JPS6224034B2 - - Google Patents
Info
- Publication number
- JPS6224034B2 JPS6224034B2 JP59121956A JP12195684A JPS6224034B2 JP S6224034 B2 JPS6224034 B2 JP S6224034B2 JP 59121956 A JP59121956 A JP 59121956A JP 12195684 A JP12195684 A JP 12195684A JP S6224034 B2 JPS6224034 B2 JP S6224034B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- polymer
- isothianaphthene
- carbon atoms
- conductive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 150000001450 anions Chemical class 0.000 claims description 12
- LYTMVABTDYMBQK-UHFFFAOYSA-N 2-benzothiophene Chemical group C1=CC=CC2=CSC=C21 LYTMVABTDYMBQK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011244 liquid electrolyte Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 229920001940 conductive polymer Polymers 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 23
- -1 isothianaphthene compound Chemical class 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000003115 supporting electrolyte Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 229910017008 AsF 6 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- PHXQIAWFIIMOKG-UHFFFAOYSA-N NClO Chemical compound NClO PHXQIAWFIIMOKG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KGKAYWMGPDWLQZ-UHFFFAOYSA-N 1,2-bis(bromomethyl)benzene Chemical compound BrCC1=CC=CC=C1CBr KGKAYWMGPDWLQZ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FNYLWPVRPXGIIP-UHFFFAOYSA-N Triamterene Chemical compound NC1=NC2=NC(N)=NC(N)=C2N=C1C1=CC=CC=C1 FNYLWPVRPXGIIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- SKECXRFZFFAANN-UHFFFAOYSA-N n,n-dimethylmethanethioamide Chemical compound CN(C)C=S SKECXRFZFFAANN-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001545 sodium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001542 sodium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Inorganic materials [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229960001288 triamterene Drugs 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
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Technical Field The present invention relates to a new electrochromic display device (hereinafter abbreviated as an ECD device), and more specifically to an ECD device using a novel polymer electrochromic material capable of developing a color tone close to colorless. It is. BACKGROUND OF THE INVENTION It is well known that in recent years, liquid crystal display devices have been put into practical use as display devices with low energy consumption and are being used for various purposes. However, liquid crystal display devices have the problem of viewing angle dependence, and further have drawbacks such as poor display clarity, lack of memory performance, and inability to display large areas. As a low-energy display device that compensates for these drawbacks, in recent years, ECD devices that utilize so-called electrochromism, in which light absorption characteristics change depending on voltage application or current, have been actively researched. Electrochromic materials used in ECD devices are broadly classified into inorganic materials and organic materials. For the former, transition metal oxides such as tungsten oxide have been mainly considered, but the colors are limited, or when protons are used as coloring ions, the response speed is fast, but the electrochemical problems of the membrane There are drawbacks such as elution and electrode deterioration. On the other hand, as the latter, viologens, phthalocyanine complexes, etc. are known, but viologens have drawbacks such as precipitation of insoluble substances when used repeatedly. Furthermore, phthalocyanine complexes still have problems in adhesion between the deposited film and the substrate. More recently, polyaniline [A.F. Deias et al., Journal of Electroanalytical Chemistry, Vol. 111, p. 111 (1980) or Yoneyama et al., Vol. 161, p. 419 (1984
)], polypyrrole [A.F. Deias et al.
Vol. 149, p. 101 (1983)], and polythiophene [M.A. Drouy et al., Journal.
Electrochromic, Vol. 44, June issue, pp. C3-595 (1983) or Kindo et al., Japan Journal of Applied Physics, Vol. 22, No. 7, p. L412 (1983), etc. Although it is being considered as a material, it has not yet reached the stage of practical use. In particular, electrochromic materials are desired to have a fast response speed, clear contrast, low power consumption, and excellent color tone. In particular, the ability to produce colorless tones is said to greatly contribute to the expansion of applications, but all of these heteroconjugated polymer materials are colored during the color change process from the oxidized state to the reduced state, and in order to increase contrast, Methods such as using a white background board are being considered, but they have not yet reached the stage of completion. Purpose of the Invention In the process of various studies on the electrochemical behavior of polymers having an isothianaphthene structure, the present inventors discovered that the above polymer has a fast response speed and a novel color tone that is almost colorless in an oxidized state. The present invention was achieved by discovering that it is an electrochromic material. It is truly surprising that this has been achieved, especially since electrochromic materials that provide an almost colorless tone are hitherto unknown. Structure of the Invention The ECD device of the present invention uses a conductive polymer thin film formed on a conductive transparent substrate as a display substrate,
A counter electrode is placed on this via a liquid electrolyte.
The ECD device is characterized in that the conductive polymer thin film is a reversibly oxidizable or reducible polymer having an isothianaphthene structure. The term "liquid electrolyte" as used herein means a supporting electrolyte dispersed or dissolved in a solvent. Detailed Description of the Invention The conductive polymer thin film to be the electrochromic layer according to the present invention has the general formula () (In the formula, R 1 and R 2 represent hydrogen or a hydrocarbon having 1 to 5 carbon atoms, X represents an anion, and y represents the ratio of anion per unit of the isothianaphthene structure. It is a reversibly oxidizable or reducible polymer having an isothianaphthene structure represented by the following general formula (), where n represents the degree of polymerization and is preferably a number from 5 to 500. It can be obtained by electrochemically polymerizing isothianaphthene compounds. (In the formula, R 1 and R 2 represent hydrogen or a hydrocarbon group having 1 to 5 carbon atoms.) Specific examples of the isothianaphthene compound represented by the general formula () include 1,3-isothianaphthene, 5-methyl-1,3-isothianaphthene,
5,6-dimethylisothianaphthene, 5-ethyl-1,3-isothianaphthene, 5-methyl-6-
Examples include ethyl-1,3-isothianaphthene. As a method for electrochemically polymerizing the above-mentioned isothianaphthene compound, a method for electrochemically polymerizing ordinary thiophene, pyrrole, etc. [for example, Solid State Communication Vol. 46, 5
No. 389 (1983)], and both the constant potential method and the constant current method can be used, but by using a conductive transparent substrate as the sample electrode, it is possible to It is desirable to form a coalesced thin film. The conductive transparent substrate used in the present invention can be easily obtained as a commercially available product made by depositing indium tin oxide, tin oxide, platinum, etc. on a transparent insulator such as glass, polyester, or film by a method such as sputtering. I can use things. The film thickness of the polymer obtained by electrochemical polymerization is 0.03 to 30 ÎŒm, preferably 0.05 to 22 ÎŒm.
m, more preferably 0.1 to 10 ÎŒm, and the film thickness can be controlled by the amount of current applied during electrochemical polymerization. If the film thickness is less than 0.03 ÎŒm, the contrast will not be clear and the value as a display material will be substantially lost. On the other hand, if it exceeds 30 ÎŒm, the contrast becomes clearer, but it is not preferable from the viewpoint of film strength or response speed. An ECD device is made by assembling the polymer thus obtained via a counter electrode and a liquid electrolyte, and the liquid electrolyte used is one in which a supporting electrolyte is dispersed or dissolved in a solvent. Supporting electrolytes used in the present invention include (i) aqueous electrolytes such as PF - 6 , SbF - 6 , AsF - 6 , and SbCl - 6 ;
halide anions of group elements, halide anions of group a elements such as BF - 4 , I - (I - 3 ),
Halogen anions such as Br - , Cl - , anions such as perchlorate anions such as ClO - 4 (general formula ()
X) and (ii) alkali metal ions such as Li + , Na + , K + , quaternary ammonium ions such as R 4 N + (R is a hydrocarbon group having 1 to 20 carbon atoms), (C 6 H 5 ) 4P +
It is possible to use combinations with phosphonium ions such as the following, but it goes without saying that the present invention is not necessarily limited to these. Specific examples of supporting electrolytes obtained by combining the above-mentioned anions (X) and cations include LiPF 6 , LiSbF 6 , LiAsF 6 , LiClO 4 , NaI,
NaPF6 , NaSbF6 , NaAsF6 , NaClO4 , KI,
KPF 6 , KSbF 6 , KAsF 6 , KClO 4 , [(n-
Bu) 4 N] +ã»(AsF 6 ) - , [(n-Bu) 4 N] +ã»(PF 6 ) -
,
[(n-Bu) 4N +ã»ClO â 4 , LiAlCl4 , LiBF4 ,
(C 6 H 5 ) 4 Pã»BF 4 , (C 6 H 5 ) 4 Pã»AsF 6 , (C 6 H 5 ) 4 Pã»
Examples include, but are not limited to, ClO 4 . These supporting electrolytes may be used alone or in combination of two or more types as required. Anion (X) other than the above is an HF - 2 anion, and cation other than the above is a pyrylium or pyridinium cation represented by the following formula (): (In the formula, Z is an oxygen atom or a nitrogen atom, R' is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms, and R'' is a halogen atom or a carbon number 1 -10 alkyl group, aryl group having 6 to 15 carbon atoms, m is 0 when X is an oxygen atom, and 1 when X is a nitrogen atom.
p is 0 or 1-5. ) or a carbonium cation represented by the following formula () or (): and [In the above formula, R 3 , R 4 and R 5 are hydrogen atoms (however, R 3 , R 4 and R 5 are never hydrogen atoms at the same time), an alkyl group having 1 to 15 carbon atoms, allyl group, an aryl group having 6 to 15 carbon atoms or -OR 7 group,
However, R 7 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R 6 represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
~15 aryl groups. ]. The HF - 2 anion used usually has the following general formula (), () or (): R' 4 N·HF 2 () M·HR 2 () [However, in the above formula, R' and R'' are a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms, and R is an alkyl group having 1 to 10 carbon atoms, a carbon A compound (hydrofluoride salt) represented by a number 6 to 15 aryl group, Z is an oxygen atom or nitrogen atom, q is 0 or a positive integer of 5 or less, M is an alkali metal] It can be obtained by dissolving it in a suitable organic solvent using it as a supporting electrolyte.Specific examples of the compounds represented by the above formulas (), () and () include H 4 Nã»HF 2 , Bu 4ã»
HF 2 , Naã»HF 2 , Kã»HF 2 , Liã»HF 2 and
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æã®å£åã¯èªããããªãã€ãã[Formula] can be given. These carbonium cations can be obtained by dissolving or dispersing a salt (carbonium salt) of them and anion (X) in a suitable organic solvent as a supporting electrolyte. Representative examples of the anion [X] used here include BF - 4 , AlCl - 4 ,
AlBr 3 Cl - , FeCl - 4 , SnCl - 3 , PF - 6 , PCl - 6 ,
SbCl - 6 , SbF - 6 , ClO - 4 , CF 3 SO - 3, etc. can be mentioned, and specific examples of carbonium salts include (C 6 H 5 ) 3 Cã»BF 4 , (CH 3 ) 3 Cã»BF 4 ,
Examples include HCOã»AlCl 4 , HCOã»BF 4 , C 6 H 5 COã»SnCl 5 and the like. As the solvent of the present invention, either an aqueous solution or a non-aqueous solution can be used, but preferably the supporting electrolyte is dissolved in a non-aqueous organic solvent. The organic solvent mentioned here is preferably one that is aprotic and has a high dielectric constant. For example, ethers, ketones, nitriles, amines, amides, sulfur compounds, phosphate ester compounds,
Phosphite compounds, borate compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds, etc. can be used, but among these, ethers, ketones, nitriles, phosphoric acid Preferred are ester compounds, phosphite compounds, boric acid ester compounds, chlorinated hydrocarbons, and carbonates. Representative examples of these include tetrahydrofuran, 2-
Methyltetrahydrofuran, 1,4-dioxane, monoglyme, acetonitrile, propionitrile, 4-methyl-2-pentanone, butyronitrile, valeronitrile, benzonitrile, 1,2
-dichloroethane, γ-butyrolactone, valerolactone, dimethoxyethane, methylformate, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, dimethylthioformamide, ethyl phosphate, methyl phosphate, ethyl phosphite, phosphorous acid Methyl, sulfolane, 3-methylsulfolane, etc. can be mentioned. Among these, nitriles or carbonates are particularly preferred in order to increase response speed. These organic solvents may be used alone or as a mixed solvent of two or more. Depending on the type of ECD device used or the type of electrode used, oxygen, water, protic solvents, etc. in these solvents may
Because it may deteriorate the characteristics of the ECD device,
In that case, it is preferable to purify according to a conventional method. In addition, in the ECD device of the present invention, polyethylene oxide and NaI are used in addition to the above-mentioned electrolyte.
It is also possible to use a highly ionic conductive organic solid electrolyte or supporting electrolyte made of NaSCN or the like simply dispersed in an organic solvent. The concentration of the supporting electrolyte used in the ECD device of the present invention cannot be unconditionally defined because it varies depending on the type of organic solvent used, the current value at the time of application, the voltage value, the operating temperature, the type of supporting electrolyte, etc. . The liquid electrolyte may be homogeneous or heterogeneous, but it is usually in the range of 0.001 to 10 mol/. The distance between the polymer conductive thin film and the counter electrode in the present invention varies depending on the type of solvent used, the type and concentration of the supporting electrolyte, the current value and voltage value at the time of application, the display area of the ECD device, etc. It is not possible to specify 0.05 to 5.
Preferably, it is mm. Further, the counter electrode used in the present invention may be made of various materials depending on the purpose. That is, when using transmitted light as a display device, it is preferable to use, for example, a conductive transparent material as described above as the counter electrode. On the other hand, when reflected light is used, it is also possible to use an opaque conductive material as the counter electrode, so for example, metal foil such as nickel or platinum or gauze can also be used. Also, to provide an almost colorless tone, a variety of tones can be selected as the background plate. In this way, the present invention can obtain
ECD devices can be applied to a wide range of applications due to their versatility in terms of materials. EXAMPLES The present invention will be explained in more detail with reference to Examples below, but it goes without saying that the technical scope of the present invention is not limited by these Examples.
In addition, in the following example, the NMR spectrum is
Varian EM-360A with TMS as internal standard
1 H-NMR was measured using a spectrometer, and infrared absorption spectra were measured using a model 281 device manufactured by PerkinElmer. Example 1 Production of polyisothianaphthene by treating 1,3-dihydroisothianaphthene-2-oxide in concentrated sulfuric acid (a) Synthesis of 1,3-dihydroisothianaphthene-2-oxide Lithium triethylboron Hydride 1
3.21 g (0.1 mol) of powdered sulfur in a Diurene flask at room temperature was added to 200 ml of the mol/solution under a nitrogen stream. A reaction occurred immediately, the sulfur powder dissolved and a yellow suspension was obtained. When this solution was exposed to a small amount of air, it turned into a pale yellow transparent solution. Separately, 26.4 g of o-xylylene dibromide was placed in a 2-four-necked flask equipped with a dropping funnel, stirrer, thermometer, and nitrogen inlet under a nitrogen atmosphere.
(0.1 mol) was dissolved in 1 mol of anhydrous tetrahydrofuran, and while stirring, 1.5 mol of the above tetrahydrofuran solution of lithium sulfide was added at room temperature.
It dripped over time. Thereafter, tetrahydrofuran was distilled off under reduced pressure, and the residue was further distilled to obtain 10.9 g (yield: 80%) of colorless 1,3-dihydroisothianaphthene, having a temperature of 74 to 76°C/3 mmHg. The infrared absorption spectrum of this product is 3060,
Absorption based on phenyl groups at 3026, 1582, and 1485 cm -1 , absorption based on methylene groups at 2910, 2840, and 1450 cm -1 , in-plane bending absorption of 1,2-substituted phenyl at 1195 cm -1 , and o at 760 cm -1 -Substituted phenyl absorption and sulfide absorption at 740 cm -1 .
Also, nuclear magnetic resonance spectra ( 1 H-NMR) in deuterated chloroform using TMS as an internal standard.
The analysis results were as follows. 4.22 (S, 4H), 7.20 (S, 4H) This compound was extremely unstable and changed from yellow to black even when stored in a tightly sealed container protected from light. Next, the obtained 1,3-dihydroisothianaphthene was added to sodium metaiodate prepared in advance.
It was added to 450 ml of 50% methanol aqueous solution in which 18.6 g (0.086 mol) was dissolved, and stirred at room temperature for 12 hours. The generated precipitate was filtered off, and the residue was washed with 50 ml of methanol and combined with the mother liquor. The filtrate was concentrated under reduced pressure, and the resulting yellow-white solid was recrystallized from ethyl acetate/cyclohexane to obtain slightly yellowish crystals. The melting point of this crystal was 87-89°C. When the obtained crystals were further recrystallized from ethyl acetate/cyclohexane, they showed a melting point of 90-91°C. In the infrared absorption spectrum of this crystal, in addition to the absorption of isothianaphthene, strong absorption of sulfoxide was observed at 1035 cm -1 , and the absorption of sulfoxide at 740 cm -1 disappeared. In addition, 1 Hâ in deuterated chloroform with TMS as an internal standard.
The NMR spectrum was as follows. 4.65 (S, 4H), 7.20 (S, 4H) The results of elemental analysis of the above crystals were as follows. Actual value
C: 63.08% H: 5.15% S: 20.87% Calculated values (as C 8 H 8 SO) C: 63.16% H: 5.26% S: 21.05% Example 2 Polydihydroisothia obtained by cationic polymerization of isothianaphthene Production of polyisothianaphthene by oxidizing naphthene using an oxidizing agent (a) Isothianaphthene (in the general formula R 1 = R 2 =
Synthesis of H) 300 mg of 1,3-dihydroisothianaphthene-2-oxide synthesized based on Example 1(a)
(1.97 mmol) and 450 mg (4.41 mmol) of neutral alumina were thoroughly ground and mixed in a mortar, placed in a sublimator, and heated under reduced pressure on an oil bath. 110â/
At 20 mmHg, 250 mg (1.87 mmol) of white needle-like crystals of isothianaphthene were obtained at the bottom of the sublimator cooling section. This monomer was immediately purified and degassed.
The mixture was dissolved in 1 ml of methylene chloride, 10 mg of trifluoroacetic acid was added at room temperature, and the mixture was left overnight. reaction solution
Pouring into 50 ml of methanol gave a white precipitate. This polymer was soluble in chloroform, chlorobenzene, tetrahydrofuran, and N.N-dimethylformamide. The infrared absorption spectrum of the polymer is shown in FIG. 1, and the 1 H-NMR spectrum is shown in FIG. 2. A gel permeation chromatograph (Varian 5000) of a solution of this polymer in tetrahydrofuran confirmed that the molecular weight was 2000 in terms of polystyrene. The electrical conductivity (Ï RT ) of this polymer at room temperature was measured using a 4-terminal conductivity meter, and it was found to be less than Ï RT =10 â8 s/cm. The results of elemental analysis were as follows. Actual value
C: 71.27% H: 4.54% S: 23.96% Calculated values (as (C 8 H 6 S) n) C: 71.64% H: 4.48% S: 23.88% In the above method, methanesulfone is used instead of trifluoroacetic acid. When an acid was used as a polymerization initiator, a polymer was obtained in the same manner, and its infrared absorption spectrum completely matched that shown in FIG. When these polymers were dissolved in 5 ml of chlorobenzene and treated with twice the molar amount of chloranil, a black precipitate was formed. The electrical conductivity Ï RT of this polymer at room temperature is 9Ã10 -2 s/cm, and the electrical conductivity of the iodine-doped product is Ï RT =9Ã
It was 10 -1 s/cm. The infrared absorption spectrum of this product was as shown in FIG. Even when the doped polymer was left in the air at room temperature for one week, there was no change in its electrical conductivity. When 1.1 times the amount of N-chlorosuccinimide was used instead of chloranil and 5 ml of chloroform was used, a black precipitate was obtained that showed exactly the same infrared absorption spectrum as shown in FIG. 3. The conductivity Ï RT of this polymer is 2.6Ã10 -1 s/cm
It was hot. Example 3 0.0788 mol/ 1,3 - isothianaphthene monomer (R 1 = R 2 =
A solution containing H compound) was used as the electrolyte, and a glass plate on which indium tin oxide was deposited was used as the sample electrode
2m with Al plate as counter electrode and Li/Li + as reference electrode.
After electrochemical polymerization at room temperature for 20 minutes at a current density of A/cm 2 , an electrochemically neutral deep blue polymer was obtained on the indium tin oxide deposited glass plate of the positive electrode. The film thickness after washing with acetonitrile and drying was 10 ÎŒm. This material was immersed in a THF solution containing 0.53 mol/LiClO 4 and the dependence of optical absorption on applied voltage was observed using Li as a counter electrode. The results are shown in FIG. In other words, as seen in this figure, the polymer
It showed a blue color at 2.50V (versus Li), and changed to a transparent light green color at 3.50V. This change was found to be reversible. Cyclic portanograms were then measured at +1.0 V to -0.7 V (vs. standard calomel electrode) using (C 4 H 9 ) 4 NClO 4 in acetonitrile as the electrolyte.
The results are shown in FIG. In the range of +0.6V to -0.7V, the polymer film is dark blue;
In the 1.0V range, the color changed to a highly transparent light green color. Using this result, an ECD device as shown in FIG. 6 was fabricated, and a propylene carbonate solution of an electrolyte containing 0.53 mol/LiBF 4 was sealed as a liquid electrolyte. When we tried a life test by applying a square wave of +0.8V to -0.4V with a cycle of 1Hz, we found that 2Ã
10 No deterioration of the electrochromic material was observed even after four coloring/decoloring tests.
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FIG. 1 is an infrared absorption spectrum diagram of the polymer produced in Example 2, and FIG. 2 is an NMR spectrum diagram of the polymer produced in Example 2. FIG. 3 is an infrared absorption spectrum diagram of the first polymer produced in Example 2 after being treated with chloranil. FIG. 4 is a diagram showing the dependence of optical absorption on applied voltage when the conductive polymer film of Example 3 is immersed in a THF solution of 0.53 mol/LiClO 4 and Li is used as a counter electrode. The figure is a cyclic portanogram of the polymer conductive membrane of Example 3 measured at +1.0V to -0.7V (vs. standard calomel electrode) when acetonitrile (C 4 H 9 ) 4 NClO 2 was used as the electrolyte. be. FIG. 6 is a schematic cross-sectional view showing an embodiment of the ECD device according to the present invention, in which 1 is a transparent glass substrate, 2 is a display electrode, 3 is an electrochromic material, 4 is a liquid electrolyte, and 5 is an opposing An electrode, 6 a protective layer, and 7 a lead wire.
Claims (1)
èã衚瀺åºæ¿ãšããŠçšããããã«æ¶²ç¶é»è§£è³ªãä»
ããŠå¯Ÿåé»æ¥µãé ããŠãªããšã¬ã¯ããã¯ãããã¯
è¡šç€ºè£ çœ®ã«ãããŠãåèšé«ååå°é»æ§èèãäžèš
ã®äžè¬åŒïŒïŒïŒ ïŒåŒäžãR1åã³R2ã¯æ°ŽçŽ åã¯ççŽ æ°ïŒãïŒã®çå
æ°ŽçŽ ãè¡šãããã¯é°ã€ãªã³ãè¡šãããïœã¯ã€ãœ
ãã¢ãããã³æ§é ã®åäœåœãã®é°ã€ãªã³ã®å²åã
è¡šããïŒã0.40ã®æ°ã§ãããïœã¯éå床ãè¡šã
ãã奜ãŸããã¯ïŒã500ã®æ°ã§ããïŒ ã§è¡šããããã€ãœãã¢ãããã³æ§é ãæããå¯é
çã«é žåãŸãã¯éå ãããéåäœã§ããããšãç¹
城ãšãããšã¬ã¯ããã¯ãããã¯è¡šç€ºè£ 眮ã[Scope of Claims] 1. An electrochromic display device in which a conductive polymer thin film formed on a conductive transparent substrate is used as a display substrate, and a counter electrode is disposed thereon via a liquid electrolyte. The conductive thin film has the following general formula (): (In the formula, R 1 and R 2 represent hydrogen or a hydrocarbon having 1 to 5 carbon atoms, X represents an anion, and y represents the proportion of anion per unit of the isothianaphthene structure of 0 to 0.40. (where n represents the degree of polymerization, preferably a number from 5 to 500). Display device.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59121956A JPS6112784A (en) | 1984-06-15 | 1984-06-15 | Electrochromic display device |
US06/736,984 US4640748A (en) | 1984-05-31 | 1985-05-22 | Polyisothianaphtene, a new conducting polymer |
CA000482753A CA1248690A (en) | 1984-05-31 | 1985-05-30 | Polyisothianaphthene, a new conducting polymer |
AT85303864T ATE53046T1 (en) | 1984-05-31 | 1985-05-31 | POLYMERS WITH ISOTHIANAPTHENE STRUCTURE AND ELECTROCHROMIC INDICATOR. |
EP85303864A EP0164974B1 (en) | 1984-05-31 | 1985-05-31 | Polymer having isothianaphthene structure and electrochromic display |
DE8585303864T DE3577860D1 (en) | 1984-05-31 | 1985-05-31 | POLYMERS WITH ISOTHIANAPHTHE STRUCTURE AND ELECTROCHROMIC DISPLAY DEVICE. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59121956A JPS6112784A (en) | 1984-06-15 | 1984-06-15 | Electrochromic display device |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6112784A JPS6112784A (en) | 1986-01-21 |
JPS6224034B2 true JPS6224034B2 (en) | 1987-05-26 |
Family
ID=14824065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP59121956A Granted JPS6112784A (en) | 1984-05-31 | 1984-06-15 | Electrochromic display device |
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JP (1) | JPS6112784A (en) |
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JP5803527B2 (en) * | 2011-09-30 | 2015-11-04 | æ ªåŒäŒç€Ÿããã㯠| Organic functional element |
EP3564229A4 (en) * | 2016-12-28 | 2020-07-08 | Showa Denko K.K. | Fused heteropolycyclic compound, and method for producing conductive polymer in which said compound is used |
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1984
- 1984-06-15 JP JP59121956A patent/JPS6112784A/en active Granted
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