KR102621023B1 - Aqueous polyamic acid composition - Google Patents
Aqueous polyamic acid composition Download PDFInfo
- Publication number
- KR102621023B1 KR102621023B1 KR1020210084721A KR20210084721A KR102621023B1 KR 102621023 B1 KR102621023 B1 KR 102621023B1 KR 1020210084721 A KR1020210084721 A KR 1020210084721A KR 20210084721 A KR20210084721 A KR 20210084721A KR 102621023 B1 KR102621023 B1 KR 102621023B1
- Authority
- KR
- South Korea
- Prior art keywords
- group
- polyamic acid
- carbon atoms
- aqueous
- formula
- Prior art date
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- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 77
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 51
- 239000003054 catalyst Substances 0.000 claims description 29
- 229920001721 polyimide Polymers 0.000 claims description 29
- 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 24
- 239000004642 Polyimide Substances 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- -1 pyridine derivative compound Chemical class 0.000 claims description 9
- 150000004985 diamines Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 125000001118 alkylidene group Chemical group 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 239000004305 biphenyl Chemical group 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 238000013007 heat curing Methods 0.000 claims description 3
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 2
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 11
- 238000013035 low temperature curing Methods 0.000 description 9
- 238000001723 curing Methods 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000006358 imidation reaction Methods 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 4
- 238000005102 attenuated total reflection Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 3
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 3
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000011149 active material Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 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 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-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 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- MTPBUCCXRGSDCR-UHFFFAOYSA-N 4-piperidin-1-ylpyridine Chemical compound C1CCCCN1C1=CC=NC=C1 MTPBUCCXRGSDCR-UHFFFAOYSA-N 0.000 description 2
- QJWQYVJVCXMTJP-UHFFFAOYSA-N 4-pyridin-4-ylmorpholine Chemical compound C1COCCN1C1=CC=NC=C1 QJWQYVJVCXMTJP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LSCYTCMNCWMCQE-UHFFFAOYSA-N n-methylpyridin-4-amine Chemical compound CNC1=CC=NC=C1 LSCYTCMNCWMCQE-UHFFFAOYSA-N 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- LERREUOVCXYKGR-UHFFFAOYSA-N (2-phenoxyphenyl)-phenylmethanone Chemical compound C=1C=CC=C(OC=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 LERREUOVCXYKGR-UHFFFAOYSA-N 0.000 description 1
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- FHTDDANQIMVWKZ-UHFFFAOYSA-N 1h-pyridine-4-thione Chemical compound SC1=CC=NC=C1 FHTDDANQIMVWKZ-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- IBTGEEMBZJBBSH-UHFFFAOYSA-N 2,6-dimethoxypyridine Chemical compound COC1=CC=CC(OC)=N1 IBTGEEMBZJBBSH-UHFFFAOYSA-N 0.000 description 1
- LISKAOIANGDBTB-UHFFFAOYSA-N 2-ethoxypyridine Chemical compound CCOC1=CC=CC=N1 LISKAOIANGDBTB-UHFFFAOYSA-N 0.000 description 1
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 1
- IWTFOFMTUOBLHG-UHFFFAOYSA-N 2-methoxypyridine Chemical compound COC1=CC=CC=N1 IWTFOFMTUOBLHG-UHFFFAOYSA-N 0.000 description 1
- VLQBSKLZRSUMTJ-UHFFFAOYSA-N 2-methylsulfanylpyridine Chemical compound CSC1=CC=CC=N1 VLQBSKLZRSUMTJ-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- JFEXPVDGVLNUSC-UHFFFAOYSA-N 3-(3-aminophenyl)sulfanylaniline Chemical compound NC1=CC=CC(SC=2C=C(N)C=CC=2)=C1 JFEXPVDGVLNUSC-UHFFFAOYSA-N 0.000 description 1
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- UVUCUHVQYAPMEU-UHFFFAOYSA-N 3-[2-(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound NC1=CC=CC(C(C=2C=C(N)C=CC=2)(C(F)(F)F)C(F)(F)F)=C1 UVUCUHVQYAPMEU-UHFFFAOYSA-N 0.000 description 1
- DVXYMCJCMDTSQA-UHFFFAOYSA-N 3-[2-(3-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=CC(N)=CC=1C(C)(C)C1=CC=CC(N)=C1 DVXYMCJCMDTSQA-UHFFFAOYSA-N 0.000 description 1
- WFBKIKKAUTUAHK-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)-4-(trifluoromethyl)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C(=CC=2)C(F)(F)F)=C1 WFBKIKKAUTUAHK-UHFFFAOYSA-N 0.000 description 1
- WWNABCFITWBKEM-UHFFFAOYSA-N 3-[3-(3-aminophenyl)phenyl]aniline Chemical compound NC1=CC=CC(C=2C=C(C=CC=2)C=2C=C(N)C=CC=2)=C1 WWNABCFITWBKEM-UHFFFAOYSA-N 0.000 description 1
- GZBHMJRTCUJCBO-UHFFFAOYSA-N 3-[3-[3-(3-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(OC=4C=C(N)C=CC=4)C=CC=3)C=CC=2)=C1 GZBHMJRTCUJCBO-UHFFFAOYSA-N 0.000 description 1
- MFIONUVRAOILLH-UHFFFAOYSA-N 3-[3-[3-(3-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=C(C=CC=2)C=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 MFIONUVRAOILLH-UHFFFAOYSA-N 0.000 description 1
- SABXTRNPHKCTFO-UHFFFAOYSA-N 3-[3-[3-(3-aminophenoxy)phenyl]sulfanylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(SC=3C=C(OC=4C=C(N)C=CC=4)C=CC=3)C=CC=2)=C1 SABXTRNPHKCTFO-UHFFFAOYSA-N 0.000 description 1
- YLTIRYJAWQHSQS-UHFFFAOYSA-N 3-[3-[3-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(C=CC=2)S(=O)(=O)C=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 YLTIRYJAWQHSQS-UHFFFAOYSA-N 0.000 description 1
- OLFCXXUMDWEXKG-UHFFFAOYSA-N 3-[3-[[3-(3-aminophenoxy)phenyl]methyl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(CC=3C=C(OC=4C=C(N)C=CC=4)C=CC=3)C=CC=2)=C1 OLFCXXUMDWEXKG-UHFFFAOYSA-N 0.000 description 1
- LBPVOEHZEWAJKQ-UHFFFAOYSA-N 3-[4-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 LBPVOEHZEWAJKQ-UHFFFAOYSA-N 0.000 description 1
- POXPSTWTPRGRDO-UHFFFAOYSA-N 3-[4-(3-aminophenyl)phenyl]aniline Chemical compound NC1=CC=CC(C=2C=CC(=CC=2)C=2C=C(N)C=CC=2)=C1 POXPSTWTPRGRDO-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 1
- NQZOFDAHZVLQJO-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 NQZOFDAHZVLQJO-UHFFFAOYSA-N 0.000 description 1
- UCQABCHSIIXVOY-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 UCQABCHSIIXVOY-UHFFFAOYSA-N 0.000 description 1
- JERFEOKUSPGKGV-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfanylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(SC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 JERFEOKUSPGKGV-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
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- VILWHDNLOJCHNJ-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfanylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1SC1=CC=C(C(O)=O)C(C(O)=O)=C1 VILWHDNLOJCHNJ-UHFFFAOYSA-N 0.000 description 1
- YJOAIOIVLVUPST-UHFFFAOYSA-N 4-(4-amino-2-methoxyphenyl)-3-methoxyaniline Chemical compound COC1=CC(N)=CC=C1C1=CC=C(N)C=C1OC YJOAIOIVLVUPST-UHFFFAOYSA-N 0.000 description 1
- MITHMOYLTXMLRB-UHFFFAOYSA-N 4-(4-aminophenyl)sulfinylaniline Chemical compound C1=CC(N)=CC=C1S(=O)C1=CC=C(N)C=C1 MITHMOYLTXMLRB-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 description 1
- GEYAGBVEAJGCFB-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GEYAGBVEAJGCFB-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-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
- BOVVHULZWVFIOX-UHFFFAOYSA-N 4-[3-(4-aminophenyl)phenyl]aniline Chemical compound C1=CC(N)=CC=C1C1=CC=CC(C=2C=CC(N)=CC=2)=C1 BOVVHULZWVFIOX-UHFFFAOYSA-N 0.000 description 1
- HCJSCAOEKCHDQO-UHFFFAOYSA-N 4-[3-[3-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=C(OC=3C=CC(N)=CC=3)C=CC=2)=C1 HCJSCAOEKCHDQO-UHFFFAOYSA-N 0.000 description 1
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- LSDYQEILXDCDTR-UHFFFAOYSA-N bis[4-(4-aminophenoxy)phenyl]methanone Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 LSDYQEILXDCDTR-UHFFFAOYSA-N 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
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- 150000003462 sulfoxides Chemical class 0.000 description 1
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- 238000002411 thermogravimetry Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1021—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the catalyst used
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
본 출원은 유기 용매가 아닌 물에서 폴리아믹산 중합 가능할 뿐 아니라, 저온 경화 시 높은 이미드화율을 구현하는 폴리아믹산 수용액 조성물을 제공한다.The present application provides an aqueous polyamic acid solution composition that not only enables polyamic acid polymerization in water rather than an organic solvent, but also realizes a high imidization rate when cured at low temperatures.
