JP5664238B2 - Styrene-modified polyethylene resin pre-expanded particles and foam-molded article comprising the styrene-modified polyethylene resin pre-expanded particles - Google Patents
Styrene-modified polyethylene resin pre-expanded particles and foam-molded article comprising the styrene-modified polyethylene resin pre-expanded particles Download PDFInfo
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- JP5664238B2 JP5664238B2 JP2010517968A JP2010517968A JP5664238B2 JP 5664238 B2 JP5664238 B2 JP 5664238B2 JP 2010517968 A JP2010517968 A JP 2010517968A JP 2010517968 A JP2010517968 A JP 2010517968A JP 5664238 B2 JP5664238 B2 JP 5664238B2
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- Prior art keywords
- styrene
- polyethylene resin
- weight
- modified polyethylene
- parts
- Prior art date
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- 239000002245 particle Substances 0.000 title claims description 182
- 229920013716 polyethylene resin Polymers 0.000 title claims description 156
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 59
- 238000005187 foaming Methods 0.000 claims description 22
- 238000010097 foam moulding Methods 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 239000003505 polymerization initiator Substances 0.000 claims description 13
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 229920005678 polyethylene based resin Polymers 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 3
- 239000004088 foaming agent Substances 0.000 description 62
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 38
- 238000006116 polymerization reaction Methods 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000008096 xylene Substances 0.000 description 18
- 229910001868 water Inorganic materials 0.000 description 17
- 239000003431 cross linking reagent Substances 0.000 description 16
- 238000004132 cross linking Methods 0.000 description 15
- 239000000178 monomer Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001816 cooling Methods 0.000 description 14
- 238000000465 moulding Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 11
- 239000006260 foam Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 9
- 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 8
- 239000007900 aqueous suspension Substances 0.000 description 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 8
- 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 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000002612 dispersion medium Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 235000019731 tricalcium phosphate Nutrition 0.000 description 7
- 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 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000001506 calcium phosphate Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- 239000001273 butane Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 5
- 229940078499 tricalcium phosphate Drugs 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 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 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012188 paraffin wax Substances 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
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-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
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000012546 transfer Methods 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
- 238000005303 weighing Methods 0.000 description 2
- 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 1
- 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
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-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
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-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
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- CIKJANOSDPPCAU-UHFFFAOYSA-N ditert-butyl cyclohexane-1,4-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1CCC(C(=O)OOC(C)(C)C)CC1 CIKJANOSDPPCAU-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 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
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 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
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 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
- PVNIQBQSYATKKL-UHFFFAOYSA-N tripalmitin Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCC PVNIQBQSYATKKL-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
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Description
本発明は耐割れ性、成形加工性の優れた発泡成形体を製造しうるスチレン改質ポリエチレン系樹脂予備発泡粒子および発泡成形体に関する。 The present invention relates to a styrene-modified polyethylene resin pre-expanded particle and a foam-molded product that can produce a foam-molded product having excellent crack resistance and molding processability.
ポリオレフィン系樹脂の発泡成形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、包装資材として広く利用されている。しかし、剛性が低く、型内発泡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 foam moldings are generally used as packaging materials because of their high elasticity and excellent strain resistance against repeated stresses, as well as excellent oil resistance and crack resistance. Yes. However, it has the disadvantages of low rigidity, easy shrinkage of the foam molded product after in-mold foam 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た、スチレン改質ポリエチレン樹脂が知られている。 As a method for improving such a defect, a styrene-modified polyethylene resin is known in which a polyethylene resin is impregnated with a styrene monomer and polymerized.
例えば、特許文献１では、ポリオレフィン系成分とスチレン系成分のグラフト反応物を生成し、耐衝撃性の高いスチレン改質ポリエチレン系樹脂を得る方法が記載されている。 For example, Patent Document 1 describes a method for producing a graft reaction product of a polyolefin component and a styrene component to obtain a styrene-modified polyethylene resin having high impact resistance.
また、特許文献２では、モノマーの追加パターン、攪拌所要動力を制御することによって樹脂表面をオレフィンリッチにし、スチレン改質ポリエチレン系樹脂の耐衝撃性や耐薬品性を高める方法が記載されている。 Patent Document 2 describes a method for improving the impact resistance and chemical resistance of a styrene-modified polyethylene resin by making the resin surface rich in olefin by controlling the additional pattern of monomer and the power required for stirring.
特許文献３では、モノマー追加パターンと重合温度を制御することによって、リサイクル性、耐衝撃性にすぐれたスチレン改質ポリエチレン系樹脂を得る方法が記載されている。 Patent Document 3 describes a method of obtaining a styrene-modified polyethylene resin excellent in recyclability and impact resistance by controlling the monomer addition pattern and the polymerization temperature.
また、特許文献４には、耐割れ性、成形加工性を両立するためのゲル量、分子量範囲に関する記載があり、優れた成形加工性を有する予備発泡粒子が得られることが記載されている。 Patent Document 4 describes a gel amount and a molecular weight range for achieving both crack resistance and molding processability, and describes that pre-expanded particles having excellent molding processability can be obtained.
しかしながら、予備発泡粒子の発泡剤逸散時の成形加工性について記載されておらず、予備発泡粒子の発泡剤逸散時でも優れた成形加工性を有するスチレン改質ポリエチレン予備発泡粒子が望まれていた。 However, there is no description on the molding processability of the pre-foamed particles when the foaming agent escapes, and there is a demand for styrene-modified polyethylene pre-foamed particles having excellent moldability even when the pre-foamed particles escape. It was.
以上のような状況に鑑み、本発明は、予備発泡粒子の発泡剤逸散時においても成形加工性に優れ、高い耐割れ性を有するスチレン改質ポリエチレン系樹脂予備発泡粒子を提供することにある。 In view of the situation as described above, the present invention is to provide styrene-modified polyethylene resin pre-foamed particles having excellent moldability and high cracking resistance even when the foaming agent is dispersed in the pre-foamed particles. .
本発明者らは、鋭意検討の結果、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１５０重量部以上３００重量部以下重合してなるスチレン改質ポリエチレン系樹脂粒子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、テトラヒドロフラン可溶部の重量平均分子量が２５万以下であり、テトラヒドロフラン可溶部が１０重量％以上４０重量％以下、かつ熱キシレン不溶のゲル成分が１５重量％以上３５重量％以下であることを特徴とするスチレン改質ポリエチレン系樹脂予備発泡粒子が、予備発泡粒子の発泡剤逸散時でも成形加工性に優れ、かつ耐割れ性の優れた発泡成形体を得ることができることを見出し本発明の完成に至った。 As a result of intensive studies, the present inventors foamed styrene-modified polyethylene resin particles obtained by polymerizing 150 parts by weight or more and 300 parts by weight or less of styrene monomer with respect to 100 parts by weight of polyethylene resin particles. Pre-expanded particles of styrene-modified polyethylene resin obtained, wherein the tetrahydrofuran-soluble part has a weight average molecular weight of 250,000 or less, the tetrahydrofuran-soluble part is 10% by weight or more and 40% by weight or less, and the gel is insoluble in hot xylene The styrene-modified polyethylene resin pre-expanded particles characterized in that the components are 15% by weight or more and 35% by weight or less are excellent in molding processability and excellent crack resistance even when the pre-expanded particles escape. The present inventors have found that a foamed molded product can be obtained and have completed the present invention.
即ち本発明の第１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１５０重量部以上３００重量部以下を重合開始剤の存在下で重合してなるスチレン改質ポリエチレン系樹脂粒子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、テトラヒドロフラン可溶部の重量平均分子量が２５万以下であり、テトラヒドロフラン可溶部が１０重量％以上４０重量％以下、かつ熱キシレン不溶のゲル成分が１５重量％以上３５重量％以下であることを特徴とするスチレン改質ポリエチレン系樹脂予備発泡粒子に関する。
That first invention, styrene-modified polyethylene-based resin obtained by polymerizing in the presence of styrene monomer 1 50 parts by weight to 300 parts by weight of a polymerization initiator relative to 100 parts by weight of polyethylene resin particles Styrene-modified polyethylene resin pre-expanded particles obtained by foaming particles, wherein the tetrahydrofuran-soluble part has a weight average molecular weight of 250,000 or less, the tetrahydrofuran-soluble part is 10% by weight to 40% by weight, and The present invention relates to pre-expanded particles of styrene-modified polyethylene resin, characterized in that the thermal xylene-insoluble gel component is 15 wt% or more and 35 wt% or less.
好ましい態様としては、重合開始剤が、過酸化ベンゾイル、ビス−３，５，５−トリメチルヘキサノニルパーオキサイド、ｐ−クロロベンゾイルパーオキサイドのいずれかである前記記載のスチレン改質ポリエチレン系樹脂予備発泡粒子に関し、別の好ましい態様としては、テトラヒドロフラン可溶部の重量平均分子量が２０万未満である前記記載のスチレン改質ポリエチレン系樹脂予備発泡粒子に関し、さらに別の好ましい態様としては、ポリエチレン系樹脂粒子がメルトフローレート１．５ｇ／１０分以下、かつ酢酸ビニル含有量が１０重量％以下であるエチレン・酢酸ビニル共重合体である前記記載のスチレン改質ポリエチレン系樹脂予備発泡粒子に関する。
As a preferred embodiment, the styrene-modified polyethylene resin prefoaming as described above, wherein the polymerization initiator is any of benzoyl peroxide, bis-3,5,5-trimethylhexanonyl peroxide, and p-chlorobenzoyl peroxide. Regarding the particles, another preferred embodiment relates to the styrene-modified polyethylene resin pre-expanded particles described above in which the weight average molecular weight of the tetrahydrofuran soluble part is less than 200,000, and as another preferred embodiment, the polyethylene resin particles Relates to the styrene-modified polyethylene resin pre-expanded particles described above, which is an ethylene / vinyl acetate copolymer having a melt flow rate of 1.5 g / 10 min or less and a vinyl acetate content of 10 wt% or less.
本発明の第２は、ポリエチレン樹脂粒子１００重量部に対し、本質的に重合が進まない温度下でスチレン系単量体２５重量部以上１００重量部以下を添加して含浸させ、残りのスチレン系単量体を加熱下で添加することを特徴とする前記記載のスチレン改質ポリエチレン樹脂予備発泡粒子の製造方法に関する。 In the second aspect of the present invention, 25 parts by weight or more and 100 parts by weight or less of a styrenic monomer are added and impregnated with 100 parts by weight of polyethylene resin particles at a temperature at which polymerization does not proceed. The present invention relates to the above-mentioned method for producing pre-expanded particles of styrene-modified polyethylene resin, wherein the monomer is added under heating.
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樹脂予備発泡粒子を型内発泡成形してなる発泡成形体に関する。 The third aspect of the present invention relates to a foam molded article obtained by in-mold foam molding the above-mentioned styrene-modified polyethylene resin pre-expanded particles.
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、スチレン改質ポリエチレン系樹脂予備発泡粒子の発泡剤逸散時であっても成形加工性に優れている。具体的には、スチレン改質ポリエチレン系樹脂予備発泡粒子の発泡剤逸散時であっても、型内発泡成形した際、良好な表面状態を有する発泡成形体が得られる為、ビーズライフが延長され、工業的に有利である。また、得られた発泡成形体は高い耐割れ性を示す。 The styrene-modified polyethylene resin pre-expanded particles of the present invention are excellent in moldability even when the blowing agent escapes from the styrene-modified polyethylene resin pre-expanded particles. Specifically, even when the foaming agent of the styrene-modified polyethylene resin pre-expanded particles is dissipated, a foamed molded article having a good surface state can be obtained when in-mold foam molding is performed, thereby extending the bead life. And industrially advantageous. Moreover, the obtained foaming molding shows high crack resistance.
本発明の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１５０重量部以上３００重量部以下、好ましくは１８０重量部以上２５０重量部以下重合させる。当該範囲内であれば、スチレン改質ポリエチレン系樹脂粒子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を型内発泡成形する際に成形加工性と耐割れ性が両立出来る発泡成形体が得られる。 In the styrene-modified polyethylene resin particles of the present invention, 150 parts by weight or more and 300 parts by weight or less, preferably 180 parts by weight or more and 250 parts by weight or less of styrene monomer is polymerized with respect to 100 parts by weight of polyethylene resin particles. . Within this range, a foamed molded article that can achieve both moldability and crack resistance when foam-molding styrene-modified polyethylene resin pre-expanded particles obtained by foaming styrene-modified polyethylene resin particles. Is obtained.
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重合させる方法としては、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に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、重合させる方法が挙げられる。重合において、添加するスチレン系単量体の添加速度を任意に選択することで、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 the present invention, as a method for polymerizing the styrene monomer to the polyethylene resin particles, for example, the styrene monomer is continuously added to an aqueous suspension containing the polyethylene resin particles charged in a container equipped with a stirrer. For example, a method of impregnating polyethylene resin particles with a styrene monomer and polymerizing them by adding them intermittently or intermittently can be mentioned. In the polymerization, 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 to be added.
本発明のスチレン改質ポリエチレン樹脂予備発泡粒子の製造方法において、好ましい態様として、重合に際し、ポリエチレン樹脂粒子１００重量部に対し、本質的に重合が進まない温度下でスチレン系単量体２５重量部以上１００重量部以下を添加して含浸させ、残りのスチレン系単量体を加熱下で添加することである。「本質的に重合が進まない温度下」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、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ゲル成分量及び重量平均分子量を調整し易い。 In the method for producing styrene-modified polyethylene resin pre-foamed particles of the present invention, as a preferred embodiment, 25 parts by weight of a styrene monomer at a temperature at which the polymerization does not proceed essentially with respect to 100 parts by weight of the polyethylene resin particles during polymerization. More than 100 parts by weight is added and impregnated, and the remaining styrenic monomer is added under heating. “At a temperature at which polymerization does not proceed essentially” means that the temperature is 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 gel component amount and the weight average molecular weight of the modified polyethylene resin pre-expanded particles.
また、本質的に重合が進まない温度下で添加するスチレン系単量体の量、及び加熱下で添加するスチレン系単量体の追加速度を調整し、重合樹脂中の未反応のスチレン系単量体の比率を１５％以上に保つようにすると、スチレン改質ポリエチレン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を所望の分子量としやすく、テトラヒドロフラン可溶部の量を所望の量としやすいため好ましい。 In addition, the amount of styrenic monomer added at a temperature at which polymerization does not proceed essentially and the additional rate of styrenic monomer added under heating are adjusted so that unreacted styrenic monomer in the polymerized resin. When the ratio of the monomer is maintained at 15% or more, the weight average molecular weight of the tetrahydrofuran soluble part of the styrene-modified polyethylene resin pre-expanded particles can be easily set to a desired molecular weight, and the amount of the tetrahydrofuran soluble part can be easily set to a desired quantity. Therefore, it is preferable.
本発明で使用するポリエチレン系樹脂粒子を構成するポリエチレン系樹脂は、高密度ポリエチレン、低密度ポリエチレン等のエチレンの単独重合体、エチレンと、例えば、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン等のα−オレフィンや酢酸ビニル、アクリル酸エステル、塩化ビニル等との共重合体があげられる。これらの中でもエチレンと酢酸ビニルの共重合体が好ましい。更に好ましくは、メルトフローレート（以下、ＭＦＲと表記する場合がある）が１．５ｇ／１０分以下で、かつ酢酸ビニル含有量が１０重量％以下であるエチレン・酢酸ビニル共重合体である。ＭＦＲが１．５ｇ／１０分を超えては耐割れ性の発現が難しくなる傾向がある。酢酸ビニルが１０重量％を超えては融点が低いため、重合時に樹脂変形を起こ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 polyethylene resin constituting the polyethylene resin particles used in the present invention is a homopolymer of ethylene such as high-density polyethylene or low-density polyethylene, ethylene and, for example, propylene, 1-butene, 1-pentene, 1-hexene. And a copolymer with α-olefin such as vinyl acetate, acrylic acid ester, vinyl chloride and the like. Among these, a copolymer of ethylene and vinyl acetate is preferable. More preferred is an ethylene / vinyl acetate copolymer having a melt flow rate (hereinafter sometimes referred to as MFR) of 1.5 g / 10 min or less and a vinyl acetate content of 10 wt% or less. If the MFR exceeds 1.5 g / 10 min, the development of crack resistance tends to be difficult. When vinyl acetate exceeds 10% by weight, the melting point is low, so that resin deformation tends to occur 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、あらかじめ、例えば押出し機、ニーダー、バンバリーミキサー、ロール等を用いて溶融することによりポリエチレン系樹脂粒子となす。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。これら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。０．１ｍｇ／粒より小さい場合は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／粒より大きい場合は成形時の充填性が悪くなる恐れがある。 The polyethylene resin is made into polyethylene resin particles by melting in advance using, for example, an extruder, a kneader, a Banbury mixer, a roll or the like. The shape is preferably a particle state such as powder or pellet. The average particle weight of these particles is preferably in the range of 0.1 mg / particle to 3 mg / particle. If it is less than 0.1 mg / grain, the foaming agent may dissipate rapidly, making it difficult to increase the magnification. If it is greater than 3 mg / grain, the filling property during molding may be deteriorated.
ポリエチレン系樹脂粒子を作製する際に、各種添加剤を添加することが出来る。各種添加剤としては、目的に応じて可塑剤、気泡調整剤等が挙げられる。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、これらは併用しても何ら差し支えない。 Various additives can be added when producing polyethylene resin particles. Examples of the various additives include a plasticizer and a bubble regulator according to the purpose. 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 And the like, organic hydrocarbons such as liquid paraffin and cyclohexane, and organic aromatic hydrocarbons such as toluene and ethylbenzene. These may be used in combination.
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、炭酸カルシウム等の無機系気泡調整剤等があげられる。また、これらの各種添加剤は重合時、発泡剤含浸時のみならず、あらかじめ前記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。 Examples of the foam regulator include organic foam regulators such as aliphatic bisamides and stearamide such as methylene bis stearic acid amide and ethylene bis stearic acid amide, inorganic foams such as talc, silica, calcium silicate, and calcium carbonate. Examples thereof include regulators. These various additives can be used not only at the time of polymerization and at the time of impregnation with a foaming agent, but also by previously mixing with the polyethylene resin particles.
特に後に示す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。 In particular, when performing pressure-reducing foaming to be described later, it is preferable to use an inorganic cell regulator, and the preferred amount used 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. . When the amount of the inorganic air-conditioning agent is less than 0.01 parts by weight, it is difficult to stably generate bubbles, and when the amount is more than 0.5 parts by weight, the fusion during molding tends to deteriorate.
本発明に使用するスチレン系単量体としては、スチレン、および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, styrene and styrene derivatives such as α-methyl styrene, paramethyl styrene, t-butyl styrene and chlorostyrene can be used as main components.
また、スチレン系単量体以外にも、スチレン系誘導体と共重合が可能な成分、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、１種または２種以上併用してもよい。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 addition to styrene monomers, components that can be copolymerized with styrene derivatives, for example, esters of acrylic acid and methacrylic acid such as methyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate, acrylonitrile, dimethyl fumarate, etc. A rate, ethyl fumarate, or the like may be used alone or in combination of two or more in a range that does not impair the effects of the styrene-modified polyethylene resin pre-expanded particles of the present invention. Furthermore, polyfunctional monomers such as divinylbenzene and alkylene glycol dimethacrylate can also be used.
