produced using the flame retardant melt-kneaded product as a flame retardant, and is excellent in thermal stability during processing during extrusion. (Recycled polystyrene resin composition) has a low molecular weight at the time of recovery, a degree of yellowing, and a small amount of black spots. Therefore, the extruded foam can be produced at low cost by using the recovered raw material.
本発明の製造方法により得られたポリスチレン系樹脂押出発泡体は、建築物の壁、床、屋根等の断熱材や畳芯材等に好適に使用することができる。 The polystyrene resin extruded foam obtained by the production method of the present invention can be suitably used for heat insulating materials such as walls, floors and roofs of buildings, tatami core materials, and the like.
次に、実施例により本発明を更に詳細に説明する。但し、本発明は実施例により限定されるものではない。 Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.
実施例１〜４、比較例１〜３
（難燃剤溶融混練物の製造）
二軸押出機（内径４７ｍｍ、Ｌ／Ｄ＝４１）を用い、表３に示す配合条件・製造条件にて臭素化ポリブタジエン系難燃剤と熱安定剤、さらにポリ−１，４−ジイソプロピルベンゼン、トリフェニルホスフェートとを溶融混練し、ストランド状に押出しペレット状にカットすることにより、実施例１〜４及び比較例１〜３の難燃剤溶融混練物を製造した。得られた難燃剤溶融混練物の押出負荷、製造安定性、ＭＦＲ、着色性（１）、黒点の有無及び難燃剤溶融混練物をポリスチレン樹脂に配合したときの、黒点の発生状況、着色性（２）を評価した。その結果を表３に示す。
Examples 1-4, Comparative Examples 1-3
(Manufacture of flame retardant melt-kneaded product)
Using a twin-screw extruder (inner diameter 47 mm, L / D = 41), the brominated polybutadiene flame retardant and heat stabilizer, poly-1,4-diisopropylbenzene, tri The flame retardant melt-kneaded materials of Examples 1 to 4 and Comparative Examples 1 to 3 were manufactured by melt-kneading phenyl phosphate and extruding it into strands and cutting them into pellets. Extrusion load, production stability, MFR, colorability (1), presence or absence of black spots, and the occurrence of black spots when the flame retardant melt kneaded material is blended with polystyrene resin, colorability ( 2) was evaluated. The results are shown in Table 3.
臭素化ポリブタジエン系難燃剤としては、表１に示すものを用い、ポリ−１，４−ジイソプロピルベンゼン、トリフェニルホスフェートとしては表２に示すものを用いた。
なお、熱安定剤の配合量は、臭素化ポリブタジエン系難燃剤１００重量部に対して、下記（１）を１０重量部、（２）を５重量部、（３）を５重量部の合計２０重量部とした。
As the brominated polybutadiene flame retardant, those shown in Table 1 were used, and those shown in Table 2 were used as poly-1,4-diisopropylbenzene and triphenyl phosphate.
The blending amount of the heat stabilizer is 10 parts by weight of the following (1), 5 parts by weight of (2), and 5 parts by weight of (3) with respect to 100 parts by weight of the brominated polybutadiene flame retardant. Part by weight.
［熱安定剤］
（１）ノボラック型エポキシ樹脂系化合物：ＤＩＣ製、商品名「ＥＰＩＣＬＯＮ Ｎ６８０」
（２）ホスファイト系化合物：ＡＤＥＫＡ製、商品名「ＰＥＰ３６」（ビス（２，６−ジ−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）
（３）フェノール系化合物：ＢＡＳＦ製、商品名「Ｉｒｇａｎｏｘ１０１０」（ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］）
[Thermal stabilizer]
(1) Novolac type epoxy resin compound: manufactured by DIC, trade name “EPICLON N680”
(2) Phosphite compound: Product name “PEP36” (bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite) manufactured by ADEKA
(3) Phenol compound: manufactured by BASF, trade name “Irganox 1010” (pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate])
表３に示す難燃剤溶融混練物製造時の押出負荷、製造安定性、難燃剤溶融混練物のＭＦＲ、着色性（１）、黒点の有無及び難燃剤溶融混練物をポリスチレン系樹脂に配合したときの、黒点の発生状況、着色性（２）の評価方法は以下のとおりである。 When extruding load, production stability, MFR of flame retardant melt kneaded material, colorability (1), presence of black spots and flame retardant melt kneaded material shown in Table 3 when blended with polystyrene resin The evaluation method of the state of occurrence of black spots and colorability (2) is as follows.
［押出負荷］
押出負荷は、下記基準より評価した。
◎：押出機のスクリュー負荷が６０％未満
○：押出機のスクリュー負荷が６０〜７０％
×：押出機のスクリュー負荷が７０％を超える
※押出機のスクリュー負荷が１００％で押出機が停止する
[Extrusion load]
The extrusion load was evaluated according to the following criteria.
A: Extruder screw load is less than 60% B: Extruder screw load is 60-70%
X: Extruder screw load exceeds 70% * Extruder stops when the screw load of the extruder is 100%
［製造安定性］
難燃剤溶融混練物の製造安定性の評価は、下記評価基準により評価した。
○：安定して難燃剤溶融混練物が得られる
△：難燃剤溶融混練物は得られるが、ストランドを安定して引き取ることができない
[Manufacturing stability]
The production stability of the flame retardant melt-kneaded product was evaluated according to the following evaluation criteria.
○: A flame retardant melt-kneaded product can be stably obtained. Δ: A flame retardant melt-kneaded product can be obtained, but the strand cannot be stably taken up.
［ＭＦＲ］
難燃剤溶融混練物のＭＦＲは、ＪＩＳ Ｋ７２１０：１９９０の条件Ｈ（２００℃、５ｋｇ荷重）にて測定した。
[MFR]
The MFR of the flame retardant melt kneaded product was measured under the condition H (200 ° C., 5 kg load) of JIS K7210: 1990.
［着色性（１）］
難燃剤溶融混練物中の着色度合いは、次のように評価した。
１５０℃に加熱したヒートプレス機を用いて、難燃剤溶融混練物をプレス加工して、縦×横×厚み＝４０×４０×２ｍｍの板を作製した。分光式色差計（日本電色工業株式会社製ＳＥ−２０００）を用いてＡＳＴＭ Ｄ１９２５に基づき反射法にて該試験片のＹＩ値（イエローインデックス）を測定した。（ｎ＝５の平均値）
[Colorability (1)]
The degree of coloring in the flame retardant melt kneaded product was evaluated as follows.
Using a heat press machine heated to 150 ° C., the flame retardant melt-kneaded product was pressed to produce a plate of length × width × thickness = 40 × 40 × 2 mm. The YI value (yellow index) of the test piece was measured by a reflection method based on ASTM D1925 using a spectroscopic color difference meter (SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.). (Average value of n = 5)
［黒点の有無］
難燃剤溶融混練物中の黒点の有無は、次のように評価した。
１５０℃に加熱したヒートプレス機を用いて、難燃剤溶融混練物をプレス加工して、縦×横×厚み＝４０×４０×２ｍｍの板を作製した。次に、作製した板に含まれる黒点の数を計測した。（ｎ＝５の平均値）
[Existence of black spots]
The presence or absence of black spots in the flame retardant melt-kneaded product was evaluated as follows.
Using a heat press machine heated to 150 ° C., the flame retardant melt-kneaded product was pressed to produce a plate of length × width × thickness = 40 × 40 × 2 mm. Next, the number of black spots contained in the produced plate was measured. (Average value of n = 5)
［難燃剤溶融混練物をポリスチレン系樹脂に配合した後の評価］
内径４７ｍｍ、Ｌ/Ｄ＝４１の二軸押出機にポリスチレン１００重量部、臭素化ポリブタジエン系難燃剤の配合量が２重量部となるように難燃剤溶融混練物を供給し、最高温度２２０℃で溶融混練し、その溶融樹脂を吐出量６０ｋｇ／ｈｒでストランド状に押出し、ペレット状にカットした。
[Evaluation after blending flame retardant melt-kneaded material with polystyrene resin]
A flame retardant melt-kneaded product is supplied to a twin screw extruder with an inner diameter of 47 mm and L / D = 41 so that the blending amount of 100 parts by weight of polystyrene and 2 parts by weight of brominated polybutadiene flame retardant is at a maximum temperature of 220 ° C. The molten resin was melted and kneaded, and the molten resin was extruded into strands at a discharge rate of 60 kg / hr and cut into pellets.
