JP2014177565A - Styrene-modified polyethylene-based pre-expanded particle and molding thereof - Google Patents
Styrene-modified polyethylene-based pre-expanded particle and molding thereof Download PDFInfo
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- JP2014177565A JP2014177565A JP2013053008A JP2013053008A JP2014177565A JP 2014177565 A JP2014177565 A JP 2014177565A JP 2013053008 A JP2013053008 A JP 2013053008A JP 2013053008 A JP2013053008 A JP 2013053008A JP 2014177565 A JP2014177565 A JP 2014177565A
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- Prior art keywords
- styrene
- weight
- modified polyethylene
- polyethylene resin
- parts
- 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
- 239000002245 particle Substances 0.000 title claims abstract description 168
- -1 polyethylene Polymers 0.000 title claims abstract description 36
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 33
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 33
- 238000000465 moulding Methods 0.000 title claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 69
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 63
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008096 xylene Substances 0.000 claims abstract description 19
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 12
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 12
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 229920013716 polyethylene resin Polymers 0.000 claims description 133
- 238000006116 polymerization reaction Methods 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 239000004088 foaming agent Substances 0.000 claims description 22
- 238000002835 absorbance Methods 0.000 claims description 9
- 238000005259 measurement Methods 0.000 claims description 9
- 239000002612 dispersion medium Substances 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 38
- 238000005187 foaming Methods 0.000 abstract description 37
- 239000001569 carbon dioxide Substances 0.000 abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000178 monomer Substances 0.000 abstract description 12
- 229920005678 polyethylene based resin Polymers 0.000 abstract description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 2
- 230000002794 monomerizing effect Effects 0.000 abstract 1
- 239000006260 foam Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 239000003431 cross linking reagent Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- 239000003505 polymerization initiator Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002270 dispersing agent Substances 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 10
- 238000007792 addition Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 7
- 239000004342 Benzoyl peroxide Substances 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 230000006837 decompression Effects 0.000 description 7
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007900 aqueous suspension Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000003570 air Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-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
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001872 inorganic gas Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- VMPHSYLJUKZBJJ-UHFFFAOYSA-N trilaurin Chemical compound CCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC)COC(=O)CCCCCCCCCCC VMPHSYLJUKZBJJ-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- TZJQCUDHKUWEFU-UHFFFAOYSA-N 2,2-dimethylpentanenitrile Chemical compound CCCC(C)(C)C#N TZJQCUDHKUWEFU-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- LZFZQYNTEZSWCP-UHFFFAOYSA-N 2,6-dibutyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC(CCCC)=C1O LZFZQYNTEZSWCP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
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- 241000282320 Panthera leo Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
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- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
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- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
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- 238000005227 gel permeation chromatography Methods 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
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- 239000008188 pellet Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
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- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
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- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- PVNIQBQSYATKKL-UHFFFAOYSA-N tripalmitin Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCC PVNIQBQSYATKKL-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-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
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- Molding Of Porous Articles (AREA)
Abstract
Description
本発明は、炭酸ガス発泡における発泡性、燃焼性に優れたスチレン改質ポリエチレン系樹脂粒子、予備発泡粒子、およびその成形体に関する。 The present invention relates to styrene-modified polyethylene resin particles, pre-expanded particles, and molded articles thereof, which are excellent in foamability and combustibility in carbon dioxide gas foaming.
ポリオレフィン系樹脂発泡体は、一般に弾性が高く、繰り返しの応力に対しても歪の回復力が大きいという特徴の他に、耐油性、耐割れ性に優れることから、包装資材や自動車部材として広く利用されている。しかし、ポリオレフィン系樹脂発泡体は剛性が低く、型内成形後の発泡成形体の収縮がおこりやすく、圧縮強度が低いという短所を有している。 Polyolefin resin foams are generally used as packaging materials and automotive parts because they are generally highly elastic and have excellent strain resistance against repeated stress, as well as excellent oil resistance and crack resistance. Has been. However, polyolefin resin foams have the disadvantages of low rigidity, easy shrinkage of the foamed molding after in-mold molding, and low compressive strength.
このような欠点を改良する方法として、ポリエチレン系樹脂にスチレン系単量体を含浸させて重合を行って得られるスチレン改質ポリエチレン樹脂を基材樹脂として用いることが知られている。 As a method for improving such a defect, it is known to use, as a base resin, a styrene-modified polyethylene resin obtained by impregnating a polyethylene resin with a styrene monomer and performing polymerization.
例えば、特許文献１、２では、ポリエチレン系樹脂としてエチレン／酢酸ビニル共重合体を用い、テトラヒドロフラン可溶部の分子量と熱キシレン不溶のゲル分の量を調整することにより、耐割れ性と成形加工性に優れた予備発泡粒子が得られている。 For example, in Patent Documents 1 and 2, an ethylene / vinyl acetate copolymer is used as the polyethylene resin, and the molecular weight of the tetrahydrofuran-soluble part and the amount of the gel component insoluble in hot xylene are adjusted, whereby the crack resistance and the molding process are performed. Pre-expanded particles having excellent properties are obtained.
特許文献３、４では、ポリエチレン系樹脂として直鎖状低密度ポリエチレンを用い、グラフト成分からなるゲル量を調整することにより、耐割れ性に優れた予備発泡粒子が得られている。 In Patent Documents 3 and 4, pre-expanded particles having excellent crack resistance are obtained by using linear low-density polyethylene as the polyethylene-based resin and adjusting the amount of gel composed of the graft component.
一方、安全性の観点、環境への配慮から、発泡剤として、現在主流である炭化水素系発泡剤の代わりに、炭酸ガス等の無機系発泡剤を使用する方法がある。 On the other hand, from the viewpoint of safety and consideration for the environment, there is a method in which an inorganic foaming agent such as carbon dioxide gas is used as the foaming agent instead of the hydrocarbon foaming agent which is currently mainstream.
特許文献５では、スチレン改質ポリオレフィン系樹脂を除圧発泡する方法が記載されており、発泡剤として炭酸ガスも挙げられている。しかしながら、実施例には炭酸ガス法での除圧発泡は記載されていない。 Patent Document 5 describes a method of decompressing and foaming a styrene-modified polyolefin resin, and carbon dioxide is also mentioned as a foaming agent. However, no decompression foaming by the carbon dioxide method is described in the examples.
特許文献６では、スチレン改質ポリオレフィン系樹脂を炭酸ガス法で発泡させる製造方法が記載されている。しかしながら、架橋により強度は高いものの、発泡性と燃焼性に関しては十分な性能とは言えなかった。 Patent Document 6 describes a production method in which a styrene-modified polyolefin resin is foamed by a carbon dioxide gas method. However, although the strength is high due to crosslinking, it cannot be said that the foaming property and combustibility are sufficient.
以上のような状況に鑑み、本発明の目的は、炭酸ガスによる発泡を行った場合においても、十分な発泡力を有し、自動車内装材として好適な燃焼性を有する成形体を得ることができるスチレン改質エチレン系予備発泡粒子を提供することにある。 In view of the above situation, the object of the present invention is to provide a molded article having sufficient foaming power and suitable combustibility as an automobile interior material even when foaming with carbon dioxide gas is performed. The object is to provide styrene-modified ethylene-based pre-expanded particles.
本発明者らは、鋭意検討の結果、ポリエチレン系樹脂１００重量部に対してスチレン系単量体１２０重量部以上５００重量部以下を含浸させて重合してなるスチレン改質ポリエチレン系樹脂を発泡して得られるスチレン改質ポリエチレン系樹脂予備発泡粒子であって、ポリエチレン系樹脂が分岐状低密度ポリエチレンであり、
スチレン改質ポリエチレン系樹脂予備発泡粒子のテトラヒドロフラン可溶部の重量平均分子量が１５万以上３５万以下であり、
スチレン改質ポリエチレン系樹脂予備発泡粒子が、揮発性成分を１％以下（←燃焼性に影響するため、残します）、熱キシレン不溶分を５重量％以上２０重量％以下、メチルエチルケトン可溶成分を５０重量％以下含有することを特徴とする、スチレン改質ポリエチレン系予備発泡粒子とすることにより、炭酸ガスによる発泡において優れた発泡体を得ることができることを見出し、本発明に至った。
As a result of intensive studies, the present inventors foamed a styrene-modified polyethylene resin obtained by polymerizing 100 parts by weight of a polyethylene resin by impregnating 120 parts by weight or more and 500 parts by weight or less of a styrene monomer. Styrene-modified polyethylene resin pre-expanded particles obtained by the following, wherein the polyethylene resin is a branched low-density polyethylene,
The weight average molecular weight of the tetrahydrofuran soluble part of the styrene-modified polyethylene resin pre-expanded particles is 150,000 to 350,000,
Styrene-modified polyethylene resin pre-expanded particles contain 1% or less of volatile components (← left to affect flammability), 5% to 20% by weight of hot xylene insolubles, and methyl ethyl ketone soluble components The present inventors have found that a foam excellent in foaming with carbon dioxide gas can be obtained by using styrene-modified polyethylene-based pre-foamed particles characterized by containing 50% by weight or less.
すなわち、本発明の第１は、
ポリエチレン系樹脂１００重量部に対してスチレン系単量体１２０重量部以上５００重量部以下を含浸させて重合してなるスチレン改質ポリエチレン系樹脂を発泡して得られるスチレン改質ポリエチレン系樹脂予備発泡粒子であって、
ポリエチレン系樹脂が分岐状低密度ポリエチレンであり、
スチレン改質ポリエチレン系樹脂予備発泡粒子のテトラヒドロフラン可溶部の重量平均分子量が１５万以上３５万以下であり、
スチレン改質ポリエチレン系樹脂予備発泡粒子が、揮発性成分が１％以下
熱キシレン不溶分を５重量％以上２０重量％以下、メチルエチルケトン可溶成分を５０重量％以下含有することを特徴とする、スチレン改質ポリエチレン系予備発泡粒子に関する。
好ましい実施態様としては、ＡＴＲ−ＩＲにおける吸光度比Ｄ０６９８／Ｄ２８５０が５．０以上２０．０以下であるスチレン改質ポリエチレン系予備発泡粒子である。
That is, the first of the present invention is
Pre-foaming of styrene-modified polyethylene resin obtained by foaming styrene-modified polyethylene resin obtained by impregnating 120 parts by weight or more and 500 parts by weight or less of styrene monomer with 100 parts by weight of polyethylene resin Particles,
The polyethylene resin is a branched low density polyethylene,
The weight average molecular weight of the tetrahydrofuran soluble part of the styrene-modified polyethylene resin pre-expanded particles is 150,000 to 350,000,
The styrene-modified polyethylene resin pre-expanded particles contain a volatile component of 1% or less and a thermal xylene insoluble content of 5% by weight to 20% by weight and a methyl ethyl ketone soluble component of 50% by weight or less. The present invention relates to modified polyethylene-based pre-expanded particles.
A preferred embodiment is a styrene-modified polyethylene pre-expanded particle having an absorbance ratio D 0698 / D 2850 in ATR-IR of 5.0 or more and 20.0 or less.
本発明の第２は、前記記載のスチレン改質ポリエチレン系予備発泡粒子の製造方法に関し、ポリエチレン系樹脂粒子にスチレン系単量体を含浸させて重合を行って得られるスチレン改質ポリエチレン系樹脂粒子を耐圧容器中に水系分散媒に分散させて加熱し、前記耐圧容器に発泡剤として無機ガスを導入して耐圧容器内を加圧した後、耐圧容器の一端を開放して、スチレン改質ポリエチレン系樹脂粒子および水系分散媒を含んでなる混合物を耐圧容器内よりも低圧雰囲気下に放出することを特徴とする。 The second aspect of the present invention relates to a method for producing the styrene-modified polyethylene pre-expanded particles described above, and the styrene-modified polyethylene resin particles obtained by polymerizing polyethylene resin particles impregnated with styrene monomers. Is heated in a pressure-resistant vessel dispersed in an aqueous dispersion medium, and after introducing an inorganic gas as a foaming agent into the pressure-resistant vessel and pressurizing the inside of the pressure-resistant vessel, one end of the pressure-resistant vessel is opened, and styrene-modified polyethylene It is characterized in that a mixture containing the system resin particles and the aqueous dispersion medium is discharged in a lower pressure atmosphere than in the pressure vessel.
本発明の第３は、前記記載のスチレン改質ポリエチレン系予備発泡粒子を成形してなる発泡成形体に関する。 3rd of this invention is related with the foaming molding formed by shape | molding the above-mentioned styrene modified polyethylene type pre-expanded particle.
本発明のスチレン改質ポリエチレン系樹脂予備発泡粒子は、炭酸ガスを発泡剤とした発泡に適しており、自動車内装材に好適な燃焼速度を有する。 The styrene-modified polyethylene resin pre-expanded particles of the present invention are suitable for foaming using carbon dioxide as a foaming agent, and have a combustion rate suitable for automobile interior materials.
本発明におけるスチレン改質ポリエチレン系樹脂粒子は、ポリエチレン系樹脂粒子１００重量部に対して、スチレン系単量体を好ましくは１２０重量部以上５００重量部以下、更に好ましくは１５０重量部以上４００重量部以下重合を添加して、含浸させ、重合させることにより得られるものである。
スチレン系単量体の総添加量が１２０重量部未満では、炭酸ガス発泡による発泡力を得ることが難しい傾向があり、５００重量部超では、成形加工性に劣る傾向がある。
The styrene-modified polyethylene resin particles in the present invention are preferably 120 parts by weight or more and 500 parts by weight or less, more preferably 150 parts by weight or more and 400 parts by weight or less based on 100 parts by weight of the polyethylene resin particles. In the following, polymerization is added, impregnated, and polymerized.
If the total addition amount of the styrenic monomer is less than 120 parts by weight, it tends to be difficult to obtain a foaming force by carbon dioxide gas foaming, and if it exceeds 500 parts by weight, the moldability tends to be inferior.
本発明において、スチレン改質ポリエチレン系樹脂粒子を得る方法としては、例えば、攪拌機を具備した容器内に仕込んだポリエチレン系樹脂粒子を含む水性懸濁液に、スチレン系単量体を連続的または断続的に添加することにより、ポリエチレン系樹脂粒子にスチレン系単量体を含浸させ、重合させる方法、等があげられる。 In the present invention, as a method for obtaining styrene-modified polyethylene resin particles, for example, a styrene monomer is continuously or intermittently added to an aqueous suspension containing polyethylene resin particles charged in a container equipped with a stirrer. For example, a method in which polyethylene resin particles are impregnated with a styrene monomer and polymerized is added.
本方法において、スチレン系単量体の添加速度を任意に選択することにより、スチレン改質ポリエチレン系樹脂予備発泡粒子の重量平均分子量を調整することが可能である。 In this method, the weight average molecular weight of the styrene-modified polyethylene resin pre-expanded particles can be adjusted by arbitrarily selecting the addition rate of the styrene monomer.
本発明におけるスチレン改質ポリエチレン系樹脂粒子の重合に際して、好ましい態様としては、添加されるスチレン系単量体の一部を、すなわち、ポリエチレン樹脂粒子１００重量部に対してスチレン系単量体３０重量部以上１５０重量部以下を、本質的に重合が進まない温度下で添加して含浸させ、残りのスチレン系単量体を重合が進む温度下で連続添加することである。 In the polymerization of the styrene-modified polyethylene resin particles in the present invention, as a preferred embodiment, a part of the added styrene monomer, that is, 30 parts by weight of the styrene monomer with respect to 100 parts by weight of the polyethylene resin particles. More than 150 parts by weight and less than 150 parts by weight are essentially added and impregnated at a temperature at which polymerization does not proceed, and the remaining styrenic monomer is continuously added at a temperature at which polymerization proceeds.
ここで、「本質的に重合が進まない温度」とは、使用する主たる重合開始剤の１０時間半減期温度以下の温度であることを言う。
重合に際して、添加するスチレン系単量体の一部を本質的に重合が進まない温度下で添加、含浸させることにより、重合場であるポリエチレン系樹脂粒子の粘度を変化させることができるため、スチレン改質ポリエチレン系樹脂予備発泡粒子の重量平均分子量を調整し易い。
Here, “the temperature at which polymerization does not proceed essentially” means a temperature not higher than the 10-hour half-life temperature of the main polymerization initiator used.
In the polymerization, by adding and impregnating a part of the styrene monomer to be added at a temperature at which the polymerization does not proceed essentially, the viscosity of the polyethylene resin particles as the polymerization site can be changed. It is easy to adjust the weight average molecular weight of the modified polyethylene resin pre-expanded particles.
残りのスチレン系単量体を連続追加する際の重合温度は、８０℃以上１００℃以下が好ましい。連続追加する温度が８０℃未満であると、ポリエチレン系樹脂へのスチレンの含浸が遅く、ポリエチレン系樹脂内での重合が進行しにくい傾向がある。連続追加する温度が１００℃超であると、樹脂同士の合着がおこりやすくなる傾向がある。 The polymerization temperature when continuously adding the remaining styrenic monomer is preferably 80 ° C. or higher and 100 ° C. or lower. When the temperature to be continuously added is less than 80 ° C., the impregnation of styrene into the polyethylene resin is slow, and the polymerization in the polyethylene resin tends not to proceed. When the temperature to be continuously added is more than 100 ° C., the resin tends to be easily bonded.
本発明で用いられるポリエチレン系樹脂は、スチレンの含浸重合性および重合時の合着性の観点から、一般的なスチレン単量体の重合温度に軟化点が近い分岐状低密度ポリエチレン樹脂が好ましい。 The polyethylene-based resin used in the present invention is preferably a branched low-density polyethylene resin having a softening point close to the polymerization temperature of a general styrene monomer from the viewpoints of styrene impregnation polymerization and coalescence during polymerization.
本発明で用いられるポリエチレン系樹脂のメルトフローレート（以降、「ＭＦＲ」と略す。）は、１．５ｇ／１０分以下であることが好ましく、１．０ｇ／１０分以下であることがより好ましい。ポリエチレン系樹脂のＭＦＲが１．５ｇ／１０分以下を超えると、重合時に樹脂同士が合着しやすい傾向がある。
なお、ＭＦＲは、ＪＩＳ Ｋ ６９２４に準拠して測定した値である。
The melt flow rate (hereinafter abbreviated as “MFR”) of the polyethylene resin used in the present invention is preferably 1.5 g / 10 min or less, and more preferably 1.0 g / 10 min or less. . If the MFR of the polyethylene resin exceeds 1.5 g / 10 min or less, the resins tend to be easily bonded together during polymerization.
The MFR is a value measured according to JIS K 6924.
前記ポリエチレン系樹脂は、予め、例えば押出機、ニーダー、バンバリーミキサー、ロール等を用いて溶融混練することにより、ポリエチレン系樹脂粒子となす。ポリエチレン系樹脂粒子の形状はパウダー、ペレット状等の粒子状態であることが好ましい。
本発明で用いられるポリエチレン系樹脂粒子の平均粒重量は、０．１ｍｇ／粒以上３ｍｇ／粒以下が好適な範囲である。ポリエチレン系樹脂粒子の平均粒重量が０．１ｍｇ／粒より小さいと、発泡剤の逸散が激しく高倍率化させにくくなる場合があり、３ｍｇ／粒より大きいと、成形時の充填性が悪くなる恐れがある。
The polyethylene-based resin is made into polyethylene-based resin particles by melt-kneading in advance using, for example, an extruder, a kneader, a Banbury mixer, a roll, or the like. The shape of the polyethylene resin particles is preferably a particle state such as powder or pellet.
The average particle weight of the polyethylene resin particles used in the present invention is preferably in the range of 0.1 mg / particle to 3 mg / particle. If the average particle weight of the polyethylene resin particles is smaller than 0.1 mg / particle, the foaming agent may be dissipated rapidly, making it difficult to increase the magnification. If it is larger than 3 mg / particle, the filling property at the time of molding is deteriorated. There is a fear.
本発明で用いられるポリエチレン系樹脂粒子には、各種添加剤として、目的に応じて、可塑剤、気泡調整剤等を配合することができる。 In the polyethylene resin particles used in the present invention, as various additives, a plasticizer, a bubble regulator and the like can be blended depending on the purpose.
可塑剤としては、例えば、ステアリン酸トリグリセライド、パルミチン酸トリグリセライド、ラウリン酸トリグリセライド、ステアリン酸ジグリセライド、ステアリン酸モノグリセライド等の脂肪酸グリセライド、ヤシ油、パーム油、パーム核油等の植物油、ジオクチルアジペート、ジブチルセバケート等の脂肪族エステル、流動パラフィン、シクロヘキサン等の有機炭化水素、トルエン、エチルベンゼン等の有機芳香族炭化水素等があげられ、これらは燃焼性に影響を与えない範囲で併用しても何ら差し支えない。 Examples of the plasticizer include stearic acid triglyceride, palmitic acid triglyceride, lauric acid triglyceride, stearic acid diglyceride, stearic acid monoglyceride and other fatty acid glycerides, palm oil, palm oil, palm kernel oil and other vegetable oils, dioctyl adipate, dibutyl sebacate Examples include aliphatic esters such as liquid paraffin, organic hydrocarbons such as liquid paraffin and cyclohexane, and organic aromatic hydrocarbons such as toluene and ethylbenzene, and these may be used in combination as long as they do not affect flammability.
気泡調整剤としては、例えば、メチレンビスステアリン酸アマイド、エチレンビスステアリン酸アマイド等の脂肪族ビスアマイドやステアリン酸アミド等の有機系気泡調整剤、タルク、シリカ、珪酸カルシウム、炭酸カルシウム、ホウ酸ナトリウム、ホウ酸亜鉛、等の無機系気泡調整剤等があげられる。
特に、後述する除圧発泡を行う場合、無機系気泡調整剤を使用することが好ましく、好ましい使用量としては、ポリエチレン系樹脂１００重量部に対し、０．０１重量部以上０．５重量部以下である。
無機系気泡調整剤が０．０１重量部より少ないと、安定的に気泡を生成することが困難となる傾向があり、０．５重量部より多く使用した場合は成形時の融着が悪化する傾向がある。
Examples of the foam regulator include, for example, aliphatic bisamides such as methylene bis stearic acid amide, ethylene bis stearic acid amide, and organic foam regulating agents such as stearamide, talc, silica, calcium silicate, calcium carbonate, sodium borate, Inorganic bubble regulators such as zinc borate are listed.
In particular, when performing depressurization foaming, which will be described later, it is preferable to use an inorganic cell regulator, and the preferred usage is 0.01 parts by weight or more and 0.5 parts by weight or less with respect to 100 parts by weight of the polyethylene resin. It is.
When the amount of the inorganic bubble regulator is less than 0.01 part by weight, it tends to be difficult to stably generate bubbles, and when it is used more than 0.5 part by weight, the fusion during molding is deteriorated. Tend.
これらの各種添加剤は、重合時、発泡剤含浸時に添加するのみならず、予めポリエチレン系樹脂粒子に混ぜ込むことで使用することもできる。 These various additives can be used not only at the time of polymerization and at the time of impregnation with the foaming agent, but also by being previously mixed with the polyethylene resin particles.
本発明で用いられるスチレン系単量体としては、例えば、スチレン、α−メチルスチレン、パラメチルスチレン、ｔ−ブチルスチレン、クロルスチレン等のスチレン系誘導体を主成分として使用することができる。 As the styrene monomer used in the present invention, for example, a styrene derivative such as styrene, α-methyl styrene, paramethyl styrene, t-butyl styrene, chlorostyrene or the like can be used as a main component.
本発明で用いられるスチレン系単量体には、スチレン系誘導体と共重合が可能な単量体を、本発明のスチレン改質ポリエチレン系樹脂予備発泡粒子の効果を阻害しない範囲において併用することができる。
スチレン系誘導体と共重合が可能な単量体としては、例えば、メチルアクリレート、ブチルアクリレート、メチルメタクリレート、エチルメタクリレート等のアクリル酸およびメタクリル酸のエステル、あるいはアクリロニトリル、ジメチルフマレート、エチルフマレート等が挙げられる。これらは、単独で使用しても良いし、２種以上併用しても良い。
更に、ジビニルベンゼン、アルキレングリコールジメタクリレート等の多官能性単量体を使用することもできる。
In the styrene monomer used in the present invention, a monomer that can be copolymerized with a styrene derivative may be used in combination as long as the effect of the styrene-modified polyethylene resin pre-expanded particles of the present invention is not impaired. it can.
Examples of monomers that can be copolymerized with styrene derivatives include acrylic acid and methacrylic acid esters such as methyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate, or acrylonitrile, dimethyl fumarate, and ethyl fumarate. Can be mentioned. These may be used alone or in combination of two or more.
Furthermore, polyfunctional monomers such as divinylbenzene and alkylene glycol dimethacrylate can also be used.
本発明におけるスチレン改質ポリエチレン系樹脂粒子の重合に用いられる重合開始剤としては、一般に熱可塑性重合体の製造に用いられるラジカル発生型重合開始剤を用いることができ、代表的なものとしては、例えば、過酸化ベンゾイル、ラウロイルパーオキサイド、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーピバレート、ｔ−ブチルパーオキシイソプロピルカーボネート、ジ−ｔ−ブチルパーオキシヘキサハイドロテレフタレート、１，１−ジ（ｔ−ブチルパーオキシ）３，３，５−トリメチルシクロヘキサン、１，１−ジ（ｔ−ブチルパーオキシ）シクロヘキサンなどの有機過酸化物や、アゾビスイソブチロニトリル、アゾビスジメチルバレロニトリルなどのアゾ化合物が挙げられる。これらの重合開始剤は、単独で使用してもよいし、２種以上を併用しても良い。 As the polymerization initiator used for the polymerization of the styrene-modified polyethylene resin particles in the present invention, a radical generating polymerization initiator generally used for the production of a thermoplastic polymer can be used. For example, benzoyl peroxide, lauroyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl perpivalate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyhexahydroterephthalate, 1 , 1-di (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, azobisisobutyronitrile, azobis Examples include azo compounds such as dimethylvaleronitrile. These polymerization initiators may be used alone or in combination of two or more.
これらの中でも、ｔ−ブチルパーオキシ−２−エチルヘキサノエート（１０時間半減期温度：７２℃）と過酸化ベンゾイル（１０時間半減期温度：７４℃）の併用が、テトラヒドロフラン可溶部の重量平均分子量、熱キシレン不溶分、熱キシレン可溶メチルエチルケトン不溶成分の量を所定の量としやすい点から、好ましい。 Among these, the combined use of t-butylperoxy-2-ethylhexanoate (10-hour half-life temperature: 72 ° C.) and benzoyl peroxide (10-hour half-life temperature: 74 ° C.) is the weight of the tetrahydrofuran soluble part. The average molecular weight, the heat xylene insoluble component, and the amount of the heat xylene soluble methyl ethyl ketone insoluble component are preferable from the viewpoint that the predetermined amount is easily obtained.
重合開始剤の使用量は、ポリスチレン系単量体１００重量部に対して０．０５重量部以上１．０重量部以下であることが好ましく、０．２重量部以上、０．７重量部以下であることがより好ましい。
重合開始剤の使用量が０．０５部未満では、重合が十分に進行せず、残存モノマーが多くなる傾向があり、１．０重量部超では、重合反応が急速に起こる為、発熱によって重合温度の調整が困難となる傾向がある。
特に、ｔ−ブチルパーオキシ−２−エチルヘキサノエートに関しては、０．３重量部以上０．６重量部以下で使用することが好ましく、０．２重量部以上０．４重量部以下で使用することがより好ましい。過酸化ベンゾイルに関しては、０．０５重量部以上０．３重量部以下使用することが好ましく、０．２重量部以上０．４重量部以下で使用することがより好ましい。
The amount of the polymerization initiator used is preferably 0.05 parts by weight or more and 1.0 parts by weight or less, based on 100 parts by weight of the polystyrene-based monomer, and is 0.2 parts by weight or more and 0.7 parts by weight or less. It is more preferable that
When the amount of the polymerization initiator used is less than 0.05 part, the polymerization does not proceed sufficiently and the residual monomer tends to increase. When the amount exceeds 1.0 part by weight, the polymerization reaction occurs rapidly. It tends to be difficult to adjust the temperature.
In particular, with respect to t-butylperoxy-2-ethylhexanoate, it is preferably used in an amount of 0.3 to 0.6 parts by weight, and used in an amount of 0.2 to 0.4 parts by weight. More preferably. With respect to benzoyl peroxide, it is preferably used in an amount of 0.05 to 0.3 parts by weight, and more preferably 0.2 to 0.4 parts by weight.
本発明におけるスチレン改質ポリエチレン系樹脂粒子の重合においては、更に、ｎ−オクチルメルカプタン、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン等メルカプタン系の連鎖移動剤や、アクリロニトリル−スチレン系樹脂の重合に一般的に用いられるα−メチルスチレンダイマー等を併用しても良い。 In the polymerization of styrene-modified polyethylene resin particles in the present invention, it is generally used for polymerization of mercaptan chain transfer agents such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and acrylonitrile-styrene resin. Α-methylstyrene dimer used in the above may be used in combination.
本発明におけるスチレン改質ポリエチレン系樹脂粒子の作製は、ポリエチレン系樹脂粒子を含む水性懸濁液中にて重合を行うが、その際樹脂粒子同士の合着を防止するために、分散剤を使用することが好ましい。 In the production of styrene-modified polyethylene resin particles in the present invention, polymerization is carried out in an aqueous suspension containing polyethylene resin particles. In this case, a dispersant is used to prevent coalescence of the resin particles. It is preferable to do.
本発明で用いられる分散剤としては、一般的に懸濁重合に用いられる分散剤、例えば、ポリビニルアルコール、ポリビニルピロリドン、ポリアクリルアミド等の高分子分散剤、例えば、リン酸カルシウム、ハイドロキシアパタイト、ピロリン酸マグネシウム、カオリン等の難水溶性無機塩があげられる。
また、難水溶性無機塩を用いる場合には、α−オレフィンスルフォン酸ソーダ、ドデシルベンゼンスルフォン酸ソーダ等のアニオン性界面活性剤を併用すると、分散安定性が増すため、好ましい。
これらの分散剤は、重合中に追加しても良い。
Examples of the dispersant used in the present invention include dispersants generally used for suspension polymerization, for example, polymer dispersants such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylamide, such as calcium phosphate, hydroxyapatite, magnesium pyrophosphate, Examples include poorly water-soluble inorganic salts such as kaolin.
Moreover, when using a poorly water-soluble inorganic salt, it is preferable to use an anionic surfactant such as α-olefin sodium sulfonate or dodecylbenzene sodium sulfonate in order to increase dispersion stability.
These dispersants may be added during the polymerization.
本発明における分散剤の使用量は、種類によるが、基本的に水１００重量部に対して０．２重量部以上１０重量部以下が好ましい。 Although the usage-amount of the dispersing agent in this invention changes with kinds, 0.2 to 10 weight part is fundamentally preferable with respect to 100 weight part of water.
本発明においては、樹脂粒子同士の合着防止のために、水溶性の重合禁止剤を併用することもできる。水溶性の重合禁止剤としては、例えば、亜硝酸ナトリウム、３，５−ジブチル−４−ヒドロキシトルエン（ＢＨＴ）等があげられる。
これら水溶性の重合禁止剤を使用する場合、水中濃度として１５０ｐｐｍ以下となるように使用することが好ましい。重合禁止剤の水中濃度が１５０ｐｐｍ超では、重合阻害を起こす可能性がある。
In the present invention, a water-soluble polymerization inhibitor may be used in combination to prevent the resin particles from sticking together. Examples of the water-soluble polymerization inhibitor include sodium nitrite and 3,5-dibutyl-4-hydroxytoluene (BHT).
When using these water-soluble polymerization inhibitors, it is preferable to use them so that the concentration in water is 150 ppm or less. If the concentration of the polymerization inhibitor in water exceeds 150 ppm, polymerization inhibition may occur.
本発明における「水性懸濁液」とは、攪拌等を用いて、樹脂粒子および単量体液滴を、水または水溶液に分散させた状態を指し、水中には水溶性の界面活性剤や単量体が溶解していても良く、また、水に不溶の分散剤、開始剤、架橋剤、気泡調整剤、難燃剤、可塑剤等が共に分散していても良い。
樹脂と水の重量比は、得られるスチレン改質ポリスチレン樹脂／水の比として、１．０／０．６〜１．０／３．０が好ましい。
The “aqueous suspension” in the present invention refers to a state in which resin particles and monomer droplets are dispersed in water or an aqueous solution by using stirring or the like. The body may be dissolved, and a water-insoluble dispersant, initiator, crosslinking agent, bubble regulator, flame retardant, plasticizer, and the like may be dispersed together.
The weight ratio of the resin and water is preferably 1.0 / 0.6 to 1.0 / 3.0 as the ratio of the styrene-modified polystyrene resin / water obtained.
本発明におけるスチレン改質ポリエチレン系樹脂粒子の作製においては、スチレン改質ポリエチレン系樹脂予備発泡粒子中の熱キシレン不溶分を生成させるため、ラジカル種発生型架橋剤を使用することが好ましい。 In the production of the styrene-modified polyethylene resin particles in the present invention, it is preferable to use a radical species-generating crosslinking agent in order to generate hot xylene-insoluble matter in the styrene-modified polyethylene resin pre-expanded particles.
架橋反応に用いられるラジカル種発生型架橋剤としては、１０時間半減期温度が１００℃以上１２５℃以下の架橋剤を使用するのが好ましい。１０時間半減期温度が１００℃より低いラジカル種発生型架橋剤を使用すると、重合時に架橋反応が進行しすぎてしまい、１２０℃以上における架橋が困難となる傾向がある。半減期温度が１２５℃を超えると、１２０℃以上の温度で架橋反応を進行させるのに時間がかかる。
１０時間半減期温度が１００℃以上１２５℃以下であるラジカル種発生型架橋剤としては、例えば、ジ−ｔ−ブチルパーオキサイド（１０時間半減期温度：１２３℃）、ジクミルパーオキサイド（１０時間半減期温度：１１６℃）、ｔ−ブチルパーオキシベンゾエ−ト（１０時間半減期温度：１０４℃）、ｔ−ブチルパーオキシアセテート（１０時間半減期温度：１０２℃）、２，２−ビス−ｔ−ブチルパーオキシブタン（１０時間半減期温度：１０３℃）等が挙げられる。
As the radical species generating type crosslinking agent used for the crosslinking reaction, it is preferable to use a crosslinking agent having a 10-hour half-life temperature of 100 ° C. or more and 125 ° C. or less. When a radical species-generating crosslinking agent having a 10-hour half-life temperature lower than 100 ° C. is used, the crosslinking reaction proceeds too much during polymerization, and crosslinking at 120 ° C. or more tends to be difficult. If the half-life temperature exceeds 125 ° C, it takes time to advance the crosslinking reaction at a temperature of 120 ° C or higher.
Examples of the radical species-generating crosslinking agent having a 10-hour half-life temperature of 100 ° C. or more and 125 ° C. or less include di-t-butyl peroxide (10-hour half-life temperature: 123 ° C.), dicumyl peroxide (10 hours) Half-life temperature: 116 ° C., t-butyl peroxybenzoate (10-hour half-life temperature: 104 ° C.), t-butyl peroxyacetate (10-hour half-life temperature: 102 ° C.), 2,2-bis -T-butylperoxybutane (10 hour half-life temperature: 103 ° C.) and the like.
これらの架橋剤は、スチレン系単量体の添加前、あるいは、スチレン系単量体と共に、重合系に添加することができる。後述する除圧発泡による発泡を行う場合には、除圧発泡の仕込み時に架橋剤を仕込み、除圧発泡の際の発泡剤含浸時に架橋反応を行っても良い。 These crosslinking agents can be added to the polymerization system before addition of the styrene monomer or together with the styrene monomer. In the case of performing foaming by decompression foaming, which will be described later, a crosslinking agent may be prepared at the time of preparation of decompression foaming, and a crosslinking reaction may be performed at the time of impregnation of the foaming agent at the time of decompression foaming.
１０時間半減期温度が１００℃以上１２５℃以下の架橋剤を用いた架橋反応としては１２０℃以上で行われるのが好ましい。架橋反応が１２０℃未満であると、架橋反応の進行に時間がかかり生産性が悪い。 The cross-linking reaction using a cross-linking agent having a 10-hour half-life temperature of 100 ° C. or higher and 125 ° C. or lower is preferably performed at 120 ° C. or higher. If the cross-linking reaction is less than 120 ° C., the cross-linking reaction takes time and the productivity is poor.
架橋剤の使用量は、架橋剤の種類によって異なるが、基本的にポリエチレン系樹脂１００重量部に対して、０．１重量部以上２．０重量部以下とすることにより、所望の範囲の熱キシレン不溶成分の含有量を得ることができるため、好ましい。 The amount of the crosslinking agent used varies depending on the type of the crosslinking agent, but basically it is 0.1 parts by weight or more and 2.0 parts by weight or less with respect to 100 parts by weight of the polyethylene resin. Since content of a xylene insoluble component can be obtained, it is preferable.
本発明において用いられる発泡剤としては、公知のものを使用することができるが、安全性、環境負荷の観点から、空気、窒素、炭酸ガス等の無機ガス、水等があげられる。これらの発泡剤は、単独で使用しても良いし、２種以上を併用しても良い。
これら発泡剤の中でも、炭酸ガスが、発泡性とセルの安定性が良いため、特に好ましい。
As the foaming agent used in the present invention, known ones can be used, and from the viewpoint of safety and environmental load, inorganic gases such as air, nitrogen and carbon dioxide, water, and the like can be mentioned. These foaming agents may be used alone or in combination of two or more.
Among these foaming agents, carbon dioxide gas is particularly preferred because of its good foamability and cell stability.
発泡剤は、一般的には前記ラジカル種発生型架橋剤による架橋反応の後に追加されるが、架橋反応が完了する前に追加しても良い。 The foaming agent is generally added after the crosslinking reaction by the radical species-generating crosslinking agent, but may be added before the crosslinking reaction is completed.
本発明における発泡剤の使用量としては、スチレン改質ポリエチレン系樹脂粒子１００重量部に対して１０重量部以上３０重量部以下であり、好ましくは１５重量部以上２５重量部以下である。発泡剤の使用量が１０重量部未満では十分な発泡倍率を得られにくい傾向がある。発泡剤の使用量が３０重量部を超えると発泡剤含浸時の樹脂の分散状態が不安定となり、樹脂同士が凝集を起こしやすくなる傾向がある。 The amount of the foaming agent used in the present invention is 10 to 30 parts by weight, preferably 15 to 25 parts by weight, based on 100 parts by weight of the styrene-modified polyethylene resin particles. When the amount of the foaming agent used is less than 10 parts by weight, it tends to be difficult to obtain a sufficient expansion ratio. When the amount of the foaming agent used exceeds 30 parts by weight, the dispersion state of the resin when impregnated with the foaming agent becomes unstable, and the resins tend to aggregate.
本発明において、ポリエチレン系樹脂粒子にスチレン系単量体を含浸、重合させたスチレン改質ポリエチレン系樹脂粒子に、発泡剤を含浸、予備発泡する方法としては、耐圧容器中でスチレン改質ポリエチレン系樹脂粒子を水性分散媒に分散させ、耐圧容器内に発泡剤を入れて該スチレン改質ポリエチレン系樹脂粒子の軟化点以上の温度に加熱し、発泡剤の蒸気圧以上の加圧下で該樹脂粒子に該発泡剤を含浸させた後、耐圧容器内の温度および圧力を一定に保ちながらスチレン改質ポリエチレン系樹脂粒子と水性分散媒との混合物を耐圧容器内よりも低圧域に放出する、いわゆる「除圧発泡」と呼ばれる方法が好ましい。 In the present invention, as a method of impregnating and pre-foaming a styrene-modified polyethylene resin particle impregnated and polymerized with a polyethylene-based resin particle and a styrene-modified polyethylene resin particle, a styrene-modified polyethylene system is used in a pressure vessel. Resin particles are dispersed in an aqueous dispersion medium, a foaming agent is placed in a pressure-resistant container, heated to a temperature equal to or higher than the softening point of the styrene-modified polyethylene resin particles, and the resin particles are pressed under a pressure equal to or higher than the vapor pressure of the foaming agent. After impregnating the foaming agent, the mixture of the styrene-modified polyethylene resin particles and the aqueous dispersion medium is discharged to a lower pressure region than in the pressure vessel while keeping the temperature and pressure in the pressure vessel constant. A method called “depressurization foaming” is preferred.
具体的には、例えば、スチレン改質ポリエチレン系樹脂粒子を、一度耐圧容器より取り出して洗浄・乾燥を行った後に、除圧発泡用の耐圧容器に仕込み、発泡剤を追加した後に過熱昇温し、前記耐圧容器内の温度および圧力を一定に保ちながら容器の一端を開放し、例えば開孔径が１〜１０ｍｍのオリフィス等を通して、該耐圧容器内よりも低圧の雰囲気中、例えば大気中等の雰囲気中に内容物を放出し発泡させることにより、均一微細な気泡構造を有する予備発泡粒子を製造することができる。 Specifically, for example, after the styrene-modified polyethylene resin particles are once taken out of the pressure vessel, washed and dried, charged into a pressure-resistant vessel for decompression foaming, and after adding a foaming agent, the temperature is increased. One end of the container is opened while keeping the temperature and pressure in the pressure vessel constant, and is passed through an orifice having a hole diameter of 1 to 10 mm, for example, in an atmosphere lower in pressure than the pressure vessel, for example, in the atmosphere The pre-expanded particles having a uniform and fine cell structure can be produced by releasing the contents and foaming.
「除圧発泡」における水性分散媒は、水に分散剤が溶解または分散したものを示し、分散剤としては、重合時と同様の種類の分散剤を使用することができる。除圧発泡時点で、可塑剤、気泡調整剤等の各種添加剤を含浸させても良い。
「除圧発泡」方法にて所望の発泡倍率まで到達しなかった場合、得られた一段予備発泡粒子を密閉容器内で空気により加圧しすることにより、一段予備発泡粒子に内圧を付加し、その後に水蒸気等により過熱することにより、二段発泡を行うことで所望の発泡倍率に到達させることができる。
The aqueous dispersion medium in “depressurization foaming” indicates a solution in which a dispersant is dissolved or dispersed in water. As the dispersant, the same type of dispersant as in the polymerization can be used. At the time of decompression foaming, various additives such as a plasticizer and a bubble regulator may be impregnated.
When the desired expansion ratio is not reached by the “depressurization foaming” method, the internal pressure is applied to the single-stage prefoamed particles by pressurizing the obtained single-stage prefoamed particles with air in a sealed container, and then By heating with water vapor or the like, the desired expansion ratio can be achieved by performing two-stage foaming.
