CN118234801A - Thermoplastic resin composition, method for preparing the same, and molded article comprising the same - Google Patents
Thermoplastic resin composition, method for preparing the same, and molded article comprising the same Download PDFInfo
- Publication number
- CN118234801A CN118234801A CN202380013891.1A CN202380013891A CN118234801A CN 118234801 A CN118234801 A CN 118234801A CN 202380013891 A CN202380013891 A CN 202380013891A CN 118234801 A CN118234801 A CN 118234801A
- Authority
- CN
- China
- Prior art keywords
- weight
- thermoplastic resin
- resin composition
- alkyl
- alkyl acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 130
- 239000011342 resin composition Substances 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 25
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 110
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 72
- 229920001971 elastomer Polymers 0.000 claims abstract description 65
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 65
- 239000005060 rubber Substances 0.000 claims abstract description 65
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 33
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 30
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 26
- -1 2H-benzotriazole-2-yl Chemical group 0.000 claims description 71
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 38
- 229920000642 polymer Polymers 0.000 claims description 38
- 238000002834 transmittance Methods 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 28
- 238000012360 testing method Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 17
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 13
- 239000012964 benzotriazole Substances 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- 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 claims description 3
- 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 claims description 3
- 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 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 230000002087 whitening effect Effects 0.000 abstract description 66
- 239000000463 material Substances 0.000 abstract description 33
- 238000005452 bending Methods 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 34
- 230000000704 physical effect Effects 0.000 description 26
- 239000000523 sample Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 20
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 19
- 238000007720 emulsion polymerization reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 239000012760 heat stabilizer Substances 0.000 description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 10
- 238000002845 discoloration Methods 0.000 description 10
- 239000008188 pellet Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 239000007983 Tris buffer Substances 0.000 description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000001923 cyclic compounds Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- FFODZTFGFDDGQQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;5-phenylpenta-2,4-dienenitrile Chemical compound CC(=C)C(O)=O.N#CC=CC=CC1=CC=CC=C1 FFODZTFGFDDGQQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000008431 aliphatic amides Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- WTBQHHMNCOSCIX-UHFFFAOYSA-N (2-tert-butylphenyl) dihydroxyphosphanyl hydrogen phosphite Chemical compound CC(C)(C)C1=CC=CC=C1OP(O)OP(O)O WTBQHHMNCOSCIX-UHFFFAOYSA-N 0.000 description 1
- OXDXXMDEEFOVHR-CLFAGFIQSA-N (z)-n-[2-[[(z)-octadec-9-enoyl]amino]ethyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCNC(=O)CCCCCCC\C=C/CCCCCCCC OXDXXMDEEFOVHR-CLFAGFIQSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 1
- KQJQPCJDKBKSLV-UHFFFAOYSA-N 1-bromo-3-ethenylbenzene Chemical compound BrC1=CC=CC(C=C)=C1 KQJQPCJDKBKSLV-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- JGRXEBOFWPLEAV-UHFFFAOYSA-N 2-ethylbutyl prop-2-enoate Chemical compound CCC(CC)COC(=O)C=C JGRXEBOFWPLEAV-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- RLFXJQPKMZNLMP-UHFFFAOYSA-N 2-phenylprop-2-enenitrile Chemical compound N#CC(=C)C1=CC=CC=C1 RLFXJQPKMZNLMP-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- KLYKQEQFQCBBRW-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid;octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O KLYKQEQFQCBBRW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- WQIXJMLUGLNSFT-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.CC1=C(C=C(C(=C1)O)C(C)(C)C)CCCC WQIXJMLUGLNSFT-UHFFFAOYSA-N 0.000 description 1
- GQEFPXSNRRKUHO-UHFFFAOYSA-N 4-methylpent-1-enylbenzene Chemical compound CC(C)CC=CC1=CC=CC=C1 GQEFPXSNRRKUHO-UHFFFAOYSA-N 0.000 description 1
- ACYXOHNDKRVKLH-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile prop-2-enoic acid Chemical group OC(=O)C=C.N#CC=CC=CC1=CC=CC=C1 ACYXOHNDKRVKLH-UHFFFAOYSA-N 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 1
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 1
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- VYGRRCKMMADGBB-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] phosphono hydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(=O)OP(O)(O)=O VYGRRCKMMADGBB-UHFFFAOYSA-N 0.000 description 1
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003831 antifriction material Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- ZEFSGHVBJCEKAZ-UHFFFAOYSA-N bis(2,4-ditert-butyl-6-methylphenyl) ethyl phosphite Chemical compound CC=1C=C(C(C)(C)C)C=C(C(C)(C)C)C=1OP(OCC)OC1=C(C)C=C(C(C)(C)C)C=C1C(C)(C)C ZEFSGHVBJCEKAZ-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002996 emotional effect Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229940064639 minipress Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- AXRSHKZFNKUGQB-UHFFFAOYSA-N octyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC)OC1=CC=CC=C1 AXRSHKZFNKUGQB-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- WFXFYZULCQKPIP-UHFFFAOYSA-N prazosin hydrochloride Chemical compound [H+].[Cl-].N=1C(N)=C2C=C(OC)C(OC)=CC2=NC=1N(CC1)CCN1C(=O)C1=CC=CO1 WFXFYZULCQKPIP-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- URRFGQHFJDWCFM-UHFFFAOYSA-N tris(2-butoxyethyl) phosphite Chemical compound CCCCOCCOP(OCCOCCCC)OCCOCCCC URRFGQHFJDWCFM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a thermoplastic resin composition, a method of preparing the composition, and a molded article comprising the composition. More specifically, the present invention relates to a thermoplastic resin composition, a method of preparing the thermoplastic resin composition, and a molded article comprising the thermoplastic resin composition, the composition comprising 100 parts by weight of a base resin comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a) containing an alkyl acrylate rubber and one or more (B) selected from the group consisting of an alkyl (meth) acrylate polymer (B-1) and an alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2); and 0.1 to 6 parts by weight of an acrylic copolymer (C), wherein the thermoplastic resin composition has an alkyl acrylate coverage (X) value of 65% by weight or more as calculated in equation 1. According to the present invention, the present invention has an effect of providing a thermoplastic resin composition having excellent processability and film processability due to excellent mechanical properties such as impact strength, tensile strength and bending strength, and flowability, being applicable to unpainted materials due to excellent transparency, and having non-whitening performance preventing whitening upon bending or impact, and being capable of providing an aesthetic appearance due to excellent ultraviolet shielding ability in a short wavelength of high energy, a method of preparing the same, and a molded article comprising the same.
Description
Cross Reference to Related Applications
The present application claims priority from korean patent application No. 10-2022-01335354 filed by the korean intellectual property office on day 10, month 20 of 2022 and korean patent application No. 10-2022-0135348 filed on day 10, 2022, each of the disclosures of which are incorporated herein by reference.
Technical Field
The present invention relates to a thermoplastic resin composition, a method of preparing the composition, and a molded article comprising the composition. More particularly, the present invention relates to a thermoplastic resin composition having excellent processability and film processability due to excellent mechanical properties such as impact strength, tensile strength and flexural strength, and flowability, applicable to unpainted materials due to excellent transparency, and having non-whitening properties preventing whitening upon bending or impact, a method of preparing the same, and a molded article comprising the same.
Background
An acrylonitrile-butadiene-styrene resin (hereinafter referred to as "ABS resin") is based on a conjugated diene rubber, has excellent workability, mechanical properties and appearance properties, and is suitable for various fields such as electric and electronic products, automobiles, toys, furniture and construction materials. However, since ABS resins are based on butadiene rubber containing chemically unstable unsaturated bonds, rubber polymers contained in ABS resins are easily damaged by ultraviolet rays. Therefore, ABS resins are very poor in weather resistance and are unsuitable for use as outdoor materials.
In order to overcome the problems of ABS resins, acrylic copolymers having no ethylenic unsaturation are used. A representative acrylic copolymer is an acrylate-styrene-acrylonitrile graft copolymer (hereinafter referred to as "ASA resin"). ASA resins have excellent physical properties such as processability, impact resistance, chemical resistance and weather resistance. Because of these advantages, ASA resins are used in various fields such as building materials, interior and exterior materials for automobiles and motorcycles, electric and electronic products, ships, leisure products, and gardening products, the demand for which is rapidly increasing.
In addition, as the demand for emotional quality and high quality increases in the market, research is being conducted to achieve a luxurious appearance and excellent colorability and weather resistance by decorating the outer surface of materials such as ABS resin, PVC, and steel sheet with ASA resin. Typically, such decorative materials are manufactured in the form of films, and then subjected to bending processes such as bending and folding according to the shape of the applied substrate to produce the final product. However, due to the nature of thermoplastic ASA resins, there are problems: that is, whitening occurs when the above-mentioned decoration treatment is performed at room temperature, resulting in loss of initial color and deterioration of aesthetic appearance. In addition, films made of ASA resins are painted to obtain desired colors and textures according to the application fields. Recently, for the purpose of being eco-friendly and reducing costs, the demand for unpainted materials that do not require painting is increasing. In addition, due to the nature of the transparent decorative material, ultraviolet shielding ability is required to prevent discoloration of the substrate in addition to weather resistance.
Therefore, it is necessary to develop a material that has excellent mechanical properties, workability, film workability, and ultraviolet shielding ability and is capable of preventing occurrence of whitening during bending processing.
[ Prior Art literature ]
[ Patent literature ]
KR 2009-0095764 A
Disclosure of Invention
Technical problem
Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide a thermoplastic resin composition having excellent processability and film processability due to excellent mechanical properties such as impact strength, tensile strength and flexural strength, and flowability, having excellent transparency, having non-whitening properties, and having excellent ultraviolet shielding ability in short wavelengths of high energy, and having a luxurious appearance.
It is another object of the present invention to provide a method for preparing a thermoplastic resin composition.
It is still another object of the present invention to provide a molded article manufactured using the thermoplastic resin composition.
The above and other objects can be accomplished by the present invention as described below.
Technical proposal
I) According to one aspect of the present invention, there is provided a thermoplastic resin composition comprising 100 parts by weight of a base resin comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a) containing an alkyl acrylate rubber, and one or more selected from the group consisting of an alkyl (meth) acrylate polymer (B-1) and an alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2); and 0.1 to 6 parts by weight of an acrylic copolymer (C), wherein the thermoplastic resin composition has an alkyl acrylate coverage (X) value of 65% by weight or more, as calculated by the following equation 1.
Equation 1 x = { (G-Y)/Y } ×100,
Wherein G represents the gel content (wt%) based on the total weight of the thermoplastic resin composition, and Y represents the content (wt%) of the alkyl acrylate in the gel based on the total weight of the thermoplastic resin composition.
II) according to I), the base resin may preferably contain 41 to 80% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A) containing an alkyl acrylate rubber having an average particle diameter of 50 to 120nm and 20 to 59% by weight of one or more selected from the group consisting of (meth) alkyl acrylate polymer (B-1) and (meth) alkyl acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2).
III) according to I) or II), the base resin may preferably comprise 45 to 75% by weight of the graft copolymer (A), 5 to 45% by weight of the polymer (b-1) and 1 to 35% by weight of the polymer (b-2).
IV) according to I) to III), the thermoplastic resin composition may preferably contain 0.3 to 4.5 parts by weight of a benzotriazole-based ultraviolet stabilizer (D).
V) according to I) to IV), the benzotriazole-based ultraviolet stabilizers (D) may preferably comprise one or more selected from the group consisting of 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) -benzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chloro-benzotriazole, 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chloro-benzotriazole, 2- (2 ' -hydroxy-3, 5-di-tert-pentylphenyl) benzotriazole, 2- [2' -hydroxy-3 ',5' -bis (1, 1-dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) benzotriazole and 2- (2H-benzotriazole-2-yl) -4- (1, 3-tetramethylbutyl) phenol.
VI) according to I) to V), the graft copolymer (A) may preferably comprise from 25 to 50% by weight, based on the total weight of the graft copolymer (A), of an alkyl acrylate rubber having an average particle diameter of from 50nm to 120nm and from 50 to 75% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer surrounding the alkyl acrylate rubber.
VII) according to I) to VI), the graft copolymer (a) may preferably comprise 25 to 50% by weight of the alkyl acrylate rubber and 50 to 75% by weight of the aromatic vinyl compound-vinyl cyanide compound copolymer surrounding the alkyl acrylate rubber, based on the total weight of the graft copolymer (a).
VIII) according to I) to VII), the graft copolymer (a) may preferably have a degree of grafting of 58% or more, as calculated by the following equation 3.
[ Equation 3]
Grafting degree (%) = [ weight of grafting monomer (g)/weight of rubber (g) ]. Times.100,
Wherein the weight (g) of the graft monomer is obtained by subtracting the weight (g) of the rubber, which is the weight (g) of the rubber component theoretically added to the graft copolymer powder, from the weight (g) of the insoluble matter (gel) obtained by dissolving the graft copolymer in acetone and centrifuging.
IX) according to I) to VIII), the polymer (b-1) and the polymer (b-2) may each independently have a weight average molecular weight of preferably 50,000g/mol to 150,000 g/mol.
X) according to I) to IX), the polymer (b-2) may preferably comprise 60% to 90% by weight of alkyl (meth) acrylate, 5% to 30% by weight of aromatic vinyl compound and 1% to 20% by weight of vinyl cyanide compound.
XI) according to I) to X), the acrylic copolymer (C) may preferably comprise an alkyl acrylate cross-link comprising 5 to 20% by weight of an alkyl acrylate monomer and 0.01 to 0.3% by weight of a cross-linking agent; 54 to 90 weight percent methyl methacrylate monomer; and 4 to 40 wt% of one or more selected from the group consisting of alkyl acrylate monomers and alkyl methacrylate monomers.
XII) according to I) to XI), the crosslinking agent may preferably comprise one or more selected from the group consisting of allyl methacrylate, trimethylolpropane, triacrylate and divinylbenzene.
XIII) according to I) to XII), the acrylic copolymer (C) may preferably have a weight average molecular weight of from 900,000g/mol to 1,300,000g/mol.
XIV) according to I) to XIII), the thermoplastic resin composition may preferably have a haze of 5.7% or less, as measured according to ASTM D1003 using an injection sample.
XV) according to I) to XIV), the thermoplastic resin composition may preferably have a haze of 10% or less, as measured according to ASTM D1003 after an Erichsen cup test by cup test of a 9mm region of a film having a thickness of 0.15mm at a motor speed of 7rpm for 1 minute using an Erichsen cup tester.
XVI) according to I) to XV), the transmittance of the thermoplastic resin composition may preferably be 8% or less, as measured at 380nm using a sheet having a thickness of 0.15mm and an ultraviolet-visible spectrophotometer.
XVII) according to another aspect of the present invention, there is provided a process for producing a thermoplastic resin composition, which comprises kneading and extruding 100 parts by weight of a base resin comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A) containing an alkyl acrylate rubber and one or more (B) selected from the group consisting of (meth) acrylic acid alkyl ester polymer (B-1) and (meth) acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2) and 0.1 parts by weight to 6 parts by weight of an acrylic acid copolymer (C) at 200℃to 300℃and 100rpm to 500rpm, wherein the thermoplastic resin composition has an alkyl acrylate coverage (X) value of 65% by weight or more, as calculated in the following equation 1.
[ Equation 1]
X＝{(G-Y)/Y}×100，
Wherein G represents the gel content (wt%) based on the total weight of the thermoplastic resin composition, and Y represents the content (wt%) of the alkyl acrylate in the gel based on the total weight of the thermoplastic resin composition.
XVIII) according to still another aspect of the present invention, there is provided a molded article comprising the thermoplastic resin composition according to any one of I) to XVI).
Advantageous effects
According to the present invention, the present invention has an effect of providing a thermoplastic resin composition having excellent processability and film processability due to excellent mechanical properties such as impact strength, tensile strength and bending strength, and flowability, capable of providing an attractive appearance due to excellent transparency, having non-whitening performance preventing whitening upon bending or impact, and applicable to unpainted materials, a method of preparing the same, and a molded article comprising the same.
In addition, according to the present invention, the present invention has the effect of providing a thermoplastic resin composition having a luxurious appearance due to excellent ultraviolet shielding ability in a short wavelength of high energy, a method of preparing the same, and a molded article comprising the same.
In addition, the present invention has the effect of providing a molded article comprising the thermoplastic resin composition of the present invention. When the molded article is used as a facing material, the molded article can provide physical properties superior to those required in the market.
Drawings
FIG. 1 shows an Erichsen cup bulge tester performing the Erichsen cup bulge test.
FIG. 2 shows the surface of the films after the Erichsen cup bulge test was performed on the films produced in example 1 and comparative example 1.
Detailed Description
Hereinafter, the thermoplastic resin composition of the present invention, the method for preparing the same, and the molded article comprising the same will be described in detail.
The present inventors confirmed that when a thermoplastic resin composition capable of providing a finishing material having an attractive appearance and applicable to unpainted materials is studied by comprising a base resin (comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer and one or more selected from the group consisting of an alkyl (meth) acrylate polymer and an alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer) in a predetermined content ratio; and an acrylic copolymer, and when the alkyl acrylate coverage value of the thermoplastic resin composition is adjusted within a predetermined range, mechanical properties such as impact strength, tensile strength and flexural strength, flowability, transparency and non-whitening properties are excellent, and processability, film processability and appearance quality are greatly improved. Because of these advantages, the thermoplastic resin composition can be applied to unpainted materials. In addition, when the benzotriazole-based ultraviolet stabilizer is contained in a small amount, weather resistance and ultraviolet shielding ability are also improved. Based on these results, the present inventors have conducted further studies to complete the present invention.
The thermoplastic resin composition of the present invention will be described in detail below.
The thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a) containing an alkyl acrylate rubber, and one or more (B) selected from the group consisting of an alkyl (meth) acrylate polymer (B-1) and an alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2); and 0.1 to 6 parts by weight of an acrylic copolymer (C). The thermoplastic resin composition has an alkyl acrylate coverage (X) value of 65 wt% or more as calculated by the following equation 1. In this case, the thermoplastic resin composition may have excellent processability and film processability due to excellent mechanical properties such as impact strength, tensile strength and flexural strength, and flowability, and the thermoplastic composition may be suitable for unpainted materials due to excellent transparency, and non-whitening properties preventing whitening upon bending or impact.
Equation 1 x= { (G-Y)/Y } ×100
In equation 1, G represents the gel content (wt%) based on the total weight of the thermoplastic resin composition, and Y represents the content (wt%) of the alkyl acrylate in the gel based on the total weight of the thermoplastic resin composition.
Hereinafter, each component of the thermoplastic resin composition of the present invention will be described in detail.
(A) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing alkyl acrylate rubber
For example, the content of the graft copolymer (a) may be 41 to 80 wt%, preferably 45 to 75 wt%, more preferably 45 to 65 wt%, and still more preferably 47 to 55 wt%, based on the total weight of the base resin. Within this range, mechanical properties such as impact strength, tensile strength, and flexural strength, transparency, and workability may be excellent.
As another example, the content of the graft copolymer (a) may be 45 to 75 wt%, preferably 50 to 70 wt%, and even more preferably 50 to 60 wt%, based on the total weight of the base resin. Within this range, mechanical properties such as impact strength, tensile strength, and flexural strength, transparency, and workability may be excellent.
For example, the graft copolymer (a) may comprise an alkyl acrylate rubber (core) and an aromatic vinyl compound-vinyl cyanide compound copolymer (shell) surrounding the alkyl acrylate rubber.
For example, the graft copolymer (a) may comprise 25 to 50 wt%, preferably 30 to 50 wt%, more preferably 35 to 50 wt% of the alkyl acrylate rubber (core), based on the total weight of the graft copolymer (a); and 50 to 75% by weight, preferably 50 to 70% by weight, more preferably 50 to 65% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer (shell) surrounding the alkyl acrylate rubber. Within this range, mechanical properties, transparency, gloss, flowability, and non-whitening properties may be excellent.
For example, the alkyl acrylate rubber may comprise an alkyl acrylate rubber having an average particle diameter of 50nm to 120nm, preferably 60nm to 120nm, more preferably 80nm to 110 nm. Within this range, excellent impact strength, gloss and non-whitening properties can be imparted to the finally produced thermoplastic resin composition.
In the present disclosure, the average particle size may be measured by dynamic light scattering, and in particular, may be measured as an intensity value in a gaussian mode using a Nicomp380 particle size analyzer (manufacturer: PSS). As a specific measurement example, a sample may be prepared by diluting 0.1g of latex (TSC: 35 to 50 wt%) 1,000 to 5,000 times with distilled water, and the average particle diameter may be measured in an autodiluted manner and in a dynamic light scattering/intensity 300 kHz/intensity-weight-gaussian analysis mode using a flow cell. At this time, the temperature may be set to 23 ℃, the measurement wavelength may be set to 632.8nm, and the channel width may be set to 10 musec.
For example, alkyl acrylate rubbers may be prepared by emulsion polymerization of alkyl acrylates. Preferably, the alkyl acrylate rubber may be prepared by mixing an acrylic acid ester compound, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte and a solvent and emulsion polymerizing the mixture. In this case, mechanical properties may be excellent due to excellent grafting efficiency.
For example, the alkyl acrylate rubber may contain an aromatic vinyl compound. In this case, the mechanical properties can be further improved. For example, the alkyl acrylate rubber may contain an aromatic vinyl compound in an amount of 0.1 to 25% by weight, preferably 2 to 23% by weight, more preferably 5 to 20% by weight, based on 100% by weight of the total alkyl acrylate rubber. Within this range, mechanical properties, gloss, and transparency may be excellent without deteriorating physical properties.
For example, the alkyl acrylate rubber may comprise seeds, preferably rubber seeds.
For example, the seed may be prepared by polymerizing 1 to 20% by weight, preferably 2 to 15% by weight, more preferably 3 to 10% by weight of one or more monomers selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and alkyl acrylates, based on 100% by weight of the graft copolymer (a). Within this range, impact resistance, weather resistance, and physical property balance may be excellent.
For example, the aromatic vinyl compound-vinyl cyanide compound copolymer (shell) may have a weight average molecular weight of 40,000g/mol to 120,000g/mol, preferably 50,000g/mol to 110,000g/mol, more preferably 60,000g/mol to 110,000g/mol. Within this range, the workability and non-whitening performance may be excellent without decreasing the impact strength.
In the present disclosure, unless otherwise defined, the weight average molecular weight may be measured using gel permeation chromatography (GPC, waters Breeze). As a specific example, the weight average molecular weight can be measured by gel permeation chromatography (GPC, waters Breeze) using Tetrahydrofuran (THF) as an eluent. In this case, the weight average molecular weight obtained is a relative value with respect to a Polystyrene (PS) standard sample. As a specific measurement example, the weight average molecular weight can be measured under the following conditions, solvent: THF, column temperature: 40 ℃, flow rate: 0.3ml/min, sample concentration: 20mg/ml, injection amount: 5 μl, column model ：1×PLgel 10μm MiniMix-B(250×4.6mm)+1×PLgel 10μmMiniMix-B(250×4.6mm)+1×PLgel 10μm MiniMix-B Guard(50×4.6mm), device name: agilent 1200 series system, refractive index detector: agilent G1362 RID, RI temperature: 35 ℃, data processing: agilent ChemStation S/W, test methods (Mn, mw and PDI): OECD TG 118.
For example, the aromatic vinyl compound-vinyl cyanide compound copolymer (shell) may comprise 55 to 85 wt% of the aromatic vinyl compound and 15 to 45 wt% of the vinyl cyanide compound, preferably 60 to 80 wt% of the aromatic vinyl compound and 20 to 40 wt% of the vinyl cyanide compound, more preferably 65 to 75 wt% of the aromatic vinyl compound and 25 to 35 wt% of the vinyl cyanide compound, based on the total weight of the aromatic vinyl compound-vinyl cyanide compound copolymer (shell). Within this range, impact resistance and weather resistance may be excellent.
The aromatic vinyl compound-vinyl cyanide compound copolymer (shell) may preferably contain an alkyl acrylate. In this case, the physical property balance between impact resistance, workability, and non-whitening properties may be excellent.
For example, the aromatic vinyl compound-vinyl cyanide compound copolymer (shell) may comprise 60 to 85 wt% of the aromatic vinyl compound, 5 to 35 wt% of the vinyl cyanide compound, and 1 to 20 wt% of the alkyl acrylate, preferably 65 to 80 wt% of the aromatic vinyl compound, 12 to 27 wt% of the vinyl cyanide compound, and 5 to 15 wt% of the alkyl acrylate, more preferably 70 to 75 wt% of the aromatic vinyl compound, 17 to 22 wt% of the vinyl cyanide compound, and 7 to 10 wt% of the alkyl acrylate, based on 100 wt% of the total aromatic vinyl compound-vinyl cyanide compound copolymer (shell). Within this range, impact resistance and weather resistance may be excellent.
In the present disclosure, for example, the alkyl acrylate may be an alkyl acrylate containing an alkyl group having 1 to 15 carbon atoms. Preferably, the alkyl acrylate may include one or more selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate and dodecyl acrylate, more preferably an alkyl acrylate containing an alkyl group having 1 to 4 carbon atoms, and even more preferably butyl acrylate, ethylhexyl acrylate or a mixture thereof.
In the present disclosure, for example, the aromatic vinyl compound may include one or more selected from the group consisting of styrene, α -methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, t-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene and vinylnaphthalene, preferably one or more selected from the group consisting of styrene and α -methylstyrene, and even more preferably styrene. In this case, workability and, for example, impact resistance may be excellent due to proper flowability.
In the present disclosure, for example, the vinyl cyanide compound may include one or more selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α -chloroacrylonitrile, preferably acrylonitrile.
For example, the graft copolymer (A) may be prepared by emulsion polymerization. In this case, the glossiness and the surface hardness may be excellent.
The emulsion polymerization method generally carried out in the art to which the present invention pertains may be used in the present invention without particular limitation. For example, an emulsion graft polymerization process may be used.
In the present disclosure, a polymer containing a certain compound (monomer) refers to a polymer prepared by polymerizing the compound (monomer), and units in the polymer are derived from the compound.
For example, the graft copolymer (a) may have a degree of grafting of 58% or more, preferably 58% to 150%, more preferably 65% to 140%, still more preferably 65% to 130%, still more preferably 65% to 100%, still more preferably 65% to 80%, as calculated by the following equation 3. Within this range, impact resistance, workability, and non-whitening performance may be excellent.
[ Equation 3]
Grafting degree (%) = [ weight of grafting monomer (g)/weight of rubber (g) ]. Times.100
In equation 3, the weight (g) of the graft monomer is obtained by subtracting the weight (g) of the rubber, which is the weight (g) of the rubber component theoretically added to the graft copolymer powder, from the weight (g) of the insoluble matter (gel) obtained by dissolving the graft copolymer in acetone and centrifuging.
When the insoluble matter (gel) weight was measured, 0.5g of the powdery graft copolymer (A) was added to 50ml of acetone, followed by stirring at room temperature for 12 hours. Then, centrifugation was performed to separate insoluble matters insoluble in acetone, followed by drying for 12 hours. Then, the weight of the insoluble matter (gel) was measured. The rubber weight (g) is the weight (g) of the rubber component theoretically added to 0.5g of the powdery graft copolymer (A).
As a specific measurement example, when the insoluble matter (gel) weight was measured, 0.5g of the powdery graft copolymer was added to 50ml of acetone, followed by stirring at 210rpm and room temperature for 12 hours using an orbital shaker (apparatus name: lab comparative SKC-6075). Then, the mixture was centrifuged at 0℃and 18,000rpm for 3 hours using a centrifuge (Supra R30, HANIL SCIENCE Co.) to separate insoluble matters insoluble in acetone, followed by drying by forced circulation in a forced convection oven (apparatus name: lab companion OF-12 GW) set at 85℃for 12 hours. Then, the weight of the insoluble matter (gel) was measured.
(B) One or more selected from the group consisting of (meth) acrylic acid alkyl ester polymer (b-1) and (meth) acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer (b-2)
For example, the content of one or more (B) selected from the group consisting of the alkyl (meth) acrylate polymer (B-1) and the alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2) may be 20 to 59% by weight, preferably 25 to 55% by weight, more preferably 35 to 55% by weight, and even more preferably 45 to 53% by weight, based on 100% by weight of the base resin. Within this range, the processability, transparency, and non-whitening properties may be excellent.
The one or more (B) selected from the group consisting of the alkyl (meth) acrylate polymer (B-1) and the alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2) may preferably be a mixture of the alkyl (meth) acrylate polymer (B-1) and the alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2). In this case, transparency, weather resistance, and ultraviolet-visible light transmittance may be excellent.
The weight ratio (b-1:b-2) of the alkyl (meth) acrylate polymer (b-1) and the alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (b-2) may preferably be 7:3 to 8.2:1.8, more preferably 7.5:2.5 to 8:2. Within this range, transparency, weather resistance, and ultraviolet-visible light transmittance may be excellent.
(B-1) alkyl (meth) acrylate polymers
For example, the content of the alkyl (meth) acrylate polymer (b-1) may be 10 to 59 wt%, preferably 25 to 45 wt%, more preferably 27 to 42 wt%, based on 100 wt% of the base resin. Within this range, transparency, gloss, and non-whitening properties may be excellent while maintaining mechanical properties.
As another example, the content of the alkyl (meth) acrylate polymer (b-1) may be 5 to 45 wt%, preferably 15 to 40wt%, more preferably 25 to 40wt%, based on 100 wt% of the base resin. Within this range, transparency, gloss, and non-whitening properties may be excellent while maintaining mechanical properties.
For example, the alkyl (meth) acrylate polymer (b-1) may include one or more selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, and dodecyl (meth) acrylate, preferably alkyl methacrylate, alkyl acrylate, or a mixture thereof, more preferably polymethyl methacrylate resin. In this case, glossiness, colorability, and scratch resistance may be excellent.
In the present disclosure, the alkyl (meth) acrylate polymer may be a polymer comprising alkyl (meth) acrylate in an amount greater than 85 wt%, 90 wt% or more, or 95 wt% or more.
In the present disclosure, unless otherwise indicated, "alkyl acrylate" or "alkyl methacrylate" may both refer to alkyl (meth) acrylates.
For example, the polymethyl methacrylate resin may contain methyl methacrylate and methyl acrylate. Preferably, the polymethyl methacrylate resin may contain methyl acrylate in an amount of 1 to 10% by weight, more preferably 2 to 7% by weight. Within this range, gloss, flowability and impact resistance can be improved due to excellent compatibility with the alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (b-2).
For example, the polymer (b-1) may have a weight average molecular weight of 50,000g/mol to 150,000g/mol, preferably 60,000g/mol to 130,000g/mol, more preferably 70,000g/mol to 120,000g/mol, and still more preferably 80,000g/mol to 110,000g/mol. Within this range, transparency, non-whitening properties, and total ultraviolet-visible light transmittance may be excellent while maintaining impact resistance.
For example, the alkyl (meth) acrylate polymer (b-1) may have a glass transition temperature of 80℃to 130℃and preferably 90℃to 120 ℃. Within this range, heat resistance may be excellent.
In the present disclosure, the glass transition temperature may be measured using a Differential Scanning Calorimeter (DSC) according to ASTM D3418. As a specific example, the glass transition temperature can be measured using a differential scanning calorimeter (Q100 DSC, TA Instruments co.) at a heating rate of 10 ℃/min.
For example, the alkyl (meth) acrylate polymer (b-1) may be prepared by suspension polymerization. The suspension polymerization method generally carried out in the art to which the present invention pertains may be used in the present invention without particular limitation.
(B-2) alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer
For example, the content of the polymer (b-2) may be 10 to 59% by weight, preferably 17 to 40% by weight, more preferably 12 to 32% by weight, based on 100% by weight of the entire base resin. Within this range, the compatibility with the alkyl (meth) acrylate polymer (b-1), mechanical properties and flowability may be excellent.
As another example, the content of the polymer (b-2) may be 1 to 35% by weight, preferably 5 to 30% by weight, more preferably 5 to 20% by weight, based on 100% by weight of the total base resin. Within this range, the compatibility with the alkyl (meth) acrylate polymer (b-1), mechanical properties and flowability may be excellent.
For example, the polymer (b-2) may contain 60 to 90% by weight of the alkyl (meth) acrylate compound, 5 to 30% by weight of the aromatic vinyl compound, and 1 to 20% by weight of the vinyl cyanide compound, based on the total weight of the polymer (b-2). Within this range, compatibility with the graft copolymer (A) and the alkyl (meth) acrylate polymer (b-1), impact resistance, transparency, ultraviolet-visible light transmittance, and non-whitening properties may be excellent.
