JP5899940B2 - Polyimide precursor aqueous solution composition and method for producing polyimide precursor aqueous solution composition - Google Patents
Polyimide precursor aqueous solution composition and method for producing polyimide precursor aqueous solution composition Download PDFInfo
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- JP5899940B2 JP5899940B2 JP2012005689A JP2012005689A JP5899940B2 JP 5899940 B2 JP5899940 B2 JP 5899940B2 JP 2012005689 A JP2012005689 A JP 2012005689A JP 2012005689 A JP2012005689 A JP 2012005689A JP 5899940 B2 JP5899940 B2 JP 5899940B2
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- Prior art keywords
- polyimide precursor
- aqueous solution
- solution composition
- water
- group
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- 229920001721 polyimide Polymers 0.000 title claims description 224
- 239000004642 Polyimide Substances 0.000 title claims description 222
- 239000002243 precursor Substances 0.000 title claims description 192
- 239000000203 mixture Substances 0.000 title claims description 160
- 239000007864 aqueous solution Substances 0.000 title claims description 141
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 108
- 239000007787 solid Substances 0.000 claims description 64
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 58
- 229920005575 poly(amic acid) Polymers 0.000 claims description 49
- -1 nitrogen-containing organic compounds Chemical class 0.000 claims description 42
- 150000007514 bases Chemical class 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000003960 organic solvent Substances 0.000 claims description 37
- 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 35
- 125000003277 amino group Chemical group 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 27
- 150000004985 diamines Chemical class 0.000 claims description 26
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 25
- 239000003125 aqueous solvent Substances 0.000 claims description 19
- 150000002460 imidazoles Chemical class 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical class NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims description 9
- 229910052751 metal Chemical class 0.000 claims description 8
- 239000002184 metal Chemical class 0.000 claims description 8
- 125000001302 tertiary amino group Chemical group 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000003235 pyrrolidines Chemical class 0.000 claims description 5
- 229940066769 systemic antihistamines substituted alkylamines Drugs 0.000 claims description 5
- 150000002357 guanidines Chemical class 0.000 claims description 4
- 150000004885 piperazines Chemical class 0.000 claims description 4
- 150000003053 piperidines Chemical class 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- SAHAMZVWSQYKHB-UHFFFAOYSA-N 4-(2,4-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 SAHAMZVWSQYKHB-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 85
- 239000011248 coating agent Substances 0.000 description 69
- 238000000576 coating method Methods 0.000 description 69
- 239000002904 solvent Substances 0.000 description 53
- 238000011156 evaluation Methods 0.000 description 48
- 125000001153 fluoro group Chemical group F* 0.000 description 33
- 239000000049 pigment Substances 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 150000004984 aromatic diamines Chemical class 0.000 description 30
- 239000003973 paint Substances 0.000 description 30
- 239000000126 substance Substances 0.000 description 30
- 239000011521 glass Substances 0.000 description 29
- 229910001873 dinitrogen Inorganic materials 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 28
- 239000000758 substrate Substances 0.000 description 27
- 125000000217 alkyl group Chemical group 0.000 description 25
- 238000012360 testing method Methods 0.000 description 23
- 125000003118 aryl group Chemical group 0.000 description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 239000011889 copper foil Substances 0.000 description 19
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 13
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000945 filler Substances 0.000 description 11
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 description 9
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration 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
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 235000019241 carbon black Nutrition 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 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 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000004103 aminoalkyl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000011863 silicon-based powder Substances 0.000 description 3
- 229910021647 smectite Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- GDXMMBDEMOUTNS-UHFFFAOYSA-N 1-(diethylamino)propan-2-one Chemical compound CCN(CC)CC(C)=O GDXMMBDEMOUTNS-UHFFFAOYSA-N 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- QLEIDMAURCRVCX-UHFFFAOYSA-N 1-propylpiperazine Chemical compound CCCN1CCNCC1 QLEIDMAURCRVCX-UHFFFAOYSA-N 0.000 description 2
- VTDIWMPYBAVEDY-UHFFFAOYSA-N 1-propylpiperidine Chemical compound CCCN1CCCCC1 VTDIWMPYBAVEDY-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-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
- WKCYFSZDBICRKL-UHFFFAOYSA-N 3-(diethylamino)propan-1-ol Chemical compound CCN(CC)CCCO WKCYFSZDBICRKL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000006358 imidation reaction Methods 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
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- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- PZZHMLOHNYWKIK-UHFFFAOYSA-N eddha Chemical compound C=1C=CC=C(O)C=1C(C(=O)O)NCCNC(C(O)=O)C1=CC=CC=C1O PZZHMLOHNYWKIK-UHFFFAOYSA-N 0.000 description 1
- ZZGUZQXLSHSYMH-UHFFFAOYSA-N ethane-1,2-diamine;propanoic acid Chemical compound NCCN.CCC(O)=O.CCC(O)=O ZZGUZQXLSHSYMH-UHFFFAOYSA-N 0.000 description 1
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 1
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- DXTIKTAIYCJTII-UHFFFAOYSA-N guanidine acetate Chemical compound CC([O-])=O.NC([NH3+])=N DXTIKTAIYCJTII-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- JVKAWJASTRPFQY-UHFFFAOYSA-N n-(2-aminoethyl)hydroxylamine Chemical compound NCCNO JVKAWJASTRPFQY-UHFFFAOYSA-N 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (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、及びポリイミド前駆体水溶液組成物の容易な製造方法に関する。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。本発明の製造方法は、水以外の溶媒を必要としないので、従来のものよりも有機溶媒の含有量が少ないポリイミド前駆体水溶液組成物、さらには、より環境適応性が高い有機溶媒を含まない水溶媒からなるポリイミド前駆体水溶液組成物を得ることができる。そして、このポリイミド前駆体水溶液組成物を用いて好適にポリイミドを得ることができる。さらに、本発明は、ポリイミド前駆体を含有する水溶液系の塗料にも関する。 The present invention relates to a polyimide precursor aqueous solution composition and a method for easily producing a polyimide precursor aqueous solution composition. This polyimide precursor aqueous solution composition is preferable because it has higher environmental adaptability than a polyimide precursor solution composition using an organic solvent. Since the production method of the present invention does not require a solvent other than water, the polyimide precursor aqueous solution composition having a lower organic solvent content than the conventional one, and further does not include an organic solvent having higher environmental adaptability. A polyimide precursor aqueous solution composition comprising an aqueous solvent can be obtained. And a polyimide can be suitably obtained using this polyimide precursor aqueous solution composition. Furthermore, the present invention also relates to an aqueous coating material containing a polyimide precursor.
テトラカルボン酸二無水物とジアミンから得られるポリイミドは、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、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）させることでポリイミドを得ている。このポリイミドを製造するためのポリアミック酸溶液組成物は有機溶媒を含み、高温での加熱処理が必要なことから、環境面で必ずしも好適ではなく、場合によっては用途が限定されることもあった。 Polyimides obtained from tetracarboxylic dianhydrides and diamines are widely used in the electrical and electronic industries because of their excellent properties such as heat resistance, mechanical strength, electrical properties, and solvent resistance. However, since polyimide has poor solubility in organic solvents, a solution composition in which a polyamic acid, which is a polyimide precursor, is dissolved in an organic solvent is usually applied onto a substrate surface, and then heated at a high temperature for dehydration. Polyimide is obtained by ring closure (imidization). Since the polyamic acid solution composition for producing this polyimide contains an organic solvent and requires heat treatment at a high temperature, it is not necessarily suitable in terms of the environment, and the use may be limited in some cases.
水溶性ポリイミド前駆体に関しては、例えば、特許文献１には、有機溶媒中でテトラカルボン酸二無水物とジアミンを重合させてポリアミド酸（ポリアミック酸）を得、これを必要に応じて加水分解した後、このワニスを水中に投入してポリアミド酸を粉砕し、ポリアミド酸に含まれる反応溶媒を抽出、除去し、これを乾燥してポリアミド酸を得、次いで、このポリアミド酸を水中で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反応させて水溶性ポリアミド酸塩にして、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（ポリイミド前駆体組成物）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。製造方法も極めて煩雑である。また、有機溶媒中で調製されたポリイミド前駆体では、塩基性の有機溶媒とポリアミド酸が塩を形成するので、水洗や真空乾燥しても、有機溶媒を完全に除去することは困難である。 With respect to the water-soluble polyimide precursor, for example, in Patent Document 1, polycarboxylic acid (polyamic acid) is obtained by polymerizing tetracarboxylic dianhydride and diamine in an organic solvent, and this is hydrolyzed as necessary. Thereafter, the varnish is poured into water to pulverize the polyamic acid, and the reaction solvent contained in the polyamic acid is extracted and removed, and dried to obtain a polyamic acid. It has been proposed to obtain a polyamic acid aqueous solution composition by reacting with a specific amine compound such as aminodiethanol to form a water-soluble polyamic acid salt. However, this polyamic acid salt aqueous solution composition (polyimide precursor composition) is difficult to have a high molecular weight, and there is room for improvement in the properties of the resulting polyimide. The manufacturing method is also very complicated. Moreover, in the polyimide precursor prepared in the organic solvent, since the basic organic solvent and the polyamic acid form a salt, it is difficult to completely remove the organic solvent even by washing with water or vacuum drying.
特許文献２には、有機溶媒中でテトラカルボン酸成分と芳香族ジアミン成分とを反応させて得られたポリアミック酸（ポリイミド前駆体）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−ルとを反応させた後、反応混合物から分離取得してなる水溶性ポリイミド前駆体が提案されている。しかし、特許文献２の実施例で得ら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のみであった。特許文献２で得られた水溶性ポリイミド前駆体は、得られるポリイミドが非結晶性で熱融着性を有しており、有機あるいは無機繊維製の織物あるいは不織布の結合剤として好適に用いられるものであるが、用途によってはポリイミドの特性に改良の余地があった。さらに、ここでは、ポリイミド前駆体の水溶液組成物は、水溶性ポリイミド前駆体を有機溶媒中で調製後、一旦分離し、この分離した水溶性ポリイミド前駆体を水溶媒に溶解する方法によって得られており、極めて複雑な操作が必要であった。しかも、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り、水に対する溶解性がなくなる）ために、得られるポリイミド前駆体水溶液組成物は有機溶媒を含むことになる。 In Patent Document 2, polyamic acid (polyimide precursor) obtained by reacting a tetracarboxylic acid component and an aromatic diamine component in an organic solvent, 1,2-dimethylimidazole and / or 1-methyl- There has been proposed a water-soluble polyimide precursor obtained by reacting 2-ethylimidazole and then separating and obtaining from the reaction mixture. However, the water-soluble polyimide precursor obtained in the example of Patent Document 2 was only an amorphous polyimide obtained by using it. In the water-soluble polyimide precursor obtained in Patent Document 2, the polyimide obtained is non-crystalline and heat-fusible, and is suitably used as a binder for woven or non-woven fabrics made of organic or inorganic fibers. However, there is room for improvement in the characteristics of polyimide depending on the application. Furthermore, here, the aqueous solution composition of the polyimide precursor is obtained by a method in which the water-soluble polyimide precursor is prepared in an organic solvent, and then once separated, and the separated water-soluble polyimide precursor is dissolved in an aqueous solvent. Therefore, an extremely complicated operation was required. Moreover, since the organic solvent cannot be completely removed from the water-soluble polyimide precursor prepared in the organic solvent (imidation occurs when heat treatment is attempted to completely remove the polyimide, resulting in loss of water solubility). The precursor aqueous solution composition will contain an organic solvent.
特許文献３の段落００２５には、水とトリエチルアミンからなる溶媒に３，３’，４，４’−ベンゾフェノンテトラカルボン酸を懸濁させ、これにｍ−キシレンジアミンを添加して反応させ、均一溶液のポリイミド前駆体水溶液組成物を得たと記載されている。しかし、濃度２０重量％にて、２０℃溶液粘度が０．３ポイズと低く、実際には重合はほとんど進んでおらず、重合体と言えるようなポリアミック酸は得られていない。実際、本発明者の実験でも重合度は上がらず、モノマーの塩が形成されているだけあると考えられる。 In paragraph 0025 of Patent Document 3, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid is suspended in a solvent composed of water and triethylamine, and m-xylenediamine is added thereto to cause a reaction. The polyimide precursor aqueous solution composition was obtained. However, at a concentration of 20% by weight, the 20 ° C. solution viscosity is as low as 0.3 poise. In fact, the polymerization has hardly progressed, and a polyamic acid that can be said to be a polymer has not been obtained. In fact, it is considered that the degree of polymerization does not increase in the experiment of the present inventor, and only a monomer salt is formed.
本発明の１態様の目的は、水溶媒を使用する環境適応性が良好なポリイミド前駆体（即ちポリアミック酸）水溶液組成物を、工業的に簡便な方法で製造する方法、およびそのような方法で製造される環境適応性が良好なポリイミド前駆体水溶液組成物を提供することである。 An object of one embodiment of the present invention is to provide an industrially simple method for producing a polyimide precursor (ie, polyamic acid) aqueous solution composition having good environmental adaptability using an aqueous solvent, and such a method. It is an object to provide a polyimide precursor aqueous solution composition having good environmental adaptability.
また、本発明の異なる１態様の目的は、ポリイミド前駆体（ポリアミック酸）を含有する水溶性塗料を提供することである。 Another object of the present invention is to provide a water-soluble paint containing a polyimide precursor (polyamic acid).
本発明は、以下の事項に関する。 The present invention relates to the following matters.
１． 水を反応溶媒として、ｐＫａが７．５以上である塩基性化合物（イミダゾール類を除く）の存在下に、テトラカルボン酸二無水物と２５℃の水に対する溶解度が０．１ｇ／Ｌ以上であるジアミンとを反応させて、ポリイミド前駆体の水溶液組成物を製造することを特徴とするポリイミド前駆体水溶液組成物の製造方法。 1. In water in the presence of a basic compound (excluding imidazoles) having a pKa of 7.5 or more, the solubility in tetracarboxylic dianhydride and water at 25 ° C. is 0.1 g / L or more using water as a reaction solvent. The manufacturing method of the polyimide precursor aqueous solution composition which makes diamine react and manufactures the aqueous solution composition of a polyimide precursor.
２． 前記塩基性化合物の使用量が、テトラカルボン酸二無水物に対して、１．６倍モル以上であることを特徴とする上記１記載の製造方法。 2. 2. The production method according to 1 above, wherein the amount of the basic compound used is 1.6 times mol or more with respect to tetracarboxylic dianhydride.
３． 前記塩基性化合物が、アンモニア、含窒素有機化合物および金属塩からなる群より選ばれることを特徴とする上記１または２に記載の製造方法。 3. 3. The production method according to 1 or 2 above, wherein the basic compound is selected from the group consisting of ammonia, a nitrogen-containing organic compound and a metal salt.
４． 前記塩基性化合物が、１〜３級アミノ基を有する化合物から選ばれることを特徴とする上記１または２に記載の製造方法。 4). 3. The production method according to 1 or 2 above, wherein the basic compound is selected from compounds having a primary to tertiary amino group.
５． 前記塩基性化合物が、ピペラジン類、グアニジンおよびグアニジン塩類、アルキルアミン類、アミノ基含有アルコール類、カルボキシル置換アルキルアミン類、ピペリジン類およびピロリジン類からなる群より選ばれることを特徴とする上記１または２に記載の製造方法。 5. 1 or 2 above, wherein the basic compound is selected from the group consisting of piperazines, guanidine and guanidine salts, alkylamines, amino group-containing alcohols, carboxyl-substituted alkylamines, piperidines and pyrrolidines. The manufacturing method as described in.
６． 前記塩基性化合物が、アルカリ金属と弱酸との塩であることを特徴とする上記１または２に記載の製造方法。 6). 3. The production method according to 1 or 2 above, wherein the basic compound is a salt of an alkali metal and a weak acid.
７． 得られるポリイミド前駆体水溶液組成物の対数粘度が０．１以上であることを特徴とする上記１〜６のいずれか１項に記載の製造方法。 7). The logarithmic viscosity of the polyimide precursor aqueous solution composition to be obtained is 0.1 or more.
８． 水溶媒が、水以外の有機溶媒を含まないことを特徴とする上記１〜７のいずれか１項に記載の製造方法。 8). 8. The production method according to any one of 1 to 7 above, wherein the aqueous solvent does not contain an organic solvent other than water.
９． 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カルボキシル基に対して１．６倍モル以上の、ｐＫａが７．５以上である塩基性化合物（イミダゾール類を除く）と共に、有機溶媒の含有量が５質量％未満である水溶媒中に均一に溶解してなるポリイミド前駆体水溶液組成物。 9. A polyamic acid composed of a repeating unit represented by the following chemical formula (1) is a basic compound (excluding imidazoles) having a pKa of 7.5 or more with respect to the carboxyl group of the polyamic acid and having a pKa of 7.5 or more. ) And a polyimide precursor aqueous solution composition which is uniformly dissolved in an aqueous solvent having an organic solvent content of less than 5% by mass.
１０． 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カルボキシル基に対して１．６倍モル以上の、ｐＫａが７．５以上である塩基性化合物（イミダゾール類、２−メチルアミノジエタノール、ジエチルアミノ−アセトン、Ｎ−エチルアミノジエタノール、Ｎ−メチルアミノエタノール、２，２−アミノジエタノール、３−ジエチルアミノ−１−プロパノール、アミノ−シクロヘキサン、トリエチルアミンおよびジエタノールアミンを除く）と共に、水溶媒中に均一に溶解してなるポリイミド前駆体水溶液組成物。
10. A basic compound (imidazoles, 2) having a pKa of 7.5 or more and a polyamic acid composed of a repeating unit represented by the following chemical formula (1) is 1.6 times mol or more with respect to the carboxyl group of the polyamic acid. -Except for methylaminodiethanol, diethylamino-acetone, N-ethylaminodiethanol, N-methylaminoethanol, 2,2-aminodiethanol, 3-diethylamino-1-propanol, amino-cyclohexane, triethylamine and diethanolamine) A polyimide precursor aqueous solution composition that is uniformly dissolved therein.
１１． 前記塩基性化合物が、上記３〜６のいずれか１項において定義される化合物であることを特徴とする上記９または１０に記載のポリイミド前駆体水溶液組成物。
11. 11. The polyimide precursor aqueous solution composition as described in 9 or 10 above, wherein the basic compound is a compound defined in any one of 3 to 6 above.
１２． 対数粘度が０．１以上であることを特徴とする上記９〜１１のいずれか１項に記載のポリイミド前駆体水溶液組成物。 12 The polyimide precursor aqueous solution composition according to any one of 9 to 11 above, wherein the logarithmic viscosity is 0.1 or more.
１３． 水溶媒が、水以外の有機溶媒を含まないことを特徴とする上記９〜１２のいずれか１項に記載のポリイミド前駆体水溶液組成物。 13. The aqueous solution of polyimide precursor according to any one of the above 9 to 12, wherein the aqueous solvent does not contain an organic solvent other than water.
１４． 前記化学式（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カルボキシル基に対して１．６倍モル以上の、ｐＫａが７．５以上である塩基性化合物またはイミダゾール類と共に、水溶媒中に均一に溶解してなるポリイミド前駆体水溶液組成物を含有する塗料。 14 The polyamic acid composed of the repeating unit represented by the chemical formula (1) is 1.6 times mol or more with respect to the carboxyl group of the polyamic acid, together with a basic compound or imidazole having a pKa of 7.5 or more, The coating material containing the polyimide precursor aqueous solution composition melt | dissolved uniformly in a water solvent.
１５． 顔料および／またはフィラーを含有することを特徴とする上記１４記載の塗料。 15. 15. The paint according to 14 above, which contains a pigment and / or a filler.
１６． 導電性の顔料および／またはフィラーを含有することを特徴とする上記１５記載の塗料。 16. 16. The paint according to 15 above, comprising a conductive pigment and / or filler.
本発明によれば、水溶媒を使用して、ポリイミド前駆体（即ちポリアミック酸）の水溶液組成物を、工業的に簡便な方法で製造する方法を提供することができる。本発明の１態様によれば、以外の有機溶媒を必要とせずに製造が可能であるため、環境適応性が極めて良好なポリイミド前駆体水溶液組成物を得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing the aqueous solution composition of a polyimide precursor (namely, polyamic acid) by an industrially simple method can be provided using an aqueous solvent. According to one aspect of the present invention, the polyimide precursor aqueous solution composition having extremely good environmental adaptability can be obtained because it can be produced without requiring any organic solvent.
本発明のポリイミド前駆体水溶液組成物を用いることにより、ポリイミドが本来的に有する優れた性能を、環境適応性が良好な水溶媒系で達成することができる。従って、本発明のポリイミド前駆体水溶液組成物は、原料のテトラカルボン酸成分およびジアミン成分の選択により、種々の用途において使用することができる。 By using the polyimide precursor aqueous solution composition of the present invention, excellent performance inherent in polyimide can be achieved in an aqueous solvent system having good environmental adaptability. Therefore, the polyimide precursor aqueous solution composition of the present invention can be used in various applications by selecting the raw material tetracarboxylic acid component and diamine component.
また、本発明の異なる１態様によれば、種々の用途に使用可能なポリイミド前駆体（ポリアミック酸）を含有する水溶性塗料を提供することができる。 Moreover, according to one different aspect of this invention, the water-soluble coating material containing the polyimide precursor (polyamic acid) which can be used for a various use can be provided.
本発明では、水を反応溶媒として、ｐＫａが７．５以上である塩基性化合物の存在下に、テトラカルボン酸二無水物とジアミンとを反応させて、ポリイミド前駆体水溶液組成物を製造する。 In this invention, tetracarboxylic dianhydride and diamine are made to react with water as a reaction solvent in presence of the basic compound whose pKa is 7.5 or more, and a polyimide precursor aqueous solution composition is manufactured.
本出願において、用語「ポリイミド前駆体」が、本発明に関連して使用されるとき、「ポリアミック酸」を意味し、モノマーの塩が溶解しただけの水溶液を含まない。 In this application, the term “polyimide precursor” as used in connection with the present invention means “polyamic acid” and does not include an aqueous solution in which the salt of the monomer is dissolved.
「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ｐＫａが７．５以上である塩基性化合物は含まれない。 “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 referred to here does not include tetracarboxylic acid components such as tetracarboxylic dianhydride, diamine components, polyimide precursors such as polyamic acid, and basic compounds having a pKa of 7.5 or more. .
前記有機溶媒としては、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. .
本発明において使用される塩基性化合物（以下、単に塩基性化合物という場合もある）は、７．５以上のｐＫａを有するものである。本発明で使用される塩基性化合物は、水溶媒中において、ポリアミック酸の重合促進に寄与する。これは、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（ポリイミド前駆体）のカルボキシル基と塩を形成して水に対する溶解性が高められるためと推定される。これに対して、含窒素有機化合物であっても、例えばＮ−メチルピロリドンのようなｐＫａの小さい化合物を水溶媒に添加しても、ポリアミック酸が得られない。従って、７．５以上程度のｐＫａを有することが重要であると考えられる。 The basic compound used in the present invention (hereinafter sometimes simply referred to as a basic compound) has a pKa of 7.5 or more. The basic compound used in the present invention contributes to the promotion of polymerization of polyamic acid in an aqueous solvent. This is presumably because the solubility in water is increased by forming a salt with a carboxyl group of a polyamic acid (polyimide precursor) produced by the reaction of the raw material tetracarboxylic dianhydride and diamine. On the other hand, even if it is a nitrogen-containing organic compound or a compound having a small pKa such as N-methylpyrrolidone is added to an aqueous solvent, a polyamic acid cannot be obtained. Therefore, it is considered important to have a pKa of about 7.5 or more.
また、塩基性化合物は、ポリイミド前駆体をイミド化（脱水閉環）する際に、高い触媒的な作用を有することもある。この結果、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ポリイミドやフレキシブルデバイス用基板を製造することが可能になることもある。 Further, the basic compound may have a high catalytic action when imidizing (dehydrating and cyclizing) the polyimide precursor. As a result, for example, it may be possible to easily produce a polyimide or a substrate for a flexible device having extremely high physical properties even by a heat treatment at a lower temperature for a shorter time.
塩基性化合物は、有機化合物であっても、無機化合物であってもよい。但し、無機塩は、イミド化した後も製品中に残ることがあるので、用途によっては好まれない場合もある。使用可能な塩基性化合物としては、例えば、アンモニア、ｐＫａが７．５以上の含窒素有機化合物、ｐＫａが７．５以上の金属塩を挙げることができる。尚、特許請求の範囲において、「イミダゾール類を除く」とあるのは、本出願時に未公開の先願（ＰＣＴ／ＪＰ２０１１／６６１４４）との重複を避けるためである。 The basic compound may be an organic compound or an inorganic compound. However, since the inorganic salt may remain in the product even after imidization, it may not be preferred depending on the application. Examples of basic compounds that can be used include ammonia, nitrogen-containing organic compounds having a pKa of 7.5 or more, and metal salts having a pKa of 7.5 or more. In the claims, “excludes imidazoles” is intended to avoid duplication with an unpublished prior application (PCT / JP2011 / 66144) at the time of this application.
含窒素有機化合物としては、分子内に少なくとも１つの１〜３級アミノ基を有する化合物（以下、１〜３級アミンという）が好ましい。本出願において、１〜３級アミノ基は中心チッ素原子に対する３つの結合がすべて単結合である構造を意味する。このような１〜３級アミノ基を１つ有していれば、分子内にその他のチッ素原子を有していてもよく、その他のチッ素原子は１〜３級アミノ基であっても、２重結合を有するイミノ基を構成してもよい。分子内にその他のチッ素原子を有する場合、アミノ基のチッ素原子と隣接しないことが好ましい。 As the nitrogen-containing organic compound, a compound having at least one primary to tertiary amino group in the molecule (hereinafter referred to as primary to tertiary amine) is preferable. In the present application, a primary to tertiary amino group means a structure in which all three bonds to the central nitrogen atom are single bonds. As long as it has one such primary to tertiary amino group, it may have another nitrogen atom in the molecule, and the other nitrogen atom may be a primary to tertiary amino group. You may comprise the imino group which has a double bond. When other nitrogen atoms are present in the molecule, it is preferable not to be adjacent to the nitrogen atom of the amino group.
１〜３級アミンとしては、脂肪族アミンが好ましく、鎖状（分岐、直鎖）であっても環状であってもよい。環状アミンの場合、飽和環が好ましい。環状アミンでない場合、アミノ基と共にイミノ基等の不飽和基を有していてもよい。また、脂肪族アミンの炭化水素基部分は、ＯＨ、アミノ基、ＣＯＯＨ等で置換されていてもよい。また、脂肪族基の中の−CＨ２−が、Ｏで置き換えられていてもよく、このときアミノ基のチッ素原子と隣接しない方が好ましい。 The primary to tertiary amines are preferably aliphatic amines, and may be chain (branched, straight chain) or cyclic. In the case of cyclic amines, saturated rings are preferred. When it is not a cyclic amine, it may have an unsaturated group such as an imino group together with an amino group. Further, the hydrocarbon group portion of the aliphatic amine may be substituted with OH, amino group, COOH or the like. In addition, —CH 2 — in the aliphatic group may be replaced by O, and at this time, it is preferable not to be adjacent to the nitrogen atom of the amino group.
例えば、ピペラジン類、グアニジンおよびグアニジン塩類、アルキルアミン類、アミノ基含有アルコール類（ＯＨ置換アルキルアミン類）、カルボキシル置換アルキルアミン類、ピペリジン類、ピロリジン類を挙げることができる。 Examples include piperazines, guanidine and guanidine salts, alkylamines, amino group-containing alcohols (OH-substituted alkylamines), carboxyl-substituted alkylamines, piperidines, and pyrrolidines.
ピペラジン類としては、無置換、またはアルキル基（好ましくは炭素数１〜６、より好ましくは炭素数１〜３のアルキル基）で置換されたピペラジンが好ましく、ここでアルキル基は、さらにアミノ基を有していてもよい。アルキル基の置換位置は、ピペラジン環中の任意の位置でよく、チッ素原子上であっても、炭素原子上であってもよい。 The piperazine is preferably piperazine which is unsubstituted or substituted with an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms), wherein the alkyl group further includes an amino group. You may have. The substitution position of the alkyl group may be any position in the piperazine ring, and may be on a nitrogen atom or on a carbon atom.
具体的には、ピペラジン、１−メチルピペラジン、１−エチルピペラジン、１−プロピルピペラジン、１，４−ジメチルピペラジン、１，４−ジエチルピペラジン、１，４−ジプロピルピペラジン、２−メチルピペラジン、２−エチルピペラジン、３−プロピルピペラジン、２，６−ジメチルピペラジン、２，６−ジエチルピペラジン、２，６−ジプロピルピペラジン、２，５−ジメチルピペラジン、２，５−ジエチルピペラジン、２，５−ジプロピルピペラジン等を挙げることができる。また、１−アミノエチルピペラジンのような、アミノアルキル基で置換されたピペラジンも好ましい。 Specifically, piperazine, 1-methylpiperazine, 1-ethylpiperazine, 1-propylpiperazine, 1,4-dimethylpiperazine, 1,4-diethylpiperazine, 1,4-dipropylpiperazine, 2-methylpiperazine, 2 -Ethylpiperazine, 3-propylpiperazine, 2,6-dimethylpiperazine, 2,6-diethylpiperazine, 2,6-dipropylpiperazine, 2,5-dimethylpiperazine, 2,5-diethylpiperazine, 2,5-di And propylpiperazine. Also preferred are piperazine substituted with an aminoalkyl group, such as 1-aminoethylpiperazine.
グアニジンおよびグアニジン塩類としては、グアニジンの他、グアニジンと弱酸との塩が挙げられ、炭酸グアニジン、シュウ酸グアニジン、酢酸グアニジン等が挙げられる。 Examples of guanidine and guanidine salts include guanidine, a salt of weak acid and guanidine carbonate, guanidine oxalate, and guanidine acetate.
アルキルアミンとしては、存在するアルキル基が互いに独立して、炭素数１〜６、特に炭素数１〜４の分岐または直鎖アルキル基、または炭素数３〜６、特に炭素数６の脂環式基を有する１〜３級アミンが好ましく、より好ましくは分子中の炭素数の合計が９以下となるようにアルキル基を有する。具体的には、トリメチルアミン、ジエチルアミン、ジメチルエチルアミン、トリエチルアミン、Ｎ−プロピルエチルアミン、Ｎ−ブチルエチルアミン、Ｎ，Ｎ−ジメチルシクロヘキシルアミン等を挙げることができる。 As alkylamines, the existing alkyl groups are independently of one another, a branched or straight chain alkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms, or an alicyclic group having 3 to 6 carbon atoms, particularly 6 carbon atoms. A primary to tertiary amine having a group is preferred, and an alkyl group is more preferred so that the total number of carbon atoms in the molecule is 9 or less. Specific examples include trimethylamine, diethylamine, dimethylethylamine, triethylamine, N-propylethylamine, N-butylethylamine, N, N-dimethylcyclohexylamine and the like.
また、アルキル基はアミノ基で置換されていてもよく、その場合２以上の１〜３級アミノ基を含有することになり、例えばエチレンジアミン、ジエチレンジアミントリアミン等のジまたはトリアミンを挙げることができる。 Further, the alkyl group may be substituted with an amino group, and in that case, it contains two or more primary to tertiary amino groups, and examples thereof include di- or triamines such as ethylenediamine and diethylenediaminetriamine.
アミノ基含有アルコール類としては、上記のアルキルアミンにおいて、アルキル基の水素がＯＨで置換された化合物が好ましく、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ，Ｎ−ジメチルアミノエタノール、Ｎ−ブチルアミノエタノール、２−（メチルアミノ）エタノール等を挙げることができる。 The amino group-containing alcohol is preferably a compound in which the hydrogen of the alkyl group is substituted with OH in the above alkylamine, and monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylaminoethanol, N-butylamino. Examples thereof include ethanol and 2- (methylamino) ethanol.
カルボキシル置換アルキルアミン類としては、上記のアルキルアミンにおいて、アルキル基の水素がＣＯＯＨで置換された化合物が挙げられ、エチレンジアミン四酢酸、１，３−プロパンジアミン四酢酸、１，２−プロパンジアミン四酢酸、１，３−ジアミノ−２−ヒドロキシプロパン四酢酸、グリコールエーテルジアミン四酢酸、トランス１，２−シクロヘキサンジアミン四酢酸、ヘキサメチレンジアミン四酢酸、ジカルボキシメチルグルタミン酸、ジカルボキシメチルアスパラギン酸、Ｓ，Ｓ−エチレンジアミン二コハク酸、エチレンジアミン二（ｏ−ヒドキシフェニル）酢酸、ヒドロキシエチルイミノ二酢酸、エチレンジアミン二酢酸、イミノ二酢酸、エチレンジアミン二プロピオン酸、ニトリロ三酢酸、ヒドロキシエチレンジアミン三酢酸、ニトリロ三プロピオン酸、メチルグリシン二酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラミン六酢酸等が挙げられる。また、カルボキシル基の一部または全部が、Ｎａ等のアルカリ金属と塩を形成していてもよい。 Examples of the carboxyl-substituted alkylamines include compounds in which the hydrogen of the alkyl group is substituted with COOH in the above alkylamine, such as ethylenediaminetetraacetic acid, 1,3-propanediaminetetraacetic acid, 1,2-propanediaminetetraacetic acid. 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, trans 1,2-cyclohexanediaminetetraacetic acid, hexamethylenediaminetetraacetic acid, dicarboxymethylglutamic acid, dicarboxymethylaspartic acid, S, S -Ethylenediamine disuccinic acid, ethylenediamine di (o-hydroxyphenyl) acetic acid, hydroxyethyliminodiacetic acid, ethylenediaminediacetic acid, iminodiacetic acid, ethylenediaminedipropionic acid, nitrilotriacetic acid, hydroxyethylenediamine Acid, nitrilotriacetic propionate, methyl glycine diacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and the like. Moreover, a part or all of the carboxyl group may form a salt with an alkali metal such as Na.
ピペリジン類としては、無置換、またはアルキル基（好ましくは炭素数１〜６、より好ましくは炭素数１〜３のアルキル基）で置換されたピペリジンが好ましく、ここでアルキル基は、さらにアミノ基を有していてもよい。アルキル基の置換位置は、ピペリジン環中の任意の位置でよく、チッ素原子上であっても、炭素原子上であってもよい。 The piperidine is preferably piperidine which is unsubstituted or substituted with an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms), wherein the alkyl group further includes an amino group. You may have. The substitution position of the alkyl group may be any position in the piperidine ring, and may be on a nitrogen atom or on a carbon atom.
具体的には、ピペリジン、１−メチルピペリジン、１−エチルピペリジン、１−プロピルピペリジン、２、３または４−メチルピペリジン、２、３または４−エチルピペリジン、２，６−ジメチルピペリジン、２，６−ジエチルピペリジン、２，６−ジプロピルピペリジン、２，４−ジメチルピペリジン、２，４−ジエチルピペリジン等を挙げることができる。また、１−アミノエチルピペリジンのような、アミノアルキル基で置換されたピペリジンも好ましい。また、モルホリンのような、Ｎに隣接しない−ＣＨ２−がＯで置き換えられた化合物も好ましい。 Specifically, piperidine, 1-methylpiperidine, 1-ethylpiperidine, 1-propylpiperidine, 2,3 or 4-methylpiperidine, 2,3 or 4-ethylpiperidine, 2,6-dimethylpiperidine, 2,6 -Diethylpiperidine, 2,6-dipropylpiperidine, 2,4-dimethylpiperidine, 2,4-diethylpiperidine and the like can be mentioned. A piperidine substituted with an aminoalkyl group such as 1-aminoethylpiperidine is also preferred. Also preferred are compounds in which —CH 2 — not adjacent to N is replaced by O, such as morpholine.
ピロリジン類としては、無置換、またはアルキル基（好ましくは炭素数１〜６、より好ましくは炭素数１〜３のアルキル基）で置換されたピロリジンが好ましく、ここでアルキル基は、さらにアミノ基を有していてもよい。アルキル基の置換位置は、ピロリジン環中の任意の位置でよく、チッ素原子上であっても、炭素原子上であってもよい。 The pyrrolidines are preferably pyrrolidine which is unsubstituted or substituted with an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms), wherein the alkyl group further includes an amino group. You may have. The substitution position of the alkyl group may be any position in the pyrrolidine ring, and may be on a nitrogen atom or a carbon atom.
具体的には、ピロリジン、１−メチルピロリジン、１−エチルピロリジン、１−プロピルピロリジン、２または３−メチルピロリジン、２または３−エチルピロリジン、２，５−ジメチルピロリジン、２，５−ジエチルピロリジン、２，５−ジプロピルピロリジン、２，４−ジメチルピロリジン、２，４−ジエチルピロリジン等を挙げることができる。また、１−アミノエチルピロリジンのような、アミノアルキル基で置換されたピロリジンも好ましい。 Specifically, pyrrolidine, 1-methylpyrrolidine, 1-ethylpyrrolidine, 1-propylpyrrolidine, 2 or 3-methylpyrrolidine, 2 or 3-ethylpyrrolidine, 2,5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, Examples include 2,5-dipropylpyrrolidine, 2,4-dimethylpyrrolidine, 2,4-diethylpyrrolidine and the like. Pyrrolidine substituted with an aminoalkyl group such as 1-aminoethylpyrrolidine is also preferable.
ｐＫａが７．５以上の金属塩としては、アルカリ金属と弱酸との塩が好ましく、アルカリ金属はＮａおよびＫが好ましく、弱酸としては炭酸、シュウ酸、酢酸、リン酸および炭素数４以下のカルボン酸が好ましく、特に炭酸、シュウ酸、酢酸、リン酸が好ましい。具体的には、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム、シュウ酸ナトリウム、シュウ酸カリウム、酢酸ナトリウム、リン酸ナトリウム、リン酸カリウム、リン酸水素二ナトリウム、リン酸水素二カリウム等を挙げることができる。 As the metal salt having a pKa of 7.5 or more, a salt of an alkali metal and a weak acid is preferable, and the alkali metal is preferably Na or K. The weak acid includes carbonic acid, oxalic acid, acetic acid, phosphoric acid, An acid is preferable, and carbonic acid, oxalic acid, acetic acid, and phosphoric acid are particularly preferable. Specifically, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium oxalate, potassium oxalate, sodium acetate, sodium phosphate, potassium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, etc. Can be mentioned.
以上の他にも、ｐＫａが７．５以上の塩基性化合物であれば使用が可能であるが、ｐＫａとして２つ以上の値を有する化合物の場合、全てのｐＫａ値が７．５以上を有することが好ましい。但し、エチレンジアミン四酢酸のように、全てのｐＫａ値が７．５以上でない化合物であっても使用可能な場合がある。 In addition to the above, any basic compound having a pKa of 7.5 or more can be used. However, in the case of a compound having two or more values as pKa, all pKa values have 7.5 or more. It is preferable. However, even if it is a compound which is not 7.5 or more of all pKa values like ethylenediaminetetraacetic acid, it may be usable.
尚、ｐＫａの値は、ケミカル・アブストラクトなどのデ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、Ａｄｖａｎｃｅｄ Ｃｈｅｍｉｓｔｒｙ Ｄｅｖｅｌｏｐｍｅｎｔ（ＡＣＤ／Ｌａｂｓ）Ｓｏｆｔｗａｒｅ Ｖ１１．０２（Ｃｏｐｙｒｉｇｈｔ １９９４−２０１１ ＡＣＤ／Ｌａｂｓ）によって算出された値を採用した。 The value of pKa can be easily searched by SciFinder (registered trademark) known as a search service based on a database such as a chemical abstract. Here, the value calculated by Advanced Chemistry Development (ACD / Labs) Software V11.02 (Copyright 1994-2011 ACD / Labs) was adopted.
なお、用いる塩基性化合物は一種であっても、複数種の混合物であってもよい。 In addition, the basic compound to be used may be one kind or a mixture of plural kinds.
本発明で用いる塩基性化合物の使用量は、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。塩基性化合物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、塩基性化合物の使用量の上限は、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。塩基性化合物の使用量が多過ぎると、非経済的になるし、且つポリイミド前駆体水溶液組成物の保存安定性が悪くなることがある。 The amount of the basic compound used in the present invention is preferably 0.8 times equivalent or more, more preferably 1 with respect to the carboxyl group of the polyamic acid produced by the reaction of the raw material tetracarboxylic dianhydride and diamine. It is 0.0 times equivalent or more, More preferably, it is 1.2 times equivalent or more. If the usage-amount of a basic compound is less than 0.8 equivalent with respect to the carboxyl group of polyamic acid, it may become easy to obtain the polyimide precursor aqueous solution composition melt | dissolved uniformly. Moreover, although the upper limit of the usage-amount of a basic compound 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 the basic compound used is too large, it may become uneconomical and the storage stability of the polyimide precursor aqueous solution composition may deteriorate.
本発明において、塩基性化合物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）の割合で塩基性化合物を用いるかを表す。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。 In the present invention, the double equivalent to the carboxyl group of the polyamic acid that defines the amount of the basic compound is basic (number of molecules) with respect to one carboxyl group forming the amic acid group of the polyamic acid. Indicates whether a compound is used. 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.
したがって、本発明で用いる塩基性化合物の使用量は、原料のテトラカルボン酸二無水物に対して（ポリアミック酸のテトラカルボン酸成分に対して）、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。 Therefore, the amount of the basic compound used in the present invention is preferably 1.6 times mol or more, more preferably, relative to the tetracarboxylic dianhydride of the raw material (relative to the tetracarboxylic acid component of the polyamic acid). It is 2.0 times mol or more, More preferably, it is 2.4 times mol or more.
前述の通り、本発明においては、好ましくは、水を反応溶媒として、塩基性化合物の存在下に、テトラカルボン酸成分とジアミン成分とを反応させることによって、ポリイミド前駆体水溶液組成物を極めて簡便に（直接的に）製造することが可能である。 As described above, in the present invention, preferably, the polyimide precursor aqueous solution composition can be made very simply by reacting a tetracarboxylic acid component and a diamine component in the presence of a basic compound using water as a reaction solvent. It can be (directly) manufactured.
この反応は、テトラカルボン酸成分（テトラカルボン酸二無水物）とジアミン成分とを略等モル用い、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、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時間程度であることが好ましい。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、生産効率よく充分な分子量のポリアミック酸を含有する水溶液組成物を容易に得ることができる。なお、反応は、空気雰囲気下でも行うことができるが、通常は不活性ガス雰囲気下、好ましくは窒素ガス雰囲気下で好適に行われる。 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 a tetracarboxylic acid component (tetracarboxylic dianhydride) and a diamine component in approximately equimolar amounts. . Although it does not limit, reaction temperature is 25 to 100 degreeC normally, Preferably it is 40 to 80 degreeC, More preferably, it is 50 to 80 degreeC, Reaction time is about 0.1 to 24 hours, Preferably It is preferably about 2 to 12 hours. By setting the reaction temperature and the reaction time within the above ranges, an aqueous solution composition containing a polyamic acid having a sufficient molecular weight can be easily obtained with high production efficiency. The reaction can be carried out in an air atmosphere, but usually it is suitably carried out in an inert gas atmosphere, preferably in a nitrogen gas atmosphere.
反応の具体的手順は特に限定されないが、塩基性化合物とジアミンが存在する水反応溶媒中に、テトラカルボン酸二無水物を添加して反応させることが、分子量の高いポリアミック酸を得るために好ましい。 Although the specific procedure of the reaction is not particularly limited, it is preferable to add tetracarboxylic dianhydride in a water reaction solvent in which a basic compound and a diamine are present in order to obtain a polyamic acid having a high molecular weight. .
また、テトラカルボン酸成分（テトラカルボン酸二無水物）とジアミン成分とを略等モルとは、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。 Moreover, the tetracarboxylic acid component (tetracarboxylic dianhydride) and the diamine component are approximately equimolar, specifically, about 0.90 to 1.10 in molar ratio [tetracarboxylic acid component / diamine component], Preferably, it is about 0.95 to 1.05.
本発明で用いるテトラカルボン酸二無水物は、脂肪族テトラカルボン酸二無水物および芳香族テトラカルボン酸二無水物から選ばれ、芳香族テトラカルボン酸二無水物はフッ素基を含有していてもよい。 The tetracarboxylic dianhydride used in the present invention is selected from an aliphatic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride, and the aromatic tetracarboxylic dianhydride may contain a fluorine group. Good.
本発明で用いるフッ素基を含有しない芳香族テトラカルボン酸二無水物は、好ましくは２〜３個の芳香族環を有するものが好ましく、例えば、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物、２，２’，３，３’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、４，４’−オキシジフタル酸二無水物、ジフェニルスルホンテトラカルボン酸二無水物、ｐ−ターフェニルテトラカルボン酸二無水物、ｍ−ターフェニルテトラカルボン酸二無水物などを好適に挙げることができる。 The aromatic tetracarboxylic dianhydride containing no fluorine group used in the present invention preferably has 2 to 3 aromatic rings. For example, 3,3 ′, 4,4′-biphenyltetracarboxylic Acid dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetra Suitable examples include carboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, diphenylsulfone tetracarboxylic dianhydride, p-terphenyl tetracarboxylic dianhydride, m-terphenyl tetracarboxylic dianhydride, and the like. Can be listed.
本発明で用いる脂肪族テトラカルボン酸二無水物としては、例えば、シクロブタン−１，２，３，４−テトラカルボン酸二無水物、１，２，４，５−シクロヘキサンテトラカルボン酸二無水物、ジシクロヘキシル−３，３’，４，４’ −テトラカルボン酸二無水物、１，２，４，５−シクロヘキサンテトラカルボン酸−１，２：４，５−二無水物、１，２，３，４−シクロブタンテトラカルボン酸二無水物、ビシクロ［２．２．２］オクト−7−エン−２，３；５，６−テトラカルボン酸二無水物などを好適に挙げることができる。 Examples of the aliphatic tetracarboxylic dianhydride used in the present invention include cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, Dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-dianhydride, 1,2,3 Preferable examples include 4-cyclobutanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3; 5,6-tetracarboxylic dianhydride and the like.
本発明で用いるフッ素基を含有する芳香族テトラカルボン酸二無水物としては、例えば、４，４’−（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、３，３’−（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、５，５’−［２，２，２−トリフルオロ−１−［３−（トリフルオロメチル）フェニル］エチリデン］ジフタル酸無水物、５，５’−［２，２，３，３，３−ペンタフルオロ−１−（トリフルオロメチル）プロピリデン］ジフタル酸無水物、１Ｈ−ジフロ［３，４−ｂ：３’，４’−ｉ］キサンテン−１，３，７，９（１１Ｈ）−テトロン、５，５’−オキシビス［４，６，７−トリフルオロ−ピロメリット酸無水物］、３，６−ビス（トリフルオロメチル）ピロメリット酸二無水物、４−（トリフルオロメチル）ピロメリット酸二無水物、１，４−ジフルオロピロメリット酸二無水物、１，４−ビス（３，４−ジカルボキシトリフルオロフェノキシ）テトラフルオロベンゼン二無水物などを好適に挙げることができる。 Examples of the aromatic tetracarboxylic dianhydride containing a fluorine group used in the present invention include 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride and 3,3 ′-(hexafluoroisopropylidene) diphthalate. Acid anhydride, 5,5 ′-[2,2,2-trifluoro-1- [3- (trifluoromethyl) phenyl] ethylidene] diphthalic anhydride, 5,5 ′-[2,2,3 3,3-pentafluoro-1- (trifluoromethyl) propylidene] diphthalic anhydride, 1H-difuro [3,4-b: 3 ′, 4′-i] xanthene-1,3,7,9 (11H ) -Tetron, 5,5′-oxybis [4,6,7-trifluoro-pyromellitic anhydride], 3,6-bis (trifluoromethyl) pyromellitic dianhydride, 4- (trifluoromethyl ) Romeritto dianhydride, 1,4-difluoro pyromellitic dianhydride, 1,4-bis (3,4-dicarboxyphenyl trifluoromethyl phenoxy) such tetrafluorobenzene dianhydride can be preferably cited.
本発明で用いるテトラカルボン酸二無水物は、（ｉ）フッ素基を含有しない芳香族テトラカルボン酸二無水物、（ｉｉ）脂肪族テトラカルボン酸二無水物、及び（ｉｉｉ）フッ素基を含有する芳香族テトラカルボン酸二無水物に分類されるが、３つのカテゴリ中の１つのカテゴリのみから選ばれる化合物を使用する必要はなく、例えば（ｉ）の化合物と（ｉｉ）の化合物の組み合わせというように２つ以上のカテゴリの混合物でもよい。また、１つのカテゴリの中から、複数種の化合物を選んで、それ自体で、または他のカテゴリから選ばれる化合物との混合物として用いることもできる。 The tetracarboxylic dianhydride used in the present invention contains (i) an aromatic tetracarboxylic dianhydride containing no fluorine group, (ii) an aliphatic tetracarboxylic dianhydride, and (iii) containing a fluorine group. Although it is classified as an aromatic tetracarboxylic dianhydride, it is not necessary to use a compound selected from only one of the three categories. For example, a combination of the compound (i) and the compound (ii) It may be a mixture of two or more categories. In addition, a plurality of types of compounds can be selected from one category and used by themselves or as a mixture with compounds selected from other categories.
本発明で用いるジアミンは、脂肪族ジアミンおよび芳香族ジアミンから選ばれ、芳香族ジアミンはフッ素基を含有していてもよい。 The diamine used in the present invention is selected from an aliphatic diamine and an aromatic diamine, and the aromatic diamine may contain a fluorine group.
本発明で用いるフッ素基を含有しない芳香族ジアミンとしては、２５℃における水に対する溶解度が０．１ｇ／Ｌ以上の化合物が好ましく、１〜２個の芳香族環を有する芳香族ジアミンが好ましい。２５℃の水に対する溶解度が０．１ｇ／Ｌ未満の芳香族ジアミンを用いた場合には、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場合がある。また、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、２５℃の水に対する溶解度が０．１ｇ／Ｌ未満になる場合があり、その結果、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場合がある。 As the aromatic diamine not containing a fluorine group used in the present invention, a compound having a solubility in water at 25 ° C. of 0.1 g / L or more is preferable, and an aromatic diamine having 1 to 2 aromatic rings is preferable. When an aromatic diamine having a solubility in water at 25 ° C. of less than 0.1 g / L is used, it may be difficult to obtain a uniformly dissolved polyimide precursor aqueous solution composition. Further, when the aromatic diamine has more than two aromatic rings, the solubility in water at 25 ° C. may be less than 0.1 g / L, and as a result, the polyimide precursor aqueous solution composition uniformly dissolved It may be difficult to get things.
本発明で用いる脂肪族ジアミンとしては、分子量（モノマーの場合は分子量、ポリマーの場合は重量平均分子量を示す）が５００以下の化合物が好ましく、２５℃の水に対する溶解度が０．１ｇ／Ｌ以上である脂肪族ジアミン、又は、１〜２個の脂環を有する脂環式ジアミンが特に好ましい。分子量が５００を超える脂肪族ジアミンを用いた場合には、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場合がある。 As the aliphatic diamine used in the present invention, a compound having a molecular weight (molecular weight in the case of a monomer, and weight average molecular weight in the case of a polymer) of 500 or less is preferable, and solubility in water at 25 ° C. is 0.1 g / L or more. Certain aliphatic diamines or alicyclic diamines having 1 to 2 alicyclic rings are particularly preferred. When an aliphatic diamine having a molecular weight exceeding 500 is used, it may be difficult to obtain a uniformly dissolved polyimide precursor aqueous solution composition.
本発明で用いるフッ素基を含有する芳香族ジアミンとしては、特に限定されないが、１〜２個の芳香族環を有するフッ素基を含有する芳香族ジアミンが好ましい。フッ素基を含有す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、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場合がある。 Although it does not specifically limit as an aromatic diamine containing the fluorine group used by this invention, The aromatic diamine containing the fluorine group which has 1-2 aromatic rings is preferable. When the aromatic diamine containing a fluorine group has more than two aromatic rings, it may be difficult to obtain a uniformly dissolved polyimide precursor aqueous solution composition.
本発明で用いる好ましいフッ素基を含有しない芳香族ジアミンとしては、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−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、得られるポリイミドが優れた特性を有するので、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。 Preferred aromatic diamines not containing a fluorine group used in the present invention are 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) L), 3,3′-dihydroxy-4,4′-diaminobiphenyl (1.3 g / L), bis (4-amino-3-carboxyphenyl) methane (200 g / L), 2,4-diaminotoluene ( 62 g / L), etc., but p-phenylenediamine is highly water-soluble and the resulting polyimide has excellent characteristics. 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.
本発明で用いる好ましい脂肪族ジアミンとしては、ｔｒａｎｓ−１，４−ジアミノシクロへキサン（１０００ｇ／Ｌ、分子量：１１４）、ｃｉｓ−１，４−ジアミノシクロへキサン（１０００ｇ／Ｌ、分子量：１１４）、１，６−ヘキサメチレンジアミン（１０００ｇ／Ｌ、分子量：１１６）、１，１０−デカメチレンジアミン（１０００ｇ／Ｌ、分子量：１７２）、１，３−ビス（アミノメチル）シクロヘキサン（１０００ｇ／Ｌ、分子量：１４２）、１，４−ビス（アミノメチル）シクロヘキサン（９９９ｇ／Ｌ、分子量：１４２）、重量平均分子量が５００以下のポリオキシプロピレンジアミンなどを挙げることができる。 Preferred aliphatic diamines used in the present invention include trans-1,4-diaminocyclohexane (1000 g / L, molecular weight: 114), cis-1,4-diaminocyclohexane (1000 g / L, molecular weight: 114). 1,6-hexamethylenediamine (1000 g / L, molecular weight: 116), 1,10-decamethylenediamine (1000 g / L, molecular weight: 172), 1,3-bis (aminomethyl) cyclohexane (1000 g / L, Examples include molecular weight: 142), 1,4-bis (aminomethyl) cyclohexane (999 g / L, molecular weight: 142), and polyoxypropylenediamine having a weight average molecular weight of 500 or less.
本発明で用いるフッ素基を含有する芳香族ジアミンとしては、例えば、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル、２，３，５，６−テトラフルオロ−１，４−ジアミノベンゼン、２，４，５，６−テトラフルオロ−１，３−ジアミノベンゼン、２，３，５，６−テトラフルオロ−１，４−ベンゼン（ジメタンアミン）、２，２’−ジフルオロ−（１，１’−ビフェニル）−４，４’−ジアミン、２，２’，６，６’−テトラフルオロ−（１，１’−ビフェニル）−４，４’−ジアミン、４，４’−ジアミノオクタフルオロビフェニル、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、４，４’−オキシビス（２，３，５，６−テトラフルオロアニリン）などを好適に挙げることができる。 Examples of the aromatic diamine containing a fluorine group used in the present invention include 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,3,5,6-tetrafluoro-1, 4-diaminobenzene, 2,4,5,6-tetrafluoro-1,3-diaminobenzene, 2,3,5,6-tetrafluoro-1,4-benzene (dimethanamine), 2,2′-difluoro- (1,1′-biphenyl) -4,4′-diamine, 2,2 ′, 6,6′-tetrafluoro- (1,1′-biphenyl) -4,4′-diamine, 4,4′- Preferred examples include diaminooctafluorobiphenyl, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-oxybis (2,3,5,6-tetrafluoroaniline) and the like.
本発明で用いるジアミンは、（ｉ）フッ素基を含有しない芳香族ジアミン、（ｉｉ）脂肪族ジアミン、及び（ｉｉｉ）フッ素基を含有する芳香族ジアミンに分類されるが、３つのカテゴリ中の１つのカテゴリのみから選ばれる化合物を使用する必要はなく、例えば（ｉ）の化合物と（ｉｉ）の化合物の組み合わせというように２つ以上のカテゴリの混合物でもよい。また、１つのカテゴリの中から、複数種の化合物を選んで、それ自体で、または他のカテゴリから選ばれる化合物との混合物として用いることもできる。フッ素基を含有しない芳香族ジアミンは、これらの水に対する溶解度が高いジアミンと他のジアミンとを組み合わせて、ジアミン成分全体として２５℃における水に対する溶解度が０．１ｇ／Ｌ以上になるようにして用いることもできる。 The diamine used in the present invention is classified into (i) an aromatic diamine containing no fluorine group, (ii) an aliphatic diamine, and (iii) an aromatic diamine containing a fluorine group. It is not necessary to use a compound selected from only one category, and it may be a mixture of two or more categories, for example, a combination of the compound (i) and the compound (ii). In addition, a plurality of types of compounds can be selected from one category and used by themselves or as a mixture with compounds selected from other categories. Aromatic diamines that do not contain fluorine groups are used in combination with diamines having high solubility in water and other diamines so that the total diamine component has a solubility in water at 25 ° C. of 0.1 g / L or more. You can also.
なお、２５℃における水に対する溶解度（２５℃の水に対する溶解度）が０．１ｇ／Ｌ以上のジアミンとは、当該ジアミンが２５℃の水１Ｌ（１０００ｍｌ）に０．１ｇ以上溶解することを意味する。２５℃に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デ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。 A diamine having a solubility in water at 25 ° C. (solubility in water at 25 ° C.) of 0.1 g / L or more means that 0.1 g or more of the diamine is dissolved in 1 L (1000 ml) of water at 25 ° C. . The solubility in water at 25 ° C. means the limit amount (g) at which the substance is dissolved in 1 L (liter) of water at 25 ° C. This value can be easily searched by SciFinder (registered trademark) known as a search service based on a database 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.
本発明のポリイミド前駆体水溶液組成物は、非常に好ましくは以上説明した製造方法によって得られるものである。従って、ポリイミド前駆体水溶液組成物は、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カルボキシル基に対して１．６倍モル以上の、ｐＫａが７．５以上である塩基性化合物（イミダゾール類を除く）と共に、水溶媒中に均一に溶解してなるポリイミド前駆体水溶液組成物に関する。 The aqueous polyimide precursor solution composition of the present invention is very preferably obtained by the production method described above. Therefore, in the polyimide precursor aqueous solution composition, the polyamic acid composed of the repeating unit represented by the following chemical formula (1) is 1.6 times mol or more with respect to the carboxyl group of the polyamic acid, and the pKa is 7.5 or more. It is related with the polyimide precursor aqueous solution composition formed by melt | dissolving uniformly in a water solvent with the basic compound (except imidazoles) which is.
化学式（１）のＡは、好ましくは２〜３個の芳香族環を有するフッ素基を含有しない芳香族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、及び／又は脂肪族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、及び／又はフッ素基を含有する芳香族テトラカルボン酸からカルボキシル基を除いた４価の基である。 A in the chemical formula (1) is preferably a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid not containing a fluorine group having 2 to 3 aromatic rings and / or an aliphatic tetracarboxylic acid. It is a tetravalent group excluding a carboxyl group and / or a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid containing a fluorine group.
化学式（１）のＡは、得られるポリアミック酸が水に対して十分な溶解性を有すると共に、得られるポリイミドが所望の特性を有するように適宜選択される。得られるポリイミドの特性として、可とう性、耐熱性、機械的強度、電気特性、耐溶剤性等の１つまたは２つ以上の特性が要求される用途、例えば、ポリイミドシームレスベルト、電極用等のバインダー樹脂、ポリイミドフレキシブルデバイス用基板、または塗料用途には、５０モル％超（１００％を含む）が２〜３個の芳香族環を有する芳香族テトラカルボン酸からカルボキシル基を除いた４価の基であり、５０モル％未満（０％を含む）が脂肪族テトラカルボン酸からカルボキシル基を除いた４価の基および／またはフッ素基を含有する芳香族テトラカルボン酸からカルボキシル基を除いた４価の基であることが好ましい。 A in the chemical formula (1) is appropriately selected so that the obtained polyamic acid has sufficient solubility in water and the obtained polyimide has desired characteristics. As the properties of the obtained polyimide, applications requiring one or more properties such as flexibility, heat resistance, mechanical strength, electrical properties, solvent resistance, such as polyimide seamless belts, electrodes, etc. For binder resins, polyimide flexible device substrates, or paint applications, more than 50 mol% (including 100%) of tetravalent aromatic tetracarboxylic acids having 2-3 aromatic rings, excluding carboxyl groups 4 wherein less than 50 mol% (including 0%) is a tetravalent group obtained by removing a carboxyl group from an aliphatic tetracarboxylic acid and / or an aromatic tetracarboxylic acid containing a fluorine group. It is preferably a valent group.
一方、得られるポリイミドの特性として、高い透明性が要求されるポリイミドフレキシブルデバイス用基板等を容易に得るためには、５０モル％以下が、好ましくは２〜３個の芳香族環を有するフッ素基を含有しない芳香族テトラカルボン酸からカルボキシル基を除いた４価の基であり、５０モル％以上が、脂肪族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、及び／又はフッ素基を含有する芳香族テトラカルボン酸からカルボキシル基を除いた４価の基であることが好ましい。ただし、化学式（１）のＢの５０モル％以上が、分子量が５００以下である脂肪族ジアミンからアミノ基を除いた２価の基、及び／又はフッ素基を含有する芳香族ジアミンからアミノ基を除いた２価の基であり、５０モル％以下が、２５℃の水に対する溶解度が０．１ｇ／Ｌ以上であるフッ素基を含有しない芳香族ジアミンからアミノ基を除いた２価の基である場合は特に限定されず、５０モル％以上が、フッ素基を含有しない芳香族テトラカルボン酸からカルボキシル基を除いた４価の基であり、５０モル％以下が、脂肪族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、及び／又はフッ素基を含有する芳香族テトラカルボン酸からカルボキシル基を除いた４価の基であってもよい。 On the other hand, in order to easily obtain a substrate for a polyimide flexible device that requires high transparency as a characteristic of the obtained polyimide, 50 mol% or less, preferably a fluorine group having 2 to 3 aromatic rings Is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid containing no carboxylic acid, and 50 mol% or more contains a tetravalent group obtained by removing a carboxyl group from an aliphatic tetracarboxylic acid and / or a fluorine group A tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid is preferable. However, 50 mol% or more of B in the chemical formula (1) is a divalent group obtained by removing an amino group from an aliphatic diamine having a molecular weight of 500 or less, and / or an amino group from an aromatic diamine containing a fluorine group. 50 mol% or less is a divalent group obtained by removing an amino group from an aromatic diamine not containing a fluorine group having a solubility in water at 25 ° C. of 0.1 g / L or more. The case is not particularly limited, and 50 mol% or more is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid not containing a fluorine group, and 50 mol% or less is an aliphatic tetracarboxylic acid to a carboxyl group. The tetravalent group which remove | excluded and / or the tetravalent group which remove | excluded the carboxyl group from the aromatic tetracarboxylic acid containing a fluorine group may be sufficient.
本発明においては、得られるポリイミドの特性から、フッ素基を含有しない芳香族テトラカルボン酸二無水物に由来する構成単位である前記化学式（１）のＡが、下記化学式（２）〜（７）のいずれか一種以上であることが好ましく、主として下記化学式（２）、（３）及び（５）のいずれか一種以上であることが特に好ましく、下記化学式（２）〜（３）のいずれか一種以上であることがさらに好ましい。 In the present invention, from the properties of the resulting polyimide, A in the chemical formula (1), which is a structural unit derived from an aromatic tetracarboxylic dianhydride containing no fluorine group, is represented by the following chemical formulas (2) to (7). Any one or more of the following chemical formulas (2), (3) and (5) are particularly preferred, and any one of the following chemical formulas (2) to (3) is preferred. More preferably, it is the above.
化学式（１）のＢは、ポリアミック酸のジアミン成分に由来する化学構造であって、好ましくは１〜２個の芳香族環を有し、２５℃の水に対する溶解度が０．１ｇ／Ｌ以上であるフッ素基を含有しない芳香族ジアミンからアミノ基を除いた２価の基、及び／又は分子量が５００以下である脂肪族ジアミン、好ましくは水に対する溶解度が０．１ｇ／Ｌ以上である脂肪族ジアミン、あるいは、１〜２個の脂環を有する脂肪族ジアミンからアミノ基を除いた２価の基、及び／又はフッ素基を含有する芳香族ジアミンからアミノ基を除いた２価の基である。 B in the chemical formula (1) is a chemical structure derived from the diamine component of the polyamic acid, preferably has 1 to 2 aromatic rings, and has a solubility in water of 25 ° C. of 0.1 g / L or more. A divalent group obtained by removing an amino group from a certain fluorine-free aromatic diamine and / or an aliphatic diamine having a molecular weight of 500 or less, preferably an aliphatic diamine having a solubility in water of 0.1 g / L or more Or a divalent group obtained by removing an amino group from an aliphatic diamine having 1 to 2 alicyclic rings and / or a divalent group obtained by removing an amino group from an aromatic diamine containing a fluorine group.
化学式（１）のＢは、得られるポリアミック酸が水に対して十分な溶解性を有すると共に、得られるポリイミドが所望の特性を有するように適宜選択される。得られるポリイミドの特性として、可とう性、耐熱性、機械的強度、電気特性、耐溶剤性等の１つまたは２つ以上の特性が要求される用途、例えば、ポリイミドシームレスベルト、電極用等のバインダー樹脂、ポリイミドフレキシブルデバイス用基板、または塗料用途には、５０モル％超が１〜２個の芳香族環を有し、２５℃の水に対する溶解度が０．１ｇ／Ｌ以上である芳香族ジアミンからアミノ基を除いた２価の基であり、５０モル％未満が分子量が５００以下である脂肪族ジアミンからアミノ基を除いた２価の基であることが好ましい。 B in the chemical formula (1) is appropriately selected so that the obtained polyamic acid has sufficient solubility in water and the obtained polyimide has desired characteristics. As the properties of the obtained polyimide, applications requiring one or more properties such as flexibility, heat resistance, mechanical strength, electrical properties, solvent resistance, such as polyimide seamless belts, electrodes, etc. For binder resins, polyimide flexible device substrates, or paint applications, more than 50 mol% has 1 to 2 aromatic rings, and the solubility in water at 25 ° C. is 0.1 g / L or more. It is preferably a divalent group obtained by removing an amino group from an aliphatic diamine having a molecular weight of 500 or less.
一方、得られるポリイミドの特性として、高い透明性が要求されるポリイミドフレキシブルデバイス用基板等を容易に得るためには、５０モル％以下が、好ましくは１〜２個の芳香族環を有し、２５℃の水に対する溶解度が０．１ｇ／Ｌ以上であるフッ素基を含有しない芳香族ジアミンからアミノ基を除いた２価の基であり、５０モル％以上が、分子量が５００以下である脂肪族ジアミンからアミノ基を除いた２価の基、及び／又はフッ素基を含有する芳香族ジアミンからアミノ基を除いた２価の基であることが好ましい。ただし、化学式（１）のＡの５０モル％以上が、脂肪族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、及び／又はフッ素基を含有する芳香族テトラカルボン酸からカルボキシル基を除いた４価の基であり、５０モル％以下が、フッ素基を含有しない芳香族テトラカルボン酸からカルボキシル基を除いた４価の基である場合は特に限定されず、５０モル％以上が、２５℃の水に対する溶解度が０．１ｇ／Ｌ以上であるフッ素基を含有しない芳香族ジアミンからアミノ基を除いた２価の基であり、５０モル％以下が、分子量が５００以下である脂肪族ジアミンからアミノ基を除いた２価の基、及び／又はフッ素基を含有する芳香族ジアミンからアミノ基を除いた２価の基であってもよい。 On the other hand, as a characteristic of the obtained polyimide, in order to easily obtain a substrate for a polyimide flexible device that requires high transparency, 50 mol% or less preferably has 1 to 2 aromatic rings, A divalent group obtained by removing an amino group from an aromatic diamine not containing a fluorine group having a solubility in water at 25 ° C. of 0.1 g / L or more, and 50 mol% or more is an aliphatic having a molecular weight of 500 or less. A divalent group obtained by removing an amino group from a diamine and / or a divalent group obtained by removing an amino group from an aromatic diamine containing a fluorine group is preferred. However, 50 mol% or more of A in the chemical formula (1) was obtained by removing the carboxyl group from the tetravalent group obtained by removing the carboxyl group from the aliphatic tetracarboxylic acid and / or the aromatic tetracarboxylic acid containing a fluorine group. It is a tetravalent group, and 50 mol% or less is not particularly limited when it is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid not containing a fluorine group. Is a divalent group obtained by removing an amino group from an aromatic diamine not containing a fluorine group having a solubility in water of 0.1 g / L or more, and 50 mol% or less is from an aliphatic diamine having a molecular weight of 500 or less. It may be a divalent group excluding an amino group and / or a divalent group excluding an amino group from an aromatic diamine containing a fluorine group.
本発明においては、得られるポリイミドの特性から、フッ素基を含有しない芳香族ジアミンに由来する構成単位である前記化学式（１）のＢが、下記化学式（８）〜（９）のいずれか一種以上であることが好ましい。 In the present invention, from the properties of the resulting polyimide, B in the chemical formula (1), which is a structural unit derived from an aromatic diamine containing no fluorine group, is one or more of the following chemical formulas (8) to (9). It is preferable that
本発明によって得られる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、好ましくは０．１以上である。用途によっては、好ましくは０．１５以上、より好ましくは０．２以上の高分子量であることが好適である場合がある。対数粘度が前記範囲よりも低い場合、例えば、０．０７程度以下では、反応生成物の分子量が低く、実質的にはポリアミック酸が生成しているとは言えない。対数粘度の低い水溶液組成物は、成膜用途、バインダー用途として不適当である。 In the polyimide precursor aqueous solution composition obtained by the present invention, measurement was performed 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). The logarithmic viscosity is preferably 0.1 or more. Depending on the application, a high molecular weight of preferably 0.15 or more, more preferably 0.2 or more may be suitable. When the logarithmic viscosity is lower than the above range, for example, at about 0.07 or less, the molecular weight of the reaction product is low, and it cannot be said that a polyamic acid is substantially generated. An aqueous solution composition having a low logarithmic viscosity is unsuitable for film formation and binder use.
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、特に限定されるものではないが、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４質量％〜４５質量％、より好ましくは５質量％〜４０質量％、さらに好ましくは７質量％〜３０質量％であることが好適である。固形分濃度が４質量％より低いと生産性、及び使用時の取り扱い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。 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 particularly limited, but is based on the total amount of the polyimide precursor and the solvent. Preferably, the content is 4% by mass to 45% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 7% by mass to 30% by mass. When the solid content concentration is lower than 4% by mass, productivity and handling during use may be deteriorated, and when it is higher than 45% by mass, the fluidity of the solution may be lost.
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、特に限定されないが、好ましくは１０００Ｐａ・ｓｅｃ以下、より好ましくは５００Ｐａ・ｓｅｃ以下、さらに好ましくは３００Ｐａ・ｓｅｃ以下、特に好ましくは２００Ｐａ・ｓｅｃ以下であり、好ましくは０．１以上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、流動性がなくなり、金属やガラスなどへの均一な塗布が困難となることがあり、また、溶液粘度が小さすぎると、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易くなったり、用途が制限されたりすることがある。 The solution viscosity at 30 ° C. of the polyimide precursor aqueous solution composition of the present invention is not particularly limited, but is preferably 1000 Pa · sec or less, more preferably 500 Pa · sec or less, still more preferably 300 Pa · sec or less, particularly preferably. It is 200 Pa · sec or less, and preferably 0.1 or more is preferable for handling. If the solution viscosity exceeds 1000 Pa · sec, the fluidity may be lost and uniform application to metal or glass may be difficult. If the solution viscosity is too low, it may sag during application to metal or glass. And repelling are likely to occur, and the application may be limited.
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、水以外の有機溶媒、例えば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よい。すなわち、本発明のポリイミド前駆体水溶液組成物は、ポリイミド前駆体であるポリアミック酸が、ｐＫａが７．５以上の塩基性化合物と共に、水単独、または水の割合が５０質量％以上、好ましくは７０質量％以上、より好ましくは９０質量％以上である水と有機溶媒との混合物である水溶媒（水性溶媒）中に溶解しているものである。 The aqueous polyimide precursor solution composition of the present invention uses an aqueous solvent, but an organic solvent other than water, for example, a known organic solvent used in preparing a polyamic acid is 50% by mass or less, preferably 30% by mass in the total solvent. % Or less, more preferably 10% by mass or less. That is, in the polyimide precursor aqueous solution composition of the present invention, the polyamic acid, which is a polyimide precursor, together with a basic compound having a pKa of 7.5 or more, water alone, or the proportion of water is 50% by mass or more, preferably 70 It is dissolved in an aqueous solvent (aqueous solvent) which is a mixture of water and an organic solvent in an amount of not less than mass%, more preferably not less than 90 mass%.
前記有機溶媒としては、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においては、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、より好ましくは２質量％未満、さらに好ましくは１質量％未満、最も好ましくは水溶媒が水以外の有機溶媒を含まないこと、すなわち水単独溶媒であることが、環境適応性の観点から特に好ましい。 In the polyimide precursor aqueous solution composition of the present invention, the organic solvent content is preferably a solvent having a content of less than 5%, more preferably less than 2% by mass, still more preferably less than 1% by mass, and most preferably water. It is particularly preferable from the viewpoint of environmental adaptability that the solvent does not contain an organic solvent other than water, that is, a water-only solvent.
また、本発明のポリイミド前駆体水溶液組成物の特定の１実施形態においては、組成物中に含有される塩基性化合物として、２−メチルアミノジエタノール、ジエチルアミノ−アセトン、Ｎ−エチルアミノジエタノール、Ｎ−メチルアミノエタノール、２，２−アミノジエタノール、３−ジエチルアミノ−１−プロパノール、アミノ−シクロヘキサン、トリエチルアミンおよびジエタノールアミンが除かれる。 In one specific embodiment of the polyimide precursor aqueous solution composition of the present invention, the basic compound contained in the composition is 2-methylaminodiethanol, diethylamino-acetone, N-ethylaminodiethanol, N- Methylaminoethanol, 2,2-aminodiethanol, 3-diethylamino-1-propanol, amino-cyclohexane, triethylamine and diethanolamine are excluded.
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、更に好ましくは１５０℃〜３５０℃で、０．０１時間〜３０時間、好ましくは０．０１〜１０時間加熱処理することが好ましい。加熱処理時に段階的に温度を上げることも好ましい。 In the polyimide precursor aqueous solution composition of the present invention, a polyimide can be suitably obtained by removing an aqueous 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., still more preferably 150 ° C. to 350 ° C., 0.01 hour to 30 hours. The heat treatment is preferably performed for 0.01 to 10 hours. It is also preferable to raise the temperature stepwise during the heat treatment.
この加熱処理は、常圧下で好適に行うこともできるが、水溶媒を効率よく除去するために減圧下で行ってもよい。また、初期段階で減圧下、比較的低温で加熱処理して脱泡処理してもよい。いきなり加熱処理温度を高くすると、発泡などの不具合が生じて良好な特性を有するポリイミドを得ることができないことがある。 This heat treatment can be suitably performed under normal pressure, but may be performed under reduced pressure in order to efficiently remove the aqueous solvent. Further, defoaming may be performed by heat treatment at a relatively low temperature under reduced pressure in the initial stage. If the heat treatment temperature is suddenly increased, problems such as foaming may occur and polyimide having good characteristics may not be obtained.
本発明のポリイミド前駆体水溶液組成物は、比較的低温（例えば１５０℃〜３００℃、好ましくは１８０℃〜２５０℃）で加熱処理するだけで、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）溶液組成物を用いた場合に較べて遜色ない、優れた特性を有するポリイミドを容易に得ることができる。 The polyimide precursor aqueous solution composition of the present invention can be obtained by simply heat-treating at a relatively low temperature (for example, 150 ° C. to 300 ° C., preferably 180 ° C. to 250 ° C.), and a polyimide precursor (polyamic acid) using an ordinary organic solvent. ) It is possible to easily obtain a polyimide having excellent characteristics that is inferior to the case of using a solution composition.
なお、本発明のポリイミド前駆体水溶液組成物は、得られるポリイミドの用途に応じて、他の添加成分を含有していてもよい。 In addition, the polyimide precursor aqueous solution composition of this invention may contain the other additive component according to the use of the polyimide obtained.
本発明のポリイミド前駆体水溶液組成物を、フレキシブルデバイス用基板、シームレスベルト、その他のフィルムの製造用途に使用する場合は、支持体の表面に塗布或いは吹き付けしてポリイミド前駆体水溶液組成物層からなる塗膜を形成し、そのポリイミド前駆体水溶液組成物を加熱処理してポリイミドフィルムを得る。好ましい方法としては、支持体上にポリイミド前駆体水溶液組成物からなる塗膜を形成し、比較的低温で加熱処理して水溶媒除去を行って自己支持性膜（皮膜の流動が発生しない状態、水溶媒の除去と共に重合及び一部イミド化反応が進んでいる）を形成し、次いで自己支持性膜をそのままの状態、或いは必要に応じて支持体から剥がした状態で加熱処理して脱水・イミド化する方法によってフィルムを好適に得ることができる。ここで用いた「水溶媒除去」或いは「脱水・イミド化」は、当該工程で、それぞれ水溶媒除去のみ或いは脱水・イミド化のみが進行することを意味しない。水溶媒除去工程でも相当程度の脱水・イミド化は進行するし、脱水・イミド化工程でも残存水溶媒の除去が進行する。 When the polyimide precursor aqueous solution composition of the present invention is used for the production of substrates for flexible devices, seamless belts, and other films, the polyimide precursor aqueous solution composition layer is formed by coating or spraying on the surface of a support. A coating film is formed, and the polyimide precursor aqueous solution composition is heat-treated to obtain a polyimide film. As a preferred method, a coating film comprising a polyimide precursor aqueous solution composition is formed on a support, and heat treatment is performed at a relatively low temperature to remove an aqueous solvent, so that a self-supporting film (a state in which the film does not flow, Polymerization and partial imidization reaction proceed with removal of water solvent), and then heat treatment in the state of the self-supporting film as it is or peeled from the support as necessary to dehydrate / imide A film can be suitably obtained by the method of converting into a film. “Water solvent removal” or “dehydration / imidization” used here does not mean that only water solvent removal or only dehydration / imidation proceeds in the step. A considerable amount of dehydration and imidization proceeds even in the water solvent removal step, and removal of the residual water solvent proceeds also in the dehydration and imidization step.
ポリイミド樹脂膜の厚さは、目的によって適宜選択することができるが、フレキシブルデバイス用基板の場合は１〜２０μｍであることが望ましく、シームレスベルトの場合は、通常２０〜２００μｍである。 The thickness of the polyimide resin film can be appropriately selected depending on the purpose, but is preferably 1 to 20 μm in the case of a flexible device substrate, and is usually 20 to 200 μm in the case of a seamless belt.
本発明のポリイミド前駆体水溶液組成物は、電極用バインダーとして、塗料およびその他の用途におけるバインダーとしても好適に使用される。 The polyimide precursor aqueous solution composition of the present invention is also suitably used as a binder for electrodes and as a binder in paints and other applications.
本発明の１態様は、ポリイミド前駆体水溶液組成物を含有する塗料に関する。この場合のポリイミド前駆体水溶液組成物は、以上説明したとおりのｐＫａが７．５以上の塩基性化合物を含有するポリイミド前駆体水溶液組成物であってよいが、ｐＫａが７．５以上の塩基性化合物の代わりにイミダゾール類を含有するポリイミド前駆体水溶液組成物であってもよい。この場合、イミダゾール類とｐＫａが７．５以上の塩基性化合物の両方を含有していてもよい。
イミダゾール類を含有するポリイミド前駆体水溶液組成物は、前記化学式（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カルボキシル基に対して１．６倍モル以上の、イミダゾール類と共に、水溶媒中に均一に溶解してなるポリイミド前駆体水溶液組成物である。
One aspect of the present invention relates to a paint containing a polyimide precursor aqueous solution composition. The polyimide precursor aqueous solution composition in this case may be a polyimide precursor aqueous solution composition containing a basic compound with a pKa of 7.5 or more as described above, but a basicity with a pKa of 7.5 or more. A polyimide precursor aqueous solution composition containing imidazoles instead of the compound may be used. In this case, both imidazoles and a basic compound having a pKa of 7.5 or more may be contained.
The polyimide precursor aqueous solution composition containing imidazoles has a polyamic acid composed of repeating units represented by the chemical formula (1) together with imidazoles having a molar ratio of 1.6 times or more with respect to the carboxyl group of the polyamic acid. A polyimide precursor aqueous solution composition that is uniformly dissolved in a water solvent.
イミダゾール類としては、イミダゾール類（化合物）としては、下記化学式（１０）の化合物を好適に挙げることができる。 As the imidazoles, as the imidazoles (compound), a compound represented by the following chemical formula (10) can be preferably exemplified.
本発明で用いるイミダゾール類としては、２５℃における水に対する溶解度が０．１ｇ／Ｌ以上、特に１ｇ／Ｌ以上であることが好ましい。 As imidazoles used in the present invention, the solubility in water at 25 ° C. is preferably 0.1 g / L or more, particularly preferably 1 g / L or more.
さらに、化学式（１０）のイミダゾール類においては、Ｘ１〜Ｘ４が、それぞれ独立に、水素原子、或いは炭素数が１〜５のアルキル基であって、Ｘ１〜Ｘ４のうち少なくとも２個が、炭素数が１〜５のアルキル基であるイミダゾール類、すなわち置換基として２個以上のアルキル基を有するイミダゾール類がより好ましい。 Furthermore, in the imidazoles of the chemical formula (10), X 1 to X 4 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and at least two of X 1 to X 4 However, imidazoles having 1 to 5 carbon atoms, that is, imidazoles having 2 or more alkyl groups as substituents are more 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、ポリイミド前駆体水溶液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。 Since imidazoles having two or more alkyl groups as substituents have high solubility in water, a polyimide precursor aqueous solution 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.
なお、２５℃に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デ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。 The solubility in water at 25 ° C. means a limit amount (g) at which the substance is dissolved in 1 L (liter) of water at 25 ° C. This value can be easily searched by SciFinder (registered trademark) known as a search service based on a database 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.
イミダゾール類を、ｐＫａが７．５以上の塩基性化合物の代わりに（あるいは塩基性化合物と共に）使用して、既に説明した製造方法と同様にしてポリイミド前駆体水溶液組成物を製造することができる。 A polyimide precursor aqueous solution composition can be produced in the same manner as the production method described above using imidazoles instead of (or with a basic compound) a basic compound having a pKa of 7.5 or more.
ポリイミド前駆体水溶液組成物は、製造されたそのままの状態で使用してもよく、またさらに溶媒（好ましくは水）で希釈して使用してもよい。 The polyimide precursor aqueous solution composition may be used as it is produced, or may be further diluted with a solvent (preferably water).
本発明の塗料（ｃｏａｔｉｎｇ）は、広い概念を有し、塗膜を形成する材料の全てを包含する。塗料は、固体成分として溶解した樹脂成分のみを含有するものであってもよく、また、顔料およびフィラーのような固形物をさらに含有していてもよい。絶縁塗料用途（顔料、フィラーのような固形物を含有しなくてもよい）、着色用途（ラッカー、ペイント、印刷インキ等）、導電性塗料用途、帯電防止処理用途、その他、塗膜を形成する全ての用途を包含する。 The coating of the present invention has a broad concept and encompasses all materials that form a coating. The paint may contain only the resin component dissolved as a solid component, or may further contain a solid material such as a pigment and a filler. Insulating paint use (does not contain solid matter such as pigment and filler), coloring use (lacquer, paint, printing ink, etc.), conductive paint use, antistatic treatment use, etc. Includes all uses.
塗料に含まれる顔料および／またはフィラーは、用途に合わせて適宜選択することができる。塗料（即ちコーティング材料）に含有される固形物は、分野によって、あるいは添加する目的により、顔料と呼ばれたり、フィラーと呼ばれたりするが、本発明において含有することのできる固形物は、一般に顔料またはフィラーと呼ばれるもののどちらであってもよいし、両方を含有させてもよい。目的、用途に合わせて、形状および大きさを、適宜選択して使用することができる。 The pigment and / or filler contained in the paint can be appropriately selected according to the application. The solid contained in the paint (that is, the coating material) is called a pigment or a filler depending on the field or the purpose of addition, but the solid that can be contained in the present invention is generally Either what is called a pigment or a filler may be sufficient, and you may contain both. The shape and size can be appropriately selected and used in accordance with the purpose and application.
導電性塗料用途および静電防止用途では、導電性フィラーとして、通常の導電性もしくは半導電性の微粉末が使用でき、例えばケッチエンブラック、アセチレンブラック等のカーボンブラック、アルミニウムやニッケル等の金属、酸化錫等の酸化金属化合物、チタン酸カリウム等が例示できる。導電性フィラーは単独、あるいは併用して使用してもよい。本発明では、カーボンブラックを導電性フィラーとして使用することが好ましいが、特に、平均一次粒子径が５〜１００ｎｍのものが好ましく、特に１０〜５０ｎｍのものが好ましい。平均一次粒子径が１００ｎｍを超えるものは、機械特性や電気抵抗値の均一性が不十分になり易い傾向がある。 In conductive paint applications and antistatic applications, normal conductive or semiconductive fine powders can be used as conductive fillers, such as carbon blacks such as Ketchen black and acetylene black, metals such as aluminum and nickel, Examples thereof include metal oxide compounds such as tin oxide and potassium titanate. The conductive filler may be used alone or in combination. In the present invention, it is preferable to use carbon black as a conductive filler, but those having an average primary particle diameter of 5 to 100 nm are particularly preferred, and those having 10 to 50 nm are particularly preferred. When the average primary particle size exceeds 100 nm, the uniformity of mechanical properties and electrical resistance tends to be insufficient.
非彩色系（白色系）の顔料、あるいは着色を特に目的としないフィラーとしては、例えば、炭酸カルシウム、非晶質シリカ、非晶質ケイ酸カルシウム、ホワイトカーボン、炭酸バリウム、炭酸マグネシウム、炭酸カルシウム、炭酸亜鉛、酸化亜鉛、酸化アルミニウム、酸化チタン、水酸化アルミニウム、水酸化マグネシウム、硫酸バリウム、タルク、ロウ石、カオリン、クレー、ケイソウ土などの無機顔料、スチレンマイクロボール、ナイロン粒子、尿素−ホルマリン充填剤、ポリエチレン粒子、セルロース充填剤、デンプン粒子、シリコン樹脂粒子などの有機顔料を挙げることができるが、これらに限定されるものではない。 Examples of non-colored (white) pigments or fillers not specifically intended for coloring include, for example, calcium carbonate, amorphous silica, amorphous calcium silicate, white carbon, barium carbonate, magnesium carbonate, calcium carbonate, Filled with inorganic pigments such as zinc carbonate, zinc oxide, aluminum oxide, titanium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, talc, wax, kaolin, clay, diatomaceous earth, styrene microballs, nylon particles, urea-formalin Organic pigments such as an agent, polyethylene particles, cellulose filler, starch particles, and silicone resin particles can be mentioned, but are not limited thereto.
また、着色系の顔料としては、有機着色顔料、無機着色顔料のどちらでもよく、例えば、酸化クロム、チタン酸コバルト、硫化亜鉛、亜鉛粉末、金属粉顔料、鉄黒、黄色酸化鉄、べんがら、黄鉛、カーボンブラック、モリブデートオレンジ、紺青、群青、カドミウム系顔料、フタロシアニン系顔料、キナクリドン系顔料、イソインドリノン系顔料、イソインドリン系顔料、キノフタロン系顔料、ペリレン・ペリノン系顔料、ジオキサジン系顔料、アンサンスロン系顔料、インダンスロン系顔料、建染染料系顔料、塩基性染料系顔料などの有機顔料、アゾ顔料、縮合アゾ顔料などのアゾ系顔料等が挙げられるが、これらに限定されるものではない。 In addition, the coloring pigment may be either an organic coloring pigment or an inorganic coloring pigment. For example, chromium oxide, cobalt titanate, zinc sulfide, zinc powder, metal powder pigment, iron black, yellow iron oxide, red pepper, yellow Lead, carbon black, molybdate orange, bitumen, ultramarine, cadmium pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline pigment, quinophthalone pigment, perylene / perinone pigment, dioxazine pigment, Examples include, but are not limited to, organic pigments such as Ansanthrone pigments, indanthrone pigments, vat dye pigments, basic dye pigments, and azo pigments such as azo pigments and condensed azo pigments. is not.
本発明の塗料は、ポリイミド前駆体水溶液組成物および顔料に加えて、更に必要に応じて分散湿潤剤、皮張り防止剤、紫外線吸収剤、酸化防止剤などの添加剤を添加してもよい。 In addition to the polyimide precursor aqueous solution composition and the pigment, the coating material of the present invention may further contain additives such as a dispersion wetting agent, an anti-skinning agent, an ultraviolet absorber, and an antioxidant as necessary.
塗料の調製には、ポリイミド前駆体水溶液組成物と顔料とを従来公知の分散機を用いて混合し、顔料を分散させることができる。分散機の例としては、限定するものではないが脱泡混練機、ディスパーサー、ホモミキサー、ビーズミル、ボールミル、２本ロール、三本ロール、加圧ニーダー、超音波分散機などを好適に挙げることができる。分散の際に、予め顔料を少量の水と親和性の大きい有機溶媒中に分散させたものをポリイミド前駆体水溶液組成物と混合してもよい。 In preparing the coating material, the aqueous polyimide precursor solution composition and the pigment can be mixed using a conventionally known disperser to disperse the pigment. Examples of the disperser include, but are not limited to, a defoaming kneader, a disperser, a homomixer, a bead mill, a ball mill, a two roll, a three roll, a pressure kneader, and an ultrasonic disperser. Can do. At the time of dispersion, a solution in which a pigment is dispersed in advance in an organic solvent having a high affinity with water may be mixed with the polyimide precursor aqueous solution composition.
顔料の含有量は、用途により適宜調節することが好ましいが、分散媒（ポリイミド前駆体水溶液組成物および、希釈する場合は、希釈溶媒を含む）に対して１〜４０質量％、好ましくは２〜２５質量％の割合で混合して分散させるのが好適である。 The content of the pigment is preferably adjusted appropriately depending on the use, but is 1 to 40% by mass, preferably 2 to 2% with respect to the dispersion medium (including the polyimide precursor aqueous solution composition and the dilution solvent when diluted). It is preferable to mix and disperse at a ratio of 25% by mass.
フィラーの含有量は、ポリイミド前駆体水溶液組成物の固形分濃度に対して０．５〜１００質量％の範囲で含まれることが好ましく、１〜５０質量％の範囲がより好ましく、３〜３０質量％の割合で混合して分散させるのが好適である。 The filler content is preferably included in the range of 0.5 to 100% by mass with respect to the solid content concentration of the polyimide precursor aqueous solution composition, more preferably in the range of 1 to 50% by mass, and 3 to 30% by mass. It is preferable to mix and disperse at a ratio of%.
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。 A method for measuring the characteristics used in the following examples is shown below.
＜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。
<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.
固形分濃度［質量％］＝（ｗ２／ｗ１）×１００ 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。
<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.
対数粘度＝｛ｌｎ（Ｔ１／Ｔ０）｝／０．５ 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.
＜分散性評価＞
顔料および／またはフィラーを含有するポリイミド前駆体水溶液の凝集物のサイズを、グラインドメーター線条法により観測した。凝集物が見られなかったものについては、「なし」とした。
<Dispersibility evaluation>
The size of the aggregate of the polyimide precursor aqueous solution containing the pigment and / or filler was observed by a grindometer method. Those for which no aggregates were found were marked as “none”.
＜付着性試験（クロスカット法）＞
付着性試験は、ＪＩＳ Ｋ ５６００−５−６に準拠して行った。なお、評価は目視により、評価基準（３）に準拠した分類０〜分類５（数字が小さいほど強固に付着している）で示した。
<Adhesion test (cross-cut method)>
The adhesion test was performed according to JIS K 5600-5-6. In addition, evaluation was shown by the classification | category 0-the classification | category 5 based on evaluation criteria (3) by visual observation (it adheres so firmly that a number is small).
分類０：どの格子の目にもはがれがない。
分類１：影響を受ける格子の目が、５％を上回ることはない。
分類２：影響を受ける格子の目が、５％を超えるが１５％を上回ることはない。
分類３：影響を受ける格子の目が、１５％を超えるが３５％を上回ることはない。
分類４：影響を受ける格子の目が、３５％を超えるが６５％を上回ることはない。
分類５：はがれの程度が分類４を超える。
Classification 0: There is no peeling in the eyes of any lattice.
Classification 1: The affected grid eyes do not exceed 5%.
Classification 2: The grid of the affected grid exceeds 5% but does not exceed 15%.
Classification 3: The grid of the affected grid exceeds 15% but does not exceed 35%.
Classification 4: The mesh of the affected grid exceeds 35% but does not exceed 65%.
Category 5: The degree of peeling exceeds Category 4.
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
ｔ−ＤＣＤＡ：ｔｒａｎｓ−ジシクロヘキシル−３，３’，４，４’ −テトラカルボン酸二無水物
ｃ−ＤＣＤＡ：ｃｉｓ−ジシクロヘキシル−３，３’，４，４’ −テトラカルボン酸二無水物
ｓ−ＢＴＡ：３，３’，４，４’−ベンゾフェノンテトラカルボン酸
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）
ｔ−ＣＨＤＡ：ｔｒａｎｓ−１，４−ジアミノシクロへキサン（２５℃における水に対する溶解度：１０００ｇ／Ｌ、分子量：１１４）
ＨＭＤ：１，６−ヘキサメチレンジアミン（２５℃における水に対する溶解度：１０００ｇ／Ｌ、分子量：１１６）
ＤＡＢ：１，４−ジアミノブタン（２５℃における水に対する溶解度：１０００ｇ／Ｌ、分子量：８８）
ＴＰＥ−Ｒ：１，３−ビス（４−アミノフェノキシ）ベンゼン（０．００１８ｇ／Ｌ）
ＥＤＴＡ：エチレンジアミン四酢酸
The abbreviations of the compounds used in the following examples are described.
s-BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride t-DCDA: trans-dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic dianhydride c-DCDA: cis -Dicyclohexyl-3,3 ', 4,4'-tetracarboxylic dianhydride s-BTA: 3,3', 4,4'-benzophenone tetracarboxylic acid PPD: p-phenylenediamine (solubility in water at 25 ° C : 120g / L)
t-CHDA: trans-1,4-diaminocyclohexane (solubility in water at 25 ° C .: 1000 g / L, molecular weight: 114)
HMD: 1,6-hexamethylenediamine (solubility in water at 25 ° C .: 1000 g / L, molecular weight: 116)
DAB: 1,4-diaminobutane (solubility in water at 25 ° C .: 1000 g / L, molecular weight: 88)
TPE-R: 1,3-bis (4-aminophenoxy) benzene (0.0018 g / L)
EDTA: ethylenediaminetetraacetic acid
〔実施例Ａ１〕
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、ピペラジンの２６．７６ｇ（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１２時間撹拌して、固形分濃度９．２質量％、溶液粘度０．１Ｐａ・ｓ、対数粘度０．１５のポリイミド前駆体水溶液を得た。
[Example A1]
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 13.44 g (0.124 mol) of PPD and 26.76 g of piperazine 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 12 hours. The solid content concentration was 9.2% by mass, the solution viscosity was 0.1 Pa · s, and the logarithmic viscosity was 0.15. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．７０ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、ペーストを調製した。ペーストを塗布した銅箔を基板上に固定し、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、厚みが１００μｍの塗膜を作製した。得られた塗膜の付着性試験を実施した。 A paste was prepared by kneading 8.70 g of the obtained polyimide precursor aqueous solution composition (solid content mass after imidization 0.8 g) and 9.2 g of silicon powder of 325 mesh pass so as to be ground in a mortar. The copper foil coated with the paste was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, then placed in a hot air drier under normal pressure, 30 minutes at 80 ° C., 30 minutes at 120 ° C. Heat treatment was performed at 200 ° C. for 10 minutes and then at 250 ° C. for 10 minutes to prepare a coating film having a thickness of 100 μm. An adhesion test of the obtained coating film was performed.
得られたポリイミド前駆体水溶液組成物の特性評価結果及び付着性試験結果を表１に示した（以下の実施例でも同じ）。 The characteristic evaluation results and adhesion test results of the obtained polyimide precursor aqueous solution composition are shown in Table 1 (the same applies to the following examples).
〔実施例Ａ２〕
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−メチルピペラジンの３１．１１ｇ（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１２時間撹拌して、固形分濃度９．８質量％、溶液粘度０．３Ｐａ・ｓ、対数粘度０．１８のポリイミド前駆体水溶液を得た。
[Example A2]
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 introduction / discharge tube, and 13.44 g (0.124 mol) of PPD and 1-methylpiperazine 31.11 g (1.25 equivalents relative 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 12 hours. The solid content concentration was 9.8% by mass, the solution viscosity was 0.3 Pa · s, and the logarithmic viscosity was 0.18. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．１６ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the obtained polyimide precursor aqueous solution composition 8.16 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was produced in the same manner as Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ３〕
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、１，４−ジメチルピペラジンの３５．４７ｇ（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１２時間撹拌して、固形分濃度９．７質量％、溶液粘度０．５Ｐａ・ｓ、対数粘度０．３４のポリイミド前駆体水溶液を得た。
[Example A3]
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 13.44 g (0.124 mol) of PPD and 1,4-dimethyl were added thereto. 35.47 g of piperazine (1.25 equivalents relative 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 12 hours. The solid content concentration was 9.7% by mass, the solution viscosity was 0.5 Pa · s, and the logarithmic viscosity was 0.34. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．２５ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the resulting polyimide precursor aqueous solution composition 8.25 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was prepared in the same manner as Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ４〕
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、１，４−ジエチルピペラジンの４４．１９ｇ（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１２時間撹拌して、固形分濃度９．５質量％、溶液粘度０．８Ｐａ・ｓ、対数粘度０．３７のポリイミド前駆体水溶液を得た。
[Example A4]
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 introduction / discharge tube, and 13.44 g (0.124 mol) of PPD and 1,4-diethyl were added thereto. 44.19 g of piperazine (1.25 equivalents relative 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 12 hours. The solid content concentration was 9.5% by mass, the solution viscosity was 0.8 Pa · s, and the logarithmic viscosity was 0.37. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．４２ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the obtained polyimide precursor aqueous solution composition 8.42 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was produced in the same manner as in Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ５〕
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−アミノエチルピペラジンの４０．１４ｇ（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１２時間撹拌して、固形分濃度９．５質量％、溶液粘度０．５Ｐａ・ｓ、対数粘度０．１９のポリイミド前駆体水溶液を得た。
[Example A5]
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 introduction / discharge tube, and 13.44 g (0.124 mol) of PPD and 1-aminoethylpiperazine were added thereto. Of 40.14 g (1.25 equivalents relative 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 12 hours. The solid content concentration was 9.5% by mass, the solution viscosity was 0.5 Pa · s, and the logarithmic viscosity was 0.19. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．４２ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the obtained polyimide precursor aqueous solution composition 8.42 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was produced in the same manner as in Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ６〕
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、トリメチルアミンの１８．３６ｇ（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１２時間撹拌して、固形分濃度９．７質量％、溶液粘度０．３Ｐａ・ｓ、対数粘度０．３３のポリイミド前駆体水溶液を得た。
[Example A6]
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 13.44 g (0.124 mol) of PPD and 18.36 g of trimethylamine 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 the mixture was stirred at 70 ° C. for 12 hours. The solid content concentration was 9.7% by mass, the solution viscosity was 0.3 Pa · s, and the logarithmic viscosity was 0.33. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．２５ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the resulting polyimide precursor aqueous solution composition 8.25 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was prepared in the same manner as Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ７〕
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、トリエチルアミンの３１．４３ｇ（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１２時間撹拌して、固形分濃度８．９質量％、溶液粘度１０．０Ｐａ・ｓ、対数粘度０．７１のポリイミド前駆体水溶液を得た。
[Example A7]
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 13.44 g (0.124 mol) of PPD and 31.43 g of triethylamine 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 12 hours. The solid content concentration was 8.9% by mass, the solution viscosity was 10.0 Pa · s, and the logarithmic viscosity was 0.71. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．９９ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the resulting polyimide precursor aqueous solution composition 8.99 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was produced in the same manner as Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ８〕
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、トリエタノールアミンの４６．３５ｇ（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１２時間撹拌して、固形分濃度８．９質量％、溶液粘度１．５Ｐａ・ｓ、対数粘度０．２９のポリイミド前駆体水溶液を得た。
[Example A8]
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 introduction / discharge tube, and 13.44 g (0.124 mol) of PPD and 46 of triethanolamine were added thereto. .35 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 70 ° C. for 12 hours. The solid content concentration was 8.9% by mass, the solution viscosity was 1.5 Pa · s, and the logarithmic viscosity was 0.29. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．９９ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the resulting polyimide precursor aqueous solution composition 8.99 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was produced in the same manner as Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ９〕
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、Ｎ−ブチルエチルアミンの３１．４３ｇ（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１２時間撹拌して、固形分濃度９．５質量％、溶液粘度０．１Ｐａ・ｓ、対数粘度０．１７のポリイミド前駆体水溶液を得た。
[Example A9]
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 pipe, and 13.44 g (0.124 mol) of PPD and N-butylethylamine 31.43 g (1.25 equivalents relative 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 12 hours. The solid content concentration was 9.5% by mass, the solution viscosity was 0.1 Pa · s, and the logarithmic viscosity was 0.17. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．４２ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the obtained polyimide precursor aqueous solution composition 8.42 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was produced in the same manner as in Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ１０〕
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、炭酸ナトリウムの３２．９３ｇ（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ｓ−ＢＰＤＡの３６．５６ｇ（０．１２４モル）を加え、７０℃で１２時間撹拌して、固形分濃度９．８質量％、溶液粘度０．２Ｐａ・ｓ、対数粘度０．１２のポリイミド前駆体水溶液を得た。
[Example A10]
450 g of water as a solvent was added 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 32. 93g (1.25 times equivalent with respect to a carboxyl group) was added, and it stirred at 25 degreeC for 1 hour, and made it melt | dissolve. 36.56 g (0.124 mol) of s-BPDA was added to this solution, and the mixture was stirred at 70 ° C. for 12 hours. The solid content concentration was 9.8% by mass, the solution viscosity was 0.2 Pa · s, and the logarithmic viscosity was 0.12. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．１６ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the obtained polyimide precursor aqueous solution composition 8.16 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was produced in the same manner as Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ１１〕
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、炭酸グアニジンの５５．９７ｇ（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１２時間撹拌して、固形分濃度９．９質量％、溶液粘度１．８Ｐａ・ｓ、対数粘度０．２７のポリイミド前駆体水溶液を得た。
[Example A11]
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 introduction / discharge pipe, and 13.44 g (0.124 mol) of PPD and 55. 97 g (1.25 equivalents relative 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 12 hours. The solid content concentration was 9.9% by mass, the solution viscosity was 1.8 Pa · s, and the logarithmic viscosity was 0.27. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．０８ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the resulting polyimide precursor aqueous solution composition (8.08 g) (solid content mass after imidization: 0.8 g), a coating film having a thickness of 100 μm was produced in the same manner as in Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ１２〕
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、モノエタノールアミンの１８．９７ｇ（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１２時間撹拌して、固形分濃度９．８質量％、溶液粘度０．２Ｐａ・ｓ、対数粘度０．１３のポリイミド前駆体水溶液を得た。
[Example A12]
450 g of water as a solvent was added 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 18 of monoethanolamine were added thereto. .97 g (1.25 times equivalent to 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 12 hours. The solid content concentration was 9.8% by mass, the solution viscosity was 0.2 Pa · s, and the logarithmic viscosity was 0.13. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．１６ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the obtained polyimide precursor aqueous solution composition 8.16 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was produced in the same manner as Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ１３〕
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、２−（メチルアミノ）エタノールの２３．３３ｇ（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１２時間撹拌して、固形分濃度９．１質量％、溶液粘度０．３Ｐａ・ｓ、対数粘度０．１４のポリイミド前駆体水溶液を得た。
[Example A13]
450 g of water as a solvent was added 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 2- (methylamino) were added thereto. ) Ethanol (23.33 g) (1.25-fold 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 12 hours. The solid content concentration was 9.1% by mass, the solution viscosity was 0.3 Pa · s, and the logarithmic viscosity was 0.14. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．７９ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the obtained polyimide precursor aqueous solution composition 8.79 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was prepared in the same manner as Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ１４〕
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、Ｎ−ｎ−ブチルアミノエタノールの３６．４１ｇ（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１２時間撹拌して、固形分濃度９．５質量％、溶液粘度０．３Ｐａ・ｓ、対数粘度０．１９のポリイミド前駆体水溶液を得た。
[Example A14]
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 Nn-butyl were added thereto. 36.41 g of aminoethanol (1.25 equivalents relative 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 12 hours. The solid content concentration was 9.5% by mass, the solution viscosity was 0.3 Pa · s, and the logarithmic viscosity was 0.19. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．４２ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the obtained polyimide precursor aqueous solution composition 8.42 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was produced in the same manner as in Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ１５〕
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、ＥＤＴＡの９０．７８ｇ（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１２時間撹拌して、固形分濃度８．７質量％、溶液粘度０．１Ｐａ・ｓ、対数粘度０．１１のポリイミド前駆体水溶液を得た。
[Example A15]
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 90.78 g of EDTA 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 12 hours. The solid content concentration was 8.7% by mass, the solution viscosity was 0.1 Pa · s, and the logarithmic viscosity was 0.11. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物９．２０ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 A coating film having a thickness of 100 μm was prepared in the same manner as in Example A1, using 9.20 g of the obtained polyimide precursor aqueous solution composition (solid content mass after imidization: 0.8 g). The evaluation results are shown in Table 1.
〔実施例Ａ１６〕
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ＤＡＢの１１．５３ｇ（０．１３１モル）と、１−メチルピペラジンの３２．７４ｇ（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３８．４７ｇ（０．１３１モル）を加え、７０℃で１２時間撹拌して、固形分濃度９．３質量％、溶液粘度０．４Ｐａ・ｓ、対数粘度０．１８のポリイミド前駆体水溶液を得た。
[Example A16]
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, and 11.53 g (0.131 mol) of DAB and 1-methylpiperazine 32.74 g (1.25 equivalents relative to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 38.47 g (0.131 mol) of s-BPDA was added and stirred at 70 ° C. for 12 hours. The solid content concentration was 9.3% by mass, the solution viscosity was 0.4 Pa · s, and the logarithmic viscosity was 0.18. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．６０ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the obtained polyimide precursor aqueous solution composition 8.60 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was prepared in the same manner as Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ１７〕
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１３．０５ｇ（０．１２１モル）と、１−メチルピペラジンの３０．２１ｇ（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ｔ−ＤＣＤＡの３６．９５ｇ（０．１２１モル）を加え、７０℃で１２時間撹拌して、固形分濃度９．８質量％、溶液粘度０．２Ｐａ・ｓ、対数粘度０．１７のポリイミド前駆体水溶液を得た。
[Example A17]
450 g of water as a solvent was added to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, and 13.05 g (0.121 mol) of PPD and 1-methylpiperazine 30.21 g (1.25 equivalents relative to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 36.95 g (0.121 mol) of t-DCDA was added and stirred at 70 ° C. for 12 hours to obtain a solid content concentration of 9.8% by mass, a solution viscosity of 0.2 Pa · s, and a logarithmic viscosity of 0.17. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．１６ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the obtained polyimide precursor aqueous solution composition 8.16 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was produced in the same manner as Example A1. The evaluation results are shown in Table 1.
〔実施例Ａ１８〕
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ＨＭＤの１３．７５ｇ（０．１１８モル）と、１−メチルピペラジンの３０．２１ｇ（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ｃ−ＤＣＤＡの３６．２５ｇ（０．１１８モル）を加え、７０℃で１２時間撹拌して、固形分濃度９．０質量％、溶液粘度０．１Ｐａ・ｓ、対数粘度０．１４のポリイミド前駆体水溶液を得た。
[Example A18]
450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, and 13.75 g (0.118 mol) of HMD and 1-methylpiperazine 30.21 g (1.25 equivalents relative to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 36.25 g (0.118 mol) of c-DCDA was added and stirred at 70 ° C. for 12 hours. The solid content concentration was 9.0% by mass, the solution viscosity was 0.1 Pa · s, and the logarithmic viscosity was 0.14. An aqueous polyimide precursor solution was obtained.
得られたポリイミド前駆体水溶液組成物８．８９ｇ（イミド化後の固形分質量０．８ｇ）を使用し、実施例Ａ１と同様にして、厚みが１００μｍの塗膜を作製した。評価結果を表１に示す。 Using the resulting polyimide precursor aqueous solution composition 8.89 g (solid content mass after imidization 0.8 g), a coating film having a thickness of 100 μm was prepared in the same manner as Example A1. The evaluation results 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、ピリジンの２４．５７ｇ（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１２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に示す。
[Comparative Example 1]
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 introduction / discharge tube, and 13.44 g (0.124 mol) of PPD and 24.57 g of pyridine 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 for 12 hours at 70 ° C., but it was not uniformly dissolved and 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、イソキノリンの４０．１２ｇ（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１２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に示す。
[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 40.12 g of isoquinoline 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 for 12 hours at 70 ° C., but it was not uniformly dissolved and 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、ヘキサメチレンテトラミンの４３．５５ｇ（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１２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に示す。
[Comparative Example 3]
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 introduction / discharge tube, and 13.44 g (0.124 mol) of PPD and 43 of hexamethylenetetramine were added thereto. .55 g (1.25 times equivalent to 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 for 12 hours at 70 ° C., but it was not uniformly dissolved and 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ＰＰＤの１３．４４ｇ（０．１２４モル）と、酢酸ナトリウムの２５．４８ｇ（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１２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に示す。
[Comparative Example 4]
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 introduction / discharge tube, and 13.44 g (0.124 mol) of PPD and 25. 48 g (1.25 equivalents relative 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 for 12 hours at 70 ° C., but it was not uniformly dissolved 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、室温でｓ−ＢＴＡ３３３．６ｇ（０．９３１モル）を水１５２０ｇ及びトリエチルアミン１８８ｇからなる溶媒に懸濁させたのち、懸濁液を攪拌しながら、ｍ−キシレンジアミン１２６．８ｇ（０．９３１モル）を徐々に１５分かけて加えた。ジアミンの添加と同時に発熱が見られたので２０℃に保温した。ジアミンの添加後、しばらくすると塩が形成され、懸濁液は褐色の均一溶液となった。このポリイミド前駆体水溶液組成物は、固形分濃度１６．５質量％、溶液粘度０．１Ｐａ・ｓ、対数粘度０．０６であり、モノマーが塩を形成して水に溶解しただけで、重合度は上がらなかった。
[Comparative Example 5]
After suspending 333.6 g (0.931 mol) of s-BTA in a solvent consisting of 1520 g of water and 188 g of triethylamine at room temperature in a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube. While stirring the suspension, 126.8 g (0.931 mol) of m-xylenediamine was gradually added over 15 minutes. Since heat generation was observed simultaneously with the addition of diamine, the temperature was kept at 20 ° C. After a while after the addition of the diamine, a salt was formed and the suspension became a brown homogeneous solution. This polyimide precursor aqueous solution composition has a solid content concentration of 16.5% by mass, a solution viscosity of 0.1 Pa · s, and a logarithmic viscosity of 0.06. Did not go up.
得られたポリイミド前駆体水溶液組成物４．８５ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、ペーストを調製した。ペーストを塗布した銅箔を基板上に固定し、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、厚みが１００μｍの塗膜を作製したが、接着性不良、あるいは発泡によるケイ素粉末の脱落が全面に見られた。部分的に得られた塗膜の付着性試験を実施した。 A paste was prepared by kneading 4.85 g of the obtained polyimide precursor aqueous solution composition (solid content mass after imidization 0.8 g) and 9.2 g of silicon powder of 325 mesh pass so as to be ground in a mortar. The copper foil coated with the paste was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, then placed in a hot air drier under normal pressure, 30 minutes at 80 ° C., 30 minutes at 120 ° C. Heat treatment was performed for 10 minutes at 200 ° C. for 10 minutes and then at 250 ° C. for 10 minutes to prepare a coating film having a thickness of 100 μm. However, adhesion failure or dropping of silicon powder due to foaming was observed on the entire surface. An adhesion test of the partially obtained coating film was performed.
得られたポリイミド前駆体水溶液組成物の特性評価結果及び付着性試験結果を表２に示した。 Table 2 shows the property evaluation results and adhesion test results of the obtained polyimide precursor aqueous solution composition.
〔参考例１〕
次に、参考例として、有機溶媒中で合成したポリイミド前駆体からポリイミド前駆体水溶液組成物を製造した例を示す。
[Reference Example 1]
Next, the example which manufactured the polyimide precursor aqueous solution composition from the polyimide precursor synthesize | combined in the organic solvent as a reference example is shown.
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。 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.
〔塗料の製造例〕
次に、塗料の製造例を示す。
[Production example of paint]
Next, production examples of paints are shown.
〔実施例Ｂ１〕
実施例Ａ４で得られたポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。
[Example B1]
The copper foil coated with the polyimide precursor aqueous solution composition obtained in Example A4 was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air dryer under normal pressure. Then, heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ２〕
実施例Ａ４で得られたポリイミド前駆体水溶液組成物の固形分濃度に対して５質量％のシリカ（電気化学工業社製、ＦＢ−５ＳＤＣ、以下同じ）を脱泡混練機により分散させ、得られたシリカ分散ポリイミド前駆体水溶液組成物の分散性評価を実施した。
[Example B2]
Obtained by dispersing 5% by mass of silica (manufactured by Denki Kagaku Kogyo Co., Ltd., FB-5SDC, hereinafter the same) with a defoaming kneader with respect to the solid content concentration of the polyimide precursor aqueous solution composition obtained in Example A4. Evaluation of dispersibility of the silica-dispersed polyimide precursor aqueous solution composition was performed.
得られたシリカ分散ポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 The copper foil coated with the obtained silica-dispersed polyimide precursor aqueous solution composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure. Heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ３〕
実施例Ａ４で得られたポリイミド前駆体水溶液組成物の固形分濃度に対して５質量％のスメクタイト（コープケミカル社製、ＳＷＮ、以下同じ）を脱泡混練機により分散させ、得られたスメクタイト分散ポリイミド前駆体水溶液組成物の分散性評価を実施した。
[Example B3]
5% by mass of smectite (manufactured by Corp Chemical Co., SWN, hereinafter the same) is dispersed by a defoaming kneader with respect to the solid content concentration of the polyimide precursor aqueous solution composition obtained in Example A4, and the obtained smectite dispersion is obtained. Dispersibility evaluation of the polyimide precursor aqueous solution composition was performed.
得られたスメクタイト分散ポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 The copper foil coated with the obtained smectite-dispersed polyimide precursor aqueous solution composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air dryer under normal pressure. Heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ４〕
実施例Ａ１０で得られたポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。
[Example B4]
The copper foil coated with the polyimide precursor aqueous solution composition obtained in Example A10 was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air dryer under normal pressure. Then, heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ５〕
実施例Ａ１０で得られたポリイミド前駆体水溶液組成物の固形分濃度に対して５質量％の酸化アルミニウム（電気化学工業社製、ＡＳＦＰ−２０）を脱泡混練機により分散させ、得られた酸化アルミニウム分散ポリイミド前駆体水溶液組成物の分散性評価を実施した。
[Example B5]
5% by mass of aluminum oxide (manufactured by Denki Kagaku Kogyo Co., Ltd., ASFP-20) was dispersed by a defoaming kneader with respect to the solid content concentration of the polyimide precursor aqueous solution composition obtained in Example A10, and the resulting oxidation was obtained. Dispersibility evaluation of the aluminum dispersion polyimide precursor aqueous solution composition was performed.
得られた酸化アルミニウム分散ポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 The obtained copper foil coated with the aluminum oxide-dispersed polyimide precursor aqueous solution composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure. Heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ６〕
実施例Ａ１０で得られたポリイミド前駆体水溶液組成物の固形分濃度に対して５質量％のスメクタイトを脱泡混練機により分散させ、得られたスメクタイト分散ポリイミド前駆体水溶液組成物の分散性評価を実施した。
[Example B6]
Dispersion evaluation of the obtained smectite-dispersed polyimide precursor aqueous solution composition was performed by dispersing 5% by mass of smectite with a defoaming kneader with respect to the solid content concentration of the polyimide precursor aqueous solution composition obtained in Example A10. Carried out.
得られたスメクタイト分散ポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 The copper foil coated with the obtained smectite-dispersed polyimide precursor aqueous solution composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air dryer under normal pressure. Heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ７〕
実施例Ａ１２で得られたポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。
[Example B7]
The copper foil coated with the polyimide precursor aqueous solution composition obtained in Example A12 was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure. Then, heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ８〕
実施例Ａ１２で得られたポリイミド前駆体水溶液組成物の固形分濃度に対して５質量％のシリカを脱泡混練機により分散させ、得られたシリカ分散ポリイミド前駆体水溶液組成物の分散性評価を実施した。
[Example B8]
Dispersion evaluation of the obtained silica-dispersed polyimide precursor aqueous solution composition was conducted by dispersing 5% by mass of silica with a defoaming kneader with respect to the solid content concentration of the polyimide precursor aqueous solution composition obtained in Example A12. Carried out.
得られたシリカ分散ポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 The copper foil coated with the obtained silica-dispersed polyimide precursor aqueous solution composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure. Heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ９〕
実施例Ａ１２で得られたポリイミド前駆体水溶液組成物の固形分濃度に対して５質量％のタルク（日本タルク社製、ＳＧ−９５）を脱泡混練機により分散させ、得られたタルク分散ポリイミド前駆体水溶液組成物の分散性評価を実施した。
[Example B9]
The talc-dispersed polyimide obtained by dispersing 5% by mass of talc (manufactured by Nippon Talc Co., Ltd., SG-95) with respect to the solid content concentration of the polyimide precursor aqueous solution composition obtained in Example A12. Dispersibility evaluation of the precursor aqueous solution composition was performed.
得られたタルク分散ポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 After fixing the copper foil coated with the obtained talc-dispersed polyimide precursor aqueous solution composition on the substrate, defoaming and predrying at 25 ° C. under reduced pressure for 30 minutes, and then putting it in a hot air drier under normal pressure, Heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ１０〕
実施例Ａ１７で得られたポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。
[Example B10]
The copper foil coated with the polyimide precursor aqueous solution composition obtained in Example A17 was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air dryer under normal pressure. Then, heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ１１〕
実施例Ａ１７で得られたポリイミド前駆体水溶液組成物の固形分濃度に対して５質量％のシリカを脱泡混練機により分散させ、得られたシリカ分散ポリイミド前駆体水溶液組成物の分散性評価を実施した。
[Example B11]
Dispersion evaluation of the obtained silica-dispersed polyimide precursor aqueous solution composition was performed by dispersing 5% by mass of silica with a defoaming kneader with respect to the solid content concentration of the polyimide precursor aqueous solution composition obtained in Example A17. Carried out.
得られたシリカ分散ポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 The copper foil coated with the obtained silica-dispersed polyimide precursor aqueous solution composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure. Heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ１２〕
実施例Ａ１７で得られたポリイミド前駆体水溶液組成物の固形分濃度に対して５質量％の硫酸バリウム（堺化学工業社製、Ｂ−３０）を脱泡混練機により分散させ、得られた硫酸バリウム分散ポリイミド前駆体水溶液組成物の分散性評価を実施した。
[Example B12]
The sulfuric acid obtained by dispersing 5% by mass of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B-30) with a defoaming kneader with respect to the solid content concentration of the polyimide precursor aqueous solution composition obtained in Example A17. Dispersibility evaluation of the barium-dispersed polyimide precursor aqueous solution composition was performed.
得られた硫酸バリウム分散ポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 The copper foil coated with the obtained barium sulfate-dispersed polyimide precursor aqueous solution composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure. Heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ１３〕
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１４．８６ｇ（０．０７４モル）及びＰＰＤの３．４４ｇ（０．０３２モル）と、１，２−ＤＭＺの２０．４３ｇ（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２１．８３ｇ（０．０７４モル）及びＯＤＰＡの９．８７ｇ（０．０３２モル）を加え、７０℃で４時間撹拌して、固形分濃度９．０質量％、溶液粘度５．２Ｐａ・ｓ、対数粘度０．４６のポリイミド前駆体水溶液組成物を得た。
[Example B13]
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 introduction / discharge tube, and 14.86 g (0.074 mol) of ODA and 3.44 g of PPD ( 0.032 mol) and 20.43 g of 1,2-DMZ (1.25 times equivalent to carboxyl group) were added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 21.83 g (0.074 mol) of s-BPDA and 9.87 g (0.032 mol) of ODPA were added and stirred at 70 ° C. for 4 hours to obtain a solid content of 9.0% by mass. A polyimide precursor aqueous solution composition having a viscosity of 5.2 Pa · s and a logarithmic viscosity of 0.46 was obtained.
得られたポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 The copper foil coated with the obtained polyimide precursor aqueous solution composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier at 80 ° C. under normal pressure. For 30 minutes, at 120 ° C. for 30 minutes, at 200 ° C. for 10 minutes, and then at 250 ° C. for 10 minutes to prepare a coating film for coating having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ１４〕
実施例Ｂ１３で得られたポリイミド前駆体水溶液組成物の固形分濃度に対して５質量％のシリカを脱泡混練機により分散させ、得られたシリカ分散ポリイミド前駆体水溶液組成物の分散性評価を実施した。
[Example B14]
5% by mass of silica was dispersed by a defoaming kneader with respect to the solid content concentration of the polyimide precursor aqueous solution composition obtained in Example B13, and the dispersibility evaluation of the obtained silica-dispersed polyimide precursor aqueous solution composition was performed. Carried out.
得られたシリカ分散ポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 The copper foil coated with the obtained silica-dispersed polyimide precursor aqueous solution composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure. Heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ１５〕
実施例Ｂ１３で得られたポリイミド前駆体水溶液組成物の固形分濃度に対して５質量％のカーボンブラック（電気化学工業社製、デンカブラック粉状品）を脱泡混練機により分散させ、得られたカーボンブラック分散ポリイミド前駆体水溶液組成物の分散性評価を実施した。
[Example B15]
Obtained by dispersing 5% by mass of carbon black (Denka Black powder, manufactured by Denki Kagaku Kogyo Co., Ltd.) with a defoaming kneader with respect to the solid content concentration of the polyimide precursor aqueous solution composition obtained in Example B13. The dispersibility of the carbon black-dispersed polyimide precursor aqueous solution composition was evaluated.
得られたカーボンブラック分散ポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 After fixing the obtained copper foil coated with the carbon black-dispersed polyimide precursor aqueous solution composition on the substrate, defoaming and pre-drying at 25 ° C. for 30 minutes under reduced pressure, and then putting in a hot air drier under normal pressure. Heat treatment was performed at 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then 250 ° C. for 10 minutes to prepare a coating film for paint having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ１６〕
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。
[Example B16]
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.
得られたポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 The copper foil coated with the obtained polyimide precursor aqueous solution composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier at 80 ° C. under normal pressure. For 30 minutes, at 120 ° C. for 30 minutes, at 200 ° C. for 10 minutes, and then at 250 ° C. for 10 minutes to prepare a coating film for coating having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
〔実施例Ｂ１７〕
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。
[Example B17]
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.
得られたポリイミド前駆体水溶液組成物を塗布した銅箔を基板上に固定し、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、厚みが１５μｍの塗料用塗膜を作製した。得られた塗膜の付着性試験を実施した。評価結果を表３に示す。 The copper foil coated with the obtained polyimide precursor aqueous solution composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier at 80 ° C. under normal pressure. For 30 minutes, at 120 ° C. for 30 minutes, at 200 ° C. for 10 minutes, and then at 250 ° C. for 10 minutes to prepare a coating film for coating having a thickness of 15 μm. An adhesion test of the obtained coating film was performed. The evaluation results are shown in Table 3.
本発明によれば、水以外の溶媒を必要とせずに、より環境適応性が高いポリイミド前駆体水溶液組成物を容易に製造できる方法を提供することができる。この製造方法によって、極めて簡便に（直接的に）有機溶媒の含有量が極めて少ないポリイミド前駆体水溶液組成物、特には有機溶媒を含まない水溶媒からなるポリイミド前駆体水溶液組成物を得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, the method which can manufacture easily the polyimide precursor aqueous solution composition with higher environmental adaptability, without requiring solvents other than water can be provided. By this production method, it is possible to obtain a polyimide precursor aqueous solution composition having a very low organic solvent content, particularly a polyimide precursor aqueous solution composition comprising an aqueous solvent not containing an organic solvent, very simply (directly). .
Claims (6)
前記塩基性化合物の使用量が、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、１．２倍当量以上３倍当量未満であり、
水溶媒が、水以外の有機溶媒を含まないことを特徴とするポリイミド前駆体水溶液組成物の製造方法。 In the presence of a basic compound (excluding imidazoles) having a pKa of 7.5 or more measured at 25 ° C. in water using water as a reaction solvent, 2,3 ′, 4,4′-biphenyltetracarboxylic acid A method for producing an aqueous solution composition of a polyimide precursor by reacting an anhydride with a diamine having a solubility in water at 25 ° C. of 0.1 g / L or more ,
The amount of the basic compound used is 1.2 times equivalent or more and less than 3 times equivalent to the carboxyl group of the polyamic acid produced by the reaction of tetracarboxylic dianhydride and diamine,
A method for producing a polyimide precursor aqueous solution composition, wherein the aqueous solvent does not contain an organic solvent other than water .
That the resulting polyimide precursor aqueous solution composition has a logarithmic viscosity of 0.1 or more 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. The manufacturing method of any one of Claims 1-5 characterized by the above-mentioned.
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| JP6011374B2 (en) * | 2013-01-31 | 2016-10-19 | 富士ゼロックス株式会社 | Polyimide precursor composition, method for producing polyimide precursor composition, transfer belt, method for producing transfer belt, transfer belt unit, and image forming apparatus |
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| JP5708778B1 (en) * | 2013-12-16 | 2015-04-30 | 富士ゼロックス株式会社 | Method for producing polyimide precursor composition |
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| JP6314707B2 (en) * | 2014-07-09 | 2018-04-25 | 宇部興産株式会社 | Polyimide precursor composition and method for producing insulating coating layer using the same |
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