JPH0426331B2 - - Google Patents
Info
- Publication number
- JPH0426331B2 JPH0426331B2 JP25263184A JP25263184A JPH0426331B2 JP H0426331 B2 JPH0426331 B2 JP H0426331B2 JP 25263184 A JP25263184 A JP 25263184A JP 25263184 A JP25263184 A JP 25263184A JP H0426331 B2 JPH0426331 B2 JP H0426331B2
- Authority
- JP
- Japan
- Prior art keywords
- dianhydride
- bis
- polyimide resin
- dicarboxyphenyl
- diaminodiphenyl
- 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.)
- Expired
Links
- 229920001721 polyimide Polymers 0.000 claims description 23
- 239000009719 polyimide resin Substances 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 15
- -1 aromatic tetracarboxylic acid Chemical class 0.000 claims description 8
- 150000002989 phenols Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 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 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000004984 aromatic diamines Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 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 4
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 4
- 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 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 3
- XYZQQAGAHKSMEK-UHFFFAOYSA-N 4,5,7-triphenyl-2-benzofuran-1,3-dione Chemical compound O=C1OC(=O)C(C=2C=3C=CC=CC=3)=C1C(C=1C=CC=CC=1)=CC=2C1=CC=CC=C1 XYZQQAGAHKSMEK-UHFFFAOYSA-N 0.000 description 2
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- CBLAIDIBZHTGLV-UHFFFAOYSA-N dodecane-2,11-diamine Chemical compound CC(N)CCCCCCCCC(C)N CBLAIDIBZHTGLV-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- XMXCPDQUXVZBGQ-UHFFFAOYSA-N 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=C(Cl)C(Cl)=C(C(O)=O)C2=C1C(O)=O XMXCPDQUXVZBGQ-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- XGKKWUNSNDTGDS-UHFFFAOYSA-N 2,5-dimethylheptane-1,7-diamine Chemical compound NCC(C)CCC(C)CCN XGKKWUNSNDTGDS-UHFFFAOYSA-N 0.000 description 1
- YXOKJIRTNWHPFS-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diamine Chemical compound NCC(C)CCC(C)CN YXOKJIRTNWHPFS-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- SDWGBHZZXPDKDZ-UHFFFAOYSA-N 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O SDWGBHZZXPDKDZ-UHFFFAOYSA-N 0.000 description 1
- JZWGLBCZWLGCDT-UHFFFAOYSA-N 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=CC(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O JZWGLBCZWLGCDT-UHFFFAOYSA-N 0.000 description 1
- RCYNJDVUURMJOZ-UHFFFAOYSA-N 2-amino-5-[(4-amino-3-hydroxyphenyl)methyl]phenol Chemical compound C1=C(O)C(N)=CC=C1CC1=CC=C(N)C(O)=C1 RCYNJDVUURMJOZ-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- IVVWBIJMWBNKFV-UHFFFAOYSA-N 3,3'-Dichloro-4,4'-diaminodiphenyl ether Chemical compound C1=C(Cl)C(N)=CC=C1OC1=CC=C(N)C(Cl)=C1 IVVWBIJMWBNKFV-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical group C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 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
- FIWRJOPVYBJBMU-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)-dimethylsilyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1[Si](C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O FIWRJOPVYBJBMU-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-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
- 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
- DFSUKONUQMHUKQ-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound OC(=O)C1=CC=CC(C(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)(C(F)(F)F)C(F)(F)F)=C1C(O)=O DFSUKONUQMHUKQ-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
- POTQBGGWSWSMCX-UHFFFAOYSA-N 3-[2-(3-aminopropoxy)ethoxy]propan-1-amine Chemical compound NCCCOCCOCCCN POTQBGGWSWSMCX-UHFFFAOYSA-N 0.000 description 1
- ZRJAHFLFCRNNMR-UHFFFAOYSA-N 3-amino-2-(4-aminophenyl)benzoic acid Chemical compound C1=CC(N)=CC=C1C1=C(N)C=CC=C1C(O)=O ZRJAHFLFCRNNMR-UHFFFAOYSA-N 0.000 description 1
- YEEIWUUBRYZFEH-UHFFFAOYSA-N 3-methoxyhexane-1,6-diamine Chemical compound NCCC(OC)CCCN YEEIWUUBRYZFEH-UHFFFAOYSA-N 0.000 description 1
- SGEWZUYVXQESSB-UHFFFAOYSA-N 3-methylheptane-1,7-diamine Chemical compound NCCC(C)CCCCN SGEWZUYVXQESSB-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- 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
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- QGRZMPCVIHBQOE-UHFFFAOYSA-N 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)CC(C)=C2C(C(O)=O)C(C(O)=O)CC(C)=C21 QGRZMPCVIHBQOE-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
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- LHECBTWFKAHFAS-UHFFFAOYSA-N 4-(4-aminophenyl)-6,6-dichlorocyclohexa-1,3-dien-1-amine Chemical compound C1C(Cl)(Cl)C(N)=CC=C1C1=CC=C(N)C=C1 LHECBTWFKAHFAS-UHFFFAOYSA-N 0.000 description 1
- HNHQPIBXQALMMN-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)-dimethylsilyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1[Si](C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 HNHQPIBXQALMMN-UHFFFAOYSA-N 0.000 description 1
- MOCQGMXEHQTAEN-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)-diphenylsilyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1[Si](C=1C=C(C(C(O)=O)=CC=1)C(O)=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MOCQGMXEHQTAEN-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
- OSGFBINRYVUILV-UHFFFAOYSA-N 4-[(4-aminophenyl)-diethylsilyl]aniline Chemical compound C=1C=C(N)C=CC=1[Si](CC)(CC)C1=CC=C(N)C=C1 OSGFBINRYVUILV-UHFFFAOYSA-N 0.000 description 1
- BLMSGSGJGUHKFW-UHFFFAOYSA-N 4-[(4-aminophenyl)-diphenylsilyl]aniline Chemical compound C1=CC(N)=CC=C1[Si](C=1C=CC(N)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BLMSGSGJGUHKFW-UHFFFAOYSA-N 0.000 description 1
- IJJNNSUCZDJDLP-UHFFFAOYSA-N 4-[1-(3,4-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 IJJNNSUCZDJDLP-UHFFFAOYSA-N 0.000 description 1
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 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
- IOUVQFAYPGDXFG-UHFFFAOYSA-N 4-[4-[2-[4-(3,4-dicarboxyphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=C(C(C(O)=O)=CC=3)C(O)=O)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 IOUVQFAYPGDXFG-UHFFFAOYSA-N 0.000 description 1
- MRTAEHMRKDVKMS-UHFFFAOYSA-N 4-[4-[4-(3,4-dicarboxyphenoxy)phenyl]sulfanylphenoxy]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC(C=C1)=CC=C1SC(C=C1)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 MRTAEHMRKDVKMS-UHFFFAOYSA-N 0.000 description 1
- VHUWVCAJOXIARC-UHFFFAOYSA-N 4-[4-[4-(3,4-dicarboxyphenoxy)phenyl]sulfonylphenoxy]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=C(C(C(O)=O)=CC=3)C(O)=O)=CC=2)C=C1 VHUWVCAJOXIARC-UHFFFAOYSA-N 0.000 description 1
- AXFZHOJOXNHNDY-UHFFFAOYSA-N 4-[[4-[(3,4-dicarboxyphenyl)-dimethylsilyl]phenyl]-dimethylsilyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1[Si](C)(C)C(C=C1)=CC=C1[Si](C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AXFZHOJOXNHNDY-UHFFFAOYSA-N 0.000 description 1
- ADUMIBSPEHFSLA-UHFFFAOYSA-N 4-[bis(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 ADUMIBSPEHFSLA-UHFFFAOYSA-N 0.000 description 1
- HWKHQQCBFMYAJZ-UHFFFAOYSA-N 4-amino-n-(3-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC(N)=C1 HWKHQQCBFMYAJZ-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- VMFQOYLCRZRUMB-UHFFFAOYSA-N 4-n-(4-aminophenyl)-4-n-butylbenzene-1,4-diamine Chemical compound C=1C=C(N)C=CC=1N(CCCC)C1=CC=C(N)C=C1 VMFQOYLCRZRUMB-UHFFFAOYSA-N 0.000 description 1
- LBNFPUAJWZYIOQ-UHFFFAOYSA-N 4-n-(4-aminophenyl)-4-n-methylbenzene-1,4-diamine Chemical compound C=1C=C(N)C=CC=1N(C)C1=CC=C(N)C=C1 LBNFPUAJWZYIOQ-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
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- NBBFBKABFFPUIW-UHFFFAOYSA-N C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C=1C=C(C(C(O)=O)=CC=1)C(O)=O)[SiH2]C1=CC=CC=C1 Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C=1C=C(C(C(O)=O)=CC=1)C(O)=O)[SiH2]C1=CC=CC=C1 NBBFBKABFFPUIW-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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- HNQHUWHQMJTWRA-UHFFFAOYSA-N NC1=CC=C(C=C1)C(C[PH2]=O)C1=CC=C(C=C1)N Chemical compound NC1=CC=C(C=C1)C(C[PH2]=O)C1=CC=C(C=C1)N HNQHUWHQMJTWRA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 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
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KADGVXXDDWDKBX-UHFFFAOYSA-N naphthalene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 KADGVXXDDWDKBX-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
- 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
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- YNVQYOQLKGNUBZ-UHFFFAOYSA-N octadecane-1,1-diamine Chemical compound CCCCCCCCCCCCCCCCCC(N)N YNVQYOQLKGNUBZ-UHFFFAOYSA-N 0.000 description 1
- JGGWKXMPICYBKC-UHFFFAOYSA-N phenanthrene-1,8,9,10-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(O)=O)=C3C(C(=O)O)=CC=CC3=C21 JGGWKXMPICYBKC-UHFFFAOYSA-N 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
- 239000002798 polar solvent Substances 0.000 description 1
- PZZICILSCNDOKK-UHFFFAOYSA-N propane-1,2,3-triamine Chemical compound NCC(N)CN PZZICILSCNDOKK-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- KRVRUAYUNOQMOV-UHFFFAOYSA-N tris(4-aminophenyl)methanol Chemical compound C1=CC(N)=CC=C1C(O)(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 KRVRUAYUNOQMOV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、有機溶媒に可溶なポリイミド樹脂の
製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a polyimide resin soluble in organic solvents.
（従来の技術）
ポリイミド樹脂は、優れた耐熱性、耐薬品性、
電気特性を有しており、電気絶縁材料として広く
利用されている。(Conventional technology) Polyimide resin has excellent heat resistance, chemical resistance,
It has electrical properties and is widely used as an electrical insulating material.
従来、ポリイミド樹脂は、テトラカルボン酸ジ
無水物と芳香族ジアミンを有機極性溶媒中で60℃
以下において付加反応させポリアミド酸を製造し
成型後脱水剤や加熱によりイミド化する方法が採
られていた（特公昭36−10999号公報、特公昭37
−97号公報、特公昭37−10945号公報など）。また
有機溶媒に可溶なポリイミド樹脂の製造方法とし
て例えば特公昭47−26878号公報には少なくとも
60モル％のアミノ基に対してオルソの位置にアル
キル基を有する芳香族ジアミンとベンゾフエノン
テトラカルボン酸２無水物とをクレゾール中、
160℃以下の温度で反応させる方法が記載されて
いる。また特公昭47−14751号公報には、１，２，
３，４プタンテトラカルボン酸類をテトラカルボ
ン酸成分としたポリイミド樹脂の製造方法が記載
されている。 Conventionally, polyimide resin is produced by mixing tetracarboxylic dianhydride and aromatic diamine in an organic polar solvent at 60°C.
In the following method, polyamic acid was produced by an addition reaction, and after molding, it was imidized using a dehydrating agent or heating (Japanese Patent Publication No. 10999/1983,
-97 Publication, Special Publication No. 37-10945, etc.). Furthermore, as a method for producing polyimide resin soluble in organic solvents, for example, Japanese Patent Publication No. 47-26878 describes at least
An aromatic diamine having an alkyl group at a position ortho to 60 mol% of an amino group and benzophenone tetracarboxylic dianhydride in cresol,
A method is described in which the reaction is carried out at a temperature of 160°C or lower. In addition, 1, 2,
A method for producing a polyimide resin using 3,4-butane tetracarboxylic acids as a tetracarboxylic acid component is described.
（発明が解決しようとする問題点）
しかし前記公知文献によるポリイミド樹脂は、
側鎖にアルキル基を持つていたり脂肪族の酸を使
用しているため、熱分解温度が低いという問題点
があつた。そのため熱分解温度が高く、有機溶媒
に可溶なポリイミド樹脂が望まれていた。(Problems to be solved by the invention) However, the polyimide resin according to the above-mentioned known document,
Because it has an alkyl group in its side chain or uses an aliphatic acid, it has a problem of a low thermal decomposition temperature. Therefore, polyimide resins that have a high thermal decomposition temperature and are soluble in organic solvents have been desired.
（問題点を解決するための手段）
本発明は前記問題点を解決することを目的に検
討を行なつた結果、有機溶媒としてフエノール類
を用い、芳香族ジアミンに３，4′−ジアミノジフ
エニルエーテルを使用し上記有機溶媒中で加熱し
水を除去しながら重合、イミド化を１段で行ない
製造したポリイミド樹脂が熱分解温度が高く、有
機溶媒に溶解することを見い出し本発明を完成し
た。(Means for Solving the Problems) As a result of studies aimed at solving the above-mentioned problems, the present invention uses phenols as an organic solvent, and uses 3,4'-diaminodiphenyl as an aromatic diamine. The present invention was completed by discovering that a polyimide resin produced by performing polymerization and imidization in one step by heating in the above-mentioned organic solvent using ether and removing water has a high thermal decomposition temperature and is soluble in the organic solvent.
本発明によるポリイミド樹脂は、イミド化率90
％以上であり、有機溶媒に可溶である。 The polyimide resin according to the present invention has an imidization rate of 90
% or more and is soluble in organic solvents.
以下本発明について具体的に説明する。 The present invention will be specifically explained below.
本発明において使用する芳香族ジアミンは３，
4′−ジアミノジフエニルエーテルを100モル％使
用するのが、製造したポリイミド樹脂の有機溶媒
に対する溶解性の点から好ましいが、30モル％以
下、好ましくは10モル％以下であれば他の芳香族
ジアミンを併用して使用することができる。 The aromatic diamine used in the present invention is 3,
It is preferable to use 100 mol% of 4'-diaminodiphenyl ether from the viewpoint of solubility of the produced polyimide resin in organic solvents, but if it is 30 mol% or less, preferably 10 mol% or less, other aromatic Diamines can be used in combination.
また本発明において使用する芳香族テトラカル
ボン酸類はとくに制限はないが、ピロメリツト酸
類を使用する場合には60モル％以下の使用量にす
るのが製造したポリイミド樹脂の有機溶媒に対す
る溶解性の点から好ましい。 Furthermore, there are no particular restrictions on the aromatic tetracarboxylic acids used in the present invention, but when using pyromellitic acids, the amount used should be 60 mol% or less from the viewpoint of solubility of the produced polyimide resin in organic solvents. preferable.
本発明で３，4′−ジアミノジフエニルエーテル
と共に使用するのに適当なジアミンの例としては
次のものがある。 Examples of diamines suitable for use with 3,4'-diaminodiphenyl ether in this invention include:
２，２−ビス（４−アミノ−フエニル）プロパ
ン、２，６−ジアミノ−ピリジン、ビス−（４−
アミノ−フエニル）ジエチルシラン、ビス−（４
−アミノ−フエニル）ジフエニルシラン、ベンジ
ジン、３，３−ジクロル−ベンジジン、３，3′−
ジメトキシベンジジン、ビス−（４−アミノ−フ
エニル）エチルホスフインオキサイド、ビス−
（４−アミノ−フエニル）−Ｎ−ブチルアミン、ビ
ス−（４−アミノ−フエニル）−Ｎ−メチルアミ
ン、３，3′−ジメチル−４，4′−ジアミノブフエ
ニル、Ｎ−（３−アミノフエニル）−４−アミノベ
ンズアミド、４−アミノフエニル−３−アミノ安
息香酸、３，3′−ジメチル−４，4′−ジアミノジ
フエニルメタン、３，3′−ジメトキシ−４，4′−
ジアミノジフエニルメタン、３，3′−ジエトキシ
−４，4′−ジアミノジフエニルメタン、３，3′−
ジカルボキシ−４，4′−ジアミノジフエニルメタ
ン、３，3′−ジフロロ−４，4′−ジアミノジフエ
ニルメタン、３，3′−ジクロロ−４，4′−ジアミ
ノジフエニルメタン、３，3′−ジブロム−４，
4′−ジアミノジフエニルメタン、３，3′−ジヒド
ロキシ−４，4′−ジアミノジフエニルメタン、
３，3′−ジスルホ−４，4′−ジアミノジフエニル
メタン、３，3′−ジスルホ−４，4′−ジアミノジ
フエニルメタン、３，3′−ジメチル−４，4′−ジ
アミノジフエニルエーテル、３，3′−ジメトキシ
−４，4′−ジアミノジフエニルエーテル、３，
3′−ジエトキシ−４，4′−ジアミノジフエニルエ
ーテル、３，3′−ジカルボキシ−４，4′−ジアミ
ノジフエニルエーテル、３，3′−ジクロロ−４，
4′−ジアミノジフエニルエーテル、３，3′−ジヒ
ドロキシ−４，4′−ジアミノジフエニルエーテ
ル、３，3′−ジスルホ−４，4′−ジアミノジフエ
ニルエーテル、３，3′−ジメチル−４，4′−ジア
ミノジフエニルスルホン、３，3′−ジメトキシ−
４，4′−ジアミノジフエニルスルホン、３，3′−
ジエトキシ−４，4′−ジアミノジフエニルスルホ
ン、３，3′−ジカルボキシ−４，4′−ジアミノジ
フエニルスルホン、３，3′−ジクロロ−４，4′−
ジアミノジフエニルスルホン、３，3′−ジヒドロ
キシ−４，4′−ジアミノジフエニルスルホン、
３，3′−ジスルホ−４，4′−ジアミノジフエニル
スルホン、３，3′−ジメチル−４，4′−ジアミノ
ジフエニルプロパン、３，3′−ジメトキシ−４，
4′−ジアミノジフエニルプロパン、３，3′−ジエ
トキシ−４，4′−ジアミノジフエニルプロパン、
３，3′−ジカルボキシ−４，4′−ジアミノジフエ
ニルプロパン、３，3′−ジクロロ−４，4′−ジア
ミノジフエニルプロパン、３，3′−ジヒドロキシ
−４，4′−ジアミノジフエニルプロパン、３，
3′−ジスルホ−４，4′−ジアミノジフエニルプロ
パン、３，3′−ジメチル−４，4′−ジアミノジフ
エニルスルフアイド、３，3′−ジメトキシ−４，
4′−ジアミノジフエニルスルフアイド、３，3′−
ジエトキシ−４，4′−ジアミノジフエニルスルフ
アイド、３，3′−ジカルボキシ−４，4′−ジアミ
ノジフエニルスルフアイド、３，3′−ジクロロ−
４，4′−ジアミノジフエニルスルフアイド、３，
3′−ジヒドロキシ−４，4′−ジアミノジフエニル
スルフアイド、３，3′−ジスルホ−４，4′−ジア
ミノジフエニルスルフアイド、３，3′−ジアミノ
ジフエニルメタン、３，3′−ジアミノジフエニル
エーテル、３，3′−ジアミノジフエニルスルホ
ン、３，3′−ジアミノジフエニルプロパン、３，
3′−ジアミノジフエニルスルフアイド、２，４−
ジアミノトルエン、２，６−ジアミノトルエン、
パラ−フエニレンジアミン、メタ−フエニレンジ
アミン、４，4′−ジアミノ−ジフエニルプロパ
ン、４，4′−ジアミノ−ジフエニルメタン、３，
3′−ジアミノベンゾフエノン、４，4′−ジアミノ
−ジフエニルスルフイト、４，4′−ジアミノ−ジ
フエニルスルホン、４，4′−ジアミノ−ジフエニ
ルエーテル、１，５−ジアミノ−ナフタレン、
３，3′−ジメトキシベンジジン、２，４−ビス
（ベーターアミノ−ｔ−ブチル）トルエン、ビス
−（パラーベーターアミノ−ｔ−ブチル−フエニ
ル）エーテル、ビス−（パラーベーターメチル−
デルタ−アミノ−ペンチル）ベンゼン、ビス−パ
ーラ−（１，１−ジメチル５−アミノ−ペンチル）
ベンゼン、１−イソプロピル−２，４−メタフタ
フエニレンジアミン、ｍ−キシレンジアミン、
１，３−（ビスアミノプロピル）−１，１，３，３
−テトラメチルジシロキサン、１，３−（ビスア
ミノブチル）−１，１，３，３−テトラメチルジ
シロキサン、ヘキサメチレンジアミン、ヘプタメ
チレンジアミン、オクタメチレンジアミン、ノナ
メチレンジアミン、デカメチレンジアミン、ジア
ミノ−プロピルテトラメチレンジアミン、３−メ
チルヘプタメチレンジアミン、４，4′−ジメチル
ヘプタメチメチレンジアミン、２，11−ジアミノ
−ドデカン、１，２−ビス−（３−アミノ−プロ
ポキシ）エタン、２，２−ジメチル−プロピレン
ジアミン、３−メトキシ−ヘキサメチレンジアミ
ン、３，3′−ジメチルベンジジン、２，５−ジメ
チルヘキサメチレンジアミン、２，５−ジメチル
ヘプタメチレンジアミン、５−メチル−ノナメチ
レンジアミン、２，17−ジアミノ−アイコサデカ
ン、１，４−ジアミノ−シクロヘキタン、１，10
−ジアミノ−１，10−ジメチルデカン、１，12−
ジアミノ−オクタデカンならびに１，３，５−ト
リアミノベンゼン、２，４，６−トリアミノ−ト
リアジン、１，２，３−トリアミノプロパン、
４，4′，4″−トリアミノトリフエニルメタン、お
よび４，4′，4″−トリアミノトリフエニルカルビ
ノールのようなトリアミン。これらジアミン類を
２種以上混合して用いることもできる。 2,2-bis(4-amino-phenyl)propane, 2,6-diamino-pyridine, bis-(4-
Amino-phenyl)diethylsilane, bis-(4
-amino-phenyl)diphenylsilane, benzidine, 3,3-dichloro-benzidine, 3,3'-
Dimethoxybenzidine, bis-(4-amino-phenyl)ethylphosphine oxide, bis-
(4-amino-phenyl)-N-butylamine, bis-(4-amino-phenyl)-N-methylamine, 3,3'-dimethyl-4,4'-diaminobuphenyl, N-(3-aminophenyl) -4-Aminobenzamide, 4-aminophenyl-3-aminobenzoic acid, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-
Diaminodiphenylmethane, 3,3'-diethoxy-4,4'-diaminodiphenylmethane, 3,3'-
Dicarboxy-4,4'-diaminodiphenylmethane, 3,3'-difluoro-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3 '-dibrome-4,
4'-diaminodiphenylmethane, 3,3'-dihydroxy-4,4'-diaminodiphenylmethane,
3,3'-disulfo-4,4'-diaminodiphenylmethane, 3,3'-disulfo-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl ether , 3,3'-dimethoxy-4,4'-diaminodiphenyl ether, 3,
3'-diethoxy-4,4'-diaminodiphenyl ether, 3,3'-dicarboxy-4,4'-diaminodiphenyl ether, 3,3'-dichloro-4,
4'-Diamino diphenyl ether, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 3,3'-disulfo-4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4 , 4'-diaminodiphenylsulfone, 3,3'-dimethoxy-
4,4'-diaminodiphenylsulfone, 3,3'-
Diethoxy-4,4'-diaminodiphenylsulfone, 3,3'-dicarboxy-4,4'-diaminodiphenylsulfone, 3,3'-dichloro-4,4'-
Diaminodiphenylsulfone, 3,3'-dihydroxy-4,4'-diaminodiphenylsulfone,
3,3'-disulfo-4,4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-dimethoxy-4,
4'-diaminodiphenylpropane, 3,3'-diethoxy-4,4'-diaminodiphenylpropane,
3,3'-dicarboxy-4,4'-diaminodiphenylpropane, 3,3'-dichloro-4,4'-diaminodiphenylpropane, 3,3'-dihydroxy-4,4'-diaminodiphenyl Propane, 3,
3'-disulfo-4,4'-diaminodiphenylpropane, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 3,3'-dimethoxy-4,
4'-diaminodiphenyl sulfide, 3,3'-
Diethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-dicarboxy-4,4'-diaminodiphenylsulfide, 3,3'-dichloro-
4,4'-diaminodiphenyl sulfide, 3,
3'-dihydroxy-4,4'-diaminodiphenyl sulfide, 3,3'-disulfo-4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylmethane, 3,3' -diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylpropane, 3,
3'-diaminodiphenyl sulfide, 2,4-
Diaminotoluene, 2,6-diaminotoluene,
Para-phenylenediamine, meta-phenylenediamine, 4,4'-diamino-diphenylpropane, 4,4'-diamino-diphenylmethane, 3,
3'-Diaminobenzophenone, 4,4'-diamino-diphenyl sulfite, 4,4'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl ether, 1,5-diamino-naphthalene ,
3,3'-dimethoxybenzidine, 2,4-bis(beta-amino-t-butyl)toluene, bis-(paravator amino-t-butyl-phenyl)ether, bis-(paravator methyl-
delta-amino-pentyl)benzene, bis-par-(1,1-dimethyl 5-amino-pentyl)
Benzene, 1-isopropyl-2,4-metaphtaphenylenediamine, m-xylenediamine,
1,3-(bisaminopropyl)-1,1,3,3
-Tetramethyldisiloxane, 1,3-(bisaminobutyl)-1,1,3,3-tetramethyldisiloxane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diamino -Propyltetramethylenediamine, 3-methylheptamethylenediamine, 4,4'-dimethylheptamethylenediamine, 2,11-diamino-dodecane, 1,2-bis-(3-amino-propoxy)ethane, 2,2 -dimethyl-propylenediamine, 3-methoxy-hexamethylenediamine, 3,3'-dimethylbenzidine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 5-methyl-nonamethylenediamine, 2, 17-diamino-icosadecane, 1,4-diamino-cyclohexane, 1,10
-diamino-1,10-dimethyldecane, 1,12-
Diamino-octadecane as well as 1,3,5-triaminobenzene, 2,4,6-triamino-triazine, 1,2,3-triaminopropane,
Triamines such as 4,4',4''-triaminotriphenylmethane, and 4,4',4''-triaminotriphenylcarbinol. Two or more of these diamines can also be used as a mixture.
本発明で使用する芳香族テトラカルボン酸類に
は特に制限はない。 There are no particular limitations on the aromatic tetracarboxylic acids used in the present invention.
ここで芳香族テトラカルボン酸類としてはテト
ラカルボン酸、その無水物、エステル化物が用い
られ、好ましくは芳香族テトラカルボン酸無水物
が用いられる。 Here, as the aromatic tetracarboxylic acids, tetracarboxylic acids, their anhydrides, and esters are used, and aromatic tetracarboxylic anhydrides are preferably used.
本発明で使用するのに適当な酸無水物の例とし
ては次のものがある。 Examples of acid anhydrides suitable for use in the present invention include:
ピロメリツト酸二無水物、２，２−ビス（２，
３−ジカルボキシフエニル）ヘキサフルオロプロ
パン二無水物、３，3′，４，4′−ジフエニルテト
ラカルボン酸二無水物、１，２，５，６−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、２，
2′，３，3′−ジフエニルテトラカルボン酸二無水
物、２，2′−ビス（３，４−ジカルボキシフエニ
ル）プロパン二無水物、ビス（３，４−ジカルボ
キシフエニル）スルホン二無水物、３，４，９，
10−ペリレンテトラカルボン酸二無水物、ビス
（３，４−ジカルボキシフエニル）エーテル二無
水物、ナフタレン−１，２，４，５−テトラカル
ボン酸二無水物、ナフタレン−１，４，５，８−
テトラカルボン酸二無水物、２，６−ジクロルナ
フタレン−１，４，５，８−テトラカルボン酸二
無水物、２，７−ジクロルナフタレン−１，４，
５，８−テトラカルボン酸二無水物、２，３，
６，７−テトラクロルナフタレン−１，４，５，
８−テトラカルボン酸二無水物、フエナンスレン
−１，８，９，10−テトラカルボン酸二無水物、
２，２−ビス（２，３−ジカルボキシフエニル）
プロパン二無水物、１，１−ビス（２，３−ジカ
ルボキシフエニル）エタン二無水物、１，１−ビ
ス（３，４−ジカルボキシフエニル）エタン二無
水物、ビス（２，３−ジカルボキシフエニル）メ
タン二無水物、ビス（３，４−ジカルボキシフエ
ニル）メタン二無水物、ビス（３，４−ジカルボ
キシフエニル）スルホン二無水物、ベンゼン−
１，２，３，４−テトラカルボン酸二無水物、
３，４，3′，4′−ベンゾフエノンテトラカルボン
酸二無水物、２，３，2′，３−ベンゾフエノンテ
トラカルボン酸二無水物、２，３，3′，4′−ベン
ゾフエノンテトラカルボン酸二無水物、デカヒド
ロナフタレン−１，４，５，８−テトラカルボン
酸二無水物、４，８−ジメチル−１，２，３，
５，６，７−ヘキサヒドロナフタレン−１，２，
５，６−テトラカルボン酸二無水物、２，３，
3′，4′−ビフエニルテトラカルボン酸二無水物、
３，４，3′，4′−ビフエニルテトラカルボン酸二
無水物、２，３，2′，3′−ビフエニルテトラカル
ボン酸二無水物、ビス（３，４−ジカルボキシフ
エニル）ジメチルシラン二無水物、ビス（３，４
−ジカルボキシフエニル）メチルフエニルシラン
二無水物、ビス（３，４−ジカルボキシフエニ
ル）ジフエニルシラン二無水物、ビス（２，３−
ジカルボキシフエニル）ジメチルシラン二無水
物、１，４−ビス（３，４−ジカルボキシフエニ
ルジメチルシリル）ベンゼン二無水物、１，３−
ビス（３，４−ジカルボキシフエニル）−１，１，
３，３−テトラメチルジシロサン二無水物、ｐ−
フエニレン−ビス（トリメリツト酸モノエステル
酸無水物）エチレングリコールビス（トリメリツ
ト酸無水物）２，２−ビス（３，４−ジカルボキ
シフエニル）ヘキサフロロプロパン二無水物、
２，２−ビス〔４−（３，４−ジカルボキシフエ
ノキシ）フエニル〕ヘキサフロロプロパン二無水
物、４，4′−ビス（３，４−ジカルボキシフエノ
キシ）ジフエニルスルフイド二無水物、ビス〔４
−（３，４−ジカルボキシフエノキシ）フエニル〕
スルホン二無水物、４，4′−（１，４−フエニレ
ン）ビス（３，５，６−トリフエニルフタル酸無
水物）、４，4′−（オキシジ−１，４−フエニレ
ン）ビス（３，５，６−トリフエニルフタル酸無
水物）、グリセリントリス（トリメリツト酸無水
物）、グリセリンビス（トリメリツト酸無水物）
モノ酢酸エステル。これら二無水物を２種以上混
合して用いることもできる。 Pyromellitic dianhydride, 2,2-bis(2,
3-Dicarboxyphenyl)hexafluoropropane dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2 ,3,6,7
-naphthalenetetracarboxylic dianhydride, 2,
2',3,3'-diphenyltetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 3,4,9,
10-perylenetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5 ,8-
Tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,
5,8-tetracarboxylic dianhydride, 2,3,
6,7-tetrachloronaphthalene-1,4,5,
8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride,
2,2-bis(2,3-dicarboxyphenyl)
Propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3 -dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, benzene-
1,2,3,4-tetracarboxylic dianhydride,
3,4,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,2',3-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzo Phenonetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,
5,6,7-hexahydronaphthalene-1,2,
5,6-tetracarboxylic dianhydride, 2,3,
3′,4′-biphenyltetracarboxylic dianhydride,
3,4,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)dimethyl Silane dianhydride, bis(3,4
-dicarboxyphenyl)methylphenylsilane dianhydride, bis(3,4-dicarboxyphenyl)diphenylsilane dianhydride, bis(2,3-
dicarboxyphenyl)dimethylsilane dianhydride, 1,4-bis(3,4-dicarboxyphenyldimethylsilyl)benzene dianhydride, 1,3-
Bis(3,4-dicarboxyphenyl)-1,1,
3,3-tetramethyldisilosane dianhydride, p-
Phenylene-bis(trimellitic acid monoester acid anhydride) ethylene glycol bis(trimellitic acid anhydride) 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride,
2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, bis[4
-(3,4-dicarboxyphenoxy)phenyl]
Sulfone dianhydride, 4,4'-(1,4-phenylene)bis(3,5,6-triphenylphthalic anhydride), 4,4'-(oxydi-1,4-phenylene)bis(3 , 5,6-triphenylphthalic anhydride), glycerin tris (trimellitic anhydride), glycerin bis (trimellitic anhydride)
Monoacetate ester. Two or more of these dianhydrides may be used in combination.
また、本発明において使用する有機溶媒は、ｐ
−クロルフエノール、ｐ−ブロムフエノール、Ｏ
−クロルフエノール、Ｏ−ブロムフエノールとい
つたハロゲン化フエノール化合物が溶解力の点か
ら最も好ましいが、フエノールｍ−クレゾールと
いつたフエノール化合物も使用できる。 Furthermore, the organic solvent used in the present invention is p
-Chlorphenol, p-bromophenol, O
Halogenated phenol compounds such as -chlorophenol and O-bromophenol are most preferred from the viewpoint of dissolving power, but phenol compounds such as phenol m-cresol can also be used.
また、酸成分の種類によつては、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−２−ピロリドンといつたアミド
系溶媒も使用できる。 Depending on the type of acid component, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone can also be used.
ジアミンとテトラカルボン酸類との使用量比
は、ほぼ等モルで使用するのが好ましいが、いず
れか一方の成分が他の成分に対して５モル％以内
の違いであれば許容される。 It is preferable that the diamine and the tetracarboxylic acid be used in approximately equimolar amounts, but it is acceptable if the difference in either component is within 5 mol % with respect to the other component.
本発明において重合、イミド化を行なう温度は
100〜200℃、好ましくは100〜170℃である。100
℃以下ではイミド化率の低い樹脂しか得られな
い。また200℃を越えるとゲル化し易く、安定し
て樹脂が得られない。 The temperature at which polymerization and imidization are carried out in the present invention is
The temperature is 100-200°C, preferably 100-170°C. 100
If the temperature is below ℃, only a resin with a low imidization rate can be obtained. Furthermore, if the temperature exceeds 200°C, gelation tends to occur and a stable resin cannot be obtained.
また、水を除去する方法は系外へ連続的に除去
できればどのような方法でも良い。反応液に窒素
ガスを吹き込み窒素ガスと伴に除去する方法が製
造した樹脂の色が淡く好ましい。 Furthermore, any method may be used to remove water as long as it can be removed continuously from the system. The resin produced by the method of blowing nitrogen gas into the reaction solution and removing it together with the nitrogen gas is preferable because it has a light color.
以下実施例を示す。 Examples are shown below.
実施例
温度計、撹拌装置、窒素導入管を備えた四つ口
フラスコに３，3′，４，4′−ベンゾフエノンテト
ラカルボン酸二無水物14.49ｇ（0.045モル）、ピ
ロメリツト酸二無水物11.95ｇ（0.055モル）、３，
4′−ジアミノジフエニルエーテル20ｇ（0.1モル）
を50℃に加温したｐ−クロルフエノール287ｇ中
に加え、撹拌しながら160℃まで昇温した。その
後160℃に保ち３時間反応させ、透明で粘稠なポ
リイミド樹脂溶液を合成した。この合成は窒素ガ
スを流しながら行なつた。Example 14.49 g (0.045 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and pyromellitic dianhydride were placed in a four-necked flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube. 11.95g (0.055mol), 3,
4′-diaminodiphenyl ether 20g (0.1mol)
was added to 287 g of p-chlorophenol heated to 50°C, and the temperature was raised to 160°C with stirring. Thereafter, the mixture was kept at 160°C and reacted for 3 hours to synthesize a transparent and viscous polyimide resin solution. This synthesis was carried out under flowing nitrogen gas.
得られたポリイミド樹脂の赤外線分光分析を行
なつた所、1780cm-1にイミド結合の特性吸収ピー
クが認められた。またアミド結合の特性吸収ピー
クが認められなかつたのでイミド化率95％以上の
ポリイミド樹脂を含有していることがわかつた。 When the obtained polyimide resin was subjected to infrared spectroscopic analysis, a characteristic absorption peak of imide bonds was observed at 1780 cm -1 . Further, since no characteristic absorption peak of amide bond was observed, it was found that the polyimide resin contained an imidization rate of 95% or more.
得られたポリイミド樹脂溶液をガラス板上に均
一に塗布した後100℃１時間、400℃１時間加熱し
溶媒を除去しポリイミド樹脂皮膜を行つた。第１
図にポリイミド樹脂皮膜の熱天秤の測定チヤート
を示す。 The obtained polyimide resin solution was uniformly applied onto a glass plate and heated at 100°C for 1 hour and at 400°C for 1 hour to remove the solvent and form a polyimide resin film. 1st
The figure shows a measurement chart of a polyimide resin film using a thermobalance.
比較例
３，4′−ジアミノジフエニルエーテルを４，
4′−ジアミノジフエニルエーテルに代え実施例と
同様にして反応させた所昇温途中に樹脂が析出
し、透明で均一なポリイミド樹脂溶液は得られな
かつた。Comparative example 3,4'-diaminodiphenyl ether was
When the reaction was carried out in the same manner as in the example except for using 4'-diaminodiphenyl ether, the resin precipitated during the temperature rise, and a transparent and uniform polyimide resin solution could not be obtained.
また４，4′−ジアミノジフエニルエーテルを使
用した場合の耐熱性を調べるため、４，4′−ジア
ミノジフエニルエーテル20ｇ（0.1モル）をＮ−
メチル−２−ピロリドン287ｇに溶解した後温度
を30℃に保ちながら３，3′，４，4′−ベンゾフエ
ノンテトラカルボン酸二無水物14.49ｇ（0.045モ
ル）、ピロメリツト酸二無水物11.99ｇ（0.055モ
ル）を添加し酸無水物が完全に溶解するまで反応
を続けポリアミド酸ワニスを合成した。 In addition, in order to investigate the heat resistance when using 4,4'-diaminodiphenyl ether, 20 g (0.1 mol) of 4,4'-diaminodiphenyl ether was added to N-
After dissolving in 287 g of methyl-2-pyrrolidone, while maintaining the temperature at 30°C, 14.49 g (0.045 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 11.99 g of pyromellitic dianhydride were added. (0.055 mol) was added and the reaction was continued until the acid anhydride was completely dissolved to synthesize a polyamic acid varnish.
得られたポリアミド酸ワニスをガラス板上に均
一に塗布した後100℃１時間、400℃１時間加熱
し、溶媒を除去するとともに、イミド化を行な
い、ポリイミド樹脂皮膜を得た。第１図にポリイ
ミド樹脂皮膜の熱天秤の測定チヤートを示す。 The resulting polyamic acid varnish was uniformly applied onto a glass plate and heated at 100°C for 1 hour and at 400°C for 1 hour to remove the solvent and imidize to obtain a polyimide resin film. FIG. 1 shows a measurement chart of polyimide resin film using a thermobalance.
芳香族ジアミンに３，4′−ジアミノジフエニル
エーテルを使用することにより耐熱性をそこなわ
ずに、有機溶媒に可溶なポリイミド樹脂が得られ
た。
By using 3,4'-diaminodiphenyl ether as the aromatic diamine, a polyimide resin soluble in organic solvents was obtained without impairing heat resistance.
第１図は、真空理工(株)製示差熱天秤TGD−
3000を用い空気中、昇温速度５℃／分で測定した
結果を示したグラフである。
Figure 1 shows the differential thermal balance TGD- manufactured by Shinku Riko Co., Ltd.
3000 in air at a heating rate of 5° C./min.
Claims (1)
4′−ジアミノジフエニルエーテルと芳香族テトラ
カルボン酸類をほぼ等モル上記有機溶媒中で加熱
し水を除去しながら重合イミド化を１段で行うこ
とを特徴とする有機溶媒に可溶なポリイミド樹脂
の製造方法。 ２ フエノール類がハロゲン化フエノールである
特許請求の範囲第１項記載の有機溶媒に可溶なポ
リイミド樹脂の製造方法。[Claims] 1. Using phenols as an organic solvent, 3.
A polyimide resin soluble in an organic solvent, characterized in that 4'-diaminodiphenyl ether and an aromatic tetracarboxylic acid are heated in substantially equal moles in the above organic solvent, and polymerization imidization is performed in one step while removing water. manufacturing method. 2. The method for producing a polyimide resin soluble in an organic solvent according to claim 1, wherein the phenols are halogenated phenols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25263184A JPS61130342A (en) | 1984-11-29 | 1984-11-29 | Preparation of polyimide resin soluble in organic solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25263184A JPS61130342A (en) | 1984-11-29 | 1984-11-29 | Preparation of polyimide resin soluble in organic solvent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61130342A JPS61130342A (en) | 1986-06-18 |
| JPH0426331B2 true JPH0426331B2 (en) | 1992-05-07 |
Family
ID=17240042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25263184A Granted JPS61130342A (en) | 1984-11-29 | 1984-11-29 | Preparation of polyimide resin soluble in organic solvent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61130342A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6225125A (en) * | 1985-07-26 | 1987-02-03 | Teijin Ltd | Polyimide having heat fusibility and heat-resistant adhesive using said polyimide |
| WO2011151898A1 (en) * | 2010-06-02 | 2011-12-08 | ソルピー工業株式会社 | Polyimide which is soluble in organic solvent and configured at component ratio of (pmda)2(dade)2(bpda)2(aromatic diamine other than dade)2 |
-
1984
- 1984-11-29 JP JP25263184A patent/JPS61130342A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61130342A (en) | 1986-06-18 |
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