Description
본 출원은 폴리아믹산 수용액 조성물, 폴리아믹산 제조 방법 및 폴리이미드 제조 방법에 관한 것이다.This application relates to a polyamic acid aqueous solution composition, a polyamic acid production method, and a polyimide production method.
5G 이동통신과 사물인터넷 (IoT)시대의 도래로 다기능, 소형화, 고집적 기능성 소재가 요구됨에 따라 전기전자용 고내열 소재로서 폴리이미드 고분자가 주목받고 있다. With the advent of the 5G mobile communication and Internet of Things (IoT) era, polyimide polymer is attracting attention as a highly heat-resistant material for electrical and electronic applications as multifunctional, miniaturized, and highly integrated functional materials are required.
폴리이미드는 높은 열적 안정성을 가진 고분자로 물질로 우수한 기계적 강도, 내화학성, 내후성, 내열성을 가지고 있으며 광범위한 온도 (-273℃~ 400℃)에서의 물성 안정성을 갖는다. 특히 전기절연성, 유연성, 불연성을 가지고 있어 전자 및 광학 분야에 그 활용이 증가하고 있다. Polyimide is a polymer material with high thermal stability. It has excellent mechanical strength, chemical resistance, weather resistance, and heat resistance, and has physical property stability over a wide range of temperatures (-273℃~400℃). In particular, its use in the electronics and optical fields is increasing because it has electrical insulation properties, flexibility, and non-flammability.
통상적으로 폴리이미드 합성은 유기 용매하에서 방향족 이무수물(dianhydride)과 방향족 디아민(diamine)을 축중합 시켜 얻어진 폴리아믹산의 탈수화에 의해 얻어진다. 이 합성 공정은 용매 하에서 축중합 시, 수분에 취약한 방향족 이무수물의 가수분해 의해 합성이 용이 하지 않을 수 있다. 이로 인해 유기계에서 합성된 폴리아믹산은 분자량 제어와 초기 빠른 반응에 의한 가교 반응을 제어하는 것 주요 문제이고, 사용한 유기 용매가 갖는 오염 문제 및 이를 해결하기 위한 비싼 처리 비용 문제는 여전히 해결해야 하는 과제이다.Typically, polyimide synthesis is obtained by dehydrating polyamic acid obtained by condensation polymerization of aromatic dianhydride and aromatic diamine in an organic solvent. This synthetic process may not be easy to synthesize due to hydrolysis of aromatic dianhydride, which is vulnerable to moisture, during condensation polymerization in a solvent. For this reason, the main problems with polyamic acids synthesized in organic systems are molecular weight control and controlling the crosslinking reaction due to the initial fast reaction, and the problem of contamination with the organic solvent used and the expensive processing cost to solve this problem still need to be solved. .
또한, 폴리이미드는 충분한 건조 및 경화를 위하여 250 ℃ 이상의 고온 열처리가 수반되는데, 이는 열에 취약한 제품 적용을 제한하는 또 다른 문제를 야기하였다.In addition, polyimide requires high temperature heat treatment of 250°C or higher for sufficient drying and curing, which has caused another problem that limits the application of products vulnerable to heat.
본 출원은 유기 용매가 아닌 물에서 중합된 폴리아믹산을 저온 경화시킴에도 높은 이미드화율을 구현하는 폴리이미드 필름을 제공한다.The present application provides a polyimide film that realizes a high imidization rate even when polyamic acid polymerized in water rather than an organic solvent is cured at low temperature.
본 출원은 폴리아믹산 수용액 조성물에 관한 것이다. 보다 상세하게 본 출원은 물에서 중합 (수계 중합) 가능하고, 저온 경화(또는 저온 이미드화라고도 함)로 높은 이미드화율을 구현하는 폴리아믹산 수용액 조성물에 관한 것이다. 일반적으로 알려진 폴리이미드의 경화는 250℃ 초과하는 온도에서 수행하며, 본 출원에서 저온 경화는 일반적인 경화 온도보다 상대적으로 낮은 온도에서 수행하는 경화를 의미하며, 예를 들어, 본 출원에서 저온 경화는 250 ℃ 이하에서 경화를 의미한다.This application relates to a polyamic acid aqueous solution composition. More specifically, this application relates to an aqueous polyamic acid solution composition that can be polymerized in water (aqueous polymerization) and realizes a high imidization rate through low-temperature curing (also called low-temperature imidization). Curing of commonly known polyimides is carried out at temperatures exceeding 250°C, and in the present application, low-temperature curing means curing carried out at a temperature relatively lower than the general curing temperature. For example, in the present application, low-temperature curing is carried out at 250° C. It means hardening below ℃.
예시적인 폴리아믹산 수용액 조성물은 디아민 단량체 및 디안하이드라이드 단량체를 중합 단위로 포함하는 폴리아믹산; 및 피리딘 유도체 화합물인 수계 촉매를 포함하고, 200℃에서 열경화 시 이미드화율이 70 내지 99.9%의 범위 내일 수 있다. 본 출원의 폴리아믹산 수용액 조성물은 상기 수계 촉매가 폴리아믹산의 카르복실기와 염을 형성할 수 있어, 유기 용매 없이 물에서 직접 폴리아믹산의 중합이 가능할 뿐 아니라, 저온 경화 시 높은 이미드화율을 나타낼 수 있다. 예를 들어, 본 출원에 따른 폴리이미드 필름은 이미드화율의 하한이 70% 이상, 75% 이상, 80% 이상, 85% 이상 또는 90% 이상일 수 있고, 상한은 99.9% 이하, 99.5% 이하, 99% 이하, 98% 이하, 97% 이하, 96% 이하, 또는 95% 이하일 수 있다.Exemplary polyamic acid aqueous solution compositions include polyamic acids comprising diamine monomers and dianhydride monomers as polymerized units; and an aqueous catalyst that is a pyridine derivative compound, and the imidization rate may be in the range of 70 to 99.9% when heat cured at 200°C. The polyamic acid aqueous solution composition of the present application allows the aqueous catalyst to form a salt with the carboxyl group of the polyamic acid, so that not only can the polyamic acid be polymerized directly in water without an organic solvent, but it can also exhibit a high imidization rate during low-temperature curing. . For example, the polyimide film according to the present application may have a lower limit of the imidization rate of 70% or more, 75% or more, 80% or more, 85% or more, or 90% or more, and the upper limit may be 99.9% or less, 99.5% or less, It may be 99% or less, 98% or less, 97% or less, 96% or less, or 95% or less.
상기 이미드화율은 Bruker ALPHA-P Infrared Spectrometer (IR)의 Attenuated Total Reflectance (ATR) 방법으로 분석하였다. IR 분석을 통해 계산된 이미드 결합의 세기를 백분율로 나타내었으며, 400℃에서 완전 이미드화된 폴리이미드의 C-N 스트레칭 (1375 cm-1) 세기를 기준값으로 하고, 폴리아믹산 수용액을 200℃까지 열처리하여 제조된 폴리이미드 필름의 C-N 스트레칭 세기와의 비를 백분율로 나타내었다. 구체적으로, 상기 이미드화율은 하기의 식 1을 이용해 계산할 수 있다.The imidization rate was analyzed using the Attenuated Total Reflectance (ATR) method of a Bruker ALPHA-P Infrared Spectrometer (IR). The strength of the imide bond calculated through IR analysis was expressed as a percentage, and the strength of CN stretching (1375 cm -1 ) of fully imidized polyimide at 400℃ was used as the reference value, and the aqueous polyamic acid solution was heat-treated up to 200℃. The ratio with the CN stretching strength of the prepared polyimide film was expressed as a percentage. Specifically, the imidation rate can be calculated using Equation 1 below.
[식 1][Equation 1]
이미드화율(%) = {(1375cm-1)200℃/(1510cm-1)200℃}/{(1375cm-1)400℃/(1510 cm-1)400℃}Imidation rate (%) = {(1375cm -1 ) 200℃ / (1510cm -1 ) 200℃ }/{(1375cm -1 ) 400℃ / (1510 cm -1 ) 400℃ }
하나의 예시에서, 상기 수계 촉매의 비점은 50℃ 내지 500℃의 범위 내일 수 있다. 예를 들어, 상기 비점의 하한은 55℃ 이상, 60℃ 이상, 65℃ 이상, 70℃ 이상, 또는 75℃ 이상일 수 있고, 상기 비점의 상한은 450℃ 이하, 400℃ 이하, 또는 350℃ 이하일 수 있다. 상기 비점을 만족하는 수계 촉매는 저온에서 우수한 촉매 활성을 나타낸다.In one example, the boiling point of the water-based catalyst may be in the range of 50°C to 500°C. For example, the lower limit of the boiling point may be 55°C or higher, 60°C or higher, 65°C or higher, 70°C or higher, or 75°C or higher, and the upper limit of the boiling point may be 450°C or lower, 400°C or lower, or 350°C or lower. there is. Aqueous catalysts that satisfy the above boiling point exhibit excellent catalytic activity at low temperatures.