本発明において使用す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、ビス−３，５，５-トリメチルヘキサノニルパーオキサイド、ｐ-クロロベンゾイルパーオキサイド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もしくは２種以上を混合して用いることができる。重量平均分子量は重合開始剤の量と反応温度により調整できる。 As the polymerization initiator used in the present invention, radical generating polymerization initiators generally used for the production of thermoplastic polymers can be used. Typical examples include benzoyl peroxide, lauroyl peroxide, t-butyl perpivalate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyhexahydroterephthalate, 1,1-di (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1 -Organic peroxides such as di (t-butylperoxy) cyclohexane, bis-3,5,5-trimethylhexanonyl peroxide, p-chlorobenzoyl peroxide, azobisisobutyronitrile, azobisdimethylvalero Examples include azo compounds such as nitrile. These polymerization initiators can be used alone or in admixture of two or more. The weight average molecular weight can be adjusted by the amount of the polymerization initiator and the reaction temperature.
中でも、過酸化ベンゾイル、ビス−３，５，５-トリメチルヘキサノニルパーオキサイド、ｐ-クロロベンゾイルパーオキサイドのいずれかを使用すると、スチレン改質ポリエチレン系樹脂予備発泡粒子中のテトラヒドロフラン可溶部を多くすることが出来る傾向があるため、好ましい。 Among these, when one of benzoyl peroxide, bis-3,5,5-trimethylhexanonyl peroxide, and p-chlorobenzoyl peroxide is used, the tetrahydrofuran-soluble part in the styrene-modified polyethylene resin pre-expanded particles is increased. This is preferable because it tends to be able to.
これら重合開始剤の使用量は、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、さらには０．１重量部以上０．５重量部以下であることが好ましい。 The amount of the polymerization initiator used is preferably 0.05 parts by weight or more and 1.0 parts by weight or less, more preferably 0.1 parts by weight or more and 0.5 parts by weight or less with respect to 100 parts by weight of the styrene monomer. Part or less.
重合温度は７０℃以上９０℃以下であると、テトラヒドロフラン可溶部の重量平均分子量が所望の分子量であるスチレン改質ポリエチレン系樹脂予備発泡粒子が得られるため、好ましい。 The polymerization temperature is preferably 70 ° C. or higher and 90 ° C. or lower because styrene-modified polyethylene resin pre-expanded particles having a desired weight average molecular weight of the tetrahydrofuran-soluble part can be obtained.
本発明における前記重合においては、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 according to the present invention, α-methylstyrene dimer generally used for polymerization of mercaptan chain transfer agents such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and acrylonitrile-styrene resin. Etc. may be used in combination.
本発明においては、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、樹脂粒子同士の融着を防止するために分散剤を使用することが好ましい。使用できる分散剤としては、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、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。 In the present invention, polymerization is carried out in an aqueous suspension containing polyethylene resin particles. At this time, it is preferable to use a dispersant in order to prevent fusion of the resin particles. Dispersants that can be used include dispersants generally used for suspension polymerization, for example, polymer dispersants such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylamide, and poorly water-soluble materials such as calcium phosphate, hydroxyapatite, magnesium pyrophosphate, and kaolin. Inorganic salts.
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ので効果的であるため好ましい。また、これらの分散剤は重合中に追加しても良い。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。 In addition, when a poorly water-soluble inorganic salt is used, it is preferable to use an anionic surfactant such as α-olefin sodium sulfonate or sodium dodecylbenzene sulfonate because the dispersion stability is increased, which is effective. These dispersants may be added during the polymerization. The amount of the dispersant used is preferably 0.2 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of water although it depends on the type.
本発明の「水性懸濁液」とは樹脂粒子と単量体液滴を攪拌等により水または水溶液に分散させた状態を指し、水性懸濁液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、可塑剤等がともに分散していても良い。ポリエチレン系樹脂粒子と水の重量比は、得られるスチレン改質ポリスチレン樹脂／水で１．０／０．６から１．０／３．０が好ましい。 The “aqueous suspension” of the present invention refers to a state in which resin particles and monomer droplets are dispersed in water or an aqueous solution by stirring or the like. In the aqueous suspension, a water-soluble surfactant or monomer is used. May be dissolved, or a water-insoluble dispersant, initiator, crosslinking agent, bubble regulator, flame retardant, plasticizer, and the like may be dispersed together. The weight ratio of the polyethylene resin particles to water is preferably 1.0 / 0.6 to 1.0 / 3.0 with respect to the obtained styrene-modified polystyrene resin / water.
本発明においては、スチレン改質ポリエチレン系樹脂予備発泡粒子中にゲルを生成させることが必要であり、その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。中でも、１０時間半減期温度が１００℃以上１２５℃以下のラジカル種発生型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る場合があり、また、後述する１２０℃以上１５０℃以下での架橋が困難となる場合がある。１０時間半減期温度が１２５℃を超えると、１２０℃以上１５０℃以下の温度で架橋反応を進行させる場合に時間がかかる。 In the present invention, it is necessary to form a gel in the styrene-modified polyethylene resin pre-expanded particles, and therefore it is preferable to use a radical species-generating crosslinking agent. Among them, it is preferable to use a radical species generating type crosslinking agent having a 10-hour half-life temperature of 100 ° C. or more and 125 ° C. or less. If a radical species-generating crosslinking agent having a 10-hour half-life temperature lower than 100 ° C is used, the crosslinking reaction may proceed excessively during polymerization, and crosslinking at 120 ° C to 150 ° C described later may be difficult. is there. When the 10-hour half-life temperature exceeds 125 ° C, it takes time to advance the crosslinking reaction at a temperature of 120 ° C or higher and 150 ° C or lower.
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、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。これらは、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。 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-hour 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 -Butyl peroxybutane (10-hour half-life temperature: 103 degreeC) etc. are mentioned. These 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は１２０℃以上１５０℃以下で行われるのが好ましい。架橋反応が１２０℃未満であると、耐衝撃性と成形加工性を両立するスチレン改質ポリエチレン系樹脂を得ることが困難になる場合がある。架橋反応温度が１５０℃を超えるとポリエチレン系樹脂が軟化しすぎ、樹脂粒子が凝集しやすくなる場合がある。架橋剤の使用量は架橋剤の種類によって異なるが、得られるスチレン改質エチレン系樹脂予備発泡粒子１００重量部に対して、０．１重量部以上１．０重量部以下使用すると所望の範囲のゲル量が得られやすいため好ましい。 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 and 150 ° C. or lower. If the cross-linking reaction is less than 120 ° C., it may be difficult to obtain a styrene-modified polyethylene resin having both impact resistance and molding processability. When the crosslinking reaction temperature exceeds 150 ° C., the polyethylene resin is too soft and the resin particles may easily aggregate. The amount of the crosslinking agent used varies depending on the type of the crosslinking agent. However, when 100 parts by weight of the styrene-modified ethylene resin pre-expanded particles obtained are used in an amount of 0.1 parts by weight or more and 1.0 parts by weight or less, the desired range is reached. This is preferable because the gel amount is easily obtained.
本発明において使用することが出来る発泡剤としては、公知のものが挙げられ、例えば、プロパン、イソブタン、ノルマルブタン、イソペンタン、ノルマルペンタン、ネオペンタン等の脂肪族炭化水素類、ジフルオロエタン、テトラフルオロエタン等のオゾン破壊係数がゼロであるハイドロフルオロカーボン類等の揮発性発泡剤、空気、窒素、二酸化炭素等の無機ガス、水等があげられる。これらの発泡剤は併用しても何ら差し支えない。 Examples of the blowing agent that can be used in the present invention include known ones such as aliphatic hydrocarbons such as propane, isobutane, normal butane, isopentane, normal pentane, and neopentane, difluoroethane, tetrafluoroethane, and the like. Examples thereof include volatile foaming agents such as hydrofluorocarbons having an ozone depletion coefficient of zero, inorganic gases such as air, nitrogen and carbon dioxide, and water. These foaming agents can be used in combination.
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 with the radical species generating crosslinking agent, but may be added before the crosslinking reaction is completed.
また、発泡剤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重量部以下であることが好ましく、より好ましくは１５重量部以上２５重量部以下である。１０重量部未満以下では十分な発泡倍率を得ることができない場合があり、成形加工性の良好な予備発泡粒子を得ることが難しい場合がある。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やすく、樹脂同士が凝集を起こす場合がある。 The amount of the foaming agent is preferably 10 parts by weight or more and 30 parts by weight or less, and more preferably 15 parts by weight or more and 25 parts by weight or less with respect to 100 parts by weight of the styrene-modified polyethylene resin particles. If it is less than 10 parts by weight, a sufficient expansion ratio may not be obtained, and it may be difficult to obtain pre-expanded particles having good moldability. If it exceeds 30 parts by weight, the dispersion state of the resin when impregnated with the foaming agent tends to be unstable, and the resins may cause aggregation.
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、（１）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、（２）ポリエチレン系樹脂粒子にスチレン系単量体を含浸、重合させた後、発泡剤を含浸させ発泡性スチレン改質ポリエチレン系樹脂粒子と成し、攪拌機を具備した容器内に発泡性スチレン改質ポリエチレン系樹脂粒子を入れ水蒸気等の熱源により加熱する方法、（３）ポリエチレン系樹脂粒子にスチレン系単量体を含浸、重合させてスチレン改質ポリエチレン系樹脂粒子と成し、攪拌機を具備した容器内にて発泡剤を含浸させ、水蒸気等の熱源により加熱する方法、等があげられるが、特に（１）の方法を選択することが、発泡剤の含浸と発泡を一連の操作で行うために過剰量の発泡剤を必要とせず、好ましい。 As a method of impregnating and pre-foaming styrene-modified polyethylene resin particles impregnated and polymerized with polyethylene-based resin particles with a foaming agent, (1) styrene-modified polyethylene resin in a pressure-resistant container Disperse the particles in an aqueous dispersion medium, place the foaming agent in a pressure-resistant container, heat to a temperature above the softening point of the styrene-modified polyethylene resin particles, and apply the resin particles under pressure above the vapor pressure of the foaming agent. After impregnating the foaming agent, the so-called "pressure-removal foaming", in which the mixture of the styrene-modified polyethylene resin particles and the aqueous dispersion medium is released to a lower pressure region than in the pressure vessel while keeping the temperature and pressure inside the pressure vessel constant (2) After impregnating and polymerizing polyethylene-based resin particles with a styrene-based monomer, and then impregnating a foaming agent into foamable styrene-modified polyethylene-based resin particles, A method in which foamable styrene-modified polyethylene resin particles are placed in a container equipped with a stirrer and heated by a heat source such as water vapor. (3) Styrene-modified by impregnating and polymerizing polyethylene resin particles with a styrene monomer. A method of impregnating a foaming agent in a container equipped with a polyethylene-based resin particle and equipped with a stirrer and heating with a heat source such as water vapor can be mentioned. In order to perform the impregnation and foaming of the agent by a series of operations, an excessive amount of the foaming agent is not required, which is preferable.