本発明におけるスチレン改質ポリエチレン系樹脂予備発泡粒子は、テトラヒドロフラン可溶分の重量平均分子量が１５万以上３５万以下であり、かつ、熱キシレン不溶分の含有量が５重量％以上２０重量％以下であることが必要である。
本発明においては、テトラヒドロフラン可溶分の重量平均分子量および熱キシレン不溶分の含有量が当該範囲内であると、炭酸ガス発泡における発泡性と燃焼速度のバランスに優れたスチレン改質ポリエチレン系樹脂予備発泡粒子を得ることができる。
さらに好ましい範囲としては、テトラヒドロフラン可溶部の重量平均分子量が１８万以上３０万以下であり、かつ、熱キシレン不溶分量の含有量が８重量％以上１５重量％以下である。
The styrene-modified polyethylene resin pre-expanded particles in the present invention have a weight average molecular weight of 150,000 or more and 350,000 or less of a tetrahydrofuran-soluble component, and a content of insoluble matter of hot xylene of 5 to 20% by weight. It is necessary to be.
In the present invention, when the weight-average molecular weight of the tetrahydrofuran-soluble component and the content of the hot xylene-insoluble component are within the above ranges, the styrene-modified polyethylene resin reserve having an excellent balance between foamability and combustion rate in carbon dioxide gas foaming Expanded particles can be obtained.
As a more preferable range, the tetrahydrofuran-soluble part has a weight average molecular weight of 180,000 or more and 300,000 or less, and the content of the heat xylene insoluble content is 8% by weight or more and 15% by weight or less.
ここで、テトラヒドロフラン可溶分とは、スチレン改質ポリエチレン系樹脂予備発泡粒子０．０２ｇをテトラヒドロフラン２０ｍｍｌに常温で２４時間浸漬させた後、孔径０．２μｍのフィルターでろ過した際のろ液である。
テトラヒドロフラン可溶分の重量平均分子量は、該ろ液をゲルパーミエーションクロマトグラフ（ＧＰＣ）法により測定し、標準ポリスチレン試料を基準として求めた値である。
テトラヒドロフラン可溶部の重量平均分子量は、重合時における追加するスチレン系単量体の追加速度、重合開始剤の量を調整することにより、制御することができる。
Here, the tetrahydrofuran-soluble component is a filtrate obtained by immersing 0.02 g of styrene-modified polyethylene resin pre-expanded particles in 20 ml of tetrahydrofuran at room temperature for 24 hours, and then filtering with a filter having a pore size of 0.2 μm. .
The weight average molecular weight of the tetrahydrofuran-soluble component is a value obtained by measuring the filtrate by a gel permeation chromatograph (GPC) method and using a standard polystyrene sample as a reference.
The weight average molecular weight of the tetrahydrofuran-soluble part can be controlled by adjusting the addition rate of the styrene monomer added during polymerization and the amount of the polymerization initiator.
ここで、熱キシレン不溶分とは、スチレン改質ポリエチレン系樹脂予備発泡粒子１．０ｇをキシレン５０ｍｌに添加し、３０分間煮沸させた後に、デカンテーション法および２００メッシュの金網を用いて回収して得られる不溶残渣である。
熱キシレン不溶分の含有量は、架橋剤の量、架橋時間を調整することにより、制御することができる。
Here, the hot xylene insoluble matter means that 1.0 g of styrene-modified polyethylene resin pre-foamed particles are added to 50 ml of xylene, boiled for 30 minutes, and then recovered using a decantation method and a 200-mesh wire mesh. It is an insoluble residue obtained.
The content of the hot xylene insoluble matter can be controlled by adjusting the amount of the crosslinking agent and the crosslinking time.
本発明におけるスチレン改質ポリエチレン系樹脂予備発泡粒子は、メチルエチルケトン可溶分が５０重量％以下であることが、ポリエチレン成分とスチレン成分のグラフト生成物が多く樹脂中に存在しており、燃焼速度の観点から好ましい。メチルエチルケトン可溶分としては、３５〜４５重量％であることがより好ましい。 The styrene-modified polyethylene resin pre-expanded particles in the present invention have a methyl ethyl ketone soluble content of 50% by weight or less, a lot of graft products of polyethylene component and styrene component are present in the resin, It is preferable from the viewpoint. The methyl ethyl ketone soluble content is more preferably 35 to 45% by weight.
ここで、メチルエチルケトン可溶分の含有量とは、以下の操作により得られるメチルエチルケトン不溶分を、元のスチレン改質ポリエチレン系樹脂予備発泡粒子の重量から差し引いた値である。
メチルエチルケトン不溶分とは、スチレン改質ポリエチレン系樹脂予備発泡粒子１．０ｇをメチルエチルケトン２０ｍｍｌに常温で２４時間浸漬させた後、遠心分離法にて回収して得られる不溶残渣である。
メチルエチルケトン可溶分の含有量は、重合時における追加するスチレン系単量体の追加速度、重合開始剤の量を調整することにより、制御することができる。
Here, the methyl ethyl ketone soluble content is a value obtained by subtracting the methyl ethyl ketone insoluble content obtained by the following operation from the weight of the original styrene-modified polyethylene resin pre-expanded particles.
The methyl ethyl ketone insoluble matter is an insoluble residue obtained by immersing 1.0 g of styrene-modified polyethylene resin pre-expanded particles in 20 ml of methyl ethyl ketone at room temperature for 24 hours and then collecting them by a centrifugal separation method.
The content of soluble methyl ethyl ketone can be controlled by adjusting the rate of addition of the styrenic monomer added during polymerization and the amount of polymerization initiator.
本発明におけるスチレン改質ポリエチレン系予備発泡粒子は、ＡＴＲ−ＩＲスペクトルにおいて、芳香族ベンゼン環面外変角の吸収スペクトルであるＤ６９８と、メチレン基のＣ−Ｈ間伸縮振動のうち対称伸縮による吸収スペクトルＤ２８５０との比であるＤ６９８／Ｄ２８５０が５．０以上２０．０以下であると、成形時の融着性が良いため、好ましい。より好ましくは５．０以上１５．０以下である。
吸光度比Ｄ６９８／Ｄ２８５０は、重合初期のスチレン系単量体の仕込み量や追加するスチレン系単量体の添加速度を制御することにより、制御することができる。
Styrene-modified polyethylene-based pre-expanded particles in the present invention is the ATR-IR spectrum, a D 698 is an absorption spectrum of an aromatic benzene ring out of plane bending, by symmetric stretching of the C-H between stretching vibration of the methylene groups It is preferable that D 698 / D 2850, which is a ratio to the absorption spectrum D 2850 , is 5.0 or more and 20.0 or less because the fusion property at the time of molding is good. More preferably, it is 5.0 or more and 15.0 or less.
The absorbance ratio D 698 / D 2850 can be controlled by controlling the charge amount of the styrene monomer at the initial stage of polymerization and the addition rate of the styrene monomer to be added.
本発明のスチレン改質ポリエチレン系予備発泡粒子は、炭化水素系発泡剤を使用しない為、揮発性成分が１重量％以下であることが好ましい。揮発性成分が１重量％以下であれば、スチレン系成分の含有量が多くても、得られる成形体の燃焼速度を低く抑えることができる。 Since the styrene-modified polyethylene pre-expanded particles of the present invention do not use a hydrocarbon-based blowing agent, the volatile component is preferably 1% by weight or less. If the volatile component is 1% by weight or less, even if the content of the styrene component is large, the burning rate of the obtained molded product can be kept low.
本発明のスチレン改質ポリエチレン系樹脂予備発泡粒子は、一般的な型内発泡成形方法によって成形される。具体的には、閉鎖し得るが密閉し得ない金型内に、スチレン改質ポリエチレン系樹脂予備発泡粒子を充填し、加熱融着せしめて発泡成形体とされる。 The styrene-modified polyethylene resin pre-expanded particles of the present invention are molded by a general in-mold foam molding method. Specifically, styrene-modified polyethylene resin pre-foamed particles are filled in a mold that can be closed but cannot be sealed, and heat-fused to obtain a foam-molded product.
本発明のスチレン改質ポリエチレン系樹脂予備発泡粒子は、炭酸ガス発泡による発泡性がよく、生産工程上安全性が高い。スチレン改質ポリエチレン系予備発泡粒子は燃焼速度に優れるため、自動車部材、緩衝材に好適に使用できる。 The styrene-modified polyethylene resin pre-expanded particles of the present invention have good foamability due to carbon dioxide gas foaming and are highly safe in the production process. Since the styrene-modified polyethylene-based pre-expanded particles have an excellent combustion rate, they can be suitably used for automobile members and cushioning materials.
以下に実施例及び比較例をあげるが、これによって本発明は制限されるものではない。尚、測定評価については以下の通り実施した。 Examples and Comparative Examples are given below, but the present invention is not limited thereby. In addition, about measurement evaluation, it implemented as follows.
＜テトラヒドロフラン可溶分の重量平均分子量の測定＞
得られたスチレン改質ポリエチレン系樹脂予備発泡粒子０．０２ｇを、テトラヒドロフラン２０ｍｍｌ中に常温で２４時間浸漬させた後、孔径０．２μｍのフィルターでろ過して、ろ液（テトラヒドロフラン可溶分）を得た。
得られたろ液を、ゲルパーミエーションコロマトグラフィー（ＧＰＣ）法により、標準ポリスチレン試料を基準として、重量平均分子量に求めた。
ＧＰＣ法の測定条件は、以下のとおりである。
測定装置： 東ソー（株）社製、高速ＧＰＣ装置、ＨＬＣ−８２２０
使用カラム：東ソー（株）製、ＳｕｐｅｒＨＺＭ−Ｈ×２本、ＳｕｐｅｒＨ−ＲＣ×２本
カラム温度：４０℃、
移動相：ＴＨＦ（テトラヒドロフラン）
流量：０．３５ｍｌ／分、注入量：１０μｌ
検出器：ＲＩ
<Measurement of weight average molecular weight of tetrahydrofuran-soluble matter>
The obtained styrene-modified polyethylene resin pre-expanded particles (0.02 g) were immersed in 20 ml of tetrahydrofuran at room temperature for 24 hours, and then filtered through a filter having a pore size of 0.2 μm to obtain a filtrate (tetrahydrofuran soluble component). Obtained.
The obtained filtrate was calculated | required by the weight average molecular weight on the basis of the standard polystyrene sample by the gel permeation chromatography (GPC) method.
The measurement conditions of the GPC method are as follows.
