JP6091305B2 - 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
- JP6091305B2 JP6091305B2 JP2013086041A JP2013086041A JP6091305B2 JP 6091305 B2 JP6091305 B2 JP 6091305B2 JP 2013086041 A JP2013086041 A JP 2013086041A JP 2013086041 A JP2013086041 A JP 2013086041A JP 6091305 B2 JP6091305 B2 JP 6091305B2
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- JP
- Japan
- Prior art keywords
- flame retardant
- melt
- polystyrene
- resin
- extruded foam
- 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.)
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- 239000006260 foam Substances 0.000 title claims description 113
- 239000003063 flame retardant Substances 0.000 title claims description 108
- 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 101
- 238000004519 manufacturing process Methods 0.000 title claims description 45
- 229920005990 polystyrene resin Polymers 0.000 title claims description 40
- 239000000463 material Substances 0.000 title claims description 24
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 53
- 229920005989 resin Polymers 0.000 claims description 48
- 239000011347 resin Substances 0.000 claims description 48
- -1 phosphorus compound Chemical class 0.000 claims description 47
- 239000004088 foaming agent Substances 0.000 claims description 37
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 37
- 238000001125 extrusion Methods 0.000 claims description 35
- 239000012760 heat stabilizer Substances 0.000 claims description 24
- 239000004793 Polystyrene Substances 0.000 claims description 23
- 229920002223 polystyrene Polymers 0.000 claims description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 15
- 238000004898 kneading Methods 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 239000011342 resin composition Substances 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 10
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 239000004604 Blowing Agent Substances 0.000 claims description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 4
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 4
- 229960003750 ethyl chloride Drugs 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 3
- 229960004132 diethyl ether Drugs 0.000 claims description 3
- 229940077445 dimethyl ether Drugs 0.000 claims description 3
- 229920000578 graft copolymer Polymers 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 229920005604 random copolymer Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000004581 coalescence Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 238000002845 discoloration Methods 0.000 description 13
- 238000005187 foaming Methods 0.000 description 11
- 238000004383 yellowing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 238000010128 melt processing Methods 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
- 235000021317 phosphate Nutrition 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
- 238000012545 processing Methods 0.000 description 7
- 239000005062 Polybutadiene Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 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
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment 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
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 3
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 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 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000002485 combustion reaction Methods 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
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003017 thermal stabilizer Substances 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
- 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 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
- 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
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 206010027146 Melanoderma Diseases 0.000 description 2
- 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 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-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
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011810 insulating material 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
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- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
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- 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
- 238000007493 shaping process Methods 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 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 2
- 239000013585 weight reducing agent Substances 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
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- 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
- PYJRTMLRHSXSLS-UHFFFAOYSA-N (3,4-diethyl-4-phenylhexan-3-yl)benzene Chemical compound C=1C=CC=CC=1C(CC)(CC)C(CC)(CC)C1=CC=CC=C1 PYJRTMLRHSXSLS-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
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- 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
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- 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
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- 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
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-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
- SPGYFDAUXPEDEC-UHFFFAOYSA-N 3-chloropropyl octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCl SPGYFDAUXPEDEC-UHFFFAOYSA-N 0.000 description 1
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- 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
- 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
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- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-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
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- 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
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 235000012211 aluminium silicate Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 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
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- RAYIMXZLSRHMTK-UHFFFAOYSA-N bis(2,3-dibromopropyl) 2,3-dichloropropyl phosphate Chemical compound ClCC(Cl)COP(=O)(OCC(Br)CBr)OCC(Br)CBr RAYIMXZLSRHMTK-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
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
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- 239000004927 clay Substances 0.000 description 1
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- 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
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
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- 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
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 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
- 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
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-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
- 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
- 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
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 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
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000000178 monomer Substances 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 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 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 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
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- PDEFQWNXOUGDJR-UHFFFAOYSA-M sodium;2,2-dichloropropanoate Chemical compound [Na+].CC(Cl)(Cl)C([O-])=O PDEFQWNXOUGDJR-UHFFFAOYSA-M 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
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229960001147 triclofos Drugs 0.000 description 1
- JZZBTMVTLBHJHL-UHFFFAOYSA-N tris(2,3-dichloropropyl) phosphate Chemical compound ClCC(Cl)COP(=O)(OCC(Cl)CCl)OCC(Cl)CCl JZZBTMVTLBHJHL-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-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
- LKOCAGKMEUHYBV-UHFFFAOYSA-N tris(3-bromo-3-chloropropyl) phosphate Chemical compound ClC(Br)CCOP(=O)(OCCC(Cl)Br)OCCC(Cl)Br LKOCAGKMEUHYBV-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
- 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
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (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であって、建築物の壁、床、屋根等の断熱材や畳芯材等に好適に使用され主に板状に形成さ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. , A novel flame retardant melt-kneaded product excellent in production stability, and a polystyrene resin extruded foam excellent in flame retardancy and recyclability using this as a flame retardant. The present invention relates to a method for producing a polystyrene-based resin extruded foam that is suitably used for a heat insulating material such as a roof, a tatami core material, and the like and is mainly formed in a plate shape.