（１）の方法において、具体的には、重合反応を行うことによって得られた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、水性分散媒に分散させ、発泡剤を追加した後に加熱昇温し、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１ｍｍから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スチレン改質ポリエチレン系樹脂予備発泡粒子を製造することができる。 In the method (1), specifically, after the styrene-modified polyethylene resin particles obtained by carrying out the polymerization reaction are once taken out from the pressure vessel, washed and dried, the pressure resistance for decompression foaming Charge into a container, disperse in an aqueous dispersion medium, add a foaming agent, and then raise the temperature by heating, open one end of the container while keeping the temperature and pressure inside the pressure-resistant container constant, for example, the hole diameter is 1 mm to 10 mm The styrene-modified polyethylene resin pre-expanded particles having a uniform and fine cell structure are produced by releasing and foaming the contents through an orifice or the like in an atmosphere at a pressure lower than that in the pressure vessel, for example, in the atmosphere. be able to.
この除圧発泡でいう水性分散媒は、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。この除圧発泡の時点で可塑剤、気泡調整剤等の各種添加剤を含浸させても良い。この方法では発泡剤の含浸と予備発泡を同時に行うことができ、また発泡剤は吸引設備により回収することができるため、効率的である。 The aqueous dispersion medium referred to as decompression foaming indicates a solution in which a dispersant is dissolved or dispersed in water, and the same type of dispersant as in the polymerization can be used as the dispersant. Various additives such as a plasticizer and a bubble adjusting agent may be impregnated at the time of the decompression foaming. This method is efficient because the foaming agent can be impregnated and pre-foamed at the same time, and the foaming agent can be recovered by a suction facility.
（２）の方法においては、具体的には、重合反応に続いて発泡剤の追加、含浸を行う。発泡剤は架橋反応の前後どのタイミングで追加してもかまわない。この際、発泡剤導入による缶内圧力の急激な上昇を防ぐため、必要に応じて発泡剤を追加しやすい温度まで冷却を行ってから発泡剤を追加し、その後に温度を上昇させて発泡剤含浸や架橋反応を行うこともできる。その後、発泡剤を含浸させたスチレン改質ポリエチレン系樹脂を耐圧容器より払い出し、洗浄・乾燥を行った後に水蒸気等によって加熱し、予備発泡粒子とすることができる。 In the method (2), specifically, a foaming agent is added and impregnated after the polymerization reaction. The blowing agent may be added at any timing before and after the crosslinking reaction. At this time, in order to prevent a sudden rise in the internal pressure due to the introduction of the foaming agent, the foaming agent is added after cooling to a temperature at which it is easy to add the foaming agent, if necessary, and then the temperature is raised to increase the foaming agent. Impregnation and crosslinking reaction can also be performed. Thereafter, the styrene-modified polyethylene resin impregnated with the foaming agent is discharged from the pressure vessel, washed and dried, and then heated with water vapor or the like to obtain pre-expanded particles.
（３）においては、具体的には、重合反応を行うことによって得られた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・乾燥を行う。更に発泡剤含浸用の攪拌機を具備した耐圧容器に移し、少量の水、分散剤と発泡剤を追加して発泡剤含浸を行った後に払い出し、水蒸気等によって加熱し、予備発泡粒子とすることができる。この方法では発泡剤含浸時に仕込む水の量を少なくすることで発泡剤含浸後の乾燥工程を省くことができるため、発泡までの発泡剤の逸散を抑えることができる。 In (3), specifically, the styrene-modified polyethylene resin particles obtained by carrying out the polymerization reaction are once taken out from the pressure vessel and washed and dried. Further, transfer to a pressure vessel equipped with a stirrer for impregnating the foaming agent, add a small amount of water, a dispersant and a foaming agent, impregnate the foaming agent, and then discharge and heat with steam to obtain pre-expanded particles. it can. In this method, since the drying step after impregnating the foaming agent can be omitted by reducing the amount of water charged when impregnating the foaming agent, the dissipation of the foaming agent until foaming can be suppressed.
以上のようにして得られた、スチレン改質ポリエチレン系樹脂予備発泡粒子は、熱キシレンに不溶なゲル成分量が１５重量％以上３５重量％以下であり、好ましくは２０重量％以上３０重量％以下である。当該範囲内であると、型内発泡成形を行う場合、高圧あるいは長時間の蒸気加熱を必要とせず、高倍率化しやすく、耐割れ性が良好な発泡成形体が得られる。 In the styrene-modified polyethylene resin pre-expanded particles obtained as described above, the amount of gel component insoluble in hot xylene is 15 wt% or more and 35 wt% or less, preferably 20 wt% or more and 30 wt% or less. It is. Within this range, when performing in-mold foam molding, high pressure or long-time steam heating is not required, and a foam molded article that is easy to increase in magnification and has good crack resistance can be obtained.
また、本発明の製造方法によって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は、テトラヒドロフランに可溶な成分の重量平均分子量が２５万以下である。好ましくは１０万以上２０万未満である。当該範囲内であると、型内発泡成形を行う場合、発泡剤逸散時でも表面状態が良好な発泡成形体が得られる。なお、本発明においては、発泡剤逸散時とは、スチレン改質ポリエチレン系樹脂予備発泡粒子の発泡剤残量が０．４重量％以上１重量％以下である状態をいう。 The styrene-modified polyethylene resin pre-expanded particles obtained by the production method of the present invention have a weight average molecular weight of 250,000 or less of components soluble in tetrahydrofuran. Preferably it is 100,000 or more and less than 200,000. Within the range, when performing in-mold foam molding, a foam molded article having a good surface state can be obtained even when the foaming agent escapes. In addition, in this invention, the time of foaming agent dispersion | distribution means the state whose foaming agent residual amount of a styrene modified polyethylene resin pre-expanded particle is 0.4 weight% or more and 1 weight% or less.
また、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部の量がスチレン改質ポリエチレン樹脂予備発泡粒子の１０重量％以上４０重量％以下である。テトラヒドラフラン可溶部の量が１０重量％より少ないと、エチレン系樹脂、エチレン系樹脂とスチレン系単量体のグラフト成分が多すぎるために成形性、とりわけ発泡剤逸散時に型内発泡成形しても良好な表面状態を有する発泡成形体を得ることが困難となる。４０重量％より多いと、スチレン系単量体の単独重合体が多くなりすぎるために耐衝撃性を得ることが困難となる。 In the styrene-modified polyethylene resin pre-expanded particles, the amount of the tetrahydrofuran soluble part is 10% by weight or more and 40% by weight or less of the styrene-modified polyethylene resin pre-expanded particles. If the amount of tetrahydrafuran soluble part is less than 10% by weight, there are too many graft components of ethylene-based resin, ethylene-based resin and styrene-based monomer, so moldability, especially when foaming agent escapes, in-mold foam molding Even so, it is difficult to obtain a foamed molded article having a good surface state. When the amount is more than 40% by weight, it becomes difficult to obtain impact resistance because the homopolymer of the styrene monomer is excessively increased.
本発明におけるテトラヒドロフラン可溶部の量は以下のようにして測定する。スチレン改質ポリエチレン系樹脂予備発泡粒子１．０ｇとテトラヒドロフラン５０ｍｌをスクリュー管に投入し、マグネチックスターラーで室温下、４８時間攪拌する。その後、ろ過することによりテトラヒドロフランを取り除き、処理後のスチレン改質ポリエチレン系樹脂予備発泡粒子を１５０℃のオーブン中で１時間乾燥させ、常温まで自然冷却させ、初期の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減少分の比率をテトラヒドラフラン可溶部としている。 The amount of the tetrahydrofuran-soluble part in the present invention is measured as follows. 1.0 g of styrene-modified polyethylene resin pre-expanded particles and 50 ml of tetrahydrofuran are put into a screw tube and stirred for 48 hours at room temperature with a magnetic stirrer. Thereafter, the tetrahydrofuran is removed by filtration, and the treated styrene-modified polyethylene resin pre-foamed particles are dried in an oven at 150 ° C. for 1 hour, allowed to cool to room temperature, and the initial styrene-modified polyethylene resin pre-foamed The ratio of the decrease to the particles is the tetrahydrafuran soluble part.
本発明における熱キシレンに不溶なゲル成分量は以下のようにして測定する。２００メッシュの金網袋中に０．４ｇのスチレン改質ポリエチレン系樹脂予備発泡粒子を入れ、大気圧下で沸騰させたキシレン４５０ｍｌ中に２時間浸漬して冷却後に一旦、取り出し、更に新たな沸騰させたキシレン中にスチレン改質ポリエチレン系樹脂予備発泡粒子を１時間浸漬して冷却後にキシレンから取り出す。その後、同様に２時間、１時間の浸漬、溶出を繰り返し、その後、常温下で１晩液切りした後に１５０℃のオーブン中で１時間乾燥させ、常温まで自然冷却させ、冷却後の残留分をゲル成分とし、初期のスチレン改質ポリエチレン系樹脂予備発泡粒子量に対するゲル成分の量の重量比率をゲル成分量としている。 The amount of gel component insoluble in hot xylene in the present invention is measured as follows. Put 0.4 g of styrene-modified polyethylene resin pre-expanded particles in a 200-mesh wire mesh bag, immerse in 450 ml of xylene boiled under atmospheric pressure for 2 hours, take it out after cooling, and boil it again. The pre-expanded styrene modified polyethylene resin particles are immersed in xylene for 1 hour, and are taken out of the xylene after cooling. Thereafter, the immersion and elution were repeated for 2 hours and 1 hour in the same manner. After that, the liquid was drained overnight at room temperature, dried in an oven at 150 ° C. for 1 hour, allowed to cool naturally to room temperature, and the residue after cooling was removed. As the gel component, the weight ratio of the amount of the gel component to the amount of the pre-expanded styrene-modified polyethylene resin pre-expanded particles is used as the gel component amount.
