JP2014214167A - Method for producing unfired composite film, polyimide-fine particle composite film, and porous polyimide film - Google Patents
Method for producing unfired composite film, polyimide-fine particle composite film, and porous polyimide film Download PDFInfo
- Publication number
- JP2014214167A JP2014214167A JP2013089812A JP2013089812A JP2014214167A JP 2014214167 A JP2014214167 A JP 2014214167A JP 2013089812 A JP2013089812 A JP 2013089812A JP 2013089812 A JP2013089812 A JP 2013089812A JP 2014214167 A JP2014214167 A JP 2014214167A
- Authority
- JP
- Japan
- Prior art keywords
- composite film
- polyimide
- film
- organic solvent
- cleaning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 239000010419 fine particle Substances 0.000 title claims abstract description 65
- 229920001721 polyimide Polymers 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 56
- 238000004140 cleaning Methods 0.000 claims abstract description 55
- 239000004642 Polyimide Substances 0.000 claims abstract description 48
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000002966 varnish Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000010304 firing Methods 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 21
- 230000037303 wrinkles Effects 0.000 abstract description 15
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 35
- 150000004985 diamines Chemical class 0.000 description 27
- -1 polypropylene Polymers 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000002994 raw material Substances 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
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- SEYKENDCALELBV-UHFFFAOYSA-N 1-N'-phenyl-2,3-dihydroindene-1,1-diamine Chemical compound NC1(CCC2=CC=CC=C12)NC1=CC=CC=C1 SEYKENDCALELBV-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 2
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 2
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 2
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-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
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N isobutyl acetate Chemical compound CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture 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
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PPCLPYQKMJUPML-UHFFFAOYSA-N (2-anilinohydrazinyl)benzene Chemical compound C=1C=CC=CC=1NNNC1=CC=CC=C1 PPCLPYQKMJUPML-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- MAPWYRGGJSHAAU-UHFFFAOYSA-N 1,3-bis(4-aminophenyl)urea Chemical compound C1=CC(N)=CC=C1NC(=O)NC1=CC=C(N)C=C1 MAPWYRGGJSHAAU-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- NKIZSFXAIKPBCL-UHFFFAOYSA-N 2,5-dichloro-3,6-dimethylpyrazine Chemical compound CC1=NC(Cl)=C(C)N=C1Cl NKIZSFXAIKPBCL-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- SMDGQEQWSSYZKX-UHFFFAOYSA-N 3-(2,3-dicarboxyphenoxy)phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O SMDGQEQWSSYZKX-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- GDGWSSXWLLHGGV-UHFFFAOYSA-N 3-(4-aminophenyl)-1,1,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC(N)=CC=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 GDGWSSXWLLHGGV-UHFFFAOYSA-N 0.000 description 1
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 1
- PAHZZOIHRHCHTH-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O PAHZZOIHRHCHTH-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- KQIKKETXZQDHGE-FOCLMDBBSA-N 4,4'-diaminoazobenzene Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=C(N)C=C1 KQIKKETXZQDHGE-FOCLMDBBSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- XTEBLARUAVEBRF-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 XTEBLARUAVEBRF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- TYNNEOUATWMCIY-UHFFFAOYSA-N 4-(4-aminophenyl)phosphonoylaniline Chemical compound C1=CC(N)=CC=C1P(=O)C1=CC=C(N)C=C1 TYNNEOUATWMCIY-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- GEYAGBVEAJGCFB-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GEYAGBVEAJGCFB-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- KSNRJOXTTHDGNZ-UHFFFAOYSA-N 4-[4-(4-aminophenyl)-4-methylpent-1-en-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)CC(=C)C1=CC=C(N)C=C1 KSNRJOXTTHDGNZ-UHFFFAOYSA-N 0.000 description 1
- ZONAQPZTLMOIAV-UHFFFAOYSA-N 4-[4-(4-aminophenyl)-4-methylpentan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)CC(C)(C)C1=CC=C(N)C=C1 ZONAQPZTLMOIAV-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- ZFWPKNMXSBDNTG-UHFFFAOYSA-N 4-pent-2-enylaniline Chemical compound CCC=CCC1=CC=C(N)C=C1 ZFWPKNMXSBDNTG-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical class C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 description 1
- SKKKJNPBIGQNEJ-UHFFFAOYSA-N 9h-fluorene-1,9-diamine Chemical class C1=CC(N)=C2C(N)C3=CC=CC=C3C2=C1 SKKKJNPBIGQNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- PKOHJIWQWDODHG-UHFFFAOYSA-N bis[2-[4-(3-aminophenoxy)phenyl]phenyl]methanone Chemical compound Nc1cccc(Oc2ccc(cc2)-c2ccccc2C(=O)c2ccccc2-c2ccc(Oc3cccc(N)c3)cc2)c1 PKOHJIWQWDODHG-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 125000000853 cresyl group Chemical class C1(=CC=C(C=C1)C)* 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 1
- SMEJCQZFRMVYGC-UHFFFAOYSA-N cyclohexane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C(C(O)=O)C1C(O)=O SMEJCQZFRMVYGC-UHFFFAOYSA-N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- GBASTSRAHRGUAB-UHFFFAOYSA-N ethylenetetracarboxylic dianhydride Chemical compound O=C1OC(=O)C2=C1C(=O)OC2=O GBASTSRAHRGUAB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropyl acetate Chemical compound CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- VCCPBPXMXHHRLN-UHFFFAOYSA-N methylsulfinylmethane;propan-2-one Chemical compound CC(C)=O.CS(C)=O VCCPBPXMXHHRLN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- UMSVUULWTOXCQY-UHFFFAOYSA-N phenanthrene-1,2,7,8-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C2C3=CC=C(C(=O)O)C(C(O)=O)=C3C=CC2=C1C(O)=O UMSVUULWTOXCQY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KIWATKANDHUUOB-UHFFFAOYSA-N propan-2-yl 2-hydroxypropanoate Chemical compound CC(C)OC(=O)C(C)O KIWATKANDHUUOB-UHFFFAOYSA-N 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- GQKZRWSUJHVIPE-UHFFFAOYSA-N sec-amyl acetate Natural products CCCC(C)OC(C)=O GQKZRWSUJHVIPE-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B11/00—Cleaning flexible or delicate articles by methods or apparatus specially adapted thereto
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cleaning In General (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
Description
本発明は、シワのない、未焼成複合膜、ポリイミド−微粒子複合膜、及び多孔質ポリイミド膜の製造方法に関する。 The present invention relates to a method for producing an unfired composite film, a polyimide-fine particle composite film, and a porous polyimide film without wrinkles.
近年、リチウムイオン電池のセパレータや燃料電池電解質膜、ガス又は液体の分離用膜、低誘電率材料として多孔質ポリイミドの研究がなされている。 In recent years, research has been conducted on porous polyimides as separators for lithium ion batteries, fuel cell electrolyte membranes, gas or liquid separation membranes, and low dielectric constant materials.
例えば、特定の混合溶剤をポリアミド酸溶液に用い多孔質化する方法、親水性ポリマーを含むポリアミド酸を加熱イミド化した後、親水性ポリマーを取り除き多孔質化する方法、シリカ粒子を含有するポリイミドからシリカを取り除き多孔質化する方法等が公知である（特許文献１〜３参照）。 For example, from a method of making a porous material using a specific mixed solvent in a polyamic acid solution, a method of heat imidizing a polyamic acid containing a hydrophilic polymer and then removing the hydrophilic polymer to make it porous, and from a polyimide containing silica particles A method of removing silica and making it porous is known (see Patent Documents 1 to 3).
なかでも、シリカ粒子を含有するポリイミドからシリカを取り除き多孔質化する方法は均質で緻密な多孔質ポリイミド膜を製造できる有効な手段である。その製造方法において、基板上に上記ポリアミド酸を成膜した後に、プロセス上の要請から、これを一旦剥離することが必要とされる。その際、ポリアミド酸膜の基板からの剥離性を高めるために、使用する基板上には離型剤が予め塗布されるのが通常であるが、ポリアミド酸膜の剥離面にこの離型剤が残存すると、最終的な製品の特性に様々な問題を及ぼすことになる。例えば、次工程でこのようなポリアミド酸膜を焼成すると、ポリイミド膜表面の離型剤が焦げ跡として残り、後の段階で洗浄を行ってもこれを取り去ることができない。 Among them, the method of removing silica from a polyimide containing silica particles to make it porous is an effective means for producing a homogeneous and dense porous polyimide film. In the manufacturing method, after the polyamic acid film is formed on the substrate, it is necessary to peel it once due to a process requirement. At that time, in order to enhance the releasability of the polyamic acid film from the substrate, a release agent is usually applied on the substrate to be used in advance, but this release agent is applied to the release surface of the polyamic acid film. Residuals can cause various problems in the final product characteristics. For example, when such a polyamic acid film is baked in the next step, the release agent on the surface of the polyimide film remains as a burnt mark and cannot be removed even if cleaning is performed at a later stage.
従来、焼成工程に入る前に上記離型剤を除去するために、微粒子を含有するポリアミド酸膜を基板から剥離した後、有機溶剤を用いて離型剤を除く洗浄工程及び有機溶剤を除去する乾燥工程が設けられてきたが、この乾燥工程中に上記ポリアミド酸膜にシワが発生することがあった。そして、上記ポリアミド酸膜に一旦生じたシワは、焼成工程を経た後も残存し、これを取り除くことは困難である。 Conventionally, in order to remove the release agent before entering the firing step, after removing the polyamic acid film containing fine particles from the substrate, the organic solvent is used to remove the release agent and the cleaning step and the organic solvent are removed. Although a drying process has been provided, wrinkles may occur in the polyamic acid film during the drying process. The wrinkles once generated in the polyamic acid film remain even after the baking process, and it is difficult to remove the wrinkles.
シワを有するポリイミド膜を積層して使用した場合、シワの部分に不必要な空間が形成されてしまう。また、微粒子を取り除いてポリイミド膜を多孔質化し、例えば、セパレータとして使用する場合にも、シワの部分に不必要な空間が形成されてしまう等の問題を生じる。 When a polyimide film having wrinkles is laminated and used, an unnecessary space is formed in the wrinkle portion. Further, when the polyimide film is made porous by removing the fine particles and used as a separator, for example, an unnecessary space is formed in the wrinkled portion.
本発明は、上記事情に鑑みてなされたものであり、シワのない、未焼成複合膜、ポリイミド−微粒子複合膜及び多孔質ポリイミド膜を製造できる製造方法を提供することを目的とする。 This invention is made | formed in view of the said situation, and it aims at providing the manufacturing method which can manufacture an unbaking composite film, a polyimide fine particle composite film, and a porous polyimide film without a wrinkle.
本発明者らは、ポリアミド酸又はポリイミドと微粒子とを含有する未焼成複合膜を基板より剥離し、有機溶剤を用いて洗浄する洗浄工程後に、水と水溶性有機溶剤との混合溶剤で上記未焼成複合膜を洗浄することによって、乾燥工程で生じるシワの発生を防止することができることを見出し、本発明を完成するに至った。 The present inventors peel off the unfired composite film containing polyamic acid or polyimide and fine particles from the substrate and wash it with an organic solvent, followed by a mixed solvent of water and a water-soluble organic solvent. It has been found that by washing the fired composite film, generation of wrinkles generated in the drying process can be prevented, and the present invention has been completed.
本発明の第一の態様は、ポリアミド酸又はポリイミドと微粒子とを含有するワニスを、離型層が形成された基板上に塗布して成膜する、未焼成複合膜の成膜工程と、上記未焼成複合膜を基板より剥離して有機溶剤を用いて洗浄する第一洗浄工程と、上記第一洗浄工程で洗浄された未焼成複合膜を、水と水溶性有機溶剤との混合溶剤であって水溶性有機溶剤の質量比が高い第二洗浄液を用いて洗浄する第二洗浄工程と、を有するポリアミド酸又はポリイミドと微粒子とを含有する未焼成複合膜の製造方法である。 According to a first aspect of the present invention, there is provided a film forming step of an unfired composite film, in which a varnish containing polyamic acid or polyimide and fine particles is applied on a substrate on which a release layer has been formed, The first cleaning step in which the unfired composite film is peeled off from the substrate and washed with an organic solvent, and the unfired composite film cleaned in the first washing step is a mixed solvent of water and a water-soluble organic solvent. And a second cleaning step of cleaning with a second cleaning liquid having a high mass ratio of the water-soluble organic solvent, and a method for producing an unfired composite film containing polyamic acid or polyimide and fine particles.
本発明の第二の態様は、ポリアミド酸又はポリイミドと微粒子とを含有するワニスを、離型層が形成された基板上に塗布して成膜する、未焼成複合膜の成膜工程と、上記未焼成複合膜を基板より剥離して有機溶剤を用いて洗浄する第一洗浄工程と、上記第一洗浄工程で洗浄された未焼成複合膜を、水と水溶性有機溶剤との混合溶剤であって水溶性有機溶剤の質量比が高い第二洗浄液を用いて洗浄する第二洗浄工程と、を有する洗浄工程と、上記洗浄工程後の未焼成複合膜を乾燥する乾燥工程と、上記乾燥工程後の未焼成複合膜を焼成する焼成工程と、を有するポリイミド−微粒子複合膜の製造方法である。 A second aspect of the present invention is a film forming step of an unfired composite film, in which a varnish containing polyamic acid or polyimide and fine particles is applied and formed on a substrate on which a release layer is formed; The first cleaning step in which the unfired composite film is peeled off from the substrate and washed with an organic solvent, and the unfired composite film cleaned in the first washing step is a mixed solvent of water and a water-soluble organic solvent. A second cleaning step for cleaning with a second cleaning liquid having a high mass ratio of the water-soluble organic solvent, a drying step for drying the unfired composite film after the cleaning step, and after the drying step And a firing step of firing the unfired composite film. A method for producing a polyimide-fine particle composite film.
本発明の第三の態様は、ポリアミド酸又はポリイミドと微粒子とを含有するワニスを、離型層が形成された基板上に塗布して成膜する、未焼成複合膜の成膜工程と、上記未焼成複合膜を基板より剥離して有機溶剤を用いて洗浄する第一洗浄工程と、上記第一洗浄工程で洗浄された未焼成複合膜を、水と水溶性有機溶剤との混合溶剤であって水溶性有機溶剤の質量比が高い第二洗浄液を用いて洗浄する第二洗浄工程と、を有する洗浄工程と、上記洗浄工程後の未焼成複合膜を乾燥する乾燥工程と、上記乾燥工程後の未焼成複合膜を焼成してポリイミド−微粒子複合膜を得る焼成工程と、上記ポリイミド−微粒子複合膜から微粒子を取り除く微粒子除去工程と、を有する多孔質ポリイミド膜の製造方法である。 According to a third aspect of the present invention, there is provided a film forming step of an unfired composite film, in which a varnish containing polyamic acid or polyimide and fine particles is applied and formed on a substrate on which a release layer is formed; The first cleaning step in which the unfired composite film is peeled off from the substrate and washed with an organic solvent, and the unfired composite film cleaned in the first washing step is a mixed solvent of water and a water-soluble organic solvent. A second cleaning step for cleaning with a second cleaning liquid having a high mass ratio of the water-soluble organic solvent, a drying step for drying the unfired composite film after the cleaning step, and after the drying step And a fine particle removing step of removing fine particles from the polyimide-fine particle composite film by firing the unfired composite film to obtain a polyimide-fine particle composite film.
本発明によれば、シワのない、未焼成複合膜、ポリイミド−微粒子複合膜、及び多孔質ポリイミド膜を製造することができる。 According to the present invention, an unfired composite film, a polyimide-fine particle composite film, and a porous polyimide film free from wrinkles can be produced.
以下、本発明の実施態様について詳細に説明するが、本発明は、以下の実施態様に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. .
［ワニスの製造］
本発明では、まず、ポリアミド酸又はポリイミドと微粒子とを含有するワニスを準備する。ワニスの準備は、所定の微粒子を分散したポリアミド酸又はポリイミドの溶液を製造することにより行う。具体的には、所定の微粒子を予め分散した有機溶剤とポリアミド酸又はポリイミドを任意の比率で混合するか、所定の微粒子を予め分散した有機溶剤中で、ポリアミド酸又はポリイミドを重合することにより行うことができる。
[Manufacture of varnish]
In the present invention, first, a varnish containing polyamic acid or polyimide and fine particles is prepared. The varnish is prepared by producing a polyamic acid or polyimide solution in which predetermined fine particles are dispersed. Specifically, an organic solvent in which predetermined fine particles are dispersed in advance and polyamic acid or polyimide are mixed in an arbitrary ratio, or polyamic acid or polyimide is polymerized in an organic solvent in which predetermined fine particles are dispersed in advance. be able to.
＜微粒子＞
本発明で用いられる微粒子の材質は、ワニスに使用する有機溶剤に不溶なものなら、特に限定されること無く公知のものが採用可能であり、弾性率、耐摩耗性、強度等の向上、熱膨張率の低減等、目的に応じ適宜選択することができる。例えば、無機材料としては、シリカ（二酸化珪素）、酸化チタン、アルミナ（Ａｌ２Ｏ３）等の金属酸化物、有機材料としては、高分子量オレフィン（ポリプロピレン，ポリエチレン等）、ポリスチレン、エポキシ樹脂、セルロース、ポリビニルアルコール、ポリビニルブチラール、ポリエステル、ポリエーテル等の有機高分子微粒子が挙げられる。
<Fine particles>
The material of the fine particles used in the present invention is not particularly limited as long as it is insoluble in the organic solvent used in the varnish, and any known material can be employed, and improvement in elastic modulus, wear resistance, strength, etc., heat It can be appropriately selected according to the purpose, such as reduction of the expansion coefficient. For example, inorganic materials include metal oxides such as silica (silicon dioxide), titanium oxide, and alumina (Al 2 O 3 ), and organic materials include high molecular weight olefins (polypropylene, polyethylene, etc.), polystyrene, epoxy resins, and cellulose. , Organic polymer fine particles such as polyvinyl alcohol, polyvinyl butyral, polyester, and polyether.
多孔質ポリイミド膜の製造を最終目的とする場合、使用する微粒子として好ましいのは、例えば、コロイダルシリカである。なかでも単分散球状シリカ粒子を選択することが、均一で微小な孔を形成するためには好ましい。 When the final purpose is to produce a porous polyimide film, for example, colloidal silica is preferable as the fine particles to be used. Among them, it is preferable to select monodispersed spherical silica particles in order to form uniform and fine pores.
本発明で用いられる微粒子は、真球率が高く、また、粒径分布指数の小さいものが好ましい。これらの条件を備えた微粒子は、ワニス中での分散性に優れ、互いに凝集しない状態で使用することができる。使用する微粒子の粒径（平均直径）としては、例えば、１００〜２０００ｎｍのものを用いることができる。これらの条件を満たすことで、微粒子を取り除いて得られる多孔質膜の孔径を揃えることができるため、特にセパレータとして使用した場合に、印加される電界を均一化でき好ましい。 The fine particles used in the present invention preferably have a high sphericity and a small particle size distribution index. The fine particles having these conditions are excellent in dispersibility in the varnish and can be used in a state where they do not aggregate with each other. As the particle diameter (average diameter) of the fine particles to be used, for example, those having a particle diameter of 100 to 2000 nm can be used. By satisfying these conditions, the pore diameter of the porous film obtained by removing the fine particles can be made uniform, so that the applied electric field can be made uniform, particularly when used as a separator.
＜ポリアミド酸＞
本発明に用いるポリアミド酸は、任意のテトラカルボン酸二無水物とジアミンを重合して得られるものが、特に限定されることなく使用できる。テトラカルボン酸二無水物及びジアミンの使用量は特に限定されないが、テトラカルボン酸二無水物１モルに対して、ジアミンを０．５０〜１．５０モル用いるのが好ましく、０．６０〜１．３０モル用いるのがより好ましく、０．７０〜１．２０モル用いるのが特に好ましい。
<Polyamide acid>
As the polyamic acid used in the present invention, those obtained by polymerizing any tetracarboxylic dianhydride and diamine can be used without any particular limitation. Although the usage-amount of tetracarboxylic dianhydride and diamine is not specifically limited, It is preferable to use 0.50-1.50 mol of diamine with respect to 1 mol of tetracarboxylic dianhydrides, and 0.60-1. It is more preferable to use 30 mol, and it is particularly preferable to use 0.70 to 1.20 mol.
テトラカルボン酸二無水物は、従来からポリアミド酸の合成原料として使用されているテトラカルボン酸二無水物から適宜選択することができる。テトラカルボン酸二無水物は、芳香族テトラカルボン酸二無水物であっても、脂肪族テトラカルボン酸二無水物であってもよいが、得られるポリイミド樹脂の耐熱性の点から、芳香族テトラカルボン酸二無水物を使用することが好ましい。テトラカルボン酸二無水物は、２種以上を組合せて用いてもよい。 The tetracarboxylic dianhydride can be appropriately selected from tetracarboxylic dianhydrides conventionally used as raw materials for synthesizing polyamic acid. The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride. From the viewpoint of the heat resistance of the resulting polyimide resin, the aromatic tetracarboxylic dianhydride may be used. Preference is given to using carboxylic dianhydrides. Tetracarboxylic dianhydride may be used in combination of two or more.
芳香族テトラカルボン酸二無水物の好適な具体例としては、ピロメリット酸二無水物、１，１−ビス（２，３−ジカルボキシフェニル）エタン二無水物、ビス（２，３−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）メタン二無水物、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、２，２，６，６−ビフェニルテトラカルボン酸二無水物、２，２−ビス（３，４−ジカルボキシフェニル）プロパン二無水物、２，２−ビス（２，３−ジカルボキシフェニル）プロパン二無水物、２，２−ビス（３，４−ジカルボキシフェニル）−１，１，１，３，３，３−へキサフルオロプロパン二無水物、２，２−ビス（２，３−ジカルボキシフェニル）−１，１，１，３，３，３−ヘキサフルオロプロパン二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、ビス（３，４−ジカルボキシフェニル）エーテル二無水物、ビス（２，３−ジカルボキシフェニル）エーテル二無水物、２，２’，３，３’−ベンゾフェノンテトラカルボン酸二無水物、４，４−（ｐ−フェニレンジオキシ）ジフタル酸二無水物、４，４−（ｍ−フェニレンジオキシ）ジフタル酸二無水物、１，２，５，６−ナフタレンテトラカルボン二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物、１，２，３，４−ベンゼンテトラカルボン酸二無水物、３，４，９，１０−ペリレンテトラカルボン酸二無水物、２，３，６，７−アントラセンテトラカルボン酸二無水物、１，２，７，８−フェナントレンテトラカルボン酸二無水物、９，９−ビス無水フタル酸フルオレン、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物等が挙げられる。脂肪族テトラカルボン酸二無水物としては、例えば、エチレンテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物、シクロへキサンテトラカルボン酸二無水物、１，２，４，５−シクロへキサンテトラカルボン酸二無水物、１，２，３，４−シクロヘキサンテトラカルボン酸二無水物等が挙げられる。これらの中では、価格、入手容易性等から、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、及びピロメリット酸二無水物が好ましい。また、これらのテトラカルボン酸二無水物は、単独あるいは二種以上混合して用いることもできる。 Preferable specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxy). Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′- Biphenyltetracarboxylic dianhydride, 2,2,6,6-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2 , 3-Dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2 -Bis (2,3-dicarboxy Enyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) Ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 4,4- (p-phenylenedioxy) diphthal Acid dianhydride, 4,4- (m-phenylenedioxy) diphthalic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid di Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride , 2, 3 6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 9,9-bisphthalic anhydride fluorene, 3,3 ′, 4,4′-diphenylsulfone Tetracarboxylic dianhydride etc. are mentioned. Examples of the aliphatic tetracarboxylic dianhydride include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, and the like. Among these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable from the viewpoint of price and availability. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.
ジアミンは、従来からポリアミド酸の合成原料として使用されているジアミンから適宜選択することができる。ジアミンは、芳香族ジアミンであっても、脂肪族ジアミンであってもよいが、得られるポリイミド樹脂の耐熱性の点から、芳香族ジアミンが好ましい。これらのジアミンは、２種以上を組合せて用いてもよい。 The diamine can be appropriately selected from diamines conventionally used as a raw material for synthesizing polyamic acid. The diamine may be an aromatic diamine or an aliphatic diamine, but an aromatic diamine is preferred from the viewpoint of the heat resistance of the resulting polyimide resin. These diamines may be used in combination of two or more.
芳香族ジアミンとしては、フェニル基が１個あるいは２〜１０個程度が結合したジアミノ化合物を挙げることができる。具体的には、フェニレンジアミン及びその誘導体、ジアミノビフェニル化合物及びその誘導体、ジアミノジフェニル化合物及びその誘導体、ジアミノトリフェニル化合物及びその誘導体、ジアミノナフタレン及びその誘導体、アミノフェニルアミノインダン及びその誘導体、ジアミノテトラフェニル化合物及びその誘導体、ジアミノヘキサフェニル化合物及びその誘導体、カルド型フルオレンジアミン誘導体である。 Examples of the aromatic diamine include diamino compounds in which one phenyl group or about 2 to 10 phenyl groups are bonded. Specifically, phenylenediamine and derivatives thereof, diaminobiphenyl compounds and derivatives thereof, diaminodiphenyl compounds and derivatives thereof, diaminotriphenyl compounds and derivatives thereof, diaminonaphthalene and derivatives thereof, aminophenylaminoindane and derivatives thereof, diaminotetraphenyl Compounds and derivatives thereof, diaminohexaphenyl compounds and derivatives thereof, and cardo-type fluorenediamine derivatives.
フェニレンジアミンはｍ−フェニレンジアミン、ｐ−フェニレンジアミン等であり、フェニレンジアミン誘導体としては、メチル基、エチル基等のアルキル基が結合したジアミン、例えば、２，４−ジアミノトルエン、２，４−トリフェニレンジアミン等である。 Phenylenediamine is m-phenylenediamine, p-phenylenediamine, etc., and phenylenediamine derivatives include diamines to which alkyl groups such as methyl group and ethyl group are bonded, such as 2,4-diaminotoluene, 2,4-triphenylene. Diamines and the like.
ジアミノビフェニル化合物は、２つのアミノフェニル基がフェニル基同士で結合したものである。例えば、４，４’−ジアミノビフェニル、４，４’−ジアミノ−２，２’−ビス（トリフルオロメチル）ビフェニル等である。 The diaminobiphenyl compound is a compound in which two aminophenyl groups are bonded to each other. For example, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, and the like.
ジアミノジフェニル化合物は、２つのアミノフェニル基同士が他の基を介して結合したものである。結合はエーテル結合、スルホニル結合、チオエーテル結合、アルキレン又はその誘導体基による結合、イミノ結合、アゾ結合、ホスフィンオキシド結合、アミド結合、ウレイレン結合等である。アルキレン結合は炭素数が１〜６程度のものであり、その誘導体基はアルキレン基の水素原子の１以上がハロゲン原子等で置換されたものである。 The diaminodiphenyl compound is obtained by bonding two aminophenyl groups to each other through another group. The bond is an ether bond, a sulfonyl bond, a thioether bond, a bond by alkylene or a derivative group thereof, an imino bond, an azo bond, a phosphine oxide bond, an amide bond, a ureylene bond, or the like. The alkylene bond has about 1 to 6 carbon atoms, and the derivative group has one or more hydrogen atoms in the alkylene group substituted with halogen atoms or the like.
ジアミノジフェニル化合物の例としては、３，３’−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、４，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルスルホン、３，４’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルホン、３，３’−ジアミノジフェニルメタン、３，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルスルフィド、３，３’−ジアミノジフェニルケトン、３，４’−ジアミノジフェニルケトン、２，２−ビス（ｐ−アミノフェニル）プロパン、２，２’−ビス（ｐ−アミノフェニル）へキサフルオロプロパン、４−メチル−２，４−ビス（ｐ−アミノフェニル）−１−ペンテン、４−メチル−２，４−ビス（ｐ−アミノフェニル）−２−ぺンテン、イミノジアニリン、４−メチル−２，４−ビス（ｐ−アミノフェニル）ペンタン、ビス（ｐ−アミノフェニル）ホスフィンオキシド、４，４’−ジアミノアゾベンゼン、４，４’−ジアミノジフェニル尿素、４，４’−ジアミノジフェニルアミド、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（３−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、ビス［４−（４−アミノフェノキシ）フェニル］スルフォン、ビス［４−（３−アミノフェノキシ）フェニル］スルフォン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン等が挙げられる。 Examples of diaminodiphenyl compounds include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone 3,4′-diaminodiphenyl ketone, 2,2-bis (p-aminophenyl) propane, 2,2′-bis (p-aminophenyl) hexafluoropropane, 4-methyl-2,4-bis ( p-aminophenyl) -1-pentene, 4-methyl-2 4-bis (p-aminophenyl) -2-pentene, iminodianiline, 4-methyl-2,4-bis (p-aminophenyl) pentane, bis (p-aminophenyl) phosphine oxide, 4,4 ′ -Diaminoazobenzene, 4,4'-diaminodiphenylurea, 4,4'-diaminodiphenylamide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl ] Sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophen ) Phenyl] hexafluoropropane, and the like.
これらの中では、価格、入手容易性等から、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、２，４−ジアミノトルエン、及び４，４’−ジアミノジフェニルエーテルが好ましい。 Among these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferable from the viewpoint of price and availability.
ジアミノトリフェニル化合物は、２つのアミノフェニル基と１つのフェニレン基が何れも他の基を介して結合したものであり、他の基は、ジアミノジフェニル化合物と同様のものが選ばれる。ジアミノトリフェニル化合物の例としては、１，３−ビス（ｍ−アミノフェノキシ）ベンゼン、１，３−ビス（ｐ−アミノフェノキシ）ベンゼン、１，４−ビス（ｐ−アミノフェノキシ）ベンゼン等を挙げることができる。 In the diaminotriphenyl compound, two aminophenyl groups and one phenylene group are both bonded via other groups, and the other groups are the same as those of the diaminodiphenyl compound. Examples of diaminotriphenyl compounds include 1,3-bis (m-aminophenoxy) benzene, 1,3-bis (p-aminophenoxy) benzene, 1,4-bis (p-aminophenoxy) benzene, and the like. be able to.
ジアミノナフタレンの例としては、１，５−ジアミノナフタレン及び２，６−ジアミノナフタレンを挙げることができる。 Examples of diaminonaphthalene include 1,5-diaminonaphthalene and 2,6-diaminonaphthalene.
アミノフェニルアミノインダンの例としては、５又は６−アミノ−１−（ｐ−アミノフェニル）−１，３，３−トリメチルインダンを挙げることができる。 Examples of aminophenylaminoindane include 5 or 6-amino-1- (p-aminophenyl) -1,3,3-trimethylindane.
ジアミノテトラフェニル化合物の例としては、４，４’−ビス（ｐ−アミノフェノキシ）ビフェニル、２，２’−ビス［ｐ−（ｐ’−アミノフェノキシ）フェニル］プロパン、２，２’−ビス［ｐ−（ｐ’−アミノフェノキシ）ビフェニル］プロパン、２，２’−ビス［ｐ−（ｍ−アミノフェノキシ）フェニル］ベンゾフェノン等を挙げることができる。 Examples of diaminotetraphenyl compounds include 4,4′-bis (p-aminophenoxy) biphenyl, 2,2′-bis [p- (p′-aminophenoxy) phenyl] propane, 2,2′-bis [ p- (p′-aminophenoxy) biphenyl] propane, 2,2′-bis [p- (m-aminophenoxy) phenyl] benzophenone, and the like.
カルド型フルオレンジアミン誘導体は、９，９−ビスアニリンフルオレン等が挙げられる。 Examples of the cardo type fluoreneamine derivative include 9,9-bisaniline fluorene.
脂肪族ジアミンは、例えば、炭素数が２〜１５程度のものがよく、具体的には、ペンタメチレンジアミン、へキサメチレンジアミン、へプタメチレンジアミン等が挙げられる。 The aliphatic diamine has, for example, about 2 to 15 carbon atoms, and specific examples include pentamethylenediamine, hexamethylenediamine, and heptamethylenediamine.
なお、これらのジアミンの水素原子がハロゲン原子、メチル基、メトキシ基、シアノ基、フェニル基等の群より選択される少なくとも１種の置換基により置換された化合物であってもよい。 A compound in which the hydrogen atom of these diamines is substituted with at least one substituent selected from the group such as a halogen atom, a methyl group, a methoxy group, a cyano group, and a phenyl group may be used.
本発明で用いられる、ポリアミド酸を製造する手段に特に制限はなく、例えば、有機溶剤中で酸、ジアミン成分を反応させる方法等の公知の手法を用いることができる。 There is no restriction | limiting in particular in the means to manufacture a polyamic acid used by this invention, For example, well-known methods, such as the method of making an acid and a diamine component react in an organic solvent, can be used.
テトラカルボン酸二無水物とジアミンとの反応は、通常、有機溶剤中で行われる。テトラカルボン酸二無水物とジアミンとの反応に使用される有機溶剤は、テトラカルボン酸二無水物及びジアミンを溶解させることができ、テトラカルボン酸二無水物及びジアミンと反応しないものであれば特に限定されない。有機溶剤は単独で又は２種以上を混合して用いることができる。 Reaction of tetracarboxylic dianhydride and diamine is normally performed in an organic solvent. The organic solvent used for the reaction of the tetracarboxylic dianhydride and the diamine is particularly capable of dissolving the tetracarboxylic dianhydride and the diamine and not reacting with the tetracarboxylic dianhydride and the diamine. It is not limited. An organic solvent can be used individually or in mixture of 2 or more types.
テトラカルボン酸二無水物とジアミンとの反応に用いる有機溶剤の例としては、Ｎ−メチル−２−ピロリドン、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，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ−メチルカプロラクタム、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルウレア等の含窒素極性溶剤；β−プロピオラクトン、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、γ−カプロラクトン、ε−カプロラクトン等のラクトン系極性溶剤；ジメチルスルホキシド；アセトニトリル；乳酸エチル、乳酸ブチル等の脂肪酸エステル類；ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジオキサン、テトラヒドロフラン、メチルセルソルブアセテート、エチルセルソルブアセテート等のエーテル類；クレゾール類等のフェノール系溶剤が挙げられる。これらの有機溶剤は単独あるいは２種以上を混合して用いることができる。有機溶剤の使用量に特に制限はないが、生成するポリアミド酸の含有量が５〜５０質量％とするのが望ましい。 Examples of the organic solvent used for the reaction of tetracarboxylic dianhydride and diamine include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N Nitrogen-containing polar solvents such as N, N-diethylformamide, N-methylcaprolactam, N, N, N ′, N′-tetramethylurea; β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone Lactone polar solvents such as γ-caprolactone and ε-caprolactone; dimethyl sulfoxide; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve acetate, ethyl Ethers such as cellosolve acetate; include phenolic solvents cresols, and the like. These organic solvents can be used alone or in admixture of two or more. Although there is no restriction | limiting in particular in the usage-amount of an organic solvent, It is desirable that content of the polyamic acid to produce shall be 5-50 mass%.
これらの有機溶剤の中では、生成するポリアミド酸の溶解性の観点から、Ｎ−メチル−２−ピロリドン、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，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ−メチルカプロラクタム、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルウレア等の含窒素極性溶剤が好ましい。 Of these organic solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, Nitrogen-containing polar solvents such as N-diethylformamide, N-methylcaprolactam, N, N, N ′, N′-tetramethylurea are preferred.
重合温度は一般的には−１０〜１２０℃、好ましくは５〜３０℃である。重合時間は使用する原料組成により異なるが、通常は３〜２４Ｈｒ（時間）である。また、このような条件下で得られるポリアミド酸溶液の固有粘度は、好ましくは１０００〜１０万ｃＰ（センチポアズ）、より一層好ましくは５０００〜７万ｃＰの範囲である。 The polymerization temperature is generally -10 to 120 ° C, preferably 5 to 30 ° C. The polymerization time varies depending on the raw material composition to be used, but is usually 3 to 24 Hr (hour). The intrinsic viscosity of the polyamic acid solution obtained under such conditions is preferably in the range of 1000 to 100,000 cP (centipoise), and more preferably in the range of 5000 to 70,000 cP.
＜ポリイミド＞
本発明に用いるポリイミドは、本発明のワニスに使用する有機溶剤に溶解可能で、側鎖にカルボキシ基等の縮合可能な官能基を有する可溶性ポリイミドなら、その構造や分子量に限定されることなく、公知のものが使用できる。
<Polyimide>
The polyimide used in the present invention is soluble in the organic solvent used in the varnish of the present invention, and is a soluble polyimide having a condensable functional group such as a carboxy group in the side chain, without being limited to its structure and molecular weight, A well-known thing can be used.
有機溶剤に可溶なポリイミドとするために、主鎖に柔軟な屈曲構造を導入するためのモノマーの使用、例えば、エチレジアミン、ヘキサメチレンジアミン、１，４−ジアミノシクロヘキサン、１，３−ジアミノシクロヘキサン、４，４’−ジアミノジシクロヘキシルメタン等の脂肪族ジアミン；ポリオキシエチレンジアミン、ポリオキシプロピレンジアミン、ポリオキシブチレンジアミン等のポリオキシアルキレンジアミン；ポリシロキサンジアミン；２−メチルー１，４−フェニレンジアミン、ｏ−トリジン、ｍ−トリジン、３，３’−ジメトキシベンジジン、４，４’−ジアミノベンズアニリド等の芳香族ジアミン；２，３，３’，４’−オキシジフタル酸無水物、３，４，３’，４’−オキシジフタル酸無水物、２，２−ビス（４−ヒドロキシフェニル）プロパンジベンゾエート−３，３’，４，４’−テトラカルボン酸二無水物等の使用が有効である。また、有機溶剤への溶解性を向上する官能基を有するモノマーの使用、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−トリフルオロメチル−１，４−フェニレンジアミン等のフッ素化ジアミンを使用することも有効である。更に、上記ポリイミドの溶解性を向上するためのモノマーに加えて、溶解性を阻害しない範囲で、上記ポリアミド酸の欄に記したものと同じモノマーを併用することもできる。 Use of a monomer to introduce a flexible bending structure into the main chain in order to obtain a polyimide soluble in an organic solvent, such as ethylenediamine, hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, Aliphatic diamines such as 4,4′-diaminodicyclohexylmethane; polyoxyalkylene diamines such as polyoxyethylene diamine, polyoxypropylene diamine, and polyoxybutylene diamine; polysiloxane diamines; 2-methyl-1,4-phenylene diamine, o- Aromatic diamines such as toridine, m-tolidine, 3,3′-dimethoxybenzidine, 4,4′-diaminobenzanilide; 2,3,3 ′, 4′-oxydiphthalic anhydride, 3,4,3 ′, 4′-oxydiphthalic anhydride, 2,2-bis (4- Rokishifeniru) propane dibenzoate-3,3 ', use of such 4,4'-tetracarboxylic dianhydride is valid. In addition, use of a monomer having a functional group that improves solubility in an organic solvent, for example, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2-trifluoromethyl-1,4 -It is also effective to use a fluorinated diamine such as phenylenediamine. Furthermore, in addition to the monomer for improving the solubility of the polyimide, the same monomers as those described in the column for the polyamic acid can be used in combination as long as the solubility is not inhibited.
本発明で用いられる、有機溶剤に溶解可能なポリイミドを製造する手段に特に制限はなく、例えば、ポリアミド酸を化学イミド化又は加熱イミド化させ、有機溶剤に溶解させる方法等の公知の手法を用いることができる。そのようなポリイミドとしては、脂肪族ポリイミド（全脂肪族ポリイミド）、芳香族ポリイミド等を挙げることができ、芳香族ポリイミドが好ましい。芳香族ポリイミドとしては、式（１）で示す繰り返し単位を有するポリアミド酸を熱又は化学的に閉環反応によって取得したもの、若しくは式（２）で示す繰り返し単位を有するポリイミドを溶媒に溶解したものでよい。式中Ａｒはアリール基を示す。
本発明のワニスは、予め微粒子が分散した有機溶剤とポリアミド酸又はポリイミドを任意の比率で混合するか、微粒子を予め分散した有機溶剤中でテトラカルボン酸二無水物及びジアミンを重合してポリアミド酸とするか、更にイミド化してポリイミドとすることで製造でき、最終的に、その粘度を３００〜１５００ｃＰとすることが好ましく、４００〜７００ｃＰの範囲がより好ましい。ワニスの粘度がこの範囲内であれば、均一に成膜をすることが可能である。 The varnish of the present invention is prepared by mixing an organic solvent in which fine particles are dispersed in advance with polyamic acid or polyimide in an arbitrary ratio, or polymerizing tetracarboxylic dianhydride and diamine in an organic solvent in which fine particles are dispersed in advance. Or can be manufactured by further imidizing to a polyimide, and finally the viscosity is preferably 300 to 1500 cP, more preferably 400 to 700 cP. If the viscosity of the varnish is within this range, it is possible to form a film uniformly.
上記ワニスには、微粒子とポリアミド酸又はポリイミドを、焼成してポリイミド−微粒子複合膜とした場合において、微粒子の材質が前記無機材料の場合は微粒子／ポリイミドの比率が２〜６（質量比）となるように微粒子とポリアミド酸又はポリイミドとを混合するとよい。３〜５（質量比）とすることが、更に好ましい。微粒子の材質が前記有機材料の場合は微粒子／ポリイミドの比率が１〜３．５（質量比）となるように微粒子とポリアミド酸又はポリイミドとを混合するとよい。１．２〜３（質量比）とすることが、更に好ましい。また、ポリイミド−微粒子複合膜とした際に微粒子／ポリイミドの体積比率が１．５〜４．５となるように微粒子とポリアミド酸又はポリイミドとを混合するとよい。１．８〜３（体積比）とすることが更に好ましい。ポリイミド−微粒子複合膜とした際に微粒子／ポリイミドの質量比又は体積比が下限値以上であれば、セパレータとして適切な密度の孔を得ることができ、上限値以下であれば、粘度の増加や膜中のひび割れ等の問題を生じることなく安定的に成膜することができる。 In the varnish, when fine particles and polyamic acid or polyimide are baked to form a polyimide-fine particle composite film, the fine particle / polyimide ratio is 2 to 6 (mass ratio) when the fine particle material is the inorganic material. The fine particles and polyamic acid or polyimide may be mixed so as to be. More preferably, it is 3-5 (mass ratio). When the material of the fine particles is the organic material, the fine particles and polyamic acid or polyimide may be mixed so that the fine particle / polyimide ratio is 1 to 3.5 (mass ratio). It is still more preferable to set it as 1.2-3 (mass ratio). Moreover, when it is set as a polyimide-microparticle composite film, it is good to mix a microparticle and a polyamic acid or a polyimide so that the volume ratio of microparticles / polyimide may be 1.5-4.5. More preferably, it is 1.8-3 (volume ratio). When the fine particle / polyimide mass ratio or volume ratio is equal to or higher than the lower limit when the polyimide-fine particle composite film is obtained, pores having an appropriate density as a separator can be obtained. It is possible to form a film stably without causing problems such as cracks in the film.
本発明のワニスには、上記した成分のほかに、帯電防止、難燃性付与、低温焼成化等を目的とし、帯電防止剤、難燃剤、化学イミド化剤、縮合剤等、適宜、公知の成分を必要に応じて含有させることができる。 In addition to the components described above, the varnish of the present invention has an antistatic agent, a flame retardant, a chemical imidizing agent, a condensing agent, etc. as appropriate for the purpose of antistatic, imparting flame retardancy, low-temperature baking, etc. Ingredients can be included as required.
［未焼成複合膜の製造］
ポリアミド酸又はポリイミドと微粒子とを含有する未焼成複合膜の成膜は、離型層を設けた基板上へ上記のワニスを塗布し、常圧又は真空下で０〜５０℃、好ましくは常圧１０〜３０℃で乾燥して行う。
[Production of unfired composite film]
The unfired composite film containing polyamic acid or polyimide and fine particles is formed by applying the above varnish on a substrate provided with a release layer, and at 0 to 50 ° C., preferably at normal pressure under normal pressure or vacuum. Dry at 10-30 ° C.
上記離型層は、基板上に離型剤を塗布して乾燥あるいは焼き付けを行って作製することができる。ここで使用される離型剤は、アルキルリン酸アンモニウム塩系、フッ素系又はシリコーン等の公知の離型剤が特に制限なく使用可能である。上記乾燥したポリアミド酸又はポリイミドと微粒子とを含有する未焼成複合膜を基板より剥離する際、未焼成複合膜の剥離面にわずかながら離型剤が残存する。この残存した離型剤は、フィルム表面の濡れ性や電気特性に大きく影響を及ぼすためこれを取り除く必要がある。 The release layer can be produced by applying a release agent on a substrate and drying or baking. As the release agent used here, known release agents such as alkyl phosphate ammonium salt, fluorine-based or silicone can be used without particular limitation. When the unfired composite film containing the dried polyamic acid or polyimide and fine particles is peeled off from the substrate, a release agent remains slightly on the peeled surface of the unfired composite film. This remaining mold release agent has a great influence on the wettability and electrical characteristics of the film surface, so it is necessary to remove it.
そこで、本発明では、上記基板より剥離した未焼成複合膜を、有機溶剤を用いて洗浄する（第一洗浄工程）。用いる有機溶剤は、離型剤を溶解し、未焼成複合膜を溶解又は膨潤させないものであれば、特に限定なく使用することができる。例えば、メチルアルコール、エチルアルコール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、２−メチル−１−プロパノール、１−ペンタノール、２−ペンタノール、４−メチル−２−ペンタノール、１，１−ジメチルエタノール、２，２−ジメチル−１−プロパノール、テトラヒドロフルフリルアルコール等のアルコール類；エチレングルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコール等のグリコール類；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−メチルピロリドン、ジメチルスルホキシドアセトン、２−ブタノン、４−ヘプタノン、２−ペンタノン、２−ヘキサノン、４−メチル−２−ペンタノン、２−ヘプタノン、シクロヘキサノン、メチルシクロヘキサノン、メシチルオキシド等のケトン類；酢酸メチル、酢酸エチル、酢酸プロピル、酢酸１−メチルエチル、酢酸ブチル、酢酸１−メチルプロピル、酢酸２−メチルプロピル、酢酸３−メトキシブチル、酢酸１，３−ジメチルブチル、酢酸ペンチル、酢酸１−メチルブチル、酢酸３−メチルブチル、プロピオン酸ブチル、乳酸１−メチルエチル等のエステル類；炭酸ジエチル等のカーボネート類；セロソルブ、メチルセロソルブ、ジエチルセロソルブ、イソプロピルセロソルブ、セロソルブアセテート、メチルセロソルブアセテート等のセルソルブ類；フルフラール、モノクロルベンゼン等の芳香族類；が挙げられる。これらの中でも、アルコール類が好ましい。また、溶剤の沸点は、６０〜１５０℃であることが好ましい。洗浄の方法としては、洗浄液にフィルムを浸漬した後取り出す方法、シャワー洗浄する方法等の公知の方法から選択することができる。 Therefore, in the present invention, the unfired composite film peeled from the substrate is cleaned using an organic solvent (first cleaning step). The organic solvent to be used can be used without particular limitation as long as it dissolves the release agent and does not dissolve or swell the unfired composite film. For example, methyl alcohol, ethyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 4-methyl-2-pentanol Alcohols such as 1,1-dimethylethanol, 2,2-dimethyl-1-propanol and tetrahydrofurfuryl alcohol; glycols such as ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and diethylene glycol; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide acetone, 2-butanone, 4-heptanone, 2-pentanone, 2-hexanone, 4-methyl-2-pentanone, 2-hept Ketones such as non, cyclohexanone, methylcyclohexanone, mesityl oxide; methyl acetate, ethyl acetate, propyl acetate, 1-methylethyl acetate, butyl acetate, 1-methylpropyl acetate, 2-methylpropyl acetate, 3-methoxybutyl acetate 1,3-dimethylbutyl acetate, pentyl acetate, 1-methylbutyl acetate, 3-methylbutyl acetate, butyl propionate, 1-methylethyl lactate, etc .; carbonates such as diethyl carbonate; cellosolve, methyl cellosolve, diethyl cellosolve , Cellosolves such as isopropyl cellosolve, cellosolve acetate and methyl cellosolve acetate; aromatics such as furfural and monochlorobenzene. Among these, alcohols are preferable. Moreover, it is preferable that the boiling point of a solvent is 60-150 degreeC. The washing method can be selected from known methods such as a method of taking out a film after immersing it in a washing solution, and a method of shower washing.
更に、本発明では、第一洗浄工程後の未焼成複合膜をそのまま乾燥するのではなく、水と水溶性有機溶剤との混合溶剤（第二洗浄液）を用いて洗浄する第二洗浄工程を設け、これを経た後に乾燥を行う。ここでとられる洗浄の方法は、上記第一洗浄工程にて説明したものから適宜に選択することができる。 Furthermore, the present invention provides a second cleaning step in which the unfired composite film after the first cleaning step is not dried as it is, but is cleaned using a mixed solvent (second cleaning solution) of water and a water-soluble organic solvent. After this, drying is performed. The cleaning method taken here can be appropriately selected from those described in the first cleaning step.
第二洗浄液に用いる水溶性有機溶剤としては、第一洗浄工程と同様、未焼成複合膜を溶解又は膨潤させないものであれば、特に限定なく使用することができる。例えば、上記第一洗浄工程で使用する溶媒のうち水溶性のものが好ましく、中でもメチルアルコール、エチルアルコール、プロピルアルコール等のアルコール類が好ましく使用できる。 As the water-soluble organic solvent used in the second cleaning liquid, as long as it does not dissolve or swell the unfired composite film, it can be used without particular limitation as in the first cleaning step. For example, water-soluble solvents are preferable among the solvents used in the first washing step, and alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol can be preferably used.
このとき、第二洗浄液中の水溶性有機溶剤の質量比を、水より高くすることを要する。水溶性有機溶剤の比がこの範囲であれば、乾燥工程中の未焼成複合膜のシワ発生を抑えることができる。例えば、水と水溶性有機溶剤の質量比（水：水溶性有機溶剤）は、４９：５１〜５：９５であることが好ましい。更に好ましくは、４５：５５〜１０：９０である。 At this time, it is necessary to make the mass ratio of the water-soluble organic solvent in the second cleaning liquid higher than that of water. If the ratio of the water-soluble organic solvent is within this range, generation of wrinkles in the unfired composite film during the drying process can be suppressed. For example, the mass ratio of water to the water-soluble organic solvent (water: water-soluble organic solvent) is preferably 49:51 to 5:95. More preferably, it is 45: 55-10: 90.
使用した洗浄液の除去を目的として、第二洗浄工程後の未焼成複合膜をそのまま乾燥してもよいが、水と水溶性有機溶剤との混合溶剤を用いて、更に複数回洗浄を繰り返し行ってもよい。その際は、第二洗浄液の水と水溶性有機溶剤の質量比とは異なるものを使用することができる。 For the purpose of removing the used cleaning solution, the unfired composite film after the second cleaning step may be dried as it is, but using a mixed solvent of water and a water-soluble organic solvent, the cleaning is further repeated several times. Also good. In that case, what is different from the mass ratio of the water and the water-soluble organic solvent of a 2nd washing | cleaning liquid can be used.
上記未焼成複合膜を乾燥するには、洗浄後の未焼成複合膜を室温で風乾する、恒温槽中で適切な設定温度まで加温する等、公知の方法が制限されることなく適用できる。例えば、未焼成複合膜の端部をＳＵＳ製の型枠等に固定し変形を防ぐ方法を採ることもできる。 In order to dry the unfired composite film, known methods such as air-drying the washed unfired composite film at room temperature or heating to an appropriate set temperature in a thermostatic bath can be applied without limitation. For example, a method of preventing deformation by fixing the end of the unfired composite film to a SUS formwork or the like can also be adopted.
［ポリイミド−微粒子複合膜の製造（焼成工程）］
上記乾燥後の未焼成複合膜に加熱による後処理（焼成）を行ってポリイミドと微粒子とからなる複合膜（ポリイミド−微粒子複合膜）とすることができる。焼成工程においてはイミド化を完結させることが好ましい。
[Production of polyimide-fine particle composite film (firing process)]
The dried unfired composite film can be post-treated (fired) by heating to obtain a composite film (polyimide-fine particle composite film) composed of polyimide and fine particles. In the firing step, it is preferable to complete imidization.
焼成温度は、未焼成複合膜に含有されるポリアミド酸又はポリイミドの構造や縮合剤の有無によっても異なるが、１２０〜３７５℃が好ましく、更に好ましくは１５０〜３５０℃である。 The firing temperature varies depending on the structure of the polyamic acid or polyimide contained in the unfired composite film or the presence or absence of a condensing agent, but is preferably 120 to 375 ° C, more preferably 150 to 350 ° C.
焼成を行うには、必ずしも乾燥工程と明確に工程を分ける必要はなく、例えば、３７５℃で焼成を行う場合、室温〜３７５℃までを３時間で昇温させた後、３７５℃で２０分間保持させる方法や室温から５０℃刻みで段階的に３７５℃まで昇温（各ステップ２０分保持）し、最終的に３７５℃で２０分保持させる等の段階的な乾燥−熱イミド化法を用いることもできる。その際、未焼成複合膜の端部をＳＵＳ製の型枠等に固定し変形を防ぐ方法を採ってもよい。 For firing, it is not always necessary to clearly separate the process from the drying process. For example, when firing at 375 ° C., the temperature is raised from room temperature to 375 ° C. in 3 hours and then held at 375 ° C. for 20 minutes. Use a stepwise drying-thermal imidization method such as increasing the temperature from room temperature to 375 ° C in steps of 50 ° C (holding 20 minutes for each step) and finally holding at 375 ° C for 20 minutes. You can also. At that time, a method may be employed in which the end of the unfired composite film is fixed to a SUS mold or the like to prevent deformation.
できあがったポリイミド−微粒子複合膜の膜厚は、例えばマイクロメータ等で複数の箇所の厚さを測定し平均することで求めることができる。どのような平均膜厚が好ましいかは、ポリイミド−微粒子複合膜又は多孔質ポリイミド膜の用途によって異なるが、例えば、セパレータ等に使用する場合は、５〜５００μｍであることが好ましく、１０〜１００μｍであることが更に好ましい。 The film thickness of the completed polyimide-fine particle composite film can be obtained by measuring and averaging the thickness of a plurality of locations with, for example, a micrometer. What average film thickness is preferable depends on the use of the polyimide-fine particle composite film or the porous polyimide film, but for example, when used for a separator or the like, it is preferably 5 to 500 μm, and 10 to 100 μm. More preferably it is.
［ポリイミド−微粒子複合膜の多孔化（微粒子除去工程）］
ポリイミド−微粒子複合膜から、微粒子を適切な方法を選択して除去することにより、微細孔を有する多孔質ポリイミド膜を再現性よく製造することができる。例えば、微粒子として、シリカを採用した場合、ポリイミド−微粒子複合膜を低濃度のフッ化水素水（ＨＦ）等によりシリカを溶解除去することで、多孔質とすることが可能である。
[Porosification of polyimide-particle composite film (particle removal step)]
By removing fine particles from the polyimide-fine particle composite film by selecting an appropriate method, a porous polyimide film having fine pores can be produced with good reproducibility. For example, when silica is employed as the fine particles, the polyimide-fine particle composite film can be made porous by dissolving and removing silica with a low concentration of hydrogen fluoride water (HF) or the like.
［多孔質ポリイミド膜の用途］
本発明の製造方法で作製した多孔質ポリイミド膜は、リチウムイオン電池のセパレータのほか、燃料電池電解質膜、ガス又は液体の分離用膜、低誘電率材料として使用することが可能である。
[Use of porous polyimide membrane]
The porous polyimide membrane produced by the production method of the present invention can be used as a fuel cell electrolyte membrane, a gas or liquid separation membrane, and a low dielectric constant material, in addition to a lithium ion battery separator.
以下、実施例を示して本発明を更に具体的に説明するが、本発明の範囲は、これらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, the scope of the present invention is not limited to these Examples.
実施例及び比較例では、以下に示すテトラカルボン酸二無水物、ジアミン、有機溶剤、微粒子、及び縮合剤を用いた。
・テトラカルボン酸二無水物：ピロメリット酸二無水物
・ジアミン：４，４’−ジアミノジフェニルエーテル
・有機溶剤：Ｎ，Ｎ−ジメチルアセトアミド
・微粒子
シリカ：７００ｎｍシリカ
In Examples and Comparative Examples, the following tetracarboxylic dianhydrides, diamines, organic solvents, fine particles, and condensing agents were used.
・ Tetracarboxylic dianhydride: pyromellitic dianhydride ・ Diamine: 4,4′-diaminodiphenyl ether ・ Organic solvent: N, N-dimethylacetamide ・ Fine particle Silica: 700 nm silica
＜実施例１＞
［ワニスの調製］
撹拌機、撹拌羽根、還流冷却機、窒素ガス導入管を備えたセパラブルフラスコに、テトラカルボン酸二無水物６．５ｇと、ジアミン６．７ｇと、有機溶剤３０ｇとを投入した。窒素ガス導入管よりフラスコ内に窒素を導入し、フラスコ内を窒素雰囲気とした。次いで、フラスコの内容物を撹拌しながら、５０℃で２０時間、テトラカルボン酸二無水物と、ジアミンとを反応させて、ポリアミド酸溶液を得た。得られたポリアミド酸溶液に、微粒子を、５３ｇ添加し撹拌してワニスを調製した。
<Example 1>
[Preparation of varnish]
In a separable flask equipped with a stirrer, a stirring blade, a reflux condenser, and a nitrogen gas introduction tube, 6.5 g of tetracarboxylic dianhydride, 6.7 g of diamine, and 30 g of an organic solvent were charged. Nitrogen was introduced into the flask through a nitrogen gas introduction tube, and the atmosphere in the flask was changed to a nitrogen atmosphere. Next, while stirring the contents of the flask, tetracarboxylic dianhydride and diamine were reacted at 50 ° C. for 20 hours to obtain a polyamic acid solution. To the obtained polyamic acid solution, 53 g of fine particles were added and stirred to prepare a varnish.
［未焼成複合膜の成膜］
上記のワニスを、離型剤を塗布したガラス板にアプリケーターを用い成膜した。７０℃で５分間プリベークして、膜厚２５μｍの未焼成複合膜を製造した。基材から未焼成複合膜を剥離後、エタノール浴に浸漬して第一洗浄を行った。更に、第二洗浄液（水：エタノール＝４０：６０（質量比））中に浸漬した後、ポリエチレンテレフタレート（ＰＥＴ）板を用いて未焼成複合膜を掬い上げ、これをポリテトラフルオロエチレン（ＰＴＦＥ）板に転写して乾燥を行った。
[Deposition of unfired composite film]
The varnish was formed into a film on a glass plate coated with a release agent using an applicator. Prebaking was performed at 70 ° C. for 5 minutes to produce an unfired composite film having a thickness of 25 μm. After peeling the unfired composite film from the substrate, it was immersed in an ethanol bath for first cleaning. Further, after being immersed in the second cleaning liquid (water: ethanol = 40: 60 (mass ratio)), the unfired composite film was scooped up using a polyethylene terephthalate (PET) plate, and this was polytetrafluoroethylene (PTFE). It transferred to the board and dried.
＜実施例２＞
第二洗浄液として、水：エタノール＝３０：７０（質量比）のものを使用したほかは、実施例１と同様にして、未焼成複合膜を作成した。
<Example 2>
An unfired composite film was prepared in the same manner as in Example 1 except that the second cleaning liquid was water: ethanol = 30: 70 (mass ratio).
＜実施例３＞
第二洗浄液として、水：エタノール＝１０：９０（質量比）のものを使用したほかは、実施例１と同様にして、未焼成複合膜を作成した。
<Example 3>
An unfired composite film was prepared in the same manner as in Example 1 except that the second cleaning liquid was water: ethanol = 10: 90 (mass ratio).
＜比較例１＞
第二洗浄液として、水：エタノール＝５０：５０（質量比）のものを使用したほかは、実施例１と同様にして、未焼成複合膜を作成した。
<Comparative Example 1>
An unfired composite film was prepared in the same manner as in Example 1 except that the second cleaning liquid was water: ethanol = 50: 50 (mass ratio).
＜比較例２＞
第二洗浄液として、水：エタノール＝０：１００（質量比）のものを使用したほかは、実施例１と同様にして、未焼成複合膜を作成した。
<Comparative example 2>
An unfired composite film was prepared in the same manner as in Example 1 except that the second cleaning liquid was water: ethanol = 0: 100 (mass ratio).
乾燥した未焼成複合膜の概観を以下の評価基準で評価し、表１に示した。
◎・・・全くシワが見られない、
○・・・端部にわずかなヨレがあるがシワはない
×・・・シワが多数見られる
An overview of the dried unfired composite film was evaluated according to the following evaluation criteria and shown in Table 1.
◎ ・ ・ ・ No wrinkles,
○ ・ ・ ・ Slight crease at the end but no wrinkles × ・ ・ ・ Many wrinkles are seen
表１の実施例及び比較例の結果から、有機溶剤で洗浄後の未焼成複合膜を乾燥する前に、本発明の第二洗浄液を用いて洗浄することにより、乾燥工程におけるシワの発生を効果的に防止できることを確認した。 From the results of the examples and comparative examples in Table 1, before drying the unfired composite film after washing with an organic solvent, washing with the second washing liquid of the present invention is effective in generating wrinkles in the drying process. It was confirmed that this can be prevented.
Claims (3)
前記未焼成複合膜を基板より剥離して有機溶剤を用いて洗浄する第一洗浄工程と、
前記第一洗浄工程で洗浄された未焼成複合膜を、水と水溶性有機溶剤との混合溶剤であって水溶性有機溶剤の質量比が高い第二洗浄液を用いて洗浄する第二洗浄工程と、
を有する未焼成複合膜の製造方法。 A film forming step of an unfired composite film, in which a varnish containing polyamic acid or polyimide and fine particles is applied and formed on a substrate on which a release layer is formed;
A first cleaning step of peeling off the unfired composite film from the substrate and cleaning with an organic solvent;
A second washing step of washing the unfired composite film washed in the first washing step using a second washing liquid which is a mixed solvent of water and a water-soluble organic solvent and has a high mass ratio of the water-soluble organic solvent; ,
The manufacturing method of the unbaking composite film which has.
前記未焼成複合膜を基板より剥離して有機溶剤を用いて洗浄する第一洗浄工程と、前記第一洗浄工程で洗浄された未焼成複合膜を、水と水溶性有機溶剤との混合溶剤であって水溶性有機溶剤の質量比が高い第二洗浄液を用いて洗浄する第二洗浄工程と、を有する洗浄工程と、
前記洗浄工程後の未焼成複合膜を乾燥する乾燥工程と、
前記乾燥工程後の未焼成複合膜を焼成する焼成工程と、
を有するポリイミド−微粒子複合膜の製造方法。 A film forming step of an unfired composite film, in which a varnish containing polyamic acid or polyimide and fine particles is applied and formed on a substrate on which a release layer is formed;
A first cleaning step in which the unfired composite film is peeled off from the substrate and cleaned using an organic solvent, and the unfired composite film cleaned in the first cleaning step is mixed with a mixed solvent of water and a water-soluble organic solvent. A second cleaning step for cleaning using a second cleaning liquid having a high mass ratio of the water-soluble organic solvent, and a cleaning step,
A drying step of drying the unfired composite film after the washing step;
A firing step of firing the unfired composite film after the drying step;
The manufacturing method of the polyimide fine particle composite film which has this.
前記未焼成複合膜を基板より剥離して有機溶剤を用いて洗浄する第一洗浄工程と、前記第一洗浄工程で洗浄された未焼成複合膜を、水と水溶性有機溶剤との混合溶剤であって水溶性有機溶剤の質量比が高い第二洗浄液を用いて洗浄する第二洗浄工程と、を有する洗浄工程と、
前記洗浄工程後の未焼成複合膜を乾燥する乾燥工程と、
前記乾燥工程後の未焼成複合膜を焼成してポリイミド−微粒子複合膜を得る焼成工程と、
前記ポリイミド−微粒子複合膜から微粒子を取り除く微粒子除去工程と、
を有する多孔質ポリイミド膜の製造方法。 A film forming step of an unfired composite film, in which a varnish containing polyamic acid or polyimide and fine particles is applied and formed on a substrate on which a release layer is formed;
A first cleaning step in which the unfired composite film is peeled off from the substrate and cleaned using an organic solvent, and the unfired composite film cleaned in the first cleaning step is mixed with a mixed solvent of water and a water-soluble organic solvent. A second cleaning step for cleaning using a second cleaning liquid having a high mass ratio of the water-soluble organic solvent, and a cleaning step,
A drying step of drying the unfired composite film after the washing step;
A firing step of firing the unfired composite film after the drying step to obtain a polyimide-fine particle composite film;
A fine particle removal step of removing fine particles from the polyimide-fine particle composite film;
The manufacturing method of the porous polyimide membrane which has this.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013089812A JP6147069B2 (en) | 2013-04-22 | 2013-04-22 | Unbaked composite film, polyimide-fine particle composite film, and method for producing porous polyimide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013089812A JP6147069B2 (en) | 2013-04-22 | 2013-04-22 | Unbaked composite film, polyimide-fine particle composite film, and method for producing porous polyimide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014214167A true JP2014214167A (en) | 2014-11-17 |
| JP6147069B2 JP6147069B2 (en) | 2017-06-14 |
Family
ID=51940277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013089812A Active JP6147069B2 (en) | 2013-04-22 | 2013-04-22 | Unbaked composite film, polyimide-fine particle composite film, and method for producing porous polyimide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6147069B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017202479A (en) * | 2016-05-09 | 2017-11-16 | 東京応化工業株式会社 | Polyimide resin film cleaning liquid, method of cleaning polyimide resin film, manufacturing method of polyimide film, manufacturing method of filter, filter medium, or filter device, manufacturing method of lithography chemical |
| WO2020075827A1 (en) * | 2018-10-12 | 2020-04-16 | 株式会社カネカ | Method for producing transparent polyimide film |
| US10696808B2 (en) | 2016-06-23 | 2020-06-30 | Fuji Xerox Co., Ltd. | Porous film and method of forming porous film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS583603A (en) * | 1981-07-01 | 1983-01-10 | Ube Ind Ltd | Production of dried separating membrane made of polyimide |
| JP2004174796A (en) * | 2002-11-26 | 2004-06-24 | Teijin Ltd | Method for manufacturing biaxially oriented polyimide film |
| JP2006348280A (en) * | 2005-05-20 | 2006-12-28 | Sumitomo Chemical Co Ltd | Porous film and laminated porous film |
| US20070100127A1 (en) * | 2002-10-07 | 2007-05-03 | Teijin Limited | Polyimide film and process for its production |
| JP2012107144A (en) * | 2010-11-18 | 2012-06-07 | Tokyo Metropolitan Univ | Method for producing porous polyimide membrane |
-
2013
- 2013-04-22 JP JP2013089812A patent/JP6147069B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS583603A (en) * | 1981-07-01 | 1983-01-10 | Ube Ind Ltd | Production of dried separating membrane made of polyimide |
| US20070100127A1 (en) * | 2002-10-07 | 2007-05-03 | Teijin Limited | Polyimide film and process for its production |
| JP2004174796A (en) * | 2002-11-26 | 2004-06-24 | Teijin Ltd | Method for manufacturing biaxially oriented polyimide film |
| JP2006348280A (en) * | 2005-05-20 | 2006-12-28 | Sumitomo Chemical Co Ltd | Porous film and laminated porous film |
| JP2012107144A (en) * | 2010-11-18 | 2012-06-07 | Tokyo Metropolitan Univ | Method for producing porous polyimide membrane |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017202479A (en) * | 2016-05-09 | 2017-11-16 | 東京応化工業株式会社 | Polyimide resin film cleaning liquid, method of cleaning polyimide resin film, manufacturing method of polyimide film, manufacturing method of filter, filter medium, or filter device, manufacturing method of lithography chemical |
| US10696808B2 (en) | 2016-06-23 | 2020-06-30 | Fuji Xerox Co., Ltd. | Porous film and method of forming porous film |
| WO2020075827A1 (en) * | 2018-10-12 | 2020-04-16 | 株式会社カネカ | Method for producing transparent polyimide film |
| CN112823184A (en) * | 2018-10-12 | 2021-05-18 | 株式会社钟化 | Method for producing transparent polyimide film |
| JPWO2020075827A1 (en) * | 2018-10-12 | 2021-09-09 | 株式会社カネカ | Method for manufacturing transparent polyimide film |
| JP7257412B2 (en) | 2018-10-12 | 2023-04-13 | 株式会社カネカ | Method for producing transparent polyimide film |
| CN112823184B (en) * | 2018-10-12 | 2023-11-07 | 株式会社钟化 | Method for producing transparent polyimide film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6147069B2 (en) | 2017-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6881644B2 (en) | Method for producing resin particle-dispersed polyimide precursor solution, resin particle-dispersed polyimide precursor solution, resin particle-containing polyimide film, method for producing porous polyimide film, and porous polyimide film. | |
| CN108504094B (en) | Polyimide precursor solution and polyimide film | |
| JP5605566B2 (en) | Method for producing porous polyimide membrane | |
| JP6404028B2 (en) | Method for producing porous polyimide film, method for producing separator, and varnish | |
| JP6596196B2 (en) | Method for producing varnish for producing porous membrane | |
| JP6950307B2 (en) | Particle-dispersed polyimide precursor solution, method for producing porous polyimide film, and porous polyimide film | |
| JP6342891B2 (en) | Varnish, porous polyimide film produced using the same, and method for producing the same | |
| JP7024225B2 (en) | Polyimide laminated film and method for manufacturing polyimide laminated film | |
| JP6876912B2 (en) | Method for producing polyimide precursor solution and porous polyimide film | |
| JPWO2016027825A1 (en) | Varnish for producing porous polyimide film and method for producing porous polyimide film using the same | |
| CN110078918B (en) | Polyimide precursor solution, method for producing porous polyimide film, and porous polyimide film | |
| JP6147069B2 (en) | Unbaked composite film, polyimide-fine particle composite film, and method for producing porous polyimide film | |
| JP6700846B2 (en) | Wiring board laminate, wiring board, and method for manufacturing wiring board laminate | |
| JP7397570B2 (en) | Porous polyimide film raw material, its manufacturing method, and composition | |
| US20230077397A1 (en) | Polyimide precursor solution, porous polyimide membrane, and insulated electric wire | |
| US20220073743A1 (en) | Polyimide precursor solution and method for producing porous polyimide film | |
| JP7498595B2 (en) | Varnish composition, method for producing precursor film of polyimide porous film, and method for producing polyimide porous film | |
| US11680140B2 (en) | Particle-dispersed polyimide precursor solution, method for producing porous polyimide film, and porous polyimide film | |
| JP7381228B2 (en) | Varnish composition, method for producing a varnish composition, method for producing a precursor film for a porous polyimide membrane, precursor film for a porous polyimide membrane, and method for producing a porous polyimide membrane | |
| US20220119596A1 (en) | Particle-dispersed polyimide precursor solution, method for producing porous polyimide film, and porous polyimide film | |
| US20220089829A1 (en) | Polyimide precursor solution and method for producing porous polyimide film | |
| JP2023034978A (en) | Polyimide precursor solution, porous polyimide film, and insulated wire | |
| CN115109272A (en) | Polyimide precursor solution and method for producing same, method for producing polyimide film, and method for producing porous polyimide film | |
| CN115124734A (en) | Polyimide precursor solution, method for producing porous polyimide film, and porous polyimide film | |
| JP2020124925A (en) | Laminate for wiring board, wiring board, and method for manufacturing laminate for wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160113 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20161027 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20161108 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161229 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170418 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170516 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6147069 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |