JP2013166880A - Method of producing polystyrene-based resin extruded foam - Google Patents
Method of producing polystyrene-based resin extruded foam Download PDFInfo
- Publication number
- JP2013166880A JP2013166880A JP2012031533A JP2012031533A JP2013166880A JP 2013166880 A JP2013166880 A JP 2013166880A JP 2012031533 A JP2012031533 A JP 2012031533A JP 2012031533 A JP2012031533 A JP 2012031533A JP 2013166880 A JP2013166880 A JP 2013166880A
- Authority
- JP
- Japan
- Prior art keywords
- polystyrene
- resin
- foam
- flame retardant
- 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.)
- Granted
Links
- 239000006260 foam Substances 0.000 title claims abstract description 129
- 229920005989 resin Polymers 0.000 title claims abstract description 56
- 239000011347 resin Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 25
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 23
- 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 claims abstract description 68
- 239000003063 flame retardant Substances 0.000 claims abstract description 56
- 229920003232 aliphatic polyester Polymers 0.000 claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011342 resin composition Substances 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 238000004898 kneading Methods 0.000 claims abstract description 8
- 229920005990 polystyrene resin Polymers 0.000 claims description 61
- 239000004088 foaming agent Substances 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 29
- 238000001125 extrusion Methods 0.000 claims description 25
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 13
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical group BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 9
- XUMFBUWGVLTWTH-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromo-2-methylpropoxy)-2-methylpropane Chemical compound BrCC(Br)(C)COCC(C)(Br)CBr XUMFBUWGVLTWTH-UHFFFAOYSA-N 0.000 claims description 8
- LXIZRZRTWSDLKK-UHFFFAOYSA-N 1,3-dibromo-5-[2-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]propan-2-yl]-2-(2,3-dibromopropoxy)benzene Chemical compound C=1C(Br)=C(OCC(Br)CBr)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 LXIZRZRTWSDLKK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004604 Blowing Agent Substances 0.000 abstract description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052794 bromium Inorganic materials 0.000 abstract description 6
- 229920006248 expandable polystyrene Polymers 0.000 abstract description 4
- 239000004645 polyester resin Substances 0.000 description 24
- -1 polytetrafluoroethylene Polymers 0.000 description 16
- 238000005187 foaming Methods 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 12
- 125000000962 organic group Chemical group 0.000 description 9
- 229930195734 saturated hydrocarbon Natural products 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000009413 insulation Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000001282 iso-butane Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000002902 bimodal effect Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000004795 extruded polystyrene foam Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 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 2
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 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
- 239000002245 particle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012545 processing Methods 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
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 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
- 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 1
- MICYFRBASVQFGY-UHFFFAOYSA-N (3-methyl-5-phenylhex-5-en-3-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(CC)CC(=C)C1=CC=CC=C1 MICYFRBASVQFGY-UHFFFAOYSA-N 0.000 description 1
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 1
- YUAPUIKGYCAHGM-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromopropoxy)propane Chemical compound BrCC(Br)COCC(Br)CBr YUAPUIKGYCAHGM-UHFFFAOYSA-N 0.000 description 1
- PWXTUWQHMIFLKL-UHFFFAOYSA-N 1,3-dibromo-5-[2-(3,5-dibromo-4-prop-2-enoxyphenyl)propan-2-yl]-2-prop-2-enoxybenzene Chemical compound C=1C(Br)=C(OCC=C)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC=C)C(Br)=C1 PWXTUWQHMIFLKL-UHFFFAOYSA-N 0.000 description 1
- CWZVMVIHYSYLSI-UHFFFAOYSA-N 1,3-dibromo-5-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]sulfonyl-2-(2,3-dibromopropoxy)benzene Chemical compound C1=C(Br)C(OCC(Br)CBr)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 CWZVMVIHYSYLSI-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 1
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- 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
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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Abstract
Description
本発明は、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 method for producing a polystyrene resin extruded foam.
従来、ポリスチレン系樹脂材料に気泡調整剤を加え、押出機で加熱溶融混練後、物理発泡剤を添加して発泡性樹脂組成物とし、この発泡性樹脂組成物を高圧域から低圧域に押出すことにより発泡させ、さらに押出機のダイ出口に連結した賦形具などにより板状に賦形することにより、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 melt-kneaded with an extruder, and then a physical foaming agent is added to form a foamable resin composition. The foamable resin composition is extruded from a high pressure region to a low pressure region. There is known a method of obtaining a polystyrene resin extruded foam (hereinafter also simply referred to as an extruded foam) by foaming and forming into a plate shape using a shaping tool connected to a die outlet of an extruder. It has been.
前記押出発泡体の製造方法における発泡剤としては、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）や水素原子含有塩化フッ化炭化水素（以下、ＨＣＦＣという）が広く使用されていた。これらの発泡剤は、発泡性に優れ、さらに気体としての熱伝導率も低く押出発泡体中にも長期に残存することから、低見掛け密度で断熱性にも優れる押出発泡体を得ることが可能であった。 As a foaming agent in the method for producing an extruded foam, chlorofluorocarbons (hereinafter referred to as CFC) such as dichlorodifluoromethane and hydrogen atom-containing chlorofluorocarbons (hereinafter referred to as HCFC) have been widely used. . These foaming agents are excellent in foamability, and also have low thermal conductivity as a gas and remain in the extruded foam for a long period of time, so it is possible to obtain extruded foams with low apparent density and excellent heat insulation Met.
一方、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（２００６）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ような高度な難燃性が要求される。そのために、押出発泡体には難燃剤が添加されており、難燃剤としては、ヘキサブロモシクロドデカンなどの臭素系難燃剤が広く使用されてきた。 On the other hand, in order to use the extruded foam as a heat insulating material for construction, for example, high flame retardance that satisfies the flammability standard of an extruded polystyrene foam heat insulating plate described in JIS A9511 (2006) is required. Therefore, a flame retardant is added to the extruded foam, and a brominated flame retardant such as hexabromocyclododecane has been widely used as the flame retardant.
しかし、地球環境保護の観点から、近年は、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発泡剤として用いられるようになっている。 However, from the viewpoint of protecting the global environment, in recent years, saturated hydrocarbons such as isobutane and isopentane having an ozone depletion coefficient of 0 (zero) and a small global warming coefficient have been used as blowing agents.
ここで、飽和炭化水素は可燃性であるため、建材用途に要求される低見掛け密度の（発泡倍率の高い）押出発泡体を飽和炭化水素のみで製造すると、難燃剤を添加しても所望の難燃性を達成しにくくなる。そこで、押出発泡体の発泡剤としては、一般に、飽和炭化水素と共に、塩化アルキルやアルキルエーテル、二酸化炭素、水等の押出発泡体から早期に散逸する発泡剤（早期散逸性発泡剤）が併用されている。早期逸散性発泡剤の併用により飽和炭化水素の配合量を減らすことで、難燃性を有しかつ低見掛け密度の押出発泡体を製造することが可能となった。 Here, since saturated hydrocarbons are flammable, if an extruded foam having a low apparent density (high foaming ratio) required for building material applications is produced only with saturated hydrocarbons, it is desirable even if a flame retardant is added. It becomes difficult to achieve flame retardancy. Therefore, as foaming agents for extruded foams, in general, together with saturated hydrocarbons, foaming agents that dissipate early from extruded foams such as alkyl chlorides, alkyl ethers, carbon dioxide, and water (early dissipative foaming agents) are used in combination. ing. By reducing the blending amount of saturated hydrocarbons in combination with an early dissipative foaming agent, it has become possible to produce extruded foams having flame retardancy and low apparent density.
これらの早期散逸性発泡剤の中でも、環境面を考慮すると、水を使用することが望まれる。しかしながら、水を含む混合発泡剤を用いた場合、発泡体の発泡倍率を高めるために水の添加量が多量になってくると、得られる押出発泡体は小径の小気泡と大径の大気泡が混在する、所謂双峰分布の気泡構造になってしまうという問題があった。 Among these early dissipative blowing agents, it is desirable to use water in consideration of environmental aspects. However, when a mixed foaming agent containing water is used, when the amount of water added is increased in order to increase the foaming ratio of the foam, the resulting extruded foam has small and large bubbles. There is a problem that a so-called bimodal distribution bubble structure is formed.
小さすぎる気泡を含む気泡構造の押出発泡体は、機械的強度が低下しやすく、さらに二次加工も難しくなる。また、小気泡が発生してしまうと、発泡体の見掛け密度を低くすることが難しくなるので、小気泡の発生を防止して、単峰分布の気泡構造の押出発泡体とすることが望ましい。 An extruded foam having a cell structure containing bubbles that are too small tends to have a low mechanical strength and is difficult to perform secondary processing. Further, if small bubbles are generated, it is difficult to lower the apparent density of the foam. Therefore, it is desirable to prevent the generation of small bubbles and to obtain an extruded foam having a single-peaked cell structure.
小気泡の発生を防止して単峰分布の気泡構造を形成する技術として、特許文献１には、ポリマー溶融液における水の溶解度を上げて押出発泡体を製造する技術が開示されている。 As a technique for preventing the generation of small bubbles and forming a unimodal cell structure, Patent Document 1 discloses a technique for producing an extruded foam by increasing the solubility of water in a polymer melt.
特許文献１の方法により、水と二酸化炭素とを含む混合発泡剤を用いた場合に、単峰分布の気泡構造の押出発泡体を製造することが可能になった。しかし、この方法では、発泡剤として炭化水素及び水を含む発泡剤を使用した場合には、得られる押出発泡体は、配合する臭素系難燃剤によって、小気泡が発生し、双峰分布の気泡構造となってしまうか、或いは全体的に気泡が微細化してしまい、場合によっては板状の押出発泡体自体を得られないという問題が生じた。 According to the method of Patent Document 1, when a mixed foaming agent containing water and carbon dioxide is used, it becomes possible to produce an extruded foam having a cell structure with a unimodal distribution. However, in this method, when a foaming agent containing hydrocarbon and water is used as the foaming agent, the resulting extruded foam generates small bubbles due to the brominated flame retardant to be blended, and has a bimodal distribution. There is a problem that the structure becomes a whole or the bubbles are made finer as a whole, and in some cases, the plate-like extruded foam itself cannot be obtained.
この小気泡の発生を防ぐために、ポリスチレン系樹脂中への水の溶解量をさらに上げようと、より多量の親水性物質を添加すると、押出発泡体の機械的物性が低下してしまうという問題が新たに生じてしまう。 In order to prevent the generation of such small bubbles, there is a problem that the mechanical properties of the extruded foam deteriorate when adding a larger amount of a hydrophilic substance to further increase the amount of water dissolved in the polystyrene resin. It will occur anew.