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、押出機のダイ出口に連結された賦形装置により板状に賦形して、高厚みのポリスチレン系樹脂押出発泡体（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 is shaped into a plate shape by a shaping apparatus connected to the die outlet of the extruder, to obtain a high-thickness polystyrene-based extruded resin foam (hereinafter also referred to as extruded foam or foam). The method 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 (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に代表されるポリスチレン−臭素化ブタジエン共重合体などの臭素化ブタジエンポリマー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 butadiene polymer type such as a polystyrene-brominated butadiene copolymer represented by Patent Document 1 has been proposed.
また、臭素化ブタジエンポリマータイプの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）。 Also, in order to improve the thermal stability of brominated butadiene polymer type flame retardants, flame retardants containing alkyl phosphite and / or epoxy compounds in brominated butadiene homopolymers or brominated styrene / butadiene block copolymers are used. A method has also been proposed (for example, Patent Document 2).
しかしながら、特許文献１の臭素化ブタジエンポリマータイプの難燃剤は、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 butadiene polymer type flame retardant disclosed in Patent Document 1 can impart excellent flame retardancy to the foam, but is inferior in thermal stability at the time of extrusion processing, resulting in foaming. There was a problem that black spots and discoloration occurred in the body.
また、特許文献２においては、上記臭素化ブタジエンポリマータイプの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 butadiene polymer 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, it is at the time of an extrusion process. The thermal stability is slightly improved.
しかし、特許文献２の難燃剤は、臭素化ブタジエンポリマータイプの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、難燃剤である臭素化ブタジエンポリマーの熱安定性がそれほど改善されず、加熱により変色や黒点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完全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 dry blending a brominated butadiene polymer type flame retardant with an alkyl phosphite or epoxy compound as a heat stabilizer, extrusion foaming in a continuously stable state. It was difficult to manufacture the body.
In addition, in this dry blend method, the above components are not uniformly mixed, so the function of the added heat stabilizer is not sufficiently exhibited, so the thermal stability of the brominated butadiene polymer as a flame retardant is not improved so much. In some cases, discoloration or black spots may occur due to heating. 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 completely suppress molecular weight reduction and yellowing due to decomposition of the resin.
このため、臭素化ブタジエンポリマータイプの難燃剤を用いて、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 have brominated butadiene polymer type flame retardants and do not have black spots or discoloration and are excellent in flame retardancy. At present, no such 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 actual 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. A novel flame retardant melt-kneaded product that can suppress lowering and yellowing and can impart high flame retardancy to an extruded foam, and a method for producing a polystyrene-based resin extruded foam using the flame retardant melt-kneaded product Providing it is an issue.
本発明のポリスチレン系樹脂押出発泡体の製造方法は、以下のことを特徴としている。
＜１＞ポリスチレン系樹脂、難燃剤及び発泡剤を押出機に供給し、これらを押出機にて混練してな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において、難燃剤が、臭素化ブタジエン系重合体を含む難燃剤と熱安定剤との溶融混練物であって、該溶融混練物が、さらにリン酸エステル及びリン酸塩から選ばれる少なくとも１種以上のリン系化合物からなる流動性向上剤を含有し、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分である難燃剤溶融混練物である。
＜２＞前記発泡剤が、（Ａ）炭素数３〜５の飽和炭化水素１０〜８０モル％と、（Ｂ）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、及び二酸化炭素の中から選択される１種又は２種以上の発泡剤９０〜２０モル％〔但し、発泡剤（Ａ）と発泡剤（Ｂ）との合計量は１００モル％〕からなる。
＜３＞前記発泡剤（Ｂ）が、水及び／又は二酸化炭素を含む。
＜４＞前記流動性向上剤が前記難燃剤１００重量部に対して３〜１５重量部配合されている。
＜５＞前記難燃剤溶融混練物は２００℃未満で溶融混練されたものである。
＜６＞前記流動性向上剤が、芳香族リン酸エステルである。
＜７＞前記臭素化ブタジエン系重合体が、臭素化ブタジエン成分単位とスチレン系単量体成分単位とを含む共重合体であって、該共重合体がブロック共重合体、ランダム共重合体又はグラフト共重合体である。
＜８＞前記熱安定剤が、臭素化されたエポキシ系化合物、ノボラック型エポキシ系化合物、ヒンダードフェノール系化合物、ヒンダードアミン系化合物及びホスファイト系化合物から選ばれる１種又は２種以上の熱安定剤である。
＜９＞前記難燃剤溶融混練物がペレット化されている。
Method for producing a port polystyrene resin extruded foam of the present invention is characterized by the following.
<1> In a method for producing an extruded foam by extruding a foamable molten resin composition obtained by supplying a polystyrene-based resin, a flame retardant and a foaming agent to an extruder and kneading them with the extruder. A melt-kneaded product of a flame retardant containing a brominated butadiene-based polymer and a heat stabilizer, the melt-kneaded product further comprising at least one phosphorus compound selected from a phosphate ester and a phosphate salt And a flame retardant melt-kneaded material having a melt flow rate of 2 to 30 g / 10 minutes under the condition H of JIS K7210: 1990 .
<2> The blowing agent is (A) 10 to 80 mol% of a saturated hydrocarbon having 3 to 5 carbon atoms, and (B) methyl chloride, ethyl chloride, dimethyl ether, diethyl ether, ethyl methyl ether, methanol, ethanol, water , And 90 to 20 mol% of one or more blowing agents selected from carbon dioxide (however, the total amount of the blowing agent (A) and the blowing agent (B) is 100 mol%) .
<3> The foaming agent (B) contains water and / or carbon dioxide .
<4> 3 to 15 parts by weight of the fluidity improver is blended with respect to 100 parts by weight of the flame retardant .
<5> The flame retardant melt-kneaded product is melt-kneaded at less than 200 ° C.
<6> The fluidity improver is an aromatic phosphate .
<7> The brominated butadiene-based polymer is a copolymer including a brominated butadiene component unit and a styrene monomer component unit, and the copolymer is a block copolymer, a random copolymer, or It is a graft copolymer .
<8> The heat stabilizer is one or more heat stabilizers selected from brominated epoxy compounds, novolak epoxy compounds, hindered phenol compounds, hindered amine compounds, and phosphite compounds. It is .
<9> The flame retardant melt-kneaded product is pelletized .
本発明に係る新規な難燃剤溶融混練物は、臭素化ブタジエン系重合体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、熱安定剤が臭素化ブタジエン系重合体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ブタジエン系重合体を安定化させ、黒点の発生や変色を抑制、防止することができ、かつ、燃焼時には臭素化ブタジエン系重合体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、特定のリン系化合物からなる流動性向上剤を含有し、そのメルトフローレートが特定範囲にあることから、溶融混練時の流動性が高く、低い加工温度でも、安定して臭素化ブタジエン系重合体を含む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、特定のリン系化合物は、臭素化ブタジエン系共重合体の優れた難燃性付与効果を阻害することがないため、安定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。 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 butadiene polymer and a heat stabilizer, the melt-kneaded product is supplied to the extruder as a flame retardant. By producing extruded foam, the thermal stabilizer acts effectively on the brominated butadiene polymer to stabilize the brominated butadiene polymer at the extrusion processing temperature, thereby generating black spots and discoloration. In addition, the brominated butadiene polymer can be effectively decomposed at the time of combustion, and high flame retardancy can be imparted to the extruded foam. Further, this flame retardant melt-kneaded product contains a fluidity improver composed of a specific phosphorus compound, and its melt flow rate is in a specific range, so that the fluidity during melt-kneading is high, even at low processing temperatures. Since the flame retardant containing a stable brominated butadiene polymer and the heat stabilizer are melt-kneaded, it is possible to more reliably suppress and prevent the generation of black spots and discoloration in the process of producing extruded foam. Furthermore, the specific phosphorus compound does not hinder the excellent flame retardancy imparting effect of the brominated butadiene copolymer, and stably imparts high flame retardancy to the extruded foam. be able to.
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、臭素化ブタジエン系重合体を含む難燃剤と熱安定剤との溶融混練物であって、該溶融混練物が、さらにリン酸エステル及びリン酸塩から選択される１以上のリン系化合物からなる流動性向上剤を含有し、ＪＩＳ Ｋ７２１０：１９９０の条件Ｈにおけるメルトフローレイトが２〜３０ｇ／１０分の範囲に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 a flame retardant containing a brominated butadiene polymer and a heat stabilizer, and the melt kneaded product is further selected from a phosphate ester and a phosphate. And a fluidity improver comprising at least one phosphorus compound and having a melt flow rate in the range of 2 to 30 g / 10 min under the condition H of JIS K7210: 1990.
上記したように、臭素化ブタジエン系重合体は、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、臭素化ブタジエン系重合体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ブタジエン系重合体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 butadiene-based polymer exhibits an excellent effect of imparting flame retardancy 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 butadiene-based polymer 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 were various problems such as cross-linking of unsaturated bonds that could cause gelation of the brominated butadiene-based polymer and generation of black spots.
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ブタジエン系重合体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 can be considered, but discoloration and coloration can be achieved by simply blending the heat stabilizer into the brominated butadiene polymer by the dry blend method. 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、臭素化ブタジエン系重合体と熱安定剤をドライブレンド法ではなく、臭素化ブタジエン系重合体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、溶融混練物中に黒点が発生せず、かつ溶融混練物が著しく変色しない加工温度条件で臭素化ブタジエン系重合体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 solve such problems, the present inventors firstly used a brominated butadiene polymer and a heat stabilizer in the production of an 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, a flame retardant melt-kneaded product is obtained by melt-kneading a brominated butadiene polymer and a heat stabilizer under processing temperature conditions in which no black spots are generated in the melt-kneaded product and the melt-kneaded product is not significantly discolored. When an extruded foam using a polystyrene-based resin as a base resin was used as a flame retardant, it was found that generation of black spots and discoloration of the extruded foam could 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、臭素化ブタジエン系重合体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最高温度が２００℃未満となるように溶融混練を試みたところ、臭素化ブタジエン系重合体の流動性が著しく悪く、押出機の負荷が高まったり、過度の剪断発熱が発生したりして、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、特定のリン系化合物からなる流動性向上剤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 generation and discoloration of black spots, the melt processing temperature of the brominated butadiene polymer and the thermal stabilizer is preferably set to a lower temperature in the extrudable temperature range. However, when low temperature, specifically, melt kneading was attempted so that the maximum temperature during extrusion was less than 200 ° C., the fluidity of the brominated butadiene polymer was remarkably poor, and the load on the extruder increased. It has been found that a desired melt-kneaded product cannot be obtained due to excessive shearing heat generation. Therefore, as a result of further investigation, unexpectedly, when a flow improver composed of a specific phosphorus compound is blended and melt-kneaded, it can be manufactured easily and stably even if the melt processing temperature is lowered. It was found that a flame retardant melt-kneaded material that is possible and that has suppressed black spot generation and discoloration in itself was 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ブタジエン系重合体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。 In the present invention, the brominated butadiene polymer 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.
一般に、難燃剤として使用される臭素化ブタジエン系重合体は、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 general, the brominated butadiene polymer 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
臭素化ブタジエン系重合体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、臭素化ブタジエン系重合体は、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、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 a brominated butadiene polymer as a flame retardant for a polystyrene resin, considering the compatibility with the polystyrene resin, the brominated butadiene polymer is a block copolymer containing a styrene monomer component unit, A random copolymer or a graft copolymer is preferable, and a block copolymer of a polystyrene-based polymer block and a brominated polybutadiene block is more preferable.
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、臭素化ブタジエン系重合体中の臭素含有率は、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 butadiene-based polymer 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.
ポリスチレン系樹脂中への分散性などを考慮すると、臭素化ブタジエン系重合体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℃、１００ｓｅｃ−１における溶融粘度は４０００〜８０００Ｐａ・ｓ程度である。 Considering dispersibility in polystyrene resin, the weight average molecular weight of the brominated butadiene polymer is preferably about 1.0 × 10 5 to 2.0 × 10 5 in terms of polystyrene. The melt viscosity at 100 ° C. and 100 sec −1 is about 4000 to 8000 Pa · s.
一般に、代表的な臭素化ブタジエン系重合体であるポリスチレン−臭素化ポリブタジエ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 polystyrene-brominated polybutadiene block copolymer which is a typical brominated butadiene-based polymer can be represented by the following general formula.
このようなポリスチレン−臭素化ポリブタジエンブロック共重合体は、たとえばポリスチレン−ポリブタジエ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 polystyrene-brominated polybutadiene block copolymer is produced, for example, by brominating a polystyrene-polybutadiene 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、流動性向上剤として、リン酸エステル及びリン酸塩から選ばれる少なくとも１種以上のリン系化合物を用いるが、かかるリン系化合物は、臭素化ブタジエン系重合体に対する可塑化効果が高く、臭素化ブタジエン系重合体の流動性を高める。
このため、臭素化ブタジエン系重合体に流動性向上剤を配合させると、溶融加工時に臭素化ブタジエン系重合体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、安定性に優れた難燃剤溶融混練物を簡便に製造することができる。
In the present invention, as the fluidity improver, at least one or more phosphorus compounds selected from phosphoric acid esters and phosphates are used. Such phosphorus compounds have a high plasticizing effect on brominated butadiene polymers. Increases the fluidity of brominated butadiene polymers.
For this reason, when a fluidity improver is added to the brominated butadiene polymer, the viscosity of the brominated butadiene polymer is reduced during melt processing, so the load on the extruder is reduced and the melt processing temperature is low. However, it is possible to easily produce a flame retardant melt-kneaded product having excellent stability.
また、上記リン系化合物は、また酸化防止能にも優れていることから、溶融加工時あるいは押出加工時において、臭素化ブタジエン系重合体の熱劣化をさらに抑制する作用を有し、押出発泡体を製造する過程でも、黒点の発生や変色のない良好な押出発泡体を与えることが容易となる。さらに上記リン系化合物は、臭素化ブタジエン系重合体が有する優れた難燃性を阻害することがないことから、難燃性に優れる押出発泡体を得ることができる。 Further, since the above phosphorus compound is also excellent in antioxidant ability, it has an action of further suppressing thermal deterioration of the brominated butadiene polymer at the time of melt processing or extrusion processing. Even in the process of manufacturing, it becomes easy to give a good extruded foam without generation of black spots or discoloration. Furthermore, since the phosphorus compound does not inhibit the excellent flame retardancy of the brominated butadiene polymer, an extruded foam having excellent flame retardancy can be obtained.
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）等の芳香族リン酸エステル、トリオクチルホスフェート、トリブトキシエチルホスフェート、トリクロロエチルホスフェート、トリス（２−クロロプロピル）ホスフェート、トリス（２，３−ジクロロプロピル）ホスフェート、トリス（２，３−ジブロモプロピル）ホスフェート、トリス（ブロモクロロプロピル）ホスフェート、ビス（２，３−ジブロモプロピル）−２，３−ジクロロプロピルホスフェート、ビス（クロロプロピル）モノオクチルホスフェート等の脂肪族リン酸エステル等が挙げられる。
また、リン酸塩の具体例としては、リン酸水素二アンモニウム、リン酸二水素アンモニウム等が挙げられる。
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 phosphate ester include triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, 1,3-phenylene bis (diphenyl phosphate), 1, Aromatic phosphate esters such as 3-phenylenebis (di-2,6-xylenyl phosphate), trioctyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (2-chloropropyl) phosphate, tris (2, 3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (bromochloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate , Bis aliphatic phosphate esters such as (chloropropyl) monooctyl phosphate, and the like.
