JP7429517B2 - スチレン系樹脂発泡体 - Google Patents
スチレン系樹脂発泡体 Download PDFInfo
- Publication number
- JP7429517B2 JP7429517B2 JP2019199569A JP2019199569A JP7429517B2 JP 7429517 B2 JP7429517 B2 JP 7429517B2 JP 2019199569 A JP2019199569 A JP 2019199569A JP 2019199569 A JP2019199569 A JP 2019199569A JP 7429517 B2 JP7429517 B2 JP 7429517B2
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- JP
- Japan
- Prior art keywords
- acid
- mass
- styrene
- foam
- styrenic resin
- Prior art date
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- 239000006260 foam Substances 0.000 title claims description 107
- 229920001890 Novodur Polymers 0.000 title claims description 103
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 131
- 239000000178 monomer Substances 0.000 claims description 83
- 229920005989 resin Polymers 0.000 claims description 64
- 239000011347 resin Substances 0.000 claims description 64
- 229920002678 cellulose Polymers 0.000 claims description 37
- 239000001913 cellulose Substances 0.000 claims description 36
- 239000002121 nanofiber Substances 0.000 claims description 30
- 229920006026 co-polymeric resin Polymers 0.000 claims description 29
- 239000000835 fiber Substances 0.000 claims description 26
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 5
- -1 polyethylene Polymers 0.000 description 49
- 235000010980 cellulose Nutrition 0.000 description 36
- 238000006116 polymerization reaction Methods 0.000 description 36
- 238000000034 method Methods 0.000 description 29
- 238000005187 foaming Methods 0.000 description 24
- 239000011342 resin composition Substances 0.000 description 24
- 239000004604 Blowing Agent Substances 0.000 description 22
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 21
- 229920001971 elastomer Polymers 0.000 description 18
- 235000014113 dietary fatty acids Nutrition 0.000 description 16
- 239000000194 fatty acid Substances 0.000 description 16
- 229930195729 fatty acid Natural products 0.000 description 16
- 239000004793 Polystyrene Substances 0.000 description 14
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 12
- 229920003043 Cellulose fiber Polymers 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 229930195734 saturated hydrocarbon Natural products 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000004088 foaming agent Substances 0.000 description 9
- 239000000314 lubricant Substances 0.000 description 9
- 239000002134 carbon nanofiber Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 239000005063 High cis polybutadiene Substances 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 238000012662 bulk polymerization Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 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 group 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 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 150000003440 styrenes Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 3
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 3
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- GQEFPXSNRRKUHO-UHFFFAOYSA-N 4-methylpent-1-enylbenzene Chemical compound CC(C)CC=CC1=CC=CC=C1 GQEFPXSNRRKUHO-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000006261 foam material Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 3
- 229920005669 high impact polystyrene Polymers 0.000 description 3
- 239000004797 high-impact polystyrene Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- ADHNUPOJJCKWRT-JLXBFWJWSA-N (2e,4e)-octadeca-2,4-dienoic acid Chemical compound CCCCCCCCCCCCC\C=C\C=C\C(O)=O ADHNUPOJJCKWRT-JLXBFWJWSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 2
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-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
- 229920000742 Cotton Polymers 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 244000082204 Phyllostachys viridis Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
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- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 229940077445 dimethyl ether Drugs 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
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- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 description 1
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- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
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- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
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- 230000002265 prevention Effects 0.000 description 1
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- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000002964 rayon Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- GDESWOTWNNGOMW-UHFFFAOYSA-N resorcinol monobenzoate Chemical compound OC1=CC=CC(OC(=O)C=2C=CC=CC=2)=C1 GDESWOTWNNGOMW-UHFFFAOYSA-N 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
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- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
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- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- APQQZDCQUWIDSV-JXGYXAOLSA-N tetradec-2-enoic acid;(z)-tetradec-9-enoic acid Chemical compound CCCCCCCCCCCC=CC(O)=O.CCCC\C=C/CCCCCCCC(O)=O APQQZDCQUWIDSV-JXGYXAOLSA-N 0.000 description 1
- ZTUXEFFFLOVXQE-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCC(O)=O ZTUXEFFFLOVXQE-UHFFFAOYSA-N 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Reinforced Plastic Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
[2]前記スチレン系樹脂(A)が、スチレン系単量体単位、不飽和カルボン酸系単量体単位、及び不飽和カルボン酸エステル系単量体単位を有する共重合樹脂であり、
前記スチレン系樹脂(A)が、スチレン系単量体単位、不飽和カルボン酸系単量体単位、及び不飽和カルボン酸エステル系単量体単位の合計含有量を100質量%としたとき、前記スチレン系単量体単位を69~98質量%含有し、且つ、前記不飽和カルボン酸系単量体単位を2~16質量%含有し、且つ、前記不飽和カルボン酸エステル系単量体単位を0~15質量%含有する[1]に記載のスチレン系樹脂発泡体。
[3]前記不飽和カルボン酸系単量体がメタクリル酸である[2]に記載のスチレン系樹脂発泡体。
[4]前記スチレン系樹脂発泡体が押出発泡である[1]~[3]のいずれか一項に記載のスチレン系樹脂発泡体。
本実施形態のスチレン系樹脂発泡体は、スチレン系樹脂(A)80.0~99.7質量%と、平均繊維径3~200nmのセルロースナノファイバー(B)0.3~20質量%とを含む。また、本実施形態のスチレン系樹脂発泡体は、発泡剤(C)を含んでもよく、必要によりさらに任意添加成分を含んでもよい。
本実施形態において、スチレン系樹脂(A)の含有量は、(A)成分及び(B)成分の合計量100質量%に対して、80~99.7質量%であり、好ましくは90.0~99.5質量%、より好ましくは95.0~99.0質量%である。当該含有量を80.0質量%以上とすることにより、衝撃性、発泡特性、発泡押出成形性を向上させることができ、当該含有量を99.7質量%以下とすることにより、耐熱性、圧縮強度を向上させることができる。
本実施形態において、ポリスチレンとはスチレン系単量体を重合した単独重合体であり、一般的に入手できるものを適宜選択して用いることができる。ポリスチレンを構成するスチレン系単量体としては、スチレンの他に、α-メチルスチレン、α-メチル-p-メチルスチレン、ο-メチルスチレン、m-メチルスチレン、p-メチルスチレン、ビニルトルエン、エチルスチレン、イソブチルスチレン、及びt-ブチルスチレン又はブロモスチレン及びインデン等のスチレン誘導体が挙げられる。特に工業的観点からスチレンが好ましい。これらのスチレン系単量体は、1種又は2種以上使用することができる。ポリスチレンは本発明の効果を損なわない範囲で、上記のスチレン系単量体単位以外の単量体単位を更に含有することを排除しないが、典型的にはスチレン系単量体単位からなる。
本実施形態において、ゴム変性スチレン系樹脂とは、マトリクスとしてのスチレン系樹脂中にゴム状重合体(a)の粒子が分散したものであり、ゴム状重合体(a)の存在下でスチレン系単量体を重合させることにより製造することができる。
平均粒子径=ΣniDri3 /ΣniDri2 (N1)
により面積平均粒子径を算出し、ゴム状重合体(a)の平均粒子径とする。本測定は、写真を200dpiの解像度でスキャナーに取り込み、画像解析装置IP-1000(旭化成社製)の粒子解析ソフトを用いて測定する。
本実施形態において、共重合樹脂とは、スチレン系単量体単位及び不飽和カルボン酸系単量体単位、さらに不飽和カルボン酸エステル系単量体単位を任意に含む樹脂である。本発明における共重合樹脂は、スチレン系単量体単位、不飽和カルボン酸系単量体単位、及び不飽和カルボン酸エステル系単量体単位の合計含有量を100質量%としたとき、スチレン系単量体単位の含有量は69~98質量%であることが好ましく、より好ましくは74~96質量%であり、さらに好ましくは77~92質量%の範囲である。当該含有量を69質量%以上とすることにより、樹脂の流動性を向上させることができる。一方、当該含有量を98質量%以下とすることにより、後述の不飽和カルボン酸系単量体単位及び任意成分である不飽和カルボン酸エステル系単量体単位を所望量存在させにくくなり、これらの単量体単位による後述の効果を得にくくなる。
本実施形態におけるセルロースナノファイバー(B)は、平均繊維径が3~200nmであるセルロースである。セルロースナノファイバー(B)の含有量は、スチレン系樹脂(A)とセルロースナノファイバー(B)の合計質量100質量%に対して、0.3~20.0質量%であり、好ましくは0.5~15.0質量%、より好ましくは1.0~10.0質量%である。セルロースナノファイバー(B)の含有量を0.3質量%以上とすることにより、発泡特性、圧縮強度を向上させることができる。一方、当該含有量が多すぎると、反対に発泡特性が低下するほか、セルロースナノファイバー(B)の凝集物とみられる外観不良が発生する。スチレン系樹脂(A)とセルロースナノファイバー(B)とを含む組成物中のセルロース含有量は、当該組成物中のスチレン系樹脂(A)が溶解する溶媒に溶かし、未溶物を取出し、所定温度、所定時間の条件で乾燥させた乾燥物の質量を測定することにより算出する。例えば、スチレン系樹脂(A)として共重合樹脂を使用する場合は、当該共重合樹脂が溶解する溶媒に溶かし、未溶物を取出し、120℃、4時間の条件で乾燥させた乾燥物の質量を測ることにより算出できる。
本実施形態のスチレン系樹脂発泡体は、難燃性発泡体であることが好ましい。以下、本発明に係るスチレン系樹脂発泡体の特性(密度、気泡径(セルサイズ)、独立気泡率、圧縮強度について説明する。
本実施形態のスチレン系樹脂発泡体の発泡倍率は、好ましくは1.5~60倍、さらに好ましくは2~30倍である。1.5倍より低いと発泡体としての特徴である衝撃吸収や断熱効果が不十分になる。また、60倍より高いと発泡体の圧縮強度が低下し施工時や使用時に破損する虞がある。
本実施形態のスチレン系樹脂発泡体の密度は、スキン層を除いて計算され、発泡体の重量(kg)を発泡体の体積(m3)で割ることで算出できる。スチレン系樹脂発泡体の密度は、20~750kg/m3であることが好ましく、より好ましくは25~500kg/m3であり、さらに好ましくは30~350kg/m3である。
本実施形態のスチレン系樹脂発泡体の平均気泡径は、ASTM・D3576-77に準拠する方法で測定され、0.01~0.4mmであることが好ましく、より好ましくは0.02~0.3mmであり、さらに好ましくは0.03~0.15mmである。
本実施形態のスチレン系樹脂発泡体の独立気泡率は、ASTM・D2856-Aに準拠する方法で測定され、優れた断熱性や機械的強度等の物性を得る観点から70%以上が好ましく、より好ましくは80%以上、特に好ましくは90%以上である。
本実施形態のスチレン系樹脂発泡体の圧縮強度は、JIS・K7220に準拠する方法で測定され、製品用途にも異なるが、建材に使用するXPS用途では30N/cm2以上であることが好ましく、35N/cm2以上であることがより好ましい。圧縮強度が低いと、施工時の破壊が多くなり、床下に施工する場合には使用時の破壊も多くなる。
本実施形態のスチレン系樹脂発泡体として、上記の好適な特性(密度、気泡径(セルサイズ)、独立気泡率、圧縮強度を備えるためには、スチレン系樹脂組成物に発泡剤(C)を添加して発泡させることが好ましい。したがって、本実施形態のスチレン系樹脂発泡体は、その総量100質量%に対して、発泡剤(C)を0.3~15質量%含有することが好ましく、0.5~10質量部含有することがより好ましく、2~8質量%含有することがさらに好ましい。
本実施形態において、スチレン系樹脂発泡体は、上記(A)~(C)成分の他に、本発明の効果を損なわない範囲で、必要に応じて従来公知の添加剤、加工助剤等の任意添加成分を含有してもよい。これら添加剤、加工助剤等としては、酸化防止剤、耐候剤、滑剤、帯電防止剤、充填剤等が挙げられる。
本実施形態のスチレン系樹脂発泡体は、実質的に(A)成分、(B)成分、(C)成分及び任意添加成分のみからなっていてもよい。
<スチレン系樹脂組成物の製造方法>
本実施形態のスチレン系樹脂組成物は、各成分を任意の方法で溶融混練することによって製造することができる。例えば、ヘンシェルミキサーに代表される高速撹拌機、バンバリーミキサーに代表されるバッチ式混練機、単軸又は二軸の連続混練機、ロールミキサー等を単独で、又は組み合わせて用いる方法が挙げられる。混練の際の加熱温度は、通常、180~260℃の範囲で選択される。
<メルトフローレート(MFR)>
本実施形態において、スチレン系樹脂(A)の流動性は、ISO1133に従って測定したメルトフローレイトが0.5グラム/10分以上であることが好ましく、より好ましくは0.8グラム/10分以上である。0.5グラム/10分未満では、流動性が低く、加工温度を上げる必要があり、セルロースナノファイバー(B)が劣化による物性低下や成形品が変色してしまう恐れがある。
<ビカット軟化温度>
本実施形態のスチレン系樹脂組成物のビカット軟化温度は、86℃以上であることが好ましく、より好ましくは103℃以上である。86℃未満であると、使用中、温度が上昇し製品が変形してしまう恐れがある。
本実施形態のスチレン系樹脂発泡体は、押出発泡されたものである。より詳細には、上記のスチレン系樹脂組成物を加熱溶融し、これに発泡剤、必要に応じて放射低減剤を添加し、これを押出発泡させることにより、スチレン系樹脂押出発泡体を製造することができる。例えば、主原料の(A)成分、(B)成分及びその他種々の添加物を押出機のホッパーに投入し、発泡剤を圧入して混練した後、冷却機でゲルを均一に冷却して、ダイから大気圧下に押出発泡することで製造することができる。
本製造方法で用いることができる発泡剤としては、上述した発泡剤(C)と同一であるためここでは省略する。
本実施形態の難燃性発泡体は、特に制限されないが、発泡押出シート(XPS,PSP)や発泡性スチレンポリマー(EPS)、発泡射出成形品として用いることが好ましく、特に発泡押出シート(XPS)がより好ましい。
本実施例及び比較例で得られた、スチレン系樹脂及びスチレン系樹脂発泡成形体の物性の測定及び評価は、次の方法に基づいて行った。
プロトン核磁気共鳴(1H-NMR)測定機で測定したスペクトルの積分比から、樹脂組成を定量した。
・試料調製:樹脂ペレット30mgをd6-DMSO 0.75mLに60℃で4~6時間加熱溶解した。
・測定機器:日本電子(株)製 JNM ECA-500
・測定条件:測定温度25℃、観測核1H、積算回数64回、繰り返し時間11秒。
ジメチルスルホキシド重溶媒中で測定されたスペクトルの帰属について、0.5~1.5ppmのピークは、メタクリル酸、メタクリル酸メチル、及び六員環酸無水物のα-メチル基の水素、1.6~2.1ppmのピークはポリマー主鎖のメチレン基の水素、3.5ppmのピークはメタクリル酸メチルのカルボン酸エステル(-COOCH3)の水素、12.4ppmのピークはメタクリル酸のカルボン酸の水素である。また、6.5~7.5ppmのピークはスチレンの芳香族環の水素である。
スチレン系樹脂の重量平均分子量を、下記の条件や手順で測定した。
・試料調製:テトラヒドロフランに樹脂を約0.05質量%で溶解させた。
・測定条件
機器:TOSOH HLC-8220GPC
(ゲルパーミエイション・クロマトグラフィー)
カラム :super HZM-H
温度 :40℃
キャリア :THF 0.35mL/min
検出器 :RI、UV:254nm
検量線 :TOSOH製の標準PSを使用して作成。
スチレン系樹脂のメルトマスフローレート(g/10分)は、ISO 1133に準拠して測定した(200℃、荷重49N)。
スチレン系樹脂発泡体のビカット軟化温度(℃)は、後述の方法で作製した試験片を用いて、ISO 306に準拠し、荷重49N、昇温速度50℃/時間の条件で測定した。
(スチレン系樹脂発泡体の重量)/(スチレン系樹脂発泡体の体積)で表わされる式から発泡体密度(kg/m3)を計算した。
ASTM・D3576-77に準じて、板状のスチレン系樹脂発泡体の押出断面の平均気泡径(mm)を測定した。具体的には、本発明に係るスチレン系樹脂発泡体の平均気泡径は、以下の測定方法から算出できる。
スチレン系樹脂発泡体をMD方向及びTD方向に沿って厚み方向に切断し、MD方向の断面及びTD方向の断面を作製する。次いで、その断面に存在する各気泡の気泡径をデジタルマイクスコープにより観察して、MD方向の気泡径の数平均値と、TD方向の気泡径の数平均値とをそれぞれ算出する。この数平均値をスチレン系樹脂発泡体の平均気泡径とする。
なお、上記測定方法において、各断面に存在する各気泡の気泡径は、気泡の断面形状における最も長い径を意味し、例えば、断面形状が真円状であれ直径を表し、断面形状が楕円状であれば長径を表す。また、上記測定方法において、MD方向、又はTD方向が定まらない場合は、以下の方法により、スチレン系樹脂発泡体の平均気泡径を測定できる。スチレン系樹脂発泡体の厚み方向の任意の断面と、該断面と直交する方向のもう一つの厚み方向の断面を作製する。そして、それぞれをMD方向の断面、TD方向の断面として、上記と同様にして発泡体シートの平均気泡径を求めることができる。
ASTM・D2856-Aに準じて、板状のスチレン系樹脂発泡体の独立気泡率(%)を測定した。
JIS K7220に準じた方法により、スチレン系樹脂発泡体の圧縮強度を測定した。
本実施例で使用したスチレン系樹脂(A)及びセルロースナノファイバー(B)と、本比較例で使用したポリマー及びセルロースファイバーと、本実施例及び比較例で使用した添加剤は、以下の通りである。
<<樹脂(a-1)>>
スチレン(ST単量体)71.3質量部、メタクリル酸(MAA単量体)7.3質量部、メタクリル酸メチル(MMA単量体)6.4質量部、エチルベンゼン15.0質量部、1,1-ビス(t-ブチルパーオキシ)シクロヘキサン0.025質量部から成る重合原料組成液を、1.1リットル/時の速度で、容量が4リットルの完全混合型反応器に、次いで、容量が2リットルの層流型反応器から成る重合装置に、さらに、未反応モノマー、重合溶媒等の揮発分を除去する単軸押出機を連結した脱揮装置に、連続的に順次供給し、スチレン系樹脂である樹脂(a-1)を調製した。
以下の表1に示すスチレン系樹脂の性状になるように組成や重合温度条件等を調整し、樹脂(a-1)と同様の方法でスチレン系樹脂である樹脂(a-2)~(a-7)を得た。得られた樹脂(a-2)~(a-7)の組成比、物性を以下の表1に示す。なお、樹脂(a-7)では、単量体として、無水マレイン酸(MAH単量体)を用いた。
・MFR2.2のポリスチレン(GPPS、PSジャパン社製、G9401)を用いた。物性を以下の表1に示す。
<セルロースナノファイバー(B)成分>
・CNF(b-1):セルロースナノファイバー(中越パルプ工業株式会社製、CNF-10、平均繊維径30nm)
・CNF(b-2):セルロースナノファイバー(ダイセルファインケム株式会社製、KY-100G、平均繊維径:100nm)
<セルロースファイバー>
・セルロースファイバー(セライト社製、SW-10、平均繊維径25μm)
<添加剤>
<<フェノール系酸化防止剤>>
・3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリル(BASF社製、Irganox1076)
<<リン系酸化防止剤>>
・トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト(BASF社製株式会社、Irgafos168)
<スチレン系樹脂組成物の製造方法>
上記表1に示す組成比のスチレン系樹脂(A)と、セルロースナノファイバー(B)との総量100質量部に対して、Irganox1076とIrgafos168とを0.2質量部ずつ添加後、予備混合した。得られた予備混合物を一括混合し、二軸押出機(東芝機械社製、TEM-26SS)を用い、180℃~220℃の範囲で溶融押出を行い、混練物としてスチレン系樹脂組成物のペレットを得た。この際、スクリュー回転数は150rpm、吐出量は10kg/hrであった。
上記スチレン系樹脂組成物のそれぞれを、単軸押出機、ミキサー、ロータリークーラー、及びダイからなる押出発泡機を用いて、当該スチレン系樹脂組成物100質量部に対して、厚さ30mmの板状のスチレン系樹脂発泡体を製造した。樹脂溶融ゾーンの温度は180~220℃、ロータリークーラー温度は150~160℃、ダイ温度を120~130℃に調整した。発泡剤(C)としてはLPG(ノルマルブタン/イソブタン=70/30<体積分率>)を5質量部添加した。得られたスチレン系樹脂発泡体の発泡体密度、平均気泡径、独立気泡率、及び圧縮強度の評価を行った。結果を以下の表2に示す。
比較例1~6は、表2に示すように組成を変更したこと以外は実施例と同様にして、非発泡押出シートを得た。各物性の測定及び評価の結果を表3に示す。
Claims (3)
- スチレン系樹脂(A)80.0~99.7質量%と、平均繊維径3~200nmのセルロースナノファイバー(B)0.3~20質量%とを含み、
前記スチレン系樹脂(A)は、スチレン系単量体単位、不飽和カルボン酸系単量体単位、及び不飽和カルボン酸エステル系単量体単位を有する共重合樹脂であり、
前記共重合樹脂は、前記スチレン系単量体単位、前記不飽和カルボン酸系単量体単位、及び前記不飽和カルボン酸エステル系単量体単位の合計含有量を100質量%としたとき、前記スチレン系単量体単位69~98質量%、不飽和カルボン酸系単量体単位2~16質量%、及び不飽和カルボン酸エステル系単量体単位0~15質量%を有し、かつ前記不飽和カルボン酸系単量体単位は、アクリル酸又はメタクリル酸である、スチレン系樹脂発泡体。 - 前記不飽和カルボン酸系単量体がメタクリル酸である、請求項1に記載のスチレン系樹脂発泡体。
- 前記スチレン系樹脂発泡体が押出発泡である、請求項1又は2のいずれかに記載のスチレン系樹脂発泡体。
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JP2013185085A (ja) | 2012-03-08 | 2013-09-19 | Kyoto City | 変性ミクロフィブリル化植物繊維を含む発泡体 |
JP2013536896A (ja) | 2010-09-07 | 2013-09-26 | イッサム リサーチ ディべロップメント カンパニー オブ ザ ヘブライ ユニバーシティー オブ エルサレム,リミテッド | セルロースをベースとする複合材料 |
WO2018110566A1 (ja) | 2016-12-14 | 2018-06-21 | 星光Pmc株式会社 | 発泡成形体用組成物及びその製造方法、発泡成形体及びその製造方法並びに発泡成形体用変性セルロース含有樹脂組成物 |
JP2018527454A (ja) | 2015-09-21 | 2018-09-20 | ストラ エンソ オーワイジェイ | 複合製品および該製品を製造するプロセス |
JP2019035026A (ja) | 2017-08-16 | 2019-03-07 | 株式会社日本触媒 | ナノセルロース含有樹脂組成物 |
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JP2013536896A (ja) | 2010-09-07 | 2013-09-26 | イッサム リサーチ ディべロップメント カンパニー オブ ザ ヘブライ ユニバーシティー オブ エルサレム,リミテッド | セルロースをベースとする複合材料 |
JP2013185085A (ja) | 2012-03-08 | 2013-09-19 | Kyoto City | 変性ミクロフィブリル化植物繊維を含む発泡体 |
JP2018527454A (ja) | 2015-09-21 | 2018-09-20 | ストラ エンソ オーワイジェイ | 複合製品および該製品を製造するプロセス |
WO2018110566A1 (ja) | 2016-12-14 | 2018-06-21 | 星光Pmc株式会社 | 発泡成形体用組成物及びその製造方法、発泡成形体及びその製造方法並びに発泡成形体用変性セルロース含有樹脂組成物 |
JP2019035026A (ja) | 2017-08-16 | 2019-03-07 | 株式会社日本触媒 | ナノセルロース含有樹脂組成物 |
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