WO2016089135A2 - Copolycarbonate resin composition and article comprising same - Google Patents
Copolycarbonate resin composition and article comprising same Download PDFInfo
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- WO2016089135A2 WO2016089135A2 PCT/KR2015/013157 KR2015013157W WO2016089135A2 WO 2016089135 A2 WO2016089135 A2 WO 2016089135A2 KR 2015013157 W KR2015013157 W KR 2015013157W WO 2016089135 A2 WO2016089135 A2 WO 2016089135A2
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- WIPO (PCT)
- Prior art keywords
- formula
- resin composition
- repeating unit
- copolycarbonate resin
- group
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 70
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 41
- -1 polysiloxane Polymers 0.000 claims description 95
- 125000003118 aryl group Chemical group 0.000 claims description 55
- 125000004432 carbon atom Chemical group C* 0.000 claims description 55
- 125000000524 functional group Chemical group 0.000 claims description 55
- 150000002430 hydrocarbons Chemical class 0.000 claims description 51
- 239000004215 Carbon black (E152) Substances 0.000 claims description 43
- 229930195733 hydrocarbon Natural products 0.000 claims description 43
- 229920000642 polymer Polymers 0.000 claims description 42
- 229920001296 polysiloxane Polymers 0.000 claims description 39
- 239000004417 polycarbonate Substances 0.000 claims description 33
- 229920000515 polycarbonate Polymers 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 125000003545 alkoxy group Chemical group 0.000 claims description 23
- 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 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000000466 oxiranyl group Chemical group 0.000 claims description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- 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 claims description 2
- 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 claims description 2
- 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 claims description 2
- 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 claims description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 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 claims description 2
- 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 claims description 2
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- HNDVYGDZLSXOAX-UHFFFAOYSA-N 2,6-dichloro-4-propylphenol Chemical compound CCCC1=CC(Cl)=C(O)C(Cl)=C1 HNDVYGDZLSXOAX-UHFFFAOYSA-N 0.000 claims 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 claims 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 claims 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims 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 claims 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 claims 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 9
- 238000012695 Interfacial polymerization Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920005668 polycarbonate resin Polymers 0.000 description 7
- 239000004431 polycarbonate resin Substances 0.000 description 7
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000002950 monocyclic group Chemical group 0.000 description 5
- 125000003367 polycyclic group Chemical group 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 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 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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 3
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 230000002378 acidificating effect Effects 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 150000007523 nucleic acids Chemical class 0.000 description 3
- 102000039446 nucleic acids Human genes 0.000 description 3
- 108020004707 nucleic acids Proteins 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241000894007 species Species 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
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000005018 aryl alkenyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000004260 weight control Methods 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
- 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 1
- HREXIBFZDJHFCF-UHFFFAOYSA-N 2,6-dibromo-4-propylphenol Chemical compound CCCC1=CC(Br)=C(O)C(Br)=C1 HREXIBFZDJHFCF-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
- 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
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-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
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 241001134446 Niveas Species 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
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 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
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- MUCRFDZUHPMASM-UHFFFAOYSA-N bis(2-chlorophenyl) carbonate Chemical compound ClC1=CC=CC=C1OC(=O)OC1=CC=CC=C1Cl MUCRFDZUHPMASM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- MOIPGXQKZSZOQX-UHFFFAOYSA-N carbonyl bromide Chemical compound BrC(Br)=O MOIPGXQKZSZOQX-UHFFFAOYSA-N 0.000 description 1
- IVSWQMIJNRQCHM-UHFFFAOYSA-N carbonyl dichloride;diphenyl carbonate Chemical compound ClC(Cl)=O.C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 IVSWQMIJNRQCHM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 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
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 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
- 239000000376 reactant Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 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
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 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
Definitions
- Copolycarbonate resin composition and article comprising the same
- the present invention relates to a copolycarbonate resin composition and an article comprising the same. More specifically, the present invention relates to a copolycarbonate resin composition having improved mechanical properties such as chemical resistance and impact resistance while maintaining the fluidity of the resin, and an article including the same.
- Polycarbonate resins are prepared by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and excellent impact strength. It has numerical stability, heat resistance and transparency, and is applied to a wide range of fields such as exterior materials for automobiles, automobile parts, building materials, and optical parts. Recently, in order to apply such polycarbonate resins to a wider variety of fields, a study for obtaining desired physical properties by copolymerizing aromatic diol compounds having different structures and introducing units having different structures into the main chain of polycarbonates has been made. Many attempts have been made. In particular, research into introducing a polysiloxane structure into the backbone of polycarbonate is being conducted, but most of the technologies have high production costs, resulting in low economic efficiency.
- the present invention is to provide a copolycarbonate resin composition with improved mechanical properties such as chemical resistance and impact resistance while maintaining the fluidity of the resin.
- the present invention also provides an article comprising the copolycarbonate resin composition.
- a copolycarbonate resin comprising an aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond; And a polysiloxane polymer containing a hydrocarbon-based functional group of 2 carbon atoms.
- an article including the copolycarbonate resin composition is also provided.
- a copolycarbonate resin comprising an aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond; And a copolycarbonate resin composition comprising a polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms may be provided.
- the inventors of the present invention can improve the impact strength, particularly impact strength at low temperatures, with fluidity by the copolycarbonate resin containing a specific repeating unit, using a copolycarbonate resin composition described above, hydrocarbon-based functional group
- the chemical stability is improved by the polysiloxane polymer containing, and the chemical resistance is secured.
- the copolycarbonate resin composition is a general copolycarbonate resin obtained by condensation polymerization of an aromatic diol such as bisphenol A and a carbonate precursor such as phosgene or a copolycarbonate resin obtained by copolymerizing aromatic diol compounds having different structures.
- the aromatic polycarbonate-based first repeating unit is formed by reacting an aromatic diol compound and a carbonate precursor. It may be represented by the following formula (1):
- Chemical Formula 1 i to R4 are each independently hydrogen, C wo alkyl, d- 10 alkoxy, or halogen,
- Z is unsubstituted or substituted with d- 10 alkylene, unsubstituted or substituted by phenyl, or 10 alkyl C 3 - 15 cycloalkylene, 0, S, SO, S0 2, or CO.
- Z is straight or branched Cwo 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 ⁇ .
- Z is cyclonucleic acid-1,1-diyl. 0. S. SO, S0 2 , or CO.
- the repeating unit represented by Formula 1 is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Sulfoxide, bis (4-hydroxyphenyl) sulphi bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2bisbis (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
- the meaning of 'derived from the aromatic diol compound' means that the hydroxyl group and the carbonate precursor of the aromatic diol compound react with the formula (1). It means forming a repeating unit to be displayed.
- a unit is represented by the following Formula 1-1.
- carbonate precursor 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. At least one selected from the group consisting of triphosgene, diphosgene, bromophosgene, and bishaloformate may be used, and preferably triphosgene or phosgene may be used.
- the aromatic polycarbonate-based 2 ′′ repeating unit having one or more siloxane bonds may include one or more or two or more repeating units selected from the group consisting of repeating units represented by the following Formulas 2 to 4. :
- ⁇ are each independently 10 alkylene
- Each R 5 is independently hydrogen; Alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted d- 10 alkoxy, or C 6 -2o aryl; halogen; d- 10 alkoxy; Allyl .; Ci-io haloalkyl; 20 is an aryl, - or C 6
- nl is an integer from 10 to 200
- Each X 2 is independently d- ⁇ alkylene
- ⁇ are each independently hydrogen, d- 6 alkyl, halogen, hydroxy, d- 6 alkoxy or C 6 - 20 aryl, and,.
- Each R 6 is independently hydrogen; Unsubstituted or oxiranyl, the CHO-alkoxy substituted by oxiranyl group, or C 6 - 20 aryl substituted with a d- 15 alkyl; halogen; Alkoxy; Allyl; d- 10 haloalkyl; 20 is an aryl, - or C 6
- n2 is an integer of 10 to 200
- 3 ⁇ 4 are each independently Cwo alkylene
- Each Y 2 is independently Cwo alkoxy
- Each R 7 is independently hydrogen; Alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted d- 10 alkoxy, or C 6 — 20 aryl; halogen; CHO alkoxy; Allyl; Cwo haloalkyl; 20 is an aryl, - or C 6
- n3 is an integer of 10-200.
- 3 ⁇ 4 are each independently C 2 - 4 alkylene and is, most preferably, propane-1,3-diyl-10 alkylene, more preferably C 2.
- 3 ⁇ 4 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.
- 3 ⁇ 4 is each independently Cl - 10 alkyl, ⁇ more preferably d- 6 alkyl, more preferably d- 3 alkyl, and most preferably methyl.
- ⁇ is i) an integer from 30 to 60, or ii) 20 or more. An integer of 25 or more, 30 or more, 40 or less, or 35 or less, or iii) 50 or more, or 55 or more, 70 or less, 65 or less, or 60 or less.
- Chemical Formula 2 is represented by the following Chemical Formula 2-1:
- 3 ⁇ 4 are each independently a C 2 - to 10 alkylene, more preferably C 2 - 6 alkylene and most preferably isobutylene.
- ⁇ is hydrogen.
- 3 ⁇ 4 is each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2'phenalpropyl, 3 '(oxyranylme) propyl, fluoro, chloro, bromo, iodo, medo Toxy, Epoxy, Propoxy, Allyl . , 2, 2, 2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl.
- 3 ⁇ 4 is each independently d-! Q alkyl, more preferably d-6 alkyl, more preferably d- 3 alkyl, and most preferably methyl.
- n2 is i) an integer from 30 to 60, or ii) 20 or more, 25 or more, or 30 or more and 40 or less. Or iii) 50 or less, or 55 or more, 70 or less, 65 or less, or 60 or less.
- Chemical Formula 3 is represented by the following Chemical Formula 3-1: [Formula 3-1]
- C 2 _ 4 alkylene most preferably, propane-1, 3-diyl eu: - preferably in the general formula (4), it is, 3 ⁇ 4 are each independently C 2 10 alkylene,.
- Y 2 is alkoxy. More preferably it is Cw alkoxy, most preferably methoxy.
- each R 7 is independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, polouro, chloro, bromo, iodo, Methoxy, ethoxy, propoxy, allyl.
- R 7 is each independently d-) alkyl, more preferably Is C- 6 alkyl, more preferably d- 3 alkyl, most preferably methyl.
- n3 is i) an integer from 30 to 60, ii) 20 or more, 25 or more, or 30 or more, 40 or less, or 35 or less, or iii) 50 or more, or 55 or more It is an integer of 70 or less, 65 or less, or 60 or less.
- Chemical Formula 4 is represented by Chemical Formula 4-1: [Formula 4-1]
- the formula (2) From the group consisting of repeating units represented by four. One or more selected units, or two or more types may be included, and specifically, two or more types thereof may be included. In the case of including two or more of the repeating units represented by Formulas 2 to 4, it was confirmed that the improvement of the room temperature impact strength, the low temperature impact strength, and the fluidity properties were remarkably increased. Is due to the complementary effect of "A 2 or more types of repeating unit” means in this invention. It means that the structure includes two or more repeating units having different structures, or two or more repeating units having the same structure but different numbers of repeating units (nl, n2, n3) of silicon oxide in the structure of Formulas 2 to 4.
- repeating unit represented by Formula 2 means in the present invention, 1) .
- the 2 repeat at least one unit: 1) a repeating unit represented by the formula (2) first species and the repeating unit one compound represented by formula (3), 2), recurring unit to be displayed one of a repeating unit 1 species, and the formula (4) represented by the formula (2) Species, or 3) represented by the formula
- the weight ratio between the two repeating units may be 1:99 to 99: 1.
- it is 3: 97-97: 3 5: 95-95: 5 10: 90-90: 10, or 15: 85-85: 15, More preferably, it is 20: 80-80: 20.
- Repetitive units represented by Formulas 2 to 4 are each represented by the following Formula 2 '
- siloxane compound represented by 2 the siloxane compound represented by following formula (3-2), and the siloxane compound represented by following formula (4-2).
- X 2 , Y 1; R 6 and n 2 are the same as defined in Formula 3,
- Y 2 , R 7 and n 3 are the same as defined in Formula 4 above.
- 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 each of Chemical Formulas 2 to 4 above.
- the carbonate precursors that can be used to form the repeating units of Formulas 2 to 4 are the same as those described above for the carbonate precursors that can be used to form the repeating units of Formula 1.
- the compounds represented by Chemical Formulas 2-2, 3-2, and 4-2 may be prepared by the methods of the following Schemes 1 to 3, respectively.
- 'It is C 2 - 10 alkenyl, and Al,, R 5, and nl are as defined above in formula (1).
- ⁇ 2 ′ is C 2 10 alkenyl, 3 ⁇ 4, Y 1; As defined in R 6 and Formula 2,
- R 7 and n 3 are the same as defined in Formula 3 above. It is preferable to perform the reactions of the reaction schemes 1 to 3 under a metal catalyst.
- a metal catalyst Pt catalyst is preferably used.
- an ashby catalyst, a Karlstedt catalyst, and a lamo are used. At least one selected from the group consisting of a Lamoreaux catalyst, a Speyer catalyst, PtCl 2 (C0D), PtC l 2 (benzonitrile) 2 , and PtBr 6 can be used.
- the metal catalyst is 0.001 parts by weight or more, 0.005 parts by weight or more, or 0.01 parts by weight or more based on 100 parts by weight of the compound represented by Formula 11, 13, or 15, 1 part by weight or less, 0.1 part by weight or less, or It can be used at 0.05 parts by weight or less.
- the reaction temperature is preferably so to ioo ° c.
- the reaction time is preferably 1 hour to 5 hours.
- the compound represented by Formula 6, 8 or 10 can be prepared by reacting the organodisiloxane and organocyclosiloxane under an acid catalyst, it is possible to control the content of the reactant to control nl, n2 and ⁇ 3 .
- the reaction temperature is preferably 50 to 70 ° C.
- the reaction time is preferably 1 hour to 6 hours.
- the organodisiloxane one or more selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, nuxamethyldisiloxane and nuxaphenyldisiloxane may be used.
- an organocyclotetrasiloxane can be used as an example, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like.
- the acid catalyst is H 2 SO 4 , HCIO 4 , AICI 3, SbCl 5 . At least one selected from the group consisting of SnCl 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 of the repeating unit is a siloxane compound used for the polymerization of the copolycarbonate, for example the formula 1- It is based on the increase ratio of the siloxane compound represented by 2, 2-2, and 3-2.
- the copolycarbonate resin composition may include a copolycarbonate resin including an aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond.
- the aromatic polycarbonate-based first repeating unit and the at least one siloxane bond the aromatic polycarbonate-based first repeating unit and the at least one siloxane bond
- the molar ratio of the aromatic polycarbonate-based second repeating unit may be 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 is 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 including the aromatic polycarbonate-based first repeating unit and the aromatic polycarbonate-based second repeating unit having one or more siloxane bonds may include 0.001 to 10 weight 3 ⁇ 4 of the second repeating unit.
- the first over-reduced second repeat unit content the first is an improvement in room temperature impact strength, low temperature impact strength and fluidity properties according to the second repeat unit it can be difficult to fully implement i.
- the second repeating unit content is When excessively increased, the flowability and moldability may decrease while the molecular weight of the copolycarbonate resin is excessively increased.
- the weight average molecular weight of the copolycarbonate resin including the aromatic polycarbonate-based crab 1 repeating unit and the aromatic polycarbonate-based 2 repeating unit having at least one siloxane bond is 1,000 to 100,000 g / mol, or 5,000 to 50,000 g / mol day Can be. In the weight average molecular weight range it can be improved ductility (ductility), and YI of the copolyester carbonate resin. It said copolycarbonate resin is at least one member selected from the group consisting of compounds represented by the formula 2-2 to 4-2,. Or it may be prepared in a manufacturing method comprising the step of polymerizing a composition comprising two or more compounds, an aromatic diol compound and a carbonate precursor.
- the polymerization method may, using the interfacial polymerization method as an example, a case is possible polymerization at normal pressure and low temperature, and has an effect which facilitates the molecular weight control.
- 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 the pre-polymerization, the coupling body is introduced, and then polymerized again. In this case, a high molecular weight copolycarbonate may be obtained.
- the material used for the interfacial polymerization is not particularly limited as long as it is a material that can be used for the polymerization of the copolycarbonate, the amount of use may be adjusted as necessary.
- the acid binder examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or pyridine. Amine compounds, such as these, can be used.
- the organic solvent is not particularly limited as long as it is a solvent usually used for polymerization of copolycarbonate. For example, halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used. Also.
- the interfacial polymerization may be carried out by reaction agents such as tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds. Can be used additionally.
- the reaction temperature of the interfacial polymerization is preferably 0 to 40 ° C, the reaction time is preferably 10 minutes to 5 hours.
- the interfacial polymerization may be performed by further including a molecular weight regulator.
- the molecular weight regulator may be added before the start of polymerization, during the start of polymerization, or after the start of polymerization.
- Mono-alkylphenols may be used as the molecular weight regulator, and the mono-alkylphenols are, for example, p-tert-butylphenol, P-cumylphenol, decylphenol.
- Dodecylphenol At least one member selected from the group consisting of tetradecylphenol, nuxadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol.
- it is p-tert- butylphenol, In this case, a 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 based on 100 parts by weight of an aromatic diol compound. It is contained in 10 weight part or less, 6 weight part or less, or 5 weight part or less, and can obtain desired molecular weight within this range.
- the polymerization At least one selected from the group consisting of compounds represented by Formulas 2-2 to 4-2, or at least two compounds and aromatic
- the compound may form a repeating unit represented by Chemical Formulas 1 to 4 above. More specifically, the general formula (2) _2 to 4-2 at least one member selected from the group consisting of compounds represented by the following.
- the copolycarbonate resin according to the present invention is a copolycarbonate comprising a repeating unit represented by Formula 1-1, a repeating unit represented by Formula 2-2 and a repeating unit represented by Formula 3-2. Resin may be included.
- the copolycarbonate resin composition has 2 or more carbon atoms, or 2 to
- polysiloxane polymers containing 2 to 100, or 2 to 50, hydrocarbon-based functional groups may form a crosslinked structure through a hydrocarbon-based or more hydrocarbon-based functional group to absorb external shocks, and may be chemically stable to maximize chemical resistance.
- the hydrocarbon-based functional group may include an aliphatic hydrocarbon functional group, at least one selected from the group consisting of alicyclic hydrocarbon and aromatic hydrocarbon functional groups functional groups.
- the aliphatic hydrocarbon functional group, alicyclic hydrocarbon functional group or aromatic hydrocarbon functional group may each be a halogen group, an alkyl group, an alkenyl group, Alkoxy group, an aryl group, an arylalkyl group, and an aryl alkenyl group. It may be substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group, a carbazolyl group, a fluorenyl group, a nitrile group and an acetylene group.
- the alicyclic hydrocarbon functional group may include a monocyclic or polycyclic cycloalkyl group having 3 or more carbon atoms, or 3 to 50 carbon atoms, and the aromatic hydrocarbon functional group may include 6 or more minor atoms, or 6 to 50 monocyclic or polycyclic aryl groups. Can be.
- the monocyclic means that a single ring is included in the functional group
- polycyclic means that two or more ring is contained in the functional group.
- the aliphatic hydrocarbon functional group may include a linear or branched alkyl group or a vinyl functional group.
- the linear or branched alkyl group having 2 or more carbon atoms is an alkyl group except for a methyl group having 1 carbon atom.
- the functional group derived from the vinyl group means a functional group in which a part of the hydrogen atoms included in the vinyl group is substituted with another atomic group.
- the vinyl-based functional group may be represented by the following formula (11). [Formula 11]
- R 10 are each independently hydrogen, a straight chain having 1 to 20 carbon atoms or Alkyl group branched-chain, "cycloalkyl group having 6 to 20 carbon atoms of the aryl group, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, having 3 to 20 carbon atoms in a ketone group or an ester group.
- An aryl group of 20, an alkenyl group of 2 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, a ketone group or an ester group may each be a halogen group, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, It may be substituted or unsubstituted with one or more substituents selected from the group consisting of an arylalkyl group, an arylalkenyl group, a heterocyclic group, a carbazolyl group, a fluorenyl group, a nitrile group and an acetylene group.
- the aryl group can be monocyclic or polycyclic in organic radicals derived from aromatic hydrocarbons by one hydrogen removal.
- the cycloalkyl group is not particularly limited, but may be monocyclic or polycyclic.
- the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms may include 0.001 to 10 mol%, or 0.01 to 1 mol%, or 0.05 to 0.5 mol% of C 2 or more hydrocarbon-based functional groups. The carbon number is less than 0.001 mol% relative to the polysiloxane polymer containing the hydrocarbon group having at least 2 carbon atoms .
- Impact resistance, chemical resistance, and fluidity improvement effect by two or more hydrocarbon-based functional groups may be difficult to be sufficiently realized, and the C 2 or more hydrocarbon-based functional group is 10 mol3 ⁇ 4 to the polysiloxane polymer containing the C 2 or more hydrocarbon-based functional group. If exceeded, the highly reactive hydrocarbon group having 2 or more carbon atoms is excessively high, and thus the compatibility with the polymer resin may be degraded, thereby reducing the mechanical and chemical properties.
- the polysiloxane polymer containing a hydrocarbon-based functional group having 2 or more carbon atoms may include a polysiloxane repeating unit and a polydimethylsiloxane repeating unit including a hydrocarbon-based functional group having 2 or more carbon atoms.
- the polysiloxane repeating unit including the hydrocarbon group having 2 or more carbon atoms may include a repeating unit represented by the following Formula 12.
- At least one of Rn to R 12 is a hydrocarbon-based functional group having at least 2 carbon atoms, and the rest are methyl groups.
- Ru is a hydrocarbon group having 2 or more carbon atoms, and R 12 may be a methyl group.
- the polydimethylsiloxane repeating unit may include? Repeating unit represented by the following formula (13). . '
- the molar ratio of the polysiloxane repeating units including the C 2 hydrocarbon-based functional group to the repeating polydimethylsiloxane units is 0.00001 0.1, or 0.0005 to 0.001. 0.01, or 0.0007 to 0.0.
- the polysiloxane polymer containing the hydrocarbon-based functional group having 2 or more carbon atoms may further include the hydrocarbon-based functional group having 2 or more carbon atoms bonded to the terminal of the polysiloxane polymer.
- the terminal of the polysiloxane polymer means both ends of the polysiloxane main chain of the polysiloxane polymer containing the hydrocarbon group having 2 or more carbon atoms, and the hydrocarbon group having 2 or more carbon atoms has both or both ends of the polysiloxane main chain.
- the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms has a carbon- 2 or more hydrocarbon-based functional group bonded to a main chain including a polysiloxane repeating unit and a polydimethylsiloxane repeating unit including a hydrocarbon-based functional group and 2 or more carbon atoms.
- the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms may include a compound represented by the following Chemical Formula 14.
- m is an integer of 10-20
- n is an integer of 6,000-11.500, and is a C2 or more hydrocarbon-type functional group.
- the content of the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms is 0.01 to 10% by weight, or 0.01 to 5% by weight, or 0.5 to 4% by weight based on the total weight of the copolycarbonate resin composition. Weight percent.
- the content of the polysiloxane polymer containing the hydrocarbon-based functional group of 2 or more carbon atoms is too small, the 2 or more carbon atoms Chemical resistance and impact resistance improvement effect by the polysiloxane polymer containing a hydrocarbon-based functional group may be difficult to implement.
- the content of the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms is too large, the mechanical or chemical properties of the copolycarbonate resin composition may be lowered.
- the weight average molecular weight of the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms is 100, 000 to 1, 000, 000 g / mol, or 300, 000 to 900.000 g / mol, or 500, 000 to 850, 000 g / mol.
- the example of the method of measuring the said weight average molecular weight is not specifically limited, For example, the weight average molecular weight of polystyrene conversion measured by the GPC method can be used.
- the copolycarbonate resin composition may include a copolycarbonate resin comprising an aromatic polycarbonate-based U repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane linkage; And a polysiloxane polymer containing a hydrocarbon-based functional group having 2 or more carbon atoms.
- a copolycarbonate resin comprising an aromatic polycarbonate-based U repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane linkage
- a polysiloxane polymer containing a hydrocarbon-based functional group having 2 or more carbon atoms may be added to the copolycarbonate resin by adding a polysiloxane polymer and mixing using a mixer.
- the copolycarbonate resin composition of the final article may further include various known additives, resins, and the like.
- the additives include antioxidants, heat stabilizers, light stabilizers, plasticizers, antistatic agents, and nucleating agents.
- the copolycarbonate resin composition may have a low temperature impact strength of 700 J / m or more measured at -30 ° C based on ASTM D256 (l / 8 inch, Notched Izod).
- the copolycarbonate resin composition may have a low silver impact strength measured at -40 ° C based on ASTM D256 (l / 4 inch, Notched Izod) more than 200 J / m.
- the copolycarbonate resin composition may be less than 10 gl 10m in melt index measured according to ASTM D1238 (300 ° C, 1.2kg conditions).
- an article including the copolycarbonate resin composition of the above embodiment may be provided.
- the article is an injection molded article.
- the article is at least one selected from the group consisting of antioxidants, thermal stabilizers, photostabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent brighteners, ultraviolet absorbers, pigments and dyes. It can be included as.
- Examples of the method for producing the article are not limited to, but for example, the step of drying the copolycarbonate resin composition according to the present invention, for example, pellet form copolycarbonate resin composition and then injection into an injection molding machine can do.
- Information on the copolycarbonate resin composition includes the above-described content with respect to the embodiment.
- Copolycarbonate resin composition and the article containing the same improved mechanical properties can be provided.
- SF39Q0C manufactured by KCC: vinyl group content: 0.07 mol% was added to the copolycarbonate resin prepared in Preparation Example 3 in a content of 1 wt%, and mixed with a mixer.
- a copolycarbonate resin composition was prepared in the same manner as in Example 1, except that SF3900C (manufactured by KCC Corporation: 0.07 mol% of vinyl groups) was added in a content of 2 wt%.
- SF3900C manufactured by KCC Corporation: 0.07 mol% of vinyl groups
- Copolycarbonate resin composition was prepared in the same manner as in Example 1 except that SF3900CXKCC Co., Ltd. product: vinyl group content 0.07 mol%) was added in a 3 wt% content. .
- Copolycarbonate resin prepared in Preparation Example 5 was used. Comparative Example 4
- a copolycarbonate resin composition was prepared in the same manner as in Example 1, except that the polycarbonate resin prepared in Preparation Example 4 was used instead of the copolycarbonate resin prepared in Preparation Example 3.
- the Agilent 1200 series was used to measure GPC using PC Standard.
- the time of denaturation by the solvent is longer than 1 hour, and has excellent chemical resistance, while no additive is included.
- the copolycarbonate resin composition of the comparative example has a time denatured by a solvent
- the melt index is not only high. It was found that the chemical resistance was bad.
- the copolycarbonate resin composition of Comparative Example 4 even though it contains an additive with the copolycarbonate resin prepared in Preparation Example 4, by using the polycarbonate resin obtained in Preparation Example 4, 1 / Low temperature impact strength at 8 inch, -30 ° C was measured low, and the melt index was increased. Accordingly, the copolycarbonate resin composition, as the additive is added together with a specific copolycarbonate resin, with improved properties of the copolycarbonate resin (eg, melt index), impact resistance and chemical resistance depending on the additive It was confirmed that this is increased.
Abstract
The present invention relates to a copolycarbonate resin composition having improved mechanical properties, such as chemical resistance and impact resistance, while maintaining resin flowability, and to an article comprising the same.
Description
【발명의 명칭】 [Name of invention]
코폴리카보네이트 수지 조성물 및 이를 포함하는 물품 Copolycarbonate resin composition and article comprising the same
【관련 출원 (들)과의 상호 인용】 ' - mutual quotation of the related application (s)] "
본 출원은 2014년 12월 4일자 한국 특허 출원 제 10-2014-0173005호， 및 2015년 12월 2일자 한국 특허 출원 제 . 10-2015-0170782호에 기초한 우선권의 이익을 주장하며， 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다. This application is a Korean patent application No. 10-2014-0173005 filed December 4, 2014, and a Korean patent application filed December 2, 2015. Claiming the benefit of priority based on 10-2015-0170782, all contents disclosed in the literature of the corresponding Korean patent applications are incorporated as part of this specification.
【기술분야】 Technical Field
본 발명은 코폴리카보네이트 수지 조성물 및 이를 포함하는 물품에 관한 것이다. 보다 상세하게는， 수지의 유동성을 유지하면서， 내화학성 및 내충격성 등의 기계적 물성이 향상된 코폴리카보네이트 수지 조성물 및 이를 포함하는 물품에 관한 것이다. The present invention relates to a copolycarbonate resin composition and an article comprising the same. More specifically, the present invention relates to a copolycarbonate resin composition having improved mechanical properties such as chemical resistance and impact resistance while maintaining the fluidity of the resin, and an article including the same.
【발명의 배경이 되는 기술】 [Technique to become background of invention]
폴리카보네이트 .수지는 비스페놀 A와 같은 방향족 디올과 포스겐과 같은 카보네이트 전구체가 축중합하여 제조되고， 우수한 충격강도. 수치안정성, 내열성 및 투명성 등을 가지며, 전기전자 제품의 외장재, 자동차 부품， 건축 소재， 광학 부품 등 광범위한 분야에 적용된다. 최근 이러한 폴리카보네이트 수지를 보다 다양한 분야에 적용하기 위해 서로 다른 구조의 방향족 디올 화합물을 공중합하여 구조가 다른 단위체를 폴리카보네이트의 주쇄에 도입하여 코폴리카보네이트를 제조함으로서， 원하는 물성을 얻고자 하는 연구가 많이 시도되고 있다. 특히 폴리카보네이트의 주쇄에 폴리실록산 구조를 도입시키는 연구도 진행되고는 있으나， 대부분의 기술들이 생산 단가가 높아 경제적 효율성이 떨어지며. 코폴리카보네이트 수지의 내화학성이나 충격강도 등이 저하되는 한계가 있었다. 이에 내화학성 및 내충격성 등의 기계적 물성이 충분히 확보될 수 있는 코폴리카보네이트 수지 조성물의 개발이 요구되고 있다.
【발명의 내용】 Polycarbonate resins are prepared by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and excellent impact strength. It has numerical stability, heat resistance and transparency, and is applied to a wide range of fields such as exterior materials for automobiles, automobile parts, building materials, and optical parts. Recently, in order to apply such polycarbonate resins to a wider variety of fields, a study for obtaining desired physical properties by copolymerizing aromatic diol compounds having different structures and introducing units having different structures into the main chain of polycarbonates has been made. Many attempts have been made. In particular, research into introducing a polysiloxane structure into the backbone of polycarbonate is being conducted, but most of the technologies have high production costs, resulting in low economic efficiency. There was a limit that the chemical resistance, impact strength, etc. of the copolycarbonate resin are lowered. Accordingly, development of a copolycarbonate resin composition capable of sufficiently securing mechanical properties such as chemical resistance and impact resistance is required. [Content of invention]
【해결하고자 하는 과제] Problem to be solved
본 발명은 수지의 유동성을 유지하면서， 내화학성 및 내충격성 등의 기계적 물성이 향상된 코폴리카보네이트 수지 조성물을 제공하기 위한 것이다. The present invention is to provide a copolycarbonate resin composition with improved mechanical properties such as chemical resistance and impact resistance while maintaining the fluidity of the resin.
또한， 본 발명은 상기 코폴리카보네이트 수지 조성물.을 포함하는 물품을 제공하기 위한 것이다. The present invention also provides an article comprising the copolycarbonate resin composition.
【과제의 해결 수단] . [Measures of problem].
본 명세서에서는， 방향족 폴리카보네이트계 제 1 반복 단위 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함하는 코폴리카보네이트 수지; 및 탄소수 2 아상의 탄화수소계 작용기를 함유한 폴리실록산 고분자를 포함하는 코폴리카보네이트 수지 조성물이 제공된다. 본 명세서에서는 또한， 상기 코폴리카보네이트 수지 조성물을 포함하는 물품이 제공된다. In the present specification, a copolycarbonate resin comprising an aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond; And a polysiloxane polymer containing a hydrocarbon-based functional group of 2 carbon atoms. In the present specification, an article including the copolycarbonate resin composition is also provided.
이하 발명의 구체적인 구현예에 따른 코폴리카보네이트 수지 조성물 및 이를 포함하는 물품에 대하여 보다 상세하게 설명하기로 한다. 발명의 일 구현예에 따르면 . 방향족 폴리카보네이트계 제 1 반복 단위 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함하는 코폴리카보네이트 수지; 및 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자를 포함하는 코폴리카보네이트 수지 조성물이 제공될 수 있다. 본 발명자들은 상술한 코폴리카보네이트 수지 조성물을 이용하면 , 특정 반복단위를 포함한 코폴리카보네이트 수지에 의해 유동성과 함께 충격강도， 특히 저온에서의 충격강도가 향상될 수 있으며， 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자에 의해 화학적 안정성이 향상되어 내화학성이 확보되며， 소량의 탄소수 2 이상의 탄화수소계
작용기에 의해 내충격성도 향상될 수 있다는 점을 실험을 통하여 확인하고 발명을 완성하였다. 상기 코폴리카보네이트 수지 조성물은 비스페놀 A와 같은 방향족 디올과 포스겐과 같은 카보네이트 전구체가 축중합된 일반적인 코폴리카보네이트 수지 또는 서로 다른 구조의 방향족 디을 화합물을 공중합한 코폴리카보네이트 수지에 대해. 상술한 탄소수 2 이상의 탄화수소계 작용기 작용기를 함유한 폴리살록산 고분자를 마스터 배치식으로 혼합함으로써, 코폴리카보네이트 수지 고유의 유동성을 그대로 유지하면서, 기계적 물성을 향상시킬 수 있다. 특히， 비스페놀 A 이외에 서로 다른 구조의 방향족 디올 화합물을 공중합하여 코폴리카보네이트의 주쇄에 폴리실록산 구조가 도입된 코폴리카보네이트 수지를 사용하는 경우. 상온충격강도 및 저온충격강도의 차이가 적어 내충격성이 크게 향상될 뿐만 아니라. 유동성도 높은 수준에서 확보될 수 있음을 확인하였다. 이하에서는 상기 코폴리카보네이트 수지 조성물에 대해 보다 구체적으로 살펴보기로 한다 . 방향족폴리카보네이트계 제 1 반복 단위 Hereinafter, a copolycarbonate resin composition and an article including the same according to specific embodiments of the present invention will be described in detail. According to one embodiment of the invention. A copolycarbonate resin comprising an aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond; And a copolycarbonate resin composition comprising a polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms may be provided. The inventors of the present invention can improve the impact strength, particularly impact strength at low temperatures, with fluidity by the copolycarbonate resin containing a specific repeating unit, using a copolycarbonate resin composition described above, hydrocarbon-based functional group The chemical stability is improved by the polysiloxane polymer containing, and the chemical resistance is secured. Experiments confirmed that the impact resistance can be improved by the functional group, and completed the invention. The copolycarbonate resin composition is a general copolycarbonate resin obtained by condensation polymerization of an aromatic diol such as bisphenol A and a carbonate precursor such as phosgene or a copolycarbonate resin obtained by copolymerizing aromatic diol compounds having different structures. By mixing the polysiloxane polymer containing a hydrocarbon-based functional group functional group having at least 2 carbon atoms in a master batch manner, mechanical properties can be improved while maintaining fluidity inherent in the copolycarbonate resin. In particular, when a copolycarbonate resin having a polysiloxane structure introduced into the main chain of the copolycarbonate by copolymerizing aromatic diol compounds having different structures in addition to bisphenol A is used. Not only the difference in room temperature impact strength and low temperature impact strength is small, but the impact resistance is greatly improved. It was confirmed that liquidity can be secured at a high level. Hereinafter, the copolycarbonate resin composition will be described in more detail. Aromatic Polycarbonate First Repeating Unit
상기 방향족 폴리카보네이트계 제 1 반복 단위는 방향족 디올 화합물 및 카보네이트 전구체가 반응하여 형성되는 것으로. 하기 화학식 1로 표시될 수 있다: The aromatic polycarbonate-based first repeating unit is formed by reacting an aromatic diol compound and a carbonate precursor. It may be represented by the following formula (1):
1] One]
상기 화학식 1에서
i 내지 R4는 각각 독립적으로 수소， Cwo 알킬， d-10 알콕시， 또는 할로겐이고， In Chemical Formula 1 i to R4 are each independently hydrogen, C wo alkyl, d- 10 alkoxy, or halogen,
Z는 비치환되거나 또는 페닐로 치환된 d-10 알킬렌, 비치환되거나 또는 10 알킬로 치환된 C3-15 사이클로알킬렌， 0， S, SO, S02, 또는 CO이다. 바람직하게는, ^ 내지 는 각각 독립적으로 수소， 메틸， 클로로， 또는 브로모이다. 또한 바람직하게는， Z는 비치환되거나 또는 페닐로 치환된 직쇄 또는 분지쇄의 Cwo 알킬렌이며, 보다 바람직하게는 메틸렌， 에탄 -1,1—디일, 프로판—2， 2-디일， 부탄 -2, 2-디일， 1-페닐에탄ᅳ 1,1-디일, 또는 디페닐메틸렌이다ᅳ 또한 바람직하게는， Z는 사이클로핵산 -1,1-디일. 0. S. SO, S02, 또는 CO이다. 바람직하게는 상기 화학식 1로 표시되는 반복단위는 비스 (4- 히드록시페닐)메탄, 비스 (4-히드톡시페닐)에테르， 비스 (4- 히드록시페닐)설폰， 비스 (4-히드록시페닐)설폭사이드, 비스 (4- 히드록시페닐)설파이 비스 (4—히드록시페닐)케톤， 1,1—비스 (4— 히드록시페닐)에탄, 비스페놀 A, 2, 2ᅳ비스 (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 (4ᅳ히드록시— 3-브로모페닐)프로판， 2, 2ᅳ비스 (4-히드록시ᅳ 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 (4ᅳ히드록시페닐)디페닐메탄， 및 3， 0 _비스[3-( 0 - 히드록시페닐)프로필]폴리디메틸실록산으로 이루어진 군으로부터 선택되는 어느 하나 이상의 방향족 디올 화합물로부터 유래할 수 있다. 상기 '방향족 디올 화합물로부터 유래한다'의 의미는, 방향족 디을 화합물의 하이드록시기와 카보네이트 전구체가 반웅하여 상기 화학식 1로
표시되는 반복단위를 형성하는 것을 의미한다. 예컨대, 방향족 디올 화합물인 비스페놀 A와 카보네이트 전구체인 트리포스겐이 중합된 경우， 상기 화학식 1로 표시되는 반복 :단위는 하기 화학식 1ᅳ 1로 표시된다. Z is unsubstituted or substituted with d- 10 alkylene, unsubstituted or substituted by phenyl, or 10 alkyl C 3 - 15 cycloalkylene, 0, S, SO, S0 2, or CO. Preferably, ^ to each independently represent hydrogen, methyl, chloro, or bromo. Also preferably, Z is straight or branched Cwo alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, propane-2, 2-diyl, butane-2 , 2-diyl, 1-phenylethane ᅳ 1,1-diyl, or diphenylmethylene ᅳ. Also preferably, Z is cyclonucleic acid-1,1-diyl. 0. S. SO, S0 2 , or CO. Preferably, the repeating unit represented by Formula 1 is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Sulfoxide, bis (4-hydroxyphenyl) sulphi bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2bisbis (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 ᅳ hydroxyphenyl) diphenylmethane, and 3, 0 _bis [3- (0- De-hydroxyphenyl) propyl] can be derived from any one or more of an aromatic diol compound is selected from the group consisting of polydimethylsiloxane. The meaning of 'derived from the aromatic diol compound' means that the hydroxyl group and the carbonate precursor of the aromatic diol compound react with the formula (1). It means forming a repeating unit to be displayed. For example, when bisphenol A, which is an aromatic diol compound, and triphosgene, which is a carbonate precursor, are polymerized, the repetition represented by Formula 1 above : a unit is represented by the following Formula 1-1.
상기 1) 방향족 폴리카보네이트계 제 1 반복 단위를 포함하는 코폴리카보네이트 수지는 코폴리카보네이트의 주쇄에 폴리실록산 구조가 도입되어 있지 않다는 점에서， 2) 방향족 폴리카보네이트계 제 1 반복 단위 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함하는 코폴리카보네이트 수지와 구분된다. 상기 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 " 반복 단위는, 하기 화학식 2 내지 4로 표시되는 반복단위로 구성되는 군으로부터 선택되는 반복단위 1종 이상， 또는 2종 이상을 포함할 수 있다: 2) the aromatic polycarbonate-based first repeating unit and at least one siloxane bond, in that the copolycarbonate resin including the aromatic polycarbonate-based first repeating unit has no polysiloxane structure introduced into the main chain of the copolycarbonate. It is distinguished from the copolycarbonate resin containing the aromatic polycarbonate-type 2nd repeating unit which has a. The aromatic polycarbonate-based 2 ″ repeating unit having one or more siloxane bonds may include one or more or two or more repeating units selected from the group consisting of repeating units represented by the following Formulas 2 to 4. :
[화학식 2]
[Formula 2]
상기 화학식 2에서, In Chemical Formula 2,
^은 각각 독립적으로 10 알킬렌이고， ^ Are each independently 10 alkylene,
R5는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐， 옥시라닐로 치환된 d-10 알콕시， 또는 C6-2o 아릴로 치환된 알킬; 할로겐; d-10 알콕시; 알릴.; Ci-io 할로알킬; 또는 C6-20 아릴이고， Each R 5 is independently hydrogen; Alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted d- 10 alkoxy, or C 6 -2o aryl; halogen; d- 10 alkoxy; Allyl .; Ci-io haloalkyl; 20 is an aryl, - or C 6
nl은 10 내지 200의:정수이고, nl is an integer from 10 to 200,
X2은 각각 독립적으로 d-ω 알킬렌이고, Each X 2 is independently d-ω alkylene,
, ^은 각각 독립적으로 수소， d-6 알킬, 할로겐, 히드록시， d-6 알콕시 또는 C6-20 아릴이고， . , ^ Are each independently hydrogen, d- 6 alkyl, halogen, hydroxy, d- 6 alkoxy or C 6 - 20 aryl, and,.
R6는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐， 옥시라닐로 치환된 CHO 알콕시, 또는 C6-20 아릴로 치환된 d-15 알킬; 할로겐; 알콕시; 알릴; d-10 할로알킬; 또는 C6-20 아릴이고， Each R 6 is independently hydrogen; Unsubstituted or oxiranyl, the CHO-alkoxy substituted by oxiranyl group, or C 6 - 20 aryl substituted with a d- 15 alkyl; halogen; Alkoxy; Allyl; d- 10 haloalkyl; 20 is an aryl, - or C 6
n2는 10 내지 200의 정수이고, n2 is an integer of 10 to 200,
[화학식 4]
[Formula 4 ]
화학식 4에서， In Formula 4,
¾는 각각 독립적으로 Cwo 알킬렌이고， ¾ are each independently Cwo alkylene,
Y2는 각각 독립적으로 Cwo 알콕시이고, Each Y 2 is independently Cwo alkoxy,
R7은 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐, 옥시라닐로 치환된 d-10 알콕시， 또는 C6— 20 아릴로 치환된 알킬; 할로겐; CHO 알콕시 ; 알릴; Cwo 할로알킬; 또는 C6-20 아릴이고， Each R 7 is independently hydrogen; Alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted d- 10 alkoxy, or C 6 — 20 aryl; halogen; CHO alkoxy; Allyl; Cwo haloalkyl; 20 is an aryl, - or C 6
n3은 10 내지 200의 정수이다. 상기 화학식 2에서. 바람직하게는, ¾는 각각 독립적으로 C2-10 알킬렌이고, 보다 바람직하게는 C2— 4 알킬렌이고, 가장 바람직하게는 프로판 -1，3-디일이다. ' 또한 바람직하게는， ¾는 각각 독립적으로 수소， 메틸, 에틸, 프로필, 3-페닐프로필. 2-페닐프로필, 3— (옥시라닐메톡시)프로필, 플루오로， 클로로, 브로모, 아이오도. 메톡시, 에록시， 프로폭시, 알릴. 2 , 2 , 2- 트리플루오로에틸, 3，3 , 3ᅳ트리플루오로프로필， 페닐， 또는 나프틸이다. 또한 바람직하게는, ¾는 각각 독립적으로 Cl-10 알킬이고ᅳ 보다 바람직하게는 d—6 알킬이고， 보다 바람직하게는 d— 3 알킬이고, 가장 바람직하게는 메틸이다. 또한 바람직하게는， ^은 i ) 30 내지 60의 정수이거나， i i ) 20 이상. 25 이상， 또는 30 이상이고， 40 이하, 또는 35 이하의 정수이거나, 또는 i i i ) 50 이상， 또는 55 이상이고， 70 이하， 65 이하， 또는 60 이하의 정수이다.
또한 바람직하게는， 상기 화학식 2는 하기 화학식 2-1로 표시된다: n3 is an integer of 10-200. In Formula 2 above. Preferably, ¾ are each independently C 2 - 4 alkylene and is, most preferably, propane-1,3-diyl-10 alkylene, more preferably C 2. ' Also preferably, ¾ 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, ¾ is each independently Cl - 10 alkyl, ᅳ more preferably d- 6 alkyl, more preferably d- 3 alkyl, and most preferably methyl. Also preferably, ^ is i) an integer from 30 to 60, or ii) 20 or more. An integer of 25 or more, 30 or more, 40 or less, or 35 or less, or iii) 50 or more, or 55 or more, 70 or less, 65 or less, or 60 or less. Also, preferably, Chemical Formula 2 is represented by the following Chemical Formula 2-1:
상기 화학식 4에서， 바람직하게는， ¾는 각각 독립적으로 C2-10 알킬렌이고, ： 보다 바람직하게는 C2_4 알킬렌이고， 가장 바람직하게는 프로판 -1， 3ᅳ디일이다. 바람직하게는， Y2는 알콕시이고 . 보다 바람직하게는 Cw 알콕시이고 , 가장 바람직하게는 메톡시이다. 바람직하게는, R7은 각각 독립적으로 수소， 메틸， 에틸， 프로필， 3- 페닐프로필， 2-페닐프로필, 3- (옥시라닐메특시)프로필, 폴루오로, 클로로, 브로모， 아이오도， 메록시， 에톡시， 프로폭시, 알릴. 2.2,2- 트리플루오로에틸, 3,3,3ᅳ트리폴루오로프로필, 페닐, 또는 나프틸아다.. 또한 바람직하게는, R7은 ᅵ각각 독립적으로 d- ) 알킬이고， 보다 바람직하게는 C-6 알킬이고， 보다 바람직하게는 d-3 알킬이고， 가장 바람직하게는 메틸이다. - 또한 바람직하게는， n3은 i) 30 내지 60의 정수이거나， ii) 20 이상， 25 이상， 또는 30 이상이고, 40 이하， 또는 35 이하의 점수이거나， 또는 iii) 50 이상, 또는 55 이상이고， 70 이하, 65 이하, 또는 60 이하의 정수이다. 또한 바람직하게는， 상기 화학식 4는 하기 화학식 4-1로 표시된다: [화학식 4-1]
And more preferably C 2 _ 4 alkylene, most preferably, propane-1, 3-diyl eu: - preferably in the general formula (4), it is, ¾ are each independently C 2 10 alkylene,. Preferably, Y 2 is alkoxy. More preferably it is Cw alkoxy, most preferably methoxy. Preferably, each R 7 is independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, polouro, chloro, bromo, iodo, Methoxy, ethoxy, propoxy, allyl. 2.2,2-trifluoroethyl, 3,3,3 ᅳ tripoloropropyl, phenyl, or naphthyl. Also preferably, R 7 is each independently d-) alkyl, more preferably Is C- 6 alkyl, more preferably d- 3 alkyl, most preferably methyl. And preferably, n3 is i) an integer from 30 to 60, ii) 20 or more, 25 or more, or 30 or more, 40 or less, or 35 or less, or iii) 50 or more, or 55 or more It is an integer of 70 or less, 65 or less, or 60 or less. Also preferably, Chemical Formula 4 is represented by Chemical Formula 4-1: [Formula 4-1]
특히, 본 발명에서는 화학식 2 내지. 4로 표시되는 반복단위로 구성되는 군으로부터. 선택되는 단위를 1종 이상, 또는 2종 이상으로 포함할 수 있으며， 구체적으로 이를 2종 이상 포함한다는 특징이 있다. 상기 화학식 2 내지 4로 표시되는 반복단위 가운데 2종 이상을 포함하는 경우 상온충격강도， 저온충격강도 및 유동성 물성의 개선 정도가 현저히 증가함을 확인할 수 있었으며， 이는 각각의 반복단위에 의하여 물성 개선 정도가 상호 보완적으로 작용한 결과에 기인한다. 본 발명에서 의미하는 ' 2종 이상의 반복단위 '란. 구조가 상이한 반복단위를 2종 이상 포함하거나 또는 구조는 동일하나 화학식 2 내지 4의 구조 내 실리콘 옥사이드의 반복단위 수 (nl , n2 , n3)가 상이한 2종 이상을 포함하는 것을 의미한다. 구체적으로, 본 발명에서 의미하는 ' 2종 이상의 반복단위 '란, 1). 화학식 2로 표시되는 반복단위 1종 및 화학식 3으로 표시되는 반복단위 1종, 2) 화학식 2로 표시되는 반복단위 1종 및 화학식 4로 표시되는 반복단위 1종 또는 3) 화학식 3으로 표시되는 반복단위 1종 및 화학식 4로 표시되는 반복단위 1종을 포함하는 것을 의미한다. 상기 2종 이상의 반복단위로 1) 화학식 2로 표시되는 반복단위 1종 및 화학식 3으로 표시되는 반복단위 1종， 2) 화학식 2로 표시되는 반복단위 1종 및 화학식 4로'표시되는 반복단위 1종， 또는 3) 화학식 3으로 표시되는
반복단위 1종 및 화학식 4로 표시되는 반복단위 1종과 같이 2종의 반복단위를 포함하는 각각의 경우에서， 2종의 반복단위 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 85:15이고， 보다 바람직하게는 20:80 내지 80:20이다. 상기 화학식 2 내지 4로 표시되는 반복 단위는 각각 하기 화학식 2ᅳIn particular, in the present invention, the formula (2). From the group consisting of repeating units represented by four. One or more selected units, or two or more types may be included, and specifically, two or more types thereof may be included. In the case of including two or more of the repeating units represented by Formulas 2 to 4, it was confirmed that the improvement of the room temperature impact strength, the low temperature impact strength, and the fluidity properties were remarkably increased. Is due to the complementary effect of "A 2 or more types of repeating unit" means in this invention. It means that the structure includes two or more repeating units having different structures, or two or more repeating units having the same structure but different numbers of repeating units (nl, n2, n3) of silicon oxide in the structure of Formulas 2 to 4. Specifically, the term 'two or more repeating units' means in the present invention, 1) . One repeating unit represented by Formula 2 and one repeating unit represented by Formula 3, 2) one repeating unit represented by Formula 2 and one repeating unit represented by Formula 4, or 3) repeating represented by Formula 3 It means to include one unit and one repeating unit represented by the formula (4). The 2 repeat at least one unit: 1) a repeating unit represented by the formula (2) first species and the repeating unit one compound represented by formula (3), 2), recurring unit to be displayed one of a repeating unit 1 species, and the formula (4) represented by the formula (2) Species, or 3) represented by the formula In each case including two repeating units such as one repeating unit and one repeating unit represented by Formula 4, the weight ratio between the two repeating units may be 1:99 to 99: 1. Preferably it is 3: 97-97: 3 5: 95-95: 5 10: 90-90: 10, or 15: 85-85: 15, More preferably, it is 20: 80-80: 20. Repetitive units represented by Formulas 2 to 4 are each represented by the following Formula 2 '
2로 표시되는 실록산 화합물， 하기 화학식 3-2로 표시되는 실록산 화합물 및 하기 화학식 4— 2로 표시되는 실록산 화합물로부터 유래한다. It is derived from the siloxane compound represented by 2, the siloxane compound represented by following formula (3-2), and the siloxane compound represented by following formula (4-2).
[화학식 2-2] [Formula 2-2]
상기 화학식 2-2에서 In Chemical Formula 2-2
Xi, R5 및 nl은 앞서 화학식 2에서 정의한 바와 같고 Xi, R 5 and nl are as defined above in formula (2)
상기 화학식 3-2에서 In Chemical Formula 3-2
X2, Y1; R6 및 n2는 앞서 화학식 3에서 정의한 바와 같고，X 2 , Y 1; R 6 and n 2 are the same as defined in Formula 3,
-2] -2]
상기 화학식 4-2에서
¾， Y2 , R7 및 n3은 앞서 화학식 4에서 정의한 바와 같다. 상기 '실록산 화합물로부터 유래한다'의 의미는, 상기 각각의 실록산 화합물의 하이드록시기와 카보네이트 전구체가 반응하여 상기 각각의 화학식 2 내지 4로 표시되는 반복 단위를 형성하는 것을 의미한다. 또한， 상기 화학식 2 내지 , 4의 반복 단위의 형성에 사용할 수 있는 카보네이트 전구체는， 앞서 설명한 화학식 1의 반복 단위의 형성에 사용할 수 있는 카보네이트 전구체에서 설명한 바와 같다. 또한， 상기 화학식 2-2， 3-2 및 4-2로 표시되는 화합물은 각각 하기 반응식 1 내지 3의 방법으로 제조할 수 있다. In Chemical Formula 4-2 ¾, Y 2 , R 7 and n 3 are the same as defined in Formula 4 above. 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 each of Chemical Formulas 2 to 4 above. In addition, the carbonate precursors that can be used to form the repeating units of Formulas 2 to 4 are the same as those described above for the carbonate precursors that can be used to form the repeating units of Formula 1. In addition, the compounds represented by Chemical Formulas 2-2, 3-2, and 4-2 may be prepared by the methods of the following Schemes 1 to 3, respectively.
[반응식 1] Scheme 1
2-2 상기 반응식 1에서， 2-2 in Scheme 1,
'는 C2-10 알케닐이고, , R5 및 nl은 앞서 화학식 1에서 정의한 바와 같고, . 'It is C 2 - 10 alkenyl, and Al,, R 5, and nl are as defined above in formula (1).
[반응식 2]
Scheme 2
8 8
Χ2'는 C2 10 알케닐이고， ¾， Y1; R6 및 화학식 2에서 정의한 바와 같고， Χ 2 ′ is C 2 10 alkenyl, ¾, Y 1; As defined in R 6 and Formula 2,
[반웅식 3] [Banungsik 3]
4-2 4-2
상기 반응식 3에서, In Scheme 3,
¾'는 C2— 10 알케닐이고， ¾， Y2). R7 및 n3은 앞서 화학식 3에서 정의한 바와 같다.
상기 반응식 1 내지 3의 반웅은, 금속 촉매 하에 수행하는 것이 바람직하다ᅳ 상기 금속 촉매로는 Pt 촉매를 사용하는 것이 바람직하며, Pt 촉매로 애쉬바이 (Ashby)촉매 , 칼스테드 (Karstedt )촉매， 라모레오 (Lamoreaux)촉매， 스파이어 (Spe i er )촉매， PtCl2(C0D) , PtC l 2(벤조니트릴 )2， 및 PtBr6로 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 이상, 또는 0.01 중량부 이상이고， 1 증량부 이하， 0. 1 중량부 이하， 또는 0. 05 중량부 이하로 사용할 수 있다. 또한.， 상기 반응 온도는 so 내지 ioo°c가 바람직하다. 또한， 상기 반웅 시간은 1시간 내지 5시간이 바람직하다. 또한, 상기 화학식 6， 8 또는 10으로 표시되는 화합물은 오르가노디실록산과 오르가노시클로실록산을 산 촉매 하에서 반웅시켜 제조할 수 있으며， 상기 반응 물질의 함량을 조절하여 nl , n2 및 η3을 조절할 수 있다. 상기 반응 온도는 50 내지 70 °C가 바람직하다. 또한， 상기 반웅 시간은 1시간 내지 6시간이 바람직하다. ᅵ상기 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. ' 상기 오르가노디실록산은， 상기 오르가노시클로실록산 100 중량부를 기준으로 0. 1 중량부 이상, 또는 2중량부 이상이고， 10 중량부 이하, 또는 8 중량부 이하로 사용할 수 있다.
상기 산 촉매로는 H2S04, HCIO4, AICI3, SbCl5. SnCl4 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 증량부 이상이고， 10 중량부 이하， 5 증량부 이하， 또는 3 중량부 이하로 사용할 수 있다. 특히, 상기 화학식 1 내지 3으로 표시되는 반복 단위의 함량을 조절하여， 코폴리카보네이트의 물성을 개선할 수 있으며， 상기 반복 단위의 중량비는 코폴리카보네이트 중합에 사용되는 실록산 화합물， 예컨대 상기 화학식 1-2, 2-2 및 3— 2로 표시되는 실록산 화합물의 증량비에 대웅된다. 코폴리카보네이트수지 ¾ 'is C 2 — 10 alkenyl, ¾, Y 2). R 7 and n 3 are the same as defined in Formula 3 above. It is preferable to perform the reactions of the reaction schemes 1 to 3 under a metal catalyst. As the metal catalyst, Pt catalyst is preferably used. As the Pt catalyst, an ashby catalyst, a Karlstedt catalyst, and a lamo are used. At least one selected from the group consisting of a Lamoreaux catalyst, a Speyer catalyst, PtCl 2 (C0D), PtC l 2 (benzonitrile) 2 , and PtBr 6 can be used. The metal catalyst is 0.001 parts by weight or more, 0.005 parts by weight or more, or 0.01 parts by weight or more based on 100 parts by weight of the compound represented by Formula 11, 13, or 15, 1 part by weight or less, 0.1 part by weight or less, or It can be used at 0.05 parts by weight or less. In addition, the reaction temperature is preferably so to ioo ° c. In addition, the reaction time is preferably 1 hour to 5 hours. In addition, the compound represented by Formula 6, 8 or 10 can be prepared by reacting the organodisiloxane and organocyclosiloxane under an acid catalyst, it is possible to control the content of the reactant to control nl, n2 and η3 . The reaction temperature is preferably 50 to 70 ° C. In addition, the reaction time is preferably 1 hour to 6 hours. As the organodisiloxane, one or more selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, nuxamethyldisiloxane and nuxaphenyldisiloxane may be used. As the organocyclosiloxane, an organocyclotetrasiloxane can be used as an example, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. "The Organic nodi siloxanes, the organo cyclosiloxanes and 100 parts by weight based on the 0.1 parts by weight or more, or 2 parts by weight or more, it is possible to use not more than 10 parts by weight or less, or 8 parts by weight. The acid catalyst is H 2 SO 4 , HCIO 4 , AICI 3, SbCl 5 . At least one selected from the group consisting of SnCl 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. In particular, by adjusting the content of the repeating unit represented by the formula 1 to 3, it is possible to improve the physical properties of the copolycarbonate, the weight ratio of the repeating unit is a siloxane compound used for the polymerization of the copolycarbonate, for example the formula 1- It is based on the increase ratio of the siloxane compound represented by 2, 2-2, and 3-2. Copolycarbonate Resin
상기 코폴리카보네이트 수지 조성물은 방향족 폴리카보네이트계 제 1 반복 단위 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함하는 코폴리카보네이트 수지를 포함할 수 있다. 상기 방향족 폴리카보네이트계 제 1 반복 단위 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함하는 코폴리카보네이트 수지에서， 상기 방향족 폴리카보네이트계 제 1 반복 단위 및 하나 이상꾀 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. 또한， 상기 방향족 폴리카보네이트계 제 1 반복 단위 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함하는 코폴리카보네이트 수지는 상기 제 2 반복단위 0.001 내지 10 중량 ¾를 포함할 수 있다. 상기 제 2반복단위 함량이 지나치게 감소할 경우， 상기 제 2 반복단위에 의한 상온충격강도， 저온충격강도 및 유동성 물성의 개선이 충분히 구현되기 어려울 수 있다ᅵ. 반면ᅳ 상기 제 2 반복단위 함량이
지나치게 증가할 경우， 상기 코폴리카보네이트 수지의 분자량이 과도하게 증가하면서 흐름성 및 성형가공성이 감소할 수 있다. 상기 방향족폴리카보네이트계 게 1 반복 단위 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계게 2 반복 단위를 포함하는 코폴리카보네이트 수지의 중량 평균 분자량은 1,000 내지 100,000 g/mol , 또는 5,000 내지 50,000 g/mol 일 수 있다. 상기 중량 평균 분자량 범위 내에서 상기 코폴리 보네이트 수지의 연성 (ductility) 및 YI가 '향상될 수 있다. 상기 코폴리카보네이트 수지는， 상기 화학식 2—2 내지 4-2로 표시되는 화합물로 구성되는 군으로부터 선택되는 1종 이상， . 또는 2종 이상의 화합물과 방향족 디올 화합물 및 카보네이트 전구체를 포함하는 조성물을 중합하는 단계를 포함하는 제조방밥으로 제조될 수 있다. The copolycarbonate resin composition may include a copolycarbonate resin including an aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond. In the copolycarbonate resin comprising the aromatic polycarbonate-based first repeating unit and the aromatic polycarbonate-based second repeating unit having at least one siloxane bond, the aromatic polycarbonate-based first repeating unit and the at least one siloxane bond The molar ratio of the aromatic polycarbonate-based second repeating unit may be 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 is 1: 0.001 to 1: 1, Or 1: 0.005 to 1: 0.1, or 1: 0.01 to 1: 0.03. In addition, the copolycarbonate resin including the aromatic polycarbonate-based first repeating unit and the aromatic polycarbonate-based second repeating unit having one or more siloxane bonds may include 0.001 to 10 weight ¾ of the second repeating unit. When the first over-reduced second repeat unit content, the first is an improvement in room temperature impact strength, low temperature impact strength and fluidity properties according to the second repeat unit it can be difficult to fully implement i. While the second repeating unit content is When excessively increased, the flowability and moldability may decrease while the molecular weight of the copolycarbonate resin is excessively increased. The weight average molecular weight of the copolycarbonate resin including the aromatic polycarbonate-based crab 1 repeating unit and the aromatic polycarbonate-based 2 repeating unit having at least one siloxane bond is 1,000 to 100,000 g / mol, or 5,000 to 50,000 g / mol day Can be. In the weight average molecular weight range it can be improved ductility (ductility), and YI of the copolyester carbonate resin. It said copolycarbonate resin is at least one member selected from the group consisting of compounds represented by the formula 2-2 to 4-2,. Or it may be prepared in a manufacturing method comprising the step of polymerizing a composition comprising two or more compounds, an aromatic diol compound and a carbonate precursor.
상기 방향족 디올 화합물와 카보네이트 전구체에 관한 내용은 상기 방향족 ¾리카보네이트계 제 1 반복 단위에서 상술한 바와 같다. 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- polymerization) 후 커플링체를 투입한 다음， 다시 중합시키는 단계를 포함할 수 있고， 이 경우 고분자량의 코폴리카보네이트를 얻을 수 있다. 상기 계면중합에 사용되는 물질들은 코폴리카보네이트의 중합에 사용될 수 있는 물질이면 특별히 제한되지 않으며， 그 사용량도 필요에 따라 조절할 수 있다. Details of the aromatic diol compound and the carbonate precursor are the same as those described above in the aromatic ¾ricarbonate-based first repeating unit. As the polymerization method, may, using the interfacial polymerization method as an example, a case is possible polymerization at normal pressure and low temperature, and has an effect which facilitates the molecular weight control. 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 the pre-polymerization, the coupling body is introduced, and then polymerized again. In this case, a high molecular weight copolycarbonate may be obtained. The material used for the interfacial polymerization is not particularly limited as long as it is a material that can be used for the polymerization of the copolycarbonate, the amount of use may be adjusted as necessary.
상기 산결합제로는 일례로 수산화나트륨， 수산화칼륨 등의 알칼리금속 수산화물 또는 피리딘. 등의 아민 화합물을 사용할 수 있다.
상기 유기 용매로는 통상 코폴리카보네이트의 중합에 사용되는 용매이면 특별히 제한되지 않으며. 일례로 메틸렌클로라이드, 클로로벤젠 등의 할로겐화 탄화수소를 사용할 수 있다. 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 반웅 촉진제를 추가로 사용할 수 있다. 상기 계면중합의 반응 온도는 0 내지 40°C인 것이 바람직하며, 반웅 시간은 10분 내지 5시간이 바람직하다. 또한， 계면중합 반응 중, pH는 9이상 또는 11이상으로 유지하는 것이 바람직하다. 또한, 상기 계면중합은 분자량 조절제를 더 포함하여 수행할 수 있다. 상기 분자량 조절제는 중합개시 전， 증합개시 중 또는 중합개시 후에 투입할 수 있다. 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. 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 증량부 이하로 포함되고， 이 범위 내에서 원하는 분자량을 얻을 수 있다. ' 상기 중합에 의하여 . 상기 화학식 2-2 내지 4— 2로 표시되는 화합물로 구성되는 군으로부터 선택되는 1종 이상, 또는 2종 이상의 화합물과 방향족
디을 화합물은 상기 화학식 1 내지 4로 표시되는 반복단위를 형성할 수 있다. 구체적으로, 상기 화학식 2_2 내지 4-2로 표시되는 화합물로 구성되는 군으로부터 선택되는 1종 이상. 또는 2종 이상의 화합물과 방향족 디올 화합물의 하이드특시기와 카보네이트 전구체가 반응하여 상기 화학식 1 내지 4로 표시되는 반복단위를 형성할 수 있다. 바람직하게는， 본 발명에 따른 코폴리카보네이트 수지는 상기 화학식 1-1로 표시되는 반복 단위， 상기 화학식 2-2로 표시되는 반복 단위 및 상기 화학식 3-2로 표시되는 반복 단위를 포함한 코폴리카보네이트 수지를 포함할 수 있다. 특히， 상기 방향족 폴리카보네이트계 제 1 반복 단위와 함께 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위로 상기 화학식 2로 표시되는 반복 단위 및 상기 화학식 3으로 표시되는 반복 단위를 포함하는 코폴리카보네이트의 경우， 상기 화학식 2로 표시되는 반복 단위와 상기 화학식 3으로 표시되는 반복 단위의 함량을 조절하여， 코폴리카보네이트 수지의 저온충격강도와 유동성을 동시에 개선할 수 있다. 폴리실록산고분자 Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or pyridine. Amine compounds, such as these, can be used. The organic solvent is not particularly limited as long as it is a solvent usually used for polymerization of copolycarbonate. For example, halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used. Also. In order to promote the reaction, the interfacial polymerization may be carried out by reaction agents such as tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds. Can be used additionally. The reaction temperature of the interfacial polymerization is preferably 0 to 40 ° C, the reaction time is preferably 10 minutes to 5 hours. Moreover, it is preferable to maintain pH at 9 or more or 11 or more during interfacial polymerization reaction. In addition, the interfacial polymerization may be performed by further including a molecular weight regulator. The molecular weight regulator may be added before the start of polymerization, during the start of polymerization, or after the start of polymerization. Mono-alkylphenols may be used as the molecular weight regulator, and the mono-alkylphenols are, for example, p-tert-butylphenol, P-cumylphenol, decylphenol. Dodecylphenol. At least one member selected from the group consisting of tetradecylphenol, nuxadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol. Preferably it is p-tert- butylphenol, In this case, a 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 based on 100 parts by weight of an aromatic diol compound. It is contained in 10 weight part or less, 6 weight part or less, or 5 weight part or less, and can obtain desired molecular weight within this range. By the polymerization. At least one selected from the group consisting of compounds represented by Formulas 2-2 to 4-2, or at least two compounds and aromatic The compound may form a repeating unit represented by Chemical Formulas 1 to 4 above. More specifically, the general formula (2) _2 to 4-2 at least one member selected from the group consisting of compounds represented by the following. Alternatively, two or more compounds, a hydride group of an aromatic diol compound, and a carbonate precursor may react to form a repeating unit represented by Chemical Formulas 1 to 4. Preferably, the copolycarbonate resin according to the present invention is a copolycarbonate comprising a repeating unit represented by Formula 1-1, a repeating unit represented by Formula 2-2 and a repeating unit represented by Formula 3-2. Resin may be included. Particularly, a copoly comprising a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3 as an aromatic polycarbonate-based second repeating unit having at least one siloxane bond together with the aromatic polycarbonate-based first repeating unit. In the case of carbonate, by controlling the content of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3), it is possible to improve the low-temperature impact strength and fluidity of the copolycarbonate resin at the same time. Polysiloxane polymer
상기 코폴리카보네이트 수지 조성물은 탄소수 2 이상， 또는 2 내지 The copolycarbonate resin composition has 2 or more carbon atoms, or 2 to
500. 또는 2 내지 100 , 또는 2 내지 50의 탄화수소계 작용기를 함유한 폴리실록산 고분자를 포함할 수 있다. 상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자는 탄소수 2 이상의 탄화수소계 작용기를 통해 가교구조를 형성하여 외부의 충격을 흡수하는 역할 뿐만 아니라, 화학적으로 안정하여 내화학특성을 극대화시킬 수 있다. 상기 탄화수소계 작용기는 지방족 탄화수소 작용기， '지환족 탄화수소 작용기 및 방향족 탄화수소 작용기로 이루어진 군에서 선택된 1종 이상을 포함할 수 있다. 상기 지방족 탄화수소 작용기, 지환족 탄화수소 작용기ᅳ 또는 방향족 탄화수소 작용기는 각각 할로겐기, 알킬기， 알케닐기,
알콕시기, 아릴기ᅳ 아릴알킬기, 아릴알케닐기. 헤테로 고리기， 카바졸릴기， 플루오레닐기， 니트릴기 및 아세틸렌기로 아루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환될 수 있다. 상기 지환족 탄화수소 작용기는 탄소수 3 이상， 또는 3 내지 50의 단환 또는 다환의 시클로알킬기를 포함할 수 있고， 상기 방향족 탄화수소 작용기는 ¾소수 6 이상， 또는 6 내지 50의 단환 또는 다환의 아릴기를 포함할 수 있다. 상기 단환이란 작용기에 단일의 고리가 포함된 것을 의미하며, 다환이란 작용기 내에 2이상꾀 고리가 포함된 것을 의미한다. 상기 지방족 탄화수소 작용기는 직쇄 또는 분지쇄의 알킬기 또는 비닐계 작용기를 포함할 수 있다. 상기 탄소수 2 이상의 직쇄 또는 분지쇄의 알킬기는 탄소수 1의 메틸기를 제외한알킬기를 와미한다. 상기 비닐계 작용가는 비닐 (vinyl )기 또는 비닐기로부터 유도된 작용기를 포함하며， 상기 비닐기는 -CH=CH2로 표시되는 작용기로, 에틸렌 (¾C=CH2) 분자에서 수소원자 하나가 없는 작용기를 의미한다. 상기 비닐기로부터 유도된 작용기란, 상기 비닐기에 포함된 수소원자 일부가 다른 원자단으로 치환된 작용기를 의미한다. 구체적으로， 상기 비닐계 작용기는 하기 화학식 11로 표시될 수 있다. [화학식 11] 500. or polysiloxane polymers containing 2 to 100, or 2 to 50, hydrocarbon-based functional groups. The polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms may form a crosslinked structure through a hydrocarbon-based or more hydrocarbon-based functional group to absorb external shocks, and may be chemically stable to maximize chemical resistance. The hydrocarbon-based functional group may include an aliphatic hydrocarbon functional group, at least one selected from the group consisting of alicyclic hydrocarbon and aromatic hydrocarbon functional groups functional groups. The aliphatic hydrocarbon functional group, alicyclic hydrocarbon functional group or aromatic hydrocarbon functional group may each be a halogen group, an alkyl group, an alkenyl group, Alkoxy group, an aryl group, an arylalkyl group, and an aryl alkenyl group. It may be substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group, a carbazolyl group, a fluorenyl group, a nitrile group and an acetylene group. The alicyclic hydrocarbon functional group may include a monocyclic or polycyclic cycloalkyl group having 3 or more carbon atoms, or 3 to 50 carbon atoms, and the aromatic hydrocarbon functional group may include 6 or more minor atoms, or 6 to 50 monocyclic or polycyclic aryl groups. Can be. The monocyclic means that a single ring is included in the functional group, polycyclic means that two or more ring is contained in the functional group. The aliphatic hydrocarbon functional group may include a linear or branched alkyl group or a vinyl functional group. The linear or branched alkyl group having 2 or more carbon atoms is an alkyl group except for a methyl group having 1 carbon atom. The vinyl functional group includes a vinyl group or a functional group derived from a vinyl group, wherein the vinyl group is a functional group represented by -CH = CH 2, and a functional group without one hydrogen atom in an ethylene (¾C = CH 2 ) molecule. Means. The functional group derived from the vinyl group means a functional group in which a part of the hydrogen atoms included in the vinyl group is substituted with another atomic group. Specifically, the vinyl-based functional group may be represented by the following formula (11). [Formula 11]
*는 결합지점을 의미하며， * Means the coupling point,
， , R10는 각각 독립적으로 수소, 탄소수 1 내지 20의 직쇄 또는
분지쇄의 알킬기， 탄소수 6 내지 20의 아릴기， 탄소수 2 내지 20의 알케닐기， 탄소수 1 내지 20의 알콕시기, 탄소수 3 내지 20의' 시클로알킬기， 케톤기 또는 에스터기이다. 상기 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬기, 탄소수 6 내지,, R 10 are each independently hydrogen, a straight chain having 1 to 20 carbon atoms or Alkyl group branched-chain, "cycloalkyl group having 6 to 20 carbon atoms of the aryl group, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, having 3 to 20 carbon atoms in a ketone group or an ester group. The linear or branched alkyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms
20의 아릴기， 탄소수 2 내지 20의 알케닐기, 탄소수 1 내지 20의 알콕시기, 탄소수 3 내지 20의 시클로알킬기， 케톤기 또는 에스터기 각각은 할로겐기, 알킬기， 알케닐기， 알콕시기， 아릴기， 아릴알킬기, 아릴알케닐기， 헤테로 고리기， 카바졸릴기, 플루오레닐기， 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환될 수 있다. 상기 아릴기는 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디컬로 단환식 또는 다환식일 수 있다. 시클로알킬기는 특별히 한정되지 않으나， 단환식 또는 다환식일 수 았다. 상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자는 탄소수 2 이상의 탄화수소계 작용기 0.001 내지 10 몰%， 또는 0.01 내지 1 몰%, 또는 0.05 내지 0.5 몰%를 포함할 수 있다. 상기 탄소수 2 이상의 탄화수소계 작용기가 상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자에 대해 0.001 몰% 미만이면， 상기 탄소수. 2 이상의 탄화수소계 작용기에 의한 내충격성, 내화학성 및 유동성 향상 효과가 층분히 구현되기 어려을 수 있으며, 상기 탄소수 2 이상의 탄화수소계 작용기가 상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자에 대해 10 몰¾ 초과이면， 반응성이 높은 탄소수 2 이상의 탄화수소계 작용기가 지나치게 많아짐에 따라， 고분자 수지와의 상용성이 떨어져 기계적 물성 내지 화학적 물성이 저하될 수 있다. 상기 탄소수 2 아상의 탄화수소계 작용기를 함유한 폴리실록산 고분자는 탄소수 2 이상의 탄화수소계 작용기를 포함한 폴리실록산 반복단위 및 폴리디메틸실록산 반복단위를 포함할 수 있다.
구체적으로. 상기 탄소수 2 이상의 탄화수소계 작용기를 포함한 폴리실록산 반복단위는 하기 화학식 12로 표시되는 반복단위를 포함할 수 있다. An aryl group of 20, an alkenyl group of 2 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, a ketone group or an ester group may each be a halogen group, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, It may be substituted or unsubstituted with one or more substituents selected from the group consisting of an arylalkyl group, an arylalkenyl group, a heterocyclic group, a carbazolyl group, a fluorenyl group, a nitrile group and an acetylene group. The aryl group can be monocyclic or polycyclic in organic radicals derived from aromatic hydrocarbons by one hydrogen removal. The cycloalkyl group is not particularly limited, but may be monocyclic or polycyclic. The polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms may include 0.001 to 10 mol%, or 0.01 to 1 mol%, or 0.05 to 0.5 mol% of C 2 or more hydrocarbon-based functional groups. The carbon number is less than 0.001 mol% relative to the polysiloxane polymer containing the hydrocarbon group having at least 2 carbon atoms . Impact resistance, chemical resistance, and fluidity improvement effect by two or more hydrocarbon-based functional groups may be difficult to be sufficiently realized, and the C 2 or more hydrocarbon-based functional group is 10 mol¾ to the polysiloxane polymer containing the C 2 or more hydrocarbon-based functional group. If exceeded, the highly reactive hydrocarbon group having 2 or more carbon atoms is excessively high, and thus the compatibility with the polymer resin may be degraded, thereby reducing the mechanical and chemical properties. The polysiloxane polymer containing a hydrocarbon-based functional group having 2 or more carbon atoms may include a polysiloxane repeating unit and a polydimethylsiloxane repeating unit including a hydrocarbon-based functional group having 2 or more carbon atoms. Specifically. The polysiloxane repeating unit including the hydrocarbon group having 2 or more carbon atoms may include a repeating unit represented by the following Formula 12.
[화학식 12] [Formula 12]
：傘
상기 화학식 12에서， ᅳ ： 傘 In Chemical Formula 12, ᅳ
*는 결합지점을 의미하며， * Means the coupling point,
Rn 내지 R12 중 적어도 하나 이상은 탄소수 2 이상의 탄화수소계 작용기이고， 나머지는 메틸기이다. At least one of Rn to R 12 is a hydrocarbon-based functional group having at least 2 carbon atoms, and the rest are methyl groups.
보다 구체적으로 상기 화학식 12에서 Ru은 상기 탄소수 2 이상의 탄화수소계 작용기이고， R12는 메틸기일 수 있다. 상기 폴리디메틸실록산 반복단위는 하기 화학식 13으로 표시되는 ᅵ반복단위를 포함할 수 있다. . ' More specifically, in Formula 12, Ru is a hydrocarbon group having 2 or more carbon atoms, and R 12 may be a methyl group. The polydimethylsiloxane repeating unit may include? Repeating unit represented by the following formula (13). . '
[화학식 13] [Formula 13]
상기 폴리디메틸실록산 반복단위에 대한 상기 탄소수 2 탄화수소계 작용기를 포함한 폴리실록산 반복단위 몰수비가 0.00001 0.1, 또는 0.0005 내지. 0.01, 또는 0.0007 내지 0.0이일 수 있다.
상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자는 상기 폴리실록산 고분자의 말단에 결합한 상기 탄소수 2 이상의 탄화수소계 작용기를 더 포함할 수 있다. 상기 폴리실록산 고분자의 말단이란， 상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자의 폴리실록산 주사슬의 양쪽 끝단부를 의미하며, 상기 탄소수 2 이상의 탄화수소계 작용기는 폴리실록산 주사슬의 양말단 모두 또는 어느 일말단에 결합할 수 있다. 즉， 상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자는 탄소수 2 이상의 ,탄화수소계 작용기를 포함한 폴리실록산 반복단위 및 폴리디메틸실록산 반복단위를 포함한 주쇄 및 상기 주쇄의 말단에 결합한 탄소수 2 이상의 탄화수소계 작용기를 포함할 수 있디- . 구체적으로， 상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자는 하기.화학식 14로 표시되는 화합물을 포함할 수 있다. The molar ratio of the polysiloxane repeating units including the C 2 hydrocarbon-based functional group to the repeating polydimethylsiloxane units is 0.00001 0.1, or 0.0005 to 0.001. 0.01, or 0.0007 to 0.0. The polysiloxane polymer containing the hydrocarbon-based functional group having 2 or more carbon atoms may further include the hydrocarbon-based functional group having 2 or more carbon atoms bonded to the terminal of the polysiloxane polymer. The terminal of the polysiloxane polymer means both ends of the polysiloxane main chain of the polysiloxane polymer containing the hydrocarbon group having 2 or more carbon atoms, and the hydrocarbon group having 2 or more carbon atoms has both or both ends of the polysiloxane main chain. Can be combined. That is, the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms has a carbon- 2 or more hydrocarbon-based functional group bonded to a main chain including a polysiloxane repeating unit and a polydimethylsiloxane repeating unit including a hydrocarbon-based functional group and 2 or more carbon atoms. Can contain. Specifically, the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms may include a compound represented by the following Chemical Formula 14.
[화학식 14] [Formula 14]
m은 10 내지 20의 정수이고， n은 6 , 000 내지 11.500의 정수이며， 탄소수 2 이상의 탄화수소계 작용기이다. 상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자의 함량은 전체 코폴리카보네이트 수지 조성물 중량을 기준으로 0.01 중량 % 내지 10 중량 %， 또는 0. 1 중량 % 내지 5 중량 %， 또는 0.5 중량 % 내지 4 중량%일 수 있다. 상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자의 함량이 지나치게 작아지면， 상기 탄소수 2 이상의
탄화수소계 작용기를 함유한 폴리실록산 고분자에 의한 내화학성 및 내충격성 향상 효과가 구현되기 어려울 수 있다. 또한， 상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자의 함량이 지나치게 커질 경우에는， 상기 코폴리카보네이트 수지 조성물의 기계적 또는 화학적 물성이 저하될 수 있다. 상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자의 중량평균분자량은 100 , 000 내지 1 , 000 , 000 g/mol , 또는 300 , 000 내지 900.000 g/mo l , 또는 500 , 000 내지 850 , 000 g/mol 일 수 있다. 상기 중량 평균 분자량을 측정하는 방법의 예가 크게 한정되는 것은 아니나， 예를 들어 GPC법에 의해 측정한 폴리스티렌 환산의 중량 평균 분자량을 이용할 수 있다. 코폴리카보네이트수지 조성물 m is an integer of 10-20, n is an integer of 6,000-11.500, and is a C2 or more hydrocarbon-type functional group. The content of the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms is 0.01 to 10% by weight, or 0.01 to 5% by weight, or 0.5 to 4% by weight based on the total weight of the copolycarbonate resin composition. Weight percent. When the content of the polysiloxane polymer containing the hydrocarbon-based functional group of 2 or more carbon atoms is too small, the 2 or more carbon atoms Chemical resistance and impact resistance improvement effect by the polysiloxane polymer containing a hydrocarbon-based functional group may be difficult to implement. In addition, when the content of the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms is too large, the mechanical or chemical properties of the copolycarbonate resin composition may be lowered. The weight average molecular weight of the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms is 100, 000 to 1, 000, 000 g / mol, or 300, 000 to 900.000 g / mol, or 500, 000 to 850, 000 g / mol. Although the example of the method of measuring the said weight average molecular weight is not specifically limited, For example, the weight average molecular weight of polystyrene conversion measured by the GPC method can be used. Copolycarbonate Resin Composition
상기 코폴리카보네이트 수지 조성물은 방향족 폴리카보네이트계 저 U 반복 단위 및 하나 이상의 실록산 결합올 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함한 코폴리카보네이트 수지; 및 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자；를 포함할 수 있다. 상기 코폴리카보네이트 수지 조성물을 제조하는 방법의 예가 크게 한정되는 것은 아니나， 예를 들어, 상기 코폴리카보네이트 수지와 폴리실록산 고분자를 흔합하는 방법을 들 수 있다. 구체적으로 상기 코폴리카보네이트 수지와 폴리실록산 고분자를 혼합하는 방법의 예로는 상기 코폴리카보네이트 수지에 폴리실록산 고분자를 첨가하고 믹서를 이용하여 흔합하거나. 상기 흔합물을 압출기로 압출성형하여 마스터 배치 (Master batch)를 제조하는 방법을 들 수 있다. 상기 마스터 배치의 형태의 예가 한정되는 것은 아니나, 예를 들어 펠릿 (pel let ) 형태를 가질 수 있다. 또한. 상기 코폴리카보네이트 수지 조성물은 최종 제조되는 물품의
목쩍에 따라， 공지된 다양한 종류의 첨가제， 수지 등을 더 포함할 수 있다. 상기 첨가제의 예로는 산화방지제, 열안정제, 광안정화제 , 가소제， 대전방지제, 핵제. 난연제, 활제， 층격보강제， 형광증백제， 자외선흡수제, 안료 및 염료로 이루어진 군으로부터 선택된 1종 이상을 들 수 있다. 상기 코폴리카보네이트 수지 조성물은 ASTM D256( l/8 inch , Notched Izod)에 의거하여 -30°C에서 측정한 저온충격강도가 700 J/m 이상일 수 있다. 또한 상기 코폴리카보네이트 수지 조성물은 ASTM D256( l/4 inch , Notched Izod)에 의거하여 -40°C에서 측정한 저은충격강도가 200 J/m 이상일 수 있다. The copolycarbonate resin composition may include a copolycarbonate resin comprising an aromatic polycarbonate-based U repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane linkage; And a polysiloxane polymer containing a hydrocarbon-based functional group having 2 or more carbon atoms. Although the example of the method of manufacturing the said copolycarbonate resin composition is not specifically limited, For example, the method of mixing the said copolycarbonate resin and a polysiloxane polymer is mentioned. Specifically, examples of the method of mixing the copolycarbonate resin and the polysiloxane polymer may be added to the copolycarbonate resin by adding a polysiloxane polymer and mixing using a mixer. And a method for producing a master batch by extruding the mixture with an extruder. Examples of the form of the master batch are not limited, but may have, for example, pellet form. Also. The copolycarbonate resin composition of the final article Depending on the look, it may further include various known additives, resins, and the like. Examples of the additives include antioxidants, heat stabilizers, light stabilizers, plasticizers, antistatic agents, and nucleating agents. And at least one member selected from the group consisting of flame retardants, lubricants, stiffeners, fluorescent brighteners, ultraviolet absorbers, pigments and dyes. The copolycarbonate resin composition may have a low temperature impact strength of 700 J / m or more measured at -30 ° C based on ASTM D256 (l / 8 inch, Notched Izod). In addition, the copolycarbonate resin composition may have a low silver impact strength measured at -40 ° C based on ASTM D256 (l / 4 inch, Notched Izod) more than 200 J / m.
또한 상기 코폴리카보네이트 수지 조성물은 ASTM D1238(300°C , 1.2kg 조건 )에 의거하여 측정한 용융지수가 10 gl 10m i n 미만일 수 있다. 한편, 발명의 다른 구현예에 따르면， 상기 일 구현예의 코폴리카보네이트 수지 조성물을 포함하는 물품이 제공될 수 있다. 바람직하게는, 상기 물품은 사출 성형품이다. 또한， 상기 물품은 일례로 산화방지제， 열안정제， 광안정화제， 가소제， 대전방지제, 핵제， 난연제, 활제, 충격보강제, 형광증백제, 자외선흡수제, 안료 및 염료로 이루어진 군으로부터 선택된 1종 이상을 추가로 포함할 수 있다. 상기 물품의 제조 방법의 예가 크게 한정되는 것은 아니나, 예를 들어， 본 발명에 따른 코폴리카보네이트 수지 조성물， 예를 들어 펠릿형태의 코폴리카보네이트 수지 조성물을 건조시킨 다음 사출성형기로 사출하는 단계를 포함할 수 있다. 상기 코폴리카보네이트 수지 조성물에 관한 내용은 상기 일 구현예에 관하여 상술한 내용을 포함한다. In addition, the copolycarbonate resin composition may be less than 10 gl 10m in melt index measured according to ASTM D1238 (300 ° C, 1.2kg conditions). Meanwhile, according to another embodiment of the present invention, an article including the copolycarbonate resin composition of the above embodiment may be provided. Preferably, the article is an injection molded article. In addition, the article is at least one selected from the group consisting of antioxidants, thermal stabilizers, photostabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent brighteners, ultraviolet absorbers, pigments and dyes. It can be included as. Examples of the method for producing the article are not limited to, but for example, the step of drying the copolycarbonate resin composition according to the present invention, for example, pellet form copolycarbonate resin composition and then injection into an injection molding machine can do. Information on the copolycarbonate resin composition includes the above-described content with respect to the embodiment.
【발명의 효과】 【Effects of the Invention】
본 발명에 따르면， 수지의 유동성을 유지하면서, 내화학성 및
내충격성. 등의 기계적 물성이 향상된 코폴리카보네이트 수지 조성물 및 이를 포함하는물품이 제공될 수 있다. According to the present invention, the chemical resistance and Impact resistance. Copolycarbonate resin composition and the article containing the same improved mechanical properties can be provided.
【발명을 실시하기 위한 구체적인 내용】 [Specific contents to carry out invention]
발명을 하기의 실시예에서 보다 상세하게 설명한다. 단, 하기의 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기의 실시예에 의하여 한정되는 것은 아니다. The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.
<제조예 1내지 4> <Production example 1-4>
제조예 1: 폴리오르가노실록산 (AP-PDMS, nl=34)의 제조 Preparation Example 1 Preparation of Polyorganosiloxane (AP-PDMS, nl = 34)
옥타메틸시클로테트라실록산 47.6 g(160 mmol), 테트라메틸디실록산 Octamethylcyclotetrasiloxane 47.6 g (160 mmol), tetramethyldisiloxane
2.4 g(17.8 mniol)을 흔합한 후. 상기 혼합물을 옥타메틸시클로테트라실록산 100 중량부 대비 산성백토 (DC-A3) 1 중량부와 함께 3L 플라스크에 넣고 60°C로 4시간 동안 반웅시켰다. 반웅 종료 후 이를 에틸아세테이트로 희석하고 셀라이트 (celite)를 사용하여 빠르게 필터링하였다. 이렇게 수득된 미변성 폴리오르가노실록산의 반복단위 (nl)는 ¾ NMR로 확인한 결과 34이었다. After mixing 2.4 g (17.8 mniol). The mixture was placed in a 3L flask with 1 part by weight of acidic clay (DC-A3) to 100 parts by weight of octamethylcyclotetrasiloxane 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 (nl) of the unmodified polyorganosiloxane thus obtained was found to be 34 NMR.
상기 수득된 말단 미변성 폴리오르가노실록산에 2-알릴페놀 4.81 g(35.9 隱 ol)과 칼스테드 백금 촉매 (Karstedt's platinum catalyst) 0.01 g(50 ppni)을 투입하여 90°C에서 3시간 동안 반웅시켰다. 반웅 종료 후, 미반응 실록산은 120°C, 1 torr의 조건으로 이베이퍼레이션하여 제거하였다. 이렇게 수득한 말단 변성 폴리오르가노실록산을 AP-PDMS(nl=34)로 명명하였다. AP-PDMS는 연황색 오일이며, Varian 500MHz을 이용하여 ¾ NMR을 통해 반복단위 (nl)는 34임을 확인하였으며， 더 이상의 정제는 필요하지 않았다. 제조예 2: 폴리오르가노실록산 (MBHB-PDMS, n2=58)의 제조 4.81 g (35.9 르 ol) of 2-allylphenol and 0.01 g (50 ppni) of Karlstedt's platinum catalyst were added to the terminal unmodified polyorganosiloxane, and the mixture was reacted at 90 ° C. for 3 hours. . After completion of reaction, unreacted siloxane was removed by evaporation at 120 ° C. and 1 torr. The terminal modified polyorganosiloxane thus obtained was named AP-PDMS (nl = 34). AP-PDMS is a light yellow oil, and it was confirmed that the repeating unit (nl) was 34 by ¾ NMR using a Varian 500 MHz, and no further purification was necessary. Preparation Example 2 Preparation of Polyorganosiloxane (MBHB-PDMS, n2 = 58)
옥타메틸시클로테트라실록산 47.60 g(160 mmo ), 테트라메틸디실록산 47.60 g (160 mmo) octamethylcyclotetrasiloxane, tetramethyldisiloxane
1.5 g(ll mmol)을 흔합한 후. 상기 흔합물을 옥타메틸시클로테트라실톡산 100 중량부 대비 산성백토 (DC-A3) 1 중량부와 함께 3L 플라스크에 넣고 60°C로 4시간 동안 반웅시켰다. 반웅 종료 후， 에틸아세테이트로 희석하고
셀라이트를 사용하여 빠르게 필터링하였다. 이렇게 수득된 말단 미변성 폴리오르가노실록산의 반복단위 (n2)는 1H NMR로 확인한 결과 58이었다. After mixing 1.5 g (ll mmol). The mixture was placed in a 3L flask with 1 part by weight of acidic clay (DC-A3) to 100 parts by weight of octamethylcyclotetrasiltoic acid and reacted at 60 ° C. for 4 hours. After completion of reaction, dilute with ethyl acetate Filter 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 폴리오르가노실톡산에 3-메틸부트 -3ᅳ에닐 4ᅳ하이드록시벤조에이트 (3-methylbut-3-enyl 4-hydroxybenzoate) 6.13 g(29.7 mmol)과 칼스테드 백금 촉매 (Karstedt ' s platinum catalyst) 0.01 g(50 ppm)을 투입하여 90°C에서 3시간 동안 반웅시켰다. 반응 종료 후， 미반응 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 ¾ NMR을 통해 반복단위 (n2)는 58임을 확인하였으며， 더 이상의 정제는 필요하지 않았다.. 제조예 3: 코폴리카보네이트 수지의 제조 6.13 g (29.7 mmol) of 3-methylbut-3-enyl 4-hydroxybenzoate and a Carlsted platinum catalyst were added to 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 the reaction was completed, unreacted siloxane was removed by evaporation at 120 ° C. and 1 torr. The terminal modified polyorganosiloxane thus obtained was named MBHB-PDMS (n2 = 58). MBHB-PDMS is a light yellow oil, and the repeat unit (n2) was 58 by ¾ NMR using a Varian 500 MHz. No further purification was required . . Preparation Example 3 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 butyl phenol) 4.3 g과 제조예 1에서 제조한 AP-PDMS(nl=34) 4.73 g 및 제조예 2에서 제조한 MBHB-PDMS(n2=58) 0.53 g의 혼합액을 MCXmethylene chloride)로 용해하여 넣어주었다. 그 다음 TPG(triphosgene) 128 g을 MC에 녹여 pH를 11 이상으로 유지시켜 주면서 1시간 동안 투입하여 반웅시킨 다음 10분 뒤에 TEA(triethylainine) 46 g을 넣어 커플링 (coupling) 반웅을 시켰다ᅳ 총 반웅시간 1시간 20분이 지난 다음 pH를 4로 낮추어 TEA를 제거하였고, 증류수로 3회 세척하여 생성된 증합체의 pH를 6~7 중성으로 맞추었다. 이렇게 얻은 중합체를 메탄올과 핵산 흔합용액에서 재침전시켜 수득한 다음, 이를 120°C에서 건조하여 최종 코폴리카보네이트 수지를 얻었다. 제조예 4: 폴리카보네이트 수지의 제조 To a polymerization reactor water 1784 g, 385 g NaOH, and BPA (bisphenol A) into a 232 g, N 2 atmosphere, were dissolved under a common combined. Here, MCXmethylene was mixed with 4.3 g of PTBP (para-tert butyl phenol), 4.73 g of AP-PDMS prepared in Preparation Example 1 (nl = 34), and 0.53 g of MBHB-PDMS prepared in Preparation Example 2 (n2 = 58). chloride) and added. Then, 128 g of TPG (triphosgene) was dissolved in MC and added for 1 hour while maintaining the pH above 11. After 10 minutes, 46 g of TEA (triethylainine) was added to react the coupling. After 1 hour and 20 minutes, the pH was lowered to 4 to remove TEA, and washed three times with distilled water to adjust the pH of the resulting polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a methanol and nucleic acid mixture solution, which was then dried at 120 ° C. to obtain a final copolycarbonate resin. Preparation Example 4 Preparation of Polycarbonate Resin
중합 반응기에 물 1784 g, NaOH 385 g 및 BPA(bisphenol A) 232 g을 넣고， N2 분위기 하에 흔합하여 녹였다. 그 다음 TPG(triphosgene) 128 g을 MC에 녹여 pH를 11 이상으로 유지시켜 주면서 1시간 동안 투입하여 반웅시킨 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 증합체의 pH를 6~7 중성으로 맞추었다. 이렇게 얻은 중합체를 메탄올과 핵산 흔합용액에서 재침전시켜 수득한 다음， 이를 120°C에서 건조하여 최종 폴리카보네이트 수지를 얻었다ᅳ 제조예 5: 코폴리카보네이트 수지의 제조 1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to the polymerization reactor, and the mixture was dissolved under N 2 atmosphere. Then, 128 g of TPG (triphosgene) was dissolved in MC and added for 1 hour while maintaining the pH above 11. After 10 minutes, 46 g of TEA (triethylamine) was added for coupling. It was a reaction. After 1 hour 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and the resultant polymer was washed three times with distilled water to adjust the pH of the resulting polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a methanol and nucleic acid mixture solution, and then dried at 120 ° C. to obtain a final polycarbonate resin. Preparation Example 5 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 1에서 제조한 AP— PDMS(nl=34) 4.73 g을 MC methylene chloride)로 용해하여 넣어주었다. 그 다음 TPG(tr iphosgene) 128 g을 MC에 녹여 pH를 11 이상으로 유지시켜 주면서 1시간 동안 투입하여 반웅시킨 다음 10분 뒤에 TEACtriethyi amine) 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 증성으로 맞추었다. 이렇게 얻은 중합체를 메탄을과 핵산 흔합용액에서 재침전시켜 수득한 다음, 이를 120°C에서 귄조하여 최종 코폴리카보네이트 수지를 얻었다. <실시예 1내지 4: 코폴리카보네이트 수지 조성물의 제조 > 1784 g of water, 385 g of NaOH, and 232 g of bisphenol A (BPA) were added to the polymerization reactor, and the mixture was dissolved under N 2 atmosphere. Here, 4.3 g of PTBP (para-tert butylphenol) and 4.73 g of AP-PDMS (nl = 34) prepared in Preparation Example 1 were dissolved in MC methylene chloride. Then, 128 g of TPG (tr iphosgene) was dissolved in MC, and the reaction was maintained for 1 hour while maintaining the pH at 11 or higher. After 10 minutes, 46 g of TEACtriethyi amine was added to form a coupling reaction. After 1 hour 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and the resulting polymer was washed three times with distilled water to adjust the pH of the resulting polymer to 6-7 thick. The polymer thus obtained was obtained by reprecipitation of methane in a nucleic acid mixture solution and then quenched at 120 ° C. to obtain a final copolycarbonate resin. <Example 1 to 4: Preparation of copolycarbonate resin composition>
실시여 U Reality U
상기 제조예 3에서 제조한 코폴라카보네이트 수지에 SF39Q0C(KCC사 제조:비닐기 함유량 0.07 몰 %)를 1중량 % 함량으로 첨가하고, 믹서로 흔합하였다. SF39Q0C (manufactured by KCC: vinyl group content: 0.07 mol%) was added to the copolycarbonate resin prepared in Preparation Example 3 in a content of 1 wt%, and mixed with a mixer.
이후， 상기 코폴리카보네이트 수지 조성물 1 증량부에 대하여， 트리스 (2,4-디 -tert—부틸페닐)포스파이트 0.050 증량부. 옥타데실 -3-(3，5_ 디 -tert-부틸ᅳ 4-히드특시페닐)프로피오네이트를 0.010 중량부， 펜타에리스리를테트라스테아레이트를 0.030 중량부 첨가하여， 벤트 부착 Φ30顧 이축압출기를 사용하여 300°C에서 압출하여 펠릿 형태의 코폴리카보네이트 수지 조성물을 제조하였다.
실시여 12 Thereafter, 0.05 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite was added to 1 part by weight of the copolycarbonate resin composition. Φ30 顧 twin-screw extruder with vent by adding 0.010 part by weight of octadecyl-3- (3,5_di-tert-butyl-4-hydricphenyl) propionate and 0.030 part by weight of pentaerythritol tetrastearate Extruded at 300 ° C using to prepare a copolycarbonate resin composition in the form of pellets. Conduct female 12
상기 SF3900C(KCC사 제조: 비닐기 함유량 0.07 몰 %)를 2중량 % 함량으로 첨가한 것을 제외하고， 상기 실시예 1과 동일하게 코폴리카보네이트 수지 조성물을 제조하였다. 실시예 3 A copolycarbonate resin composition was prepared in the same manner as in Example 1, except that SF3900C (manufactured by KCC Corporation: 0.07 mol% of vinyl groups) was added in a content of 2 wt%. Example 3
상기 SF3900CXKCC사 제조: 비닐기 함유량 0.07 몰 %)를 3중량 % 함량으로 첨가한 것을 제외하고, 상기 실시예 1과 동일하게 코폴리카보네이트 수지 조성물을 제조하였다. . Copolycarbonate resin composition was prepared in the same manner as in Example 1 except that SF3900CXKCC Co., Ltd. product: vinyl group content 0.07 mol%) was added in a 3 wt% content. .
<비교예 1 내지 4: 코폴리카보네이트 수지 조성물 및 물품의 제조 > 비교여 u Comparative Examples 1 to 4: Preparation of Copolycarbonate Resin Compositions and Articles
상기 SF3900C(KCC사 제조: 비닐기 함유량 0.07 몰 %)를 첨가하지 않은 것을 제외하고，ᅵ 상기 실시예 1과 동일하게 코폴리카보네이트 수지 조성물을 제조하였다. 비교예 2 Except that SF3900C (manufactured by KCC: 0.07 mol% of vinyl group content) was not added, the copolycarbonate resin composition was prepared in the same manner as in Example 1. Comparative Example 2
상기 SF3900C(KCC사 제조: 비닐기 함유량 0. 07 몰 %)# 첨가하지 않고 상기 제조예 3에서 제조한 코폴리카보네이트 수지 대신 제조예 4에서 제조한 폴리카보네이트 수지를 사용한 것을 제외하고, 상기 실시예 1과 동일하게 코폴리카보네이트 수지 조성물을 제조하였다. 비교여 13 The above Example, except that the SF3900C (manufactured by KCC: vinyl group content: 0.007 mol%) # was used instead of the polycarbonate resin prepared in Preparation Example 4 instead of the copolycarbonate resin prepared in Preparation Example 3. Copolycarbonate resin composition was prepared in the same manner as 1. Compare 13
상기 제조예 5에서 제조한 코폴리카보네이트 수지를 사용하였다. 비교예 4 Copolycarbonate resin prepared in Preparation Example 5 was used. Comparative Example 4
상기 제조예 3에서 제조한 코폴리카보네이트 수지 대신 제조예 4에서 제조한 폴리카보네이트 수지를 사용한 것을 제외하고, 상기 실시예 1과 동일하게 코폴리카보네이트 수지 조성물을 제조하였다ᅳ
<실험예 ： 실시예 및 비교예에서 얻어진 코폴리카보네이트 수지 조성물의 물성 측정 > A copolycarbonate resin composition was prepared in the same manner as in Example 1, except that the polycarbonate resin prepared in Preparation Example 4 was used instead of the copolycarbonate resin prepared in Preparation Example 3. Experimental Example: Measurement of Physical Properties of Copolycarbonate Resin Compositions Obtained in Examples and Comparative Examples
상기 실시예 및 비교예에서 얻어진 코폴리카보네이트 수지 조성물에 대해， JSW (주) N-20C 사출성형기를 사용하여 실린더 온도 300 °C, 금형온도 80°C에서 사출성형하여 시편을 제조하였다. For the copolycarbonate resin composition obtained in the above Examples and Comparative Examples, a specimen was prepared by injection molding at a cylinder temperature of 300 ° C, mold temperature 80 ° C using a JSW Co., Ltd. N-20C injection molding machine.
이후， 상기 시편의 물성을 하기 방법으로 측정하였으며, 그 결과를 표 1 에 나타내었다. 1. 용융지수 (melt flow rate, MFR) Then, the physical properties of the specimens were measured by the following method, and the results are shown in Table 1. Melt Flow Rate (MFR)
ASTM D1238(300°C , 1.2kg조건)에 의거하여 측정하였다. It measured according to ASTM D1238 (300 ° C, 1.2kg conditions).
2. 중량 평균 분자량 2. Weight average molecular weight
Agilent 1200 series를 이용하여 PC 스텐다드 (Standard)를 이용한 GPC로 측정하였다. The Agilent 1200 series was used to measure GPC using PC Standard.
3. 저온충격강도 3. Low temperature impact strength
3-1. — 3CTC에서의 충격강도 (J/m) 3-1. — Impact Strength at 3CTC (J / m)
ASTM D256(l/8 inch, Notched Izod)에 의거하여 -30°C에서 측정하였다. It was measured at -30 ° C according to ASTM D256 (l / 8 inch, Notched Izod).
3-2. -40°C에서의 충격강도 (J/m) 3-2. Impact strength at -40 ° C (J / m)
ASTM D256(l/4 inch, Notched Izod)에 의거하여 ᅳ 40°C에서 측정하였다. 4. 내화학성 It was measured at ᅳ 40 ° C according to ASTM D256 (l / 4 inch, Notched Izod). 4. Chemical resistance
ASTM D638에 의거하여， 인장응력 (Tensile strength)을 측정하기 위한 시편 (두께 ： 3.2誦)을 제조하여， ASTM D543( PRACTICE B)에 의거하여 JIG Strain Rl.O을 기준으로 내화학성을 측정하였다. According to ASTM D638, a specimen (thickness: 3.2 kPa) for measuring tensile stress was prepared, and chemical resistance was measured based on JIG Strain Rl.O according to ASTM D543 (PRACTICE B).
구체적으로, 상온 (23°C)에서 면재질의 헝겊 (2 cm X 2 cm)을 시편 중앙에 얹어놓고， 용매 (니베아© 아쿠아 프로텍트 선스프레이 -SPF30,
바이어스도르프사 제조) 2m.e을 헝겊에 떨어뜨린 순간으로부터 각 시편의 파괴가 일어나는데까지 걸리는 시간을 측정하고， 하기 기준하에 평가하였다. Specifically, place a cotton cloth (2 cm X 2 cm) in the center of the specimen at room temperature (23 ° C), and then use a solvent (NIVEA © Aqua Protect Sunspray -SPF30, The time taken from the moment when 2 m.e of Beiersdorf Co., Ltd. was dropped on the cloth to the destruction of each test piece was measured, and evaluated under the following criteria.
© ： 24시간 이상 ― © ： More than 24 hours ―
O ： . 1시간 내지 24시간 O:. 1 hour to 24 hours
ᅀ ： 1분 내지 1시간 ： 1 minute to 1 hour
X ： 1분 이내, X ： Within 1 minute
【표 1】 Table 1
실시예 및 비교예의 조성 및 실험예 결과 Composition and Experimental Results of Examples and Comparative Examples
상기 표 1에 나타난 바와 같이. 첨가제가 포함된 실시예의 코폴리카보네이트 수지 조성물의 경우， 용매에 의해 변성되는 시간이 1시간 이상으로 길어, 우수한 내화학성을 갖는 반면, 첨가제가 포함되지 않은
비교예의 코폴리카보네이트 수지 조성물은 용매에 의해 변성되는 시간이As shown in Table 1 above. In the case of the copolycarbonate resin composition of the embodiment including the additive, the time of denaturation by the solvent is longer than 1 hour, and has excellent chemical resistance, while no additive is included. The copolycarbonate resin composition of the comparative example has a time denatured by a solvent
1시간 미만으로 짧아， 상대적으로 실시예에 비해 내화학성이 나쁘다는 것을 확인할 수 있다. 또한， 상기 실시예 1 내지 3의 코폴리카보네이트 수지 조성물과 비교예 1의 코폴리카보네이트 수지 조성물을 비교하면， 제조예 3에서. 제조된 실리콘 함유 코폴리카보네이트 수지를 동일하게 포함하고 있음에도, 첨가제가 추가로 투입된 실시예 1 내지 3에서 저온 충격강도 값이 증가한 것을 확인할 수 있다. 그리고， 동일하게 제조예 3의 실리콘 함유 코폴리카보네이트 수지를 포함한 결과, 용융지수 특성은 동등 수준에서 측정되었다. 상기 비교예 3의 코폴리카보네이트 수지 조성물의 경우， 첨가제 없이 제조예 5에서 제조된 코폴리카보네이트 수지만을 포함함에 따라， 실시예에. 비해 저온 충격강도가 낮게 측정되었고， 용융지수가 높아질 뿐아니라. 내화학성이 나쁜 것으로 나타났다. 상기 비교예 4의 코폴리카보네이트 수지 조성물의 경우, 제조예 4에서 제조된 코폴리카보네이트 수지와 함께 첨가제를 포함하고 있음에도, 제조예 4에서 얻어진 폴리카보네이트 수지를 사용함에 따라， 실시예에 비해 1/8 inch, -30°C에서의 저온 충격강도가 낮게 측정되었고, 용융지수가 높아지는 것으로 나타났다. 이에 따라， 상기 코폴리카보네이트 수지 조성물은 특정의 코폴리카보네이트 수지와 함께 첨가제를 투입함에 따라， 향상된 코폴리카보네이트 수지의 특성 (예를 들어， 용융지수)과 함께， 첨가제에 따라 내충격성 및 내화학성이 증가되는 것을 확인할 수 있었다.
It is shorter than 1 hour, it can be seen that the chemical resistance is relatively poor compared to the embodiment. In addition, when the copolycarbonate resin composition of Examples 1 to 3 and the copolycarbonate resin composition of Comparative Example 1 is compared, in Production Example 3. Even though the prepared silicone-containing copolycarbonate resin was included in the same manner, it can be confirmed that the low-temperature impact strength value was increased in Examples 1 to 3 to which the additive was added. And the same as the result of including the silicone-containing copolycarbonate resin of Preparation Example 3, the melt index characteristics were measured at the equivalent level. In the case of the copolycarbonate resin composition of Comparative Example 3, only the copolycarbonate resin prepared in Preparation Example 5 without additives, in the Example. Compared with low temperature impact strength, the melt index is not only high. It was found that the chemical resistance was bad. In the case of the copolycarbonate resin composition of Comparative Example 4, even though it contains an additive with the copolycarbonate resin prepared in Preparation Example 4, by using the polycarbonate resin obtained in Preparation Example 4, 1 / Low temperature impact strength at 8 inch, -30 ° C was measured low, and the melt index was increased. Accordingly, the copolycarbonate resin composition, as the additive is added together with a specific copolycarbonate resin, with improved properties of the copolycarbonate resin (eg, melt index), impact resistance and chemical resistance depending on the additive It was confirmed that this is increased.
Claims
【청구항 1】 . 【Claim 1】.
방향족 폴리카보네이트계. 게 1 반복 단위 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함한 코폴리카보네이트 수지 ; 및 Aromatic polycarbonate type. A copolycarbonate resin comprising a first repeating unit and a second aromatic polycarbonate-based repeating unit having at least one siloxane bond; and
탄소수 2 이상의 탄화수소계 작용기를 .함유한 폴리실록산 고분자；를 포함하는， 코폴리카보네이트 수지 조성물. A copolycarbonate resin composition comprising a polysiloxane polymer containing a hydrocarbon-based functional group having 2 or more carbon atoms.
【청구항 2】 【Claim 2 】
제 1항에 있어서， In clause 1,
상기 폴리실록산 고분자는 탄소수 2 이상의 탄화수소계 작용ᅳ？ᅵ 0.001 몰% 내지 10 몰%를 포함하는， 코폴리카보네이트 수지 조성물. The polysiloxane polymer is a copolycarbonate resin composition containing 0.001 mol% to 10 mol% of hydrocarbon-based function having 2 or more carbon atoms.
【청구항 3】 【Claim 3】
게 1항에 있어서， In paragraph 1,
상기 폴리실록산 고분자는 탄소수 2 이상의 탄화수소계 작용기를 포함한 폴리실록산 반복단위 및 폴리디메틸실록산 반복단위를 포함하는， 코폴리카보네이트 수지 조성물. The polysiloxane polymer is a copolycarbonate resin composition comprising a polysiloxane repeating unit and a polydimethylsiloxane repeating unit containing a hydrocarbon-based functional group having 2 or more carbon atoms.
[청구항 4】 [Claim 4]
제 1항에 있어서， In clause 1,
상기 탄화수소계 작용기는 지방족 탄화수소 작용기， 지환족 탄화수소 작용기 및 방향족 탄화수소 작용기로 이루어진 군에서 선택된 1종 이상을 포함하는， 폴리카보이트 수지 조성물. A polycarvoite resin composition wherein the hydrocarbon-based functional group includes at least one selected from the group consisting of an aliphatic hydrocarbon functional group, an alicyclic hydrocarbon functional group, and an aromatic hydrocarbon functional group.
【청구항 5】 【Claim 5】
제 4항에 있어서, According to clause 4,
상기 지방족 탄화수소 작용기는 직쇄 또는 분지쇄의 알킬기 또는 비닐계 작용기를 포함하는， 폴리카보이트 수지 조성물.
A polycarvoite resin composition in which the aliphatic hydrocarbon functional group includes a straight-chain or branched alkyl group or a vinyl-based functional group.
【청구항 6】 【Claim 6】
제 5항에 있어서， In clause 5,
상기 바닐계 작용가는 하기 화학식 11로 표시되는 작용기를 포함하는， 폴리카보이트 수지 조성물: The vanyl-based functional group includes a functional group represented by the following Chemical Formula 11, a polycarvoite resin composition:
[화학식 11] [Formula 11]
*는 결합지점을 의미하몌 * indicates the joining point.
， Rg , Rio는 각각 독립적으로 수소， 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬기, 탄소수 6 내지 20의 아릴기， 탄소수 2 내지 20의 알케닐기, 탄소수 1 내지 20의 알콕시기， 탄소수 3 내지 20의 시클로알킬기, 케톤기 또는 에스터기이다. , Rg and Rio are each independently hydrogen, a straight or branched alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, and 3 to 20 carbon atoms. It is a cycloalkyl group, ketone group, or ester group.
[청구항 7】 [Claim 7]
제 1항에 있어서， In clause 1,
상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 반복단위는 하기 화학식 12로 표시되는 반복단위를 포함하는, 코폴리카보네이트 수지 조성물: A copolycarbonate resin composition, wherein the polysiloxane repeating unit containing a hydrocarbon-based functional group having 2 or more carbon atoms includes a repeating unit represented by the following formula (12):
[화학식 12] [Formula 12]
*는 결합지점을 의미하며
Rn 내지 Ri2 중 적어도 하나 이상은 탄소수 2 이상의 탄화수소계 작용기이고， 나머지는 메틸기이다. * refers to the joining point At least one of Rn to Ri 2 is a hydrocarbon-based functional group having 2 or more carbon atoms, and the remainder is a methyl group.
【청구항 8】 【Claim 8】
제 3항에 있어서, According to clause 3,
상기 폴리디메틸실록산 반복단위에 대한 상기 탄소수 2 이상의 탄화수소계 작용기를 포함한 폴리실록산 반복단위의 몰수비가 0.00001 내지 0. 1인， 코폴리카보네이트 수지 조성물. A copolycarbonate resin composition wherein the mole ratio of the polysiloxane repeating unit containing a hydrocarbon-based functional group having 2 or more carbon atoms to the polydimethylsiloxane repeating unit is 0.00001 to 0.1.
【청구항 9】 【Claim 9】
제 1항에 있어서' In paragraph 1, '
상기 폴리실록산 고분자는 상기 폴리실록산 고분자의 말단에 결합한 탄소수 2 이상의 탄화수소계 작용기를 더 포함하는, 코폴리카보네이트 수지 조성물. The polysiloxane polymer further includes a hydrocarbon-based functional group having 2 or more carbon atoms bonded to an end of the polysiloxane polymer.
[청구항 10】 [Claim 10]
제 1항에 있어서， In clause 1,
상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자는 하기 화학식 14로 표시되는 화합물을 포함하는， 코폴리카보네이트 수지 조성물: The polysiloxane polymer containing a hydrocarbon-based functional group having 2 or more carbon atoms includes a compound represented by the following formula (14): A copolycarbonate resin composition:
[화학식 14] [Formula 14]
상기 화학식 14에서， In Formula 14 above,
m은 10 내지 20의 정수이고, n은 6000 내지 11500의 정수이며 m is an integer from 10 to 20, n is an integer from 6000 to 11500,
D는 탄소수 2 이상의 탄화수소계 작용기이다. D is a hydrocarbon-based functional group having 2 or more carbon atoms.
【청구항 11】
제 1항에 있어서, 【Claim 11】 According to clause 1,
상기 탄소수 2 이상의 탄화수소계 작용기를 함유한 폴리실록산 고분자의 함량은 전체 코폴리카보네이트 수지 조성물 중량을 기준으로 0.01 중량 % 내지 10 중량 ¾>인， 코폴리카보네이트 수지 조성물. A copolycarbonate resin composition wherein the content of the polysiloxane polymer containing a hydrocarbon-based functional group having 2 or more carbon atoms is 0.01% by weight to 10% by weight based on the total weight of the copolycarbonate resin composition.
【청구항 12】 【Claim 12】
.제 1항에 있어서 , .In clause 1,
상기 탄소수 2 아상의 탄화수소계 작용기를 함유한 폴리실록산 고분자의 중량평균 분자량은 100 , 000 g/mol 내지 1 , 000 , 000 g/m이인 코폴리카보네이트 수지 조성물.' ― A copolycarbonate resin composition wherein the polysiloxane polymer containing a hydrocarbon-based functional group having 2 carbon atoms has a weight average molecular weight of 100,000 g/mol to 1,000,000 g/m. ' -
【청구항 13】 【Claim 13】
제 1항에 있어서' In paragraph 1'
상기 제 1 반복 단위는 하기 화학식 1로 표시되는 반복단위를 포함하는， 코폴리카보네이트 수지 조,성물: The first repeating unit is a copolycarbonate resin composition comprising a repeating unit represented by the following formula (1):
상가화학식 1에서， In general chemical formula 1,
Ri 내지 는 각각 독립적으로 수소， d-10 알킬, Ci-10 알콕시， 또는 할로겐이고， Ri to are each independently hydrogen, d- 10 alkyl, Ci- 10 alkoxy, or halogen,
Z는 비치환되거나 또는 페닐로 치환된 d-10 알킬렌， 비치환되거나 또는 Cwo 알킬로 치환된 C3-15 사이클로알킬렌， 0， S , SO, S02 , 또는 CO이다. Z is d- 10 alkylene unsubstituted or substituted with phenyl, C 3-15 cycloalkylene unsubstituted or substituted with Cwo alkyl, 0, S, SO , SO 2 , or CO.
【청구항 14】 【Claim 14】
제 13항에 있어서, According to clause 13,
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-디브로모페,닐)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, 1，1一 비스 (4-히드록시페닐 )—1-페닐에탄， 비스 (4-히드록시페닐)디페닐메탄， 및 α， ω-비스 [3-( 0 -히드록시페닐)프로필]폴리디메틸실록산으로 이루어진 군으로부터 선택되는 어느 하나 이상의 방향족 디올 화합물로부터 유래한 것을 특징으로 하는, 코폴리카보네이트 수지 조성물. The repeating unit represented by Formula 1 is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, . Bis (4- Hydroxyphenyl) 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 1 bis (4-hydroxyphenyl )—1-phenylethane, bis (4-hydroxyphenyl)diphenylmethane, and α, ω-bis [3-(0-hydroxyphenyl)propyl]polydimethylsiloxane. At least one aromatic selected from the group consisting of A copolycarbonate resin composition, characterized in that it is derived from a diol compound.
【청구항 15】 【Claim 15】
제 13항에 있어서， In clause 13,
상기 화학식 1은 하가 화학식 1—1로 표시되는 것을 특징으로 하는, 코폴리카보네이트 수지 조성물: Formula 1 is a copolycarbonate resin composition, characterized in that it is represented by the chemical formula 1—1:
-1] -One]
【청구항 16】 【Claim 16】
제 1항에 있어서, According to clause 1,
상기 제 2 반복 단위는 하기 화학식 2 내지 4로 표시되는 반복단위로 구성되는 군으로부터 선택되는 반복단위 1종 이상을 포함하는， 코폴리카보네이트 수지 조성물: A copolycarbonate resin composition wherein the second repeating unit includes one or more repeating units selected from the group consisting of repeating units represented by the following formulas 2 to 4:
[화^ ^식 2]
[Hwa ^^ Equation 2]
상기 화학식 2에서, In Formula 2,
¾은 각각 독립적으로 Cwo 알킬렌이고， ¾ is each independently Cwo alkylene,
¾는 . 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐， 옥시라닐로 치환된 d-10 알콕시， 또는 C6-20 아릴로 치환된 d-15 알킬; 할로겐; d— 10 .알콕시 ; 알릴; C -10 할로알킬; 또는 C6— 20 아릴이고， ¾ is . Each independently hydrogen; unsubstituted or d - 10 alkoxy substituted with oxiranyl, oxiranyl, or d- 15 alkyl substituted with C 6-20 aryl; halogen; d— 10.alkoxy ; allyl; C - 10 haloalkyl; or C 6 — 20 aryl,
nl은 10 내지 200의 정수이고， nl is an integer from 10 to 200,
¾은 각각 독립적으로 d-10 알킬렌이고. ¾ is each independently d- 10 alkylene.
^은 각각 독립적으로 수소， d-6 알킬, 할로겐. 히드록시. d-6 알콕시 또는 C6-20 아릴이고, ^ are each independently hydrogen, d-6 alkyl, and halogen. Hydroxy. d - 6 alkoxy or C6-20 aryl,
¾는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐， 옥시라닐로 치환된 d-10 알콕시， 또는 C6-20 아릴로 치환된 CW5 알킬; 할로겐; Cwo 알콕시 ; 알릴; Cwo 할로알킬; 또는 C6-20 아릴이고. ¾ are each independently hydrogen; C W5 alkyl that is unsubstituted or substituted with oxiranyl, d - 10 alkoxy substituted with oxiranyl, or C 6-20 aryl; halogen; Cwo alkoxy; allyl; Cwo haloalkyl; or C 6 - 20 aryl.
n2는 10 내지 200의 정수이고， n2 is an integer from 10 to 200,
[화학식 4]
[Formula 4]
상기 화학식 4에서' In Formula 4 above,
¾는 각각 독립적으로 Cwo 알킬렌이고, ¾ is each independently Cwo alkylene,
Y2는 각각 독립적으로 d— 10 알콕시이고， Y 2 is each independently d— 10 alkoxy,
R7은 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐, 옥시라닐로 치환된 d— 10 알콕시， 또는 20 아릴로 치환된 d-15 알킬; 할로겐; d-10 알콕시 ; 알릴; d-κ) 할로알킬; 또는 C6-20 아릴이고， R 7 is each independently hydrogen; unsubstituted or d- 10 alkoxy substituted with oxiranyl, oxiranyl, or d- 15 alkyl substituted with 20 aryl; halogen; d- 10 alkoxy; allyl; d-κ) haloalkyl; or C 6-20 aryl ,
n3은 10 내지 200의 정수이다. n3 is an integer from 10 to 200.
【청구항 17】 【Claim 17】
제 16항에 있어서. In clause 16.
상기 화학식 2로 표시되는 반복 단위는， 하기 화학식 2-1로 표시되는 것을 특징으로 하는, 코폴리카보네이트 수지 조성물: The repeating unit represented by Formula 2 is a copolycarbonate resin composition, characterized in that it is represented by the following Formula 2-1:
ᅳ 1] ᅳ 1]
【청구항 18】 【Claim 18】
제 16항에 있어서, According to clause 16,
상기 화학식 3으로 표시되는 반복 단위는， 하기 화학식 3-1로 표시되는 것을 특징으로 하는, 코폴리카보네이트 수지 조성물: The repeating unit represented by Formula 3 is a copolycarbonate resin composition, characterized in that it is represented by the following Formula 3-1:
[화학식 3ᅳ 1]
[Formula 3ᅳ 1]
【청구항 19】 【Claim 19】
제 16항에 있어서， . In clause 16, .
상기 화학식 4로 표시되는 반복 단위는， 하기 화학식 4-1로 표시되는 것을 특징으로 하는， 코폴리카보네이트 수지 조성물: The repeating unit represented by Formula 4 is a copolycarbonate resin composition, characterized in that it is represented by the following Formula 4-1:
[화학식 4-1] [Formula 4-1]
【청구항 20】 【Claim 20】
제 1항에' 있어서， In paragraph 1, ‘ in
상기 방향족 폴리카보네이트계 제 1 반복 단위 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함하는 코폴리카보네이트 수지는 상기 제 2 반복단위 0.001 중량 % 내지 10 중량 %를 포함하는, 코폴리카보네이트 수지 조성물. The copolycarbonate resin comprising the aromatic polycarbonate-based first repeating unit and the aromatic polycarbonate-based second repeating unit having at least one siloxane bond contains 0.001% by weight to 10% by weight of the second repeating unit. Carbonate resin composition.
【청구항 21】 【Claim 21】
제 1항에 있어서, . According to clause 1, .
상기 방향족 폴리카보네이트계 제 1 반복 단위 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함하는
코폴리카보네이트 수지의 중량 평균 분자량이 1,000 g/mol내지 100,000 g/lTOl인 . 코폴리카보네이트 수지 조성물. Comprising the aromatic polycarbonate-based first repeating unit and the aromatic polycarbonate-based second repeating unit having at least one siloxane bond The weight average molecular weight of the copolycarbonate resin is 1,000 g/mol to 100,000 g/lTOl. Copolycarbonate resin composition.
【청구항 22】 【Claim 22】
제 1항 내지 제 21항 중 어느 한 항의 코폴리카보네이트 수지 조성물을 포함하는, 물품.
An article comprising the copolycarbonate resin composition of any one of claims 1 to 21.
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| EP15864965.7A EP3159367B1 (en) | 2014-12-04 | 2015-12-03 | Copolycarbonate resin composition and article comprising same |
| CN201580039083.8A CN106661219B (en) | 2014-12-04 | 2015-12-03 | Copolycarbonate resin composition and product comprising the copolycarbonate resin composition |
| US15/500,242 US10196516B2 (en) | 2014-12-04 | 2015-12-03 | Copolycarbonate resin composition and article including the same |
| PL15864965T PL3159367T3 (en) | 2014-12-04 | 2015-12-03 | Copolycarbonate resin composition and article comprising same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020256494A1 (en) * | 2019-06-20 | 2020-12-24 | 주식회사 엘지화학 | Method for analyzing copolycarbonate |
| KR20200145751A (en) * | 2019-06-20 | 2020-12-30 | 주식회사 엘지화학 | Method for analyzing copolycarbonate |
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| DE69211382T2 (en) * | 1991-02-22 | 1996-11-28 | Mitsubishi Gas Chemical Co | Thermoplastic resin composition of siloxane polycarbonate |
| JP3457805B2 (en) * | 1996-06-28 | 2003-10-20 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition |
| TWI453551B (en) * | 2007-09-27 | 2014-09-21 | Mitsubishi Gas Chemical Co | A resin composition for electrophotographic photoreceptor, and an electrophotographic photoreceptor using the same |
| US20130313493A1 (en) * | 2012-05-24 | 2013-11-28 | Sabic Innovative Plastics Ip B.V. | Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same |
| KR101534336B1 (en) * | 2012-12-11 | 2015-07-06 | 제일모직주식회사 | Polycarbonate Resin Composition with Good Flame Retardancy and Light stability |
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| WO2020256494A1 (en) * | 2019-06-20 | 2020-12-24 | 주식회사 엘지화학 | Method for analyzing copolycarbonate |
| KR20200145751A (en) * | 2019-06-20 | 2020-12-30 | 주식회사 엘지화학 | Method for analyzing copolycarbonate |
| KR102554769B1 (en) * | 2019-06-20 | 2023-07-12 | 주식회사 엘지화학 | Method for analyzing copolycarbonate |
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