従って、発泡剤として炭化水素及び水を含む発泡剤を使用し、かつ臭素系難燃剤を配合してポリスチレン系樹脂押出発泡体を製造する際に、機械的強度を維持したまま、小気泡の発生を防止することが可能なポリスチレン系樹脂押出発泡体の製造方法の開発が望まれている。 Therefore, when a foaming agent containing hydrocarbon and water is used as a foaming agent and a brominated flame retardant is blended to produce a polystyrene resin extruded foam, small bubbles are generated while maintaining the mechanical strength. Development of a method for producing a polystyrene-based resin extruded foam capable of preventing the above is desired.
本発明は、発泡剤として炭化水素及び水を含む発泡剤を使用し、かつ難燃剤として臭素系難燃剤を使用した場合に、小気泡の発生を防止し、かつ気泡を拡大できる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。 The present invention relates to a polystyrene resin extrusion that prevents the generation of small bubbles and expands bubbles when a blowing agent containing hydrocarbon and water is used as a blowing agent and a brominated flame retardant is used as a flame retardant. An object of the present invention is to provide a method for producing a foam.
本発明によれば、以下に示すポリスチレン系樹脂押出発泡体の製造方法が提供される。
［１］ ポリスチレン系樹脂と、炭素数３〜５の炭化水素及び水を含む物理発泡剤と、臭素系難燃剤とを溶融混練してなる発泡性ポリスチレン系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、該発泡性ポリスチレン系樹脂組成物に、脂肪族ポリエステル系樹脂が配合されており、該脂肪族ポリエステル系樹脂の配合量が、ポリスチレン系樹脂１００重量部に対して５重量部以下（ただし、０は含まず。）であることを特徴とするポリスチレン系樹脂押出発泡体の製造方法。
［２］ 前記脂肪族ポリエステル系樹脂が、ガラス転移温度１２０℃以下の非晶性脂肪族ポリエステル系樹脂、及び／又は融点１２０℃以下の結晶性脂肪族ポリエステル系樹脂であることを特徴とする前記１に記載のポリスチレン系樹脂押出発泡体の製造方法。
［３］ 前記臭素系難燃剤が、臭素化ビスフェノールＡ系難燃剤を含むことを特徴とする前記１又は２に記載のポリスチレン系樹脂押出発泡体の製造方法。
［４］ 前記臭素化ビスフェノールＡ系難燃剤が、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）及び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）であることを特徴とする前記３に記載のポリスチレン系樹脂押出発泡体の製造方法。
［５］ 前記臭素系難燃剤が、臭素化イソシアヌレート系難燃剤を含むことを特徴とする前記１〜４のいずれかに記載のポリスチレン系樹脂押出発泡体の製造方法。
［６］ 前記臭素系難燃剤の総配合量が、ポリスチレン系樹脂１００重量部に対して１重量部以上であることを特徴とする前記１〜５のいずれかに記載のポリスチレン系樹脂押出発泡体の製造方法。
［７］ 前記水の配合量が、ポリスチレン系樹脂１００重量部に対して０．５重量部以上であることを特徴とする前記１〜６のいずれかに記載のポリスチレン系樹脂押出発泡体の製造方法。
［８］ 前記押出発泡体の見掛け密度が２０〜３０ｋｇ／ｍ３であり、厚みが１０〜１５０ｍｍであることを特徴とする前記１〜７のいずれかに記載のポリスチレン系樹脂押出発泡体の製造方法。
［９］ 前記押出発泡体の平均気泡径が０．２ｍｍ以上であり、気泡径の変動係数が６０％以下であることを特徴とする前記１〜８のいずれかに記載のポリスチレン系樹脂押出発泡体の製造方法。
According to this invention, the manufacturing method of the polystyrene-type resin extrusion foam shown below is provided.
[1] An extruded foam is obtained by extruding a foamable polystyrene resin composition obtained by melt-kneading a polystyrene resin, a physical foaming agent containing 3 to 5 carbon atoms and water, and a brominated flame retardant. In the manufacturing method, an aliphatic polyester resin is blended in the foamable polystyrene resin composition, and the blending amount of the aliphatic polyester resin is 5 parts by weight or less with respect to 100 parts by weight of the polystyrene resin. (However, 0 is not included.) A method for producing a polystyrene-based resin extruded foam, wherein:
[2] The aliphatic polyester-based resin is an amorphous aliphatic polyester-based resin having a glass transition temperature of 120 ° C. or lower and / or a crystalline aliphatic polyester-based resin having a melting point of 120 ° C. or lower. 2. A process for producing a polystyrene resin extruded foam according to 1.
[3] The method for producing a polystyrene-based resin extruded foam as described in 1 or 2 above, wherein the brominated flame retardant comprises a brominated bisphenol A flame retardant.
[4] The brominated bisphenol A flame retardant is tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether) and tetrabromobisphenol A-bis (2,3-dibromopropyl ether). 4. The method for producing a polystyrene-based resin extruded foam as described in 3 above.
[5] The method for producing a polystyrene-based resin extruded foam as described in any one of 1 to 4, wherein the brominated flame retardant includes a brominated isocyanurate-based flame retardant.
[6] The polystyrene resin extruded foam as described in any one of 1 to 5 above, wherein the total amount of the brominated flame retardant is 1 part by weight or more based on 100 parts by weight of the polystyrene resin. Manufacturing method.
[7] Production of polystyrene resin extruded foam as described in any one of 1 to 6 above, wherein the blending amount of water is 0.5 parts by weight or more with respect to 100 parts by weight of polystyrene resin. Method.
[8] Production of polystyrene-based resin extruded foam as described in any one of 1 to 7 above, wherein the extruded foam has an apparent density of 20 to 30 kg / m 3 and a thickness of 10 to 150 mm. Method.
[9] The extruded polystyrene foam according to any one of 1 to 8, wherein the extruded foam has an average cell diameter of 0.2 mm or more and a coefficient of variation of the cell diameter of 60% or less. Body manufacturing method.
本発明によれば、発泡剤としてして炭化水素及び水を含む発泡剤を使用し、かつ臭素系難燃剤を用いてポリスチレン系樹脂押出発泡体を製造する際に、脂肪族ポリエステル系樹脂を配合することにより、発泡時に小気泡の発生を防止し、かつ気泡を拡大することによって、単峰分布の気泡構造で低見掛け密度の押出発泡体を得ることができる。 According to the present invention, when a foaming agent containing hydrocarbon and water is used as a foaming agent and a polystyrene resin extruded foam is produced using a brominated flame retardant, an aliphatic polyester resin is blended. By doing so, the generation of small bubbles at the time of foaming is prevented and the bubbles are enlarged, thereby obtaining an extruded foam having a single-peaked cell structure and a low apparent density.
以下、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においては、ポリスチレン系樹脂、難燃剤及び発泡剤を押出機にて溶融混練して得られた発泡性ポリスチレン系樹脂組成物を、ダイを通して高圧の押出機内より低圧域に押出して発泡させることにより、ポリスチレン系樹脂押出発泡体（以下、単に押出発泡体、又は発泡体ともいう。）が製造される。この際、該ダイの出口に、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装置（以下、ガイダーとも言う。）や成形ロール等の成形具を配置し、押出された発泡体を該成形具を通過させることによって、板状に賦形することができる。
Hereinafter, the manufacturing method of the polystyrene-type resin extrusion foam of this invention is demonstrated in detail.
In the method for producing a polystyrene resin extruded foam of the present invention, a foamable polystyrene resin composition obtained by melting and kneading a polystyrene resin, a flame retardant and a foaming agent in an extruder is extruded through a die at high pressure. A polystyrene resin extruded foam (hereinafter also simply referred to as an extruded foam or a foam) is produced by extruding and foaming in a low pressure region from the inside of the machine. At this time, an apparatus (hereinafter also referred to as a guider) composed of two upper and lower plates made of polytetrafluoroethylene resin or the like installed at the outlet of the die so as to expand in parallel or gently from the inlet to the outlet. ) Or a molding roll and the like, and the extruded foam can be shaped into a plate shape by passing through the molding tool.
本発明におけるポリスチレン系樹脂としては、例えばスチレン単独重合体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−メタクリル酸共重合体、スチレン−無水マレイン酸共重合体、、スチレン−メチルスチレン共重合体、スチレン−メタクリル酸メチル共重合体（ＭＳ）、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（ＡＢＳ）、耐衝撃性ポリスチレン（ＨＩＰＳ）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 resin in the present invention include a styrene homopolymer, a styrene-acrylic acid copolymer containing styrene as a main component, a styrene-methacrylic acid copolymer, a styrene-maleic anhydride copolymer, and styrene-methyl. Examples include styrene copolymers, styrene-methyl methacrylate copolymers (MS), styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers (ABS), and high impact polystyrene (HIPS). The styrene unit component content in the styrenic copolymer is preferably 50 mol% or more, particularly preferably 80 mol% or more.
本発明の目的、作用、効果が達成される範囲内において、上記ポリスチレン系樹脂にはその他の重合体を混合してもよい。その他の重合体としては、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）、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）、ポリフェニレンエーテル樹脂などの熱可塑性樹脂、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−エチレン共重合体などの熱可塑性エラストマー等が挙げられ、これらの他の重合体は、ポリスチレン系樹脂中で好ましくは３０重量％未満となるように、特に好ましくは０〜１０重量％となるように、目的に応じて混合することができる。 Other polymers may be mixed with the polystyrene resin within the range in which the object, function, and effect of the present invention are achieved. Other polymers include polyethylene resin (ethylene homopolymer and ethylene copolymer having an ethylene unit component content of 50 mol% or more), polypropylene resin (propylene homopolymer and propylene unit component content of 50 mol). % Propylene copolymer), thermoplastic resin such as polyphenylene ether resin, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer hydrogenated product , A styrene-isoprene-styrene block copolymer hydrogenated product, a thermoplastic elastomer such as a styrene-ethylene copolymer, and the like. These other polymers are preferably less than 30% by weight in a polystyrene resin. Particularly preferably 0 to 10% by weight. As it can be mixed according to the purpose.
本発明においては、前記発泡性ポリスチレン系樹脂組成物に、脂肪族ポリエステル系樹脂が配合される。脂肪族ポリエステル系樹脂を配合することにより、発泡時に小気泡の発生を防止すると共に気泡を拡大して単峰分布の気泡構造を有する低見掛け密度の押出発泡体を得ることができる。
脂肪族ポリエステル系樹脂を配合することにより、小気泡の発生を防止し、気泡を拡大できる理由は定かではないが、水のポリスチレン系樹脂中への溶解度を向上させる程の配合量ではなく極少量の配合でも前記効果が得られていることから、脂肪族ポリエステル系樹脂がポリスチレン系樹脂に微細に分散しやすく、微細に分散した脂肪族ポリエステル系樹脂がポリスチレン系樹脂組成物中への水の分散性を向上させることにより小気泡の発生を抑えると共に、界面活性剤的な作用により気泡を拡大しているものと推察される。
In the present invention, an aliphatic polyester resin is blended with the expandable polystyrene resin composition. By blending the aliphatic polyester-based resin, it is possible to obtain an extruded foam having a low apparent density having a unimodal distribution of cell structures by preventing the generation of small bubbles during foaming and expanding the cells.
