KR102271028B1 - Method of preparing Polyamic acid and Polyamic acid, Polyimide resin and Polyimide film thereby - Google Patents
Method of preparing Polyamic acid and Polyamic acid, Polyimide resin and Polyimide film thereby Download PDFInfo
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- KR102271028B1 KR102271028B1 KR1020170184018A KR20170184018A KR102271028B1 KR 102271028 B1 KR102271028 B1 KR 102271028B1 KR 1020170184018 A KR1020170184018 A KR 1020170184018A KR 20170184018 A KR20170184018 A KR 20170184018A KR 102271028 B1 KR102271028 B1 KR 102271028B1
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- South Korea
- Prior art keywords
- bis
- block structure
- pmda
- polyamic acid
- 6fda
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 55
- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 17
- 150000004985 diamines Chemical class 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 70
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 61
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 57
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 26
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 18
- 238000002834 transmittance Methods 0.000 claims description 16
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 13
- -1 aminophenyl Chemical group 0.000 claims description 12
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 10
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 9
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 9
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 claims description 8
- RXNKCIBVUNMMAD-UHFFFAOYSA-N 4-[9-(4-amino-3-fluorophenyl)fluoren-9-yl]-2-fluoroaniline Chemical compound C1=C(F)C(N)=CC=C1C1(C=2C=C(F)C(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 RXNKCIBVUNMMAD-UHFFFAOYSA-N 0.000 claims description 6
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 claims description 5
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- YQRIQVXKVPMXMW-UHFFFAOYSA-N 3-fluoro-1-phenyl-9H-fluoren-2-amine Chemical compound C1C2=CC=CC=C2C3=CC(=C(C(=C31)C4=CC=CC=C4)N)F YQRIQVXKVPMXMW-UHFFFAOYSA-N 0.000 claims 3
- FPRFOKKPDUHQEH-UHFFFAOYSA-N 1-phenyl-9h-fluoren-2-amine Chemical compound NC1=CC=C2C3=CC=CC=C3CC2=C1C1=CC=CC=C1 FPRFOKKPDUHQEH-UHFFFAOYSA-N 0.000 claims 2
- 150000004678 hydrides Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000004642 Polyimide Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 50
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 38
- 239000011521 glass Substances 0.000 description 25
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 238000011049 filling Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000006159 dianhydride group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 2
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical compound COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- AEJWKVGGBGUSOA-UHFFFAOYSA-N 4-[(1,3-dioxo-2-benzofuran-4-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound O=C1OC(=O)C2=C1C=CC=C2S(=O)(=O)C1=CC=CC2=C1C(=O)OC2=O AEJWKVGGBGUSOA-UHFFFAOYSA-N 0.000 description 1
- HNHQPIBXQALMMN-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)-dimethylsilyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1[Si](C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 HNHQPIBXQALMMN-UHFFFAOYSA-N 0.000 description 1
- HWBVOOWDSUQMHR-UHFFFAOYSA-N 4-[1-(3,4-dicarboxyphenyl)-1,2,2,3,3,3-hexafluoropropyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(F)(C(F)(F)C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 HWBVOOWDSUQMHR-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- JYCTWJFSRDBYJX-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-3a,4,5,9b-tetrahydrobenzo[e][2]benzofuran-1,3-dione Chemical compound O=C1OC(=O)CC1C1C2=CC=CC=C2C(C(=O)OC2=O)C2C1 JYCTWJFSRDBYJX-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 1
- WVOLTBSCXRRQFR-SJORKVTESA-N Cannabidiolic acid Natural products OC1=C(C(O)=O)C(CCCCC)=CC(O)=C1[C@@H]1[C@@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-SJORKVTESA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- WVOLTBSCXRRQFR-DLBZAZTESA-M cannabidiolate Chemical compound OC1=C(C([O-])=O)C(CCCCC)=CC(O)=C1[C@H]1[C@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-DLBZAZTESA-M 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YQYUWUKDEVZFDB-UHFFFAOYSA-N mmda Chemical compound COC1=CC(CC(C)N)=CC2=C1OCO2 YQYUWUKDEVZFDB-UHFFFAOYSA-N 0.000 description 1
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
본 발명은 폴리아믹산의 제조방법, 이로부터 제조된 폴리아믹산, 폴리이미드 수지 및 폴리이미드 필름에 관한 것으로, 1종의 디아민 투입 시 분할 투입하는 방법으로 변경함으로써 이로부터 제조된 폴리이미드 필름의 선형열팽창계수가 개선된 폴리이미드 조성 개발에 관한 것이다.The present invention relates to a method for producing a polyamic acid, a polyamic acid prepared therefrom, a polyimide resin, and a polyimide film, and the linear thermal expansion of the polyimide film prepared therefrom by changing to a divided input method when one type of diamine is added It relates to the development of polyimide compositions with improved modulus.
Description
본 발명은 폴리아믹산의 제조방법, 이로부터 제조된 폴리아믹산, 폴리이미드 수지 및 폴리이미드 필름에 관한 것이다. The present invention relates to a method for producing a polyamic acid, a polyamic acid prepared therefrom, a polyimide resin, and a polyimide film.
일반적으로 폴리이미드(PI) 필름은 폴리이미드 수지를 필름화한 것으로, 폴리이미드 수지는 방향족 디안하이드라이드와 방향족 디아민 또는 방향족 디이소시아네이트를 용액 중합하여 폴리아믹산 유도체를 제조한 후, 고온에서 폐환 탈수시켜 이미드화하여 제조되는 고내열 수지를 일컫는다.In general, a polyimide (PI) film is a film formed of a polyimide resin, and the polyimide resin is obtained by solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, followed by ring closure dehydration at high temperature. It refers to a high heat-resistant resin manufactured by imidization.
이와 같은 폴리이미드 필름은 뛰어난 기계적, 내열성, 전기절연성을 가지고 있기 때문에 반도체의 절연막, TFT-LCD의 전극 보호막 플렉시블 인쇄 배선 회로용 기판 등의 전자재료에 광범위한 분야에서 사용되어지고 있다. Because such polyimide films have excellent mechanical, heat resistance and electrical insulation properties, they are used in a wide range of electronic materials such as semiconductor insulating films, TFT-LCD electrode protective films, and flexible printed wiring circuit boards.
그러나 폴리이미드 수지는 높은 방향족 고리 밀도로 인하여 갈색 및 황색으로 착색되어 있어 가시광선 영역에서의 투과도가 낮고 노란색 계열의 색을 나타내어 광투과율을 낮게 하며 큰 복굴절률을 가지게 하여 광학부재로 사용하기에는 곤란한 점이 있다. However, the polyimide resin is colored brown and yellow due to its high aromatic ring density, so it has low transmittance in the visible light region, shows a yellow color, low light transmittance, and has a large birefringence, making it difficult to use as an optical member. have.
미국특허 제4595548호, 제4603061호, 제4645824, 제4895972호, 제5218083호, 제5093453호, 제5218077호, 제5367046호, 제5338826호. 제5986036호, 제6232428호 및 대한민국 특허공개공보 제2003-0009437호에는 -O-, -SO2-, CH2- 등의 연결기와 p-위치가 아닌 m-위치로의 연결된 굽은 구조의 단량체이거나 -CF3 등의 치환기를 갖는 방향족 디안하이드라이드 이무수물과 방향족 디아민 단량체를 사용하여 열적 특성이 크게 저하되지 않는 한도에서 투과도 및 색상의 투명도를 향상시킨 신규 구조의 폴리이미드를 제조한 보고가 있으나, 기계적 특성, 내열성, 복굴절 측면에서 OLED, TFT-LCD, 플렉시블 디스플레이 등의 표시소자 소재로 사용하기에는 부족한 결과를 보였다.U.S. Patent Nos. 4595548, 4603061, 4645824, 4895972, 5218083, 5093453, 5218077, 5367046, 5338826. No. 5986036, No. 6232428 and Korean Patent Laid-Open No. 2003-0009437 disclose that -O-, -SO 2 -, CH 2 -, etc., is a monomer of a bent structure connected to the m-position, not the p-position, or -CF 3 There is a report of manufacturing a polyimide having a novel structure with improved transmittance and color transparency to the extent that thermal properties are not significantly reduced by using an aromatic dianhydride dianhydride and an aromatic diamine monomer having a substituent such as -CF 3 In terms of mechanical properties, heat resistance, and birefringence, the results were insufficient for use as a material for display devices such as OLED, TFT-LCD, and flexible display.
본 발명은 기존 조성의 같은 원료 및 사용량을 유지하되, 투입 방법을 변경하여 광학 물성을 유지하면서 선형열팽창계수가 개선된 폴리아믹산의 제조방법, 이로부터 제조된 폴리아믹산, 폴리이미드 수지 및 폴리이미드 필름, 이를 포함하는 영상 표시소자를을 제공하는데 있다. The present invention provides a method for producing a polyamic acid with improved linear thermal expansion coefficient while maintaining the same raw materials and amount of the existing composition, but changing the input method to maintain optical properties, polyamic acid, polyimide resin and polyimide film produced therefrom , to provide an image display device including the same.
본 발명의 바람직한 일 구현예는 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)를 포함하는 디아민 및 피로멜리틱 디안하이드라이드(1,2,4,5-benzene tetracarboxylic dianhydride, PMDA)를 포함하는 디안하이드라이드를 투입하는 단계; 및 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)를 포함하는 디아민 및 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(6FDA) 및 비페닐 테트라카르복실릭 디안하이드라이드 (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) 중에서 선택되는 1종 이상을 포함하는 디안하이드라이드를 투입하는 단계를 포함하는 폴리아믹산의 제조방법을 제공하는 것이다.A preferred embodiment of the present invention is a diamine containing bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) and pyromellitic dianhydride (1,2,4,5-benzene tetracarboxylic) adding dianhydride, including dianhydride, PMDA); and diamines including bis trifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) And biphenyl tetracarboxylic dianhydride (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) provides a method for producing a polyamic acid comprising the step of adding a dianhydride comprising at least one selected from the group consisting of will do
상기 PMDA대 6FDA 및 BPDA 중에서 선택되는 1종 이상의 몰비는 90 내지 25 : 10 내지 75인 것을 특징으로 한다.The PMDA to at least one molar ratio selected from 6FDA and BPDA is 90 to 25: 10 to 75.
