JP7535857B2 - Styrene copolymer resin - Google Patents
Styrene copolymer resin Download PDFInfo
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- JP7535857B2 JP7535857B2 JP2020017315A JP2020017315A JP7535857B2 JP 7535857 B2 JP7535857 B2 JP 7535857B2 JP 2020017315 A JP2020017315 A JP 2020017315A JP 2020017315 A JP2020017315 A JP 2020017315A JP 7535857 B2 JP7535857 B2 JP 7535857B2
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- styrene
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 293
- 229920006026 co-polymeric resin Polymers 0.000 title claims description 77
- 239000000178 monomer Substances 0.000 claims description 101
- 238000006116 polymerization reaction Methods 0.000 claims description 59
- 125000004432 carbon atom Chemical group C* 0.000 claims description 52
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 34
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 34
- 229930016911 cinnamic acid Natural products 0.000 claims description 34
- 235000013985 cinnamic acid Nutrition 0.000 claims description 34
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 125000003545 alkoxy group Chemical group 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 125000005843 halogen group Chemical group 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 125000003277 amino group Chemical group 0.000 claims description 19
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 15
- 230000009477 glass transition Effects 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 69
- 229920005989 resin Polymers 0.000 description 43
- 239000011347 resin Substances 0.000 description 43
- 239000000203 mixture Substances 0.000 description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- 238000000034 method Methods 0.000 description 25
- 239000003921 oil Substances 0.000 description 22
- 229920001577 copolymer Polymers 0.000 description 18
- 239000002994 raw material Substances 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 13
- 238000001914 filtration Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- -1 n-octyl Chemical group 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 5
- 150000001733 carboxylic acid esters Chemical class 0.000 description 5
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 150000003440 styrenes Chemical class 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 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical compound NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 description 2
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 235000021156 lunch Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- 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
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- OUCGLXKNITVPJS-OUKQBFOZSA-N 2-ethylhexyl (e)-3-phenylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=CC=C1 OUCGLXKNITVPJS-OUKQBFOZSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-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
- GQEFPXSNRRKUHO-UHFFFAOYSA-N 4-methylpent-1-enylbenzene Chemical compound CC(C)CC=CC1=CC=CC=C1 GQEFPXSNRRKUHO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- OLLPXZHNCXACMM-CMDGGOBGSA-N Propyl cinnamate Chemical compound CCCOC(=O)\C=C\C1=CC=CC=C1 OLLPXZHNCXACMM-CMDGGOBGSA-N 0.000 description 1
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 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
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 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 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001819 propan-2-yl (E)-3-phenylprop-2-enoate Substances 0.000 description 1
- RGACABDFLVLVCT-UHFFFAOYSA-N propan-2-yl 3-phenylprop-2-enoate Chemical compound CC(C)OC(=O)C=CC1=CC=CC=C1 RGACABDFLVLVCT-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000001572 propyl (E)-3-phenylprop-2-enoate Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、スチレン系共重合樹脂に関する。 The present invention relates to a styrene-based copolymer resin.
スチレン系樹脂は成形加工性に優れ、且つ比較的安価なことから、食品包装容器や、弁当、惣菜等の食品の容器包装材料、住宅の断熱材用の発泡ボード、拡散剤を入れた液晶テレビの拡散板等に広く用いられている。 Styrene-based resins have excellent moldability and are relatively inexpensive, so they are widely used in food packaging containers, food container and packaging materials for boxed lunches and prepared foods, foam boards for insulating housing, and diffusion panels for LCD televisions that contain diffusion agents.
一方、地球温暖化防止ならびに枯渇資源である石油使用量低減の意識の高まりにより、従来の石油由来プラスチック材料からカーボンニュートラルな植物由来プラスチック材料への置き換えが検討されている。近年、コンビニエンスストアー等の業務用に使用する電子レンジの普及、及び電子レンジの使用時間の短縮のため、より高出力（短時間で、より高温になりやすい）の機器が使用されている。 Meanwhile, with growing awareness of the need to prevent global warming and reduce the use of petroleum, a defunct resource, there is a growing interest in replacing conventional petroleum-derived plastic materials with carbon-neutral plant-derived plastic materials. In recent years, with the spread of commercial microwave ovens at convenience stores and other locations, and the shortening of microwave oven operating times, higher-output devices (which can easily reach higher temperatures in a shorter time) are being used.
耐熱性の高いスチレン系樹脂としては、スチレン－メタクリル酸樹脂等があげられる。当該樹脂については、より耐熱性の高い樹脂を得るにはメタクリル酸の含量を増やすことが必要であり、この場合、メタクリル酸に起因するゲル化物の発生がしやすくなり、シート表面に外観不良が見られる場合がある。特許文献１には、スチレン－メタクリル酸樹脂が記載され、実施例では、重合原料液にオクチルアルコールを添加してゲル化を抑制する方法が記載されている。非特許文献１では、植物から採取可能な「桂皮酸」から誘導されるエステル類若しくはアミド若しくはアルデヒドとスチレンとを単官能の開始剤を利用して共重合することでガラス転移温度の高い共重合体を得る技術が提案されている。 Examples of styrene-based resins with high heat resistance include styrene-methacrylic acid resins. In order to obtain a resin with higher heat resistance, it is necessary to increase the content of methacrylic acid. In this case, gelation due to methacrylic acid is likely to occur, and poor appearance may be observed on the sheet surface. Patent Document 1 describes a styrene-methacrylic acid resin, and in the examples, a method of suppressing gelation by adding octyl alcohol to the polymerization raw material liquid. Non-Patent Document 1 proposes a technology to obtain a copolymer with a high glass transition temperature by copolymerizing esters, amides, or aldehydes derived from "cinnamic acid" that can be extracted from plants with styrene using a monofunctional initiator.
しかしながら、特許文献１に記載された発明では、樹脂の耐熱性及び外観の観点で不十分である。非特許文献１では数平均分子量Ｍｎ及び重量平均分子量Ｍｗの双方が低いため成形体としての利用が困難である。したがって、耐熱性、外観双方に優れる樹脂が求められている。そこで、本発明は、耐熱性、外観、及び成形性に優れたスチレン系共重合樹脂を提供することを目的とする。 However, the invention described in Patent Document 1 is insufficient in terms of the heat resistance and appearance of the resin. In Non-Patent Document 1, both the number average molecular weight Mn and the weight average molecular weight Mw are low, making it difficult to use as a molded product. Therefore, a resin that is excellent in both heat resistance and appearance is required. Therefore, the object of the present invention is to provide a styrene-based copolymer resin that is excellent in heat resistance, appearance, and moldability.
本発明者らは、上記問題点に鑑み、鋭意研究を進めた結果、スチレン類と桂皮酸誘導体とを共重合して得られた樹脂により、耐熱性、外観、及び成形性に優れる耐熱スチレン系樹脂が得られることを見出し、本発明を完成するに至った。すなわち、本発明は以下の通りである。 In view of the above problems, the present inventors have conducted intensive research and have discovered that a heat-resistant styrene-based resin with excellent heat resistance, appearance, and moldability can be obtained by copolymerizing styrenes with cinnamic acid derivatives, leading to the completion of the present invention. That is, the present invention is as follows.
［１］本発明は、スチレン系単量体単位と、桂皮酸系単量体単位とを有し、重量平均分子量が５００００以上のスチレン系共重合樹脂である。 [1] The present invention is a styrene-based copolymer resin having a styrene-based monomer unit and a cinnamic acid-based monomer unit and a weight-average molecular weight of 50,000 or more.
「２」本発明において、前記スチレン系単量体単位及び前記桂皮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が５～９５質量％であることが好ましい。 "2" In the present invention, when the total content of the styrene-based monomer units and the cinnamic acid-based monomer units is taken as 100% by mass, it is preferable that the content of the styrene-based monomer units is 5 to 95% by mass.
「３」本発明において、前記スチレン系単量体単位及び前記桂皮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が１０～９０質量％であることが好ましい。 "3" In the present invention, when the total content of the styrene-based monomer units and the cinnamic acid-based monomer units is taken as 100% by mass, it is preferable that the content of the styrene-based monomer units is 10 to 90% by mass.
「４」本発明において、前記スチレン系単量体単位は、以下の一般式（１）で表わされることが好ましい。
「５」本発明において、前記桂皮酸系単量体単位は、一般式（２）で表わされることが好ましい。
「６」本発明において、一般式（３）で表わされる繰り返し単位を有することが好ましい。
[5] In the present invention, the cinnamic acid-based monomer unit is preferably represented by general formula (2).
"6" In the present invention, it is preferable to have a repeating unit represented by general formula (3).
「７」本発明において、ガラス転移温度が１０６℃～１６０℃であることが好ましい。 "7" In the present invention, it is preferable that the glass transition temperature is 106°C to 160°C.
本発明により、耐熱性、外観、及び成形性に優れたスチレン系共重合樹脂を提供することができる。 The present invention provides a styrene copolymer resin with excellent heat resistance, appearance, and moldability.
以下、本発明の実施形態を詳細に説明する。
［スチレン系単量体単位と桂皮酸系単量体単位との共重合樹脂及び当該共重合樹脂を含む樹脂組成物］
本発明の一様態は、スチレン系単量体単位、桂皮酸系単量体単位を有する共重合樹脂であり、重量平均分子量が５００００以上のスチレン系共重合樹脂を提供する。
これにより、耐熱性、外観、及び成形性に優れたスチレン系共重合樹脂を提供できる。
Hereinafter, an embodiment of the present invention will be described in detail.
[Copolymer resin of styrene-based monomer unit and cinnamic acid-based monomer unit and resin composition containing said copolymer resin]
One aspect of the present invention provides a styrene-based copolymer resin having a styrene-based monomer unit and a cinnamic acid-based monomer unit, the styrene-based copolymer resin having a weight average molecular weight of 50,000 or more.
This makes it possible to provide a styrene-based copolymer resin excellent in heat resistance, appearance and moldability.
＜スチレン系単量体単位と桂皮酸系単量体単位とを有するスチレン系共重合樹脂＞
本実施形態において、スチレン誘導体と桂皮酸誘導体とから形成されたスチレン系樹脂は、スチレン系単量体単位及び桂皮酸単量体単位を含む共重合体であり、その分子量は５００００以上である。
<Styrene-based copolymer resin having styrene-based monomer units and cinnamic acid-based monomer units>
In this embodiment, the styrene-based resin formed from a styrene derivative and a cinnamic acid derivative is a copolymer containing a styrene-based monomer unit and a cinnamic acid monomer unit, and has a molecular weight of 50,000 or more.
＜＜スチレン系単量体単位＞＞
本実施形態におけるスチレン系単量体単位としては、以下の一般式（１）で表わされることが好ましい。
The styrene-based monomer unit in this embodiment is preferably represented by the following general formula (1).
上記一般式（１）中、Ｒ１は、水素原子、置換若しくは無置換の炭素原子数１から１０までの直鎖状若しくは分岐状のアルキル基又はフェニル基が好ましく、水素原子、置換若しくは無置換の炭素原子数１から８までの直鎖状若しくは分岐状のアルキル基又はフェニル基が好ましく、より好ましくは水素原子、置換若しくは無置換の炭素原子数１から３までの直鎖状若しくは分岐状のアルキル基である。 In the above general formula (1), R 1 is preferably a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a phenyl group, more preferably a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms, or a phenyl group, and more preferably a hydrogen atom, or a substituted or unsubstituted linear or branched alkyl group having 1 to 3 carbon atoms.
上記一般式（１）中、Ｒ２は、水素原子、ハロゲン原子、水酸基、置換若しくは無置換の炭素原子数１から１０までの直鎖状若しくは分岐状のアルコキシ基、アミノ基、ニトロ基、シアノ基、置換若しくは無置換の炭素原子数１から１０までの直鎖状若しくは分岐状のアルキル基が好ましく、水素原子、ハロゲン原子、水酸基、置換若しくは無置換の炭素原子数１から８までの直鎖状若しくは分岐状のアルコキシ基、アミノ基、ニトロ基、シアノ基、置換若しくは無置換の炭素原子数１から８までの直鎖状若しくは分岐状のアルキル基が好ましく、水素原子、ハロゲン原子、水酸基、置換若しくは無置換の炭素原子数１から８までの直鎖状若しくは分岐状のアルコキシ基、置換若しくは無置換の炭素原子数１から８までの直鎖状若しくは分岐状のアルキル基がより好ましく、水素原子、ハロゲン原子、水酸基、無置換の炭素原子数１から３までの直鎖状若しくは分岐状のアルコキシ基、又は無置換の炭素原子数１から３までの直鎖状若しくは分岐状のアルキル基がさらに好ましい。 In the above general formula (1), R 2 is preferably a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 10 carbon atoms, an amino group, a nitro group, a cyano group, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms, a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 8 carbon atoms, a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms is more preferred, a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 8 carbon atoms, a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms is more preferred, a hydrogen atom, a halogen atom, a hydroxyl group, a non-substituted linear or branched alkoxy group having 1 to 3 carbon atoms, or a non-substituted linear or branched alkyl group having 1 to 3 carbon atoms is even more preferred.
上記一般式（１）中、アルキル基又はアルコキシ基が置換される場合の置換基Ｓとしては、ハロゲン原子（フッ素原子、塩素原子、臭素原子）、水酸基、炭素原子数１～３の直鎖状又は分岐状のアルコキシ基、アミノ基、ニトロ基、又はシアノ基が好ましい。 In the above general formula (1), when an alkyl group or an alkoxy group is substituted, the substituent S is preferably a halogen atom (a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, a linear or branched alkoxy group having 1 to 3 carbon atoms, an amino group, a nitro group, or a cyano group.
上記一般式（１）中、ａは、１～５の整数を表し、１～３が好ましく、１～２がより好ましい。 In the above general formula (1), a represents an integer of 1 to 5, preferably 1 to 3, and more preferably 1 to 2.
本明細書における「炭素原子数１から１０までの直鎖状若しくは分岐状のアルキル基」としては、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基等が挙げられる。 In this specification, examples of "straight-chain or branched alkyl groups having 1 to 10 carbon atoms" include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl groups.
本明細書における「炭素原子数１から１０までの直鎖状若しくは分岐状のアルコキシ基」としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基、ｎ－ペントキシ基、ｎ－ヘキソキシ基、ｎ－ヘプトキシ基、ｎ－オクトキシ基、２－エチルヘキソキシ基等が挙げられる。 In this specification, examples of "linear or branched alkoxy groups having 1 to 10 carbon atoms" include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, and 2-ethylhexoxy groups.
本実施形態において、スチレン系単量体単位を形成するスチレン系単量体としては、例えば、スチレン、α－メチルスチレン、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、クロロスチレン、インデン等のスチレン誘導体が挙げられる。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、一種単独で又は二種以上を組み合わせて使用することができる。 In this embodiment, examples of styrene-based monomers that form the styrene-based monomer units include styrene, α-methylstyrene, α-methyl-p-methylstyrene, ο-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, ethylstyrene, isobutylstyrene, t-butylstyrene, bromostyrene, chlorostyrene, and styrene derivatives such as indene. From an industrial viewpoint, styrene is preferred. These styrene-based monomers can be used alone or in combination of two or more.
本明細書における「スチレン系単量体単位」とは、スチレン系単量体由来の繰り返し単位を意味し、より詳細には、スチレン系単量体が重合反応又は架橋反応により、当該単量体中の不飽和二重結合が単結合になった構造単位をいう。 In this specification, the term "styrene monomer unit" refers to a repeating unit derived from a styrene monomer, and more specifically, refers to a structural unit in which the unsaturated double bond in the styrene monomer is converted to a single bond through a polymerization reaction or crosslinking reaction.
本実施形態において、スチレン系共重合樹脂中のスチレン系単量体単位、及び桂皮酸系単量体単位の合計含有量を１００質量％としたときに、スチレン系単量体の含有量は、５～９５質量％であることが好ましく、より好ましくは１０～９０質量％、さらに好ましくは２０～８５質量％、よりさらに好ましくは３０～８０質量％である。この含有量が５質量％未満では、樹脂の流動性が低下し、他方、９５質量％を超えると、桂皮酸系単量体単位を所望量存在させることができないため、所望の効果が得られない。 In this embodiment, when the total content of the styrene-based monomer units and the cinnamic acid-based monomer units in the styrene-based copolymer resin is taken as 100% by mass, the content of the styrene-based monomer is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 85% by mass, and even more preferably 30 to 80% by mass. If this content is less than 5% by mass, the fluidity of the resin decreases, while if it exceeds 95% by mass, the desired amount of cinnamic acid-based monomer units cannot be present, and the desired effect cannot be obtained.
＜＜桂皮酸系単量体単位＞＞
本実施形態における桂皮酸系単量体単位は、以下の一般式（２）で表わされることが好ましい。
The cinnamic acid-based monomer unit in this embodiment is preferably represented by the following general formula (2).
上記一般式（２）中、Ｒ３は、水素原子、水酸基、置換若しくは無置換の炭素原子数１から１０までの直鎖状のアルコキシ基、又はアミノ基が好ましく、水素原子、水酸基、又は置換若しくは無置換の炭素原子数１から１０までの直鎖状のアルコキシ基、又はアミノ基がより好ましく、水酸基又は置換若しくは無置換の炭素原子数１から８までの直鎖状のアルコキシ基がさらに好ましい。 In the above general formula (2), R3 is preferably a hydrogen atom, a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 10 carbon atoms, or an amino group, more preferably a hydrogen atom, a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 10 carbon atoms, or an amino group, and still more preferably a hydroxyl group or a substituted or unsubstituted linear alkoxy group having 1 to 8 carbon atoms.
上記一般式（２）中、Ｒ４は、水素原子、ハロゲン原子、水酸基、置換若しくは無置換の炭素原子数１から１０までの直鎖状若しくは分岐状のアルコキシ基、アミノ基、ニトロ基、シアノ基、又は置換若しくは無置換の炭素原子数１から１０までの直鎖状若しくは分岐状のアルキル基、又はフェニル基が好ましく、水素原子、水酸基、置換若しくは無置換の炭素原子数１から８までの直鎖状若しくは分岐状のアルキル基、又はフェニル基がより好ましく、水素原子、置換若しくは無置換の炭素原子数１から３までの直鎖状若しくは分岐状のアルキル基、又はフェニル基がさらに好ましい。 In the above general formula (2), R 4 is preferably a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 10 carbon atoms, an amino group, a nitro group, a cyano group, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a phenyl group, more preferably a hydrogen atom, a hydroxyl group, a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms, or a phenyl group, and even more preferably a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 3 carbon atoms, or a phenyl group.
