JPH0350529A - Electrolyte composition and electrochromic element - Google Patents
Electrolyte composition and electrochromic elementInfo
- Publication number
- JPH0350529A JPH0350529A JP18623389A JP18623389A JPH0350529A JP H0350529 A JPH0350529 A JP H0350529A JP 18623389 A JP18623389 A JP 18623389A JP 18623389 A JP18623389 A JP 18623389A JP H0350529 A JPH0350529 A JP H0350529A
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- compd
- thiol
- solvent
- acid
- 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.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- -1 thiol compound Chemical class 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000007784 solid electrolyte Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 150000001408 amides Chemical class 0.000 abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 abstract description 3
- 229920001021 polysulfide Polymers 0.000 abstract description 2
- 239000005077 polysulfide Substances 0.000 abstract description 2
- 150000008117 polysulfides Polymers 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N hydroxymethylethylene Natural products OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PMDCZENCAXMSOU-UHFFFAOYSA-N N-ethylacetamide Chemical compound CCNC(C)=O PMDCZENCAXMSOU-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920001079 Thiokol (polymer) Polymers 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical class OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001227 electron beam curing Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- PLFFHJWXOGYWPR-HEDMGYOXSA-N (4r)-4-[(3r,3as,5ar,5br,7as,11as,11br,13ar,13bs)-5a,5b,8,8,11a,13b-hexamethyl-1,2,3,3a,4,5,6,7,7a,9,10,11,11b,12,13,13a-hexadecahydrocyclopenta[a]chrysen-3-yl]pentan-1-ol Chemical compound C([C@]1(C)[C@H]2CC[C@H]34)CCC(C)(C)[C@@H]1CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@@H]1[C@@H](CCCO)C PLFFHJWXOGYWPR-HEDMGYOXSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- CAQYAZNFWDDMIT-UHFFFAOYSA-N 1-ethoxy-2-methoxyethane Chemical compound CCOCCOC CAQYAZNFWDDMIT-UHFFFAOYSA-N 0.000 description 1
- GFISDBXSWQMOND-UHFFFAOYSA-N 2,5-dimethoxyoxolane Chemical compound COC1CCC(OC)O1 GFISDBXSWQMOND-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004969 ion scattering spectroscopy Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- OCAAZRFBJBEVPS-UHFFFAOYSA-N prop-2-enyl carbamate Chemical class NC(=O)OCC=C OCAAZRFBJBEVPS-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 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
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は電解液組成物、有機固体電解質の製法およびエ
レクトロクロミック（以後ＥＣと略す）素子に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrolyte composition, a method for producing an organic solid electrolyte, and an electrochromic (hereinafter abbreviated as EC) device.
［従来の技術］
従来、電解液組成物としては有機溶媒に電解質を溶解さ
せた組成物（特開昭６０−４１７７４号公報、特開昭６
０−４１７７８号公報等）、有機固体電解質の製法とし
てはポリエチレングリコール誘導体を使用したもの（特
開昭８０−１４８００３号公報、特開昭８０−２１７２
６３号公報、特開昭６ １−２８０５５７号公報等）お
よびＥＣ素子としては＠前液を使用したもの（特開昭６
１−２３８０２８公報、特開昭８２−３１８２８公報等
）が知られている。[Prior Art] Conventionally, electrolytic solution compositions include compositions in which an electrolyte is dissolved in an organic solvent (Japanese Unexamined Patent Application Publication No. 60-41774, Japanese Unexamined Patent Publication No. 60-417,
0-41778, etc.), methods for producing organic solid electrolytes using polyethylene glycol derivatives (JP-A-80-148003, JP-A-80-2172)
No. 63, JP-A-6 1-280557, etc.) and EC devices using @preliquid (JP-A-6 No. 1-280557, etc.)
1-238028, JP-A-82-31828, etc.) are known.
［発明が解決しようとする課題コ
しかしながら、従来の電解液組成物は液体である故に液
漏れ対策が必要である。また従来の有機固体電解質は伝
導度が低いためそれを使用した二次電池は電池特性が悪
く、またＥＣ素子に用いた場合は着色、消色の速度が遅
いという問題点かある。[Problems to be Solved by the Invention] However, since conventional electrolyte compositions are liquids, measures against leakage are required. Further, since conventional organic solid electrolytes have low conductivity, secondary batteries using them have poor battery characteristics, and when used in EC devices, there is a problem that the speed of coloring and decoloring is slow.