Measuring device: manufactured by Tosoh Corporation, high-speed GPC device, HLC-8220
Column used: Tosoh Co., Ltd., SuperHZM-H x 2, SuperH-RC x 2
Column temperature: 40 ° C
Mobile phase: THF (tetrahydrofuran)
Flow rate: 0.35 ml / min, injection volume: 10 μl
Detector: RI
＜熱キシレン不溶分の量＞
得られたスチレン改質ポリエチレン系樹脂予備発泡粒子１．０ｇに、キシレン５０ｍｌを加えて加熱する。３０分煮沸させた後に、可溶分をデカンテーション法により、ビーカーに分別する。この際、不溶分の混入を防ぐために、２００メッシュの金網を可溶分のビーカーの上に置く。
得られた不溶分に対して、キシレンの添加・煮沸、デカンテーションの操作を２回実施して、熱キシレン不溶分を回収した。回収物を７０℃で８時間真空乾燥させた後、重量を測定した。
<Amount of hot xylene insoluble matter>
To 1.0 g of the styrene-modified polyethylene resin pre-expanded particles obtained, 50 ml of xylene is added and heated. After boiling for 30 minutes, the soluble component is fractionated into a beaker by decantation. At this time, in order to prevent the insoluble matter from being mixed, a 200-mesh wire mesh is placed on the beaker of the soluble content.
The xylene addition, boiling, and decantation operations were performed twice on the obtained insoluble matter to recover the hot xylene insoluble matter. The collected material was vacuum-dried at 70 ° C. for 8 hours, and then the weight was measured.
＜メチルエチルケトン可溶分の量＞
得られたスチレン改質ポリエチレン系樹脂予備発泡粒子１．０ｇを、メチルエチルケトン５０ｍｌ中に常温で２４時間浸漬させた後、遠心分離機［国産遠心機株式会社製 Ｈ−２００型］を用いて、１２，０００ｒｐｍ×３０分の条件にて遠心分離して、メチルエチルケトン不溶分を分別する。
得られた不溶分に対して、メチルエチルケトンへの浸漬、遠心分離の操作を２回実施して、メチルエチルケトン不溶分を回収した。回収したメチルエチルケトン不溶分を、７０℃で１２時間乾燥させた後、室温に戻して、重量を測定した。
メチルエチルケトン可溶分の量は、１．０ｇからメチルエチルケトン不溶分を差し引いた値である。
<Amount of soluble methyl ethyl ketone>
After immersing 1.0 g of the obtained styrene-modified polyethylene resin pre-expanded particles in 50 ml of methyl ethyl ketone at room temperature for 24 hours, using a centrifuge [type H-200 manufactured by Kokusan Centrifuge Co., Ltd.], 12 Centrifugation is performed under the condition of 3,000 rpm × 30 minutes to fractionate methyl ethyl ketone insoluble matter.
The obtained insoluble matter was immersed in methyl ethyl ketone and centrifuged twice to recover the methyl ethyl ketone insoluble matter. The recovered methyl ethyl ketone insoluble matter was dried at 70 ° C. for 12 hours, then returned to room temperature, and the weight was measured.
The amount of methyl ethyl ketone solubles is a value obtained by subtracting methyl ethyl ketone insolubles from 1.0 g.
＜吸光度比（Ｄ６９８／Ｄ２８５０）の測定方法＞
得られたスチレン改質ポリエチレン系樹脂予備発泡粒子に対するＡＴＲ−ＦＴＩＲ測定は、ＰｅｒｋｉｎＥｌｍｅｒ社製ＳｐｅｃｔｒｕｍＯｎｅに、ユニバーサルＡＴＲアクセサリーを接続して測定した。高屈折率結晶はダイアモンドとし、測定領域は４０００〜４００ｃｍ−１、検出器ＴＧＳ、分解能４ｃｍ−１、積算回数４回、入射角４５°±１°で実施した。
得られたスペクトルチャートにおいて、８００ｃｍ−１と６６０ｃｍ−１結ぶ直線をベースラインとして、８００〜６６０ｃｍ−１間の最大吸光度をＦ、
２９９０ｃｍ−１と２７８０ｃｍ−１結ぶ直線をベースラインとして２９９０〜２７８０ｃｍ−１間の最大吸光度をＧとし、
以下の式により発泡成形体表面の吸光度比（Ｄ６９８／Ｄ２８５０）とした。
Ｄ６９８／Ｄ２８５０＝Ｆ／Ｇ
なお、測定箇所としては、得られた予備発泡粒子の比較的平滑な場所を選択して１０箇所測定し、１０点の平均値を発泡成形体表面の吸光度比（Ｄ６９８／Ｄ２８５０）とした。測定の際には、発泡粒子がプリズムに押し付けられて十分に潰れた状態で測定した。
<Measurement Method of Absorbance Ratio (D 698 / D 2850 )>
ATR-FTIR measurement on the obtained styrene-modified polyethylene resin pre-expanded particles was performed by connecting a Universal ATR accessory to SpectrumOne manufactured by PerkinElmer. High refractive index crystals and diamond, the measurement area is 4000 to 400 -1, detector TGS, resolution 4 cm -1, the number of integrations 4 times, was carried out at an incident angle of 45 ° ± 1 °.
In the obtained spectrum chart, a line connecting 800 cm -1 and 660 cm -1 as a baseline, the maximum absorbance between 800~660cm -1 F,
The straight line connecting 2990Cm -1 and 2780cm -1 absorbance maxima between 2990～2780Cm -1 and G as a baseline,
The absorbance ratio (D 698 / D 2850 ) on the surface of the foamed molded product was obtained by the following formula.
D 698 / D 2850 = F / G
In addition, as a measurement location, the comparatively smooth location of the obtained pre-expanded particle was selected, and it measured 10 locations, and made the average value of 10 points | pieces the absorbance ratio ( D698 / D2850 ) of the foaming molding surface. . At the time of measurement, the measurement was performed in a state where the foamed particles were sufficiently crushed by being pressed against the prism.
＜発泡力＞
炭酸ガスを用いた、保持温度１５５℃、容器内圧３．０ＭＰａの除圧発泡において得られた一段発泡粒子の、水没倍率により、以下の基準にて判断した。
○：一段発泡粒子の水没倍率が５倍以上。
×：一段発泡粒子の水没倍率が５倍未満。
なお、水没倍率は、一段発泡粒子約５ｇを５０ｃｃのエタノールに水没させ、水没前後のエタノールの体積変化量と一段発泡粒子の重量から以下の式により求めた。
水没倍率＝水没前後のエタノール体積変化量（ｃｃ）／一段発泡粒子の重量（ｇ）
<Foaming power>
The following criteria were used to determine the submerged magnification of the first-stage expanded particles obtained by decompression foaming using carbon dioxide gas at a holding temperature of 155 ° C. and a container internal pressure of 3.0 MPa.
○: The submerged magnification of the first-stage expanded particles is 5 times or more.
X: The submerged magnification of the first-stage expanded particles is less than 5 times.
The submerged ratio was obtained by substituting about 5 g of the first-stage expanded particles in 50 cc of ethanol and calculating the volume change amount of ethanol before and after the submersion and the weight of the first-stage expanded particles by the following formula.
Submerging ratio = ethanol volume change before and after submersion (cc) / weight of single-stage expanded particles (g)
＜揮発性成分＞
得られたスチレン改質ポリエチレン系予備発泡粒子を約２ｇ計量し、１５０℃の乾燥機の中で３０分加熱し、揮発性成分を逸散させた。冷却後、揮発性成分逸散後のスチレン改質ポリエチレン予備発泡粒子の重量を測定し、その重量変化から揮発性成分の含有量を求めた。
<Volatile component>
About 2 g of the obtained styrene-modified polyethylene pre-expanded particles were weighed and heated in a dryer at 150 ° C. for 30 minutes to dissipate volatile components. After cooling, the weight of the styrene-modified polyethylene pre-expanded particles after dissipation of the volatile component was measured, and the content of the volatile component was determined from the weight change.
＜燃焼速度＞
得られた型内発泡成形体から、熱線スライサーを用いて、長さ３６０ｍｍ×幅１０１．６ｍｍ×厚み１２ｍｍのサンプルに切断して、燃焼試験用試験片を得た。
燃焼速度は、得られた試験片を用いて、米国自動車安全基準ＦＭＶＳＳ３０２に準拠した方法で測定した。
<Burning rate>
The obtained in-mold foam molded article was cut into a sample having a length of 360 mm, a width of 101.6 mm, and a thickness of 12 mm using a heat ray slicer to obtain a test piece for combustion test.
The burning rate was measured by the method based on the US automobile safety standard FMVSS302 using the obtained test piece.
＜成形時の融着性＞
得られた発泡成形体に、カッターナイフで約３ｍｍの切り込みを入れた後、この切り込み部から発泡成形体を破断して、破断面を観察した。
破断面を構成するスチレン改質ポリエチレン系樹脂発泡粒子数に対する、破壊された（粒子表面でなく粒子内部で破断している）スチレン改質ポリエチレン系樹脂発泡粒子数の割合を融着率（％）として求めた。
<Fusibility during molding>
After cutting about 3 mm with a cutter knife into the obtained foamed molded product, the foamed molded product was broken from the cut portion, and the fracture surface was observed.
The ratio of the number of styrene-modified polyethylene resin foam particles destroyed (breaking inside the particle, not the particle surface) to the number of styrene-modified polyethylene resin foam particles constituting the fracture surface is the fusion rate (%) As sought.
