WO2011093394A1 - 新規アゾメチンオリゴマー - Google Patents
新規アゾメチンオリゴマー Download PDFInfo
- Publication number
- WO2011093394A1 WO2011093394A1 PCT/JP2011/051637 JP2011051637W WO2011093394A1 WO 2011093394 A1 WO2011093394 A1 WO 2011093394A1 JP 2011051637 W JP2011051637 W JP 2011051637W WO 2011093394 A1 WO2011093394 A1 WO 2011093394A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- azomethine
- carbon atoms
- azomethine oligomer
- formula
- Prior art date
Links
- 125000003118 aryl group Chemical group 0.000 claims abstract description 219
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 105
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000002904 solvent Substances 0.000 claims abstract description 102
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- 239000004065 semiconductor Substances 0.000 claims abstract description 50
- 125000003277 amino group Chemical group 0.000 claims abstract description 39
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 19
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract description 17
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims abstract description 7
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims abstract description 7
- 229940057867 methyl lactate Drugs 0.000 claims abstract description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 181
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 120
- 150000002430 hydrocarbons Chemical class 0.000 claims description 119
- 125000005843 halogen group Chemical group 0.000 claims description 96
- 125000000217 alkyl group Chemical group 0.000 claims description 83
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 56
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 42
- 125000001424 substituent group Chemical group 0.000 claims description 35
- 229910052717 sulfur Inorganic materials 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 125000004434 sulfur atom Chemical group 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 229930003836 cresol Natural products 0.000 claims description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 23
- 239000003759 ester based solvent Substances 0.000 abstract description 7
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 251
- 238000006243 chemical reaction Methods 0.000 description 192
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 168
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 150
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 114
- 238000002425 crystallisation Methods 0.000 description 112
- 230000008025 crystallization Effects 0.000 description 112
- 125000003545 alkoxy group Chemical group 0.000 description 77
- 239000002994 raw material Substances 0.000 description 72
- 238000003756 stirring Methods 0.000 description 68
- 230000015572 biosynthetic process Effects 0.000 description 62
- 238000003786 synthesis reaction Methods 0.000 description 60
- 239000007787 solid Substances 0.000 description 54
- 238000001704 evaporation Methods 0.000 description 50
- 230000008020 evaporation Effects 0.000 description 50
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 49
- 230000004807 localization Effects 0.000 description 49
- 229910052757 nitrogen Inorganic materials 0.000 description 49
- 229920000343 polyazomethine Polymers 0.000 description 36
- 125000004429 atom Chemical group 0.000 description 27
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 21
- VATYWCRQDJIRAI-UHFFFAOYSA-N p-aminobenzaldehyde Chemical compound NC1=CC=C(C=O)C=C1 VATYWCRQDJIRAI-UHFFFAOYSA-N 0.000 description 20
- 239000000758 substrate Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 12
- 125000005842 heteroatom Chemical group 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 10
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 9
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 9
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 description 8
- -1 LEDs Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
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- 125000000623 heterocyclic group Chemical group 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 6
- 239000003849 aromatic solvent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 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 5
- 229920000547 conjugated polymer Polymers 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 4
- CFRFHWQYWJMEJN-UHFFFAOYSA-N 9h-fluoren-2-amine Chemical compound C1=CC=C2C3=CC=C(N)C=C3CC2=C1 CFRFHWQYWJMEJN-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- QJXCFMJTJYCLFG-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzaldehyde Chemical compound FC1=C(F)C(F)=C(C=O)C(F)=C1F QJXCFMJTJYCLFG-UHFFFAOYSA-N 0.000 description 3
- RHEAZRNOBUGZRX-UHFFFAOYSA-N 3-hexylthiophene-2,5-dicarbaldehyde Chemical compound CCCCCCC=1C=C(C=O)SC=1C=O RHEAZRNOBUGZRX-UHFFFAOYSA-N 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- 0 CC(*)CC(C)CC1C=Cc2ccc*(C)c2[C@]1*(C)=CC=C Chemical compound CC(*)CC(C)CC1C=Cc2ccc*(C)c2[C@]1*(C)=CC=C 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
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- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
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- 239000006184 cosolvent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 150000002825 nitriles Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
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- WCZNKVPCIFMXEQ-UHFFFAOYSA-N 2,3,5,6-tetramethylbenzene-1,4-diamine Chemical compound CC1=C(C)C(N)=C(C)C(C)=C1N WCZNKVPCIFMXEQ-UHFFFAOYSA-N 0.000 description 2
- ISDBWOPVZKNQDW-UHFFFAOYSA-N 4-phenylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=CC=C1 ISDBWOPVZKNQDW-UHFFFAOYSA-N 0.000 description 2
- SNCJAJRILVFXAE-UHFFFAOYSA-N 9h-fluorene-2,7-diamine Chemical compound NC1=CC=C2C3=CC=C(N)C=C3CC2=C1 SNCJAJRILVFXAE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- 150000007513 acids Chemical class 0.000 description 2
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
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- 229910052794 bromium Inorganic materials 0.000 description 2
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- ZNWNWEHQFXOPGK-UHFFFAOYSA-N decanedial Chemical compound O=CCCCCCCCCC=O ZNWNWEHQFXOPGK-UHFFFAOYSA-N 0.000 description 2
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- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 description 2
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- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
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- 239000007858 starting material Substances 0.000 description 2
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- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-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
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- FEHLIYXNTWAEBQ-UHFFFAOYSA-N 4-(4-formylphenyl)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=C(C=O)C=C1 FEHLIYXNTWAEBQ-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- YAEGPDBHSBKYRW-UHFFFAOYSA-N 5-[5-(5-formylthiophen-2-yl)thiophen-2-yl]thiophene-2-carbaldehyde Chemical compound S1C(C=O)=CC=C1C1=CC=C(C=2SC(C=O)=CC=2)S1 YAEGPDBHSBKYRW-UHFFFAOYSA-N 0.000 description 1
- OXEUETBFKVCRNP-UHFFFAOYSA-N 9-ethyl-3-carbazolamine Chemical compound NC1=CC=C2N(CC)C3=CC=CC=C3C2=C1 OXEUETBFKVCRNP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- JRROIMXZWUYQAC-OOWNKLLOSA-N C(CNc1cccc(Nc2cccc(/N=C/c3ccccc3)n2)n1)COCCOCCOCCCNc1cccc(/N=C/c2cccc(/N=C/c3ccccc3)n2)n1 Chemical compound C(CNc1cccc(Nc2cccc(/N=C/c3ccccc3)n2)n1)COCCOCCOCCCNc1cccc(/N=C/c2cccc(/N=C/c3ccccc3)n2)n1 JRROIMXZWUYQAC-OOWNKLLOSA-N 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N C(c1ccccc1)=C/c1ccccc1 Chemical compound C(c1ccccc1)=C/c1ccccc1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- UAKWVKRWJCVOSN-UHFFFAOYSA-N CC(CCC(C)=C1C(c2c3cccc2)=O)=C1C3=O Chemical compound CC(CCC(C)=C1C(c2c3cccc2)=O)=C1C3=O UAKWVKRWJCVOSN-UHFFFAOYSA-N 0.000 description 1
- CLEWIJBDWTYMJB-RWRHWQIFSA-N CCCCCCc1c(C=O)[s]c(/C=N/CCCOCCOCCOCCC/N=C/c2cc(CC)c(C=O)[s]2)c1 Chemical compound CCCCCCc1c(C=O)[s]c(/C=N/CCCOCCOCCOCCC/N=C/c2cc(CC)c(C=O)[s]2)c1 CLEWIJBDWTYMJB-RWRHWQIFSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- WQKLYSAGSGWIAV-GDNBJRDFSA-N Nc(cc1)ccc1/N=C\c1ccccc1 Chemical compound Nc(cc1)ccc1/N=C\c1ccccc1 WQKLYSAGSGWIAV-GDNBJRDFSA-N 0.000 description 1
- FYMUFNZLDXTAJN-RIYZIHGNSA-N Nc1ccc(/N=C/c2ccccc2)nc1 Chemical compound Nc1ccc(/N=C/c2ccccc2)nc1 FYMUFNZLDXTAJN-RIYZIHGNSA-N 0.000 description 1
- DCYMNVHWVNOCNI-PXLXIMEGSA-N O=Cc1ccc(/C=N/CCOCCOCCNc2ccc(C=O)cc2)cc1 Chemical compound O=Cc1ccc(/C=N/CCOCCOCCNc2ccc(C=O)cc2)cc1 DCYMNVHWVNOCNI-PXLXIMEGSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- MIROPXUFDXCYLG-UHFFFAOYSA-N pyridine-2,5-diamine Chemical compound NC1=CC=C(N)N=C1 MIROPXUFDXCYLG-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- PMWXGSWIOOVHEQ-UHFFFAOYSA-N pyridine-2,6-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=N1 PMWXGSWIOOVHEQ-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OTMRXENQDSQACG-UHFFFAOYSA-N thiophene-2,5-dicarbaldehyde Chemical compound O=CC1=CC=C(C=O)S1 OTMRXENQDSQACG-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000012982 x-ray structure analysis Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/36—Nitrogen atoms
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
Definitions
- the present invention relates to a novel azomethine oligomer.
- a conventional polyazomethine has an aromatic ring, a hetero ring, or an aromatic ring and a hetero ring in the main chain, and these aromatic rings and / or hetero rings connected by an azomethine group are connected. It has a conjugated polymer structure.
- polyazomethine As an organic semiconductor material, in order to form the semiconductor layer on the substrate, a method of dissolving polyazomethine in a solvent and applying the obtained solution on the substrate is simple and costly. Low.
- the polyazomethine is a compound having a conjugated system, high planarity and a rigid structure as described above, and therefore has poor solubility in an organic solvent. For this reason, the polyazomethine cannot be dissolved in an organic solvent and applied onto the substrate.
- Patent Document 1 Regarding the solvent solubility of polyazomethine disclosed in Patent Document 1, in a protonic acid such as m-cresol or an organic solvent containing the same, the polyazomethine forms a reversible Lewis acid-base pair, It has been found that it exhibits solubility in a solvent in this state (see Non-Patent Documents 1 to 4).
- Patent Document 2 discloses an invention relating to an organic LED element containing polyazomethine, and the polyazomethine is represented by the following general formula (I).
- Patent Document 2 such polyazomethine is polymerized in m-cresol or benzene, and the obtained polyazomethine solution is subjected to a substrate (anode) by a wet film formation method such as spin coating or dip coating. ) To form a polyazomethine layer by heating in an inert gas atmosphere.
- Patent Document 2 does not describe at all whether the polyazomethine represented by the above general formula (I) was actually synthesized.
- m-cresol and benzene in which polyazomethine disclosed in Patent Document 2 is dissolved are versatile. As described above, m-cresol is corrosive, and benzene is carcinogenic, both of which are harmful to the human body.
- Patent Document 2 neither describes nor suggests whether or not the polyazomethine is dissolved in another versatile solvent (for example, alcohol).
- polyazomethine having low solubility in organic solvents
- polyazomethine can be converted into chloroform by introducing an alkyl group or alkoxy group into the aromatic ring, hetero ring or aromatic ring and hetero ring in the main chain.
- THF, DMF, DMSO, NMP, m-cresol and the like have been reported to be soluble (see Non-Patent Document 5).
- the solvent species used may have a halogen-containing structure, in which case the solvent species exhibits a high boiling point. For this reason, it is difficult to say that it is preferable to use the solvent for industrial reasons because of high health requirements for the health management of the handler and the drying process of the solvent.
- the present invention secures sufficient carrier mobility as a semiconductor material, and furthermore, a hydrophobic solvent such as toluene, an alcohol solvent such as methanol and ethanol, a glycol solvent such as propylene glycol monomethyl ether, or an ester such as methyl lactate. It is an object of the present invention to provide a novel azomethine oligomer that is soluble in a relatively versatile organic solvent such as a system solvent.
- the present invention has a divalent hydrocarbon group which may have a group having an oxygen atom, a sulfur atom or a cycloalkylene group in the main skeleton, and azomethine groups at both ends of the hydrocarbon group.
- the azomethine oligomer is characterized in that the aromatic group and the aromatic ring-containing conjugated group are not reactive with an aldehyde group and an amino group.
- polyazomethine has an aromatic ring, a heterocycle, or an aromatic ring and a heterocycle in the main chain, and these aromatic rings and / or heterocycles are connected by an azomethine group.
- the conjugated polymer structure was connected. This is because carriers are moved within one molecule of polyazomethine.
- the conjugated polymer structure has caused low solubility of polyazomethine in organic solvents.
- it has also been proposed to introduce an alkyl group or an alkoxy group into the aromatic ring and / or hetero ring as a side chain Non-patent Document 5
- this proposed method has a problem in that raw material monomers for synthesizing such polyazomethine are not commercially available.
- the present inventor can not only dissolve in a highly versatile solvent by changing the idea of the following two points, but also enables easy and industrial production, and is sufficient as a semiconductor.
- the inventors invented an azomethine oligomer that ensures carrier mobility. (1) Rather than move the carrier within one molecule, the conjugated system (aromatic ring) of the compound is stacked between the compound molecules (orienting the conjugated structure portion between the molecules), so that the carrier is a molecule. (2) Instead of introducing an alkyl group or the like as a side chain of a polymer, it is introduced as a part of the main chain of an oligomer (that is, a conjugated structure is linked by a non-conjugated spacer). thing.
- the hydrocarbon group may have a branch and may be substituted with a halogen atom, an alkylene group having 2 to 1024 carbon atoms, an ether bond and / or a thioether bond in the group
- the molecular weight of the azomethine oligomer of the present invention is preferably in the range of 150 to 15000.
- the azomethine oligomer is usually cresol, toluene, THF, cyclopentyl methyl ether, acetone, MEK, MIBK, cyclopentanone, chloroform, Dichloromethane, carbon tetrachloride, chlorobenzene, carbon disulfide, ethyl acetate, butyl acetate, methyl lactate, methanol, ethanol, isopropyl alcohol, benzyl alcohol, n-butanol, t-butanol, pentyl alcohol, ethylene glycol, propylene glycol, propylene glycol Any solvent selected from monomethyl ether, pyridine, NMP, sulfuric acid, formic acid, acetic acid, hydrochloric acid, lactic acid, triethylamine, dibutylamine, or two or more kinds
- the azomethine oligomer of the present invention can be represented by the following general formula (I), for example.
- two Ars independently represent a monovalent aromatic group which may have a substituent, or an azomethine group and a divalent aromatic group which may have a substituent.
- A is an azomethine group,
- R is an alkylene group having 2 to 1024 carbon atoms which may have a branch and may be substituted with a halogen atom, and has an ether bond and / or a thioether bond in the group, and is substituted with a halogen atom.
- the divalent hydrocarbon group having 2 to 1024 carbon atoms may be used.
- the azomethine oligomer of the present invention is suitable for semiconductor applications, and can be formed on an electrode by a coating method to produce a pn junction element.
- a positive electrode terminal is connected to an electrode on the P-type semiconductor side
- a negative electrode terminal is connected to an electrode on the N-type semiconductor side. It is a feature of the azomethine oligomer of the present invention that a voltage can be applied within the range of ⁇ 5 V to +5 V, and the forward electric energy / reverse electric energy> 1.0.
- the method for producing an azomethine oligomer of the present invention includes a step of reacting 2 equivalents of an aromatic ring-containing compound represented by the following general formula (III) with 1 equivalent of a hydrocarbon compound represented by the following general formula (II). It is characterized by that.
- two Xs are both an aldehyde group or an amino group
- Two Ar are independently a divalent aromatic group which may have a substituent
- A is an azomethine group
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom or a carboxyl group
- Z is a divalent group having an oxygen atom, a sulfur atom or a cycloalkylene group
- m and n are independently 0 or 1
- i is 0 or 1
- h and j are each independently an integer of 0 to 12 (provided that when Z is an oxygen atom or a sulfur atom, h and j are both 1 or more)
- k is an integer from 1 to 10, when h is 2 or more, a plurality of R 1 may be the same or different; when j is 2 or more, a plurality of R 2 may be the same or different; When k is 2 or more, a
- Y is an amino group when X in the above formula (II) is an aldehyde group, and is an aldehyde group when X is an amino group
- Ar 1 is a monovalent aromatic group which may have a substituent
- Ar 2 is a divalent aromatic group which may have a substituent
- A is an azomethine group
- p is an integer from 0 to 5
- p is 2 or more, a plurality of Ar 2 may be the same or different.
- aromatic ring-containing compound examples include compounds represented by the following formula.
- hydrocarbon compound examples include compounds represented by the following formula.
- both X are amino groups or aldehyde groups, and t is an integer of 6-12.
- the azomethine oligomer of the present invention ensures sufficient carrier mobility as a semiconductor material, and furthermore, a hydrophobic solvent such as toluene, an alcohol solvent such as methanol and ethanol, a glycol solvent such as propylene glycol monomethyl ether, or methyl lactate High solubility in highly versatile organic solvents such as ester solvents.
- a hydrophobic solvent such as toluene, an alcohol solvent such as methanol and ethanol, a glycol solvent such as propylene glycol monomethyl ether, or methyl lactate
- the azomethine oligomer of the present invention it is possible to form a semiconductor layer on a substrate by a coating method, instead of orienting polyazomethine on the substrate by vacuum deposition as in the case of a conventional conjugated polymer. .
- the said hydrocarbon group which comprises the azomethine oligomer of this invention may have group which has an oxygen atom, a sulfur atom, or a cycloalkylene group, and if the valence is 2, it will not specifically limit.
- This hydrocarbon group contributes to the high solubility of the azomethine oligomer of the present invention in an organic solvent.
- hydrocarbon group examples include an alkylene group having 2 to 1024 carbon atoms which may be branched or substituted with a halogen atom, an ether bond and / or a thioether bond in the group, A divalent hydrocarbon group having 2 to 1024 carbon atoms which may be substituted with an atom, a cycloalkylene group having 3 to 50 carbon atoms which may have a substituent, and a carboxyl group in the group; And a divalent hydrocarbon group having 2 to 1024 carbon atoms which may be substituted with a halogen atom.
- halogen atom examples include a fluorine atom, a chlorine atom and a bromine atom.
- Examples of the substituent in the cycloalkylene group include a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.
- the cycloalkylene group may have a plurality of cyclic structures, and the cyclic structures may be further linked by an alkylene group.
- the number of carbon atoms of the alkylene group is preferably from 3 to 20, and preferably from 4 to 12, from the viewpoint of compatibility between the affinity of the azomethine oligomer of the present invention for an organic solvent and intermolecular crystallinity in the solid state. More preferably, it is 6-12.
- the number of carbon atoms of the divalent hydrocarbon group which has an ether bond and / or a thioether bond in the group and may be substituted with a halogen atom depends on the affinity of the azomethine oligomer of the present invention for the organic solvent and the solid state. From the standpoint of achieving intermolecular crystallinity, it is preferably 3-20, more preferably 4-12, and even more preferably 6-12.
- the number of carbon atoms of the cycloalkylene group which may have a substituent is 3 to 30 from the viewpoint of compatibility of the azomethine oligomer of the present invention with an organic solvent and crystallinity between molecules in a solid state. It is preferably 6 to 15.
- the number of carbon atoms of the divalent hydrocarbon group which has a carboxyl group in the group and may be substituted with a halogen atom depends on the affinity of the azomethine oligomer of the present invention for the organic solvent and the intermolecular crystal in the solid state. From the viewpoint of coexistence of properties, it is preferably 3 to 20, more preferably 4 to 12, and still more preferably 6 to 12.
- the divalent hydrocarbon group constituting the azomethine oligomer of the present invention has a relatively low polarity such as toluene and exhibits solubility in a highly hydrophobic solvent from the viewpoint of affinity with an organic solvent.
- the divalent hydrocarbon group preferably has a structure having an ether bond in the group.
- the divalent hydrocarbon group in order to develop solubility in a halogen-containing solvent, preferably has a structure having a halogen atom in the group (substituted with a halogen atom).
- the aromatic group which has an azomethine group and may have a substituent constituting the azomethine oligomer of the present invention has a structure in which an azomethine group and a monovalent aromatic group are bonded and conjugated, If there is no reactivity with an aldehyde group and an amino group, it will not specifically limit. The significance of having no reactivity with aldehyde groups and amino groups will be described in the section of the method for producing an azomethine oligomer of the present invention described later.
- the azomethine oligomer of the present invention Due to the conjugated structure of the monovalent aromatic group and azomethine group, the azomethine oligomer of the present invention has a carrier transport function between molecules.
- a monovalent aromatic group is bonded to the end of the hydrocarbon group by the azomethine group.
- Examples of the monovalent aromatic group in the aromatic group which has an azomethine group and may have a substituent include groups represented by the following formulas A-1 to A-23.
- Ra is a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, or a hydrocarbon group having 1 to 15 carbon atoms including an ether bond or an alkoxy group in the group.
- the halogen atom include F, Cl and Br. The same applies to the following formulas A-2 to A-23.
- Ra is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom having a small van der Waals radius.
- Sa is an integer of 1 to 5, and when Sa is 2 or more, a plurality of Ras may be the same or different.
- Sa is preferably 4 or 5, more preferably 4 from the viewpoint of further reducing electron localization in the aromatic ring.
- Or 5 and the aromatic group is substituted so as to have a symmetrical element as a whole.
- the symmetrical element refers to the symmetry of the structural part of the aromatic group, not the entire azomethine oligomer molecule.
- Sd is 2 or more, a plurality of Rd may be the same or different.
- Sd is preferably 6 or 7, and more preferably 7, from the viewpoint of reducing electron localization in the aromatic ring.
- Xc is selected from CH 2 , O, S, NH, N (C x H 2x + 1 ) (X is an integer of 1 to 20) and N (Ph), and the azomethine oligomer of the present invention From the viewpoint of high crystallization between molecules, CH 2 , O, S and NH are preferable because they have small steric hindrance and high planarity.
- Ya is selected from CH and N, and all are preferable from the viewpoint of high crystallization between molecules of the azomethine oligomer of the present invention.
- Se is an integer of 1 to 11, and when Se is 2 or more, a plurality of Re may be the same or different.
- Se is preferably an integer of 9 to 11, preferably 9 or 10, from the viewpoint of reducing localization of electrons in the aromatic ring in order to achieve high crystallization between molecules of the azomethine oligomer of the present invention. More preferably.
- Rf is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group.
- Rf is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom having a small van der Waals radius.
- Sf is an integer of 1 to 9 when Xd is CH.
- Sf is preferably 8 or 9, more preferably 9, from the viewpoint of reducing electron localization in the aromatic ring. .
- Sf is an integer of 1 to 7, and Sf is preferably 6 or 7, more preferably 7, from the same viewpoint as described above.
- a plurality of Rf may be the same or different.
- Rk is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between molecules of the azomethine oligomer of the present invention, it is preferable that Rk is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and a small van der Waals radius. More preferably it is an atom.
- Xg is selected from O, S, NH, N (CH 3 ), N (C 2 H 5 ) and N (Ph).
- Xg is preferably S or NH from the viewpoint of high planarity of the intramolecular conjugated system of the azomethine oligomer of the present invention.
- Rm is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between the molecules of the azomethine oligomer of the present invention, it is preferable that Rm is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms and having a small van der Waals radius. More preferably it is an atom.
- Sn is an integer of 1 to 17.
- Sn is preferably an integer of 10 to 17, and preferably 17 from the viewpoint of reducing electron localization in the aromatic ring. Further preferred.
- Sn is an integer of 1 to 9. From the same viewpoint as described above, Sn is preferably an integer of 7 to 9, and more preferably 9.
- Xi is selected from CH and N, and is preferably CH from the viewpoint of commercial availability of the raw material of the azomethine oligomer of the present invention.
- So when Xi is CH, So is an integer of 1 to 3. When So is 2 or more, a plurality of Ro may be the same or different. In order to achieve high crystallization between molecules of the azomethine oligomer of the present invention, it is more preferable that So is 3 from the viewpoint of reducing the localization of electrons in the aromatic ring.
- Xj is selected from S and O, and is preferably S from the viewpoint of commercial availability of the raw material of the azomethine oligomer of the present invention.
- Sp is an integer of 1 to 5.
- a plurality of Rp may be the same or different.
- Sp is preferably 4 or 5, and more preferably 5, from the viewpoint of reducing electron localization in the aromatic ring. .
- Rq is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between molecules of the azomethine oligomer of the present invention, it is preferable that Rq is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms and a small van der Waals radius. More preferably it is an atom.
- Sq is an integer of 1 to 3.
- a plurality of Rq may be the same or different.
- Sq is preferably an odd number from the viewpoint of reducing the localization of electrons in the aromatic ring, and a symmetric element as a whole of the aromatic group. More preferably, it is substituted to have.
- Rr is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between the molecules of the azomethine oligomer of the present invention, it is preferable that Rr is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms and having a small van der Waals radius. More preferably it is an atom.
- Sr is an integer of 1 to 5.
- a plurality of Rr may be the same or different.
- Sr is preferably an odd number from the viewpoint of reducing electron localization in the aromatic ring, and the aromatic group as a whole has a symmetric element. More preferably, the substitution is as follows.
- Rs is a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, or a hydrocarbon group having 1 to 15 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between molecules of the azomethine oligomer of the present invention, it is preferable that Rs is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 15 carbon atoms, and a hydrogen having a small van der Waals radius. More preferably it is an atom.
- Ss is an integer of 1 to 3.
- a plurality of Rs may be the same or different.
- Ss is preferably 2 or 3, and more preferably 3, from the viewpoint of reducing electron localization in the aromatic ring. .
- St is an integer of 1 to 7. When St is 2 or more, a plurality of Rt may be the same or different. In order to achieve high crystallization between the molecules of the azomethine oligomer of the present invention, St is an odd number from the viewpoint of reducing electron localization in the aromatic ring, and has a symmetrical element as a whole aromatic group. More preferably it is substituted.
- Su is an integer of 1 to 3.
- a plurality of Ru may be the same or different.
- Su is 2 from the viewpoint of further reducing the localization of electrons in the aromatic ring.
- Rv is a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, or a hydrocarbon group having 1 to 15 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between the molecules of the azomethine oligomer of the present invention, it is preferable that Rv is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 15 carbon atoms, and having a small van der Waals radius. More preferably it is an atom.
- Sv is an integer of 1 to 5.
- a plurality of Rv may be the same or different.
- Sv is an odd number from the viewpoint of reducing the localization of electrons in the aromatic ring, and the aromatic group as a whole has a symmetrical element. More preferably it is substituted.
- Rw is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between molecules of the azomethine oligomer of the present invention, it is preferable that Rw is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and a small van der Waals radius. More preferably it is an atom.
- Sw is an integer of 1 to 7.
- a plurality of Rw may be the same or different.
- Sw is an odd number from the viewpoint of reducing electron localization in the aromatic ring, and has a symmetrical element as a whole aromatic group. More preferably it is substituted.
- Rx is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between the molecules of the azomethine oligomer of the present invention, it is preferable that Rx is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms and having a small van der Waals radius. More preferably it is an atom.
- Sx is an integer of 1 to 7.
- a plurality of Rx may be the same or different.
- Sx is an odd number from the viewpoint of reducing electron localization in the aromatic ring, and has a symmetrical element as a whole aromatic group. More preferably it is substituted.
- the aromatic ring-containing conjugated group is bonded to the end of the hydrocarbon group by the azomethine group.
- Ra is a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, or a hydrocarbon group having 1 to 15 carbon atoms including an ether bond or an alkoxy group in the group.
- the halogen atom include F, Cl and Br. The same applies to the following formulas B-2 to B-24.
- Sa is an integer of 1 to 4, and from the viewpoint of further reducing the localization of electrons in the aromatic ring for high crystallization between molecules of the azomethine oligomer of the present invention, Sa is It is preferable that the number is even, and it is more preferable that Sa is an even number and is substituted so as to have a symmetrical element as a whole aromatic group.
- a plurality of Ras may be the same or different.
- Rb is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group.
- Rb is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom having a small van der Waals radius.
- Sb is an integer of 1 to 3, and Sb is preferably an odd number from the viewpoint of reducing the localization of electrons in the aromatic ring for high crystallization between molecules. More preferably, Sb is an odd number and is substituted so as to have a symmetric element as a whole aromatic group.
- Sb is 2 or more, a plurality of Rb may be the same or different.
- Sc when Yb is CH, Sc is 1 or 2.
- Sc is preferably 2
- Sc is 2, and aromatic from the viewpoint of further reducing the localization of electrons in the aromatic ring. More preferably, the entire ring-containing group is substituted with a symmetric element.
- two Rc may be the same or different.
- Xb is CH 2 , C (C x H 2x + 1 ) 2 (X is an integer of 2 to 20), NH, N (C x H 2x + 1 ) (X is an integer of 2 to 20) ), N (Ph) and S. From the viewpoint of high crystallization between molecules of the azomethine oligomer of the present invention, as Xb, C and NH having small steric hindrance and high planarity are preferable.
- Sd is preferably an even number, Sd is an even number, and aromatics from the viewpoint of reducing the localization of electrons in the aromatic ring. It is preferred that the whole group is substituted to have a symmetric element.
- Sd is 2 or more, a plurality of Rd may be the same or different.
- Xc is selected from O, S, NH, N (C x H 2x + 1 ) (X is an integer of 1 to 20) and N (Ph). From the viewpoint of high crystallization between the molecules of the azomethine oligomer of the present invention, Xc is preferably O, S, and NH having low steric hindrance and high planarity.
- Ya is selected from CH and N, and both are preferable from the viewpoint of high crystallization between molecules of the azomethine oligomer of the present invention.
- Re is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group.
- Re is a hydrogen atom or a halogen atom, and more preferably a hydrogen atom having a small van der Waals radius.
- Se is an integer of 1 to 10.
- Se is preferably an even number
- Se is an even number
- aromatic from the viewpoint of reducing the localization of electrons in the aromatic ring. More preferably, the whole group is substituted to have a symmetric element.
- Se is an integer from 1 to 8. From the same viewpoint as described above, Se is preferably an even number, and more preferably, Se is an even number, and the aromatic group is substituted so as to have a symmetrical element as a whole.
- a plurality of Re may be the same or different.
- Xd is selected from CH and N, and all are preferable from the viewpoint of high crystallization between molecules of the azomethine oligomer of the present invention.
- Rf is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group.
- Rf is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom having a small van der Waals radius.
- Sf is an integer of 1 to 8 when Xd is CH.
- Sf is preferably an even number, Sf is an even number, and aromatics from the viewpoint of reducing the localization of electrons in the aromatic ring. More preferably, the whole group is substituted to have a symmetric element.
- Sf is an integer of 1 to 6, and from the same viewpoint as above, Sf is preferably an even number, Sf is an even number, and the symmetric element as a whole aromatic group is selected. More preferably, it is substituted to have.
- a plurality of Rf may be the same or different.
- Rg is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group.
- Rg is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom having a small van der Waals radius.
- Sg is an integer of 1 to 10
- Rg may be bonded onto an ethenylene group connecting two benzene rings.
- Sg is preferably an even number
- Sg is an even number
- aromatics from the viewpoint of reducing the localization of electrons in the aromatic ring. It is preferred that the whole group is substituted to have a symmetric element.
- Sg is 2 or more, a plurality of Rg may be the same or different.
- Rh is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group.
- Rh is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom having a small van der Waals radius.
- Sh is an integer of 1-6.
- Sh is preferably an even number, Sh is an even number, and is aromatic from the viewpoint of reducing the localization of electrons in the aromatic ring. More preferably, the whole group is substituted to have a symmetric element.
- a plurality of Rh may be the same or different.
- Ri is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between molecules of the azomethine oligomer of the present invention, Ri is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom having a small van der Waals radius.
- Si is an integer of 1 to 8 when Xe is CH.
- Si is preferably an even number, Si is an even number, and aromatics from the viewpoint of reducing the localization of electrons in the aromatic ring. More preferably, the whole group is substituted to have a symmetric element.
- Si is an integer of 1 to 6 when Xe is N. From the same viewpoint as described above, Si is preferably an even number, Si is an even number, and the aromatic group as a whole has a symmetrical element. More preferably, it is substituted to have.
- a plurality of Ri may be the same or different.
- Rj is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group.
- Rj is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom having a small van der Waals radius.
- Sj is an integer of 1 to 8.
- Sj is preferably an even number, Sj is an even number, and aromatic, from the viewpoint of reducing the localization of electrons in the aromatic ring. More preferably, the whole group is substituted to have a symmetric element.
- a plurality of Rj may be the same or different.
- Xf is selected from CH and N. From the viewpoint of high crystallization between molecules of the azomethine oligomer of the present invention, Xf is preferably N.
- Rk is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group.
- Rk is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom having a small van der Waals radius.
- Sk is an integer of 1 to 8 when Xf is CH.
- Sk is preferably an even number, Sk is an even number, and aromatic, from the viewpoint of reducing the localization of electrons in the aromatic ring. More preferably, the whole group is substituted to have a symmetric element.
- a plurality of Rk may be the same or different.
- Xg is selected from CH and N. From the viewpoint of high crystallization between molecules of the azomethine oligomer of the present invention, Xg is preferably N.
- Rm is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group.
- Rm is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom having a small van der Waals radius.
- Sm is an integer of 1 to 8 when Xg is CH.
- Sm is preferably an even number, Sm is an even number, and aromatics from the viewpoint of reducing the localization of electrons in the aromatic ring. More preferably, the whole group is substituted to have a symmetric element.
- Sm is an integer of 1 to 6 when Xg is N. From the same viewpoint as described above, Sm is preferably an even number, Sm is an even number, and the aromatic group as a whole has a symmetrical element. More preferably, it is substituted to have.
- Xh is selected from O, S, NH, N (CH 3 ), N (C 2 H 5 ) and N (Ph). From the viewpoint of high planarity of the intramolecular conjugated system of the azomethine oligomer of the present invention, Xh is preferably S or NH.
- Sn is an integer of 1 to 4.
- a plurality of Rn may be the same or different.
- Sn is preferably an integer of 2 to 4, and is preferably an integer of 2 to 4, from the viewpoint of reducing electron localization in the aromatic ring. More preferably.
- Xi is selected from O, S, NH, N (CH 3 ), N (C 2 H 5 ) and N (Ph). From the viewpoint of high planarity of the intramolecular conjugated system of the azomethine oligomer of the present invention, Xi is preferably S or NH.
- Rp is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between the molecules of the azomethine oligomer of the present invention, it is preferable that Rp is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms and having a small van der Waals radius. More preferably it is an atom.
- Sp is an integer of 1 to 8.
- a plurality of Rp may be the same or different.
- Sp is preferably an integer of 4 to 8, preferably 4 or 8, from the viewpoint of reducing electron localization in the aromatic ring. More preferably.
- Xj is selected from CH and N, and is preferably CH from the viewpoint of commercial availability of the raw material of the azomethine oligomer of the present invention.
- Rq is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between the molecules of the azomethine oligomer of the present invention, it is preferable that Rq is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms and having a small van der Waals radius. More preferably it is an atom.
- Xk is selected from S and O, and is preferably S from the viewpoint of commercial availability of the raw material of the azomethine oligomer of the present invention.
- Rr is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between the molecules of the azomethine oligomer of the present invention, it is preferable that Rr is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms and having a small van der Waals radius. More preferably it is an atom.
- Sr is an integer of 1 to 4. When Sr is 2 or more, a plurality of Rr may be the same or different. In order to achieve high crystallization between molecules of the azomethine oligomer of the present invention, Sr is preferably 3 or 4, and more preferably 4, from the viewpoint of reducing electron localization in the aromatic ring. .
- Rs is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group.
- Rs is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and a hydrogen having a small van der Waals radius. More preferably it is an atom.
- Ru is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between the molecules of the azomethine oligomer of the present invention, it is preferable that Ru is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms and having a small van der Waals radius. More preferably it is an atom.
- Su is 1 or 2.
- two Rus may be the same or different.
- Su is 2 and the aromatic group as a whole has a symmetric element. It is preferably substituted.
- Rv is a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, or a hydrocarbon group having 1 to 15 carbon atoms including an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between the molecules of the azomethine oligomer of the present invention, it is preferable that Rv is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 15 carbon atoms, and having a small van der Waals radius. More preferably it is an atom.
- Sx is 1 or 2.
- two Rx may be the same or different.
- Sx is preferably 2 from the viewpoint of further reducing the localization of electrons in the aromatic ring.
- Sz is an integer of 1 to 6.
- a plurality of Rz may be the same or different.
- Sz is an even number and the aromatic group as a whole has a symmetrical element. It is preferably substituted.
- Raa is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms including an ether bond or an alkoxy group in the group.
- Raa is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and a hydrogen having a small van der Waals radius. More preferably it is an atom.
- Saa is an integer of 1 to 6.
- a plurality of Raa may be the same or different.
- Saa is an even number from the viewpoint of reducing electron localization in the aromatic ring, and the aromatic group as a whole has a symmetrical element. It is preferably substituted.
- the conjugated state may affect the crystallinity between molecules depending on the direction of the azomethine group. That is, the direction of the azomethine group is the direction in which N is closer to the heterocycle among N and C constituting the azomethine group, and the heteroatom of the heterocycle is near N constituting the azomethine group.
- the expansion of the intramolecular conjugated system in the solid state of the azomethine oligomer of the present invention occurs, and the electronic structure in the conjugated system may be greatly affected, which is preferable.
- the azomethine oligomer of the present invention has the above-described hydrocarbon group in its structure, and since this portion does not have crystallinity, various versatile organic solvents such as hydrophobic solvents, alcohol solvents, glycols High solubility in system solvents or ester solvents.
- the azomethine oligomer is usually cresol, toluene, THF, cyclopentyl methyl ether, acetone, MEK, MIBK, cyclopentanone, chloroform, dichloromethane, carbon tetrachloride, chlorobenzene, carbon disulfide, ethyl acetate, acetic acid.
- cresol, chlorobenzene and the like are corrosive or harmful to the human body. In the present invention, these are usually mixed in a small amount with other versatile solvents such as toluene and used as a co-solvent.
- the azomethine oligomer of the present invention having high versatility and high solubility in a variety of organic solvents does not have a polymer structure like conventional polyazomethine, but has electrons and holes. It has a high function of transporting the carrier and is suitable for semiconductor applications.
- azomethine oligomers are molecules with high affinity (that is, hydrocarbon groups are hydrocarbon groups, aromatic groups and aromatic ring-containing conjugated groups are aromatic groups and aromatic ring-containing conjugated groups). overlap. And in the location where the aromatic group or aromatic ring containing conjugated group is stacked, the carrier can move freely. That is, the conventional polyazomethine secures the carrier mobility by a specific structure in the molecule, whereas in the present invention, the carrier mobility is secured by the stack between molecules.
- the azomethine oligomer of the present invention has a high carrier transport function, is suitable for semiconductor applications, and exhibits high solubility in highly versatile organic solvents. Therefore, the azomethine oligomer can be dissolved in a highly versatile organic solvent, and the obtained azomethine oligomer solution can be used to form a semiconductor layer safely and easily on the substrate by a coating method such as spin coating or dip coating. it can.
- a solution of the azomethine oligomer of the present invention having such a carrier transport function can be applied on an electrode and formed into a film to produce a pn junction element.
- the N-type semiconductor layer uses a semiconductor material (eg, fullerene) that exhibits an electron affinity (eV) that is larger than the ionization potential (eV) of azomethine.
- the P-type semiconductor layer is a semiconductor material having an ionization potential that is smaller than the electron affinity (eV) of the azomethine oligomer (for example, poly (3- Hexylthiophene)).
- a film is prepared by applying an azomethine oligomer solution on a negative electrode substrate and drying.
- a p-n junction element can be fabricated by depositing a P-type semiconductor material on the film by coating or vapor deposition, and vapor-depositing the positive electrode on the obtained P-type semiconductor layer.
- an N-type semiconductor material is formed on the negative electrode substrate by coating or vapor deposition, and an azomethine oligomer solution is formed on the film.
- a pn junction element can be produced by forming a P-type semiconductor layer by coating and drying, and further depositing a positive electrode on the P-type semiconductor layer.
- the thickness of the bonded layer of these P-type and N-type semiconductor materials is usually 10 to 900 nm.
- the p-n junction element thus produced can be applied to the organic electronics field such as a diode, an organic EL, an organic thin film solar cell, an organic thin film transistor, and a thermoelectric power generation element.
- the ionization potential and the electron affinity can be experimentally obtained as HOMO (highest occupied orbit) and LUMO (lowest unoccupied orbit), respectively.
- LUMO can be determined by calculating the electrochemical reduction level and converting it to LUMO, as well as calculating the LUMO from the absorption start wavelength of the UV-visible light absorption spectrum of the sample and the HOMO value obtained above.
- the method of converting is mentioned.
- the N-type semiconductor characteristics of the azomethine oligomer of the present invention can be improved by adjusting the electron affinity of the molecule.
- the electron affinity of a molecule can be increased by the following two methods. (1) Select heterocycles such as pyridine, bipyridine, phenanthroline, etc. that tend to lack electrons as conjugated systems (aromatic groups or aromatic ring-containing conjugated groups) (2) Electron withdrawing properties such as F and CF 3 By introducing the substituent of ## STR3 ## into the conjugated system, the electron density in the conjugated system is lowered and the electrons are localized.
- a pn junction element can be prepared from the azomethine oligomer of the present invention having excellent semiconductor characteristics as described above.
- a positive electrode terminal is connected to an electrode on the P-type semiconductor side
- a negative electrode terminal is connected to an electrode on the N-type semiconductor side
- a voltage can be applied within the range of ⁇ 5V to + 5V, and the forward power amount / reverse power amount> 1.0.
- the azomethine oligomer of the present invention can be used as, for example, p-type and n-type semiconductors.
- a hole injection phase and an electron injection layer may be separately provided between the P-type semiconductor layer and the electrode and between the N-type semiconductor layer and the electrode, respectively.
- azomethine oligomers Specific examples of the azomethine oligomer of the present invention described above include compounds represented by the following general formula (I).
- Examples of the monovalent aromatic group include groups represented by the following formula. Note that, in the following formula, the part enclosed in half brackets is a bond.
- divalent aromatic groups exemplified below are preferred from the viewpoint of high intermolecular crystallinity when the azomethine oligomer of the present invention is in a solid state.
- the azomethine oligomer of the present invention described above is suitable for semiconductor applications because carriers can be freely moved at positions where aromatic groups or aromatic ring-containing conjugated groups are stacked between molecules.
- the azomethine oligomer is used for a highly versatile organic solvent such as a hydrophobic solvent such as toluene, an alcohol solvent such as methanol and ethanol, a glycol solvent such as propylene glycol monomethyl ether, or an ester solvent such as methyl lactate. And has high solubility. Therefore, the semiconductor layer can be easily formed on the substrate by a coating method using the azomethine oligomer solution obtained by dissolving the azomethine oligomer of the present invention in the organic solvent.
- the azomethine oligomer of the present invention can be obtained by reacting two molecules of an aromatic ring-containing compound with one molecule of a hydrocarbon compound utilizing a reaction between an aldehyde group and an amino group.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom or a carboxyl group.
- R 1 and R 2 are preferably a hydrogen atom and an alkyl group having 5 to 12 carbon atoms from the viewpoint of solubility in an organic solvent and crystallinity of the film during film formation.
- Z is a divalent group having an oxygen atom, a sulfur atom or a cycloalkylene group, and is preferably an oxygen atom from the viewpoint that the raw material is relatively commercially available.
- h and j are each independently an integer of 0 to 12, and preferably an integer of 0 to 3. However, when Z is an oxygen atom or a sulfur atom, h and j are both 1 or more.
- a hydrocarbon compound in which m or n is 1 and the other is 0 can be easily obtained by reacting a commercially available compound.
- a hydrocarbon compound in which both m and n are 1 can be obtained by repeating the above reaction (reacting the compound obtained by the above reaction with p-aminobenzaldehyde), and also as described below. It is also possible to obtain it by a one-step reaction.
- the one-step reaction as described above becomes possible.
- a hydrocarbon compound having an amino group as X can be obtained.
- X has an aldehyde group and an azomethine group.
- a hydrocarbon compound having the opposite direction is obtained.
- Such a reaction can be carried out under known and usual reaction conditions for reacting an amino group and an aldehyde group.
- the reaction temperature is 30 to 120 ° C.
- the reaction time is usually 2 to 48 hours.
- reaction solvent examples include ester solvents such as ethyl acetate and butyl acetate, aromatic solvents such as toluene and xylene, ether solvents such as THF and cyclopentylmethyl ether, ketone solvents such as MEK and cyclopentanone, m -Proton donor aromatic solvents such as cresol and phenol (preferably used in acid catalyzed reaction conditions), halogen-containing solvents such as chloroform, methylene chloride, tetrachloroethane, and benzene chloride, NMP, DMF, pyridine, Examples include proton-accepting solvents such as piperidine (preferably used under reaction conditions catalyzed by base catalysis), and nitrile solvents such as acetonitrile and benzonitrile.
- ester solvents such as ethyl acetate and butyl acetate
- aromatic solvents such as toluene and xylene
- the hydrocarbon compound which is a raw material for producing the azomethine oligomer of the present invention is commercially available or can be easily obtained by reacting a commercially available product.
- both X are amino groups or aldehyde groups, and t is an integer of 6-12.
- Y is an amino group when X in the formula (II) is an aldehyde group, and is an aldehyde group when X is an amino group.
- Ar 1 is a condensed ring system such as fluorene and phenanthrolin, or an aromatic ring such as biphenyl, bipyridine, and terthiophene, from the viewpoint of achieving both expansion of the conjugated system of the azomethine oligomer of the present invention and solubility in a solvent.
- Ar 2 is a divalent aromatic group which may have a substituent.
- Specific examples thereof include groups represented by the above formulas B-1 to B-24. Is mentioned.
- A is an azomethine group, and its direction varies depending on the selection of a compound used as a raw material substrate for producing an aromatic ring-containing compound, as will be described later.
- p is an integer of 0 to 5, and is preferably an integer of 1 to 3 from the viewpoint of coexistence of expansion of the conjugated system of the azomethine oligomer of the present invention and solubility in a solvent.
- p is 2 or more, a plurality of Ar 2 may be the same or different.
- Y is an aldehyde group or an amino group.
- the two amino groups or aldehyde groups of the hydrocarbon compound react with the aldehyde group or amino group of the aromatic ring-containing compound to form an azomethine group, and the azomethine group and aromatic group (alternately To form a conjugated structure (the above aromatic group or aromatic ring-containing conjugated group).
- the aromatic ring-containing compound since the aromatic ring-containing compound has no portion reactive with the aldehyde group or amino group other than the aldehyde group or amino group involved in the reaction with the hydrocarbon compound, the aromatic ring is further added after the reaction. A reaction with the contained compound or hydrocarbon compound does not occur, and an azomethine oligomer is obtained instead of polyazomethine.
- the reaction temperature in the above reaction is usually 30 to 120 ° C., and preferably 60 to 100 ° C. from the viewpoint of reaction efficiency.
- a 100 mL Schlenk tube purged with nitrogen was charged with 10.0 g (74.4 mmol) of terephthalaldehyde, 5 g of m-cresol, and 30 g of toluene, and the reaction solution was heated to 70 ° C. while stirring. Thereafter, a solution obtained by dissolving 2.30 g (24.8 mmol) of aniline in 30 g of toluene was dropped into the above solution over 3 hours, followed by stirring for 3 hours, and then the reaction was completed. After evaporation of the volatile solvent in the reaction solution, the concentrated solution was vacuum-dried and washed with hot hexane and acetonitrile.
- Monoamine body (raw material 10) 1.14 g (3.99 mmol)
- monoamine body (raw material 4) 0.78 g (3.99 mmol)
- m-cresol 20 g obtained by synthesizing into a nitrogen-substituted 50 mL Schlenk tube were added and stirred.
- the reaction solution was heated to 70 ° C. while Thereafter, a solution obtained by dissolving 2.11 g (2.66 mmol) of the dialdehyde body (starting material 22) of the above scheme obtained by synthesis in 10 g of m-cresol was dropped into the solution over 3 hours, and then stirred for 6 hours. After the completion of the reaction, the reaction was terminated.
- the azomethine oligomer of the present invention having a flexible hydrocarbon group and a rigid aromatic group or aromatic ring-containing conjugated group is methanol, ethanol, acetonitrile, acetone, IPA, THF. It can be seen that it is soluble in at least one solvent of MEK and toluene. On the other hand, it can also be seen that an azomethine oligomer consisting only of an aromatic ring-containing conjugated group having a rigid structure does not exhibit any solubility in the solvent.
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Abstract
Description
(1)キャリアを1分子内において移動させるのではなく、化合物が有する共役系(芳香環)を、化合物分子間でスタックさせること(分子間で共役構造部分を配向させること)により、キャリアが分子間で移動するようにさせること
(2)アルキル基等をポリマーの側鎖として導入するのではなく、オリゴマーの主鎖の一部として導入する(すなわち、共役系構造を非共役スペーサーで連結する)こと。
Aはアゾメチン基であり、
Rは、分岐を有していてもよくハロゲン原子で置換されていてもよい炭素数2~1024のアルキレン基、基中にエーテル結合および/またはチオエーテル結合を有し、ハロゲン原子で置換されていてもよい炭素数2~1024の二価の炭化水素基、置換基を有していてもよい炭素数3~50のシクロアルキレン基、または基中にカルボキシル基を有し、ハロゲン原子で置換されていてもよい炭素数2~1024の二価の炭化水素基である。
二つのArは独立に置換基を有していてもよい二価の芳香族基であり、
Aはアゾメチン基であり、
R1およびR2は独立に水素原子、炭素数1~20のアルキル基、ハロゲン原子またはカルボキシル基であり、
Zは酸素原子、硫黄原子またはシクロアルキレン基を有する二価の基であり、
mおよびnは独立に0または1であり、
iは0または1であり、
hおよびjは独立に0~12の整数であり(ただし、Zが酸素原子または硫黄原子である場合には、hおよびjはともに1以上である)、
kは1~10の整数であり、
hが2以上の場合、複数存在するR1は同一でも異なっていてもよく、
jが2以上の場合、複数存在するR2は同一でも異なっていてもよく、
kが2以上の場合、複数存在する(-(CHR1)h-(O)i-(CHR2)j-)は、同一でも異なっていてもよく、(-(CHR1)h-(Z)i-(CHR2)j-)kで表わされる構造中の炭素原子数は、2~1024である。
Ar1は置換基を有していてもよい一価の芳香族基であり、
Ar2は置換基を有していてもよい二価の芳香族基であり、
Aはアゾメチン基であり、
pは0~5の整数であり、
pが2以上の場合には、複数存在するAr2は同一でも異なっていてもよい。
以下、本発明のアゾメチンオリゴマーが有する、上記二価の炭化水素基、芳香族基及び芳香族環含有共役基について詳細に説明する。
本発明のアゾメチンオリゴマーを構成する上記炭化水素基は、酸素原子、硫黄原子またはシクロアルキレン基を有する基を有していてもよく、その価数が2であれば特に限定されない。
本発明のアゾメチンオリゴマーを構成する、アゾメチン基を有し置換基を有していてもよい芳香族基は、アゾメチン基と一価の芳香族基とが結合して共役した構造をとっており、アルデヒド基及びアミノ基と反応性を有しなければ特に限定されない。アルデヒド基及びアミノ基と反応性を有しないことの意義については、後記の本発明のアゾメチンオリゴマーの製造方法の項にて説明する。
本発明のアゾメチンオリゴマーを構成する芳香族環含有共役基は、アゾメチン基と置換基を有していてもよい二価の芳香族基とが交互に結合して共役した構造をとっており、アルデヒド基及びアミノ基と反応性を有しなければ特に限定されない。アルデヒド基及びアミノ基と反応性を有しないことの意義については、後記の本発明のアゾメチンオリゴマーの製造方法の項にて説明する。なお、芳香族環含有共役基を構成する芳香族基のうち、本発明のアゾメチンオリゴマーの分子末端となる芳香族基は、二価ではなく一価である。
本発明のアゾメチンオリゴマーにおいては、以上説明した炭化水素基の両末端に、上記芳香族基または芳香族環含有共役基が、アゾメチン基を介して結合している。
(1)共役系(芳香族基または芳香族環含有共役基)として、電子豊富なナフタレン、アントラセン等の縮環系ユニットを選択すること
(2)メチル基、フェニル基等の電子供与性の置換基を共役系に導入することにより、共役系内の電子密度を大きくし、電子を非局在化させること。
(1)共役系(芳香族基または芳香族環含有共役基)として、電子不足の傾向をもつピリジン、ビピリジン、フェナントロリン等の複素環を選択すること
(2)F、CF3等の電子吸引性の置換基を共役系に導入することにより、共役系内の電子密度を低くし、電子を局在化させること。
以上説明した本発明のアゾメチンオリゴマーの具体例としては、下記一般式(I)で表わされる化合物が挙げられる。
本発明のアゾメチンオリゴマーの製造方法は、下記一般式(II)で表わされる炭化水素化合物1当量に対して、下記一般式(III)で表わされる芳香族環含有化合物2当量を反応させる工程を有している。
上記式(II)において、二つのXは、前述のようにともにアルデヒド基またはアミノ基である。二つのArは独立に置換基を有していてもよい二価の芳香族基であり、その具体例としては、上記式B-1~B-24で表わされる基が挙げられる。
一般式(II)において、mおよびnが0である炭化水素化合物は、市販されており、容易に入手可能である。
以上説明した一般式(II)で表わされる炭化水素化合物の具体例としては、下記式で表わされる化合物が挙げられる。
一般式(III)を再度示す。
一般式(III)において、pが0である芳香族環含有化合物は市販されており、容易に入手可能である。
以上説明した芳香族環含有化合物の具体例としては、下記式で表わされる化合物が挙げられる。
本発明のアゾメチンオリゴマーの製造方法においては、上記一般式(II)で表わされる炭化水素化合物1当量に対して、上記一般式(III)で表わされる芳香族環含有化合物2当量を反応させる。炭化水素化合物および芳香族環含有化合物の分子量を適宜選択(調節)することにより、得られる本発明のアゾメチンオリゴマーの分子量を調節することができる。
FAB-MS:m/z=252[M+H]+。
FAB-MS:m/z=324[M+H]+ 。
3-ヘキシルチオフェン-2,5-ジカルボアルデヒド(原料)の合成
実施例1~21および比較例1~5で得られたアゾメチンオリゴマーの、下記表1に示す溶媒への溶解性を評価した。
Claims (10)
- 主骨格中に、酸素原子、硫黄原子またはシクロアルキレン基を有する基を有していてもよい二価の炭化水素基を有し、
前記炭化水素基の両末端に、アゾメチン基を有し置換基を有していてもよい芳香族基、または、アゾメチン基と置換基を有していてもよい二価の芳香族基とが交互に結合して共役した芳香族環含有共役基が、該アゾメチン基により結合してなり、
該芳香族基および芳香族環含有共役基は、アルデヒド基及びアミノ基と反応性を有しないことを特徴とするアゾメチンオリゴマー。 - 前記炭化水素基が、分岐を有していてもよくハロゲン原子で置換されていてもよい炭素数2~1024のアルキレン基、基中にエーテル結合および/またはチオエーテル結合を有し、ハロゲン原子で置換されていてもよい炭素数2~1024の二価の炭化水素基、置換基を有していてもよい炭素数3~50のシクロアルキレン基、および、基中にカルボキシル基を有し、ハロゲン原子で置換されていてもよい炭素数2~1024の二価の炭化水素基からなる群より選ばれるいずれかの基であることを特徴とする請求項1に記載のアゾメチンオリゴマー。
- 前記アゾメチンオリゴマーの分子量が150~15000の範囲内にあることを特徴とする請求項1または2に記載のアゾメチンオリゴマー。
- 前記アゾメチンオリゴマーが、クレゾール、トルエン、THF、シクロペンチルメチルエーテル、アセトン、MEK、MIBK、シクロペンタノン、クロロホルム、ジクロロメタン、四塩化炭素、クロロベンゼン、二硫化炭素、酢酸エチル、酢酸ブチル、乳酸メチル、メタノール、エタノール、イソプロピルアルコール、ベンジルアルコール、n-ブタノール、t-ブタノール、ペンチルアルコール、エチレングリコール、プロピレングリコール、プロピレングリコールモノメチルエーテル、ピリジン、NMP、硫酸、蟻酸、酢酸、塩酸、乳酸、トリエチルアミン、ジブチルアミンの中から選択されるいずれかの溶媒、または二種以上の共溶媒100gに対し、25℃において0.1g以上の溶解性を有することを特徴とする請求項1~3のいずれかに記載のアゾメチンオリゴマー。
- 前記アゾメチンオリゴマーが、下記一般式(I)で表わされることを特徴とする請求項1~4のいずれかに記載のアゾメチンオリゴマー:
Aはアゾメチン基であり、
Rは、分岐を有していてもよくハロゲン原子で置換されていてもよい炭素数2~1024のアルキレン基、基中にエーテル結合および/またはチオエーテル結合を有し、ハロゲン原子で置換されていてもよい炭素数2~1024の二価の炭化水素基、置換基を有していてもよい炭素数3~50のシクロアルキレン基、または基中にカルボキシル基を有し、ハロゲン原子で置換されていてもよい炭素数2~1024の二価の炭化水素基である。)。 - 前記アゾメチンオリゴマーをP型半導体層またはN型半導体層の形成材料として使用して作製したp-n接合素子について、P型半導体側の電極に正極端子を、N型半導体側の電極に負極端子を接続し、-5V~+5Vの範囲内において電圧を印可することができ、順方向の電力量/逆方向の電力量>1.0となることを特徴とする請求項1~6のいずれかに記載のアゾメチンオリゴマー。
- 下記一般式(II)で表わされる炭化水素化合物1当量に対して、下記一般式(III)で表わされる芳香族環含有化合物2当量を反応させる工程を有することを特徴とする請求項1に記載のアゾメチンオリゴマーの製造方法:
二つのArは独立に置換基を有していてもよい二価の芳香族基であり、
Aはアゾメチン基であり、
R1およびR2は独立に水素原子、炭素数1~20のアルキル基、ハロゲン原子またはカルボキシル基であり、
Zは酸素原子、硫黄原子またはシクロアルキレン基を有する二価の基であり、
mおよびnは独立に0または1であり、
iは0または1であり、
hおよびjは独立に0~12の整数であり(ただし、Zが酸素原子または硫黄原子である場合には、hおよびjはともに1以上である)、
kは1~10の整数であり、
hが2以上の場合、複数存在するR1は同一でも異なっていてもよく、
jが2以上の場合、複数存在するR2は同一でも異なっていてもよく、
kが2以上の場合、複数存在する(-(CHR1)h-(Z)i-(CHR2)j-)は、同一でも異なっていてもよく、
(-(CHR1)h-(Z)i-(CHR2)j-)kで表わされる構造中の炭素原子数は、2~1024である;
上記式(III)において、Yは、上記式(II)におけるXがアルデヒド基の場合にはアミノ基であり、Xがアミノ基の場合にはアルデヒド基であり、
Ar1は置換基を有していてもよい一価の芳香族基であり、
Ar2は置換基を有していてもよい二価の芳香族基であり、
Aはアゾメチン基であり、
pは0~5の整数であり、
pが2以上の場合には、複数存在するAr2は同一でも異なっていてもよい。)。
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