Specific examples of the phosphate include diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
Among these, aromatic phosphate esters such as triphenyl phosphate (TPP) are preferable because handleability and effect expression are more remarkable.
前記難燃剤溶融混練物の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。難燃剤溶融混練物のＭＦＲが２〜３０ｇ／１０分となるように上記流動性向上剤を臭素化ブタジエン系重合体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することができる。そのため、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、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。さらに、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。 The melt flow rate (MFR) of the flame retardant melt-kneaded material under JIS K7210: 1990 condition H (200 ° C., 5 kg load) is in the range of 2-30 g / 10 minutes, preferably 5-30 g / 10 minutes, more preferably 5 to 20 g / 10 minutes. By adding the above fluidity improver to the brominated butadiene polymer and melt-kneading so that the MFR of the flame retardant melt-kneaded product is 2 to 30 g / 10 minutes, black spots are generated in the melt-kneaded product. In addition, discoloration of the melt-kneaded product itself can be suppressed. Therefore, by adding the flame retardant melt-kneaded product to a thermoplastic resin such as polystyrene as a flame retardant and extruding it, it is possible to impart high flame retardancy to the thermoplastic resin and heating during the extrusion process. Even underneath, generation of black spots and discoloration of the thermoplastic resin can be effectively suppressed. Furthermore, the melt-kneaded product can be efficiently and stably produced with a high discharge rate.
上記臭素化ブタジエン系重合体に対するリン系化合物からなる流動性向上剤の配合量は、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ブタジエン系重合体１００重量部に対して３〜１５重量部配合されていることが好ましく、更に５〜１０重量部配合されていることがより好ましい。 The blending amount of the fluidity improver composed of a phosphorus compound with respect to the brominated butadiene polymer is particularly within the range where the function of improving the fluidity of the melt-kneaded product is exhibited and the flame retardancy imparting effect is not hindered. Although there are no restrictions, it is preferable that the fluidity improver is blended in an amount of 3 to 15 parts by weight, more preferably 5 to 10 parts by weight, based on 100 parts by weight of the brominated butadiene polymer. .
溶融混練時の温度は、臭素化ブタジエン系重合体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最高温度は低いほど好ましく、概ね２００℃未満、好ましくは１９５℃以下、より好ましくは１９０℃以下とする。一方、上記観点からは、溶融混練時の温度の下限は特に制限されることはないが、臭素化ブタジエン系重合体と熱安定剤、さらには流動性向上剤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℃以上とすることがより好ましく、１６０℃以上とすることがさらに好ましい。
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 temperature at the time of melt-kneading is preferably as the maximum temperature at the time of melt-kneading is lower in order to effectively suppress the liberation of bromine from the brominated butadiene-based polymer, generally less than 200 ° C, preferably 195 ° C or less, more Preferably it shall be 190 degrees C or less. On the other hand, from the above viewpoint, the lower limit of the temperature at the time of melt-kneading is not particularly limited, but in order to stably melt-knead the brominated butadiene polymer, the thermal stabilizer, and further the fluidity improver. Is preferably about 140 ° C. or higher, more preferably 150 ° C. or higher, and still more preferably 160 ° 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.
難燃剤溶融混練物には、熱安定剤が配合される。
熱安定剤としては、臭素化されたエポキシ系化合物、ノボラック型エポキシ系化合物、ヒンダードフェノール系化合物、ヒンダードアミン系化合物、ホスファイト系化合物から選択される１又は２以上の熱安定剤が挙げられる。
A heat stabilizer is blended in the flame retardant melt kneaded product.
Examples of the heat stabilizer include one or more heat stabilizers selected from brominated epoxy compounds, novolak epoxy compounds, hindered phenol compounds, hindered amine compounds, and phosphite compounds.
臭素化されたエポキシ系化合物やノボラック型エポキシ系化合物としては、たとえばＩＣＬ−ＩＰ製Ｆ２２００ＨＭ、ＤＩＣ製ＥＰＩＣＬＯＮシリーズ、ＨＵＮＴＵＭＡＮ製Ａｒａｌｄａｉｔｅ ＥＣＮ１２８０等を挙げることができる。 Examples of brominated epoxy compounds and novolak epoxy compounds include ICL-IP F2200HM, DIC EPICLON series, HUNTUMAN Araldaite ECN1280, and the like.
ヒンダードフェノール系化合物としては、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］等が挙げられる。
これらは、単独又は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 hindered phenol compound 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-tert-butyl-4-hydroxyphenyl) propinate] methane, 2,2-methylenebis (4-methyl-6-tert-butylphenol), 1,6-hexanediol -Bis [3- (3,5-di-t-butyl-4-droxyphenyl) propionate] and the like.
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.