The reason why small bubbles can be prevented and bubbles can be expanded by blending with aliphatic polyester resin is not clear, but it is not a blending amount to improve the solubility of water in polystyrene resin, but a very small amount The above effect is also obtained by blending, so that the aliphatic polyester resin is easily finely dispersed in the polystyrene resin, and the finely dispersed aliphatic polyester resin is dispersed in the polystyrene resin composition. It is presumed that the generation of small bubbles is suppressed by improving the property and the bubbles are enlarged by the action of a surfactant.
本発明で用いられる脂肪族ポリエステル系樹脂としては、脂肪族ヒドロキシカルボン酸成分単位を主たる構成成分とする重合体、脂肪族多価カルボン酸成分単位と脂肪族多価アルコール成分単位とを主たる構成成分とする重合体が挙げられる。 The aliphatic polyester-based resin used in the present invention includes a polymer mainly composed of an aliphatic hydroxycarboxylic acid component unit, a component mainly composed of an aliphatic polycarboxylic acid component unit and an aliphatic polyhydric alcohol component unit. And the following polymer.
前記脂肪族ヒドロキシカルボン酸を主たる構成成分とする重合体としては、グリコール酸、乳酸、ヒドロキシプロピオン酸、ヒドロキシ酪酸、ヒドロキシ吉草酸、ヒドロキシカプロン酸などの重合体、もしくはこれらの共重合体を例示することができる。 Examples of the polymer mainly composed of the aliphatic hydroxycarboxylic acid include polymers such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, and copolymers thereof. be able to.
前記脂肪族ポリエステル系樹脂中の脂肪族多価カルボン酸成分単位としては、シュウ酸、コハク酸、アジピン酸、セバシン酸、ドデカンジオン酸等の脂肪族ジカルボン酸が挙げられ、これらの脂肪族多価カルボン酸成分単位は、単独であってもよく２種以上であってもよい。なお、多価カルボン酸成分単位には、本発明の所期の目的を阻害しない範囲において、テレフタル酸などの芳香族多価カルボン酸成分単位が少量含まれていてもよく、その量は、多価カルボン酸成分単位中に５０ｍｏｌ％以下であることが好ましく、より好ましくは４０ｍｏｌ％以下である。 Examples of the aliphatic polyvalent carboxylic acid component unit in the aliphatic polyester-based resin include aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, and the like. A carboxylic acid component unit may be individual, and may be 2 or more types. The polyvalent carboxylic acid component unit may contain a small amount of an aromatic polyvalent carboxylic acid component unit such as terephthalic acid as long as the intended purpose of the present invention is not impaired. It is preferable that it is 50 mol% or less in a monovalent | monohydric carboxylic acid component unit, More preferably, it is 40 mol% or less.
前記脂肪族系樹脂中の脂肪族多価アルコール成分単位としてはエチレングリコール、プロピレングリコール、トリメチレングリコール、ジエチレングリコール、１，４−ブタンジオール、ネオペンチルグリコール等の脂肪族ジオールを挙げることができ、これらの脂肪族多価アルコール成分は、単独であってもよく２種以上であってもよい。 Examples of the aliphatic polyhydric alcohol component unit in the aliphatic resin include aliphatic diols such as ethylene glycol, propylene glycol, trimethylene glycol, diethylene glycol, 1,4-butanediol, and neopentyl glycol. These aliphatic polyhydric alcohol components may be used alone or in combination of two or more.
前記脂肪族ポリエステル系樹脂は、例えば少量の安息香酸，ベンゾイル安息香酸，メトキシポリエチレングリコール等のごとき単官能化合物から誘導される成分単位によって分子末端を封止されていてもよい。また、ピロメリット酸、トリメリット酸、トリメシン酸、グリセリン、ペンタエリスリトール等の多官能化合物から誘導される成分単位を少量含んでいてもよい。 The aliphatic polyester-based resin may have its molecular ends sealed with component units derived from a monofunctional compound such as a small amount of benzoic acid, benzoylbenzoic acid, methoxypolyethylene glycol, and the like. Moreover, a small amount of component units derived from a polyfunctional compound such as pyromellitic acid, trimellitic acid, trimesic acid, glycerin, pentaerythritol may be included.
本発明においては、脂肪族ポリエステル系樹脂として、ガラス転移温度１２０℃以下の非晶性脂肪族ポリエステル系樹脂、及び／又は融点１２０℃以下の結晶性脂肪族ポリエステル系樹脂を用いることが好ましい。これらの脂肪族ポリエステル系樹脂を用いると、押出発泡時に、脂肪族ポリエステル系樹脂がポリスチレン系樹脂中で十分に変形可能なため、気泡を破壊しにくく、さらに小気泡の発生を防ぎつつ気泡を拡大させやすくなる。かかる観点から、非晶性脂肪族ポリエステル系樹脂のガラス転移温度は、１００℃以下が好ましく、より好ましくは８０℃である。また、結晶性脂肪族ポリエステル系樹脂の融点は、１００℃以下が好ましく、より好ましくは８０℃である。 In the present invention, it is preferable to use an amorphous aliphatic polyester resin having a glass transition temperature of 120 ° C. or lower and / or a crystalline aliphatic polyester resin having a melting point of 120 ° C. or lower as the aliphatic polyester resin. When these aliphatic polyester resins are used, during extrusion foaming, the aliphatic polyester resin can be sufficiently deformed in polystyrene resin, making it difficult to destroy bubbles and expanding bubbles while preventing the generation of small bubbles. It becomes easy to let you. From such a viewpoint, the glass transition temperature of the amorphous aliphatic polyester resin is preferably 100 ° C. or lower, more preferably 80 ° C. The melting point of the crystalline aliphatic polyester resin is preferably 100 ° C. or lower, more preferably 80 ° C.
本発明においては、ガラス転移温度１２０℃以下の非晶性脂肪族ポリエステル系樹脂として非晶性ポリ乳酸が好ましいものとして挙げられる。 In the present invention, amorphous polylactic acid is preferred as an amorphous aliphatic polyester resin having a glass transition temperature of 120 ° C. or lower.
なお、本発明において、「非晶性」とは、脂肪族ポリエステル系樹脂を熱流束示差走査熱量測定（以下、ＤＳＣ測定と言う。）により２００℃で１０分間保持した後冷却速度１０℃／分で冷却した際に得られるＤＳＣ曲線において求められる発熱ピークの熱量が５Ｊ／ｇ以下（０を含む。）、好ましくは３Ｊ／ｇ以下（０を含む。）、より好ましくは０であることを意味する。 In the present invention, “amorphous” means that the aliphatic polyester-based resin is held at 200 ° C. for 10 minutes by heat flux differential scanning calorimetry (hereinafter referred to as DSC measurement) and then cooled at a rate of 10 ° C./min. It means that the calorific value of the exothermic peak obtained in the DSC curve obtained upon cooling at 5 J / g or less (including 0), preferably 3 J / g or less (including 0), more preferably 0. To do.
本発明において、前記非晶性脂肪族ポリエステルのガラス転移温度は、次のように求められる。ＪＩＳ Ｋ７１２１（１９８７）に記載の「一定の熱処理を行った後、ガラス転移温度を測定する場合」（試験片の状態調節における加熱速度と冷却速度は、いずれも１０℃／分とする。）を採用し、熱流束示差走査熱量測定装置（以下、ＤＳＣ装置という。）を使用し、加熱速度１０℃／分で得られるＤＳＣ曲線に基づいて測定される中間点ガラス転移温度を本発明におけるガラス転移温度とする。 In the present invention, the glass transition temperature of the amorphous aliphatic polyester is determined as follows. JIS K7121 (1987) "when measuring the glass transition temperature after performing a certain heat treatment" (both the heating rate and the cooling rate in the condition adjustment of the test piece are 10 ° C./min). The glass transition temperature in the present invention is determined by using a heat flux differential scanning calorimeter (hereinafter referred to as DSC apparatus) and measuring the midpoint glass transition temperature measured based on the DSC curve obtained at a heating rate of 10 ° C./min. Let it be temperature.
融点１２０℃以下の結晶性脂肪族ポリエステルとしては、例えば、ポリカプロラクトン、ポリカプロラクトンジオール、ポリカプロラクトントリオール、ポリブチレンアジペート、ポリブチレンサクシネート、ポリブチレンアジペートサクシネートが挙げられる。 Examples of the crystalline aliphatic polyester having a melting point of 120 ° C. or lower include polycaprolactone, polycaprolactone diol, polycaprolactone triol, polybutylene adipate, polybutylene succinate, and polybutylene adipate succinate.
本発明において、前記結晶性脂肪族ポリエステルの融点は、次のように求められる。ＪＩＳ Ｋ７１２１（１９８７）に記載の「一定の熱処理を行った後、融解温度を測定する場合」（試験片の状態調節における加熱速度と冷却速度は、いずれも１０℃／分とする。）を採用し、熱流束示差走査熱量測定装置（以下、ＤＳＣ装置という。）を使用し、加熱速度１０℃／分で得られるＤＳＣ曲線に基づいて測定される融解ピーク温度を本発明における融点とする。 In the present invention, the melting point of the crystalline aliphatic polyester is determined as follows. “When melting temperature is measured after performing a certain heat treatment” described in JIS K7121 (1987) (the heating rate and cooling rate in adjusting the state of the test piece are both 10 ° C./min) is adopted. The melting peak temperature measured using a heat flux differential scanning calorimeter (hereinafter referred to as DSC apparatus) based on a DSC curve obtained at a heating rate of 10 ° C./min is defined as the melting point in the present invention.
前記脂肪族ポリエステル系樹脂の配合量は、ポリスチレン系樹脂１００重量部に対して５重量部以下（ただし、０を含まず。）である。小気泡の発生をより効果的に防ぐためには、その配合量の下限は、ポリスチレン系樹脂１００重量部に対して０．００５重量部であることが好ましく、０．０１重量部であることがより好ましく、更に好ましくは０．０５重量部であり、特に好ましくは０．１重量部である。一方、一般に脂肪族ポリエステル系樹脂はポリスチレン系樹脂に比べて機械的物性に劣り、また発泡を阻害することがあるので、該配合量が多すぎると、得られる押出発泡体の機械的物性が低下しやすくなるため、該配合量の上限は、ポリスチレン系樹脂１００重量部に対して、５重量部であり、好ましくは４重量部であり、より好ましくは３重量部であり、さらに好ましくは２重量部、特に好ましくは１重量部である。 The blending amount of the aliphatic polyester-based resin is 5 parts by weight or less (excluding 0) with respect to 100 parts by weight of the polystyrene-based resin. In order to more effectively prevent the generation of small bubbles, the lower limit of the blending amount is preferably 0.005 parts by weight, more preferably 0.01 parts by weight with respect to 100 parts by weight of the polystyrene resin. Preferably, it is 0.05 part by weight, more preferably 0.1 part by weight. On the other hand, aliphatic polyester resins are generally inferior in mechanical properties to polystyrene resins and may inhibit foaming. If the amount is too large, the mechanical properties of the resulting extruded foam will be reduced. Therefore, the upper limit of the blending amount is 5 parts by weight, preferably 4 parts by weight, more preferably 3 parts by weight, and further preferably 2 parts by weight with respect to 100 parts by weight of the polystyrene-based resin. Part, particularly preferably 1 part by weight.
本発明においては、炭素数３〜５の炭化水素及び水を含む物理発泡剤が用いられる。前記炭素数３〜５の飽和炭化水素としては、プロパン、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタン、ネオペンタンなどが挙げられる。これらの炭素数３〜５の飽和炭化水素の中では、発泡性の点からプロパン、ノルマルブタン、イソブタンあるいはこれらの混合物が好ましい。また、得られる発泡体の断熱性能の点からノルマルブタン、イソブタンあるいはこれらの混合物が好ましく、特に好ましくはイソブタンである。難燃性の観点から、上記飽和炭化水素の配合量は、ポリスチレン系樹脂１００重量部に対して４重量部以下が好ましく、より好ましくは３．５重量部以下である。一方、低見掛け密度の押出発泡体を得る上で、押出発泡時の安定性や押出直後の発泡体の収縮を防ぐという観点からは、該配合量の下限は１重量部程度である。 In the present invention, a physical blowing agent containing a hydrocarbon having 3 to 5 carbon atoms and water is used. Examples of the saturated hydrocarbon having 3 to 5 carbon atoms include propane, normal butane, isobutane, normal pentane, isopentane, neopentane and the like. Among these saturated hydrocarbons having 3 to 5 carbon atoms, propane, normal butane, isobutane or a mixture thereof is preferable from the viewpoint of foamability. Moreover, normal butane, isobutane, or a mixture thereof is preferable from the viewpoint of the heat insulating performance of the obtained foam, and isobutane is particularly preferable. From the viewpoint of flame retardancy, the blending amount of the saturated hydrocarbon is preferably 4 parts by weight or less, more preferably 3.5 parts by weight or less with respect to 100 parts by weight of the polystyrene resin. On the other hand, when obtaining an extruded foam having a low apparent density, the lower limit of the blending amount is about 1 part by weight from the viewpoint of stability during extrusion foaming and prevention of shrinkage of the foam immediately after extrusion.
本発明における物理発泡剤は、水を含むものであり、水を用いることにより前記炭化水素の添加量を抑えつつ低見掛け密度の押出発泡体を得ることができる。かかる観点から、水の配合量は、ポリスチレン系樹脂１００重量部に対して０．５重量部以上が好ましく、より好ましくは０．７重量部以上である。また、水の配合量が多すぎると、ダイ内で水が分離しやすくなり、発泡体の表面に穴が発生しやくなることから、その上限は１．５重量部が好ましく、より好ましくは１．２重量部である。 The physical foaming agent in the present invention contains water. By using water, it is possible to obtain an extruded foam having a low apparent density while suppressing the amount of the hydrocarbon added. From this viewpoint, the blending amount of water is preferably 0.5 parts by weight or more, more preferably 0.7 parts by weight or more with respect to 100 parts by weight of the polystyrene resin. In addition, when the amount of water is too large, water is easily separated in the die, and holes are easily generated on the surface of the foam. Therefore, the upper limit is preferably 1.5 parts by weight, more preferably 1 .2 parts by weight.
本発明における物理発泡剤には、有機系物理発泡剤や無機系物理発泡剤などのその他の物理発泡剤を配合することができる。
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、エチルメチルエーテル、ジエチ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、ｔｅｒｔ−ブチルアルコールなどのアルコール類、蟻酸メチル、蟻酸エチルプロピオン酸メチルなどのカルボン酸エステル類、塩化メチル、塩化エチルなどのハロゲン化アルキルなどが挙げられる。また、フッ化炭化水素の中でも、地球温暖化係数の小さい１、３、３、３−テトラフルオロプロペンなどのハイドロフルオロオレフィン等を用いることもできる。前記無機系物理発泡剤としては、例えば二酸化炭素などが挙げられる。
これら、その他の物理発泡剤は、単独または２種以上混合して使用することができる。
In the physical foaming agent in the present invention, other physical foaming agents such as an organic physical foaming agent and an inorganic physical foaming agent can be blended.
Examples of the organic physical foaming agent include ethers such as dimethyl ether, ethyl methyl ether, and diethyl ether, methanol, ethanol, propyl alcohol, i-propyl alcohol, butyl alcohol, i-butyl alcohol, and tert-butyl alcohol. Examples thereof include alcohols, carboxylic acid esters such as methyl formate and ethyl propionate, and alkyl halides such as methyl chloride and ethyl chloride. In addition, among fluorocarbons, hydrofluoroolefins such as 1, 3, 3, 3-tetrafluoropropene having a small global warming potential can be used. Examples of the inorganic physical foaming agent include carbon dioxide.
These other physical foaming agents can be used alone or in admixture of two or more.
また、前記物理発泡剤に加えて化学発泡剤を用いることもできる。該化学発泡剤としては、例えばアゾ化合物、テトラゾールなどの化学発泡剤などが挙げられる。 In addition to the physical foaming agent, a chemical foaming agent can also be used. Examples of the chemical foaming agent include chemical foaming agents such as azo compounds and tetrazole.
前記その他の物理発泡剤の中では、発泡性、発泡体成形性、押出発泡体の寸法の早期安定性などの点から、塩化メチル、塩化エチル、ジメチルエーテル、メタノール、エタノール、蟻酸メチル、二酸化炭素が好ましく、環境面を考慮すると、二酸化炭素が特に好ましい。 Among the other physical foaming agents, methyl chloride, ethyl chloride, dimethyl ether, methanol, ethanol, methyl formate, and carbon dioxide are included in terms of foamability, foam moldability, and early stability of the dimensions of the extruded foam. Preferably, carbon dioxide is particularly preferable in consideration of environmental aspects.
本発明における発泡剤の総配合量（圧入量）は、ポリスチレン系樹脂１００重量部に対して、２〜１０重量部が好ましく、３〜８重量部がより好ましい。発泡剤の総配合量が少なすぎると、得られる押出発泡体の見掛け密度が高くなり、発泡体としての軽量、断熱などの特性が発揮されにくくなる。発泡剤の総配合量が多すぎると、押出発泡体中にボイドなどの不良が生じやすくなる。 2-10 weight part is preferable with respect to 100 weight part of polystyrene-type resins, and, as for the total compounding quantity (press-fit amount) of the foaming agent in this invention, 3-8 weight part is more preferable. When the total blending amount of the foaming agent is too small, the apparent density of the obtained extruded foam becomes high, and it becomes difficult to exhibit characteristics such as light weight and heat insulation as the foam. If the total amount of the foaming agent is too large, defects such as voids are likely to occur in the extruded foam.
本発明においては、前記ポリスチレン系樹脂と前記物理発泡剤とに加えて、難燃性を付与するために臭素系難燃剤が配合されて、溶融混練してなる発泡性ポリスチレン系樹脂組成物が押出されて押出発泡体が製造される。 In the present invention, in addition to the polystyrene resin and the physical foaming agent, a foamable polystyrene resin composition obtained by blending a brominated flame retardant to impart flame retardancy and melt-kneading is extruded. Thus, an extruded foam is produced.
上記臭素系難燃剤としては、例えば、ヘキサブロモシクロドデカンやテトラブロモシクロオクタンなどの臭素化脂環式炭化水素系難燃剤、臭素化ビスフェノール系難燃剤、臭素化イソシアヌレート系難燃剤、臭素含有リン化合物系難燃剤、臭素含有ポリスチレン系難燃剤等、従来公知のものが挙げられる。これらの臭素系難燃剤は、単独又は２種以上を混合して使用できる。 Examples of the brominated flame retardant include brominated alicyclic hydrocarbon-based flame retardants such as hexabromocyclododecane and tetrabromocyclooctane, brominated bisphenol-based flame retardants, brominated isocyanurate-based flame retardants, and bromine-containing phosphorus. Conventionally known compounds such as compound flame retardants and bromine-containing polystyrene flame retardants may be mentioned. These brominated flame retardants can be used alone or in admixture of two or more.
本発明において、臭素化ビスフェノール系難燃剤とは下記式（１）で示される、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、又はこれらの誘導体の臭素化物である。 In the present invention, the brominated bisphenol-based flame retardant is a brominated product of bisphenol A, bisphenol F, bisphenol S, or a derivative thereof represented by the following formula (1).
［式中，Ｚは、ＣＨ３−Ｃ−ＣＨ３、ＣＨ２、ＳＯ２から選ばれる有機基、Ｒ４，Ｒ５は、水素原子、炭素数１〜８のアルキル基、−Ｙ−Ｘで表される有機基（式中，Ｙは炭素数１〜６のアルキレン基、Ｘはエポキシ基、カルボキシル基、水酸基、アミノ基、フェニル基である）、およびフェニル基のうちから選ばれるもの、および、これらの原子及び原子団のうち、少なくとも１つの水素原子が臭素原子に置換されている有機基である。尚、Ｒ４，Ｒ５の原子及び原子団は相互に異なる有機基であっても同じものであってもよい。］
[In the formula, Z represents an organic group selected from CH 3 —C—CH 3 , CH 2 and SO 2 ; R 4 and R 5 represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and —Y—X An organic group represented by the formula (wherein Y is an alkylene group having 1 to 6 carbon atoms, X is an epoxy group, a carboxyl group, a hydroxyl group, an amino group, or a phenyl group), and a phenyl group; and In these atoms and atomic groups, at least one hydrogen atom is an organic group substituted with a bromine atom. The atoms and atomic groups of R 4 and R 5 may be different organic groups or the same. ]
臭素化ビスフェノール系難燃剤の具体例としては、テトラブロモビスフェノールＡ、テトラブロモビスフェノールＡ−ビス（２，３−ジブロモプロピルエーテル）、テトラブロモビスフェノールＡ−ビス（２，３−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、テトラブロモビスフェノールＳ−ビス（２，３−ジブロモプロピルエーテル）、テトラブロモビスフェノールＳ−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、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）、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）テトラブロモビスフェノールＡ−ビス（アリルエーテル）、テトラブロモビスフェノールＡポリカーボネートオリゴマー、テトラブロモビスフェノールＡオリゴマーのエポキシ基付加物等が挙げられる。上記の臭素化ビスフェノ−ル系難燃剤の中でも、特に、テトラブロモビスフェノ−ルＡビス（２，３−ジブロモプロピルエーテル）、テトラブロモビスフェノールＡ−ビス（２，３−ジブロモプロピルエーテル）、が、ポリスチレン系樹脂との混練時において分解しにくく、難燃効果も高く発現し易いため好ましい。更に、テトラブロモビスフェノ−ルＡ−ビス（２，３−ジブロモプロピルエーテル）と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）とを併用すると、難燃性に優れた押出発泡体となると共に、押出時の熱安定に優れるので好ましい。 Specific examples of brominated bisphenol-based flame retardants include tetrabromobisphenol A, tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (2,3-dibromo-2methylpropyl ether). ), Tetrabromobisphenol S, tetrabromobisphenol S-bis (2,3-dibromopropyl ether), tetrabromobisphenol S-bis (2,3-dibromo-2methylpropyl ether), tetrabromobisphenol F, tetrabromobisphenol F-bis (2,3-dibromopropyl ether), tetrabromobisphenol F-bis (2,3-dibromo-2methylpropyl ether) tetrabromobisphenol A-bis (allyl ether), tetrabromobis Phenol A polycarbonate oligomer, an epoxy group adduct of tetrabromobisphenol A oligomers and the like. Among the brominated bisphenol flame retardants described above, tetrabromobisphenol A bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), It is preferable because it is difficult to be decomposed during kneading with a polystyrene resin and has a high flame retardancy effect. Furthermore, when tetrabromobisphenol A-bis (2,3-dibromopropyl ether) and tetrabromobisphenol A-bis (2,3-dibromo-2methylpropyl ether) are used in combination, the flame retardancy is excellent. It is preferable because it becomes an extruded foam and has excellent thermal stability during extrusion.
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）と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）とを併用する場合、その混合比は、重量比で９０：１０〜３０：７０であることが好ましく、より好ましくは６０：４０〜４０：６０である。この重量比の混合難燃剤は、難燃性に優れると共に、熱安定に優れるものである。 When tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether) and tetrabromobisphenol A-bis (2,3-dibromopropyl ether) are used in combination, the mixing ratio is 90 by weight. : 10 to 30: 70 is preferable, and 60: 40 to 40: 60 is more preferable. The mixed flame retardant having this weight ratio is excellent in flame retardancy and heat stability.
ここで、脂肪族ポリエステル系樹脂を配合せずに、飽和炭化水素及び水を含む物理発泡剤を用いてポリスチレン系樹脂押出発泡体を製造する場合、上記臭素系難燃剤の中でも、臭素化ビスフェノール系難燃剤を使用すると、特に小気泡が発生しやすい傾向にあり、特にポリスチレン系樹脂と相溶性が異なるビスフェノール系難燃剤を併用した場合、例えば、テトラブロモビスフェノールＡ−ビス（２，３−ジブロモプロピルエーテル）と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）とを併用した場合に、特に双峰分布の気泡構造となる傾向にある。また、臭素化ビスフェノール系難燃剤の配合量を増やすと、小気泡がより発生しやすくなる傾向にある。また、臭素化ポリブタジエン−ポリスチレンブロック共重合体などの臭素含有ポリスチレン系難燃剤を使用した場合にも、同様に気泡が微細化する傾向にある。本発明においては、脂肪族ポリエステル系樹脂を配合することより、小気泡の発生を防ぐことができる。 Here, when a polystyrene resin extruded foam is produced using a physical foaming agent containing saturated hydrocarbon and water without blending an aliphatic polyester resin, among the brominated flame retardants, brominated bisphenol type When a flame retardant is used, there is a tendency that small bubbles are particularly likely to be generated. In particular, when a bisphenol flame retardant having a different compatibility with a polystyrene resin is used in combination, for example, tetrabromobisphenol A-bis (2,3-dibromopropyl) When ether) and tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether) are used in combination, the cell structure tends to have a bimodal distribution. Further, when the blending amount of the brominated bisphenol-based flame retardant is increased, small bubbles tend to be more easily generated. Further, when a bromine-containing polystyrene flame retardant such as a brominated polybutadiene-polystyrene block copolymer is used, the bubbles tend to be similarly refined. In the present invention, the generation of small bubbles can be prevented by blending the aliphatic polyester resin.
さらに、本発明で用いられる臭素系難燃剤は、臭素化イソシアヌレート系難燃剤を含むことが好ましい。該臭素化イソシアヌレート系難燃剤は、難燃効果を有すると共に、前記脂肪族ポリエステル系樹脂との相乗効果により、小気泡の発生を防止して単峰分布の気泡構造の形成を容易にすることができるものである。 Furthermore, the brominated flame retardant used in the present invention preferably contains a brominated isocyanurate-based flame retardant. The brominated isocyanurate-based flame retardant has a flame retardant effect, and, due to a synergistic effect with the aliphatic polyester-based resin, prevents the formation of small bubbles and facilitates the formation of a single-peaked cell structure. Is something that can be done.
該臭素化イソシアヌレート系難燃剤とは、下記式（２）に示される、イソシアヌル酸又はイソシアヌル酸誘導体の臭素化物である。 The brominated isocyanurate-based flame retardant is a brominated product of isocyanuric acid or an isocyanuric acid derivative represented by the following formula (2).
［式中、Ｒ１，Ｒ２，Ｒ３は、水素原子、炭素数１〜８のアルキル基、−Ｙ−Ｘで表される有機基（式中、Ｙは炭素数１〜６のアルキレン基、Ｘはエポキシ基、カルボキシル基、水酸基、アミノ基、フェニル基である）、およびフェニル基の中から選択される有機基、および、これらの原子及び原子団のうち、少なくとも１つの水素原子が臭素原子に置換されている有機基である。但し、Ｒ１，Ｒ２，Ｒ３のうち少なくとも１つは、前記原子及び原子団のうち少なくとも１つの水素原子が臭素原子に置換されている有機基とする。尚、Ｒ１，Ｒ２，Ｒ３の原子及び原子団は相互に異なる有機基であっても同じものであってもよい。］
[Wherein R 1 , R 2 and R 3 are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an organic group represented by —Y—X (wherein Y is an alkylene group having 1 to 6 carbon atoms, X is an epoxy group, a carboxyl group, a hydroxyl group, an amino group, or a phenyl group), an organic group selected from phenyl groups, and at least one hydrogen atom among these atoms and atomic groups is bromine An organic group substituted with an atom. However, at least one of R 1 , R 2 , and R 3 is an organic group in which at least one hydrogen atom of the atoms and atomic groups is substituted with a bromine atom. The atoms and atomic groups of R 1 , R 2 , and R 3 may be different organic groups or the same. ]
上記臭素化イソシアヌレート計難燃剤の具体例としては、モノ（２，３−ジブロモプロピル）イソシアヌレート、ジ（２，３−ジブロモプロピル）イソシアヌレート、トリス（２，３−ジブロモプロピル）イソシアヌレート、モノ（２，３，４−トリブロモブチル）イソシアヌレート、ジ（２，３，４−トリブロモブチル）イソシアヌレート、トリス（２，３，４−トリブロモブチル）イソシアヌレート等が挙げられる。また、上記の臭素化イソシアヌレートの中で特に、トリス（２，３−ジブロモプロピル）イソシアヌレートは、極めて高い難燃効果が容易に発現すると共に、小気泡の発生を防止する効果が高いため好ましい。 Specific examples of the brominated isocyanurate flame retardant include mono (2,3-dibromopropyl) isocyanurate, di (2,3-dibromopropyl) isocyanurate, tris (2,3-dibromopropyl) isocyanurate, Examples include mono (2,3,4-tribromobutyl) isocyanurate, di (2,3,4-tribromobutyl) isocyanurate, and tris (2,3,4-tribromobutyl) isocyanurate. Further, among the brominated isocyanurates, tris (2,3-dibromopropyl) isocyanurate is preferable because it exhibits an extremely high flame retardant effect and has a high effect of preventing the generation of small bubbles. .
上記臭素化イソシアヌレート系難燃剤の配合量はポリスチレン系樹脂１００重量部に対して０．１重量部以上が好ましく、より好ましくは０．２重量部以上であり、更に好ましくは０．５重量部である。また、その上限は、小気泡の発生を抑制するという観点からは特に制限されるものではないが、概ね５重量部程度である。 The amount of the brominated isocyanurate-based flame retardant is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, and still more preferably 0.5 parts by weight with respect to 100 parts by weight of the polystyrene resin. It is. Further, the upper limit is not particularly limited from the viewpoint of suppressing the generation of small bubbles, but is approximately 5 parts by weight.
上記臭素系難燃剤の配合量は、所望の難燃性に応じて適宜決定されるものであるが、ＪＩＳＡ ９５１１（２００６Ａ）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ポリスチレン系樹脂押出発泡体を得るためには、臭素系難燃剤を、ポリスチレン１００重量部に対して合計１重量部以上配合することが好ましく、より好ましくは合計２重量部以上、更に好ましくは合計３重量部以上である。該難燃剤の合計配合量が少なすぎると、高度な難燃性を達成できなくなる虞がある。一方、臭素系難燃剤の合計配合量の上限は、１０重量部が好ましく、より好ましくは８重量部である。難燃剤の配合量が多すぎると、発泡性ポリスチレン系樹脂組成物の流動性が向上し過ぎ、製造時にダイ内で内部発泡を起こしやすくなり、表面状態の良好な発泡体を得ることができなくなる虞があるばかりか、得られる発泡体の圧縮、曲げ等の機械物性が低くなる虞がある。 The blending amount of the brominated flame retardant is appropriately determined according to the desired flame retardancy, but is a polystyrene resin extruded material that satisfies the flammability standard of the extruded polystyrene foam heat insulating plate described in JISA 9511 (2006A). In order to obtain a foam, it is preferable to add a total of 1 part by weight or more of a brominated flame retardant with respect to 100 parts by weight of polystyrene, more preferably 2 parts by weight or more, further preferably 3 parts by weight or more. is there. If the total amount of the flame retardant is too small, there is a possibility that high flame retardancy cannot be achieved. On the other hand, the upper limit of the total amount of the brominated flame retardant is preferably 10 parts by weight, and more preferably 8 parts by weight. When the amount of the flame retardant is too large, the flowability of the expandable polystyrene resin composition is excessively improved, and internal foaming is likely to occur in the die during production, making it impossible to obtain a foam having a good surface condition. In addition to the fear, mechanical properties such as compression and bending of the obtained foam may be lowered.
該難燃剤のポリスチレン系樹脂への配合方法としては、所定割合の難燃剤をポリスチレン系樹脂と共に押出機上流に設けられている供給部に供給し、押出機中にて混練する方法を採用することができる。その他、押出機途中に設けられた難燃剤供給部より溶融ポリスチレン樹脂中に難燃剤を供給する方法も採用することができる。尚、難燃剤を押出機に供給する場合、難燃剤とポリスチレン系樹脂とをドライブレンドしたものを押出機に供給する方法、難燃剤とポリスチレン系樹脂をニーダー等により混練した溶融混練物を押出機に供給する方法や難燃剤マスターバッチを作製し押出機に供給する方法を採用することができる。特に、分散性の点から難燃剤マスターバッチを作製し押出機に供給する方法を採用することが好ましい。 As a method of blending the flame retardant into the polystyrene resin, a method of supplying a predetermined ratio of the flame retardant together with the polystyrene resin to a supply unit provided upstream of the extruder and kneading in the extruder is adopted. Can do. In addition, a method of supplying a flame retardant into the molten polystyrene resin from a flame retardant supply unit provided in the middle of the extruder can also be employed. When supplying a flame retardant to an extruder, a method of supplying a dry blend of a flame retardant and a polystyrene resin to the extruder, a melt kneaded material obtained by kneading the flame retardant and a polystyrene resin with a kneader, etc. It is possible to adopt a method of supplying to the extruder and a method of producing a flame retardant master batch and supplying it to the extruder. In particular, it is preferable to adopt a method of preparing a flame retardant master batch and supplying it to an extruder from the viewpoint of dispersibility.
本発明においては、難燃助剤として、２，３−ジメチル−２，３−ジフェニルブタン、２，３−ジエチル−２，３−ジフェニルブタンなどのジフェニルアルカンや、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−ペンテンなどのジフェニルアルケンを添加することができる。 In the present invention, as flame retardant aids, diphenylalkanes such as 2,3-dimethyl-2,3-diphenylbutane and 2,3-diethyl-2,3-diphenylbutane, and 2,4-diphenyl-4- Diphenylalkenes such as methyl-1-pentene and 2,4-diphenyl-4-ethyl-1-pentene can be added.
本発明においては、ヒンダードフェノール系安定剤、リン系安定剤、およびヒンダードアミン系安定剤等の安定剤を添加することができる。安定剤は、加工時に臭素系難燃剤が分解して発生するハロゲンラジカルやハロゲンイオンを補足することにより、ポリスチレン系樹脂の分子量低下や着色を抑制することができるものである。 In the present invention, stabilizers such as hindered phenol stabilizers, phosphorus stabilizers, and hindered amine stabilizers can be added. The stabilizer can suppress a decrease in molecular weight or coloring of the polystyrene resin by capturing halogen radicals or halogen ions generated by decomposition of the brominated flame retardant during processing.
本発明の製造方法において、発泡性溶融樹脂組成物には、難燃剤以外に、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０．５〜１０ｍｍのタルクが好ましい。 In the production method of the present invention, in addition to the flame retardant, a foam adjusting agent 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 10 mm 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、酸化チタンやアルミニウム等の断熱性向上剤、着色剤、酸化防止剤、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、前記気泡調整剤、着色剤等の各種添加剤の押出発泡工程における添加方法としては、前記難燃剤の添加方法と同様の添加方法が採用できる。 In the production method of the present invention, in addition to the above-mentioned air conditioner and flame retardant, a heat-insulating agent such as graphite, hydrotalcite, carbon black, titanium oxide, and aluminum, as long as the object and effect of the present invention are not impaired. Various additives such as colorants, antioxidants, fillers and lubricants can be appropriately added. In addition, the addition method similar to the addition method of the said flame retardant can be employ | adopted as the addition method in an extrusion foaming process of various additives, such as the said bubble regulator and a coloring agent.
軽量性と機械的強度とのバランスを考慮すると、ポリスチレン系樹脂押出発泡体の見掛け密度は、２０〜６０ｋｇ／ｍ３が好ましく、より好ましくは２２〜５０ｋｇ／ｍ３である。
ここで、押出発泡時に小気泡が発生してしまうと、発泡過程において気泡が成長しにくくなるため、見掛け密度３０ｋｇ／ｍ３以下の押出発泡体を製造しにくくなる。本発明においては、脂肪族ポリエステル系樹脂を配合することより、小気泡の発生を防ぐことができる。
Considering the balance between lightness and mechanical strength, the apparent density of the extruded polystyrene resin foam is preferably 20 to 60 kg / m 3 , more preferably 22 to 50 kg / m 3 .
Here, if small bubbles are generated at the time of extrusion foaming, the bubbles are difficult to grow in the foaming process, so that it is difficult to produce an extruded foam having an apparent density of 30 kg / m 3 or less. In the present invention, the generation of small bubbles can be prevented by blending the aliphatic polyester resin.
本発明により得られるポリスチレン系樹脂押出発泡体を建築用断熱材や、土木用途に使用する場合には、該押出発泡体の厚みは１０〜１５０ｍｍが好ましく、より好ましくは２０〜１００ｍｍである。 When the polystyrene-based resin extruded foam obtained by the present invention is used for a heat insulating material for construction or civil engineering, the thickness of the extruded foam is preferably 10 to 150 mm, more preferably 20 to 100 mm.
機械的強度と断熱性とのバランスを考慮すると、ポリスチレン系樹脂押出発泡体の厚み方向の平均気泡径は０．０８〜１ｍｍであることが好ましく、より好ましくは０．１〜０．８ｍｍである。一般に、平均気泡径が一定の範囲において大きい程、ポリスチレン系樹脂押出発泡体は機械的強度に優れたものとなり、断熱性は低下する傾向にある。一方、平均気泡径が一定の範囲において小さい程、機械的強度は低下し、断熱性は向上する傾向にある。ここで、特に圧縮強さなどの機械的強度に優れた押出発泡体とするためには、０．１ｍｍ以下の気泡は少ないほど好ましく、さらに厚み方向の平均気泡径が０．２ｍｍ以上であることが好ましい。 Considering the balance between mechanical strength and heat insulating properties, the average cell diameter in the thickness direction of the polystyrene-based resin extruded foam is preferably 0.08 to 1 mm, more preferably 0.1 to 0.8 mm. . Generally, the larger the average cell diameter is in a certain range, the more the polystyrene-based resin extruded foam has excellent mechanical strength, and the heat insulation tends to decrease. On the other hand, the smaller the average bubble diameter is, the lower the mechanical strength and the better the heat insulation. Here, in order to obtain an extruded foam having excellent mechanical strength such as compression strength, the number of bubbles of 0.1 mm or less is preferably as small as possible, and the average cell diameter in the thickness direction is 0.2 mm or more. Is preferred.
本明細書における平均気泡径とは、次の測定方法により求められる気泡径を意味する。
押出発泡体厚み方向の平均気泡径（ＤＴ：ｍｍ）及び押出発泡体幅方向の平均気泡径（ＤＷ：ｍｍ）は、押出発泡体の幅方向垂直断面（押出発泡体の押出方向と直交する垂直断面）に存在する個々の気泡に対して、厚み方向及び幅方向に平行な四辺を有し、かつ気泡に外接する長方形の厚み方向の辺の長さ及び幅方向の辺の長さを計測して、それぞれを各気泡の厚み方向の気泡径、幅方向の気泡径を求め、各々の算術平均値を厚み方向の平均気泡径（ＤＷ）、幅方向の平均気泡径（ＤＴ）とする。
一方、押出発泡体押出方向の平均気泡径（ＤＬ：ｍｍ）は、押出発泡体の押出方向垂直断面（押出発泡体の押出方向に平行に、幅方向の中央部で二等分した垂直断面）に存在する個々の気泡に対して、厚み方向及び押出方向に平行な四辺を有し、かつ気泡に外接する長方形の押出方向の辺の長さを計測して、各気泡の厚み方向の気泡径を求め、それらの算術平均値を押出方向の平均気泡径（ＤＬ）とする。。
また、押出発泡体の水平方向の平均気泡径（ＤＨ：ｍｍ）は、ＤＷとＤＬの相加平均値とする。
The average bubble diameter in this specification means the bubble diameter calculated | required with the following measuring method.
The average cell diameter (DT: mm) in the thickness direction of the extruded foam and the average cell size (DW: mm) in the width direction of the extruded foam are vertical cross-sections in the width direction of the extruded foam (vertical perpendicular to the extrusion direction of the extruded foam). For each bubble in the cross section), measure the length of the side of the rectangle in the thickness direction and the length of the side of the width direction of the rectangle that has four sides parallel to the thickness direction and the width direction and circumscribes the bubble. Thus, the bubble diameter in the thickness direction and the bubble diameter in the width direction of each bubble are obtained, and the arithmetic average values are taken as the average bubble diameter (DW) in the thickness direction and the average bubble diameter (DT) in the width direction.
On the other hand, the average cell diameter (DL: mm) in the extrusion direction of the extruded foam is the vertical cross section in the extrusion direction of the extruded foam (vertical cross section parallel to the extrusion direction of the extruded foam and bisected at the center in the width direction). Measure the length of the sides in the extrusion direction of the rectangle that has four sides parallel to the thickness direction and the extrusion direction, and circumscribe the bubbles, and the bubble diameter in the thickness direction of each bubble. And the arithmetic average value thereof is defined as the average cell diameter (DL) in the extrusion direction. .
Moreover, let the average bubble diameter (DH: mm) of the horizontal direction of an extrusion foam be an arithmetic mean value of DW and DL.
