WO2016089138A1 - Polycarbonate-based resin composition and molded article thereof - Google Patents
Polycarbonate-based resin composition and molded article thereof Download PDFInfo
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- WO2016089138A1 WO2016089138A1 PCT/KR2015/013160 KR2015013160W WO2016089138A1 WO 2016089138 A1 WO2016089138 A1 WO 2016089138A1 KR 2015013160 W KR2015013160 W KR 2015013160W WO 2016089138 A1 WO2016089138 A1 WO 2016089138A1
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- WIPO (PCT)
- Prior art keywords
- polycarbonate
- formula
- weight
- resin composition
- repeating unit
- Prior art date
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 58
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 58
- 239000011342 resin composition Substances 0.000 title claims abstract description 49
- 239000000126 substance Substances 0.000 claims abstract description 43
- -1 polyethylene terephthalate Polymers 0.000 claims description 54
- 125000003118 aryl group Chemical group 0.000 claims description 46
- 239000004431 polycarbonate resin Substances 0.000 claims description 45
- 229920005989 resin Polymers 0.000 claims description 45
- 239000011347 resin Substances 0.000 claims description 45
- 229920005668 polycarbonate resin Polymers 0.000 claims description 44
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 18
- 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 claims description 18
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 229920001971 elastomer Polymers 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000005060 rubber Substances 0.000 claims description 15
- 125000000466 oxiranyl group Chemical group 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000012744 reinforcing agent Substances 0.000 claims description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229920000578 graft copolymer Polymers 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- AWYVETCHVQGXMB-UHFFFAOYSA-N (3-hydroxyphenyl) diphenyl phosphate Chemical compound OC1=CC=CC(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)=C1 AWYVETCHVQGXMB-UHFFFAOYSA-N 0.000 claims description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical class [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims 2
- 150000001993 dienes Chemical class 0.000 claims 1
- 150000003014 phosphoric acid esters Chemical class 0.000 claims 1
- 230000009885 systemic effect Effects 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000002243 precursor Substances 0.000 description 17
- 230000000704 physical effect Effects 0.000 description 16
- 239000003607 modifier Substances 0.000 description 14
- 239000010409 thin film Substances 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 239000004609 Impact Modifier Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- 238000012695 Interfacial polymerization Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- 0 CC(*)(*)Oc1ccccc1 Chemical compound CC(*)(*)Oc1ccccc1 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004426 Lupoy Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- MUCRFDZUHPMASM-UHFFFAOYSA-N bis(2-chlorophenyl) carbonate Chemical compound ClC1=CC=CC=C1OC(=O)OC1=CC=CC=C1Cl MUCRFDZUHPMASM-UHFFFAOYSA-N 0.000 description 2
- PDYNXWPJDVOHDW-UHFFFAOYSA-N bis(3-methylphenyl) carbonate Chemical compound CC1=CC=CC(OC(=O)OC=2C=C(C)C=CC=2)=C1 PDYNXWPJDVOHDW-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- MOIPGXQKZSZOQX-UHFFFAOYSA-N carbonyl bromide Chemical compound BrC(Br)=O MOIPGXQKZSZOQX-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000007523 nucleic acids Chemical class 0.000 description 2
- 102000039446 nucleic acids Human genes 0.000 description 2
- 108020004707 nucleic acids Proteins 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000010473 stable expression Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000006681 (C2-C10) alkylene group Chemical group 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- XBQRPFBBTWXIFI-UHFFFAOYSA-N 2-chloro-4-[2-(3-chloro-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(Cl)=CC=1C(C)(C)C1=CC=C(O)C(Cl)=C1 XBQRPFBBTWXIFI-UHFFFAOYSA-N 0.000 description 1
- FDIPWBUDOCPIMH-UHFFFAOYSA-N 2-decylphenol Chemical compound CCCCCCCCCCC1=CC=CC=C1O FDIPWBUDOCPIMH-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- QEMHBAGGYKJNSS-UHFFFAOYSA-N 2-icosylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O QEMHBAGGYKJNSS-UHFFFAOYSA-N 0.000 description 1
- JOONSONEBWTBLT-UHFFFAOYSA-N 2-tetradecylphenol Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1O JOONSONEBWTBLT-UHFFFAOYSA-N 0.000 description 1
- OREKREJVUNVFJP-UHFFFAOYSA-N 2-triacontylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O OREKREJVUNVFJP-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- CKNCVRMXCLUOJI-UHFFFAOYSA-N 3,3'-dibromobisphenol A Chemical compound C=1C=C(O)C(Br)=CC=1C(C)(C)C1=CC=C(O)C(Br)=C1 CKNCVRMXCLUOJI-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
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001091551 Clio Species 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- RWYWPJMTQVQCGK-UHFFFAOYSA-N OC1=CC=C(C(=O)OCCC(=C)C)C=C1 Chemical compound OC1=CC=C(C(=O)OCCC(=C)C)C=C1 RWYWPJMTQVQCGK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- 108010019477 S-adenosyl-L-methionine-dependent N-methyltransferase Proteins 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- YFRNYWVKHCQRPE-UHFFFAOYSA-N buta-1,3-diene;prop-2-enoic acid Chemical compound C=CC=C.OC(=O)C=C YFRNYWVKHCQRPE-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- KLYWPNJEVUKXPU-UHFFFAOYSA-N dibutyl carbonate diethyl carbonate Chemical compound C(OCC)(OCC)=O.C(CCC)OC(OCCCC)=O KLYWPNJEVUKXPU-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 description 1
- QZRXRMPNCPCMSW-UHFFFAOYSA-N phosphanyl(phosphanylidene)phosphane Chemical compound PP=P QZRXRMPNCPCMSW-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
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- PTUUTGJMRQWABQ-UHFFFAOYSA-N triphenyl(phenylsilyloxy)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[SiH2]C1=CC=CC=C1 PTUUTGJMRQWABQ-UHFFFAOYSA-N 0.000 description 1
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/38—General preparatory processes using other monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
- C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Definitions
- the present invention relates to a polycarbonate-based resin composition and a molded article thereof, and more particularly, to a polycarbonate-based resin composition and a molded article formed therefrom exhibiting high fluidity, excellent chemical resistance and impact resistance.
- Polycarbonate resins are thermoplastic resins formed by the polycondensation of aromatic di-likes such as bisphenol A and carbonate precursors such as phosgene, and have excellent layer strength, numerical stability, heat resistance, and transparency. It is applied to a wide range of fields such as, building materials and optical components.
- the polycarbonate-based material exhibits high fluidity in a molten state and thus excellent thin film formability. Need to indicate However, it is true that the existing polycarbonate-based materials did not show a good fluidity and thin film formability.
- the present invention is to provide a polycarbonate-based resin composition showing a high fluidity, excellent chemical resistance and layer resistance, even if a relatively low content of the layer reinforcing agent.
- This invention also provides the molded article containing the said polycarbonate-type resin composition.
- the present invention is a polycarbonate resin consisting of an aromatic polycarbonate-based first repeating unit,
- Copolycarbonate resin comprising an aromatic polycarbonate-based crab 1 repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, an impact modifier comprising a rubber-modified vinyl graft copolymer, and a thermoplastic polyester-based A flow modifier comprising a polymer or phosphate ester compound;
- the first repeating units each independently include a repeating unit represented by the following Formula 1;
- the second repeating unit provides a polycarbonate-based resin composition comprising at least one repeating unit selected from the group consisting of Formula 3 below:
- R 1 to R 4 are each independently hydrogen, C 1-10 alkyl, C 1-10 alkoxy, or halogen,
- Z is Cw 0 alkylene unsubstituted or substituted with phenyl, C 3-15 cycloalkylene unsubstituted or substituted with C 1-10 alkyl, O, S, S (D, S0 2 , or CO;
- X 2 are each independently C 1-10 alkylene
- Each Y 1 is independently hydrogen, C 1-6 alkyl, halogen, hydroxy, d_ 6 alkoxy or C 6 20 aryl,
- Each R 6 is independently hydrogen; C 1-15 alkyl unsubstituted or substituted with oxiranyl, C 1-10 alkoxy substituted with oxiranyl, or C 6-20 aryl; halogen; C 1-10 alkoxy; Allyl; C 1-10 haloalkyl; Or C 6-20 aryl,
- n2 is an integer of 10-200.
- the present invention also provides a molded article comprising the above-mentioned recarbonate-based resin composition.
- a molded article comprising the above-mentioned recarbonate-based resin composition.
- first component may also be referred to as the second component, and similarly the second component may be referred to as the first component.
- Copolycarbonate resin comprising an aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, an impact modifier comprising a rubber-modified vinyl-based graft copolymer, and a thermoplastic polyester-based A flow modifier comprising a polymer or phosphate ester compound;
- the first repeating units each independently include a repeating unit represented by the following Formula 1;
- the second repeating unit is provided with a polycarbonate-based resin composition comprising at least one repeating unit selected from the group consisting of:
- R 1 to R 4 are each independently hydrogen, C 1-10 alkyl, Cwo alkoxy, or halogen,
- z is c 1-10 alkylene unsubstituted or substituted with phenyl, unsubstituted or
- X 2 are each independently C 1-10 alkylene
- Each Y 1 is independently hydrogen, C 1-6 alkyl, halogen, hydroxy, C 1-6 alkoxy or C 6-20 aryl,
- Each R 6 is independently hydrogen; D_ 15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C 1-10 alkoxy, or C 6-20 aryl; halogen; Cwo alkoxy; Allyl; C 1-10 haloalkyl; Or C 6-20 aryl,
- n2 is an integer of 10-200.
- the second repeating unit of the copolycarbonate resin may further include one or more repeating units selected from the group consisting of:
- Each X 1 is independently C 1-10 alkylene
- Each R 5 is independently hydrogen; C 1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C 1-10 alkoxy, or C 6-20 aryl; halogen; C 1-10 alkoxy; Allyl; c 1-10 haloalkyl; Or c 6-20 aryl,
- n1 is an integer of 10-200.
- the copolycarbonate resin in which the specific siloxane bond of Formula 3, more preferably, the siloxane bonds of Formula 2 and 3 is introduced into the polycarbonate backbone supplements the physical properties of general aromatic polycarbonate resins. It was confirmed that the resin composition of one embodiment can exhibit more excellent impact strength (layer resistance), chemical resistance, and the like. In addition, the resin composition of one embodiment including a copolycarbonate resin and a general aromatic polycarbonate resin may exhibit a fluidity and thin film formability of a certain level or more through the interaction of two base resins. ⁇
- the resin composition of one embodiment exhibits some improved impact strength by the use of the copolycarbonate resin
- such a resin composition may exhibit excellent layer strength (impact resistance) while including a reduced amount of layer reinforcement. Accordingly, problems such as gas generation or appearance defects during thin film molding according to a high content of the layer reinforcement agent can be solved.
- the resin composition of one embodiment may further include a specific flow modifier to exhibit higher flowability and thin film formability.
- the resin composition of one embodiment may exhibit both high flowability and thin film formability, excellent chemical resistance and impact resistance, which can be appropriately used as materials for portable electronic devices such as smartphones.
- the components that can be included in the polycarbonate-based resin composition according to the embodiment of the present invention will be described in detail.
- the polycarbonate resin is a base resin contained in the polycarbonate-based resin composition and comprises an aromatic polycarbonate-based first repeating unit.
- Such a polycarbonate resin is composed of an aromatic polycarbonate-based first repeating unit, and has an aromatic polycarbonate-based repeat having a siloxane bond. It can be distinguished from the copolycarbonate resin described later in that it does not have a unit (for example, 2 repeat units).
- the aromatic polycarbonate-based first repeating unit is formed by the reaction of a diol compound and a carbonate precursor, and may suitably include a repeating unit represented by Formula 1 below, and the structure of the repeating unit may be described later. It may be the same as the first repeating unit included in the polycarbonate resin, but may be different from this:
- R 1 to R 4 are each independently hydrogen, C 1-10 alkyl, C 1 -10 alkyl, or halogen,
- Z is Cwo alkylene unsubstituted or substituted with phenyl, C 3-15 cycloalkylene unsubstituted or substituted with CLIO alkyl, S, SO, SO 2 , or CO.
- R 1 to R 4 are each independently hydrogen, methyl, chloro, or bromo.
- Z is straight or branched C 1-10 alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1, 1-diyl, propane-2,2-diyl, Butane-2,2-diyl, 1-phenylethane-1, 1-diyl, or diphenylmethylene.
- ⁇ is cyclonucleic acid-1, 1-diyl, S, SO, S0 2 , or CO.
- the repeating unit represented by Formula 1 may be bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy Phenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2-bis (4- Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclonucleic acid, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4 -Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2- Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-
- derived from an aromatic diol compound means that a hydroxyl group of the aromatic diol compound reacts with a carbonate precursor to form a repeating unit represented by the formula (1).
- the repeating unit of Formula 1 may be represented by the following Formula 1-1:
- Examples of the carbonate precursor include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di- m -cresyl carbonate, and dinaphthyl carbonate,
- One or more selected from the group consisting of bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate may be used, and preferably triphosgene or phosgene may be used.
- the polycarbonate resin may have a weight average molecular weight of 1,000 to 100,000 g / mol, preferably 5,000 to 50,000 g / mol. More preferably, the extended average molecular weight (g / mol) is at least 1,000, at least 5,000, at least 10,000, at least 21,000, at least 22,000, at least 23,000, at least 24,000, at least 25,000, at least 26,000, at least 27,000, or More than 28,000. The weight average molecular weight is 100,000 or less, 50,000 or less, 34,000 or less, 33,000 or less, or 32,000 or less.
- the polycarbonate resin is melted from 5 g / 10 minutes to 50 g / 10 minutes, or 10 g / 10 minutes to 40 g / 10 minutes according to ASTM D1238 (300 ° C and 1.2 kg load; measured for 10 minutes) Stable expression of physical properties of the composition having an index (Ml) It may be preferred in terms of aspects.
- the polycarbonate resin may be appropriate in terms of stable expression of the physical properties of the composition comprising two or more polycarbonate resin having a different melt index (Ml).
- Ml melt index
- the polycarbonate resin composition contains two kinds of polycarbonate resin having different melt index (Ml), having a melt index (Ml) of 5 g / 10 minutes to 15 g / 10 minutes, One having a melt index (Ml) of 20 g / 10 min to 40 g / 10 min can be applied.
- the polycarbonate resin described above may be directly synthesized according to a well-known synthetic method of a general aromatic polycarbonate resin, or may be obtained by using an aromatic polycarbonate commercially available.
- the content of the polycarbonate resin may vary depending on the physical properties of the composition to be adjusted.
- the _ polycarbonate resin may be included in an amount of, based on the total content of the resin composition of example one embodiment, from 40 to 90 increased 0 /., Or 50 to 80 weight 0 /.
- Such a polycarbonate resin is a component included as a base resin together with a copolycarbonate resin, which will be described later, and if the content is excessively large, the content of the copolycarbonate resin is relatively decreased, so that the layer composition (impact strength) or chemical resistance Fluidity, etc., may be disrupted.
- the content of the polycarbonate resin is too small, mechanical properties such as rigidity may not be sufficient.
- the copolycarbonate resin may improve the physical properties of the above-described polycarbonate resin, in particular, impact strength and chemical resistance, and may be combined with the polycarbonate resin to improve fluidity of the resin composition according to one embodiment.
- the copolycarbonate resin may be included with the polycarbonate resin as a base resin in the resin composition of one embodiment.
- Such copolycarbonate resin includes an aromatic polycarbonate-based second repeating unit having an aromatic polycarbonate-based first repeating unit and at least one siloxane bond.
- the copolycarbonate resin is polysiloxane in the backbone of the polycarbonate It can be distinguished from the above-described polycarbonate resin (for example, having only an aromatic polycarbonate main chain without introducing a polysiloxane structure) in that a structure is introduced.
- the aromatic polycarbonate-based first repeating unit is formed by reaction of the diol compound and the carbonate precursor, and may include the repeating unit represented by Chemical Formula 1 described above.
- R 1 to R 4 are each independently hydrogen, alkoxy, or halogen
- Z is c 1-10 alkylene unsubstituted or substituted with phenyl, c 3-15 cycloalkylene unsubstituted or substituted with c 1-10 alkyl, S, SO, SO 2 , or CO. .
- the R 1 to R 4 and Z may have the same or different structure as the group corresponding to the repeating unit forming the polycarbonate resin described above.
- the repeating unit of Formula 1 may be represented by the following Formula 1-1:
- carbonate precursors examples include dimethyl carbonate, diethyl carbonate dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, and dinaphthyl carbonate, Bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene,
- One or more selected from the group consisting of bromophosgene and bishaloformates can be used, and preferably triphosphene or phosgene can be used.
- the second polycarbonate-based repeating unit having at least one siloxane bond is formed by reacting at least one siloxane compound and a carbonate precursor, in a specific example, at least one repeating unit selected from the group consisting of It may include, more preferably may further include one or more repeating units selected from the group consisting of:
- Each X 1 is independently C 1-10 alkylene
- Each R 5 is independently hydrogen; C 1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C 1-10 alkoxy, or C 6-20 aryl; halogen; C 1-10 alkoxy; Allyl; C 1-10 haloalkyl; Or C 6-20 aryl,
- eta is an integer from 10 to 200;
- X 2 are each independently C 1-10 alkylene
- Each Y 1 is independently hydrogen, C 1-6 alkyl, halogen, hydroxy, C 1-6 alkoxy C 6-20 aryl,
- Each R 6 is independently hydrogen; Unsubstituted or oxiranyl, oxiranyl Substituted c 1-10 alkoxy, or c 1-15 alkyl substituted with c 6-20 aryl; halogen; c 1-10 alkoxy; Allyl; c 1-10 haloalkyl; Or c 6 . 20 aryl,
- n2 is an integer of 10-200.
- X 1 may be each independently C 2-10 alkylene, preferably C 2-4 alkylene, more preferably propane-1,3-diyl.
- each of R 5 is independently hydrogen, methyl, ethyl, propyl 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, meso Hydroxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl.
- each of R 5 is independently C 1-10 alkyl, more preferably C 1-6 alkyl, more preferably at 3 alkyl, and most preferably
- N1 is an integer of 10 to 200, preferably i) an integer of 30 to 60, ii) 20 or more, 25 or more, or 30 or more, 40 or less, or an integer of 35 or less, or iii. ) 50 or more, or 55 or more, and may be an integer of 70 or less, 65 or less, or 60 or less.
- the repeating unit of Formula 2 may be represented by the following Formula 2-1:
- R 5 and n i are the same as defined in Chemical Formula 2, respectively.
- each of X 2 is independently C 2 -io alkylene, more preferably C 2-6 alkylene, and most preferably isobutylene.
- Y 1 may be hydrogen
- R 6 in Formula 3 is each independently hydrogen, methyl, ethyl, propyl, 3- Phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl , 3,3,3-trifluoropropyl, phenyl, or naphthyl.
- each of R 6 may be independently C 1-10 alkyl, more preferably C 1-6 alkyl, more preferably alkyl, and most preferably methyl.
- n2 is an integer of 10 to 200, preferably ⁇ ) an integer of 30 to 60, ii) 20 or more, 25 or more, or 30 or more, 40 or less, or an integer of 35 or less, or ⁇ ) 50 or more, or 55 or more, 70 or less, 65 or less, or 60 or less.
- repeating unit of Formula 3 may be represented by the following Formula 3-1:
- R 6 and ⁇ 2 are the same as defined in Chemical Formula 3, respectively.
- the copolycarbonate resin may include at least one repeating unit selected from the group consisting of Formula 3, more preferably at least one repeating unit selected from the group consisting of Formula (2) It may further include.
- the copolycarbonate resin may include two or more kinds of each repeating unit of Formula 2 and / or 3.
- the term 'two or more repeating units' means each chemical formula. It means that two or more repeating units having different structures within the structure, or two or more repeating units having the same structure but different number (n1 or n2) of the silicon oxide in the structure of formulas (2) and (3).
- two or more kinds of repeating units as used in the present invention means: i) one repeating unit represented by Formula 2 and the other repeating unit represented by Formula 2, or ii) the above formula. It means to include one repeating unit represented by 3 and the other repeating unit represented by the formula (3).
- the weight ratio between the two repeating units may be 1:99 to 99: 1.
- the repeating unit represented by Formula 2 and Formula 3 may be derived from a siloxane compound represented by Formula 2-2 and a siloxane compound represented by Formula 3-2, respectively:
- X 1 , R 5 and n 1 are each as defined in Chemical Formula 2;
- X 2 , Y 1 , R 6 and n 2 are the same as defined in Chemical Formula 3, respectively.
- the meaning of 'derived from the siloxane compound' means that the hydroxy group and the carbonate precursor of each of the siloxane compounds react to form a repeating unit represented by the formulas (2) and (3), respectively.
- Formula 2 And the carbonate precursor that can be used for formation of the repeating unit of 3 are the same as those described for the carbonate precursor that can be used for the formation of the repeating unit of the formula (1).
- X 1a is an alkenyl C 2 -10
- X 1 , R 5 and n 1 are each as defined in Chemical Formula 2;
- X 2a is C 2-10 alkenyl
- X 2 , Y 1 , R 6 and n 2 are the same as defined in Chemical Formula 3, respectively. It is preferable to perform reaction of said reaction formula 1 and 2 under a metal catalyst.
- a metal catalyst it is preferable to use an R catalyst, and as an R catalyst, an ashby catalyst, a Karlstedt catalyst, a Lamoreaux catalyst, a Speyer catalyst, a PtCI 2 (COD), One or more selected from the group consisting of PtCI 2 (benzonitrile) 2, and H 2 RBr 6 can be used.
- the metal catalyst is 0.001 part by weight, 0.005 part by weight subphase, or 0.01 part by weight or more based on 100 parts by weight of the compound represented by Formula 11, 13, or 15, 1 part by weight, 0.1 part by weight, or 0.05 part by weight. It can be used in parts or less.
- reaction temperature is preferably 80 to 10C C.
- reaction time is preferably 1 hour to 5 hours.
- the compound represented by the formula (C2 or C4) can be prepared by reacting the organodisiloxane and organocyclosiloxane under an acid catalyst, by adjusting the content of the reaction material n1 and n2 I can regulate it.
- the reaction temperature is preferably 50 to 70 ° C.
- the reaction time is preferably 1 hour to 6 hours.
- organodisiloxane one or more selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, nuxamethyldisiloxane and nuxaphenyldisiloxane can be used.
- organocyclosiloxane an organocyclotetrasiloxane can be used as an example, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like.
- the organodisiloxane may be 0.1 part by weight or more, or 2 parts by weight or more, 10 parts by weight or less, or 8 parts by weight or less, based on 100 parts by weight of the organocyclosiloxy acid.
- the acid catalyst at least one selected from the group consisting of H 2 SO 4 , HCI0 4 , AICI3, SbCI 5) SnCI 4 and acidic clay may be used.
- the acid catalyst may be used in an amount of 0.1 parts by weight, 0.5 parts by weight, or 1 part by weight, 10 parts by weight, 5 parts by weight, or 3 parts by weight or less based on 100 parts by weight of organocyclosiloxane. have.
- the weight ratio is a siloxane compound used for copolycarbonate polymerization, such as
- the molar ratio of the aromatic polycarbonate-based crab 1 repeating unit and the aromatic polycarbonate-based second repeating unit having at least one siloxane bond is 1: 0.0001 to 1: 0.01, or 1: 0.0005 to 1: 0.008 Or 1: 0.001 to 1: 0.006, and the weight ratio may be 1: 0.001 to 1: 1, or 1: 0.005 to 1: 0.1, or 1: 0.01 to 1: 0.03.
- the copolycarbonate resin may include the above 11 repeating units of 90 to 99.999 weight 0 /. And the second repeating units of 0.001 to 10 weight 0 /. That is, when the content of the second repeating unit is excessively reduced, it may be difficult to sufficiently realize improvement of room temperature stratification strength, low temperature stratification strength, chemical resistance, and fluidity physical properties by the second repeating unit. On the other hand, when the content of the second repeating unit is excessively increased, the fluidity and molding processability may decrease while the molecular weight of the copolycarbonate resin is excessively increased.
- the copolycarbonate resin may have a weight average molecular weight of 1,000 to 100,000 g / mol, preferably 5,000 to 50,000 g / mo. Within the weight average molecular weight range, appropriate ductility and YI of the copolycarbonate resin can be ensured. More preferably, the weight average molecular weight (g / mol) is at least 1,000, at least 5,000, at least 10,000, at least 21,000, at least 22,000, at least 23,000, at least 24,000, at least 25,000, at least 26,000, at least 27,000, or More than 28,000. In addition, the said weight average molecular weight is 100,000 or less, 50,000 or less, 34,000 or less, 33,000 aha, or 32,000 or less.
- the content of the copolycarbonate resin may vary depending on the physical properties of the composition to be adjusted.
- the copolycarbonate resin may be included in 5 to 50 weight 0 /., Or 10 to 40 weight 0 /. Based on the total content of the resin composition of one embodiment.
- the copolycarbonate resin is a total resin so that the above-described physical properties such as the above-described layer resistance, chemical resistance and fluidity can be expressed to provide a molded article exhibiting proper physical properties even when a layer reinforcing agent is used in a low content. It is included suitable for a composition to more than 5 parts by weight 0 /. However, when the copolycarbonate resin is added in an excessive amount, the transparency of the resin composition may be lowered, and an improvement effect such as layer strength may reach a threshold or rather decrease. In this respect, the copolycarbonate resin may contain less than 40 wt. 0/0.
- the aforementioned copolycarbonate resin may be prepared using the aromatic diol compound, the carbonate precursor, and one or more siloxane compounds.
- the one or more siloxane compounds, aromatic diol compound, a carbonate precursor and at least one siloxane compound total 100 parts by weight 0 / for 0 0.1 0 /. Above, 0.5 parts by weight 0 /. Above, 1 weight 0 / . or higher, or 0.5 and 1 wt. 0 /. above, 20 parts by weight 0 /. or less, 10 parts by weight 0 / hereinafter, 7 parts by weight 0/0 or less, 5 parts by weight 0 /. or less, and 4 wt. 0/0 or less, 3 A weight of 0 / ° or less, or 2 weights of 0 / ° or less may be used.
- the above described aromatic compound is dieul, dieul aromatic compound, a carbonate precursor and at least one siloxane compound 40 parts by weight based on total 100 parts by weight ./. 0 /. Above 50 increase 0 /., Or 55 weight 0/0 or more, 80 weights 0 /. Or less, 70 weights 0 /. Or less, or 65 weights 0 /.
- the carbonate precursor, the aromatic diol compound, a carbonate precursor and at least one siloxane compound total 100 parts by weight 0 / about 0 10 weight 0 /. Above, 20 parts by weight 0 /. Or more, or 30% by weight, 60 parts by weight 0 / Or less, 50 weight 0 or less, or 40 weight% or less.
- the polymerization method for example, an interfacial polymerization method can be used.
- the polymerization reaction is possible at atmospheric pressure and low temperature, and the molecular weight can be easily controlled.
- the interfacial polymerization is preferably carried out in the presence of an acid binder and an organic solvent.
- the interfacial polymerization may include, for example, after pre-p ymerization, a coupling agent is added, and then polymerized again. In this case, a high molecular weight copolycarbonate may be obtained.
- the materials used for the interfacial polymerization are not particularly limited as long as they are materials that can be used for the polymerization of polycarbonate, and the amount of the materials used may be adjusted as necessary.
- an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide
- an amine compound such as pyridine
- organic solvent if it is a solvent normally used for superposition
- halogenated hydrocarbons such as methylene chloride and chlorobenzene, can be used.
- the interfacial polymerization is a reaction such as a tertiary amine compound such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compound, quaternary phosphonium compound, etc. to promote the reaction. Accelerators may additionally be used.
- the reaction silver of the interfacial polymerization is preferably 0 to 40 ° C, the reaction time is preferably 10 minutes to 5 hours. In addition, it is preferable to maintain pH at 9 or more or 11 or more during interfacial polymerization reaction.
- the interfacial polymerization may be performed by further including a molecular weight regulator.
- the molecular weight modifier may be added before the start of the polymerization, during the start of the polymerization or after the start of the polymerization.
- Mono-alkylphenol may be used as the molecular weight modifier, and the mono-alkylphenol is, for example, p-tert-butylphenol, P-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nucledecylphenol, octadecyl It is at least one selected from the group consisting of phenol, eicosylphenol, docosylphenol and triacontylphenol, preferably P-tert-butylphenol, in which case the molecular weight control effect is large.
- the molecular weight modifier is, for example, 0.01 part by weight, 0,1 part by weight, or 1 part by weight or more, 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of the aromatic diol compound.
- the desired molecular weight was obtained within this range.
- the resin composition of one embodiment further includes an impact modifier in addition to the above-described BEAS resin.
- an impact modifier in addition to the above-described BEAS resin.
- a layer reinforcing agent may be used including a rubber-modified vinyl-based graft copolymer in order to appropriately reinforce the impact strength of the resin composition and molded article thereof of one embodiment.
- the resin composition of one embodiment may include a low content of the impact modifier due to the use of the above-described copolycarbonate resin, but may exhibit excellent layer strength, and the like, and thus improve chemical resistance due to the application of such a low content of the impact modifier.
- high content Disadvantages in using an impact modifier for example, gas generation and appearance characteristics during thin film molding, can be solved.
- the rubber modified vinyl graft copolymer is a diene rubber
- vinyl unsaturated monomers may be grafted to form a graft copolymer having a core-shell structure in which a shell is formed.
- an impact modifier may be used in the resin composition of one embodiment to more appropriately reinforce the laminar strength and the like even under a low content.
- the rubber may be one or more of diene rubbers having 4 to 6 carbon atoms, (meth) acrylate rubbers or silicone rubbers, and the structural stability of the layer reinforcing agent.
- silicone-acrylate rubber or (meth) acrylate-butadiene rubber can be used more appropriately.
- the (meth) acrylate-based rubber is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n- butyl (meth) acrylate, 2-ethyl Rubber formed from (meth) acrylate monomers such as nuclear chamber (meth) acrylate or nuclear chamber (meth) acrylate .
- the silicone rubber may be prepared from cyclosiloxane, specific examples thereof include nuxamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclonuxasiloxane, trimethyltriphenylcyclo Those produced from one or more selected from the group consisting of trisiloxane, tetramethyltetraphenylcyclotetrosiloxane, and octaphenylcyclotetrasiloxane can be used.
- a curing agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, or tetraethoxysilane can be further used.
- vinyl-based unsaturated grafted to the rubber As a monomer, 1 or more types of monomers etc. which can be copolymerized with an aromatic vinylic monomer or the said aromatic vinylic monomer can be used.
- the aromatic vinyl monomer may include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, para t-butylstyrene, ethyl styrene, or the like. These may be used alone or in combination of two or more.
- a vinyl cyanide compound alkyl (meth) acrylate having 1 to 12 carbon atoms, (meth) acrylate or alkyl having 1 to 12 carbon atoms or phenyl nucleosubstituted maleimide may be used. Can be. These may be used alone or in combination of two or more.
- the layered reinforcing agent in the form of the rubber-modified vinyl-based graft copolymer described above may be directly synthesized according to methods well known to those skilled in the art, or may be commercially available.
- the above-described layered reinforcing agent may be included in an amount of 1 to 10 weight 0 /., Or 1.5 to 5 weight 0 /., Or 2 to 4 weight 0 /. Based on the total content of the resin composition of one embodiment. Can be.
- the content of such a layer reinforcing agent is excessively large, there is substantially no additional effect of improving the layer strength, and the resin composition of one embodiment may hardly exhibit excellent chemical resistance, and gas generation or poor appearance quality during thin film molding, etc. This can happen.
- the content of the layer reinforcing agent is too small, impact resistance such as the layer strength of the resin composition and the molded article of one embodiment may not be sufficient.
- the flow modifier may improve the flowability of the resin composition of one embodiment. That is, since the improved fluidity can be further improved due to the addition of the above-described copolycarbonate resin, the resin composition of one embodiment can exhibit high flowability and excellent thin film formability.
- the flow modifier may be a thermoplastic polyester-based polymer or a phosphate ester-based compound.
- the thermoplastic polyester-based polymer may include polyethylene terephthalate, polybutylene terephthalate or polycyclonucleic acid terephthalate modified with ethylene glycol. And the like, these You may use together 2 or more types selected from these.
- the said phosphate ester type compound triphenyl phosphate, bisphenol A diphenyl phosphate, resorcinol diphenyl phosphate, etc. are mentioned, Two or more types selected from these can also be used together.
- various thermoplastic polyester-based polymers or phosphate ester-based compounds may be used as the flow modifier.
- the flow modifier may be included in an amount of 0.5 to 15 weight 0 /., Or 1 to 10 weight 0 /. Or 1 to 7 weight 0 /. Based on the total content of the resin composition of one embodiment.
- the content of the flow modifier is too low, it is difficult for the resin composition of one embodiment to have high fluidity and excellent thin film formability, and the like, on the contrary, when the content of the flow modifier is too high, the solidification rate of the polycarbonate resin is lowered, thereby causing problems in molding. May occur, and mechanical properties may be degraded.
- the composition may include drip inhibitors such as fluorine-based polymers such as polytetrafluoroethylene (PTFE), if necessary; Flame retardants such as phosphorus flame retardants; Surfactants; Nucleating agent; Coupling crab; Layering agent; Plasticizers; Lubricant; Antibacterial agents; Release agents; Heat stabilizer; Antioxidants; uv stabilizer; Compatibilizers; Staining 1; Antistatic agents; Pigments; dyes; Additives such as a flame retardant may further be included.
- drip inhibitors such as fluorine-based polymers such as polytetrafluoroethylene (PTFE), if necessary; Flame retardants such as phosphorus flame retardants; Surfactants; Nucleating agent; Coupling crab; Layering agent; Plasticizers; Lubricant; Antibacterial agents; Release agents; Heat stabilizer; Antioxidants; uv stabilizer; Compatibilizers; Staining 1; Antistatic agents; Pigments; dyes; Additives such as a flame retardant may
- the content of such additives may vary depending on the physical properties to be applied to the supernatant.
- the additive may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin.
- the total content of the additive is 20 parts by weight based on 100 parts by weight of the polycarbonate resin. Or less, or 15 parts by weight or less, or 10 parts by weight or less.
- a molded article including the polycarbonate resin composition described above is provided.
- the molded article uses the above-described polycarbonate resin composition as a raw material It is the article obtained by shape
- the molding method and its conditions can be appropriately selected and adjusted according to the type of molded article.
- the molded article may be obtained by mixing and extruding the polycarbonate-based resin composition to produce pellets, and then drying and injecting the pellets.
- the molded article may exhibit high fluidity and excellent thin film formability, excellent chemical resistance and layer resistance as formed from the polycarbonate resin composition, and may be suitably used as a material for a portable electronic device such as a smartphone.
- the polycarbonate-based resin composition and the molded article thereof according to the present invention may exhibit high fluidity and excellent thin film formability, excellent chemical resistance and impact resistance, and may be suitably used as a material for a portable electronic device such as a smartphone.
- Example 1 To the pellets were prepared by the addition of each component in the composition of Table 1 and then melted and shaken. After drying the prepared pellets for 6 hours at 70 ° C, it was injected to prepare a specimen for evaluation of physical properties.
- the components used in each Example and Comparative Example are as follows.
- the polycarbonate resin was a polymer of bisphenol A, the melt index (Ml) of which was measured as weight (g) measured for 10 minutes under a temperature of 300 t and a load of 1.2 kg according to ASTM D1238.
- Ml melt index
- an aromatic polycarbonate resin (A-1; LUPOY 1300-10 manufactured by LG Chemical Co., Ltd.) having a melt index of 10 g / 10 minutes and an aromatic polycarbonate resin (A-2; LUPOY manufactured by LG Chemical Co., Ltd.) having 30 g / 10 minutes 1300-10) were used respectively.
- C flow modifier
- Thermoplastic polyester-based polymer PET polymer of Sky PET BB8055 manufactured by SK Chemicals was used.
- Comparative Example 2 may be included in the current independent claim 1, and deleted. Comparative Example 2 will be used as a result of additional experiment if necessary in the later screening process.
- Melt Index (Ml) Calculated as weight (g) measured for 10 minutes under a temperature of 300 ° C. and a load of 1.2 kg according to ASTM D1238.
- Comparative Example 1 exhibited poor chemical resistance compared to the Example, and it was confirmed that the Comparative Example 1 was also inferior to the Example in terms of fluidity or delamination strength.
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Abstract
The present invention relates to a polycarbonate-based resin composition and a molded article thereof. More particularly, the present invention relates to a polycarbonate-based resin composition having high fluidity and excellent chemical resistance and impact resistance, and a molded article formed from the same.
Description
【발명의 명칭】 [Name of invention]
폴리카보네이트계 수지 조성물 및 이의 성형품 Polycarbonate-based resin composition and molded article thereof
【관련 출원 (들)과의 상호 인용】 [Cross Citation with Related Application (s)]
본 출원은 2014년 12월 4일자 한국 특허 출원 제 10-2014-0173005 호 및 2015년 12월 2일자 한국 특허 출원 제 10-2015-0170828 호에 기초한 우선권의 이익을 주장하며， 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다. This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0173005 dated December 4, 2014 and Korean Patent Application No. 10-2015-0170828 dated December 2, 2015. All content disclosed in the literature is included as part of this specification.
【기술분야】 Technical Field
본 발명은 폴리카보네이트계 수지 조성물 및 이의 성형품에 관한 것으로, 보다 구체적으로, 높은 유동성과， 우수한 내화학성 및 내충격성을 나타내는 폴리카보네이트계 수지 조성물과 이로부터 형성된 성형품에 관한 것이다. The present invention relates to a polycarbonate-based resin composition and a molded article thereof, and more particularly, to a polycarbonate-based resin composition and a molded article formed therefrom exhibiting high fluidity, excellent chemical resistance and impact resistance.
【배경기술】 Background Art
폴리카보네이트 수지는 비스페놀 A와 같은 방향족 디을과 포스겐과 같은 카보네이트 전구체의 축중합에 의해 형성되는 열가소성 수지로서, 우수한 층격 강도, 수치안정성, 내열성, 및 투명성 등을 가지며, 전기전자 제품의 외장재, 자동차 부품, 건축 소재, 광학 부품 등 광범위한 분야에 적용된다. Polycarbonate resins are thermoplastic resins formed by the polycondensation of aromatic di-likes such as bisphenol A and carbonate precursors such as phosgene, and have excellent layer strength, numerical stability, heat resistance, and transparency. It is applied to a wide range of fields such as, building materials and optical components.
최근 들어, 스마트폰이나 휴대폰 등 휴대용 전자 기기에 폴리카보네이트계 소재의 적용이 검토되고 있다. 그런데， 이러한 폴리카보네이트계 소재를 사용할 경우 저은 사용 환경 등에서의 충격 강도가 층분치 못하고, 최근의 높은 디자인 관련 요구에 부웅하기 위해 도장을 진행하면 상기 폴리카보네이트계 소재의 내화학성 등이 취약하여 적용이 어렵게 되는 단점이 있었다. Recently, application of polycarbonate-based materials to portable electronic devices such as smartphones and mobile phones has been considered. However, when using such a polycarbonate-based material, low impact strength in the use environment, etc. is insufficient, and if the coating is carried out to meet the recent high design-related demands, the chemical resistance of the polycarbonate-based material is weak and applied. There was a disadvantage that became difficult.
더구나， 최근 스마트폰 등에 대한 디자인적 요구에 따라， 상기 폴리카보네이트계 소재를 사용해 형성되는 성형품이 박막화될 필요성이 높아지고 있는데， 이를 위해서는 상기 폴리카보네이트계 소재가 용융 상태에서 높은 유동성을 나타내어 뛰어난 박막 성형성을 나타낼 필요가 있다. 그러나， 기존의 폴라카보네이트계 소재는 층분한 유동성 및 박막 성형성을 나타내지 못하였던 것이 사실이다. In addition, in recent years, according to the design demand for a smart phone, the necessity of thinning a molded article formed using the polycarbonate-based material is increasing. For this purpose, the polycarbonate-based material exhibits high fluidity in a molten state and thus excellent thin film formability. Need to indicate However, it is true that the existing polycarbonate-based materials did not show a good fluidity and thin film formability.
상술한 몇 가지 문제점을 해결하기 위해, 폴리카보네이트계 소재에 충격 보강제 등을 첨가하여 충격 강도를 보강하고자 하는 시도가 이루어진 바 있다.
그러나, 박막화된 성형품에 적절한 수준의 충격 강도를 달성하기 위해 일정 수준 이상의 층격 보강제를 첨가하는 경우, 성형시 충격 보강제에서 유래된 가스 등이 발생하여 성형품의 외관 불량이 발생하고, 고온 성형시 변색 등이 일어나는 문제점이 있어 왔다. In order to solve the above-mentioned problems, attempts have been made to reinforce impact strength by adding an impact modifier to a polycarbonate-based material. However, when a layered reinforcement of a certain level is added to the thin molded article to achieve an appropriate level of impact strength, a gas or the like derived from the impact reinforcing agent is generated during molding, resulting in poor appearance of the molded article, and discoloration during high temperature molding. There has been a problem with this happening.
또한, 몇 가지 첨가제의 사용으로도， 층격 강도 및 고유동성 (박막 성형성)을 동시에 달성하기 곤란하였던 것이 사실이며, 첨가제만으로 이들 물성을 달성하기 위해서는 상당량의 첨가제 추가가 필요하여 폴리카보네이트계 소재 자체의 물성 저하가 일어나는 경우가 많아 한계가 있어 왔다. . In addition, even with the use of several additives, it was true that it was difficult to simultaneously achieve laminar strength and high fluidity (thin film formability), and in order to achieve these properties only with additives, a large amount of additives were required. In many cases, a decrease in physical properties has occurred and there is a limit. .
【발명의 내용】 [Content of invention]
【해결하려는 과제】 [Problem to solve]
이에 본 발명은 상대적으로 낮은 함량의 층격 보강제를 포함하더라도， 높은 .유동성과, 우수한 내화학성 및 내층격성을 나타내는 플리카보네이트계 수지 조성물을 제공하는 것이다. Accordingly, the present invention is to provide a polycarbonate-based resin composition showing a high fluidity, excellent chemical resistance and layer resistance, even if a relatively low content of the layer reinforcing agent.
본 발명은 또한, 상기 폴리카보네이트계 수지 조성물을 포함하는 성형품을 제공하는 것이다. This invention also provides the molded article containing the said polycarbonate-type resin composition.
【과제의 해결 수단】 [Measures of problem]
본 발명은 방향족 폴리카보네이트계 제 1 반복 단위로 이루어진 폴리카보네이트 수지, The present invention is a polycarbonate resin consisting of an aromatic polycarbonate-based first repeating unit,
방향족 폴리카보네이트계 게 1 반복 단위와， 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함한 코폴리카보네이트 수지， 고무변성 비닐계 그라프트 공중합체를 포함하는 충격 보강제， 및 열가소성 폴리에스테르계 중합체 또는 인산 에스테르계 화합물을 포함하는 유동 개질제를 포함하고; Copolycarbonate resin comprising an aromatic polycarbonate-based crab 1 repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, an impact modifier comprising a rubber-modified vinyl graft copolymer, and a thermoplastic polyester-based A flow modifier comprising a polymer or phosphate ester compound;
상기 제 1 반복 단위는 각각 독립적으로 하기 화학식 1로 표시되는 반복 단위를 포함하고; The first repeating units each independently include a repeating unit represented by the following Formula 1;
상기 제 2 반복 단위는 하기 화학식 3으로 이루어진 군에서 선택된 1종 이상의 반복 단위를 포함하는 폴리카보네이트계 수지 조성물을 제공한다: The second repeating unit provides a polycarbonate-based resin composition comprising at least one repeating unit selected from the group consisting of Formula 3 below:
[화학식 1]
[Formula 1]
상기 화학식 1에서, In Chemical Formula 1,
R1 내지 R4는 각각 독립적으로 수소， C1-10 알킬， C1-10 알콕시, 또는 할로겐이고, R 1 to R 4 are each independently hydrogen, C 1-10 alkyl, C 1-10 alkoxy, or halogen,
Z는 비치환되거나 또는 페닐로 치환된 Cw0 알킬렌, 비치환되거나 또는 C1-10 알킬로 치환된 C3-15 사이클로알킬렌， O, S, S(D, S02, 또는 CO이고; Z is Cw 0 alkylene unsubstituted or substituted with phenyl, C 3-15 cycloalkylene unsubstituted or substituted with C 1-10 alkyl, O, S, S (D, S0 2 , or CO;
[화학식 3] [Formula 3]
X2은 각각 독립적으로 C1-10 알킬렌이고， X 2 are each independently C 1-10 alkylene,
Y1은 각각 독립적으로 수소， C1-6 알킬， 할로겐， 히드록시， d_6 알콕시 또는 C6 20 아릴이고, Each Y 1 is independently hydrogen, C 1-6 alkyl, halogen, hydroxy, d_ 6 alkoxy or C 6 20 aryl,
R6는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐,， 옥시라닐로 치환된 C1-10 알콕시, 또는 C6-20 아릴로 치환된 C1-15 알킬; 할로겐; C1-10 알콕시; 알릴; C1-10 할로알킬; 또는 C6-20 아릴이고, Each R 6 is independently hydrogen; C 1-15 alkyl unsubstituted or substituted with oxiranyl, C 1-10 alkoxy substituted with oxiranyl, or C 6-20 aryl; halogen; C 1-10 alkoxy; Allyl; C 1-10 haloalkyl; Or C 6-20 aryl,
n2는 10 내지 200의 정수이다. n2 is an integer of 10-200.
본 발명은 또한, 상기 리카보네이트계 수지 조성물을 포함하는 성형품을 제공한다. 이하， 발명의 구체적인 구현 예들에 따른 폴리카보네이트계 수지 조성물 및 이의 성형품에 대하여 보다 상세하게 설명하기로 한다. The present invention also provides a molded article comprising the above-mentioned recarbonate-based resin composition. Hereinafter, the polycarbonate-based resin composition and the molded article thereof according to specific embodiments of the present invention will be described in more detail.
그에 앞서， 본 명세서에 사용되는 전문 용어는 단지 특정 구현예를 언급하기 위한 것이며， 본 발명을 한정하는 것을 의도하지 않는다. 그리고,
여기서 사용되는 단수 형태들은 문구들이 이와 명백히 반대의 의미를 나타내지 않는 한 복수 형태들도 포함한다. Prior to this, the terminology used herein is for reference only to specific embodiments and is not intended to limit the invention. And, As used herein, the singular forms “a,” “an,” and “the” include plural forms as well, unless the phrases clearly indicate the opposite.
또한, 본 명세서에서 사용되는 '포함' 또는 '함유 '의 의미는 특정 특성， 영역, 정수, 단계, 동작， 요소 또는 성분을 구체화하며, 다른 특정 특성, 영역， 정수， 단계, 동작, 요소， 또는 성분의 부가를 제외시키는 것은 아니다. Also, as used herein, the meaning of 'comprise' or 'contains' embodies a particular characteristic, region, integer, step, operation, element or component, and other specific characteristics, region, integer, step, operation, element, or It does not exclude the addition of ingredients.
그리고, 본 명세서에서 '제 r 및 '제 2' 등과 같이 서수를 포함하는 용어는 하나의 구성요소를 다른 구성요소로부터 구별하는 목적으로 사용되며, 상기 서수에 의해 한정되지 않는다. 예를 들어, 본 발명의 권리 범위 내에서 제 구성요소는 제 2 구성요소로도 명명될 수 있고, 유사하게 게 2 구성요소는 제 1 구성요소로 명명될 수 있다. In this specification, terms including ordinal numbers such as 'th' and 'second' are used for the purpose of distinguishing one component from other components and are not limited by the ordinal number. For example, within the scope of the present invention, the first component may also be referred to as the second component, and similarly the second component may be referred to as the first component.
I. 폴리카보네이트계 수지 조성물 I. Polycarbonate Resin Composition
발명의 일 구현 예에 따르면， According to one embodiment of the invention,
방향족 폴리카보네이트계 제 1 반복 '단위로 이루어진 폴리카보네이트 수지， An aromatic polycarbonate-series first iteration, a polycarbonate resin made of a unit,
방향족 폴리카보네이트계 제 1 반복 단위와， 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함한 코폴리카보네이트 수지, 고무변성 비닐계 그라프트 공중합체를 포함하는 충격 보강제， 및 열가소성 폴리에스테르계 중합체 또는 인산 에스테르계 화합물을 포함하는 유동 개질제를 포함하고; Copolycarbonate resin comprising an aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, an impact modifier comprising a rubber-modified vinyl-based graft copolymer, and a thermoplastic polyester-based A flow modifier comprising a polymer or phosphate ester compound;
상기 제 1 반복 단위는 각각 독립적으로 하기 화학식 1로 표시되는 반복 단위를 포함하고; The first repeating units each independently include a repeating unit represented by the following Formula 1;
상기 제 2 반복 단위는 하기 화학식 3으로 이루어진 군에서 선택된 1종 이상의 반복 단위를 포함하는 폴리카보네이트계 수지 조성물이 제공된다: The second repeating unit is provided with a polycarbonate-based resin composition comprising at least one repeating unit selected from the group consisting of:
상기 화학식 1에서
R1 내지 R4는 각각 독립적으로 수소， C1-10 알킬, Cwo 알콕시， 또는 할로겐이고, In Chemical Formula 1 R 1 to R 4 are each independently hydrogen, C 1-10 alkyl, Cwo alkoxy, or halogen,
z는 비치환되거나 또는 페닐로 치환된 c1-10 알킬렌, 비치환되거나 또는z is c 1-10 alkylene unsubstituted or substituted with phenyl, unsubstituted or
C1-10 알킬로 치환된 C3-15 사이클로알킬렌,ᄋ， S, SO, S02, 또는 CO이고; C 3-15 cycloalkylene substituted with C 1-10 alkyl, S, SO, SO 2 , or CO;
X2은 각각 독립적으로 C1-10 알킬렌이고， X 2 are each independently C 1-10 alkylene,
Y1은 각각 독립적으로 수소, C1-6 알킬, 할로겐， 히드록시， C1-6 알콕시 또는 C6-20 아릴이고， Each Y 1 is independently hydrogen, C 1-6 alkyl, halogen, hydroxy, C 1-6 alkoxy or C 6-20 aryl,
R6는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐， 옥시라닐로 치환된 C1-10 알콕시, 또는 C6-20 아릴로 치환된 d_15 알킬; 할로겐; Cwo 알콕시; 알릴; C1-10 할로알킬; 또는 C6-20 아릴이고， Each R 6 is independently hydrogen; D_ 15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C 1-10 alkoxy, or C 6-20 aryl; halogen; Cwo alkoxy; Allyl; C 1-10 haloalkyl; Or C 6-20 aryl,
n2는 10 내지 200의 정수이다. n2 is an integer of 10-200.
또한, 상기 일 구현예의 조성물에서, 상기 코폴리카보네이트 수지의 제 2 반복 단위는 하기 화학식 2로 이루어진 군에서 선택된 1종 이상의 반복 단위를 더 포함할 수 있다: In addition, in the composition of the embodiment, the second repeating unit of the copolycarbonate resin may further include one or more repeating units selected from the group consisting of:
상기 화학식 2에서， In Chemical Formula 2,
X1은 각각 독립적으로 C1-10 알킬렌이고， Each X 1 is independently C 1-10 alkylene,
R5는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐， 옥시라닐로 치환된 C1-10 알콕시， 또는 C6-20 아릴로 치환된 C1-15 알킬; 할로겐; C1-10 알콕시;
알릴; c1-10 할로알킬; 또는 c6-20 아릴이고, Each R 5 is independently hydrogen; C 1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C 1-10 alkoxy, or C 6-20 aryl; halogen; C 1-10 alkoxy; Allyl; c 1-10 haloalkyl; Or c 6-20 aryl,
n1은 10 내지 200의 정수이다. n1 is an integer of 10-200.
본 발명자들의 계속적인 연구 결과， 상기 화학식 3의 특정 실록산 결합, 보다 적절하게는 화학식 2 및 3의 실록산 결합을 폴리카보네이트 주쇄에 도입된 코폴리카보네이트 수지는 일반적인 방향족 폴리카보네이트 수지의 물성을 보완하여 상기 일 구현예의 수지 조성물이 보다 우수한 충격 강도 (내층격성)나 내화학성 등을 나타내게 할 수 있음이 확인되었다. 또한, 코폴리카보네이트 수지 및 일반적인 방향족 폴리카보네이트 수지를 함께 포함하는 일 구현예의 수지 조성물은 2 가지 베이스 수지의 상호 작용으로 일정 수준 이상의 유동성 및 박막 성형성을 나타낼 수 있다. 、 As a result of continuous research by the present inventors, the copolycarbonate resin in which the specific siloxane bond of Formula 3, more preferably, the siloxane bonds of Formula 2 and 3 is introduced into the polycarbonate backbone, supplements the physical properties of general aromatic polycarbonate resins. It was confirmed that the resin composition of one embodiment can exhibit more excellent impact strength (layer resistance), chemical resistance, and the like. In addition, the resin composition of one embodiment including a copolycarbonate resin and a general aromatic polycarbonate resin may exhibit a fluidity and thin film formability of a certain level or more through the interaction of two base resins. 、
또한, 일 구현예의 수지 조성물이 상기 코폴리카보네이트 수지의 사용에 의해 일부 향상된 충격 강도를 나타냄에 따라, 이러한 수지 조성물은 감소된 함량의 층격 보강제를 포함하면서도 우수한 층격 강도 (내충격성)를 나타낼 수 있으며， 이에 따라 높은 함량의 층격 보강제에 따른 박막 성형시의 가스 발생이나 외관 블량 등의 문제점을 해결할 수 있다. In addition, as the resin composition of one embodiment exhibits some improved impact strength by the use of the copolycarbonate resin, such a resin composition may exhibit excellent layer strength (impact resistance) while including a reduced amount of layer reinforcement. Accordingly, problems such as gas generation or appearance defects during thin film molding according to a high content of the layer reinforcement agent can be solved.
부가하여， 일 구현예의 수지 조성물은 특정한 유동 개질제를 더 포함하여， 더욱 높은 유동성 및 박막 성형성을 나타낼 수 있다. In addition, the resin composition of one embodiment may further include a specific flow modifier to exhibit higher flowability and thin film formability.
그러므로， 일 구현예의 수지 조성물은 스마트폰 등 휴대용 전자 기기용 소재로서 적절시 사용될 수 있는 높은 유동성 및 박막 성형성과, 우수한 내화학성 및 내충격성을 함께 나타낼 수 있다. . 이하, 발명의 일 구현 예에 따른 폴리카보네이트계 수지 조성물에 포함될 수 있는 성분들에 대하여 상세히 설명한다. (1 ) 폴리카보네이트수지 Therefore, the resin composition of one embodiment may exhibit both high flowability and thin film formability, excellent chemical resistance and impact resistance, which can be appropriately used as materials for portable electronic devices such as smartphones. . Hereinafter, the components that can be included in the polycarbonate-based resin composition according to the embodiment of the present invention will be described in detail. (1) Polycarbonate resin
상기 폴리카보네이트 수지는 상기 폴리카보네이트계 수지 조성물에 포함되는 베이스 수지로서， 방향족 폴리카보네이트계 제 1 반복 단위로 이루어진다. The polycarbonate resin is a base resin contained in the polycarbonate-based resin composition and comprises an aromatic polycarbonate-based first repeating unit.
이러한 폴리카보네이트 수지는 방향족 폴리카보네이트계 제 1 반복 단위로 이루어지는 것으로서， 실록산 결합을 갖는 방향족 폴리카보네이트계 반복
단위 (예를 들어, 상기 게 2 반복 단위)를 갖지 않는다는 점에서, 후술하는 코폴리카보네이트 수지와 구분될 수 있다. Such a polycarbonate resin is composed of an aromatic polycarbonate-based first repeating unit, and has an aromatic polycarbonate-based repeat having a siloxane bond. It can be distinguished from the copolycarbonate resin described later in that it does not have a unit (for example, 2 repeat units).
구체적으로 상기 방향족 폴리카보네이트계 제 1 반복 단위는 디올 화합물 및 카보네이트 전구체의 반응에 의해 형성된 것으로, 적절하게는 하기 화학식 1로 표시되는 반복 단위를 포함할 수 있으며, 이러한 반복 단위의 구조는 후술하는 코폴리카보네이트 수지에 포함되는 제 1 반복 단위와 동일하게 될 수도 있지만, 이와 상이하게 될 수도 있다: Specifically, the aromatic polycarbonate-based first repeating unit is formed by the reaction of a diol compound and a carbonate precursor, and may suitably include a repeating unit represented by Formula 1 below, and the structure of the repeating unit may be described later. It may be the same as the first repeating unit included in the polycarbonate resin, but may be different from this:
상기 화학식 1에서， In Chemical Formula 1,
R1 내지 R4는 각각 독립적으로 수소, C1-10 알킬, C1 -10 알콕시, 또는 할로겐이고, R 1 to R 4 are each independently hydrogen, C 1-10 alkyl, C 1 -10 alkyl, or halogen,
Z는 비치환되거나 또는 페닐로 치환된 Cwo 알킬렌, 비치환되거나 또는 CLIO 알킬로 치환된 C3-15 사이클로알킬렌，ᄋ, S, SO, SO2, 또는 CO이다. Z is Cwo alkylene unsubstituted or substituted with phenyl, C 3-15 cycloalkylene unsubstituted or substituted with CLIO alkyl, S, SO, SO 2 , or CO.
바람직하게는 상기 R1 내지 R4는 각각 독립적으로 수소, 메틸, 클로로, 또는 브로모이다. Preferably, R 1 to R 4 are each independently hydrogen, methyl, chloro, or bromo.
또한 바람직하게는, Z는 비치환되거나 또는 페닐로 치환된 직쇄 또는 분지쇄의 C1-10 알킬렌이며， 보다 바람직하게는 메틸렌, 에탄 -1 , 1 -디일, 프로판 -2,2- 디일, 부탄 -2,2-디일， 1 -페닐에탄 -1 , 1 -디일, 또는 디페닐메틸렌이다. 또한 바람직하게는 , Ζ는 사이클로핵산 -1 , 1 -디일 ,ᄋ， S, SO, S02, 또는 CO이다. Also preferably, Z is straight or branched C 1-10 alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1, 1-diyl, propane-2,2-diyl, Butane-2,2-diyl, 1-phenylethane-1, 1-diyl, or diphenylmethylene. Also preferably, Ζ is cyclonucleic acid-1, 1-diyl, S, SO, S0 2 , or CO.
비 제한적인 예로, 상기 화학식 1로 표시되는 반복 단위는 비스 (4- 히드록시페닐)메탄， 비스 (4-히드록시페닐)에테르, 비스 (4-히드록시페닐)설폰, 비스 (4-히드록시페닐)설폭사이드, 비스 (4-히드록시페닐)설파이드, 비스 (4- 히드록시페닐)케톤, 1 , 1 -비스 (4-히드록시페닐)에탄， 비스페놀 A, 2,2-비스 (4- 히드록시페닐)부탄, 1 , 1 -비스 (4-히드록시페닐)시클로핵산, 2,2-비스 (4-히드록시 -3,5- 디브로모페닐)프로판， 2，2-비스 (4-히드록시 -3,5-디클로로페닐)프로판, 2,2-비스 (4- 히드록시 -3-브로모페닐)프로판, 2,2-비스 (4-히드록시 -3-클로로페닐)프로판， 2,2-
비스 (4-히드록시 -3-메틸페닐)프로판, 2,2-비스 (4-히드록시 -3,5-디메틸페닐)프로판， 1 ,1 -비스 (4-히드록시페닐 )-1 -페닐에탄， 비스 (4-히드록시페닐)디페닐메탄， 및 알파,오메가 -비스 [3-(o-히드록시페닐)프로필]폴리디메틸실록산으로 이루어진 군에서 선택된 하나 이상의 방향족 디올 화합물로부터 유래된 것일 수 있다. As a non-limiting example, the repeating unit represented by Formula 1 may be bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy Phenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2-bis (4- Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclonucleic acid, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4 -Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2- Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1 -bis (4-hydroxyphenyl) -1 -phenylethane , Bis (4-hydroxyphenyl) diphenylmethane, and alpha, omega-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane may be derived from one or more aromatic diol compounds selected from the group consisting of .
상기 '방향족 디올 화합물로부터 유래한다'는 것은, 상기 방향족 디올 화합물의 하이드록시기와 카보네이트 전구체가 반응하여 상기 화학식 1로 표시되는 반복 단위를 형성하는 것을 의미한다. The term “derived from an aromatic diol compound” means that a hydroxyl group of the aromatic diol compound reacts with a carbonate precursor to form a repeating unit represented by the formula (1).
비 제한적인 예로, 방향족 디올 화합물인 비스페놀 A와 카보네이트 전구체인 트리포스겐이 중합된 경우, 상기 화학식 1의 반복 단위는 하기 화학식 1 -1로 표시될 수 있다: As a non-limiting example, when the aromatic diol compound bisphenol A and the carbonate precursor triphosgene are polymerized, the repeating unit of Formula 1 may be represented by the following Formula 1-1:
상기 카보네이트 전구체로는， 디메틸 카보네이트， 디에틸 카보네이트， 디부틸 카보네이트， 디시클로핵실 카보네이트, 디페닐 카보네이트， 디토릴 카보네이트, 비스 (클로로페닐) 카보네이트, 디 -m-크레실 카보네이트， 디나프틸 카보네이트, 비스 (디페닐) 카보네이트, 포스겐, 트리포스겐, 디포스겐, 브로모포스겐 및 비스할로포르메이트로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있으며， 바람직하게는, 트리포스겐 또는 포스겐을 사용할 수 있다. Examples of the carbonate precursor include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di- m -cresyl carbonate, and dinaphthyl carbonate, One or more selected from the group consisting of bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate may be used, and preferably triphosgene or phosgene may be used.
상기 폴리카보네이트 수지는 1 ,000 내지 100,000 g/mol, 바람직하게는 5,000 내지 50,000 g/mol의 중량 평균 분자량을 가질 수 있다. 보다 바람직하게는， 상기 증량 평균 분자량 (g/mol)은 1 ,000 이상, 5,000 이상, 10,000 이상， 21 ,000 이상， 22,000 이상， 23,000 이상, 24,000 이상, 25,000 이상, 26,000 이상, 27,000 이상， 또는 28,000 이상이다. 또한， 상기 중량 평균 분자량은 100,000 이하, 50，000 이하, 34,000 이하， 33,000 이하， 또는 32,000 이하이다. The polycarbonate resin may have a weight average molecular weight of 1,000 to 100,000 g / mol, preferably 5,000 to 50,000 g / mol. More preferably, the extended average molecular weight (g / mol) is at least 1,000, at least 5,000, at least 10,000, at least 21,000, at least 22,000, at least 23,000, at least 24,000, at least 25,000, at least 26,000, at least 27,000, or More than 28,000. The weight average molecular weight is 100,000 or less, 50,000 or less, 34,000 or less, 33,000 or less, or 32,000 or less.
그리고, 상기 폴리카보네이트 수지는 ASTM D1238 (300 °C 및 1.2 kg 하중; 10분간 측정)에 따른 5 g/10분 내지 50 g/10분, 혹은 10 g/10분 내지 40 g/10분의 용융지수 (Ml)를 갖는 것이 조성물이 갖는 물성의 안정적인 발현
측면에서 바람직할 수 있다. And, the polycarbonate resin is melted from 5 g / 10 minutes to 50 g / 10 minutes, or 10 g / 10 minutes to 40 g / 10 minutes according to ASTM D1238 (300 ° C and 1.2 kg load; measured for 10 minutes) Stable expression of physical properties of the composition having an index (Ml) It may be preferred in terms of aspects.
특히， 상기 폴리카보네이트 수지는 서로 다른 용융지수 (Ml)를 갖는 2 종 이상의 폴리카보네이트 수지를 포함하는 것이 조성물이 갖는 물성의 안정적인 발현의 측면에서 적절할 수 있다. 예컨대， 상기 폴리카보네이트계 수지 조성물에 서로 다른 용융지수 (Ml)를 갖는 2 종의 폴리카보네이트 수지가 포함되는 경우， 5 g/10분 내지 15 g/10분의 용융지수 (Ml)를 갖는 것과， 20 g/10분 내지 40 g/10분의 용융지수 (Ml)를 갖는 것이 적용될 수 있다. In particular, the polycarbonate resin may be appropriate in terms of stable expression of the physical properties of the composition comprising two or more polycarbonate resin having a different melt index (Ml). For example, when the polycarbonate resin composition contains two kinds of polycarbonate resin having different melt index (Ml), having a melt index (Ml) of 5 g / 10 minutes to 15 g / 10 minutes, One having a melt index (Ml) of 20 g / 10 min to 40 g / 10 min can be applied.
상술한 폴리카보네이트 수지는 일반적인 방향족 폴리카보네이트 수지의 잘 알려진 합성 방법에 따라 직접 합성하거나， 상업적으로 시판되고 있는 방향족 폴리카보네이트를 입수하여 사용할 수 있다. The polycarbonate resin described above may be directly synthesized according to a well-known synthetic method of a general aromatic polycarbonate resin, or may be obtained by using an aromatic polycarbonate commercially available.
또, 상기 폴리카보네이트 수지의 함량은 조절하고자 하는 조성물의 물성에 따라 달라질 수 있다. 예를 들어， 상기 _폴리카보네이트 수지는 일 구현예의 수지 조성물의 전체 함량을 기준으로， 40 내지 90 증량0 /。, 혹은 50 내지 80 중량 0/。의 함량으로 포함될 수 있다. 이러한 폴리카보네이트 수지는 후술하는 코폴리카보네이트 수지와 함께 베이스 수지로 포함되는 성분으로서， 그 함량이 지나치게 많아지면 상대적으로 코폴리카보네이트 수지의 함량이 줄어들어 수지 조성물의 내층격성 (충격 강도) 또는 내화학성이나 유동성 등이 층분치 못하게 될 수 있다. 또한, 폴리카보네이트 수지의 함량이 지나치게 작아지면, 강성 등의 기계적 물성이 충분치 못할 수 있다. In addition, the content of the polycarbonate resin may vary depending on the physical properties of the composition to be adjusted. For example, the _ polycarbonate resin may be included in an amount of, based on the total content of the resin composition of example one embodiment, from 40 to 90 increased 0 /., Or 50 to 80 weight 0 /. Such a polycarbonate resin is a component included as a base resin together with a copolycarbonate resin, which will be described later, and if the content is excessively large, the content of the copolycarbonate resin is relatively decreased, so that the layer composition (impact strength) or chemical resistance Fluidity, etc., may be disrupted. In addition, when the content of the polycarbonate resin is too small, mechanical properties such as rigidity may not be sufficient.
. .
(2)코폴리카보네이트수지 (2) Copolycarbonate resin
상기 코폴리카보네이트 수지는, 상술한 폴리카보네이트 수지가 갖는 물성의 개선， 특히 충격 강도 및 내화학성 등을 개선할 수 있으며， 상기 폴리카보네이트 주시와 조합되어 일 구현예에 의한 수지 조성물의 유동성을 개선할 수 있는 성분이다., 이러한 물성의 조절을 위해, 상기 코폴리카보네이트 수지는 일 구현예의 수지 조성물에 베이스 수지로서 폴리카보네이트 수지와 함께 포함될 수 있다. 이러한 코폴리카보네이트 수지는 방향족 플리카보네이트계 제 1 반복 단위와 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함한다. The copolycarbonate resin may improve the physical properties of the above-described polycarbonate resin, in particular, impact strength and chemical resistance, and may be combined with the polycarbonate resin to improve fluidity of the resin composition according to one embodiment. In order to control such physical properties, the copolycarbonate resin may be included with the polycarbonate resin as a base resin in the resin composition of one embodiment. Such copolycarbonate resin includes an aromatic polycarbonate-based second repeating unit having an aromatic polycarbonate-based first repeating unit and at least one siloxane bond.
즉, 상기 코폴리카보네이트 수지는 폴리카보네이트의 주쇄에 폴리실록산
구조가 도입되어 있다는 점에서 상술한 폴리카보네이트 수지 (예를 들어, 폴리실록산 구조의 도입 없이 방향족 폴리카보네이트 주쇄만을 갖는 것)와 구분될 수 있다. That is, the copolycarbonate resin is polysiloxane in the backbone of the polycarbonate It can be distinguished from the above-described polycarbonate resin (for example, having only an aromatic polycarbonate main chain without introducing a polysiloxane structure) in that a structure is introduced.
[제 1 반복 단위] [First repeating unit]
구체적으로, 상기 방향족 폴리카보네이트계 제 1 반복 단위는 디올 화합물 및 카보네이트 전구체의 반웅에 의해 형성된 것으로, 상술한 화학식 1로 표시되는 반복 단위를 포함할 수 있다. Specifically, the aromatic polycarbonate-based first repeating unit is formed by reaction of the diol compound and the carbonate precursor, and may include the repeating unit represented by Chemical Formula 1 described above.
상기 화학식 1에서, In Chemical Formula 1,
R1 내지 R4는 각각 독립적으로 수소, 알콕시， 또는 할로겐이고, R 1 to R 4 are each independently hydrogen, alkoxy, or halogen,
Z는 비치환되거나 또는 페닐로 치환된 c1-10 알킬렌., 비치환되거나 또는 c1-10 알킬로 치환된 c3-15 사이클로알킬렌，ᄋ, S, SO, SO2, 또는 CO이다. Z is c 1-10 alkylene unsubstituted or substituted with phenyl, c 3-15 cycloalkylene unsubstituted or substituted with c 1-10 alkyl, S, SO, SO 2 , or CO. .
여기서, 상기 R1 내지 R4와 Z는 상술한 폴리카보네이트 수지를 이루는 반복 단위에 대응하는 그룹과 같거나 다른 구조를 가질 수 있다. Here, the R 1 to R 4 and Z may have the same or different structure as the group corresponding to the repeating unit forming the polycarbonate resin described above.
비 제한적인 예로, 방향족 디올 화합물인 비스페놀 A와 카보네이트 전구체인 트리포스겐이 중합된 경우， 상기 화학식 1의 반복 단위는 하기 화학식 1 -1로 표시될 수 있다: As a non-limiting example, when the aromatic diol compound bisphenol A and the carbonate precursor triphosgene are polymerized, the repeating unit of Formula 1 may be represented by the following Formula 1-1:
상기 카보네이트 전구체로는， 디메틸 카보네이트， 디에틸 카보네 디부틸 카보네이트， 디시클로핵실 카보네이트， 디페닐 카보네이트, 디토릴 카보네이트, 비스 (클로로페닐) 카보네이트, 디 -m-크레실 카보네이트， 디나프틸 카보네이트, 비스 (디페닐) 카보네이트， 포스겐, 트리포스겐, 디포스겐, Examples of the carbonate precursors include dimethyl carbonate, diethyl carbonate dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, and dinaphthyl carbonate, Bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene,
m
브로모포스겐 및 비스할로포르메이트로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있으며, 바람직하게는, 트리포스겐 또는 포스겐을 사용할 수 있다. m One or more selected from the group consisting of bromophosgene and bishaloformates can be used, and preferably triphosphene or phosgene can be used.
[제 2 반복단위】 [Second repeating unit]
한편， 상기 하나 이상의 실록산 결합을 갖는 폴리카보네이트계 제 2 반복 단위는, 하나 이상의 실록산 화합물과 카보네이트 전구체가 반응하여 형성되는 것으로， 구체적인 예에서, 하기 화학식 3으로 이루어진 군에서 선택된 1종 이상의 반복 단위를 포함할 수 있으며, 보다 적절하게는 하기 화학식 2로 이루어진 군에서 선택된 1종 이상의 반복 단위를 더 포함할 수 있다: On the other hand, the second polycarbonate-based repeating unit having at least one siloxane bond is formed by reacting at least one siloxane compound and a carbonate precursor, in a specific example, at least one repeating unit selected from the group consisting of It may include, more preferably may further include one or more repeating units selected from the group consisting of:
상기 화학식 2에서, In Chemical Formula 2,
X1은 각각 독립적으로 C1-10 알킬렌이고, Each X 1 is independently C 1-10 alkylene,
R5는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐, 옥시라닐로 치환된 C1-10 알콕시， 또는 C6-20 아릴로 치환된 C1-15 알킬; 할로겐; C1-10 알콕시; 알릴; C1-10 할로알킬; 또는 C6-20 아릴이고, Each R 5 is independently hydrogen; C 1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C 1-10 alkoxy, or C 6-20 aryl; halogen; C 1-10 alkoxy; Allyl; C 1-10 haloalkyl; Or C 6-20 aryl,
η1은 10 내지 200의 정수이고; eta is an integer from 10 to 200;
X2은 각각 독립적으로 C1-10 알킬렌이고， X 2 are each independently C 1-10 alkylene,
Y1은 각각 독립적으로 수소, C1-6 알킬， 할로겐， 히드록시, C1-6 알콕시 C6-20 아릴이고， Each Y 1 is independently hydrogen, C 1-6 alkyl, halogen, hydroxy, C 1-6 alkoxy C 6-20 aryl,
R6는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐, 옥시라닐로
치환된 c1-10 알콕시， 또는 c6-20 아릴로 치환된 c1-15 알킬; 할로겐; c1-10 알콕시; 알릴; c1-10 할로알킬; 또는 c6.20 아릴이고, Each R 6 is independently hydrogen; Unsubstituted or oxiranyl, oxiranyl Substituted c 1-10 alkoxy, or c 1-15 alkyl substituted with c 6-20 aryl; halogen; c 1-10 alkoxy; Allyl; c 1-10 haloalkyl; Or c 6 . 20 aryl,
n2는 10 내지 200의 정수이다. n2 is an integer of 10-200.
상기 화학식 2에서, 상기 X1은 각각 독립적으로 C2-10 알킬렌일 수 있고, 바람직하게는 C2-4 알킬렌, 보다 바람직하게는 프로판 -1 ,3-디일일 수 있다. In Formula 2, X 1 may be each independently C 2-10 alkylene, preferably C 2-4 alkylene, more preferably propane-1,3-diyl.
상기 .화학식 2에서， 상기 R5는 각각 독립적으로 수소, 메틸, 에틸, 프로필 3-페닐프로필， 2-페닐프로필, 3- (옥시라닐메특시)프로필, 플루오로, 클로로, 브로모， 아이오도， 메록시, 에톡시, 프로폭시， 알릴, 2,2,2-트리플루오로에틸, 3，3，3- 트리플루오로프로필， 페닐, 또는 나프틸일 수 있다. 또한 바람직하게는, 상기 R5는 각각 독립적으로 C1-10 알킬이고, 보다 바람직하게는 C1-6 알킬이고, 보다 바람직하게는 에3 알킬이고, 가장 바람직하게는 Above . In Formula 2, each of R 5 is independently hydrogen, methyl, ethyl, propyl 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, meso Hydroxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl. Also preferably, each of R 5 is independently C 1-10 alkyl, more preferably C 1-6 alkyl, more preferably at 3 alkyl, and most preferably
상기 화학식 2에서 상기 n1은 10 내지 200의 정수로서， 바람직하게는 i) 30 내지 60의 정수이거나， ii) 20 이상， 25 이상, 또는 30 이상이고， 40 이하, 또는 35 이하의 정수이거나 또는 iii) 50 이상， 또는 55 이상이고， 70 이하, 65 이하, 또는 60 이하의 정수일 수 있다. N1 is an integer of 10 to 200, preferably i) an integer of 30 to 60, ii) 20 or more, 25 or more, or 30 or more, 40 or less, or an integer of 35 or less, or iii. ) 50 or more, or 55 or more, and may be an integer of 70 or less, 65 or less, or 60 or less.
예컨대, 상기 화학식 2의 반복 단위는 하기 화학식 2-1로 표시될 수 있다: For example, the repeating unit of Formula 2 may be represented by the following Formula 2-1:
상기 화학식 2-1에서, In Chemical Formula 2-1,
상기 R5 및 ni은 각각 상기 화학식 2에서 정의된 바와 같다. R 5 and n i are the same as defined in Chemical Formula 2, respectively.
그리고, 상기 화학식 3에서, 바람직하게는, 상기 X2는 각각 독립적으로 C2-io 알킬렌이고, 보다 바람직하게는 C2-6 알킬렌이고, 가장 바람직하게는 이소부틸렌일 수 있다. In Formula 3, preferably, each of X 2 is independently C 2 -io alkylene, more preferably C 2-6 alkylene, and most preferably isobutylene.
바람직하게는, 상기 화학식 3에서 상기 Y1은 수소일 수 있다. Preferably, in Formula 3, Y 1 may be hydrogen.
상기 화학식 3에서 R6는 각각 독립적으로 수소， 메틸， 에틸， 프로필, 3-
페닐프로필， 2-페닐프로필, 3- (옥시라닐메특시)프로필, 플루오로， 클로로， 브로모, 아이오도， 메록시, 에록시， 프로폭시, 알릴, 2,2,2-트리플루오로에틸, 3,3,3- 트리플루오로프로필， 페닐, 또는 나프틸일 수 있다. 또한 바람직하게는， 상기 R6는 각각 독립적으로 C1-10 알킬이고, 보다 바람직하게는 C1-6 알킬이고, 보다 바람직하게는 알킬이고, 가장 바람직하게는 메틸일 수 있다. R 6 in Formula 3 is each independently hydrogen, methyl, ethyl, propyl, 3- Phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl , 3,3,3-trifluoropropyl, phenyl, or naphthyl. Also preferably, each of R 6 may be independently C 1-10 alkyl, more preferably C 1-6 alkyl, more preferably alkyl, and most preferably methyl.
상기 화학식 3에서 상기 n2는 10 내지 200의 정수로서, 바람직하게는 ί) 30 내지 60의 정수이거나， ii) 20 이상, 25 이상， 또는 30 이상이고, 40 이하， 또는 35 이하의 정수이거나， 또는 Πί) 50 이상， 또는 55 이상이고， 70 이하, 65 이하, 또는 60 이하의 장수일 수 있다. In Formula 3, n2 is an integer of 10 to 200, preferably ί) an integer of 30 to 60, ii) 20 or more, 25 or more, or 30 or more, 40 or less, or an integer of 35 or less, or Πί) 50 or more, or 55 or more, 70 or less, 65 or less, or 60 or less.
예컨대， 상기 화학식 3의 반복 단위는 하기 화학식 3-1로 표시될 수 있다: For example, the repeating unit of Formula 3 may be represented by the following Formula 3-1:
상기 R6 및 η2는 각각 상기 화학식 3에서 정의된 바와 같다. R 6 and η 2 are the same as defined in Chemical Formula 3, respectively.
발명의 구현 예에 따르면, 상기 코폴리카보네이트 수지는 상기 화학식 3으로 이루어진 군에서 선택된 1종 이상의 반복 단위를 포함할 수 있고, 보다 적절하게는 상기 화학식 2로 이루어진 군에서 선택된 1종 이상의 반복 단위를 더 포함할 수 있다. 또한, 상기 코폴리카보네이트 수지는 상기 화학식 2 및 /또는 3의 각 반복 단위를 2종 이상으로 포함할 수도 있다. According to an embodiment of the invention, the copolycarbonate resin may include at least one repeating unit selected from the group consisting of Formula 3, more preferably at least one repeating unit selected from the group consisting of Formula (2) It may further include. In addition, the copolycarbonate resin may include two or more kinds of each repeating unit of Formula 2 and / or 3.
상기 화학식 2 및 3의 반복 단위를 함께 포함하거나， 각 반복 단위의 2종 이상을 함께 포함하는 경우 상온 층격 강도, 저온 층격 강도 및 유동성의 개선 정도가 현저히 증가함을 확인할 수 있었으며， 이는 각각의 반복 단위에 의하여 물성 개선 정도가 상호 보완적으로 작용한 결과에 기인한다. Including the repeating units of Formulas 2 and 3 together, or including two or more of each repeating unit, it was confirmed that the improvement in room temperature stratification strength, low temperature stratification strength, and fluidity was significantly increased, which is repeated for each. It is due to the result that the degree of improvement of physical properties by the unit works complementarily.
본 발명에서 의미하는 '2종 이상의 반복 단위'란， 각 화학식의 범주
내에서 구조가 상이한 반복 단위를 2종 이상 포함하거나 또는 구조는 동일하나 화학식 2 및 3의 구조 내 실리콘 옥사이드의 반복단위 수 (n1 또는 n2)가 상이한 2종 이상을 포함하는 것을 의미한다. As used herein, the term 'two or more repeating units' means each chemical formula. It means that two or more repeating units having different structures within the structure, or two or more repeating units having the same structure but different number (n1 or n2) of the silicon oxide in the structure of formulas (2) and (3).
예컨대， 본 발명에서 의미하는 '2종 이상의 반복 단위'란, i) 상기 화학식 2로 표시되는 하나의 반복 단위와 상기 화학식 2로 표시되는 다른 하나의 반복 단위, 또는 ii) 상기 화학식. 3으로 표시되는 하나의 반복 단위와 화학식 3으로 표시되는 다른 하나의 반복 단위를 포함하는 것을 의미한다. For example, "two or more kinds of repeating units" as used in the present invention means: i) one repeating unit represented by Formula 2 and the other repeating unit represented by Formula 2, or ii) the above formula. It means to include one repeating unit represented by 3 and the other repeating unit represented by the formula (3).
상기 2종의 반복 단위를 포함하는 각각의 경우에서， 2종의 반복 단위 간의 중량비는 1 :99 내지 99:1가 될 수 있다. 바람직하게는 3:97 내지 97:3， 5:95 내지 95:5, 10:90 내지 90:10, 또는 15:85 내지 85:15 일 수 있고, 보다 바람직하게는 20:80 내지 80:20 일 수 있다. In each case including the two repeating units, the weight ratio between the two repeating units may be 1:99 to 99: 1. Preferably 3:97 to 97: 3, 5:95 to 95: 5, 10:90 to 90:10, or 15:85 to 85:15, and more preferably 20:80 to 80:20 Can be.
상기 화학식 2 및 화학식 3으로 표시되는 반복 단위는 각각 하기 화학식 2-2로 표시되는 실록산 화합물 및 하기 화학식 3-2로 표시되는 실록산 화합물로부터 유래한 것일 수 있다: The repeating unit represented by Formula 2 and Formula 3 may be derived from a siloxane compound represented by Formula 2-2 and a siloxane compound represented by Formula 3-2, respectively:
상기 화학식 2-2에서， In Chemical Formula 2-2,
상기 X1, R5 및 n1은 각각 상기 화학식 2에서 정의된 바와 같고; X 1 , R 5 and n 1 are each as defined in Chemical Formula 2;
상기 화학식 3-2에서， In Chemical Formula 3-2,
상기 X2, Y1, R6 및 n2는 각각 상기 화학식 3에서 정의된 바와 같다. 상기 '실록산 화합물로부터 유래한다'의 의미는, 상기 각각의 실록산 화합물의 하이드록시기와 카보네이트 전구체가 반응하여 상기 각각의 화학식 2 및 3으로 표시되는 반복 단위를 형성하는 것을 의미한다. 또한， 상기 화학식 2
및 3의 반복 단위의 형성에 사용할 수 있는 카보네이트 전구체는, 앞서 설명한 화학식 1의 반복 단위의 형성에 사용할 수 있는 카보네이트 전구체에서 설명한 바와 같다. X 2 , Y 1 , R 6 and n 2 are the same as defined in Chemical Formula 3, respectively. The meaning of 'derived from the siloxane compound' means that the hydroxy group and the carbonate precursor of each of the siloxane compounds react to form a repeating unit represented by the formulas (2) and (3), respectively. In addition, Formula 2 And the carbonate precursor that can be used for formation of the repeating unit of 3 are the same as those described for the carbonate precursor that can be used for the formation of the repeating unit of the formula (1).
또한, 상기 화학식 2-2 및 3-2으로 표시되는 화합물은 각각 하기 반웅식 1 및 2의 방법으로 제조할 수 있다: In addition, the compounds represented by Chemical Formulas 2-2 and 3-2 may be prepared by the methods of the following reactions 1 and 2, respectively:
2-2 2-2
상기 반웅식 1에서， In the reaction form 1,
X1a는 C2-10 알케닐이고, X 1a is an alkenyl C 2 -10,
상기 X1, R5 및 n1은 각각 상기 화학식 2에서 정의된 바와 같고; X 1 , R 5 and n 1 are each as defined in Chemical Formula 2;
3-2 3-2
상기 반웅식 2에서, In the reaction form 2,
X2a는 C2-10 알케닐이고, X 2a is C 2-10 alkenyl,
상기 X2, Y1, R6 및 n2는 각각 상기 화학식 3에서 정의된 바와 같다.
상기 반웅식 1 및 2의 반응은, 금속 촉매 하에 수행하는 것이 바람직하다. 상기 금속 촉매로는 R 촉매를 사용하는 것이 바람직하며, R촉매로 애쉬바이 (Ashby)촉매, 칼스테드 (Karstedt)촉매, 라모레오 (Lamoreaux)촉매， 스파이어 (Speier)촉매， PtCI2(COD), PtCI2(벤조니트릴) 2, 및 H2RBr6로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 상기 금속 촉매는 상기 화학식 11 , 13 또는 15로 표시되는 화합물 100 중량부를 기준으로 0.001 중량부 이상, 0.005 중량부 아상， 또는 0.01 중량부 이상이고， 1 중량부 이하, 0.1 중량부 이하, 또는 0.05 중량부 이하로 사용할 수 있다. X 2 , Y 1 , R 6 and n 2 are the same as defined in Chemical Formula 3, respectively. It is preferable to perform reaction of said reaction formula 1 and 2 under a metal catalyst. As the metal catalyst, it is preferable to use an R catalyst, and as an R catalyst, an ashby catalyst, a Karlstedt catalyst, a Lamoreaux catalyst, a Speyer catalyst, a PtCI 2 (COD), One or more selected from the group consisting of PtCI 2 (benzonitrile) 2, and H 2 RBr 6 can be used. The metal catalyst is 0.001 part by weight, 0.005 part by weight subphase, or 0.01 part by weight or more based on 100 parts by weight of the compound represented by Formula 11, 13, or 15, 1 part by weight, 0.1 part by weight, or 0.05 part by weight. It can be used in parts or less.
또한 상기 반응 온도는 80 내지 10C C가 바람직하다. 또한， 상기 반응 시간은 1시간 내지 5시간이 바람직하다. In addition, the reaction temperature is preferably 80 to 10C C. In addition, the reaction time is preferably 1 hour to 5 hours.
또한， 상기 반응식 1 및 2에서， 상기 화학식 C2 또는 C4로 표시되는 화합물은 오르가노디실록산과 오르가노시클로실록산을 산 촉매 하에서 반웅시켜 제조할 수 있으며, 상기 반웅 물질의 함량을 조절하여 n1 및 n2를 조절할 수 있다. 상기 반웅 온도는 50 내지 70 °C가 바람직하다. 또한, 상기 반웅 시간은 1시간 내지 6시간이 바람직하다. In addition, in the reaction schemes 1 and 2, the compound represented by the formula (C2 or C4) can be prepared by reacting the organodisiloxane and organocyclosiloxane under an acid catalyst, by adjusting the content of the reaction material n1 and n2 I can regulate it. The reaction temperature is preferably 50 to 70 ° C. In addition, the reaction time is preferably 1 hour to 6 hours.
상기 오르가노디실록산으로, 테트라메틸디실록산, 테트라페닐디실록산, 핵사메틸디실록산 및 핵사페닐디실록산으로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 또한, 상기 오르가노시클로실록산은 일례로 오르가노시클로테트라실록산을 사용할 수 있으며， 이의 일례로 옥타메틸시클로테트라실록산 및 옥타페닐시클로테트라실록산 등을 들 수 있다. As the organodisiloxane, one or more selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, nuxamethyldisiloxane and nuxaphenyldisiloxane can be used. As the organocyclosiloxane, an organocyclotetrasiloxane can be used as an example, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like.
상기 오르가노디실록산은, 상기 오르가노시클로실톡산 100 중량부를 기준으로 0.1 중량부 이상, 또는 2 중량부 이상이고， 10 중량부 이하, 또는 8 중량부 이하로 사용할 수 있다. The organodisiloxane may be 0.1 part by weight or more, or 2 parts by weight or more, 10 parts by weight or less, or 8 parts by weight or less, based on 100 parts by weight of the organocyclosiloxy acid.
상기 산 촉매로는 H2SO4, HCI04, AICI3, SbCI5) SnCI4 및 산성 백토로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 또한， 상기 산 촉매는 오르가노시클로실록산 100 중량부를 기준으로 0.1 중량부 이상， 0.5 중량부 이상， 또는 1 중량부 이상이고, 10 중량부 이하, 5 중량부 이하， 또는 3 중량부 이하로 사용할 수 있다. As the acid catalyst, at least one selected from the group consisting of H 2 SO 4 , HCI0 4 , AICI3, SbCI 5) SnCI 4 and acidic clay may be used. The acid catalyst may be used in an amount of 0.1 parts by weight, 0.5 parts by weight, or 1 part by weight, 10 parts by weight, 5 parts by weight, or 3 parts by weight or less based on 100 parts by weight of organocyclosiloxane. have.
상기 화학식 2 및 3으로 표시되는 반복 단위의 함량을 조절하여， 코폴리카보네이트 수지의 물성을 개선할 수 있다. 여기서， 상기 반복 단위의
중량비는 코폴리카보네이트 중합에 사용되는 실록산 화합물， 예컨대 상기 화학식By adjusting the content of the repeating units represented by Formulas 2 and 3, it is possible to improve the physical properties of the copolycarbonate resin. Where the repeating unit The weight ratio is a siloxane compound used for copolycarbonate polymerization, such as
2-2 및 3-2로 표시되는 실록산 화합물의 중량비에 대응된다. It corresponds to the weight ratio of the siloxane compound represented by 2-2 and 3-2.
[코폴리카보네이트수지의 조성 및 제조방법] [Composition and Manufacturing Method of Copolycarbonate Resin]
상기 코폴리카보네이트 수지에서, 상기 방향족 폴리카보네이트계 게 1 반복 단위 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위의 몰비는 1 :0.0001 내지 1 :0.01 , 또는 1 :0.0005 내지 1 :0.008， 또는 1 :0.001 내지 1 :0.006일 수 있으며, 중량비는 1 :0.001 내지 1 :1 , 또는 1 :0.005 내지 1 :0.1 , 또는 1 :0.01 내지 1 :0.03일 수 있다. In the copolycarbonate resin, the molar ratio of the aromatic polycarbonate-based crab 1 repeating unit and the aromatic polycarbonate-based second repeating unit having at least one siloxane bond is 1: 0.0001 to 1: 0.01, or 1: 0.0005 to 1: 0.008 Or 1: 0.001 to 1: 0.006, and the weight ratio may be 1: 0.001 to 1: 1, or 1: 0.005 to 1: 0.1, or 1: 0.01 to 1: 0.03.
또한， 상기 코폴리카보네이트 수지는 90 내지 99.999 중량 0/。의 상기 거 11 반복 단위와 0.001 내지 10 중량 0/。의 상기 제 2 반복 단위를 포함할 수 있다. 즉, 상기 제 2 반복 단위의 함량이 지나치게 감소할 경우， 상기 제 2 반복단위에 의한 상온 층격 강도， 저온 층격 강도, 내화학성 및 유동성 물성의 개선이 충분히 구현되기 어려울 수 있다. 반면, 상기 제 2 반복 단위 함량이 지나치게 증가할 경우, 상기 코폴리카보네이트 수지의 분자량이 과도하게 증가하면서 유동성 및 성형 가공성이 감소할 수 있다. In addition, the copolycarbonate resin may include the above 11 repeating units of 90 to 99.999 weight 0 /. And the second repeating units of 0.001 to 10 weight 0 /. That is, when the content of the second repeating unit is excessively reduced, it may be difficult to sufficiently realize improvement of room temperature stratification strength, low temperature stratification strength, chemical resistance, and fluidity physical properties by the second repeating unit. On the other hand, when the content of the second repeating unit is excessively increased, the fluidity and molding processability may decrease while the molecular weight of the copolycarbonate resin is excessively increased.
그리고, 상기 코폴리카보네이트 수지는 1 ,000 내지 100,000 g/mol, 바람직하게는 5,000 내지 50,000 g/moᅵ의 중량 평균 분자량을 가질 수 있다. 상기 중량 평균 분자량 범위 내에서 상기 코폴리카보네이트 수지의 적절한 연성 (ductility)과 YI가 확보될 수 있다. 보다 바람직하게는, 상기 중량 평균 분자량 (g/mol)은 1 ,000 이상， 5,000 이상， 10,000 이상, 21 ,000 이상, 22,000 이상, 23,000 이상, 24,000 이상, 25,000 이상, 26,000 이상， 27,000 이상， 또는 28,000 이상이다. 또한, 상기 중량 평균 분자량은 100,000 이하, 50,000 이하， 34,000 이하, 33,000 아하， 또는 32,000 이하이다. In addition, the copolycarbonate resin may have a weight average molecular weight of 1,000 to 100,000 g / mol, preferably 5,000 to 50,000 g / mo. Within the weight average molecular weight range, appropriate ductility and YI of the copolycarbonate resin can be ensured. More preferably, the weight average molecular weight (g / mol) is at least 1,000, at least 5,000, at least 10,000, at least 21,000, at least 22,000, at least 23,000, at least 24,000, at least 25,000, at least 26,000, at least 27,000, or More than 28,000. In addition, the said weight average molecular weight is 100,000 or less, 50,000 or less, 34,000 or less, 33,000 aha, or 32,000 or less.
상기 코폴리카보네이트 수지의 함량은 조절하고자 하는 조성물의 물성에 따라 달라질 수 있다. 예를 들어, 상기 코폴리카보네이트 수지는 일 구현예의 수지 조성물의 전체 함량을 기준으로， 5 내지 50 중량0 /。, 혹은 10 내지 40 중량 0/。로 포함될 수 있다. The content of the copolycarbonate resin may vary depending on the physical properties of the composition to be adjusted. For example, the copolycarbonate resin may be included in 5 to 50 weight 0 /., Or 10 to 40 weight 0 /. Based on the total content of the resin composition of one embodiment.
즉， 상술한 내층격성, 내화학성 및 유동성 등의 물성 향상 효과를 발현시켜 층격 보강제를 낮은 함량으로 사용하더라도 적절한 물성을 나타내는 성형품 등을 제공할 수 있도록 상기 코폴리카보네이트 수지는 전체 수지
조성물에 대해 5 중량0 /。 이상으로 포함됨이 적절하다. 다만, 상기 코폴리카보네이트 수지가 과량으로 첨가될 경우 수지 조성물의 투명성이 저하될 수 있고 층격 강도 등의 향상 효과가 임계치에 다다르거나 오히려 저하될 수 있다. 이러한 면에서 상기 코폴리카보네이트 수지는 40 중량0 /0 이하로 포함될 수 있다. That is, the copolycarbonate resin is a total resin so that the above-described physical properties such as the above-described layer resistance, chemical resistance and fluidity can be expressed to provide a molded article exhibiting proper physical properties even when a layer reinforcing agent is used in a low content. It is included suitable for a composition to more than 5 parts by weight 0 /. However, when the copolycarbonate resin is added in an excessive amount, the transparency of the resin composition may be lowered, and an improvement effect such as layer strength may reach a threshold or rather decrease. In this respect, the copolycarbonate resin may contain less than 40 wt. 0/0.
한편, 상술한 코폴리카보네이트 수지는 상술한 방향족 디올 화합물, 카보네이트 전구체， 및 하나 이상의 실록산 화합물을 사용하여 제조될 수 있다. Meanwhile, the aforementioned copolycarbonate resin may be prepared using the aromatic diol compound, the carbonate precursor, and one or more siloxane compounds.
상기 화합물들의 중합시, 상기 하나 이상의 실록산 화합물은, 방향족 디올 화합물, 카보네이트 전구체 및 하나 이상의 실록산 화합물 총합 100 중량0 /0에 대해 0.1 중량0 /。 이상， 0.5 중량0 /。 이상, 1 중량0 /。 이상, 또는 1 .5 중량0 /。 이상이고， 20 중량0 /。 이하, 10 중량0 /。 이하， 7 중량0 /0 이하, 5 중량0 /。 이하， 4 중량0 /0 이하， 3 중량0 /。 이하， 또는 2 중량0 /。 이하를 사용할 수 있다. 또한， 상기 방향족 디을 화합물은， 방향족 디을 화합물， 카보네이트 전구체 및 하나 이상의 실록산 화합물 총합 100 중량。/。에 대해 40 중량0 /。 이상， 50 증량0 /。 이상, 또는 55 중량0 /0 이상이고, 80 중량0 /。 이하, 70 중량0 /。 이하, 또는 65 중량0 /。 이하로 사용할 수 있다. 또한, 상기 카보네이트 전구체는， 방향족 디올 화합물， 카보네이트 전구체 및 하나 이상의 실록산 화합물 총합 100 중량0 /0에 대해 10 중량0 /。 이상， 20 중량0 /。 이상, 또는 30 중량 %이고, 60 중량0 /。 이하, 50 중량0 /。 이하， 또는 40 중량 % 이하로 사용할 수 있다. During the polymerization of the compound, the one or more siloxane compounds, aromatic diol compound, a carbonate precursor and at least one siloxane compound total 100 parts by weight 0 / for 0 0.1 0 /. Above, 0.5 parts by weight 0 /. Above, 1 weight 0 / . or higher, or 0.5 and 1 wt. 0 /. above, 20 parts by weight 0 /. or less, 10 parts by weight 0 / hereinafter, 7 parts by weight 0/0 or less, 5 parts by weight 0 /. or less, and 4 wt. 0/0 or less, 3 A weight of 0 / ° or less, or 2 weights of 0 / ° or less may be used. In addition, the above described aromatic compound is dieul, dieul aromatic compound, a carbonate precursor and at least one siloxane compound 40 parts by weight based on total 100 parts by weight ./. 0 /. Above 50 increase 0 /., Or 55 weight 0/0 or more, 80 weights 0 /. Or less, 70 weights 0 /. Or less, or 65 weights 0 /. In addition, the carbonate precursor, the aromatic diol compound, a carbonate precursor and at least one siloxane compound total 100 parts by weight 0 / about 0 10 weight 0 /. Above, 20 parts by weight 0 /. Or more, or 30% by weight, 60 parts by weight 0 / Or less, 50 weight 0 or less, or 40 weight% or less.
또한， 상기 중합 방법으로는， 일례로 계면중합 방법을 사용할 수 있으며, 이 경우 상압과 낮은 온도에서 중합 반응이 가능하며 분자량 조절이 용이한 효과가 있다. 상기 계면중합은 산결합제 및 유기용매의 존재 하에 수행하는 것이 바람직하다. 또한, 상기 계면중합은 일례로 선중합 (pre-p ymerization) 후 커플링제를 투입한 다음, 다시 중합시키는 단계를 포함할 수 있고, 이 경우 고분자량의 코폴리카보네이트를 얻을 수 있다. In addition, as the polymerization method, for example, an interfacial polymerization method can be used. In this case, the polymerization reaction is possible at atmospheric pressure and low temperature, and the molecular weight can be easily controlled. The interfacial polymerization is preferably carried out in the presence of an acid binder and an organic solvent. In addition, the interfacial polymerization may include, for example, after pre-p ymerization, a coupling agent is added, and then polymerized again. In this case, a high molecular weight copolycarbonate may be obtained.
상기 계면중합에 사용되는 물질들은 폴리카보네이트의 중합에 사용될 수 있는 물질이면 특별히 제한되지 않으며， 그 사용량도 필요에 따라 조절할수 있다. The materials used for the interfacial polymerization are not particularly limited as long as they are materials that can be used for the polymerization of polycarbonate, and the amount of the materials used may be adjusted as necessary.
상기 산결합제로는 일례로 수산화나트륨, 수산화칼륨 등의 알칼리금속 수산화물 또는 피리딘 등의 아민 화합물을 사용할 수 있다. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine can be used.
상기 유기 용매로는 통상 폴리카보네이트의 중합에 사용되는 용매이면
특별히 제한되지 않으며, 일례로 메틸렌클로라이드, 클로로벤젠 등의 할로겐화 탄화수소를 사용할 수 있다. As said organic solvent, if it is a solvent normally used for superposition | polymerization of polycarbonate, There is no restriction | limiting in particular, For example, halogenated hydrocarbons, such as methylene chloride and chlorobenzene, can be used.
또한， 상기 계면중합은 반응 촉진을 위해 트리에틸아민， 테트라 -n- 부틸암모늄브로마이드， 테트라 -n-부틸포스포늄브로마이드 등의 3차 아민 화합물, 4차 암모늄 화합물, 4차 포스포늄 화합물 등과 같은 반응 촉진제를 추가로 사용할 수 있다. In addition, the interfacial polymerization is a reaction such as a tertiary amine compound such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compound, quaternary phosphonium compound, etc. to promote the reaction. Accelerators may additionally be used.
상기 계면중합의 반응 은도는 0 내지 40°C인 것이 바람직하며， 반웅 시간은 10분 내지 5시간이 바람직하다. 또한, 계면중합 반응 중, pH는 9이상 또는 1 1이상으로 유지하는 것이 바람직하다. The reaction silver of the interfacial polymerization is preferably 0 to 40 ° C, the reaction time is preferably 10 minutes to 5 hours. In addition, it is preferable to maintain pH at 9 or more or 11 or more during interfacial polymerization reaction.
또한， 상기 계면중합은 분자량 조절제를 더 포함하여 수행할 수 있다. 상기 분자량 조절제는 증합개시 전， 중합개시 중 또는 중합개시 후에 투입할 수 있다. In addition, the interfacial polymerization may be performed by further including a molecular weight regulator. The molecular weight modifier may be added before the start of the polymerization, during the start of the polymerization or after the start of the polymerization.
상기 분자량 조절제로 모노 -알킬페놀을 사용할 수 있으며, 상기 모노- 알킬페놀은 일례로 p-tert-부틸페놀, P-쿠밀페놀， 데실페놀， 도데실페놀, 테트라데실페놀， 핵사데실페놀, 옥타데실페놀， 에이코실페놀, 도코실페놀 및 트리아콘틸페놀로 이루어진 군으로부터 선택된 1종 이상이고, 바람직하게는 P- tert-부틸페놀이며， 이 경우 분자량 조절 효과가 크다. Mono-alkylphenol may be used as the molecular weight modifier, and the mono-alkylphenol is, for example, p-tert-butylphenol, P-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nucledecylphenol, octadecyl It is at least one selected from the group consisting of phenol, eicosylphenol, docosylphenol and triacontylphenol, preferably P-tert-butylphenol, in which case the molecular weight control effect is large.
상기 분자량 조절제는 일례로 방향족 디올 화합물 100 중량부를 기준으로 0.01 중량부 이상, 0,1 중량부 이상, 또는 1 중량부 이상이고， 10 중량부 이하， 6 중량부 이하， 또는 5 중량부 이하로 포함되고, 이 범위 내에서 원하는 분자량을 얻을 수 았다. The molecular weight modifier is, for example, 0.01 part by weight, 0,1 part by weight, or 1 part by weight or more, 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of the aromatic diol compound. The desired molecular weight was obtained within this range.
(3) 층격 보강제 (3) layered reinforcement
일 구현예의 수지 조성물은 상술한 베아스 수지 외에 충격 보강제를 더 포함한다. 이러한 층격 보강제로는 일 구현예의 수지 조성물 및 이의 성형품의 충격 강도를 적절히 보강하기 위해 고무변성 비닐계 그라프트 공중합체를 포함하는 것을 사용할 수 있다. 다만， 일 구현예의 수지 조성물은 상술한 코폴리카보네이트 수지의 사용으로 인해 낮은 함량의 충격 보강제를 포함하면서도 우수한 층격 강도 등을 나타낼 수 있으며, 이와 같은 낮은 함량의 충격 보강제의 적용으로 인해 내화학성을 향상시킬 수 있는 동시에, 고함량의
충격 보강제 사용시의 단점， 예를 들어, 박막 성형시의 가스 발생이나 외관 특성 저하 등을 해결할 수 있다. The resin composition of one embodiment further includes an impact modifier in addition to the above-described BEAS resin. Such a layer reinforcing agent may be used including a rubber-modified vinyl-based graft copolymer in order to appropriately reinforce the impact strength of the resin composition and molded article thereof of one embodiment. However, the resin composition of one embodiment may include a low content of the impact modifier due to the use of the above-described copolycarbonate resin, but may exhibit excellent layer strength, and the like, and thus improve chemical resistance due to the application of such a low content of the impact modifier. At the same time, high content Disadvantages in using an impact modifier, for example, gas generation and appearance characteristics during thin film molding, can be solved.
상기 고무변성 비닐계 그라프트 공중합체는 디엔계 고무, The rubber modified vinyl graft copolymer is a diene rubber,
(메트)아크릴레이트계 고무 및 실리콘계 고무로 이루어진 군에서 선택된 1종 이상의 고무를 포함하는 코어 구조에， 비닐계 불포화 단량체가 그라프트되어 쉘이 형성된 코어-쉘 구조의 그라프트 공중합체로 될 수 있으며, 이러한 충격 보강제가 일 구현예의 수지 조성물에 사용되어 낮은 함량 하에서도 층격 강도 등을 보다 적절히 보강할 수 있음이 확인되었다. In the core structure comprising at least one rubber selected from the group consisting of (meth) acrylate rubber and silicone rubber, vinyl unsaturated monomers may be grafted to form a graft copolymer having a core-shell structure in which a shell is formed. In addition, it was confirmed that such an impact modifier may be used in the resin composition of one embodiment to more appropriately reinforce the laminar strength and the like even under a low content.
이러한 그라프트 공중합체 형태의 충격 보강제에서, 상기 고무로는 탄소수 4 내지 6의 디엔계 고무， (메트)아크릴레이트계 고무 또는 실리콘계 고무 등을 1종 이상 사용할 수 있고， 상기 층격 보강제의 구조적 안정성 측면에서， 실리콘- 아크릴레이트계 고무 또는 (메트)아크릴레이트 -부타디엔계 고무 등을 보다 적절히 사용할 수 있다. In the graft copolymer-type impact modifiers, the rubber may be one or more of diene rubbers having 4 to 6 carbon atoms, (meth) acrylate rubbers or silicone rubbers, and the structural stability of the layer reinforcing agent. In the above, silicone-acrylate rubber or (meth) acrylate-butadiene rubber can be used more appropriately.
보다 구체적인 예에서， 상기 (메트)아크릴레이트계 고무로는 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, n-프로필 (메타)아크릴레이트, n- 부틸 (메타)아크릴레이트， 2-에틸핵실 (메타)아크릴레이트， 또는 핵실 (메타)아크릴레이트 등의 (메타)아크릴레이트 단량체로부터 형성된 고무를. 사용할 수 있고, 이러한 고무의 형성을 위해 에틸렌글리콜디 (메타)아크릴레이트, 프로필렌글리콜디 (메타)아크릴레이트, 1 ,3-부틸렌글리콜디 (메타)아크릴레이트， 1 ,4- 부틸렌글리콜디 (메타)아크릴레이트, 알릴 (메타)아크릴레이트， 또는 트리알릴시아누레이트 등의 경화제를 더 사용할 수 있다. In a more specific example, the (meth) acrylate-based rubber is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n- butyl (meth) acrylate, 2-ethyl Rubber formed from (meth) acrylate monomers such as nuclear chamber (meth) acrylate or nuclear chamber (meth) acrylate . Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di Curing agents, such as (meth) acrylate, allyl (meth) acrylate, or triallyl cyanurate, can be used further.
또한， 상기 실리콘계 고무로는 시클로실록산으로부터 제조되는 것을 사용할 수 있고, 이의 구체적인 예로는 핵사메틸시클로트리실록산, 옥타메틸시클로테트라실록산, 데카메틸시클로펜타실록산, 도데카메틸시클로핵사실록산, 트리메틸트리페닐시클로트리실록산, 테트라메틸테트라페닐시클로테트로실록산, 및 옥타페닐시클로테트라실록산으로 이루어진 군에서 선택된 1 종 이상으로부터 제조된 것을 사용할 수 있다. 이러한 실리콘계 고무의 형성을 위해, 트리메록시메틸실란, 트리에톡시페닐실란， 테트라메톡시실란, 또는 테트라에특시실란 등의 경화제를 더 사용할 수 있다. In addition, the silicone rubber may be prepared from cyclosiloxane, specific examples thereof include nuxamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclonuxasiloxane, trimethyltriphenylcyclo Those produced from one or more selected from the group consisting of trisiloxane, tetramethyltetraphenylcyclotetrosiloxane, and octaphenylcyclotetrasiloxane can be used. For the formation of such silicone rubber, a curing agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, or tetraethoxysilane can be further used.
또한， 상술한 충격 보강제에서， 상기 고무에 그라프트되는 비닐계 불포화
단량체로는 방향족 비닐계 단량체 또는 상기 방향족 비닐계 단량체와 공중합 가능한 단량체 등을 1종 이상 사용할 수 있다. In addition, in the above-described impact modifier, vinyl-based unsaturated grafted to the rubber As a monomer, 1 or more types of monomers etc. which can be copolymerized with an aromatic vinylic monomer or the said aromatic vinylic monomer can be used.
상기 방향족 비닐 단량체로는 스티렌， α -메틸스티렌, β -메틸스티렌, Ρ- 메틸스티렌, 파라 t-부틸스티렌, 또는 에틸스티렌 등이 포함될 수 있다. 이들은 단독 또는 2종 이상 흔합하여 사용될 수 있다. 그리고, 상기 방향족 비닐계 단량체와 공중합 가능한 단량체로는 시안화 비닐 화합물， 탄소수 1 내지 12의 알킬 (메타)아크릴레이트, (메타)아크릴레이트 또는 탄소수 1 내지 12의 알킬 또는 페닐 핵치환 말레이미드 등이 사용될 수 있다. 이들은 단독 또는 2종 이상 흔합하여 사용될 수 있다. The aromatic vinyl monomer may include styrene, α-methylstyrene, β-methylstyrene, Ρ-methylstyrene, para t-butylstyrene, ethyl styrene, or the like. These may be used alone or in combination of two or more. As the monomer copolymerizable with the aromatic vinyl monomer, a vinyl cyanide compound, alkyl (meth) acrylate having 1 to 12 carbon atoms, (meth) acrylate or alkyl having 1 to 12 carbon atoms or phenyl nucleosubstituted maleimide may be used. Can be. These may be used alone or in combination of two or more.
상술한 고무변성 비닐계 그라프트 공중합체 형태의 층격 보강제는 당업자에게 잘 알려진 방법에 따라 직접 합성하거나, 상업적으로 입수하여 사용할 수 있다. The layered reinforcing agent in the form of the rubber-modified vinyl-based graft copolymer described above may be directly synthesized according to methods well known to those skilled in the art, or may be commercially available.
그리고, 상술한 층격 보강제는 일 구현예의 수지 조성물의 전체 함량을 기준으로， 1 내지 10 중량0 /。, 혹은 1 .5 내지 5 중량0 /。, 혹은 2 내지 4 중량0 /。의 함량으로 포함될 수 있다. 이러한 층격 보강제의 함량이 지나치게 크게 될 경우에는, 추가적인 층격 강도의 향상 효과가 실질적으로 없고, 일 구현예의 수지 조성물이 우수한 내화학성을 나타내기 어려울 수 있으며, 박막 성형시의 가스 발생 또는 외관 품질 불량 등이 발생할 수 있다. 반대로， 층격 보강제의 함량이 지나치게 작아지면, 일 구현예의 수지 조성물 및 성형품의 층격 강도 등 내충격성이 층분치 못할 수 있다. In addition, the above-described layered reinforcing agent may be included in an amount of 1 to 10 weight 0 /., Or 1.5 to 5 weight 0 /., Or 2 to 4 weight 0 /. Based on the total content of the resin composition of one embodiment. Can be. When the content of such a layer reinforcing agent is excessively large, there is substantially no additional effect of improving the layer strength, and the resin composition of one embodiment may hardly exhibit excellent chemical resistance, and gas generation or poor appearance quality during thin film molding, etc. This can happen. On the contrary, when the content of the layer reinforcing agent is too small, impact resistance such as the layer strength of the resin composition and the molded article of one embodiment may not be sufficient.
(4)유동 개질제 (4) flow modifiers
상기 유동 개질제는 일 구현예의 수지 조성물의 유동성을 향상시킬 수 있다. 즉， 상술한 코폴리카보네이트 수지의 부가로 인해 향상된 유동성을 더욱 향상시킬 수 있으므로， 일 구현예의 수지 조성물이 고유동성 및 우수한 박막 성형성을 나타내게 할 수 있다. The flow modifier may improve the flowability of the resin composition of one embodiment. That is, since the improved fluidity can be further improved due to the addition of the above-described copolycarbonate resin, the resin composition of one embodiment can exhibit high flowability and excellent thin film formability.
이러한 유동 개질제로는 열가소성 폴리에스테르계 중합체 또는 인산 에스테르계 화합물을 사용할 수 있는데, 상기 열가소성 폴리에스테르계 중합체의 예로는, 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트 또는 에틸렌글리콜로 개질된 폴리시클로핵산테레프탈레이트 등을 들 수 있으며, 이들
중에 선택된 2종 이상을 함께 사용할 수도 있다. 또, 상기 인산 에스테르계 화합물의 예로는， 트리페닐포스페이트， 비스페놀 A 디페닐포스페이트 또는 레소시놀 디페닐포스페이트 등을 들 수 있으며, 이들 중에 선택된 2종 이상을 함께 사용할 수도 있다. 이외에도, 다양한 열가소성 폴리에스테르계 중합체 도는 인산 에스테르계 화합물을 상기 유동 개질제로 사용할 수 있다. The flow modifier may be a thermoplastic polyester-based polymer or a phosphate ester-based compound. Examples of the thermoplastic polyester-based polymer may include polyethylene terephthalate, polybutylene terephthalate or polycyclonucleic acid terephthalate modified with ethylene glycol. And the like, these You may use together 2 or more types selected from these. Moreover, as an example of the said phosphate ester type compound, triphenyl phosphate, bisphenol A diphenyl phosphate, resorcinol diphenyl phosphate, etc. are mentioned, Two or more types selected from these can also be used together. In addition, various thermoplastic polyester-based polymers or phosphate ester-based compounds may be used as the flow modifier.
상기 유동 개질제는 일 구현예의 수지 조성물의 전체 함량을 기준으로， 0.5 내지 15 중량0 /。, 혹은 1 내지 10 중량0 /。, 혹은 1 내지 7 중량0 /。의 함량으로 포함될 수 있다. 유동 개질제의 함량이 지나치게 낮아지면, 일 구현예의 수지 조성물이 높은 유동성 및 우수한 박막 성형성 등을 갖기 어렵고, 반대로 유동 개질제의 함량이 지나치게 높아지면， 폴리카보네이트 수지의 고화 속도가 저하되어 성형시 문제가 발생할 수 있고, 기계적 특성이 저하될 수 있다. The flow modifier may be included in an amount of 0.5 to 15 weight 0 /., Or 1 to 10 weight 0 /. Or 1 to 7 weight 0 /. Based on the total content of the resin composition of one embodiment. When the content of the flow modifier is too low, it is difficult for the resin composition of one embodiment to have high fluidity and excellent thin film formability, and the like, on the contrary, when the content of the flow modifier is too high, the solidification rate of the polycarbonate resin is lowered, thereby causing problems in molding. May occur, and mechanical properties may be degraded.
(5) 기타 성분 (5) other ingredients
한편, 일 구현예에 따른 수지 . 조성물에는 필요에 따라 polytetrafluoroethylene (PTFE) 등의 불소계 중합체와 같은 적하 억제제 (drip inhibitor); 인계 난연제 등의 난연제; 계면활성제; 핵제; 커플링게; 층전제; 가소제; 활제; 항균제; 이형제; 열 안정게; 산화 방지제; uv 안정제; 상용화제; 착색거 1; 정전기 방지제; 안료; 염료; 방염제 등의 첨가제가 추가로 포함될 수 있다. Meanwhile, the resin according to the embodiment . The composition may include drip inhibitors such as fluorine-based polymers such as polytetrafluoroethylene (PTFE), if necessary; Flame retardants such as phosphorus flame retardants; Surfactants; Nucleating agent; Coupling crab; Layering agent; Plasticizers; Lubricant; Antibacterial agents; Release agents; Heat stabilizer; Antioxidants; uv stabilizer; Compatibilizers; Staining 1; Antistatic agents; Pigments; dyes; Additives such as a flame retardant may further be included.
이러한 첨가제의 함량은 초성물에 부여하고자 하는 물성에 따라 달라질 수 있다. 예를 들어， 상기 첨가제는 상기 폴리카보네이트 수지 100 중량부에 대하여 각각 0.01 내지 10 중량부로 포함될 수 있다. The content of such additives may vary depending on the physical properties to be applied to the supernatant. For example, the additive may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin.
다만， 상기 폴리카보네이트계 수지 조성물이 갖는 내열성， 층격 강도， 내화학성 등이 상기 첨가제의 적용에 의해 저하되는 것을 방지하기 위하여， 상기 첨가제의 총 함량은 상기 폴리카보네이트 수지 100 중량부에 대하여 20 중량부 이하, 또는 15 중량부 이하， 또는 10 중량부 이하인 것이 적절하다. However, in order to prevent the heat resistance, layer strength, chemical resistance, etc. of the polycarbonate resin composition from being lowered by the application of the additive, the total content of the additive is 20 parts by weight based on 100 parts by weight of the polycarbonate resin. Or less, or 15 parts by weight or less, or 10 parts by weight or less.
II. 폴리카보네이트계 수지 성형품 II. Polycarbonate Resin Molded Products
본 발명의 다른 구현 예에 따르면， 상술한 폴리카보네이트계 수지 조성물을 포함하는 성형품이 제공된다. According to another embodiment of the present invention, a molded article including the polycarbonate resin composition described above is provided.
상기 성형품은 상술한 폴리카보네이트계 수지 조성물을 원료로 사용하여
압줄, 사출, 또는 캐스팅 등의 방법으로 성형하여 얻어지는 물품이다. 상기 성형 방법 및 그 조건은 성형품의 종류에 따라 적절히 선택 및 조절될 수 있다. The molded article uses the above-described polycarbonate resin composition as a raw material It is the article obtained by shape | molding by a method such as a pressure line, injection, or casting. The molding method and its conditions can be appropriately selected and adjusted according to the type of molded article.
비 제한적인 예로, 상기 성형품은 상기 폴리카보네이트계 수지 조성물을 흔합 및 압출 성형하여 펠릿으로 제조한 후， 상기 펠릿을 건조하여 사출하는 방법으로 얻어질 수 있다. ' As a non-limiting example, the molded article may be obtained by mixing and extruding the polycarbonate-based resin composition to produce pellets, and then drying and injecting the pellets. '
특히 , 상기 성형품은 상기 폴리카보네이트계 수지 조성물로부터 형성됨에 따라 높은 유동성 및 우수한 박막 성형성과， 우수한 내화학성 및 내층격성을 나타낼 수 있고， 스마트폰 등 휴대용 전자 기기용 소재로서 적절히 사용될 수 있다. In particular, the molded article may exhibit high fluidity and excellent thin film formability, excellent chemical resistance and layer resistance as formed from the polycarbonate resin composition, and may be suitably used as a material for a portable electronic device such as a smartphone.
【발명의 효과] 【Effects of the Invention]
본 발명에 따른 폴리카보네이트계 수지 조성물과 이의 성형품은 고유동성 및 우수한 박막 성형성과, 우수한 내화학성 및 내충격성을 나타낼 수 있고, 스마트폰 등 휴대용 전자 기기용 소재로서 적절히 사용될 수 있다. The polycarbonate-based resin composition and the molded article thereof according to the present invention may exhibit high fluidity and excellent thin film formability, excellent chemical resistance and impact resistance, and may be suitably used as a material for a portable electronic device such as a smartphone.
【발명을 실시하기 위한 구체적인 내용】 [Specific contents to carry out invention]
이하, 발명의 이해를 돕기 위하여 바람직한 실시예들이 제시된다. 그러나 하기의 실시예들은 발명을 예시하기 위한 것일 뿐, 발명을 이들만으로 한정하는 것은 아니다. 제조예 1 Hereinafter, preferred embodiments are presented to help understand the invention. However, the following examples are only to illustrate the invention, not limited to the invention only. Preparation Example 1
： 옥타메틸시클로테트라실록산 47.6 g(160 mmol), 테트라메틸디실록산 2.4 g(17.8 mm )을 흔합한 후， 상기 흔합물을 옥타메틸시클로테트라실록산 100 중량부 대비 산성백토 (DC-A3) 1 중량부와 함께 3L 플라스크에 넣고 60 °C로 4시간 동안 반응시켰다. 반웅 종료 후 이를 에틸아세테이트로 희석하고 샐라이트 (celite)를 사용하여 빠르게 필터링하였다. 이렇게 수득된 미변성 폴리오르가노실록산의 반복단위 (n1 )는 1H NMR로 확인한 결과 34이었다.
상기 수득된 말단 미변성 폴리오르가노실록산에 2-알릴페놀 4.81 g(35.9 mm )과 칼스테드 백금 촉매 (Karstedt's platinum catalyst) 0.01 g(50 ppm)을 투입하여 90 °C에서 3시간 동안 반응시켰다. 반웅 종료 후, 미반응 실록산은 120 °C , 1 torr의 조건으로 이베이퍼레이션하여 제거하였다. 이렇게 수득한 말단 변성 폴리오르가노실록산을 AP-PDMS(n1 =34)로 명명하였다. AP-PDMS는 연황색 오일이며, Varian 500MHz을 이용하여 1H NMR을 통해 반복단위 (n1 )는 34임을 확인하였으며, 더 이상의 정제는 필요하지 않았다. 제조예 2 : After mixing 47.6 g (160 mmol) of octamethylcyclotetrasiloxane and 2.4 g (17.8 mm) of tetramethyldisiloxane, the mixture was mixed with 100 parts by weight of octamethylcyclotetrasiloxane (1 part by weight of acidic clay (DC-A3)). It was put in a 3L flask with a portion and reacted at 60 ° C for 4 hours. After completion of reaction, it was diluted with ethyl acetate and filtered quickly using celite. The repeating unit (n1) of the unmodified polyorganosiloxane thus obtained was found to be 34 by 1 H NMR. 4.81 g (35.9 mm) of 2-allylphenol and 0.01 g (50 ppm) of Karlstedt's platinum catalyst were added to the terminal unmodified polyorganosiloxane, and reacted at 90 ° C. for 3 hours. After the reaction was completed, unreacted siloxane was removed by evaporation at 120 ° C. and 1 torr. The terminal modified polyorganosiloxane thus obtained was named AP-PDMS (n1 = 34). AP-PDMS is a light yellow oil, and the repeat unit (n1) was found to be 34 by 1 H NMR using a Varian 500 MHz, and no further purification was necessary. Preparation Example 2
：옥타메틸시클로테트라실록산 47.60 g(160 mmol), 테트라메틸디실록산 1 .5 g(1 1 mm )을 흔합한 후， 상기 흔합물을 옥타메틸시클로테트라실록산 100 중량부 대비 산성백토 (DC-A3) 1 중량부와 함께 3L 플라스크에 넣고 60 °C로 4시간 동안 반웅시켰다. 반응 종료 후， 에틸아세테이트로 희석하고 셀라이트를 사용하여 빠르게 필터링하였다. 이렇게 수득된 말단 미변성 폴리오르가노실록산의 반복단위 (n2)는 1H NMR로 확인한 결과 58이었다. : After mixing 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 1.5 g (1 1 mm) of tetramethyldisiloxane, the mixture was mixed with 100 parts by weight of octamethylcyclotetrasiloxane (DC-A3). ) Into a 3L flask with 1 part by weight and reacted at 60 ° C for 4 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and filtered quickly using celite. The repeating unit (n2) of the terminal unmodified polyorganosiloxane thus obtained was found to be 58 by 1 H NMR.
상기 수득된 말단 미변성 폴리오르가노실록산에 3-메틸부트 -3-에닐 4- 하이드록시벤조에이트 (3-methylbut-3-enyl 4-hyd roxybenzoate) 6.13 g(29.7 mm )과 칼스테드 백금 촉매 (Karstedt's platinum catalyst) 0.01 g(50 ppm)을 투입하여 90 °C에서 3시간 동안 반웅시켰다. 반응 종료 후， 미반웅 실록산은 120 °C , 1 torr의 조건으로 이베이퍼레이션하여 제거하였다. 이렇게 수득한 말단 변성 폴리오르가노실록산을 MBHB-PDMS(n2=58)로 명명하였다. MBHB-PDMS는 연황색 오일이며， Varian 500MHz을 이용하여 1H NMR을 통해 반복단위 (n2)는 58임을 확인하였으며， 더 이상의 정제는 필요하지 않았다.
제조예 3 6.13 g (29.7 mm) of 3-methylbut-3-enyl 4-hyd roxybenzoate and a Carlsted platinum catalyst were prepared in the terminal unmodified polyorganosiloxane obtained above. 0.01 g (50 ppm) of Karstedt's platinum catalyst was added thereto and reacted at 90 ° C. for 3 hours. After completion of the reaction, Mibanung siloxane was removed by evaporation at 120 ° C, 1 torr. The terminal modified polyorganosiloxane thus obtained was named MBHB-PDMS (n2 = 58). MBHB-PDMS is a light yellow oil, it was confirmed that the repeating unit (n2) is 58 by 1 H NMR using a Varian 500MHz, no further purification was required. Preparation Example 3
코폴리카보네이트 수지의 제조 Preparation of Copolycarbonate Resin
： 중합 반응기에 물 1784 g, NaOH 385 g 및 BPA(bisphenol A) 232 g을 넣고， N2 분위기 하에 흔합하여 녹였다. 여기에 PTBP(para-tert butylphenol) 4.3 g과 제조예 1에 따른 AP-PDMS(n1 =34) 4.72 g 및 제조예 2에 따른 MBHB- PDMS(n2=58) 0.52 g의 흔합액을 MC(methylene chloride)로 용해하여 넣어주었다. 그 다음 TPG(triphosgene) 128 g을 MC에 녹여 pH를 11 이상으로 유지시켜 주면서 1시간 동안 투입하여 반응시킨 다음 10분 뒤에 TEA(triethylamine) 46 g을 넣어 커플링 (coupling) 반웅을 시켰다. 총 반웅시간 1시간 20분이 지난 다음 PH를 4로 낮추어 TEA를 제거하였고， 증류수로 3회 세척하여 생성된 중합체의 pH를 6~7 중성으로 맞추었다. 이렇게 얻은 중합체를 메탄을과 핵산 흔합용액에서 재침전시켜 수득한 다음， 이를 12C C에서 건조하여 최종적으로 코폴리카보네이트 수지 (Mw=3으 500)를 얻었다. 실시예 및 비교예 : 1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to a polymerization reactor, and the mixture was dissolved under N 2 atmosphere. A mixed solution of 4.3 g of PTBP (para-tert butylphenol), 4.72 g of AP-PDMS according to Preparation Example 1 (n1 = 34) and 0.52 g of MBHB-PDMS (n2 = 58) according to Preparation Example 2 was added to MC (methylene). chloride) and added. Then, 128 g of TPG (triphosgene) was dissolved in MC for 1 hour while maintaining the pH at 11 or more, followed by reaction for 10 hours, and then 46 g of TEA (triethylamine) was added for coupling reaction. Was banung total time of 1 hour 20 minutes later, and then lowering the P 4 H a remove TEA, it was adjusted the pH of the polymer produced was washed three times with distilled water to the 6-7 neutral. The polymer thus obtained was obtained by reprecipitation of methane in a mixture of nucleic acid and nucleic acid, which was then dried at 12C C to finally obtain a copolycarbonate resin (Mw = 3 to 500). Examples and Comparative Examples
하기 표 1의 조성으로 각 성분을 첨가한 후 용융 및 흔련 압출하여 펠렛을 제조하였다. 제조된 펠렛을 70°C에서 6 시간 건조한 후， 이를 사출하여 물성 평가를 위한 시편을 제조하였다. 각 실시예 및 비교예에서 사용된 성분들은 다음과 같다. To the pellets were prepared by the addition of each component in the composition of Table 1 and then melted and shaken. After drying the prepared pellets for 6 hours at 70 ° C, it was injected to prepare a specimen for evaluation of physical properties. The components used in each Example and Comparative Example are as follows.
(A) 비스페놀 A폴리카보네이트 수지 (PC) (A) Bisphenol A polycarbonate resin (PC)
폴리카보네이트 수지는 비스페놀 A의 중합체로서， 이의 용융지수 (Ml)는 ASTM D1238에 따라, 300 t의 온도 및 1.2kg의 하중 하에서 10분간 측정되는 무게 (g)로서 측정하였다. 이러한 측정 결과， 용융지수가 I0g/10분으로 되는 방향족 폴리카보네이트 수지 (A-1 ; 엘지화학사제 LUPOY 1300-10) 및 30g/10분으로 되는 방향족 폴리카보네이트 수지 (A-2; 엘지화학사제 LUPOY 1300- 10)를 각각 사용하였다. The polycarbonate resin was a polymer of bisphenol A, the melt index (Ml) of which was measured as weight (g) measured for 10 minutes under a temperature of 300 t and a load of 1.2 kg according to ASTM D1238. As a result of these measurements, an aromatic polycarbonate resin (A-1; LUPOY 1300-10 manufactured by LG Chemical Co., Ltd.) having a melt index of 10 g / 10 minutes and an aromatic polycarbonate resin (A-2; LUPOY manufactured by LG Chemical Co., Ltd.) having 30 g / 10 minutes 1300-10) were used respectively.
(B) 상기 제조예 3에 따른 코폴리카보네이트 수지 (PC 8000-05, LG (B) copolycarbonate resin according to Preparation Example 3 (PC 8000-05, LG
Chem.) Chem.)
(C) 유동 개질제
(C-1 ) 열가소성 폴리에스테르계 중합체: SK케미칼 사의 Sky PET BB8055의 PET 중합체를 사용하였다. (C) flow modifier (C-1) Thermoplastic polyester-based polymer: PET polymer of Sky PET BB8055 manufactured by SK Chemicals was used.
(C-2) 인산에스테르계 화합물: 일본 다이하찌의 PX-200을 사용하였다. (D) 충격 보강제 (C-2) Phosphate ester compound: PX-200 from Daihachi, Japan was used. (D) impact modifier
(D-1 ) MMA-BD계 고무가 포함되어 코어-쉘 구조를 이루고 있는 엘지화학의 EM505를 사용하였다. (D-1) LG Chem's EM505 containing a MMA-BD-based rubber to form a core-shell structure was used.
(D-2) silicone-acrylate 고무가 포함되어 코어-쉘 구조를 이루고 있는 일본 MRC사의 Metablen S-2100을 사용하였다. (D-2) Metablen S-2100 manufactured by MRC of Japan, which is a core-shell structure including silicone-acrylate rubber, was used.
[표 1] TABLE 1
(확인 사항: 수정 사항을 확인한 결과， 비교예 2는 현재의 본건 독립항 1에 포괄될 우려가 있어 삭제하였습니다. 비교예 2는 추후 심사 과정에서 필요할 경우， 추가실험 결과로 활용하도록하겠습니다.) (Confirmation: As a result of confirming the correction, Comparative Example 2 may be included in the current independent claim 1, and deleted. Comparative Example 2 will be used as a result of additional experiment if necessary in the later screening process.)
시험예 Test Example
상기 실시예 및 비교예의 조성물로부터 형성된 각각의 시편에 대하여 아래와 같은 방법으로 물성을 측정하였고, 그 결과를 하기 표 2에 나타내었다. Physical properties of the specimens formed from the compositions of Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 2 below.
(1 ) 용융 지수 (Ml): ASTM D1238에 따라, 300 °C의 온도 및 1.2kg의 하중 하에서 10분간 측정되는 무게 (g)로서 산출하였다. (1) Melt Index (Ml): Calculated as weight (g) measured for 10 minutes under a temperature of 300 ° C. and a load of 1.2 kg according to ASTM D1238.
(2) 충격 강도 (IZOD): ASTM D256에 의거하여 23 °C 하에서 1/4 inch
(Notched lzod, J/m)로 측정하였다. (2) Impact Strength (IZOD): 1/4 inch under 23 ° C according to ASTM D256 (Notched lzod, J / m).
(3) 내화학성: 상기 조성물을 사용해 벤트 부착 Φ 40ιηιη 이축압출기를 사용하여 펠릿화한 후, ENGEL 80톤 사출성형기를 사용하여 실린더 은도 300 °C , 금형 온도 80 °C로 사출성형하여 ASTM D638 평가용 인장 시편을 사출 성형 및 제조하였다. 이러한 시편을 ESCR (Environmental Stress-Cracking Resistance) 지그에 고정시킨 후, 메탄올 및 아세톤을 4 ： 6의 중량비로 흔합한 흔합용매를 적하하여 크택 발생 시간을 관찰하였다. 하기 표 2에는 크랙 발생이 관찰되기 시작하는 시간 (초)으로 내화학성 평가 결과를 정리하였다. (3) Chemical resistance: After pelletizing using a vented Φ 40ιηιη twin-screw extruder using the composition, the injection molding using a ENGEL 80 ton injection molding machine at a cylinder silver degree of 300 ° C, mold temperature 80 ° C evaluated ASTM D638 Tensile specimens were injection molded and prepared. After fixing these specimens to an ESCR (Environmental Stress-Cracking Resistance) jig, a mixed solvent mixed with methanol and acetone in a weight ratio of 4: 6 was added dropwise to observe the stacking time. Table 2 below summarizes the results of chemical resistance evaluation by the time (seconds) at which the occurrence of cracks is observed.
[표 2]TABLE 2
Claims
【청구범위】 【Claims】
【청구항 11 【Claim 11
방향족 폴리카보네이트계 게 1 반복 단위로 이루어진 폴리카보네이트 수지， A polycarbonate resin consisting of one repeating unit based on aromatic polycarbonate,
방향족 폴리카보네이트계 제 1 반복 단위와， 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함한 코폴리카보네이트 수지, 고무변성 비닐계 그라프트 공중합체를 포함하는 층격 보강제, 및 열가소성 폴리에스테르계 중합체 또는 인산 에스테르계 화합물을 포함하는 유동 개질제를 포함하고; A copolycarbonate resin containing an aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, a layer reinforcing agent containing a rubber-modified vinyl-based graft copolymer, and a thermoplastic polyester-based Contains a rheology modifier including a polymer or phosphoric acid ester-based compound;
상기 제 1 반복 단위는 각각 독립적으로 하기 화학식 1로 표시되는 반복 단위를 포함하고; The first repeating units each independently include repeating units represented by the following formula (1);
상기 제 2 반복 단위는 하기 화학식 3으로 이루어진 군에서 선택된 1종 이상의 반복 단위를 포함하는 폴리카보네이트계 수지 조성물: A polycarbonate-based resin composition wherein the second repeating unit includes one or more repeating units selected from the group consisting of the following Chemical Formula 3:
상기 화학식 1에서, In Formula 1,
R1 내지 R4는 각각 독립적으로 수소, C1-10 알킬, C1-10 알콕시， 또는 할로겐이고， R 1 to R 4 are each independently hydrogen, C 1-10 alkyl, C 1-10 alkoxy, or halogen,
Z는 비치환되거나 또는 페닐로 치환된 Cwo 알킬렌, 비치환되거나 또는 Ci-10 알킬로 치환된 c3-15 사이클로알킬렌,ᄋ, S, SO, S02, 또는 CO이고; Z is Cwo alkylene unsubstituted or substituted with phenyl, c 3-15 cycloalkylene unsubstituted or substituted with Ci -10 alkyl, ᄋ, S, SO, SO 2 , or CO;
Y1은 각각 독립적으로 수소, 알킬, 할로겐， 히드특시, c1-6 알콕시 또는 c6-20 아릴이고, Y 1 is each independently hydrogen, alkyl, halogen, hydroxy, c 1-6 alkoxy, or c 6-20 aryl,
R6는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐, 옥시라닐로 치환된 C1-10 알콕시, 또는 C6-20 아릴로 치환된 C1-15 알킬; 할로겐; C1-10 알콕시; 알릴; C1-10 할로알킬; 또는 C6ᅳ 20 아릴이고, R 6 is each independently hydrogen; C 1-15 alkyl unsubstituted or substituted with oxiranyl, C 1-10 alkoxy substituted with oxiranyl, or C 6-20 aryl; halogen; C 1-10 alkoxy; allyl; C 1-10 haloalkyl; or C 6 ᅳ 20 aryl,
n2는 10 내지 200의 정수이다. n2 is an integer from 10 to 200.
【청구항 2】 【Claim 2】
제 1 항에 있어서, 상기 폴리카보네이트 수지는 300°C의 온도 및 The method of claim 1, wherein the polycarbonate resin is heated to a temperature of 300 ° C and
1.2kg의 하증 하에서 5 g/10분 내지 50 g/10분의 용융지수 (Ml)를 갖는 폴리카보네이트계 수지 조성물. A polycarbonate-based resin composition having a melt index (Ml) of 5 g/10 min to 50 g/10 min under loading of 1.2 kg.
【청구항 3】 【Claim 3】
제 1 항에 있어서, 상기 제 2 반복 단위는 하기 화학식 2로 이루어진 군에서 선택된 1종 이상의 반복 단위를 더 포함하는 폴리카보네이트계 수지 조성물: The polycarbonate-based resin composition of claim 1, wherein the second repeating unit further includes one or more repeating units selected from the group consisting of the following formula (2):
상기 화학식 2에서, In Formula 2,
X1은 각각 독립적으로 C1-10 알킬렌이고, X 1 is each independently C 1-10 alkylene,
R5는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐， 옥시라닐로 치환된 c1-10 알콕시， 또는 c6-20 아릴로 치환된 c1-15 알킬; 할로겐; c1-10 알콕시; 알릴; c1-10 할로알킬; 또는 c6ᅳ 20 아릴이고， R 5 is each independently hydrogen; unsubstituted or oxiranyl, c 1-10 alkoxy substituted with oxiranyl, or c 1-15 alkyl substituted with c 6-20 aryl; halogen; c 1-10 alkoxy; allyl; c 1-10 haloalkyl; Or c 6 ᅳ 20 aryl,
n1은 10 내지 200의 정수이다. n1 is an integer from 10 to 200.
【청구항 4】
제 1 항에 있어서， 상기 화학식 1의 반복 단위는 하기 화학식 표시되는 폴리카보네이트계 수지 조성물: 【Claim 4】 The polycarbonate-based resin composition according to claim 1, wherein the repeating unit of Formula 1 is represented by the following formula:
【청구항 5】 【Claim 5】
제 3 항에 있어서, 상기 화학식 2의 반복 단위는 하기 화학식 표시되는 폴리카보네이트계 수지 조성물: The polycarbonate-based resin composition according to claim 3, wherein the repeating unit of Formula 2 is represented by the following formula:
상기 화학식 2-1에서， In Formula 2-1,
상기 R5 및 n1은 각각 상기 화학식 2에서 정의된 바와 같다. R 5 and n1 are each as defined in Formula 2 above.
【청구항 6】 【Claim 6】
제 1 항에 있어서， 상기 화학식 3의 반복 단위는 하기 화학식 표시되는 폴리카보네이트계 수지 조성물: The polycarbonate-based resin composition according to claim 1, wherein the repeating unit of Formula 3 is represented by the following formula:
상기 R6 및 n2는 각각 상기 화학식 3에서 정의된 바와 같다. R 6 and n2 are each as defined in Formula 3 above.
【청구항 7】 【Claim 7】
제 1 항에 있어서, 상기 코폴리카보네이트 수지는 90 내지 99.999 중량 %의 상기 제 1 반복 단위와 0.001 내지 10 중량0 /。의 상기 제 2 반복 단위를 포함하는 폴리카보네이트계 수자 조성물. The polycarbonate-based material composition according to claim 1, wherein the copolycarbonate resin includes 90 to 99.999% by weight of the first repeating unit and 0.001 to 10% by weight of the second repeating unit.
【청구항 8】 【Claim 8】
제 1 항에 있어서， 상기 폴리카보네이트 수지 및 상기 코폴리카보네이트 수지는 각각 1 ,000 내지 100,000 g/m이의 중량 평균 분자량을 갖는 폴리카보네이트계 수지 조성물. The polycarbonate-based resin composition according to claim 1, wherein the polycarbonate resin and the copolycarbonate resin each have a weight average molecular weight of 1,000 to 100,000 g/m.
【청구항 9】 【Claim 9】
제 1 항에 있어서， 상기 고무변성 비닐계 그라프트 공중합체는 디엔계 고무, 아크릴레이트계 고무 및 실리콘계 고무로 이루어진 군에서 선택된 1종 이상의 고무를 포함하는 코어 구조에, The method of claim 1, wherein the rubber-modified vinyl-based graft copolymer has a core structure comprising at least one rubber selected from the group consisting of diene-based rubber, acrylate-based rubber, and silicone-based rubber,
비닐계 불포화 단량체가 그라프트되어 쉘이 형성된 코어-쉘 구조의 그라프트 공중합체인 폴리카보네이트계 수지 조성물. A polycarbonate-based resin composition that is a graft copolymer of a core-shell structure in which a vinyl-based unsaturated monomer is grafted to form a shell.
【청구항 10] [Claim 10]
제 1 항에 있어서， 상기 열가소성 폴리에스테르계 중합체는 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트 및 에틸렌글리콜로 개질된 폴리시클로핵산테레프탈레이트로 이루어진 군에서 선택된 1종 이상의 폴리에스테르계 중합체를 포함하는 폴리카보네이트계 수지 조성물. The method of claim 1, wherein the thermoplastic polyester polymer is a polycarbonate comprising at least one polyester polymer selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, and polycyclohexane terephthalate modified with ethylene glycol. Systemic resin composition.
【청구항 1 1 1 【Claim 1 1 1
제 1 항에 있어서, 인산 에스테르계 화합물은 트리페닐포스페이트, 비스페놀 A 디페닐포스페이트 및 레소시놀 디페닐포스페이트로 이루어진 군에서
선택된 1종 이상의 화합물을 포함하는 폴리카보네이트계 수지 조성물. The method of claim 1, wherein the phosphoric acid ester compound is selected from the group consisting of triphenyl phosphate, bisphenol A diphenyl phosphate, and resorcinol diphenyl phosphate. A polycarbonate-based resin composition comprising one or more selected compounds.
【청구항 12】 【Claim 12】
제 1 항에 있어서， According to claim 1,
40 내지 90 중량 0/。와폴리카보네이트 수지 40 to 90 weight 0 /. and polycarbonate resin
5 내지 50 중량 0/。의 코폴리카보네이트 수지, 5 to 50 weight 0 /。 of copolycarbonate resin,
1 내지 10 중량 0/。의 층격 보강제, 및 1 to 10 weight 0 /。 of impact reinforcing agent, and
0.5 내지 15 중량0 /。의 유동 개질제를 포함하는 폴리카보네이트계 수 조성물. A polycarbonate-based water composition comprising 0.5 to 15 weight 0 /。 of a rheology modifier.
【청구항 13] [Claim 13]
제 1 항의 폴리카보네이트계 수지 조성물을 포함하는 성형품.
A molded article comprising the polycarbonate-based resin composition of claim 1.
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| CN201580058335.1A CN107075101A (en) | 2014-12-04 | 2015-12-03 | Polycarbonate resin composition and its mechanograph |
| US15/517,136 US10081730B2 (en) | 2014-12-04 | 2015-12-03 | Polycarbonate-based resin composition and molded article thereof |
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| US11078360B2 (en) * | 2018-07-26 | 2021-08-03 | Lotte Advanced Materials Co., Ltd. | Polycarbonate/polycarbonate-polysiloxane composition |
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