本発明におけるテトラヒドロフランに可溶分の重量平均分子量とは、スチレン改質ポリエチレン系樹脂予備発泡粒子０．０２ｇを常温のテトラヒドロフラン２０ｍｌに２４時間浸漬させることで抽出される成分を０．２μｍのフィルターでろ過したものを、ゲル・パーミエーション・クロマトグラフィーにより標準ポリスチレン試料を基準に求められた値である。 In the present invention, the weight-average molecular weight soluble in tetrahydrofuran is determined by immersing 0.02 g of styrene-modified polyethylene resin pre-foamed particles in 20 ml of normal temperature tetrahydrofuran for 24 hours using a 0.2 μm filter. The value obtained by filtering gel permeation chromatography with reference to a standard polystyrene sample.
このようにして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えない金型内に充填し、加熱融着せしめて発泡成形体とされる。得られた発泡成形体は、剛性が高く、優れた耐割れ性を示す。 The styrene-modified polyethylene resin pre-expanded particles thus obtained are molded by a general in-mold foam molding method. Specifically, it is filled in a mold that can be closed but cannot be sealed, and is heat-sealed to obtain a foam molded article. The obtained foamed molded article has high rigidity and excellent crack resistance.
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.
＜耐割れ性（半数破壊高さの測定）＞
発泡直後の予備発泡粒子から得られた発泡成形体を２００×２０×２０（ｔ）ｍｍに切り出したサンプル片にてＪＩＳ Ｋ ７２１１に準拠して３２１ｇの鋼球を落下させ半数破壊高さを測定した。<Crack resistance (measurement of half fracture height)>
Measure the half-height fracture height by dropping a 321 g steel ball in accordance with JIS K 7211 with a sample piece obtained by cutting a foamed molded body obtained from pre-expanded particles immediately after foaming into 200 × 20 × 20 (t) mm. did.
＜発泡剤逸散時に型内発泡成形を行った発泡成形体の表面状態＞
発泡剤逸散時とは具体的には、スチレン改質ポリエチレン系樹脂予備発泡粒子の発泡剤残量が１％以下である状態を示す。スチレン改質ポリエチレン系樹脂予備発泡粒子中の残存発泡剤量は、約２ｇのスチレン改質ポリエチレン系樹脂予備発泡粒子を計量し、１５０℃のオーブンで３０分乾燥を行った後に室温まで冷却してから再度計量を行い、逸散分の重量％を求めることにより測定できる。<Surface condition of foamed molded product that was foam-molded in mold when foaming agent escapes>
Specifically, when the foaming agent escapes, the styrene-modified polyethylene resin pre-expanded particles have a foaming agent remaining amount of 1% or less. The amount of residual foaming agent in the styrene-modified polyethylene resin pre-expanded particles was measured by weighing about 2 g of styrene-modified polyethylene resin pre-expanded particles, drying in an oven at 150 ° C. for 30 minutes, and then cooling to room temperature. It is possible to measure by measuring again and obtaining the weight% of the dissipation.
発泡成形体の表面状態は、型内発泡成形後に約３５℃の乾燥室で１日保管したものを目視観察にて評価した。数値が大きいほうが粒子同士の隙間が少ない表面状態であり、３以上を合格とした。
５：隙間がみあたらない
４：部分的に隙間があるがほとんどわからない
３：所々隙間があるが、全体としては許容レベル
２：隙間が目立つ
１：隙間が多い
＜テトラヒドロフラン可溶部の測定＞
スチレン改質ポリエチレン系樹脂予備発泡粒子１．０ｇとテトラヒドロフラン５０ｍｌをスクリュー管に投入し、マグネチックスターラーで室温下、４８時間攪拌した。その後、ろ過することによりテトラヒドロフランを取り除き、処理後のスチレン改質ポリエチレン系樹脂予備発泡粒子を１５０℃のオーブン中で１時間乾燥させ、常温まで自然冷却させ、初期の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減少分の比率をテトラヒドラフラン可溶部とした。The surface state of the foam molded product was evaluated by visual observation after being stored in a drying room at about 35 ° C. for one day after in-mold foam molding. The higher the numerical value, the smaller the surface state between the particles, and 3 or more were acceptable.
5: No gaps are present 4: Partial gaps are present but are almost unknown 3: Although there are gaps in some places, the overall tolerance level 2: Conspicuous gaps 1: Lots of gaps <Measurement of tetrahydrofuran soluble part>
1.0 g of styrene-modified polyethylene resin pre-expanded particles and 50 ml of tetrahydrofuran were put into a screw tube and stirred for 48 hours at room temperature with a magnetic stirrer. Thereafter, the tetrahydrofuran is removed by filtration, and the treated styrene-modified polyethylene resin pre-foamed particles are dried in an oven at 150 ° C. for 1 hour, allowed to cool to room temperature, and the initial styrene-modified polyethylene resin pre-foamed The ratio of the decrease to the particles was taken as the tetrahydrafuran soluble part.
＜テトラヒドロフラン可溶部の重量平均分子量の測定＞
スチレン改質ポリエチレン系樹脂予備発泡粒子０．０２ｇを常温のテトラヒドロフラン２０ｍｌに２４時間浸漬させることで抽出される成分を０．２μｍのフィルターでろ過したもの、ゲル・パーミエーション・クロマトグラフィーにより標準ポリスチレン試料を基準に求めた。<Measurement of weight average molecular weight of tetrahydrofuran soluble part>
Ingredients extracted by immersing 0.02 g of styrene-modified polyethylene resin pre-expanded particles in 20 ml of normal temperature for 24 hours with a 0.2 μm filter, standard polystyrene sample by gel permeation chromatography Based on the above.
＜熱キシレン不溶のゲル成分量の測定＞
２００メッシュの金網袋中に０．４ｇのスチレン改質ポリエチレン系樹脂予備発泡樹脂粒子を入れ、大気圧下で沸騰させたキシレン４５０ｍｌ中に２時間浸漬して冷却後に一旦、取り出し、更に新たな沸騰させたキシレン中に樹脂を１時間浸漬して冷却後にキシレンから取り出す。その後、同様に２時間、１時間の浸漬、溶出を繰り返し、その後、常温下で１晩液切りした後に１５０℃のオーブン中で１時間乾燥させ、常温まで自然冷却させ、冷却後の残留分をゲル成分とし、初期のスチレン改質ポリエチレン系樹脂予備発泡粒子量に対するゲル成分の量の重量比率をゲル成分量とした。<Measurement of amount of gel component insoluble in hot xylene>
Put 0.4g of styrene-modified polyethylene resin pre-expanded resin particles in a 200 mesh wire mesh bag, immerse in 450ml of xylene boiled under atmospheric pressure for 2 hours, take out once after cooling, and further boil The resin is soaked in xylene for 1 hour, cooled, and taken out from xylene. Thereafter, the immersion and elution were repeated for 2 hours and 1 hour in the same manner. After that, the liquid was drained overnight at room temperature, dried in an oven at 150 ° C. for 1 hour, allowed to cool naturally to room temperature, and the residue after cooling was removed. The gel component was used, and the weight ratio of the amount of the gel component to the initial amount of the pre-expanded styrene-modified polyethylene resin pre-expanded particles was defined as the gel component amount.
（実施例１）
ポリエチレン系樹脂として住友化学株式会社製「エバテートＦ１１０３−１」（ＭＦＲ＝０．５ｇ／１０分、酢酸ビニル含有量５重量％）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重量部を混合し押出機内で溶融混合して造粒し水中に押出した直後にカッティングすることで粒重量約１ｍｇ／粒の球状としたポリエチレン系樹脂粒子を作製した。Example 1
Sumitomo Chemical Co., Ltd. “Evertate F1103-1” (MFR = 0.5 g / 10 min, vinyl acetate content 5% by weight) is used as the polyethylene resin, and talc 0.2 with respect to 100 parts by weight of the polyethylene resin. Part by weight was mixed, melted and mixed in an extruder, granulated, and cut immediately after being extruded into water to produce spherical polyethylene resin particles having a particle weight of about 1 mg / particle.
続いて６Ｌオートクレーブに水１５０重量部に、第３リン酸カルシウム１重量部、α−オレフィンスルフォン酸ソーダ０．０２４重量部、ポリエチレン系樹脂粒子３０重量部を懸濁させ、スチレン１５重量部に、重合開始剤として過酸化ベンゾイル０．１８重量部（１０時間半減期温度：７４℃）、架橋剤としてジクミルパーオキサイド（１０時間半減期温度：１１６℃）０．２９重量部を溶解させた溶液を添加した。その後、この水性懸濁液を７０℃まで昇温し、３０分間維持することでポリエチレン系樹脂粒子にスチレン単量体溶液を含浸させた。更に８５℃まで昇温し、スチレン単量体５５重量部を３時間４０分かけて反応系中に滴下し、滴下終了後８５℃で１時間保持した。その後、１４０℃昇温して３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。 Subsequently, 150 parts by weight of water, 1 part by weight of tribasic calcium phosphate, 0.024 parts by weight of sodium α-olefin sulfonate, and 30 parts by weight of polyethylene resin particles are suspended in a 6 L autoclave, and polymerization is started on 15 parts by weight of styrene. Add 0.18 parts by weight of benzoyl peroxide (10-hour half-life temperature: 74 ° C.) as an agent and 0.29 parts by weight of dicumyl peroxide (10-hour half-life temperature: 116 ° C.) as a crosslinking agent did. Thereafter, this aqueous suspension was heated to 70 ° C. and maintained for 30 minutes to impregnate the polyethylene resin particles with the styrene monomer solution. The temperature was further raised to 85 ° C., 55 parts by weight of a styrene monomer was dropped into the reaction system over 3 hours and 40 minutes, and the mixture was held at 85 ° C. for 1 hour after the completion of dropping. Thereafter, the temperature was raised to 140 ° C. and held for 3 hours to carry out a crosslinking reaction, and after cooling, washing, dehydration and drying were performed to obtain styrene-modified polyethylene resin particles.