Preferably, the polymer (b-2) may comprise 65 to 85% by weight of the alkyl (meth) acrylate compound, 10 to 25% by weight of the aromatic vinyl compound, and1 to 15% by weight of the vinyl cyanide compound, based on the total weight of the polymer (b-2). Within this range, compatibility with the graft copolymer (A) and the alkyl (meth) acrylate polymer (b-1), mechanical properties, transparency, ultraviolet-visible light transmittance, and non-whitening properties may be excellent.
More preferably, the polymer (b-2) may contain 70 to 80% by weight of the alkyl (meth) acrylate compound, 15 to 20% by weight of the aromatic vinyl compound, and 5 to 10% by weight of the vinyl cyanide compound, based on the total weight of the polymer (b-2). Within this range, compatibility with the graft copolymer (A) and the alkyl (meth) acrylate polymer (b-1), mechanical properties, transparency, ultraviolet-visible light transmittance, and non-whitening properties may be excellent.
In the present disclosure, for example, the alkyl (meth) acrylate compound may include one or more selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, and dodecyl (meth) acrylate.
The types of the aromatic vinyl compound and the vinyl cyanide compound contained in the polymer (b-2) may be the same as those contained in the graft copolymer (A) of the present invention.
For example, the polymer (b-2) may have a weight average molecular weight of 50,000g/mol to 150,000g/mol, preferably 50,000g/mol to 140,000g/mol, more preferably 60,000g/mol to 130,000g/mol, and still more preferably 70,000g/mol to 130,000g/mol. Within this range, tensile strength, flexural strength, impact strength and non-whitening properties may be excellent.
For example, the polymer (b-2) may be prepared by bulk polymerization. The bulk polymerization method generally carried out in the art to which the present invention pertains can be used in the present invention without particular limitation.
(C) Acrylic acid copolymer
For example, the content of the acrylic copolymer (C) may be 0.1 to 6 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, still more preferably 0.5 to 3.5 parts by weight, still more preferably 0.8 to 3 parts by weight, still more preferably 0.8 to 2.5 parts by weight, based on 100 parts by weight of the base resin. Within this range, mechanical properties, flowability, transparency, non-whitening properties, and film processability may be excellent.
For example, the acrylic copolymer (C) may comprise, based on the total weight of the acrylic copolymer (C): an alkyl acrylate cross-link comprising 5 to 20 wt% of an alkyl acrylate monomer and 0.01 to 0.3 wt% of a cross-linking agent; 54 to 90 weight percent methyl methacrylate monomer; and 4 to 40 wt% of one or more selected from the group consisting of alkyl acrylate monomers and alkyl methacrylate monomers. In this case, mechanical properties, flowability, transparency, non-whitening properties, and film processability may be excellent.
For example, the crosslinking agent may include one or more selected from the group consisting of allyl methacrylate, trimethylolpropane, triacrylate, and divinylbenzene.
In the present disclosure, a cross-linked body may refer to a polymer whose molecular weight increases due to chain extension thereof by a cross-linking agent. In the present invention, the alkyl acrylate cross-linked body plays a role in improving the release swelling property by increasing the swelling degree of the acrylic copolymer.
For example, the alkyl acrylate cross-linked body may have a swelling index of 3 to 10, preferably 4 to 9. Within this range, film workability may be excellent.
In the present disclosure, to calculate the swelling index, acetone was added to 1g of an alkyl acrylate-based crosslinked powder, stirred at room temperature for 24 hours, centrifuged to obtain an acetone-insoluble fraction, and then the fraction was dried. Then, the weights of the fractions before and after drying were measured, and the swelling index was calculated by the following equation 5.
[ Equation 5]
Swelling index = weight after centrifugation before drying (g)/weight after centrifugation after drying (g)
For example, the alkyl acrylate compound of the cross-linked body may be a linear, branched or cyclic compound containing an alkyl group having 1 to 18 carbon atoms.
For example, the alkyl acrylate compound as a monomer may be a linear, branched or cyclic compound containing an alkyl group having 1 to 18 carbon atoms. Preferably, the alkyl acrylate compound as a monomer may include one or more selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate.
For example, the alkyl methacrylate as a monomer may be a linear, branched or cyclic compound containing an alkyl group having 2 to 18 carbon atoms. Preferably, the alkyl methacrylate as the monomer may include one or more selected from the group consisting of n-butyl methacrylate, dodecyl methacrylate, stearyl methacrylate, tridecyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate.
For example, the acrylic copolymer (C) may be prepared by emulsion polymerization, suspension polymerization or solution polymerization, with emulsion polymerization being preferred. In this case, workability and impact strength may be excellent.
The emulsion polymerization, suspension polymerization or solution polymerization methods generally carried out in the art to which the present invention pertains may be used in the present invention without particular limitation.
The method for producing the acrylic copolymer (C) may preferably include: a step (i) of preparing an alkyl acrylate cross-linked body having a swelling degree of 3 to 10 by comprising 5 to 20 parts by weight of an alkyl acrylate monomer and 0.01 to 0.3 parts by weight of a cross-linking agent; a step (ii) of adding 27.5 to 45 parts by weight of methyl methacrylate, 2 to 20 parts by weight of one or more monomers selected from the group consisting of alkyl acrylate compounds (containing an alkyl group having 1 to 18 carbon atoms) and alkyl methacrylate compounds (containing an alkyl group having 2 to 18 carbon atoms), an emulsifier, a crosslinking agent, a polymerization initiator, and a redox catalyst, and emulsion-polymerizing to prepare a polymer, before or after the step (i) of preparing an alkyl acrylate crosslinked body; and a step (iii) of adding 27.5 to 45 parts by weight of methyl methacrylate, 2 to 20 parts by weight of one or more monomers selected from the group consisting of an alkyl acrylate compound (containing an alkyl group having 1 to 18 carbon atoms) and an alkyl methacrylate compound (containing an alkyl group having 2 to 18 carbon atoms), an emulsifier, a crosslinking agent, a polymerization initiator, and a redox catalyst to the alkyl acrylate cross-linked body prepared in step (i) and the polymer prepared in step (ii) to complete emulsion polymerization. In this case, mechanical properties, transparency, and non-whitening properties may be excellent. In addition, workability and film workability may be excellent due to the reduced flowability.
For example, steps (I) and (I) may be performed in separate locations or reactors.
For example, the acrylic copolymer (C) may have a weight average molecular weight of 900,000g/mol to 1300,000g/mol, preferably 950,000g/mol to 250,000g/mol, more preferably 1,000,000g/mol to 1,200,000g/mol. Within this range, mechanical properties may be excellent, and flowability may be improved.
For example, the acrylic copolymer (C) may have a relative viscosity of 1.0 to 10.0, preferably 1.5 to 7.0, more preferably 1.8 to 5.5, and even more preferably 2.0 to 4.0, as measured according to ISO 3105. Within this range, fluidity can be improved, and film workability can be excellent.
The acrylic copolymer (C) may be prepared, or a commercially available product may be used as long as the product meets the definition of the present invention.
(D) Benzotriazole ultraviolet stabilizer
For example, the content of the benzotriazole-based ultraviolet stabilizer (D) may be 0.3 to 4.5 parts by weight, preferably 0.7 to 3 parts by weight, more preferably 0.7 to 2.5 parts by weight, and even more preferably 0.7 to 1.5 parts by weight, based on 100 parts by weight of the base resin. Within this range, mechanical properties, flowability, transparency, glossiness, weather resistance, and ultraviolet shielding ability may be excellent.
For example, the benzotriazole-based ultraviolet light stabilizer (D) may include one or more selected from the group consisting of 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) -benzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chloro-benzotriazole, 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chloro-benzotriazole, 2- (2 ' -hydroxy-3, 5-di-tert-pentylphenyl) benzotriazole, 2- [2' -hydroxy-3 ',5' -bis (1, 1-dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) benzotriazole, and 2- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol. Preferably, the benzotriazole-based ultraviolet stabilizer (D) may be 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chloro-benzotriazole, 2- [2' -hydroxy-3 ',5' -bis (1, 1-dimethylbenzyl) phenyl ] -2H-benzotriazole or a mixture thereof, more preferably 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chloro-benzotriazole. In this case, mechanical properties, flowability, transparency, glossiness, weather resistance, and ultraviolet shielding ability may be excellent.
Thermoplastic resin composition
The thermoplastic resin composition may have an alkyl acrylate coverage value (X) of 65 wt% or more, preferably 75 wt% or more, more preferably 85 wt% or more, still more preferably 85 wt% to 130 wt%, still more preferably 85 wt% to 120 wt%, as calculated by the following equation 1. Within this range, mechanical properties such as tensile strength, flexural strength and impact strength, flowability, transparency and glossiness may be excellent. In particular, occurrence of whitening during bending processing can be reduced due to excellent non-whitening performance.
[ Equation 1]
X＝{(G-Y)/Y}×100
In equation 1, G represents the gel content (wt%) based on the total weight of the thermoplastic resin composition, and Y represents the content (wt%) of the alkyl acrylate in the gel based on the total weight of the thermoplastic resin composition.
In equation 1, the alkyl acrylate content in the gel of the thermoplastic resin composition refers to the alkyl acrylate content (based on 100% by weight of the total added thermoplastic resin) in insoluble matters collected in the process of calculating the above gel content. Here, the gel content refers to the content of insoluble matters based on 100% by weight of the total thermoplastic resin.
The alkyl acrylate content is quantitatively measured by Nuclear Magnetic Resonance (NMR) analysis or fourier transform infrared (FT-IR) analysis.
In the present disclosure, unless otherwise indicated, NMR analysis refers to analysis by 1 H NMR.
In the present disclosure, NMR analysis may be performed using methods commonly used in the art. Specific measurement examples are as follows.
-Device name: bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable broadband with z gradient) Prodigy Probe
-Measuring conditions: 1 H NMR (zg 30): ns=32, d1=5s, tce-d2, at room temperature.
In the present disclosure, FT-IR analysis can be performed using methods commonly used in the art. Specific measurement examples are as follows.
-Device name: AGILENT CARY 660,660
-Measuring conditions: ATR mode
When the gel content was measured, 1g of the thermoplastic resin composition was added to 30ml of acetone, followed by stirring at room temperature for 12 hours. Then, centrifugation was performed to separate insoluble matters insoluble in acetone, followed by drying for 12 hours. Then, the weight of the insoluble matter was measured, and the gel content was calculated by the following equation 2. As a specific measurement example, when the gel content is measured, 1g of the thermoplastic resin composition is added to 30ml of acetone, followed by stirring at 210rpm and room temperature for 12 hours using an orbital shaker (apparatus name: lab comparative SKC-6075). Then, the insoluble matters insoluble in acetone were separated by centrifugation at 18,000rpm for 3 hours at 0℃using a centrifuge (Supra R30, HANIL SCIENCE Co.) and then dried by forced circulation in a forced convection oven (apparatus name: lab companion OF-12 GW) set at 85℃for 12 hours. Then, the weight of the insoluble matter was measured.