前記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−テトラメチルピレ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−ペイタメチル−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。これらのうちでも、押出安定性、難燃性の点から、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）−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 the hindered amine compound include 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, or 4-hydroxy-1- Octyloxy-2,2,6,6-tetramethylpyridine aliphatic or aromatic carboxylic acid ester, 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- -Piperidinyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-paytamethyl-4-piperidinyl) -1,2,3,4-butanetetracarboxylate, etc. Can be mentioned.
You may use these individually or in combination of 2 or more types. Among these, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, or bis (from the point of extrusion stability and flame retardancy) 2,2,6,6-tetramethyl-4-piperidinyl) sebacate is preferred.
ホスファイト系化合物としては、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（２，４−ジ−ｔ−ブチルフェニル）ペンタエリストールジホスファイト、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（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、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、トリスデシルホスファイトなどがあげられる。これらは、単独又は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、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリストールジホスファイト又はビス（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 compound include tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, and bis (2,6 -Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) -4,4'-butylidene-bis ( 2-t-butyl-5-methylphenyl) diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bisstearyl pentaerythritol diphosphite, mono (dinonylphenyl) mono-p-nonylphenyl phosphite, tris (mono Nonylphenyl) phosphite, tetraalkyl (C = 12- 6) -4,4′-isopropylidene- (bisphenyl) diphosphite, hexatridecyl-1,1,3-tris (3-tert-butyl-6-methyl-4oxyphenyl) -3-methylpropane triphosphite , Diphenylisodecyl phosphite, trisdecyl phosphite and the like. You may use these individually or in combination of 2 or more types. Among these, from the viewpoint of extrusion stability, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite or bis (2,6-di-t-butyl-4-methylphenyl) penta Erythritol diphosphite is preferred.
上記熱安定剤の合計配合量としては、前記難燃剤１００重量部に対して、概ね５〜３５重量部が好ましく、より好ましくは１０〜３０重量部である。 As a total compounding quantity of the said heat stabilizer, 5-35 weight part is preferable with respect to 100 weight part of said flame retardants, More preferably, it is 10-30 weight part.
前記臭素化ブタジエン系重合体のほかに、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 butadiene-based polymer, other flame retardants can be mixed and used as long as the objects and effects of the present invention are not impaired. 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発泡する押出発泡体の製法が採用される。
Below, the manufacturing method of the polystyrene-type resin extrusion foam of this invention is demonstrated in detail.
The manufacturing method of the polystyrene resin extruded foam of the present invention employs a method of manufacturing an extruded foam that extrudes and foams a foamable molten resin composition obtained by kneading a polystyrene resin, the flame retardant melt-kneaded product, and the foaming agent. Is done.
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、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、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、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。
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。
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 foamable 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 the high pressure extruder and foamed, and a molding die disposed at the outlet of the die Molding of parallel plates or plates composed of two upper and lower polytetrafluoroethylene resins (hereinafter also referred to as guiders) installed so as to expand gently from the entrance to the exit. A method of forming a polystyrene resin extruded foam (hereinafter also simply referred to as an extruded foam) by forming a plate by passing the tool is used.
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.
上記ポリスチレン系樹脂としては、発泡性や成形性の観点から、その溶融粘度（２００℃、剪断速度１００ｓｅｃ−１の条件下）が５００〜２０００Ｐａ・ｓ程度のものを用いることが好ましく、より好ましくは６００〜１８００Ｐａ・ｓ、さらに好ましくは７００〜１５００Ｐａ・ｓである。 As said polystyrene resin, it is preferable to use the thing whose melt viscosity (200 degreeC and the conditions of shear rate 100sec- 1 ) is about 500-2000 Pa.s from a foamable or moldable viewpoint, More preferably 600 to 1800 Pa · s, more preferably 700 to 1500 Pa · s.
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、臭素化ブタジエン系重合体も、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、臭素化ブタジエン系重合体を含むが特定の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 butadiene-based polymers also have a lower plasticizing effect than HBCD, which has been used as a flame retardant, 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 butadiene-based polymer but has excellent 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、臭素化ブタジエン系重合体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 such that the blending amount of the flame retardant containing the brominated butadiene polymer is 1 to 10 parts by weight with respect to 100 parts by weight of the polystyrene resin charged into the extruder, more preferably 1.5. ~ 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、ポリアルキルベンゼ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 diphenylalkane, diphenylalkene, and polyalkylbenzene 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.
前記ジフェエ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、ポリアルキレンベンゼンは具体的には、ポリ−１，４−ジイソプロピルベンゼンが例示される。 Specific examples of the diphenylenyl alkane include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, and 3,4-dimethyl-3,4-diphenylhexane. 3,4-diethyl-3,4-diphenylhexane. Specific examples of diphenylalkene include 2,4-diphenyl-4-methyl-1-pentene, 2,4-diphenyl-4-ethyl-1-pentene, and polyalkylenebenzene. , 4-diisopropylbenzene.
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.