４．５Ｌオートクレーブに水３３０重量部、第３リン酸カルシウム２重量部、ｎ−パラフィンスルホン酸ソーダ０．０１重量部、スチレン改質ポリエチレン系樹脂粒子１００重量部を仕込んだ。発泡剤としてノルマルリッチブタン（ノルマルブタン／イソブタン＝７５／２５）２２重量部をオートクレーブに添加した後、１４０℃に昇温し３０分保持することで発泡剤を含浸させた。その後、オートクレーブより開口径４ｍｍのオリフィスを通して水性分散媒と共にスチレン改質ポリエチレン系樹脂粒子を大気圧下に放出し、発泡嵩倍率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。大気圧下に放出している間、高圧窒素を導入することでオートクレーブ内の圧力が一定に保持されるように調整した。 A 4.5 L autoclave was charged with 330 parts by weight of water, 2 parts by weight of tricalcium phosphate, 0.01 parts by weight of sodium n-paraffin sulfonate, and 100 parts by weight of styrene-modified polyethylene resin particles. After adding 22 parts by weight of normal rich butane (normal butane / isobutane = 75/25) as a foaming agent, the temperature was raised to 140 ° C. and held for 30 minutes to impregnate the foaming agent. Thereafter, the styrene-modified polyethylene resin particles together with the aqueous dispersion medium were discharged under atmospheric pressure through an orifice having an opening diameter of 4 mm from the autoclave to obtain styrene-modified polyethylene resin pre-expanded particles having an expansion bulk ratio of 30 times. During the discharge under atmospheric pressure, the pressure in the autoclave was adjusted to be kept constant by introducing high-pressure nitrogen.
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のテトラヒドロフラン可溶部の重量平均分子量は２３万であり、テトラヒドロフラン可溶部は３３重量％、熱キシレン不溶のゲル成分量は２２重量％であった。 The weight average molecular weight of the tetrahydrofuran-soluble part of the obtained styrene-modified polyethylene resin pre-expanded particles was 230,000, the tetrahydrofuran-soluble part was 33% by weight, and the amount of the gel component insoluble in hot xylene was 22% by weight. .
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を洗浄・脱水・乾燥した後に、室温で２日間養生させた予備発泡粒子（以下、「発泡直後の予備発泡粒子」と称す場合がある）、および約３５℃の乾燥室で残存発泡剤量が発泡粒子に対して１重量％以下となるまで乾燥した予備発泡粒子（以下、「発泡剤逸散時の予備発泡粒子」と称す場合がある）、の２種類を作製し、それぞれダイセンＫＲ−５７成形機を用いて３００×４５０×２５（ｔ）ｍｍサイズの金型にて型内発泡成形を行い、発泡成形体を得た。発泡直後の予備発泡粒子から得られた発泡成形体の耐割れ性を評価したところ３４ｃｍであった。なお、スチレン改質ポリエチレン系樹脂予備発泡粒子中の残存発泡剤量は、約２ｇのスチレン改質ポリエチレン系樹脂予備発泡粒子を計量し、１５０℃のオーブンで３０分乾燥を行った後に室温まで冷却してから再度計量を行い、逸散分の重量％を求めることにより測定した。発泡剤逸散時の予備発泡粒子から得られた発泡成形体の表面状態は３であった。 Pre-expanded particles obtained by washing, dehydrating and drying the obtained styrene-modified polyethylene resin pre-expanded particles, and then curing at room temperature for 2 days (hereinafter, referred to as “pre-expanded particles immediately after expansion”), and Pre-foamed particles dried in a drying room at about 35 ° C. until the amount of remaining foaming agent is 1% by weight or less with respect to the foamed particles (hereinafter sometimes referred to as “pre-foamed particles when the foaming agent escapes”), Were produced, and each was subjected to in-mold foam molding with a 300 × 450 × 25 (t) mm size mold using a Daisen KR-57 molding machine to obtain a foam molded article. It was 34 cm when crack resistance of the foaming molding obtained from the pre-expanded particles immediately after foaming was evaluated. The amount of foaming agent remaining in the styrene-modified polyethylene resin pre-expanded particles was measured by weighing about 2 g of styrene-modified polyethylene resin pre-expanded particles, drying in an oven at 150 ° C. for 30 minutes, and then cooling to room temperature. Then, the measurement was carried out again, and the measurement was made by calculating the weight% of the escaped portion. The surface state of the foamed molded article obtained from the pre-expanded particles when the foaming agent escaped was 3.
（実施例２）
実施例１と同様にポリエチレン系樹脂粒子を作製した。(Example 2)
Polyethylene resin particles were prepared in the same manner as in Example 1.
続いて６Ｌオートクレーブに水１５０重量部に、第３リン酸カルシウム１重量部、α−オレフィンスルフォン酸ソーダ０．０２４重量部、ポリエチレン系樹脂粒子３５重量部を懸濁させ、スチレン１７．５重量部に、重合開始剤として過酸化ベンゾイル０．２４重量部（１０時間半減期温度：７４℃）、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℃）０．５６重量部を溶解させた溶液を添加した。その後、この水性懸濁液を７０℃まで昇温し、３０分間維持することでポリエチレン系樹脂粒子にスチレン単量体溶液を含浸させた。更に８５℃まで昇温し、スチレン単量体４７．５重量部を２時間４０分かけて反応系中に滴下し、滴下終了後更８５℃で１時間保持した。その後、１２０℃に昇温して１時間保持し、スチレンモノマーの重合を完結させた。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。 Subsequently, 150 parts by weight of water, 1 part by weight of tricalcium phosphate, 0.024 part by weight of sodium α-olefin sulfonate, and 35 parts by weight of polyethylene resin particles were suspended in a 6 L autoclave, and 17.5 parts by weight of styrene was suspended. 0.24 parts by weight of benzoyl peroxide (10 hours half-life temperature: 74 ° C.) as a polymerization initiator and 0.56 parts by weight of t-butyl peroxybenzoate (10 hours half-life temperature: 104 ° C.) as a crosslinking agent are dissolved. Solution was added. Thereafter, this aqueous suspension was heated to 70 ° C. and maintained for 30 minutes to impregnate the polyethylene resin particles with the styrene monomer solution. The temperature was further raised to 85 ° C., and 47.5 parts by weight of styrene monomer was dropped into the reaction system over 2 hours and 40 minutes. After completion of the dropping, the mixture was further maintained at 85 ° C. for 1 hour. Then, it heated up at 120 degreeC and hold | maintained for 1 hour, and superposition | polymerization of the styrene monomer was completed. After cooling, styrene-modified polyethylene resin particles were obtained by washing, dehydration and drying.
４．５Ｌオートクレーブに水３３０重量部、第３リン酸カルシウム２重量部、ｎ−パラフィンスルホン酸ソーダ０．０１重量部、スチレン改質ポリエチレン系樹脂粒子１００重量部を仕込んだ。発泡剤としてノルマルリッチブタン（ノルマルブタン／イソブタン＝７５／２５）２２．５重量部をオートクレーブに添加した後、１４０℃に昇温し５０分保持することで発泡剤の含浸を行うとともに架橋反応を進行させた。その後、オートクレーブより開口径４ｍｍのオリフィスを通して水性分散媒と共にスチレン改質ポリエチレン系樹脂粒子を大気圧下に放出し、発泡嵩倍率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。大気圧下に放出している間、高圧窒素を導入することでオートクレーブ内の圧力が一定に保持されるように調整した。 A 4.5 L autoclave was charged with 330 parts by weight of water, 2 parts by weight of tricalcium phosphate, 0.01 parts by weight of sodium n-paraffin sulfonate, and 100 parts by weight of styrene-modified polyethylene resin particles. After adding 22.5 parts by weight of normal rich butane (normal butane / isobutane = 75/25) as a foaming agent to the autoclave, the temperature is raised to 140 ° C. and held for 50 minutes to impregnate the foaming agent and perform a crosslinking reaction. Proceeded. Thereafter, the styrene-modified polyethylene resin particles together with the aqueous dispersion medium were discharged under atmospheric pressure through an orifice having an opening diameter of 4 mm from the autoclave to obtain styrene-modified polyethylene resin pre-expanded particles having an expansion bulk ratio of 30 times. During the discharge under atmospheric pressure, the pressure in the autoclave was adjusted to be kept constant by introducing high-pressure nitrogen.
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のテトラヒドロフラン可溶部の重量平均分子量は１９万であり、テトラヒドロフラン可溶部は１６重量％、熱キシレン不溶のゲル成分量は２６重量％であった。 The weight average molecular weight of the tetrahydrofuran-soluble part of the obtained styrene-modified polyethylene resin pre-expanded particles was 190,000, the tetrahydrofuran-soluble part was 16% by weight, and the amount of the gel component insoluble in hot xylene was 26% by weight. .
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は実施例１と同様に成形して評価した。耐割れ性は４２ｃｍであった。発泡剤逸散時の予備発泡粒子から得られた発泡成形体の表面状態は３であった。 The obtained styrene-modified polyethylene resin pre-expanded particles were molded and evaluated in the same manner as in Example 1. The crack resistance was 42 cm. The surface state of the foamed molded article obtained from the pre-expanded particles when the foaming agent escaped was 3.