（実施例１）
［ポリエチレン樹脂粒子の作製］
ポリエチレン系樹脂として分岐性低密度ポリエチレン（ＬＤＰＥ）［日本ダウケミカル社製、ＮＵＣポリエチレンＤＦＤＪ−６７７５］を使用し、ポリエチレン系樹脂１００重量部に対してタルク０．２重量部を混合した後、５０ｍｍ単軸押出機内で、吐出量２５ｋｇ／時間、樹脂温度２４０℃で溶融混合して、押出機先端に設置されたダイスを通して押し出した後、カッティングすることにより、粒重量約１ｍｇ／粒のポリエチレン系樹脂粒子を作製した。
［スチレン改質ポリエチレン系樹脂粒子の作製］
６Ｌオートクレーブに、水１５０重量部、第３リン酸カルシウム２．０重量部、α−オレフィンスルフォン酸ソーダ０．０４８重量部、亜硝酸ナトリウム０．００９重量部、得られたポリエチレン系樹脂粒子４０重量部を懸濁させた。
スチレン単量体２０重量部に、重合開始剤としてｔ−ブチルパーオキシ−２−エチルヘキサノエート（１０時間半減期温度：７２℃）０．５２重量部、過酸化ベンゾイル（１０時間半減期温度：７４℃）０．２０重量部、架橋剤としてｔ−ブチルパーオキシベンゾエート（１０時間半減期温度：１０４℃）０．２４重量部を溶解させた溶液を、上記水性懸濁液に添加した。
その後、水性懸濁液の温度を９２℃まで昇温し、スチレン単量体４０重量部を２時間２０分かけて反応系中に滴下した。スチレン単量体の滴下終了後、９２℃で１時間保持することにより、重合反応を進行させた。
その後、水性懸濁液の温度を１２０℃に昇温して１時間保持して架橋反応を行い、冷却後、洗浄・脱水・乾燥することによりスチレン改質ポリエチレン系樹脂粒子を得た。
［スチレン改質ポリエチレ系樹脂予備発泡粒子の作製］
１０Ｌオートクレーブに、水３００重量部、第３リン酸カルシウム０．５重量部、ｎ−パラフィンスルホン酸ソーダ０．０２８重量部、得られたスチレン改質ポリエチレン系樹脂粒子１００重量部、セバシン酸ジブチル０．５重量部、４級アンモニウム塩［ライオン・アクゾ（株）製、製品名：アーカード２ＨＰ］０．５重量部を仕込み、炭酸ガスにて１．０ＭＰａまで加圧した。
上記水系分散物を１５５℃まで加温した後、炭酸ガスを導入して、容器内圧を３．０ＭＰａに加圧し、３０分間保持した。温度、圧力を保持しつつ、耐圧容器下部のバルブを開いて水分散物を開孔径３．６ｍｍφのオリフィス板を通して、９４℃の飽和水蒸気で満たされた筒中に放出することによって、一段発泡粒子を得た。
得られた一段発泡粒子内に、空気含浸により０．３０ＭＰａの内圧を付与した後、攪拌機を取り付けた密閉容器内で水蒸気により加熱し、発泡倍率約３０倍のスチレン改質ポリエチレン系樹脂予備発泡粒子を得た。
得られたスチレン改質ポリエチレン系樹脂予備発泡粒子について、熱キシレン不溶分量、メチルエチルケトン可溶分量、テトラヒドロフラン可溶部の重量平均分子量測定を実施した。結果は表１に示した。
［スチレン改質ポリエチレン系樹脂型内発泡体の作製］
耐圧容器内で空気加圧して約０．２０ＭＰａの内圧を付与したスチレン改質ポリエチレン系樹脂予備発泡粒子を、長さ４００ｍｍ×幅３００ｍｍ×厚み１２ｍｍの金型に充填し、予備発泡粒子同士を圧力０．１０ＭＰａ（ゲージ圧）の水蒸気で加熱、融着させ、スチレン改質ポリエチレン系樹脂型内発泡成形体を得た。
得られた型内発泡成形体について、燃焼速度を測定した。結果は表１に示した。
Example 1
[Production of polyethylene resin particles]
Using a branched low density polyethylene (LDPE) [NUC polyethylene DFDJ-6775, manufactured by Nippon Dow Chemical Co., Ltd.] as a polyethylene resin, 0.2 parts by weight of talc is mixed with 100 parts by weight of the polyethylene resin, and then 50 mm. In a single screw extruder, melt-mixed at a discharge rate of 25 kg / hour and a resin temperature of 240 ° C., extruded through a die installed at the tip of the extruder, and then cut to obtain a polyethylene resin having a grain weight of about 1 mg / grain. Particles were made.
[Production of styrene-modified polyethylene resin particles]
In a 6 L autoclave, 150 parts by weight of water, 2.0 parts by weight of tricalcium phosphate, 0.048 parts by weight of sodium α-olefin sulfonate, 0.009 parts by weight of sodium nitrite, and 40 parts by weight of the obtained polyethylene resin particles were added. Suspended.
20 parts by weight of styrene monomer, 0.52 parts by weight of t-butylperoxy-2-ethylhexanoate (10-hour half-life temperature: 72 ° C.) as a polymerization initiator, benzoyl peroxide (10-hour half-life temperature) : 74 ° C) 0.20 parts by weight, and a solution in which 0.24 parts by weight of t-butyl peroxybenzoate (10-hour half-life temperature: 104 ° C) as a crosslinking agent was dissolved was added to the aqueous suspension.
Thereafter, the temperature of the aqueous suspension was raised to 92 ° C., and 40 parts by weight of a styrene monomer was dropped into the reaction system over 2 hours and 20 minutes. After completion of the dropwise addition of the styrene monomer, the polymerization reaction was advanced by maintaining at 92 ° C. for 1 hour.
Thereafter, the temperature of the aqueous suspension was raised to 120 ° C. and held for 1 hour to carry out a crosslinking reaction, and after cooling, washing, dehydration, and drying were performed to obtain styrene-modified polyethylene resin particles.
[Preparation of styrene-modified polyethylene resin pre-expanded particles]
In a 10 L autoclave, 300 parts by weight of water, 0.5 part by weight of tribasic calcium phosphate, 0.028 part by weight of sodium n-paraffin sulfonate, 100 parts by weight of the resulting styrene-modified polyethylene resin particles, 0.5 part of dibutyl sebacate 0.5 parts by weight of quaternary ammonium salt [manufactured by Lion Akzo Co., Ltd., product name: ARCARD 2HP] was charged and pressurized to 1.0 MPa with carbon dioxide gas.
After the aqueous dispersion was heated to 155 ° C., carbon dioxide gas was introduced, and the internal pressure of the container was increased to 3.0 MPa and held for 30 minutes. While maintaining the temperature and pressure, the valve at the lower part of the pressure vessel is opened, and the aqueous dispersion is discharged through a orifice plate having an opening diameter of 3.6 mm into a cylinder filled with saturated steam at 94 ° C. Obtained.
After applying an internal pressure of 0.30 MPa to the obtained single-stage expanded particles by air impregnation, the styrene-modified polyethylene resin pre-expanded particles are heated with water vapor in a sealed container equipped with a stirrer and have an expansion ratio of about 30 times. Got.
The obtained styrene-modified polyethylene resin pre-expanded particles were measured for the weight-average molecular weight of the hot xylene-insoluble matter, the methyl ethyl ketone-soluble matter, and the tetrahydrofuran-soluble part. The results are shown in Table 1.
[Production of styrene-modified polyethylene resin-in-mold foam]
Styre-modified polyethylene resin pre-expanded particles, which have been pressurized with air in a pressure-resistant container to give an internal pressure of about 0.20 MPa, are filled in a mold having a length of 400 mm × width of 300 mm × thickness of 12 mm, and the pre-expanded particles are pressurized. Heating and fusing with water vapor of 0.10 MPa (gauge pressure) gave a styrene-modified polyethylene resin in-mold foam molded product.
The burning rate was measured for the obtained in-mold foam molded article. The results are shown in Table 1.
（実施例２）
［スチレン改質ポリエチレン系樹脂粒子の作製］において、ポリエチレン樹脂量を２５重量部、ｔ−ブチルパーオキシベンゾエート量を０．１６重量部に変更し、さらに、９２℃でのスチレン単量体連続滴下においてスチレン単量体５５重量部を３時間１０分かけて滴下した以外は、実施例１と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系樹脂予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。結果は、表１に示した。
(Example 2)
In [Preparation of styrene-modified polyethylene resin particles], the amount of polyethylene resin was changed to 25 parts by weight, the amount of t-butyl peroxybenzoate was changed to 0.16 parts by weight, and styrene monomer was continuously dropped at 92 ° C. In the same manner as in Example 1, except that 55 parts by weight of the styrene monomer was dropped over 3 hours and 10 minutes, styrene-modified polyethylene resin particles, styrene-modified polyethylene resin pre-expanded particles, and in-mold foaming were performed. Molded bodies were prepared and evaluated in the same manner. The results are shown in Table 1.
（実施例３）
［スチレン改質ポリエチレン系樹脂粒子の作製］において、ポリエチレン樹脂量を３０重量部、重合開始剤としての過酸化ベンゾイルを０．１０重量部に変更し、さらに、９２℃でのスチレン単量体滴下においてスチレン単量体５０重量部を２時間５０分かけて滴下した以外は、実施例１と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系樹脂予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。結果は表１に示した。
(Example 3)
In [Production of styrene-modified polyethylene resin particles], the amount of polyethylene resin was changed to 30 parts by weight, benzoyl peroxide as a polymerization initiator was changed to 0.10 parts by weight, and styrene monomer was dropped at 92 ° C. In the same manner as in Example 1, except that 50 parts by weight of the styrene monomer was dropped over 2 hours and 50 minutes, styrene-modified polyethylene resin particles, styrene-modified polyethylene resin pre-expanded particles, and in-mold foaming were performed. Molded bodies were prepared and evaluated in the same manner. The results are shown in Table 1.
（実施例４）
[スチレン改質ポリエチレン系樹脂粒子の作製]において、重合開始剤として過酸化ベンソイルの量を０．１０重量部、さらに、架橋剤としてｔ−ブチルパーオキシベンゾエートの量を０．６０重量部に変更した以外は、実施例２と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。
結果は、表１に示した。
Example 4
In [Production of styrene-modified polyethylene resin particles], the amount of benzoyl peroxide as a polymerization initiator was changed to 0.10 parts by weight, and the amount of t-butyl peroxybenzoate as a crosslinking agent was changed to 0.60 parts by weight. Except that, styrene-modified polyethylene resin particles, styrene-modified polyethylene pre-foamed particles, and in-mold foam molded articles were produced in the same manner as in Example 2, and the same evaluation was performed.
The results are shown in Table 1.
(実施例５)
[スチレン改質ポリエチレン系樹脂粒子の作製]において、重合開始剤としてｔ−ブチルパーオキシ−２−エチルヘキサノエート０．４０重量部のみを使用し、さらに、架橋剤としてｔ−ブチルパーオキシベンゾエートの量を０．３０重量部に変更した以外は、実施例２と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。
結果は、表１に示した。
(Example 5)
In [Production of styrene-modified polyethylene resin particles], only 0.40 parts by weight of t-butylperoxy-2-ethylhexanoate is used as a polymerization initiator, and t-butylperoxybenzoate is used as a crosslinking agent. A styrene-modified polyethylene resin particle, a styrene-modified polyethylene pre-foamed particle, and an in-mold foam molded article were produced in the same manner as in Example 2 except that the amount of was changed to 0.30 parts by weight. Was evaluated.
The results are shown in Table 1.
（比較例１）
［スチレン改質ポリエチレン系樹脂粒子の作製］において、重合開始剤として過酸化ベンゾイル０．２６重量部のみを使用した以外は、実施例３と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系樹脂予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。
結果は、表２に示した。
(Comparative Example 1)
In [Production of styrene-modified polyethylene resin particles], styrene-modified polyethylene resin particles and styrene were produced in the same manner as in Example 3 except that only 0.26 parts by weight of benzoyl peroxide was used as a polymerization initiator. Modified polyethylene resin pre-foamed particles and in-mold foam molded articles were produced and evaluated in the same manner.
The results are shown in Table 2.