［黒点の発生状況］
前記ペレットを１８０℃に加熱したヒートプレス機を用いて、プレス加工して、縦×横×厚み＝４０×４０×２ｍｍの板を作製した。次に、作製した板に含まれる黒点の数を計測した。（ｎ＝５の平均値）
[Spot generation status]
The pellets were pressed using a heat press machine heated to 180 ° C. to produce a plate of length × width × thickness = 40 × 40 × 2 mm. Next, the number of black spots contained in the produced plate was measured. (Average value of n = 5)
［着色性（２）］
前記ペレットを１８０℃に加熱したヒートプレス機を用いて、プレス加工して、縦×横×厚み＝４０×４０×２ｍｍの板を作製した。分光式色差計（日本電色工業株式会社製ＳＥ−２０００）を用いてＡＳＴＭ Ｄ１９２５に基づき反射法にて該試験片のＹＩ値（イエローインデックス）を測定した。（ｎ＝５の平均値）
[Colorability (2)]
The pellets were pressed using a heat press machine heated to 180 ° C. to produce a plate of length × width × thickness = 40 × 40 × 2 mm. The YI value (yellow index) of the test piece was measured by a reflection method based on ASTM D1925 using a spectroscopic color difference meter (SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.). (Average value of n = 5)
表３から、本発明の実施例１〜４の難燃剤溶融混練物１〜４は、熱安定剤と共にポリ−１，４−ジイソプロピルベンゼンを流動性向上剤として含有し、かつそのＭＦＲが所定の範囲内（ＪＩＳ Ｋ７２１０：１９９０の条件ＨにおけるＭＦＲが２〜３０ｇ／１０分）にあることから、スクリュー負荷が小さく製造安定性に優れ、しかも黒点の発生や変色が抑制されたものであることが分かる。またこの難燃剤溶融混練物を原料ポリスチレン系樹脂に配合しても、たとえば図１に示されるように、黒点の発生や変色が生じていないことがわかる。
これに対して、ポリ−１，４−ジイソプロピルベンゼンを含有されておらず、かつ前記ＭＦＲが本発明の範囲外（０．７ｇ／１０分）である、比較例１〜２の難燃剤溶融混練物５〜６を原料ポリスチレン系樹脂に配合した場合にも黒点の発生や着色が著しいことがわかる。また、比較例３のように、ポリ−１，４−ジイソプロピルベンゼンが含有されていても、そのＭＦＲが本発明の範囲外（６３ｇ／１０分）である、難燃剤溶融混練物７はスクリュー負荷は小さく、黒点が含まれていない混練物得られるが、製造安定性に劣り、しかも、この難燃剤溶融混練物を原料ポリスチレン系樹脂に配合させると、図２に示されるように、黒点の発生が著しく実使用に耐え得るものでないことがわかる。
From Table 3, the flame retardant melt kneaded materials 1 to 4 of Examples 1 to 4 of the present invention contain poly-1,4-diisopropylbenzene as a fluidity improver together with a heat stabilizer, and the MFR is predetermined. Since it is within the range (MFR in condition H of JIS K7210: 1990 is 2 to 30 g / 10 min), the screw load is small, the production stability is excellent, and the generation and discoloration of black spots are suppressed. I understand. Moreover, even if this flame retardant melt-kneaded material is blended with the raw polystyrene resin, it can be seen that, for example, as shown in FIG. 1, no black spots are generated or discolored.
On the other hand, the flame retardant melt kneading of Comparative Examples 1-2, which does not contain poly-1,4-diisopropylbenzene and the MFR is outside the scope of the present invention (0.7 g / 10 min). It can be seen that the occurrence of black spots and coloring are remarkable even when the products 5 to 6 are blended with the raw polystyrene resin. Further, as in Comparative Example 3, even when poly-1,4-diisopropylbenzene is contained, the flame retardant melt kneaded product 7 whose MFR is outside the scope of the present invention (63 g / 10 min) is a screw load. Is small and does not contain black spots, but is inferior in production stability, and when this flame retardant melt-kneaded material is blended with the raw polystyrene resin, as shown in FIG. It can be seen that is not remarkably resistant to actual use.
（実施例５〜１０、比較例４〜７）
（ポリスチレン系樹脂押出発泡体の製造）
実施例５〜１０及び比較例４〜７の押出発泡体を得るために、以下に示す装置及び材料を用いた。
(Examples 5-10, Comparative Examples 4-7)
(Manufacture of polystyrene resin extruded foam)
In order to obtain the extruded foams of Examples 5 to 10 and Comparative Examples 4 to 7, the following apparatuses and materials were used.
［押出装置］
内径６５ｍｍの第１押出機と内径９０ｍｍの第２押出機が直列に連結されており、発泡剤注入口が第１押出機の終端付近に設けられており、横断面が長方形の樹脂排出口（ダイリップ）を備えたフラットダイが第２押出機の出口に連結され、第２押出機の樹脂出口にはこれと平行するように設置された上下一対のポリテトラフルオロエチレン樹脂からなる板により構成された賦形装置（ガイダー）が付設された装置を用いた。
[Extruding equipment]
A first extruder having an inner diameter of 65 mm and a second extruder having an inner diameter of 90 mm are connected in series, a foaming agent inlet is provided near the end of the first extruder, and a resin outlet having a rectangular cross section ( A flat die having a die lip) is connected to the outlet of the second extruder, and the resin outlet of the second extruder is constituted by a plate made of a pair of upper and lower polytetrafluoroethylene resins installed so as to be parallel thereto. A device provided with an additional shaping device (guider) was used.
［ポリスチレン系樹脂］
（１）ＰＳ１：ポリスチレン（重量平分子量２７万）
（２）ＲＰＳ１：再生ポリスチレン系樹脂組成物
実施例５で得られたポリスチレン系樹脂押出発泡板を破砕し、その破砕物を内径９０ｍｍ、Ｌ／Ｄ＝５０の単軸押出機に供給して最高温度２２０℃で混練し、その溶融樹脂を吐出量２５０ｋｇ／ｈｒでストランド状に押出し、ペレット状にカットすることにより再生ＰＳ樹脂組成物のペレット（ＲＰＳ１）を得た。
[Polystyrene resin]
(1) PS1: polystyrene (weight average molecular weight 270,000)
(2) RPS1: Recycled polystyrene resin composition The polystyrene resin extruded foam plate obtained in Example 5 was crushed, and the crushed material was supplied to a single screw extruder having an inner diameter of 90 mm and L / D = 50. Kneaded at a temperature of 220 ° C., the molten resin was extruded into a strand at a discharge rate of 250 kg / hr, and cut into a pellet to obtain a recycled PS resin composition pellet (RPS1).
［難燃剤］
難燃剤としては、上記表３に示す難燃剤溶融混練物を用いた。
なお、比較例４では難燃剤溶融混練物１と同一組成のドライブレンド品を難燃剤として用いた。
[Flame retardants]
As the flame retardant, the flame retardant melt kneaded material shown in Table 3 above was used.
In Comparative Example 4, a dry blend product having the same composition as the flame retardant melt-kneaded product 1 was used as the flame retardant.
［気泡調整剤］
タルク（松村産業製、ハイフィラー＃１２）
[Bubble conditioner]
Talc (Matsumura Sangyo, high filler # 12)
前記押出機に表４、５中に示すそれぞれの配合量となるように樹脂、難燃剤及び気泡調整剤を、前記第１押出機に供給し、２２０℃まで加熱し、これらを混練し、第１押出機の先端付近に設けられた発泡剤注入口から表中に示す配合組成の物理発泡剤を表中に示す割合で溶融物に供給し混練した発泡性樹脂溶融物を、続く第２押出機に供給して樹脂温度を表中に示すような発泡適性温度（表中では発泡樹脂温度と表記した。この発泡温度は押出機とダイとの接合部の位置で測定された発泡性樹脂溶融物の温度である）に調整した後、吐出量７０ｋｇ／ｈｒでダイリップからガイダー内に押出し、押出発泡体を製造した。 A resin, a flame retardant, and a bubble regulator are supplied to the first extruder so as to have the blending amounts shown in Tables 4 and 5 to the extruder, heated to 220 ° C., kneaded, The foaming resin melt obtained by supplying and kneading the physical foaming agent having the blending composition shown in the table to the melt from the foaming agent injection port provided in the vicinity of the front end of the one extruder, and then kneading the melt is then added to the second extrusion. The resin temperature is supplied to the machine, and the foaming temperature is shown in the table (in the table, it is expressed as the foaming resin temperature. This foaming temperature is measured by the position of the joint between the extruder and the die. It was extruded into a guider from a die lip at a discharge rate of 70 kg / hr to produce an extruded foam.
実施例５〜１０及び比較例４〜７で得られたポリスチレン系樹脂押出発泡体の、見掛け密度、厚み、独立気泡率、難燃性、黒点の数、着色性（３）、重量平均分子量、再生樹脂の重量平均分子量及び着色性（４）を表４〜５に示す。 Apparent density, thickness, closed cell ratio, flame retardancy, number of sunspots, colorability (3), weight average molecular weight of the polystyrene resin extruded foams obtained in Examples 5 to 10 and Comparative Examples 4 to 7 Tables 4 to 5 show the weight average molecular weight and colorability (4) of the recycled resin.
表４〜５に示す押出発泡体の各種物性の測定方法及び評価方法は以下のとおりである。 The measurement methods and evaluation methods for various physical properties of the extruded foams shown in Tables 4 to 5 are as follows.
（見掛け密度）
押出発泡体の見掛け密度は、次のようにして求めた。得られた押出発泡体の幅方向の中央部、両端部付近から５０×５０×４０ｍｍの立方体の試料を各々切り出して重量を測定し、該重量を体積で割算することにより夫々の試料の見掛け密度を求め、それらの算術平均値を当該見掛け密度とした。
(Apparent density)
The apparent density of the extruded foam was determined as follows. A sample of a cube of 50 × 50 × 40 mm is cut out from each of the center and both ends in the width direction of the obtained extruded foam, the weight is measured, and the weight is divided by the volume so that the appearance of each sample is apparent. The density was determined, and the arithmetic average value thereof was taken as the apparent density.
（厚み）
押出発泡体の幅方向中央部付近において、等間隔に５点の厚みを測定し、それらの測定値の算術平均値を押出発泡体の厚み（ｍｍ）とした。
(Thickness)
In the vicinity of the central portion in the width direction of the extruded foam, thicknesses at five points were measured at equal intervals, and the arithmetic average value of these measured values was defined as the thickness (mm) of the extruded foam.
（独立気泡率）
押出発泡体の独立気泡率は、次のようにして求めた。まず、押出発泡体を幅方向に５等分し、それらの中央部付近から２５ｍｍ×２５ｍｍ×２０ｍｍのサイズに成形表皮を持たないカットサンプル（計５個）を切り出した。次に、ＡＳＴＭ−Ｄ２８５６−７０の手順Ｃに従って、各カットサンプルの真の体積Ｖｘを測定し、下記（１）式により独立気泡率Ｓ（％）を計算し、それら計算値の算術平均値を押出発泡体の独立気泡率とした。なお、測定装置として東芝ベックマン株式会社の空気比較式比重計９３０型を使用した。
(Closed cell rate)
The closed cell ratio of the extruded foam was determined as follows. First, the extruded foam was divided into 5 equal parts in the width direction, and cut samples (total of 5 pieces) having no molded skin with a size of 25 mm × 25 mm × 20 mm were cut out from the vicinity of the central part thereof. Next, according to the procedure C of ASTM-D2856-70, the true volume Vx of each cut sample is measured, the closed cell ratio S (%) is calculated by the following formula (1), and the arithmetic average value of these calculated values is calculated. The closed cell ratio of the extruded foam was used. In addition, Toshiba Beckman Co., Ltd. air comparison type hydrometer 930 type was used as a measuring apparatus.
Ｓ（％）＝（Ｖｘ−Ｗ／ρ）×１００／（Ｖａ−Ｗ／ρ） （１）
ただし、Ｖｘ：上記空気比較式比重計による測定により求められるカットサンプルの真の体積（ｃｍ３）（押出発泡体のカットサンプルを構成する樹脂組成物の容積と、カットサンプル内の独立気泡部分の気泡全容積との和に相当する。）
Ｖａ：測定に使用されたカットサンプルの外形寸法から算出されたカットサンプルの見掛け上の体積（ｃｍ３）
Ｗ：測定に使用されたカットサンプル全重量（ｇ）
ρ：押出発泡体を構成する樹脂組成物の密度（ｇ／ｃｍ３）
S (%) = (Vx−W / ρ) × 100 / (Va−W / ρ) (1)
However, Vx: the true volume (cm 3 ) of the cut sample obtained by measurement with the above air comparison hydrometer (the volume of the resin composition constituting the cut sample of the extruded foam and the closed cell portion in the cut sample (This corresponds to the sum of the total volume of bubbles.)
Va: Apparent volume of the cut sample calculated from the outer dimensions of the cut sample used for measurement (cm 3 )
W: Total weight of cut sample used for measurement (g)
ρ: density of the resin composition constituting the extruded foam (g / cm 3 )
（難燃性評価−ＪＩＳ Ａ９５１１）
製造直後の押出発泡体を気温２３℃、相対湿度５０％の部屋に移し、その部屋で４週間放置した後、押出発泡体から試験片を無作為に５個切り出して（Ｎ＝５）、ＪＩＳ Ａ９５１１（２００６Ｒ）の５．１３．１「測定方法Ａ」に基づいて燃焼性を測定し、５個の試験片の平均燃焼時間により、押出発泡体の難燃性を評価した。
(Flame retardancy evaluation-JIS A9511)
The extruded foam immediately after production was transferred to a room with an air temperature of 23 ° C. and a relative humidity of 50%, left in that room for 4 weeks, and then five test pieces were randomly cut out from the extruded foam (N = 5). Combustibility was measured based on 5.13.1 “Measurement method A” of A9511 (2006R), and the flame retardancy of the extruded foam was evaluated based on the average burning time of five test pieces.