上記一般式（２）中、Ｒ５は、水素原子、ハロゲン原子、水酸基、置換若しくは無置換の炭素原子数１から１０までの直鎖状若しくは分岐状のアルコキシ基、アミノ基、ニトロ基、シアノ基、置換若しくは無置換の炭素原子数１から１０までの直鎖状若しくは分岐状のアルキル基が好ましく、さらに好ましくは水素原子、水酸基、ハロゲン原子、置換若しくは無置換の炭素原子数１から８までの直鎖状若しくは分岐状のアルコキシ基、又は置換若しくは無置換の炭素原子数１から３までの直鎖状若しくは分岐状のアルキル基が好ましい。 In the above general formula (2), R5 is preferably a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 10 carbon atoms, an amino group, a nitro group, a cyano group, or a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom, a hydroxyl group, a halogen atom, a substituted or unsubstituted linear or branched alkoxy group having 1 to 8 carbon atoms, or a substituted or unsubstituted linear or branched alkyl group having 1 to 3 carbon atoms.
上記一般式（２）中、アルキル基が置換される場合の置換基Ｌとしては、ハロゲン原子、水酸基、アルコキシ基、アミノ基、ニトロ基、シアノ基が好ましい。 In the above general formula (2), when the alkyl group is substituted, the substituent L is preferably a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, or a cyano group.
上記一般式（２）中、ｂは、１～５の整数を表し、１～３が好ましく、１～２がより好ましい。 In the above general formula (2), b represents an integer of 1 to 5, preferably 1 to 3, and more preferably 1 to 2.
上記桂皮酸系単量体としては、例えば、桂皮酸、桂皮酸メチル、桂皮酸エチル、桂皮酸プロピル、桂皮酸２エチルヘキシル、パラメチル桂皮酸メチル、パラメトキシ桂皮酸メチル、桂皮酸アミド、桂皮アルデヒド等が挙げられる。これらは単独で又は混合して使用することができる。耐熱性の向上効果が大きく、４０度にて液状でハンドリング性に優れることから桂皮酸メチル、桂皮酸エチルが好ましい。 Examples of the cinnamic acid monomer include cinnamic acid, methyl cinnamate, ethyl cinnamate, propyl cinnamate, 2-ethylhexyl cinnamate, methyl paramethylcinnamate, methyl paramethoxycinnamate, cinnamic acid amide, cinnamic aldehyde, etc. These can be used alone or in combination. Methyl cinnamate and ethyl cinnamate are preferred because they have a large effect of improving heat resistance, are liquid at 40 degrees, and have excellent handling properties.
本明細書における「桂皮酸系単量体単位」とは、桂皮酸系単量体由来の繰り返し単位を意味し、より詳細には、桂皮酸系単量体が重合反応又は架橋反応により、当該単量体中の不飽和二重結合が単結合になった構造単位をいう。 In this specification, the term "cinnamic acid monomer unit" refers to a repeating unit derived from a cinnamic acid monomer, and more specifically, refers to a structural unit in which the unsaturated double bond in the cinnamic acid monomer is converted to a single bond through a polymerization reaction or crosslinking reaction.
本実施形態において、桂皮酸系単量体単位は、耐熱性の向上に寄与する。前記共重合樹脂中のスチレン系単量体単位、及び桂皮酸系単量体単位の合計含有量を１００質量％としたときに、桂皮酸系単量体単位の含有量は、５～９５質量％であることが好ましく、より好ましくは１０～９０質量％、さらに好ましくは１５～８０質量％、よりさらに好ましくは２０～７０質量％の範囲である。この含有量が５質量％未満では耐熱性向上の効果の発現が不十分であり、他方、９５質量％を超えると、前記共重合樹脂中の流動性が低下し成形性の悪化を招来するため好ましくない。 In this embodiment, the cinnamic acid monomer units contribute to improving heat resistance. When the total content of the styrene monomer units and the cinnamic acid monomer units in the copolymer resin is taken as 100% by mass, the content of the cinnamic acid monomer units is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, even more preferably 15 to 80% by mass, and even more preferably 20 to 70% by mass. If this content is less than 5% by mass, the effect of improving heat resistance is insufficient, while if it exceeds 95% by mass, the fluidity in the copolymer resin decreases, leading to deterioration of moldability, which is not preferable.
＜＜その他の単量体単位＞＞
本発明に係るスチレン系樹脂は、スチレン系単量体単位と、桂皮酸系単量体とを、必須に含む共重合体であり、必要により、不飽和カルボン酸系単量体単位及び／又は不飽和カルボン酸エステル系単量体単位を含有する共重合体であることが好ましい。
<<Other monomer units>>
The styrene-based resin according to the present invention is a copolymer essentially containing a styrene-based monomer unit and a cinnamic acid-based monomer, and is preferably a copolymer containing an unsaturated carboxylic acid-based monomer unit and/or an unsaturated carboxylic acid ester-based monomer unit as necessary.
――不飽和カルボン酸系単量体単位――
本発明に係るスチレン系樹脂は、スチレン系単量体単位と、桂皮酸系単量体と、不飽和カルボン酸系単量体単位と、を含有する共重合体であることが好ましい。本発明に係るスチレン系樹脂中に不飽和カルボン酸系単量体単位が存在すると、耐熱性を向上させるという効果をさらに奏する。
--Unsaturated carboxylic acid monomer units--
The styrene-based resin according to the present invention is preferably a copolymer containing a styrene-based monomer unit, a cinnamic acid-based monomer, and an unsaturated carboxylic acid-based monomer unit. When the unsaturated carboxylic acid-based monomer unit is present in the styrene-based resin according to the present invention, the effect of improving heat resistance is further achieved.
本明細書において「不飽和カルボン酸系単量体単位」は、不飽和カルボン酸系単量体由来の繰り返し単位をいう。当該不飽和カルボン酸系単量体としては、無水マレイン酸、マレイン酸、フマル酸、イタコン酸等が挙げられる。 In this specification, "unsaturated carboxylic acid monomer unit" refers to a repeating unit derived from an unsaturated carboxylic acid monomer. Examples of such unsaturated carboxylic acid monomers include maleic anhydride, maleic acid, fumaric acid, and itaconic acid.
本発明に係るスチレン系樹脂中における不飽和カルボン酸系単量体単位の含有量はスチレン系単量体単位、桂皮酸系単量体、及びその他単量体単位の合計量を（１００質量％）に対して、１～８質量％であることが好ましい。 The content of unsaturated carboxylic acid monomer units in the styrene-based resin according to the present invention is preferably 1 to 8% by mass relative to the total amount (100% by mass) of styrene-based monomer units, cinnamic acid-based monomers, and other monomer units.
不飽和カルボン酸系単量体単位が共重合体中に１質量％以上存在すると、耐熱性を向上させるという効果を奏する。不飽和カルボン酸系単量体単位が共重合体中に８質量％以下存在すると、耐熱性と流動性のバランスに優れるという効果を奏する。 When the unsaturated carboxylic acid monomer unit is present in the copolymer at 1% by mass or more, the effect of improving heat resistance is achieved. When the unsaturated carboxylic acid monomer unit is present in the copolymer at 8% by mass or less, the effect of achieving an excellent balance between heat resistance and fluidity is achieved.
――不飽和カルボン酸エステル系単量体単位――
本発明に係るスチレン系樹脂は、スチレン系単量体単位と、桂皮酸系単量体と、不飽和カルボン酸エステル系単量体単位と、を含有する共重合体であることが好ましい。
--Unsaturated carboxylate monomer units--
The styrene-based resin according to the present invention is preferably a copolymer containing a styrene-based monomer unit, a cinnamic acid-based monomer, and an unsaturated carboxylate-based monomer unit.
スチレン系樹脂は、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以外のその他の単量体単位を、所望の効果を損なわない範囲で更に含有することができるが、典型的には、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からなる。その他の単量体単位の含有量は、スチレン系共重合樹脂１００質量％に対して、０～１０質量％としてよい。 The styrene-based resin may further contain other monomer units besides the styrene-based monomer units, unsaturated carboxylic acid-based monomer units, and unsaturated carboxylic acid ester-based monomer units to the extent that the desired effect is not impaired, but typically consists of styrene-based monomer units, unsaturated carboxylic acid-based monomer units, and unsaturated carboxylic acid ester-based monomer units. The content of the other monomer units may be 0 to 10% by mass relative to 100% by mass of the styrene-based copolymer resin.
スチレン系共重合樹脂中のスチレン系単量体単位、桂皮酸系単量体単位、及び任意成分の不飽和カルボン酸エステル系単量体単位の含有量は、それぞれ、前記共重合樹脂を核磁気共鳴（１Ｈ－ＮＭＲ）測定装置で測定したときのスペクトルの積分比から求めることができる。 The contents of the styrene-based monomer unit, the cinnamic acid-based monomer unit, and the optional unsaturated carboxylate-based monomer unit in the styrene-based copolymer resin can be determined from the integral ratio of the spectrum when the copolymer resin is measured with a nuclear magnetic resonance ( 1H -NMR) measurement device.
本実施形態において、スチレン系共重合樹脂の重量平均分子量（Ｍｗ）は、５００００以上であり、５万～５０万であることが好ましい。Ｍｗは、より好ましくは５万～４０万、更に好ましくは６万～３０万である。Ｍｗが５万～５０万であると、成形性と流動性とのバランスに優れる樹脂が得られる傾向にある。スチレン系共重合樹脂のＭｎ、及びＭｗは、ゲルパーミエイション・クロマトグラフィーによりポリスチレン標準換算で測定することができる。 In this embodiment, the weight average molecular weight (Mw) of the styrene copolymer resin is 50,000 or more, and preferably 50,000 to 500,000. Mw is more preferably 50,000 to 400,000, and even more preferably 60,000 to 300,000. When Mw is 50,000 to 500,000, a resin with an excellent balance between moldability and fluidity tends to be obtained. The Mn and Mw of the styrene copolymer resin can be measured by gel permeation chromatography in terms of standard polystyrene.
