JP5733070B2 - Polyimide precursor aqueous solution composition - Google Patents
Polyimide precursor aqueous solution composition Download PDFInfo
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- JP5733070B2 JP5733070B2 JP2011154896A JP2011154896A JP5733070B2 JP 5733070 B2 JP5733070 B2 JP 5733070B2 JP 2011154896 A JP2011154896 A JP 2011154896A JP 2011154896 A JP2011154896 A JP 2011154896A JP 5733070 B2 JP5733070 B2 JP 5733070B2
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- polyimide precursor
- aqueous solution
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- solution composition
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- 229920001721 polyimide Polymers 0.000 title claims description 128
- 239000004642 Polyimide Substances 0.000 title claims description 119
- 239000002243 precursor Substances 0.000 title claims description 101
- 239000000203 mixture Substances 0.000 title claims description 80
- 239000007864 aqueous solution Substances 0.000 title claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 239000003960 organic solvent Substances 0.000 claims description 32
- 229920005575 poly(amic acid) Polymers 0.000 claims description 32
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 26
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 22
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 21
- 150000002460 imidazoles Chemical class 0.000 claims description 17
- 150000004984 aromatic diamines Chemical class 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000003125 aqueous solvent Substances 0.000 claims description 13
- 150000004985 diamines Chemical class 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 8
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 5
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- QEFLNYXPYKZGEX-UHFFFAOYSA-N 4-ethyl-1-methylimidazole Chemical compound CCC1=CN(C)C=N1 QEFLNYXPYKZGEX-UHFFFAOYSA-N 0.000 claims description 3
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 60
- 239000002904 solvent Substances 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 239000011521 glass Substances 0.000 description 25
- 229910001873 dinitrogen Inorganic materials 0.000 description 23
- 239000007787 solid Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007810 chemical reaction solvent Substances 0.000 description 8
- 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 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 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
- 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 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical class C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 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 description 3
- 229940018564 m-phenylenediamine Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 2
- QRUWUSOUUMPANJ-UHFFFAOYSA-N 2-amino-5-[(4-amino-3-carboxyphenyl)methyl]benzoic acid Chemical compound C1=C(C(O)=O)C(N)=CC=C1CC1=CC=C(N)C(C(O)=O)=C1 QRUWUSOUUMPANJ-UHFFFAOYSA-N 0.000 description 2
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical class OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-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
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 2
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical class 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 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-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
- 230000009477 glass transition Effects 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- UINDRJHZBAGQFD-UHFFFAOYSA-N 2-ethyl-1-methylimidazole Chemical compound CCC1=NC=CN1C UINDRJHZBAGQFD-UHFFFAOYSA-N 0.000 description 1
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical class C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 1
- UNIBAJHMJGXVHL-UHFFFAOYSA-N 3-phenylbenzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C=2C=CC=CC=2)=C1C(O)=O UNIBAJHMJGXVHL-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-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
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QQPYIXJPRJQUDC-UHFFFAOYSA-N 5-(3-phenylphenyl)benzene-1,2,3,4-tetracarboxylic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=C(C=CC=2)C=2C=CC=CC=2)=C1C(O)=O QQPYIXJPRJQUDC-UHFFFAOYSA-N 0.000 description 1
- JJJDAERKXDTMPH-UHFFFAOYSA-N 5-(4-phenylphenyl)benzene-1,2,3,4-tetracarboxylic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC(=CC=2)C=2C=CC=CC=2)=C1C(O)=O JJJDAERKXDTMPH-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- -1 amine compounds Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 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 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、ポリイミド前駆体水溶液組成物に関する。このポリイミド前駆体水溶液組成物は、有機溶媒を用いたポリイミド前駆体溶液組成物に較べて環境適応性が高いので好適である。しかも、このポリイミド前駆体水溶液組成物を用いて得られる芳香族ポリイミドは、高い結晶性を有し、したがって耐熱性、機械的強度、電気特性、耐溶剤性などの優れた特性を有する。 The present invention relates to a polyimide precursor aqueous solution composition. This polyimide precursor aqueous solution composition is suitable because it has higher environmental adaptability than a polyimide precursor solution composition using an organic solvent. Moreover, the aromatic polyimide obtained by using this polyimide precursor aqueous solution composition has high crystallinity, and thus has excellent characteristics such as heat resistance, mechanical strength, electrical characteristics, and solvent resistance.
芳香族テトラカルボン酸二無水物と芳香族ジアミンから得られる芳香族ポリイミドは、耐熱性、機械的強度、電気特性、耐溶剤性などの特性が優れるために、電気電子産業分野などで広く用いられている。しかし、芳香族ポリイミドは有機溶媒への溶解性が悪いので、通常は、ポリイミド前駆体のポリアミック酸を有機溶媒に溶解した溶液組成物を、例えば基材表面上に塗布し、次いで高温で加熱して脱水閉環(イミド化)させることで芳香族ポリイミドを得ている。このポリアミック酸溶液組成物は、有機溶媒を用いることや高温の熱処理が必要なことから、環境面で必ずしも好適とは云えず、場合によっては用途が限定されることもあった。 Aromatic polyimides obtained from aromatic tetracarboxylic dianhydrides and aromatic diamines have excellent heat resistance, mechanical strength, electrical properties, solvent resistance, and other properties, so they are widely used in the electrical and electronics industries. ing. However, since aromatic polyimides have poor solubility in organic solvents, a solution composition in which a polyimide precursor polyamic acid is dissolved in an organic solvent is usually applied onto a substrate surface, and then heated at a high temperature. Thus, aromatic polyimide is obtained by dehydration ring closure (imidization). Since this polyamic acid solution composition uses an organic solvent or requires high-temperature heat treatment, it is not necessarily suitable for the environment, and its use may be limited in some cases.
このために、水溶性ポリイミド前駆体が提案されている。例えば、特許文献1には、有機溶媒中で得られたポリアミド酸を加水分解した後で水中に投入してポリアミド酸粉末を得、そのポリアミド酸粉末をさらに温水中で粉砕及び洗浄し、次いで、水及び2−メチルアミノジエタノールなどの特定のアミン化合物と混合してポリアミド酸塩水溶液組成物を得ることが提案されている。しかし、このポリアミド酸塩水溶液組成物は、高分子量化し難く、また得られるポリイミドの特性にも改良の余地があった。 For this reason, water-soluble polyimide precursors have been proposed. For example, in Patent Document 1, the polyamic acid obtained in an organic solvent is hydrolyzed and then poured into water to obtain a polyamic acid powder. The polyamic acid powder is further pulverized and washed in warm water, It has been proposed to obtain an aqueous polyamic acid salt composition by mixing with water and specific amine compounds such as 2-methylaminodiethanol. However, this polyamic acid salt aqueous solution composition is difficult to achieve a high molecular weight, and there is room for improvement in the properties of the resulting polyimide.
さらに、特許文献2には、有機溶媒中で得られたポリアミック酸と1,2−ジメチルイミダゾ−ル及び/又は1−メチル−2−エチルイミダゾ−ルとの反応混合物から分離取得した水溶性ポリイミド前駆体が提案されている。しかし、ここで具体的に提案された水溶性ポリイミド前駆体は、それを用いて得られる芳香族ポリイミドが非結晶性のものであった。さらに、ここでは、水溶性ポリイミド前駆体は、有機溶媒中で調製後、分離し、水溶媒に溶解されるが、有機溶媒中で調製された水溶性ポリイミド前駆体からは有機溶媒を完全に除去できない(完全に除去しようとして加熱処理するとイミド化が起こる)ために、水溶液組成物中に有機溶媒が同伴するなどの問題があった。 Further, Patent Document 2 discloses a water-soluble polyimide obtained by separation from a reaction mixture of a polyamic acid obtained in an organic solvent and 1,2-dimethylimidazole and / or 1-methyl-2-ethylimidazole. Precursors have been proposed. However, in the water-soluble polyimide precursor specifically proposed here, the aromatic polyimide obtained using the precursor is amorphous. Furthermore, here, the water-soluble polyimide precursor is prepared in an organic solvent, then separated and dissolved in an aqueous solvent, but the organic solvent is completely removed from the water-soluble polyimide precursor prepared in the organic solvent. Since it cannot be performed (imidation occurs when heat treatment is performed to completely remove it), there is a problem that an organic solvent is accompanied in the aqueous solution composition.