（難燃性評価−ＬＯＩ−酸素指数）
製造直後の押出発泡体を気温２３℃、相対湿度５０％の部屋に移し、その部屋で４週間放置した後、押出発泡体から試験片を切り出し、ＪＩＳ Ｋ７２０１−２：２００７に準拠して測定し、難燃性を評価した。点火器の熱源の種類は、液化石油ガス（ＬＰＧ）を使用し、点火手順はＡ法を使用し、試験片を試験機内の所定の位置に自立させて行った。試験場所の温度は２３℃、湿度５０％で行った。
(Flame retardant evaluation-LOI-Oxygen index)
The extruded foam immediately after production was transferred to a room with an air temperature of 23 ° C. and a relative humidity of 50%, left in that room for 4 weeks, and then a test piece was cut out from the extruded foam and measured according to JIS K7201-2: 2007. The flame retardancy was evaluated. The type of the heat source of the igniter was liquefied petroleum gas (LPG), the ignition procedure was method A, and the test piece was performed independently at a predetermined position in the tester. The test place temperature was 23 ° C. and humidity 50%.
（押出発泡体の重量平均分子量，再生樹脂の重量平均分子量）
それぞれの実施例にて得られた発泡体、及び発泡体をリサイクル用の押出機にて溶融しリペレット化したものの重量平均分子量を測定した。リペレットは、得られた発泡体を押出機に供給可能な大きさに破砕し、その破砕物を内径９０ｍｍ、Ｌ／Ｄ＝５０の単軸押出機に供給して最高温度２２０℃で溶融混練し、その溶融樹脂を吐出量２５０ｋｇ／ｈｒでストランド状に押出し、ペレット状にカットすることによって行なった。
重量平均分子量は、発泡体１０ｍｇ又はスチレン系樹脂１０ｍｇをＴＨＦ（テトラヒドロフラン）１０ｍＬに溶解させ、ＧＰＣ（ゲルパーミエーションクロマトグラフ）法により測定し、標準ポリスチレンで校正した値である。上記ＧＰＣ分析は、使用機器：東ソー（株）製、ＳＣ−８０２０型、カラム：昭和電工（株）製、Ｓｈｏｄｅｘ ＡＣ−８０Ｍ ２本を直列に連結、カラム温度：４０℃、流速：１．０ｍｌ／分、検出器：東ソー（株）製、紫外可視光検出機ＵＶ−８０２０型、を用いて測定した。
(Weight average molecular weight of extruded foam, weight average molecular weight of recycled resin)
The weight average molecular weights of the foams obtained in the respective examples and those obtained by melting and re-pelletizing the foams with a recycle extruder were measured. The re-pellet is crushed into a size that can be supplied to an extruder, and the crushed material is supplied to a single-screw extruder having an inner diameter of 90 mm and L / D = 50, and melt kneaded at a maximum temperature of 220 ° C. The molten resin was extruded into strands at a discharge rate of 250 kg / hr and cut into pellets.
The weight average molecular weight is a value obtained by dissolving 10 mg of foam or 10 mg of styrene resin in 10 mL of THF (tetrahydrofuran), measuring by GPC (gel permeation chromatography) method, and calibrating with standard polystyrene. The above GPC analysis was performed using equipment: Tosoh Corporation, SC-8020 type, column: Showa Denko KK, Shodex AC-80M, connected in series, column temperature: 40 ° C., flow rate: 1.0 ml. / Min. Detector: Measured using an ultraviolet-visible light detector UV-8020 manufactured by Tosoh Corporation.
（黒点の個数）
得られた発泡板の流れ方向に対し垂直に切断した断面部において、黒点の数を数えた。断面部の観察は任意に５箇所で測定し、その合計数を黒点の個数とした。
(Number of sunspots)
In the cross section cut perpendicular to the flow direction of the obtained foamed plate, the number of black spots was counted. Observation of the cross section was arbitrarily measured at five locations, and the total number was taken as the number of black spots.
（着色性（３））
押出発泡体の黄変度を外観により測定した。
○：着色していない
×：着色がみられる
(Colorability (3))
The degree of yellowing of the extruded foam was measured by appearance.