상기 PMDA대 6FDA의 몰비는 90 내지 70 : 10 내지 30인 것을 특징으로 한다.The molar ratio of PMDA to 6FDA is 90 to 70: 10 to 30.
상기 PMDA대 BPDA의 몰비는 90 내지 25 : 10 내지 75인 것을 특징으로 한다. The molar ratio of PMDA to BPDA is 90 to 25: 10 to 75.
상기 PMDA대 6FDA대 BPDA의 몰비는 90 내지 50 : 5 내지 30 : 5 내지 20인 것을 특징으로 한다.The molar ratio of PMDA to 6FDA to BPDA is 90 to 50: 5 to 30: 5 to 20.
상기 디아민은 비스 아미노 페닐 풀루오렌 (9,9-Bis(4-aminophenyl)fluorene, FDA) 및 비스 플루오로 아미노 페닐 플루오렌 ( 9,9-Bis(3-fluoro-4-aminophenyl)fluorene, FFDA) 중에서 선택된 1종 이상을 추가로 투입하는 것을 특징으로 한다.The diamine is bisaminophenyl fluorene (9,9-Bis(4-aminophenyl)fluorene, FDA) and bisfluoroaminophenyl fluorene (9,9-Bis(3-fluoro-4-aminophenyl)fluorene, FFDA) It is characterized in that one or more selected from among are additionally added.
상기 비스 아미노 페닐 풀루오렌 (9,9-Bis(4-aminophenyl)fluorene, FDA) 및 비스 플루오로 아미노 페닐 플루오렌 ( 9,9-Bis(3-fluoro-4-aminophenyl)fluorene, FFDA) 중에서 선택된 1종 이상은 디아민 총 몰에 대하여 1몰% 내지 20몰%의 함량으로 투입되는 것을 특징으로 한다.selected from the above bisaminophenyl fluorene (9,9-Bis(4-aminophenyl)fluorene, FDA) and bisfluoroaminophenyl fluorene (9,9-Bis(3-fluoro-4-aminophenyl)fluorene, FFDA) At least one type is characterized in that it is added in an amount of 1 mol% to 20 mol% based on the total moles of diamine.
본 발명의 바람직한 다른 일 구현예는 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)로부터 유래된 반복단위 및 피로멜리틱 디안하이드라이드(1,2,4,5-benzene tetracarboxylic dianhydride, PMDA)로부터 유래된 반복단위를 포함하는 블록 구조 및 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)로부터 유래된 반복단위 및 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(6FDA) 및 비페닐 테트라카르복실릭 디안하이드라이드 (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) 중에서 선택되는 1종 이상으로부터 유래된 반복단위를 포함하는 블록 구조를 포함하는 것인 폴리아믹산을 제공하는 것이다.Another preferred embodiment of the present invention is a repeating unit derived from bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) and pyromellitic dianhydride (1,2,4,5- A block structure containing a repeating unit derived from benzene tetracarboxylic dianhydride, PMDA) and a repeating unit derived from bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) and 2,2-bis(3) Derived from at least one selected from ,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and biphenyl tetracarboxylic dianhydride (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) It is to provide a polyamic acid comprising a block structure including a repeating unit.
상기 제1 블록 구조에서의 PMDA대 제2 블록 구조에서의 6FDA 및 BPDA 중에서 선택되는 1종 이상의 몰비는 90 내지 25 : 10 내지 75인 것을 특징으로 한다.In the first block structure, PMDA to at least one selected from 6FDA and BPDA in the second block structure is a molar ratio of 90 to 25: 10 to 75.
상기 제1 블록 구조에서의 PMDA대 제2 블록 구조에서의 6FDA의 몰비는 90 내지 70 : 10 내지 30인 것을 특징으로 한다.A molar ratio of PMDA in the first block structure to 6FDA in the second block structure is 90 to 70: 10 to 30.
상기 제1 블록 구조에서의 PMDA대 제2 블록 구조에서의 BPDA의 몰비는 90 내지 25 : 10 내지 75인 것을 특징으로 한다.A molar ratio of PMDA in the first block structure to BPDA in the second block structure is 90 to 25: 10 to 75.
상기 제1 블록 구조에서의 PMDA대 제2 블록 구조에서의 6FDA대 제2 블록 구조에서의 BPDA의 몰비는 90 내지 50 : 5 내지 30 : 5 내지 20인 것을 특징으로 한다.The molar ratio of PMDA in the first block structure to 6FDA in the second block structure to BPDA in the second block structure is 90 to 50: 5 to 30: 5 to 20.
상기 비스 TFDB로부터 유래된 반복단위 및 6FDA 및 BPDA 중에서 선택되는 1종 이상으로부터 유래된 반복단위를 포함하는 블록 구조는 비스 아미노 페닐 풀루오렌 (9,9-Bis(4-aminophenyl)fluorene, FDA) 및 비스 플루오로 아미노 페닐 플루오렌 (9,9-Bis(3-fluoro-4-aminophenyl)fluorene, FFDA) 중에서 선택된 1종 이상으로부터 유래된 반복단위를 더 포함하는 것을 특징으로 한다.The block structure comprising a repeating unit derived from the bis TFDB and a repeating unit derived from at least one selected from 6FDA and BPDA is bisaminophenyl fluorene (9,9-Bis(4-aminophenyl)fluorene, FDA) and It is characterized in that it further comprises a repeating unit derived from at least one selected from bisfluoroaminophenyl fluorene (9,9-Bis(3-fluoro-4-aminophenyl)fluorene, FFDA).
상기 FDA 및 FFDA 중에서 선택된 1종 이상의 함량은 디아민 총 몰에 대하여 1몰% 내지 20몰%인 것을 특징으로 한다.The content of at least one selected from FDA and FFDA is characterized in that it is 1 mol% to 20 mol% based on the total moles of diamine.
본 발명의 바람직한 다른 일 구현예는 상술한 폴리아믹산으로부터 제조된 폴리이미드 수지를 제공하는 것이다.Another preferred embodiment of the present invention is to provide a polyimide resin prepared from the above-described polyamic acid.
본 발명의 바람직한 다른 일 구현예는 상기 폴리이미드 수지로 제조된 폴리이미드 필름을 제공하는 것이다.Another preferred embodiment of the present invention is to provide a polyimide film made of the polyimide resin.
상기 폴리이미드 필름은 50~350℃에서 열팽창계수(Coefficient of Thermal Expansion)가 30ppm/℃ 이하이고, UV분광계로 투과도 측정시 550㎚에서 투과도가 85% 이상이고, 황색도가 10 이하인 것을 특징으로 한다.The polyimide film has a coefficient of thermal expansion (Coefficient of Thermal Expansion) of 30ppm/°C or less at 50 to 350°C, a transmittance of 85% or more at 550 nm when the transmittance is measured with a UV spectrometer, and a yellowness of 10 or less. .
본 발명의 바람직한 다른 일 구현예는 폴리이미드 필름을 포함하는 영상 표시소자를 제공하는 것이다.Another preferred embodiment of the present invention is to provide an image display device including a polyimide film.
본 발명에 따르면, 필름이나 막 형성 후, 황색도 및 투과도를 유지하면서 선형열팽창계수가 개선된 폴리아믹산의 제조방법, 이로부터 제조된 폴리아믹산, 폴리이미드 수지 및 폴리이미드 필름을 제공할 수 있다.According to the present invention, it is possible to provide a method for producing a polyamic acid having an improved linear thermal expansion coefficient while maintaining yellowness and transmittance after forming a film or film, and a polyamic acid, polyimide resin and polyimide film prepared therefrom.
본 발명의 일 구현예에 따르면, 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)를 포함하는 디아민 및 피로멜리틱 디안하이드라이드(1,2,4,5-benzene tetracarboxylic dianhydride, PMDA)를 포함하는 디안하이드라이드를 투입하는 단계; 및 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)를 포함하는 디아민 및 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(6FDA) 및 비페닐 테트라카르복실릭 디안하이드라이드 (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) 중에서 선택되는 1종 이상을 포함하는 디안하이드라이드를 투입하는 단계를 포함하는 폴리아믹산의 제조방법을 제공한다.According to an embodiment of the present invention, diamine and pyromellitic dianhydride (1,2,4,5-benzene including bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB)) adding dianhydride containing tetracarboxylic dianhydride, PMDA); and diamines including bis trifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) And biphenyl tetracarboxylic dianhydride (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) provides a method for producing a polyamic acid comprising the step of adding a dianhydride comprising at least one selected from the group consisting of do.
본 발명은 1종의 디아민을 특정 조건 하에 1회 이상, 예를 들어 1차 및 2차로 나누어 투입하여 광학특성을 우수한 수준으로 유지하면서 선형열팽창계수를 향상시키는 효과를 얻을 수 있다.The present invention can obtain the effect of improving the coefficient of linear thermal expansion while maintaining the optical properties at an excellent level by introducing one or more diamines at least once under specific conditions, for example, divided into primary and secondary.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 일 구현예에 따른 폴리아믹산의 제조방법에서는 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)를 포함하는 디아민 및 피로멜리틱 디안하이드라이드(1,2,4,5-benzene tetracarboxylic dianhydride, PMDA)를 포함하는 디안하이드라이드를 투입하는 단계; 및 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)를 포함하는 디아민 및 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(6FDA) 및 비페닐 테트라카르복실릭 디안하이드라이드 (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) 중에서 선택되는 1종 이상을 포함하는 디안하이드라이드를 2차 투입하는 단계를 포함하여 실시하는 것이 바람직하다.In the method for producing a polyamic acid according to an embodiment of the present invention, diamine and pyromellitic dianhydride (1,2, 4,5-benzene tetracarboxylic dianhydride (PMDA) containing dianhydride; and diamines including bis trifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and biphenyl tetracarboxylic dianhydride (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) It is preferable to carry out including the step of secondary input of a dianhydride containing at least one selected from the group consisting of .
상기 PMDA대 6FDA 및 BPDA 중에서 선택되는 1종 이상의 몰비는 90 내지 25 : 10 내지 75, 바람직하게는 90 내지 30 : 10 내지 70인 것이 좋다. The molar ratio of at least one selected from PMDA to 6FDA and BPDA is preferably 90 to 25:10 to 75, preferably 90 to 30:10 to 70.
상기 PMDA 및 6FDA 및 BPDA 중에서 선택되는 1종 이상이 상기 몰비 범위를 벗어나는 경우 10 이상의 황색도를 가지거나 30ppm/℃ 이상의 열팽창계수를 가지는 문제가 있을 수 있다.When at least one selected from PMDA, 6FDA, and BPDA is out of the molar ratio range, there may be a problem of having a yellowness of 10 or more or a coefficient of thermal expansion of 30 ppm/°C or more.
본 명세서에서는 상기 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)를 포함하는 디아민 및 피로멜리틱 디안하이드라이드(1,2,4,5-benzene tetracarboxylic dianhydride, PMDA)를 포함하는 디안하이드라이드를 투입하는 단계를 1차 투입으로 명명하고, 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)를 포함하는 디아민 및 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(6FDA) 및 비페닐 테트라카르복실릭 디안하이드라이드 (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) 중에서 선택되는 1종 이상을 포함하는 디안하이드라이드를 투입하는 단계를 2차 투입으로 명명할 수 있으나, 이는 투입 순서를 한정하는 것이 아니며, 투입단계를 구분하기 위하여 명명할 뿐이다.In the present specification, diamine and pyromellitic dianhydride (1,2,4,5-benzene tetracarboxylic dianhydride, PMDA) including the bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) The step of adding the dianhydride containing is named as the first input, and diamine and 2,2-bis(3) containing bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) , 4-dicarboxyphenyl) containing at least one selected from hexafluoropropane dianhydride (6FDA) and biphenyl tetracarboxylic dianhydride (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) The step of inputting the dianhydride may be named as the secondary input, but this does not limit the order of the input, and is only named to distinguish the input step.
이 때, 상기 2차 투입시의 6FDA 및 BPDA 중에서 선택되는 1종 이상에서 2종 이상이 투입되는 경우 2차 투입시의 디안하이드라이드 총 몰을 상기 1차 투입시의 PMDA 대비 투입함을 의미한다. At this time, when two or more types are added from one or more selected from 6FDA and BPDA at the time of the second input, it means that the total moles of dianhydride at the time of the second input is added compared to PMDA at the time of the first input .
또한, 상기 2차 투입시의 6FDA 및 BPDA 중에서 선택되는 1종 이상에서 6FDA를 선택하여 투입하는 경우 상기 1차 투입시의 PMDA대 2차 투입시의 6FDA의 몰비는 90 내지 70 : 10 내지 30, 바람직하게는 90 내지 75 : 10 내지 25 인 것이 좋다.In addition, when 6FDA is selected and added from one or more selected from 6FDA and BPDA at the time of the second input, the molar ratio of PMDA at the first input to 6FDA at the second input is 90 to 70: 10 to 30, Preferably it is 90 to 75: 10 to 25 is good.
상기 1차 투입시의 PMDA 및 2차 투입시의 6FDA가 상기 몰비 범위를 벗어나는 경우 PMDA의 비율이 범위보다 높아지면 선형열팽창계수는 매우 낮아지지만 황색도가 매우 높아지는 문제가 있을 수 있으며, 6FDA의 비율이 범위보다 높아지면 황색도는 매우 낮아지는 장점이 있지만 선형열팽창계수가 증가하는 문제가 있을 수 있다. When the PMDA at the time of the first input and 6FDA at the time of the second input are out of the molar ratio range, if the ratio of PMDA is higher than the range, the linear thermal expansion coefficient is very low, but there may be a problem that the yellowness is very high, and the ratio of 6FDA If it is higher than this range, the yellowness is very low, but there may be a problem in that the linear thermal expansion coefficient increases.
또한, 상기 2차 투입시의 6FDA 및 BPDA 중에서 선택되는 1종 이상에서 BPDA를 선택하여 투입하는 경우 상기 1차 투입시의 PMDA대 2차 투입시의 BPDA의 몰비는 90 내지 25 : 10 내지 75, 바람직하게는 85 내지 30 : 15 내지 70 인 것이 좋다.In addition, when BPDA is selected from at least one selected from 6FDA and BPDA at the time of the second input, the molar ratio of PMDA at the time of the first input to BPDA at the time of the second input is 90 to 25: 10 to 75, Preferably 85 to 30: It is good that 15 to 70.
상기 1차 투입시의 PMDA 및 2차 투입시의 BPDA가 상기 몰비 범위를 벗어나는 경우 PMDA의 비율이 범위보다 높아지면 선형열팽창계수는 매우 낮아지지만 황색도가 매우 높아지는 문제가 있을 수 있으며, BPDA의 비율이 범위보다 높아지면 PMDA 대비 황색도는 낮아지는 장점이 있지만 선형열팽창계수가 증가되는 문제가 있을 수 있다.When PMDA at the time of the first input and BPDA at the time of the second input are out of the molar ratio range, if the ratio of PMDA becomes higher than the range, the linear thermal expansion coefficient is very low, but there may be a problem that the yellowness is very high, and the ratio of BPDA If it is higher than this range, there may be a problem in that the yellowness is lowered compared to PMDA, but the linear thermal expansion coefficient is increased.
본 발명의 일 구현에서는 상기 2차 투입시의 6FDA 및 BPDA 중에서 선택되는 1종 이상에서 2종 이상이 투입되는 경우 상기 1차 투입시의 PMDA대 2차 투입시의 6FDA대 2차 투입시의 BPDA의 몰비는 90 내지 50 : 5 내지 30 : 5 내지 20인 것이 보다 바람직하다. In one embodiment of the present invention, when two or more kinds are input from one or more selected from 6FDA and BPDA at the time of the second input, PMDA at the first input vs. 6FDA at the time of the second input vs. BPDA at the second input The molar ratio of 90-50:5-30:5-20 is more preferable.
상기 1차 투입시의 PMDA 및 2차 투입시의 6FDA 및 BPDA가 상기 몰비 범위를 벗어나는 경우 10 이상의 황색도를 가지거나 30ppm/℃ 이상의 열팽창계수를 가지는 문제가 있을 수 있다.When PMDA at the time of the first input and 6FDA and BPDA at the time of the second input are out of the molar ratio range, there may be a problem of having a yellowness of 10 or more or a coefficient of thermal expansion of 30 ppm/°C or more.
본 발명에서는 상기 PMDA를 포함하는 디안하이드라이드를 먼저 투입한 후, 6FDA 및 BPDA 중에서 선택되는 1종 이상을 포함하는 디안하이드라이드를 투입하는 것이 PMDA를 포함하는 디안하이드라이드를 나중에 투입하는 경우보다 선형열팽창계수 및 황색도를 동시에 향상시킬 수 있다는 점에서 보다 바람직하다. In the present invention, after inputting the dianhydride containing PMDA first, the input of the dianhydride containing at least one selected from 6FDA and BPDA is more linear than when the dianhydride containing PMDA is added later. It is more preferable in that the thermal expansion coefficient and yellowness can be improved simultaneously.
즉, 본 발명의 일 구현예에서는 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)를 포함하는 디아민 및 피로멜리틱 디안하이드라이드(1,2,4,5-benzene tetracarboxylic dianhydride, PMDA)를 포함하는 디안하이드라이드를 먼저 투입하고, 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)를 포함하는 디아민 및 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(6FDA) 및 비페닐 테트라카르복실릭 디안하이드라이드(3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) 중에서 선택되는 1종 이상을 포함하는 디안하이드라이드를 나중에 투입하는 것이 본 발명의 물성을 보다 개선시킬 수 있다는 점에서 바람직하다.That is, in one embodiment of the present invention, diamine and pyromellitic dianhydride (1,2,4,5-benzene including bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB)) Dianhydride containing tetracarboxylic dianhydride, PMDA) is added first, and diamine containing bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) and 2,2-bis(3,4) -Dicarboxyphenyl) dianhydride comprising at least one selected from hexafluoropropane dianhydride (6FDA) and biphenyl tetracarboxylic dianhydride (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) It is preferable that the ride is added later in that the physical properties of the present invention can be further improved.
또한, 상기 2차 투입시의 디아민은 비스 아미노 페닐 풀루오렌(9,9-Bis(4-aminophenyl)fluorene, FDA) 및 비스 플루오로 아미노 페닐 플루오렌(9,9-Bis(3-fluoro-4-aminophenyl)fluorene, FFDA) 중에서 선택된 1종 이상을 추가로 투입할 수 있다. 상기 FDA 및 FFDA 중에서 선택된 1종 이상을 추가로 투입하는 경우 유리전이온도를 개선시키는 효과를 얻을 수 있다.In addition, the diamine in the secondary input is bisaminophenyl fluorene (9,9-Bis(4-aminophenyl)fluorene, FDA) and bisfluoroaminophenyl fluorene (9,9-Bis(3-fluoro-4) -aminophenyl)fluorene, FFDA) may be additionally added. When one or more selected from the FDA and FFDA is additionally added, the effect of improving the glass transition temperature can be obtained.
상기 FDA 및 FFDA 중에서 선택된 1종 이상은 디아민 총 몰에 대하여 1몰% 내지 20몰%, 바람직하게는 1 내지 10몰%의 함량으로 포함되는 것이 좋다. 상기 FDA 및 FFDA 중에서 선택된 1종 이상이 상기 범위를 벗어나는 경우 1몰% 미만인 경우 함량이 적어 유리전이온도 개선효과가 거의 없을 수 있으며, 20몰%을 초과하는 경우 황색도 및 열팽창계수가 저하되는 문제가 있을 수 있다.At least one selected from the FDA and FFDA is preferably included in an amount of 1 mol% to 20 mol%, preferably 1 to 10 mol%, based on the total mole of diamine. When at least one selected from the FDA and FFDA is out of the above range, when the content is less than 1 mol%, the glass transition temperature improvement effect may be hardly improved, and when it exceeds 20 mol%, the yellowness and thermal expansion coefficient are lowered. there may be
본 발명의 일 구현예에 따르면, 상기 2차 투입하고, 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)를 포함하는 디아민 및 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(6FDA) 및 비페닐 테트라카르복실릭 디안하이드라이드 (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) 중에서 선택되는 1종 이상을 포함하는 디안하이드라이드를 3차 투입하는 단계는 포함하여 실시할 수 있다.According to one embodiment of the present invention, diamine and 2,2-bis (3,4-) containing bis trifluoromethyl benzidine (2,2'-bis (trifluoromethyl) benzidine, TFDB) as the secondary input Dianhydride comprising at least one selected from dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and biphenyl tetracarboxylic dianhydride (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) The third inputting step can be carried out including.
상기 3차 투입시의 디아민 및 디안하이드라이드는 상술한 1차 및 2차 투입시의 디아민 및 디안하이드라이드의 몰비 범위 내에서 적절히 조절하여 첨가할 수 있다. The diamine and dianhydride at the time of the third input may be added by appropriately adjusting the molar ratio of the diamine and the dianhydride at the time of the first and second input as described above.
본 발명의 일 구현예에서 사용되는 디아민으로서 TFDB, FDA 및 FFDA 이외에 옥시디아닐린(4,4'-Oxydianiline, ODA), p-페닐렌디아민(para-phenylene diamine, pPDA), m-페닐렌디아민(meta-phenylene diamine, mPDA), p-메틸렌디아닐린(para-Methylene Dianiline, pMDA), m-메틸렌디아닐린(meta-Methylene Dianiline, mMDA), 비스 아미노페녹시 벤젠(1,3-bis(3-aminophenoxy) benzene, 133APB), 비스 아미노페녹시 벤젠(1,3-bis(4-aminophenoxy) benzene, 134APB),비스 아미노 페녹시 페닐 헥사플루오로프로판 (2,2'-bis[4(4- aminophenoxy)phenyl] hexafluoropropane, 4BDAF), 비스 아미노페닐 헥사플루오로 프로판(2,2'-bis(3-aminophenyl)hexafluoropropane, 33-6F), 비스 아미노페닐 헥사플루오로 프로판(2,2'-bis(4-aminophenyl)hexafluoropropane, 44-6F), 비스 아미노페닐술폰(bis(4- aminophenyl)sulfone, 4DDS), 비스 아미노페닐술폰(bis(3- aminophenyl)sulfone, 3DDS), 사이클로헥산디아민(1,3-Cyclohexanediamine,13CHD), 사이클로헥산 디아민(1,4-Cyclohexanediamine, 14CHD), 비스 아미노 페녹시 페닐프로판(2,2-Bis[4-(4-aminophenoxy)-phenyl]propane, 6HMDA), 비스 아미노하이드록시 페닐 헥사플로오로프로판2,2-Bis(3-amino-4-hydroxy -phenyl)-hexafluoropropane, 6FAP), 비스 아미노페녹시 디페닐 술폰(4,4'-Bis(3-amino phenoxy) diphenyl sulfone, DBSDA) 중에서 선택되는 1종 이상을 포함할 수 있으며, 이에 언급한 종류로 한정하진 않는다.As diamines used in one embodiment of the present invention, in addition to TFDB, FDA and FFDA, oxydianiline (4,4'-Oxydianiline, ODA), p-phenylene diamine (pPDA), m-phenylenediamine (meta-phenylene diamine, mPDA), p-methylene dianiline (para-Methylene Dianiline, pMDA), m-methylene dianiline (meta-Methylene Dianiline, mMDA), bisaminophenoxy benzene (1,3-bis(3) -aminophenoxy) benzene, 133APB), bisaminophenoxybenzene (1,3-bis(4-aminophenoxy) benzene, 134APB), bisaminophenoxyphenyl hexafluoropropane (2,2'-bis[4(4- aminophenoxy)phenyl] hexafluoropropane, 4BDAF), bisaminophenyl hexafluoropropane (2,2'-bis(3-aminophenyl)hexafluoropropane, 33-6F), bisaminophenyl hexafluoropropane (2,2'-bis() 4-aminophenyl)hexafluoropropane, 44-6F), bis(4-aminophenyl)sulfone, 4DDS), bis(3-aminophenyl)sulfone (3DDS), cyclohexanediamine (1,3) -Cyclohexanediamine, 13CHD), cyclohexanediamine (1,4-Cyclohexanediamine, 14CHD), bisaminophenoxyphenylpropane (2,2-Bis[4-(4-aminophenoxy)-phenyl]propane, 6HMDA), bisaminohydr Roxyphenyl hexafluoropropane2,2-Bis(3-amino-4-hydroxy-phenyl)-hexafluoropropane, 6FAP), bisaminophenoxy diphenyl sulfone (4,4'-Bis(3-amino phenoxy) diphenyl sulfone , DBSDA) may contain one or more selected from and is not limited to the above-mentioned types.
한편, 본 발명에서 사용되는 디안하이드라이드는 PMDA, 6FDA, BPDA 이외에, 4-(2,5-디옥소테트라하이드로푸란-3-일)-1,2,3,4-테트라하이드로나프탈렌-1,2-디카르복실릭안하이드라이드(TDA), 벤조페논 테트라카르복실릭 디안하이드라이드 (3,3,4,4-Benzophenone tetracarboxylic dianhydride, BTDA), 옥시디프탈릭 디안하이드라이드 (4,4-Oxydiphthalic dianhydride,ODPA), 비스카르복시페닐 디메틸 실란 디안하이드라이드( Bis(3,4dicarboxyphenyl)dimethyl-silane dianhydride, SiDA), 비스 디카르복시페녹시 디페닐 설파이드 디안하이드라이드(4,4-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, BDSDA), 술포닐 디프탈릭안하이드라이드(Sulfonyldiphthalic anhydride, SO2DPA), 사이클로부탄 테트라카르복실릭 디안하이드라이드(Cyclobutane -1,2,3,4 - tetracarboxylic dianhydride, CBDA), 이소프로필리덴이페녹시 비스 프탈릭안하이드라이드(4,4'-(4,4'-Isopropylidenediphenoxy)bis(phthalic anhydride), 6HBDA) 중에서 선택되는 1종 이상을 포함할 수 있으며, 이에 언급한 종류로 한정하진 않는다.On the other hand, the dianhydride used in the present invention is, in addition to PMDA, 6FDA, and BPDA, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride (TDA), benzophenone tetracarboxylic dianhydride (3,3,4,4-Benzophenone tetracarboxylic dianhydride, BTDA), oxydiphthalic dianhydride (4,4-Oxydiphthalic dianhydride) ,ODPA), biscarboxyphenyl dimethyl silane dianhydride ( Bis(3,4dicarboxyphenyl)dimethyl-silane dianhydride, SiDA), bisdicarboxyphenoxy diphenyl sulfide dianhydride (4,4-bis(3,4-dicarboxyphenoxy) )diphenyl sulfide dianhydride, BDSDA), sulfonyldiphthalic anhydride (SO 2 DPA), cyclobutane tetracarboxylic dianhydride (Cyclobutane -1,2,3,4 - tetracarboxylic dianhydride, CBDA), may include one or more selected from isopropylidene iphenoxy bis phthalic anhydride (4,4'-(4,4'-Isopropylidenediphenoxy)bis(phthalic anhydride), 6HBDA), and the above-mentioned types not limited to
본 발명의 일 구현예에서는 상술한 디아민 및 디안하이드라이드 성분을 포함하여 중합 반응에 참여한다. In one embodiment of the present invention, it participates in the polymerization reaction including the above-described diamine and dianhydride components.
상기 반응시의 조건은 특별히 한정되지 않지만 반응 온도는 0~80℃가 바람직하고, 반응시간은 2~48시간이 바람직하다. 또한 반응 시 아르곤이나 질소 등의 불활성 기체 분위기인 것이 보다 바람직하다.Although the conditions at the time of the said reaction are not specifically limited, 0-80 degreeC of reaction temperature is preferable, and 2-48 hours of reaction time are preferable. In addition, it is more preferable to use an inert gas atmosphere such as argon or nitrogen during the reaction.
상기 단량체들의 용액 중합반응을 위한 유기용매는 폴리아믹산을 용해하는 용매이면 특별히 한정되지 않는다. 공지된 반응용매로서 m-크레졸, N-메틸-2-피롤리돈(NMP), 디메틸포름아미드(DMF), 디메틸아세트아미드(DMAc), 디메틸설폭사이드(DMSO), 아세톤, 에틸아세테이트, 디에틸포름아미드(DEF), 디에틸아세트아미드(DEA), Propylene glycol monomethyl ether(PGME), Propylene glycol monomethyl ether Acetate(PGMEA), Ethyl, Lactate, 3-Methoxy-N,N-Dimethylpropionamide, 3-Butoxy-N,N-methylpropionamide 중에서 선택된 하나 이상의 극성용매를 사용한다. 이외에도 테트라하이드로퓨란(THF), 클로로포름과 같은 저비점 용액 또는 γ-부티로락톤과 같은 저흡수성 용매를 사용할 수 있다. 이에 언급한 종류로 한정하지 않으며 이러한 용매는 목적에 따라 단독 혹은 2종 이상 사용할 수 있다.The organic solvent for the solution polymerization of the monomers is not particularly limited as long as it dissolves the polyamic acid. Known reaction solvents include m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, ethyl acetate, diethyl Formamide (DEF), diethylacetamide (DEA), Propylene glycol monomethyl ether (PGME), Propylene glycol monomethyl ether Acetate (PGMEA), Ethyl, Lactate, 3-Methoxy-N,N-Dimethylpropionamide, 3-Butoxy-N , Use at least one polar solvent selected from N-methylpropionamide. In addition, a low-boiling-point solution such as tetrahydrofuran (THF), chloroform, or a low-absorption solvent such as γ-butyrolactone may be used. It is not limited to the above-mentioned types, and these solvents may be used alone or in two or more types depending on the purpose.
유기용매의 함량에 대하여 특별히 한정되지는 않으나, 적절한 폴리아믹산 용액의 분자량과 점도를 얻기 위하여 유기용매의 함량은 전체 폴리아믹산 용액 중 50~95중량%가 바람직하고, 더욱 좋게는 70~90중량%인 것이 보다 바람직하다. The content of the organic solvent is not particularly limited, but in order to obtain an appropriate molecular weight and viscosity of the polyamic acid solution, the content of the organic solvent is preferably 50 to 95% by weight of the total polyamic acid solution, more preferably 70 to 90% by weight It is more preferable that
본 발명의 다른 일 구현예에 따르면, 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)로부터 유래된 반복단위 및 피로멜리틱 디안하이드라이드(1,2,4,5-benzene tetracarboxylic dianhydride, PMDA)로부터 유래된 반복단위를 포함하는 제1 블록 구조 및 비스 트리플루오로메틸 벤지딘(2,2'-bis(trifluoromethyl)benzidine, TFDB)로부터 유래된 반복단위 및 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(6FDA) 및 비페닐 테트라카르복실릭 디안하이드라이드 (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) 중에서 선택되는 1종 이상으로부터 유래된 반복단위를 포함하는 제2 블록 구조를 포함하는 것인 폴리아믹산을 제공하는 것이다.According to another embodiment of the present invention, a repeating unit and pyromellitic dianhydride (1,2,4,5) derived from bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) -Bene tetracarboxylic dianhydride (PMDA) with a first block structure including a repeating unit and bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) with a repeating unit and 2,2- At least one selected from bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and biphenyl tetracarboxylic dianhydride (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) To provide a polyamic acid comprising a second block structure comprising a repeating unit derived from.
상기 폴리아믹산은 상술한 제조방법으로 제조되는 것이 바람직하다.The polyamic acid is preferably prepared by the above-described manufacturing method.
상기 제조방법으로 제조된 폴리아믹산은 1종의 디아민을 분할 투입하여 1종의 디아민이 특정함량으로 포함된 제1 블록 구조 및 제2 블록 구조를 포함함으로써 기존 방법처럼 한꺼번에 투입하는 방법에 의해 제조된 폴리아믹산에 비해 황색도 및 투과도가 저하되지 않고 선형열팽창계수가 개선된 효과를 얻을 수 있는 것이다.The polyamic acid prepared by the above manufacturing method is prepared by a method in which one type of diamine is divided and added at once like the existing method by including a first block structure and a second block structure containing one type of diamine in a specific content. Compared to polyamic acid, yellowness and transmittance are not lowered, and the effect of improving the linear thermal expansion coefficient can be obtained.
상기 제1 블록 구조에서의 PMDA대 제2 블록 구조에서의 6FDA 및 BPDA 중에서 선택되는 1종 이상의 몰비는 90 내지 25 : 10 내지 75, 바람직하게는 90 내지 30 : 10 내지 70인 것이 좋다. At least one molar ratio selected from PMDA in the first block structure to 6FDA and BPDA in the second block structure is 90 to 25:10 to 75, preferably 90 to 30:10 to 70.
상기 제1 블록 구조에서의 PMDA 및 제2 블록 구조에서의 6FDA 및 BPDA 중에서 선택되는 1종 이상이 상기 몰비 범위를 벗어나는 경우 10 이상의 황색도를 가지거나 30ppm/℃ 이상의 열팽창계수를 가지는 문제가 있을 수 있다.When at least one selected from PMDA in the first block structure and 6FDA and BPDA in the second block structure is out of the molar ratio range, there may be a problem having a yellowness of 10 or more or a coefficient of thermal expansion of 30 ppm/℃ or more. have.
또한, 상기 제1 블록 구조에서의 PMDA대 제2 블록 구조에서의 6FDA의 몰비는 90 내지 70 : 10 내지 30, 바람직하게는 90 내지 75 : 10 내지 25 인 것이 좋다.In addition, the molar ratio of PMDA in the first block structure to 6FDA in the second block structure is 90 to 70:10 to 30, preferably 90 to 75:10 to 25.
상기 제1 블록 구조에서의 PMDA 및 제2 블록 구조에서의 6FDA가 상기 몰비 범위를 벗어나는 경우 PMDA의 비율이 범위보다 높아지면 선형열팽창계수는 매우 낮아지지만 황색도가 매우 높아지는 문제가 있을 수 있으며, 6FDA의 비율이 범위보다 높아지면 황색도는 매우 낮아지는 장점이 있지만 선형열팽창계수가 증가하는 문제가 있을 수 있다.When PMDA in the first block structure and 6FDA in the second block structure are out of the molar ratio range, if the ratio of PMDA is higher than the range, the linear thermal expansion coefficient is very low, but there may be a problem that the yellowness is very high, and 6FDA If the ratio of is higher than the range, the yellowness is very low, but there may be a problem in that the linear thermal expansion coefficient increases.
또한, 상기 제1 블록 구조에서의 PMDA대 제2 블록 구조에서의 BPDA의 몰비는 90 내지 25 : 10 내지 75, 바람직하게는 85 내지 30 : 15 내지 70 인 것이 좋다.In addition, the molar ratio of PMDA in the first block structure to BPDA in the second block structure is 90 to 25:10 to 75, preferably 85 to 30:15 to 70.
상기 제1 블록 구조에서의 PMDA 및 제2 블록 구조에서의 BPDA가 상기 몰비 범위를 벗어나는 경우 PMDA의 비율이 범위보다 높아지면 선형열팽창계수는 매우 낮아지지만 황색도가 매우 높아지는 문제가 있을 수 있으며, BPDA의 비율이 범위보다 높아지면 PMDA 대비 황색도는 낮아지는 장점이 있지만 선형열팽창계수가 증가되는 문제가 있을 수 있다.When PMDA in the first block structure and BPDA in the second block structure are out of the molar ratio range, if the ratio of PMDA is higher than the range, the linear thermal expansion coefficient is very low, but there may be a problem that the yellowness is very high, BPDA When the ratio of is higher than the range, there is an advantage of lowering the yellowness compared to PMDA, but there may be a problem in that the linear thermal expansion coefficient is increased.
본 발명의 일 구현에서는 상기 제1 블록 구조에서의 PMDA대 제2 블록 구조에서의 6FDA대 제2 블록 구조에서의 BPDA의 몰비는 90 내지 50 : 5 내지 30 : 5 내지 20, 바람직하게는 90 내지 55 : 5 내지 30 : 5 내지 15인 것이 보다 바람직하다. In one embodiment of the present invention, the molar ratio of PMDA in the first block structure to 6FDA in the second block structure to BPDA in the second block structure is 90 to 50: 5 to 30: 5 to 20, preferably 90 to 55:5-30: It is more preferable that it is 5-15.
상기 제1 블록 구조에서의 PMDA 및 제2 블록 구조에서의 6FDA 및 BPDA가 상기 몰비 범위를 벗어나는 경우 10 이상의 황색도를 가지거나 30ppm/℃ 이상의 열팽창계수를 가지는 문제가 있을 수 있다.When PMDA in the first block structure and 6FDA and BPDA in the second block structure are out of the molar ratio range, there may be a problem of having a yellowness of 10 or more or a coefficient of thermal expansion of 30 ppm/°C or more.
또한, 상기 비스 TFDB로부터 유래된 반복단위 및 6FDA 및 BPDA 중에서 선택되는 1종 이상으로부터 유래된 반복단위를 포함하는 블록 구조는 비스 아미노 페닐 풀루오렌 (9,9-Bis(4-aminophenyl)fluorene, FDA) 및 비스 플루오로 아미노 페닐 플루오렌 ( 9,9-Bis(3-fluoro-4-aminophenyl)fluorene, FFDA) 중에서 선택된 1종 이상으로부터 유래된 반복단위를 더 포함할 수 있다. 상기 FDA 및 FFDA 중에서 선택된 1종 이상을 더 포함하는 경우 유리전이 온도를 개선시키는 효과를 얻을 수 있다.In addition, the block structure comprising a repeating unit derived from the bis TFDB and a repeating unit derived from at least one selected from 6FDA and BPDA is bisaminophenyl fluorene (9,9-Bis(4-aminophenyl)fluorene, FDA ) and bisfluoroaminophenyl fluorene (9,9-Bis(3-fluoro-4-aminophenyl)fluorene, FFDA) may further include a repeating unit derived from at least one selected from the group consisting of. When one or more selected from the FDA and FFDA is further included, the effect of improving the glass transition temperature can be obtained.
상기 FDA 및 FFDA 중에서 선택된 1종 이상은 디아민 총 몰에 대하여 1몰% 내지 20몰%, 바람직하게는 1 내지 10의 함량으로 포함되는 것이 좋다. 상기 FDA 및 FFDA 중에서 선택된 1종 이상이 상기 범위를 벗어나는 경우 1몰% 미만인 경우 함량이 적어 유리전이온도 개선효과가 거의 없을 수 있으며, 20몰%을 초과하는 경우 황색도 및 열팽창계수가 저하되는 문제가 있을 수 있다.At least one selected from the FDA and FFDA is preferably included in an amount of 1 to 20 mol%, preferably 1 to 10, based on the total mole of diamine. When at least one selected from the FDA and FFDA is out of the above range, when the content is less than 1 mol%, the glass transition temperature improvement effect may be hardly improved, and when it exceeds 20 mol%, the yellowness and thermal expansion coefficient are lowered. there may be
상술한 폴리아믹산을 이미드화하여 폴리이미드 수지를 제조하는 방법은 특별히 한정되는 것이 아니고, 종래부터 공지된 방법을 사용할 수 있다. 상기 폴리아믹산의 이미드화시키는 방법으로는 열이미드화법, 화학이미드화법, 열이미드화법과 화학이미드화법을 병용하여 적용할 수 있는데, 열이미드화법을 사용하는 것이 보다 바람직하다. 보다 바람직하기는 화학이미드화법을 실시한 용액을 침전을 실시한 후 정제, 건조 후 다시 용매에 녹여서 사용한다. 이 용매는 상기에 언급한 용매와 같다. 화학 이미드화법은 폴리아믹산 용액에 아세트산무수물 등의 산무수물로 대표되는 탈수제와 이소퀴놀린, β-피콜린, 피리딘 등의 3급 아민류 등으로 대표되는 이미드화 촉매를 적용시키는 방법이다. 화학 이미드화법에 열 이미드화법을 병용할 수 있으며, 가열 조건은 폴리아믹산 용액의 종류, 필름의 두께 등에 의하여 변동될 수 있다.The method of imidating the above-mentioned polyamic acid to manufacture a polyimide resin is not specifically limited, A conventionally well-known method can be used. As a method for imidizing the polyamic acid, a thermal imidization method, a chemical imidization method, a thermal imidization method and a chemical imidization method may be used in combination, but it is more preferable to use a thermal imidization method. More preferably, the solution subjected to the chemical imidization method is precipitated, purified, dried, and then dissolved again in a solvent before use. This solvent is the same as the solvent mentioned above. Chemical imidization is a method of applying a dehydrating agent represented by an acid anhydride such as acetic anhydride and an imidization catalyst represented by tertiary amines such as isoquinoline, β-picoline, and pyridine to a polyamic acid solution. Thermal imidization may be used in combination with chemical imidization, and heating conditions may vary depending on the type of polyamic acid solution, the thickness of the film, and the like.
본 발명의 다른 일 구현예에 따르면, 상기 폴리이미드 수지로 제조된 폴리이미드 필름을 제공하는 것이다. According to another embodiment of the present invention, there is provided a polyimide film made of the polyimide resin.
상기 폴리이미드 필름은 수득된 폴리아믹산 용액을 이미드화한 후, 이미드화한 용액을 제 2 용매에 투입하고 침전, 여과 및 건조하여 폴리이미드 수지의 고형분을 수득하고, 수득된 폴리이미드 수지 고형분을 제 1 용매에 용해시킨 폴리이미드 용액을 이용하여 제막공정을 통하여 얻을 수도 있다.The polyimide film is obtained by imidizing the obtained polyamic acid solution, then adding the imidized solution to a second solvent, precipitation, filtration, and drying to obtain a solid content of a polyimide resin, and prepare the obtained polyimide resin solid content 1 It can also be obtained through a film forming process using a polyimide solution dissolved in a solvent.
즉, 상술한 폴리아믹산을 화학 이미드화법으로 폴리이미드 수지를 제조한 후 침전, 건조하여 용매에 녹여 용액화 하여 지지체에 도포하는데 도포된 용액은 건조 공기 및 열처리에 의해 지지체 위에서 필름화된다. That is, after preparing a polyimide resin by chemical imidization of the above-described polyamic acid, precipitation, drying, dissolving in a solvent to form a solution, and applying to the support, the applied solution is filmed on the support by dry air and heat treatment.
상기 제 1 용매는 폴리아믹산 용액 중합시 사용한 용매와 동일한 용매를 사용할 수 있고, 상기 제 2 용매는 폴리아믹산 수지의 고형분을 수득하기 위하여 제 1 용매보다 극성이 낮은 것을 사용하며, 구체적으로는 물, 알코올류, 에테르류 및 케톤류 중 선택된 1종 이상인 것일 수 있다. 이때, 상기 제 2 용매의 함량은 특별히 한정되는 것은 아니지만, 폴리아믹산 용액의 중량 대비 5 내지 20 중량배인 것이 바람직하다.The first solvent may be the same solvent as the solvent used for polymerization of the polyamic acid solution, and the second solvent is used with a lower polarity than the first solvent in order to obtain a solid content of the polyamic acid resin, specifically water, It may be at least one selected from alcohols, ethers and ketones. In this case, the content of the second solvent is not particularly limited, but is preferably 5 to 20 times by weight relative to the weight of the polyamic acid solution.
상기 도포된 필름의 필름화 온도 조건은 250~500℃가 바람직하며 지지체로는 유리판, 알루미늄박, 순환 스테인레스 벨트, 스테인레스 드럼 등을 사용할 수 있다.The film forming temperature condition of the coated film is preferably 250 ~ 500 ℃, and as a support, a glass plate, aluminum foil, a circulating stainless belt, a stainless drum, etc. can be used.
필름화에 필요한 처리 시간은 온도, 지지체의 종류, 도포된 폴리아믹산 용액의 양, 촉매의 혼합조건에 따라 다르며 일정한 시간으로 한정되어 있지 않다. 바람직하기로는 5분~30분 사이의 범위에서 시행하는 것이 좋다.The processing time required for film formation depends on the temperature, the type of support, the amount of the applied polyamic acid solution, and the mixing conditions of the catalyst, and is not limited to a certain time. Preferably, it is good to carry out in the range between 5 minutes and 30 minutes.
열처리온도는 100~500℃ 사이에서 진행하며 처리 시간은 1분~30분 사이에서 진행한다. 열처리하여 건조 및 이미드화를 완료시킨 후, 지지체로부터 박리한다. The heat treatment temperature is between 100 and 500°C, and the treatment time is between 1 and 30 minutes. After completion of drying and imidization by heat treatment, it is peeled off from the support.
얻어지는 폴리이미드 필름의 두께는 특별히 한정되는 것은 아니지만, 10~250㎛의 범위인 것이 바람직하고, 보다 바람직하게는 10~100㎛인 것이 좋다.Although the thickness of the polyimide film obtained is not specifically limited, It is preferable that it is the range of 10-250 micrometers, It is good that it is 10-100 micrometers more preferably.
본 발명에서 제조된 폴리이미드 필름은 50~350℃에서 열팽창계수(Coefficient of Thermal Expansion)가 30ppm/℃ 이하인 것이 바람직하다. The polyimide film prepared in the present invention preferably has a coefficient of thermal expansion (Coefficient of Thermal Expansion) of 30 ppm/°C or less at 50 to 350°C.
본 발명에서 제조된 폴리이미드 필름은 두께 10~100㎛를 기준으로 UV분광계로 투과도 측정시 550㎚에서 투과도가 85% 이상, 바람직하게는 90% 이상인 것이 좋다. The polyimide film prepared in the present invention preferably has a transmittance of 85% or more, preferably 90% or more at 550 nm when the transmittance is measured with a UV spectrometer based on a thickness of 10 to 100 μm.
또한 폴리이미드 필름은 필름 두께 10~100㎛를 기준으로 황색도가 10 이하, 바람직하게는 5 이하인 것이 좋다.In addition, the polyimide film preferably has a yellowness of 10 or less, preferably 5 or less, based on a film thickness of 10 to 100 μm.
이하, 본 발명을 실시예를 통하여 보다 상세히 설명하나, 본 발명의 범위가 하기 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples, but the scope of the present invention is not limited to the following examples.
<실시예 1> <Example 1>
반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 500ml 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 273.882g을 채운 후에 TFDB 28.821을 용해한 후, PMDA 19.631g을 투입한 후 3시간 교반하였다. 그 후 추가로 TFDB 3.202g을 용해시킨 후, 6FDA 4.443g을 넣고 15시간 반응하였다. 그 결과 고형분의 농도가 17 중량%인 폴리아믹산 용액을 수득하였다. 반응 종료 후 수득된 용액을 유리판에 도포한 후 80℃의 열풍으로 20분 처리하고 370℃ 도달 후 30분간 등온 처리하여 경화하였다. 그 후 서서히 냉각해 유리판으로부터 분리하여 폴리이미드 필름을 얻었다.After filling 273.882 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and cooler as a reactor, TFDB 28.821 was dissolved, PMDA 19.631 g was added and stirred for 3 hours. Thereafter, 3.202 g of TFDB was further dissolved, and 4.443 g of 6FDA was added thereto, followed by reaction for 15 hours. As a result, a polyamic acid solution having a solid content of 17 wt% was obtained. After completion of the reaction, the obtained solution was applied to a glass plate, treated with hot air at 80° C. for 20 minutes, and then cured by isothermal treatment for 30 minutes after reaching 370° C. Then, it cooled gradually, isolate|separated from the glass plate, and obtained the polyimide film.
<실시예 2> <Example 2>
반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 500ml 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 284.922g을 채운 후에 TFDB 25.618g을 용해한 후, PMDA 17.450g을 투입한 후 3시간 교반하였다. 그 후 추가로 TFDB 6.405g을 용해시킨 후, 6FDA 8.885g을 넣고 15시간 반응하였다. 그 결과 고형분의 농도가 17 중량%인 폴리아믹산 용액을 수득하였다. 반응 종료 후 수득된 용액을 유리판에 도포한 후 80℃의 열풍으로 20분 처리하고 370℃ 도달 후 30분간 등온 처리하여 경화하였다. 그 후 서서히 냉각해 유리판으로부터 분리하여 폴리이미드 필름을 얻었다.After filling 284.922 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and cooler as a reactor, 25.618 g of TFDB was dissolved, and PMDA After adding 17.450 g, the mixture was stirred for 3 hours. After that, 6.405 g of TFDB was further dissolved, and 8.885 g of 6FDA was added thereto, followed by reaction for 15 hours. As a result, a polyamic acid solution having a solid content of 17 wt% was obtained. After completion of the reaction, the obtained solution was applied to a glass plate, treated with hot air at 80° C. for 20 minutes, and then cured by isothermal treatment for 30 minutes after reaching 370° C. Then, it cooled gradually, isolate|separated from the glass plate, and obtained the polyimide film.
<실시예 3><Example 3>
반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 500ml 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 295.963g을 채운 후에 TFDB 22.416g을 용해한 후, PMDA 15.268g을 투입한 후 3시간 교반하였다. 그 후 추가로 TFDB 9.607g을 용해시킨 후, 6FDA 13.328g을 넣고 15시간 반응하였다. 그 결과 고형분의 농도가 17 중량%인 폴리아믹산 용액을 수득하였다. 반응 종료 후 수득된 용액을 유리판에 도포한 후 80℃의 열풍으로 20분 처리하고 370℃ 도달 후 30분간 등온 처리하여 경화하였다. 그 후 서서히 냉각해 유리판으로부터 분리하여 폴리이미드 필름을 얻었다.After filling 295.963 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and cooler as a reactor, 22.416 g of TFDB was dissolved, and then PMDA After adding 15.268 g, the mixture was stirred for 3 hours. After that, after dissolving 9.607 g of TFDB in addition, 13.328 g of 6FDA was added and reacted for 15 hours. As a result, a polyamic acid solution having a solid content of 17 wt% was obtained. After completion of the reaction, the obtained solution was applied to a glass plate, treated with hot air at 80° C. for 20 minutes, and then cured by isothermal treatment for 30 minutes after reaching 370° C. Then, it cooled gradually, isolate|separated from the glass plate, and obtained the polyimide film.
<실시예 4><Example 4>
반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 500ml 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 295.963g을 채운 후에 TFDB 9.607g을 용해한 후, 6FDA 13.328g을 투입한 후 3시간 교반하였다. 그 후 추가로 TFDB 22.416g을 용해시킨 후, PMDA 15.268g을 넣고 15시간 반응하였다. 그 결과 고형분의 농도가 17 중량%인 폴리아믹산 용액을 수득하였다. 반응 종료 후 수득된 용액을 유리판에 도포한 후 80℃의 열풍으로 20분 처리하고 370℃ 도달 후 30분간 등온 처리하여 경화하였다. 그 후 서서히 냉각해 유리판으로부터 분리하여 폴리이미드 필름을 얻었다.After filling 295.963 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and cooler as a reactor, 9.607 g of TFDB was dissolved, and then 6FDA After adding 13.328 g, the mixture was stirred for 3 hours. Thereafter, 22.416 g of TFDB was further dissolved, and 15.268 g of PMDA was added thereto, followed by reaction for 15 hours. As a result, a polyamic acid solution having a solid content of 17 wt% was obtained. After completion of the reaction, the obtained solution was applied to a glass plate, treated with hot air at 80° C. for 20 minutes, and then cured by isothermal treatment for 30 minutes after reaching 370° C. Then, it cooled gradually, isolate|separated from the glass plate, and obtained the polyimide film.
<실시예 5> <Example 5>
반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 500ml 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 281.419g을 채운 후에 TFDB 16.012g을 용해한 후, PMDA 10.906g을 투입한 후 3시간 교반하였다. 그 후 추가로 TFDB 16.012g을 용해시킨 후, BPDA 14.711g을 넣고 15시간 반응하였다. 그 결과 고형분의 농도가 17 중량%인 폴리아믹산 용액을 수득하였다. 반응 종료 후 수득된 용액을 유리판에 도포한 후 80℃의 열풍으로 20분 처리하고 350℃ 도달 후 10분간 등온 처리하여 경화하였다. 그 후 서서히 냉각해 유리판으로부터 분리하여 폴리이미드 필름을 얻었다.After filling 281.419 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen into a 500 ml reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and cooler as a reactor, 16.012 g of TFDB was dissolved, and then PMDA After adding 10.906 g, the mixture was stirred for 3 hours. After that, 16.012 g of TFDB was further dissolved, and 14.711 g of BPDA was added thereto and reacted for 15 hours. As a result, a polyamic acid solution having a solid content of 17 wt% was obtained. After completion of the reaction, the obtained solution was applied to a glass plate, treated with hot air at 80° C. for 20 minutes, and then cured by isothermal treatment for 10 minutes after reaching 350° C. Then, it cooled gradually, isolate|separated from the glass plate, and obtained the polyimide film.
<실시예 6> <Example 6>
반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 500ml 반응기에 질소를 통과시키면서 N,N-디메틸아세트아마이드(DMAc) 283.076g을 채운 후에 TFDB 13.450g을 용해한 후, PMDA 9.161g을 투입한 후 3시간 교반하였다. 그 후 추가로 TFDB 23.825g과 FFDA 1.384g을 용해시킨 후, BPDA 22.949g을 넣고 15시간 반응하였다. 그 결과 고형분의 농도가 20 중량%인 폴리아믹산 용액을 수득하였다. 반응 종료 후 수득된 용액을 유리판에 도포한 후 80℃의 열풍으로 20분 처리하고 350℃ 도달 후 10분간 등온 처리하여 경화하였다. 그 후 서서히 냉각해 유리판으로부터 분리하여 폴리이미드 필름을 얻었다.As a reactor, 283.076 g of N,N-dimethylacetamide (DMAc) was filled while passing nitrogen through a 500 ml reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller, and cooler. After dissolving 13.450 g of TFDB, 9.161 g of PMDA was added and stirred for 3 hours. Thereafter, 23.825 g of TFDB and 1.384 g of FFDA were further dissolved, and 22.949 g of BPDA was added thereto, followed by reaction for 15 hours. As a result, a polyamic acid solution having a solid content of 20% by weight was obtained. After completion of the reaction, the obtained solution was applied to a glass plate, treated with hot air at 80° C. for 20 minutes, and then cured by isothermal treatment for 10 minutes after reaching 350° C. Then, it cooled gradually, isolate|separated from the glass plate, and obtained the polyimide film.
<실시예 7> <Example 7>
반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 500ml 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 288.638을 채운 후에 TFDB 22.416g을 용해한 후, PMDA 15.268g을 투입한 후 3시간 교반하였다. 그 후 추가로 TFDB 9.607g을 용해시킨 후, 6FDA 8.885g을 넣고 3시간 반응하였다. 마지막으로 BPDA 2.942g을 넣고 15시간 반응하였다. 그 결과 고형분의 농도가 17 중량%인 폴리아믹산 용액을 수득하였다. 반응 종료 후 수득된 용액을 유리판에 도포한 후 80℃의 열풍으로 20분 처리하고 370℃ 도달 후 30분간 등온 처리하여 경화하였다. 그 후 서서히 냉각해 유리판으로부터 분리하여 폴리이미드 필름을 얻었다.As a reactor, N-methyl-2-pyrrolidone (NMP) 288.638 was filled in a 500ml reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and cooler while passing nitrogen. After dissolving 22.416 g of TFDB, PMDA 15.268 g was added and stirred for 3 hours. After that, after dissolving 9.607 g of TFDB in addition, 8.885 g of 6FDA was added and reacted for 3 hours. Finally, 2.942 g of BPDA was added and reacted for 15 hours. As a result, a polyamic acid solution having a solid content of 17 wt% was obtained. After completion of the reaction, the obtained solution was applied to a glass plate, treated with hot air at 80° C. for 20 minutes, and then cured by isothermal treatment for 30 minutes after reaching 370° C. Then, it cooled gradually, isolate|separated from the glass plate, and obtained the polyimide film.
<실시예 8> <Example 8>
반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 500ml 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 288.638을 채운 후에 TFDB 22.416g을 용해한 후, PMDA 15.268g을 투입한 후 3시간 교반하였다. 그 후 추가로 TFDB 6.405g을 용해시킨 후, 6FDA 8.885g을 넣고 3시간 반응하였다. 마지막으로 TFDB 3.202g을 용해시킨 후, BPDA 2.942g을 넣고 15시간 반응하였다. 그 결과 고형분의 농도가 17 중량%인 폴리아믹산 용액을 수득하였다. 반응 종료 후 수득된 용액을 유리판에 도포한 후 80℃의 열풍으로 20분 처리하고 370℃ 도달 후 30분간 등온 처리하여 경화하였다. 그 후 서서히 냉각해 유리판으로부터 분리하여 폴리이미드 필름을 얻었다.As a reactor, N-methyl-2-pyrrolidone (NMP) 288.638 was filled in a 500ml reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and cooler while passing nitrogen. After dissolving 22.416 g of TFDB, PMDA 15.268 g was added and stirred for 3 hours. Thereafter, 6.405 g of TFDB was further dissolved, and 8.885 g of 6FDA was added thereto, followed by reaction for 3 hours. Finally, after dissolving 3.202 g of TFDB, 2.942 g of BPDA was added and reacted for 15 hours. As a result, a polyamic acid solution having a solid content of 17 wt% was obtained. After completion of the reaction, the obtained solution was applied to a glass plate, treated with hot air at 80° C. for 20 minutes, and then cured by isothermal treatment for 30 minutes after reaching 370° C. Then, it cooled gradually, isolate|separated from the glass plate, and obtained the polyimide film.
<비교예 1> <Comparative Example 1>
반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 500ml 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 268.362g을 채운 후에 TFDB 32.023g을 용해한 후, PMDA 20.721g을 투입한 후 3시간 교반하였다. 그 후 6FDA 2.221g을 넣고 15시간 반응하였다. 그 결과 고형분의 농도가 17 중량%인 폴리아믹산 용액을 수득하였다. 반응 종료 후 수득된 용액을 유리판에 도포한 후 80℃의 열풍으로 20분 처리하고 370℃ 도달 후 30분간 등온 처리하여 경화하였다. 그 후 서서히 냉각해 유리판으로부터 분리하여 폴리이미드 필름을 얻었다.After filling 268.362 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and cooler as a reactor, 32.023 g of TFDB was dissolved, and PMDA After adding 20.721 g, the mixture was stirred for 3 hours. After that, 2.221 g of 6FDA was added and reacted for 15 hours. As a result, a polyamic acid solution having a solid content of 17 wt% was obtained. After completion of the reaction, the obtained solution was applied to a glass plate, treated with hot air at 80° C. for 20 minutes, and then cured by isothermal treatment for 30 minutes after reaching 370° C. Then, it cooled gradually, isolate|separated from the glass plate, and obtained the polyimide film.
<비교예 2> <Comparative Example 2>
반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 500ml 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 295.963g을 채운 후에 TFDB 32.023g을 용해한 후, PMDA 15.268g을 투입한 후 3시간 교반하였다. 그 후 6FDA 13.328g을 넣고 15시간 반응하였다. 그 결과 고형분의 농도가 17 중량%인 폴리아믹산 용액을 수득하였다. 반응 종료 후 수득된 용액을 유리판에 도포한 후 80℃의 열풍으로 20분 처리하고 370℃ 도달 후 30분간 등온 처리하여 경화하였다. 그 후 서서히 냉각해 유리판으로부터 분리하여 폴리이미드 필름을 얻었다.After filling 295.963 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and cooler as a reactor, 32.023 g of TFDB was dissolved, and PMDA After adding 15.268 g, the mixture was stirred for 3 hours. After that, 13.328 g of 6FDA was added and reacted for 15 hours. As a result, a polyamic acid solution having a solid content of 17 wt% was obtained. After completion of the reaction, the obtained solution was applied to a glass plate, treated with hot air at 80° C. for 20 minutes, and then cured by isothermal treatment for 30 minutes after reaching 370° C. Then, it cooled gradually, isolate|separated from the glass plate, and obtained the polyimide film.
<비교예 3> <Comparative Example 3>
반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 500ml 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 295.963g을 채운 후에 TFDB 32.023g을 용해한 후, 6FDA 13.328g을 투입한 후 3시간 교반하였다. 그 후 PMDA 15.268g을 넣고 15시간 반응하였다. 그 결과 고형분의 농도가 17 중량%인 폴리아믹산 용액을 수득하였다. 반응 종료 후 수득된 용액을 유리판에 도포한 후 80℃의 열풍으로 20분 처리하고 370℃ 도달 후 30분간 등온 처리하여 경화하였다. 그 후 서서히 냉각해 유리판으로부터 분리하여 폴리이미드 필름을 얻었다.After filling 295.963 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and cooler as a reactor, 32.023 g of TFDB was dissolved, and then 6FDA After adding 13.328 g, the mixture was stirred for 3 hours. After that, 15.268 g of PMDA was added and reacted for 15 hours. As a result, a polyamic acid solution having a solid content of 17 wt% was obtained. After completion of the reaction, the obtained solution was applied to a glass plate, treated with hot air at 80° C. for 20 minutes, and then cured by isothermal treatment for 30 minutes after reaching 370° C. Then, it cooled gradually, isolate|separated from the glass plate, and obtained the polyimide film.
<비교예 4> <Comparative Example 4>
반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 500ml 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 301.483g을 채운 후에 TFDB 32.023g을 용해한 후, PMDA 14.178g을 투입한 후 3시간 교반하였다. 그 후 6FDA 15.549g을 넣고 15시간 반응하였다. 그 결과 고형분의 농도가 17 중량%인 폴리아믹산 용액을 수득하였다. 반응 종료 후 수득된 용액을 유리판에 도포한 후 80℃의 열풍으로 20분 처리하고 370℃ 도달 후 30분간 등온 처리하여 경화하였다. 그 후 서서히 냉각해 유리판으로부터 분리하여 폴리이미드 필름을 얻었다.After filling 301.483 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and cooler as a reactor, 32.023 g of TFDB was dissolved, and PMDA After adding 14.178 g, the mixture was stirred for 3 hours. After that, 15.549 g of 6FDA was added and reacted for 15 hours. As a result, a polyamic acid solution having a solid content of 17 wt% was obtained. After completion of the reaction, the obtained solution was applied to a glass plate, treated with hot air at 80° C. for 20 minutes, and then cured by isothermal treatment for 30 minutes after reaching 370° C. Then, it cooled gradually, isolate|separated from the glass plate, and obtained the polyimide film.
상기 실시예 및 비교예로 제조된 폴리이미드 필름을 하기의 방법으로 물성을 평가하였으며, 그 결과를 하기 표 1에 나타내었다. The physical properties of the polyimide films prepared in Examples and Comparative Examples were evaluated by the following method, and the results are shown in Table 1 below.
(1) 투과도(TT) 측정(1) Measurement of transmittance (TT)
UV분광계(코티카 미놀타 CM-3700d)를 이용하여 550nm에서 투과도를 3번 측정 하여 평균값을 표 1에 기재하였다.The transmittance was measured three times at 550 nm using a UV spectrometer (Cotica Minolta CM-3700d), and the average value is shown in Table 1.
(2) 황색도(Y.I.) 측정(2) Measurement of yellowness (Y.I.)
UV분광계 (Konita Minolta, CM-3700d)를 이용하여 ASTM E313규격으로 황색도를 측정하였다.Yellowness was measured according to ASTM E313 standard using a UV spectrometer (Konita Minolta, CM-3700d).
(3) 열팽창 계수(CTE) 측정(3) Measurement of coefficient of thermal expansion (CTE)
TMA(TA Instrument사, Q400)을 이용하여 TMA- Method에 따라 2번에 걸쳐 50~350℃에서의 선형 열팽창 계수를 측정하였다. 시편의 크기는 4mm×24mm, 하중은 0.02N으로 승온 속도는 10℃/min으로 하였다. 필름을 제막하고 열처리를 통하여 필름 내에 잔류 응력이 남아 있을 수 있기 때문에 첫 번째 작동(Run)으로 잔류응력을 완전히 제거 후, 두 번째 값을 실측정치로 제시하였다.Using TMA (TA Instrument, Q400), the coefficient of linear thermal expansion at 50 to 350° C. was measured twice according to the TMA-Method. The size of the specimen was 4 mm×24 mm, the load was 0.02 N, and the temperature increase rate was 10° C./min. Since residual stress may remain in the film through heat treatment after forming the film, the residual stress is completely removed by the first run, and the second value is presented as an actual measurement value.
두께(㎛)film
Thickness (㎛)
시
예room
city
Yes
-TFDB(10)-6FDA(10)TFDB(90)-PMDA(90)
-TFDB(10)-6FDA(10)
-TFDB(20)-6FDA(20)TFDB(80)-PMDA(80)
-TFDB(20)-6FDA(20)
-TFDB(30)-6FDA(30)TFDB(70)-PMDA(70)
-TFDB(30)-6FDA(30)
TFDB(70)-PMDA(70)TFDB(30)-6FDA(30)
TFDB(70)-PMDA(70)
-TFDB(50)-BPDA(50)TFDB(50)-PMDA(50)
-TFDB(50)-BPDA(50)
-TFDB(62)-FFDA(3)-BPDA(65)TFDB(35)-PMDA(35)
-TFDB(62)-FFDA(3)-BPDA(65)
-TFDB(30)-6FDA(20)-BPDA(10)TFDB(70)-PMDA(70)
-TFDB(30)-6FDA(20)-BPDA(10)
-TFDB(20)-6FDA(20)
-TFDB(10)-BPDA(10)TFDB(70)-PMDA(70)
-TFDB(20)-6FDA(20)
-TFDB(10)-BPDA(10)
교
예ratio
school
Yes
-PMDA(95)-6FDA(5)TFDB(100)
-PMDA(95)-6FDA(5)
-PMDA(70)-6FDA(30)TFDB(100)
-PMDA(70)-6FDA(30)
-6FDA(30)-PMDA(70)TFDB(100)
-6FDA(30)-PMDA(70)
-PMDA(65)-6FDA(35)TFDB(100)
-PMDA(65)-6FDA(35)
상기 표 1에서 보는 바와 같이 실시예와 비교예를 각각 비교해보면 TFDB를 나누어서 투입하는 실시예 1 내지 8의 경우 황색도, 투과도 및 선형열팽창계수 모두를 우수한 수준으로 만족하고 있으나, 비교예 1은 투과도가 현저히 저하되었으며, 비교예 2 내지 4는 선형열팽창계수가 현저하게 저하되는 물성을 보였다. As shown in Table 1, when comparing Examples and Comparative Examples respectively, in the case of Examples 1 to 8, in which the TFDB is divided, all of the yellowness, transmittance, and coefficient of linear thermal expansion are satisfied at excellent levels, but Comparative Example 1 has transmittance was significantly lowered, and Comparative Examples 2 to 4 showed physical properties in which the linear thermal expansion coefficient was significantly lowered.
이로부터 실시예 1 내지 8은 TFDB를 나누어서 투입하여 황색도 및 선형열팽계수의 트레이드 오프(trade-off) 관계를 극복하였음을 알 수 있었다. From this, it can be seen that Examples 1 to 8 overcome the trade-off relationship between yellowness and linear thermal expansion coefficient by dividing TFDB.
또한, 1차 디안하이드라이드를 PMDA로 2차 디안하이드라이드를 6FDA로 할 경우 PMDA 함량은 30ppm/℃ 이하의 선형열팽창계수를 갖기 위해 65몰% 넘는 것이 바람직하고, 황색도 저하를 막기 위해 90몰%를 넘지 않는 것이 바람직하다. 또한 2차 디안하이드라이드를 BPDA로 적용하여도 같은 효과를 볼 수 있으며, 추가적으로 FFDA를 적용하여도 TFDB를 분할 투입함으로써 선형열팽창계수를 개선시킬 수 있다. 실시예 3 및 4를 보면 1차 투입 디안하이드라이드가 PMDA일 경우가 6FDA일 경우보다 개선 효과가 큰 것을 알 수 있다. 그리고 실시예 7 및 8을 보면 3차 디안하이드라이드 적용 시 TFDB의 분할 투입이 많아질수록 선형열팽창계수는 더욱 개선됨을 확인할 수 있었다.In addition, when the primary dianhydride is PMDA and the secondary dianhydride is 6FDA, the PMDA content is preferably over 65 mol% to have a linear thermal expansion coefficient of 30 ppm/℃ or less, and 90 mol to prevent yellowness deterioration It is preferable not to exceed %. In addition, the same effect can be seen even when the secondary dianhydride is applied as BPDA, and even when FFDA is additionally applied, the linear thermal expansion coefficient can be improved by dividingly inputting TFDB. Looking at Examples 3 and 4, it can be seen that the improvement effect is greater when the primary input dianhydride is PMDA than when 6FDA is used. And, looking at Examples 7 and 8, it was confirmed that the linear thermal expansion coefficient was further improved as the divided input of TFDB increased when the tertiary dianhydride was applied.
Claims (18)
상기 제1 블록 구조 형성 단계 후에 상기 제2 블록 구조 형성 단계를 실시하는 폴리아믹산의 제조방법.Diamine containing bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) and dianhydride containing pyromellitic dianhydride (1,2,4,5-benzene tetracarboxylic dianhydride, PMDA) inputting hydride (a first block structure formation step); and diamines including bis trifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) And biphenyl tetracarboxylic dianhydride (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) the step of adding a dianhydride containing at least one selected from (second block structure formation step); including,
A method of producing a polyamic acid in which the second block structure forming step is performed after the first block structure forming step.
제1항의 제조방법에 의해 제조된 폴리아믹산. A repeating unit derived from bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) and a pyromellitic dianhydride (1,2,4,5-benzene tetracarboxylic dianhydride, PMDA) derived from A first block structure including a repeating unit and a repeating unit derived from bistrifluoromethyl benzidine (2,2'-bis(trifluoromethyl)benzidine, TFDB) and 2,2-bis(3,4-dicarboxyphenyl) A second comprising a repeating unit derived from at least one selected from hexafluoropropane dianhydride (6FDA) and biphenyl tetracarboxylic dianhydride (3,3,4,4-Biphenyltetracarboxylic dianhydride, BPDA) By including a block structure,
A polyamic acid prepared by the method of claim 1 .
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| JP2020532593A JP6980919B2 (en) | 2017-12-29 | 2018-12-26 | Method for producing polyamic acid, polyamic acid, polyimide resin, and polyimide film produced from this. |
| CN201880084832.2A CN111542562B (en) | 2017-12-29 | 2018-12-26 | Method for preparing polyamic acid, polyamic acid prepared by same, polyimide resin and polyimide film |
| PCT/KR2018/016671 WO2019132515A1 (en) | 2017-12-29 | 2018-12-26 | Method for preparing polyamic acid, and polyamic acid, polyimide resin, and polyimide film which are manufactured thereby |
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