したがって、本発明の目的は、水溶媒を使用することによって環境適応性が良好であって、しかも、それを用いて得られる芳香族ポリイミドは高い結晶性を有するために耐熱性、機械的強度、電気特性、耐溶剤性などの特性が優れる、好ましくは高分子量であって水溶媒が水以外の有機溶媒を含まない、ポリイミド前駆体水溶液組成物を提供することである。 Therefore, the object of the present invention is that the environmental adaptability is good by using an aqueous solvent, and the aromatic polyimide obtained by using it has high crystallinity, and therefore has heat resistance, mechanical strength, An object is to provide a polyimide precursor aqueous solution composition having excellent characteristics such as electric characteristics and solvent resistance, preferably having a high molecular weight and containing no organic solvent other than water.
本発明は、以下の各項に関する。 The present invention relates to the following items.
1. テトラカルボン酸成分とジアミン成分とが反応して得られる、下記化学式(1)で表される繰返し単位からなるポリアミック酸が、前記ポリアミック酸のテトラカルボン酸成分に対して1.6倍モル以上の、置換基として2個以上のアルキル基を有するイミダゾール類と共に、水溶媒中に溶解してなるポリイミド前駆体水溶液組成物。 1. A polyamic acid comprising a repeating unit represented by the following chemical formula (1) obtained by reacting a tetracarboxylic acid component and a diamine component is 1.6 times mol or more with respect to the tetracarboxylic acid component of the polyamic acid. A polyimide precursor aqueous solution composition dissolved in an aqueous solvent together with imidazoles having two or more alkyl groups as substituents.
2. 置換基として2個以上のアルキル基を有するイミダゾール類が、1,2−ジメチルイミダゾール、2−エチル−4−メチルイミダゾール、4−エチル−2−メチルイミダゾール、及び1−メチル−4−エチルイミダゾールからなる群から選択されるイミダゾール類であることを特徴とする前記求項1に記載のポリイミド前駆体水溶液組成物。 2. Imidazoles having two or more alkyl groups as substituents are from 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, and 1-methyl-4-ethylimidazole. The polyimide precursor aqueous solution composition according to claim 1, which is an imidazole selected from the group consisting of:
3. 化学式(1)のAが、下記化学式(2)〜(7)或いはそれらの混合物であることを特徴とする前記項1または2に記載のポリイミド前駆体水溶液組成物。 3. Item 3. The polyimide precursor aqueous solution composition according to Item 1 or 2, wherein A in the chemical formula (1) is the following chemical formulas (2) to (7) or a mixture thereof.
4. 化学式(1)のBが、下記化学式(8)〜(9)或いはそれらの混合物であることを特徴とする前記項1〜3のいずれかに記載のポリイミド前駆体水溶液組成物。 4). Item 4. The polyimide precursor aqueous solution composition according to any one of Items 1 to 3, wherein B in the chemical formula (1) is the following chemical formulas (8) to (9) or a mixture thereof.
5. 対数粘度が0.2以上であることを特徴とする前記項1〜4のいずれかに記載のポリイミド前駆体水溶液組成物。 5. Item 5. The polyimide precursor aqueous solution composition according to any one of Items 1 to 4, which has a logarithmic viscosity of 0.2 or more.
6. 有機溶媒の含有量が5%未満であることを特徴とする前記項1〜5のいずれかに記載のポリイミド前駆体水溶液組成物。 6). Item 6. The polyimide precursor aqueous solution composition according to any one of Items 1 to 5, wherein the content of the organic solvent is less than 5%.
7. 水溶媒が、実質的に水以外の有機溶媒を含まないことを特徴とする前記項1〜6のいずれかに記載のポリイミド前駆体水溶液組成物。 7). Item 7. The polyimide precursor aqueous solution composition according to any one of Items 1 to 6, wherein the aqueous solvent contains substantially no organic solvent other than water.
本発明によって、水溶媒を使用することによって環境適応性が良好であって、しかも、それを用いて得られる芳香族ポリイミドは高い結晶性を有するために耐熱性、機械的強度、電気特性、耐溶剤性などの特性が優れる、好ましくは高分子量であって水溶媒が水以外の有機溶媒を含まない、ポリイミド前駆体水溶液組成物を提供することができる。
本発明のポリイミド前駆体水溶液組成物から得られる芳香族ポリイミドは、耐熱性、機械的強度、電気特性、耐溶剤性などの特性が優れているので電気・電子機器や複写機などの各種精密機器用の部品として、例えばフレキシブルプリント配線板などの各種材料、複写機の中間転写、定着、或いは搬送用のシームレスベルトなどとして好適に用いることができる。また、電池環境下でも膨潤度が小さく、また優れた靱性を有することから、電池の電極バインダー用途などにも好適に用いることができる。
According to the present invention, the environmental adaptability is good by using an aqueous solvent, and the aromatic polyimide obtained by using the water solvent has high crystallinity, so that it has heat resistance, mechanical strength, electrical properties, resistance to resistance. It is possible to provide a polyimide precursor aqueous solution composition having excellent solvent properties and the like, preferably having a high molecular weight and containing no organic solvent other than water.
Aromatic polyimide obtained from the polyimide precursor aqueous solution composition of the present invention has excellent heat resistance, mechanical strength, electrical properties, solvent resistance, and other precision devices such as electric / electronic devices and copying machines. For example, it can be suitably used as various parts such as a flexible printed wiring board, a seamless belt for intermediate transfer, fixing, or conveyance of a copying machine. In addition, since the degree of swelling is small even in a battery environment and it has excellent toughness, it can be suitably used for battery electrode binder applications.
本発明のポリイミド前駆体水溶液組成物を構成するポリアミック酸は、前記化学式(1)で表される繰返し単位からなる。 The polyamic acid which comprises the polyimide precursor aqueous solution composition of this invention consists of a repeating unit represented by the said Chemical formula (1).
化学式(1)のAは、2〜3個の芳香族環を有するテトラカルボン酸からカルボキシル基を除いた4価の基であって、好ましくは前記化学式(2)〜(7)或いはそれらの混合物である。すなわち、本発明で用いるポリアミック酸のテトラカルボン酸成分は、2〜3個の芳香族環を有するテトラカルボン酸類(テトラカルボン酸、その二無水物或いはエステル化物など)であって、例えば、3,3’,4,4’−ビフェニルテトラカルボン酸類、2,3,3’,4’−ビフェニルテトラカルボン酸類、2,2’,3,3’−ビフェニルテトラカルボン酸類、4,4’−オキシジフタル酸類、3,3’,4,4’−ベンゾフェノンテトラカルボン酸類、3,3’,4,4’−ジフェニルスルホンテトラカルボン酸類、p−ターフェニルテトラカルボン酸類、m−ターフェニルテトラカルボン酸類など、及びそれらの混合物を好適に例示することができる。この中で好ましくは、3,3’,4,4’−ビフェニルテトラカルボン酸類、3,3’,4,4’−ベンゾフェノンテトラカルボン酸類、4,4’−オキシジフタル酸類であり、3,3’,4,4’−ビフェニルテトラカルボン酸類、4,4’−オキシジフタル酸類、及びそれらの混合物がより好ましい。これら以外のテトラカルボン酸成分を用いると、水溶性のポリイミド前駆体を得るのが難しくなったり、得られるポリイミドの結晶性が低下して高い特性が得られなくなったりする場合がある。 A in the chemical formula (1) is a tetravalent group obtained by removing a carboxyl group from a tetracarboxylic acid having 2 to 3 aromatic rings, preferably the chemical formulas (2) to (7) or a mixture thereof. It is. That is, the tetracarboxylic acid component of the polyamic acid used in the present invention is a tetracarboxylic acid (tetracarboxylic acid, dianhydride or esterified product thereof) having 2 to 3 aromatic rings, for example, 3, 3 ′, 4,4′-biphenyltetracarboxylic acids, 2,3,3 ′, 4′-biphenyltetracarboxylic acids, 2,2 ′, 3,3′-biphenyltetracarboxylic acids, 4,4′-oxydiphthalic acids 3,3 ′, 4,4′-benzophenone tetracarboxylic acids, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acids, p-terphenyl tetracarboxylic acids, m-terphenyl tetracarboxylic acids, and the like, and A mixture thereof can be preferably exemplified. Among these, 3,3 ′, 4,4′-biphenyltetracarboxylic acids, 3,3 ′, 4,4′-benzophenonetetracarboxylic acids, and 4,4′-oxydiphthalic acids are preferable. 4,4′-biphenyltetracarboxylic acids, 4,4′-oxydiphthalic acids, and mixtures thereof are more preferred. If a tetracarboxylic acid component other than these is used, it may be difficult to obtain a water-soluble polyimide precursor, or the crystallinity of the resulting polyimide may be reduced, and high characteristics may not be obtained.