일 구체예에서, 상기 수계 촉매의 pKa는 전자 주게의 종류에 따라 다양하게 나타나며, 예를 들어, 상기 수계 촉매의 pKa는 pKa 0.01 내지 100의 범위 내일 수 있다. 예를 들면, 상기 pKa 하한은 0.05 이상, 0.1 이상, 0.3 이상, 0.5 이상 또는 0.7 이상일 수 잇고, pKa 상한은 90이하, 80이하, 70이하, 60이하, 50이하, 40이하, 30이하, 20이하 또는 15이하일 수 있다.In one embodiment, the pKa of the aqueous catalyst varies depending on the type of electron donor. For example, the pKa of the aqueous catalyst may be in the range of pKa 0.01 to 100. For example, the lower pKa limit may be 0.05 or more, 0.1 or more, 0.3 or more, 0.5 or more, or 0.7 or more, and the upper pKa limit may be 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, and 20 or less. It may be less than or equal to 15.
하나의 예시에서, 상기 수계 촉매는 하기 화학식 1을 만족할 수 있다.In one example, the water-based catalyst may satisfy Formula 1 below.
[화학식 1][Formula 1]
상기 화학식 1에서, 상기 R1 내지 R3 중 적어도 하나는 탄소수 1 내지 4의 알킬아민기, 히드록시기, 탄소수 1 내지 4의 알콕시기, 티올기, 탄소수 1 내지 4의 티올에테르기, 탄소수 1 내지 4의 알킬기 또는 헤테로사이클릭기이다.In Formula 1, at least one of R 1 to R 3 is an alkylamine group having 1 to 4 carbon atoms, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a thiol group, a thiol ether group having 1 to 4 carbon atoms, or a C 1 to 4 group. It is an alkyl group or heterocyclic group.
상기 화학식 1을 만족하는 수계 촉매의 예로는 4-(메틸아미노)피리딘, 4-(디메틸아미노)피리딘, 2-히드록시피리딘, 4-히드록시피리딘, 4-메톡시피리딘, 2-메톡시피리딘, 2,6-디메톡시피리딘, 2-에톡시피리딘, 4-머캅토피리딘, 2-머캅토피리딘, 4-(메틸티오)피리딘, 2-(메틸티오)피리딘), 4-메틸피리딘, 2-메틸피리딘, 4-에틸피리딘, 2-에틸피리딘, 4-프로필피리딘, 2, 4, 6-트리메틸피리딘, 4-피페리디노피리딘, 4-모르노폴리노피리딘 또는 4-피롤리디노피리딘일 수 있다.Examples of aqueous catalysts satisfying Formula 1 include 4-(methylamino)pyridine, 4-(dimethylamino)pyridine, 2-hydroxypyridine, 4-hydroxypyridine, 4-methoxypyridine, and 2-methoxypyridine. , 2,6-dimethoxypyridine, 2-ethoxypyridine, 4-mercaptopyridine, 2-mercaptopyridine, 4-(methylthio)pyridine, 2-(methylthio)pyridine), 4-methylpyridine, 2 -methylpyridine, 4-ethylpyridine, 2-ethylpyridine, 4-propylpyridine, 2, 4, 6-trimethylpyridine, 4-piperidinopyridine, 4-morpholinopyridine or 4-pyrrolidinopyridinyl You can.
또 하나의 예시에서, 상기 수계 촉매는 하기 화학식 2를 만족할 수 있다.In another example, the water-based catalyst may satisfy Formula 2 below.
[화학식 2][Formula 2]
상기 화학식 2에서, R4 및 R5 중 적어도 하나는 탄소수 1 내지 4의 모노알킬아미노기, 탄소수 1 내지 4의 디알킬아미노기, 피페리디노기, 모르폴리노기, 피롤리디노기이다.In Formula 2, at least one of R 4 and R 5 is a monoalkylamino group having 1 to 4 carbon atoms, a dialkylamino group having 1 to 4 carbon atoms, a piperidino group, a morpholino group, and a pyrrolidino group.
본 출원의 구체예에서, 상기 화학식 2를 만족하는 수계 촉매의 예로는 4-디메틸아미노피리딘, 2-디메틸아미노피리딘, 4-메틸아미노피리딘, 4-피페리디노피리딘, 4-모르노폴리노피리딘 또는 4-피롤리디노피리딘일 수 있다.In an embodiment of the present application, examples of aqueous catalysts satisfying Formula 2 include 4-dimethylaminopyridine, 2-dimethylaminopyridine, 4-methylaminopyridine, 4-piperidinopyridine, and 4-morpholinopyridine. Or it may be 4-pyrrolidinopyridine.
본 출원의 조성물은 상기와 같이 화학식 1 및/또는 2를 만족하는 수계 촉매를 통해 수계 중합 및 저온 경화가 가능할 수 있다.The composition of the present application may be capable of aqueous polymerization and low-temperature curing through an aqueous catalyst satisfying Formula 1 and/or 2 as described above.
본 출원의 구체예에서, 상기 수계 촉매는 폴리아믹산 내의 카르복실기 1 당량에 대해 0.5 내지 1.5배 당량 범위 내일 수 있다. 하나의 예시에서, 상기 수계 촉매는 상기 폴리아믹산 내의 카르복실기 1 당량에 대해 0.55배 당량 이상, 0.6배 당량 이상, 0.7배 당량 이상, 0.8배 당량 이상, 0.83배 당량 이상 또는 0.93 배 당량 이상일 수 있고, 또한, 상한은 1.4 배 당량 이하, 1.3 배 당량 이하, 1.2 배 당량 이하, 1.15 배 당량 이하 또는 1.05 배 당량 이하일 수 있다.In an embodiment of the present application, the water-based catalyst may be in the range of 0.5 to 1.5 times the equivalent weight based on 1 equivalent of the carboxyl group in the polyamic acid. In one example, the water-based catalyst may be 0.55 times the equivalent, 0.6 times the equivalent, 0.7 times the equivalent, 0.8 times the equivalent, 0.83 times the equivalent, or 0.93 times the equivalent, based on 1 equivalent of the carboxyl group in the polyamic acid, Additionally, the upper limit may be 1.4 times the equivalent or less, 1.3 times the equivalent or less, 1.2 times the equivalent or less, 1.15 times the equivalent or less, or 1.05 times the equivalent or less.
본 명세서에서, 수계 촉매의 양을 규정하는 "폴리아믹산 내의 카르복실기에 대한 당량" 이란, 폴리아믹산 내의 카르복실기 1 개에 대해 사용된 수계 촉매 또는 금속 이온의 개수 (몰수)를 의미할 수 있다.In this specification, “equivalent to the carboxyl group in the polyamic acid” that defines the amount of the aqueous catalyst may mean the number (moles) of the aqueous catalyst or metal ion used for one carboxyl group in the polyamic acid.
하나의 구체적인 예에서, 상기 폴리아믹산 조성물은 전체 중량을 기준으로 고형분을 1 내지 50 중량% 포함할 수 있고, 예를 들어, 1 내지 45 중량%, 1 내지 40 중량% 또는 1 내지 35 중량% 포함할 수 있다. 본 출원은 상기 폴리아믹산 조성물의 고형분 함량을 조절함으로써, 점도 상승을 제어하면서 경화 과정에서 다량의 용매를 제거해야 하는 제조 비용과 공정 시간 증가를 방지할 수 있다.In one specific example, the polyamic acid composition may include 1 to 50% by weight of solid content based on the total weight, for example, 1 to 45% by weight, 1 to 40% by weight, or 1 to 35% by weight. can do. In the present application, by controlling the solid content of the polyamic acid composition, it is possible to control the increase in viscosity and prevent the increase in manufacturing cost and process time that requires removal of a large amount of solvent during the curing process.
본 출원의 폴리아믹산 수용액 조성물은 수계 중합되는 조성물로서, 유기 용매를 실질적으로 포함하지 않을 수 있다. 본 명세서에서 실질적으로 포함하지 않는다는 의미는 유기 용매가 5 중량% 미만, 3 중량% 미만, 1 중량% 미만 또는 0 중량% 내지 0.5 중량%으로 포함됨을 의미할 수 있다. 수계 중합 가능한 폴리아믹산 조성물은 공정 측면 및 환경적인 측면에서 유리할 수 있다.The polyamic acid aqueous solution composition of the present application is a water-based polymerized composition and may not substantially contain an organic solvent. Substantially not included in the present specification may mean that the organic solvent is included in less than 5% by weight, less than 3% by weight, less than 1% by weight, or 0% to 0.5% by weight. A water-based polymerizable polyamic acid composition can be advantageous from a process and environmental perspective.
본 명세서에서 용어 폴리아믹산 조성물과 폴리아믹산 용액, 폴리아믹산 수용액 조성물 및 폴리이미드 전구체 조성물은 동일한 의미로 사용될 수 있다. 또한 본 명세서에서 용어 경화와 이미드화는 동일한 의미로 사용될 수 있다.In this specification, the terms polyamic acid composition, polyamic acid solution, polyamic acid aqueous solution composition, and polyimide precursor composition may be used with the same meaning. Additionally, in this specification, the terms curing and imidization may be used with the same meaning.
폴리아믹산 용액의 제조에 사용될 수 있는 디안하이드라이드 단량체는 방향족 테트라카르복실릭 디안하이드라이드일 수 있다. 예를 들면, 상기 디안하이드라이드 단량체는 하기 화학식 3으로 표시되는 화합물을 적어도 하나 이상 포함한다.The dianhydride monomer that can be used to prepare the polyamic acid solution may be aromatic tetracarboxylic dianhydride. For example, the dianhydride monomer includes at least one compound represented by the following formula (3).
[화학식 3][Formula 3]
상기 X는 페닐, 바이페닐, 또는 알릭사이클릭이고,Wherein X is phenyl, biphenyl, or aliccyclic,
상기 M은 단일 결합, 알킬렌기, 알킬리덴기, 카보닐기, 알킬카보닐기, 알콕시기, 및 설포닐기를 포함하는 군 중에서 적어도 하나 이상을 포함하고, 상기 M은 불소 및 알킬기를 포함하는 군 중에서 적어도 하나 이상으로 치환되거나 비치환된다. 상기 M은 화학식 3의 M은 적어도 하나 이상의 불소로 치환된 알킬기를 치환기로 갖는 알킬렌기일 수 있다. 일 예로서, 적어도 하나 이상의 불소로 치환된 탄소수 1 내지 6의 알킬기는 퍼플루오르알킬기일 수 있으며, 구체적으로, 퍼플루오르메틸기일 수 있다. 또 다른 예시에서, 디안하이드라이드 단량체 성분은 적어도 하나 이상의 불소로 치환된 디안하이드라이드 단량체를 적어도 하나 이상 포함할 수 있다.M includes at least one from the group including a single bond, an alkylene group, an alkylidene group, a carbonyl group, an alkylcarbonyl group, an alkoxy group, and a sulfonyl group, and M includes at least one from the group including a fluorine and an alkyl group. It is substituted or unsubstituted by one or more. M in Formula 3 may be an alkylene group having at least one alkyl group substituted with fluorine as a substituent. As an example, an alkyl group having 1 to 6 carbon atoms substituted with at least one fluorine may be a perfluoroalkyl group, and specifically, may be a perfluoromethyl group. In another example, the dianhydride monomer component may include at least one dianhydride monomer substituted with at least one fluorine.
본 명세서에서 용어 「단일 결합」은, 어떠한 원자 없이 양쪽 원자를 잇는 결합을 의미할 수 있다. 예를 들면, 상기 화학식 3에서 M이 단일 결합인 경우, 양쪽 방향족 고리가 서로 직접 연결될 수 있다.As used herein, the term “single bond” may mean a bond connecting both atoms without any atoms. For example, in Formula 3, when M is a single bond, both aromatic rings may be directly connected to each other.
본 명세서에서 용어 「알킬기」는, 특별히 달리 규정하지 않는 한, 탄소수 1 내지 30, 탄소수 1 내지 25, 탄소수 1 내지 20, 탄소수 1 내지 16, 탄소수 1 내지 12, 탄소수 1 내지 8 또는 탄소수 1 내지 4의 알킬기를 의미할 수 있다. 상기 알킬기는 직쇄형, 분지쇄형 또는 고리형 구조를 가질 수 있으며, 임의적으로 하나 이상의 치환기에 의해서 치환되어 있을 수 있다. 상기 치환기는 예를 들어, 극성 관능기 등이 예시될 수 있다.In this specification, unless otherwise specified, the term “alkyl group” refers to a group having 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. It may mean an alkyl group of. The alkyl group may have a straight-chain, branched-chain, or cyclic structure, and may be optionally substituted with one or more substituents. The substituent may be, for example, a polar functional group.
본 명세서에서 용어 「알케닐기」는, 특별히 달리 규정하지 않는 한, 탄소수 1 내지 30, 탄소수 1 내지 25, 탄소수 1 내지 20, 탄소수 1 내지 16, 탄소수 1 내지 12, 탄소수 1 내지 8 또는 탄소수 1 내지 4의 알케닐기를 의미할 수 있다. 상기 알케닐기는 직쇄형, 분지쇄형 또는 고리형 구조를 가질 수 있으며, 임의적으로 하나 이상의 치환기에 의해서 치환되어 있을 수 있다. 상기 치환기는 예를 들어, 극성 관능기 등이 예시될 수 있다.In this specification, unless otherwise specified, the term “alkenyl group” refers to a group having 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 1 carbon number. It may mean an alkenyl group of 4. The alkenyl group may have a straight-chain, branched-chain, or cyclic structure, and may be optionally substituted with one or more substituents. The substituent may be, for example, a polar functional group.
본 명세서에서 용어 「알키닐기」는, 특별히 달리 규정하지 않는 한, 탄소수 1 내지 30, 탄소수 1 내지 25, 탄소수 1 내지 20, 탄소수 1 내지 16, 탄소수 1 내지 12, 탄소수 1 내지 8 또는 탄소수 1 내지 4의 알키닐기를 의미할 수 있다. 상기 알키닐기는 직쇄형, 분지쇄형 또는 고리형 구조를 가질 수 있으며, 임의적으로 하나 이상의 치환기에 의해서 치환되어 있을 수 있다. 상기 치환기는 예를 들어, 극성 관능기 등이 예시될 수 있다.In this specification, the term “alkynyl group” refers to a group having 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 8 carbon atoms, unless otherwise specified. It may mean an alkynyl group of 4. The alkynyl group may have a straight-chain, branched-chain, or cyclic structure, and may be optionally substituted with one or more substituents. The substituent may be, for example, a polar functional group.
본 명세서에서 용어 「알킬렌기」는, 특별히 달리 규정하지 않는 한, 탄소수 2 내지 30, 탄소수, 2 내지 25, 탄소수, 2 내지 20, 탄소수 2 내지 16, 탄소수 2 내지 12, 탄소수 2 내지 10 또는 탄소수 2 내지 8의 알킬렌기를 의미할 수 있다. 상기 알킬렌기는 직쇄형, 분지쇄형 또는 고리형 구조를 가질 수 있으며, 임의적으로 하나 이상의 치환기에 의해서 치환되어 있을 수 있다. 상기 치환기는 예를 들어, 극성 관능기 등이 예시될 수 있다.In this specification, unless otherwise specified, the term “alkylene group” refers to a group having 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 10 carbon atoms, or 2 to 10 carbon atoms. It may mean 2 to 8 alkylene groups. The alkylene group may have a straight-chain, branched-chain, or cyclic structure, and may be optionally substituted with one or more substituents. The substituent may be, for example, a polar functional group.
본 명세서에서 용어 「알킬리덴기」는, 특별히 달리 규정하지 않는 한, 탄소수 2 내지 30, 탄소수, 2 내지 25, 탄소수, 2 내지 20, 탄소수 2 내지 16, 탄소수 2 내지 12, 탄소수 2 내지 10 또는 탄소수 2 내지 8의 알킬리덴기를 의미할 수 있다. 상기 알킬리덴기는 직쇄형, 분지쇄형 또는 고리형 구조를 가질 수 있으며, 임의적으로 하나 이상의 치환기에 의해서 치환되어 있을 수 있다. 상기 치환기는 예를 들어, 극성 관능기 등이 예시될 수 있다.In this specification, the term “alkylidene group” refers to a group having 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 10 carbon atoms, or It may refer to an alkylidene group having 2 to 8 carbon atoms. The alkylidene group may have a straight-chain, branched-chain, or cyclic structure, and may be optionally substituted with one or more substituents. The substituent may be, for example, a polar functional group.
상기 화학식 3을 만족하는 상기 방향족 테트라카르복실릭 디안하이드라이드는 피로멜리틱 디안하이드라이드(또는 PMDA), 3,3',4,4'-바이페닐테트라카르복실릭 디안하이드라이드(또는 BPDA), 2,3,3',4'-바이페닐테트라카르복실릭 디안하이드라이드(또는 a-BPDA), 옥시디프탈릭 디안하이드라이드(또는 ODPA), 디페닐설폰-3,4,3',4'-테트라카르복실릭 디안하이드라이드(또는 DSDA), 비스(3,4-디카르복시페닐)설파이드 디안하이드라이드, 2,2-비스(3,4-디카르복시페닐)-1,1,1,3,3,3-헥사플루오로프로페인 디안하이드라이드, 2,3,3',4'- 벤조페논테트라카르복실릭 디안하이드라이드, 3,3',4,4'-벤조페논테트라카르복실릭 디안하이드라이드(또는 BTDA), 비스(3,4-디카르복시페닐)메테인 디안하이드라이드, 2,2-비스(3,4-디카르복시페닐)프로페인 디안하이드라이드, p-페닐렌비스(트라이멜리틱 모노에스터 애시드 안하이드라이드), p-바이페닐렌비스(트라이멜리틱 모노에스터 애시드 안하이드라이드), m-터페닐-3,4,3',4'-테트라카르복실릭 디안하이드라이드, p-터페닐-3,4,3',4'-테트라카르복실릭 디안하이드라이드, 1,3-비스(3,4-디카르복시페녹시)벤젠 디안하이드라이드, 1,4-비스(3,4-디카르복시페녹시)벤젠 디안하이드라이드, 1,4-비스(3,4-디카르복시페녹시)바이페닐 디안하이드라이드, 2,2-비스〔(3,4-디카르복시 페녹시)페닐〕프로페인 디안하이드라이드(BPADA), 2,3,6,7-나프탈렌테트라카복실산 디안하이드라이드, 1,4,5,8-나프탈렌테트라카르복실릭 디안하이드라이드, 4,4'-(2,2-헥사플루오로아이소프로필리덴)디프탈산 디안하이드라이드(6-FDA) 등을 예로 들 수 있다. The aromatic tetracarboxylic dianhydride satisfying Formula 3 is pyromellitic dianhydride (or PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (or BPDA) , 2,3,3',4'-biphenyltetracarboxylic dianhydride (or a-BPDA), oxydiphthalic dianhydride (or ODPA), diphenylsulfone-3,4,3',4 '-Tetracarboxylic dianhydride (or DSDA), bis(3,4-dicarboxyphenyl)sulfide dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1, 3,3,3-Hexafluoropropane dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxyl Rick dianhydride (or BTDA), bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, p-phenylenebis (trimelytic monoester acid anhydride), p-biphenylenebis (trimelytic monoester acid anhydride), m-terphenyl-3,4,3',4'-tetracarboxylic diane Hydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4- Bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[(3,4-dicarboxy) Phenoxy) phenyl] propane dianhydride (BPADA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4' Examples include -(2,2-hexafluoroisopropylidene)diphthalic acid dianhydride (6-FDA).
상기 디안하이드라이드 단량체는 필요에 따라, 단독 또는 2 종 이상을 조합하여 이용할 수 있지만, 본 출원은 결합 해리에너지를 고려하여, 예를 들면, 피로멜리틱 디안하이드라이드(PMDA), 3,3',4,4'-바이페닐테트라카르복실릭 디안하이드라이드(s-BPDA) 또는 2,3,3',4'-바이페닐테트라카르복실릭 디안하이드라이드(a-BPDA)를 포함할 수 있다.The dianhydride monomer may be used alone or in combination of two or more types as needed, but in this application, considering the bond dissociation energy, for example, pyromellitic dianhydride (PMDA), 3,3' , 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) or 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA). .
또한, 폴리아믹산 용액 제조에 사용될 수 있는 디아민 단량체는 방향족 디아민으로서, 이하와 같이 분류하여 예를 들 수 있다.In addition, diamine monomers that can be used to prepare polyamic acid solutions are aromatic diamines, and examples can be classified as follows.
1) 1,4-디아미노벤젠(또는 파라페닐렌디아민, PDA), 1,3-디아미노벤젠, 2,4-디아미노톨루엔, 2,6-디아미노톨루엔, 3,5-디아미노벤조익 애시드(또는 DABA) 등과 같이, 구조 상 벤젠 핵 1개를 갖는 디아민으로서, 상대적으로 강직한 구조의 디아민;1) 1,4-diaminobenzene (or paraphenylenediamine, PDA), 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzo A diamine having one benzene nucleus in structure, such as diamine acid (or DABA), and having a relatively rigid structure;
2) 4,4'-디아미노디페닐에테르(또는 옥시디아닐린, ODA), 3,4'-디아미노디페닐에테르 등의 디아미노디페닐에테르, 4,4'-디아미노디페닐메테인(메틸렌디아민), 3,3'-디메틸-4,4'-디아미노바이페닐, 2,2'-디메틸-4,4'-디아미노바이페닐, 2,2'-비스(트라이플루오로메틸)-4,4'-디아미노바이페닐, 3,3'-디메틸-4,4'-디아미노디페닐메테인, 3,3'-디카복시-4,4'-디아미노디페닐메테인, 3,3',5,5'-테트라메틸-4,4'-디아미노디페닐메테인, 비스(4-아미노페닐)설파이드, 4,4'-디아미노벤즈아닐라이드, 3,3'-디클로로벤지딘, 3,3'-디메틸벤지딘(또는 o-톨리딘), 2,2'-디메틸벤지딘(또는 m-톨리딘), 3,3'-디메톡시벤지딘, 2,2'-디메톡시벤지딘, 3,3'-디아미노디페닐에테르, 3,4'-디아미노디페닐에테르, 4,4'-디아미노디페닐에테르, 3,3'-디아미노디페닐설파이드, 3,4'-디아미노디페닐설파이드, 4,4'-디아미노디페닐설파이드, 3,3'-디아미노디페닐설폰, 3,4'-디아미노디페닐설폰, 4,4'-디아미노디페닐설폰, 3,3'-디아미노벤조페논, 4,4'-디아미노벤조페논, 3,3'-디아미노-4,4'-디클로로벤조페논, 3,3'-디아미노-4,4'-디메톡시벤조페논, 3,3'-디아미노디페닐메테인, 3,4'-디아미노디페닐메테인, 4,4'-디아미노디페닐메테인, 2,2-비스(3-아미노페닐)프로페인, 2,2-비스(4-아미노페닐)프로페인, 2,2-비스(3-아미노페닐)-1,1,1,3,3,3-헥사플루오로프로페인, 2,2-비스(4-아미노페닐)-1,1,1,3,3,3-헥사플루오로프로페인, 3,3'-디아미노디페닐설폭사이드, 3,4'-디아미노디페닐설폭사이드, 4,4'-디아미노디페닐설폭사이드 등과 같이, 구조 상 벤젠 핵 2개를 갖는 디아민;2) Diaminodiphenyl ether such as 4,4'-diaminodiphenyl ether (or oxydianiline, ODA), 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane (methylenediamine), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl )-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane , 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis(4-aminophenyl)sulfide, 4,4'-diaminobenzanilide, 3,3' -Dichlorobenzidine, 3,3'-dimethylbenzidine (or o-tolidine), 2,2'-dimethylbenzidine (or m-tolidine), 3,3'-dimethoxybenzidine, 2,2'-dimethoxy Benzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4' -diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone , 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4' -Dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(3- Aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodi Diamines having two benzene nuclei in structure, such as phenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, etc.;
3) 1,3-비스(3-아미노페닐)벤젠, 1,3-비스(4-아미노페닐)벤젠, 1,4-비스(3-아미노페닐)벤젠, 1,4-비스(4-아미노 페닐)벤젠, 1,3-비스(4-아미노페녹시)벤젠, 1,4-비스(3-아미노페녹시)벤젠(또는 TPE-Q), 1,4-비스(4-아미노페녹시)벤젠(또는 TPE-Q), 1,3-비스(3-아미노페녹시)-4-트라이플루오로메틸벤젠, 3,3'-디아미노-4-(4-페닐)페녹시벤조페논, 3,3'-디아미노-4,4'-디(4-페닐페녹시)벤조페논, 1,3-비스(3-아미노페닐설파이드)벤젠, 1,3-비스(4-아미노페닐설파이 드)벤젠, 1,4-비스(4-아미노페닐설파이드)벤젠, 1,3-비스(3-아미노페닐설폰)벤젠, 1,3-비스(4-아미노페닐설폰)벤젠, 1,4-비스(4-아미노페닐설폰)벤젠, 1,3-비스〔2-(4-아미노페닐)아이소프로필〕벤젠, 1,4-비스〔2-(3-아미노페닐)아이소프로필〕벤젠, 1,4-비스〔2-(4-아미노페닐)아이소프로필〕벤젠 등과 같이, 구조 상 벤젠 핵 3개를 갖는 디아민;3) 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-amino) Phenyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene (or TPE-Q), 1,4-bis(4-aminophenoxy) Benzene (or TPE-Q), 1,3-bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3'-diamino-4-(4-phenyl)phenoxybenzophenone, 3 ,3'-diamino-4,4'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenyl sulfide)benzene, 1,3-bis(4-aminophenyl sulfide) Benzene, 1,4-bis (4-aminophenyl sulfide) benzene, 1,3-bis (3-aminophenyl sulfone) benzene, 1,3-bis (4-aminophenyl sulfone) benzene, 1,4-bis ( 4-aminophenylsulfone) benzene, 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4- Diamines having three benzene nuclei in structure, such as bis[2-(4-aminophenyl)isopropyl]benzene;
4) 3,3'-비스(3-아미노페녹시)바이페닐, 3,3'-비스(4-아미노페녹시)바이페닐, 4,4'-비스(3-아미노페녹시)바이페닐, 4,4'-비스(4-아미노페녹시)바이페닐, 비스〔3-(3-아미노페녹시)페닐〕에테르, 비스〔3-(4-아미노페녹시)페닐〕에테르, 비스〔4-(3-아미노페녹시)페닐〕에테르, 비스〔4-(4-아미노페녹시)페닐〕에테르, 비스〔3-(3-아미노페녹시)페닐〕케톤, 비스〔3-(4-아미노페녹시)페닐〕케톤, 비스〔4-(3-아미노페녹시)페닐〕케톤, 비스〔4-(4-아미노 페녹시)페닐〕케톤, 비스〔3-(3-아미노페녹시)페닐〕설파이드, 비스〔3-(4-아미노페녹시)페닐〕설파이드, 비스 〔4-(3-아미노페녹시)페닐〕설파이드, 비스〔4-(4-아미노페녹시)페닐〕설파이드, 비스〔3-(3-아미노페녹시)페닐〕설폰, 비스〔3-(4-아미노페녹시)페닐〕설폰, 비스〔4-(3-아미노페녹시)페닐〕설폰, 비스〔4-(4-아미노페녹시)페닐〕설폰, 비스〔3-(3-아미노페녹시)페닐〕메테인, 비스〔3-(4-아미노페녹시)페닐〕메테인, 비스〔4-(3-아미노페녹시)페닐〕메테인, 비스〔4-(4-아미노페녹시)페닐〕메테인, 2,2-비스〔3-(3-아미노페녹시)페닐〕프로페인, 2,2-비스〔3-(4-아미노페녹시)페닐〕프로페인, 2,2-비스〔4-(3-아미노페녹시)페닐〕프로페인, 2,2-비스〔4-(4-아미노페녹시)페닐〕프로페인(BAPP), 2,2-비스〔3-(3-아미노페녹시)페닐〕-1,1,1,3,3,3-헥사플루오로프로페인, 2,2-비스〔3-(4-아미노페녹시)페닐〕-1,1,1,3,3,3-헥사플루오로프로페인, 2,2-비스〔4-(3-아미노페녹시)페닐〕-1,1,1,3,3,3-헥사플루오로프로페인, 2,2-비스〔4-(4-아미노페녹시)페닐〕-1,1,1,3,3,3-헥사플루오로프로페인 등과 같이, 구조 상 벤젠 핵 4개를 갖는 디아민.4) 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4- (3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[3-(3-aminophenoxy)phenyl]ketone, bis[3-(4-aminophenok) Cy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[3-(3-aminophenoxy)phenyl]sulfide , bis[3-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[3- (3-aminophenoxy)phenyl]sulfone, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy) Cy)phenyl]sulfone, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl 〕Methane, bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4) -aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane ( BAPP), 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-) aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3 Structure, such as 3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, etc. A diamine with four benzene nuclei.
상기 디아민 단량체는 필요에 따라, 단독 또는 2 종 이상을 조합하여 이용할 수 있다.The above diamine monomers can be used individually or in combination of two or more types, as needed.
본 출원의 폴리아믹산 조성물은 저점도 특성을 갖는 조성물일 수 있다. 본 출원의 폴리아믹산 조성물은 25℃ 온도 및 30s-1의 전단속도 조건으로 측정한 점도가 20,000cps 이하, 10,000 cps 이하, 6,000 cps 이하일 수 있다. 그 하한은 특별히 한정되지 않으나, 10 cps 이상, 15 cps 이상, 30 cps 이상, 100 cps 이상, 300 cps 이상, 500 cps 이상 또는 1000 cps 이상일 수 있다. 상기 점도는 예를 들어, Haake 사의 VT-550을 사용하여 측정한 것일 수 있고 30/s의 전단 속도, 25℃온도 및 1 mm 플레이트 갭 조건에서 측정한 것일 수 있다. 본 출원은 상기 점도 범위를 조절함으로써, 우수한 공정성을 갖는 전구체 조성물을 제공할 수 있다.The polyamic acid composition of the present application may be a composition having low viscosity characteristics. The polyamic acid composition of the present application may have a viscosity of 20,000 cps or less, 10,000 cps or less, and 6,000 cps or less, as measured at a temperature of 25°C and a shear rate of 30 s -1 . The lower limit is not particularly limited, but may be 10 cps or more, 15 cps or more, 30 cps or more, 100 cps or more, 300 cps or more, 500 cps or more, or 1000 cps or more. The viscosity may be measured using, for example, Haake's VT-550 and may be measured under the conditions of a shear rate of 30/s, a temperature of 25°C, and a plate gap of 1 mm. The present application can provide a precursor composition with excellent processability by adjusting the viscosity range.
하나의 예시에서, 상기 폴리아믹산 조성물은 그의 고형분 농도에 기초하여 온도 30 ℃ 및 농도 0.5 g/100 mL (물에 용해)에서 측정한 대수 점도가 0.1 이상 또는 0.2 이상일 수 있다. 상한은 특별히 제한되지 않으나, 5 이하, 3 이하 또는 2.5 이하일 수 있다. 본 출원은 상기 대수 점도를 조절함으로써, 적정량의 폴리아믹산 분자량을 조절하고, 공정성을 확보할 수 있다.In one example, the polyamic acid composition may have a logarithmic viscosity of 0.1 or more or 0.2 or more as measured at a temperature of 30° C. and a concentration of 0.5 g/100 mL (dissolved in water) based on its solid content concentration. The upper limit is not particularly limited, but may be 5 or less, 3 or less, or 2.5 or less. In this application, by controlling the logarithmic viscosity, an appropriate amount of polyamic acid molecular weight can be adjusted and fairness can be secured.
일 구체예에서, 본 출원의 폴리아믹산 조성물은 경화 후 중량평균분자량이 10,000 내지 200,000g/mol, 15,000 내지 80,000 g/mol, 18,000 내지 70,000 g/mol, 20,000 내지 60,000 g/mol, 25,000 내지 55,000 g/mol 또는 30,000 내지 50,000 g/mol의 범위 내일 수 있다. 본 출원에서 용어 중량평균분자량은, GPC(Gel permeation Chromatograph)로 측정한 표준 폴리스티렌에 대한 환산 수치를 의미한다. In one embodiment, the polyamic acid composition of the present application has a weight average molecular weight of 10,000 to 200,000 g/mol, 15,000 to 80,000 g/mol, 18,000 to 70,000 g/mol, 20,000 to 60,000 g/mol, and 25,000 to 55,000 g after curing. /mol or 30,000 to 50,000 g/mol. In this application, the term weight average molecular weight refers to the converted value for standard polystyrene measured by GPC (Gel permeation Chromatograph).
본 출원의 폴리아믹산 수용액 조성물은 경화물로 제조되는 경우, 상기 경화물은 이하에서 설명하는 다양한 물성을 만족하여 기계적 강도, 내열성 등 우수한 물성을 나타낼 수 있다. 본 출원에서 상기 폴리아믹산 수용액 조성물의 경화물은 폴리이미드를 의미한다.When the polyamic acid aqueous solution composition of the present application is manufactured into a cured product, the cured product satisfies various physical properties described below and can exhibit excellent physical properties such as mechanical strength and heat resistance. In this application, the cured product of the polyamic acid aqueous solution composition refers to polyimide.
하나의 예시에서, 폴리아믹산 수용액 조성물의 경화물은 ASTM D882에 따른 인장 강도가 50 내지 400MPa의 범위 내일 수 있다. 경화물은 인장 강도가 상기 범위로 조절됨에 따라, 우수한 기계적 물성을 나타낸다.In one example, the cured product of the polyamic acid aqueous solution composition may have a tensile strength in the range of 50 to 400 MPa according to ASTM D882. The cured product exhibits excellent mechanical properties as its tensile strength is adjusted to the above range.
또한, 상기 폴리아믹산 수용액 조성물의 경화물은 열중량분석기 (TGA, TA instrument, Q5000, USA)를 이용하여 측정한 5% 열분해 온도(Td)가 450 내지 700 ℃의 범위 내일 수 있다.In addition, the cured product of the polyamic acid aqueous solution composition may have a 5% thermal decomposition temperature (Td) in the range of 450 to 700 ° C. measured using a thermogravimetric analyzer (TGA, TA instrument, Q5000, USA).
본 출원은 또한, 폴리아믹산의 제조 방법에 관한 것이다. 일 예시에서, 상기 폴리아믹산 수용액 조성물의 제조 방법은 피리딘 유도체 화합물인 수계 촉매를 사용하여 폴리아믹산을 제조하는 단계를 포함할 수 있다. 본 출원의 제조 방법은 상기 수계 촉매를 사용함에 따라 수계 중합 및 저온 경화가 가능한 폴리아믹산을 제조할 수 있다. 상기 수계 촉매와 관련된 자세한 설명은 전술한 내용과 중복되므로 이하에서 생략하기로 한다.The present application also relates to a method for producing polyamic acid. In one example, the method for producing the polyamic acid aqueous solution composition may include preparing polyamic acid using an aqueous catalyst that is a pyridine derivative compound. The production method of the present application can produce polyamic acid capable of aqueous polymerization and low-temperature curing by using the aqueous catalyst. A detailed description related to the water-based catalyst will be omitted below since it overlaps with the above-described content.
본 출원은 폴리이미드 제조 방법에 관한 것이다. 상기 폴리이미드 제조 방법은 피리딘 유도체 화합물인 수계 촉매를 사용하여 폴리아믹산을 제조하는 단계; 및 상기 폴리아믹산을 250℃ 이하에서 열 경화하여 폴리이미드를 제조하는 단계를 포함한다. 예를 들어, 상기 단계는 250℃ 미만, 230℃ 미만, 210℃ 미만에서 열 경화할 수 있다. 본 출원은 전술한 수계 촉매가 폴리아믹산의 카르복실기와 염을 형성함에 따라, 저온 경화를 수행하더라도 높은 이미드화율로 폴리이미드를 제공할 수 있다.This application relates to a method for producing polyimide. The polyimide production method includes producing polyamic acid using an aqueous catalyst that is a pyridine derivative compound; and manufacturing polyimide by heat curing the polyamic acid at 250°C or lower. For example, this step may be heat cured at less than 250°C, less than 230°C, or less than 210°C. The present application can provide polyimide with a high imidization rate even when low-temperature curing is performed, as the above-mentioned water-based catalyst forms a salt with the carboxyl group of polyamic acid.
본 출원은 또한 폴리이미드에 관한 것이다. 상기 폴리이미드는 전술한 폴리아믹산 수용액 조성물로부터 유래된 것일 수 있다. 상기 폴리이미드는 다양한 전기전자용 소재에 적용될 수 있으며, 예를 들어, 상기 리튬 전지의 전극용 바인더로 사용될 수 있다. The present application also relates to polyimides. The polyimide may be derived from the polyamic acid aqueous solution composition described above. The polyimide can be applied to various electrical and electronic materials, for example, it can be used as a binder for electrodes of the lithium battery.
일반적으로 리튬 전지에서 양극판 및 음극판은 활물질, 도전재 및 바인더를 습식 방법으로 혼합함으로써 제조된다. 전기적 에너지를 발생시키는 상기 양, 음극의 극판들은 제조할 때 그 건조 상태가 우수하게 되어야만, 전기적 에너지의 발생을 원활하게 할 수 있다. 상기 극판들에 수분이나 오일, 가스 등의 불순물이 함유될 경우에는 수분이나 오일 및 불순물의 함유량에 따라 극성의 작용이 불규칙하거나, 불량하게 되어 정격 에너지를 발생시키지 못하게 된다. 또 상기 수분이나 오일 및 불순물에 의하여 재충전상태가 불량하게 되어 전지 수명이 현저하게 짧게 되는 폐단이 있기 때문에 극판의 건조는 전지의 수명을 좌우하게 되는 매우 중요한 제조 공정이다.Generally, positive and negative plates in lithium batteries are manufactured by mixing active materials, conductive materials, and binders using a wet method. The positive and negative electrode plates that generate electrical energy must be in an excellent dry state when manufactured to facilitate the generation of electrical energy. If the electrode plates contain impurities such as moisture, oil, or gas, the polarity action becomes irregular or poor depending on the content of moisture, oil, and impurities, making it impossible to generate rated energy. In addition, since the moisture, oil, and impurities cause poor recharging and significantly shorten the life of the battery, drying the electrode plates is a very important manufacturing process that determines the life of the battery.
그러나, 충분한 건조를 위하여 건조 온도를 올리는 경우 극판의 열변형에 의한 뒤틀림이 발생하거나 바인더가 부분 용해되어 집전체가 활물질간의 접착력이 감소하는 문제가 있었다. 또한, 기존 폴리이미드 전구체는 250℃ 초과하는 높은 이미드화 온도를 필요로 하기 때문에 건조 과정에서 이미드화를 동반할 시 극판의 변형이 발생하며, 구리의 경우 산화가 일어날 가능성이 높다. 또한, 고온의 건조로 활물질, 도전재, 바인더가 집전체로부터 박리가 일어나는 문제가 있었다.However, when the drying temperature is raised for sufficient drying, there is a problem that the electrode plate is distorted due to thermal deformation or the binder is partially dissolved and the adhesive strength between the active materials of the current collector is reduced. In addition, because existing polyimide precursors require a high imidization temperature exceeding 250°C, deformation of the electrode plate occurs when imidization occurs during the drying process, and in the case of copper, oxidation is highly likely to occur. In addition, there was a problem in which the active material, conductive material, and binder peeled off from the current collector due to drying at high temperatures.
그러나, 본 출원의 폴리이미드는 전술한 폴리아믹산 수용액 조성물을 통해 저온 이미드화로 제조됨에 따라, 고온으로 나타날 수 있는 상기 문제들을 해결할 수 있다.However, since the polyimide of the present application is manufactured by low-temperature imidization using the above-described polyamic acid aqueous solution composition, the above problems that may occur at high temperatures can be solved.
본 출원은 유기 용매가 아닌 물에서 폴리아믹산 중합 가능할 뿐 아니라, 높은 이미드화율로 저온 경화가 가능한 폴리아믹산 수용액 조성물을 제공한다.The present application provides a polyamic acid aqueous solution composition that not only allows polymerization of polyamic acid in water rather than an organic solvent, but also allows low-temperature curing with a high imidization rate.
도 1은 본 출원의 실시예에 따른 이미드화율 실험 결과를 나타내는 그래프이다.Figure 1 is a graph showing the results of an imidization rate experiment according to an example of the present application.
이하, 본 출원에 따른 실시예를 통해 본 출원을 보다 상세히 설명하지만, 본 출원의 범위가 하기 제시될 실시예에 제한되는 것은 아니다.Hereinafter, the present application will be described in more detail through examples according to the present application, but the scope of the present application is not limited to the examples to be presented below.
실시예 1Example 1
온도조절기를 구비하고 질소로 충전된 반응기에 용매로 증류수 63.7 g을 넣었다. 여기에 p-페닐렌디아민 (pPDA) 1.0814 g (0.0094 mol), 4-디메틸아미노피리딘을 카르복실기 대비 2.5 당량 첨가한 후, 25℃에서 1시간 동안 기계식 교반기를 이용하여 혼합물을 용해시켰다. 그 후, 3,3',4,4'-바이페닐테트라카르복실릭 다이안하이드라이드 (s-BPDA) 2.9422 g (0.01 mol) 을 첨가하고, 혼합물을 70℃에서 18 시간 동안 교반하며 중합반응을 진행하여 수용성 폴리아믹산을 제조하였다.63.7 g of distilled water was added as a solvent to a reactor equipped with a temperature controller and filled with nitrogen. Here, 1.0814 g (0.0094 mol) of p-phenylenediamine (pPDA) and 2.5 equivalents of 4-dimethylaminopyridine were added relative to the carboxyl group, and the mixture was dissolved using a mechanical stirrer at 25°C for 1 hour. Afterwards, 2.9422 g (0.01 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) was added, and the mixture was stirred at 70°C for 18 hours to conduct polymerization. Proceed to prepare water-soluble polyamic acid.
이 후, 얻어진 폴리아믹산을 유리기판에 바 코터로 캐스팅하고, 진공상태 오븐의 25℃에서 2 시간 탈포 및 건조 후에, 80℃에서 30 분간, 120℃에서 30 분간, 180℃에서 30 분간, 200℃에서 30분간 단계적으로 열적 이미드화하여 두께가 25㎛ 의 폴리이미드 필름을 제조하였다.Afterwards, the obtained polyamic acid was cast on a glass substrate with a bar coater, degassed and dried in a vacuum oven at 25°C for 2 hours, then 80°C for 30 minutes, 120°C for 30 minutes, 180°C for 30 minutes, and 200°C. A polyimide film with a thickness of 25㎛ was prepared by stepwise thermal imidization for 30 minutes.
이하, 표 1에 나타난 조성에 따라 실시예 1과 동일한 방법으로 다양한 실시예 및 비교예의 폴리아믹산 수용액 조성물 및 폴리이미드 필름을 제조하였다 (단, 실시예 및 비교예에 첨가된 수계 촉매의 함량은 카르복실기 대비 2.5 당량이였다.).Hereinafter, polyamic acid aqueous solution compositions and polyimide films of various Examples and Comparative Examples were prepared in the same manner as Example 1 according to the composition shown in Table 1 (however, the content of the aqueous catalyst added in the Examples and Comparative Examples was determined by carboxyl group It was 2.5 equivalents.).
비교예 1은 유기 용매 하에서 폴리아믹산 중합한 예이고, 비교예 3의 경우 물에서 폴리아믹산 중합 되었으나 200℃에서의 이미드화율이 낮게 나타났다. 그리고, 비교예 2는 물에서 폴리아믹산으로 중합되지 않았다.Comparative Example 1 is an example of polyamic acid polymerization in an organic solvent, and Comparative Example 3 was polymerization of polyamic acid in water, but the imidization rate at 200°C was low. And, Comparative Example 2 was not polymerized into polyamic acid in water.
반면, 실시예 2 내지 21은 폴리아믹산 수계 중합되었고, 중합된 폴리아믹산을 200℃에서 열 경화한 결과, 높은 이미드화율로 폴리이미드된 것을 확인할 수 있었다.On the other hand, Examples 2 to 21 were water-based polymerization of polyamic acid, and as a result of heat curing the polymerized polyamic acid at 200°C, it was confirmed that it was polyimide with a high imidation rate.
1. 용액 점도 측정1. Solution viscosity measurement
실시예 및 비교예에서 제조된 폴리아믹산 조성물에 대해, Haake 사의 VT-550을 사용하여 30/s의 전단 속도, 25℃ 온도 및 1 mm 플레이트 갭 조건에서 측정하였고, 그 결과는 상기 표 1에 나타내었다.The polyamic acid compositions prepared in Examples and Comparative Examples were measured using Haake's VT-550 at a shear rate of 30/s, a temperature of 25°C, and a plate gap of 1 mm, and the results are shown in Table 1 above. It was.
2. 대수 점도2. Logarithmic viscosity
실시예 및 비교예에서 제조된 폴리아믹산 조성물을 고형분 농도에 기초하여 농도 0.5 g/dl (용매: 물) 가 되도록 희석하였다. 상기 희석액의 유하 시간 (T1)을 30℃에서 Cannon-Fenske 점도계 No. 100을 이용해 측정하였다. 대수 점도는 블랭크 물의 유하 시간 (T0)을 이용해 이하의 식으로 산출하였고, 그 결과는 상기 표 1에 나타내었다.The polyamic acid composition prepared in Examples and Comparative Examples was diluted to a concentration of 0.5 g/dl (solvent: water) based on the solid content concentration. The flow time (T 1 ) of the diluted solution was measured at 30°C using a Cannon-Fenske viscometer No. It was measured using 100. The logarithmic viscosity was calculated using the flow time (T 0 ) of the blank water using the following equation, and the results are shown in Table 1 above.
대수 점도 = {ln(T1/T0)}/0.5Logarithmic viscosity = {ln(T 1 /T 0 )}/0.5
3. 이미드화율 측정3. Imidation rate measurement
몇몇 실시예 및 비교예의 이미드화율은 Bruker ALPHA-P Infrared Spectrometer (IR)의 Attenuated Total Reflectance (ATR) 방법으로 분석하였다. IR 분석을 통해 계산된 이미드 결합의 세기를 백분율로 나타내었으며, 400℃에서 완전 이미드화된 폴리이미드의 C-N 스트레칭 (1375 cm-1) 세기를 기준값으로 하고, 각 실시예 또는 비교예의 폴리아믹산 수용액에서 200℃까지 열처리하여 제조된 폴리이미드의 C-N 스트레칭 세기와의 비를 백분율로 나타내었다. 이미드화율은 하기의 식을 이용해 계산하였고, 그 결과를 도 1 및 표 2에 나타내었다. The imidization rates of some examples and comparative examples were analyzed by the Attenuated Total Reflectance (ATR) method of Bruker ALPHA-P Infrared Spectrometer (IR). The strength of the imide bond calculated through IR analysis was expressed as a percentage, and the CN stretching (1375 cm -1 ) strength of the fully imidized polyimide at 400°C was used as the reference value, and the polyamic acid aqueous solution of each example or comparative example was used as a reference value. The ratio with the CN stretching strength of the polyimide manufactured by heat treatment from 0 to 200°C was expressed as a percentage. The imidization rate was calculated using the formula below, and the results are shown in Figure 1 and Table 2.
[식][ceremony]
이미드화율(%) = {(1375cm-1)200℃/(1510cm-1)200℃}/{(1375cm-1)400℃/(1510 cm-1)400℃}Imidation rate (%) = {(1375cm -1 ) 200℃ / (1510cm -1 ) 200℃ }/{(1375cm -1 ) 400℃ / (1510 cm -1 ) 400℃ }
도 1은 실시예 1의 이미드화율 결과 그래프이다. 도 1로부터 실시예 1에 따른 폴리아믹산 수용액 조성물은 저온 경화에서 안정적으로 높은 이미드화율을 나타내는 것을 확인할 수 있었다.Figure 1 is a graph of the imidization rate results of Example 1. From Figure 1, it was confirmed that the polyamic acid aqueous solution composition according to Example 1 showed a stably high imidization rate at low temperature curing.
4. 인장 강도4. Tensile strength
몇몇 실시예 및 비교예의 폴리이미드 필름을 폭 10 mm, 길이 40 mm로 자른 후 인스트론(Instron)사의 Instron5564 UTM 장비를 사용하여 ASTM D-882 방법으로 모듈러스 및 인장강도를 측정하였다. 이때의 Cross Head Speed는 50 mm/min의 조건으로 측정하였고 그 결과는 하기 표 2에 나타내었다.The polyimide films of some examples and comparative examples were cut to 10 mm in width and 40 mm in length, and then the modulus and tensile strength were measured by ASTM D-882 using Instron5564 UTM equipment. The cross head speed at this time was measured under the condition of 50 mm/min, and the results are shown in Table 2 below.
5. 5% 열분해 온도 5. 5% pyrolysis temperature
TA사 열중량 분석(thermogravimetric analysis) Q5000 모델을 사용하였으며, 몇몇 실시예 및 비교예의 폴리이미드 필름을 질소 분위기하에서 10℃/분의 속도로 800℃까지 승온 하여 5% 중량 감소가 발생하는 온도를 측정하였고, 그 결과는 하기 표 2에 나타내었다.TA's thermogravimetric analysis Q5000 model was used, and the polyimide films of several examples and comparative examples were heated to 800°C at a rate of 10°C/min under a nitrogen atmosphere to measure the temperature at which 5% weight loss occurred. and the results are shown in Table 2 below.
Claims (11)
200℃에서 열 경화 시 이미드화율이 70 내지 99.9%의 범위 내이며,
상기 수계 촉매는 하기 화학식 1을 만족하는 폴리아믹산 수용액 조성물:
[화학식 1]
상기 화학식 1에서, 상기 R1 내지 R3 중 적어도 하나는 탄소수 1 내지 4의 알킬아민기, 히드록시기, 탄소수 1 내지 4의 알콕시기, 티올기, 탄소수 1 내지 4의 티올에테르기 또는 헤테로사이클릭기이다.Polyamic acid containing diamine monomer and dianhydride monomer as polymerized units; and an aqueous catalyst that is a pyridine derivative compound,
When heat cured at 200°C, the imidization rate is in the range of 70 to 99.9%,
The water-based catalyst is an aqueous polyamic acid solution composition that satisfies the following Chemical Formula 1:
[Formula 1]
In Formula 1, at least one of R 1 to R 3 is an alkylamine group having 1 to 4 carbon atoms, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a thiol group, a thiol ether group having 1 to 4 carbon atoms, or a heterocyclic group. am.
[화학식 2]
상기 화학식 2에서, R4 및 R5 중 적어도 하나는 탄소수 1 내지 4의 모노알킬아미노기, 탄소수 1 내지 4의 디알킬아미노기, 피페리디노기, 모르폴리노기, 피롤리디노기이다.The aqueous polyamic acid solution composition according to claim 1, wherein the aqueous catalyst satisfies the following formula (2):
[Formula 2]
In Formula 2, at least one of R 4 and R 5 is a monoalkylamino group having 1 to 4 carbon atoms, a dialkylamino group having 1 to 4 carbon atoms, a piperidino group, a morpholino group, and a pyrrolidino group.
[화학식 3]
상기 X는 페닐, 바이페닐, 또는 알릭사이클릭이고,
상기 M은 단일 결합, 알킬렌기, 알킬리덴기, 카보닐기, 알킬카보닐기, 알콕시기, 및 설포닐기를 포함하는 군 중에서 적어도 하나 이상을 포함하고, 상기 M은 불소 및 알킬기를 포함하는 군 중에서 적어도 하나 이상으로 치환되거나 비치환된다.The polyamic acid aqueous solution composition according to claim 1, wherein the dianhydride monomer includes at least one compound represented by the following formula (3):
[Formula 3]
Wherein X is phenyl, biphenyl, or aliccyclic,
M includes at least one from the group including a single bond, an alkylene group, an alkylidene group, a carbonyl group, an alkylcarbonyl group, an alkoxy group, and a sulfonyl group, and M includes at least one from the group including a fluorine and an alkyl group. It is substituted or unsubstituted by one or more.
상기 수계 촉매는 하기 화학식 1을 만족하는 폴리아믹산 제조 방법:
[화학식 1]
상기 화학식 1에서, 상기 R1 내지 R3 중 적어도 하나는 탄소수 1 내지 4의 알킬아민기, 히드록시기, 탄소수 1 내지 4의 알콕시기, 티올기, 탄소수 1 내지 4의 티올에테르기 또는 헤테로사이클릭기이다.Comprising the step of producing polyamic acid using an aqueous catalyst that is a pyridine derivative compound,
The water-based catalyst is a polyamic acid production method that satisfies the following formula (1):
[Formula 1]
In Formula 1, at least one of R 1 to R 3 is an alkylamine group having 1 to 4 carbon atoms, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a thiol group, a thiol ether group having 1 to 4 carbon atoms, or a heterocyclic group. am.
상기 폴리아믹산을 210℃미만에서 열 경화하여 폴리이미드를 제조하는 단계를 포함하고,
상기 수계 촉매는 하기 화학식 1을 만족하는, 폴리이미드 제조 방법:
[화학식 1]
상기 화학식 1에서, 상기 R1 내지 R3 중 적어도 하나는 탄소수 1 내지 4의 알킬아민기, 히드록시기, 탄소수 1 내지 4의 알콕시기, 티올기, 탄소수 1 내지 4의 티올에테르기 또는 헤테로사이클릭기이다.Preparing polyamic acid using an aqueous catalyst that is a pyridine derivative compound; and
Comprising the step of producing polyimide by heat curing the polyamic acid at less than 210°C,
The aqueous catalyst satisfies the following formula (1):
[Formula 1]
In Formula 1, at least one of R 1 to R 3 is an alkylamine group having 1 to 4 carbon atoms, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a thiol group, a thiol ether group having 1 to 4 carbon atoms, or a heterocyclic group. am.
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