更に、本発明で得られる押出発泡体においては、気泡変形率が０．７〜２．０であることが好ましい。気泡変形率とは、上記測定方法により求められたＤＴをＤＨで除すことにより算出される値（ＤＴ／ＤＨ）であり、該気泡変形率が１よりも小さいほど気泡は扁平であり、１よりも大きいほど縦長である。気泡変形率が小さすぎる場合は、気泡が扁平なので圧縮強度が低下する虞れがあり、扁平な気泡は球形に戻ろうとする傾向が強いので、押出発泡体の寸法安定性も低下する虞がある。気泡変形率が大きすぎる場合は、厚み方向における気泡数が少なくなるので、気泡形状による断熱性向上効果が小さくなる。そのような観点から、上記気泡変形率は、０．８〜１．５であることが好ましく、０．８〜１．２であることがより好ましい。気泡変形率が上記範囲内にあることにより、機械的強度に優れ、かつ更に高い断熱性を有する押出発泡体となる。 Furthermore, in the extruded foam obtained in the present invention, the cell deformation rate is preferably 0.7 to 2.0. The bubble deformation rate is a value (DT / DH) calculated by dividing DT obtained by the above measurement method by DH. The smaller the bubble deformation rate is, the flatter the bubble is. The larger it is, the longer it is. If the bubble deformation rate is too small, the compression strength may decrease because the bubbles are flat, and the flat bubbles tend to return to a spherical shape, so the dimensional stability of the extruded foam may also decrease. . When the bubble deformation rate is too large, the number of bubbles in the thickness direction is reduced, so that the effect of improving heat insulation by the bubble shape is reduced. From such a viewpoint, the bubble deformation rate is preferably 0.8 to 1.5, and more preferably 0.8 to 1.2. When the bubble deformation rate is within the above range, an extruded foam having excellent mechanical strength and higher heat insulation is obtained.
本発明により得られる押出発泡体は、前記の通り小気泡の発生が防止されて単峰分布の気泡構造を有するものである。押出発泡体の断面における気泡は様々な位置で切断された気泡の集合であることから、元々ある程度の分散度を有するが、厚み方向の気泡径（ＤＴ）の変動係数は６０％以下であることが好ましく、より好ましくは５０％以下である。 As described above, the extruded foam obtained by the present invention has a unimodal bubble structure in which the generation of small bubbles is prevented. Since the bubbles in the cross section of the extruded foam are aggregates of bubbles cut at various positions, they originally have a certain degree of dispersion, but the variation coefficient of the bubble diameter (DT) in the thickness direction is 60% or less. Is preferable, and more preferably 50% or less.
気泡径の変動係数Ｃｖ（％）は、厚み方向の個々の気泡径（ＤＴｉ）の［標準偏差Ｖ（ｍｍ）／厚み方向の気泡径平均値（ＤＴａｖ：ｍｍ）］×１００で求められる値であり、気泡径のバラツキ度合いを表す指標である。なお、気泡径の標準偏差（Ｖ）は次式（３）により求められる。
Ｖ（ｍｍ）＝｛Σ（ＤＴｉ−ＤＴａｖ）２／（ｎ−１）｝１／２ （３）
The variation coefficient Cv (%) of the bubble diameter is a value obtained by [standard deviation V (mm) / average bubble diameter value in the thickness direction (DTav: mm)] × 100 of individual bubble diameters (DTi) in the thickness direction. Yes, it is an index representing the degree of variation in bubble diameter. The standard deviation (V) of the bubble diameter is obtained by the following equation (3).
V (mm) = {Σ (DTi−DTav) 2 / (n−1)} 1/2 (3)
式（３）において、ＤＴｉは平均気泡径の測定の際に測定した個々の厚み方向の気泡径の測定値を、ＤＴａｖは厚み方向の気泡径平均値を、ｎは測定数をそれぞれ表す。
変動係数（Ｃｖ）は（３）式により求めた標準偏差（Ｖ）を用いて、次式（４）によって求められる。
Ｃｖ（％）＝（Ｖ／ＤＴａｖ）×１００ （４）
In Formula (3), DTi represents the measured value of the bubble diameter in the thickness direction measured at the time of measuring the average bubble diameter, DTav represents the average value of the bubble diameter in the thickness direction, and n represents the number of measurements.
The coefficient of variation (Cv) is obtained by the following equation (4) using the standard deviation (V) obtained by the equation (3).
Cv (%) = (V / DTav) × 100 (4)
本発明で得られる押出発泡体の独立気泡率は９０％以上であることが好ましく、９３％以上であることがより好ましい。独立気泡率が高い程、高い断熱性能を維持することができる。独立気泡率Ｓ（％）は、ＡＳＴＭ−Ｄ２８５６−７０の手順Ｃに従って、空気比較式比重計（例えば、東芝ベックマン（株）製、空気比較式比重計、型式：９３０型）を使用して測定された押出発泡体の真の体積Ｖｘを用い、下記式（５）により算出される。
測定試料は、押出発泡体において中央部および幅方向両端部付近の計３箇所からカットサンプルを切り出して各々のカットサンプルについて独立気泡率を測定し、３箇所の独立気泡率の算術平均値を押出発泡体の独立気泡率とする。なお、カットサンプルは押出発泡体から縦２５ｍｍ×横２５ｍｍ×厚み２０ｍｍの大きさに切断された、押出発泡体表皮を有しないサンプルとし、厚みが薄く厚み方向に２０ｍｍのサンプルが切り出せない場合には、例えば縦２５ｍｍ×横２５ｍｍ×厚み１０ｍｍの大きさに切断された試料（カットサンプル）を２枚重ねて測定する。
The closed cell ratio of the extruded foam obtained in the present invention is preferably 90% or more, and more preferably 93% or more. The higher the closed cell ratio, the higher the heat insulation performance can be maintained. The closed cell ratio S (%) is measured using an air comparison type hydrometer (for example, Toshiba Beckman Co., Ltd., air comparison type hydrometer, model: 930 type) according to the procedure C of ASTM-D2856-70. The true volume Vx of the extruded foam thus obtained is calculated by the following formula (5).
Measurement samples were cut out from a total of three locations near the center and both ends in the width direction of the extruded foam, and the closed cell ratio was measured for each cut sample, and the arithmetic average value of the three closed cell ratios was extruded. The closed cell ratio of the foam is used. The cut sample is a sample that is cut from the extruded foam to a size of 25 mm long × 25 mm wide × 20 mm thick and does not have an extruded foam skin. If the sample is thin and 20 mm in the thickness direction cannot be cut out, For example, two samples (cut samples) cut into a size of 25 mm long × 25 mm wide × 10 mm thick are stacked and measured.
Ｓ（％）＝（Ｖｘ−Ｗ／ρ）×１００／（ＶＡ−Ｗ／ρ） （５）
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寸法から算出されたカットサンプルの見かけ上の体積（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の密度（ｇ／ｃｍ３）
S (%) = (Vx−W / ρ) × 100 / (VA−W / ρ) (5)
However, Vx: the true volume (cm 3 ) of the cut sample obtained by measurement with the above air comparison type hydrometer (the volume of the resin constituting the cut sample of the extruded foam, and all the bubbles in the closed cell portion in the cut sample Equivalent to the sum of volume.)
VA: apparent volume (cm 3 ) of the cut sample calculated from the outer dimensions of the cut sample used for measurement
W: Total weight of cut sample used for measurement (g)
ρ: Density of resin constituting the extruded foam (g / cm 3 )
以下、本発明のポリスチレン系樹脂押出発泡体について、実施例により詳細に説明する。但し、本発明は実施例に限定されるものではない。 Hereinafter, the polystyrene resin extruded foam of the present invention will be described in detail with reference to examples. However, the present invention is not limited to the examples.
［装置］
内径６５ｍｍの第１押出機と内径９０ｍｍの第２押出機と内径１５０ｍｍの第３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、間隙１ｍｍ×幅９０ｍｍの幅方向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３押出機の出口に連結されており、該フラットダイの樹脂出口には、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（間隔２８ｍｍ）が付設されている装置を用いた。
[apparatus]
A first extruder with an inner diameter of 65 mm, a second extruder with an inner diameter of 90 mm, and a third extruder with an inner diameter of 150 mm are connected in series, and a blowing agent inlet is provided near the end of the first extruder, A flat die having a resin discharge port (die lip) having a rectangular cross section in the width direction of 1 mm × width 90 mm is connected to the outlet of the third extruder, and the resin outlet of the flat die is parallel to the outlet. The apparatus provided with the shaping apparatus (space | interval 28mm) comprised by the board which consists of the installed upper and lower pair of polytetrafluoroethylene resin was used.
［ポリスチレン系樹脂］
ＰＳ１：ＰＳジャパン株式会社製「ＧＸ１５４（ＭＦＲ：１．６ｇ／１０分）」５０重量％とＰＳジャパン株式会社製「６７９（ＭＦＲ：１８ｇ／１０分）」５０重量％との混合樹脂
[Polystyrene resin]
PS1: Mixed resin of 50% by weight of “GX154 (MFR: 1.6 g / 10 min)” manufactured by PS Japan and 50% by weight of “679 (MFR: 18 g / 10 min)” manufactured by PS Japan
［ポリエステル系樹脂］
表１に示すポリエステル系樹脂を用いた。
[Polyester resin]
Polyester resins shown in Table 1 were used.
［臭素系難燃剤］
表２に示す難燃剤を含有する難燃剤マスターバッチを、ポリスチレン系樹脂に対する難燃剤としての添加量が表３及び４に示す量となるようにポリスチレン系樹脂に添加した。
[Brominated flame retardant]
The flame retardant masterbatch containing the flame retardant shown in Table 2 was added to the polystyrene resin so that the amount added as a flame retardant to the polystyrene resin was the amount shown in Tables 3 and 4.
［気泡調整剤マスターバッチ］
ポリスチレン樹脂をベースレジンとし、タルク（松村産業（株）製、商品名：ハイフィラー＃１２）６０重量％を含有するタルクマスターバッチを用いた。
[Bubble conditioner master batch]
A talc masterbatch containing 60% by weight of talc (manufactured by Matsumura Sangyo Co., Ltd., trade name: High Filler # 12) using polystyrene resin as a base resin was used.
実施例１〜１４、比較例１〜７
表３及び４に示す配合及び配合量となるようにポリスチレン系樹脂、ポリエステル系樹脂、難燃剤、さらに気泡調整剤マスターバッチ０．２重量部を、前記第１押出機に供給し、２２０℃まで加熱し、これらを溶融、混練し、発泡剤注入口から表３及び４に示す配合組成、量の発泡剤を溶融物に供給してさらに溶融混練し、得られた発泡性溶融樹脂組成物を、順に第２押出機、第３押出機に供給して樹脂温度を表３及び４に示すような発泡に適した発泡樹脂温度（押出機とダイとの接合部の位置で測定された発泡性溶融樹脂組成物の温度）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、ガイダー内を通過させることにより板状に成形（賦形）しポリスチレン系樹脂押出発泡体を製造した。
Examples 1-14, Comparative Examples 1-7
Polystyrene-based resin, polyester-based resin, flame retardant, and 0.2 parts by weight of air-conditioning agent master batch are supplied to the first extruder so as to have the blending and blending amounts shown in Tables 3 and 4, up to 220 ° C. These are heated, melted and kneaded, the blending composition and amount of the foaming agent shown in Tables 3 and 4 are supplied to the melt from the foaming agent inlet and further melt-kneaded, and the resulting foamable molten resin composition is obtained. The resin temperature was supplied to the second extruder and the third extruder in order, and the resin temperature suitable for foaming as shown in Tables 3 and 4 (foamability measured at the position of the junction between the extruder and the die) After adjusting to the temperature of the molten resin composition), it was extruded from the die lip into the guider at a discharge rate of 70 kg / hr, and molded into a plate shape (shaped) by passing through the guider to produce a polystyrene resin extruded foam. .
なお、表３及び４中のポリエステル系樹脂、及び難燃剤の配合量［重量部］は、ポリスチレン系樹脂１００重量部に対する値であり、発泡剤の配合量［モル／ｋｇ］は、ポリスチレン系樹脂１ｋｇあたりの添加量である。また、表中の発泡剤の「ｉ−Ｂｕ」はイソブタンを、「ＣＯ２」は二酸化炭素を意味する。 In Tables 3 and 4, the blending amount [parts by weight] of the polyester resin and the flame retardant is a value relative to 100 parts by weight of the polystyrene resin, and the blending amount [mol / kg] of the foaming agent is the polystyrene resin. It is the amount added per kg. In the table, “i-Bu” of the blowing agent means isobutane, and “CO 2 ” means carbon dioxide.
実施例、比較例で得られた押出発泡体における厚み方向の平均気泡径（ＤＴ）、気泡変形率（ＤＴ／ＤＨ）、厚み方向の気泡径の変動係数（Ｃｖ）、全気泡中に占める０．１ｍｍ以下の小気泡の個数基準の割合（小気泡の割合）、見掛け密度、独立気泡率、難燃性などの物性を表３及び４に示す。 In the extruded foams obtained in Examples and Comparative Examples, the average cell diameter in the thickness direction (DT), the bubble deformation rate (DT / DH), the coefficient of variation in the cell diameter in the thickness direction (Cv), 0 in all the bubbles Tables 3 and 4 show physical properties such as the number-based ratio of small bubbles of 1 mm or less (ratio of small bubbles), apparent density, closed cell ratio, and flame retardancy.
表３及び４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下記の通りである。 The measurement methods and evaluation methods for various physical properties of the extruded foams shown in Tables 3 and 4 are as follows.
［平均気泡径、気泡変形率］
厚み方向の平均気泡径（ＤＴ）、気泡変形率（ＤＴ／ＤＨ）については、前記方法により測定した。厚み方向の平均気泡径（ＤＴ）及び幅方向の平均気泡径（ＤＴ）は、押出発泡体の幅方向垂直断面の中央部及び両端部付近の計三箇所の拡大倍率５０倍の拡大写真を得、各々の写真上において、ナノシステム株式会社製の画像処理ソフトＮＳ２Ｋ−ｐｒｏを用いて個々の気泡の厚み方向の気泡径及び幅方向の気泡径を計測し、それらの値を各々算術平均することにより求めた。また、押出方向の平均気泡径（ＤＬ）は、押出発泡体の幅方向を二等分する位置で押出発泡体を切断した押出方向垂直断面の中央部及び両端部付近の計三箇所の拡大倍率５０倍の拡大写真を得、各々の写真上において、ナノシステム株式会社製の画像処理ソフトＮＳ２Ｋ−ｐｒｏを用いて個々の気泡の押出方向の気泡径を計測し、それらの値を各々算術平均することにより求めた。
[Average bubble diameter, bubble deformation rate]
The average cell diameter (DT) in the thickness direction and the cell deformation rate (DT / DH) were measured by the above methods. For the average cell diameter (DT) in the thickness direction and the average cell diameter (DT) in the width direction, an enlarged photograph with a magnification of 50 times is obtained at a total of three locations near the center and both ends of the vertical cross section of the extruded foam. In each photograph, the bubble diameter in the thickness direction and the bubble diameter in the width direction of each bubble are measured using the image processing software NS2K-pro manufactured by Nanosystem Co., Ltd., and the respective values are arithmetically averaged. Determined by In addition, the average cell diameter (DL) in the extrusion direction is an enlargement ratio of a total of three locations near the center and both ends of the vertical cross section in the extrusion direction when the extruded foam is cut at a position that bisects the width direction of the extruded foam. 50 times magnified photographs were obtained, and on each photograph, the bubble diameter in the extrusion direction of each bubble was measured using image processing software NS2K-pro manufactured by Nanosystem Co., Ltd., and these values were arithmetically averaged. Was determined by
［変動係数］
変動係数Ｃｖについては、上記で計測した個々の気泡の厚み方向の気泡径から前記方法により求めた。
[Coefficient of variation]
The coefficient of variation Cv was determined by the above method from the bubble diameter in the thickness direction of each bubble measured above.
［小気泡の割合］
上記で厚み方向の気泡径を計測した個々の気泡のうち、厚み方向の気泡径が０．１ｍｍ以下の気泡の数の割合（個数基準）を１００分率で表した値を小気泡の割合とした。
[Percentage of small bubbles]
Of the individual bubbles whose thickness direction was measured in the above, the ratio of the number of bubbles whose bubble diameter in the thickness direction is 0.1 mm or less (number basis) is expressed as the ratio of small bubbles. did.
［見掛け密度］
ＪＩＳ Ｋ７２２２（１９８５）に基づいて測定された値である。
[Apparent density]
It is a value measured based on JIS K7222 (1985).
［独立気泡率］
押出発泡体の幅方向中央部及び両端部付近から、それぞれ２５ｍｍ×２５ｍｍ×２０ｍｍのサイズの成形表皮を持たないサンプルを切り出し、前記ＡＳＴＭ−Ｄ２８５６−７０の手順Ｃにより各サンプルの独立気泡率を測定し、それらの測定値を算術平均した値を押出発泡板の独立気泡率とした。
[Closed cell ratio]
Samples that do not have a molded skin of 25 mm × 25 mm × 20 mm each are cut from the widthwise center and both ends of the extruded foam, and the closed cell ratio of each sample is measured by Procedure C of ASTM-D2856-70. The value obtained by arithmetically averaging these measured values was defined as the closed cell ratio of the extruded foam plate.
［難燃性］
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、ＪＩＳ Ａ９５１１（２００６Ｒ）の５．１３．１「測定方法Ａ」に基づいて測定した。尚、測定は一つの発泡体から試験片を５個切り出して（Ｎ＝５）下記の評価基準にて評価した。
◎：全ての試験片において３秒以内で消え、且つ、５個の試験片の平均燃焼時間が２秒以内である。
○：全ての試験片において３秒以内で消え、且つ、５個の試験片の平均燃焼時間が２秒を超え３秒以内である。
×：５個の試験片の平均燃焼時間が３秒を越える。
[Flame retardance]
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 measured in accordance with 5.13.1 “Measurement Method A” of JIS A9511 (2006R). . In the measurement, five test pieces were cut out from one foam (N = 5) and evaluated according to the following evaluation criteria.
A: All specimens disappeared within 3 seconds, and the average burning time of 5 specimens is within 2 seconds.
○: All specimens disappear within 3 seconds, and the average burning time of 5 specimens exceeds 2 seconds and is within 3 seconds.
X: The average burning time of 5 test pieces exceeds 3 seconds.
実施例１〜１４においては、脂肪族ポリエステル系樹脂を配合することにより、いずれも小気泡の発生が抑制されており、さらに全体的に気泡が拡大され、低見掛け密度の良好な押出発泡体が得られている。これに対し、脂肪族ポリエステル系樹脂を配合していない比較例１〜６においては、小気泡が発生してしまい、比較例１〜４においては、気泡が十分に成長できないため、同発泡条件下で実施例と比べると高見掛け密度の押出発泡体しか得られておらず、比較例５及び６においては、気泡が微細すぎて板状の押出発泡体に成形することができなかった。また、比較例７は、脂肪族ポリエステル系樹脂の代わりに、芳香族ポリエステル系樹脂を配合した例であるが、やはり小気泡の発生を抑制することができず、同発泡条件下で実施例と比べると高見掛け密度の押出発泡体しか得られていない。 In Examples 1 to 14, by adding an aliphatic polyester-based resin, the generation of small bubbles is suppressed in all cases, and the bubbles are expanded as a whole, and an extruded foam having a low low apparent density is obtained. Has been obtained. On the other hand, in Comparative Examples 1 to 6 in which no aliphatic polyester-based resin is blended, small bubbles are generated, and in Comparative Examples 1 to 4, the bubbles cannot grow sufficiently. In comparison with Examples, only an extruded foam having a high apparent density was obtained. In Comparative Examples 5 and 6, the bubbles were too fine to be formed into a plate-like extruded foam. In addition, Comparative Example 7 is an example in which an aromatic polyester resin is blended instead of the aliphatic polyester resin, but it is still impossible to suppress the generation of small bubbles, and under the same foaming conditions as in the example. In comparison, only an extruded foam having a high apparent density is obtained.
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| JP2015089921A (en) * | 2013-11-06 | 2015-05-11 | 株式会社ジェイエスピー | Method for producing polystyrene-based resin extruded foam plate |
| JP2015174865A (en) * | 2014-03-12 | 2015-10-05 | 株式会社ジェイエスピー | Method for producing polystyrene-based resin extrusion foam |
| JP2015183125A (en) * | 2014-03-25 | 2015-10-22 | 株式会社ジェイエスピー | Polystyrene-based resin foam production method |
| JP2017149997A (en) * | 2017-06-13 | 2017-08-31 | 株式会社ジェイエスピー | Polystyrene-based resin extrusion foamed plate |
| JP2017149996A (en) * | 2017-06-13 | 2017-08-31 | 株式会社ジェイエスピー | Manufacturing method of polystyrene resin extrusion foamed plate |
| JP2017160461A (en) * | 2017-06-13 | 2017-09-14 | 株式会社ジェイエスピー | Method for producing polystyrene resin extruded foam plate |
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| JP2015089921A (en) * | 2013-11-06 | 2015-05-11 | 株式会社ジェイエスピー | Method for producing polystyrene-based resin extruded foam plate |
| JP2015174865A (en) * | 2014-03-12 | 2015-10-05 | 株式会社ジェイエスピー | Method for producing polystyrene-based resin extrusion foam |
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| JP2018184562A (en) * | 2017-04-27 | 2018-11-22 | 株式会社カネカ | Styrenic resin extruded foamed body and method for producing the same |
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| JP2017149997A (en) * | 2017-06-13 | 2017-08-31 | 株式会社ジェイエスピー | Polystyrene-based resin extrusion foamed plate |
| JP2017149996A (en) * | 2017-06-13 | 2017-08-31 | 株式会社ジェイエスピー | Manufacturing method of polystyrene resin extrusion foamed plate |
| JP2017160461A (en) * | 2017-06-13 | 2017-09-14 | 株式会社ジェイエスピー | Method for producing polystyrene resin extruded foam plate |
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