[ Equation 2]
Gel content (wt%) = [ weight of insoluble substance (gel) (g)/weight of sample (g) ]×100
In the present disclosure, the alkyl acrylate coverage value is a parameter indicating the dispersity of the aromatic vinyl compound-vinyl cyanide compound polymer grafted onto the alkyl acrylate rubber in the thermoplastic resin composition. The high alkyl acrylate coverage value indicates a uniform distribution of the aromatic vinyl compound-vinyl cyanide compound polymer grafted onto the alkyl acrylate rubber. That is, the polymer uniformly surrounds the rubber. In this case, gloss may be increased, and tensile strength, colorability, and non-whitening performance may be excellent. In addition, as the alkyl acrylate coverage value increases, the distance between rubber particles decreases. In this case, voids caused by cracks occurring in the thermoplastic resin composition can be reduced, thereby preventing occurrence of whitening during bending processing.
The difference between the alkyl acrylate coverage value and the degree of grafting is that the alkyl acrylate coverage value represents the degree of dispersion of the aromatic vinyl compound-vinyl cyanide compound polymer grafted onto the alkyl acrylate in the thermoplastic resin composition, while the degree of grafting represents the amount of aromatic vinyl compound-vinyl cyanide compound polymer grafted onto the alkyl acrylate in the alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer.
In addition, the coverage value of the alkyl acrylate is calculated based on the content of the alkyl acrylate actually present in the thermoplastic resin composition using an NMR analyzer or FT-IR, and the degree of grafting is calculated based on the content of the rubber component added during the polymerization.
The thermoplastic resin composition may have a melt flow index (220 ℃ C., 10 kg) of preferably 4.5g/10min or more, more preferably 5.5g/10min or more, still more preferably 6.5g/10min to 15g/10min, still more preferably 7.5g/10min to 13g/10min, as measured according to ASTM D1238. Within this range, the physical property balance and the film workability may be excellent.
As another example, the thermoplastic resin composition may have a melt flow index of preferably 6.5g/10min or more, more preferably 7g/10min or more, still more preferably 8g/10min or more, still more preferably 9g/10min to 17g/10min, as measured at 220 ℃ under a load of 10kg according to ASTM D1238. Within this range, the physical property balance and the film workability may be excellent.
The thermoplastic resin composition may have an Izod impact strength (sample thickness: 1/4', room temperature) of preferably 5.3 kgf-cm/cm or more, more preferably 5.5 kgf-cm/cm or more, still more preferably 5.5 kgf-cm/cm to 10 kgf-cm/cm, as measured according to ASTM D256. Within this range, the physical property balance and the film workability may be excellent.
In the present disclosure, room temperature may be a point in the range of 20 ℃ ± 5 ℃.
The thermoplastic resin composition may have a tensile strength of 300kgf/cm 2 or more, preferably 350kgf/cm 2 or more, more preferably 350kgf/cm 2 to 500kgf/cm 2, as measured according to ASTM D638 using a sample having a thickness of 3.2mm at a crosshead speed of 50 mm/min. Within this range, the physical property balance and the film workability may be excellent.
The thermoplastic resin composition may have a flexural strength of preferably 530kgf/cm 2 or more, more preferably 580kgf/cm 2 or more, still more preferably 580kgf/cm 2 to 750kgf/cm 2, as measured according to ASTM D790 using a sample having a thickness of 3.2mm at a span of 50mm and a test speed of 50 mm/min. Within this range, the physical property balance and the film workability may be excellent.
The thermoplastic resin composition may have a total light transmittance (Tt) of preferably 78% or more, more preferably 82% or more, and still more preferably 82% to 100%, as measured according to ASTM D1003 using an injection sample having a thickness of 3 mm. Within this range, the thermoplastic resin composition can be suitable for unpainted products due to excellent balance of physical properties and transparency.
The thermoplastic resin composition may have a total light transmittance (Tt) of preferably 78% or more, more preferably 82% or more, and still more preferably 82% to 100%, as measured according to ASTM D1003 using a sheet having a thickness of 0.15 mm. Within this range, an attractive appearance can be provided due to the excellent balance of physical properties and transparency.
The thermoplastic resin composition may have a haze of preferably 5.7% or less, more preferably 4.5% or less, still more preferably 4.1% or less, still more preferably 0.1% to 4.1%, as measured according to ASTM D1003 using an injection sample having a thickness of 3 mm. Within this range, the thermoplastic resin composition can be suitable for unpainted products due to excellent balance of physical properties and transparency.
The thermoplastic resin composition may have a haze of preferably 5.7% or less, more preferably 4.5% or less, and still more preferably 0.1% to 4.5%, as measured according to ASTM D1003 using a sheet having a thickness of 0.15 mm. Within this range, an attractive appearance can be provided due to the excellent balance of physical properties and transparency.
After an Erichsen cupping test using a ball having a diameter of 20mm set in an Erichsen cupping tester at a motor speed of 7rpm for 1 minute on a 9mm region of a central portion of a sheet having a thickness of 0.15mm, a Machining Direction (MD) of 20cm and a Transverse Direction (TD) of 10cm, the thermoplastic resin composition may have a haze of preferably 10% or less, more preferably 9.2% or less, and even more preferably 0.1% to 9.2% when the haze is measured according to ASTM D1003. Within this range, the thermoplastic resin composition can be used as an unpainted material due to the excellent balance of physical properties.
An example of an Erichsen cupping tester of the present invention is shown in figure 1.
According to the Erichsen cup test, a sheet having a thickness of 0.15mm, a Machine Direction (MD) of 20cm, and a Transverse Direction (TD) of 10cm was produced using a T-die extruder (Techline T manufactured by Collins co., screw diameter: 20mm, l/d=25) at a molding temperature of 230 ℃, a screw rotation speed of 100rpm, a roll rotation speed of 85 ℃ and a roll rotation speed of 3.5m/min, and the Erichsen cup test was performed on a 9mm region of the sheet at a motor speed of 7rpm for 1 minute by using a ball having a diameter of 20mm set in the Erichsen cup tester. Then, haze and total light transmittance were measured, and occurrence of whitening was determined.
After the Erichsen cupping test by cupping a 9mm area of a sheet having a thickness of 0.15mm, a Machining Direction (MD) of 20cm and a Transverse Direction (TD) of 10cm for 1 minute at a motor speed of 7rpm using a ball having a diameter of 20mm set in an Erichsen cupping tester, the thermoplastic resin composition may have a total light transmittance of preferably 80% or more, more preferably 82% or more, still more preferably 82% to 100% when the total light transmittance is measured according to ASTM D1003. Within this range, the thermoplastic resin composition can be used as an unpainted material due to the excellent balance of physical properties.
Whitening may not occur when the surface of a sheet (manufactured from a thermoplastic resin composition) is evaluated by visual observation after an Erichsen cup test by cup-embossing for 1 minute with a 9mm area of a sheet having a thickness of 0.15mm, a Machining Direction (MD) of 20cm, and a Transverse Direction (TD) of 10cm using a ball having a diameter of 20mm set in an Erichsen cup-embossing tester at a motor speed of 7 rpm. In this case, the physical property balance may be excellent. In addition, an attractive appearance can be achieved even after bending or folding.
The thermoplastic resin composition may have an ultraviolet-visible light transmittance of preferably 8% or less, more preferably 6% or less, still more preferably 4% or less, still more preferably 3% or less, still more preferably 0.01% to 3%, as measured at 380nm using a sheet having a thickness of 0.15mm and an ultraviolet-visible light spectrophotometer. Within this range, physical properties may be excellent, and ultraviolet shielding ability may be excellent in short wavelengths of high energy, thereby preventing discoloration of the substrate.
The high ultraviolet-visible light transmittance value at 380nm indicates excellent ultraviolet shielding ability.
When a sheet having a thickness of 0.15mm is laminated as an upper layer sheet on an opaque PVC material having a thickness of 3mm as a base material, the laminated product is left in a weather resistance instrument according to ASTM G155-1 for 250 hours, the degree of discoloration is measured using a color difference meter, and the weather resistance (Δe) is calculated from the following equation 4, and the thermoplastic resin composition may have a weather resistance (Δe) of preferably 5.5 or less, more preferably 4.7 or less, still more preferably 4.4 or less, still more preferably 0.01 to 4.4. Within this range, physical properties may be excellent. In addition, discoloration can be prevented even after a long-term external exposure, and thus an attractive appearance can be achieved.
[ Equation 4]
In equation 4, L ', a ' and b ' represent L, a and b values, respectively, measured using the CIE LAB color coordinate system after placing the sample, and L 0、a0 and b 0 represent L, a and b values, respectively, measured using the CIE LAB color coordinate system before placing the sample.
In the present disclosure, lamination of the top sheet and the substrate may be performed using a mini-press (QMESYS HEATING PLATE TESTER) at 160 ℃.
When a sheet having a thickness of 0.15mm as an upper sheet is laminated on an opaque PVC material having a thickness of 3mm as a base material, the laminated product is placed in a weather resistance meter according to ASTM G155-1 for 2,500 hours, and the degree of discoloration is measured using a color difference meter, and the weather resistance (Δe) is calculated from the following equation 4, and the thermoplastic resin composition may have a weather resistance (Δe) of preferably 5.7 or less, more preferably 4.5 or less, still more preferably 3.5 or less, and still more preferably 0.01 to 3.5. Within this range, physical properties may be excellent. In addition, discoloration can be prevented even after a long-term external exposure, and thus an attractive appearance can be achieved.
When a sheet having a thickness of 0.15mm as an upper sheet is laminated on an opaque PVC material having a thickness of 3mm as a base material, the laminated product is placed in a weather resistance meter according to ASTM G155-1 for 3,000 hours, the degree of discoloration is measured using a color difference meter, and the weather resistance (Δe) is calculated from the following equation 4, and the thermoplastic resin composition may have a weather resistance (Δe) of preferably 6.5 or less, more preferably 5.5 or less, still more preferably 4.5 or less, and still more preferably 0.01 to 4.5. Within this range, physical properties may be excellent. In addition, discoloration can be prevented even after a long-term external exposure, and thus an attractive appearance can be achieved.
When a film having a thickness of 0.04mm is produced using a T-die extruder at a molding temperature of 230 ℃, a screw rotation speed of 40rpm, a roll rotation speed of 85 ℃ and a roll rotation speed of 3.5m/min, the produced film is cut into pieces having a length of 50cm, the thickness is measured at five or more points in a region excluding a region of 1cm to 2cm at both ends of the pieces, and a thickness deviation is calculated based on a difference between the maximum thickness and the minimum thickness, and the thermoplastic resin composition may have a thickness deviation of preferably 0.02mm or less, more preferably 0.01mm or less. Within this range, a luxurious appearance can be provided due to the excellent balance of physical properties and film workability.
Techline 20T (screw diameter: 20mm, L/D=25, collins Co.) was used as a T-die extruder.
In the present disclosure, the thickness may be measured using an ABSOLUTE ID-C1012BS (Mitutoyo co.).
When a sheet made of the thermoplastic resin composition having a thickness of 0.15mm (10 cm in the Machine Direction (MD) ×10cm in the Transverse Direction (TD)) was diagonally folded by hand, and the occurrence of whitening on the curved surface was observed with the naked eye, no whitening was observed, indicating that the non-whitening performance was excellent. Thus, a luxurious appearance can be provided.
The thermoplastic resin composition may further comprise, if necessary, 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, still more preferably 0.5 to 1 part by weight of each of one or more selected from the group consisting of heat stabilizers, lubricants, dyes, pigments, colorants, antistatic agents, antibacterial agents, processing aids, metal deactivators, flame retardants, smoke suppressants, anti-dripping agents, anti-friction agents and anti-wear agents, based on 100 parts by weight of the base resin. Within this range, the desired physical properties of the thermoplastic resin composition of the present invention can be achieved without deterioration of the inherent physical properties thereof.
The heat stabilizer may preferably comprise a first heat stabilizer and a second heat stabilizer.
For example, the first heat stabilizer may be a phenolic heat stabilizer. Preferably, the first heat stabilizer may comprise a heat stabilizer selected from the group consisting of 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3, 5-di-t-pentylphenyl) ethyl ] -4, 6-di-t-pentylphenyl acrylate, 1, 6-hexanediol di- [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 2-thiodiethylene di- [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], diethyl 3, 5-di-t-butyl-4-hydroxybenzylphosphonate, tris (2, 6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, tris (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris [ (3, 5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl ] isocyanurate, tris (4-t-butyl-2, 6-dimethyl-3-hydroxybenzyl) isocyanurate, 2' -di-t-butyl-4-hydroxybenzyl) isocyanurate, tris (2, 6-dimethyl-4-hydroxybenzyl) isocyanurate, and (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate 3, 9-bis [1, 1-dimethyl-2- { β - (3-tert-butyl-4-hydroxy-5-methyl-phenyl) propionyloxy } ethyl ] -2,4,8, 10-tetraoxaspiro [5,5] undecane, 2-bis [4- (2-3, 5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethoxyphenyl ] propane, and one or more of the group consisting of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid stearate, more preferably octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (IR 1076).
For example, the second heat stabilizer may be a phosphorus heat stabilizer. Preferably, the second heat stabilizer may comprise a catalyst selected from the group consisting of bis (dialkylphenyl) pentaerythritol diphosphate, phosphite, trioctyl phosphite, tris (dodecyl) phosphite, tridecyl phosphite, (octyl) diphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1, 3-tris (2-methyl-5-t-butyl-4-hydroxy-phenyl) butane diphosphite, tetra (C12-C15 mixed alkyl) -4,4' -isopropylidenediphenyl diphosphite, tetra (tridecyl) -4,4' -butylidenediphenyl (3-methyl-6-t-butylphenol) diphosphite, tris (mono-and di-mixed nonylphenyl) phosphite, hydrogenated-4, 4' -isopropylidenediphenol polyphosphite, phenyl (4, 4' -isopropylidenediphenol) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris [4,4' -diisopropylidenediphenyl (2-t-butylphenyl) diphosphite, 4' -diisodecyl-4-butylphenyl) bisphenol, 4' -diisobutylphenyl phosphite One or more of the group consisting of bis (2, 4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2- [ {2,4,8, 10-tetra-tert-butyldibenzo [ d, f ] [1.3.2] -dioxaheptin-6-yl } oxy ] -N, N-bis [2- [ {2,4,8, 10-tetra-tert-butyl-dibenzo [ d, f ] [1.3.2] -dioxaheptin-6-yloxy ] ethyl ] -ethylamine and 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2,4,8, 10-tetra-tert-butyldibenzo [ d, f ] [1.3.2] -dioxaheptin, more preferably tris (2, 4-di-tert-butylphenyl) phosphite (IF 168).
The lubricant may preferably include one or more selected from the group consisting of aliphatic amide type lubricants, fatty acid ester type lubricants, and olefin type waxes.
The aliphatic amide-based lubricant may preferably include one or more selected from the group consisting of stearamide, oleamide, sinapiamide, ethylene bis-stearamide and ethylene bis-oleamide.
The fatty acid ester type lubricant may preferably include one or more selected from the group consisting of fatty acid esters of alcohols or polyols, hardened oils, butyl stearate, monoglyceride stearate, pentaerythritol tetrastearate, stearyl stearate, ester waxes, and alkyl phosphate esters.
The olefinic wax may preferably be a polyethylene wax.
Process for producing thermoplastic resin composition
The method for producing the thermoplastic resin composition of the present invention comprises the steps of kneading and extruding at 200 to 300 ℃ and 100 to 500 rpm: 100 parts by weight of a base resin comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a) containing an alkyl acrylate rubber and one or more (B) selected from the group consisting of an alkyl (meth) acrylate polymer (B-1) and an alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2); and 0.1 to 6 parts by weight of an acrylic copolymer (C). In this case, the thermoplastic resin composition has an alkyl acrylate coverage (X) value of 65 wt% or more as calculated in the following equation 1. In this case, the thermoplastic resin composition may have excellent processability and film processability due to excellent mechanical properties such as impact strength, tensile strength and flexural strength, and flowability, and may be suitable for unpainted materials due to excellent transparency and non-whitening properties preventing whitening upon bending or impact. In addition, it is possible to provide an aesthetic appearance due to excellent ultraviolet shielding ability in a short wavelength of high energy.
[ Equation 1]
X＝{(G-Y)/Y}×100
In equation 1, G represents the gel content (wt%) based on the total weight of the thermoplastic resin composition, and Y represents the content (wt%) of the alkyl acrylate in the gel based on the total weight of the thermoplastic resin composition.
The process for preparing the thermoplastic resin composition has all the technical features of the thermoplastic composition described above. Therefore, a repetitive description thereof will be omitted.
Kneading and extrusion may be performed at a temperature of preferably 200℃to 300℃and more preferably 210℃to 260℃and still more preferably 220℃to 250℃using an extrusion kneader. Within this range, extrusion can be stably performed and kneading can be effectively performed. At this time, the temperature is the temperature set in the cartridge.
For example, kneading and extrusion may be performed at a screw rotation rate of 100rpm to 500rpm, preferably 150rpm to 450rpm, more preferably 200rpm to 400 rpm. In this case, the processing efficiency may be excellent due to the proper throughput per unit time.
For example, the thermoplastic resin composition obtained by extrusion may be prepared into pellets using a pelletizer.
The extrusion kneader commonly used in the art to which the present invention pertains may be used without particular limitation, and a twin-screw extrusion kneader is preferably used.
Molded article
The molded article of the present invention comprises a thermoplastic resin composition. In this case, workability and film workability may be excellent due to excellent mechanical properties such as impact strength, tensile strength, and bending strength, as well as flowability. In addition, because of excellent non-whitening properties, whitening does not occur even at bending or impact, and thus the molded article can be applied to unpainted materials. In addition, it can provide a luxurious appearance due to excellent ultraviolet shielding ability in a short wavelength of high energy.
For example, the molded article may be a film or sheet, preferably a finishing material, more preferably a decorative sheet for indoor furniture and decoration, a finishing material for outdoor building materials or a finishing material for roofs. In this case, an aesthetic appearance can be obtained and discoloration of the substrate can be prevented due to excellent non-whitening properties, weather resistance and ultraviolet shielding ability.
The method of manufacturing the molded article preferably includes the step of manufacturing an extrudate by kneading and extruding at 200 to 300 ℃ and 100 to 500 rpm: 100 parts by weight of a base resin comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a) containing an alkyl acrylate rubber and one or more (B) selected from the group consisting of an alkyl (meth) acrylate polymer (B-1) and an alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2); and 0.1 to 6 parts by weight of an acrylic copolymer (C); and a step of producing a molded article by molding the extrudate, wherein the extrudate has an alkyl acrylate coverage (X) value of 65 wt% or more as calculated by the following equation 1. In this case, workability and film workability may be excellent due to excellent mechanical properties such as impact strength, tensile strength, and bending strength, as well as flowability. In addition, because of excellent non-whitening properties, whitening does not occur even at bending or impact, and thus the molded article can be applied to unpainted materials. In addition, it can provide a luxurious appearance due to excellent ultraviolet shielding ability in a short wavelength of high energy.
[ Equation 1]
X＝{(G-Y)/Y}×100
In equation 1, G represents the gel content (wt%) based on the total weight of the thermoplastic resin composition, and Y represents the content (wt%) of the alkyl acrylate in the gel based on the total weight of the thermoplastic resin composition.
For example, the extrudate may have a particulate shape or a plate shape.
In the present disclosure, the plate shape is not particularly limited as long as the plate shape is generally defined as a plate shape in the field to which the present invention pertains. For example, the plate shape may include a flat plate shape, a sheet shape, and a film shape.
In describing the thermoplastic resin composition, the method of preparing the composition, and the molded article comprising the composition of the present invention, it should be noted that other conditions or apparatuses not explicitly described herein may be appropriately selected within the scope of common practice in the art without being particularly limited.
Hereinafter, the present invention will be described in more detail with reference to the following preferred embodiments. However, these examples are provided for illustrative purposes only and should not be construed as limiting the scope and spirit of the invention. In addition, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and that such changes and modifications are also within the scope of the appended claims.
Examples
The materials used in the following examples and comparative examples are as follows.
* (A-1) ASA graft copolymer: ASA graft copolymer (core (rubber)) comprising 38% by weight of butyl acrylate and 7% by weight of styrene, a shell comprising 4% by weight of butyl acrylate, 40% by weight of styrene and 11% by weight of acrylonitrile, a grafting degree of 70%, was prepared by emulsion polymerization and contained an alkyl acrylate rubber having an average particle diameter of 90nm to 110 nm.
* (A-2) ASA graft copolymer: ASA graft copolymer (core (rubber)) of 45% by weight of butyl acrylate and 5% by weight of styrene, shell 15% by weight of butyl acrylate, 25% by weight of styrene and 10% by weight of acrylonitrile, grafting degree: 60%, prepared by emulsion polymerization and containing alkyl acrylate rubber having an average particle diameter of 90nm to 110 nm.
* (B-1) PMMA resin (prepared by emulsion polymerization): polymethyl methacrylate resin (methyl methacrylate: 99% by weight or more, weight average molecular weight: 80,000 g/mol).
* (B-2) SAMMA resin (prepared by bulk polymerization): polymethyl methacrylate-styrene-acrylonitrile copolymer (weight average molecular weight: 80,000 g/mol) comprising 75 wt% methyl methacrylate, 18 wt% styrene and 7 wt% acrylonitrile.
* (C) acrylic copolymer: copolymer (weight average molecular weight: 1,000,000 g/mol) comprising a crosslinked body containing 9.9% by weight of butyl acrylate and 0.1% by weight of allyl methacrylate (as a crosslinking agent), 76.4% by weight of methyl methacrylate and 13.6% by weight of butyl acrylate.
Examples 1 to 5 and comparative examples 1 to 3
The ingredients shown in tables 1 and 2 were fed into a twin screw extruder according to the contents shown in tables 1 and 2. Then, melt kneading and extrusion were performed at 230℃and 150rpm to prepare pellets. The melt flow index and alkyl acrylate coverage values of the prepared pellets were measured. The pellets were then injected using an injector (VC 330/80TECJ PRO,ENGEL Co.) at 220℃and screw speeds of 100rpm to 200rpm to obtain samples for evaluation of appearance and physical properties. In addition, a sheet having a thickness of 0.15mm was produced using the prepared pellets and a T-die extruder (Techline T manufactured by Collins Co., screw diameter: 20mm, L/D=25) at a molding temperature of 230℃at a screw speed of 100rpm, a roll temperature of 85℃and a roll speed of 3.5 m/min. Then, film processability and haze, total light transmittance and non-whitening properties after Erichsen cupping test were measured.
Test case
The properties of the particles and samples prepared in examples 1 to 5 and comparative examples 1 to 3 were measured according to the following methods, and the results are shown in tables 1 and 2 below and fig. 2.
Measurement method
* Alkyl acrylate coverage value (X value, wt.%): the alkyl acrylate coverage value is calculated from the following equation 1.
[ Equation 1]
X＝{(G-Y)/Y}×100
In equation 1, G represents the gel content (wt%) based on the total weight of the thermoplastic resin composition, and Y represents the content (wt%) of the alkyl acrylate in the gel based on the total weight of the thermoplastic resin composition.
Here, the alkyl acrylate content of the gel was quantitatively measured using 1 NMR analyzer or FT-IR. Specific measurement conditions are as follows.
1H NMR
-Device name: bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable broadband with z gradient) Prodigy Probe
-Measuring conditions: 1 H NMR (zg 30): ns=32, d1=5s, tce-d2, at room temperature.
FT-IR
-Device name: AGILENT CARY 66 and 66
-Measuring conditions: ATR mode
* Gel content (%): 1g of the thermoplastic resin composition pellets were added to 30ml of acetone, followed by stirring at 210rpm and room temperature for 12 hours using an orbital shaker (apparatus name: lab comparative SKC-6075). Then, the insoluble matters insoluble in acetone were separated by centrifugation at 18,000rpm for 3 hours at 0℃using a centrifuge (Supra R30, HANIL SCIENCE Co.) and then dried by forced circulation in a forced convection oven (apparatus name: lab companion OF-12 GW) set at 85℃for 12 hours. Then, the weight of the insoluble matter was measured, and the gel content was calculated by the following equation 2.
[ Equation 2]
Gel content (wt%) = [ weight of insoluble substance (gel) (g)/weight of sample (g) ]×100
* Degree of grafting (%): 0.5g of the powdery graft copolymer was added to 50ml of acetone, followed by stirring at room temperature for 12 hours, and centrifugation was performed to separate only insoluble matters insoluble in acetone, and the separated insoluble matters were dried for 12 hours. Then, the weight of the dried insoluble matter was measured, and the degree of grafting was calculated by the following equation 3.
[ Equation 3]
Grafting degree (%) = [ weight of grafting monomer (g)/weight of rubber (g) ]. Times.100
In equation 3, the weight (g) of the graft monomer is obtained by subtracting the weight (g) of the rubber, which is the weight (g) of the rubber component theoretically added to the graft copolymer powder, from the weight (g) of the insoluble matter (gel) obtained by dissolving the graft copolymer in acetone and centrifuging.
As a specific measurement example, when the insoluble matter (gel) weight (g) was measured, 0.5g of the powdery graft copolymer was added to 50ml of acetone, followed by stirring at 210rpm and room temperature for 12 hours using an orbital shaker (apparatus name: lab comparative SKC-6075). Then, the mixture was centrifuged at 0℃and 18,000rpm for 3 hours using a centrifuge (Supra R30, HANIL SCIENCE Co.) to separate insoluble matters insoluble in acetone, followed by drying by forced circulation in a forced convection oven (apparatus name: lab companion OF-12 GW) set at 85℃for 12 hours. Then, the weight of the insoluble matter (gel) was measured.
* Melt flow index (g/10 min): melt flow index was measured at 220℃under a load of 10kg for 10 minutes according to ASTM D1238.
* Izod impact Strength (kgf cm/cm): izod impact strength was measured at room temperature using an injection sample (thickness: 1/4 ") according to ASTM D256.
* Tensile strength (kgf/cm 2): tensile strength was measured according to ASTM D638 using an injection sample (thickness: 3.2 mm) at a crosshead speed of 50 mm/min.
* Flexural Strength (kgf/cm 2): flexural strength was measured according to ASTM D638 using an injection sample (thickness: 3.2 mm) at a span of 50mm and a test speed of 50 mm/min.
* Haze (%): haze was measured according to ASTM D1003 using an injection sample.
* Total light transmittance (Tt,%): total light transmittance was measured according to ASTM D1003 using an injected sample.
* Haze and total light transmittance (%) of the sheet after Erichse cup convex test: after cupping a 9mm area of a sheet having a thickness of 0.15mm, a Machine Direction (MD) of 20cm and a Transverse Direction (TD) of 10cm for 1 minute at a motor speed of 7rpm using a ball with a diameter of 20mm set in an Erichsen cup bow tester, haze and total light transmittance were measured according to ASTM D1003.
* Non-whitening performance: after cupping a 9mm area of a sheet having a thickness of 0.15mm, a Machine Direction (MD) of 20cm and a Transverse Direction (TD) of 10cm for 1 minute using an Erichsen cup tester at a motor speed of 7rpm, it was visually determined whether whitening occurred on the sheet, and non-whitening performance was evaluated based on the following criteria.
O: no whitening (non-whitening) occurs
Delta: slight whitening occurred.
X: excessive whitening occurs.
* Thickness deviation of film: a film having a thickness of 0.04mm was produced using a T-die extruder (Techline T manufactured by Collins co., screw diameter: 20mm, l/d=25) at a molding temperature of 230 ℃, a screw rotation speed of 40rpm, a roll temperature of 85 ℃ and a roll rotation speed of 3.5m/min, the produced film was cut into pieces having a length of 50cm, the thickness was measured at five or more points in a region excluding the regions of 1cm to 2cm at both ends of the pieces, and thickness deviation was calculated based on the difference between the maximum thickness and the minimum thickness. Then, the thickness deviation was evaluated based on the following criteria.
Thickness was measured using an ABSOLUTE ID-C1012BS (Mitutoyo co.).
OK: the thickness deviation of the film is less than or equal to 0.02mm.
NG: the thickness deviation of the film exceeds 0.02mm.
TABLE 1
TABLE 2
As shown in tables 1 and 2, the thermoplastic resin compositions according to examples 1 to 5 of the present invention exhibited mechanical properties such as impact strength, tensile strength, flexural strength, and melt flow index equal to or better than those of comparative examples 1 to 3 outside the scope of the present invention. In addition, in the cases of examples 1 to 5, both the haze of the injected sample and the film after Erichsen test were low, the total light transmittance was high, the non-whitening property was excellent, and the thickness deviation of the film was small, indicating that the processability and the film processability were excellent.
Specifically, in the case of comparative example 1 in which the alkyl acrylate coverage value of the thermoplastic resin composition is smaller than the range of the present invention, the total light transmittance of the injected sample and the total light transmittance and haze after the Erichsen cupping test are poor. In addition, non-whitening performance is poor.
In addition, in the case of comparative example 2 containing no acrylic copolymer (C), the film workability was lowered due to an increase in film thickness deviation. In the case of comparative example 3 containing the acrylic copolymer (C) in an amount exceeding the range of the present invention, the melt flow index was very low, and the total light transmittance, haze and whitening resistance of the injected sample and film after the Erichsen cup test were poor. In addition, since the thickness deviation of the film increases, the film workability decreases.
Additional examples
The materials used in the following additional examples and additional comparative examples are as follows.
* (A-1) ASA graft copolymer: ASA graft copolymer (core (rubber)) comprising 38% by weight of butyl acrylate and 7% by weight of styrene, a shell comprising 4% by weight of butyl acrylate, 40% by weight of styrene and 11% by weight of acrylonitrile, a grafting degree of 70%, prepared by emulsion polymerization and comprising an alkyl acrylate rubber having an average particle diameter of 90nm to 110nm
* (A-2) ASA graft copolymer: ASA graft copolymer (core (rubber)) of 45% by weight of butyl acrylate and 5% by weight of styrene, shell 15% by weight of butyl acrylate, 25% by weight of styrene and 10% by weight of acrylonitrile, grafting degree: 60%, prepared by emulsion polymerization and containing alkyl acrylate rubber having an average particle diameter of 90nm to 110 nm.
* (A-3) ASA graft copolymer: ASA graft copolymer (core (rubber)) comprising 48% by weight of butyl acrylate and 2% by weight of styrene, a shell comprising 2% by weight of butyl acrylate, 37% by weight of styrene and 11% by weight of acrylonitrile, the degree of grafting being 45%, was prepared by emulsion polymerization and contained an alkyl acrylate rubber having an average particle diameter of 100nm to 130 nm.
* (A-4) ASA graft copolymer: ASA graft copolymer (core (rubber)) comprising 34% by weight of butyl acrylate and 11% by weight of styrene, shell 4% by weight of butyl acrylate, 40% by weight of styrene and 11% by weight of acrylonitrile, grafting degree: 75%, prepared by emulsion polymerization and containing alkyl acrylate rubber having an average particle diameter of 90nm to 110 nm.
* (B-1) PMMA resin (prepared by emulsion polymerization): polymethyl methacrylate resin (methyl methacrylate: 99% by weight or more, weight average molecular weight: 80,000 g/mol).
* (B-2) SAMMA resin (prepared by bulk polymerization): polymethyl methacrylate-styrene-acrylonitrile copolymer (weight average molecular weight: 80,000 g/mol) comprising 75 wt% methyl methacrylate, 18 wt% styrene and 7 wt% acrylonitrile.
* (C) acrylic copolymer: copolymer (weight average molecular weight: 1,000,000 g/mol) comprising a crosslinked body containing 9.9% by weight of butyl acrylate and 0.1% by weight of aryl methacrylate (as a crosslinking agent), 76.4% by weight of methyl methacrylate and 13.6% by weight of butyl acrylate.
* (D-1) UV326 (BASF co.): benzotriazole ultraviolet stabilizers.
* (D-2) UV234 (BASF co.): benzotriazole ultraviolet stabilizers.
Additional examples 1 to 7 and additional comparative examples 1 to 3
The ingredients shown in tables 3 and 4 were fed into a twin screw extruder according to the contents shown in tables 3 and 4. Then, melt kneading and extrusion were performed at 230℃and 150rpm to prepare pellets. The melt flow index and alkyl acrylate coverage values of the prepared pellets were measured. The pellets were then injected using an injector (VC 330/80TECJ PRO,ENGEL Co.) at 220℃and screw speeds of 100rpm to 200rpm to obtain samples for evaluation of appearance and physical properties. In addition, a sheet having a thickness of 0.15mm was produced using the produced pellets and a T-die extruder (Techline T manufactured by Collins Co., screw diameter: 20mm, L/D=25) at a molding temperature of 230 ℃, a screw rotation speed of 40rpm, a roll temperature of 85℃and a roll rotation speed of 3.5 m/min. Then, film processability and haze, total light transmittance, haze, ultraviolet-visible total light transmittance, weather resistance, and non-whitening properties were measured.
Test case
The properties of the particles and samples prepared in additional examples 1 to 7 and additional comparative examples 1 to 3 were measured according to the following methods, and the results are shown in tables 3 and 4 below.
Measurement method
* Alkyl acrylate coverage values (X values, wt%) and melt flow index (g/10 min) were measured according to the same methods as described in [ example ].
* Haze (Hz,%): haze was measured according to ASTM D1003 using a sheet having a thickness of 0.15 mm.
* Total light transmittance (Tt,%): total light transmittance was measured according to ASTM D1003 using a sheet having a thickness of 0.15 mm.
* Non-whitening performance: a sheet (10 cm in the Machine Direction (MD) ×10cm in the Transverse Direction (TD)) prepared at a screw rotation speed of 160rpm and having a thickness of 0.15mm was diagonally folded by hand, and the occurrence of whitening on the curved surface was visually observed. The non-whitening performance was then evaluated based on the following criteria.
O: no whitening (non-whitening) occurs.
X: excessive whitening occurs.
* Ultraviolet-visible light transmittance (%): ultraviolet-visible light transmittance was measured at 380nm using a sheet having a thickness of 0.15mm and an ultraviolet-visible spectrophotometer.
* Weather resistance: the sheet having a thickness of 0.15mm as the upper sheet was laminated on the opaque PVC sheet having a thickness of 3mm as the base material using a small-sized hot press (QMESYS HEATING PLATE TESTER), the laminated product was placed in a weather resistance apparatus according to ASTM G155-1 for 250 hours, 2,500 hours and 3,000 hours, and the degree of discoloration was measured using a color difference meter, and the weather resistance (Δe) was calculated from the following equation 4.
[ Equation 4]
In equation 4, L ', a ' and b ' represent L, a and b values, respectively, measured using the CIE LAB color coordinate system after placing the sample, and L 0、a0 and b 0 represent L, a and b values, respectively, measured using the CIE LAB color coordinate system before placing the sample.
* Thickness deviation of film: a film having a thickness of 0.04mm was produced using a T-die extruder (Techline T manufactured by Collins co., screw diameter: 20mm, l/d=25) at a molding temperature of 230 ℃, a screw rotation speed of 40rpm, a roll temperature of 85 ℃ and a roll rotation speed of 3.5m/min, the produced film was cut into pieces having a length of 50cm, the thickness was measured at five or more points in a region excluding the regions of 1cm to 2cm at both ends of the pieces, and thickness deviation was calculated based on the difference between the maximum thickness and the minimum thickness. Then, the thickness deviation of the film was evaluated based on the following criteria.
Thickness was measured using an ABSOLUTE ID-C1012BS (Mitutoyo co.).
OK: the thickness deviation of the film is less than or equal to 0.02mm.
NG: the thickness deviation of the film exceeds 0.02mm.
TABLE 3
TABLE 4
As shown in tables 3 and 4, in the case of the thermoplastic resin compositions according to additional examples 1 to 7 of the present invention, melt flow index, total light transmittance, haze, non-whitening property, ultraviolet-visible light transmittance, weather resistance and thickness deviation were excellent as compared with additional comparative examples 1 to 3 outside the scope of the present invention. These results indicate that in the case of additional examples 1 to 7, transparency, film processability and ultraviolet shielding ability are excellent.
Specifically, in the case of the additional comparative example 1 containing no acrylic copolymer (C) and benzotriazole-based ultraviolet stabilizer, the non-whitening property and weather resistance were poor, the film thickness deviation was large, and the ultraviolet-visible light transmittance was very poor.
In addition, in the case of the additional comparative example 2 containing an excessive amount of the acrylic copolymer (C), the melt flow index was small, and the weather resistance and thickness deviation were poor. In the case of the additional comparative example 3 containing the ASA graft copolymer (A-2), the alkyl acrylate coverage value was less than the range of the present invention, and the non-whitening performance was poor.
In summary, when the thermoplastic resin composition is prepared by polymerizing (A) a thermoplastic resin composition comprising a base resin comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A) and one or more monomers selected from the group consisting of an alkyl (meth) acrylate polymer (B-1) and an alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2) in a predetermined content ratio; and the acrylic copolymer (C) and adjusting the alkyl acrylate coverage value in the thermoplastic resin composition within a predetermined range, the thermoplastic resin composition may have excellent processability and film processability due to excellent mechanical properties such as impact strength, tensile strength and flexural strength, and flowability. In addition, the thermoplastic resin composition can be suitable for unpainted materials due to excellent transparency and non-whitening characteristic properties that prevent whitening upon bending or impact. Further, when the benzotriazole-based ultraviolet stabilizer (D) is contained, the ultraviolet shielding ability can be excellent in a short wavelength of high energy, and thus an attractive appearance can be achieved.
In addition, as shown in fig. 2 below, in the case of example 1 according to the present invention, whitening did not occur after the Erichsen cupping test compared to comparative example 1.
Claims (18)
1. A thermoplastic resin composition, the thermoplastic resin composition comprising:
100 parts by weight of a base resin comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a) containing an alkyl acrylate rubber, and one or more (B) selected from the group consisting of an alkyl (meth) acrylate polymer (B-1) and an alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2); and
0.1 To 6 parts by weight of an acrylic copolymer (C),
Wherein the alkyl acrylate coverage (X) value of the thermoplastic resin composition is 65 wt% or more calculated according to the following equation 1,
[ Equation 1]
X＝{(G-Y)/Y}×100，
Wherein G represents a gel content (wt%) based on the total weight of the thermoplastic resin composition, and Y represents a content (wt%) of an alkyl acrylate in the gel based on the total weight of the thermoplastic resin composition.
2. The thermoplastic resin composition according to claim 1, wherein the base resin comprises 41 to 80% by weight of the alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a) containing an alkyl acrylate rubber having an average particle diameter of 50 to 120nm, and 20 to 59% by weight of one or more selected from the group consisting of the alkyl (meth) acrylate polymer (B-1) and the alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2).
3. The thermoplastic resin composition of claim 1, wherein said base resin comprises 45 to 75% by weight of said graft copolymer (A), 5 to 45% by weight of said polymer (b-1), and 1 to 35% by weight of said polymer (b-2).
4. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises 0.3 to 4.5 parts by weight of the benzotriazole-based ultraviolet stabilizer (D).
5. The thermoplastic resin composition according to claim 4, wherein said benzotriazole-based ultraviolet light stabilizer (D) comprises one or more selected from the group consisting of 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) -benzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chloro-benzotriazole, 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chloro-benzotriazole, 2- (2 ' -hydroxy-3, 5-di-tert-pentylphenyl) benzotriazole, 2- [2' -hydroxy-3 ',5' -bis (1, 1-dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) benzotriazole and 2- (2H-benzotriazole-2-yl) -4- (1, 3-tetramethylbutyl) phenol.
6. The thermoplastic resin composition of claim 1, wherein said graft copolymer (a) comprises 25 to 50% by weight of an alkyl acrylate rubber having an average particle diameter of 50 to 120nm and 50 to 75% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer surrounding said alkyl acrylate rubber, based on the total weight of said graft copolymer (a).
7. The thermoplastic resin composition of claim 1, wherein said graft copolymer (a) comprises 25 to 50% by weight of an alkyl acrylate rubber and 50 to 75% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer surrounding said alkyl acrylate rubber, based on the total weight of said graft copolymer (a).
8. The thermoplastic resin composition of claim 1, wherein the grafting degree of said graft copolymer (A) is 58% or more calculated according to the following equation 3,
[ Equation 3]
Grafting degree (%) = [ weight of grafting monomer (g)/weight of rubber (g) ]. Times.100,
Wherein the weight (g) of the graft monomer is obtained by subtracting the weight (g) of the rubber from the weight (g) of the insoluble matter (gel) obtained by dissolving the graft copolymer in acetone and centrifuging, and the weight (g) of the rubber is the weight (g) of the rubber component theoretically added to the graft copolymer powder.
9. The thermoplastic resin composition of claim 1, wherein said polymer (b-1) and polymer (b-2) each independently have a weight average molecular weight of 50,000g/mol to 150,000g/mol.
10. The thermoplastic resin composition of claim 1, wherein said polymer (b-2) comprises 60 to 90% by weight of alkyl (meth) acrylate, 5 to 30% by weight of aromatic vinyl compound, and 1 to 20% by weight of vinyl cyanide compound.
11. The thermoplastic resin composition according to claim 1, wherein the acrylic copolymer (C) comprises, based on the total weight of the acrylic copolymer (C): an alkyl acrylate cross-link comprising 5 to 20wt% of an alkyl acrylate monomer and 0.01 to 0.3 wt% of a cross-linking agent; 54 to 90 weight percent methyl methacrylate monomer; and 4 to 40wt% of one or more selected from the group consisting of alkyl acrylate monomers and alkyl methacrylate monomers.
12. The thermoplastic resin composition of claim 11, wherein said crosslinking agent comprises one or more selected from the group consisting of allyl methacrylate, trimethylolpropane, triacrylate, and divinylbenzene.
13. The thermoplastic resin composition as claimed in claim 1, wherein the weight average molecular weight of the acrylic copolymer (C) is 900,000g/mol to 1,300,000g/mol.
14. The thermoplastic resin composition of claim 1, wherein said thermoplastic resin composition has a haze of 5.7% or less, as measured according to ASTM D1003 using an injection sample.
15. The thermoplastic resin composition of claim 1, wherein said thermoplastic resin composition has a haze of 10% or less, as measured according to ASTM D1003 after a cupping test for 1 minute using an Erichsen cupping tester at a motor speed of 7rpm on a 9mm area of a film having a thickness of 0.15 mm.
16. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a light transmittance of 8% or less as measured at 380nm using a sheet having a thickness of 0.15mm and an ultraviolet-visible spectrophotometer.
17. A process for producing a thermoplastic resin composition, which comprises kneading and extruding at 200 ℃ to 300 ℃ and 100rpm to 500rpm 100 parts by weight of a base resin comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A) containing an alkyl acrylate rubber and one or more (B) selected from the group consisting of (meth) acrylic acid alkyl ester polymers (B-1) and (meth) acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B-2) and 0.1 parts by weight to 6 parts by weight of an acrylic copolymer (C),
Wherein the alkyl acrylate coverage (X) value of the thermoplastic resin composition is 65 wt% or more calculated according to the following equation 1,
[ Equation 1]
X＝{(G-Y)/Y}×100，
Wherein G represents a gel content (wt%) based on the total weight of the thermoplastic resin composition, and Y represents a content (wt%) of an alkyl acrylate in the gel based on the total weight of the thermoplastic resin composition.
18. A molded article comprising the thermoplastic resin composition of any one of claims 1 to 16.
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