前記化学式(1)のBは、1〜2個の芳香族環を有する芳香族ジアミンからアミノ基を除いた2価の基であって、前記芳香族ジアミンの25℃における水に対する溶解度が0.1g/L以上のものである。すなわち、本発明で用いるポリアミック酸の芳香族ジアミン成分は、1〜2個の芳香族環を有する芳香族ジアミンあって、前記芳香族ジアミンの25℃における水に対する溶解度が0.1g/L以上のものである。
芳香族ジアミンが2個を越える芳香族環を持つ場合には、通常芳香族ジアミン分子中に複数の屈曲性が高い結合が含まれるので、その様な芳香族ジアミンから得られる芳香族ポリイミドは結晶性が低下して高い特性を得ることが難しくなる。
また、芳香族ジアミンの25℃における水に対する溶解度が0.1g/L以上であることは、ポリイミド前駆体水溶液組成物を得るために特に必要な特性であって、水に対する溶解度が0.1g/L未満では、均一に溶解したポリイミド前駆体水溶液組成物を得るのが難しくなるので好ましくない。
B in the chemical formula (1) is a divalent group obtained by removing an amino group from an aromatic diamine having 1 to 2 aromatic rings, and the solubility of the aromatic diamine in water at 25 ° C. is 0. 1 g / L or more. That is, the aromatic diamine component of the polyamic acid used in the present invention is an aromatic diamine having 1 to 2 aromatic rings, and the solubility of the aromatic diamine in water at 25 ° C. is 0.1 g / L or more. Is.
When the aromatic diamine has more than two aromatic rings, since the aromatic diamine molecule usually contains a plurality of highly flexible bonds, the aromatic polyimide obtained from such an aromatic diamine is crystalline. It becomes difficult to obtain high characteristics due to a decrease in properties.
Further, the solubility of the aromatic diamine in water at 25 ° C. is 0.1 g / L or more, which is a particularly necessary characteristic for obtaining a polyimide precursor aqueous solution composition, and the solubility in water is 0.1 g / L. If it is less than L, it is difficult to obtain a uniformly dissolved polyimide precursor aqueous solution composition, which is not preferable.
本発明で用いる芳香族ジアミン成分としては、p−フェニレンジアミン(25℃における水に対する溶解度は120g/L、以下同様)、m−フェニレンジアミン(77g/L)、4,4’−ジアミノジフェニルエーテル(0.19g/L)、3,4’−ジアミノジフェニルエーテル(0.24g/L)、4,4’−ジアミノジフェニルメタン(0.54g/L)、2,4−トルエンジアミン(62g/L)、3,3’−ジヒドロキシ−4,4’−ジアミノビフェニル(1.3g/L)、ビス(4−アミノ−3−カルボキシフェニル)メタン(200g/L)、2,4−TDA:2,4−ジアミノトルエン(62g/L)などを例示できるが、水溶性が高く、且つ得られるポリイミドの結晶性が高くて優れた特性を得ることができるので、p−フェニレンジアミン、m−フェニレンジアミン、4,4’−ジアミノジフェニルエーテル、3,4’−ジアミノジフェニルエーテル、及びそれらの混合物が好ましく、さらにp−フェニレンジアミン、4,4’−ジアミノジフェニルエーテル、及びそれらの混合物がより好ましい。
なお、25℃おける水に対する溶解度は、当該物質が、25℃の水1L(リットル)に溶解する限界量(g)を意味する。この値は、ケミカル・アブストラクトなどのベータベースに基づいた検索サービスとして知られるSciFinder(登録商標)によって容易に検索することができる。ここでは、種々の条件下での溶解度のうち、Advanced Chemistry Development(ACD/Labs)Software V11.02(Copyright 1994−2011 ACD/Labs)によって算出されたpHが7における値を採用した。
Examples of the aromatic diamine component used in the present invention include p-phenylenediamine (the solubility in water at 25 ° C. is 120 g / L, the same applies hereinafter), m-phenylenediamine (77 g / L), 4,4′-diaminodiphenyl ether (0 19 g / L), 3,4′-diaminodiphenyl ether (0.24 g / L), 4,4′-diaminodiphenylmethane (0.54 g / L), 2,4-toluenediamine (62 g / L), 3, 3′-dihydroxy-4,4′-diaminobiphenyl (1.3 g / L), bis (4-amino-3-carboxyphenyl) methane (200 g / L), 2,4-TDA: 2,4-diaminotoluene (62 g / L) and the like. However, since the water-soluble property and the crystallinity of the resulting polyimide are high and excellent characteristics can be obtained, p-Fe Range amine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and mixtures thereof are preferred, and p-phenylenediamine, 4,4′-diaminodiphenyl ether, and mixtures thereof are more preferred. More preferred.
In addition, the solubility with respect to the water in 25 degreeC means the limit amount (g) which the said substance melt | dissolves in 1 L (liter) of water of 25 degreeC. This value can be easily searched by SciFinder (registered trademark) known as a search service based on a beta base such as a chemical abstract. Here, among the solubility under various conditions, the value at pH 7 calculated by Advanced Chemistry Development (ACD / Labs) Software V11.02 (Copyright 1994-2011 ACD / Labs) was adopted.
本発明で用いる置換基として2個以上のアルキル基を有するイミダゾール類(化合物)は、好ましくは下記化学式(10)の化合物が好適である。 As the imidazole (compound) having two or more alkyl groups as a substituent used in the present invention, a compound represented by the following chemical formula (10) is preferable.
置換基として2個以上のアルキル基を有するイミダゾール類は、水に対する溶解性が高いので、それらを用いることによって、ポリイミド前駆体組成物を容易に製造することができる。これらのイミダゾール類としては、1,2−ジメチルイミダゾール(25℃における水に対する溶解度は239g/L、以下同様)、2−エチル−4−メチルイミダゾール(1000g/L)、4−エチル−2−メチルイミダゾール(1000g/L)、及び1−メチル−4−エチルイミダゾール(54g/L)などが好適である。
なお、25℃おける水に対する溶解度は、当該物質が、25℃の水1L(リットル)に溶解する限界量(g)を意味する。この値は、ケミカル・アブストラクトなどのベータベースに基づいた検索サービスとして知られるSciFinder(登録商標)によって容易に検索することができる。ここでは、種々の条件下での溶解度のうち、Advanced Chemistry Development(ACD/Labs)Software V11.02(Copyright 1994−2011 ACD/Labs)によって算出されたpHが7における値を採用した。
Since imidazoles having two or more alkyl groups as a substituent have high solubility in water, a polyimide precursor composition can be easily produced by using them. As these imidazoles, 1,2-dimethylimidazole (solubility in water at 25 ° C. is 239 g / L, hereinafter the same), 2-ethyl-4-methylimidazole (1000 g / L), 4-ethyl-2-methyl Imidazole (1000 g / L), 1-methyl-4-ethylimidazole (54 g / L), and the like are preferable.
In addition, the solubility with respect to the water in 25 degreeC means the limit amount (g) which the said substance melt | dissolves in 1 L (liter) of water of 25 degreeC. This value can be easily searched by SciFinder (registered trademark) known as a search service based on a beta base such as a chemical abstract. Here, among the solubility under various conditions, the value at pH 7 calculated by Advanced Chemistry Development (ACD / Labs) Software V11.02 (Copyright 1994-2011 ACD / Labs) was adopted.
本発明で用いる置換基として2個以上のアルキル基を有するイミダゾール類の使用量は、原料のテトラカルボン酸二無水物とジアミンとの反応によって生成するポリアミック酸のカルボキシル基に対して、好ましくは0.8倍当量以上、より好ましくは1.0倍当量以上、さらに好ましくは1.2倍当量以上である。イミダゾール類の使用量がポリアミック酸のカルボキシル基に対して0.8倍当量未満では、均一に溶解したポリイミド前駆体水溶液組成物を得るのが容易でなくなる場合がある。また、イミダゾール類の使用量の上限は、特に限定されないが、通常は10倍当量未満、好ましくは5倍当量未満、より好ましくは3倍当量未満である。イミダゾール類の使用量が多過ぎると、非経済的になるし、且つ組成物の保存安定性が悪くなることがある。
本発明において、イミダゾール類の量を規定するポリアミック酸のカルボキシル基に対する倍当量とは、ポリアミック酸のアミド酸基を形成するカルボキシル基1個に対して何個(何分子)の割合でイミダゾール類を用いるかを表す。なお、ポリアミック酸のアミド酸基を形成するカルボキシル基の数は、原料のテトラカルボン酸成分1分子当たり2個のカルボキシル基を形成するものとして計算される。
したがって、本発明で用いるイミダゾール類の使用量は、ポリアミック酸のテトラカルボン酸成分に対して、つまり原料のテトラカルボン酸二無水物に対して、好ましくは1.6倍モル以上、より好ましくは2.0倍モル以上、さらに好ましくは2.4倍モル以上である。
The amount of the imidazole having two or more alkyl groups as a substituent used in the present invention is preferably 0 with respect to the carboxyl group of the polyamic acid generated by the reaction of the raw material tetracarboxylic dianhydride and diamine. More than 8 times equivalent, More preferably, it is 1.0 times equivalent or more, More preferably, it is 1.2 times equivalent or more. If the amount of imidazole used is less than 0.8 equivalents relative to the carboxyl group of the polyamic acid, it may not be easy to obtain a uniformly dissolved polyimide precursor aqueous solution composition. Moreover, although the upper limit of the usage-amount of imidazoles is not specifically limited, Usually, it is less than 10 times equivalent, Preferably it is less than 5 times equivalent, More preferably, it is less than 3 times equivalent. If the amount of imidazole used is too large, it may be uneconomical and the storage stability of the composition may be deteriorated.
In the present invention, the double equivalent to the carboxyl group of the polyamic acid that defines the amount of imidazoles is the number (number of molecules) of imidazoles in one carboxyl group that forms the amic acid group of the polyamic acid. Indicates whether to use. Note that the number of carboxyl groups forming the amic acid group of the polyamic acid is calculated as forming two carboxyl groups per molecule of the starting tetracarboxylic acid component.
Therefore, the amount of the imidazoles used in the present invention is preferably 1.6 times mol or more, more preferably 2 with respect to the tetracarboxylic acid component of the polyamic acid, that is, with respect to the raw material tetracarboxylic dianhydride. It is 0.0 times mol or more, More preferably, it is 2.4 times mol or more.
本発明で用いるイミダゾール類の特徴は、ポリアミック酸のカルボキシル基と塩を形成して水に対する溶解性を高めるだけでなく、さらにポリイミド前駆体をイミド化(脱水閉環)してポリイミドにする際に、極めて高い触媒的な作用を有することにある。この結果、本発明のポリイミド前駆体水溶液組成物を用いると、例えばより低温且つ短時間の加熱処理によっても容易に、極めて高い物性を有する芳香族ポリイミドを得ることが可能になる。 The characteristics of imidazoles used in the present invention are not only to increase the solubility in water by forming a salt with a carboxyl group of polyamic acid, but also when imidizing (dehydrating cyclization) the polyimide precursor into a polyimide, It has an extremely high catalytic action. As a result, when the polyimide precursor aqueous solution composition of the present invention is used, an aromatic polyimide having extremely high physical properties can be easily obtained, for example, by a heat treatment at a lower temperature for a shorter time.
本発明のポリイミド前駆体水溶液組成物は、特許文献1,2などの方法に準じ、
(i) 有機溶媒を反応溶媒とし、テトラカルボン酸成分とジアミン成分とを反応して得られたポリアミド酸を水中に投入してポリアミド酸粉末を得、そのポリアミド酸粉末を水溶媒中でイミダゾール類(好ましくは2個以上のアルキル基を有するイミダゾール類)と共に混合溶解して水溶液組成物を得る方法、
(ii) 有機溶媒を反応溶媒とし、イミダゾール類(好ましくは2個以上のアルキル基を有するイミダゾール類)の存在下にテトラカルボン酸成分とジアミン成分とを反応して水溶性ポリイミド前駆体を得、それを分離後、水溶媒に溶解する方法、或いは、
(iii) 有機溶媒を反応溶媒とし、テトラカルボン酸成分とジアミン成分とを反応してポリアミック酸を得、そのポリアミック酸を、有機溶媒を反応溶媒として、イミダゾール類(好ましくは2個以上のアルキル基を有するイミダゾール類)と反応して水溶性ポリイミド前駆体を得、それを分離後、水溶媒に溶解する方法
などでも得ることができる。但し、前述の通り、有機溶媒の含有量が極めて少ない、さらには有機溶媒を含まないポリイミド前駆体水溶液組成物を得るためには、ポリイミド前駆体を有機溶媒中で調製することは好ましくない。
The polyimide precursor aqueous solution composition of the present invention conforms to the methods of Patent Documents 1 and 2,
(i) Polyamic acid obtained by reacting a tetracarboxylic acid component with a diamine component using an organic solvent as a reaction solvent is poured into water to obtain a polyamic acid powder, and the polyamic acid powder is imidazoles in an aqueous solvent. (Preferably a method of obtaining an aqueous solution composition by mixing and dissolving together with imidazoles having two or more alkyl groups),
(ii) A water-soluble polyimide precursor is obtained by reacting a tetracarboxylic acid component and a diamine component in the presence of imidazoles (preferably imidazoles having two or more alkyl groups) using an organic solvent as a reaction solvent, A method of dissolving it in an aqueous solvent after separating it, or
(iii) A polyamic acid is obtained by reacting a tetracarboxylic acid component and a diamine component using an organic solvent as a reaction solvent, and the polyamic acid is converted into an imidazole (preferably two or more alkyl groups) using the organic solvent as a reaction solvent. It can also be obtained by a method in which a water-soluble polyimide precursor is obtained by reacting with an imidazole having a solvent, and is separated and then dissolved in an aqueous solvent. However, as described above, it is not preferable to prepare the polyimide precursor in an organic solvent in order to obtain a polyimide precursor aqueous solution composition having an extremely small organic solvent content and further not containing an organic solvent.
本発明のポリイミド前駆体水溶液組成物は、好ましくは、水を反応溶媒として、置換基として2個以上のアルキル基を有するイミダゾール類の存在下に、テトラカルボン酸成分と芳香族ジアミン成分とを反応することによって、極めて簡便に(直接的に)製造することが可能である。 The polyimide precursor aqueous solution composition of the present invention preferably reacts a tetracarboxylic acid component with an aromatic diamine component in the presence of imidazoles having two or more alkyl groups as substituents using water as a reaction solvent. By doing so, it is possible to manufacture very simply (directly).
この反応は、テトラカルボン酸成分と芳香族ジアミン成分を略等モル用い、イミド化反応を抑制するために100℃以下好ましくは80℃以下の比較的低温で行なわれる。限定するものではないが、通常の反応温度は、25℃〜100℃、好ましくは40℃〜80℃、より好ましくは50℃〜80℃であり、反応時間は0.1〜24時間程度、好ましくは2〜12時間程度が好適である。反応温度及び反応時間を前記範囲内とすることによって、生産効率よく高分子量のポリイミド前駆体水溶液組成物を容易に得ることができる。なお、反応は、空気雰囲気下でも構わないが、通常は不活性ガス好ましくは窒素ガス雰囲気下で好適に行われる。
また、テトラカルボン酸成分と芳香族ジアミン成分を略等モルとは、具体的にはモル比[テトラカルボン酸成分/ジアミン成分]で0.90〜1.10程度、好ましくは0.95〜1.05程度である。
This reaction is carried out at a relatively low temperature of 100 ° C. or less, preferably 80 ° C. or less in order to suppress the imidization reaction, using approximately equimolar amounts of a tetracarboxylic acid component and an aromatic diamine component. Although not limited, the normal reaction temperature is 25 ° C to 100 ° C, preferably 40 ° C to 80 ° C, more preferably 50 ° C to 80 ° C, and the reaction time is about 0.1 to 24 hours, preferably Is preferably about 2 to 12 hours. By setting the reaction temperature and reaction time within the above ranges, a high-molecular weight polyimide precursor aqueous solution composition can be easily obtained with high production efficiency. The reaction may be carried out in an air atmosphere, but usually it is suitably carried out in an inert gas, preferably a nitrogen gas atmosphere.
Further, the substantially equimolar amount of the tetracarboxylic acid component and the aromatic diamine component specifically refers to a molar ratio [tetracarboxylic acid component / diamine component] of about 0.90 to 1.10, preferably 0.95 to 1. .05 or so.
本発明のポリイミド前駆体水溶液組成物においては、ポリイミド前駆体(実質的にポリアミック酸)に起因する固形分濃度に基づいて温度30℃、濃度0.5g/100mL(水溶解)で測定した対数粘度が0.2以上、好ましくは0.4以上、より好ましくは0.6以上、さらに好ましくは0.8以上、特に好ましくは1.0以上または超の高分子量であることが好適である。対数粘度が前記範囲よりも低くい場合には、ポリイミド前駆体の分子量が低いことから、本発明のポリイミド前駆体水溶液組成物を用いても、高い特性の芳香族ポリイミドを得ることが難しくなることがある。 In the polyimide precursor aqueous solution composition of the present invention, the logarithmic viscosity measured at a temperature of 30 ° C. and a concentration of 0.5 g / 100 mL (dissolved in water) based on the solid content concentration resulting from the polyimide precursor (substantially polyamic acid). Is 0.2 or more, preferably 0.4 or more, more preferably 0.6 or more, still more preferably 0.8 or more, and particularly preferably 1.0 or more, or a high molecular weight. When the logarithmic viscosity is lower than the above range, the molecular weight of the polyimide precursor is low, so that it is difficult to obtain an aromatic polyimide having high characteristics even when using the polyimide precursor aqueous solution composition of the present invention. There is.
本発明のポリイミド前駆体水溶液組成物は、水溶媒を用いるが、水以外のポリアミック酸を調製する際に用いられる公知の有機溶媒を全溶媒中50質量%以下、好ましくは30質量%以下、より好ましくは10質量%以下の割合で用いても構わない。 The polyimide precursor aqueous solution composition of the present invention uses an aqueous solvent, but a known organic solvent used when preparing a polyamic acid other than water is 50% by mass or less, preferably 30% by mass or less, based on the total solvent. Preferably, you may use in the ratio of 10 mass% or less.
「水を反応溶媒として」とは、溶媒の主成分として水を用いることを意味する。したがって、水以外の有機溶媒を全溶媒中50質量%以下、好ましくは30質量%以下、より好ましくは10質量%以下の割合で用いてもよい。なお、ここで言う有機溶媒には、テトラカルボン酸二無水物等のテトラカルボン酸成分、ジアミン成分、ポリアミック酸等のポリイミド前駆体、及びイミダゾール類は含まれない。 “Water as a reaction solvent” means that water is used as a main component of the solvent. Therefore, an organic solvent other than water may be used in a proportion of 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less in the total solvent. The organic solvent mentioned here does not include tetracarboxylic acid components such as tetracarboxylic dianhydride, diamine components, polyimide precursors such as polyamic acid, and imidazoles.
前記有機溶媒とは、例えばN,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N,N−ジエチルアセトアミド、N−メチル−2−ピロリドン、N−エチル−2−ピロリドン、1,3−ジメチル−2−イミダゾリジノン、N−メチルカプロラクタム、ヘキサメチルホスホロトリアミド、1,2−ジメトキシエタン、ビス(2−メトキシエチル)エーテル、1,2−ビス(2−メトキシエトキシ)エタン、テトラヒドロフラン、ビス[2−(2−メトキシエトキシ)エチル]エーテル、1,4−ジオキサン、ジメチルスルホキシド、ジメチルスルホン、ジフェニルエーテル、スルホラン、ジフェニルスルホン、テトラメチル尿素、アニソール、m−クレゾール、フェノール、γ−ブチロラクトンなどが挙げられる。 Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl- 2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotriamide, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [ 2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane, dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, anisole, m-cresol, phenol, γ-butyrolactone, and the like. .
本発明のポリイミド前駆体水溶液組成物の製造方法においては、環境適応性が高いので、反応溶媒が、有機溶媒の含有量が5%未満である溶媒であることが好ましく、水以外の有機溶媒を含まない水溶媒であることが特に好ましい。反応溶媒の組成は、製造するポリイミド前駆体水溶液組成物の所望の溶媒組成に応じて適宜選択することができ、ポリイミド前駆体水溶液組成物の所望の溶媒組成と同一であることが好ましい場合がある。 In the manufacturing method of the polyimide precursor aqueous solution composition of the present invention, since the environmental adaptability is high, the reaction solvent is preferably a solvent having an organic solvent content of less than 5%, and an organic solvent other than water is used. It is particularly preferable that the aqueous solvent does not contain. The composition of the reaction solvent can be appropriately selected according to the desired solvent composition of the polyimide precursor aqueous solution composition to be produced, and may be preferably the same as the desired solvent composition of the polyimide precursor aqueous solution composition. .
本発明のポリイミド前駆体水溶液組成物は、ポリイミド前駆体(実質的にポリアミック酸)に起因する固形分濃度が、限定されないが、ポリイミド前駆体と溶媒との合計量に対して、好ましくは5質量%〜45質量%、より好ましくは7質量%〜40質量%、さらに好ましくは9質量%〜30質量%であることが好適である。固形分濃度が5質量%より低いと著しく生産性が悪くなることがあり、45質量%より高いと溶液の流動性がなくなることがある。また本発明のポリイミド前駆体水溶液組成物の30℃における溶液粘度は、限定されないが、好ましくは1000Pa・sec以下、より好ましくは0.5〜500Pa・sec、さらに好ましくは1〜300Pa・sec、特に好ましくは3〜200Pa・secであることが取り扱い上好適である。
溶液粘度が1000Pa・secを超えると、流動性がなくなるため金属やガラスなどへの均一な塗布が困難となり、また、0.5Pa・secよりも低いと、金属やガラスなどへの塗布時にたれやハジキなどが生じるので好ましくなく、また高い特性の芳香族ポリイミドを得ることが難しくなることがある。
In the polyimide precursor aqueous solution composition of the present invention, the solid content concentration resulting from the polyimide precursor (substantially polyamic acid) is not limited, but is preferably 5 mass with respect to the total amount of the polyimide precursor and the solvent. % To 45% by mass, more preferably 7% to 40% by mass, and still more preferably 9% to 30% by mass. If the solid content concentration is lower than 5% by mass, the productivity may be remarkably deteriorated, and if it is higher than 45% by mass, the fluidity of the solution may be lost. The solution viscosity at 30 ° C. of the polyimide precursor aqueous solution composition of the present invention is not limited, but is preferably 1000 Pa · sec or less, more preferably 0.5 to 500 Pa · sec, still more preferably 1 to 300 Pa · sec, The handling is preferably 3 to 200 Pa · sec.
If the solution viscosity exceeds 1000 Pa · sec, the fluidity is lost, so that uniform application to metal or glass becomes difficult, and if it is lower than 0.5 Pa · sec, it may sag during application to metal or glass. Since cissing and the like occur, it is not preferable, and it may be difficult to obtain an aromatic polyimide having high characteristics.
本発明のポリイミド前駆体水溶液組成物は、通常は加熱処理によって水溶媒を除去するとともにイミド化(脱水閉環)することによって好適に芳香族ポリイミドを得ることができる。加熱処理条件は、特に限定されないが、概ね100℃以上、好ましくは120℃〜600℃、より好ましくは150℃〜500℃で、0.01時間〜30時間、好ましくは0.01〜10時間である。
本発明のポリイミド前駆体水溶液を用いて得られる芳香族ポリイミドの特性は、比較的低温(例えば150℃〜300℃、好ましくは200℃〜280℃)で加熱処理しただけで、通常の有機溶媒を用いたポリイミド前駆体(ポリアミック酸)溶液組成物に較べて遜色なく、好適には、例えば金属類などとの接着性が高いというような優れた特性を発揮することができる。
The polyimide precursor aqueous solution composition of the present invention can suitably obtain an aromatic polyimide by removing the water solvent by heat treatment and imidizing (dehydrating ring closure). The heat treatment conditions are not particularly limited, but are generally 100 ° C. or higher, preferably 120 ° C. to 600 ° C., more preferably 150 ° C. to 500 ° C., 0.01 hours to 30 hours, preferably 0.01 to 10 hours. is there.
The characteristic of the aromatic polyimide obtained using the polyimide precursor aqueous solution of the present invention is that a normal organic solvent is used only by heat treatment at a relatively low temperature (for example, 150 ° C. to 300 ° C., preferably 200 ° C. to 280 ° C.). Compared to the polyimide precursor (polyamic acid) solution composition used, it is possible to exhibit excellent characteristics such as high adhesiveness with, for example, metals.
以下、本発明を実施例及び比較例により更に具体的に説明するが、本発明は、これら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.
以下の例で用いた特性の測定方法を以下に示す。
<固形分濃度>
試料溶液(その質量をw1とする)を、熱風乾燥機中120℃で10分間、250℃で10分間、次いで350℃で30分間加熱処理して、加熱処理後の質量(その質量をw2とする)を測定する。固形分濃度[質量%]は、次式によって算出した。
固形分濃度[質量%]=(w2/w1)×100
A method for measuring the characteristics used in the following examples is shown below.
<Concentration of solid content>
The sample solution (whose mass is designated as w1) is heat-treated in a hot air dryer at 120 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then at 350 ° C. for 30 minutes. Measure). Solid content concentration [mass%] was computed by the following formula.
Solid content concentration [% by mass] = (w2 / w1) × 100
<対数粘度>
試料溶液を、固形分濃度に基づいて濃度が0.5g/dl(溶媒は水)になるように希釈した。この希釈液を、30℃にて、キャノンフェンスケNo.100を用いて流下時間(T1)を測定した。対数粘度は、ブランクの水の流下時間(T0)を用いて、次式から算出した。
対数粘度={ln(T1/T0)}/0.5
<Logarithmic viscosity>
The sample solution was diluted to a concentration of 0.5 g / dl (solvent is water) based on the solid content concentration. This diluted solution was added to Cannon Fenceke No. The flow-down time (T 1 ) was measured using 100. The logarithmic viscosity was calculated from the following equation using the flow time (T 0 ) of blank water.
Logarithmic viscosity = {ln (T 1 / T 0 )} / 0.5
<溶液粘度(回転粘度)>
トキメック社製E型粘度計を用いて30℃で測定した。
<Solution viscosity (rotational viscosity)>
It measured at 30 degreeC using the Tokimec E-type viscosity meter.
<ポリイミドフィルムサンプルの作成>
得られたポリイミド前駆体水溶液組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下25℃で30分間、脱泡及び予備乾燥した後で、常圧下、熱風乾燥器に入れて、80℃で30分間、120℃で30分間、200℃で10分間、次いで250℃で10分間加熱処理して、厚さが50μmのポリイミドフィルムを形成した。このポリイミドフィルムを用いて特性を評価した。
<Preparation of polyimide film sample>
The obtained polyimide precursor aqueous solution composition was coated on a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then heated under normal pressure under hot air. It put into the dryer and heat-processed at 80 degreeC for 30 minutes, 120 degreeC for 30 minutes, 200 degreeC for 10 minutes, and then 250 degreeC for 10 minutes, and formed the 50-micrometer-thick polyimide film. Properties were evaluated using this polyimide film.
<機械的特性(引張試験)>
引張り試験機(オリエンテック社製RTC−1225A)を用いて、ASTM D882に準拠して引張試験を行い、引張弾性率、引張破断伸び、引張破断強度を求めた。
<Mechanical properties (tensile test)>
Using a tensile tester (Orientec RTC-1225A), a tensile test was performed in accordance with ASTM D882 to determine the tensile modulus, tensile break elongation, and tensile break strength.
<ガラス転移温度測定>
TAインスツルメンツ(株)製 固体粘弾性アナライザー RSAIII(圧縮モード 動的測定、周波数62.8rad/sec(10Hz)、歪量はサンプル高さの3%に設定)を用い、雰囲気窒素気流中、−140℃から450℃まで温度ステップ3℃で、各温度到達後30秒後に測定を行ない次の温度に昇温して測定を繰り返す方法で、損失弾性率(E'')の極大点を求め、その温度をガラス転移点(Tg)として求めた。
<Glass transition temperature measurement>
TA Instruments Co., Ltd. solid viscoelasticity analyzer RSAIII (compression mode dynamic measurement, frequency 62.8 rad / sec (10 Hz), strain amount set to 3% of sample height), −140 Measure from 30 ° C to 450 ° C at a temperature step of 3 ° C, measure 30 seconds after reaching each temperature, raise the temperature to the next temperature and repeat the measurement to obtain the maximum point of loss elastic modulus (E ''), The temperature was determined as the glass transition point (Tg).
以下の例で使用した化合物の略号について説明する。
s−BPDA:3,3’,4,4’−ビフェニルテトラカルボン酸二無水物
ODPA:4,4’−オキシジフタル酸二無水物
PMDA:ピロメリット酸二無水物
a−BPDA:2,3’,3,4’−ビフェニルテトラカルボン酸二無水物
i−BPDA:2,2’,3,3’−ビフェニルテトラカルボン酸二無水物
DSDA:3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物
BTDA:3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物
PPD:p−フェニレンジアミン(25℃における水に対する溶解度:120g/L、以下同様)
ODA:4,4’−ジアミノジフェニルエーテル(0.19g/L)
MPD:m−フェニレンジアミン(77g/L)
2,4−TDA:2,4−ジアミノトルエン(62g/L)
HAB:3,3’−ジヒドロキシ−4,4’−ジアミノビフェニル(1.3g/L)
MBAA:ビス(4−アミノ−3−カルボキシフェニル)メタン(200g/L)
BAPP:2,2−ビス〔4−(4−アミノフェノキシ)フェニル〕プロパン(0.000019g/L)
TPE−R:1,3−ビス(4−アミノフェノキシ)ベンゼン(0.0018g/L)
1,2−DMZ:1,2−ジメチルイミダゾ−ル
2E4MZ:2−エチル−4−メチルイミダゾール
2MZ:2−メチルイミダゾ−ル
DBU:1,8−ジアザビシクロ[5,4,0]ウンデカ−7−エン
NMP:N−メチル−2−ピロリドン
The abbreviations of the compounds used in the following examples are described.
s-BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride ODPA: 4,4′-oxydiphthalic dianhydride PMDA: pyromellitic dianhydride a-BPDA: 2,3 ′ 3,4′-biphenyltetracarboxylic dianhydride i-BPDA: 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride DSDA: 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid Dianhydride BTDA: 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride PPD: p-phenylenediamine (solubility in water at 25 ° C .: 120 g / L, the same applies hereinafter)
ODA: 4,4′-diaminodiphenyl ether (0.19 g / L)
MPD: m-phenylenediamine (77 g / L)
2,4-TDA: 2,4-diaminotoluene (62 g / L)
HAB: 3,3′-dihydroxy-4,4′-diaminobiphenyl (1.3 g / L)
MBAA: bis (4-amino-3-carboxyphenyl) methane (200 g / L)
BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane (0.000019 g / L)
TPE-R: 1,3-bis (4-aminophenoxy) benzene (0.0018 g / L)
1,2-DMZ: 1,2-dimethylimidazole 2E4MZ: 2-ethyl-4-methylimidazole 2MZ: 2-methylimidazole DBU: 1,8-diazabicyclo [5,4,0] undec-7- En NMP: N-methyl-2-pyrrolidone
〔実施例1〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの13.44g(0.124モル)と、1,2−DMZの29.87g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの36.56g(0.124モル)を加え、25℃で12時間撹拌して、固形分濃度9.0質量%、溶液粘度16.3Pa・s、対数粘度0.95のポリイミド前駆体水溶液を得た。
得られたポリイミド前駆体水溶液組成物及びポリイミドフィルムについて、その特性を表1に示した。
[Example 1]
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 13.44 g (0.124 mol) of PPD and 1,2-DMZ were added thereto. Of 29.87 g (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 36.56 g (0.124 mol) of s-BPDA was added and stirred at 25 ° C. for 12 hours. The solid content concentration was 9.0% by mass, the solution viscosity was 16.3 Pa · s, and the logarithmic viscosity was 0.95. An aqueous polyimide precursor solution was obtained.
The properties of the obtained polyimide precursor aqueous solution composition and polyimide film are shown in Table 1.
〔実施例2〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの13.44g(0.124モル)と、1,2−DMZの29.87g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの36.56g(0.124モル)を加え、50℃で8時間撹拌して、固形分濃度9.1質量%、溶液粘度35.5Pa・s、対数粘度1.25のポリイミド前駆体水溶液を得た。
得られたポリイミド前駆体水溶液組成物及びポリイミドフィルムについて、その特性を表1に示した。
[Example 2]
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 13.44 g (0.124 mol) of PPD and 1,2-DMZ were added thereto. Of 29.87 g (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to this solution, and the mixture was stirred at 50 ° C. for 8 hours. The solid content concentration was 9.1% by mass, the solution viscosity was 35.5 Pa · s, and the logarithmic viscosity was 1.25. An aqueous polyimide precursor solution was obtained.
The properties of the obtained polyimide precursor aqueous solution composition and polyimide film are shown in Table 1.
〔実施例3〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの13.44g(0.124モル)と、1,2−DMZの29.87g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの36.56g(0.124モル)を加え、70℃で4時間撹拌して、固形分濃度9.1質量%、溶液粘度63.0Pa・s、対数粘度1.86のポリイミド前駆体水溶液を得た。
得られたポリイミド前駆体水溶液組成物及びポリイミドフィルムについて、その特性を表1に示した。
Example 3
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 13.44 g (0.124 mol) of PPD and 1,2-DMZ were added thereto. Of 29.87 g (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 36.56 g (0.124 mol) of s-BPDA was added and stirred at 70 ° C. for 4 hours. The solid content concentration was 9.1% by mass, the solution viscosity was 63.0 Pa · s, and the logarithmic viscosity was 1.86. An aqueous polyimide precursor solution was obtained.
The properties of the obtained polyimide precursor aqueous solution composition and polyimide film are shown in Table 1.
〔実施例4〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの13.44g(0.124モル)と、2E4MZの34.23g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの36.56g(0.124モル)を加え、70℃で4時間撹拌して、固形分濃度9.6質量%、溶液粘度10.3Pa・s、対数粘度0.64のポリイミド前駆体水溶液を得た。
得られたポリイミド前駆体水溶液組成物及びポリイミドフィルムについて、その特性を表1に示した。
Example 4
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 13.44 g (0.124 mol) of PPD and 34.23 g of 2E4MZ were added thereto. (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 36.56 g (0.124 mol) of s-BPDA was added and stirred at 70 ° C. for 4 hours to obtain a solid content concentration of 9.6% by mass, a solution viscosity of 10.3 Pa · s, and a logarithmic viscosity of 0.64. An aqueous polyimide precursor solution was obtained.
The properties of the obtained polyimide precursor aqueous solution composition and polyimide film are shown in Table 1.
〔実施例5〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにODAの20.25g(0.101モル)と、1,2−DMZの24.31g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの29.75g(0.101モル)を加え、70℃で4時間撹拌して、固形分濃度8.7質量%、溶液粘度32.0Pa・s、対数粘度0.42のポリイミド前駆体水溶液を得た。
得られたポリイミド前駆体水溶液組成物及びポリイミドフィルムについて、その特性を表1に示した。
Example 5
450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 20.25 g (0.101 mol) of ODA and 1,2-DMZ were added thereto. Of 24.31 g (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 29.75 g (0.101 mol) of s-BPDA was added and stirred at 70 ° C. for 4 hours. The solid content concentration was 8.7% by mass, the solution viscosity was 32.0 Pa · s, and the logarithmic viscosity was 0.42. An aqueous polyimide precursor solution was obtained.
The properties of the obtained polyimide precursor aqueous solution composition and polyimide film are shown in Table 1.
〔実施例6〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにMPDの13.44g(0.124モル)と、1,2−DMZの29.87g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの36.56g(0.124モル)を加え、70℃で4時間撹拌して、固形分濃度8.9質量%、溶液粘度13.5Pa・s、対数粘度0.75のポリイミド前駆体水溶液を得た。
得られたポリイミド前駆体水溶液組成物及びポリイミドフィルムについて、その特性を表1に示した。
Example 6
450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 13.44 g (0.124 mol) of MPD and 1,2-DMZ were added thereto. Of 29.87 g (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 36.56 g (0.124 mol) of s-BPDA was added and stirred at 70 ° C. for 4 hours. The solid content concentration was 8.9% by mass, the solution viscosity was 13.5 Pa · s, and the logarithmic viscosity was 0.75. An aqueous polyimide precursor solution was obtained.
The properties of the obtained polyimide precursor aqueous solution composition and polyimide film are shown in Table 1.
〔実施例7〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これに2,4−TDAの14.67g(0.120モル)と、1,2−DMZの28.86g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの35.33g(0.120モル)を加え、70℃で4時間撹拌して、固形分濃度8.8質量%、溶液粘度1.0Pa・s、対数粘度0.21のポリイミド前駆体水溶液を得た。
得られたポリイミド前駆体水溶液組成物について、その特性を表1に示した。
Example 7
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, and 14.67 g (0.120 mol) of 2,4-TDA was added thereto. , 2-DMZ (28.86 g (1.25 equivalents relative to carboxyl group)) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 35.33 g (0.120 mol) of s-BPDA was added and stirred at 70 ° C. for 4 hours. The solid content concentration was 8.8% by mass, the solution viscosity was 1.0 Pa · s, and the logarithmic viscosity was 0.21. An aqueous polyimide precursor solution was obtained.
The characteristics of the obtained polyimide precursor aqueous solution composition are shown in Table 1.
〔実施例8〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにHABの21.18g(0.098モル)と、1,2−DMZの47.09g(カルボキシル基に対して2.50倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの28.82g(0.098モル)を加え、70℃で4時間撹拌して、固形分濃度9.4質量%、溶液粘度1.5Pa・s、対数粘度0.50のポリイミド前駆体水溶液を得た。
得られたポリイミド前駆体水溶液組成物について、その特性を表1に示した。
Example 8
450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet pipe, and 21.18 g (0.098 mol) of HAB was added to this and 1,2-DMZ. Was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 28.82 g (0.098 mol) of s-BPDA was added and stirred at 70 ° C. for 4 hours. The solid content concentration was 9.4% by mass, the solution viscosity was 1.5 Pa · s, and the logarithmic viscosity was 0.50. An aqueous polyimide precursor solution was obtained.
The characteristics of the obtained polyimide precursor aqueous solution composition are shown in Table 1.
〔実施例9〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにMBAAの24.66g(0.086モル)と、1,2−DMZの41.41g(カルボキシル基に対して2.50倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの25.34g(0.086モル)を加え、70℃で4時間撹拌して、固形分濃度9.5質量%、溶液粘度2.0Pa・s、対数粘度0.75のポリイミド前駆体水溶液を得た。
得られたポリイミド前駆体水溶液組成物について、その特性を表1に示した。
Example 9
450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 24.66 g (0.086 mol) of MBAA and 1,2-DMZ were added thereto. Of 41.41 g (2.50 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 25.34 g (0.086 mol) of s-BPDA was added and stirred at 70 ° C. for 4 hours. The solid content concentration was 9.5% by mass, the solution viscosity was 2.0 Pa · s, and the logarithmic viscosity was 0.75. An aqueous polyimide precursor solution was obtained.
The characteristics of the obtained polyimide precursor aqueous solution composition are shown in Table 1.
〔実施例10〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの12.93g(0.120モル)と、1,2−DMZの28.73g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にODPAの37.07g(0.120モル)を加え、70℃で4時間撹拌して、固形分濃度8.9質量%、溶液粘度2.0Pa・s、対数粘度0.58のポリイミド前駆体水溶液を得た。
得られたポリイミド前駆体水溶液組成物について、その特性を表1に示した。
Example 10
450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 12.93 g (0.120 mol) of PPD and 1,2-DMZ were added thereto. Of 28.73 g (1.25 equivalents relative to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 37.07 g (0.120 mol) of ODPA was added and stirred at 70 ° C. for 4 hours to obtain a polyimide having a solid content concentration of 8.9% by mass, a solution viscosity of 2.0 Pa · s, and a logarithmic viscosity of 0.58. A precursor aqueous solution was obtained.
The characteristics of the obtained polyimide precursor aqueous solution composition are shown in Table 1.
〔実施例11〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの13.44g(0.124モル)と、1,2−DMZの29.87g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にi−BPDAの36.56g(0.124モル)を加え、70℃で4時間撹拌して、固形分濃度8.6質量%、溶液粘度0.8Pa・s、対数粘度0.22のポリイミド前駆体水溶液を得た。
得られたポリイミド前駆体水溶液組成物について、その特性を表1に示した。
Example 11
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 13.44 g (0.124 mol) of PPD and 1,2-DMZ were added thereto. Of 29.87 g (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. 36.56 g (0.124 mol) of i-BPDA was added to this solution, and the mixture was stirred at 70 ° C. for 4 hours. The solid content concentration was 8.6% by mass, the solution viscosity was 0.8 Pa · s, and the logarithmic viscosity was 0.22. An aqueous polyimide precursor solution was obtained.
The characteristics of the obtained polyimide precursor aqueous solution composition are shown in Table 1.
〔実施例12〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの11.59g(0.107モル)と、1,2−DMZの25.77g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にDSDAの38.41g(0.107モル)を加え、70℃で4時間撹拌して、固形分濃度8.7質量%、溶液粘度1.2Pa・s、対数粘度0.35のポリイミド前駆体水溶液を得た。
得られたポリイミド前駆体水溶液組成物について、その特性を表1に示した。
Example 12
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 11.59 g (0.107 mol) of PPD and 1,2-DMZ were added thereto. Of 25.77 g (1.25 equivalents relative to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 38.41 g (0.107 mol) of DSDA was added and stirred at 70 ° C. for 4 hours to obtain a polyimide having a solid content concentration of 8.7% by mass, a solution viscosity of 1.2 Pa · s, and a logarithmic viscosity of 0.35. A precursor aqueous solution was obtained.
The characteristics of the obtained polyimide precursor aqueous solution composition are shown in Table 1.
〔実施例13〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの12.57g(0.116モル)と、1,2−DMZの27.93g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にBTDAの37.43g(0.116モル)を加え、70℃で4時間撹拌して、固形分濃度8.8質量%、溶液粘度73.8Pa・s、対数粘度0.45の水溶性ポリイミド前駆体溶液を得た。
得られたポリイミド前駆体水溶液組成物について、その特性を表1に示した。
Example 13
450 g of water was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 12.57 g (0.116 mol) of PPD and 1,2-DMZ were added thereto. Of 27.93 g (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution was added 37.43 g (0.116 mol) of BTDA, and the mixture was stirred at 70 ° C. for 4 hours. A conductive polyimide precursor solution was obtained.
The characteristics of the obtained polyimide precursor aqueous solution composition are shown in Table 1.
〔比較例1〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの13.44g(0.124モル)と、1,2−DMZの17.92g(カルボキシル基に対して0.75倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの36.56g(0.124モル)を加え、70℃で4時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶性を得ることができなかった。
結果を表2に示した。
[Comparative Example 1]
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 13.44 g (0.124 mol) of PPD and 1,2-DMZ were added thereto. Of 17.92 g (0.75 equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to this solution and stirred for 4 hours at 70 ° C., but it did not dissolve uniformly, and the polyimide precursor water solubility could not be obtained.
The results are shown in Table 2.
〔比較例2〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの13.44g(0.124モル)と、2MZの25.50g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの36.56g(0.124モル)を加え、70℃で4時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶性を得ることができなかった。
結果を表2に示した。
[Comparative Example 2]
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, and 13.44 g (0.124 mol) of PPD and 25.50 g of 2MZ were added thereto. (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to this solution and stirred for 4 hours at 70 ° C., but it did not dissolve uniformly, and the polyimide precursor water solubility could not be obtained.
The results are shown in Table 2.
〔比較例3〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの13.44g(0.124モル)と、DBUの47.29g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの36.56g(0.124モル)を加え、70℃で4時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶性を得ることができなかった。
結果を表2に示した。
[Comparative Example 3]
450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 13.44 g (0.124 mol) of PPD and 47.29 g of DBU were added thereto. (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to this solution and stirred for 4 hours at 70 ° C., but it did not dissolve uniformly, and the polyimide precursor water solubility could not be obtained.
The results are shown in Table 2.
〔比較例4〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにBAPPの29.13g(0.071モル)と、1,2−DMZの17.05g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs−BPDAの20.87g(0.071モル)を加え、70℃で4時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶性を得ることができなかった。
結果を表2に示した。
[Comparative Example 4]
450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 29.13 g (0.071 mol) of BAPP and 1,2-DMZ were added thereto. Of 17.05 g (1.25 equivalents relative to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. 20.87 g (0.071 mol) of s-BPDA was added to this solution and stirred for 4 hours at 70 ° C., but it did not dissolve uniformly, and polyimide precursor water solubility could not be obtained.
The results are shown in Table 2.
〔比較例5〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにTPE−Rの24.92g(0.085モル)と、1,2−DMZの20.49g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にa−BPDAの25.08g(0.085モル)を加え、70℃で4時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶性を得ることができなかった。
結果を表2に示した。
[Comparative Example 5]
450 g of water was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 24.92 g (0.085 mol) of TPE-R was added to the reaction vessel. -20.49 g of DMZ (1.25 equivalents relative to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. 25.08 g (0.085 mol) of a-BPDA was added to this solution and stirred for 4 hours at 70 ° C., but it did not dissolve uniformly, and the polyimide precursor water solubility could not be obtained.
The results are shown in Table 2.
〔比較例6〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにODAの23.93g(0.120モル)と、1,2−DMZの28.73g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にPMDAの26.07g(0.120モル)を加え、70℃で4時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶性を得ることができなかった。
結果を表2に示した。
[Comparative Example 6]
450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 23.93 g (0.120 mol) of ODA and 1,2-DMZ were added thereto. Of 28.73 g (1.25 equivalents relative to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 26.07 g (0.120 mol) of PMDA was added and stirred at 70 ° C. for 4 hours. However, the solution was not uniformly dissolved, and water solubility of the polyimide precursor could not be obtained.
The results are shown in Table 2.
〔比較例7〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにTPE−Rの24.26g(0.083モル)と、2E4MZの22.86g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にODPAの25.74g(0.083モル)を加え、70℃で4時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶性を得ることができなかった。
結果を表2に示した。
[Comparative Example 7]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 450 g of water was added as a solvent, and 24.26 g (0.083 mol) of TPE-R and 2E4MZ 22 .86 g (1.25 equivalents relative to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 25.74 g (0.083 mol) of ODPA was added and stirred at 70 ° C. for 4 hours. However, the solution was not uniformly dissolved, and water solubility of the polyimide precursor could not be obtained.
The results are shown in Table 2.
〔比較例8〕
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの8.94g(0.083モル)と、ODAの11.03g(0.055モル)と、1,2−DMZの33.10g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にPMDAの30.03g(0.138モル)を加え、70℃で4時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶性を得ることができなかった。
結果を表2に示した。
[Comparative Example 8]
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet / outlet tube, and 8.94 g (0.083 mol) of PPD and 11.03 g of ODA were added thereto. (0.055 mol) and 33.10 g of 1,2-DMZ (1.25 equivalents relative to the carboxyl group) were added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 30.03 g (0.138 mol) of PMDA was added and stirred at 70 ° C. for 4 hours. However, the solution was not uniformly dissolved, and water solubility of the polyimide precursor could not be obtained.
The results are shown in Table 2.
〔参考例1〕
TPE−Rの29.23g(0.1モル)とDMAcの234.60gとを、攪拌機、還流冷却器(水分分離器付き)、温度計、窒素導入管を備えた1000mLのガラス製反応容器に、25℃において添加し、その混合液に窒素ガス流通下攪拌しながら、a−BPDAの29.42g(0.1モル)を添加し、2時間反応させポリイミド前駆体溶液を得た。そして、この溶液をDMAcの293.25gで希釈し30℃において1.3ポイズとした。この溶液にDMZの5.87g(0.06モル)を添加し、この溶液を、ホモジナイザーを備えたアセトン(6.5L)に徐々に加えポリイミド前駆体粉末を析出させた。この懸濁液を濾過し、アセトン洗浄し、40℃で10時間真空乾燥して、60.52gのポリイミド前駆体の粉末を得た。
[Reference Example 1]
29.23 g (0.1 mol) of TPE-R and 234.60 g of DMAc were placed in a 1000 mL glass reaction vessel equipped with a stirrer, a reflux condenser (with a water separator), a thermometer, and a nitrogen introduction tube. The mixture was added at 25 ° C., and 29.42 g (0.1 mol) of a-BPDA was added to the mixed solution while stirring under a nitrogen gas flow, and reacted for 2 hours to obtain a polyimide precursor solution. This solution was then diluted with 293.25 g of DMAc to 1.3 poise at 30 ° C. To this solution, 5.87 g (0.06 mol) of DMZ was added, and this solution was gradually added to acetone (6.5 L) equipped with a homogenizer to precipitate a polyimide precursor powder. This suspension was filtered, washed with acetone, and vacuum-dried at 40 ° C. for 10 hours to obtain 60.52 g of polyimide precursor powder.
このポリイミド前駆体粉末3gに対して、水の26.10gおよび1,2−DMZの0.9g(0.0094モル)を加え、60℃で攪拌しながら2時間で溶解し均一なポリイミド前駆体水溶液を得た。この水溶液をGC−MSを用いて発生ガスの分析を行ったところ、6.28%のDMAcが検出され、有機溶媒の残存が確認された。 To 3 g of this polyimide precursor powder, 26.10 g of water and 0.9 g (0.0094 mol) of 1,2-DMZ were added and dissolved in 2 hours while stirring at 60 ° C. to obtain a uniform polyimide precursor An aqueous solution was obtained. When this aqueous solution was analyzed for generated gas using GC-MS, 6.28% of DMAc was detected, and the remaining organic solvent was confirmed.
本発明によって、水溶媒を使用することによって環境適応性が良好であって、しかも、それを用いて得られる芳香族ポリイミドは高い結晶性を有するために耐熱性、機械的強度、電気特性、耐溶剤性などの特性が優れる、好ましくは高分子量であって水溶媒が水以外の有機溶媒を含まない、ポリイミド前駆体水溶液組成物を提供することができる。 According to the present invention, the environmental adaptability is good by using an aqueous solvent, and the aromatic polyimide obtained by using the water solvent has high crystallinity, so that it has heat resistance, mechanical strength, electrical properties, resistance to resistance. It is possible to provide a polyimide precursor aqueous solution composition having excellent solvent properties and the like, preferably having a high molecular weight and containing no organic solvent other than water.
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