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１〜６、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・製造条件にて難燃剤と熱安定剤、さらに流動性向上剤とを溶融混練し、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１〜６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製造安定性、ＭＦＲ、黒点の発生の有無、着色性等を評価した。その結果を表３に示す。
Examples 1-6, Comparative Examples 1-3
(Manufacture of flame retardant melt-kneaded product)
Using a twin-screw extruder (inner diameter 47 mm, L / D = 41), the flame retardant, heat stabilizer, and fluidity improver are melt-kneaded under the blending conditions and production conditions shown in Table 3 and extruded into a strand. The flame retardant melt kneaded materials of Examples 1 to 6 and Comparative Examples 1 to 3 were manufactured by cutting into pellets. The resulting flame retardant melt-kneaded product was evaluated for production stability, MFR, presence / absence of black spots, colorability, and the like. The results are shown in Table 3.
難燃剤としては、下記の熱安定剤を含有する表１に示すものを用い、流動性向上剤としては表２に示すものを用いた。
なお、熱安定剤の配合量は、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 flame retardant, those shown in Table 1 containing the following heat stabilizer were used, and as the fluidity improver, those shown in Table 2 were used.
The blending amount of the heat stabilizer was 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 flame retardant. .
[熱安定剤]
（１）ノボラック型エポキシ系化合物：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）ヒンダード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］）
[Heat stabilizer]
(1) Novolac-type epoxy compound: 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) Hindered phenol-based 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の製造安定性、黒点の発生の有無、着色性評価方法は以下のとおりである。 The production stability of the flame retardant melt-kneaded material shown in Table 3, the presence / absence of black spots, and the coloring evaluation method are as follows.
［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。
◎：特に安定して、難燃剤溶融混練物が得られる
○：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、吐出量が安定しない
×：押出機の負荷が大きいため、スクリューが停止しやすく、難燃剤溶融混練物が安定して得られない
[Manufacturing stability]
The production stability of the flame retardant melt-kneaded product was evaluated according to the following evaluation criteria.
A: A flame retardant melt-kneaded product can be obtained particularly stably. O: A flame retardant melt-kneaded product can be obtained stably. Δ: A flame retardant melt-kneaded product can be obtained, but the discharge amount is not stable. Because of the large load, the screw is easy to stop and the flame retardant melt kneaded material cannot be obtained stably
［ＭＦＲ］
難燃剤溶融混練物のＭＦＲは、ＪＩＳ Ｋ７２１０：１９９０の条件Ｈ（２００℃、５ｋｇ加重）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.
［黒点］
難燃剤溶融混練物中の黒点の発生状況は、次のように評価した。
１８０℃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計測し、下記の基準で評価した。
○：黒点数０個
△：黒点数１〜１９個
×：黒点数２０個以上
[Spots]
The occurrence of black spots in the flame retardant melt-kneaded product was evaluated as follows.
Using a heat press machine heated to 180 ° 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 and evaluated according to the following criteria.
○: Number of black spots △: Number of black spots 1-19 ×: Number of black spots 20
［着色性］
難燃剤溶融混練物の黄変度を外観により測定した。
○：着色していない
△：あまり着色していない
×：着色度合いが大きい
[Colorability]
The yellowing degree of the flame retardant melt kneaded product was measured by appearance.
○: Not colored Δ: Not colored very much ×: Coloring degree is large
表３から以下のことがわかる。
本発明によれば、特定のリン系化合物からなる流動性向上剤を用いたことで、溶融加工温度を低くしても、黒点の発生や変色が抑制された難燃剤溶融混練物を安定的に得ることができる。
Table 3 shows the following.
According to the present invention, by using a fluidity improver composed of a specific phosphorus compound, it is possible to stably produce a flame retardant melt kneaded product in which generation of black spots and discoloration are suppressed even when the melt processing temperature is lowered. Can be obtained.
（実施例７〜１４、比較例４〜５）
（ポリスチレン系樹脂押出発泡体の製造）
実施例７〜１４及び比較例４〜５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 7-14, Comparative Examples 4-5)
(Manufacture of polystyrene resin extruded foam)
In order to obtain the extruded foams of Examples 7 to 14 and Comparative Examples 4 to 5, 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、２００℃、１００ｓｅｃ−１における溶融粘度１０００Ｐａ・ｓ）
（２）ＲＰＳ１：再生ポリスチレン系樹脂組成物
実施例１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, melt viscosity 1000 Pa · s at 200 ° C., 100 sec −1 )
(2) RPS1: Recycled polystyrene resin composition The polystyrene resin extruded foam plate obtained in Example 1 is crushed, and the crushed material is 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。
[Flame retardants]
As the flame retardant, the flame retardant melt kneaded material shown in Table 3 above was used.
［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、溶融混練物及び気泡調整剤マスターバッチを、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溶融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。
評価結果を表４〜５にまとめて示す。
The resin, melt-kneaded product and bubble regulator master batch are supplied to the first extruder so as to have the respective compounding amounts shown in Tables 4 and 5 to the extruder, heated to 220 ° C., and kneaded. The foamable resin melt obtained by supplying the physical foaming agent of the blending composition shown in the table from the foaming agent inlet provided near the tip of the first extruder to the melt at the ratio shown in the table and melt-kneading the melt, Then, the resin temperature was supplied to the second extruder, and the resin temperature was expressed as the foaming suitable temperature as shown in the table (in the table, it was expressed as the foamed resin temperature. This foaming temperature was measured at the position of the junction between the extruder and the die. The temperature of the foamable resin melt was adjusted) and extruded from the die lip into the guider at a discharge rate of 70 kg / hr to produce an extruded foam.
The evaluation results are summarized in Tables 4-5.
実施例７〜１４及び比較例４〜５で得られたポリスチレン系樹脂押出発泡体の、押出安定性、見掛け密度、厚み、独立気泡率、難燃性、黒点の発生状況、着色性、重量平均分子量、再生樹脂の重量平均分子量、着色性を表４〜５に示す。 Extrusion stability, apparent density, thickness, closed cell ratio, flame retardance, occurrence of black spots, colorability, weight average of polystyrene resin extruded foams obtained in Examples 7 to 14 and Comparative Examples 4 to 5 Tables 4 to 5 show the molecular weight, the weight average molecular weight of the recycled resin, and the colorability.
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.
（押出安定性）
押出安定性の評価は、下記基準により評価した。
○：発泡体が安定して得られる
△：圧力変動が生じやすく、得られる発泡体の寸法変動が起きるなど発泡体が安定して得られない
(Extrusion stability)
The extrusion stability was evaluated according to the following criteria.
○: The foam is stably obtained. Δ: Pressure fluctuation is likely to occur, and the foam cannot be stably obtained, for example, due to dimensional fluctuation of the obtained foam.
（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５０×５０×５０ｍｍ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 50 × 50 × 50 mm cube was cut out from the center and both ends in the width direction of the obtained extruded foam, and the weight was measured. The apparent weight of each sample was divided by the volume. 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.
（黒点）
得られた発泡体の押出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。
(Spot)
In the cross section cut perpendicular to the extrusion direction of the foam obtained, 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）
得られた発泡体の黄変度を外観により測定した。
○：着色していない
×：着色が見られる
(Colorability)
The yellowing degree of the obtained foam was measured by appearance.
○: Not colored ×: Colored
（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（再生樹脂）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又は再生樹脂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 (recycled resin) 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 regenerated 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.
（着色性）
再生樹脂の黄変度を外観により測定した。
◎：ほとんど着色していない
○：若干黄色味がかっているが発泡体製造上問題ないレベル
×：着色度合いが大きい
(Colorability)
The yellowing degree of the recycled resin was measured by appearance.
◎: Almost uncolored ○: Slightly yellowish but no problem in foam production ×: High degree of coloring
実施例７〜１４の結果は、本発明方法によれば、難燃剤溶融混練物１〜６を用いたことからＪＩＳ Ａ９５１１の規格による燃焼試験において極めて良好であり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、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 7 to 14 show that, according to the method of the present invention, the flame retardant melt-kneaded materials 1 to 6 were used, so that the foam having extremely high flame retardancy was very good in the combustion test according to the standard of JIS A9511. In addition, this foam has excellent thermal stability during extrusion processing, and has reduced recycle characteristics and reduced molecular weight due to decomposition of the base resin polystyrene resin. It shows that it is a resin extruded foam.
比較例４は、リン系流動性向上剤を使用しない例である。この比較例４では、押出発泡体に黒点が著しく発生し、更には再生樹脂の着色性が×と極めて悪く、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 no phosphorus fluidity improver is used. In Comparative Example 4, black spots are remarkably generated in the extruded foam, and the colorability of the recycled resin is very poor as x, so that high thermal stability cannot be achieved.
さらに、比較例５は実施例１１と対比されるものであって、リン系流動性向上剤を使用しない例である。この比較例５では、二酸化炭素及び水を含む発泡剤を用いた場合に、押出発泡体製造時における押出安定性が悪く、さらに、得られた押出発泡体の独立気泡率が低下した。また、比較例４と同様に押出発泡体に黒点が著しく発生し、更には再生樹脂の着色性が×と極めて悪く、高い熱安定性を兼備することができない。
Further, Comparative Example 5 is contrasted with Example 11, and is an example in which no phosphorus fluidity improver is used. In Comparative Example 5, when a foaming agent containing carbon dioxide and water was used, the extrusion stability during production of the extruded foam was poor, and the closed cell ratio of the obtained extruded foam was lowered. Further, as in Comparative Example 4, a black spot is remarkably generated in the extruded foam, and further, the colorability of the recycled resin is very poor, and it cannot have high thermal stability.
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| JPH0794574B2 (en) * | 1992-11-13 | 1995-10-11 | 旭化成工業株式会社 | Molding processability improver and thermoplastic resin composition containing the same |
| JPH06192474A (en) * | 1992-12-24 | 1994-07-12 | Asahi Chem Ind Co Ltd | Thermoplastic resin composition excellent in flow and heat resistance |
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| ES2703732T3 (en) * | 2010-12-17 | 2019-03-12 | Dow Global Technologies Llc | Extrusion process of polystyrene in the molten state |
| CN103649211A (en) * | 2011-07-14 | 2014-03-19 | 陶氏环球技术有限责任公司 | Impact-modified styrenic polymers containing brominated vinyl aromatic-butadiene copolymer |
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