本発明に係るスチレン系共重合樹脂は、ランダム共重合体、交互共重合体、ブロック共重合体、又はグラフト共重合体が挙げられ、ランダム共重合体がより好ましい。 The styrene-based copolymer resin according to the present invention may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer, with a random copolymer being more preferred.
本発明に係るスチレン系共重合樹脂は、一般式（３）で表わされる繰り返し単位を有することが好ましい。
本実施形態における好適なスチレン系共重合樹脂の一例としては、上記一般式（３）で表わされる繰り返し単位を有し、且つ上記一般式（３）中、Ｒ１及びＲ４はそれぞれ独立して、水素原子、炭素原子数１～３の直鎖状又は分岐状のアルキル基、又はフェニル基を表し、Ｒ２及びＲ５はそれぞれ独立して、水素原子、ハロゲン原子又は炭素原子数１～５の直鎖状又は分岐状のアルキル基を表し、Ｒ３は、水酸基、又は炭素原子数１～１０の直鎖状又は分岐状のアルコキシ基を表し、ａ及びｂはそれぞれ独立して、１～３の整数を表す、スチレン系共重合樹脂が好ましい。 An example of a suitable styrene-based copolymer resin in this embodiment is a styrene-based copolymer resin having a repeating unit represented by the above general formula (3), in which, in the above general formula (3), R 1 and R 4 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a phenyl group; R 2 and R 5 each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms; R 3 represents a hydroxyl group, or a linear or branched alkoxy group having 1 to 10 carbon atoms; and a and b each independently represent an integer of 1 to 3.
上記一般式（３）において、ｎ／（ｎ＋ｍ）が０．０５～０．９０であることが好ましい。また、別の観点では、ｎ／（ｎ＋ｍ）が０．１０～０．８５であることが好ましい。さらに、上記一般式（３）において、ｍ／（ｎ＋ｍ）が０．１０～０．９５であることが好ましい。また、別の観点では、ｍ／（ｎ＋ｍ）が、０．１５～０．９０であることが好ましい。そして、本発明に係るスチレン系共重合樹脂が、一般式（３）で表わされる繰り返し単位から構成される二元共重合体である場合は、ｎ／（ｎ＋ｍ）とｍ／（ｎ＋ｍ）との合計が概ね１になることが好ましい。 In the above general formula (3), n/(n+m) is preferably 0.05 to 0.90. From another perspective, n/(n+m) is preferably 0.10 to 0.85. Furthermore, in the above general formula (3), m/(n+m) is preferably 0.10 to 0.95. From another perspective, m/(n+m) is preferably 0.15 to 0.90. And, when the styrene-based copolymer resin according to the present invention is a binary copolymer composed of repeating units represented by general formula (3), it is preferable that the sum of n/(n+m) and m/(n+m) is approximately 1.
一方、本発明に係るスチレン系共重合樹脂が、一般式（３）で表わされる繰り返し単位と、上記の不飽和カルボン酸系単量体単位及び／又は不飽和カルボン酸エステル系単量体単位と、を有する３以上の多元共重合体である場合において、不飽和カルボン酸系単量体単位の重合度をｐとし、不飽和カルボン酸エステル系単量体単位をｑとすると、
ｎ／（ｎ＋ｍ＋ｐ＋ｑ）は、０．０５～０．８０が好ましい。そして、ｍ／（ｎ＋ｍ＋ｐ＋ｑ）は、０．０５～０．８０が好ましい。また、ｐ／（ｎ＋ｍ＋ｐ＋ｑ）は、０．０１～０．３０が好ましく、ｑ／（ｎ＋ｍ＋ｐ＋ｑ）は、０．０１～０．３０が好ましい。
On the other hand, in the case where the styrene-based copolymer resin according to the present invention is a multicomponent copolymer having three or more repeating units represented by the general formula (3) and the above-mentioned unsaturated carboxylic acid-based monomer units and/or unsaturated carboxylic acid ester-based monomer units, the degree of polymerization of the unsaturated carboxylic acid-based monomer units is represented by p and the degree of polymerization of the unsaturated carboxylic acid ester-based monomer units is represented by q,
n/(n+m+p+q) is preferably 0.05 to 0.80. And, m/(n+m+p+q) is preferably 0.05 to 0.80. Also, p/(n+m+p+q) is preferably 0.01 to 0.30, and q/(n+m+p+q) is preferably 0.01 to 0.30.
＜スチレン系共重合樹脂の製造方法＞
スチレン系共重合樹脂の重合方法については、特に制限はないが、ラジカル重合法として、塊状重合法又は溶液重合法を採用できる。重合方法は、主に、重合原料（単量体成分）を重合させる重合工程と、重合生成物から未反応モノマー、重合溶媒等の揮発分を除去する脱揮工程とからなる。
<Method of producing styrene copolymer resin>
The polymerization method for the styrene copolymer resin is not particularly limited, but a bulk polymerization method or a solution polymerization method can be adopted as a radical polymerization method. The polymerization method mainly comprises a polymerization step of polymerizing the polymerization raw materials (monomer components) and a devolatilization step of removing volatile matters such as unreacted monomers and polymerization solvent from the polymerization product.
スチレン系共重合樹脂の重合方法については、特に制限はないが、ラジカル重合法として、塊状重合法又は溶液重合法を採用できる。重合方法は、主に、重合原料（単量体成分）を重合させる重合工程と、重合生成物から未反応モノマー、重合溶媒等の揮発分を除去する脱揮工程とからなる。 There are no particular limitations on the polymerization method for styrene-based copolymer resins, but bulk polymerization or solution polymerization can be used as radical polymerization methods. The polymerization method mainly consists of a polymerization process in which the polymerization raw materials (monomer components) are polymerized, and a devolatilization process in which volatile matters such as unreacted monomers and polymerization solvents are removed from the polymerization product.
以下、本実施形態のスチレン系共重合樹脂の重合方法についてより詳細に説明する。
スチレン系共重合樹脂を得るために重合原料を重合させる際には、重合原料組成物中に、典型的には重合開始剤及び連鎖移動剤を含有させる。重合開始剤としては、有機過酸化物、例えば、２，２－ビス（ｔ－ブチルペルオキシ）ブタン、１，１－ビス（ｔ－ブチルペルオキシ）シクロヘキサン、ｎ－ブチル－４，４ービス（ｔ－ブチルペルオキシ）バレレート等のペルオキシケタール類、ジ－ｔ－ブチルペルオキシド、ｔ－ブチルクミルペルオキシド、ジクミルペルオキシド等のジアルキルペルオキシド類、アセチルペルオキシド、イソブチリルペルオキシド等のジアシルペルオキシド類、ジイソプロピルペルオキシジカーボネート等のペルオキシジカーボネート類、ｔ－ブチルペルオキシイソプロピルモノカーボネート等のモノカーボネート類、ｔ－ブチルペルオキシアセテート等のペルオキシエステル類、アセチルアセトンペルオキシド等のケトンペルオキシド類、ｔ－ブチルヒドロペルオキシド等のヒドロペルオキシド類等が挙げられる。分解速度と重合速度との観点から、とりわけｔ－ブチルペルオキシイソプロピルモノカーボネートならびに１，１－ビス（ｔ－ブチルペルオキシ）シクロヘキサンが好ましい。
Hereinafter, the polymerization method for the styrene-based copolymer resin of this embodiment will be described in more detail.
When the polymerization raw materials are polymerized to obtain a styrene-based copolymer resin, a polymerization initiator and a chain transfer agent are typically contained in the polymerization raw material composition. Examples of the polymerization initiator include organic peroxides, for example, peroxyketals such as 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)cyclohexane, and n-butyl-4,4-bis(t-butylperoxy)valerate, dialkyl peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide, and dicumyl peroxide, diacyl peroxides such as acetyl peroxide and isobutyryl peroxide, peroxydicarbonates such as diisopropyl peroxydicarbonate, monocarbonates such as t-butylperoxyisopropyl monocarbonate, peroxyesters such as t-butylperoxyacetate, ketone peroxides such as acetylacetone peroxide, and hydroperoxides such as t-butyl hydroperoxide. From the viewpoints of decomposition rate and polymerization rate, t-butylperoxyisopropyl monocarbonate and 1,1-bis(t-butylperoxy)cyclohexane are particularly preferred.
スチレン系共重合樹脂の重合時には必要に応じて連鎖移動剤を使用することもできる。連鎖移動剤としては、例えば、αメチルスチレンリニアダイマー、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、ｎ－オクチルメルカプタン等が挙げられる。 When polymerizing the styrene copolymer resin, a chain transfer agent can be used as necessary. Examples of chain transfer agents include α-methylstyrene linear dimer, n-dodecyl mercaptan, t-dodecyl mercaptan, and n-octyl mercaptan.