（実施例３）
６Ｌオートクレーブの重合において、架橋剤としてｔ−ブチルパーオキシベンゾエート０．５６重量部の代りにジクミルパーオキサイド０．４０重量部を使用し、１２０℃で１時間保持したところを１４０℃で３時間保持した以外は実施例２と同様の操作を行い、スチレン改質ポリエチレン系樹脂粒子を得た。Example 3
In the polymerization of 6L autoclave, 0.40 part by weight of dicumyl peroxide was used instead of 0.56 part by weight of t-butyl peroxybenzoate as a cross-linking agent, and the mixture was held at 120 ° C for 1 hour, but at 140 ° C for 3 hours. Except for holding, the same operation as in Example 2 was performed to obtain styrene-modified polyethylene resin particles.
４．５Ｌオートクレーブにおいて、実施例２と同様にして発泡嵩倍率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作製した。 In a 4.5 L autoclave, styrene-modified polyethylene resin pre-expanded particles having a foam volume ratio of 30 times were produced in the same manner as in Example 2.
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のテトラヒドロフラン可溶部の重量平均分子量は１８万であり、テトラヒドロフラン可溶部は１５重量％、熱キシレン不溶のゲル成分量は３０重量％であった。 The weight average molecular weight of the tetrahydrofuran-soluble part of the obtained styrene-modified polyethylene resin pre-expanded particles was 180,000, the tetrahydrofuran-soluble part was 15% by weight, and the amount of the gel component insoluble in hot xylene was 30% by weight. .
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は実施例１と同様に成形して評価した。耐割れ性は３９ｃｍであった。発泡剤逸散時の予備発泡粒子から得られた発泡成形体の表面状態は３であった。 The obtained styrene-modified polyethylene resin pre-expanded particles were molded and evaluated in the same manner as in Example 1. The crack resistance was 39 cm. The surface state of the foamed molded article obtained from the pre-expanded particles when the foaming agent escaped was 3.
（比較例１）
ポリエチレン系樹脂として住友化学株式会社製「エバテートＦ１１０３−１」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重量部を混合し押出機内で溶融混合して造粒し水中に押出した直後にカッティングすることで粒重量約１ｍｇ／粒の球状としたポリエチレン系樹脂粒子を作製した。(Comparative Example 1)
“Evaate F1103-1” manufactured by Sumitomo Chemical Co., Ltd. is used as the polyethylene resin, 0.2 parts by weight of talc is mixed with 100 parts by weight of the polyethylene resin, melt-mixed in the extruder, granulated, and extruded into water. By cutting immediately after the formation, spherical polyethylene resin particles having a particle weight of about 1 mg / particle were produced.
続いて６Ｌオートクレーブに水１５０重量部に、第３リン酸カルシウム１重量部、α−オレフィンスルフォン酸ソーダ０．０２４重量部、ポリエチレン系樹脂粒子３０重量部を懸濁させ、スチレン３０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０．７７重量部（１０時間半減期温度：７４℃）、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℃）０．４５重量部を溶解させた溶液を添加した。その後、この水性懸濁液を７０℃まで昇温し、３０分間維持することでポリエチレン系樹脂粒子にスチレン単量体溶液を含浸させた。更に８０℃まで昇温し、１．５時間保持した。その後、７０℃に冷却してスチレン単量体４０重量部に過酸化ベンゾイル０．０６重量部溶解させた溶液を１．５時間かけて反応系中に滴下し、滴下終了後７０℃で３時間保持し、更に８５℃に昇温して０．５時間保持することで重合反応を進行させた。その後、１２５℃昇温して３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。 Subsequently, 150 parts by weight of water, 1 part by weight of tribasic calcium phosphate, 0.024 parts by weight of sodium α-olefin sulfonate, and 30 parts by weight of polyethylene resin particles are suspended in a 6 L autoclave, and polymerization is started on 30 parts by weight of styrene. 0.77 parts by weight of t-butylperoxy-2-ethylhexanoate (10 hour half-life temperature: 74 ° C.) as an agent, and t-butyl peroxybenzoate (10 hour half-life temperature: 104 ° C.) as a crosslinking agent A solution in which 45 parts by weight were dissolved was added. Thereafter, this aqueous suspension was heated to 70 ° C. and maintained for 30 minutes to impregnate the polyethylene resin particles with the styrene monomer solution. The temperature was further raised to 80 ° C. and held for 1.5 hours. Thereafter, a solution obtained by cooling to 70 ° C. and dissolving 0.06 part by weight of benzoyl peroxide in 40 parts by weight of the styrene monomer was dropped into the reaction system over 1.5 hours, and after completion of dropping, the solution was kept at 70 ° C. for 3 hours. The polymerization reaction was allowed to proceed by maintaining the temperature and further raising the temperature to 85 ° C. and maintaining for 0.5 hours. Thereafter, the temperature was raised to 125 ° C. and held for 3 hours to carry out a crosslinking reaction. After cooling, washing, dehydration and drying were performed to obtain styrene-modified polyethylene resin particles.
４．５Ｌオートクレーブにおいて、使用するブタンの量を２４重量部とした以外は実施例１と同様にして発泡嵩倍率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作製した。 In a 4.5 L autoclave, styrene-modified polyethylene resin pre-expanded particles having an expansion bulk ratio of 30 times were prepared in the same manner as in Example 1 except that the amount of butane used was 24 parts by weight.
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のテトラヒドロフラン可溶部の重量平均分子量は４１万であり、テトラヒドロフラン可溶部は３重量％、熱キシレン不溶のゲル成分量は２４重量％であった。 The weight average molecular weight of the tetrahydrofuran-soluble part of the obtained styrene-modified polyethylene resin pre-expanded particles was 410,000, the tetrahydrofuran-soluble part was 3% by weight, and the amount of the gel component insoluble in hot xylene was 24% by weight. .
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は実施例１と同様に型内発泡成形して評価した。耐割れ性は４１ｃｍであった。発泡剤逸散時の予備発泡粒子から得られた発泡成形体の表面状態は１であった。 The obtained styrene-modified polyethylene resin pre-foamed particles were evaluated by in-mold foam molding in the same manner as in Example 1. The crack resistance was 41 cm. The surface state of the foamed molded product obtained from the pre-expanded particles when the foaming agent escaped was 1.
（比較例２）
スチレン４０重量部に溶解する過酸化ベンゾイルを０．６８重量部とした以外は比較例１と同様にし、改質ポリエチレン系樹脂粒子、更にはスチレン改質ポリエチレン系樹脂予備発泡粒子を得た。(Comparative Example 2)
Modified polyethylene resin particles and further styrene modified polyethylene resin pre-expanded particles were obtained in the same manner as in Comparative Example 1 except that benzoyl peroxide dissolved in 40 parts by weight of styrene was changed to 0.68 parts by weight.
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のテトラヒドロフラン可溶部の重量平均分子量は２０万であり、テトラヒドロフラン可溶部は５重量％、熱キシレン不溶のゲル成分量は２２重量％であった。 The weight average molecular weight of the tetrahydrofuran-soluble part of the obtained styrene-modified polyethylene resin pre-expanded particles was 200,000, the tetrahydrofuran-soluble part was 5% by weight, and the amount of the gel component insoluble in hot xylene was 22% by weight. .
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は実施例１と同様に型内発泡成形して評価した。耐割れ性は３７ｃｍであった。発泡剤逸散時の予備発泡粒子から得られた発泡成形体の表面状態は２であった。 The obtained styrene-modified polyethylene resin pre-foamed particles were evaluated by in-mold foam molding in the same manner as in Example 1. The crack resistance was 37 cm. The surface state of the foamed molded article obtained from the pre-expanded particles when the foaming agent escaped was 2.
（比較例３）
６Ｌオートクレーブの重合において、８５℃への昇温後に１時間保持してから、スチレン単量体の追加を開始した以外は実施例１と同様の操作を行い、スチレン改質ポリエチレン系樹脂粒子を得た。(Comparative Example 3)
In the polymerization of the 6 L autoclave, the same operation as in Example 1 was performed except that the addition of the styrene monomer was started after the temperature was raised to 85 ° C. and held for 1 hour to obtain styrene-modified polyethylene resin particles. It was.
４．５Ｌオートクレーブにおいて、実施例１と同様にして発泡嵩倍率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作製した。 In a 4.5-L autoclave, styrene-modified polyethylene resin pre-expanded particles having an expansion bulk ratio of 30 times were produced in the same manner as in Example 1.
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のテトラヒドロフラン可溶部の重量平均分子量は３３万であり、テトラヒドロフラン可溶部は３２重量％、熱キシレン不溶のゲル成分量は２１重量％であった。 The weight average molecular weight of the tetrahydrofuran-soluble part of the obtained styrene-modified polyethylene resin pre-expanded particles was 330,000, the tetrahydrofuran-soluble part was 32% by weight, and the amount of the gel component insoluble in hot xylene was 21% by weight. .
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は実施例１と同様に型内発泡成形して評価した。耐割れ性は４６ｃｍであった。発泡剤逸散時の予備発泡粒子から得られた発泡成形体の表面状態は１であった。 The obtained styrene-modified polyethylene resin pre-foamed particles were evaluated by in-mold foam molding in the same manner as in Example 1. The crack resistance was 46 cm. The surface state of the foamed molded product obtained from the pre-expanded particles when the foaming agent escaped was 1.
（比較例４）
６Ｌオートクレーブの重合において、重合開始剤として過酸化ベンゾイル０．４３重量部（１０時間半減期温度：７４℃）、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℃）０．４５重量部を使用した以外には比較例１と同様の操作を行い、スチレン改質ポリエチレン系樹脂粒子を得た。(Comparative Example 4)
In the polymerization of a 6 L autoclave, 0.43 parts by weight of benzoyl peroxide (10 hour half-life temperature: 74 ° C.) as a polymerization initiator and t-butyl peroxybenzoate (10 hour half-life temperature: 104 ° C.) as a crosslinking agent Except for using 45 parts by weight, the same operation as in Comparative Example 1 was performed to obtain styrene-modified polyethylene resin particles.