○: Not colored ×: Colored
［着色性（４）］
再生樹脂の黄色度を前記着色性（１）と同じ基準により評価した。まず、１８０℃に加熱したヒートプレス機を用いて、再生樹脂をプレス加工して、縦×横×厚み＝４０×４０×２ｍｍの板状の試験片を作製した。分光式色差計（日本電色工業株式会社製ＳＥ−２０００）を用いてＡＳＴＭ Ｄ１９２５に基づき反射法にて該試験片のＹＩ値（イエローインデックス）を測定した（ｎ＝５）。
[Colorability (4)]
The yellowness of the recycled resin was evaluated according to the same criteria as the colorability (1). First, using a heat press machine heated to 180 ° C., the recycled resin was pressed to prepare a plate-shaped test piece of length × width × thickness = 40 × 40 × 2 mm. The YI value (yellow index) of the test piece was measured by a reflection method based on ASTM D1925 using a spectroscopic color difference meter (SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.) (n = 5).
実施例５〜１０の結果は、本発明方法によれば、難燃剤溶融混練物１〜４を用いたことから、ＪＩＳ規格による燃焼試験が極めて良好であり、かつ十分な酸素指数（具体的にはＬＯＩ値：２６．０〜２６．５）を有する高度な難燃性を有する発泡体を得ることができ、しかもこの発泡体は押出加工時の熱安定性に優れ、黒点の発生がなく、また基材樹脂であるポリスチレン系樹脂の分解による分子量の低下や黄変を抑制された、リサイクル特性に優れたポリスチレン系樹脂押出発泡体であることを示している。 The results of Examples 5 to 10 show that according to the method of the present invention, flame retardant melt-kneaded materials 1 to 4 were used, so that the combustion test according to JIS standards was extremely good and a sufficient oxygen index (specifically, Can obtain a highly flame-retardant foam having a LOI value of 26.0 to 26.5), and this foam is excellent in thermal stability during extrusion processing and has no black spots. Moreover, it shows that it is a polystyrene resin extruded foam excellent in recycling characteristics in which a decrease in molecular weight and yellowing due to decomposition of the polystyrene resin as a base resin are suppressed.
比較例４は、難燃剤溶融混練物１の代わりにこれと同一組成のドライブレンド品を難燃剤とした例である。この比較例４の発泡体は、高度な難燃性を示すが、黒点が著しく発生し、高い熱安定性を兼備することができない。 Comparative Example 4 is an example in which a dry blend product having the same composition as that of the flame retardant melt kneaded material 1 is used as a flame retardant. The foam of Comparative Example 4 exhibits a high degree of flame retardancy, but has a marked black spot and cannot have high thermal stability.
さらに、比較例５〜６は、ポリ−１，４−ジイソプロピルベンゼンを含有していない難燃剤溶融混練物５〜６を用いた例である。この比較例５〜６で得られる発泡体はＪＩＳ規格による燃焼試験の値が極めて悪く（３．５，４．０）、また、酸素指数（ＬＯＩ）も低く（２５．５，２５．０）、難燃性の改善がみられない。また、これらの押出発泡体には黒点が著しく発生し、また変色が著しく、更には、再生樹脂の着色性（４）が極めて悪く、高い熱安定性を兼備することができない。 Further, Comparative Examples 5 to 6 are examples using flame retardant melt kneaded materials 5 to 6 not containing poly-1,4-diisopropylbenzene. The foams obtained in Comparative Examples 5 to 6 have extremely poor combustion test values according to JIS standards (3.5, 4.0) and low oxygen index (LOI) (25.5, 25.0). There is no improvement in flame retardancy. Further, these extruded foams are markedly black spots, discolored remarkably, and the colorability (4) of the recycled resin is extremely poor, so that high heat stability cannot be achieved.
比較例７は、ポリ−１，４−ジイソプロピルベンゼンが含有されていても、そのＭＦＲが本発明の範囲外（６３ｇ／１０分）の難燃剤溶融混練物７を用いた例である。この比較例７で得られる発泡体は、ＪＩＳ規格による燃焼試験は１．３と良好であるが、酸素指数ＬＯＩが２５となり、難燃性の改善がそれほどみられない。しかも、この発泡体は比較例５〜６と同様に黒点が著しく発生し、また変色が著しく、熱安定性に劣るものであった。 The comparative example 7 is an example using the flame retardant melt kneaded material 7 whose MFR is outside the range of the present invention (63 g / 10 min) even when poly-1,4-diisopropylbenzene is contained. The foam obtained in Comparative Example 7 is as good as 1.3 in the combustion test according to JIS standard, but the oxygen index LOI is 25, and the flame retardancy is not so much improved. In addition, this foam had markedly black spots as in Comparative Examples 5 to 6, and the discoloration was remarkable, resulting in poor thermal stability.