スチレン系共重合樹脂の重合方法として、必要に応じて、重合溶媒を用いた溶液重合を採用できる。用いられる重合溶媒としては、芳香族炭化水素類、例えば、エチルベンゼン、ジアルキルケトン類、例えば、メチルエチルケトン等、アミド類、例えば、ジメチルホルムアミド等が挙げられ、それぞれ、単独で用いてもよいし２種以上を組み合わせて用いてもよい。重合生成物の溶解性を低下させない範囲で、他の重合溶媒、例えば、脂肪族炭化水素類等を、芳香族炭化水素類に更に混合することができる。これらの重合溶媒は、全単量体１００質量部に対して、３０質量部を超えない範囲で使用するのが好ましい。全単量体１００質量部に対して重合溶媒が３０質量部以下であれば、重合速度の低下、及び得られる樹脂の機械的強度の低下が抑制されるため好ましい。重合前に、全単量体１００質量部に対して５～３０質量部の割合で添加しておくことが、品質が均一化し易く、重合温度制御の点でも好ましい。 As a polymerization method for the styrene-based copolymer resin, solution polymerization using a polymerization solvent can be adopted as necessary. Examples of the polymerization solvent to be used include aromatic hydrocarbons, such as ethylbenzene, dialkyl ketones, such as methyl ethyl ketone, and amides, such as dimethylformamide. Each of these may be used alone or in combination of two or more. Other polymerization solvents, such as aliphatic hydrocarbons, can be further mixed with the aromatic hydrocarbons as long as the solubility of the polymerization product is not reduced. It is preferable to use these polymerization solvents in an amount not exceeding 30 parts by mass per 100 parts by mass of the total monomers. If the polymerization solvent is 30 parts by mass or less per 100 parts by mass of the total monomers, the decrease in the polymerization rate and the decrease in the mechanical strength of the resulting resin are suppressed, which is preferable. It is preferable to add 5 to 30 parts by mass per 100 parts by mass of the total monomers before polymerization, as this makes it easier to uniformize the quality and is also preferable in terms of polymerization temperature control.
本実施形態のスチレン系共重合樹脂には、スチレン系樹脂において使用が一般的な各種添加剤を、適宜添加してもよい。例えば、安定剤、酸化防止剤、紫外線吸収剤、滑剤、離型剤、可塑剤、ブロッキング防止剤、帯電防止剤、防曇剤、ゴム状重合体粒子（スチレン系共重合樹脂を内包してもよい）、鉱油等が挙げられる。また、スチレン－ブタジエンブロック共重合体やＭＢＳ樹脂等の補強材についても物性を損なわない範囲で添加してもよい。これらの各種添加剤の含有量は、スチレン系共重合樹脂１００質量％に対して、１０質量％以下であることが好ましい。添加剤の配合の方法については特に規定はないが、例えば、共重合体の重合時に添加して重合する方法や樹脂組成物を得る際、ブレンダーで予め添加剤を混合し、押出機やバンバリーミキサー等にて溶融混錬する方法等が挙げられる。 The styrene copolymer resin of this embodiment may be appropriately added with various additives that are generally used in styrene resins. Examples include stabilizers, antioxidants, UV absorbers, lubricants, release agents, plasticizers, antiblocking agents, antistatic agents, antifogging agents, rubber-like polymer particles (which may contain styrene copolymer resins), mineral oils, etc. Reinforcing materials such as styrene-butadiene block copolymers and MBS resins may also be added to the extent that they do not impair the physical properties. The content of these various additives is preferably 10% by mass or less relative to 100% by mass of the styrene copolymer resin. There are no particular regulations regarding the method of blending the additives, but examples include a method in which the additives are added during polymerization of the copolymer and polymerized, or a method in which the additives are mixed in advance in a blender when obtaining a resin composition, and then melt-kneaded in an extruder, Banbury mixer, etc.
スチレン系共重合樹脂を得るための重合工程で用いる装置は、特に制限はなく、用いる重合方法に応じて適宜選択すればよい。例えば、塊状重合による場合には、完全混合型反応器を１基又は複数基連結した重合装置を用いることができる。 There are no particular limitations on the apparatus used in the polymerization process to obtain a styrene-based copolymer resin, and it may be selected appropriately depending on the polymerization method used. For example, in the case of bulk polymerization, a polymerization apparatus having one or more connected complete mixing reactors can be used.
また、脱揮工程についても特に制限はなく、塊状重合で行う場合、最終的に未反応モノマーが、好ましくは５０質量％以下、より好ましくは４０質量％以下になるまで重合を進め、かかる未反応モノマー等の揮発分を除去するために、既知の方法にて脱揮処理する。例えば、フラッシュドラム、二軸脱揮器、薄膜蒸発器、押出機等の通常の脱揮装置を用いることができるが、滞留部の少ない脱揮装置が好ましい。脱揮方法としては、例えば、加熱下で減圧して揮発分を除去する方法、又は揮発分除去の目的に設計された押出機等を通して除去する方法が望ましい。 There are also no particular limitations on the devolatilization step. When bulk polymerization is used, polymerization is continued until the final amount of unreacted monomer is preferably 50% by mass or less, more preferably 40% by mass or less, and devolatilization treatment is performed by a known method to remove volatile matters such as unreacted monomer. For example, a conventional devolatilizer such as a flash drum, twin-screw devolatilizer, thin-film evaporator, or extruder can be used, but a devolatilizer with a small retention area is preferred. Desirable devolatilization methods include, for example, a method of removing volatile matters by reducing pressure under heating, or a method of removing volatile matters through an extruder or the like designed for the purpose of removing volatile matters.
「スチレン系樹脂の製造方法」
本発明に係るスチレン系共重合樹脂の製造方法の一例について、以下説明する。
本発明に係るスチレン系共重合樹脂の好ましい製造方法は、スチレン系単量体と、桂皮酸系単量体と、を混合して混合溶液を調製する工程と、前記混合溶液を所定の重合条件で重合する工程とを含む。
"Method of manufacturing styrene-based resin"
An example of the method for producing the styrene copolymer resin according to the present invention will be described below.
A preferred method for producing the styrene-based copolymer resin according to the present invention includes the steps of mixing a styrene-based monomer and a cinnamic acid-based monomer to prepare a mixed solution, and polymerizing the mixed solution under predetermined polymerization conditions.
＜＜所定の重合条件＞＞
上述した所定の重合条件とは、混合溶液を反応器にフィードし、その混合溶液を６０～２００度にする工程を含み、反応器中は窒素等の不活性ガス雰囲気若しくは空気雰囲気でもよい。重合は熱重合、開始剤重合、光重合のいずれでもよく、光重合の場合の好ましい照射条件の波長は１５０～４００ｎｍである。重合の反応活性種はラジカル、アニオン、カチオンのいずれでもよく、望ましくはラジカルである。
<<Prescribed Polymerization Conditions>>
The above-mentioned predetermined polymerization conditions include a step of feeding the mixed solution into a reactor and heating the mixed solution to 60 to 200 degrees, and the reactor may be in an inert gas atmosphere such as nitrogen or an air atmosphere. The polymerization may be any of thermal polymerization, initiator polymerization, and photopolymerization, and the preferred irradiation condition in the case of photopolymerization is a wavelength of 150 to 400 nm. The reactive species of the polymerization may be any of radicals, anions, and cations, and is preferably a radical.
＜スチレン系共重合樹脂を含む組成物＞
本発明に係るスチレン系共重合樹脂は、１種単独の樹脂としてもよく、２種以上を組み合わせた混合樹脂としてもよい。混合樹脂の場合、スチレン系共重合樹脂の諸物性は、混合樹脂について定められてよい。混合樹脂は、２種以上の樹脂を混練することにより得ることができる。
<Composition containing styrene copolymer resin>
The styrene-based copolymer resin according to the present invention may be a single resin or a mixed resin of two or more types. In the case of a mixed resin, the physical properties of the styrene-based copolymer resin may be determined for the mixed resin. The mixed resin can be obtained by kneading two or more resins.
本実施形態のスチレン系共重合樹脂を含む組成物は、上記スチレン系共重合樹脂以外に、一般的な各種添加剤を、公知の作用効果を達成するために添加してもよい。例えば安定剤、酸化防止剤、紫外線吸収剤、滑剤、離型剤、可塑剤、ブロッキング防止剤、帯電防止剤、防曇剤、ゴム状重合体粒子（スチレン系共重合樹脂を内包してもよい）、鉱油等があげられる。また、スチレン－ブタジエンブロック共重合体又はＭＢＳ樹脂等の補強材についても物性を損なわない範囲で添加してもよい。配合の方法については特に規定はないが、例えば、重合時に添加して重合する方法、又は重合後溶融混練する前に、ブレンダーであらかじめ添加剤を混合し、その後、押出機又はバンバリーミキサー等にて溶融混錬する方法等が挙げられる。 In addition to the styrene copolymer resin, the composition containing the styrene copolymer resin of this embodiment may contain various general additives to achieve known effects. Examples of such additives include stabilizers, antioxidants, UV absorbers, lubricants, release agents, plasticizers, antiblocking agents, antistatic agents, antifogging agents, rubber-like polymer particles (which may contain styrene copolymer resins), and mineral oils. Reinforcing materials such as styrene-butadiene block copolymers or MBS resins may also be added to the extent that they do not impair the physical properties. There are no particular restrictions on the method of blending, but examples include a method in which the additives are added during polymerization and polymerized, or a method in which the additives are mixed in a blender before melt-kneading after polymerization, and then melt-kneaded in an extruder or Banbury mixer.
本実施形態において、上述のようスチレン系共重合樹脂を含む組成物には各種添加剤を添加させることができるが、スチレン系共重合樹脂を含む組成物中のスチレン系共重合樹脂の含有量は、特に限定されないが９５質量％以上であることが好ましく、より好ましくは９７質量％であり、さらに好ましくは９９質量％以上である。 In this embodiment, various additives can be added to the composition containing the styrene-based copolymer resin as described above, but the content of the styrene-based copolymer resin in the composition containing the styrene-based copolymer resin is not particularly limited, but is preferably 95% by mass or more, more preferably 97% by mass, and even more preferably 99% by mass or more.
以下、本発明を実施例及び比較例に具体的に説明するが、本発明はこれらの実施例に限定されると解されるべきでない。なお、実施例及び比較例における樹脂の分析、評価方法は、下記のとおりである。 The present invention will be specifically described below with reference to examples and comparative examples, but it should not be understood that the present invention is limited to these examples. The resins in the examples and comparative examples were analyzed and evaluated as follows.
［分析・評価方法］
（１）ガラス転移温度の測定
得られたスチレン系共重合樹脂０．１ｇを５ｇのトルエンに溶解し、その溶液を２０ｍｌのメタノール中に０．２ｍｌ／ｓｅｃの速度で滴下した。沈殿物をろ過して回収した。この操作を２回繰り返し、沈殿物風乾後、１６０℃、真空下で１時間乾燥した。そして、得られた乾燥後の共重合樹脂のＴｇを（株）島津製作所製のＤＳＣ－６０を使って、ＪＩＳ Ｋ７１２１に準拠して求めた。
具体的には、窒素下、１０℃／ｍｉｎで室温から２００℃まで昇温し、その後１０℃／ｍｉｎで室温まで戻し、再び１０℃／ｍｉｎで２００℃まで昇温した。２度目の昇温過程で測定されるガラス転移温度をＴｇとした。
[Analysis and evaluation method]
(1) Measurement of glass transition temperature 0.1 g of the obtained styrene copolymer resin was dissolved in 5 g of toluene, and the solution was dropped into 20 ml of methanol at a rate of 0.2 ml/sec. The precipitate was collected by filtration. This operation was repeated twice, and the precipitate was air-dried and then dried at 160°C under vacuum for 1 hour. The Tg of the obtained copolymer resin after drying was measured using a DSC-60 manufactured by Shimadzu Corporation in accordance with JIS K7121.
Specifically, the temperature was increased from room temperature to 200° C. at 10° C./min under nitrogen, then returned to room temperature at 10° C./min, and again increased to 200° C. at 10° C./min. The glass transition temperature measured during the second temperature increase was taken as Tg.
（２）重量平均分子量、数平均分子量、及びＺ平均分子量の測定
得られたスチレン系共重合樹脂の重量平均分子量（Ｍｗ）、スチレン系共重合樹脂の数平均分子量（Ｍｎ）、Ｚ平均分子量（Ｍｚ）、分子量分布（Ｍｚ／Ｍｗ）は、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）を用いて以下の条件で測定した。
試料調製 ：テトラヒドロフランにスチレン系共重合樹脂を約０．０５質量％となるよう溶解
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使用
(2) Measurement of Weight Average Molecular Weight, Number Average Molecular Weight, and Z Average Molecular Weight The weight average molecular weight (Mw) of the obtained styrene-based copolymer resin, the number average molecular weight (Mn), Z average molecular weight (Mz), and molecular weight distribution (Mz/Mw) of the obtained styrene-based copolymer resin were measured using gel permeation chromatography (GPC) under the following conditions.
Sample preparation: Dissolve styrene copolymer resin in tetrahydrofuran to a concentration of approximately 0.05% by mass. Measurement conditions: Instrument: TOSOH HLC-8220GPC
(Gel Permeation Chromatography)
Column: super HZM-H
Temperature: 40°C
Carrier: THF 0.35 mL/min
Detector: RI, UV: 254 nm
Calibration curve: Using standard PS manufactured by TOSOH
（３）スチレン系単量体単位、桂皮酸系単量体単位、及び任意成分であるその他単量体単位の含有量の測定
スチレン系共重合樹脂中のスチレン系単量体単位、桂皮酸系単量体単位、及び任意成分であるその他単量体単位の含有量（質量％）は、核磁気共鳴（１Ｈ－ＮＭＲ）装置で測定したスペクトルの積分比から、組成比を定量した。試料調製：スチレン系共重合樹脂７５ｍｇをｄ３－クロロホルム ０．７５ｍＬに室温で溶解した。
測定機器：日本電子（株）製、ＪＮＭ ＥＣＡ－５００
測定条件：測定温度６０℃、観測核１Ｈ、積算回数２５６回、繰返し時間４５秒
(3) Measurement of the contents of styrene-based monomer units, cinnamic acid-based monomer units, and other optional monomer units The contents (mass%) of styrene-based monomer units, cinnamic acid-based monomer units, and other optional monomer units in the styrene-based copolymer resin were quantified from the integral ratio of the spectrum measured by a nuclear magnetic resonance ( 1H -NMR) device. Sample preparation: 75 mg of the styrene-based copolymer resin was dissolved in 0.75 mL of d3-chloroform at room temperature.
Measuring equipment: JEOL Ltd., JNM ECA-500
Measurement conditions: Measurement temperature 60°C, observation nucleus 1H , number of integrations 256, repetition time 45 seconds
（４）成形性の評価
２００℃にて得られたスチレン系共重合樹脂を、長辺６ｃｍ×短辺１．５ｃｍ×厚み０．３ｃｍの空間を有する圧縮成形用金型に入れアルミ板で挟み、それを２００℃で予熱を４分行い、続いて２００℃、１０ＭＰａで１分間加圧し、その後水冷した圧縮板で冷却を２分間行うことにより圧縮成形を行った。そして、取出しの際に成形片に割れが生じたものは、成形性を不良（×）とし、割れなく取り出せた際は成形性を良（○）として評価を行った。
(4) Evaluation of moldability The styrene copolymer resin obtained at 200°C was placed in a compression molding mold having a space of 6 cm long side x 1.5 cm short side x 0.3 cm thick, sandwiched between aluminum plates, preheated at 200°C for 4 minutes, pressurized at 200°C and 10 MPa for 1 minute, and then cooled with a water-cooled compression plate for 2 minutes to perform compression molding. The moldability was evaluated as poor (x) when the molded piece cracked when removed, and as good (o) when the molded piece could be removed without cracking.
（５）ゲル化の評価
スチレン系共重合樹脂の外観不良の原因である樹脂中のゲルは、脱揮工程若しくは押し出し機内での長時間滞留部で脱水縮合により生成される。評価用促進試験として、真空ポンプを備えた乾燥機中にて、サンプルとして５×１０２Ｐａで２３０℃、６時間加熱したスチレン系共重合樹脂を０．１ｇ取り、テトラヒドロフラン１０ｍＬに溶解させ２４時間静置し、不要物の有無を目視にて観測した。
(5) Evaluation of gelation The gel in the resin, which is the cause of the poor appearance of the styrene copolymer resin, is generated by dehydration condensation in the devolatilization process or in the long-term residence part in the extruder. As an accelerated evaluation test, 0.1 g of a styrene copolymer resin heated at 230°C for 6 hours at 5 x 102 Pa in a dryer equipped with a vacuum pump was taken as a sample, dissolved in 10 mL of tetrahydrofuran, and left to stand for 24 hours, and the presence or absence of unnecessary matter was visually observed.
［実施例１］
重合原料組成液をスチレン３９．９８質量部、桂皮酸４０質量部、Ｎ，Ｎ－ジメチルホルムアミド２０質量部、ｔ－ブチルペルオキシイソプロピルモノカーボネート（以下パーブチルＩ）０．０２質量部を混合溶解させ、攪拌機を備えた１．０Ｌのフラスコに加え、１００℃に設定したオイルバスに浸漬し、攪拌しながら所定時間反応経過後オイルバスから取り出した。室温まで冷却後全量をメタノールに沈殿させ沈殿物をろ過して回収した。これを５００ｍＬのＴＨＦに溶解しメタノールに再度沈殿させ、得られたスチレン系共重合樹脂を風乾後、１６０℃、真空下で１時間乾燥させ、スチレン系共重合樹脂Ａを製造した。上述の製造法によって得られた共重合組成及び評価結果を表１に示す。
[Example 1]
The polymerization raw material composition liquid was mixed and dissolved with 39.98 parts by mass of styrene, 40 parts by mass of cinnamic acid, 20 parts by mass of N,N-dimethylformamide, and 0.02 parts by mass of t-butylperoxyisopropyl monocarbonate (hereinafter referred to as Perbutyl I), and added to a 1.0 L flask equipped with a stirrer, immersed in an oil bath set at 100 ° C., and after a predetermined reaction time while stirring, removed from the oil bath. After cooling to room temperature, the entire amount was precipitated in methanol, and the precipitate was collected by filtration. This was dissolved in 500 mL of THF and precipitated again in methanol, and the obtained styrene-based copolymer resin was air-dried and then dried at 160 ° C. under vacuum for 1 hour to produce styrene-based copolymer resin A. The copolymer composition and evaluation results obtained by the above-mentioned production method are shown in Table 1.
［実施例２］
重合原料組成液をスチレン９．９８質量部、桂皮酸メチル９０質量部、パーブチルＩ ０．０２質量部を混合溶解させ、攪拌機を備えた１．０Ｌのフラスコに加え、１００℃に設定したオイルバスに浸漬し、攪拌しながら所定時間反応経過後オイルバスから取り出した。室温まで冷却後全量をメタノールに沈殿させ沈殿物をろ過して回収した。これを５００ｍＬのＴＨＦに溶解しメタノールに再度沈殿させ、得られたスチレン系共重合樹脂を風乾後、１６０℃、真空下で１時間乾燥させ、スチレン系共重合樹脂Ｂを製造した。上述の製造法によって得られた共重合組成及び評価結果を表１に示す。
[Example 2]
The polymerization raw material composition liquid was mixed and dissolved with 9.98 parts by mass of styrene, 90 parts by mass of methyl cinnamate, and 0.02 parts by mass of Perbutyl I, and added to a 1.0 L flask equipped with a stirrer, immersed in an oil bath set at 100 ° C., and after a predetermined reaction time while stirring, it was removed from the oil bath. After cooling to room temperature, the entire amount was precipitated in methanol, and the precipitate was collected by filtration. This was dissolved in 500 mL of THF and precipitated again in methanol, and the obtained styrene-based copolymer resin was air-dried and then dried at 160 ° C. under vacuum for 1 hour to produce styrene-based copolymer resin B. The copolymer composition and evaluation results obtained by the above-mentioned production method are shown in Table 1.