４．５Ｌオートクレーブにおいて、使用するブタン量を２０重量部とした以外は実施例１と同様にして発泡嵩倍率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作製した。 In a 4.5 L autoclave, styrene-modified polyethylene resin pre-expanded particles having an expansion bulk ratio of 30 times were prepared in the same manner as in Example 1 except that the amount of butane used was 20 parts by weight.
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のテトラヒドロフラン可溶部の重量平均分子量は１５万であり、テトラヒドロフラン可溶部は４２重量％、熱キシレン不溶のゲル成分量は１４重量％であった。 The weight average molecular weight of the tetrahydrofuran soluble part of the obtained styrene-modified polyethylene resin pre-expanded particles was 150,000, the tetrahydrofuran soluble part was 42% by weight, and the amount of gel component insoluble in hot xylene was 14% by weight. .
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は実施例１と同様に型内発泡成形して評価した。耐割れ性は１６ｃｍであった。発泡剤逸散時に型内発泡成形を行った発泡成形体の表面状態は４であった。 The obtained styrene-modified polyethylene resin pre-foamed particles were evaluated by in-mold foam molding in the same manner as in Example 1. The crack resistance was 16 cm. The surface state of the foamed molded article that was subjected to in-mold foam molding when the foaming agent dissipated was 4.
(比較例５)
特開２００６−２９８９５６号公報記載の実施例３を実施した。(Comparative Example 5)
Example 3 described in Japanese Patent Application Laid-Open No. 2006-29895 was performed.
ポリエチレン系樹脂として住友化学株式会社製「エバテートＦ１１０３−１」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重量部を混合し押出機内で溶融混合して造粒し、水槽により冷却しながらストランド状に引き取りながらカッティングすることで粒重量約１ｍｇ／粒の円柱状としたポリエチレン系樹脂粒子を作製した。 Using "Evaate F1103-1" manufactured by Sumitomo Chemical Co., Ltd. as the polyethylene resin, 0.2 parts by weight of talc is mixed with 100 parts by weight of the polyethylene resin, melted and mixed in the extruder, and granulated. By taking a strand shape while cooling and cutting, a polyethylene resin particle having a grain weight of about 1 mg / grain was produced.
続いて６Ｌオートクレーブに水１５０重量部に、第３リン酸カルシウム５重量部、α−オレフィンスルフォン酸ソーダ０．０２重量部、ポリエチレン系樹脂粒子３０重量部、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０．５４重量部（１０時間半減期温度：７４℃）、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℃）０．２１重量部を懸濁させた。その後、この水性懸濁液を８０℃まで昇温し、スチレン７０重量部を４時間３０分間かけて追加し、ポリエチレン系樹脂粒子にスチレンを含浸させながら、重合反応を進行させた。その後、１２５℃昇温して２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。 Subsequently, 150 parts by weight of water in a 6 L autoclave, 5 parts by weight of tricalcium phosphate, 0.02 parts by weight of α-olefin sodium sulfonate, 30 parts by weight of polyethylene resin particles, t-butylperoxy-2-2 as a polymerization initiator 0.54 parts by weight of ethylhexanoate (10 hour half-life temperature: 74 ° C.) and 0.21 part by weight of t-butyl peroxybenzoate (10 hour half-life temperature: 104 ° C.) as a crosslinking agent were suspended. Thereafter, the aqueous suspension was heated to 80 ° C., 70 parts by weight of styrene was added over 4 hours and 30 minutes, and the polymerization reaction was allowed to proceed while impregnating the polyethylene resin particles with styrene. Thereafter, the temperature was raised to 125 ° C. and held for 2 hours to carry out a crosslinking reaction. After cooling, washing, dehydration and drying were performed to obtain styrene-modified polyethylene resin particles.
４．５Ｌオートクレーブに水１５０重量部、第３リン酸カルシウム２重量部、ｎ−パラフィンスルホン酸ソーダ０．００６重量部、スチレン改質ポリエチレン系樹脂粒子１００重量部を仕込んだ。発泡剤としてノルマルリッチブタン（ノルマルブタン／イソブタン＝７５／２５）２０重量部をオートクレーブに添加した後、１４０℃に昇温し３０分保持することで発泡剤を含浸させた。その後、オートクレーブより開口径４ｍｍのオリフィスを通して水性分散媒と共にスチレン改質ポリエチレン系樹脂粒子を大気圧下に放出し、発泡嵩倍率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。大気圧下に放出している間、高圧窒素を導入することでオートクレーブ内の圧力が一定に保持されるように調整した。 A 4.5 L autoclave was charged with 150 parts by weight of water, 2 parts by weight of tricalcium phosphate, 0.006 parts by weight of sodium n-paraffin sulfonate, and 100 parts by weight of styrene-modified polyethylene resin particles. After adding 20 parts by weight of normal rich butane (normal butane / isobutane = 75/25) as a foaming agent, the temperature was raised to 140 ° C. and held for 30 minutes to impregnate the foaming agent. Thereafter, the styrene-modified polyethylene resin particles together with the aqueous dispersion medium were discharged under atmospheric pressure through an orifice having an opening diameter of 4 mm from the autoclave to obtain styrene-modified polyethylene resin pre-expanded particles having an expansion bulk ratio of 30 times. During the discharge under atmospheric pressure, the pressure in the autoclave was adjusted to be kept constant by introducing high-pressure nitrogen.
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のテトラヒドロフラン可溶部の重量平均分子量は２７万であり、テトラヒドロフラン可溶部は４重量％、熱キシレン不溶のゲル成分量は２２重量％であった。 The weight average molecular weight of the tetrahydrofuran soluble part of the styrene-modified polyethylene resin pre-expanded particles thus obtained was 270,000, the tetrahydrofuran soluble part was 4% by weight, and the amount of gel component insoluble in hot xylene was 22% by weight. .
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は実施例１と同様に型内発泡成形して評価した。耐割れ性は４０ｃｍであった。発泡剤逸散時に型内発泡成形を行った発泡成形体の表面状態は１であった。 The obtained styrene-modified polyethylene resin pre-foamed particles were evaluated by in-mold foam molding in the same manner as in Example 1. The crack resistance was 40 cm. The surface state of the foamed molded article that was subjected to in-mold foam molding when the foaming agent dissipated was 1.
実施例のものは本発明の要件を満たしているため、耐割れ性と発泡剤逸散時の発泡成形体の表面状態が良好である。比較例１、比較例２、比較例３、比較例５はテトラヒドロフラン可溶部の量と重量平均分子量のいずれかを満たしておらず、発泡剤逸散時の成形性に劣る。比較例４はゲル量が少なく、耐割れ性に劣る。比較例５は、テトラヒドロフラン可溶分が少ないため、発泡剤逸散時の発泡成形体の表面状態がよくない。 Since the thing of an Example satisfy | fills the requirements of this invention, the surface state of the foaming molding at the time of a crack resistance and foaming agent dispersion | distribution is favorable. Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 5 do not satisfy either the amount of the tetrahydrofuran soluble part or the weight average molecular weight, and are inferior in moldability when the foaming agent escapes. In Comparative Example 4, the gel amount is small and the crack resistance is poor. Since the comparative example 5 has little tetrahydrofuran soluble content, the surface state of the foaming molding at the time of foaming agent dispersion | distribution is not good.
本発明の製造方法によって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は、予備発泡直後でなく、発泡剤逸散後であっても成形加工性に優れ、また、得られた発泡成形体は、耐割れ性に優れているため、とりわけ自動車部材、緩衝材に好適に使用できる。 The styrene-modified polyethylene resin pre-expanded particles obtained by the production method of the present invention are excellent in molding processability not only immediately after the pre-expansion but also after the foaming agent escapes. Since it is excellent in crack resistance, it can be suitably used especially for automobile members and cushioning materials.
Claims (6)
テトラヒドロフラン可溶部の重量平均分子量が２５万以下であり、テトラヒドロフラン可溶部が１０重量％以上４０重量％以下、かつ熱キシレン不溶のゲル成分が１５重量％以上３５重量％以下であることを特徴とするスチレン改質ポリエチレン系樹脂予備発泡粒子。 Styrene obtained by foaming styrene-modified polyethylene resin particles obtained by polymerizing 50 to 300 parts by weight of a styrene monomer 1 in the presence of a polymerization initiator with respect to 100 parts by weight of polyethylene resin particles. Modified polyethylene resin pre-expanded particles,
The tetrahydrofuran-soluble part has a weight average molecular weight of 250,000 or less, the tetrahydrofuran-soluble part is 10% to 40% by weight, and the thermal xylene-insoluble gel component is 15% to 35% by weight. Styrene-modified polyethylene resin pre-expanded particles.
A foam-molded product obtained by in-mold foam-molding the styrene-modified polyethylene resin pre-expanded particles according to any one of claims 1 to 4 .
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| JP2005097555A (en) * | 2003-08-29 | 2005-04-14 | Sekisui Plastics Co Ltd | Olefin modified polystyrene-based resin pre-expansion particle, method for producing the same and its foamed molding |
| JP2006298956A (en) * | 2005-04-15 | 2006-11-02 | Kaneka Corp | Pre-expanded particle of modified polyethylene-based resin and method for producing the same |
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| JPH08151471A (en) * | 1994-11-28 | 1996-06-11 | Sekisui Plastics Co Ltd | Expandable particle for producing impact-resistant foam and production thereof |
| JP2005097555A (en) * | 2003-08-29 | 2005-04-14 | Sekisui Plastics Co Ltd | Olefin modified polystyrene-based resin pre-expansion particle, method for producing the same and its foamed molding |
| JP2006298956A (en) * | 2005-04-15 | 2006-11-02 | Kaneka Corp | Pre-expanded particle of modified polyethylene-based resin and method for producing the same |
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