（比較例２）
［スチレン改質ポリエチレン系樹脂粒子の作製］において、重合開始剤としてｔ−ブチルパーオキシ−２−エチルヘキサノエート０．５２重量部のみを使用した以外は、実施例２と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系樹脂予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。
結果は、表２に示した。
(Comparative Example 2)
In [Production of styrene-modified polyethylene resin particles], except that only 0.52 parts by weight of t-butylperoxy-2-ethylhexanoate was used as a polymerization initiator, Styrene-modified polyethylene resin particles, styrene-modified polyethylene resin pre-expanded particles, and in-mold foam molded articles were produced and evaluated in the same manner.
The results are shown in Table 2.
（比較例３）
［スチレン改質ポリエチレン系樹脂粒子の作製］において、架橋剤としてのt-ブチルパーオキシベンゾエートを０重量部に変更した以外は、実施例２と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系樹脂予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。結果は、表２に示した。
(Comparative Example 3)
In [Production of styrene-modified polyethylene resin particles], styrene-modified polyethylene resin particles, by the same method as in Example 2, except that t-butylperoxybenzoate as a crosslinking agent was changed to 0 parts by weight, Styrene-modified polyethylene resin pre-foamed particles and in-mold foam molded bodies were prepared and evaluated in the same manner. The results are shown in Table 2.
（比較例４）
［スチレン改質ポリエチレン系樹脂粒子の作製］において、架橋剤としてのt-ブチルパーオキシベンゾエートを０．６０重量部に変更した以外は、実施例２と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系樹脂予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。結果は表２１に示した。
(Comparative Example 4)
In [Production of styrene-modified polyethylene resin particles], a styrene-modified polyethylene resin was obtained in the same manner as in Example 2 except that t-butyl peroxybenzoate as a crosslinking agent was changed to 0.60 parts by weight. Particles, styrene-modified polyethylene resin pre-foamed particles, and in-mold foamed articles were prepared and evaluated in the same manner. The results are shown in Table 21.
（比較例５）
［スチレン改質ポリエチレン系樹脂粒子の作製］において、初期のスチレンを０重量部とし、９２℃でのスチレン単量体滴下においてスチレン単量体７５重量部を４時間５０分かけて滴下した以外は、実施例２と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系樹脂予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。結果は、表２に示した。
(Comparative Example 5)
In [Production of styrene-modified polyethylene resin particles], except that initial styrene was 0 parts by weight and styrene monomer was dropped at 92 ° C. over 75 hours by weight of styrene monomer over 4 hours and 50 minutes. In the same manner as in Example 2, styrene-modified polyethylene resin particles, styrene-modified polyethylene resin pre-expanded particles, and in-mold foam molded articles were produced and evaluated in the same manner. The results are shown in Table 2.
（比較例６）
[スチレン改質ポリエチレン系樹脂粒子の作製]において、初期のスチレンを１０重量部とし、９２℃でのスチレン単量体滴下においてスチレン単量体６５重量部を４時間かけて滴下した以外は、実施例２と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。結果は、表２に示した。
(Comparative Example 6)
In [Preparation of styrene-modified polyethylene resin particles], except that 10 parts by weight of the initial styrene was added and 65 parts by weight of the styrene monomer was dropped over 92 hours at 92 ° C. By the same method as in Example 2, styrene-modified polyethylene resin particles, styrene-modified polyethylene pre-foamed particles, and in-mold foam molded articles were produced and evaluated in the same manner. The results are shown in Table 2.
（比較例７）
[スチレン改質ポリエチレン系樹脂粒子の作製]において、ポリエチレン系樹脂として分岐型低密度ポリエチレン(ＬＤＰＥ)「日本ダウケミカル社製 ＮＵＣポリエチレン ＤＦＤＪ−６７７５」を５０重量部とし、９２℃でのスチレン単量体滴下においてスチレン単量体３０重量部を１時間３０分かけて滴下した以外は、実施例２と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。結果は、表２に示した。
(Comparative Example 7)
In [Production of Styrene-modified Polyethylene Resin Particles], 50 parts by weight of branched low density polyethylene (LDPE) “NUC Polyethylene DFDJ-6775” manufactured by Nippon Dow Chemical Co., Ltd. is used as the polyethylene resin, and the amount of styrene at 92 ° C. Styrene modified polyethylene resin particles, styrene modified polyethylene pre-expanded particles and in-mold were produced in the same manner as in Example 2 except that 30 parts by weight of styrene monomer was added dropwise over 1 hour 30 minutes. A foam-molded article was produced and evaluated in the same manner. The results are shown in Table 2.
（比較例８）
[スチレン改質ポリエチレン系樹脂粒子の作製]において、ポリエチレン系樹脂として分岐型低密度ポリエチレン(ＬＤＰＥ)「日本ダウケミカル社製 ＮＵＣポリエチレン ＤＦＤＪ−６７７５」を１５重量部とし、９２℃でのスチレン単量体滴下においてスチレン単量体６５重量部を４時間かけて滴下した以外は、実施例２と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。結果は、表２に示した。
(Comparative Example 8)
In [Production of styrene-modified polyethylene resin particles], 15 parts by weight of branched low density polyethylene (LDPE) “NUC polyethylene DFDJ-6775” manufactured by Nippon Dow Chemical Co., Ltd. is used as the polyethylene resin, and the amount of styrene at 92 ° C. Styrene modified polyethylene resin particles, styrene modified polyethylene pre-expanded particles and in-mold foam molding were carried out in the same manner as in Example 2 except that 65 parts by weight of the styrene monomer was dropped over 4 hours. A body was prepared and evaluated in the same manner. The results are shown in Table 2.
（比較例９）
[スチレン改質ポリエチレン系樹脂粒子の作製]において、ポリエチレン系樹脂として直差型低密度ポリエチレン(ＬＬＤＰＥ)「プライムポリマー製 ウルトゼックス ３０２３Ｈ」とした以外は、実施例２と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。結果は、表２に示した。
(Comparative Example 9)
In [Production of Styrene-modified Polyethylene Resin Particles], styrene modification was carried out in the same manner as in Example 2 except that direct-type low-density polyethylene (LLDPE) “Prime Polymer Wortzex 3023H” was used as the polyethylene resin. -Like polyethylene resin particles, styrene-modified polyethylene-based pre-foamed particles, and in-mold foam-molded bodies were produced and evaluated in the same manner. The results are shown in Table 2.
（比較例１０）
[スチレン改質ポリエチレン系樹脂粒子の作製]において、ポリエチレン系樹脂としてエチレン−酢酸ビニル共重合体(ＥＶＡ) 「住友化学製 エバテート Ｆ１１０３−１」とした、スチレンの滴下を８５℃で実施した以外は実施例２と同様の方法により、スチレン改質ポリエチレン系樹脂粒子、スチレン改質ポリエチレン系予備発泡粒子および型内発泡成形体を作製し、同様の評価を行った。結果は、表２に示した。
(Comparative Example 10)
In [Production of styrene-modified polyethylene resin particles], ethylene-vinyl acetate copolymer (EVA) “Evalate F1103-1 manufactured by Sumitomo Chemical” was used as the polyethylene resin, except that styrene was dropped at 85 ° C. By the same method as in Example 2, styrene-modified polyethylene resin particles, styrene-modified polyethylene pre-foamed particles, and in-mold foam molded articles were produced, and the same evaluation was performed. The results are shown in Table 2.
（比較例１１)
［スチレン改質ポリエチレン系樹脂粒子の作製］においては、実施例２と同様の方法により、スチレン改質ポリエチレン系樹脂粒子を得た。
［スチレン改質ポリエチレ系樹脂予備発泡粒子の作製］において、４級アンモニウム塩を使用せず、炭酸ガスに代えてブタン（ノルマルブタン７５％とイソブタン２５％の混合品）２５重量部を加え、１４０℃に昇温して更に２．５ＭＰａとなるまでブタンを追加して加圧した以外は、実施例２と同様の方法により、スチレン改質ポリエチレン系予備発泡粒子を得た。
［スチレン改質ポリエチレン系樹脂型内発泡体の作製］においては、空気による内圧付与を行わなかった以外は、実施例２と同様の方法により、型内発泡成形体を作製し、同様の評価を行った。
結果は、表２に示した。
(Comparative Example 11)
In [Production of styrene-modified polyethylene resin particles], styrene-modified polyethylene resin particles were obtained in the same manner as in Example 2.
In [Preparation of pre-expanded styrene-modified polyethylene resin particles], quaternary ammonium salt is not used, but 25 parts by weight of butane (mixture of normal butane 75% and isobutane 25%) is added in place of carbon dioxide gas. Styrene-modified polyethylene-based pre-expanded particles were obtained in the same manner as in Example 2 except that the pressure was increased by adding butane to 2.5 MPa and raising the pressure to 2.5 MPa.
In [Production of styrene-modified polyethylene-based resin in-mold foam], an in-mold foam-molded article was produced in the same manner as in Example 2 except that no internal pressure was applied by air, and the same evaluation was performed. went.
The results are shown in Table 2.
実施例は、本件特許の要件を満たしている為、炭酸ガスを使用した発泡性が良く、良好な燃焼速度を有する。比較例は、熱キシレンテトラヒドロフラン可溶部の重量平均分子量、熱キシレン不要分量、メチルエチルケトン可溶部量、ＡＴＲ−ＩＲにおける吸光度比のいずれかを満たしておらず、発泡力または燃焼速度に劣る。
Since the examples satisfy the requirements of this patent, the foaming property using carbon dioxide gas is good, and the burning rate is good. The comparative example does not satisfy any of the weight average molecular weight of the hot xylene tetrahydrofuran soluble part, the amount of unnecessary hot xylene, the methyl ethyl ketone soluble part, or the absorbance ratio in ATR-IR, and is inferior in foaming power or burning rate.
Claims (5)
ポリエチレン系樹脂が分岐状低密度ポリエチレンであり、
スチレン改質ポリエチレン系予備発泡粒子のテトラヒドロフラン可溶部の重量平均分子量が１５万以上３５万以下であり、
スチレン改質ポリエチレン系予備発泡粒子が、揮発性成分が１％以下、熱キシレン不溶分を５重量％以上２０重量％以下、メチルエチルケトン可溶分を５０重量％以下含有することを特徴とする、スチレン改質ポリエチレン系予備発泡粒子。 Styrene-modified polyethylene resin pre-expanded particles obtained by polymerizing by impregnating 120 parts by weight or more and 500 parts by weight or less of styrene monomer with respect to 100 parts by weight of polyethylene resin,
The polyethylene resin is a branched low density polyethylene,
The weight average molecular weight of the tetrahydrofuran-soluble part of the styrene-modified polyethylene pre-expanded particles is 150,000 to 350,000,
Styrene-modified polyethylene-based pre-expanded particles have a volatile component of 1% or less, a thermal xylene insoluble content of 5% by weight to 20% by weight, and a methyl ethyl ketone soluble content of 50% by weight or less. Modified polyethylene-based pre-expanded particles.
The foamed molded article according to claim 4, wherein the combustion rate in the FMVSS302 combustion test is 100 mm / min or less at an expansion ratio of 30 times.
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