［実施例３］
重合原料組成液をスチレン４９．９８質量部、桂皮酸メチル５０質量部、パーブチルＩ ０．０２質量部を混合溶解させ、攪拌機を備えた１．０Ｌのフラスコに加え、１００℃に設定したオイルバスに浸漬し、攪拌しながら所定時間反応経過後オイルバスから取り出した。室温まで冷却後全量をメタノールに沈殿させ沈殿物をろ過して回収した。これを５００ｍＬのＴＨＦに溶解しメタノールに再度沈殿させ、得られたスチレン系共重合樹脂を風乾後、１６０℃、真空下で１時間乾燥させ、スチレン系共重合樹脂Ｃを製造した。上述の製造法によって得られた共重合組成及び評価結果を表１に示す。
[Example 3]
The polymerization raw material composition liquid was mixed and dissolved with 49.98 parts by mass of styrene, 50 parts by mass of methyl cinnamate, and 0.02 parts by mass of Perbutyl I, and added to a 1.0 L flask equipped with a stirrer, immersed in an oil bath set at 100 ° C., and after a predetermined reaction time while stirring, it was removed from the oil bath. After cooling to room temperature, the entire amount was precipitated in methanol, and the precipitate was collected by filtration. This was dissolved in 500 mL of THF and precipitated again in methanol, and the obtained styrene-based copolymer resin was air-dried and then dried at 160 ° C. under vacuum for 1 hour to produce styrene-based copolymer resin C. The copolymer composition and evaluation results obtained by the above-mentioned production method are shown in Table 1.
［実施例４］
重合原料組成液をスチレン９９．９８質量部、桂皮酸エチル９０質量部、パーブチルＩ ０．０２質量部を混合溶解させ、攪拌機を備えた１．０Ｌのフラスコに加え、１００℃に設定したオイルバスに浸漬し、攪拌しながら所定時間反応経過後オイルバスから取り出した。室温まで冷却後全量をメタノールに沈殿させ沈殿物をろ過して回収した。これを５００ｍＬのＴＨＦに溶解しメタノールに再度沈殿させ、得られたスチレン系共重合樹脂を風乾後、１６０℃、真空下で１時間乾燥させ、スチレン系共重合樹脂Ｄを製造した。上述の製造法によって得られた共重合組成及び評価結果を表１に示す。
[Example 4]
The polymerization raw material composition liquid was mixed and dissolved with 99.98 parts by mass of styrene, 90 parts by mass of ethyl cinnamate, and 0.02 parts by mass of Perbutyl I, and added to a 1.0 L flask equipped with a stirrer, immersed in an oil bath set at 100 ° C., and after a predetermined reaction time while stirring, it was removed from the oil bath. After cooling to room temperature, the entire amount was precipitated in methanol, and the precipitate was collected by filtration. This was dissolved in 500 mL of THF and precipitated again in methanol, and the obtained styrene-based copolymer resin was air-dried and then dried at 160 ° C. under vacuum for 1 hour to produce styrene-based copolymer resin D. The copolymer composition and evaluation results obtained by the above-mentioned production method are shown in Table 1.
［実施例５］
重合原料組成液をスチレン９．９８質量部、桂皮酸エチル９０質量部、パーブチルＩ ０．０２質量部を混合溶解させ、攪拌機を備えた１．０Ｌのフラスコに加え、１００℃に設定したオイルバスに浸漬し、攪拌しながら所定時間反応経過後オイルバスから取り出した。室温まで冷却後全量をメタノールに沈殿させ沈殿物をろ過して回収した。これを５００ｍＬのＴＨＦに溶解しメタノールに再度沈殿させ、得られたスチレン系共重合樹脂を風乾後、１６０℃ 、真空下で１時間乾燥させ、スチレン系共重合樹脂Ｅを製造した。上述の製造法によって得られた共重合組成及び評価結果を表１に示す。
[Example 5]
The polymerization raw material composition liquid was mixed and dissolved with 9.98 parts by mass of styrene, 90 parts by mass of ethyl cinnamate, and 0.02 parts by mass of Perbutyl I, and added to a 1.0 L flask equipped with a stirrer, immersed in an oil bath set at 100 ° C., and after a predetermined reaction time while stirring, it was removed from the oil bath. After cooling to room temperature, the entire amount was precipitated in methanol, and the precipitate was collected by filtration. This was dissolved in 500 mL of THF and precipitated again in methanol, and the obtained styrene-based copolymer resin was air-dried and then dried at 160 ° C. under vacuum for 1 hour to produce styrene-based copolymer resin E. The copolymer composition and evaluation results obtained by the above-mentioned production method are shown in Table 1.
［実施例６］
重合原料組成液をスチレン４９．９８質量部、桂皮酸イソプロピル５０質量部、パーブチルＩ ０．０２質量部を混合溶解させ、攪拌機を備えた１．０Ｌのフラスコに加え、１００℃に設定したオイルバスに浸漬し、攪拌しながら所定時間反応経過後オイルバスから取り出した。室温まで冷却後全量をメタノールに沈殿させ沈殿物をろ過して回収した。これを５００ｍＬのＴＨＦに溶解しメタノールに再度沈殿させ、得られたスチレン系共重合樹脂を風乾後、１６０℃、真空下で１時間乾燥させ、スチレン系共重合樹脂Ｆを製造した。上述の製造法によって得られた共重合組成及び評価結果を表１に示す。
[Example 6]
The polymerization raw material composition liquid was mixed and dissolved with 49.98 parts by mass of styrene, 50 parts by mass of isopropyl cinnamate, and 0.02 parts by mass of Perbutyl I, and added to a 1.0 L flask equipped with a stirrer, immersed in an oil bath set at 100 ° C., and after a predetermined reaction time while stirring, it was removed from the oil bath. After cooling to room temperature, the entire amount was precipitated in methanol, and the precipitate was collected by filtration. This was dissolved in 500 mL of THF and precipitated again in methanol, and the obtained styrene-based copolymer resin was air-dried and then dried at 160 ° C. under vacuum for 1 hour to produce styrene-based copolymer resin F. The copolymer composition and evaluation results obtained by the above-mentioned production method are shown in Table 1.
［実施例７］
重合原料組成液をスチレン８９．９６質量部、桂皮酸メチル１０質量部、パーブチルＩ ０．０２質量部を混合溶解させ、攪拌機を備えた１．０Ｌのフラスコに加え、１００℃に設定したオイルバスに浸漬し、攪拌しながら所定時間反応経過後オイルバスから取り出した。室温まで冷却後全量をメタノールに沈殿させ沈殿物をろ過して回収した。これを５００ｍＬのＴＨＦに溶解しメタノールに再度沈殿させ、得られたスチレン系樹脂を風乾後、１６０℃、真空下で１時間乾燥させ、スチレン系樹脂Ｇを製造した。上述の製造法によって得られた共重合組成及び評価結果を表１に示す。
[Example 7]
The polymerization raw material composition liquid was mixed and dissolved with 89.96 parts by mass of styrene, 10 parts by mass of methyl cinnamate, and 0.02 parts by mass of Perbutyl I, and added to a 1.0 L flask equipped with a stirrer, immersed in an oil bath set at 100 ° C., and after a predetermined reaction time while stirring, it was removed from the oil bath. After cooling to room temperature, the entire amount was precipitated in methanol, and the precipitate was collected by filtration. This was dissolved in 500 mL of THF and precipitated again in methanol, and the obtained styrene-based resin was air-dried and then dried at 160 ° C. under vacuum for 1 hour to produce styrene-based resin G. The copolymerization composition and evaluation results obtained by the above-mentioned production method are shown in Table 1.
［実施例８］
重合原料組成液をスチレン９．９８質量部、桂皮酸メチル４５質量部、桂皮酸エチル４５質量部、パーブチルＩ ０．０２質量部を混合溶解させ、攪拌機を備えた１．０Ｌのフラスコに加え、１００℃に設定したオイルバスに浸漬し、攪拌しながら所定時間反応経過後オイルバスから取り出した。室温まで冷却後全量をメタノールに沈殿させ沈殿物をろ過して回収した。これを５００ｍＬのＴＨＦに溶解しメタノールに再度沈殿させ、得られたスチレン系共重合樹脂を風乾後、１６０℃、真空下で１時間乾燥させ、スチレン系共重合樹脂Ｈを製造した。上述の製造法によって得られた共重合組成及び評価結果を表１に示す。
[Example 8]
The polymerization raw material composition liquid was mixed and dissolved with 9.98 parts by mass of styrene, 45 parts by mass of methyl cinnamate, 45 parts by mass of ethyl cinnamate, and 0.02 parts by mass of Perbutyl I, and added to a 1.0 L flask equipped with a stirrer, immersed in an oil bath set at 100 ° C., and after a predetermined time of reaction while stirring, it was removed from the oil bath. After cooling to room temperature, the entire amount was precipitated in methanol, and the precipitate was collected by filtration. This was dissolved in 500 mL of THF and precipitated again in methanol, and the obtained styrene-based copolymer resin was air-dried and then dried at 160 ° C. under vacuum for 1 hour to produce styrene-based copolymer resin H. The copolymer composition and evaluation results obtained by the above-mentioned production method are shown in Table 1.
［比較例１］
重合原料組成液をスチレン９９．９８質量部、パーブチルＩ ０．０２質量部を混合溶解させ、攪拌機を備えた１．０Ｌのフラスコに加え、１００℃に設定したオイルバスに浸漬し、攪拌しながら所定時間反応経過後オイルバスから取り出した。室温まで冷却後全量をメタノールに沈殿させ沈殿物をろ過して回収した。これを５００ｍＬのＴＨＦに溶解しメタノールに再度沈殿させ、得られたスチレン系樹脂を風乾後、１６０℃、真空下で１時間乾燥させ、スチレン系樹脂Ｉを製造した。上述の製造法によって得られた共重合組成及び評価結果を表１に示す。桂皮酸系単量体が含まれていないため、スチレン系樹脂ＨのＴｇは１０５℃にであった。
[Comparative Example 1]
The polymerization raw material composition liquid was mixed and dissolved with 99.98 parts by mass of styrene and 0.02 parts by mass of Perbutyl I, and added to a 1.0 L flask equipped with a stirrer, immersed in an oil bath set at 100 ° C., and after a predetermined time of reaction while stirring, it was removed from the oil bath. After cooling to room temperature, the entire amount was precipitated in methanol, and the precipitate was collected by filtration. This was dissolved in 500 mL of THF and precipitated again in methanol, and the obtained styrene-based resin was air-dried and then dried at 160 ° C. under vacuum for 1 hour to produce styrene-based resin I. The copolymerization composition and evaluation results obtained by the above-mentioned production method are shown in Table 1. Since no cinnamic acid-based monomer was contained, the Tg of styrene-based resin H was 105 ° C.
［比較例２］
重合原料組成液をスチレン９３．９６質量部、桂皮酸メチル６質量部、パーブチルＩ ０．０４質量部を混合溶解させ、攪拌機を備えた１．０Ｌのフラスコに加え、１００℃に設定したオイルバスに浸漬し、攪拌しながら所定時間反応経過後オイルバスから取り出した。室温まで冷却後全量をメタノールに沈殿させ沈殿物をろ過して回収した。これを５００ｍＬのＴＨＦに溶解しメタノールに再度沈殿させ、得られたスチレン系樹脂を風乾後、１６０℃、真空下で１時間乾燥させ、スチレン系樹脂Ｊを製造した。上述の製造法によって得られた共重合組成及び評価結果を表１に示す。ガラス転移温度は１０７℃と耐熱性は向上したが、開始剤量を増加させたため、得られたスチレン系樹脂Ｉの重量平均分子量Ｍｗが４５０００まで低下し、圧縮成形時に割れが生じ成形が不良であった。
[Comparative Example 2]
The polymerization raw material composition liquid was mixed and dissolved with 93.96 parts by mass of styrene, 6 parts by mass of methyl cinnamate, and 0.04 parts by mass of Perbutyl I, and added to a 1.0 L flask equipped with a stirrer, immersed in an oil bath set at 100 ° C., and after a predetermined time of reaction while stirring, it was removed from the oil bath. After cooling to room temperature, the entire amount was precipitated in methanol, and the precipitate was collected by filtration. This was dissolved in 500 mL of THF and precipitated again in methanol, and the obtained styrene-based resin was air-dried and then dried at 160 ° C. under vacuum for 1 hour to produce styrene-based resin J. The copolymerization composition and evaluation results obtained by the above-mentioned production method are shown in Table 1. The glass transition temperature was 107 ° C., and heat resistance was improved, but the amount of initiator was increased, so the weight average molecular weight Mw of the obtained styrene-based resin I was reduced to 45,000, and cracks occurred during compression molding, resulting in poor molding.
［比較例３］
重合原料組成液をスチレン４９．９６質量部、桂皮酸メチル５０質量部、パーブチルＩ ０．０４質量部を混合溶解させ、攪拌機を備えた１．０Ｌのフラスコに加え、１００℃に設定したオイルバスに浸漬し、攪拌しながら所定時間反応経過後オイルバスから取り出した。室温まで冷却後全量をメタノールに沈殿させ沈殿物をろ過して回収した。これを５００ｍＬのＴＨＦに溶解しメタノールに再度沈殿させ、得られたスチレン系樹脂を風乾後、１６０℃、真空下で１時間乾燥させ、スチレン系樹脂Ｋを製造した。上述の製造法によって得られた共重合組成及び評価結果を表１に示す。開始剤量を増加させたため、得られたスチレン系樹脂Ｋの重量平均分子量Ｍｗが４１０００まで低下し、圧縮成形時に割れが生じ成形が不良であった。
[Comparative Example 3]
The polymerization raw material composition liquid was mixed and dissolved with 49.96 parts by mass of styrene, 50 parts by mass of methyl cinnamate, and 0.04 parts by mass of Perbutyl I, and added to a 1.0 L flask equipped with a stirrer, immersed in an oil bath set at 100 ° C., and after a predetermined time of reaction while stirring, it was removed from the oil bath. After cooling to room temperature, the entire amount was precipitated in methanol, and the precipitate was collected by filtration. This was dissolved in 500 mL of THF and precipitated again in methanol, and the obtained styrene-based resin was air-dried and then dried at 160 ° C. under vacuum for 1 hour to produce styrene-based resin K. The copolymerization composition and evaluation results obtained by the above-mentioned production method are shown in Table 1. Since the amount of initiator was increased, the weight average molecular weight Mw of the obtained styrene-based resin K was reduced to 41,000, and cracks occurred during compression molding, resulting in poor molding.
［比較例４］
重合原料組成液をスチレン７０．８質量部、メタクリル酸５．２質量部、エチルベンゼン２３．９７質量部、パーヘキサＣ０．０３質量部を混合溶解させ、攪拌機を備え、温度コントロール可能な４．２Ｌの完全混合型反応器から連続して排出される重合体溶液を真空ベントつき押出機で、１０ｔｏｒｒの減圧下、脱揮後ペレタイズし、スチレン系樹脂Ｌを製造した。押出機の温度は２００～２５０℃に設定した。上述の製造法によって得られた共重合組成及び評価結果を表１に示す。スチレン系樹脂ＬのＴｇは１２３℃であったが、加熱試験にてゲルが発生した。
The polymerization raw material composition liquid was mixed and dissolved with 70.8 parts by mass of styrene, 5.2 parts by mass of methacrylic acid, 23.97 parts by mass of ethylbenzene, and 0.03 parts by mass of Perhexa C, and the polymer solution continuously discharged from a 4.2 L complete mixing type reactor equipped with a stirrer and capable of controlling the temperature was pelletized after devolatilization under a reduced pressure of 10 torr in an extruder equipped with a vacuum vent to produce styrene-based resin L. The temperature of the extruder was set to 200 to 250°C. The copolymerization composition and evaluation results obtained by the above-mentioned production method are shown in Table 1. The Tg of styrene-based resin L was 123°C, but gel was generated in a heating test.
本発明のスチレン系樹脂組成物は、耐熱性、機械的強度、外観、及び透明性に優れるため、非発泡及び発泡の押出板、シート、更にこれらの二次加工による成形品、例えば、射出成形等による成形品（例えば、弁当、惣菜等の食品の容器包装材料）の製造に好適に使用可能である。 The styrene-based resin composition of the present invention has excellent heat resistance, mechanical strength, appearance, and transparency, and can therefore be suitably used for the manufacture of non-foamed and foamed extruded boards and sheets, as well as molded products obtained by secondary processing of these, such as molded products obtained by injection molding (e.g., food container packaging materials for boxed lunches, prepared meals, and other foods).
Claims (6)
Ｒ ４ 及びＲ ５ はそれぞれ独立して、水素原子、ハロゲン原子、置換若しくは無置換の炭素原子数１から１０までの直鎖状若しくは分岐状のアルコキシ基、アミノ基、ニトロ基、シアノ基、置換若しくは無置換の炭素原子数１から１０までの直鎖状若しくは分岐状のアルキル基、又はフェニル基を表し、Ｒ ３ はそれぞれ独立して、ハロゲン原子、置換若しくは無置換の炭素原子数１から１０までの直鎖状若しくは分岐状のアルコキシ基、アミノ基、ニトロ基、置換若しくは無置換の炭素原子数１から１０までの直鎖状若しくは分岐状のアルキル基、又はフェニル基を表し、ｎ及びｍはそれぞれ独立して重合度を表わし、ａ及びｂはそれぞれ独立して、１～５の整数を表わす。） The styrene copolymer resin according to any one of claims 1 to 4, having a repeating unit represented by general formula (3).
R 4 and R 5 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted linear or branched alkoxy group having 1 to 10 carbon atoms, an amino group, a nitro group, a cyano group, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a phenyl group; R 3 each independently represents a halogen atom, a substituted or unsubstituted linear or branched alkoxy group having 1 to 10 carbon atoms, an amino group, a nitro group, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a phenyl group; n and m each independently represent a degree of polymerization; and a and b each independently represent an integer of 1 to 5.
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| CN104861105A (en) | 2014-02-21 | 2015-08-26 | 上海飞凯光电材料股份有限公司 | Copolymerization resin and preparation method thereof |
| JP2018095848A (en) | 2016-12-07 | 2018-06-21 | 東ソー株式会社 | Copolymer and retardation film using the same |
| JP2019172867A (en) | 2018-03-29 | 2019-10-10 | 東ソー株式会社 | Copolymer and optical film using the same |
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| CN104861105A (en) | 2014-02-21 | 2015-08-26 | 上海飞凯光电材料股份有限公司 | Copolymerization resin and preparation method thereof |
| JP2018095848A (en) | 2016-12-07 | 2018-06-21 | 東ソー株式会社 | Copolymer and retardation film using the same |
| JP2019172867A (en) | 2018-03-29 | 2019-10-10 | 東ソー株式会社 | Copolymer and optical film using the same |
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