Claims (5)
該熱安定剤の配合量が該臭素化ポリブタジエン系難燃剤１００重量部に対して５〜３５重量部であり、該溶融混練物のＪＩＳ Ｋ７２１０：１９９０の条件Ｈにおけるメルトフローレイトが２〜３０ｇ／１０分であることを特徴とする難燃剤溶融混練物。 A melt-kneaded product of a brominated polybutadiene flame retardant, poly-1,4-diisopropylbenzene and a heat stabilizer,
The blending amount of the heat stabilizer is 5 to 35 parts by weight with respect to 100 parts by weight of the brominated polybutadiene flame retardant, and the melt flow rate of the melt-kneaded product under the condition H of JIS K7210: 1990 is 2 to 30 g / A flame retardant melt kneaded product characterized by being 10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013131128A JP6099495B2 (en) | 2013-06-21 | 2013-06-21 | Flame retardant melt kneaded material and method for producing polystyrene resin extruded foam using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013131128A JP6099495B2 (en) | 2013-06-21 | 2013-06-21 | Flame retardant melt kneaded material and method for producing polystyrene resin extruded foam using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015004019A JP2015004019A (en) | 2015-01-08 |
| JP6099495B2 true JP6099495B2 (en) | 2017-03-22 |
Family
ID=52300174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013131128A Active JP6099495B2 (en) | 2013-06-21 | 2013-06-21 | Flame retardant melt kneaded material and method for producing polystyrene resin extruded foam using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6099495B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3070118B1 (en) | 2013-11-14 | 2020-02-26 | Kaneka Corporation | Extruded styrenic resin foam and method for manufacturing same |
| JP6500619B2 (en) * | 2015-06-12 | 2019-04-17 | 株式会社ジェイエスピー | Expandable composite resin particles |
| JP6588245B2 (en) * | 2015-06-15 | 2019-10-09 | 株式会社ジェイエスピー | Method for producing polystyrene resin foam |
| CN107418047A (en) * | 2017-06-02 | 2017-12-01 | 中山康诺德新材料有限公司 | A kind of High glow wire halogen-free flame retardant polyolefin composition and preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007058736A1 (en) * | 2005-11-12 | 2007-05-24 | Dow Global Technologies Inc. | Brominated butadiene/vinyl aromatic copolymers, blends of such copolymers with a vinyl aromatic polymer, and polymeric foams formed from such blends |
-
2013
- 2013-06-21 JP JP2013131128A patent/JP6099495B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015004019A (en) | 2015-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6113576B2 (en) | Method for producing extruded polystyrene resin foam | |
| JP6099495B2 (en) | Flame retardant melt kneaded material and method for producing polystyrene resin extruded foam using the same | |
| JP6133150B2 (en) | Method for producing polystyrene resin foam using flame retardant melt kneaded material | |
| JP5787358B2 (en) | Method for producing extruded polystyrene resin foam | |
| JP6141099B2 (en) | Method for producing extruded polystyrene resin foam | |
| JP6389591B2 (en) | Method for producing polystyrene resin foam | |
| JP5943730B2 (en) | Method for producing extruded polystyrene resin foam | |
| JP6061742B2 (en) | Method for producing extruded polystyrene resin foam | |
| JP2014208736A5 (en) | ||
| JP6173038B2 (en) | Method for producing extruded polystyrene resin foam | |
| JP6257023B2 (en) | Method for producing polystyrene resin extruded foam plate, and polystyrene resin extruded foam plate | |
| JP6381223B2 (en) | Polystyrene resin foam | |
| JP6335367B2 (en) | Method for producing polystyrene resin extruded foam plate | |
| JP6185413B2 (en) | Method for producing polystyrene resin foam | |
| JP6091305B2 (en) | Flame retardant melt kneaded material and method for producing polystyrene resin extruded foam using the same | |
| JP6192106B2 (en) | Method for producing polystyrene resin extruded foam plate | |
| JP6061780B2 (en) | Method for producing extruded polystyrene resin foam | |
| JP6395214B2 (en) | Polystyrene resin foam | |
| JP6588245B2 (en) | Method for producing polystyrene resin foam | |
| JP6335368B2 (en) | Method for producing polystyrene resin extruded foam plate | |
| JP6366149B2 (en) | Polystyrene resin extrusion foam board | |
| JP6128940B2 (en) | Method for producing polystyrene resin extruded foam plate | |
| JP6512580B2 (en) | Method for producing polystyrene resin foam board | |
| JP6541555B2 (en) | Method for producing polystyrene resin foam board | |
| JP6124484B2 (en) | Method for producing extruded polystyrene resin foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160310 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20161222 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170106 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170117 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170214 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170221 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6099495 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |