JP7477388B2 - スチレン系樹脂組成物及び成形品 - Google Patents
スチレン系樹脂組成物及び成形品 Download PDFInfo
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- JP7477388B2 JP7477388B2 JP2020125523A JP2020125523A JP7477388B2 JP 7477388 B2 JP7477388 B2 JP 7477388B2 JP 2020125523 A JP2020125523 A JP 2020125523A JP 2020125523 A JP2020125523 A JP 2020125523A JP 7477388 B2 JP7477388 B2 JP 7477388B2
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- Prior art keywords
- styrene
- acid
- mass
- based resin
- monomer unit
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 46
- 229920001890 Novodur Polymers 0.000 title 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 339
- 229920005989 resin Polymers 0.000 claims description 104
- 239000011347 resin Substances 0.000 claims description 104
- 239000000178 monomer Substances 0.000 claims description 101
- 229920002678 cellulose Polymers 0.000 claims description 72
- 239000001913 cellulose Substances 0.000 claims description 72
- 239000011324 bead Substances 0.000 claims description 60
- -1 ο-methylstyrene Chemical compound 0.000 claims description 59
- 229920006026 co-polymeric resin Polymers 0.000 claims description 40
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 26
- 150000003440 styrenes Chemical class 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 20
- 239000000194 fatty acid Substances 0.000 claims description 20
- 229930195729 fatty acid Natural products 0.000 claims description 20
- 235000007586 terpenes Nutrition 0.000 claims description 19
- 150000003505 terpenes Chemical class 0.000 claims description 17
- 239000004793 Polystyrene Substances 0.000 claims description 14
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 13
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 13
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 229920002223 polystyrene Polymers 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 5
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 4
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 4
- GQEFPXSNRRKUHO-UHFFFAOYSA-N 4-methylpent-1-enylbenzene Chemical compound CC(C)CC=CC1=CC=CC=C1 GQEFPXSNRRKUHO-UHFFFAOYSA-N 0.000 claims description 4
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 claims description 4
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 36
- 238000000034 method Methods 0.000 description 28
- 239000000203 mixture Substances 0.000 description 18
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 16
- 150000001733 carboxylic acid esters Chemical class 0.000 description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 230000007423 decrease Effects 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229920000297 Rayon Polymers 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920005669 high impact polystyrene Polymers 0.000 description 6
- 239000004797 high-impact polystyrene Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 239000005063 High cis polybutadiene Substances 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000012662 bulk polymerization Methods 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 4
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 3
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 3
- 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 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
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- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 3
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- 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 3
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- 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
- 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
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000003760 tallow Substances 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 239000010409 thin film Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- XJPBRODHZKDRCB-UHFFFAOYSA-N trans-alpha-ocimene Natural products CC(=C)CCC=C(C)C=C XJPBRODHZKDRCB-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- SGKKYCDALBXNCG-UHFFFAOYSA-N tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-5-methylphenyl] phosphite Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C(=CC(OP(OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)=C(C=2)C(C)(C)C)C)=C1 SGKKYCDALBXNCG-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- IHPKGUQCSIINRJ-UHFFFAOYSA-N β-ocimene Natural products CC(C)=CCC=C(C)C=C IHPKGUQCSIINRJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
[1]スチレン系樹脂(a)45.0~99.5質量%と、セルロースビーズ(b)0.5~55.0質量%と、を含有することを特徴とする、スチレン系樹脂組成物。
[2]本発明において、前記セルロースビーズ(b)が、多孔質であること好ましい。
[3]本発明において、前記スチレン系樹脂(a)が、不飽和カルボン酸系単量体単位を含むことが好ましい。
[4]本発明において、前記スチレン系樹脂組成物の総量100質量部に対して分散剤(c)0.5~2.0質量部をさらに含有することが好ましい。
[5]本発明において、前記分散剤(c)が、脂肪酸エステル系化合物、ポリエチレングリコール系化合物、テルペン系化合物、及びロジン系化合物からなる群から選択される1種又は2種以上の化合物であることが好ましい。
[5]本発明は、上記[1]~[4]のいずれか1項に記載のスチレン系樹脂組成物を含む、成形品である。
本実施形態のスチレン系樹脂組成物は、スチレン系樹脂(a)を45.0~99.5質量%と、セルロースビーズ(b)を0.5~55.0質量%とを含有する。
本実施形態において、スチレン系樹脂(a)の含有量は、スチレン系樹脂組成物全体(100質量%)に対して、45.0~99.5質量%であり、好ましくは50.0~97.0質量%、より好ましくは60.0~95.0質量%である。当該含有量を45.0質量%以上とすることにより、流動性、外観を高めることができる。一方、当該含有量を99.5質量%以下とすることにより、セルロースビーズ(b)の合計含有量を確保することができ、寸法精度、剛性等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)
(上記数式(N1)中、niは、粒子径Driのゴム状重合体(a)粒子の個数であり、粒子径Driは、写真中の粒子の面積から円相当径として算出した粒子径である。)
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、スチレン系共重合樹脂とは、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を含む樹脂であることが好ましい。
本実施形態におけるセルロースビーズ(b)は、セルロースを粒状に成形した球状体である。そして、当該セルロースビーズ(b)の平均粒径が10~300μmであり、かつそのアスペクト比である最大直径と最小直径の比(最大直径/最小直径)が1.0~1.5であることが好ましい。さらに、当該セルロースビーズ(b)のα-セルロース量が90%以上であることが好ましい。
(b)成分の含有量を5質量%以上とすることにより、寸法精度と剛性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、衝撃強度が低下するほか、流動性低下により成形性を著しく低下させる。スチレン系樹脂組成物中のセルロースビーズ(b)の含有量は、当該組成物をスチレン系樹脂(a)が溶解する溶媒に溶かし、未溶物を取出し、120℃、4時間の条件で乾燥させたものの質量を測ることでわかる。
本実施形態において、セルロースビーズ(b)の分散性を向上させる目的で、分散剤(c)を、スチレン系樹脂組成物の総量(100質量部)に対して0.5~2.0質量部含有してもよく、より好ましくは、分散剤(c)を0.8~1.8質量部含有する。分散剤(c)をスチレン系樹脂組成物中に添加することにより、セルロースビーズ(b)とスチレン系樹脂(a)とを複合化する際に使用する押出機のヤケ、或いは目やに(いわゆる溶融樹脂カス)を防止し、成形外観をより向上させることができる。分散剤が所定量より少ないと、大きな効果が期待できなく、所定量より多いと大きな耐熱性が得られにくい。スチレン系樹脂(a)との親和性に優れる分散剤が、より大きな効果を示す傾向にある。
本実施形態のスチレン系樹脂組成物は、上記(a)~(c)成分の他に、本発明の効果を損なわない範囲で、必要に応じて公知の添加剤、加工助剤等の添加成分を添加することができる。これら添加剤及び加工助剤等としては、酸化防止剤、耐候剤、帯電防止剤、充填剤等が挙げられる。
<線膨張係数>
本実施形態のスチレン系樹脂組成物から得られた成形体の線膨張係数は、6×10-5/℃以下であることが好ましく、より好ましくは5×10-5/℃以下である。また、MD方向(成形時の流れ方向)とTD方向(MD方向の垂直方向)の線膨張係数の比(TD/MD比)が0.8~1.3であることが好ましく、より好ましくは0.9~1.2である。線膨張係数が6×10-5/℃より大きいと、熱膨張により、製品に不具合を生じたり、金属などとの接着する製品では金属が剥がれたりすることがある。また、TD/MD比が範囲外であると製品が熱により反ってしまうことがある。なお本開示で、線膨張係数はJIS K7197のTMA法に準拠して測定される値である。また、本実施形態のスチレン系樹脂組成物を用いて製造する成形体における寸法精度は、線膨張係数の値により評価する。
本実施形態のスチレン系樹脂組成物のメルトフローレートは、1グラム/10分以上であることが好ましく、より好ましくは2グラム/10分以上である。1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、(b)多孔質セルロースビーズが劣化による物性低下又は成形品が変色してしまう恐れがある。
本実施形態のスチレン系樹脂組成物から得られた成形体の真密度は、1.25以下であることが好ましく、より好ましくは1.20以下である。1.25より大きいと、製品の軽量化が不十分となる場合がある。
本実施形態のスチレン系樹脂組成物の曲げ弾性率は2500MPa以上であることが好ましく、より好ましくは3000MPa以上である。2500MPa未満であると製品の肉厚を薄くすることができず、軽量化できない。
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、180~250℃の範囲で選択される。
本発明の成形品は、上記のスチレン系樹脂組成物を含むことを特徴とする。
各実施例及び比較例で得られた樹脂組成物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。
・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-メチル基の水素由来のピーク、1.6~2.1ppmのピークはポリマー主鎖のメチレン基の水素由来のピーク、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)の水素由来のピーク、12.4ppmのピークはメタクリル酸のカルボン酸の水素由来のピークである。また、6.5~7.5ppmのピークはスチレンの芳香族環の水素由来のピークである。なお、本実施例及び比較例の樹脂では六員環酸無水物の含有量が少ないため、本測定方法では通常定量化は難しい。
スチレン系樹脂(a)の重量平均分子量を、下記の条件や手順で測定した。
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を使用して作製。
線膨張係数(/℃)は、後述の方法で作製した試験片(a)の中央部を10×5×4mmの大きさにMD方向、TD方向で切削加工し、JIS K7197のTMA法(-30℃~80℃)に準拠してMD方向とTD方向を測定した。
スチレン系樹脂(a)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)。
密度は、後述の方法で作製した試験片(a)を用いて、ISO1183に準拠し、測定した。
曲げ弾性率(MPa)は、後述の方法で作製した試験片(a)を用いて、ISO 178に準拠して測定した。
表面外観は、後述の方法で作製した試験片(b)の一方の表面を観察し、開口が0.1mm以上の寸法の凹みが10個未満存在する場合を「合格:○」とし、20個以上存在する場合を「不良;×」と評価した。
[GPPS]
・MFR7.8のポリスチレン(GPPS、PSジャパン社製、HF77)を用いた。
・MFR3.0のポリスチレン(HIPS、PSジャパン社製、HT478)を用いた。
スチレン(ST)70.0質量部、メタクリル酸ブチル(BA)15.0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、スチレン系共重合樹脂である共重合樹脂(1)を調製した。
・上記HIPS(HT478)にスチレン無水マレイン酸(SMA)共重合体(POLYSCOPE社製、XIBOND250)を5質量%配合させたものであり、MFRは3.8であった。
・上記のスチレン系共重合樹脂にスチレン無水マレイン酸(SMA)共重合体(POLYSCOPE社製、XIBOND250)を5質量%配合させたものであり、MFRは5.0であった。
セルロース濃度9.0%、粘度4,500センチポイズ、塩化アンモニウム価8.5、アルカリ濃度6.1%のビスコース400gと炭酸カルシウム(株式会社カルファイン製KS800平均粒径7.8μm)37gを12ビーカーに入れて撹拌機にて700rpmで20分間撹拌を行うことにより、ビスコース液を調製した。当該ビスコース液をビーカーより吸引、加圧して、ノズルから噴霧し、そのまま塩酸中に落としてビスコースを凝固させて、その後脱硫、洗浄及び乾燥を行うことによりセルロースビーズ(b-1)を調製した。また、当該セルロースビーズ(b-1)の平均粒径は60μmであり、嵩比重0.8であり、アスペクト比(最大直径/最小直径))が1.0~1.5の範囲内であり、α―セルロース量は95%であった。
セルロース濃度9.0%、粘度4,500センチポイズ、塩化アンモニウム価8.5、アルカリ濃度6.1%のビスコース400gと炭酸カルシウム(株式会社カルファイン製KS800平均粒径7.8μm) 37gを12ビーカーに入れて撹拌機にて700rpmで20分間撹拌を行うことにより、炭酸カルシウムを含有するビスコース液を調製した。当該ビスコース液をビーカーより吸引、加圧し、ノズルから噴霧し、そのまま塩酸中に落としてビスコースを凝固させるとともに、炭酸カルシウムの反応による発泡を生じさせ、その後脱硫、洗浄並びに乾燥を行うことにセルロースビーズ(b-2)を調製した。また、当該セルロースビーズ(b-2)は多孔質体であり、セルロースビーズ(b-2)の平均粒径85μmであり、アスペクト比(最大直径/最小直径))が1.0~1.5の範囲内であり、嵩比重0.3であり、α―セルロース量は95%であった。
・セルロースファイバー(セライト社製、SW-10、平均太さ20μm、平均長700μm、嵩比重1.5)
[分散剤]
・脂肪酸エステル:グリセリンモノステアレート(理研ビタミン社製:S‐100)
・テルペン:芳香族変性テルペン樹脂(ヤスハラケミカル社製:YSレジンTO-105)
[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)
[実施例1~10]
表1に示す組成比で各成分を添加し、(a)~(c)成分100質量部に対して、酸化防止剤として、Irganox1076とIrgafos168とをそれぞれ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。このようにして得られたペレットを、ISO規格試験片タイプ(a)金型を備え付けた日本製鋼所社製の射出成形機を用い、シリンダー温度220℃、金型温度50℃、射出圧力(ゲージ圧40-60MPa)、射出速度(パネル設定値)50%、射出時間/冷却時間=5sec/20secで成形して試験片(a)を作製した。得られた試験片(a)を用いて、線膨張係数、密度、曲げ弾性率を評価した。
比較例1~11は、表2に示すように組成を変更したこと以外は実施例1と同様に実施した。各物性の測定及び評価の結果を表2に示す。
Claims (4)
- スチレン系樹脂(a)45.0~99.5質量%と、平均粒径10~300μmの粒状であるセルロースビーズ(b)0.5~55.0質量%と、を含有する、スチレン系樹脂組成物であって、
前記スチレン系樹脂(a)は、スチレン系単量体を重合した単独重合体であるポリスチレン、スチレン系単量体を重合したマトリックスにゴム状重合体(A)の粒子が分散したゴム変性スチレン系樹脂、並びに、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を有するスチレン系共重合樹脂からなる群から選択される1種以上であり、
前記スチレン系共重合樹脂は、前記スチレン系単量体単位及び前記不飽和カルボン酸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の含有量は69~98質量%であり、
前記スチレン系単量体単位が、スチレン、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、t-ブチルスチレン、ブロモスチレン又はインデンの単量体単位であり、
前記不飽和カルボン酸系単量体単位は、メタクリル酸、アクリル酸、無水マレイン酸、マレイン酸、フマル酸、イタコン酸、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル又は(メタ)アクリル酸シクロヘキシルの単量体単位であり、
前記セルロースビーズ(b)が、多孔質である、スチレン系樹脂組成物。 - 前記スチレン系樹脂組成物の総量100質量部に対して分散剤を(c)0.5~2.0質量部さらに含有する、請求項1に記載のスチレン系樹脂組成物。
- 前記分散剤(c)が、脂肪酸エステル系化合物、ポリエチレングリコール系化合物、テルペン系化合物及びロジン系化合物からなる群から選択される1種又は2種以上の化合物である、請求項2に記載のスチレン系樹脂組成物。
- 請求項1~3のいずれか1項に記載のスチレン系樹脂組成物を含む、成形品。
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