KR20210041493A - Acrylate-styrene-acrylonitrile based resin composition, article comprising the same and method for manufacturing the article - Google Patents
Acrylate-styrene-acrylonitrile based resin composition, article comprising the same and method for manufacturing the article Download PDFInfo
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- KR20210041493A KR20210041493A KR1020200124402A KR20200124402A KR20210041493A KR 20210041493 A KR20210041493 A KR 20210041493A KR 1020200124402 A KR1020200124402 A KR 1020200124402A KR 20200124402 A KR20200124402 A KR 20200124402A KR 20210041493 A KR20210041493 A KR 20210041493A
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- alkyl methacrylate
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- 239000011342 resin composition Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- ACYXOHNDKRVKLH-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile prop-2-enoic acid Chemical compound OC(=O)C=C.N#CC=CC=CC1=CC=CC=C1 ACYXOHNDKRVKLH-UHFFFAOYSA-N 0.000 title 1
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 91
- -1 poly(alkyl methacrylate Chemical compound 0.000 claims abstract description 60
- 229920001971 elastomer Polymers 0.000 claims abstract description 35
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000000314 lubricant Substances 0.000 claims description 20
- 238000000465 moulding Methods 0.000 claims description 17
- 239000008188 pellet Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000012760 heat stabilizer Substances 0.000 claims description 6
- 238000001746 injection moulding Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 16
- 238000012545 processing Methods 0.000 abstract description 9
- 239000003086 colorant Substances 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 17
- 239000003999 initiator Substances 0.000 description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 15
- 238000002347 injection Methods 0.000 description 14
- 239000007924 injection Substances 0.000 description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 8
- 239000004816 latex Substances 0.000 description 8
- 229920000126 latex Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000012662 bulk polymerization Methods 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 238000010422 painting Methods 0.000 description 5
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- 239000011541 reaction mixture Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 230000002542 deteriorative effect Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 2
- VKLDCBNUFZIAFK-UHFFFAOYSA-N 1,1-bis[2,4-bis(2-phenylpropan-2-yl)phenyl]-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C1=CC=CC=C1)C1=C(C=CC(=C1)C(C)(C)C1=CC=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C1=CC=CC=C1)C(C)(C)C1=CC=CC=C1 VKLDCBNUFZIAFK-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 2
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- CHNGPLVDGWOPMD-UHFFFAOYSA-N 2-ethylbutyl 2-methylprop-2-enoate Chemical compound CCC(CC)COC(=O)C(C)=C CHNGPLVDGWOPMD-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 2
- CCMZKOAOMQSOQA-UHFFFAOYSA-N 3-methyl-2-methylidenebutanenitrile Chemical compound CC(C)C(=C)C#N CCMZKOAOMQSOQA-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- HVDJXXVDNDLBQY-UHFFFAOYSA-N 5-butyl-5-ethyl-2-(2,4,6-tritert-butylphenoxy)-1,3,2-dioxaphosphinane Chemical compound O1CC(CCCC)(CC)COP1OC1=C(C(C)(C)C)C=C(C(C)(C)C)C=C1C(C)(C)C HVDJXXVDNDLBQY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
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- 239000004793 Polystyrene Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- FMMQDMHSGNXJSQ-UHFFFAOYSA-N n,n-diphenylhydroxylamine Chemical compound C=1C=CC=CC=1N(O)C1=CC=CC=C1 FMMQDMHSGNXJSQ-UHFFFAOYSA-N 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 2
- HRJXKKSJPNWKCP-UNXDAHLPSA-N (1E,2Z)-3-hydroxy-5,9,17-trioxo-4,5:9,10-disecoandrosta-1(10),2-dien-4-oic acid Chemical compound C1CC(=O)[C@@H](CCC(=O)C(=C/C=C(\O)C(O)=O)/C)[C@@H]2CCC(=O)[C@]21C HRJXKKSJPNWKCP-UNXDAHLPSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- BWJKLDGAAPQXGO-UHFFFAOYSA-N 2,2,6,6-tetramethyl-4-octadecoxypiperidine Chemical compound CCCCCCCCCCCCCCCCCCOC1CC(C)(C)NC(C)(C)C1 BWJKLDGAAPQXGO-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
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- ITLDHFORLZTRJI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-5-octoxyphenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1N1N=C2C=CC=CC2=N1 ITLDHFORLZTRJI-UHFFFAOYSA-N 0.000 description 1
- RTNVDKBRTXEWQE-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-butan-2-yl-4-tert-butylphenol Chemical compound CCC(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O RTNVDKBRTXEWQE-UHFFFAOYSA-N 0.000 description 1
- VQMHSKWEJGIXGA-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-dodecyl-4-methylphenol Chemical compound CCCCCCCCCCCCC1=CC(C)=CC(N2N=C3C=CC=CC3=N2)=C1O VQMHSKWEJGIXGA-UHFFFAOYSA-N 0.000 description 1
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- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- LHHLLQVLJAUUDT-UHFFFAOYSA-N 2-ethylhexyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCC(CC)CCCC)=CC(N2N=C3C=CC=CC3=N2)=C1O LHHLLQVLJAUUDT-UHFFFAOYSA-N 0.000 description 1
- AWEVLIFGIMIQHY-UHFFFAOYSA-N 2-ethylhexyl 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCC(CC)CCCC)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O AWEVLIFGIMIQHY-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- GUCMKIKYKIHUTM-UHFFFAOYSA-N 3,3,5,5-tetramethyl-1-[2-(3,3,5,5-tetramethyl-2-oxopiperazin-1-yl)ethyl]piperazin-2-one Chemical compound O=C1C(C)(C)NC(C)(C)CN1CCN1C(=O)C(C)(C)NC(C)(C)C1 GUCMKIKYKIHUTM-UHFFFAOYSA-N 0.000 description 1
- YLUZWKKWWSCRSR-UHFFFAOYSA-N 3,9-bis(8-methylnonoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCC(C)C)OCC21COP(OCCCCCCCC(C)C)OC2 YLUZWKKWWSCRSR-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- VXVUDUCBEZFQGY-UHFFFAOYSA-N 4,4-dimethylpentanenitrile Chemical compound CC(C)(C)CCC#N VXVUDUCBEZFQGY-UHFFFAOYSA-N 0.000 description 1
- HPFWYRKGZUGGPB-UHFFFAOYSA-N 4,6-dichloro-n-(2,4,4-trimethylpentan-2-yl)-1,3,5-triazin-2-amine Chemical compound CC(C)(C)CC(C)(C)NC1=NC(Cl)=NC(Cl)=N1 HPFWYRKGZUGGPB-UHFFFAOYSA-N 0.000 description 1
- UQAMDAUJTXFNAD-UHFFFAOYSA-N 4-(4,6-dichloro-1,3,5-triazin-2-yl)morpholine Chemical compound ClC1=NC(Cl)=NC(N2CCOCC2)=N1 UQAMDAUJTXFNAD-UHFFFAOYSA-N 0.000 description 1
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- BVNWQSXXRMNYKH-UHFFFAOYSA-N 4-phenyl-2h-benzotriazole Chemical compound C1=CC=CC=C1C1=CC=CC2=C1NN=N2 BVNWQSXXRMNYKH-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229940122361 Bisphosphonate Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BSYVARKFDABJOO-UHFFFAOYSA-N C(C)(C)(C)N(O)C(C)(C)C.C(C)(C)(C)N(O)C(C)(C)C Chemical compound C(C)(C)(C)N(O)C(C)(C)C.C(C)(C)(C)N(O)C(C)(C)C BSYVARKFDABJOO-UHFFFAOYSA-N 0.000 description 1
- XBNLOTGSWNMQBY-UHFFFAOYSA-N CC1(NC(CC(C1)C(C(=O)O)(CCCCCCCC(=O)O)C1CC(NC(C1)(C)C)(C)C)(C)C)C.C(CCCCCCCCC(=O)OC1CC(NC(C1)(C)C)(C)C)(=O)OC1CC(NC(C1)(C)C)(C)C Chemical compound CC1(NC(CC(C1)C(C(=O)O)(CCCCCCCC(=O)O)C1CC(NC(C1)(C)C)(C)C)(C)C)C.C(CCCCCCCCC(=O)OC1CC(NC(C1)(C)C)(C)C)(=O)OC1CC(NC(C1)(C)C)(C)C XBNLOTGSWNMQBY-UHFFFAOYSA-N 0.000 description 1
- XTJYYRKHFBFRJV-UHFFFAOYSA-N CC1(NC(CC(C1)C(C(=O)O)N(C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)(C)C)C Chemical compound CC1(NC(CC(C1)C(C(=O)O)N(C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)(C)C)C XTJYYRKHFBFRJV-UHFFFAOYSA-N 0.000 description 1
- NGNMLTBWULBASN-UHFFFAOYSA-N CC1=C(C=CC(=C1)C)N(O)C1=C(C=C(C=C1)C)C.CC1=C(C=CC(=C1)C)N(O)C1=C(C=C(C=C1)C)C Chemical compound CC1=C(C=CC(=C1)C)N(O)C1=C(C=C(C=C1)C)C.CC1=C(C=CC(=C1)C)N(O)C1=C(C=C(C=C1)C)C NGNMLTBWULBASN-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- HNMRRUQBVGLAAH-UHFFFAOYSA-N N,N-dibenzylhydroxylamine Chemical compound C(C1=CC=CC=C1)N(O)CC1=CC=CC=C1.C(C1=CC=CC=C1)N(O)CC1=CC=CC=C1 HNMRRUQBVGLAAH-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BVVRPVFKRUVCJX-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)CO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)CO BVVRPVFKRUVCJX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)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 BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- OBIWICSASILRRH-UHFFFAOYSA-K [Na+].C(CCCCC)C(C(C(=O)[O-])S(=O)(=O)[O-])(C(=O)[O-])CCCCCC.[Na+].[Na+] Chemical compound [Na+].C(CCCCC)C(C(C(=O)[O-])S(=O)(=O)[O-])(C(=O)[O-])CCCCCC.[Na+].[Na+] OBIWICSASILRRH-UHFFFAOYSA-K 0.000 description 1
- GMMUEAUOVZZIAE-UHFFFAOYSA-K [Na+].C1(CCCCC1)C(C(C(=O)[O-])S(=O)(=O)[O-])(C(=O)[O-])C1CCCCC1.[Na+].[Na+] Chemical compound [Na+].C1(CCCCC1)C(C(C(=O)[O-])S(=O)(=O)[O-])(C(=O)[O-])C1CCCCC1.[Na+].[Na+] GMMUEAUOVZZIAE-UHFFFAOYSA-K 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003831 antifriction material Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- OSIVCXJNIBEGCL-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCCCCCCCC)C(C)(C)C1 OSIVCXJNIBEGCL-UHFFFAOYSA-N 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- VRBLLGLKTUGCSG-UHFFFAOYSA-N methyl 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O VRBLLGLKTUGCSG-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- UKJARPDLRWBRAX-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine Chemical compound C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 UKJARPDLRWBRAX-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XQAABEDPVQWFPN-UHFFFAOYSA-N octyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCCCCCCCC)=CC(N2N=C3C=CC=CC3=N2)=C1O XQAABEDPVQWFPN-UHFFFAOYSA-N 0.000 description 1
- DMFXLIFZVRXRRR-UHFFFAOYSA-N octyl 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCCCCCCCC)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O DMFXLIFZVRXRRR-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- ZPNJBTBYIHBSIG-UHFFFAOYSA-N phenyl-(2,2,6,6-tetramethylpiperidin-4-yl)methanone Chemical compound C1C(C)(C)NC(C)(C)CC1C(=O)C1=CC=CC=C1 ZPNJBTBYIHBSIG-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- PFMVLFSAAABWQD-UHFFFAOYSA-M potassium;octadecyl sulfate Chemical compound [K+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O PFMVLFSAAABWQD-UHFFFAOYSA-M 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- WQQPDTLGLVLNOH-UHFFFAOYSA-M sodium;4-hydroxy-4-oxo-3-sulfobutanoate Chemical compound [Na+].OC(=O)CC(C([O-])=O)S(O)(=O)=O WQQPDTLGLVLNOH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- SKIVFJLNDNKQPD-UHFFFAOYSA-N sulfacetamide Chemical compound CC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 SKIVFJLNDNKQPD-UHFFFAOYSA-N 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000012360 testing method Methods 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
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- PDJWOCLSJFHNTE-UHFFFAOYSA-N tris(2,4-ditert-butylphenyl) phosphite Chemical compound P(OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)(OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C.P(OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)(OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C PDJWOCLSJFHNTE-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/06—Making preforms by moulding the material
- B29B11/10—Extrusion moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract
Description
본 발명은 ASA계 수지 조성물, 이를 포함하는 성형품 및 이 성형품의 제조방법에 관한 것으로, 보다 상세하게는 기계적 물성과 가공성이 우수하고, 특히 일정 이상의 가공 두께에서도 착색성과 투명도가 뛰어나 무도장, 투명, 고채도 또는 특수 칼라 등의 성질을 갖는 고부가가치의 제품에 적용 가능한 ASA계 수지 조성물, 이를 포함하는 성형품 및 이 성형품의 제조방법에 관한 것이다. The present invention relates to an ASA-based resin composition, a molded article including the same, and a method of manufacturing the molded article, and more particularly, it has excellent mechanical properties and processability. Or, it relates to an ASA-based resin composition applicable to high value-added products having properties such as special colors, a molded article including the same, and a method of manufacturing the molded article.
아크릴레이트 화합물-스티렌-아크릴로니트릴 공중합체(이하, 'ASA 수지'라 함)는 중합체 내에 불안정한 이중결합을 포함하지 않아 내후성이 매우 우수하여 전기·전자 부품, 건축용 자재(비닐 사이딩 등), 압출 프로파일(Profile), 자동차 부품 등 다양한 분야에 광범위하게 적용되고 있다.The acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as'ASA resin') does not contain unstable double bonds in the polymer, so it has excellent weather resistance. It is widely applied in various fields such as Profile and automobile parts.
다만, 최근에 옥외용 제품 분야에서 무도장, 투명, 고채도, 특수 칼라 등의 성질을 갖는 고부가가치의 제품에 대한 시장의 요구가 지속적으로 증가하고 있으나, ASA 수지 자체의 착색성과 투명성의 태생적 한계를 극복하지 못하고 있어, 시장의 요구를 충족시킬 수 있는 ASA 수지에 대한 개발이 필요한 실정이다. However, in the field of outdoor products, market demands for high value-added products with properties such as non-painting, transparency, high saturation, and special colors are constantly increasing, but the inherent limitations of colorability and transparency of ASA resin itself have been overcome. As such, there is a need to develop an ASA resin that can meet the demands of the market.
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 기계적 물성과 가공성이 우수하고, 특히 일정 이상의 가공 두께에서도 착색성과 투명도가 뛰어나 무도장, 투명, 고채도 또는 특수 칼라 등의 성질을 갖는 고부가가치의 제품에 적용 가능한 ASA계 수지 조성물, 이를 포함하는 성형품 및 이 성형품의 제조방법을 제공하는 것을 목적으로 한다. In order to solve the problems of the prior art as described above, the present invention has excellent mechanical properties and workability, and in particular, excellent colorability and transparency even at a certain processing thickness or higher, a high value-added product having properties such as non-painting, transparency, high saturation or special color It is an object of the present invention to provide an ASA resin composition applicable to, a molded article including the same, and a method of manufacturing the molded article.
본 발명의 상기 목적 및 기타 목적들은 하기 설명된 본 발명에 의하여 모두 달성될 수 있다.All of the above and other objects of the present invention can be achieved by the present invention described below.
상기의 목적을 달성하기 위하여, 본 발명은 평균입경 50 내지 150 nm의 아크릴레이트 고무를 코어로 하는 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체 20 내지 47 중량%, 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체 23 내지 55 중량% 및 폴리(알킬 메타크릴레이트) 수지 25 내지 45 중량%를 포함하는 ASA계 수지 조성물 및 이를 포함하는 성형품을 제공한다. In order to achieve the above object, the present invention is an acrylate rubber having an average particle diameter of 50 to 150 nm as a core-an aromatic vinyl compound-a vinyl cyan compound graft copolymer 20 to 47% by weight, an alkyl methacrylate- It provides an ASA-based resin composition comprising 23 to 55% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer and 25 to 45% by weight of a poly(alkyl methacrylate) resin, and a molded article including the same.
또한, 본 발명은 평균입경 50 내지 150 nm의 아크릴레이트 고무를 코어로 하는 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체 20 내지 47 중량%, 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체 23 내지 55 중량% 및 폴리(알킬 메타크릴레이트) 수지 25 내지 45 중량%를 200 내지 300 ℃ 및 100 내지 500 rpm 조건 하에서 혼련 및 압출하여 펠렛으로 제조하는 단계; 및 제조된 펠렛을 성형온도 200 내지 300 ℃에서 시트성형 또는 사출성형하여 성형품을 제조하는 단계를 포함하는 성형품의 제조방법을 제공한다.In addition, the present invention is an acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer 20 to 47% by weight of an acrylate rubber having an average particle diameter of 50 to 150 nm as a core, alkyl methacrylate-aromatic vinyl compound-vinyl cyanide Preparing a pellet by kneading and extruding 23 to 55% by weight of a compound copolymer and 25 to 45% by weight of a poly(alkyl methacrylate) resin under conditions of 200 to 300°C and 100 to 500 rpm; And sheet molding or injection molding the produced pellets at a molding temperature of 200 to 300° C. to produce a molded product.
본 발명에 따르면 기계적 물성과 가공성이 우수하고, 특히 일정 이상의 가공 두께에서도 착색성과 투명도가 뛰어나 무도장, 투명, 고채도 또는 특수 칼라 등의 성질을 갖는 고부가가치의 제품에 적용 가능한 ASA계 수지 조성물, 이를 포함하는 성형품 및 이 성형품의 제조방법을 제공하는 효과가 있다. According to the present invention, excellent mechanical properties and processability, in particular, excellent colorability and transparency even at a certain processing thickness or higher, ASA resin composition applicable to high value-added products having properties such as non-painting, transparency, high saturation or special color, including the same. There is an effect of providing a molded article and a method of manufacturing the molded article.
이하 본 기재의 ASA계 수지 조성물, 이를 포함하는 성형품 및 이 성형품의 제조방법을 상세하게 설명한다. Hereinafter, the ASA-based resin composition of the present disclosure, a molded article including the same, and a method of manufacturing the molded article will be described in detail.
본 발명자들은 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체, 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체 및 폴리(알킬 메타크릴레이트) 수지를 소정 함량비로 포함하는 ASA계 수지 조성물의 경우, 기계적 물성과 가공성이 종래 ASA계 수지 조성물 대비 동등 또는 그 이상을 유지하면서도 0.5 T 이상의 가공 두께에서 착색성과 투명도 등이 뛰어남을 확인하고, 이를 토대로 더욱 연구에 매진하여 본 발명을 완성하게 되었다.The inventors of the present invention are ASA-based resins comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, an alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer, and a poly(alkyl methacrylate) resin in a predetermined content ratio. In the case of the composition, it was confirmed that the mechanical properties and processability were equal to or higher than those of the conventional ASA-based resin composition, while the colorability and transparency were excellent at a processing thickness of 0.5 T or more, and based on this, further research was conducted to complete the present invention. Became.
본 발명의 ASA계 수지 조성물은 평균입경 50 내지 150 nm의 아크릴레이트 고무를 코어로 하는 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체 20 내지 47 중량%, 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체 23 내지 55 중량% 및 폴리(알킬 메타크릴레이트) 수지 25 내지 45 중량%를 포함하는 것을 특징으로 한다. 이 범위 내에서 기계적 물성과 가공성이 우수하고, 특히 일정 이상의 가공 두께에서도 착색성과 투명도가 뛰어나 무도장, 투명, 고채도 또는 특수 칼라 등의 성질을 갖는 고부가가치의 제품에 적용 가능한 이점이 있다.The ASA-based resin composition of the present invention comprises an acrylate rubber having an average particle diameter of 50 to 150 nm as a core-an acrylate-aromatic vinyl compound-a vinyl cyan compound graft copolymer of 20 to 47% by weight, an alkyl methacrylate-aromatic vinyl compound -It is characterized by comprising 23 to 55% by weight of a vinyl cyan compound copolymer and 25 to 45% by weight of a poly(alkyl methacrylate) resin. Within this range, mechanical properties and processability are excellent, and in particular, the colorability and transparency are excellent even at a certain thickness or more, and there is an advantage that can be applied to high value-added products having properties such as non-painting, transparency, high saturation or special color.
이하, 본 기재의 열가소성 수지 조성물을 구성하는 각 성분을 상세히 살펴보면 다음과 같다.Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure will be described in detail.
A) 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체A) Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
본 기재의 A) 그라프트 공중합체의 아크릴레이트 고무는 일례로 평균입경이 50 내지 150 nm일 수 있고, 바람직하게는 60 내지 140 nm며, 보다 바람직하게는 70 내지 140 nm, 더욱 바람직하게 80 내지 140 nm인데, 이 범위 내에서 최종 제조되는 열가소성 수지 조성물에 우수한 내후성, 착색성, 충격강도 및 표면 광택 특성을 부여할 수 있다.The acrylate rubber of the A) graft copolymer of the present disclosure may, for example, have an average particle diameter of 50 to 150 nm, preferably 60 to 140 nm, more preferably 70 to 140 nm, even more preferably 80 to It is 140 nm, and within this range, excellent weather resistance, colorability, impact strength, and surface gloss properties can be imparted to the final thermoplastic resin composition.
본 기재에서 평균입경은 동적 광산란법(dynamic light scattering)을 이용하여 측정할 수 있고, 상세하게는 Nicomp 380 장비(제조사: PSS)를 이용하여 가우시안 모드로 인텐시티(intensity) 값으로 측정할 수 있다.In the present description, the average particle diameter can be measured using dynamic light scattering, and in detail, it can be measured as an intensity value in Gaussian mode using Nicomp 380 equipment (manufacturer: PSS).
상기 A) 그라프트 공중합체는 일례로 20 내지 47 중량%, 바람직하게 20 내지 40 중량%, 보다 바람직하게는 20 내지 35 중량%, 더욱 바람직하게는 20 내지 30 중량%이며, 이 범위 내에서 기계적 강도와 유동성의 밸런스가 우수하고, 특히 투명도와 착색성 및 내후성이 뛰어난 효과가 있다.The A) graft copolymer is, for example, 20 to 47% by weight, preferably 20 to 40% by weight, more preferably 20 to 35% by weight, even more preferably 20 to 30% by weight, and mechanically within this range It has an excellent balance of strength and fluidity, and is particularly effective in transparency, colorability, and weather resistance.
상기 A) 그라프트 공중합체는 일례로 아크릴레이트 고무 40 내지 60 중량%, 방향족 비닐 화합물 25 내지 45 중량% 및 비닐시안 화합물 10 내지 20 중량%를 포함하여 이루어질 수 있고, 이 범위 내에서 내후성, 유동성, 인장강도 및 충격강도가 우수한 효과가 있다.The A) graft copolymer may include, for example, 40 to 60% by weight of an acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound, and within this range, weather resistance and fluidity , Tensile strength and impact strength are excellent.
바람직한 예로, 상기 A) 그라프트 공중합체는 아크릴레이트 고무 45 내지 55 중량%, 방향족 비닐 화합물 30 내지 50 중량% 및 비닐시안 화합물 5 내지 20 중량%를 포함하여 이루어질 수 있고, 이 범위 내에서 내후성, 유동성, 인장강도 및 충격강도가 우수한 효과가 있다.As a preferred example, the A) graft copolymer may comprise 45 to 55% by weight of an acrylate rubber, 30 to 50% by weight of an aromatic vinyl compound, and 5 to 20% by weight of a vinyl cyanide compound, and within this range, weather resistance, It has excellent fluidity, tensile strength and impact strength.
보다 바람직한 예로, 상기 A) 그라프트 공중합체는 아크릴레이트 고무 45 내지 55 중량%, 방향족 비닐 화합물 30 내지 40 중량% 및 비닐시안 화합물 10 내지 20 중량%를 포함하여 이루어질 수 있고, 이 범위 내에서 내후성, 유동성, 인장강도 및 충격강도가 우수한 효과가 있다.In a more preferred example, the A) graft copolymer may comprise 45 to 55% by weight of an acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound, and weather resistance within this range , Fluidity, tensile strength and impact strength are excellent.
본 기재에서 어떤 화합물을 포함하여 이루어진 중합체란 그 화합물을 포함하여 중합된 중합체를 의미하는 것으로, 중합된 중합체 내 단위체가 그 화합물로부터 유래한다.In the present description, a polymer comprising a compound refers to a polymer polymerized including the compound, and the unit in the polymerized polymer is derived from the compound.
상기 아크릴레이트는 일례로 알킬기의 탄소수가 2 내지 8개인 알킬 아크릴레이트로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 바람직하게는 알킬기의 탄소수가 4 내지 8 개인 알킬 아크릴레이트이며, 더욱 바람직하게는 부틸 아크릴레이트 또는 에틸헥실 아크릴레이트일 수 있다.The acrylate may be, for example, one or more selected from the group consisting of alkyl acrylates having 2 to 8 carbon atoms in the alkyl group, preferably alkyl acrylates having 4 to 8 carbon atoms in the alkyl group, and more preferably butyl acrylic Rate or ethylhexyl acrylate.
상기 방향족 비닐 화합물은 일례로 스티렌, α-메틸스티렌, m-메틸스티렌, p-메틸스티렌 및 p-tert-부틸스티렌으로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 바람직하게는 스티렌이다.The aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-tert-butylstyrene, preferably styrene.
상기 비닐시안 화합물은 일례로 아크릴로니트릴, 메타니트롤로니트릴, 에틸아크릴로니트릴 및 이소프로필아크릴로니트릴로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 바람직하게는 아크릴로니트릴이다.The vinyl cyan compound may be one or more selected from the group consisting of acrylonitrile, metanitroonitrile, ethyl acrylonitrile, and isopropyl acrylonitrile, for example, and is preferably acrylonitrile.
상기 A) 그라프트 공중합체는 일례로 겔 함량이 90 중량% 미만, 30 내지 90 중량%, 바람직하게는 50 내지 90 중량%일 수 있고, 상기 범위 내에서 충격강도, 굴곡강도 등의 기계적 물성이 우수하면서도 내후성이 개선되는 효과가 있다. The A) graft copolymer may have, for example, a gel content of less than 90% by weight, 30 to 90% by weight, preferably 50 to 90% by weight, and mechanical properties such as impact strength and flexural strength within the above range. It is excellent and has the effect of improving weather resistance.
상기 A) 그라프트 공중합체는 일례로 팽윤지수가 6 내지 14, 6 내지 12, 바람직하게는 6 내지 10일 수 있으며, 상기 범위내에서 충격강도, 굴곡강도 등의 기계적 물성이 우수하면서도 내후성이 개선되는 효과가 있다. The A) graft copolymer may have, for example, a swelling index of 6 to 14, 6 to 12, preferably 6 to 10, and has excellent mechanical properties such as impact strength and flexural strength within the above range, while improving weatherability. Has the effect of being.
상기 A) 그라프트 공중합체는 일례로 그라프트율이 20 내지 80%, 25 내지 60%, 바람직하게는 25 내지 40%일 수 있으며, 상기 범위내에서 충격강도, 굴곡강도 등의 기계적 물성이 우수하면서도 내후성이 개선되는 효과가 있다.The A) graft copolymer may have, for example, a graft rate of 20 to 80%, 25 to 60%, preferably 25 to 40%, and has excellent mechanical properties such as impact strength and flexural strength within the above range, while having excellent weather resistance. This has the effect of improving.
본 기재의 겔 함량 및 팽윤지수는 그라프트 공중합체 분말 1g에 아세톤을 가한 후 상온에서 24 hr 동안 교반한 후에 원심분리하여 아세톤에 녹지 않는 부분만 채취한 후에 건조 전/후의 무게를 측정하여 아래의 식으로 겔 함량 및 팽윤지수를 측정할 수 있다.The gel content and swelling index of this substrate are determined by adding acetone to 1 g of the graft copolymer powder, stirring at room temperature for 24 hr, centrifuging, collecting only the part that is not dissolved in acetone, and measuring the weight before/after drying. The gel content and swelling index can be measured by the equation.
* 겔 함량(%) = [원심분리 후 건조 후 무게/시료무게] * 100* Gel content (%) = [Weight/sample weight after centrifugation and drying] * 100
* 팽윤지수=원심분리 후 건조 전 무게/원심분리 후 건조 후 무게* Swelling index = weight before drying after centrifugation / weight after drying after centrifugation
본 기재의 그라프트율은 그라프트 중합체의 수지 라텍스를 응고, 세척, 및 건조하여 분말 형태를 얻고, 이 분말 2g을 아세톤 300㎖에 넣고 24 시간 동안 교반한 후, 이 용액을 초원심 분리기를 이용하여 분리한 후, 분리된 아세톤 용액을 메탄올에 떨어뜨려 그라프트 되지 않는 부분을 얻고, 이를 건조시켜 무게를 측정한다. 이 무게들로부터 하기의 식에 따라서 그라프트율을 계산한다.The graft rate of the present description is obtained by coagulating, washing, and drying the resin latex of the graft polymer to obtain a powder form, and 2 g of this powder is added to 300 ml of acetone and stirred for 24 hours, and the solution is separated using an ultracentrifuge. After that, the separated acetone solution was dropped into methanol to obtain a non-grafted portion, and dried to measure the weight. From these weights, the graft rate is calculated according to the following equation.
* 그라프트율(%) = (그라프트된 단량체의 무게(g) / 고무질 무게(g)) x 100* Graft rate (%) = (weight of grafted monomer (g) / rubbery weight (g)) x 100
상기 A) 그라프트 공중합체는 일례로 유화 중합으로 제조될 수 있고, 상기 유화 중합은 본 발명이 속한 기술분야에서 통상적으로 실시되는 유화 중합인 경우 특별히 제한되지 않지만 알킬 아크릴레이트 고무에 방향족 비닐 단량체 및 비닐시안 단량체를 유화 그라프트 중합하여 제조할 수 있다.The A) graft copolymer may be prepared by emulsion polymerization as an example, and the emulsion polymerization is not particularly limited in the case of emulsion polymerization commonly carried out in the technical field to which the present invention belongs, but an aromatic vinyl monomer and an aromatic vinyl monomer and It can be prepared by emulsion graft polymerization of a vinyl cyano monomer.
상기 A) 그라프트 공중합체 내 포함되는 알킬 아크릴레이트 고무는 일례로, 알킬 아크릴레이트를 유화 중합하여 제조할 수 있으며, 구체적인 예로는 알킬 아크릴레이트, 유화제, 개시제, 그라프트제, 가교제, 전해질 및 물을 첨가하여 유화 중합하는 방법으로 제조될 수 있다.The alkyl acrylate rubber contained in the A) graft copolymer may be prepared by emulsion polymerization of an alkyl acrylate as an example, and specific examples include an alkyl acrylate, an emulsifier, an initiator, a graft agent, a crosslinking agent, an electrolyte, and water. It can be prepared by adding and performing emulsion polymerization.
상기 유화제는 일례로 수용액의 pH가 3 내지 9, 탄소수 12 내지 18인 알킬술포숙신산 금속염 유도체, 또는 탄소수 12 내지 20인 알킬 황산에스테르 또는 그의 술폰산 금속염 유도체인 것이 바람직하다. The emulsifier is preferably an alkyl sulfosuccinic acid metal salt derivative having an aqueous solution having a pH of 3 to 9 and a carbon number of 12 to 18, or an alkyl sulfate ester having 12 to 20 carbon atoms or a metal sulfonic acid derivative thereof.
구체적인 예로, 상기 pH가 3 내지 9, 탄소수 12 내지 18인 알킬술포숙신산금속염 유도체로는 디시클로헥실술포숙신산 나트륨염, 디헥실술포숙신산 나트륨염, 디-2-에틸헥실술포숙신산 나트륨염, 디-2-에틸헥실술포숙신산 칼륨염 또는 디-2-에틸헥실술포숙신산 리튬염이 바람직하며, 탄소수 12 내지 20인 알킬황산에스테르 또는 그의 술폰산 금속염 유도체로는 소듐라우릭술페이트, 소듐도데실술페이트, 소듐도데실벤젠술페이트, 소듐옥타데실술페이트, 소듐올레익술페이트, 포타슘도데실술페이트 또는 포타슘옥타데실술페이트인 것이 바람직하다.As a specific example, examples of the alkyl sulfosuccinic acid metal salt derivative having a pH of 3 to 9 and having 12 to 18 carbon atoms include dicyclohexyl sulfosuccinic acid sodium salt, dihexyl sulfosuccinic acid sodium salt, di-2-ethylhexyl sulfosuccinic acid sodium salt, di- 2-ethylhexyl sulfosuccinate potassium salt or di-2-ethylhexyl sulfosuccinate lithium salt is preferred, and the alkyl sulfuric acid ester having 12 to 20 carbon atoms or its sulfonic acid metal salt derivative is sodium lauric sulfate, sodium dodecyl sulfate, sodium dode It is preferably silbenzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate or potassium octadecyl sulfate.
상기 유화제의 사용량은 상기 알킬 아크릴레이트 고무 총 100 중량부를 기준으로 하여 0.1 내지 1 중량부인 것이 바람직하다.The amount of the emulsifier is preferably 0.1 to 1 parts by weight based on 100 parts by weight of the alkyl acrylate rubber.
상기 개시제는 일례로 무기 또는 유기 과산화물이 바람직하며, 구체적으로는 포타슘퍼술페이트, 소듐퍼술페이트, 또는 암모늄퍼술페이트와 같은 수용성 개시제, 또는 큐멘하이드로퍼옥사이드 또는 벤조일퍼옥사이드 등과 같은 지용성 개시제인 것이 바람직하다. The initiator is preferably an inorganic or organic peroxide, specifically, a water-soluble initiator such as potassium persulfate, sodium persulfate, or ammonium persulfate, or a fat-soluble initiator such as cumene hydroperoxide or benzoyl peroxide. .
상기 개시제의 사용량은 상기 알킬 아크릴레이트 고무 총 100 중량부를 기준으로 0.05 내지 0.2 중량부인 것이 바람직하다.The amount of the initiator used is preferably 0.05 to 0.2 parts by weight based on 100 parts by weight of the alkyl acrylate rubber.
본 기재에서 알킬 아크릴레이트 고무 총 100 중량부는 제조된 알킬 아크릴레이트 고무 자체의 무게이거나, 이의 중합 제조 시 투입된 단량체의 총 중량일 수 있다.In the present description, 100 parts by weight of the total amount of the alkyl acrylate rubber may be the weight of the prepared alkyl acrylate rubber itself, or the total weight of the monomers introduced during the polymerization thereof.
상기 그라프트제는 일례로 알릴메타크릴레이트, 트리알릴이소시아누레이트, 트리알릴아민 및 디알릴아민으로 이루어진 군으로부터 선택된 1종 이상인 것이 바람직하고, 그 사용량은 상기 알킬 아크릴레이트 고무 총 100 중량부를 기준으로 0.01 내지 0.07 중량부가 바람직한데, 이 범위 내에서 본 발명의 목적 달성에 보다 유리하다. The graft agent is preferably at least one selected from the group consisting of allyl methacrylate, triallyl isocyanurate, triallylamine and diallylamine, and the amount used is based on a total of 100 parts by weight of the alkyl acrylate rubber. It is preferably 0.01 to 0.07 parts by weight, which is more advantageous in achieving the object of the present invention within this range.
상기 가교제는 일례로 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 1,3-부탄디올디메타크릴레이트, 1,6-헥산디올디메타크릴레이트, 네오펜틸글리콜디메타크릴레이트, 트리메틸올프로판트리메타크릴레이트 및 트리메틸올메탄트리아크릴레이트로 이루어진 군으로부터 선택된 1종 이상이 바람직하고, 그 사용량은 상기 알킬 아크릴레이트 고무 총 100 중량부를 기준으로 0.02 내지 0.3 중량부가 바람직하다.The crosslinking agent is, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neo At least one selected from the group consisting of pentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, and trimethylolmethane triacrylate is preferred, and the amount used is 0.02 to 0.3 based on a total of 100 parts by weight of the alkyl acrylate rubber. Part by weight is preferred.
상기 그라프트제 및 가교제의 사용으로 본 발명에 따른 상기 알킬 아크릴레이트 고무는 탄성이 더욱 증가할 수 있고 충격강도 등의 물성이 더욱 개선될 수 있다.With the use of the graft agent and the crosslinking agent, the alkyl acrylate rubber according to the present invention can further increase elasticity and improve physical properties such as impact strength.
상기 전해질은 NaHCO3, Na2S2O7 및 K2CO3로 이루어진 군으로부터 선택된 1종 이상이 바람직하고, 그 사용량은 상기 알킬 아크릴레이트 고무 총 100 중량부를 기준으로 0.05 내지 0.4 중량부가 바람직하다.The electrolyte is preferably at least one selected from the group consisting of NaHCO 3 , Na 2 S 2 O 7 and K 2 CO 3 , and the amount used is preferably 0.05 to 0.4 parts by weight based on the total 100 parts by weight of the alkyl acrylate rubber. .
상기 물은 유화 중합이 진행되는 매질의 역할을 하며, 이온교환수인 것이 바람직하고, 그 사용량은 필요에 따라 적절히 선택할 수 있다.The water serves as a medium through which emulsion polymerization proceeds, and is preferably ion-exchanged water, and the amount of water used may be appropriately selected as necessary.
상기 알킬 아크릴레이트 고무의 제조에 사용되는 성분들은 일례로, 연속 투입하거나 또는 연속투입과 일괄투입을 병용하는 방법으로 반응기에 투입하고, 본 발명이 속하는 기술 분야에서 일반적으로 알려진 중합조건을 이용하여 유화 중합함으로써 알킬 아크릴레이트 고무를 제조할 수 있다. 또한, 수득되는 알킬 아크릴레이트 고무는 라텍스의 형태가 될 수 있다.Components used in the manufacture of the alkyl acrylate rubber are, for example, introduced into the reactor by continuous injection or a combination of continuous injection and batch injection, and emulsification using polymerization conditions generally known in the technical field to which the present invention pertains. The alkyl acrylate rubber can be produced by polymerization. In addition, the alkyl acrylate rubber obtained may be in the form of a latex.
상기 알킬 아크릴레이트 고무의 pH는 일례로, 중합 완료 직후 라텍스 상태에서 5 내지 9가 바람직하고, 더욱 바람직하게는 pH가 6 내지 8이며, 이 범위 내에서 라텍스의 안정성 등이 우수한 효과가 있다.As an example, the pH of the alkyl acrylate rubber is preferably 5 to 9 in the latex state immediately after completion of polymerization, more preferably 6 to 8, and the stability of the latex within this range is excellent.
본 기재에서 pH는 pH 미터기를 이용하여 측정할 수 있다.In the present description, the pH can be measured using a pH meter.
상기 A) 그라프트 공중합체는 상기 알킬 아크릴레이트 고무 중합체 백본(backbone)에 방향족 비닐 화합물-비닐시안 화합물 공중합체가 그라프트된 그라프트 공중합체로서 구체적인 예로 상기 알킬 아크릴레이트 고무를 방향족 비닐 화합물, 비닐시안 화합물 및 필요에 따라 중합 첨가제와 혼합하여 유화 중합함으로써 제조할 수 있다.The A) graft copolymer is a graft copolymer in which an aromatic vinyl compound-vinyl cyan compound copolymer is grafted onto the alkyl acrylate rubber polymer backbone. It can be produced by emulsion polymerization by mixing with a cyan compound and a polymerization additive if necessary.
상기 중합 첨가제는 일례로 그라프트제 및/또는 가교제를 포함할 수 있고, 이 그라프트제와 가교제는 상술한 알킬 아크릴레이트 고무의 제조시 사용된 그라프트제와 가교제와 종류면에서 같으며, 그 사용량은 고무를 제외한 단량체 총 100 중량부를 기준으로 같은 중량부 범위 내에서 사용할 수 있다.The polymerization additive may include, for example, a graft agent and/or a crosslinking agent, and the graft agent and the crosslinking agent are the same as the graft agent and the crosslinking agent used in the manufacture of the above-described alkyl acrylate rubber. It may be used within the same range of parts by weight based on a total of 100 parts by weight of the monomer except for.
본 기재에서 단량체는 알킬 아크릴레이트, 알킬 메타크릴레이트, 방향족 비닐 화합물 및 비닐시안 화합물을 포함한다.In the present description, the monomer includes an alkyl acrylate, an alkyl methacrylate, an aromatic vinyl compound, and a vinyl cyan compound.
상기 A) 그라프트 공중합체의 유화 중합은 상기 알킬 아크릴레이트 고무, 방향족 비닐 화합물 및 비닐시안 화합물 외에 용도에 따라 본 발명이 속하는 기술분야에서 통상적으로 사용되는 유화제, 중합 개시제, 분자량 조절제 및 물 등을 사용할 수 있다. 또한, 유화 중합 직후 제조되는 그라프트 공중합체는 라텍스 형태가 될 수 있다.In the emulsion polymerization of the A) graft copolymer, in addition to the alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound, an emulsifier, a polymerization initiator, a molecular weight modifier, and water, which are commonly used in the technical field to which the present invention pertains, depending on the use. Can be used. In addition, the graft copolymer prepared immediately after emulsion polymerization may be in the form of latex.
상기 유화제는 일례로 수용액의 pH가 9 내지 13이고, 탄소수 12 내지 20의 지방산 금속염, 로진산 금속염 등의 카르복실산 금속염 유도체인 것이 바람직하다.The emulsifier is preferably a carboxylic acid metal salt derivative such as a metal salt of a fatty acid having 12 to 20 carbon atoms and a metal salt of rosin acid having a pH of 9 to 13 in an aqueous solution.
상기 탄소수 12 내지 20의 지방산 금속염은 일례로 지방산 나트륨, 라우릴산 나트륨, 올레인산 나트륨 및 올레인산 칼륨으로 이루어진 군으로부터 선택된 1종 이상이 바람직하며, 상기 탄소수 12 내지 20의 로진산 금속염은 일례로 로진산 나트륨, 로진산 칼륨 또는 이들의 혼합이 바람직하다.The fatty acid metal salt having 12 to 20 carbon atoms is preferably at least one selected from the group consisting of fatty acid sodium, sodium laurate, sodium oleate, and potassium oleate, and the metal salt of rosin acid having 12 to 20 carbon atoms is for example rosin acid Sodium, potassium rosinate or mixtures thereof are preferred.
상기 유화제의 사용량은 일례로 반응 혼합물인 알킬 아크릴레이트 고무, 방향족 비닐 화합물 및 비닐시안 화합물을 합한 총 100 중량부를 기준으로 1 내지 2 중량부의 범위 이내의 양으로 사용되는 것이 바람직하다.The amount of the emulsifier is preferably used in an amount within the range of 1 to 2 parts by weight based on a total of 100 parts by weight of the reaction mixture of alkyl acrylate rubber, aromatic vinyl compound, and vinyl cyan compound.
상기 개시제는 일례로 상기 알킬 아크릴레이트 고무의 제조 시 사용될 수 있는 개시제의 종류와 동일한 종류의 개시제가 사용될 수 있으며, 그 사용량은 일례로 상기 반응 혼합물 총 100 중량부를 기준으로 0.05 내지 0.3 중량부가 바람직하다.The initiator may be, for example, an initiator of the same type as that of the initiator that can be used in the manufacture of the alkyl acrylate rubber, and the amount of the initiator is preferably 0.05 to 0.3 parts by weight based on the total 100 parts by weight of the reaction mixture. .
상기 분자량 조절제는 일례로 t-도데실메르캅탄, n-옥틸메르캅탄 또는 이들의 혼합을 사용할 수 있고, 그 사용량은 상기 반응 혼합물 100 중량부를 기준으로 0.02 내지 0.2 중량부가 바람직하다.The molecular weight modifier may be t-dodecyl mercaptan, n-octyl mercaptan, or a mixture thereof, and the amount thereof is preferably 0.02 to 0.2 parts by weight based on 100 parts by weight of the reaction mixture.
상기 물은 이온교환수인 것이 바람직하고, 본 발명이 속하는 기술 분야에서 일반적으로 사용되는 중량으로 사용될 수 있다.The water is preferably ion-exchanged water, and may be used in a weight generally used in the technical field to which the present invention pertains.
상기 유화 그라프트 중합 시 상기 반응 혼합물 및 유화제 등과 같은 중합 첨가제들을 일괄 투입하면 중합시스템의 pH가 일시적으로 상승되어 그라프팅이 어렵고 공중합체 입자의 안정성이 저하되어 입자 내부 구조가 균일하지 못하게 되므로, 유화 그라프트 중합에 의한 상기 A) 그라프트 공중합체의 제조 시에는 상기 반응 혼합물 및 중합 첨가제들을 연속 투입, 구체적인 예로 전체 반응 시간 내에서 1 내지 10 시간 또는 1 내지 5 시간 동안 연속 투입하는 것이 바람직하다. During the emulsion graft polymerization, if polymerization additives such as the reaction mixture and emulsifier are added at once, the pH of the polymerization system is temporarily raised, making grafting difficult and the stability of the copolymer particles decreases, making the internal structure of the particles uneven. When preparing the A) graft copolymer by graft polymerization, it is preferable to continuously add the reaction mixture and polymerization additives, specifically, for 1 to 10 hours or 1 to 5 hours within the total reaction time.
본 기재에서 설명되지 않은 중합 조건은 본 발명이 속하는 기술 분야에서 일반적으로 알려진 중합 조건을 적절히 선택할 수 있음은 당업자에게 자명한 사항임을 밝혀 둔다.It should be noted that polymerization conditions not described herein are obvious to those skilled in the art that the polymerization conditions generally known in the art can be appropriately selected.
본 기재에서 연속 투입이란 일괄 투입과 반대되는 의미로 일정 시간 동안 끊임없이 또는 일정 시간 내에 단계적으로 나누어 투입하는 것을 지칭한다.In the present description, continuous input refers to continuous input for a predetermined period of time or stepwise divided within a predetermined time, as opposed to batch input.
상기 A) 그라프트 공중합체는 일례로, 중합 완료 직후 라텍스 상태에서 pH가 8 내지 11인 것이 바람직하며, 더욱 바람직하게는 pH가 9 내지 10.5인 것이고, 이 범위에서 라텍스의 안정성이 우수한 효과가 있다.The A) graft copolymer is, for example, preferably a pH of 8 to 11 in the latex state immediately after completion of polymerization, more preferably a pH of 9 to 10.5, and the stability of the latex is excellent in this range. .
상기 A) 그라프트 공중합체 라텍스는 구체적인 예로 염화칼슘 수용액을 사용하여 80 내지 90℃ 또는 82 내지 88℃ 및 상압 조건에서 응집하고, 90℃ 초과 내지 100℃ 이하, 또는 92 내지 98℃에서 숙성시켜 탈수 및 세척한 다음, 85 내지 95℃ 또는 88 내지 92℃의 열풍으로 20분 내지 1시간, 또는 30분 내지 40분 동안 건조하여 분말 형태로 제조될 수 있다.The A) graft copolymer latex is a specific example by using an aqueous calcium chloride solution to aggregate under 80 to 90°C or 82 to 88°C and atmospheric pressure conditions, and aged at more than 90°C to 100°C or less, or 92 to 98°C to dehydrate and After washing, it can be prepared in a powder form by drying for 20 minutes to 1 hour, or 30 minutes to 40 minutes with hot air of 85 to 95 ℃ or 88 to 92 ℃.
B) 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체B) Alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer
본 기재의 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체는 바람직하게는 상기 ASA계 수지 조성물(A+B+C) 총 중량에 대하여 23 내지 55 중량%, 보다 바람직하게는 25 내지 50 중량%, 더욱 바람직하게는 25 내지 45 중량%, 보다 더욱 바람직하게는 30 내지 40 중량%일 수 있고, 이 범위 내에서 투명도 및 착색성이 뛰어난 효과가 있다.The alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer of the present disclosure is preferably 23 to 55% by weight, more preferably 25 to 50, based on the total weight of the ASA-based resin composition (A+B+C). It may be a weight%, more preferably 25 to 45% by weight, even more preferably 30 to 40% by weight, there is an effect excellent in transparency and colorability within this range.
상기 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체는 바람직하게는 알킬 메타크릴레이트 40 내지 90 중량%, 방향족 비닐 화합물 9 내지 40 중량% 및 비닐시안 화합물 1 내지 20 중량%를 포함하여 이루어질 수 있고, 보다 바람직하게는 알킬 메타크릴레이트 50 내지 85 중량%, 방향족 비닐 화합물 12 내지 35 중량% 및 비닐시안 화합물 3 내지 15 중량%를 포함하여 이루어질 수 있으며, 더욱 바람직하게는 알킬 메타크릴레이트 55 내지 65 중량%, 방향족 비닐 화합물 25 내지 35 중량% 및 비닐시안 화합물 5 내지 10 중량%를 포함하여 이루어질 수 있고, 이 범위 내에서 투명도 및 착색성이 우수한 이점이 있다.The alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer preferably comprises 40 to 90% by weight of an alkyl methacrylate, 9 to 40% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyanide compound. And more preferably 50 to 85% by weight of an alkyl methacrylate, 12 to 35% by weight of an aromatic vinyl compound, and 3 to 15% by weight of a vinyl cyan compound, and more preferably 55 to an alkyl methacrylate. To 65% by weight, 25 to 35% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyan compound, and there is an advantage of excellent transparency and colorability within this range.
상기 알킬 메타크릴레이트는 일례로 알킬기의 탄소수가 1 내지 15인 알킬 메타크릴레이트일 수 있고, 구체적인 예로 메틸 메타크릴레이트, 에틸 메타크릴레이트, 부틸 메타크릴레이트, 2-에틸부틸 메타크릴레이트, 2-에틸헥실 메타크릴레이트 및 라우릴 메타크릴레이트로 이루어진 군으로부터 선택된 1종 이상일 수 있으며, 바람직하게는 탄소수 1 내지 4개의 사슬 알킬기를 포함하는 알킬 메타크릴레이트일 수 있고, 보다 바람직하게는 메틸 메타크릴레이트일 수 있다.The alkyl methacrylate may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples thereof are methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2 -It may be one or more selected from the group consisting of ethylhexyl methacrylate and lauryl methacrylate, preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, more preferably methyl methacrylate It may be a acrylate.
상기 방향족 비닐 화합물은 일례로 스티렌, α-메틸스티렌, m-메틸스티렌, p-메틸스티렌 및 p-tert-부틸스티렌으로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 바람직하게는 스티렌이다.The aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-tert-butylstyrene, preferably styrene.
상기 비닐시안 화합물은 일례로 아크릴로니트릴, 메타니트롤로니트릴, 에틸아크릴로니트릴 및 이소프로필아크릴로니트릴로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 바람직하게는 아크릴로니트릴이다.The vinyl cyan compound may be one or more selected from the group consisting of acrylonitrile, metanitroonitrile, ethyl acrylonitrile, and isopropyl acrylonitrile, for example, and is preferably acrylonitrile.
상기 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체는 중량 평균 분자량이 바람직하게 10,000 내지 150,000 g/mol, 보다 바람직하게는 40,000 내지 120,000 g/mol일 수 있고, 이 범위 내에서 고무의 분산도를 높여 충격 강도, 가공성, 투명도 및 착색성이 우수한 이점이 있다.The alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer may have a weight average molecular weight of preferably 10,000 to 150,000 g/mol, more preferably 40,000 to 120,000 g/mol, and dispersion of rubber within this range. By increasing the degree, there are advantages of excellent impact strength, processability, transparency, and colorability.
본 기재에서 중량 평균 분자량은 달리 정의되지 않는 이상, 분말을 아세톤에 녹인 후 아세톤 상에 녹아 있는 부분(sol)을 추출하여 THF 용액에 녹인 후, GPC를 이용하여 표준 PS(standard polystyrene) 시료에 대한 상대 값으로 측정할 수 있다.In this description, unless otherwise defined, the weight average molecular weight is determined by dissolving the powder in acetone, extracting the sol dissolved in the acetone, dissolving it in a THF solution, and then using GPC for standard PS (standard polystyrene) samples. It can be measured as a relative value.
상기 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체는 일례로 용액 중합, 괴상 중합, 유화 중합 또는 현탁 중합으로 제조될 수 있고, 상기 용액 중합, 괴상 중합, 유화 중합 및 현탁 중합은 각각 본 발명이 속한 기술분야에서 통상적으로 실시되는 유화 중합 및 현탁 중합 방법에 의하는 경우 특별히 제한되지 않는다.The alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer may be prepared by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and the solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization are each In the case of the emulsion polymerization and suspension polymerization method commonly carried out in the technical field to which the invention belongs, it is not particularly limited.
상기 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체는 바람직한 일 실시예로 무용매 상태 하에 또는 반응 용매 하에 알킬 메타크릴레이트, 방향족 비닐 화합물 및 비닐시안 화합물 총 100 중량부에 개시제 및 분자량 조절제 중 1종 이상을 각각 0.01 내지 0.5 중량부, 바람직하게는 0.02 내지 0.15 중량부, 보다 바람직하게는 0.02 내지 0.1 중량부를 투입한 후 연속반응기를 이용하여 괴상 중합 또는 용액 중합하여 제조될 수 있고, 이 경우 경제적이며 잔류 불순물이 적은 이점이 있다.In a preferred embodiment, the alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer is an initiator and a molecular weight modifier in a total of 100 parts by weight of an alkyl methacrylate, an aromatic vinyl compound and a vinyl cyan compound in a solvent-free state or in a reaction solvent. After adding at least one of 0.01 to 0.5 parts by weight, preferably 0.02 to 0.15 parts by weight, more preferably 0.02 to 0.1 parts by weight, respectively, it may be prepared by bulk polymerization or solution polymerization using a continuous reactor. It is economical and has the advantage of less residual impurities.
상기 반응 용매는 본 발명이 속한 기술분야에서 괴상 중합 또는 용액 중합 시 통상적으로 사용되는 반응 용매인 경우 특별히 제한되지 않고, 일례로 방향족 탄화수소일 수 있으며, 바람직하게는 톨루엔, 자일렌, 에틸벤젠, 큐멘 및 테트랄린으로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 보다 바람직하게는 톨루엔이다.The reaction solvent is not particularly limited if it is a reaction solvent commonly used in bulk polymerization or solution polymerization in the technical field of the present invention, and may be an aromatic hydrocarbon, preferably toluene, xylene, ethylbenzene, cumene. And it may be one or more selected from the group consisting of tetralin, more preferably toluene.
상기 A) 그라프트 공중합체의 중량은 바람직하게는 상기 B) 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체의 중량 보다 크지 않고, 보다 바람직하게는 상기 A) 그라프트 공중합체와 B) 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체의 중량비(A:B)가 1:1 내지 1:2.5일 수 있으며, 더욱 바람직하게는 1:1 내지 1:2일 수 있고, 이 범위 내에서 기계적 강도와 유동성의 밸런스가 우수하고, 특히 투명도와 착색성 및 내후성이 뛰어난 효과가 있다.The weight of the A) graft copolymer is preferably not greater than the weight of the B) alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer, and more preferably the A) graft copolymer and B) The weight ratio (A:B) of the alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer may be 1:1 to 1:2.5, more preferably 1:1 to 1:2, and this range It has an excellent balance of mechanical strength and fluidity within, and particularly has excellent transparency, colorability, and weather resistance.
C) 폴리(알킬 메타크릴레이트) 수지C) poly(alkyl methacrylate) resin
본 기재의 C) 폴리(알킬 메타크릴레이트) 수지는 바람직하게는 25 내지 45 중량%일 수 있고, 보다 바람직하게 30 내지 45 중량%, 더욱 바람직하게 30 내지 40 중량%이며, 이 범위 내에서 종래의 ASA계 수지 조성물 대비 기계적 물성 및 가공성 등이 동등 이상으로 유지되면서 투명도 및 착색성이 크게 향상되는 이점이 있다.The C) poly(alkyl methacrylate) resin of the present disclosure may preferably be 25 to 45% by weight, more preferably 30 to 45% by weight, even more preferably 30 to 40% by weight, within this range conventionally Compared to the ASA-based resin composition, the mechanical properties and processability are maintained equal or higher, while the transparency and coloring properties are greatly improved.
상기 폴리(알킬 메타크릴레이트) 수지는 일례로 알킬기의 탄소수가 1 내지 15인 알킬 메타크릴레이트를 포함하여 이루어진 중합체일 수 있다.The poly(alkyl methacrylate) resin may be, for example, a polymer comprising an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group.
상기 알킬 메타크릴레이트는 바람직하게는 메틸 메타크릴레이트, 에틸 메타크릴레이트, 부틸 메타크릴레이트, 2-에틸부틸 메타크릴레이트, 2-에틸헥실 메타크릴레이트 및 라우릴 메타크릴레이트로 이루어진 군으로부터 선택된 1종 이상일 수 있으며, 보다 바람직하게는 탄소수 1 내지 4개의 사슬 알킬기를 포함하는 알킬 메타크릴레이트일 수 있고, 더욱 바람직하게는 메틸 메타크릴레이트일 수 있다.The alkyl methacrylate is preferably selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate. It may be one or more, more preferably an alkyl methacrylate including a chain alkyl group having 1 to 4 carbon atoms, and more preferably methyl methacrylate.
상기 폴리(알킬 메타크릴레이트) 수지는 바람직하게는 중량 평균 분자량이 50,000 내지 200,000 g/mol이고, 보다 바람직하게는 50,000 내지 150,000 g/mol, 더욱 바람직하게는 50,000 내지 100,000 g/mol이며, 이 범위 내에서 내후성이 보다 우수하고, 유동성, 인장 강도 및 충격 강도가 우수하며, 투명도 및 착색성이 뛰어난 효과가 있다.The poly(alkyl methacrylate) resin preferably has a weight average molecular weight of 50,000 to 200,000 g/mol, more preferably 50,000 to 150,000 g/mol, even more preferably 50,000 to 100,000 g/mol, and this range It has superior weather resistance within, excellent fluidity, tensile strength and impact strength, and excellent transparency and coloring properties.
상기 폴리(알킬 메타크릴레이트) 수지는 일례로 알킬 메타크릴레이트를 포함하는 단량체에 가교제 및 개시제를 혼합한 후 괴상중합, 용액중합, 현탁중합 또는 유화중합하여 제조할 수 있고, 바람직하게는 현탁중합 또는 유화중합하여 제조하는 것이다.The poly(alkyl methacrylate) resin may be prepared by mixing a crosslinking agent and an initiator with a monomer including alkyl methacrylate, for example, and then bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, and preferably suspension polymerization Or it is prepared by emulsion polymerization.
상기 개시제는 폴리(알킬 메타크릴레이트) 수지 제조 시 사용되는 통상적인 개시제인 경우 특별히 제한되지 않고, 일례로 2,2'-아조비스 2'4-디메틸-발레로니트릴 등의 아조계 개시제가 바람직할 수 있다.The initiator is not particularly limited if it is a conventional initiator used in the production of a poly(alkyl methacrylate) resin, and an azo initiator such as 2,2'-azobis 2'4-dimethyl-valeronitrile is preferable. can do.
상기 중합 방법에 따라 추가나 변경되어야 하는, 용매, 유화제 등과 같은 반응에 필요한 물질이나 중합온도, 중합시간 등과 같은 조건은 폴리(알킬 메타크릴레이트) 수지 제조 시 각각의 중합 방법에 따라 일반적으로 적용되는 물질이나 조건인 경우 특별히 제한되지 않고, 필요에 따라 적절히 선택할 수 있다.Substances required for reaction such as solvents and emulsifiers, which must be added or changed according to the polymerization method, or conditions such as polymerization temperature and polymerization time are generally applied according to each polymerization method when preparing poly(alkyl methacrylate) resins. In the case of or conditions, it is not particularly limited, and may be appropriately selected as necessary.
ASA계 수지 조성물ASA resin composition
본 기재의 ASA계 수지 조성물은 바람직하게는 총 고무 함량이 8 내지 23 중량%일 수 있고, 보다 바람직하게는 10 내지 20 중량%, 더욱 바람직하게는 10 내지 17 중량%, 보다 더 바람직하게는 10 내지 15 중량%일 수 있으며, 이 범위 내에서 기계적 물성이 우수하고, 특히 내후성, 투명도 및 착색성이 우수한 효과가 있다.The ASA-based resin composition of the present disclosure may preferably have a total rubber content of 8 to 23% by weight, more preferably 10 to 20% by weight, still more preferably 10 to 17% by weight, even more preferably 10 It may be in the range of 15% by weight, and within this range, mechanical properties are excellent, and in particular, weather resistance, transparency, and colorability are excellent.
본 기재에서 ASA계 수지는 알킬 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체를 지칭한다.In the present description, the ASA-based resin refers to an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound copolymer.
상기 ASA계 수지 조성물은 바람직하게 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체, 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체 및 폴리(알킬 메타크릴레이트) 수지를 합한 총 100 중량부에 대하여 활제, 열안정제 및 자외선 안정제 중 1 이상을 0.05 내지 5 중량부로 포함할 수 있고, 이 범위 내에서 ASA계 수지 조성물의 물성을 저하시키지 않으면서 이들 본연의 효과가 잘 발현되는 이점이 있다.The ASA-based resin composition is preferably a total of 100 acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer, and poly(alkyl methacrylate) resin. One or more of a lubricant, a heat stabilizer, and an ultraviolet stabilizer may be contained in an amount of 0.05 to 5 parts by weight based on parts by weight, and within this range, these natural effects are well expressed without deteriorating the physical properties of the ASA-based resin composition. have.
상기 활제는 바람직하게 0.3 중량부 이상 내지 2 중량부 미만으로 포함할 수 있고, 보다 바람직하게는 0.5 내지 1.9 중량부로 포함할 수 있으며, 더욱 바람직하게 0.9 내지 1.5 중량부로 포함할 수 있고, 이 범위 내에서 충격강도 및 유동성이 모두 우수한 효과가 있다.The lubricant may preferably be included in an amount of 0.3 parts by weight or more to less than 2 parts by weight, more preferably 0.5 to 1.9 parts by weight, more preferably 0.9 to 1.5 parts by weight, and within this range It has excellent effects in both impact strength and fluidity.
상기 활제는 일례로 에스테르계 활제, 금속염계 활제, 카르복실산계 활제, 탄화수소계 활제 및 아마이드계 활제로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 바람직하게는 아마이드계 활제이며, 보다 바람직하게는 스테라미드계 활제이고, 더욱 바람직하게는 알킬렌의 탄소수가 1 내지 10인 알킬렌 비스(스테라미드)이며, 이 경우 수지의 기계적 물성 및 열안정성을 떨어뜨리지 않으면서도 활제 본연의 효과가 잘 발현되는 이점이 있다.The lubricant may be, for example, one or more selected from the group consisting of an ester-based lubricant, a metal salt-based lubricant, a carboxylic acid-based lubricant, a hydrocarbon-based lubricant, and an amide-based lubricant, and is preferably an amide-based lubricant, and more preferably, stera. It is a mid-based lubricant, more preferably alkylene bis (steramide) having 1 to 10 carbon atoms of the alkylene. In this case, the original effect of the lubricant is well expressed without deteriorating the mechanical properties and thermal stability of the resin. There is an advantage.
본 기재에서 스테라미드계 활제는 스테라미드(stearamide) 및 이의 수소 중 1 이상이 다른 치환기(예로, C1 내지 C10의 알킬, 할로겐 등)로 치환된 스테라미드 치환체를 포함할 수 있다.In the present description, the steramid lubricant may include a steramid substituent in which at least one of steramid and its hydrogen is substituted with another substituent (eg, C1 to C10 alkyl, halogen, etc.).
상기 에스테르계 활제, 금속염계 활제, 카르복실산계 활제, 탄화수소계 활제 및 아마이드계 활제는 각각 본 발명이 속한 기술분야에서 통상적으로 해당 종류의 활제로 사용되는 물질인 경우 특별히 제한되지 않는다.The ester-based lubricants, metal salt-based lubricants, carboxylic acid-based lubricants, hydrocarbon-based lubricants, and amide-based lubricants are not particularly limited as long as each is a material commonly used as a corresponding type of lubricant in the technical field to which the present invention belongs.
상기 열안정제는 일례로 아민계 열안정제 및 인계 열안정제로 이루어진 군으로부터 선택된 1종 이상으로, 각각 0.01 내지 3 중량부 범위 내에서 포함될 수 있고, 이 범위 내에서 열안정성, 투명성 및 착색성이 모두 우수한 효과가 있다.The heat stabilizer is one or more selected from the group consisting of an amine-based heat stabilizer and a phosphorus-based heat stabilizer, for example, and may be included within the range of 0.01 to 3 parts by weight, and within this range, both heat stability, transparency and colorability are excellent. It works.
상기 아민계 열안정제는 일례로 N,N-디-t-부틸 하이드록실아민(N,N-di-t-butyl hydroxylamine), N,N-디스테아릴 하이드록실아민(N,N-distearyl hydroxylamine; DSHA), N,N-디페닐 하이드록실아민(N,N-diphenyl hydroxylamine; DPHA), N,N-디벤질 하이드록실아민(N,N-dibenzyl hydroxylamine), N,N-벤질페닐 하이드록실아민 (N,N-benzylphenyl hydroxylamine), N,N-디(2,4-디메틸페닐) 하이드록실아민 (N,N-di(2,4-dimethylphenyl) hydroxylamine) 및 N,N-나프틸 하이드록실아민 (N,N-naphthyl hydroxylamine)으로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 일례로 0.01 내지 3 중량부 범위 내에서 포함될 수 있으며, 바람직하게는 0.05 내지 2 중량부, 보다 바람직하게는 0.1 내지 1 중량부 범위로 포함될 수 있고, 이 범위 내에서 열안정성, 투명성 및 착색성이 모두 우수한 효과가 있다.The amine-based thermal stabilizer is, for example, N,N-di-t-butyl hydroxylamine (N,N-di-t-butyl hydroxylamine), N,N-distearyl hydroxylamine (N,N-distearyl hydroxylamine). ; DSHA), N,N-diphenyl hydroxylamine (N,N-diphenyl hydroxylamine; DPHA), N,N-dibenzyl hydroxylamine (N,N-dibenzyl hydroxylamine), N,N-benzylphenyl hydroxyl Amine (N,N-benzylphenyl hydroxylamine), N,N-di(2,4-dimethylphenyl) hydroxylamine (N,N-di(2,4-dimethylphenyl) hydroxylamine) and N,N-naphthyl hydroxyl It may be one or more selected from the group consisting of amines (N,N-naphthyl hydroxylamine), for example, may be included within the range of 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1 It may be included in the range of parts by weight, and within this range, there are excellent effects in both heat stability, transparency, and colorability.
상기 인계 열안정제는 일례로 트리스(노닐페닐) 포스파이트(tris (nonylphenyl) phosphite), 트리스(2,4-디-t-부틸페닐) 포스파이트(tris (2,4-di-t-butyl phenyl) phosphite; TBPP), 2,4,6-트리-tert-부틸페닐-2-부틸-2-에틸-1,3-프로판디올 포스파이트(2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite), 디이소데실 펜타에리쓰리톨 디포스파이트(diisodecyl pentaerythritol diphosphite), 디스테아릴 펜타에리쓰 리톨 디포스파이트(distearyl pentaerythritol diphosphite), 비스 (2,4-디-t-부틸페닐) 펜타에리쓰리톨 디포스파이트(bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite; PEP24), 비스(2,4-디-큐밀페닐) 펜타에리쓰리톨 디포스파이트(bis (2,4-di-cumylphenyl) pentaerythritol diphosphite) 및 테트라키스(2,4-디-t-부틸페닐)[1,1-바이페닐]-4,4’-디일 비스포스포나이트(tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’-diyl bisphosphonite)로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 일례로 0.01 내지 3 중량부 범위 내에서 포함될 수 있으며, 바람직하게는 0.05 내지 2 중량부, 보다 바람직하게는 0.1 내지 1 중량부 범위로 포함될 수 있고, 이 범위 내에서 열안정성, 투명성 및 착색성이 모두 우수한 효과가 있다.The phosphorus-based heat stabilizer is, for example, tris (nonylphenyl) phosphite (tris (nonylphenyl) phosphite), tris (2,4-di-t-butylphenyl) phosphite (tris (2,4-di-t-butyl phenyl) ) phosphite; TBPP), 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite (2,4,6-tri-tert-butylphenyl-2- butyl-2-ethyl-1,3-propanediol phosphite), diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4- Di-t-butylphenyl) pentaerythritol diphosphite (bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite; PEP24), bis (2,4-di-cumylphenyl) pentaerythritol diphosphite ( bis (2,4-di-cumylphenyl) pentaerythritol diphosphite) and tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl]-4,4'-diyl bisphosphonate (tetrakis ( 2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diyl bisphosphonite) may be one or more selected from the group consisting of, for example, may be included within the range of 0.01 to 3 parts by weight, , Preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1 parts by weight may be included, and within this range, there are excellent effects in both heat stability, transparency, and colorability.
상기 자외선 안정제는 일례로 벤조트리아졸계 자외선 흡수제 및 HALS계 자외선 안정제로 이루어진 군으로부터 선택된 1종 이상을 0.1 내지 2.5 중량부 범위 내에서 포함할 수 있고, 바람직하게는 벤조트리아졸계 자외선 흡수제 0.1 내지 2.0 중량부 및 HALS계 자외선 안정제 0.1 내지 2.0 중량부를 포함할 수 있으며, 보다 바람직하게는 벤조트리아졸계 자외선 흡수제 0.1 내지 1.0 중량부 및 HALS계 자외선 안정제 0.1 내지 1.0 중량부를 포함할 수 있고, 더욱 바람직하게는 벤조트리아졸계 자외선 흡수제 0.2 내지 0.7 중량부 및 HALS계 자외선 안정제 0.2 내지 0.7 중량부를 포함할 수 있으며, 보다 더욱 바람직하게는 벤조트리아졸계 자외선 흡수제 0.3 내지 0.6 중량부 및 HALS계 자외선 안정제 0.3 내지 0.6 중량부를 포함할 수 있고, 이 범위 내에서 충격강도 및 유동성을 저해하지 않으면서도 내후성을 크게 개선시키는 이점이 있다.The ultraviolet stabilizer may include, for example, one or more selected from the group consisting of benzotriazole-based ultraviolet absorbers and HALS-based ultraviolet stabilizers within the range of 0.1 to 2.5 parts by weight, preferably 0.1 to 2.0 parts by weight of the benzotriazole-based ultraviolet absorber And 0.1 to 2.0 parts by weight of a HALS-based ultraviolet stabilizer, more preferably 0.1 to 1.0 parts by weight of a benzotriazole-based ultraviolet absorber and 0.1 to 1.0 parts by weight of a HALS-based ultraviolet stabilizer, more preferably benzo It may contain 0.2 to 0.7 parts by weight of a triazole-based ultraviolet absorber and 0.2 to 0.7 parts by weight of a HALS-based ultraviolet stabilizer, more preferably 0.3 to 0.6 parts by weight of a benzotriazole-based ultraviolet absorber and 0.3 to 0.6 parts by weight of a HALS-based ultraviolet stabilizer. In this range, there is an advantage of greatly improving weather resistance without impairing impact strength and fluidity.
상기 벤조트리아졸계 자외선 흡수제는 일례로 하이드록시벤조트리아졸일 수 있고, 바람직하게는 2-(2'-하이드록시페닐)벤조트리아졸일 수 있으며, 보다 바람직하게는 2-(2'-하이드록시-5'-메틸페닐)벤조트리아졸, 2-(3',5'-디-tert-부틸-2'-하이드록시페닐)벤조트리아졸, 2-(5'-tert-부틸-2'-하이드록시페닐)벤조트리아졸, 2-(2'-하이드록시-5'-(1,1,3,3-테트라메틸부틸)페닐)벤조트리아졸, 2-(3',5'-디-tert-부틸-2'-하이드록시페닐)-5-클로로벤조트리아졸, 2-(3'-tert-부틸-2'-하이드록시-5'-메틸페닐-5-클로로벤조트리아졸, 2-(3'-sec-부틸-5'-tert-부틸-2'-하이드록시페닐)벤조트리아졸, 2-(2'-하이드록시-4'-옥틸옥시페닐)벤조트리아졸, 2-(3',5'-디-tert-아밀-2'-하이드록시페닐)벤조트리아졸, 2-(3',5'-비스(α,α-디메틸벤질)-2'-하이드록시페닐)벤조트리아졸, 2-(3'-tert-부틸-2'-하이드록시-5'-(2-옥틸옥시-카보닐에틸)페닐)-5-클로로벤조트리아졸, 2-(3'-tert-부틸-5'-[2-(2-에틸헥실옥시)카보닐에틸]-2'-하이드록시페닐)-5-클로로벤조트리아졸, 2-(3'-tert-부틸-2'-하이드록시-5'-(2-메톡시카보닐에틸)페닐)-5-클로로벤조트리아졸, 2-(3'-tert-부틸-2'-하이드록시-5'-(2-메톡시카보닐에틸)페닐)벤조트리아졸, 2-(3'-tert-부틸-2'-하이드록시-5'-(2-옥틸옥시카보닐에틸)페닐)벤조트리아졸, 2-(3'-tert-부틸-5'-[2-(2-에틸헥실옥시)카보닐에틸]-2'-하이드록시페닐)벤조트리아졸, 2-(3'-도데실-2'-하이드록시-5'-메틸페닐)벤조트리아졸, 2-(3'-tert-부틸-2'-하이드록시-5'-(2-이소옥틸옥시카보닐에틸)페닐벤조트리아졸, 2,2'-메틸렌비스[4-(1,1,3,3-테트라메틸부틸)-6-벤조트리아졸-2-일페놀], 및 2-[3'-tert-부틸-5'-(2-메톡시카보닐에틸)-2'-하이드록시페닐]-2H-벤조트리아졸과 폴리에틸렌글리콜의 에스테르 교환 생성물로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 이러한 경우 충격강도 및 유동성을 저해하지 않으면서 내후성을 크게 개선시키는 이점이 있다.The benzotriazole-based ultraviolet absorber may be, for example, hydroxybenzotriazole, preferably 2-(2'-hydroxyphenyl)benzotriazole, more preferably 2-(2'-hydroxy-5 '-Methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl )Benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl -2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2-(3'- sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5' -Di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-octyloxy-carbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'- [2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'- (2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzo Triazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'- [2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole , 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[4-(1,1, 3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol], and 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxy Phenyl]-2H-benzotriazole and polyethylene glycol It may be one or more selected from the group consisting of transesterification products, and in this case, there is an advantage of greatly improving weather resistance without impairing impact strength and fluidity.
상기 HALS계 자외선 안정제는 바람직하게 1,1-비스(2,2,6,6-테트라메틸-4-피페리딜)숙시네이트, 비스(2,2,6,6-테트라메틸-4-피페리딜)세바케이트, 비스(1,2,2,6,6-펜타메틸-4-피페리딜)세바케이트, 비스(1-옥틸옥시-2,2,6,6-테트라메틸-4-피페리딜)세바케이트, 비스(1,2,2,6,6-펜타메틸-4-피페리딜)-N-부틸-3,5-디-tert-부틸-4-하이드록시벤질말로네이트, 1-(2-하이드록시에틸)-2,2,6,6-테트라메틸-4-하이드록시피페리딘과 숙신산의 축합 생성물, N,N'-비스(2,2,6,6-테트라메틸-4-피페리딜)헥사메틸렌 디아민과 4-tert-옥틸아미노-2,6-디-클로로-1,3,5-트리아진의 선형 또는 고리형 축합 생성물, 트리스(2,2,6,6-테트라메틸-4-피페리딜)니트릴로트리아세테이트, 테트라키스(2,2,6,6-테트라메틸-4-피페리딜)-1,2,3,4-부탄 테트라카복실레이트, 1,1'-(1,2-에탄디일)-비스(3,3,5,5-테트라메틸피페라진온), 4-벤조일-2,2,6,6-테트라메틸피페리딘, 4-스테아릴옥시-2,2,6,6-테트라메틸피페리딘, N,N'-비스(2,2,6,6-테트라메틸-4-피페리딜)헥사메틸렌 디아민과 4-모르포리노-2,6-디클로로-1,3,5-트리아진의 선형 또는 고리형 축합 생성물, 및 7,7,9,9-테트라메틸-2-사이클로운데실-1-옥사-3,8-디아자-4-옥소스피로-[4,5]데칸과 에피클로로하이드린의 반응 생성물로 이루어진 군으로부터 선택된 1종 이상이고, 보다 바람직하게는 비스(2,2,6,6-테트라메틸-4-피페리딜)세바케이드(Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate), 2-(2H-벤조트리아졸-2-yl)-4-(-(1,1,3,3-테트라메틸뷰틸)페놀(2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) 또는 이들의 혼합일 수 있으며, 이러한 경우 충격강도 및 유동성을 저해하지 않으면서 내후성을 크게 개선시키는 이점이 있다.The HALS-based UV stabilizer is preferably 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethyl-4-pi) Peridyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4- Piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-N-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate , 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensation product, N,N'-bis(2,2,6,6- Linear or cyclic condensation product of tetramethyl-4-piperidyl)hexamethylene diamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-triazine, tris(2,2, 6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate , 1,1'-(1,2-ethandiyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine and 4- Linear or cyclic condensation products of morpholino-2,6-dichloro-1,3,5-triazine, and 7,7,9,9-tetramethyl-2-cyclodecyl-1-oxa-3, 8-diaza-4-oxopyro-[4,5]decane and at least one selected from the group consisting of a reaction product of epichlorohydrin, more preferably bis(2,2,6,6-tetramethyl -4-piperidyl) sebacate (Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate), 2-(2H-benzotriazole-2-yl)-4-(-(1, 1,3,3-tetramethylbutyl)phenol (2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) or a mixture thereof, in which case the impact There is an advantage of greatly improving weather resistance without impairing strength and fluidity.
상기 ASA계 수지 조성물은 필요에 따라 선택적으로 염료, 안료, 착색제, 이형제, 대전방지제, 항균제, 가공조제, 금속 불활성화제, 난연제, 억연제, 적하방지제, 내마찰제 및 내마모제로 이루어진 군으로부터 선택된 1종 이상의 첨가제를 상기 총 100 중량부에 대하여 0.01 내지 5 중량부, 0.05 내지 3 중량부, 0.1 내지 2 중량부 또는 0.5 내지 1 중량부로 더 포함할 수 있고, 이 범위 내에서 ASA계 수지 조성물 본연의 물성을 저하시키지 않으면서도 첨가제의 효능이 잘 구현되는 효과가 있다.The ASA-based resin composition is optionally selected from the group consisting of dyes, pigments, colorants, releasing agents, antistatic agents, antibacterial agents, processing aids, metal deactivators, flame retardants, inhibitors, anti-drip agents, anti-friction agents and anti-wear agents. It may further include 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 parts by weight based on the total 100 parts by weight of the additives, and within this range, the natural ASA resin composition There is an effect that the efficacy of the additive is well realized without deteriorating the physical properties.
상기 ASA계 수지 조성물은 바람직하게 ASTM D1238에 의거하여 측정한 용융지수(220 ℃, 10 kg)가 8 g/10min 이상일 수 있고, 보다 바람직하게는 8 내지 11 g/10min, 더욱 바람직하게는 9 내지 11 g/10min일 수 있으며, 이 범위 내에서 충격강도, 내후성 및 유동성의 밸런스가 우수한 효과가 있다.The ASA-based resin composition may preferably have a melt index (220° C., 10 kg) measured according to ASTM D1238 of 8 g/10 min or more, more preferably 8 to 11 g/10 min, more preferably 9 to It may be 11 g/10min, and within this range, there is an excellent effect in balance of impact strength, weather resistance and fluidity.
상기 ASA계 수지 조성물은 바람직하게 ASTM D256에 의거하여 측정한 아이조드 충격강도(1/4inch, 23 ℃)가 3 kgf·cm/cm2 이상, 보다 바람직하게는 3 내지 8 kgf·cm/cm2, 더욱 바람직하게는 3 내지 4 kgf·cm/cm2일 수 있고, 이 범위 내에서 충격강도, 내후성 및 유동성의 밸런스가 우수한 효과가 있다.The ASA-based resin composition preferably has an Izod impact strength (1/4inch, 23°C) measured according to ASTM D256 of 3 kgf·cm/cm 2 or more, more preferably 3 to 8 kgf·cm/cm 2 , More preferably, it may be 3 to 4 kgf·cm/cm 2 , and within this range, there is an excellent effect in balance of impact strength, weather resistance and fluidity.
상기 ASA계 수지 조성물은 일례로 ASTM 638에 의거한 인장강도(1/8 inch)가 570 ㎏/㎠ 이상이며, 바람직하게 570 내지 700 ㎏/㎠이고, 보다 바람직하게 580 내지 650 ㎏/㎠이며, 더욱 바람직하게 580 내지 610 ㎏/㎠이고, 이 범위 내에서 충격강도, 인장강도, 내후성 및 유동성의 밸런스가 우수한 효과가 있다.The ASA-based resin composition, for example, has a tensile strength (1/8 inch) of 570 kg/cm2 or more, preferably 570 to 700 kg/cm2, and more preferably 580 to 650 kg/cm2 according to ASTM 638, More preferably, it is 580 to 610 kg/cm 2, and within this range, the balance of impact strength, tensile strength, weather resistance and fluidity is excellent.
상기 ASA계 수지 조성물은 일례로 ASTM 790에 의거한 굴곡강도가 850 ㎏/㎠ 이상이며, 바람직하게 850 내지 1,000 ㎏/㎠이고, 보다 바람직하게 860 내지 950 ㎏/㎠이며, 더욱 바람직하게 870 내지 920 ㎏/㎠이고, 이 범위 내에서 충격강도, 인장강도, 굴곡강도, 내후성 및 유동성의 밸런스가 우수한 효과가 있다.The ASA-based resin composition, for example, has a flexural strength of 850 kg/cm2 or more, preferably 850 to 1,000 kg/cm2, more preferably 860 to 950 kg/cm2, and even more preferably 870 to 920 according to ASTM 790. ㎏/㎠, and within this range, the balance of impact strength, tensile strength, flexural strength, weather resistance and fluidity is excellent.
상기 ASA계 수지 조성물은 바람직하게 ASTM D528 방법으로 측정한 표면광택(45 °)이 80 이상, 보다 바람직하게 85 이상, 95 이상일 수 있고, 이 범위 내에서 투명성 및 착색성이 우수하고, 다른 물성과의 밸런스가 좋은 이점이 있다.The ASA-based resin composition preferably has a surface gloss (45 °) measured by ASTM D528 method of 80 or more, more preferably 85 or more, 95 or more, and has excellent transparency and colorability within this range, and There is a good balance advantage.
상기 ASA계 수지 조성물은 바람직하게는 ASTM D1003에 의거하여 측정된 투명도(Haze)가 7 이하일 수 있고, 보다 바람직하게는 6 이하, 더욱 바람직하게는 5 이하일 수 있으며, 이 범위 내에서 기계적 물성 및 가공성이 우수하면서도 동시에 투명성 및 착색성이 뛰어난 이점이 있다.The ASA-based resin composition may preferably have a transparency (Haze) of 7 or less, more preferably 6 or less, more preferably 5 or less, measured according to ASTM D1003, and mechanical properties and processability within this range. There is an advantage of being excellent in this and at the same time excellent in transparency and colorability.
상기 ASA계 수지 조성물은 웨더-오미터(Weather-Ometer)를 사용하여 ASTM J1960 조건에서 6,000 시간 경과하였을 때의 내후성(△E)이 바람직하게는 1.3 이하, 보다 바람직하게는 1.2 이하일 수 있고, 이 범위 내에서 기계적 물성, 가공성, 착색성 및 내후성이 모두 뛰어난 이점이 있다.The ASA-based resin composition may have a weather resistance (ΔE) of preferably 1.3 or less, more preferably 1.2 or less, when 6,000 hours have elapsed under ASTM J1960 conditions using Weather-Ometer. Within the range, mechanical properties, processability, coloring and weatherability are all excellent advantages.
상기 ASA계 수지 조성물의 제조방법은 바람직하게 평균입경 50 내지 150 nm의 아크릴레이트 고무를 코어로 하는 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체 20 내지 47 중량%, 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체 23 내지 55 중량% 및 폴리(알킬 메타크릴레이트) 수지 25 내지 45 중량%를 200 내지 300 ℃ 및 100 내지 500 rpm 조건 하에서 혼련 및 압출하여 펠렛으로 제조하는 단계를 포함할 수 있다.The method for preparing the ASA-based resin composition is preferably an acrylate having an average particle diameter of 50 to 150 nm as a core-an aromatic vinyl compound-a vinyl cyan compound graft copolymer 20 to 47% by weight, an alkyl methacrylate- A step of preparing a pellet by kneading and extruding 23 to 55% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer and 25 to 45% by weight of a poly(alkyl methacrylate) resin under conditions of 200 to 300°C and 100 to 500 rpm. Can include.
상기 혼련 및 압출에 사용되는 압출 혼련기는 본 발명이 속한 기술분야에서 통상적으로 사용되는 압출 혼련기인 경우 특별히 제한되지 않으며, 일례로 일축 압출기, 이축 압출기, 또는 벤버리 믹서를 통해 수행될 수 있고, 바람직하게는 이축 압출기이며, 이 경우 조성물이 균일하게 분산되어 상용성이 우수한 효과가 있다.The extrusion kneader used for the kneading and extrusion is not particularly limited if it is an extrusion kneader commonly used in the technical field to which the present invention belongs, and may be performed through, for example, a single screw extruder, a twin screw extruder, or a Benbury mixer, and is preferably It is a twin-screw extruder, and in this case, the composition is uniformly dispersed, so that the compatibility is excellent.
상기 혼련 및 압출은 배럴 온도(온도 조건)가 바람직하게는 210 내지 300 ℃, 보다 바람직하게는 210 내지 280 ℃, 더욱 바람직하게는 220 내지 250 ℃인 범위 내에서 수행될 수 있고, 이 경우 단위 시간당 처리량이 적절하면서도 충분한 용융 혼련이 가능할 수 있으며, 수지 성분의 열분해 등의 문제점을 야기하지 않는 효과가 있다.The kneading and extrusion may be carried out within the range of the barrel temperature (temperature condition) is preferably 210 to 300 ℃, more preferably 210 to 280 ℃, more preferably 220 to 250 ℃, in this case per unit time Although the processing amount is appropriate, sufficient melt-kneading may be possible, and there is an effect that does not cause problems such as thermal decomposition of the resin component.
상기 혼련 및 압출은 스크류 회전수(rpm)가 바람직하게는 150 내지 400 rpm, 보다 바람직하게는 100 내지 350 rpm, 더욱 바람직하게는 200 내지 310rpm, 보다 더욱 바람직하게는 250 내지 350 rpm인 조건 하에 수행될 수 있고, 이 경우 단위 시간당 처리량이 적절하여 공정 효율이 우수하면서도, 과도한 절단을 억제하는 효과가 있다.The kneading and extrusion is carried out under conditions in which the screw rotation speed (rpm) is preferably 150 to 400 rpm, more preferably 100 to 350 rpm, more preferably 200 to 310 rpm, even more preferably 250 to 350 rpm. In this case, the processing amount per unit time is appropriate, so that the process efficiency is excellent, and there is an effect of suppressing excessive cutting.
상기 ASA계 수지 조성물의 제조방법은 전술한 ASA계 수지 조성물의 모든 기술적인 특징을 공유한다. 따라서 중첩되는 부분에 대한 설명은 생략하기로 한다.The manufacturing method of the ASA-based resin composition shares all the technical characteristics of the above-described ASA-based resin composition. Therefore, a description of the overlapping part will be omitted.
성형품Molded article
본 기재의 성형품은 본 기재의 열가소성 수지 조성물로 제조될 수 있고, 이 경우 상용성이 증가하여 충격강도 등의 기계적 물성이 우수하면서도 투명성 및 착색성이 우수한 효과가 있다.The molded article of the present substrate may be made of the thermoplastic resin composition of the present substrate, and in this case, compatibility is increased, and thus mechanical properties such as impact strength are excellent, and transparency and coloring properties are excellent.
상기 성형품은 일례로 압출성형품 또는 사출성형품일 수 있고, 바람직하게는 에어컨, 진공 청소기, 세탁기, 냉장고 및 TV 백커버 등과 같은 가전제품의 하우징; 컴퓨터, 노트북, 모니터, 팩시밀리, 전화기, 복사기 및 스캐너 등과 같은 OA 기기의 하우징; 자동차 내외장재와 같은 자동차용 부품; 건축 내외장재; 완구용 부재; 레저 용품; 및 실내장식품 등일 수 있고, 보다 바람직하게는 외장재, 마감재, 무도장 제품 또는 압출 프로파일일 수 있으며, 이 경우 본 기재의 열가소성 수지 조성물에 의해 시장에서 요구하는 품질 이상의 고품질로 제공 가능한 이점이 있다.The molded product may be, for example, an extrusion molded product or an injection molded product, and preferably, a housing of a home appliance such as an air conditioner, a vacuum cleaner, a washing machine, a refrigerator, and a TV back cover; Housings of OA equipment such as computers, notebooks, monitors, facsimiles, telephones, copiers and scanners; Automobile parts such as automobile interior and exterior materials; Construction interior and exterior materials; A toy member; Leisure goods; And interior decoration, and more preferably, an exterior material, a finish material, an unpainted product, or an extrusion profile. In this case, the thermoplastic resin composition of the present disclosure has an advantage of being able to provide higher quality than the quality required in the market.
상기 성형품은 바람직하게는 가공 두께, 일례로 면 두께가 0.5 T(mm) 이상일 수 있다.The molded article may preferably have a processing thickness, for example, a surface thickness of 0.5 T (mm) or more.
성형품의 제조방법Manufacturing method of molded article
본 기재의 성형품의 제조방법은 바람직하게 평균입경 50 내지 150 nm의 아크릴레이트 고무를 코어로 하는 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체 20 내지 47 중량%, 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체 23 내지 55 중량% 및 폴리(알킬 메타크릴레이트) 수지 25 내지 45 중량%를 200 내지 300 ℃ 및 100 내지 500 rpm 조건 하에서 혼련 및 압출하여 펠렛으로 제조하는 단계; 및 제조된 펠렛을 성형온도 200 내지 300 ℃에서 시트성형 또는 사출성형하여 성형품을 제조하는 단계를 포함하는 것을 특징으로 한다. 이러한 경우 일정 이상의 가공 두께에서도 착색성과 투명도가 뛰어나 무도장, 투명, 고채도 또는 특수 칼라 등의 성질을 갖는 고부가가치의 ASA계 수지 제품을 제조할 수 있는 이점이 있다.The manufacturing method of the molded article of the present disclosure is preferably 20 to 47% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 50 to 150 nm as a core, and an alkyl methacrylate-aromatic Producing a pellet by kneading and extruding 23 to 55% by weight of a vinyl compound-vinyl cyan compound copolymer and 25 to 45% by weight of a poly(alkyl methacrylate) resin under conditions of 200 to 300°C and 100 to 500 rpm; And sheet molding or injection molding the produced pellets at a molding temperature of 200 to 300° C. to produce a molded article. In this case, there is an advantage of being able to manufacture a high value-added ASA-based resin product having properties such as non-painting, transparency, high saturation, or special color due to excellent colorability and transparency even at a certain processing thickness.
상기 성형품을 제조하는 단계는 바람직한 예로 제조된 펠렛을 성형온도 180 내지 300 ℃ 조건 하에 시트성형하는 것을 포함할 수 있고, 보다 바람직한 예로는 성형온도 180 내지 300 ℃ 및 성형압력 50 내지 300 Kgf/㎠ 조건 하에 시트성형하는 것을 포함할 수 있으며, 이러한 경우 투명성 및 착색성이 우수한 대형 시트성형품을 쉽게 제조할 수 있는 이점이 있다.The step of preparing the molded article may include sheet molding under conditions of a molding temperature of 180 to 300 °C, and a more preferred example is a molding temperature of 180 to 300 °C and a molding pressure of 50 to 300 Kgf/cm2. It may include sheet molding under, and in this case, there is an advantage in that a large-sized sheet molding product having excellent transparency and colorability can be easily manufactured.
상기 성형온도는 바람직하게 200 내지 230 ℃, 보다 바람직하게는 210 내지 220 ℃이고, 이 범위 내에서 투명성 및 착색성이 우수한 대형 시트성형품을 쉽게 제조 가능한 이점이 있다.The molding temperature is preferably 200 to 230 °C, more preferably 210 to 220 °C, and within this range, there is an advantage that a large-sized sheet molded article having excellent transparency and colorability can be easily manufactured.
상기 성형압력은 바람직하게 190 내지 270 Kgf/㎠, 보다 바람직하게는 200 내지 250 Kgf/㎠이고, 이 범위 내에서 충격강도가 높은 대형 사출성형품을 쉽게 제조 가능한 이점이 있다.The molding pressure is preferably 190 to 270 Kgf/cm2, more preferably 200 to 250 Kgf/cm2, and within this range, there is an advantage that it is possible to easily manufacture large-sized injection molded products having high impact strength.
또 다른 바람직한 예로, 상기 성형품을 제조하는 단계는 제조된 펠렛을 사출온도 200 내지 260 ℃, 사출압력 60 내지 100 bar 및 보압 25 내지 55 bar 조건 하에 사출성형하는 것을 포함할 수 있고, 이러한 경우 투명성 및 착색성이 우수한 대형 사출성형품을 쉽게 제조할 수 있는 이점이 있다.In another preferred example, the step of manufacturing the molded article may include injection molding the manufactured pellets under conditions of an injection temperature of 200 to 260° C., an injection pressure of 60 to 100 bar, and a holding pressure of 25 to 55 bar. In this case, transparency and There is an advantage of being able to easily manufacture large-sized injection molded products with excellent coloring properties.
상기 사출온도는 바람직하게 200 내지 230 ℃, 보다 바람직하게는 210 내지 220 ℃이고, 이 범위 내에서 투명성 및 착색성이 우수한 대형 사출성형품을 쉽게 제조 가능한 이점이 있다.The injection temperature is preferably 200 to 230 °C, more preferably 210 to 220 °C, and within this range, there is an advantage that a large injection molded article having excellent transparency and colorability can be easily manufactured.
상기 사출압력은 바람직하게 70 내지 90 bar, 보다 바람직하게는 75 내지 85 bar이고, 이 범위 내에서 충격강도가 높은 대형 사출성형품을 쉽게 제조 가능한 이점이 있다.The injection pressure is preferably 70 to 90 bar, more preferably 75 to 85 bar, and within this range, there is an advantage that a large injection molded article having high impact strength can be easily manufactured.
상기 보압은 바람직하게 30 내지 50 bar일 수 있고, 보다 바람직하게는 35 내지 45 bar이며, 이 범위 내에서 충격강도가 높은 대면적 사출성형품을 쉽게 제조할 수 있는 이점이 있다.The holding pressure may be preferably 30 to 50 bar, more preferably 35 to 45 bar, and within this range, there is an advantage of being able to easily manufacture a large-area injection molded article having high impact strength.
본 기재의 열가소성 수지 조성물, 이의 제조방법 및 성형품을 설명함에 있어서, 명시적으로 기재하지 않은 다른 조건이나 장비 등은 당업계에서 통상적으로 실시되는 범위 내에서 적절히 선택할 수 있고, 특별히 제한되지 않음을 명시한다.In the description of the thermoplastic resin composition of the present disclosure, its manufacturing method, and molded article, it is stated that other conditions or equipment that are not explicitly described can be appropriately selected within the range commonly practiced in the art, and are not particularly limited. do.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, a preferred embodiment is presented to aid in the understanding of the present invention, but it is obvious to those skilled in the art that various changes and modifications are possible within the scope of the present invention and the scope of the technical idea, but the following examples are only illustrative of the present invention, It is natural that such modifications and modifications fall within the scope of the appended claims.
[실시예][Example]
하기 실시예에서 사용된 물질은 다음과 같다.Materials used in the following examples are as follows.
A) 유화중합 방식의 그라프트 공중합체(코어: 평균입경 150 nm의 부틸아크릴레이트 중합체 유래 단위 50 중량%, 쉘: 스티렌 유래 단위 35 중량%, 아크릴니트릴 유래 단위 15 중량%)A) Graft copolymer of emulsion polymerization method (core: 50% by weight of units derived from butyl acrylate polymer having an average particle diameter of 150 nm, shell: 35% by weight of units derived from styrene, 15% by weight of units derived from acrylonitrile)
B) 벌크중합 방식 SAMMA 수지: 하기와 같은 방법으로 제조됨B) Bulk polymerization method SAMMA resin: prepared by the following method
톨루엔 20 중량부, 스티렌 24 중량부, 메틸 메타크릴레이트 50 중량부 및 아크릴로니트릴 6 중량부를 녹인 혼합 용액에 1,1-비스(t-부틸퍼옥시)-3,3,5-트리메틸사이클로헥산 0.02 중량부, n-도데실 메르캅탄 0.08 중량부 및 힌더드 페놀계 산화방지제로서 Irgacure(1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione) 0.1 중량부를 첨가한 중합 용액을 14 L/hr의 속도로 26 L 반응기에 투입하면서 첫 번째 반응기에서 140 ℃의 온도에서 중합하고, 두 번째 반응기에서 150 ℃의 온도에서 중합하여, 중합 전환율이 약 60% 이상 되었을 때, 휘발조에서 215 ℃의 온도로 미반응 단량체와 반응 매질을 제거하고 펠렛 형태의 스티렌-아크릴로니트릴-메틸 메타크릴레이트(SAMMA) 수지를 제조하였다. 이렇게 제조된 SAMMA 수지의 중량 평균 분자량은 7만 g/mol이었다.1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane in a mixed solution in which 20 parts by weight of toluene, 24 parts by weight of styrene, 50 parts by weight of methyl methacrylate and 6 parts by weight of acrylonitrile are dissolved 0.02 parts by weight, 0.08 parts by weight of n-dodecyl mercaptan, and Irgacure(1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1, as a hindered phenolic antioxidant, 3,5-triazine-2,4,6-(1H,3H,5H)-trione) 0.1 parts by weight of the polymerization solution was added to the 26 L reactor at a rate of 14 L/hr. Polymerization at temperature and polymerization at a temperature of 150 ℃ in the second reactor, when the polymerization conversion rate is more than about 60%, remove the unreacted monomer and the reaction medium at a temperature of 215 ℃ in the volatilization tank, styrene-acrylic in the form of pellets A ronitrile-methyl methacrylate (SAMMA) resin was prepared. The weight average molecular weight of the thus prepared SAMMA resin was 70,000 g/mol.
C) 벌크중합 방식 PMMA 수지: 하기와 같은 방법으로 제조됨C) bulk polymerization method PMMA resin: prepared by the following method
질소 치환된 반응기에 메틸 메타크릴레이트 100 중량부, 증류수 200 중량부, 현탁제로 폴리비닐알코올 0.3 중량부, n-옥틸 메르캅탄 2.0 중량부를 일괄 투여하고, 반응기 내온을 80 ℃로 올려주고 개시제로 AIBN 0.05 중량부를 투입하여 반응을 개시시켜 주고, 반응조 내온을 80 ℃로 유지시키면서 90분간 중합 반응을 진행한 후, 반응조 온도를 110 ℃까지 올려서 30 분간 추가 중합을 실시하였다. 중합된 비드(bead)는 탈수기를 이용하여 세척하고, 유동층 건조기에서 80 ℃에서 2시간 건조하였다. 제조된 PMMA 수지의 중량 평균 분자량은 10만 g/mol이었다.100 parts by weight of methyl methacrylate, 200 parts by weight of distilled water, 0.3 parts by weight of polyvinyl alcohol, and 2.0 parts by weight of n-octyl mercaptan as a suspension were batch-administered to a nitrogen-substituted reactor, and the reactor internal temperature was raised to 80° C. and AIBN as an initiator. 0.05 parts by weight was added to initiate the reaction, and the polymerization reaction was carried out for 90 minutes while maintaining the internal temperature of the reaction tank at 80° C., and then the reaction tank temperature was raised to 110° C. and further polymerization was performed for 30 minutes. The polymerized beads were washed using a dehydrator and dried at 80° C. for 2 hours in a fluidized bed dryer. The weight average molecular weight of the produced PMMA resin was 100,000 g/mol.
실시예 1 내지 5 및 비교예 1 내지 6Examples 1 to 5 and Comparative Examples 1 to 6
각각 하기 표 1에 기재된 성분 및 함량에 활제로 EBS 수지(선구화학 제조) 1 중량부, 산화방지제로 songnox 1076 및 songnox 1680(Songwan 제조) 각각 0.5 중량부 및 자외선 안정제로 Tinuvin 770(BASF 제조) 및 Sunsorb 329(썬화인글로벌 제조) 각각 0.5 중량부를 더하여 이축 압출기에서 230 ℃ 및 150 rpm 하에 혼련 및 압출하여 펠렛을 제조하였다. 제조된 펠렛으로 용융지수를 측정하였다. 또한 제조된 펠렛으로 성형온도 220 ℃ 및 성형압력 200 Kgf/㎠ 하에서 0.5T의 시트를 제조해 표면광택, Tt 및 Haze를 측정하였다. 나아가, 상기 제조된 펠렛을 성형온도 220 ℃, 사출압력 50 bar 및 보압 35 bar 하에서 사출하여 물성 측정용 시편을 제작하였고, 이를 이용하여 충격강도, 인장강도, 굴곡강도, 착색성 및 내후성을 측정하였다. In the components and contents shown in Table 1 below, 1 part by weight of EBS resin (manufactured by Sungo Chemical) as a lubricant, 0.5 parts by weight of songnox 1076 and songnox 1680 (manufactured by Songwan) as an antioxidant, and Tinuvin 770 (manufactured by BASF) as an ultraviolet stabilizer, and Each 0.5 parts by weight of Sunsorb 329 (manufactured by Sunfine Global) was added and kneaded and extruded in a twin screw extruder at 230° C. and 150 rpm to prepare pellets. The melt index was measured with the prepared pellets. In addition, a 0.5T sheet was prepared from the prepared pellets under a molding temperature of 220°C and a molding pressure of 200 Kgf/cm2 to measure the surface gloss, Tt, and Haze. Further, the prepared pellets were injected under a molding temperature of 220° C., an injection pressure of 50 bar and a holding pressure of 35 bar to prepare a specimen for measuring physical properties, and impact strength, tensile strength, flexural strength, colorability and weather resistance were measured using this.
[시험예][Test Example]
상기 실시예 1 내지 5 및 비교예 1 내지 6에서 제조된 펠렛, 시트 및 시편의 특성을 하기의 방법으로 측정하였고, 그 결과를 하기의 표 1에 나타내었다.The properties of the pellets, sheets, and specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were measured by the following method, and the results are shown in Table 1 below.
* 고무함량(중량%): FT-IR에 의거하여 측정하였다.* Rubber content (% by weight): It was measured based on FT-IR.
* 표면 광택도(%): 45°에서 ASTM D528에 의거하여 측정하였다. * Surface gloss (%): measured according to ASTM D528 at 45°.
* 아이조드 충격강도(kgf·cm/cm): ASTM 256 방법으로 측정하였다. * Izod impact strength (kgf·cm/cm): measured by ASTM 256 method.
* 굴곡강도(kgf/cm2): ASTM 790 방법으로 측정하였다.* Flexural strength (kgf/cm 2 ): Measured by ASTM 790 method.
* 인장강도(kgf/cm2): ASTM 638 방법으로 측정하였다.* Tensile strength (kgf/cm 2 ): Measured by ASTM 638 method.
* 용융지수(melt index; MI): 제조된 펠렛을 220 ℃, 10 ㎏의 조건하에 ASTM D1238 방법으로 측정하였다. * Melt index (MI): The prepared pellets were measured by ASTM D1238 method under conditions of 220° C. and 10 kg.
* 투명도(광확산도 및 광투과율): ASTM D-1003을 사용하여 두께 0.5 mm 시트의 헤이즈 값(haze value)와 전광선 투과율(light transmittance; Tt)을 각각 측정하였다. 헤이즈는 낮을수록 투과율은 높을수록 투명도가 우수한 것으로 평가된다.* Transparency (light diffusivity and light transmittance): Using ASTM D-1003, the haze value and light transmittance (Tt) of a 0.5 mm-thick sheet were measured, respectively. The lower the haze is, the higher the transmittance is, the better the transparency is evaluated.
* 표면경도: ASTM D785에 의거하여 측정하였다.* Surface hardness: Measured according to ASTM D785.
* 착색성: CIELAB 모드에 의거하여 Color eye 7000A 색차계(X-rite 제조)로 착색성 측정 시편의 L값을 측정하였다. L값이 높을수록 시편 뒤판의 백색 플레이트의 색이 투영되므로 착색성이 높다.* Colorability: The L value of the colorability measurement specimen was measured with a Color eye 7000A color difference meter (manufactured by X-rite) according to the CIELAB mode. The higher the L value, the higher the colorability, since the color of the white plate on the back plate of the specimen is projected.
* 내후성 △E: 내후성 장비(Weather-Ometer)를 사용하여 ASTM J1960 조건에서 6,000 시간 경과하였을 때, 색을 측정하여 초기 색과 비교하였다. △E가 작을수록 색 변화 정도가 작은 것으로 내후성이 우수함을 의미한다.* Weather resistance △E: When 6,000 hours elapsed in ASTM J1960 conditions using a weather resistance equipment (Weather-Ometer), the color was measured and compared with the initial color. The smaller ΔE, the smaller the degree of color change, which means excellent weatherability.
상기 표 1 및 2에 나타낸 바와 같이, 본 발명에 따른 ASA계 수지 조성물(실시예 1 내지 5)은 본 발명에 따르지 않는 비교예 1 내지 6 대비하여 충격강도, 인장강도 등과 같은 기계적 강도 및 MI로 표현되는 가공성은 동등 또는 그 이상의 값을 가지면서 투명도(haze), 착색성 및 내후성이 크게 뛰어남을 확인할 수 있었다. 특히, 보다 바람직한 범위의 조성비와 고무함량을 가진 실시예 1 내지 3은 투명도(haze), 착색성 및 내후성이 모두 뛰어남을 확인할 수 있었다.As shown in Tables 1 and 2, the ASA-based resin compositions (Examples 1 to 5) according to the present invention have mechanical strength such as impact strength and tensile strength, and MI compared to Comparative Examples 1 to 6 that do not conform to the present invention. It was confirmed that the expressed processability had a value equal to or higher than that in terms of transparency (haze), colorability, and weather resistance. In particular, it was confirmed that Examples 1 to 3 having a more preferable range of composition ratio and rubber content were excellent in all of transparency (haze), colorability, and weather resistance.
따라서, 본 발명에 따른 ASA계 수지 조성물은 기계적 물성과 가공성을 종래 ASA계 조성물 대비 동등 이상을 유지하면서 일정 이상의 가공 두께에서도 착색성과 투명도가 모두 뛰어나 무도장, 투명, 고채도 또는 특수 칼라 등의 성질을 갖는 고부가가치의 제품에 적용 가능함을 확인할 수 있었다.Therefore, the ASA-based resin composition according to the present invention maintains mechanical properties and processability equal to or higher than that of the conventional ASA-based composition, and is excellent in both colorability and transparency even at a certain processing thickness. It was confirmed that it can be applied to high value-added products.
Claims (12)
ASA계 수지 조성물.Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer 20 to 47% by weight, alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer 23 to having an average particle diameter of 50 to 150 nm as a core It characterized in that it comprises 55% by weight and 25 to 45% by weight of a poly(alkyl methacrylate) resin
ASA resin composition.
상기 ASA계 수지 조성물은 ASTM D1003에 의거하여 측정된 투명도(Haze)가 7 이하인 것을 특징으로 하는
ASA계 수지 조성물.The method of claim 1,
The ASA-based resin composition is characterized in that the transparency (Haze) measured according to ASTM D1003 is 7 or less.
ASA resin composition.
상기 ASA계 수지 조성물은 총 고무 함량이 10 내지 23 중량%인 것을 특징으로 하는
ASA계 수지 조성물.The method of claim 1,
The ASA-based resin composition is characterized in that the total rubber content is 10 to 23% by weight
ASA resin composition.
상기 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체는 아크릴레이트 고무 40 내지 60 중량%, 방향족 비닐 화합물 25 내지 45 중량% 및 비닐시안 화합물 10 내지 20 중량%를 포함하여 이루어지는 것을 특징으로 하는
ASA계 수지 조성물.The method of claim 1,
The acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises 40 to 60% by weight of an acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinylcyan compound.
ASA resin composition.
상기 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체는 알킬 메타크릴레이트 45 내지 65 중량%, 방향족 비닐 화합물 25 내지 35 중량% 및 비닐시안 화합물 10 내지 20 중량%를 포함하여 이루어진 것을 특징으로 하는
ASA계 수지 조성물.The method of claim 1,
The alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer comprises 45 to 65% by weight of an alkyl methacrylate, 25 to 35% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinylcyan compound. doing
ASA resin composition.
상기 알킬 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체는 중량 평균 분자량이 10,000 내지 150,000 g/mol인 것을 특징으로 하는
ASA계 수지 조성물.The method of claim 1,
The alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of 10,000 to 150,000 g/mol.
ASA resin composition.
상기 폴리(알킬 메타크릴레이트) 수지는 알킬기의 탄소수가 1 내지 15인 알킬 메타크릴레이트를 포함하여 이루어진 중합체인 것을 특징으로 하는
ASA계 수지 조성물.The method of claim 1,
The poly(alkyl methacrylate) resin is a polymer comprising an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group.
ASA resin composition.
상기 폴리(알킬 메타크릴레이트) 수지는 중량 평균 분자량이 50,000 내지 200,000 g/mol인 것을 특징으로 하는
ASA계 수지 조성물.The method of claim 1,
The poly(alkyl methacrylate) resin has a weight average molecular weight of 50,000 to 200,000 g/mol.
ASA resin composition.
상기 ASA계 수지 조성물은 활제, 열안정제 및 자외선 안정제 중 1 이상을 0.05 내지 5 중량부로 포함하는 것을 특징으로 하는
ASA계 수지 조성물.The method of claim 1,
The ASA-based resin composition comprises 0.05 to 5 parts by weight of at least one of a lubricant, a heat stabilizer, and an ultraviolet stabilizer.
ASA resin composition.
성형품.It characterized in that it is prepared from the ASA-based resin composition of any one of claims 1 to 9
Molded products.
상기 성형품은 외장재, 마감재, 무도장 제품 또는 압출 프로파일인 것을 특징으로 하는
성형품.The method of claim 10,
The molded product is an exterior material, a finish material, an unpainted product, or an extrusion profile.
Molded products.
성형품의 제조방법.
Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer 20 to 47% by weight, alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer 23 to having an average particle diameter of 50 to 150 nm as a core Preparing a pellet by kneading and extruding 55% by weight and 25 to 45% by weight of a poly(alkyl methacrylate) resin under 200 to 300°C and 100 to 500 rpm conditions; And sheet molding or injection molding the produced pellets at a molding temperature of 200 to 300° C. to produce a molded article.
Manufacturing method of molded products.
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| CN202080016926.3A CN113490719A (en) | 2019-10-07 | 2020-09-28 | ASA-based resin composition, molded article comprising ASA-based resin composition, and method for producing molded article |
| US17/435,511 US20220135786A1 (en) | 2019-10-07 | 2020-09-28 | Asa-based resin composition, molded article including asa-based resin composition, and method of manufacturing molded article |
| PCT/KR2020/013200 WO2021071156A1 (en) | 2019-10-07 | 2020-09-28 | Asa-based resin composition, molded product comprising same, and method for manufacturing molded product |
| EP20874125.6A EP3916051A4 (en) | 2019-10-07 | 2020-09-28 | Asa-based resin composition, molded product comprising same, and method for manufacturing molded product |
| TW109133950A TW202115180A (en) | 2019-10-07 | 2020-09-29 | Asa-based resin composition, molded article including asa-based resin composition, and method of manufacturing molded article |
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| KR20180075743A (en) * | 2016-12-26 | 2018-07-05 | 주식회사 엘지화학 | Thermoplastic resin composition, method for preparing the same composition and molding product comprising the same composition |
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| WO2013100448A1 (en) * | 2011-12-30 | 2013-07-04 | 제일모직주식회사 | Asa graft copolymer having superior shock resistance, weather resistance, coloring properties, and method for manufacturing same |
| KR101486564B1 (en) * | 2012-07-04 | 2015-01-26 | 제일모직 주식회사 | Thermoplastic resin composition and molded product using the same |
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| US20030162895A1 (en) * | 2002-02-28 | 2003-08-28 | General Electric Company | Weatherable styrenic blends with improved translucency |
| KR20090095764A (en) | 2008-03-06 | 2009-09-10 | 주식회사 엘지화학 | Termoplastic Resin Composition Having A Good Weather Resistance And Low Gloss |
| KR20180075743A (en) * | 2016-12-26 | 2018-07-05 | 주식회사 엘지화학 | Thermoplastic resin composition, method for preparing the same composition and molding product comprising the same composition |
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