［課題を解決するための手段コ
本発明者は液漏れのない電解液組成物、電池特性の良好
な二次電池、コンデンサーなどに使用する有機固体電解
質の製法、ならびに着色、消色の速度が速いＥＣ素子に
つき鋭意検討した結果、本発明に到達した。[Means for Solving the Problems] The present inventor has developed an electrolyte composition that does not leak, a secondary battery with good battery characteristics, a method for producing an organic solid electrolyte used in capacitors, etc., and a method that improves the speed of coloring and decoloring. As a result of intensive research into fast EC elements, we have arrived at the present invention.
すなわち、本発明は電解質塩、溶媒、チオール化合物、
チオール化合物と反応する化合物、わよび必要によりそ
の他の助剤からなることを特徴とする電解液組成物；請
求項１記載の電解液組成物を光および／または熱により
重合することを特徴とする有機固体電解質の製法； Ｅ
Ｃ層を有する導電性基板と対向電極板との間に、請求項
２または３記載の有機固体電解質を介在させてなるＥＣ
素子である。That is, the present invention provides an electrolyte salt, a solvent, a thiol compound,
An electrolytic solution composition characterized by comprising a compound that reacts with a thiol compound and, if necessary, other auxiliary agents; characterized by polymerizing the electrolytic solution composition according to claim 1 with light and/or heat. Manufacturing method of organic solid electrolyte; E
An EC comprising an organic solid electrolyte according to claim 2 or 3 interposed between a conductive substrate having a C layer and a counter electrode plate.
It is element.
本発明において、電解質塩としてはアルカリ（土類）金
属塩およびアンモニウム塩が使用できる。In the present invention, alkali (earth) metal salts and ammonium salts can be used as electrolyte salts.
アルカリ（土類）金属塩としては、工族（Ｌｌ１Ｎａ１
Ｋ等）または■族（Ｍｇ＋Ｃａ，Ｂａ，Ｚｎ等）の金属
塩が挙げられる。これらのうち好ましいものは陽イオン
半径の小さいＬＩ＋ＮａおよびＫ塩、アンモニウム塩で
ある。これらの塩の陰イオンとしてはハロゲンイオン、
チオシアン酸イオン、過塩素酸イオン、トリフルオロメ
タンスルホン酸イオン、フルオロホウ酸イオン、カルボ
ン酸イオン（蟻酸、酢酸等）などが使用できる。これら
のうち好ましいものは、過塩素酸イオン、フルオロホウ
酸イオンおよびカルボン酸イオンである。Alkali (earth) metal salts include engineering group (Ll1Na1
K, etc.) or metal salts of the group II (Mg+Ca, Ba, Zn, etc.). Among these, LI+Na and K salts and ammonium salts having a small cation radius are preferred. The anions of these salts include halogen ions,
Thiocyanate ion, perchlorate ion, trifluoromethanesulfonate ion, fluoroborate ion, carboxylate ion (formic acid, acetic acid, etc.), etc. can be used. Preferred among these are perchlorate ion, fluoroborate ion and carboxylate ion.
溶媒としてはアミド溶媒［Ｎ−メチルホルムアミド、Ｎ
一エチルホルムアミド、Ｎ， Ｎ−ジメチルホルムア
ミド、Ｎ， Ｎ−ジエチルホルムアミド、Ｎ−メチル
アセトアミド、Ｎ一エチルアセトアミド、Ｎ−メチルピ
ロジリノン等コ、ラクトン溶媒［γ−プチロラクトン、
γ−バレロラクトン、δ一バレロラクトン、３−メチル
−１．３−オキサゾリジン−２−オン等コ、カーボネー
ト溶媒［エチレンヵーボネート、プロピレンヵーボネー
ト、ブチレンカーポネート等コ、アルコール溶媒［エチ
レンクリコール、グリセリン、メチノレセノレソノレブ
、エチレングリコーノレ、プロピレングリコール、１．
２−ブタンジオール、１，３−ブタンジオール、１
．４−ブタンジオール、グリセリン，ジグリセリン、ボ
リオキシアルキレンポリオール、シクロヘキサンジオー
ル、キシリレングリコール等コ、エーテル溶媒［メチラ
ール、１，２−ジメトキシエタン、１−エトキシ−２−
メトキシエタン、１．２−ジエトキシエタン、アルコキ
シボリアルキレンエーテル等コ、ニトリル溶媒［アセト
ニトリル、３−メトキシブロビオニトリル等コ、燐酸類
および燐酸エステル溶媒［正燐酸，メタ燐酸，ピロ燐酸
，ポリ燐酸，亜燐酸、 トリメチルホスフェート等コ、
フラン溶媒［２．５−ジメトキシテトラヒドロフラン等
コ、２−イミダゾリジノン溶媒［１，３−ジメチル−２
−イミダゾリジノン等］ピロリドン溶媒、スルフォラン
溶媒［テトラメチレンスルフォン等コの単独あるいは混
合溶媒が使用できる。これらのうち好ましいものはアミ
ド溶媒、ラクトン溶媒、カーボネート溶媒、アル，一ル
溶媒、エーテル溶媒、ニトリル溶媒およびスルフォラン
溶媒である。As a solvent, amide solvent [N-methylformamide, N
monoethylformamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylacetamide, N-ethylacetamide, N-methylpyrodilinone, etc., lactone solvent [γ-butyrolactone,
γ-valerolactone, δ-valerolactone, 3-methyl-1,3-oxazolidin-2-one, etc., carbonate solvents [ethylene carbonate, propylene carbonate, butylene carbonate, etc.], alcohol solvents [ethylene carbonate, etc.] Recall, glycerin, methinoresonol, ethylene glycol, propylene glycol, 1.
2-butanediol, 1,3-butanediol, 1
．． 4-butanediol, glycerin, diglycerin, boroxyalkylene polyol, cyclohexanediol, xylylene glycol, etc., ether solvents [methylal, 1,2-dimethoxyethane, 1-ethoxy-2-
Methoxyethane, 1,2-diethoxyethane, alkoxyborealkylene ether, etc., nitrile solvents [acetonitrile, 3-methoxybrobionitrile, etc.], phosphoric acids and phosphoric acid ester solvents [orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid , phosphorous acid, trimethyl phosphate, etc.
Furan solvent [2,5-dimethoxytetrahydrofuran etc., 2-imidazolidinone solvent [1,3-dimethyl-2
-imidazolidinone, etc.] Pyrrolidone solvent, sulfolane solvent [tetramethylene sulfone, etc. alone or in combination can be used. Among these, preferred are amide solvents, lactone solvents, carbonate solvents, al, monol solvents, ether solvents, nitrile solvents and sulfolane solvents.
チオール化合物としては液状ポリサルファイド［チオコ
ールＬＰ（東レチオコール（製）］；脂肪族、脂環式お
よび芳香族（ポリ）チオール化合物［メタン（ジ）チオ
ール、エタン（ジ）チオール等］；及びメルカブトカル
ボン酸エステル［ペンタエリスリトールテトラキスチオ
グリコレート等コがあげられる。メルカブトカルボン酸
エステルはメルカプ′トカ．ルボン酸［２−メルカプト
酢酸、３−メルカプトプロピオン酸等コと多価アルコー
ノレ［エチレングリフール、トリメチローノレプロパン
、グリセリン、ペンタエリスリトーノレ、シロ糖等およ
びこれらのアルキレンオキサイド付加物（エチレンオキ
サイド、プロピレンオキサイド、プチレンオキサイド等
）等コのエステル化反応およびメルカプトカルポン酸ア
ルキルエステル［２ーメルカプト酢酸エチルエステル、
３−メルカプトプロビオン酸メチルエステル等コと上記
記載の多４Ｉ ７ ／ｌ／ ：７−ルのエステル交換反
応により得られる化合物が挙げられる。これらのうち好
ましいものは分子中にＳＨ基を２個以上有するチオール
化合物である。Examples of thiol compounds include liquid polysulfide [Thiokol LP (manufactured by Toray Thiokol)]; aliphatic, alicyclic, and aromatic (poly)thiol compounds [methane (di) thiol, ethane (di) thiol, etc.]; and mercabutocarvone. Acid esters [such as pentaerythritol tetrakisthioglycolate, etc.].Merkabutocarboxylic acid esters include mercaptocarboxylic acids [2-mercaptoacetic acid, 3-mercaptopropionic acid, etc.] and polyhydric alcohols [ethylene glycol, trimester, etc.]. Esterification reaction of thyronolepropane, glycerin, pentaerythritone, silosaccharide, etc. and their alkylene oxide adducts (ethylene oxide, propylene oxide, butylene oxide, etc.), and mercaptocarboxylic acid alkyl ester [2-mercaptoacetic acid] ethyl ester,
Examples include compounds obtained by transesterification of 3-mercaptoprobionic acid methyl ester and the above-mentioned poly(4I 7 /l/:7-l). Among these, preferred are thiol compounds having two or more SH groups in the molecule.
本発明においてチオール化合物と反応する化合物として
は（ポリ）アリル化合物、エボキシ化合物、 （ポリ）
インシアネート化合物等があげられる。In the present invention, compounds that react with thiol compounds include (poly)allyl compounds, epoxy compounds, (poly)
Examples include incyanate compounds.
（ポリ）アリル化合物としてはアリルエーテル化合物［
例えば置換、未置換のアリルアルコールにエボキシ基、
例えばエチレンオキサイド、プロピレンオキサイド、プ
チレンオキサイド、スチレンオキサイド、シクロヘキセ
ンオキサイド、エビハロヒドリン、アリルグリシジルエ
ーテル等）を付加した化合物コ （以後化合物１と略す
。）：アリルエステル化合物［例えばアリルアルフーノ
レまたは化合物１とカルボン酸（脂肪族，脂環式および
芳香族の、飽和および不飽和の、１４Ｉｌｉおよび多価
カルボン酸、 （例えば酢酸，プロピオン酸，酪酸，オ
クタン酸，ラウリン酸，ステアリン酸，オレイン酸，安
息香酸などのモノカルボン酸（炭素数１〜２０）； ア
ジピン酸，フタル酸などのジカルボン酸等）の反応物コ
（以後化合物２と路す。）：アリルウレタン化合物［
例えばアリルアルコールまたは化合物１と（ポリ）イン
シアネート（例えばトリレンイソシアネート、トリレン
ジイソシアネート等）の反応物コ （以後化合物３と略
す）があげられる。分子中に２個以上のアリル基を有す
る化合物１、２、３のボリアリル化合物も使用できる。As the (poly)allyl compound, allyl ether compound [
For example, substituted or unsubstituted allyl alcohol with epoxy group,
(For example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, shrimp halohydrin, allyl glycidyl ether, etc.) (hereinafter abbreviated as compound 1): Allyl ester compound [e.g. allyl alfunole or compound 1 and carboxylic acids (aliphatic, cycloaliphatic and aromatic, saturated and unsaturated, 14Ili and polyhydric carboxylic acids, such as acetic acid, propionic acid, butyric acid, octanoic acid, lauric acid, stearic acid, oleic acid, benzoic acid) Reactants of monocarboxylic acids such as acids (1 to 20 carbon atoms); dicarboxylic acids such as adipic acid and phthalic acid (hereinafter referred to as compound 2): Allyl urethane compounds [
Examples include allyl alcohol or a reaction product of Compound 1 and (poly)incyanate (eg, tolylene isocyanate, tolylene diisocyanate, etc.) (hereinafter abbreviated as Compound 3). Polyaryl compounds of Compounds 1, 2, and 3 having two or more allyl groups in the molecule can also be used.
エボキシ化合物としては（ポリ）グリシジルエーテル［
エチレングリコールジグリシジルエーテル、ポリエチレ
ングリコールジグリシジルエーテル、 トリメチロール
プロパントリグリシジルエーテル等コなどが使用できる
。Eboxy compounds include (poly)glycidyl ether [
Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, etc. can be used.
（ポリ）インシアネート化合物としては「最新ポリウレ
タン応用技術」（（株）シーエムシー発行）１３頁〜２
１頁記載のポリイソシアネートおよびモノイソシアネー
ト（フェニルイソシアネート等）があげられる。For (poly) incyanate compounds, see "Latest Polyurethane Application Technology" (published by CMC Co., Ltd.), pages 13-2.
Examples include polyisocyanates and monoisocyanates (phenylisocyanate, etc.) described on page 1.
チオール化合物と反応する化合物のうち、好ましいもの
は（ポリ）アリル化合物、 （ポリ）インシアネート化
合物およびこれらの併用である＠木発明において重合は
光および／または熱により行う。光としては波長が２０
０〜７００ｎｍのものが使用できる。重合速度を調整す
るために重合開始剤を使用することもできる。その具体
例としてはｒＵＶ，ＥＢ硬化技術」（（株）総合技術セ
ンター発行）１５３頁〜１５６頁記載の光開始剤が使用
でき、そのうちアセトフエノン類、ペンゾフェノン類、
ベンジルジメチルケタール類およびチオキサンソン類が
好ましい。またラジカル開始剤例えば過酸化物、アゾ化
合物等を併用してもよい。Among the compounds that react with the thiol compound, preferred are (poly)allyl compounds, (poly)incyanate compounds, and combinations thereof. In the invention, polymerization is carried out by light and/or heat. The wavelength of light is 20
Those with a wavelength of 0 to 700 nm can be used. Polymerization initiators can also be used to adjust the polymerization rate. As specific examples, photoinitiators described in "rUV, EB Curing Technology" (published by Sogo Gijutsu Center Co., Ltd.), pages 153 to 156, can be used, among which acetophenones, penzophenones,
Benzyl dimethyl ketals and thioxansones are preferred. Further, radical initiators such as peroxides and azo compounds may be used in combination.
熱による重合は特に制限はないが通常、０℃〜１００℃
、好ましくはＯ℃〜５０゛Ｃで行う。重合速度を調製す
るために触媒（ジブチルチンジラウレート、トリエチレ
ンジアミン等）を使用してもよい。There are no particular restrictions on thermal polymerization, but it is usually 0°C to 100°C.
, preferably at 0°C to 50°C. Catalysts (dibutyltin dilaurate, triethylenediamine, etc.) may be used to adjust the polymerization rate.
本発明において必要によりその他の助剤を使用すること
ができる。その他の助剤としては、光重合性モノマー
光重合仕プレボリマー 増感剤および貯蔵安定剤などが
使用される。その具体例としては「ＵＶ，ＥＢ硬化技術
」（（株）総合技術センター発行）１４２頁〜１５９頁
記載の光重合性モノマー 光重合性プレポリマー 増感
剤および貯蔵安定剤が使用できる。光重合性七ノマー光
重合性プレポリマーは単官能アクリレートが好ましい。In the present invention, other auxiliary agents can be used if necessary. Other auxiliary agents include photopolymerizable monomers
Photopolymerized prebolymer, sensitizer, storage stabilizer, etc. are used. As specific examples thereof, the photopolymerizable monomers, photopolymerizable prepolymers, sensitizers, and storage stabilizers described in "UV, EB Curing Technology" (published by Sogo Gijutsu Center Co., Ltd.), pages 142 to 159, can be used. The photopolymerizable heptanomer photopolymerizable prepolymer is preferably a monofunctional acrylate.
増感剤は尿素、ニトリル化合物（Ｎ．Ｎ−ジ置換一ｐ−
アミノベンゾニトリル等）、燐化合物（トリーｎ−プチ
ルホスフィン等）が好ましく、貯蔵安定剤は狛４級アン
モニウムクロライド、ペンゾチアゾール、ハイドロキノ
ンが好ましい。Sensitizers include urea, nitrile compounds (N.N-disubstituted p-
(aminobenzonitrile, etc.), phosphorus compounds (tri-n-butylphosphine, etc.) are preferred, and the storage stabilizers are preferably quaternary ammonium chloride, penzothiazole, and hydroquinone.
好適な添加量の範囲について記述する。電解質塩は溶媒
に対し通常２〜４０重量％、好ましくは３〜３５重量％
である。この範囲外では伝導度が低いか、または塩の飽
和濃度以上となり溶媒から塩が析出する。溶媒は電解液
全量中通常５０〜９５ｍｆｆｉ％である。この範囲外で
は伝導度が低い。A suitable range of addition amount will be described. The electrolyte salt is usually 2 to 40% by weight, preferably 3 to 35% by weight based on the solvent.
It is. Outside this range, the conductivity is low, or the salt concentration exceeds the saturation concentration of the salt, causing the salt to precipitate from the solvent. The amount of the solvent is usually 50 to 95 mffi% in the total amount of the electrolyte. Outside this range, conductivity is low.
