JP3023486B2 - Functional composite and method for producing the same - Google Patents
Functional composite and method for producing the sameInfo
- Publication number
- JP3023486B2 JP3023486B2 JP31979790A JP31979790A JP3023486B2 JP 3023486 B2 JP3023486 B2 JP 3023486B2 JP 31979790 A JP31979790 A JP 31979790A JP 31979790 A JP31979790 A JP 31979790A JP 3023486 B2 JP3023486 B2 JP 3023486B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamic acid
- organic compound
- compounds
- molecular
- functional
- 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 - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920005575 poly(amic acid) Polymers 0.000 claims description 129
- 150000002894 organic compounds Chemical class 0.000 claims description 106
- 229920000642 polymer Polymers 0.000 claims description 66
- 239000000126 substance Substances 0.000 claims description 45
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 41
- 239000004973 liquid crystal related substance Substances 0.000 claims description 37
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 33
- 229920001721 polyimide Polymers 0.000 claims description 31
- 239000004642 Polyimide Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 150000004984 aromatic diamines Chemical class 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229920000768 polyamine Polymers 0.000 claims description 21
- 238000006297 dehydration reaction Methods 0.000 claims description 15
- 230000018044 dehydration Effects 0.000 claims description 13
- 238000007363 ring formation reaction Methods 0.000 claims description 12
- -1 porphyrin compounds Chemical class 0.000 claims description 10
- 230000004044 response Effects 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 8
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 7
- WLPATYNQCGVFFH-UHFFFAOYSA-N 2-phenylbenzonitrile Chemical group N#CC1=CC=CC=C1C1=CC=CC=C1 WLPATYNQCGVFFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 claims description 4
- 125000004802 cyanophenyl group Chemical group 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 claims description 4
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 claims description 4
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical class [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 claims description 3
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 3
- 150000001454 anthracenes Chemical class 0.000 claims description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical class C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003983 crown ethers Chemical class 0.000 claims description 3
- 150000002790 naphthalenes Chemical class 0.000 claims description 3
- 150000003220 pyrenes Chemical class 0.000 claims description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 3
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 claims description 3
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims description 3
- 150000004350 1,4-dihydroxyanthraquinones Chemical class 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 108060003552 hemocyanin Chemical class 0.000 claims description 2
- 239000000499 gel Substances 0.000 description 52
- 239000000243 solution Substances 0.000 description 50
- 239000010408 film Substances 0.000 description 42
- 239000011259 mixed solution Substances 0.000 description 31
- 239000003960 organic solvent Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 29
- 239000002904 solvent Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- 150000001412 amines Chemical class 0.000 description 17
- 238000002156 mixing Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 230000003287 optical effect Effects 0.000 description 14
- 108010025899 gelatin film Proteins 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 208000005156 Dehydration Diseases 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000012024 dehydrating agents Substances 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- RDISTOCQRJJICR-UHFFFAOYSA-N 4-(4-pentoxyphenyl)benzonitrile Chemical group C1=CC(OCCCCC)=CC=C1C1=CC=C(C#N)C=C1 RDISTOCQRJJICR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000006358 imidation reaction Methods 0.000 description 3
- 230000010365 information processing Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KJDSORYAHBAGPP-UHFFFAOYSA-N 4-(3,4-diaminophenyl)benzene-1,2-diamine;hydron;tetrachloride Chemical compound Cl.Cl.Cl.Cl.C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 KJDSORYAHBAGPP-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
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 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 2
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-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
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- IGUXFXNMXMXLCK-UHFFFAOYSA-N (3-aminophenyl)-(3,4-diaminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C(N)=CC=2)=C1 IGUXFXNMXMXLCK-UHFFFAOYSA-N 0.000 description 1
- DWRXFZDFCLDVQG-UHFFFAOYSA-N (4-butoxyphenyl)-(4-butoxyphenyl)imino-oxidoazanium Chemical compound C1=CC(OCCCC)=CC=C1N=[N+]([O-])C1=CC=C(OCCCC)C=C1 DWRXFZDFCLDVQG-UHFFFAOYSA-N 0.000 description 1
- KAEZRSFWWCTVNP-UHFFFAOYSA-N (4-methoxyphenyl)-(4-methoxyphenyl)imino-oxidoazanium Chemical compound C1=CC(OC)=CC=C1N=[N+]([O-])C1=CC=C(OC)C=C1 KAEZRSFWWCTVNP-UHFFFAOYSA-N 0.000 description 1
- ZISCOWXWCHUSMH-VOTSOKGWSA-N (E)-4-nitrostilbene Chemical compound C1=CC([N+](=O)[O-])=CC=C1\C=C\C1=CC=CC=C1 ZISCOWXWCHUSMH-VOTSOKGWSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 1
- NZFLWVDXYUGFAV-UHFFFAOYSA-N 1-methyl-2-acetylpyrrole Chemical compound CC(=O)C1=CC=CN1C NZFLWVDXYUGFAV-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- JORFLUCVQONOPN-UHFFFAOYSA-N 12-pyren-1-yldodecanoic acid Chemical compound C1=C2C(CCCCCCCCCCCC(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 JORFLUCVQONOPN-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- YENVMPPRTXICRT-UHFFFAOYSA-N 2-(2,6-dicarboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C1=C(C(O)=O)C=CC=C1C(O)=O YENVMPPRTXICRT-UHFFFAOYSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- DZLUPKIRNOCKJB-UHFFFAOYSA-N 2-methoxy-n,n-dimethylacetamide Chemical compound COCC(=O)N(C)C DZLUPKIRNOCKJB-UHFFFAOYSA-N 0.000 description 1
- XTTIQGSLJBWVIV-UHFFFAOYSA-N 2-methyl-4-nitroaniline Chemical compound CC1=CC([N+]([O-])=O)=CC=C1N XTTIQGSLJBWVIV-UHFFFAOYSA-N 0.000 description 1
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical group C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-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
- NDXGRHCEHPFUSU-UHFFFAOYSA-N 3-(3-aminophenyl)aniline Chemical group NC1=CC=CC(C=2C=C(N)C=CC=2)=C1 NDXGRHCEHPFUSU-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
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical compound C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
【発明の詳細な説明】 〔技術分野〕 本発明は、ポリイミド系の機能性複合体、並びに、こ
れらの製造法に関する。Description: TECHNICAL FIELD The present invention relates to a polyimide-based functional composite and a method for producing the same.
この機能性複合体は、熱、光、電気、力等の外的刺激
によって性質を変化させる性能を有し、例えば静電防止
材料、半導体素子として使用することができる。This functional composite has a property of changing its properties by an external stimulus such as heat, light, electricity, or force, and can be used as, for example, an antistatic material or a semiconductor element.
従来、機能性低分子有機化合物の中には、熱、光、電
気、力等の外的刺激により相転移や分子配向のように物
理的状態を変化させるか、あるいは、化学反応を起こす
か等の応答作用を示すものがあり、これらの応答が可逆
的であるものも多く、その性質を利用した機能性有機材
料が広く用いられている。Conventionally, functional low-molecular-weight organic compounds include those that change the physical state, such as phase transition or molecular orientation, by external stimuli such as heat, light, electricity, or force, or that cause a chemical reaction. Some of them exhibit a reversible action, and many of these responses are reversible, and functional organic materials utilizing their properties are widely used.
例えば、染料中間体、蛍光物質のように光により作用
するもの、液晶物質のように熱、電場、磁場に作用する
もの、導電性物質のように電気により作用するものが、
それである。その他に、吸着・吸収性、圧電性、焦電
性、非線形光学性等を示すものも多い。これらは、単品
で、あるいは、基材に充填又は塗布されて複合体で使用
される。For example, dye intermediates, those that act on light such as fluorescent substances, those that act on heat, electric and magnetic fields like liquid crystal substances, and those that act on electricity like conductive substances,
That is it. In addition, many of them exhibit adsorption / absorption, piezoelectricity, pyroelectricity, non-linear optical properties, and the like. These are used alone or in a composite after being filled or applied to a substrate.
また、機能性低分子有機材料を高分子物質と複合して
機能性複合体として使用する試みも数多く提案されてい
る。高分子物質を主成分とする基材上にラミネートする
技術や、高分子に練り込む、あるいは、溶解して混ぜ込
む等の方法によりブレンド物として使用する技術が、数
多くの学術文献、特許公報に示されている。Also, many attempts have been made to use a low-molecular organic material as a functional composite by combining it with a high-molecular substance. Numerous academic literatures and patent publications describe technologies for laminating on a base material mainly composed of a polymer substance, and techniques for kneading the polymer or using it as a blend by dissolving and mixing. It is shown.
一例を挙げると、Journal of Applied Polymer Scien
ce.,29.3955（1984）には、高分子に液晶物質を混合し
て、高分子／液晶複合膜を調製した例が報告されてい
る。また、特開昭63−265932号公報には、高分子物質に
導電性のある低分子有機化合物を混合する技術が、特開
昭62−177803号公報には、フタロシアニンを芳香族ポリ
アミドに入れて導電性フィルムを作る技術が、特開平２
−29721号公報には、高分子に非線形光学化合物を入れ
る技術が、それぞれ示されている。One example is the Journal of Applied Polymer Scien
ce., 29 in the .3955 (1984), by mixing liquid crystal material in a polymer, examples were prepared polymer / liquid crystal composite film have been reported. JP-A-63-265932 discloses a technique of mixing a conductive substance with a low-molecular-weight organic compound in a polymer substance, and JP-A-62-177803 discloses a technique in which phthalocyanine is added to an aromatic polyamide. The technology for making conductive films is disclosed in
Japanese Patent No. 29721 discloses a technique for incorporating a nonlinear optical compound into a polymer.
一方、ポリイミドの前駆体であるポリアミド酸に機能
性低分子有機化合物を混合させることに関して、特開平
２−3013号公報には、液晶物質とブレンドすること、特
開平１−282265号公報には、顔料をポリイミドに入れカ
ラーフィルターを作ることが示されている。On the other hand, with respect to mixing a functional low-molecular-weight organic compound with polyamic acid, which is a precursor of polyimide, JP-A-2-3013 discloses blending with a liquid crystal substance, and JP-A-1-282265 discloses that It is shown that the pigment is put into polyimide to make a color filter.
このようにポリアミド酸あるいはポリイミドに機能性
低分子有機化合物をブレンドする場合に、フィルムの機
能性を高めるために、機能性低分子有機化合物を均質に
複合化する、あるいは、機能性低分子有機化合物の配合
量を多くし機能化を高める等の複合体の高次構造を制御
することが必要である。When blending a functional low-molecular-weight organic compound with a polyamic acid or a polyimide as described above, in order to enhance the functionality of the film, the functional low-molecular-weight organic compound is uniformly compounded, or the functional low-molecular-weight organic compound is It is necessary to control the higher order structure of the composite, for example, by increasing the blending amount of the compound to enhance the functionalization.
また、これらのブレンド物等は、ポリマーと機能性低
分子有機化合物を単に物理的手段により混合させる方法
により、例えば、高分子に機械的に練り込む、あるい
は、溶融、溶解して混ぜ込む等の方法により、複合体と
するのが通例である。In addition, these blends and the like, by a method of simply mixing the polymer and the functional low-molecular-weight organic compound by physical means, for example, mechanically kneading the polymer, or melting and dissolving and mixing It is customary to form a composite by a method.
このような方法によって複合化された複合体は、ポリ
マーと機能性低分子有機化合物との相溶性などの関係か
ら、機能性低分子有機化合物の配合量によっては相分離
状態や不均一な混合状態になる場合が多く、複合体の機
械的性質と機能性を兼備させた素材の開発は、これまで
難しいものであった。特に、機能性を高めるために機能
性低分子有機化合物を高配合させた材料においては、成
形体が脆性化し強度を低下させる傾向が強いため、強靭
で且つ機能性に優れた複合体を得ることは容易ではなか
った。Due to the compatibility between the polymer and the functional low-molecular-weight organic compound, the composite compounded by such a method may be in a phase-separated state or a non-uniform mixed state depending on the blending amount of the functional low-molecular-weight organic compound. In many cases, it has been difficult to develop a material that combines the mechanical properties and functionality of a composite. In particular, in a material in which a functional low-molecular-weight organic compound is highly blended in order to enhance the functionality, since a molded article has a strong tendency to become brittle and reduce the strength, it is necessary to obtain a tough composite having excellent functionality. Was not easy.
本発明の目的は、機能性低分子有機化合物が本来有す
る機能性を高度に発現し、且つ、良好な機械的性質を有
する機能性複合体、及び、その製造法を提供することで
ある。An object of the present invention is to provide a functional complex which expresses the functionality inherent in a functional low molecular weight organic compound to a high degree and has good mechanical properties, and a method for producing the same.
この目的を達成するため、機能性低分子有機化合物と
ポリマーの複合化を行う際に、物理的手段に加え化学的
反応を採り入れ、機能性低分子有機化合物が複合体中に
均一に分散・混合されるようにしたものである。In order to achieve this purpose, when combining the functional low-molecular-weight organic compound with the polymer, a chemical reaction is adopted in addition to physical means, and the functional low-molecular-weight organic compound is uniformly dispersed and mixed in the composite. It is made to be done.
つまり、テトラカルボン酸二無水物、芳香族ジアミン
及び多価アミンを主成分としたポリアミド酸溶液に機能
性低分子有機化合物を配合するという物理的な手法に加
え、両者の混合溶液中で高分子ゲルを化学反応により形
成させるという化学的な手法を採り入れ、この独特な手
法により、機能性を有する機能性低分子有機化合物をポ
リマー中に均一に複合して、更に脱水・閉環反応によ
り、耐熱性に優れた成形体を与えるポリイミド系複合体
の前駆体としても有用である。In other words, in addition to the physical method of blending a functional low-molecular-weight organic compound into a polyamic acid solution containing tetracarboxylic dianhydride, aromatic diamine, and polyamine as main components, a polymer solution is mixed in a mixed solution of both. Adopting a chemical method of forming a gel by a chemical reaction, this unique method uniformly combines functional low-molecular organic compounds with functionality in a polymer, and furthermore, heat-resistant by dehydration and ring closure reaction It is also useful as a precursor of a polyimide-based composite that gives a molded article having excellent heat resistance.
また、本発明の目的は、このポリイミド系複合体、及
び、その製造法を提供することである。Another object of the present invention is to provide the polyimide-based composite and a method for producing the same.
本発明は、下記の通りである。 The present invention is as follows.
（１）機能性低分子有機化合物〔Ａ〕と、テトラカルボ
ン酸二無水物、芳香族ジアミン及び多価アミンを主成分
としたポリアミド酸の三次元網目構造体（高分子ゲル）
〔Ｂ〕の脱水・閉環反応により生成したポリイミド化体
〔Ｃ〕とからなるポリイミド系機能性複合体。(1) Three-dimensional network structure (polymer gel) of functional low molecular weight organic compound [A] and polyamic acid containing tetracarboxylic dianhydride, aromatic diamine and polyamine as main components
A polyimide-based functional composite comprising the polyimide (C) produced by the dehydration and ring closure reaction of (B).
（２）機能性低分子有機化合物が、外的刺激により応答
作用を示す物質であり、シッフ系液晶物質、アゾキシ系
液晶物質、シアノビフェニル系液晶物質、シアノフェニ
ル系液晶物質、ナフタレン誘導体、スピロピラン系化合
物、アゾベンゼン系化合物、フタロシアニン系化合物、
ポリフィリン系化合物、シアニン系化合物、キニザリン
系化合物、スチルベン系化合物、ヘミシアニン系化合
物、クラウンエーテル類、テトラチアフルバレン、ビス
エチレンジチオテトラチアフルバレン、テトラシアノキ
ノジメタン、テトラシアノエチレン、ピレン誘導体、ピ
ロール系化合物、アセチレン系化合物、アントラセン誘
導体の中から選ばれた少なくとも一種類の物質である請
求項（１）記載のポリアミド酸系機能性複合体。(2) A functional low molecular organic compound is a substance that exhibits a response action by an external stimulus, and is a Schiff liquid crystal substance, an azoxy liquid crystal substance, a cyanobiphenyl liquid crystal substance, a cyanophenyl liquid crystal substance, a naphthalene derivative, a spiropyran derivative. Compounds, azobenzene compounds, phthalocyanine compounds,
Porphyrin-based compounds, cyanine-based compounds, quinizarin-based compounds, stilbene-based compounds, hemocyanin-based compounds, crown ethers, tetrathiafulvalene, bisethylenedithiotetrathiafulvalene, tetracyanoquinodimethane, tetracyanoethylene, pyrene derivatives, pyrrole-based compounds The polyamic acid-based functional complex according to claim 1, which is at least one substance selected from a compound, an acetylene-based compound, and an anthracene derivative.
（３）フィルム状である請求項（１）記載のポリイミド
系機能性複合体。(3) The polyimide-based functional composite according to (1), which is in the form of a film.
（４）機能性低分子有機化合物〔Ａ〕と、テトラカルボ
ン酸二無水物、芳香族ジアミン及び多価アミンを主成分
としたポリアミド酸の三次元網目構造体（高分子ゲル）
〔Ｂ〕とからなるポリアミド系機能性複合体を脱水・閉
環反応させることを特徴とするポリイミド系機能性複合
体の製造法。(4) A three-dimensional network structure (polymer gel) of a functional low molecular organic compound [A] and a polyamic acid containing tetracarboxylic dianhydride, aromatic diamine and polyamine as main components.
A method for producing a polyimide-based functional composite, comprising subjecting the polyamide-based functional composite comprising [B] to a dehydration and ring-closing reaction.
本発明にかかるポリイミド系機能性複合体の前駆体で
あるポリアミド酸系機能性複合体（以下、単に、「機能
性複合体」ということがある）は、複合体の全量に対
し、97重量％を超えない量の有機溶媒を含んだ状態で、
形状を 保持できるような自己支持性のある三次元網目構造体
である高分子ゲルを経由して与えられるものである。こ
の高分子ゲルより溶媒を除去して得られた複合体は、高
分子物質であるポリアミド酸を支持体（マトリックス）
として働かせ、且つ、マトリックス中に分散した機能性
低分子有機化合物が本来有するところの外的刺激（熱、
光、電気、力など）により応答作用を示す機能性を発現
させた材料であって、高分子物質の強靭さと機能性低分
子有機化合物の機能性を兼備した優れた材料である。The polyamic acid-based functional composite (hereinafter, sometimes simply referred to as “functional composite”), which is a precursor of the polyimide-based functional composite according to the present invention, is 97% by weight based on the total amount of the composite. Containing an amount of organic solvent not exceeding
It is provided via a polymer gel, which is a three-dimensional network structure having self-supporting properties that can maintain its shape. The complex obtained by removing the solvent from this polymer gel is made of a polymer material, polyamic acid, as a support (matrix).
And external stimuli (heat,
It is a material that exhibits functionality exhibiting a response action by light, electricity, force, etc., and is an excellent material that has both the toughness of a polymer substance and the functionality of a functional low-molecular organic compound.
本発明では、主に以下の調製法により、機能性低分子
有機化合物とポリアミド酸とからなる機能性複合体を得
ることができる。In the present invention, a functional complex comprising a functional low-molecular-weight organic compound and a polyamic acid can be obtained mainly by the following preparation method.
主にテトラカルボン酸二無水物、芳香族ジアン及び多
価アミンを有機溶媒中で重付加反応させ、有機溶媒に均
一に溶解したポリアミド酸溶液を調製する。A polycarboxylic acid solution in which a tetracarboxylic dianhydride, an aromatic dian and a polyvalent amine are mainly subjected to a polyaddition reaction in an organic solvent to be uniformly dissolved in the organic solvent is prepared.
機能性低分子有機化合物を、前述のポリアミド酸溶液
に溶解又は分散させる。The functional low molecular weight organic compound is dissolved or dispersed in the above-mentioned polyamic acid solution.
機能性低分子有機化合物とポリアミド酸との混合溶液
がゲル化し、高分子ゲルを形成する前に、フィルム等の
形状に賦形させるため、基材上等に混合溶液を流延させ
る。Before the mixed solution of the functional low-molecular-weight organic compound and the polyamic acid gels and forms a polymer gel, the mixed solution is cast on a substrate or the like so as to be shaped into a film or the like.
基材上に流延された機能性低分子有機化合物とポリア
ミド酸との混合溶液を、０〜100℃の温度条件で少なく
とも１分間以上静置し、ポリアミド酸成分の官能基によ
る架橋反応を更に進め、賦形された機能性低分子有機化
合物とポリアミド酸との複合された高分子ゲルを得る。The mixed solution of the functional low-molecular-weight organic compound and the polyamic acid cast on the substrate is allowed to stand for at least 1 minute at a temperature of 0 to 100 ° C. to further perform a cross-linking reaction by a functional group of the polyamic acid component. By proceeding, a composite polymer gel of the shaped functional low molecular organic compound and the polyamic acid is obtained.
機能性低分子有機化合物／ポリアミド酸の複合化され
た高分子ゲルからポリアミド酸成分の脱水・閉環反応を
進め、ポリアミド酸成分をポリイミド化する。The polyamic acid component is dehydrated and ring-closed from the composite polymer gel of the functional low molecular weight organic compound / polyamic acid, and the polyamic acid component is converted into a polyimide.
以下、調製方法の詳細について述べる。 Hereinafter, details of the preparation method will be described.
ポリアミド酸成分の重付加反応は、主にテトラカルボ
ン酸二無水物、芳香族ジアミン及び多価アミンを有機溶
媒中で混合させることにより行われ、有機溶媒に均一に
溶解したポリアミド酸溶液が得られる。The polyaddition reaction of the polyamic acid component is mainly performed by mixing tetracarboxylic dianhydride, aromatic diamine and polyvalent amine in an organic solvent, and a polyamic acid solution uniformly dissolved in the organic solvent is obtained. .
本発明において、テトラカルボン酸二無水物、芳香族
ジアミン及び多価アミンを重付加反応させることによ
り、最初は有機溶媒に均一に溶解したポリアミト酸溶液
が得られる。しかし、このポリアミド酸溶液の状態は中
間体的なものであり、ポリアミド酸に含まれる官能基に
よる架橋反応が有機溶媒中で徐々に進行することによ
り、ポリアミド酸成分の三次元網目構造が形成され、最
終的には、有機溶媒を含んだポリアミド酸の高分子ゲル
となる。In the present invention, by performing a polyaddition reaction of a tetracarboxylic dianhydride, an aromatic diamine, and a polyamine, a polyamitic acid solution which is initially uniformly dissolved in an organic solvent can be obtained. However, the state of the polyamic acid solution is an intermediate state, and a three-dimensional network structure of the polyamic acid component is formed by the cross-linking reaction by the functional group contained in the polyamic acid gradually progressing in the organic solvent. Finally, a polyamic acid polymer gel containing an organic solvent is obtained.
テトラカルボン酸二無水物、芳香族ジアミン及び多価
アミンの反応は、結局のところ、テトラカルボン酸二無
水物とアミン類との反応であり、具体的な調製方法で
は、窒素ガスのような不活性雰囲気下、芳香族ジアミン
と多価アミンを有機溶媒で溶解させた溶液中にテトラカ
ルボン酸二無水物を加えればよい。テトラカルボン酸二
無水物は、固形で加えても、溶媒で溶解させた液状で加
えてもよい。テトラカルボン酸二無水物に、芳香族ジア
ミンと多価アミンを加える方法でもよい。The reaction of tetracarboxylic dianhydride, aromatic diamine and polyamine is, after all, a reaction of tetracarboxylic dianhydride with amines. Under an active atmosphere, tetracarboxylic dianhydride may be added to a solution in which an aromatic diamine and a polyamine are dissolved in an organic solvent. The tetracarboxylic dianhydride may be added in a solid form or in a liquid form dissolved in a solvent. A method of adding an aromatic diamine and a polyamine to the tetracarboxylic dianhydride may be used.
本発明で用いられテトラカルボン酸二無水物の代表例
は、ピロメリット酸二無水物、3,3′,4,4′−ベンゾフ
ェノンテトラカルボン酸二無水物、3,3′,4,4′−ビフ
ェニルテトラカルボン酸二無水物、2,3,3′,4′−ビフ
ェニルテトラカルボン酸二無水物、2,2′,3,3′−ビフ
ェニルテトラカルボン酸二無水物、2,2′,6,6′−ビフ
ェニル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、1,2,5,6−ナフタレンテ
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、ビス（3,4−ジカルボ
キシフェニル）スルホン二無水物、ビス（3,4−ジカル
ボキシフェニル）エーテル二無水物、3,4,9,10−ペリレ
ンテトラカルボン酸二無水物、ナフタレン−1,24,5−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、ベンゼン−1,2,3,4−テトラカ
ルボン酸二無水物などである。また、分子中にアミド
基、エステル基、エーテル基、スルホン基、メチレン
基、プロパン基、フェニレン基、イミダゾール基、チア
ゾール基等を任意に組合せた比較的分子量の大きいテト
ラカルボン酸二無水物やフッ素等のハロゲン基を構造中
に含むテトラカルボン酸二無水物等も使用できる。これ
らは、単独又は二種以上の混合物で用いることができ
る。Representative examples of the tetracarboxylic dianhydride used in the present invention include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4 ' -Biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2 ', 6,6'-biphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, naphthalene-1,24,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracar And boric acid dianhydride and benzene-1,2,3,4-tetracarboxylic acid dianhydride. Further, tetracarboxylic dianhydride or fluorine having a relatively large molecular weight in which any combination of an amide group, an ester group, an ether group, a sulfone group, a methylene group, a propane group, a phenylene group, an imidazole group, a thiazole group, etc. A tetracarboxylic dianhydride containing a halogen group in its structure can also be used. These can be used alone or in a mixture of two or more.
テトラカルボン酸二無水物と反応させる芳香族ジアミ
ンの代表例としては、メタフェニレンジアミン、パラフ
ェニレンジアミン、4,4′−ジアミノジフェニルプロパ
ン、4,4′−ジアミノジフェニルメタン、3,3′−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、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エーテル、
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′−ジアミノベンゾフェノ
ン、3,3′−ジアミノベンゾフェノン、2,2′−ビス（４
−アミノフェニル）プロパン、ベンジジン、3,3′−ジ
アミノビフェニル、2,6−ジアミノピリジン、2,5−ジア
ミノピリジン、3,4−ジアミノピリジン、ビス〔４−
（４−アミノフェノキシ）フェニル〕スルホン、ビス
〔４−（３−アミノフェノキシ）フェニル〕スルホン、
ビス〔４−（４−アミノフェノキシ）フェニル〕エーテ
ル、ビス〔４−（３−アミノフェノキシ）フェニル〕エ
ーテル、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−（３−アミノ
フェノキシ）フェニル〕プロパン、4,4′−ビス（４−
アミノフェノキシ）ビフェニル、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、2,2′−ビス〔４−（３−アミノフ
ェノキシ）フェニル〕ヘキサフロロプロパン、1,5−ジ
アミノナフタレン、2,6−ジアミノナフタレン及びこれ
らの誘導体等が挙げられる。また、イソフタル酸ジヒド
ラジド等のジヒドラジド化合物も使用できる。これら
は、単独又は二種以上の混合物で用いることができる。Representative examples of aromatic diamines to be reacted with tetracarboxylic dianhydride include metaphenylenediamine, paraphenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane , 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-
Diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether,
3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 2,2'-bis (4
-Aminophenyl) propane, benzidine, 3,3'-diaminobiphenyl, 2,6-diaminopyridine, 2,5-diaminopyridine, 3,4-diaminopyridine, bis [4-
(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone,
Bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 2,2'-bis [4- (4-aminophenoxy)
Phenyl] propane, 2,2'-bis [4- (3-aminophenoxy) phenyl] propane, 4,4'-bis (4-
Aminophenoxy) biphenyl, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2'-bis [4- (3-aminophenoxy) phenyl] hexafluoro Examples include propane, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene and derivatives thereof. Further, dihydrazide compounds such as isophthalic acid dihydrazide can also be used. These can be used alone or in a mixture of two or more.
多価アミンの代表例としては、3,3′,4,4′−テトラ
アミノジフェニルエーテル、3,3′,4,4′−テトラアミ
ノジフェニルメタン、3,3′,4,4′−テトラアミノベン
ゾフェノン、3,3′,4,4′−テトラアミノジフェニルス
ルホン、3,3′,4,4′−テトラアミノビフェニル、1,2,
4,5−テトラアミノベンゼン、3,3′,4−トリアミノジフ
ェニルエーテル、3,3′,4−トリアミノジフェニルメタ
ン、3,3′,4−トリアミノベンゾフェノン、3,3′,4−ト
リアミノジフェニルスルホン、3,3′,4−トリアミノビ
フェニル、1,2,4−トリアミノベンゼン及びこれらの化
合物の官能基を第四級アンモニウム塩の形に変えた化合
物類、例えば3,3′,4,4′−テトラアミノビフェニル・
四塩酸塩等が挙げられる。第四級アンモニウム塩として
は、塩酸塩の他に、硫酸塩、水酸塩の形で用いることも
できる。これらの化合物の中には、多価アミンの官能基
の全てが第四級アンモニウム塩の形でないものも含まれ
る。また、上記物質の中には、水和物として存在してい
るものもあり、これらの多価アミン類は、単独又は二種
以上の混合物で用いることもできる。脂肪族類の多価ア
ミンを使用することも可能である。Representative examples of polyamines include 3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminodiphenylmethane, 3,3 ', 4,4'-tetraaminobenzophenone , 3,3 ', 4,4'-tetraaminodiphenylsulfone, 3,3', 4,4'-tetraaminobiphenyl, 1,2,
4,5-tetraaminobenzene, 3,3 ', 4-triaminodiphenyl ether, 3,3', 4-triaminodiphenylmethane, 3,3 ', 4-triaminobenzophenone, 3,3', 4-triamino Diphenyl sulfone, 3,3 ', 4-triaminobiphenyl, 1,2,4-triaminobenzene and compounds in which the functional group of these compounds has been changed to a quaternary ammonium salt, for example, 3,3', 4,4'-tetraaminobiphenyl
Tetrahydrochloride and the like. As the quaternary ammonium salt, in addition to the hydrochloride, it can be used in the form of sulfate or hydroxide. Some of these compounds include those in which all of the functional groups of the polyamine are not in the form of a quaternary ammonium salt. In addition, some of the above substances exist as hydrates, and these polyamines can be used alone or as a mixture of two or more kinds. It is also possible to use aliphatic polyvalent amines.
テトラカルボン酸二無水物、芳香族ジアミン及び多価
アミンを主成分としたポリアミド酸の反応において用い
られる有機溶媒は、反応に対して不活性であると同時
に、使用するモノマー類及び重合された高分子量物を溶
解させることが必要である。代表的なものとして、N,N
−ジメチルホルムアミド、N,N−ジメチルアセトアミ
ド、N,N−ジエチルホルムアミド、N,N−ジエチルアセト
アミド、ジメチルスルホキシド、Ｎ−メチル−２−ピロ
リドン、N,N−ジメチルメトキシアセトアミド、ヘキサ
メチルホスホアミド、ピリジン、ジメチルスルホン、テ
トラメチレンスルホン、クレゾール、フェノール、キシ
レノール等のフェノール類や、ベンゼン、トルエン、キ
シレン、ベンゾニトリル、ジオキサン、シクロヘキサン
等が挙げられる。The organic solvent used in the reaction of the polyamic acid containing tetracarboxylic dianhydride, aromatic diamine and polyamine as the main components is inert to the reaction, and at the same time, the monomers used and the polymerized high It is necessary to dissolve the molecular weight material. Typically, N, N
-Dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylmethoxyacetamide, hexamethylphosphamide, pyridine And phenols such as dimethylsulfone, tetramethylenesulfone, cresol, phenol and xylenol, and benzene, toluene, xylene, benzonitrile, dioxane and cyclohexane.
これらの溶媒は、単独又は二種以上混合して使用され
る。These solvents are used alone or in combination of two or more.
テトラカルボン酸二無水物、芳香族ジアミン及び多価
アミンを主成分としたポリアミド酸の反応は、有機溶媒
中、−10〜30℃の温度条件下、特に好ましくは、−５〜
20℃の温度範囲で反応させる。反応時間は、５時間以
内、好ましくは２時間以内である。The reaction of polycarboxylic acid containing tetracarboxylic dianhydride, aromatic diamine and polyamine as main components is carried out in an organic solvent at a temperature of -10 to 30 ° C, particularly preferably -5 to -30 ° C.
React in a temperature range of 20 ° C. The reaction time is within 5 hours, preferably within 2 hours.
反応温度が−10℃より低い場合は、取扱性や反応方法
の難しさに加え、温度が低すぎるため反応自身が充分に
進まない場合があり、好ましくない。反応温度が30℃を
超える場合は、架橋反応が有機溶媒中で進行する速度が
速くポリアミド酸成分の三次元網目構造が形成されると
ころの所謂ゲル化に至るまでの反応が過度に速くなる。
複合化に際して、ゲル化が起こる前に、両者を複合させ
ることが好ましい。機能性低分子有機化合物を複合化さ
せる以前に、ポリアミド酸成分のゲル化が起こった場
合、均一な複合体が得られないことがある。従って、ポ
リアミド酸成分の反応温度は、−10〜30℃の温度条件
下、特に好ましくは、−５〜20℃の温度範囲で反応させ
る。If the reaction temperature is lower than -10 ° C, the reaction itself may not proceed sufficiently because the temperature is too low, in addition to the difficulty in handling and the reaction method, which is not preferable. When the reaction temperature is higher than 30 ° C., the rate at which the cross-linking reaction proceeds in the organic solvent is so fast that the reaction until the so-called gelation where the three-dimensional network structure of the polyamic acid component is formed becomes excessively fast.
At the time of compounding, it is preferable that both are compounded before gelation occurs. If the gelling of the polyamic acid component occurs before the functional low molecular weight organic compound is complexed, a uniform complex may not be obtained. Accordingly, the polyamic acid component is reacted at a temperature of -10 to 30C, particularly preferably in a temperature range of -5 to 20C.
一般に、テトラカルボン酸二無水物と芳香族ジアミン
からポリアミド酸を調製する場合、分子量を上げるため
に両成分を可能な限り等モルで反応させることが好まし
い。Generally, when preparing a polyamic acid from a tetracarboxylic dianhydride and an aromatic diamine, it is preferable to react both components in the same molar amount as possible in order to increase the molecular weight.
本発明においても、重合度を高めるため、テトラカル
ボン酸二無水物／芳香族ジアミンのモル比を100/（50〜
100）、テトラカルボン酸二無水物／芳香族ジアミン／
多価アミンのモル比を、100/（50〜100）／（２〜25）
の範囲内にとどめ、且つ、テトラカルボン酸二無水物と
アミン類の反応基の当量比（酸価／アミン価の比）を0.
95〜1.05の範囲内に合わせることが、機械的性質等に優
れた複合体の高分子ゲルあるいは成形体を得る上で好適
である。In the present invention, in order to increase the degree of polymerization, the molar ratio of tetracarboxylic dianhydride / aromatic diamine is set to 100 / (50 to 50).
100), tetracarboxylic dianhydride / aromatic diamine /
The molar ratio of the polyvalent amine is 100 / (50-100) / (2-25)
And the equivalent ratio of the reactive group between tetracarboxylic dianhydride and amines (ratio of acid value / amine value) is set to 0.1.
It is preferable to set it within the range of 95 to 1.05 in order to obtain a composite polymer gel or molded article having excellent mechanical properties and the like.
この範囲を外れた組成でモノマーを配合し反応させた
場合、ポリアミド酸の重合度が上らず、得られる複合体
の性質、例えば、機械的性質等も著しく低いものとな
る。また、未反応のモノマー類が重合溶液中に不純物と
して残存するため、乾燥後に得られた複合体の機能性等
に悪影響を及ぼすことにもなる。When a monomer having a composition outside this range is blended and reacted, the degree of polymerization of the polyamic acid does not increase, and the properties of the resulting composite, for example, mechanical properties and the like are extremely low. In addition, since unreacted monomers remain as impurities in the polymerization solution, the functions and the like of the composite obtained after drying are adversely affected.
反応させるテトラカルボン酸二無水物／多価アミンの
モル比は、100/（２〜25）であることが好ましく、特に
好ましくは、100/（４〜15）の範囲であるが、用いるモ
ノマーの種類によりその好適な組成範囲が若干ずれる場
合もある。The molar ratio of tetracarboxylic dianhydride / polyamine to be reacted is preferably 100 / (2 to 25), particularly preferably in the range of 100 / (4 to 15). The preferred composition range may slightly deviate depending on the type.
多価アミンは、ポリアミド酸の高分子ゲルの架橋点と
して働き、その配合比によりポリアミド酸の高分子ゲル
中に存在する網目濃度（架橋密度）を変化させる。多価
アミンの配合モル数が、テトラカルボン酸二無水物100
モルに対し２モルより小さいと、溶液中でのポリアミド
酸成分の架橋点が少なくなり、三次元網目構造が不完全
になり、自己支持性のある高分子ゲルとなりにくい。多
価アミンの配合モル数が25モルより大きいと、三次元網
目構造の架橋点の増加と架橋点間分子量の低下を招き、
ポリアミド酸成分の膨潤性を低下させ、むしろ脆性的な
機能性複合体を与える。従って、多価アミンの配合モル
数は、テトラカルボン酸二無水物100モルに対し２〜25
モルの範囲内がよい。これらのテトラカルボン酸二無水
物、芳香族ジアミン及び多価アミンは、それぞれ単独又
は二種以上の混合物で用いられるため、得られるポリマ
ーは共重合体のものを含む。また、特定の成分からなる
ポリアミド酸と、このポリアミド酸の構成成分の少なく
とも一種類が異なるポリアミド酸とが混合した、ポリア
ミド酸の混合物も含まれる。The polyvalent amine functions as a crosslinking point of the polyamic acid polymer gel, and changes the network concentration (crosslink density) existing in the polyamic acid polymer gel depending on the blending ratio. The compounding mole number of the polyvalent amine is tetracarboxylic dianhydride 100
If it is less than 2 moles, the number of cross-linking points of the polyamic acid component in the solution decreases, the three-dimensional network structure becomes incomplete, and a polymer gel having a self-supporting property is hardly obtained. When the compounding mole number of the polyvalent amine is more than 25 moles, the crosslinking points of the three-dimensional network structure increase and the molecular weight between the crosslinking points decreases,
It reduces the swelling of the polyamic acid component and gives a rather brittle functional composite. Therefore, the compounding mole number of the polyvalent amine is 2 to 25 with respect to 100 moles of tetracarboxylic dianhydride.
It is better to be within the molar range. Since these tetracarboxylic dianhydrides, aromatic diamines and polyamines are used alone or as a mixture of two or more, the resulting polymers include copolymers. Further, a polyamic acid mixture in which a polyamic acid composed of a specific component and a polyamic acid in which at least one of the constituent components of the polyamic acid is different is also included.
このようにして得られたポリアミド酸溶液は、前述の
ように、ポリアミド酸の高分子ゲルに至るまでの中間的
なものであり、ポリアミド酸に含まれる官能基による架
橋反応が有機溶媒中で徐々に進行することにより、ポリ
アミド酸成分の三次元網目構造が形成されゲル化を起こ
し、最終的には、有機溶媒を含んだポリアミド酸の高分
子ゲルを与えるものである。また、この高分子ゲルの中
には、テトラカルボン酸二無水物と芳香族ジアミンの反
応により、主に生成された三次元網目構造に関与しない
線状の高分子量物も含まれる。As described above, the polyamic acid solution thus obtained is intermediate between the polyamic acid and the polymer gel, and the crosslinking reaction by the functional group contained in the polyamic acid is gradually performed in an organic solvent. As a result, a three-dimensional network structure of the polyamic acid component is formed and gelation occurs, and finally, a polyamic acid polymer gel containing an organic solvent is provided. In addition, this polymer gel includes a linear high molecular weight material not involved in the three-dimensional network structure, which is mainly generated by the reaction between the tetracarboxylic dianhydride and the aromatic diamine.
次に、機能性低分子有機化合物を、前述のポリアミド
酸溶液に溶解又は分散させて、複合化を行わせる。Next, the functional low-molecular-weight organic compound is dissolved or dispersed in the above-mentioned polyamic acid solution to perform complexation.
機能性低分子有機化合物とポリアミド酸とを複合する
方法としては、次のような方法がある。As a method of combining the functional low molecular weight organic compound and the polyamic acid, there is the following method.
未だゲル化に至っていないテトラカルボン酸二無水
物、芳香族ジアミン及び多価アミンを主成分としたポリ
アミド酸溶液に、機能性低分子有機化合物を混合し、溶
解あるいは分散させ、混合溶液の状態を経由して複合化
を行わせる。この場合、機能性低分子有機化合物を予め
有機溶媒に溶解又は分散させた後にポリアミド酸溶液に
加え、混合溶液としてもよい。A functional low-molecular-weight organic compound is mixed with a polyamic acid solution mainly composed of tetracarboxylic dianhydride, aromatic diamine and polyamine which has not yet been gelled, and dissolved or dispersed. And make it composite via In this case, the functional low molecular weight organic compound may be dissolved or dispersed in an organic solvent in advance and then added to the polyamic acid solution to form a mixed solution.
機能性低分子有機化合物を溶かし込んだ有機溶媒の
溶液中で、ポリアミド酸成分の重付加反応を行わせ、混
合溶液の状態を経由して複合化を行わせる。A polyaddition reaction of a polyamic acid component is performed in a solution of an organic solvent in which a functional low-molecular-weight organic compound is dissolved, and a complex is formed via a mixed solution.
ポリアミド酸成分に複合される機能性を有する機能性
低分子有機化合物としては、刺激−応答作用などの機能
性を有する物質であり、例えば、液晶物質であるシッフ
系液晶、アゾキシ系液晶、シアノビフェニル系液晶、シ
アノフェニル系液晶等や、光機能性を有するナフタレン
誘導体、スピロピラン系化合物、アゾベンゼン系化合
物、フタロシアニン系化合物、ポルフィリン系化合物、
シアニン系化合物、キニザリン系化合物、スチルベン系
化合物、ヘミシアニン系化合物、クラウンエーテル類、
電子供与体のテトラチアフルバレン、ビスエチレンジチ
オテトラチアフルバレン、電子受容体のテトラシアノキ
ノエチレン、テトラシアノエチレン、その他ピレン誘導
体、ピロール系化合物、アセチレン化合物、アントラセ
ン誘導体等が機能性低分子有機化合物の代表として挙げ
られる。具体的な機能性低分子有機化合物としては、Ｐ
−エトキシベンジリデン−Ｐ′−ブチルアニリン、Ｐ−
アルキルベンジリデン−Ｐ′−シアノアニリン、4,4′
−アゾキシアニソール、4,4′−ジ−ｎ−ブトキシアゾ
キシベンゼン、４′−ペントキシ−４−シアノビフェニ
ル、コレステリルアセテート、４′−ｎ−ブトキシベン
ジリデン−４−シアノアニリン、Ｐ−カルボキシフェニ
ル−ｎ−アミノカーボネート、４′−シアノベンジリデ
ン−４−ｎ−ブトキシアニリン、テレフタルビス（Ｐ−
フロロアニリン）、４−ｎ−アミノ安息香酸−４−ｎ−
ブトキシフェニルエステル、N,N′−ビスベンジリデン
ベンジジン、4,4′−ｎ−アミノキシビフェニル（以
上、液晶物質）、ナフトール、ナフチルフタルアミック
酸、1,3,3−トリメチルインドリノベンゾピリロスピラ
ン、1,3,3−トリメチルインドリノナフトスピロオキサ
ジン、2,2′−アゾビス（２−アミジノプロピル）、1,
1′−アゾビス（シクロヘキサン−１−カルボニトリ
ル）、テトラアミノフタロシアニン銅錯体、フタロシア
ニンニッケル錯体、テトラカルボキシフタロシアニンコ
バルト錯体、5,10,15,20−テトラ（２−ニトロフェニ
ル）ポルフィリン、コバルト（II）2,3,7,8,12,13,17,1
8−オクタエチルポルフィリン、亜鉛（II）5,10,15,20
−テトラフェニルポルフィリン、Ｎ−オクタデシルメロ
シアニン、Ｎ−メチルメロシアニン、キニザリン、４−
ニトロスチルベン、４−アミノ−４′−ニトロスチルベ
ン、トランス−スチルベンオキサイド、ヘミシアニン、
12−クラウン４−エーテル、18−クラウン６−エーテ
ル、ジシクロヘキシル−18−クラウン６、ピレン、12
（１−ピレン）ドデカン酸、２−アセチル−Ｎ−メチル
ピロール、1,4−ジフェニルブタジエン、３−アミノフ
ェニルアセチレン、1,4,9,10−テトラヒドロキシアント
ラセン、１−アミノアントラセン、アントラキノン、Ｐ
−ニトロアニリン、Ｐ−フロロニトロベンゼン、２−メ
チル−４−ニトロアニリン等を例示することができる。Functional low molecular weight organic compounds having a function of being compounded with a polyamic acid component include substances having a function such as a stimulus-response action, for example, a liquid crystal substance such as a Schiff liquid crystal, an azoxy liquid crystal, or a cyanobiphenyl. Liquid crystal, cyanophenyl liquid crystal and the like, naphthalene derivatives having optical functionality, spiropyran compounds, azobenzene compounds, phthalocyanine compounds, porphyrin compounds,
Cyanine compounds, quinizarin compounds, stilbene compounds, hemicyanine compounds, crown ethers,
Electron donors tetrathiafulvalene, bisethylenedithiotetrathiafulvalene, electron acceptors tetracyanoquinoethylene, tetracyanoethylene, other pyrene derivatives, pyrrole compounds, acetylene compounds, anthracene derivatives, etc. are functional low molecular organic compounds. Representative. Specific examples of functional low-molecular organic compounds include P
-Ethoxybenzylidene-P'-butylaniline, P-
Alkylbenzylidene-P'-cyanoaniline, 4,4 '
Azoxyanisole, 4,4'-di-n-butoxyazoxybenzene, 4'-pentoxy-4-cyanobiphenyl, cholesteryl acetate, 4'-n-butoxybenzylidene-4-cyanoaniline, P-carboxyphenyl- n-aminocarbonate, 4'-cyanobenzylidene-4-n-butoxyaniline, terephthalbis (P-
Fluoroaniline), 4-n-aminobenzoic acid-4-n-
Butoxyphenyl ester, N, N'-bisbenzylidenebenzidine, 4,4'-n-aminoxybiphenyl (above, liquid crystal material), naphthol, naphthylphthalamic acid, 1,3,3-trimethylindolinobenzopyrrospirane , 1,3,3-trimethylindolinonaphthospiroxazine, 2,2'-azobis (2-amidinopropyl),
1'-azobis (cyclohexane-1-carbonitrile), tetraaminophthalocyanine copper complex, phthalocyanine nickel complex, tetracarboxyphthalocyanine cobalt complex, 5,10,15,20-tetra (2-nitrophenyl) porphyrin, cobalt (II) 2,3,7,8,12,13,17,1
8-octaethylporphyrin, zinc (II) 5,10,15,20
-Tetraphenylporphyrin, N-octadecylmerocyanine, N-methylmerocyanine, quinizarin, 4-
Nitrostilbene, 4-amino-4'-nitrostilbene, trans-stilbene oxide, hemicyanine,
12-crown 4-ether, 18-crown 6-ether, dicyclohexyl-18-crown 6, pyrene, 12
(1-pyrene) dodecanoic acid, 2-acetyl-N-methylpyrrole, 1,4-diphenylbutadiene, 3-aminophenylacetylene, 1,4,9,10-tetrahydroxyanthracene, 1-aminoanthracene, anthraquinone, P
-Nitroaniline, P-fluoronitrobenzene, 2-methyl-4-nitroaniline and the like.
機能性低分子有機化合物は、有機溶媒に可溶な物質で
あることが望まれるが、有機溶媒に溶解しない物質に関
しては、微粉化し有機溶媒に分散させて使用してもよ
い。The functional low molecular weight organic compound is desired to be a substance soluble in an organic solvent, but a substance that does not dissolve in the organic solvent may be used after being pulverized and dispersed in the organic solvent.
混合の際に、機能性低分子有機化合物を溶解させる溶
媒としては、代表的なものとして、N,N−ジメチルホル
ムアミド、N,N−ジメチルアセトアミド等のアミド系溶
媒、クレゾール、フェノール、キシレノール等のフェノ
ール類、ジメチルスルホン、テトラメチレンスルホン、
ジメチルスルホキシド等のスルホン系溶媒、ベンゼン、
トルエン、キシレン、シクロヘキサン等の炭化水素類、
塩化メチレン、ジクロロエタン等の塩素系溶媒、ケトン
類、アルコール類、Ｎ−メチル−２−ピロリドン、ベン
ゾニトリル、ピリジン、ジオキサン、ポリリン酸、N,N
−ジエチルアニリン等が挙げられる。これらの溶媒は、
単独又は二種以上混合して使用される。As a solvent for dissolving the functional low-molecular-weight organic compound at the time of mixing, N, N-dimethylformamide, N, N-dimethylacetamide and other amide solvents, cresol, phenol, xylenol, etc. Phenols, dimethyl sulfone, tetramethylene sulfone,
Sulfone solvents such as dimethyl sulfoxide, benzene,
Hydrocarbons such as toluene, xylene and cyclohexane,
Chlorine solvents such as methylene chloride and dichloroethane, ketones, alcohols, N-methyl-2-pyrrolidone, benzonitrile, pyridine, dioxane, polyphosphoric acid, N, N
-Diethylaniline and the like. These solvents are
Used alone or in combination of two or more.
テトラカルボン酸二無水物、芳香族ジアミン及び多価
アミンからなるポリアミド酸と機能性低分子有機化合物
との混合時に使用する有機溶媒の量は、機能性低分子有
機化合物とポリアミド酸成分との合計量（機能性複合体
の構成成分）が有機溶媒中に３〜40重量％、好ましくは
５〜30重量％含まれるように調整することが取扱性の点
で好ましい。機能性複合体の成分が３重量％未満では、
得られたゲルの自己支持性が悪く、40重量％超では固形
分濃度が高過ぎるため、フィルムに賦形する等の成形操
作が難しくなり、良好な成形体が得られない場合があ
る。The amount of the organic solvent used at the time of mixing the polyamic acid consisting of tetracarboxylic dianhydride, aromatic diamine and polyamine with the functional low molecular weight organic compound is the total of the functional low molecular weight organic compound and the polyamic acid component. It is preferable from the viewpoint of handleability that the amount (component of the functional complex) is adjusted to be 3 to 40% by weight, preferably 5 to 30% by weight in the organic solvent. When the component of the functional complex is less than 3% by weight,
If the self-supporting property of the obtained gel is poor, and if it exceeds 40% by weight, the solid content concentration is too high, so that a molding operation such as shaping on a film becomes difficult, and a good molded product may not be obtained.
これらの機能性低分子有機化合物に加えて、熱硬化性
樹脂あるいは熱可塑性樹脂のような高分子量成分、充填
剤、添加剤、強化繊維の少なくとも一種類を、共に含ん
だ状態で使用して機能性複合体を調製する場合もある。In addition to these functional low molecular weight organic compounds, at least one of high molecular weight components such as thermosetting resins or thermoplastic resins, fillers, additives, and reinforcing fibers are used in a state where they are contained together. In some cases, a complex is prepared.
有機溶媒に溶解したポリアミド酸溶液と機能性を有す
る機能性低分子有機化合物の混合溶液は、０〜100℃の
間の温度条件で少なくとも１分間以上静置することによ
り、ポリアミド酸に含まれる官能基による三次元架橋反
応が有機溶媒中で進み、ゲル化現象が起こり、機能性低
分子有機化合物とポリアミド酸とが複合化され、有機溶
媒を含んだ状態の高分子ゲルが生成する。A mixed solution of a polyamic acid solution dissolved in an organic solvent and a functional low-molecular-weight organic compound having a functional property is allowed to stand at a temperature condition of 0 to 100 ° C. for at least 1 minute or more to obtain a functional component contained in the polyamic acid. The three-dimensional cross-linking reaction by the group proceeds in an organic solvent, a gelling phenomenon occurs, the functional low-molecular organic compound and the polyamic acid are complexed, and a polymer gel containing the organic solvent is generated.
ポリアミド酸と機能性低分子有機化合物の複合された
混合溶液より、フィルム等の成形体を賦形するために、
混合溶液を基材上等に流延又は成形型に流入させた後
に、ゲル化を起こさせることにより、均一なゲル状のフ
ィルム等の成形体が得られる。From a mixed solution of a polyamic acid and a functional low-molecular-weight organic compound, to shape a molded product such as a film,
After the mixed solution is cast on a base material or the like or cast into a mold, gelation is caused to obtain a uniform molded body such as a gel-like film.
混合溶液を流延させる基材としては、表面の平滑なフ
ィルム状の素材が用いられ、ステンレス等の金属フィル
ム、ポリエステル等の高分子フィルム等が主として用い
られる。また、基材としてガラス板等も使用できる。As a substrate on which the mixed solution is cast, a film-shaped material having a smooth surface is used, and a metal film such as stainless steel, a polymer film such as polyester, and the like are mainly used. Further, a glass plate or the like can be used as a base material.
前駆体である機能性低分子有機化合物／ポリアミド酸
の複合された高分子ゲルにおいて、テトラカルボン酸二
無水物、芳香族ジアミン及び多価アミンの重合物である
ポリアミド酸が三次元網目構造を形成するところの所謂
ゲル化を起こす前に、機能性低分子有機化合物を混合さ
せておくことが望まれる。In a polymer gel in which a functional low molecular organic compound / polyamic acid is a precursor, a polyamic acid, which is a polymer of tetracarboxylic dianhydride, an aromatic diamine and a polyvalent amine, forms a three-dimensional network structure. It is desired to mix a functional low molecular weight organic compound before the so-called gelation occurs.
しかし、ポリアミド酸溶液が、三次元架橋反応を起こ
し、高分子ゲルとなった後でも、機能性低分子有機化合
物と複合化させることができる。その方法としては、テ
トラカルボン酸二無水物、芳香族ジアミン及び多価アミ
ンからなるポリアミド酸の高分子ゲルに、機能性低分子
有機化合物が溶解させられた溶液液を接触させ、有機化
合物を含む溶液を高分子ゲルの三次元網目構造中に浸透
させた後、溶媒を除去するような手法等があり、これに
より機能性低分子有機化合物／ポリアミド酸複合体を調
製することも可能である。However, even after the polyamic acid solution undergoes a three-dimensional cross-linking reaction and becomes a polymer gel, it can be complexed with a functional low-molecular organic compound. As the method, a solution in which a functional low-molecular-weight organic compound is dissolved is brought into contact with a polymer gel of polyamic acid composed of tetracarboxylic dianhydride, aromatic diamine and polyvalent amine, and contains the organic compound. There is a method of removing the solvent after infiltrating the solution into the three-dimensional network structure of the polymer gel, and thereby, it is possible to prepare a functional low-molecular organic compound / polyamic acid complex.
以上のような操作により、テトラカルボン酸二無水
物、芳香族ジアミン及び多価アミンからなるポリアミド
酸と機能性低分子有機化合物が共存した、機能性低分子
有機化合物／ポリアミド酸の複合された高分子ゲルが調
製される。By the operation as described above, the functional low molecular weight organic compound / polyamic acid complex is obtained in which the polyamic acid composed of tetracarboxylic dianhydride, aromatic diamine and polyamine coexists with the functional low molecular weight organic compound. A molecular gel is prepared.
機能性低分子有機化合物／ポリアミド酸複合体の有機
溶媒を含む高分子ゲルより、有機溶媒を除去することに
より、フィルム等の成形体を得ることができる。このも
のを、機能性低分子有機化合物／ポリイミド成形体の前
駆体としても用いる。A molded article such as a film can be obtained by removing the organic solvent from the polymer gel containing the organic solvent of the functional low-molecular organic compound / polyamic acid complex. This is also used as a precursor of a functional low molecular organic compound / polyimide molded article.
脱溶媒は、常圧又は真空下で溶媒を蒸発させるか、有
機溶媒を他の溶媒と置換させた後に乾燥させるか等の方
法により行わせることができる。The solvent can be removed by a method such as evaporating the solvent under normal pressure or under vacuum, or drying after replacing the organic solvent with another solvent.
機能性低分子有機化合物／ポリアミド酸の複合された
高分子ゲルより、有機溶媒を蒸発させ除去するために
は、第一段階として常圧又は真空下で100℃以下の温度
で処理することが好ましい。最初から100℃以上の温度
で処理した場合、急激な溶媒の蒸発による成形体の発
泡、あるいは、ポリアミド酸成分の脱水・閉環反応によ
るイミド化の進行等の不都合が起こり好ましくない。脱
溶媒により、機能性低分子有機化合物／ポリアミド酸の
高分子ゲル中に含まれる溶媒の含有率を50重量％以下、
好ましくは、40重量％以下に調整した後、基材上より機
能性低分子有機化合物／ポリアミド酸複合体を離脱さ
せ、フィルム等の成形体として得られる。あるいは、基
材上で引続き更に加熱温度を上げ、ポリアミド酸成分の
脱水・閉環反応を進めてもよく、このような処理により
均質で良好な成形体を得ることもできる。In order to evaporate and remove the organic solvent from the functional low molecular weight organic compound / polyamic acid composite polymer gel, it is preferable to perform the treatment at a temperature of 100 ° C. or less under normal pressure or vacuum as a first step. . If the treatment is carried out at a temperature of 100 ° C. or higher from the beginning, disadvantages such as foaming of the molded article due to rapid evaporation of the solvent, or progress of imidization due to dehydration and ring closure of the polyamic acid component are not preferred. By removing the solvent, the content of the solvent contained in the functional low-molecular organic compound / polyamic acid polymer gel is reduced to 50% by weight or less,
Preferably, after adjusting the content to 40% by weight or less, the functional low-molecular-weight organic compound / polyamic acid composite is released from the base material to obtain a molded product such as a film. Alternatively, the heating temperature may be further raised on the substrate to promote the dehydration / ring closure reaction of the polyamic acid component, and a uniform and good molded article can be obtained by such treatment.
溶媒を含んだ機能性低分子有機化合物／ポリアミド酸
の複合された高分子ゲルを、ポリアミド酸複合体の貧溶
媒を凝固浴とした浴中に浸漬せしめ、複合体中に残存す
る有機溶媒の溶媒置換を行わせ、続いて、乾燥させるこ
とにより機能性低分子有機化合物／ポリアミド酸複合体
の成形体を得ることもできる。A high-molecular-weight composite gel of a functional low-molecular-weight organic compound / polyamic acid containing a solvent is immersed in a bath using a poor solvent for the polyamic acid composite as a coagulation bath, and the solvent of the organic solvent remaining in the composite is dissolved. By performing substitution and subsequently drying, a molded article of a functional low-molecular-weight organic compound / polyamic acid composite can also be obtained.
この場合、凝固液としては、水、メタノールやエタノ
ール等のアルコール類、アセトン等のようなケトン類の
単独又は混合系が用いられる。少量であれば、N,N−ジ
メチルアセトアミド等のアミド系溶媒、1,2−ジクロロ
エタンのような塩素系溶媒等を凝固液の中に含んでもよ
い。機能性低分子有機化合物／ポリアミド酸複合体を溶
解あるいは膨潤させて、その形状を著しく損ねるような
凝固液は使用できない。以上のような操作によって、機
能性低分子有機化合物とポリアミド酸成分との複合され
た成形体が得られ、このものは、機能性低分子有機化合
物／ポリアミド複合体の前駆体として用いられる。In this case, a single or mixed system of water, alcohols such as methanol and ethanol, and ketones such as acetone is used as the coagulating liquid. If the amount is small, an amide-based solvent such as N, N-dimethylacetamide or a chlorinated solvent such as 1,2-dichloroethane may be contained in the coagulating liquid. A coagulating liquid that dissolves or swells the functional low molecular organic compound / polyamic acid complex and significantly impairs its shape cannot be used. By the operation as described above, a molded article in which the functional low molecular organic compound and the polyamic acid component are composited is obtained, and this is used as a precursor of the functional low molecular organic compound / polyamide composite.
機能性低分子有機化合物／ポリイミド複合体（ポリイ
ミド系機能性複合体。以下単に「機能性複合体」という
ことがある。）とするためには、機能性低分子有機化合
物／ポリアミド酸複合体のポリアミド酸成分を脱水・閉
環反応させ、ポリアミド酸成分をポリイミドに変えるこ
とで達成される。In order to obtain a functional low-molecular-weight organic compound / polyimide composite (polyimide-based functional composite, hereinafter sometimes simply referred to as “functional composite”), a functional low-molecular-weight organic compound / polyamic acid composite is used. This is achieved by subjecting the polyamic acid component to a dehydration and ring-closing reaction to convert the polyamic acid component to polyimide.
機能性低分子有機化合物／ポリアミド酸複合体中に含
まれるポリアミド酸成分の脱水・閉環反応によるイミド
化の完了は、一般のポリイミド樹脂で用いられているイ
ミド化の方法と同様の方法で達成することができるが、
イミド化のための処理の方法によっては、含まれる機能
性低分子有機化合物を蒸発、変質、分解させないように
条件を選択する必要が出てくる。Completion of imidation by dehydration and ring-closure reaction of the polyamic acid component contained in the functional low molecular weight organic compound / polyamic acid complex is achieved by the same method as the imidation method used in general polyimide resins. Can be
Depending on the method of treatment for imidization, it is necessary to select conditions so that the functional low-molecular-weight organic compound contained is not evaporated, altered, or decomposed.
例えば、高温処理によりイミド化を完了させる場合
は、機能性低分子有機化合物／ポリアミド酸の複合体を
50〜200℃で少なくとも10秒以上乾燥させ、更に、高温
処理が可能の場合は、150〜500℃の高温で熱処理させ
る。フィルムの一対の両端を固定枠、チャックあるいは
ピンガイド等で固定して処理すると、寸法安定性や機械
的特性に優れたフィルムが得られやすい。機能性低分子
有機化合物が熱処理によって蒸発あるいは酸化等の化学
変化を起こす場合は、成形体を密封あるいは不活性ガス
雰囲気下で処理してもよい。For example, when the imidization is completed by high-temperature treatment, a complex of a functional low-molecular-weight organic compound / polyamic acid is used.
Dry at 50 to 200 ° C for at least 10 seconds or more, and if high temperature treatment is possible, heat treat at a high temperature of 150 to 500 ° C. When the film is processed by fixing both ends of the film with a fixing frame, a chuck, a pin guide, or the like, a film having excellent dimensional stability and mechanical characteristics is easily obtained. When the functional low molecular organic compound causes a chemical change such as evaporation or oxidation by heat treatment, the molded body may be sealed or treated in an inert gas atmosphere.
また、機能性低分子有機化合物／ポリアミド酸複合体
を脱水剤に浸漬すること、あるいは、複合体中に脱水剤
を含ませるような化学的処理をすることにより、ポリア
ミド酸成分を脱水・閉環反応させ、イミド化を進める方
法もある。化学的処理によるポリアミド酸成分の脱水・
閉環反応においては、アミン類を触媒とし酸無水物を脱
水剤として用いるのが効果的である。Also, the polyamic acid component is dehydrated and ring-closed by immersing the functional low-molecular-weight organic compound / polyamic acid complex in a dehydrating agent or by performing a chemical treatment so that the dehydrating agent is included in the composite. There is also a method in which imidization is promoted. Dehydration of polyamic acid component by chemical treatment
In the ring closure reaction, it is effective to use an acid anhydride as a dehydrating agent using an amine as a catalyst.
酸無水物の例としては、無水酢酸、無水プロピオン
酸、無水酪酸などの脂肪族酸無水物、無水安息香酸など
の芳香族酸無水物がある。これらは、単独又は二種以上
の混合物として用いることができる。Examples of the acid anhydride include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, and aromatic acid anhydrides such as benzoic anhydride. These can be used alone or as a mixture of two or more.
化学的脱水反応において添加する酸無水物の量は、ポ
リアミド酸に存在するカルボキシル基１当量に対して１
〜５当量、好ましくは１〜３当量である。また、アミド
酸基の部分的な脱水・閉環反応によるイミド化を行う場
合は、ポリアミド酸に存在するカルボキシル基１当量に
対して１当量以下でもよい。The amount of the acid anhydride added in the chemical dehydration reaction is 1 to 1 equivalent of the carboxyl group present in the polyamic acid.
-5 equivalents, preferably 1-3 equivalents. In the case of performing imidation by partial dehydration / ring-closure reaction of the amide acid group, the amount may be 1 equivalent or less relative to 1 equivalent of the carboxyl group present in the polyamic acid.
触媒としてのアミン類（広義）の例は、トリメチルア
ミン、トリエチルアミン、トリエチレンジアミン、トリ
ブチルアミン、ジメチルアニリン、ビリジン、α−ピコ
ラン、β−ピコリン、γ−ピコリン、イソキノリン、ル
チジン、等の第３級アミンの中から選ばれる少なくとも
一種のアミン類である。Examples of amines (broadly defined) as catalysts include tertiary amines such as trimethylamine, triethylamine, triethylenediamine, tributylamine, dimethylaniline, pyridine, α-picolane, β-picoline, γ-picoline, isoquinoline and lutidine. It is at least one kind of amines selected from the group.
触媒の量は、ポリアミド酸に存在するカルボキシル基
１当量に対して0.01〜1.5当量、好ましくは.2〜１当量
である。The amount of the catalyst is 0.01 to 1.5 equivalents, preferably 0.2 to 1 equivalent, per equivalent of the carboxyl group present in the polyamic acid.
化学的処理による脱水・閉環反応においては、前駆体
である機能性低分子有機化合物／ポリアミド酸複合体中
に含まれる機能性低分子有機化合物が、その種類によっ
ては酸無水物やアミン類などの脱水剤に溶解あるいは膨
潤し、成形体の形状変化を引き起こす場合がある。この
ようなときは、ポリアミド酸のゲル化を形成させる以前
に予め脱水剤を含ませる等の方法を用いるのが、良好な
成形体を得る上で効果的である。In the dehydration / ring closure reaction by chemical treatment, the functional low-molecular-weight organic compound contained in the functional low-molecular-weight organic compound / polyamic acid complex, which is a precursor, depends on the type thereof, such as acid anhydrides and amines. It may dissolve or swell in the dehydrating agent and cause a change in the shape of the molded article. In such a case, it is effective to use a method of including a dehydrating agent in advance before gelling the polyamic acid to form a good molded body.
以上のようにして、機能性低分子有機化合物／ポリア
ミド酸の複合された高分子ゲルよりポリアミド酸成分の
脱水・閉環反応により機能性低分子有機化合物／ポリイ
ミドの成形体が得られる。As described above, a molded article of the functional low-molecular-weight organic compound / polyimide is obtained from the composite polymer gel of the functional low-molecular-weight organic compound / polyamic acid by the dehydration and ring-closing reaction of the polyamic acid component.
機能性低分子有機化合物／ポリアミド酸複合体からの
機能性低分子有機化合物／ポリイミド複合体の形状は、
繊維、フィルム状のものを含む。この高分子ゲルを経由
させる手法を用いて、１μｍ以下の厚さを有する薄膜を
形成させることも可能である。The shape of the functional low molecular organic compound / polyimide complex from the functional low molecular organic compound / polyamic acid composite is
Including fibers and films. It is also possible to form a thin film having a thickness of 1 μm or less using this technique of passing through a polymer gel.
また、これらの機能性複合体の中には、他の物質、例
えば、各種金属化合物、無機充填剤、着色剤、強化繊維
等が含まれてもよい。Further, these functional composites may contain other substances, for example, various metal compounds, inorganic fillers, coloring agents, reinforcing fibers, and the like.
複合体に含まれる機能性低分子有機化合物は、ポリア
ミド酸成分に対し１〜80重量％であることが好ましい。
本発明では、ポリアミド酸と機能性低分子有機化合物と
の混合溶液中でゲル化反応が起こるため、ポリアミド酸
成分の分子鎖が比較的ランダムに溶液中に広がった三次
元網目構造中に機能性低分子有機化合物が分散した状態
で高分子ゲルを生成する。これを脱溶媒させて得られた
複合体は、ポリアミド酸成分が連続相を形成した三次元
網目構造の中に機能性低分子有機化合物が分散・混合さ
せられた状態の成形体を与え、得られた機能性複合体も
優れた機械的性質と機能性を兼備した性質を有するもの
である。The content of the functional low molecular weight organic compound contained in the composite is preferably 1 to 80% by weight based on the polyamic acid component.
In the present invention, since a gelling reaction occurs in a mixed solution of a polyamic acid and a functional low-molecular-weight organic compound, a functional chain is formed in a three-dimensional network structure in which the polyamic acid component molecular chains are relatively randomly spread in the solution. A high molecular gel is formed in a state where the low molecular organic compound is dispersed. The complex obtained by desolvation is a molded article in which a functional low-molecular-weight organic compound is dispersed and mixed in a three-dimensional network structure in which a polyamic acid component forms a continuous phase. The obtained functional composite also has excellent mechanical properties and properties.
本発明のポリイミド複合体において、機能性低分子有
機化合物が１重量％より少ない領域では、機能性低分子
有機化合物を入れることによる機能性の発現、例えば、
光学特性、電気的特性等を発現する効果が顕著でない。
また、機能性低分子有機化合物が80重量％以上の場合、
ポリイミド酸成分が少なくなり三次元網目構造が不完全
なものとなるため、自己支持性のある高分子ゲルが形成
されないようになり、結果的に、ポリイミド複合体の機
械的特性や機能性をむしろ低下させるようになる。In the polyimide composite of the present invention, in a region where the amount of the functional low-molecular-weight organic compound is less than 1% by weight, the expression of functionality by adding the functional low-molecular-weight organic compound, for example,
The effect of expressing optical characteristics, electrical characteristics, and the like is not significant.
When the content of the functional low-molecular-weight organic compound is 80% by weight or more,
Since the amount of the polyimide acid component is reduced and the three-dimensional network structure is incomplete, a polymer gel having self-supporting properties is not formed, and as a result, the mechanical properties and functionality of the polyimide composite are rather reduced. Will lower it.
本発明のテトラカルボン酸二無水物、芳香族ジアミン
及び多価アミンを主成分としたポリアミド酸は、溶液中
で反応を進めることにより多量の有機溶媒を含んでも流
動を起こさず、形状を保持できるような自己支持性のあ
る三次元網目構造（高分子ゲル）を形成する。このよう
なゲル化反応は、溶液中に他種の成分、例えば、機能性
低分子有機化合物が含まれた混合溶液中でも同様の反応
を起こし、混合溶液の状態から高分子ゲルを形成するも
のである。The polycarboxylic acid containing tetracarboxylic dianhydride, aromatic diamine and polyamine of the present invention as main components does not cause flow even if it contains a large amount of organic solvent by advancing the reaction in a solution, and can maintain its shape. A self-supporting three-dimensional network structure (polymer gel) is formed. In such a gelation reaction, a similar reaction occurs even in a mixed solution containing another kind of component, for example, a functional low molecular weight organic compound in the solution, and a polymer gel is formed from the state of the mixed solution. is there.
本発明に係るポリイミドの前駆体である機能性低分子
有機化合物／ポリアミド酸複合体の高分子ゲルは、主に
共有結合、イオン結合及び水素結合による三次元網目構
造からなる構造体と推定され、このものは、ポリアミド
酸と機能性低分子有機化合物の両者の混合溶液から自己
支持性のあるゲル状の構造体を作る。機能性低分子有機
化合物は、ポリアミド酸の三次元網目構造体の中に分子
状に分散・混合していると考えられる。これを高温処理
あるいは化学的脱水処理することでポリアミド酸成分の
イミド化が完了し、ポリイミドの三次元的に結合した分
子鎖の中に機能性低分子有機化合物が均一分散した分子
構造の複合体となる。この構造は、単純にポリアミド酸
と機能性低分子有機化合物を混合しただけの系では、達
成されない構造である。The functional low molecular organic compound / polyamic acid composite polymer gel which is a precursor of the polyimide according to the present invention is presumed to be a structure having a three-dimensional network structure mainly formed by covalent bonds, ionic bonds and hydrogen bonds, It produces a self-supporting gel-like structure from a mixed solution of both a polyamic acid and a functional low molecular organic compound. It is considered that the functional low-molecular-weight organic compound is molecularly dispersed and mixed in the three-dimensional network structure of polyamic acid. The imidization of the polyamic acid component is completed by high-temperature treatment or chemical dehydration treatment, and a complex with a molecular structure in which functional low-molecular-weight organic compounds are uniformly dispersed in the three-dimensionally bonded molecular chains of polyimide. Becomes This structure cannot be achieved by a system in which a polyamic acid and a functional low molecular weight organic compound are simply mixed.
このような方法により得られた機能性低分子有機化合
物／ポリアミド酸複合体は、調製方法の特異性から、機
能性低分子有機化合物成分がポリアミド酸成分の分子鎖
の中に比較的均一に分散・混合された新規なポリアミド
酸複合体であるため、ポリイミド成分の優れた耐熱性及
び機械的特性と機能性低分子有機化合物の刺激−応答作
用、即ち熱、光、電気、力等の外的刺激による応答作用
等の機能性を兼備する優れた特性の機能性複合体とな
る。Due to the specificity of the preparation method, the functional low molecular organic compound / polyamic acid complex obtained by such a method has the functional low molecular organic compound component dispersed relatively uniformly in the molecular chain of the polyamic acid component.・ Since it is a novel mixed polyamic acid complex, it has excellent heat resistance and mechanical properties of the polyimide component and stimulus-response action of the functional low molecular organic compound, that is, external heat, light, electricity, force, etc. It becomes a functional complex with excellent properties that also has functionality such as response action by stimulation.
また、溶媒を多量に含んだ機能性低分子有機化合物／
ポリアミド酸の高分子ゲルの状態で、外部より電場、磁
場あるいは剪断力等の外力を高分子ゲル複合体に加え、
ゲル中に含まれ分散している機能性低分子有機化合物を
配向させることで、複合体の構造に異方性を持たせるこ
とが可能である。この状態を保ったまま溶媒を除去し
て、一体化させることにより、機能性低分子有機化合物
の配列が制御された機能性複合体を得ることができる。
特に、複合される機能性低分子有機化合物が、極性基を
有する機能性低分子有機化合物の場合には、外力により
機能性低分子有機化合物の分子が容易に配向し、機能性
の発現に効果的な場合が多い。In addition, functional low molecular organic compounds containing a large amount of solvent /
In the state of the polyamic acid polymer gel, an external force such as an electric field, a magnetic field or a shear force is applied to the polymer gel composite from the outside,
By orienting the functional low molecular weight organic compound contained and dispersed in the gel, it is possible to impart anisotropy to the structure of the composite. By removing and integrating the solvent while maintaining this state, a functional complex in which the arrangement of the functional low-molecular-weight organic compound is controlled can be obtained.
In particular, when the functional low-molecular-weight organic compound to be combined is a functional low-molecular-weight organic compound having a polar group, the molecules of the functional low-molecular-weight organic compound are easily oriented by an external force, which is effective in expressing the functionality. Often.
高分子ゲル、即ち溶媒を含んだ状態で処理することに
より、ゲル中に含まれる分散している機能性低分子有機
化合物が外力により動き易いため、高次構造の制御が容
易である。機能性低分子有機化合物／ポリアミド酸の複
合された高分子ゲルは、機能性低分子有機化合物の高配
合領域においても形状が保持され、自己支持性であるた
め、処理する際の取扱性も良好で、配向による機能性の
発現も顕著である。By treating with a polymer gel, that is, a state containing a solvent, the dispersed functional low-molecular-weight organic compound contained in the gel is easily moved by an external force, so that control of a higher-order structure is easy. The polymer gel, which is a composite of a functional low-molecular organic compound / polyamic acid, retains its shape even in a high blending area of the functional low-molecular organic compound, and is self-supporting, so that it is easy to handle when processing. Thus, the expression of the functionality due to the orientation is also remarkable.
例えば、液晶物質であるシッフ系液晶、アゾキシ系液
晶、シアノビフェニル系液晶、シアノフェニル系液晶等
の複合された複合体においては、液晶物質が大きな永久
双極子モーメントを有し、棒状の分子構造のものが多い
ため、電場、磁場あるいは剪断力等の外力により容易に
配向し、光学異方的な機能性複合体が与えられる。For example, in a composite compound of a liquid crystal substance such as a Schiff liquid crystal, an azoxy liquid crystal, a cyanobiphenyl liquid crystal, and a cyanophenyl liquid crystal, the liquid crystal substance has a large permanent dipole moment and has a rod-like molecular structure. Since there are many such materials, they are easily oriented by an external force such as an electric field, a magnetic field, or a shear force, and an optically anisotropic functional complex is provided.
また、液晶物質の中には非線形光学効果を示すものも
含まれ、複合体中の機能性低分子有機化合物の配合量や
配向処理により光学異方性の大きな材料となる。このも
のは、表示材料、記録媒体あるいはセンサーとして有用
である。In addition, some liquid crystal substances exhibit a non-linear optical effect, and a material having high optical anisotropy can be obtained by the amount of the functional low molecular organic compound in the composite and the alignment treatment. This is useful as a display material, a recording medium, or a sensor.
例えば、電荷移動錯体として知られているテトラチア
フルバレンと7,7,8,8−テトラシアノ−ｐ−キノジメタ
ンとの混合物、あるいは、フタロシアニン系錯体等は、
導電性を示す機能性低分子有機化合物であり、前述の高
分子ゲルを前駆体とする方法により調製された複合体
は、電気伝導性を示し、静電防止材料、半導体素子、バ
ッテリー等に用いられる材料となる。For example, a mixture of tetrathiafulvalene and 7,7,8,8-tetracyano-p-quinodimethane known as a charge transfer complex, or a phthalocyanine-based complex,
A complex prepared by a method using the above-mentioned polymer gel as a precursor, which is a functional low-molecular-weight organic compound exhibiting conductivity, exhibits electrical conductivity, and is used in antistatic materials, semiconductor elements, batteries, and the like. Material.
例えば、高分子ゲルを前駆体とする方法により調製さ
れたポリマーのマトリックス中に、フタロシアニン系化
合物やポリフィリン系化合物の均質に分散された複合体
は、位相の揃った強いレーザー光を照射することによっ
て、光化学反応を起こし元の物質とは異なった波長に吸
収を持つようになるため、レーザー照射の部分だけ吸収
が減少するところの所謂フォトケミカルホールバーニン
グ現象を起こす材料となる。このものは、光記録材料と
して高速情報処理システムに有用である。For example, in a matrix of a polymer prepared by a method using a polymer gel as a precursor, a complex in which a phthalocyanine-based compound or a porphyrin-based compound is homogeneously dispersed is irradiated with intense laser light having a uniform phase. Since a photochemical reaction is caused to cause absorption at a wavelength different from that of the original substance, the material is a material that causes a so-called photochemical hole burning phenomenon in which absorption is reduced only in a portion irradiated with laser. This is useful for a high-speed information processing system as an optical recording material.
例えば、ｐ−ニトロアニリンやメロシアニンとの複合
体は、レーザー光の波長変換等の非線形光学効果を示す
材料となり、光変調器、光情報処理デバイスとして有用
である。For example, a complex with p-nitroaniline or merocyanine becomes a material exhibiting a nonlinear optical effect such as wavelength conversion of laser light, and is useful as an optical modulator or an optical information processing device.
このように複合体の高分子ゲルを経由させる新しい手
法により、ポリマーの三次元網目構造体の中に機能性低
分子有機化合物の分子が均一に分散・混合させられ、更
には、外部からの力により異方的な分子の配列も可能で
あり、複合体の高次構造が制御された特異な構造の機能
性複合体を作り出すことができる。これらは、刺激−応
答作用を有する機能性材料として有用である。In this way, the new method of passing through the composite polymer gel allows the molecules of the functional low-molecular-weight organic compound to be uniformly dispersed and mixed in the three-dimensional network structure of the polymer. Thus, anisotropic molecular arrangement is possible, and a functional complex having a specific structure in which the higher-order structure of the complex is controlled can be created. These are useful as functional materials having a stimulus-response action.
本発明の機能性複合体は、ポリイミドの前駆体である
ポリアミド酸成分と刺激−応答作用等の機能性を有する
機能性低分子有機化合物の混合溶液の中で、高分子ゲル
を形成させるという新規な手法を用いて得られた新しい
構造の高分子構造であるため、従来のポリマー混合系で
は達成されないような高度分散の状態を採り、且つ、ポ
リアミド酸成分が連続相を形成した構造を採るものであ
る。従って、このものは、ポリマーの有する耐熱性や機
械的特性等の優れた特性と機能性低分子有機化合物の機
能性を兼備した強靭な複合体を与える。The functional complex of the present invention is a novel compound that forms a polymer gel in a mixed solution of a polyamic acid component, which is a precursor of polyimide, and a functional low-molecular organic compound having a function such as stimulus-response action. Is a polymer structure with a new structure obtained using a simple technique, so that it adopts a highly dispersed state that cannot be achieved with conventional polymer mixed systems, and adopts a structure in which the polyamic acid component forms a continuous phase. It is. Therefore, this gives a tough composite which has both the excellent properties of the polymer, such as heat resistance and mechanical properties, and the functionality of a functional low molecular organic compound.
これらは、表示材料、記録媒体、センサー静電防止材
料、半導体素子、バッテリー、光記録材料、光変調器あ
るいは光情報処理デバイスの材料として有用である。These are useful as materials for display materials, recording media, antistatic materials for sensors, semiconductor elements, batteries, optical recording materials, optical modulators, or optical information processing devices.
以下、本発明を実施例により説明する。 Hereinafter, the present invention will be described with reference to examples.
参考例（前駆体合成例） 300mlの四つ口セパラブルフラスコ中に、0.841g（0.0
042モル）の精製した4,4′−ジアミノジフェニルエーテ
ル（略称:4,4′−DPE）と0.158g（0.0004モル）の3,
3′,4,4′−テトラアミノビフェニル・四塩酸塩・二水
和物（略称:TABT）を採取し、20gの蒸留されたN,N−ジ
メチルホルムアミド（略称:DMF）を加え、攪拌し溶解さ
て溶液を得た。Reference example (Precursor synthesis example) In a 300 ml four-neck separable flask, 0.841 g (0.0
042 mol) of purified 4,4'-diaminodiphenyl ether (abbreviation: 4,4'-DPE) and 0.158 g (0.0004 mol) of 3,4
3 ′, 4,4′-Tetraaminobiphenyl / tetrahydrochloride / dihydrate (abbreviation: TABT) was collected, 20 g of distilled N, N-dimethylformamide (abbreviation: DMF) was added, and the mixture was stirred. Upon dissolution, a solution was obtained.
窒素雰囲気の下、外部水槽の温度を５℃にコントロー
ルし、上記溶液を攪拌しながら1.611g（0.005モル）の
精製した3,3′,4,4′−ベンゾフェノンテトラカルボン
酸二無水物（略称:BTDA）を固形のまま、溶液の温度が
上らないように注意しながら徐々に添加し、全て加え終
った後、攪拌を続け均一なポリアミド酸溶液を調製し
た。一方、3.915g（固形分の60重量％）の液晶物質であ
る４′−ペントキシ−４−シアノビフェニルを採取し、
100mlのビーカー中で10gの蒸留されたDMFに溶解させ
た。これらの液晶物質を完全に溶解させた後、得られた
溶液をBTDA/4,4′−DPE/TABTからなる前述のポリアミド
酸溶液に加え攪拌し、均一な液晶物質／ポリアミド酸の
混合溶液を得た。Under a nitrogen atmosphere, the temperature of the external water tank was controlled at 5 ° C., and 1.611 g (0.005 mol) of purified 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (abbreviated name) was stirred with the above solution. : BTDA) was added in a solid state while being careful not to raise the temperature of the solution, and after all the addition was completed, stirring was continued to prepare a uniform polyamic acid solution. On the other hand, 3.915 g (60% by weight of solid content) of 4'-pentoxy-4-cyanobiphenyl which is a liquid crystal substance was collected.
Dissolved in 10 g of distilled DMF in a 100 ml beaker. After completely dissolving these liquid crystal substances, the resulting solution was added to the above-mentioned polyamic acid solution composed of BTDA / 4,4'-DPE / TABT and stirred, and a uniform liquid crystal substance / polyamic acid mixed solution was added. Obtained.
この混合溶液をガラス板上に流延した。溶液の塗布量
は、スペーサーによりコントロールし、約0.4mmの厚さ
になるようにした。しばらく静置すると、流延された混
合溶液がゲル化を起こし、ポリアミド酸／液晶物質複合
体の高分子ゲル（ゲルフィルム）が得られた。This mixed solution was cast on a glass plate. The coating amount of the solution was controlled by a spacer so that the thickness was about 0.4 mm. After standing for a while, the cast mixed solution gelled, and a polyamic acid / liquid crystal substance composite polymer gel (gel film) was obtained.
得られたゲルフィルムは、自重による形状変化を起こ
さず、自己支持性のものであった。The obtained gel film did not change its shape due to its own weight and was self-supporting.
このゲルフィルムを30℃で真空乾燥させ、高分子ゲル
の中の溶媒を飛散させた後、フィルムの形でガラス板よ
り離脱させた。The gel film was vacuum-dried at 30 ° C. to disperse the solvent in the polymer gel, and then separated from the glass plate in the form of a film.
更に、30℃で24時間真空乾燥させ、残存溶媒を0.5％
以下にしたフィルムは、引張り強さが約5Kgf/mm2であ
り、機械的特性に優れたものであった。示差走査熱量計
にてフィルムの熱的性質を測定したところ、このフィル
ムは、53℃にて液晶物質の結晶から液晶への転移に伴う
吸熱ピーク、及び、68℃にて液晶から等方相への転移に
伴なう熱挙動が観測された。この転移挙動は、可逆的
で、且つ、０〜100℃の温度範囲における数回の繰返し
測定でも同様の結果を示した。In addition, vacuum drying at 30 ° C for 24 hours
The film described below had a tensile strength of about 5 kgf / mm 2 and was excellent in mechanical properties. When the thermal properties of the film were measured with a differential scanning calorimeter, the film showed an endothermic peak accompanying the transition from the crystal of the liquid crystal material to the liquid crystal at 53 ° C, and a liquid crystal to an isotropic phase at 68 ° C. The thermal behavior accompanying the transition of was observed. This transition behavior was reversible and showed similar results in several repeated measurements in the temperature range of 0-100 ° C.
このポリアミド酸／液晶物質複合フィルムを、ITO電
極を有するガラス基板間にはさみ、60℃にて膜面に垂直
方向の電界を印加することにより、可逆的に光透過姓が
変化し、電界による光スイッチ作用が認められた。This polyamic acid / liquid crystal material composite film is sandwiched between glass substrates having ITO electrodes, and by applying an electric field in the direction perpendicular to the film surface at 60 ° C., the light transmission reversibly changes, and the light generated by the electric field is changed. A switching effect was observed.
比較例（多価アミンを使用しない例） 300mlの四つ口セパラブルフラスコ中に、1001g（0.00
5モル）の精製した4,4′−ジアミノジフェニルエーテル
（（略称:4,4′−DPE）を採取し、20gの蒸留されたN,N
−ジメチルホルムアミド（略称:DMF）を加え、攪拌し溶
解させて溶液を得た。Comparative Example (Example not using polyamine) In a 300 ml four-neck separable flask, 1001 g (0.001 g) was added.
5 mol) of purified 4,4'-diaminodiphenyl ether (abbreviation: 4,4'-DPE) was collected and 20 g of distilled N, N
-Dimethylformamide (abbreviation: DMF) was added, stirred and dissolved to obtain a solution.
窒素雰囲気の下、外部水槽の温度を５℃にコントロー
ルし、上記溶液を攪拌しながら1.611g（0.005モル）の
精製した3,3′,4,4′−ベンゾフェノンテトラカルボン
酸二無水物（略称:BTDA）を固形のまま、溶液の温度が
上らないように注意しながら徐々に添加し、すべて加え
終った後、攪拌を続け均一なポリアミド酸溶液を調製し
た。Under a nitrogen atmosphere, the temperature of the external water tank was controlled at 5 ° C., and 1.611 g (0.005 mol) of purified 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (abbreviated name) was stirred with the above solution. : BTDA) was added in a solid state while paying attention not to raise the temperature of the solution, and after all the addition was completed, stirring was continued to prepare a uniform polyamic acid solution.
一方、3.918g（固形分の60重量％）の液晶物質である
４′−ペントキシ−４−シアノビフェニルを採取し、10
0mlのビーカー中で10gの蒸留されたDMFに溶解させた。
これらの液晶物質を完全に溶解させた後、得られた溶液
をBTDA/4,4′−DPEからなる前述のポリアミド酸溶液に
加え攪拌し、均一な液晶物質／ポリアミド酸の混合溶液
を得た。この混合溶液をガラス板上に流延した。溶液の
塗布量は、スペーサーによりコントロールし約0.4mmの
厚さになるようにした。On the other hand, 3.918 g (60% by weight of solid content) of 4'-pentoxy-4-cyanobiphenyl as a liquid crystal substance was collected, and 10
Dissolved in 10 g of distilled DMF in a 0 ml beaker.
After completely dissolving these liquid crystal substances, the obtained solution was added to the above-mentioned polyamic acid solution composed of BTDA / 4,4'-DPE and stirred to obtain a uniform liquid crystal substance / polyamic acid mixed solution. . This mixed solution was cast on a glass plate. The coating amount of the solution was controlled by a spacer so as to have a thickness of about 0.4 mm.
このものは、室温で５時間以上静置しても、混合溶液
がゲル化を起こさず、流動的なものであった。Even when the mixture was allowed to stand at room temperature for 5 hours or longer, the mixed solution did not gel and was fluid.
参考例と同様な方法で、このポリアミド酸／液晶物質
の混合溶液からフィルムを調製したが、このフィルム
は、脆性的で引張り強さが1Kgf/mm2以下であり、機械的
性質に優れるものではなかった。A film was prepared from the mixed solution of the polyamic acid and the liquid crystal substance in the same manner as in the reference example. However, the film was brittle, had a tensile strength of 1 kgf / mm 2 or less, and had excellent mechanical properties. Did not.
実施例１ 300mlの四つ口セパラブルフラスコ中に、0.324g（0.0
03モル）の精製したパラフェニレンジアミンと0.320g
（0.0016モル）の精製した4,4′−ジアミノジフェニル
エーテル（略称:4,4′−DPE）及び0.792g（0.0002モ
ル）の3,3′,4,4′−テトラアミノビフェニル・四塩酸
塩・二水和物（略称:TABT）の採取し、20gの蒸留された
Ｎ−メチル−２−ピロリドン（略称:NMP）を加え、攪拌
し溶解させて溶液を得た。窒素雰囲気の下、外部水槽の
温度を５℃にコントロールし、上記溶液を攪拌しながら
1.092g（0.005モル）の精製した無水のピロメリット酸
二無水物（略称:PMDA）を固形のまま、溶液の温度が上
らないように注意しながら徐々に添加し、全て加え終っ
た後、攪拌を続け均一なポリアミド酸溶液を調製した。Example 1 In a 300 ml four-neck separable flask, 0.324 g (0.0
03 mol) of purified paraphenylenediamine and 0.320 g
(0.0016 mol) of purified 4,4'-diaminodiphenyl ether (abbreviation: 4,4'-DPE) and 0.792 g (0.0002 mol) of 3,3 ', 4,4'-tetraaminobiphenyl tetrahydrochloride. A dihydrate (abbreviation: TABT) was collected, 20 g of distilled N-methyl-2-pyrrolidone (abbreviation: NMP) was added, and the mixture was stirred and dissolved to obtain a solution. Under a nitrogen atmosphere, the temperature of the external water tank is controlled at 5 ° C., and the above solution is stirred.
1.092 g (0.005 mol) of purified anhydrous pyromellitic dianhydride (abbreviation: PMDA) was gradually added while keeping the temperature of the solution as it was solid, and after all the addition was completed, Stirring was continued to prepare a uniform polyamic acid solution.
このポリアミド酸溶液に0.605g（固形分の25重量％）
のパラニトロアニリンを溶解させ、均一なポリアミド酸
／パラニトロアニリンの混合溶液を得た。0.605g (25% by weight of solids) in this polyamic acid solution
Was dissolved to obtain a uniform polyamic acid / paranitroaniline mixed solution.
この混合溶液をガラス板上に流延した。溶液の塗布量
は、スペーサーによりコントロールし、約0.4mmの厚さ
になるようにした。しばらく静置すると、流延された混
合溶液がゲル化を起こし、ポリアミド酸／パラニトロア
ニリン複合体の高分子ゲル（ゲルフィルム）が得られ
た。This mixed solution was cast on a glass plate. The coating amount of the solution was controlled by a spacer so that the thickness was about 0.4 mm. After standing for a while, the cast mixed solution gelled, and a polyamic acid / paranitroaniline composite polymer gel (gel film) was obtained.
得られたゲルフィルムは、自重による形状変化を起こ
さず、自己支持性のものであった。The obtained gel film did not change its shape due to its own weight and was self-supporting.
このゲルフィルムに、30℃にて膜面に対し垂直方向に
50KV/cmの電界を印加しながら真空下で乾燥させ、更
に、80℃で２時間処理し、残存溶媒を0.5重量％以下に
したフィルムを調製した。Apply this gel film at 30 ° C in the direction perpendicular to the membrane surface.
The film was dried under vacuum while applying an electric field of 50 KV / cm, and further treated at 80 ° C. for 2 hours to prepare a film having a residual solvent of 0.5% by weight or less.
更に、このフイルムをテフロンでコートされたポリイ
ミドフィルム２枚に100μｍのアルミフィルムのスペー
サーを介して挟み、微小な圧力の下で150℃にて30分間
保った後、放冷して均一なポリアミド酸／パラニトロア
ニリン複合フィルムを得た。Further, this film is sandwiched between two polyimide films coated with Teflon via a spacer of 100 μm aluminum film, kept at 150 ° C. for 30 minutes under a small pressure, and then cooled to obtain a uniform polyamic acid. / Paranitroaniline composite film was obtained.
この複合フィルムにレーザー光源より1.06μｍのレー
ザー光を照射したところ、0.53μｍの第２高調波が観測
され、非線形光学効果のあることが確認された。When this composite film was irradiated with a laser beam of 1.06 μm from a laser light source, a second harmonic of 0.53 μm was observed, confirming that there was a nonlinear optical effect.
このポリアミド酸溶液に0.320g（固形分の15重量％）
のテトラフェニルポルフィリンを溶解させ、均一なポリ
アミド酸／テトラフェニルポルフィリンの混合溶液を得
た。0.320 g (15% by weight of solids) in this polyamic acid solution
Was dissolved to obtain a homogeneous polyamic acid / tetraphenylporphyrin mixed solution.
この混合溶液をガラス板上に流延した。溶液の塗布量
は、スペーサーによりコントロールし、約0.4mmの厚さ
になるようにした。しばらく静置すると、流延された混
合溶液がゲル化を起こし、ポリアミド酸／パラニトロア
ニリン複合体の高分子ゲル（ゲルフィルム）が得られ
た。This mixed solution was cast on a glass plate. The coating amount of the solution was controlled by a spacer so that the thickness was about 0.4 mm. After standing for a while, the cast mixed solution gelled, and a polyamic acid / paranitroaniline composite polymer gel (gel film) was obtained.
このゲルフィルムを30℃で真空乾燥させ、高分子ゲル
の中の溶媒を飛散させた後、フィルムの形でガラス板よ
り離脱させた。更に、80℃で２時間真空乾燥させたフィ
ルムは、引張り強さが約10kgf/mm2であり、機械的特性
に優れたものであった。The gel film was vacuum-dried at 30 ° C. to disperse the solvent in the polymer gel, and then separated from the glass plate in the form of a film. Further, the film dried under vacuum at 80 ° C. for 2 hours had a tensile strength of about 10 kgf / mm 2 and was excellent in mechanical properties.
このフィルムに、照射強度0.08〜1.0mW/cm2のHe−Ne
レーザーを膜面に垂直方向より入射させ、透過光の吸収
スペクトルを分光器により測定したところ、吸収帯の一
部に鋭いくぼみ（ホール）が観測され、フォトケミカル
ホールバーニング現象が認められた。He-Ne with an irradiation intensity of 0.08 to 1.0 mW / cm 2
When the laser was incident on the film surface in a perpendicular direction and the absorption spectrum of the transmitted light was measured by a spectroscope, a sharp pit (hole) was observed in a part of the absorption band, and the photochemical hole burning phenomenon was recognized.
実施例２ 300mlの四つ口セパラブルフラスコ中に、0.601g（0.0
03モル）の精製した4,4′−ジアミノジフェニルエーテ
ル（略称:4,4′−DPE）と0.350g（0.0012モル）の精製
した1,4−ビス（４−アミノフェノキシ）ベンゼン（略
称:TPE−Ｑ）と0.158g（0.0004モル）の3,3′,4,4′−
テトラアミノビフェニル・四塩酸塩・二水和物（略称:T
ABT）を採取し、20gの蒸留されたN,N−ジメチルアセト
アミド（略称:DMAc）を加え、攪拌し溶解させて溶液を
得た。Example 2 In a 300 ml four-neck separable flask, 0.601 g (0.0
03 mol) of purified 4,4'-diaminodiphenyl ether (abbreviation: 4,4'-DPE) and 0.350 g (0.0012 mol) of purified 1,4-bis (4-aminophenoxy) benzene (abbreviation: TPE- Q) and 0.158 g (0.0004 mol) of 3,3 ', 4,4'-
Tetraaminobiphenyl tetrahydrochloride dihydrate (abbreviation: T
ABT) was collected, 20 g of distilled N, N-dimethylacetamide (abbreviation: DMAc) was added, and the mixture was stirred and dissolved to obtain a solution.
窒素雰囲気の下、外部水槽の温度を５℃にコントロー
ルし、上記溶液を攪拌しながら1.470g（0.005モル）の
精製した3,3′−4,4′−ビフェニルテトラカルボン酸二
無水物（略称:BPDA）を固形のまま、溶液の温度が上ら
ないように注意しながら徐々に添加し、全て加え終わっ
た後、攪拌を続け均一なポリアミド酸溶液を調製した。Under a nitrogen atmosphere, the temperature of the external water tank was controlled at 5 ° C., and while stirring the above solution, 1.470 g (0.005 mol) of purified 3,3′-4,4′-biphenyltetracarboxylic dianhydride (abbreviation) : BPDA) as a solid, and gradually added while being careful not to raise the temperature of the solution. After all the addition was completed, stirring was continued to prepare a uniform polyamic acid solution.
このポリアミド酸溶液に3.868g（固形分の60重量％）
のニッケルフタロシアニンを溶解させ、均一なポリアミ
ド酸／ニッケルフタロシアニンの混合溶液を得た。3.868 g (60% by weight of solids) in this polyamic acid solution
Was dissolved to obtain a homogeneous polyamic acid / nickel phthalocyanine mixed solution.
この混合溶液をガラス板上に流延した。溶液の塗布量
は、スペーサーによりコントロールし、約40mmの厚さに
なるようにした。しばらく静置すると、流延された混合
溶液がゲル化を起こし、ポリアミド酸／ニッケルフタロ
シアニン複合体の高分子ゲル（ゲルフィルム）が得られ
た。得られたゲルフィルムは、自重による形状変化を起
こさず、自己支持性のものであった。This mixed solution was cast on a glass plate. The amount of the solution applied was controlled by a spacer so as to have a thickness of about 40 mm. After standing for a while, the cast mixed solution gelled, and a polyamic acid / nickel phthalocyanine composite polymer gel (gel film) was obtained. The obtained gel film did not change its shape due to its own weight and was self-supporting.
このゲルフィルムをガラス板上に保持させたまま、ヨ
ウ素４重量％、ヨウ化カリウム１重量％含む50℃水溶液
中に浸漬し凝固させた後、30℃で８時間真空乾燥させ、
フィルムを得た。更に、80℃で２時間真空乾燥させたフ
ィルムは、引張り強さが約5kgf/mm2であり、機械的特性
に優れたものであった。この複合フィルムの導電度は、
1.8S/cmであり、電気伝導性を示すフィルムであること
が確認された。While holding the gel film on a glass plate, the gel film is immersed in a 50 ° C. aqueous solution containing 4% by weight of iodine and 1% by weight of potassium iodide to coagulate, and then vacuum-dried at 30 ° C. for 8 hours.
A film was obtained. Further, the film dried under vacuum at 80 ° C. for 2 hours had a tensile strength of about 5 kgf / mm 2 and was excellent in mechanical properties. The conductivity of this composite film is
It was 1.8 S / cm, and it was confirmed that the film exhibited electrical conductivity.
更に、このフィルムをアルミニウムのフィルムに包
み、150℃で１時間、200℃で１時間、250℃１時間での
条件で連続的に処理し、ポリアミド酸数分のイミド化を
進め、均一なポリイミド／ニッケルフタロシアニン複合
フィルムを得た。得られたフィルムの赤外線吸収スペク
トルで分析したところ、1780cm-1,1720cm-1にイミド基
の特性吸収帯が観測された。Furthermore, this film is wrapped in an aluminum film, and is continuously treated under the conditions of 150 ° C. for 1 hour, 200 ° C. for 1 hour, and 250 ° C. for 1 hour. / Nickel phthalocyanine composite film was obtained. When the obtained film was analyzed by an infrared absorption spectrum, characteristic absorption bands of imide groups were observed at 1780 cm -1 and 1720 cm -1 .
このポリイミド／ニッケルフタロシアニン複合フィル
ムの導電度を測定したところ、1.5S/cmであり、電気伝
導性を示すフィルムが確認された。When the conductivity of this polyimide / nickel phthalocyanine composite film was measured, it was 1.5 S / cm, and a film showing electrical conductivity was confirmed.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08L 79/00 - 79/08 C08G 73/00 - 73/26 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C08L 79/00-79/08 C08G 73/00-73/26 CA (STN) REGISTRY (STN)
Claims (4)
カルボン酸二無水物、芳香族ジアミン及び多価アミンを
主成分としたポリアミド酸の三次元網目構造体（高分子
ゲル）〔Ｂ〕の脱水・閉環反応により生成したポリイミ
ド化体〔Ｃ〕とからなるポリイミド系機能性複合体。1. A three-dimensional network structure (polymer gel) of a functional low molecular weight organic compound [A] and a polyamic acid containing tetracarboxylic dianhydride, aromatic diamine and polyamine as main components. And a polyimide-functionalized compound [C] produced by the dehydration / ring-closure reaction of the present invention.
り応答作用を示す物質であり、シッフ系液晶物質、アゾ
キシ系液晶物質、シアノビフェニル系液晶物質、シアノ
フェニル系液晶物質、ナフタレン誘導体、スピロピラン
系化合物、アゾベンゼン系化合物、フタロシアニン系化
合物、ポリフィリン系化合物、シアニン系化合物、キニ
ザリン系化合物、スチルベン系化合物、ヘミシアニン系
化合物、クラウンエーテル類、テトラチアフルバレン、
ビスエチレンジチオテトラチアフルバレン、テトラシア
ノキノジメタン、テトラシアノエチレン、ピレン誘導
体、ピロール系化合物、アセチレン系化合物、アントラ
セン誘導体の中から選ばれた少なくとも一種類の物質で
ある請求項（１）記載のポリアミド酸系機能性複合体。2. A functional low molecular weight organic compound which is a substance exhibiting a response action by an external stimulus, such as a Schiff liquid crystal substance, an azoxy liquid crystal substance, a cyanobiphenyl liquid crystal substance, a cyanophenyl liquid crystal substance, a naphthalene derivative, Spiropyran compounds, azobenzene compounds, phthalocyanine compounds, porphyrin compounds, cyanine compounds, quinizarin compounds, stilbene compounds, hemocyanin compounds, crown ethers, tetrathiafulvalene,
The method according to claim 1, wherein the substance is at least one substance selected from bisethylenedithiotetrathiafulvalene, tetracyanoquinodimethane, tetracyanoethylene, a pyrene derivative, a pyrrole compound, an acetylene compound, and an anthracene derivative. Polyamic acid based functional composite.
イミド系機能性複合体。3. The polyimide-based functional composite according to claim 1, which is in the form of a film.
カルボン酸二無水物、芳香族ジアミン及び多価アミンを
主成分としたポリアミド酸の三次元網目構造体（高分子
ゲル）〔Ｂ〕とからなるポリイミド系機能性複合体を脱
水・閉環反応させることを特徴とするポリイミド系機能
性複合体の製造法。4. A three-dimensional network structure (polymer gel) of a functional low molecular weight organic compound [A] and a polyamic acid containing tetracarboxylic dianhydride, aromatic diamine and polyamine as main components. A method for producing a polyimide-based functional composite, comprising subjecting the polyimide-based functional composite to dehydration and ring-closing reactions.
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|---|---|---|---|
| JP31979790A JP3023486B2 (en) | 1990-11-22 | 1990-11-22 | Functional composite and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31979790A JP3023486B2 (en) | 1990-11-22 | 1990-11-22 | Functional composite and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04189865A JPH04189865A (en) | 1992-07-08 |
| JP3023486B2 true JP3023486B2 (en) | 2000-03-21 |
Family
ID=18114296
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| Country | Link |
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|---|---|---|---|---|
| JPH01240511A (en) * | 1988-03-18 | 1989-09-26 | Hitachi Chem Co Ltd | Production of bisphenol a novolak resin |
| JP2919106B2 (en) * | 1991-03-29 | 1999-07-12 | 三菱電機株式会社 | Polyimide resin composition for laser processing |
| JP2002121281A (en) * | 2000-10-18 | 2002-04-23 | Kanegafuchi Chem Ind Co Ltd | A method for producing a polyamic acid copolymer, a polyimide copolymer, and a polyimide film. |
| CN117430880B (en) * | 2022-07-13 | 2025-09-23 | 南京航空航天大学 | A light-controlled electromechanical material and its preparation method and application |
| CN117285820B (en) * | 2023-11-16 | 2024-04-16 | 乌镇实验室 | A polyimide high temperature dielectric composite film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2678979B2 (en) | 1994-04-28 | 1997-11-19 | フォスター・ホイーラー・エナージイ・コーポレイション | Pressurized fluid bed combustor with integrated recirculation heat exchanger and method of operating same |
| JP2709360B2 (en) | 1989-09-21 | 1998-02-04 | 東邦レーヨン株式会社 | Molded product having polyimide resin three-dimensional network structure and method for producing the same |
| JP2722008B2 (en) | 1990-04-27 | 1998-03-04 | 東邦レーヨン株式会社 | Polyimide resin composition and method for producing the same |
| JP2883196B2 (en) | 1990-11-22 | 1999-04-19 | 東邦レーヨン株式会社 | High performance polyimide molded article and method for producing the same |
-
1990
- 1990-11-22 JP JP31979790A patent/JP3023486B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2709360B2 (en) | 1989-09-21 | 1998-02-04 | 東邦レーヨン株式会社 | Molded product having polyimide resin three-dimensional network structure and method for producing the same |
| JP2722008B2 (en) | 1990-04-27 | 1998-03-04 | 東邦レーヨン株式会社 | Polyimide resin composition and method for producing the same |
| JP2883196B2 (en) | 1990-11-22 | 1999-04-19 | 東邦レーヨン株式会社 | High performance polyimide molded article and method for producing the same |
| JP2678979B2 (en) | 1994-04-28 | 1997-11-19 | フォスター・ホイーラー・エナージイ・コーポレイション | Pressurized fluid bed combustor with integrated recirculation heat exchanger and method of operating same |
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