チオール化合物とチオール化合物と反応する化合物の合
計量は電解液全量中通常５〜６０重量％、好ましくは５
〜４０重量％である。重合開始剤およびアミン触媒はチ
オール化合物とチオール化合物と反応する化合物の合計
量に対し、通常Ｏ．ｌ〜１０重量％である。その他の助
剤は電解液全量に対し通常０．０１〜２０重量％、好ま
しくは０．１〜１５重量％である。The total amount of the thiol compound and the compound that reacts with the thiol compound is usually 5 to 60% by weight, preferably 5% by weight based on the total amount of the electrolyte.
~40% by weight. The polymerization initiator and amine catalyst are usually used in an amount of O. 1 to 10% by weight. The amount of other auxiliary agents is usually 0.01 to 20% by weight, preferably 0.1 to 15% by weight based on the total amount of the electrolyte.
チオール化合物とチオール化合物と反応する化合物の配
合比は特に限定はないが反応する基が化学量論的に当量
であることが好ましい。The blending ratio of the thiol compound and the compound that reacts with the thiol compound is not particularly limited, but it is preferable that the groups that react are stoichiometrically equivalent.
本発明の有機固体電解質は電解液組成物を２００〜７０
０ｎｍの波長を透過する容器に充填後あるいは、支持体
（金属板、紙、プラスチック、発泡など）の表面にコー
ティング後に光を照射して硬化することにより得られる
。光としては波長２００〜７００ｎｍのものが使用でき
る。重合は光だけでなく、熱と併用してもよい。The organic solid electrolyte of the present invention has an electrolyte composition of 200 to 70%
It can be obtained by filling a container that transmits light with a wavelength of 0 nm or by coating the surface of a support (metal plate, paper, plastic, foam, etc.) and then curing it by irradiating it with light. As the light, one having a wavelength of 200 to 700 nm can be used. Polymerization may be carried out using not only light but also heat.
本発明で使用するＥＣ層を有する導電性基板は無機また
は有機のＥＣ剤を導電性基板上に、前者の場合は蒸着、
イオンスバッタ等により、後者の場合は電解、コーティ
ングすることにより作成することができる。無機のＥＣ
剤としては三酸化タングステン、二酸化モリブデン、酸
化インジューム等が挙げられる。有機のＥＣ剤としては
ブタロシアニン、ビピリジン、ビオロゲン、高分子コン
プレックス（高分子ビオロゲン／高分子スルホン酸、バ
ソフェナントロリンスルフォン酸／ 高分子四級アンモ
ニウム塩等）、導電性ポリマー（ポリチオフェン、ポリ
ピロール、ポリアニリン、ポリインチアナフテン等）が
挙げられる。このうち、無機のＥＣ剤、フタロシアニン
および導電性ボリマーが好ましい。The conductive substrate having an EC layer used in the present invention is prepared by depositing an inorganic or organic EC agent on the conductive substrate, in the case of the former by vapor deposition,
It can be produced by ion scattering or the like, or in the latter case by electrolysis or coating. Inorganic EC
Examples of the agent include tungsten trioxide, molybdenum dioxide, and indium oxide. Organic EC agents include butalocyanine, bipyridine, viologen, polymer complexes (polymer viologen/polymer sulfonic acid, bathophenanthroline sulfonic acid/polymer quaternary ammonium salt, etc.), conductive polymers (polythiophene, polypyrrole, polyaniline, polypropylene, etc.). Inchanaphthene, etc.). Among these, inorganic EC agents, phthalocyanines and conductive polymers are preferred.
本発明における導電性基板はガラスまたはフィルム上に
インジュームチンオキサイドを蒸着したものやポリイソ
チアナフテン等の導電性ボリマーが使用できる。導電性
基板は透明であることが好ましい。対向電極板は導電性
基板と同じものが使用できる。The conductive substrate in the present invention may be glass or a film on which indium tin oxide is vapor-deposited, or a conductive polymer such as polyisothianaphthene. Preferably, the conductive substrate is transparent. The counter electrode plate can be the same as the conductive substrate.
本発明のＥＣ素子はＥＣｉを有する導電性基板と対向電
極板の間に電解液組成物の重合物を介在させることによ
り得られる。具体的にはコーティング法またはシート法
により作成することができる。The EC element of the present invention is obtained by interposing a polymer of an electrolyte composition between a conductive substrate having ECi and a counter electrode plate. Specifically, it can be produced by a coating method or a sheet method.
コーティング法はＥＣ層を有する導電性基板のＥＣ層上
および／または対向電極板上に電解液組或物をコーティ
ングして光および／または熱をあてて電解液組成物を重
合せしめそれを張り合わせる方法である。シート法は電
解液組底物を重合した得たシートを予め作成しておき、
そのシートをＥＣ層を有する導電住基板と対向電極板の
間に挟む方法である。The coating method involves coating an electrolyte composition on the EC layer of a conductive substrate having an EC layer and/or on a counter electrode plate, and applying light and/or heat to polymerize the electrolyte composition and laminate it. It's a method. In the sheet method, a sheet obtained by polymerizing an electrolyte solution is prepared in advance, and
This is a method in which the sheet is sandwiched between a conductive housing substrate having an EC layer and a counter electrode plate.
［実施例コ
以下、実施例により本発明を更に説明するが、本発明は
これに限定されるものではない。以下において部は重量
部を示す。実施例で使用した化合物の略号と組成は次の
通りである。[Example] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto. In the following, parts indicate parts by weight. The abbreviations and compositions of the compounds used in the examples are as follows.
化合物Ａ●−●●◆ポリエチレングリコール（平均分子
ｆｆｉ４００）４００部にアリルグリシジルエーテル３
４２部を付加したもの。Compound A●-●●◆Allyl glycidyl ether 3 in 400 parts of polyethylene glycol (average molecular ffi400)
Added 42 copies.
実施例１
過塩素酸リチウム９．２部、プロピレンカーボネー｝９
０部、ジアリルフタレート４．７ｆｆｉ、ペンタエリス
リトールテトラキスチオグリコレート５．３部およびべ
冫ゾフエノン０．１部を均一に溶解し電解液とした。そ
の電解液に高圧水銀灯で紫外線を照射して硬化させ有機
固体電解質を得た。Example 1 Lithium perchlorate 9.2 parts, propylene carbonate}9
0 parts of diallyl phthalate, 4.7 ffi of diallyl phthalate, 5.3 parts of pentaerythritol tetrakisthioglycolate, and 0.1 part of bezophenone were uniformly dissolved to prepare an electrolytic solution. The electrolyte was cured by irradiating it with ultraviolet light using a high-pressure mercury lamp to obtain an organic solid electrolyte.
交流インピーダンス法により２５℃の伝導度を測定し、
値は８ Ｘ １ ０ −” Ｓ ／ ａｍであった。Measure the conductivity at 25°C using the AC impedance method,
The value was 8×10-”S/am.
実施例２
過塩素酸リチウム９部、γブチロラクトンを９１部、化
合物八６．４部、ぺ冫タエルスリトールテトラキスチオ
グリコレート３．６部およびメチルベンゾイルフｔ−メ
ート０．０４部を混合して電解液とした。その電解液に
高圧水銀灯で紫外線を照射して硬化させ有機固体電解質
を得た。交流インピーダンス法により２５℃の伝導度を
測定し、値は５ Ｘ １ ０””Ｓ／ ｃｍであった。Example 2 9 parts of lithium perchlorate, 91 parts of γ-butyrolactone, 6.4 parts of compound 8, 3.6 parts of petaerthritol tetrakisthioglycolate and 0.04 part of methylbenzoylpht-mate were mixed. and used as an electrolyte. The electrolyte was cured by irradiating it with ultraviolet light using a high-pressure mercury lamp to obtain an organic solid electrolyte. The conductivity at 25° C. was measured by AC impedance method and the value was 5×10””S/cm.
実施例３
三酸化タングステンをネサガラス上に５００ＯＡの厚さ
に蒸ｅ Ｅ Ｃ 層を有する導電性基板とした。Example 3 Tungsten trioxide was made into a conductive substrate with a 500 OA thick evaporated EEC layer on Nesa glass.
対向電極板はネサガラスを使用した。実施例１で作成し
た厚さ１ｍｍの有機固体電解質を両基板で挟み本発明の
ＥＣ素子とした。対向電極を陰極とし３Ｖの直流電圧を
印加すると青の鮮明な着色が認められ、逆電圧とすると
消色した。発消色の時間は０． ８秒程度であった。Nesa glass was used for the counter electrode plate. The 1 mm thick organic solid electrolyte prepared in Example 1 was sandwiched between both substrates to provide an EC element of the present invention. When a DC voltage of 3 V was applied using the counter electrode as a cathode, clear blue coloring was observed, and when the reverse voltage was applied, the color disappeared. The time for color development and fading is 0. It took about 8 seconds.
また寿命試験とじて両極性電源を用い、印加電圧３ Ｖ
， 矩形波０．ＩＨＺの条件で発消色を１０６回繰り
返した後、該ＥＣ素子の劣化状態を調べたが変化は認め
られず、初期の性能が維持されていた。また、該素子は
液漏れしなかった。In addition, as a life test, a bipolar power supply was used, and the applied voltage was 3 V.
, square wave 0. After repeating color development and decolorization 106 times under IHZ conditions, the deterioration state of the EC element was examined, but no change was observed, and the initial performance was maintained. Further, the device did not leak.
比較例１
実施例２の化合物Ａおよびペンタエリスリ１・ールテト
ラキスチオグリコレートの代わりにヒドロキシルエチル
メタアクリレートを使用した以外は実施例２と同様に行
ったが、硬化しなかった。Comparative Example 1 The same procedure as in Example 2 was carried out except that hydroxylethyl methacrylate was used in place of Compound A and pentaerythri-1-rutetrakisthioglycolate in Example 2, but no curing occurred.
［発明の効果コ
本発明による電解液組成物は液漏れを起こさない有機固
体電解質ができ、その有機固体電解質は高伝導性を示す
。従って、二次電池、コンデンサー センサー 心電図
電極、導電材として特に有用である。さらに本発明のＥ
Ｃ素子は消、着色速度が速いという効果を奏する。[Effects of the Invention] The electrolytic solution composition according to the present invention produces an organic solid electrolyte that does not cause liquid leakage, and the organic solid electrolyte exhibits high conductivity. Therefore, it is particularly useful as secondary batteries, capacitor sensors, electrocardiogram electrodes, and conductive materials. Furthermore, E of the present invention
The C element has the effect of fast erasing and coloring speed.
Claims (1)
と反応する化合物、および必要によりその他の助剤から
なることを特徴とする電解液組成物。 ２、請求項１記載の電解液組成物を光および／または熱
により重合することを特徴とする有機固体電解質の製法
。 ３、請求項１記載の電解液組成物の光および／または熱
の重合物からなる有機固体電解質。 ４、エレクトロクロミック層を有する導電性基板と対向
電極板との間に、請求項２または３記載の有機固体電解
質を介在させてなるエレクトロクロミック素子。[Scope of Claims] 1. An electrolyte composition comprising an electrolyte salt, a solvent, a thiol compound, a compound that reacts with the thiol compound, and other auxiliary agents if necessary. 2. A method for producing an organic solid electrolyte, which comprises polymerizing the electrolyte composition according to claim 1 with light and/or heat. 3. An organic solid electrolyte comprising a photo and/or thermal polymer of the electrolyte composition according to claim 1. 4. An electrochromic device comprising the organic solid electrolyte according to claim 2 or 3 interposed between a conductive substrate having an electrochromic layer and a counter electrode plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18623389A JPH0350529A (en) | 1989-07-19 | 1989-07-19 | Electrolyte composition and electrochromic element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18623389A JPH0350529A (en) | 1989-07-19 | 1989-07-19 | Electrolyte composition and electrochromic element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0350529A true JPH0350529A (en) | 1991-03-05 |
Family
ID=16184684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18623389A Pending JPH0350529A (en) | 1989-07-19 | 1989-07-19 | Electrolyte composition and electrochromic element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0350529A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100880523B1 (en) * | 2005-12-30 | 2009-01-28 | 주식회사 엘지화학 | Electrochromic device having electrolyte comprising eutectic mixture |
| WO2010010793A1 (en) * | 2008-07-23 | 2010-01-28 | コニカミノルタホールディングス株式会社 | Display device |
-
1989
- 1989-07-19 JP JP18623389A patent/JPH0350529A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100880523B1 (en) * | 2005-12-30 | 2009-01-28 | 주식회사 엘지화학 | Electrochromic device having electrolyte comprising eutectic mixture |
| WO2010010793A1 (en) * | 2008-07-23 | 2010-01-28 | コニカミノルタホールディングス株式会社 | Display device |
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