WO2015129515A1 - 導電性高分子製造用酸化剤兼ドーパント、その溶液、それらのいずれかを用いて製造した導電性高分子およびその導電性高分子を電解質として用いた電解コンデンサ - Google Patents
導電性高分子製造用酸化剤兼ドーパント、その溶液、それらのいずれかを用いて製造した導電性高分子およびその導電性高分子を電解質として用いた電解コンデンサ Download PDFInfo
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- WO2015129515A1 WO2015129515A1 PCT/JP2015/054353 JP2015054353W WO2015129515A1 WO 2015129515 A1 WO2015129515 A1 WO 2015129515A1 JP 2015054353 W JP2015054353 W JP 2015054353W WO 2015129515 A1 WO2015129515 A1 WO 2015129515A1
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- WIPO (PCT)
- Prior art keywords
- dopant
- conductive polymer
- acid
- oxidizing agent
- solution
- Prior art date
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- OHYOZELFYOGAOI-UHFFFAOYSA-N didodecoxyborinic acid Chemical compound CCCCCCCCCCCCOB(O)OCCCCCCCCCCCC OHYOZELFYOGAOI-UHFFFAOYSA-N 0.000 description 1
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- JSJFLHPWPFCJTN-UHFFFAOYSA-N dimethyl phosphono phosphate Chemical compound COP(=O)(OC)OP(O)(O)=O JSJFLHPWPFCJTN-UHFFFAOYSA-N 0.000 description 1
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- VBMSSIXNKVFLAJ-UHFFFAOYSA-N dipropoxyborinic acid Chemical compound CCCOB(O)OCCC VBMSSIXNKVFLAJ-UHFFFAOYSA-N 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- DQCOURVTDJUHQM-UHFFFAOYSA-N hydroxy-dioctoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCOP(O)(=S)OCCCCCCCC DQCOURVTDJUHQM-UHFFFAOYSA-N 0.000 description 1
- GSJYSUQLJKYYRS-UHFFFAOYSA-N hydroxy-octoxy-octylsulfanyl-sulfanylidene-lambda5-phosphane Chemical compound CCCCCCCCOP(O)(=S)SCCCCCCCC GSJYSUQLJKYYRS-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
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- ILGYWHOGBUPIIQ-UHFFFAOYSA-N octan-3-yl dihydrogen phosphite Chemical compound CCCCCC(CC)OP(O)O ILGYWHOGBUPIIQ-UHFFFAOYSA-N 0.000 description 1
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- JRCSBZBPEOYWSO-UHFFFAOYSA-N phosphorous acid 2,2,2-trihydroxyethyl 2-methylprop-2-enoate Chemical compound OP(O)O.CC(=C)C(=O)OCC(O)(O)O JRCSBZBPEOYWSO-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
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- 238000005476 soldering Methods 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- OACSUWPJZKGHHK-UHFFFAOYSA-N tribenzyl phosphate Chemical compound C=1C=CC=CC=1COP(OCC=1C=CC=CC=1)(=O)OCC1=CC=CC=C1 OACSUWPJZKGHHK-UHFFFAOYSA-N 0.000 description 1
- GAJQCIFYLSXSEZ-UHFFFAOYSA-L tridecyl phosphate Chemical compound CCCCCCCCCCCCCOP([O-])([O-])=O GAJQCIFYLSXSEZ-UHFFFAOYSA-L 0.000 description 1
- OHRVKCZTBPSUIK-UHFFFAOYSA-N tridodecyl phosphate Chemical compound CCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCC)OCCCCCCCCCCCC OHRVKCZTBPSUIK-UHFFFAOYSA-N 0.000 description 1
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- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- QTPJMTACJMLPLL-UHFFFAOYSA-N triethoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound CCOP(=S)(OCC)OCC QTPJMTACJMLPLL-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- KDQYHGMMZKMQAA-UHFFFAOYSA-N trihexyl borate Chemical compound CCCCCCOB(OCCCCCC)OCCCCCC KDQYHGMMZKMQAA-UHFFFAOYSA-N 0.000 description 1
- XWSLYQXUTWUIKM-UHFFFAOYSA-N trimethoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound COP(=S)(OC)OC XWSLYQXUTWUIKM-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
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- DTBRTYHFHGNZFX-UHFFFAOYSA-N trioctyl borate Chemical compound CCCCCCCCOB(OCCCCCCCC)OCCCCCCCC DTBRTYHFHGNZFX-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- IKXFIBBKEARMLL-UHFFFAOYSA-N triphenoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=S)OC1=CC=CC=C1 IKXFIBBKEARMLL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- JNDQYJLNXLSCPA-UHFFFAOYSA-N tripropoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound CCCOP(=S)(OCCC)OCCC JNDQYJLNXLSCPA-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 description 1
- JLEXUIVKURIPFI-UHFFFAOYSA-N tris phosphate Chemical compound OP(O)(O)=O.OCC(N)(CO)CO JLEXUIVKURIPFI-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
- H01G9/0036—Formation of the solid electrolyte layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/15—Solid electrolytic capacitors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/43—Chemical oxidative coupling reactions, e.g. with FeCl3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
Definitions
- the present invention relates to an oxidizing agent / dopant for producing a conductive polymer, a solution thereof, a conductive polymer produced using any of them, and an electrolytic capacitor using the conductive polymer as an electrolyte.
- Conductive polymers are used as electrolytes such as aluminum electrolytic capacitors, tantalum electrolytic capacitors, and niobium electrolytic capacitors because of their high conductivity.
- conductive polymer in this application for example, those obtained by chemical oxidative polymerization or electrolytic oxidative polymerization of thiophene or a derivative thereof are used.
- the organic sulfonic acid is mainly used as a dopant when performing chemical oxidative polymerization of the thiophene or a derivative thereof, and a transition metal is used as an oxidizing agent.
- ferric iron is said to be suitable.
- a ferric salt of an organic sulfonic acid is used as an oxidizing agent and a dopant in chemical oxidative polymerization of thiophene or a derivative thereof (Patent Documents 1 and 2).
- an electrolytic capacitor manufactured using a conductive polymer manufactured using a ferric salt of organic sulfonic acid as an oxidant and dopant has a large leakage current, particularly in a high temperature atmosphere. There was a problem.
- the present invention provides an oxidizing agent / dopant for producing a conductive polymer that can produce a conductive polymer suitable for producing an electrolytic capacitor with low leakage current, and a solution thereof, and any one of them. It is an object of the present invention to provide a conductive polymer suitable for manufacturing an electrolytic capacitor with a low leakage current and to provide an electrolytic capacitor with a low leakage current using the conductive polymer as an electrolyte.
- the present invention has been intensively studied, and specific phosphoric acid based additives, phosphorous acid based additives, boric acid based additives, thiophosphoric acid based additives are added to ferric organic sulfonates.
- the present inventors have found that an oxidizing agent / dopant prepared by adding an agent or a dithiophosphoric acid-based additive can solve the above-mentioned problems, and has been completed on the basis thereof.
- the present invention relates to ferric organic sulfonate, phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphoric acid ester, dithiophosphoric acid and dithiophosphoric acid ester It contains at least 1 sort (s) chosen from the group which consists of an oxidizing agent and dopant for electroconductive polymer manufacture characterized by the above-mentioned.
- the present invention also includes an oxidant and dopant for producing a conductive polymer, wherein the oxidant and dopant for producing a conductive polymer contains a compound having a glycidyl group or a ring-opening compound thereof.
- An oxidizing agent / dopant solution for producing a conductive polymer obtained by dissolving an oxidizing agent / dopant for producing a conductive polymer in water, alcohol or a mixture of water and alcohol, and an oxidizing agent for producing the conductive polymer.
- a conductive polymer produced by oxidative polymerization of a monomer such as thiophene or a derivative thereof using an agent / dopant or a solution thereof, and an electrolytic capacitor using the conductive polymer as an electrolyte are also objects of the invention.
- an oxidizing agent / dopant for producing a conductive polymer and a solution thereof that can produce a conductive polymer suitable for producing an electrolytic capacitor with a small leakage current.
- the oxidizing agent / dopant for producing the conductive polymer of the present invention includes ferric organic sulfonate, phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, boric acid, boric acid ester. , Thiophosphoric acid, thiophosphoric acid ester, dithiophosphoric acid and at least one selected from the group consisting of dithiophosphoric acid esters, of which organic ferric sulfonate has been used so far in this field. First, the specific acid or acid ester component of the counterpart will be described first.
- the acid or acid ester component is selected from the group consisting of phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphoric acid ester, dithiophosphoric acid and dithiophosphoric acid ester
- the phosphoric acid ester is, for example, methyl phosphate, dimethyl phosphate, trimethyl phosphate, ethyl phosphate, diethyl phosphate, triethyl phosphate, propyl phosphate, dipropyl phosphate, Tripropyl phosphate, butyl phosphate, dibutyl phosphate, tributyl phosphate, ethyl hexyl phosphate, diethyl hexyl phosphate, triethyl hexyl phosphate, benzyl phosphate, dibenzyl phosphate, tribenzyl phosphate, phenyl
- phosphate esters for example, dialkyl phosphates such as dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, diethylhexyl phosphate, phosphate diesters such as dibenzyl phosphate and diphenyl phosphate,
- phosphate triesters such as tributyl phosphate are particularly preferable.
- phosphite ester examples include methyl phosphite, dimethyl phosphite, trimethyl phosphite, ethyl phosphite, diethyl phosphite, triethyl phosphite, propyl phosphite, dipropyl phosphite, Tripropyl phosphite, butyl phosphite, dibutyl phosphite, tributyl phosphite, ethylhexyl phosphite, diethylhexyl phosphite, triethylhexyl phosphite, benzyl phosphite, dibenzyl phosphite, phosphorus Tribenzyl acid, phenyl phosphite, diphenyl phosphite, triphenyl phosphite, trisethoxy
- dialkyl phosphites such as dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, diethylhexyl phosphite, dibenzyl phosphite
- phosphorous acid diesters such as diphenyl phosphate and phosphorous acid triesters such as tributyl phosphite.
- borate ester examples include methyl borate, dimethyl borate, trimethyl borate, ethyl borate, diethyl borate, triethyl borate, propyl borate, dipropyl borate, tripropyl borate, butyl borate, Dibutyl borate, tributyl borate, ethyl hexyl borate, diethyl hexyl borate, triethyl hexyl borate, benzyl borate, dibenzyl borate, tribenzyl borate, phenyl borate, diphenyl borate, triphenyl borate, hexyl borate , Dihexyl borate, trihexyl borate, octyl borate, dioctyl borate, trioctyl borate, decyl borate, didecyl borate, tridecyl borate, dodecyl borate, didodecyl
- boric acid esters for example, dimethyl borate, diethyl borate, dibutyl borate, dialkyl borate such as diethylhexyl borate, dibenzyl borate, boric acid diester such as diphenyl borate, for example, Boric acid triesters such as tributyl borate are preferred.
- thiophosphate ester examples include methyl thiophosphate, dimethyl thiophosphate, trimethyl thiophosphate, ethyl thiophosphate, diethyl thiophosphate, triethyl thiophosphate, propyl thiophosphate, dipropyl thiophosphate, tripropyl thiophosphate, butyl thiophosphate, Dibutyl thiophosphate, tributyl thiophosphate, hexyl thiophosphate, dihexyl thiophosphate, trihexyl thiophosphate, octyl thiophosphate, dioctyl thiophosphate, trihexyl thiophosphate, ethyl hexyl thiophosphate, diethylhexyl thiophosphate, triethylhexyl thiophosphate, benzyl thiophosphate, Dibenzyl thio
- thiophosphate diesters such as dimethyl thiophosphate, diethyl thiophosphate, dipropyl thiophosphate, dibutyl thiophosphate, diethylhexyl thiophosphate, dibenzyl thiophosphate, diphenyl thiophosphate
- thiophosphate triesters such as tributyl thiophosphate are preferable.
- dithiophosphate examples include, for example, methyl dithiophosphate, dimethyl dithiophosphate, trimethyl dithiophosphate, ethyl dithiophosphate, diethyl dithiophosphate, triethyl dithiophosphate, propyl dithiophosphate, dipropyl dithiophosphate, tripropyl dithiophosphate, butyl dithiophosphate, Dibutyl dithiophosphate, tributyl dithiophosphate, hexyl dithiophosphate, dihexyl dithiophosphate, trihexyl dithiophosphate, octyl dithiophosphate, dioctyl dithiophosphate, trioctyl dithiophosphate, ethylhexyl dithiophosphate, diethylhexyl dithiophosphate, triethylhexyl dithiophosphate, dithiophosphoric acid Dibenzyl dithiophosphate
- dithiophosphate diesters such as dimethyl diphosphate, diethyl dithiophosphate, dipropyl dithiophosphate, dibutyl dithiophosphate, diethylhexyl dithiophosphate, benzyl dithiophosphate, diphenyl dithiophosphate
- dithiophosphate triesters such as tributyl dithiophosphate are preferred.
- phosphoric acid ester phosphorous acid, phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphoric acid ester, dithiophosphoric acid, dithiophosphoric acid ester, etc.
- phosphoric acid ester, phosphorous acid Esters, thiophosphoric acid esters, and dithiophosphoric acid esters are particularly preferable.
- phosphoric acid diesters, phosphorous acid diesters, thiophosphoric acid diesters, and dithiophosphoric acid diesters are preferable, and phosphoric acid diesters and phosphite diesters are particularly preferable.
- the addition amount of at least one selected from the group consisting of phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphoric acid ester, dithiophosphoric acid and dithiophosphoric acid ester is 1 to 100% by mass relative to ferric organic sulfonate (that is, phosphoric acid, phosphoric ester, phosphorous acid, phosphorous ester, boric acid relative to 100 parts by mass of organic ferric sulfonate , Boric acid ester, thiophosphoric acid, thiophosphoric acid ester, dithiophosphoric acid and dithiophosphoric acid ester are preferably at least one selected from the group consisting of 1 to 100 parts by mass).
- Addition amount of at least one selected from the group consisting of phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphoric acid ester, dithiophosphoric acid and dithiophosphoric acid ester If it is less than the range, the effect of reducing the leakage current may not be sufficiently exhibited, and phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphorus
- ESR may be increased, and characteristics under high temperature and high humidity may be deteriorated.
- the amount of addition to one type of organic sulfonic acid ferric acid is more preferably 1.5% or more, further preferably 3% or more, and more preferably 20% or less, based on mass with respect to ferric organic sulfone. 15% or less is more preferable, and 10% or less is more preferable.
- organic sulfonic acid of ferric organic sulfonate for example, aromatic sulfonic acid such as benzene sulfonic acid or its derivative, naphthalene sulfonic acid or its derivative, anthraquinone sulfonic acid or its derivative, polystyrene Sulfonic acid, sulfonated polyester, phenol sulfonic acid novolak resin, polymer sulfonic acid such as styrene sulfonic acid and non-sulfonic acid monomer copolymer described in detail later, methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, A chain sulfonic acid such as butanesulfonic acid can be used.
- aromatic sulfonic acid such as benzene sulfonic acid or its derivative, naphthalene sulfonic acid or its derivative, anthraquinone sulfonic acid
- aromatic sulfonic acids are easy to produce electrolytic capacitors with excellent capacitor characteristics such as low ESR and large capacitance, and can be used alone.
- organic sulfonic acid for construction. Since chain sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and butanesulfonic acid have higher acidity than aromatic sulfonic acid, the above aromatic sulfonic acid is used rather than used alone. It is preferable to use together.
- aromatic sulfonic acids are suitable for reaction under low humidity (humidity of about 35% or less), and it is easy to obtain conductive polymers with good characteristics, but high humidity (humidity of about 50% or more). Below, it has the property that the reaction is difficult to proceed. Therefore, it is possible to improve the reaction with the strong acidity of the chain sulfonic acid so that the reaction can proceed appropriately.
- Examples of the benzenesulfonic acid derivative in the benzenesulfonic acid or derivatives thereof include toluenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid, methoxybenzenesulfonic acid, and ethoxybenzenesulfone. Acid, propoxybenzene sulfonic acid, butoxybenzene sulfonic acid, phenol sulfonic acid, cresol sulfonic acid, benzene disulfonic acid and the like.
- naphthalene sulfonic acid derivatives in naphthalene sulfonic acid or its derivatives include naphthalene disulfonic acid, naphthalene tri Sulfonic acid, methyl naphthalene sulfonic acid, ethyl naphthalene sulfonic acid, propyl naphthalene sulfonic acid, butyl naphthalene sulfone Acid and the like.
- the anthraquinone sulfonic acid derivatives in anthraquinone sulfonic acid or its derivatives e.g., anthraquinone disulfonic acid, anthraquinone-trisulfonic acid.
- aromatic sulfonic acids toluene sulfonic acid, methoxybenzene sulfonic acid, phenol sulfonic acid, naphthalene sulfonic acid, naphthalene trisulfonic acid, and the like are preferable, and paratoluene sulfonic acid, methoxybenzene sulfonic acid, and naphthalene sulfonic acid are particularly preferable.
- Naphthalenesulfonic acid is particularly preferable.
- aromatic sulfonic acids can be used alone or in combination of two or more. And as mentioned above, also when using two or more types together, it is preferable to use naphthalenesulfonic acid as one aromatic sulfonic acid, as a preferable combination example when using two or more types together, for example, The combined use of naphthalene sulfonic acid and methane sulfonic acid and the combined use of naphthalene sulfonic acid and paratoluene sulfonic acid are mentioned.
- the ferric organic sulfonate is preferably one in which the molar ratio of the organic sulfonic acid to the iron is less than 1: 3. This is because the reaction rate of the ferric organic sulfonate can be slightly reduced by making the organic sulfonic acid to iron molar ratio less than the stoichiometric molar ratio of 1: 3.
- the molar ratio of organic sulfonic acid to iron is preferably up to about 1: 2, more preferably about 1: 2.2, more preferably about 1: 2.4, and about 1: 2.75. Even more preferred is.
- the oxidant / dopant for producing a conductive polymer can be used as it is, that is, in the form of a solid such as a powder.
- the oxidant / dopant for producing a conductive polymer is used. Is preferably used as a solution by dissolving it in water, alcohol, a mixed solution of water and alcohol, or the like. That is, by making it into a solution, workability is improved, and the mixed state with the monomer becomes more uniform, and the function as an oxidizing agent and dopant can be more effectively exhibited.
- Examples of the alcohol used as the solvent include monohydric alcohols such as methanol (methyl alcohol), ethanol (ethyl alcohol), propanol (propyl alcohol), butanol (butyl alcohol), ethylene glycol, propylene glycol, diethylene glycol, Polyhydric alcohols such as ethylene glycol and polyethylene glycol can be used, and among these, monohydric alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol and butanol are preferred.
- monohydric alcohols such as methanol (methyl alcohol), ethanol (ethyl alcohol), propanol (propyl alcohol), butanol (butyl alcohol), ethylene glycol, propylene glycol, diethylene glycol, Polyhydric alcohols such as ethylene glycol and polyethylene glycol can be used, and among these, monohydric alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol and butanol are preferred.
- the concentration of the oxidizing agent / dopant for producing conductive polymer (hereinafter sometimes referred to simply as “oxidizing agent / dopant”) in the oxidizing polymer / dopant solution for producing conductive polymer is 20 to 70% by mass. Preferably there is.
- concentration of the oxidant and dopant is lower than 20% by mass, the oxidizing power is weakened, and there is a risk that the polymerization of the monomer will not sufficiently proceed.
- the concentration of the oxidant and dopant is higher than 70% by mass, The viscosity becomes so high that it is difficult to soak into the capacitor element, which may make it difficult to manufacture the capacitor.
- the concentration of the oxidant / dopant in the oxidant / dopant solution is preferably 25% by mass or more, more preferably 30% by mass or more, and 65% by mass or less within the range of 20 to 70% by mass. Is more preferable, and 60 mass% or less is still more preferable.
- the oxidizing agent and dopant of the present invention includes ferric organic sulfonate, phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphoric acid ester, dithiophosphoric acid and By including at least one selected from the group consisting of dithiophosphates, it is possible to provide an electrolytic capacitor with low leakage current. Furthermore, a compound having a glycidyl group (that is, an epoxy group) or a compound thereof By including the ring-opening compound, an electrolytic capacitor having a high breakdown voltage (that is, excellent withstand voltage) can be manufactured in addition to the characteristic that the original leakage current is small.
- Examples of the compound having a glycidyl group include a monoglycidyl compound represented by the following general formula (1), a diglycidyl compound represented by the general formula (2), a diglycidyl compound represented by the general formula (3), Glycerin diglycidyl ether, diglycerin tetraglycidyl ether, alcohol-soluble epoxy resin, alcohol-soluble polyglycerin polyglycidyl and their ring-opening compounds, epoxy polysiloxane (the above “polysiloxane” means “two or more siloxane bonds” And the ring-opened compounds thereof are preferable.
- a monoglycidyl compound represented by the following general formula (1) a diglycidyl compound represented by the general formula (2), a diglycidyl compound represented by the general formula (3), Glycerin diglycidyl ether, diglycerin tetraglycidyl ether, alcohol-soluble epoxy resin, alcohol-soluble polyglycerin polyglycidy
- said diglycerin tetraglycidyl ether is represented by following Formula (5).
- the ring-opening compound such as those means a compound in which the glycidyl group of the compound having a glycidyl group is ring-opened as shown in the following formula (6) to form a glycol.
- a compound having 1 to 4 glycidyl groups or a compound having 1 to 4 glycidyl groups or a ring-opening compound thereof is preferably used.
- the ring-opening compound examples include alcohol-soluble epoxy resins or ring-opening compounds thereof, alcohol-soluble polyglycerin polyglycidyl or ring-opening compounds thereof and epoxy polysiloxanes in addition to the above-described compounds having 1 to 4 glycidyl groups or ring-opening compounds thereof.
- a ring-opening compound thereof can be used.
- said alcohol soluble epoxy resin what is marketed with the brand name of "water sol BC-3010" from DIC Corporation can be used conveniently, for example.
- the alcohol-soluble polyglycerin polyglycidyl for example, those commercially available from Sakamoto Pharmaceutical Co., Ltd. under the trade name “SR-4GLS” can be preferably used.
- epoxy polysiloxane examples include those commercially available from Shin-Etsu Chemical Co., Ltd. under trade names such as “X-41-1053”, “X-41-1056”, and “X-41-1059A”. It can be suitably used.
- ring-opening compounds such as alcohol-soluble epoxy resins, alcohol-soluble polyglycerin polyglycidyls, and epoxy polysiloxanes are also those in which the glycidyl group they have opened to become glycol, as shown in the above formula (6). .
- the ring-opening compound of the compound having a glycidyl group described above is a glycidyl compound having two or more glycidyl groups, and it is not necessary that all glycidyl groups are ring-opened. May be.
- specific examples of the monoglycidyl compound represented by the above general formula (1) or the ring-opening compound thereof include, for example, epoxy propanol (that is, glycidol), methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl.
- butyl glycidyl ether epoxy butane (ie glycidyl methane), epoxy pentane (ie glycidyl ethane), epoxy hexane (ie glycidyl propane), epoxy heptane (ie glycidyl butane), epoxy octane (ie glycidyl pentane) , Glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane Examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, glycidyl methacrylate, etc., and in particular, epoxypropanol, butylglycidyl ether, epoxybutane, 2- (3,4-epoxycyclohexyl)
- Examples of the diglycidyl compound represented by the general formula (2) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, pentylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, Examples include glycerin diglycidyl ether, and ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether are particularly preferable.
- Examples of the diglycidyl compound represented by the general formula (3) include diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, Examples thereof include polypropylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether is particularly preferable.
- the above glycidyl group-containing compounds and ring-opening compounds thereof can be used alone or in combination of two or more.
- Some of the above-mentioned compounds having a glycidyl group and ring-opening compounds thereof have high boiling points (for example, ethylene glycol diglycidyl ether has a boiling point of 112 ° C./0.6 kPa), and they are removed by ordinary drying. However, even if it remains, it does not cause an increase in ESR or a decrease in capacitance as shown in the examples below, and it has a withstand voltage resistance. Does not cause a drop in
- the amount of the compound having a glycidyl group or its ring-opening compound added to the ferric organic sulfonate is 5 to 100% on a mass basis (that is, the glycidyl group is added to 100 parts by weight of the organic ferric sulfonate).
- the ring-opening compound thereof is preferably 5 to 100 parts by mass), and when the addition amount of the compound having a glycidyl group or the ring-opening compound is less than the above, the effect of increasing the voltage resistance is not sufficiently exhibited, In addition, when the amount of the compound having a glycidyl group or its ring-opening compound is larger than the above, the increase in the effect due to the increase in the amount of addition is small, resulting in high costs and immiscibility, and the oxidizing agent / dopant solution. There is a risk of lowering the storage stability.
- the addition amount with respect to ferric organic sulfonate of the compound which has this glycidyl group or its ring-opening compound is more preferably 10% or more, more preferably 14% or more on a mass basis within the above range, and 40 % Or less is more preferable, and 36% or less is more preferable.
- polyhydric alcohol those having 2 to 3 hydroxy groups in an aliphatic hydrocarbon having 2 to 10 carbon atoms are preferable.
- polyhydric alcohol include, for example, ethylene glycol, propanediol, Examples include butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, glycerol, and the like, and glycerol, ethylene glycol, propanediol, and butanediol are particularly preferable.
- the amount of polyhydric alcohol added to the oxidizing agent / dopant solution is 20% or less based on the weight of polyhydric alcohol relative to ferric organic sulfonate (that is, based on 100 parts by weight of organic ferric sulfonate).
- the polyhydric alcohol is preferably 20 parts by mass or less.
- the effect of adding a polyhydric alcohol increases with the addition amount even if added in a small amount, but in order to express the effect of the addition more clearly than ferric organic sulfonate.
- the alcohol content is preferably 4% or more by mass, and the viscosity of the oxidant / dopant solution increases with the addition of the polyhydric alcohol.
- the polyhydric alcohol is more preferably 20% or less by mass.
- thiophene or a derivative thereof, pyrrole or a derivative thereof, aniline or a derivative thereof, and the like can be used as a monomer for producing a conductive polymer, and it is particularly preferable to use thiophene or a derivative thereof.
- this is because the conductive polymer obtained by polymerizing thiophene or its derivative has a good balance between conductivity and heat resistance, and an electrolytic capacitor having superior capacitor characteristics compared to other monomers. It is based on the reason that it is easy to obtain.
- Examples of the thiophene derivative in the thiophene or the derivative thereof include, for example, 3,4-ethylenedioxythiophene, 3-alkylthiophene, 3-alkoxythiophene, 3-alkyl-4-alkoxythiophene, 3,4-alkylthiophene 3,4-alkoxythiophene, alkylated ethylenedioxythiophene obtained by modifying the above 3,4-ethylenedioxythiophene with an alkyl group, and the like.
- the alkyl group or alkoxy group has 1 to 16 carbon atoms. Is preferable, 1 to 10 is more preferable, and 1 to 4 is more preferable.
- the alkylated ethylenedioxythiophene obtained by modifying the 3,4-ethylenedioxythiophene with an alkyl group will be described in detail.
- the 3,4-ethylenedioxythiophene and the alkylated ethylenedioxythiophene are represented by the following general formula ( It corresponds to the compound represented by 7).
- R 4 in the general formula (7) is hydrogen is 3,4-ethylenedioxythiophene, which is expressed by the IUPAC name, “2,3-dihydro-thieno [3,4-b ], [1,4] dioxin (2,3-Dihydro-thieno [3,4-b] [1,4] dioxine) ”, but this compound has a generic name rather than the IUPAC name. Since it is often indicated by “3,4-ethylenedioxythiophene”, in this document, “2,3-dihydro-thieno [3,4-b] [1,4] dioxin” is referred to as “3,4”. -Ethylenedioxythiophene ".
- R 4 in the general formula (7) is an alkyl group
- the alkyl group preferably has 1 to 10 carbon atoms, and particularly preferably has 1 to 4 carbon atoms. That is, as the alkyl group, a methyl group, an ethyl group, a propyl group, and a butyl group are particularly preferable.
- a compound in which R 4 in the general formula (7) is a methyl group is represented by an IUPAC name.
- R 4 in the general formula (7) is an ethyl group
- IUPAC name “2-ethyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxin (2 -Ethyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxine) ”, but in this document, this is simplified and expressed as“ ethylated ethylenedioxythiophene ”.
- a compound in which R 4 is a propyl group is represented by IUPAC name: “2-propyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxin (2 -Propyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxine) ”, but in this document, this is simplified and expressed as“ propylated ethylenedioxythiophene ”.
- a compound in which R 4 in the general formula (7) is a butyl group is represented by “UPL name”, “2-butyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxin”.
- alkylated ethylenedioxythiophenes methylated ethylenedioxythiophene, ethylated ethylenedioxythiophene, propylated ethylenedioxythiophene, and butylated ethylenedioxythiophene are preferable.
- 3,4-ethylenedioxythiophene ie 2,3-dihydro-thieno [3,4-b] [1,4] dioxin
- alkylated ethylenedioxythiophene ie 2-alkyl-2, 3-dihydro-thieno [3,4-b] [1,4] dioxin
- the mixing ratio is 0.05: 1 to 1: 0.1, particularly in molar ratio. It is preferably 0.1: 1 to 1: 0.1, particularly 0: 2: 1 to 1: 0.2, and more preferably 0.3: 1 to 1: 0.3.
- the oxidizing agent and dopant of the present invention includes ferric organic sulfonate, phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphoric acid
- ferric organic sulfonate phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphoric acid
- ferric organic sulfonate phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphoric acid
- esters dithiophosphoric acid and dithiophosphoric acid esters
- thiophosphoric acid thiophosphoric acid
- thiophosphoric acid By including at least one selected from the group consisting of esters, dithiophosphoric acid and dithiophospho
- the production of the conductive polymer using the oxidant / dopant solution of the present invention is usually performed when the conductive polymer is produced and when the electrolytic polymer is produced, the so-called “in situ polymerization” is performed. It can be applied to both production of conductive polymers by
- thiophene and its derivatives as monomers are liquid at room temperature, they can be used as they are for polymerization, and in order to make the polymerization reaction proceed more smoothly, for example, monomers such as methanol, ethanol, propanol, butanol, It may be diluted with an organic solvent such as acetone or acetonitrile and used as an organic solvent solution.
- monomers such as methanol, ethanol, propanol, butanol
- organic solvent such as acetone or acetonitrile
- a particularly preferred thiophene or a derivative thereof will be described as a representative.
- pyrrole or a derivative thereof, aniline or a derivative thereof can be used in the same manner as the thiophene or the derivative thereof.
- this normal conductive polymer is manufactured means that the conductive polymer is not manufactured by “in situ polymerization” at the time of manufacturing an electrolytic capacitor).
- a mixture of the oxidant / dopant solution of the present invention and the monomer thiophene or a derivative thereof is used (the mixing ratio is preferably 5: 1 to 15: 1 for the oxidant / dopant: monomer on a mass basis). ), For example, by oxidative polymerization at 5 to 95 ° C. for 1 to 72 hours.
- the oxidant and dopant of the present invention is mixed with the monomer in the production of the electrolytic capacitor, the oxidant and dopant of the present invention is previously mixed with ferric organic sulfonate before mixing with the monomer.
- At least one selected from the group consisting of phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphoric acid ester, dithiophosphoric acid and dithiophosphoric acid ester It may not be prepared as an oxidizing agent and dopant, and ferric organic sulfonate, phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphorus At least one selected from the group consisting of acid ester, dithiophosphoric acid and dithiophosphoric acid ester and monomer are mixed simultaneously.
- oxidant / dopant of the present invention Is the same as the mixture of the oxidant / dopant of the present invention and the monomer as described above, and may be so, and the monomer, phosphoric acid, phosphate ester, phosphorous acid in advance.
- Phosphorous acid ester, boric acid, boric acid ester, thiophosphoric acid, thiophosphoric acid ester, dithiophosphoric acid, and at least one selected from the group consisting of dithiophosphoric acid ester and ferric organic sulfonate Are mixed in the same state as the mixture of the oxidant / dopant and monomer of the present invention, so that the oxidant / dopant of the present invention is prepared as shown in the above example in the production of an electrolytic capacitor. Also good.
- the oxidant / dopant solution of the present invention as described above has been developed so that the monomer thiophene or its derivative is suitable for producing a conductive polymer by so-called “in-situ polymerization”, particularly at the time of producing an electrolytic capacitor. This is explained in detail below.
- electrolytic capacitors include aluminum electrolytic capacitors, tantalum electrolytic capacitors, niobium electrolytic capacitors, etc., and among these aluminum electrolytic capacitors, there are wound aluminum electrolytic capacitors and laminated or flat plate aluminum electrolytic capacitors, Since the oxidizing agent / dopant solution of the present invention can be applied to the production of a wound aluminum electrolytic capacitor, this will be described first.
- a lead terminal is attached to the anode formed by the chemical conversion treatment and the dielectric layer is formed, and the lead is connected to the cathode made of the aluminum foil. It is preferable to use what was prepared by attaching terminals and winding the anode and cathode with lead terminals through a separator.
- the capacitor element is immersed in a mixture of the oxidant / dopant solution of the present invention and a monomer (thiophene or a derivative thereof), pulled up (after removal), and then polymerized at room temperature or under heating to polymerize the thiophene or After forming an electrolyte layer made of a conductive polymer having a polymer of the derivative as a polymer skeleton, a capacitor element having the electrolyte layer is packaged with an exterior material to produce a wound aluminum electrolytic capacitor.
- the monomer is diluted with an organic solvent such as methanol as described above, and the monomer solution
- the capacitor element is immersed in the oxidant / dopant solution of the present invention and then pulled up, and then the monomer is polymerized at room temperature or under heating.
- the capacitor element is dipped in the monomer, pulled up, polymerized at room temperature or under heating, and thereafter wound in the same manner as described above.
- a rotary aluminum electrolytic capacitor is manufactured.
- porous capacitor metals such as aluminum, tantalum, and niobium are used as capacitor elements.
- the capacitor element is used in the same manner as in the case of the wound aluminum electrolytic capacitor, using an anode made of a body and a dielectric layer made of an oxide film of the valve metal.
- the monomer is polymerized at room temperature or under heating, or the capacitor element is immersed in the monomer solution and then lifted and dried, and then the capacitor element is used as the oxidizing agent of the present invention.
- the capacitor element is immersed in the mixture of the oxidizer / dopant solution of the present invention and the monomer, the monomer solution or the oxidant dopant solution of the present invention, and the capacitor element is impregnated with them.
- they may be applied to the capacitor element by, for example, spraying and impregnating them.
- an electrolytic capacitor As described above, after producing a conductive polymer using the oxidant / dopant solution of the present invention, a ⁇ -conjugated conductive polymer is dispersed on the conductive polymer. It is good also as the electrolytic capacitor which formed the electroconductive polymer layer using the liquid and comprised electrolyte by both.
- ⁇ -conjugated conductive polymer a ⁇ -conjugated conductive polymer using a polymer anion as a dopant is used.
- the polymer anion is mainly composed of a high molecular weight sulfonic acid.
- the polymer anion will be described in detail.
- examples of the polymer anion include polystyrene sulfonic acid, sulfonated polyester, phenol sulfonic acid novolak resin, and styrene sulfonic acid. Examples thereof include a copolymer with a sulfonic acid monomer.
- the polystyrene sulfonic acid preferably has a weight average molecular weight of 10,000 to 1,000,000.
- the weight average molecular weight of the polystyrene sulfonic acid when the weight average molecular weight of the polystyrene sulfonic acid is smaller than 10,000, the conductivity of the obtained conductive polymer may be lowered. Further, when the weight average molecular weight of the polystyrene sulfonic acid is larger than 1,000,000, the viscosity of the conductive polymer dispersion becomes high, which may make it difficult to use in the production of an electrolytic capacitor.
- the polystyrene sulfonic acid has a weight average molecular weight within the above range, preferably 20,000 or more, more preferably 40,000 or more, and preferably 800,000 or less. More preferable is 1,000 or less.
- the sulfonated polyester is a polycondensation product of dicarboxybenzenesulfonic acid diester such as sulfoisophthalic acid ester or sulfoterephthalic acid ester and alkylene glycol in the presence of a catalyst such as antimony oxide or zinc oxide.
- the modified polyester preferably has a weight average molecular weight of 5,000 to 300,000.
- the sulfonated polyester preferably has a weight average molecular weight within the above range of 10,000 or more, more preferably 20,000 or more, and preferably 100,000 or less. More preferable is 1,000 or less.
- the phenolsulfonic acid novolak resin preferably has a weight average molecular weight of 5,000 to 500,000.
- the phenol sulfonic acid novolak resin preferably has a weight average molecular weight within the above range of 10,000 or more, more preferably 400,000 or less, and more preferably 80,000 or less. preferable.
- Polymer anions such as polystyrene sulfonic acid, sulfonated polyester, and phenol sulfonic acid novolak resin can be used alone or in combination of two or more.
- a copolymer of the styrene sulfonic acid and at least one non-sulfonic acid monomer selected from the group consisting of a methacrylic acid ester, an acrylic acid ester, an unsaturated hydrocarbon-containing alkoxysilane compound or a hydrolyzate thereof (hereinafter, A conductive polymer obtained by oxidative polymerization of thiophene or a derivative thereof using a styrene sulfonic acid and a non-sulfonic acid monomer as a dopant) is highly conductive, Moreover, since it has excellent heat resistance, it is suitable for manufacturing an electrolytic capacitor having low ESR, high reliability under high temperature conditions, and low leakage current.
- a copolymer of the styrene sulfonic acid and at least one non-sulfonic acid monomer selected from the group consisting of a methacrylic acid ester, an acrylic acid ester, an unsaturated hydrocarbon-containing alkoxysilane compound or a hydrolyzate thereof is synthesized.
- a monomer to be copolymerized with styrene sulfonic acid at least one selected from the group consisting of methacrylic acid ester, acrylic acid ester and unsaturated hydrocarbon-containing alkoxysilane compound or a hydrolyzate thereof is used.
- Esters include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, diphenylbutyl methacrylate, methacrylate.
- hydroxyalkyl methacrylate such as hydroxybutyl, hydroxyhexyl methacrylate, hydroxystearyl methacrylate, hydroxypolyoxyethylene methacrylate, methoxyhydroxypropyl methacrylate, ethoxyhydroxypropyl methacrylate, dihydroxypropyl methacrylate, dihydroxybutyl methacrylate, etc.
- those having a glycidyl group such as glycidyl methacrylate and methyl glycidyl methacrylate have a structure containing a hydroxyl group by ring opening of the glycidyl group.
- alkyl it is preferable from the viewpoint of characteristics as a dopant when copolymerized with styrenesulfonic acid.
- acrylate ester examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, stearyl acrylate, cyclohexyl acrylate, diphenylbutyl acrylate, dimethylaminoethyl acrylate, Acrylic acid such as diethylaminoethyl acrylate, sodium sulfohexyl acrylate, glycidyl acrylate, methyl glycidyl acrylate, hydroxyalkyl acrylate, ie hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate Hydroxyalkyl and the like can be used, but hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, The number of carbon atoms in the alkyl group, such as Le acid hydroxybutyl acrylate,
- those having a glycidyl group such as glycidyl acrylate and methyl glycidyl acrylate have a structure containing a hydroxyl group by ring opening of the glycidyl group.
- alkyl it is preferable from the viewpoint of characteristics as a dopant when copolymerized with styrenesulfonic acid.
- Examples of the unsaturated hydrocarbon-containing alkoxysilane compound or a hydrolyzate thereof include, for example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3- Methacryloxypropyldimethylethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxymethyldimethoxysilane, 3-acryloxymethyldiethoxysilane, 3-acryloxytriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, p-styrylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxy Silane, can be used an unsaturated hydrocarbon containing alkoxysilane compound
- the unsaturated hydrocarbon-containing alkoxysilane compound is the above-mentioned 3-methacryloxypropyltrimethoxysilane
- the hydrolyzate of the unsaturated hydrocarbon-containing alkoxysilane compound is converted into a hydroxyl group by hydrolysis of the methoxy group.
- the resulting structure is 3-methacryloxytrihydroxysilane, or silanes are condensed to form an oligomer, and a compound having a structure in which a methoxy group not used in the reaction is converted into a hydroxyl group is obtained.
- Examples of the unsaturated hydrocarbon-containing alkoxysilane compound include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrimethoxysilane, and the like. It is preferable from the standpoint of properties as a dopant when copolymerized.
- Styrene in a copolymer of this styrene sulfonic acid and at least one non-sulfonic acid monomer selected from the group consisting of methacrylic acid esters, acrylic acid esters and unsaturated hydrocarbon-containing alkoxysilane compounds or hydrolysates thereof As a ratio of sulfonic acid and at least one non-sulfonic acid monomer selected from the group consisting of methacrylic acid ester, acrylic acid ester and unsaturated hydrocarbon-containing alkoxysilane compound or a hydrolyzate thereof, It is preferably 1: 0.01 to 0.1: 1.
- the molecular weight is preferably about 5,000 to 500,000 in terms of weight average molecular weight from the viewpoint of water solubility and characteristics as a dopant, and more preferably about 40,000 to 200,000 in terms of weight average molecular weight.
- a copolymer of this styrene sulfonic acid and a non-sulfonic acid monomer can also be used in combination with a polymer anion such as the above-mentioned polystyrene sulfonic acid, sulfonated polyester, phenol sulfonic acid novolak resin, and the styrene sulfonic acid. It is also possible to use a mixture of a conductive polymer dispersion synthesized using a copolymer of sulfonic acid and a non-sulfonic acid monomer as a dopant and a conductive polymer dispersion synthesized using the polymer sulfonic acid as a dopant. .
- Copolymers of at least one non-sulfonic acid monomer selected from the group consisting of alkoxysilane compounds or hydrolysates thereof, etc. are all aqueous liquids comprising water or a mixture of water and a water-miscible solvent. Oxidative polymerization is water-soluble. Or carried out in aqueous solution.
- water-miscible solvent constituting the aqueous liquid examples include methanol, ethanol, propanol, acetone, acetonitrile, and the like.
- the mixing ratio of these water-miscible solvents with water is 50 in the entire aqueous liquid. The mass% or less is preferable.
- Either chemical oxidative polymerization or electrolytic oxidative polymerization can be employed as the oxidative polymerization for producing the conductive polymer.
- persulfate is used as an oxidizing agent in performing chemical oxidative polymerization.
- the persulfate include ammonium persulfate, sodium persulfate, potassium persulfate, calcium persulfate, and barium persulfate. Is used.
- the conditions during the polymerization are not particularly limited, but the temperature during chemical oxidative polymerization is preferably 5 ° C. to 95 ° C., more preferably 10 ° C. to 30 ° C., and polymerization
- the time is preferably 1 hour to 72 hours, more preferably 8 hours to 24 hours.
- Electrolytic oxidation polymerization is be carried out even at a constant voltage at a constant current, for example, when performing electrolytic oxidation polymerization at a constant current, preferably 0.05mA / cm 2 ⁇ 10mA / cm 2 as the current value, 0.2 mA / cm 2 to 4 mA / cm 2 is more preferable.
- the voltage is preferably 0.5 V to 10 V, more preferably 1.5 V to 5 V.
- the temperature during the electrolytic oxidation polymerization is preferably 5 ° C to 95 ° C, particularly preferably 10 ° C to 30 ° C.
- the polymerization time is preferably 1 hour to 72 hours, more preferably 8 hours to 24 hours.
- ferrous sulfate or ferric sulfate may be added as a catalyst.
- the conductive polymer obtained as described above is obtained immediately after polymerization in a state of being dispersed in water or an aqueous liquid, and includes persulfate as an oxidizing agent, iron sulfate used as a catalyst, and decomposition products thereof. Contains. Therefore, it is preferable to remove the metal component with a cation exchange resin after the impurities are dispersed by applying a dispersion of the conductive polymer containing the impurities to a dispersing machine such as an ultrasonic homogenizer, a high-pressure homogenizer, or a planetary ball mill.
- a dispersing machine such as an ultrasonic homogenizer, a high-pressure homogenizer, or a planetary ball mill.
- the particle size of the conductive polymer measured by the dynamic light scattering method at this time is preferably 100 ⁇ m or less, more preferably 10 ⁇ m or less, 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more. Then, it is preferable to remove what was produced
- an electrolytic capacitor using a conductive polymer obtained by oxidative polymerization of a monomer such as thiophene or a derivative thereof using an oxidizing agent / dopant for producing a conductive polymer as described above or a solution thereof as an electrolyte In addition, an electrolytic capacitor using the above conductive polymer and a conductive polymer obtained from a dispersion of a ⁇ -conjugated conductive polymer having a polymer anion as a dopant as an electrolyte May be configured. Further, they include a conductive auxiliary liquid containing a high boiling point organic solvent having a boiling point of 150 ° C. or higher or a high boiling point organic solvent having a boiling point of 150 ° C. or higher and an aromatic compound having at least one hydroxyl group or carboxyl group. An electrolytic capacitor may be configured.
- an electrolytic capacitor is formed using a conductive polymer obtained from a dispersion of a conductive polymer as an electrolyte, a monomer such as thiophene or a derivative thereof using an oxidizing agent / dopant for manufacturing a conductive polymer or a solution thereof.
- the leakage current of the electrolytic capacitor can be further reduced as compared with the case where the electrolytic capacitor is configured by using only the conductive polymer obtained by oxidative polymerization of as an electrolyte.
- a conductive auxiliary liquid containing a high boiling point organic solvent having a boiling point of 150 ° C. or higher or a high boiling point organic solvent having a boiling point of 150 ° C. or higher and an aromatic compound having at least one hydroxyl group or carboxyl group is included. If an electrolytic capacitor is configured, the ESR of the electrolytic capacitor can be further reduced and the heat resistance can be further improved.
- the above-mentioned conductive auxiliary liquid is a conductive solution whose conductivity (electrical conductivity) is lower than that of a normal electrolytic solution (usually having a conductivity of 3 mS / cm or more), and the conductivity is equal to or higher than that of the electrolytic solution. It is a concept including a conductive solution, or by forming an electrolytic capacitor including such a conductive solution, a boiling point of 150% which does not include an aromatic compound having at least one hydroxyl group or carboxyl group.
- the ESR of the electrolytic capacitor can be made lower and the heat resistance can be made better than when the electrolytic capacitor is configured by including a high boiling point organic solvent at or above ° C.
- the conductive auxiliary liquid is characterized in that even if the conductivity is lower than that of the electrolytic solution, the ESR of the electrolytic capacitor can be further lowered and the heat resistance can be further improved. If the conductivity is 1 ⁇ S / cm or more, it can be used, the conductivity is more preferably 5 ⁇ S / cm or more, and the conductivity is more preferably 8 ⁇ S / cm or more.
- the conductivity of the conductive auxiliary liquid is measured at a temperature of 25 ° C. with a conductivity measuring instrument (F-55) manufactured by Horiba, Ltd., but may be measured with an equivalent conductivity measuring instrument. .
- the conductive auxiliary liquid includes a high-boiling organic solvent having a boiling point of 150 ° C. or higher and an aromatic compound having at least one hydroxyl group or carboxyl group.
- Examples of the high-boiling organic solvent having a boiling point of 150 ° C. or higher as described above include ⁇ -butyrolactone (boiling point: 203 ° C.), butanediol (boiling point: 230 ° C.), dimethyl sulfoxide (boiling point: 189 ° C.), sulfolane (boiling point).
- Polyethylene glycol may have no boiling point under normal pressure, such as polyethylene glycol 600 and polyethylene glycol 1500 (the number after polyethylene glycol represents molecular weight), but any polyethylene glycol may be used. Since there is nothing that boils below 150 ° C. under normal pressure, this polyethylene glycol is also included in the category of high-boiling organic solvents having a boiling point of 150 ° C. or higher.
- Such a high-boiling organic solvent having a boiling point of 150 ° C. or higher is used as a solvent for dissolving an aromatic compound having at least one hydroxyl group or carboxyl group in the conductive auxiliary liquid.
- the use of such a high-boiling organic solvent has the effect of lowering the ESR of the electrolytic capacitor and improving the heat resistance, as described above. This is because an increase in internal pressure during soldering when manufacturing an electrolytic capacitor can be suppressed and volatilization of the organic solvent can be suppressed over a long period of time.
- the hydroxyl group in the aromatic compound having at least one hydroxyl group means a hydroxyl group bonded to the constituent carbon of the aromatic ring, and does not mean an —OH moiety such as in a carboxyl group.
- the aromatic compound having at least one hydroxyl group or carboxyl group any of benzene-based compounds, naphthalene-based compounds, and anthracene-based compounds can be used.
- hydroxy Benzene carboxylic acid nitrophenol, dinitrophenol, trinitrophenol, aminonitrophenol, hydroxyanisole, hydroxydinitrobenzene, dihydroxydinitrobenzene, alkylhydroxyanisole, hydroxynitroanisole, hydroxynitrobenzenecarboxylic acid (ie hydroxynitrobenzoic acid), Dihydroxynitrobenzenecarboxylic acid (ie, dihydroxynitrobenzoic acid), phenol, dihydroxybenzene, trihydroxybenzene, di- Droxybenzenecarboxylic acid, trihydroxybenzenecarboxylic acid, hydroxybenzenedicarboxylic acid, dihydroxybenzenedicarboxylic acid, hydroxytoluenecarboxylic acid, nitronaphthol, aminonaphthol, dinitronaphthol, hydroxynaphthalenecarboxylic acid, dihydroquinaphthalenecarboxylic acid, trihydroxynaphthalene Carboxylic acid,
- an aromatic compound having at least one hydroxyl group or carboxyl group is used because the aromatic compound having at least one hydroxyl group or carboxyl group is an electron conducting agent of the conductive polymer. This is because the deterioration of the conductive polymer can be suppressed by the antioxidant action of the aromatic compound.
- a high boiling point organic solvent having a boiling point of 150 ° C. or more serves as a solvent
- an aromatic compound having at least one hydroxyl group or carboxyl group serves as a solute.
- the concentration in the conductive auxiliary liquid of the aromatic compound having at least one or more is preferably 0.5 to 50% by mass, within that range, more preferably 2% by mass or more, and further preferably 5% by mass or more, Moreover, 30 mass% or less is more preferable, and 20 mass% or less is further more preferable. That is, when the concentration of the aromatic compound having at least one hydroxyl group or carboxyl group is lower than the above, the ESR of the electrolytic capacitor is not lowered as expected, and the heat resistance is not improved. When the concentration of the aromatic compound having at least one hydroxyl group or carboxyl group is higher than the above, precipitation of the aromatic compound is likely to occur and handling becomes difficult, and ESR of the electrolytic capacitor is deteriorated. There is a fear.
- At least one binder selected from the group consisting of an epoxy compound or a hydrolyzate thereof, a silane compound or a hydrolyzate thereof and a polyalcohol is added to the high boiling point organic solvent having a boiling point of 150 ° C. or higher or a conductive auxiliary liquid. If it is contained, the effect of improving the voltage resistance of the electrolytic capacitor is increased, which is preferable.
- the concentration of the binder in the high-boiling organic solvent or conductive auxiliary liquid having a boiling point of 150 ° C. or higher is preferably 0.05 to 20% by mass, and more preferably 0.5 to 5% by mass.
- Examples of the epoxy compound or a hydrolyzate thereof include polyethylene glycol diglycidyl ether, diethylene glycol glycidyl, glycidyl methacrylate, epoxy propanol (that is, glycidol), methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, and butyl glycidyl.
- epoxybutane ie glycidylmethane
- epoxypentane ie glycidylethane
- epoxyhexane ie glycidylpropane
- epoxyheptane ie glycidylbutane
- epoxyoctane ie glycidylpentane
- epoxycyclohexene Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene Cole diglycidyl ether, pentylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, glycerin diglycidyl ether and the like.
- silane compound or a hydrolyzate thereof examples include 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropylmethyl Examples include polymethoxysilane, 3-isocyanatopropyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, silica sol, etc. Ethylene glycol, polypropylene glycol, and polybutylene glycol.
- Example shows an electrolytic capacitor manufactured using an oxidizing agent / dopant solution for manufacturing a conductive polymer and a conductive polymer manufactured using the same as an electrolyte.
- Oxidizing Agent / Dopant Solution for Conductive Polymer Production (1) In the preparation (1) of this oxidant / dopant solution for producing a conductive polymer (hereinafter sometimes referred to simply as “oxidant / dopant solution”), the oxidant / dopant solution of Examples 1 to 30 and It shows about the oxidizing agent and dopant solution of the comparative example 1. These oxidizing agent / dopant solutions of Examples 1 to 30 are used in the manufacture of the tantalum electrolytic capacitors of Examples 31 to 60 described later, and the oxidizing agent / dopant solution of Comparative Example 1 is the tantalum of Comparative Example 2 described later. It is used in the manufacture of electrolytic capacitors.
- Example 1 10 kg of an ethanol solution (water content 1%) in which 5.7 kg of ferric naphthalene sulfonate (molar ratio of iron to naphthalene sulfonic acid 1: 2.70) was dissolved was prepared.
- Example 2 Instead of 10 kg ethanol solution in which 5.7 kg ferric naphthalene sulfonate was dissolved, 4.7 kg ferric naphthalene sulfonate (molar ratio of iron to naphthalene sulfonic acid 1: 2.70) and 1 kg methane All operations were the same as in Example 1 except that 10 kg of an ethanol solution (water content 1%) in which ferric sulfonate (molar ratio of iron and methanesulfonic acid was 1: 2.70) was used. And an oxidant / dopant solution was prepared.
- Example 2 As in Example 1, 300 g of dibutyl phosphate was added to the oxidizing agent / dopant solution of Example 2, and the amount of dibutyl phosphate added was determined by using ferric naphthalene sulfonate and methane sulfonic acid. It is 5.26% with respect to ferric organic sulfonate consisting of ferric iron.
- Example 3 Instead of 10 kg of ethanol solution in which 5.7 kg of ferric naphthalene sulfonate was dissolved, 4.7 kg of paratoluenesulfonic acid ferric acid (molar ratio of iron to paratoluenesulfonic acid 1: 2.70) and 1 kg The same as Example 1 except that 10 kg of an ethanol solution (water content 1%) in which ferric methanesulfonate (molar ratio of iron to methanesulfonate 1: 2.70) was dissolved was used. Operation was performed to prepare an oxidant / dopant solution.
- Example 2 As in Example 1, 300 g of dibutyl phosphate was added to the oxidant / dopant solution of Example 3, and the amount of dibutyl phosphate added was paratoluenesulfonic acid ferric acid and methanesulfone. It is 5.26% with respect to ferric organic sulfonate which consists of ferric acid.
- Example 4 Instead of 10 kg ethanol solution in which 5.7 kg ferric naphthalene sulfonate was dissolved, 4.7 kg ferric naphthalene sulfonate (molar ratio of iron to naphthalene sulfonic acid 1: 2.70) and 1 kg paraffin were added. Except for using 10 kg of an ethanol solution (water content: 1%) in which ferric toluenesulfonate (molar ratio of iron to p-toluenesulfonic acid is 1.2.70) was used, all were the same as in Example 1. Operation was performed to prepare an oxidant / dopant solution.
- Example 2 As in Example 1, 300 g of dibutyl phosphate was added to the oxidizing agent / dopant solution of Example 4, and the amount of dibutyl phosphate added was determined by using ferric naphthalene sulfonate and paratoluene sulfone. It is 5.26% with respect to ferric organic sulfonate which consists of ferric acid.
- Example 5 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 300 g of tributyl phosphate was added instead of 300 g of dibutyl phosphate.
- the addition amount of tributyl phosphate in the oxidizing agent / dopant solution of Example 5 is 5.26% with respect to ferric naphthalene sulfonate.
- Example 6 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 500 g of dibutyl phosphate was added instead of 300 g of dibutyl phosphate. The addition amount of dibutyl phosphate in the oxidizing agent / dopant solution of Example 6 is 8.77% with respect to ferric naphthalene sulfonate.
- Example 7 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 100 g of dibutyl phosphate was added instead of 300 g of dibutyl phosphate. The addition amount of dibutyl phosphate in the oxidizing agent / dopant solution of Example 7 is 1.75% with respect to ferric naphthalene sulfonate.
- Example 8 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 200 g of phosphoric acid was added instead of 300 g of dibutyl phosphate. The addition amount of phosphoric acid in the oxidizing agent / dopant solution of Example 8 is 3.51% with respect to ferric naphthalene sulfonate.
- Example 9 An oxidizing agent and dopant solution was prepared in the same manner as in Example 1 except that 200 g of phosphorous acid was added instead of 300 g of dibutyl phosphate. The addition amount of phosphorous acid in the oxidizing agent / dopant solution of Example 9 is 3.51% with respect to ferric naphthalene sulfonate.
- Example 10 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 300 g of dibutyl phosphite was added instead of 300 g of dibutyl phosphate.
- the addition amount of dibutyl phosphite in the oxidizing agent / dopant solution of Example 10 is 5.26% with respect to ferric naphthalene sulfonate.
- Example 11 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 300 g of tributyl phosphite was added instead of 300 g of dibutyl phosphate. The addition amount of tributyl phosphite in the oxidizing agent / dopant solution of Example 11 is 5.26% with respect to ferric naphthalene sulfonate.
- Example 12 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 200 g of boric acid was added instead of 300 g of dibutyl phosphate. The addition amount of boric acid in the oxidizing agent / dopant solution of Example 12 is 3.51% with respect to ferric naphthalene sulfonate.
- Example 13 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 200 g of tributyl borate was added instead of 300 g of dibutyl phosphate. The addition amount of tributyl borate in the oxidizing agent / dopant solution of Example 13 is 3.51% with respect to ferric naphthalene sulfonate.
- Example 14 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 300 g of diethylhexyl phosphate was added instead of 300 g of dibutyl phosphate. The addition amount of diethylhexyl phosphate in the oxidizing agent / dopant solution of Example 14 is 5.26% with respect to ferric naphthalenesulfonate.
- Example 15 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 200 g of dithiophosphoric acid was added instead of 300 g of dibutyl phosphate. The addition amount of dithiophosphoric acid in the oxidizing agent / dopant solution of Example 15 is 3.51% with respect to ferric naphthalene sulfonate.
- Example 16 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 200 g of diethylhexyl dithiophosphate was added instead of 300 g of dibutyl phosphate. The addition amount of diethylhexyl dithiophosphate in the oxidizing agent / dopant solution of Example 16 is 3.51% with respect to ferric naphthalenesulfonate.
- Example 17 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 200 g of thiophosphoric acid was added instead of 300 g of dibutyl phosphate. The amount of thiophosphoric acid added in the oxidizing agent / dopant solution of Example 17 is 3.51% with respect to ferric naphthalene sulfonate.
- Example 18 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 300 g of diethyl thiophosphate was added instead of 300 g of dibutyl phosphate.
- the addition amount of diethyl thiophosphate in the oxidizing agent / dopant solution of Example 18 is 5.26% with respect to ferric naphthalene sulfonate.
- Example 19 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 200 g of dimethyl phosphate was added instead of 300 g of dibutyl phosphate. The addition amount of dimethyl phosphate in the oxidizing agent / dopant solution of Example 19 is 3.51% with respect to ferric naphthalene sulfonate.
- Example 20 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 200 g of diethyl phosphate was added instead of 300 g of dibutyl phosphate. The addition amount of diethyl phosphate in the oxidizing agent / dopant solution of Example 20 is 3.51% with respect to ferric naphthalene sulfonate.
- Example 21 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 250 g of dipropyl phosphate was added instead of 300 g of dibutyl phosphate. The addition amount of dipropyl phosphate in the oxidizing agent / dopant solution of Example 21 is 4.39% with respect to ferric naphthalene sulfonate.
- Example 22 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 570 g of dibenzyl phosphate was added instead of 300 g of dibutyl phosphate.
- the addition amount of dibenzyl phosphate in the oxidizing agent / dopant solution of Example 22 is 10.00% with respect to ferric naphthalene sulfonate.
- Example 23 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 250 g of diphenyl phosphate was added instead of 300 g of dibutyl phosphate. The addition amount of diphenyl phosphate in the oxidizing agent / dopant solution of Example 23 is 4.39% with respect to ferric naphthalene sulfonate.
- Example 24 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 200 g of dimethyl phosphite was added instead of 300 g of dibutyl phosphate. The addition amount of dimethyl phosphite in the oxidizing agent / dopant solution of Example 24 is 3.51% with respect to ferric naphthalene sulfonate.
- Example 25 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 200 g of diethyl phosphite was added instead of 300 g of dibutyl phosphate. The addition amount of diethyl phosphite in the oxidizing agent / dopant solution of Example 25 is 3.51% with respect to ferric naphthalene sulfonate.
- Example 26 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 250 g of dipropyl phosphite was added instead of 300 g of dibutyl phosphate. The addition amount of dipropyl phosphite in the oxidizing agent / dopant solution of Example 26 is 4.39% with respect to ferric naphthalene sulfonate.
- Example 27 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 350 g of dibenzyl phosphite was added instead of 300 g of dibutyl phosphate. The addition amount of dibenzyl phosphite in the oxidizing agent / dopant solution of Example 27 is 6.14% with respect to ferric naphthalene sulfonate.
- Example 28 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 300 g of diphenyl phosphite was added instead of 300 g of dibutyl phosphate. The addition amount of diphenyl phosphite in the oxidizing agent / dopant solution of Example 28 is 5.26% with respect to ferric naphthalene sulfonate.
- Example 29 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 250 g of ethyl phosphate was added instead of 300 g of dibutyl phosphate.
- the addition amount of ethyl phosphate in the oxidizing agent / dopant solution of Example 29 is 4.39% with respect to ferric naphthalene sulfonate.
- Example 30 An oxidizing agent / dopant solution was prepared in the same manner as in Example 1 except that 250 g of ethyl phosphite was added instead of 300 g of dibutyl phosphate. The amount of ethyl phosphite added in the oxidizing agent / dopant solution of Example 30 is 4.39% with respect to ferric naphthalene sulfonate.
- Comparative Example 1 Except that 300 g of dibutyl phosphate was not added, the same operation as in Example 1 was carried out to prepare an oxidizing agent / dopant solution.
- the characteristics evaluation of the oxidizing agent / dopant solutions of Examples 1 to 30 and Comparative Example 1 prepared as described above were conducted using a conductive polymer produced by using them and using the conductive polymer as an electrolyte. This is done by measuring the characteristics of the tantalum electrolytic capacitors of Examples 31 to 60 and Comparative Example 2.
- Example 31 As a capacitor element of this tantalum electrolytic capacitor, a tantalum sintered body designed to have a rated voltage of 16 V, an ESR of 20 m ⁇ or less, a capacitance of 150 ⁇ F or more, and a leakage current of 100 ⁇ A or less was used.
- the capacitor element was immersed in a monomer solution prepared by adding 80 ml of ethanol to 20 ml of a mixture of 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene in a mass ratio of 4: 6. After a minute, it was pulled up and dried at room temperature for 10 minutes. Thereafter, the capacitor element was immersed in a diluted solution of oxidant / dopant diluted by adding 500 g of ethanol to 500 g of the oxidant / dopant solution of Example 1, pulled up after 30 seconds, and allowed to stand at room temperature for 80 minutes for polymerization. And a conductive polymer layer was formed.
- the capacitor element having the conductive polymer layer formed as described above was immersed in pure water, allowed to stand for 30 minutes, then pulled up and dried at 105 ° C. for 30 minutes. This operation was repeated 10 times. Thereafter, the capacitor element was immersed in the oxidant / dopant solution of Example 1, pulled up after 30 seconds, and dried at 50 ° C. for 10 minutes, and 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene were added in mass. It was immersed in a mixed solution mixed at a ratio of 4: 6, pulled up after 1 minute, and allowed to stand at room temperature for 80 minutes for polymerization to form a conductive polymer layer.
- the capacitor element having the conductive polymer layer formed as described above was immersed in pure water, allowed to stand for 30 minutes, then pulled up and dried at 150 ° C. for 30 minutes. After repeating this operation three times, the electrolyte layer made of a conductive polymer was covered with a carbon paste and a silver paste, and was covered with an exterior material, whereby the tantalum electrolytic capacitor of Example 1 was manufactured.
- Examples 32 to 60 and Comparative Example 2 In place of the oxidizing agent / dopant solution of Example 1 above, the oxidizing agent / dopant solution of Examples 2 to 30 and Comparative Example 1 were used separately, and the other operations were performed in the same manner as in Example 31.
- the tantalum electrolytic capacitors of Examples 32 to 60 and Comparative Example 2 using the oxidizing agent / dopant solution were prepared.
- ESR Using an LCR meter (4284A) manufactured by HEWLETT PACKARD, measurement is performed at 100 kHz under the condition of 25 ° C.
- Capacitance Using an LCR meter (4284A) manufactured by HEWLETT PACKARD, measurement is performed at 120 Hz under the condition of 25 ° C.
- Leak current A voltage of 16 V is applied to the capacitor at 25 ° C. for 60 seconds, and then the leakage current is measured with a digital oscilloscope.
- the tantalum electrolytic capacitors of Examples 31 to 60 had an ESR of 15.0 to 15.6 m ⁇ . Satisfying the set ESR of 20 m ⁇ or less, the capacitance of 156 to 166 ⁇ F, the set capacitance of 150 ⁇ F or more, the leakage current of 14 to 30 ⁇ A, and the set leakage current of 100 ⁇ A or less. As compared with the capacitor of Comparative Example 2 whose characteristics are shown in Table 2, the leakage current was much smaller.
- the capacitors of Examples 31 to 60 are equivalent to or better than the capacitor of Comparative Example 2 with respect to ESR and capacitance, and Comparative Example 2 does not cause deterioration in characteristics with respect to ESR and capacitance. Compared with the capacitor, leakage current could be greatly reduced.
- Oxidizing Agent / Dopant Solution for Conducting Polymer Production (2) In the preparation (2) of the oxidant / dopant solution for producing a conductive polymer (hereinafter sometimes referred to simply as “oxidant / dopant solution”), the oxidant / dopant solution of Examples 61 to 91 and The oxidizing agent / dopant solutions of Comparative Examples 3 to 4 are shown. These oxidizing agent / dopant solutions are used for manufacturing the wound aluminum electrolytic capacitors of Examples 92 to 122 and Comparative Examples 5 to 6 described later.
- Example 61 10 kg of an ethanol solution (water content 1%) in which 5.7 kg of ferric naphthalene sulfonate (molar ratio of iron to naphthalene sulfonic acid 1: 2.70) was dissolved was prepared.
- the addition amount of dibutyl phosphate in the oxidizing agent / dopant solution of Example 61 is 5.26% with respect to ferric naphthalene sulfonate, and the addition amount of glycerin diglycidyl ether is with respect to ferric naphthalene sulfonate. 17.54%.
- Example 62 Instead of 10 kg ethanol solution in which 5.7 kg ferric naphthalene sulfonate was dissolved, 4.7 kg ferric naphthalene sulfonate (molar ratio of iron to naphthalene sulfonic acid 1: 2.70) and 1 kg methane
- an oxidant / dopant solution was prepared.
- Example 61 As in Example 61, 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether were added to the oxidizing agent / dopant solution of Example 62.
- the amount of dibutyl phosphate added was the amount of naphthalenesulfonic acid
- the amount of glycerin diglycidyl ether added is 5.26% with respect to ferric organic sulfonate composed of ferric iron and ferric methanesulfonate, and the amount of glycerin diglycidyl ether added is ferric naphthalene sulfonate and ferric methanesulfonate. And 17.54% based on ferric organic sulfonate.
- Example 63 Instead of 10 kg of ethanol solution in which 5.7 kg of ferric naphthalene sulfonate was dissolved, 4.7 kg of paratoluenesulfonic acid ferric acid (molar ratio of iron to paratoluenesulfonic acid 1: 2.70) and 1 kg Except for using 10 kg of an ethanol solution (water content: 1%) in which ferric methanesulfonate (molar ratio of iron and methanesulfonate: 1.2.70) was dissolved, the same as Example 61 Operation was performed to prepare an oxidizing agent / dopant solution.
- Example 61 As in Example 61, 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether were added to the oxidizing agent / dopant solution of Example 63.
- the amount of dibutyl phosphate added was paratoluenesulfone.
- the amount of glycerin diglycidyl ether added is 5.26% with respect to ferric sulfonate composed of ferric acid and ferric methanesulfonate. It is 17.54% based on ferric organic sulfonate composed of diiron.
- Example 64 Instead of 10 kg ethanol solution in which 5.7 kg ferric naphthalene sulfonate was dissolved, 4.7 kg ferric naphthalene sulfonate (molar ratio of iron to naphthalene sulfonic acid 1: 2.70) and 1 kg paraffin were added. Except for using 10 kg of an ethanol solution (water content: 1%) in which ferric toluenesulfonate (molar ratio of iron to p-toluenesulfonic acid is 1.2.70) was used, all the same as Example 61 Operation was performed to prepare an oxidant / dopant solution.
- Example 61 As in Example 61, 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether were added to the oxidizing agent / dopant solution of Example 64.
- the amount of dibutyl phosphate added was the amount of naphthalenesulfonic acid
- the amount of glycerin diglycidyl ether added is 5.26% with respect to ferric organic sulfonate composed of ferric iron and ferric paratoluenesulfonate. It is 17.54% with respect to ferric organic sulfonate which consists of iron.
- Example 65 The same procedure as in Example 61 was performed except that 300 g of diethylhexyl phosphate and 1 kg of cresyl glycidyl ether were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. Was prepared.
- the addition amount of diethylhexyl phosphate in the oxidizing agent / dopant solution of Example 65 was 5.26% with respect to ferric naphthalene sulfonate, and the addition amount of cresyl glycidyl ether was added to ferric naphthalene sulfonate. Compared to 17.54%.
- Example 66 Except for adding 300 g of diethyl hexyl phosphate and 1 kg of glycidyl methacrylate in place of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether, all operations were performed in the same manner as in Example 61 to obtain an oxidizing agent / dopant solution. Prepared.
- the addition amount of diethylhexyl phosphate in the oxidizing agent / dopant solution of Example 66 was 5.26% with respect to ferric naphthalene sulfonate, and the addition amount of glycidyl methacrylate was with respect to ferric naphthalene sulfonate. 17.54%.
- Example 67 Implemented except that 300 g of diethyl hexyl phosphate, 500 g of glycidyl methacrylate and 500 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. The same operation as in Example 61 was performed to prepare an oxidizing agent / dopant solution.
- the addition amount of diethylhexyl phosphate in the oxidizing agent / dopant solution of Example 67 was 5.26% with respect to ferric naphthalene sulfonate, and the addition amount of glycidyl methacrylate was with respect to ferric naphthalene sulfonate.
- the amount of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane added is 8.77% with respect to ferric naphthalene sulfonate.
- Example 68 An oxidizing agent / dopant solution was prepared in the same manner as in Example 61 except that 500 g of dibutyl phosphate was added instead of 300 g of dibutyl phosphate.
- the amount of dibutyl phosphate added in the oxidizing agent / dopant solution of Example 68 is 8.77% with respect to ferric naphthalene sulfonate.
- 1 kg of glycerin diglycidyl ether was added as in Example 61, but the addition amount of the glycerin diglycidyl ether to ferric naphthalene sulfonate was 17.54%.
- Example 69 An oxidizing agent / dopant solution was prepared in the same manner as in Example 61 except that 100 g of dibutyl phosphate was added instead of 300 g of dibutyl phosphate.
- the amount of dibutyl phosphate added in the oxidizing agent / dopant solution of Example 69 is 1.75% with respect to ferric naphthalene sulfonate. And in this oxidizing agent and dopant solution of Example 69, 1 kg of glycerin diglycidyl ether was added as in Example 61, but the addition amount of the glycerin diglycidyl ether to ferric naphthalene sulfonate was 17.54%.
- Example 70 An oxidizing agent / dopant solution was prepared in the same manner as in Example 61 except that 200 g of phosphoric acid was added instead of 300 g of dibutyl phosphate.
- the amount of phosphoric acid added in the oxidizing agent / dopant solution of Example 70 is 3.51% with respect to ferric naphthalene sulfonate. And, in the oxidizing agent / dopant solution of Example 70, 1 kg of glycerin diglycidyl ether was added as in Example 61. The amount of glycerin diglycidyl ether added to ferric naphthalene sulfonate was 17.54%.
- Example 71 An oxidizing agent / dopant solution was prepared in the same manner as in Example 61 except that 200 g of phosphorous acid was added instead of 300 g of dibutyl phosphate.
- the amount of phosphorous acid added in the oxidizing agent / dopant solution of Example 71 is 3.51% with respect to ferric naphthalene sulfonate. And, in this oxidizing agent / dopant solution of Example 71, 1 kg of glycerin diglycidyl ether was added as in Example 61. The amount of glycerin diglycidyl ether added to ferric naphthalene sulfonate was 17.54%.
- Example 72 An oxidizing agent / dopant solution was prepared in the same manner as in Example 61 except that 300 g of dibutyl phosphite was added instead of 300 g of dibutyl phosphate.
- the amount of dibutyl phosphite added in the oxidizing agent / dopant solution of Example 72 is 5.26% with respect to ferric naphthalene sulfonate. And in this oxidizing agent and dopant solution of Example 72, 1 kg of glycerin diglycidyl ether was added as in Example 61, but the addition amount of the glycerin diglycidyl ether to ferric naphthalene sulfonate was 17.54%.
- Example 73 An oxidizing agent / dopant solution was prepared in the same manner as in Example 61 except that 300 g of tributyl phosphite was added instead of 300 g of dibutyl phosphate.
- the amount of tributyl phosphite added in the oxidizing agent / dopant solution of Example 73 is 5.26% with respect to ferric naphthalene sulfonate. And in this oxidizing agent and dopant solution of Example 73, 1 kg of glycerin diglycidyl ether was added as in Example 61, but the addition amount of the glycerin diglycidyl ether to ferric naphthalene sulfonate was 17.54%.
- Example 74 An oxidizing agent / dopant solution was prepared in the same manner as in Example 61 except that 200 g of boric acid was added instead of 300 g of dibutyl phosphate.
- the amount of boric acid added in the oxidizing agent / dopant solution of Example 74 is 3.51% with respect to ferric naphthalene sulfonate. And, in the oxidizing agent / dopant solution of Example 74, 1 kg of glycerin diglycidyl ether was added as in Example 61. The amount of glycerin diglycidyl ether added to ferric naphthalene sulfonate was 17.54%.
- Example 75 An oxidizing agent / dopant solution was prepared in the same manner as in Example 61 except that 300 g of tributyl phosphate and 1 kg of glycidyl methacrylate were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. did.
- the addition amount of tributyl phosphate in the oxidizing agent / dopant solution of Example 75 was 5.26% with respect to ferric naphthalene sulfonate, and the addition amount of glycidyl methacrylate was with respect to ferric naphthalene sulfonate. 17.54%.
- Example 76 The same procedure as in Example 61 was performed except that 200 g of dithiophosphoric acid and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. Thus, an oxidizing agent / dopant solution was prepared.
- the addition amount of dithiophosphoric acid in the oxidizing agent / dopant solution of Example 76 was 3.51% with respect to ferric naphthalenesulfonate, and naphthalenesulfone of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
- the addition amount to ferric acid is 17.54%.
- Example 77 The same as Example 61, except that 200 g of diethyl hexyl dithiophosphate and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. Operation was performed to prepare an oxidant / dopant solution.
- the addition amount of diethylhexyl dithiophosphate in the oxidizing agent / dopant solution of Example 77 was 3.51% with respect to ferric naphthalene sulfonate, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane The amount of addition to ferric naphthalene sulfonate is 17.54%.
- Example 78 The same procedure as in Example 61 was performed except that 200 g of thiophosphoric acid and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. Thus, an oxidizing agent / dopant solution was prepared.
- the addition amount of thiophosphoric acid in the oxidizing agent / dopant solution of Example 78 was 3.51% with respect to ferric naphthalenesulfonate, and naphthalenesulfone of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
- the addition amount to ferric acid is 17.54%.
- Example 79 All operations were the same as in Example 61 except that 300 g of diethyl thiophosphate and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. To prepare an oxidizing agent / dopant solution.
- the addition amount of diethyl thiophosphate in the oxidizing agent / dopant solution of Example 79 was 5.26% with respect to ferric naphthalenesulfonate, and naphthalene of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
- the amount of addition to ferric sulfonate is 17.54%.
- Example 80 Except for adding 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether, the same procedure as in Example 61 was performed except that 200 g of dimethyl phosphate and 1 kg of 3-glycidoxypropyltrimethoxysilane were added. An agent / dopant solution was prepared.
- the addition amount of dimethyl phosphate in the oxidizing agent / dopant solution of Example 80 was 3.51% with respect to ferric naphthalenesulfonate, and the addition amount of 3-glycidoxypropyltrimethoxysilane was naphthalenesulfonic acid. 17.54% relative to ferric iron.
- Example 81 Implemented except that 200 g of diethyl phosphate and 1 kg of epoxy polysiloxane “X-41-1053” (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. The same operation as in Example 61 was performed to prepare an oxidizing agent / dopant solution.
- the addition amount of diethyl phosphate in the oxidizing agent / dopant solution of Example 81 was 3.51% with respect to ferric naphthalene sulfonate, and the above-mentioned epoxy polysiloxane “X-41-1053” (trade name)
- the amount of addition to ferric naphthalene sulfonate is 17.54%.
- Example 82 Except for adding 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether, everything was carried out except that 250 g of dipropyl phosphate and 1 kg of epoxy polysiloxane “X-41-1056” (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. were added. The same operation as in Example 61 was performed to prepare an oxidizing agent / dopant solution.
- the addition amount of dipropyl phosphate in the oxidizing agent / dopant solution of Example 82 was 4.39% with respect to ferric naphthalene sulfonate, and the above-mentioned epoxy polysiloxane “X-41-1056” (trade name)
- the amount of addition to ferric naphthalene sulfonate is 17.54%.
- Example 83 All operations were the same as in Example 61 except that 570 g of dibenzyl phosphate and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. To prepare an oxidizing agent / dopant solution.
- the addition amount of dibenzyl phosphate in the oxidizing agent / dopant solution of Example 83 was 10.00% with respect to ferric naphthalene sulfonate, and the addition of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. The amount is 17.54% with respect to ferric naphthalene sulfonate.
- Example 84 The same procedure as in Example 61 except that 250 g of diphenyl phosphate and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. To prepare an oxidizing agent / dopant solution.
- the addition amount of diphenyl phosphate in the oxidizing agent / dopant solution of Example 84 was 4.39% with respect to ferric naphthalenesulfonate, and the addition of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. The amount is 17.54% with respect to ferric naphthalene sulfonate.
- Example 85 The same as Example 61 except that 200 g of dimethyl phosphite and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. Operation was performed to prepare an oxidant / dopant solution.
- the addition amount of dimethyl phosphite in the oxidizing agent / dopant solution of Example 85 was 3.51% with respect to ferric naphthalene sulfonate, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane The amount added is 17.54% with respect to ferric naphthalene sulfonate.
- Example 86 The same as Example 61 except that 200 g of diethyl phosphite and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. Operation was performed to prepare an oxidant / dopant solution.
- the addition amount of diethyl phosphite in the oxidizing agent / dopant solution of Example 86 was 3.51% with respect to ferric naphthalene sulfonate, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane The amount added is 17.54% with respect to ferric naphthalene sulfonate.
- Example 87 The same as Example 61 except that 250 g of dipropyl phosphite and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. Operation was performed to prepare an oxidant / dopant solution.
- the amount of dipropyl phosphite added to the oxidizing agent / dopant solution of Example 87 was 4.39% with respect to ferric naphthalene sulfonate, and the amount of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was The amount of addition to ferric naphthalene sulfonate is 17.54%.
- Example 88 The same as Example 61, except that 350 g of dibenzyl phosphite and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. Operation was performed to prepare an oxidant / dopant solution.
- the amount of dibenzyl phosphite added to the oxidizing agent / dopant solution of Example 88 was 6.14% with respect to ferric naphthalene sulfonate, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane The amount added is 17.54% with respect to ferric naphthalene sulfonate.
- Example 89 The same as Example 61 except that 300 g of dibutyl phosphite and 1 kg of glycerin diglycidyl ether were used instead of 300 g of diphenyl phosphite and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Operation was performed to prepare an oxidant / dopant solution.
- the addition amount of diphenyl phosphite in the oxidizing agent / dopant solution of Example 89 was 5.26% with respect to ferric naphthalene sulfonate, and the amount of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was The amount added is 17.54% with respect to ferric naphthalene sulfonate.
- Example 90 The same operation as in Example 61 except that 250 g of ethyl phosphate and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added instead of 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether. To prepare an oxidizing agent / dopant solution.
- the addition amount of ethyl phosphate in the oxidizing agent / dopant solution of Example 90 was 4.39% with respect to ferric naphthalenesulfonate, and the addition of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. The amount is 17.54% with respect to ferric naphthalene sulfonate.
- Example 91 The same as Example 61, except that 300 g of dibutyl phosphate and 1 kg of glycerin diglycidyl ether were used instead of 250 mg of ethyl phosphite and 1 kg of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Operation was performed to prepare an oxidant / dopant solution.
- the addition amount of ethyl phosphite in the oxidizing agent / dopant solution of Example 91 was 4.39% with respect to ferric naphthalene sulfonate, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane The addition amount is 17.54% with respect to ferric naphthalene sulfonate.
- Comparative Example 3 10 kg of an ethanol solution (water content: 1%) of ferric naphthalene sulfonate having a concentration of 57% (molar ratio of iron to naphthalene sulfonic acid 1: 2.70) was prepared. An agent / dopant solution was obtained. The oxidant / dopant solution of Comparative Example 3 is used in the manufacture of a wound aluminum electrolytic capacitor, and the composition thereof is the same as that of the oxidant / dopant solution of Comparative Example 1, and this comparison is made.
- Comparative Example 4 Except that 300 g of dibutyl phosphate was not added, the same operation as in Example 61 was performed to prepare an oxidizing agent / dopant solution. As in the oxidizing agent / dopant solution of Example 61, the oxidizer / dopant solution of Comparative Example 4 contains 17.54% of glycerin diglycidyl ether added to ferric naphthalene sulfonate. Dibutyl acid is not added.
- the characteristics evaluation of the oxidizing agent / dopant solutions of Examples 61 to 91 and Comparative Examples 3 to 4 prepared as described above were conducted by producing a conductive polymer and using the conductive polymer as an electrolyte. This is done by measuring the characteristics of the wound aluminum electrolytic capacitors of Examples 92 to 122 and Comparative Examples 5 to 6.
- Example 92 In Example 92, an example is shown in which a conductive polymer is manufactured using the oxidizing agent / dopant solution of Example 61, and a wound aluminum electrolytic capacitor is manufactured using the conductive polymer as an electrolyte.
- Etching the surface of the aluminum foil immersing the etched aluminum foil in a 12% aqueous ammonium solution, applying a voltage of 75 V to the aluminum foil in the aqueous ammonium solution, and applying an aluminum oxide film on the surface of the aluminum foil
- a dielectric layer is formed to form an anode, a lead terminal is attached to the anode, a lead terminal is attached to a cathode made of aluminum foil, and the anode with the lead terminal and the cathode are wound through a separator.
- a capacitor element for manufacturing a wound aluminum electrolytic capacitor having a set ESR of 30 m ⁇ or less, a set capacitance of 50 ⁇ F or more, a set leakage current of 100 ⁇ A or less, and a set breakdown voltage of 50 V or more was produced.
- the above capacitor element was immersed in a monomer solution prepared by adding 80 ml of ethanol to 20 ml of a mixed solution of 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene in a mass ratio of 4: 6 for 1 minute. Then, after lifting, it was dried at 50 ° C. for 10 minutes. Thereafter, the capacitor element was immersed in 100 ml of the oxidizing agent / dopant solution of Example 61 for 15 seconds, pulled up, heated at 70 ° C. for 2 hours, and 180 ° C.
- An electrolyte layer composed of a conductive polymer having a polymer skeleton of a copolymer of 1,4-ethylenedioxythiophene and butylated ethylenedioxythiophene is formed and packaged with an exterior material.
- a rotary aluminum electrolytic capacitor was manufactured.
- Examples 93 to 122 and Comparative Examples 5 to 6 In place of the oxidizing agent / dopant solution of Example 61 above, the oxidizing agent / dopant solutions of Examples 62 to 91 and Comparative Examples 3 to 4 were used separately, and the same operations as in Example 92 were performed except that. The wound aluminum electrolytic capacitors of Examples 93 to 122 and Comparative Examples 5 to 6 using the respective oxidizing agent / dopant solutions were produced.
- ESR wound type aluminum electrolytic capacitors
- capacitance leakage current
- the breakdown voltage was measured by using PRk650-2.5 manufactured by Matsusada Precision Co., Ltd. and increasing the voltage at a rate of 1 V / min at 25 ° C. The number of measurements is 10 for each sample, and the breakdown voltage values shown in Tables 3 to 4 are obtained by calculating an average of 10 values and rounding off the decimals.
- the capacitors of Examples 92 to 122 have an ESR of 17 to 20 m ⁇ , satisfy a set ESR of 30 m ⁇ or less, a capacitance of 52 to 55 ⁇ F, and 50 ⁇ F or more.
- the set capacitance is satisfied, the leakage current is 3 to 21 ⁇ A, the set leakage current is 100 ⁇ A or less, the breakdown voltage is 69 to 72 V, and the set breakdown voltage is 50 V or more.
- the leakage current was small.
- ESR is equal to or lower than that of Comparative Examples 5 to 6
- capacitance is equal to or higher than that of Comparative Examples 5 to 6, and ESR and The leakage current could be greatly reduced as compared with the capacitors of Comparative Examples 5 to 6 without causing deterioration of the characteristics regarding the capacity.
- the capacitors of Examples 92 to 122 are high, and even in a wound aluminum electrolytic capacitor that requires excellent voltage resistance, a high conductive property manufactured using the oxidizing agent and dopant of the present invention. It was clear that a wound aluminum electrolytic capacitor manufactured using a molecule as an electrolyte can sufficiently meet the requirements.
- Example 123 All the examples except that only the butylated ethylenedioxythiophene was used as the monomer instead of the monomer mixture obtained by mixing 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at a mass ratio of 4: 6
- the wound aluminum electrolytic capacitor of Example 123 was manufactured in the same manner as in Example 92.
- Example 124 All the examples except that only the butylated ethylenedioxythiophene was used as the monomer instead of the monomer mixture obtained by mixing 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at a mass ratio of 4: 6 The same operation as in Example 97 was performed to produce a wound aluminum electrolytic capacitor of Example 124.
- Example 125 All the examples except that only the butylated ethylenedioxythiophene was used as the monomer instead of the monomer mixture obtained by mixing 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at a mass ratio of 4: 6 The same operation as in No. 98 was performed to produce a wound aluminum electrolytic capacitor of Example 125.
- Comparative Example 7 The wound aluminum electrolytic capacitor of Comparative Example 7 was obtained by performing the same operation as in Example 123 except that the oxidizing agent / dopant solution of Comparative Example 3 was used instead of the oxidizing agent / dopant solution of Example 61. Manufactured.
- Comparative Example 8 The wound aluminum electrolytic capacitor of Comparative Example 8 was manufactured in the same manner as in Example 123 except that the oxidizing agent / dopant solution of Comparative Example 4 was used instead of the oxidizing agent / dopant solution of Example 61. Manufactured.
- the capacitors of Examples 123 to 125 each have an ESR of 20 m ⁇ , satisfy the set ESR of 30 m ⁇ or less, have a capacitance of 52 ⁇ F, and have a capacitance of 50 ⁇ F or more.
- the leakage currents are all 1 ⁇ A, satisfy the set leakage current of 100 ⁇ A or less, the breakdown voltage is 72 to 74 V, satisfy the set breakdown voltage of 50 V or more, and the capacitors of Comparative Examples 7 to 8 In comparison, there was less leakage current.
- the capacitors of Examples 123 to 125 have a slightly lower ESR than the capacitors of Comparative Examples 7 to 8, and have a slightly higher capacitance than the capacitors of Comparative Examples 7 to 8, resulting in deterioration in characteristics with respect to ESR and capacitance.
- the leakage current could be significantly reduced as compared with the capacitors of Comparative Examples 7-8.
- the capacitors of Examples 123 to 125 were high, and even in a wound aluminum electrolytic capacitor that required excellent voltage resistance, the requirements could be sufficiently met.
- the capacitor of Example 123 is similarly leaked compared to the capacitor of Example 92 using the oxidant / dopant solution of Example 61.
- the capacitor of Example 124 also has less leakage current than the capacitor of Example 97 using the oxidant and dopant solution of Example 66, and the capacitor of Example 125 is similarly implemented. Compared to the capacitor of Example 98 using the oxidant / dopant solution of Example 67, there was less leakage current.
- the capacitors of Example 123, Example 124, and Example 125 using only butylated ethylenedioxythiophene as the monomer were respectively 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene as monomers.
- the leakage current was smaller.
- a conductive polymer layer is formed by so-called “in-situ polymerization” to form a first electrolyte layer, and ⁇ conjugate is formed on the first electrolyte layer.
- the characteristic evaluation about the tantalum electrolytic capacitor which manufactured the conductive polymer layer formed using the dispersion liquid of a system conductive polymer as a 2nd electrolyte layer or a 2nd and 3rd electrolyte layer is shown.
- the reaction solution after the polymerization reaction is treated with an ultrafiltration device (Vivaflow 200 (trade name) manufactured by Sartorius, molecular weight fraction 50,000) to remove free low-molecular components in the solution, and water is added to the concentration. Adjusted to 3%.
- an ultrafiltration device Vivaflow 200 (trade name) manufactured by Sartorius, molecular weight fraction 50,000
- the treated liquid is passed through a filter having a pore size of 1 ⁇ m, and the passing liquid is treated with an ultrafiltration apparatus (Vivaflow 200 (trade name), molecular weight fraction 50,000, manufactured by Sartorius Co., Ltd.). Ingredients were removed. 3 g of dimethyl sulfoxide was added to 50 g of a solution obtained by diluting the treated solution with water to adjust the concentration to 2%, thereby obtaining a conductive polymer dispersion (I).
- an ultrafiltration apparatus Vivaflow 200 (trade name), molecular weight fraction 50,000, manufactured by Sartorius Co., Ltd.
- the mixture was diluted 4 times with water, and then subjected to a dispersion treatment for 30 minutes with an ultrasonic homogenizer [Nippon Seiki Co., Ltd., US-T300 (trade name)]. Thereafter, 100 g of cation exchange resin Amberlite 120B (trade name) manufactured by Organo Corporation was added and stirred with a stirrer for 1 hour. Filtered on 131. The operation from dispersion to filtration was repeated three times to remove all cationic components.
- the above filtrate was passed through a filter having a pore size of 1 ⁇ m, and free low-molecular components were removed from the passing solution using an ultrafiltration device (Vivaflow 200 (trade name) manufactured by Sartorius, molecular weight fraction 50,000). 4 g of dimethyl sulfoxide was added to 40 g of a liquid whose concentration was adjusted to 5% by adding water to this solution to obtain a dispersion (II) of a conductive polymer.
- Example 126 As the capacitor element for the tantalum electrolytic capacitor of Example 126, a tantalum sintered body designed to have a rated voltage of 16 V, an ESR of 20 m ⁇ or less, a capacitance of 150 ⁇ F or more, and a leakage current of 100 ⁇ A or less was used. .
- the capacitor element was immersed in a monomer solution prepared by adding 80 ml of ethanol to 20 ml of a mixture of 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene in a mass ratio of 4: 6. After a minute, it was pulled down and dried at room temperature for 10 minutes. Thereafter, the capacitor element was immersed in a diluted solution of oxidant / dopant diluted by adding and mixing 500 g of ethanol to 500 g of the oxidant / dopant solution of Example 1, pulled up after 30 seconds, and left at room temperature for 80 minutes. Polymerization was performed to form a conductive polymer layer.
- the capacitor element having the conductive polymer layer formed as described above was immersed in pure water, allowed to stand for 30 minutes, then pulled up and dried at 70 ° C. for 30 minutes. By repeating this operation four times, the high conductivity of the capacitor mixture by “in-situ polymerization” of a monomer mixture in which 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene were mixed at a mass ratio of 4: 6. A first electrolyte layer made of molecules was formed.
- dibutyl phosphate was 5% of ferric naphthalenesulfonate. 26% is added.
- the capacitor element on which the first electrolyte layer was formed was immersed in a conductive polymer dispersion (II) for 1 minute, pulled out, and dried at 150 ° C. for 30 minutes. This operation was repeated three times to form a second electrolyte layer based on impregnation and drying of the conductive polymer dispersion (II) on the first electrolyte layer by the above-mentioned “in situ polymerization”.
- the tantalum electrolytic capacitor of Example 126 was manufactured by covering the electrolyte layer with a carbon paste and a silver paste and covering with an exterior material.
- Example 127 In the same manner as in Example 126, the diluted solution of the oxidizing agent / dopant of Example 1 was used for the capacitor element similar to Example 126, and 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene were in a mass ratio. A first electrolyte layer made of a conductive polymer produced by polymerizing the monomer mixture mixed at 4: 6 was formed.
- the capacitor element having the first electrolyte layer was immersed in the conductive polymer dispersion (I) produced as described above for 2 minutes, pulled out, and dried at 150 ° C. for 30 minutes.
- the second electrolyte layer (hereinafter, referred to as “impregnated into the dispersion liquid (I) of the conductive polymer and dried) on the first electrolyte layer by the above-mentioned“ in situ polymerization ”. This was simplified to form “second electrolyte layer based on conductive polymer dispersion (I)”.
- the capacitor element is immersed in the conductive polymer dispersion (II) for 1 minute, pulled out, and then dried at 150 ° C. for 30 minutes, based on the conductive polymer dispersion (I). Impregnation of conductive polymer in dispersion liquid (II) on second electrolyte layer and third electrolyte layer based on drying [hereinafter referred to as “based on dispersion of conductive polymer (II)” The third electrolyte layer ”is formed.
- the above electrolyte layer was covered with a carbon paste and a silver paste, and was covered with an exterior material to produce a tantalum electrolytic capacitor of Example 127.
- the capacitors of Examples 126 to 127 have an ESR of 14.4 to 14.7 m ⁇ , satisfy a set ESR of 20 m ⁇ or less, a capacitance of 156 to 158 ⁇ F, and 150 ⁇ F or more. And the leakage current was 4 to 9 ⁇ A, and the setting leakage current of 100 ⁇ A or less was satisfied.
- Examples 126 to 127 When comparing the capacitors (tantalum electrolytic capacitors) of Examples 126 to 127 with the tantalum solid electrolytic capacitor of Example 31 using the oxidizing agent / dopant of Example 1 in the same manner, Examples 126 to The capacitor of 127 had a smaller leakage current than the capacitor of Example 31.
- the leakage current of the capacitor of Example 31 is 18 ⁇ A as shown in Table 1, whereas the leakage current of the capacitor of Example 126 is 9 ⁇ A as shown in Table 6, and the leakage of the capacitor of Example 127
- the current is 4 ⁇ A
- the leakage current of the capacitors of Examples 126 to 127 is smaller than the leakage current of the capacitor of Example 31, and is on the first electrolyte layer made of a conductive polymer by so-called “in situ polymerization”.
- the ferric organic sulfonate and phosphoric acid corresponding to the oxidizing agent / dopant solution for producing the conductive polymer of the present invention
- An oxidant / dopant solution for producing a conductive polymer containing an inorganic acid ester-based additive such as an ester or phosphite is formed, and the monomer is polymerized with the oxidant dopant solution for producing the conductive polymer to conduct electricity.
- a wound aluminum electrolytic capacitor is manufactured through a step of forming an electrolyte layer made of a conductive polymer, and its characteristics are evaluated.
- Example 128 Etching the surface of the aluminum foil, immersing the etched aluminum foil in a 12% aqueous ammonium solution, applying a voltage of 75 V to the aluminum foil in the aqueous ammonium solution, and applying an aluminum oxide film on the surface of the aluminum foil
- a dielectric layer is formed to form an anode, a lead terminal is attached to the anode, a lead terminal is attached to a cathode made of aluminum foil, and the anode with the lead terminal and the cathode are wound through a separator.
- the addition amount of glycerin diglycidyl ether in this oxidant / dopant solution is 17.54% with respect to ferric naphthalene sulfonate, and this oxidant / dopant solution is phosphorous from the oxidant / dopant solution of Example 61. It has the same structure as that excluding dibutyl acid.
- the capacitor element was immersed in 100 ml of the monomer solution prepared as described above for 60 seconds, pulled up, and then dried at 50 ° C. for 10 minutes. Since the ethanol is almost dried by this drying, 24% of the volume inside the capacitor element is filled with the monomer and dibutyl phosphate, and 4% of the volume is occupied by dibutyl phosphate.
- the capacitor element was immersed in 100 ml (110 g in mass) of an oxidizing agent / dopant solution not containing dibutyl phosphate prepared as described above, and then pulled up after 20 seconds. By this operation, 76% of the volume inside the capacitor element was filled with the oxidizing agent / dopant solution. Since the oxidant / dopant solution filled in the capacitor element is 0.076 ml and the specific gravity is 1.1, the mass of the oxidant / dopant solution filled in the capacitor element is 0.00.
- the mass of ferric naphthalene sulfonate filled in the capacitor element is 0.0433 g. .
- the mixture of the monomer and dibutyl phosphate filled in the capacitor element is 0.024 ml, and the dibutyl phosphate in 0.024 ml of the mixture of this monomer and dibutyl phosphate is 0.004 ml.
- Example 1208 Since the mass of the dibutyl phosphate is 0.00424 g as apparent from the above, in Example 128, the ferric naphthalene sulfonate and dibutyl phosphate filled in the capacitor element were used. The relationship corresponds to a case where 9.79% of dibutyl phosphate is added to ferric naphthalenesulfonate on a mass basis.
- the monomer is polymerized by heating at 70 ° C. for 2 hours and at 180 ° C. for 1 hour, so that a copolymer of 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene is used as a polymer skeleton.
- An electrolyte layer made of a conductive polymer was formed, and it was packaged with an exterior material to produce a wound aluminum electrolytic capacitor of Example 128.
- Example 129 9.32 kg of an ethanol solution (water content 1%) in which 3.9 kg of ferric naphthalene sulfonate (molar ratio of iron to naphthalene sulfonic acid 1: 2.70) was dissolved was prepared.
- diethyl hexyl phosphate (3 mass as the mass of diethyl hexyl phosphate) is added to 20 ml of the monomer mixture obtained by mixing 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at a mass ratio of 4: 6.
- diethyl hexyl phosphate 3 mass as the mass of diethyl hexyl phosphate
- Example 128 a capacitor element similar to that used in Example 128 was immersed in 100 ml of the oxidizing agent / dopant solution prepared as described above for 30 seconds, pulled up, and dried at 105 ° C. for 30 minutes. Since the ethanol was almost dried by this drying, about 31% of the volume inside the capacitor element was filled with a mixture of ferric naphthalene sulfonate and glycerin diglycidyl ether derived from the oxidizing agent / dopant solution.
- the specific gravity of this mixture of ferric naphthalene sulfonate and glycerin diglycidyl ether is about 1.48
- the mixture of ferric naphthalene sulfonate and glycerin diglycidyl ether filled inside the capacitor element The mass is about 0.046 g, and the mass of ferric naphthalene sulfonate filled inside the capacitor element is determined from the composition ratio of each component in the mixture of ferric naphthalene sulfonate and glycerin diglycidyl ether. And about 0.039 g.
- the capacitor element was immersed in 69 ml of a monomer solution containing diethylhexyl phosphate prepared as described above and pulled up after 10 seconds. By this operation, 69% of the volume inside the capacitor element was filled with the monomer solution.
- the monomer solution filled in the capacitor element in this way is 0.069 ml, and the volume occupied by diethylhexyl phosphate in this monomer solution is apparent from the amount of diethylexyl phosphate added at the time of preparing the monomer solution.
- ferric naphthalene sulfonate filled in the capacitor element was found to be 0.004 ml and the mass of diethylhexyl phosphate was 0.00386 g as apparent from the above. And diethylhexyl phosphate correspond to the addition of 9.90% diethylhexyl phosphate to ferric naphthalene sulfonate on a mass basis.
- the monomer is polymerized by heating at 70 ° C. for 2 hours and at 180 ° C. for 1 hour, so that a copolymer of 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene is used as a polymer skeleton.
- An electrolyte layer made of a conductive polymer was formed, and it was packaged with an exterior material to produce a wound aluminum electrolytic capacitor of Example 129.
- Example 130 4 ml of diphenyl phosphate (this corresponds to 3.04 g as the mass of diphenyl phosphate) with respect to 20 ml of the monomer mixture obtained by mixing 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at a mass ratio of 4: 6 To prepare a monomer solution.
- the monomer solution (24 ml) and the same oxidizing agent / dopant solution 76 ml (mass 83.6 g) used in Example 128 were mixed.
- a capacitor element similar to that used in Example 128 was immersed in 100 ml of the obtained mixed solution and pulled up after 30 seconds.
- 0.076 ml of the oxidizing agent / dopant solution and 0.024 ml of the monomer solution were filled in the capacitor element.
- the mass of the oxidizing agent / dopant solution 0.076 ml is 0.0836. From the composition ratio of each component of the oxidizing agent / dopant solution, the naphthalenesulfonic acid filled in the capacitor element is obtained.
- the mass of ferrous iron was determined to be 0.0433 g.
- diphenyl phosphate in 0.024 ml of the monomer solution is 0.004 ml
- the mass of 0.004 ml of diphenyl phosphate is 0.00034 g as described above.
- the relationship between ferric naphthalene sulfonate and diphenyl phosphate filled in the capacitor element corresponds to the addition of 7.02% diphenyl phosphate to ferric naphthalene sulfonate on a mass basis.
- the monomer is polymerized by heating at 70 ° C. for 2 hours and at 180 ° C. for 1 hour, so that a copolymer of 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene is used as a polymer skeleton.
- An electrolyte layer made of a conductive polymer was formed, and it was packaged with an exterior material to produce a wound aluminum electrolytic capacitor of Example 130.
- Example 131 A wound aluminum electrolytic capacitor of Example 131 was manufactured in the same manner as in Example 128 except that dibutyl phosphite was used in place of dibutyl phosphate.
- Example 132 A wound aluminum electrolytic capacitor of Example 132 was manufactured in the same manner as in Example 129 except that diethylhexyl phosphite was used instead of diethylhexyl phosphate.
- Example 133 A wound aluminum electrolytic capacitor of Example 133 was manufactured in the same manner as in Example 130 except that diphenyl phosphite was used in place of diphenyl phosphate.
- the capacitors of Examples 128 to 133 have an ESR of 17 to 20 m ⁇ , satisfy a set ESR of 30 m ⁇ or less, a capacitance of 52 to 55 ⁇ F, and a set electrostatic capacity of 50 ⁇ F or more. The capacity was satisfied, the leakage current was 5 to 10 ⁇ A, the set leakage current of 100 ⁇ A or less was satisfied, the breakdown voltage was 69 to 72 V, and the set breakdown voltage of 50 V or more was satisfied.
- the capacitors of Examples 128 to 133 had less leakage current and higher breakdown voltage than the capacitors of Comparative Examples 5 to 6 whose characteristics are shown in Table 4.
- Example of Preparation of Conductive Auxiliary Solution (1) 50 g of hydroxybenzenecarboxylic acid, 5 g of nitrobenzoic acid (ie, nitrobenzenecarboxylic acid) and 1 g of 3-glycidide in 500 g of ⁇ -butyrolactone placed in a 1 L beaker equipped with a stirrer After adjusting to pH 4 by adding xylpropyltrimethoxysilane and further adding ethylamine, a conductive auxiliary liquid (1) was prepared by stirring for 24 hours.
- this conductive auxiliary liquid (1) When the conductivity of this conductive auxiliary liquid (1) was measured under the condition of 25 ° C. with a conductivity meter (F-55) manufactured by Horiba, Ltd., the conductivity of this conductive auxiliary liquid (1) was It was 0.9 mS / cm.
- conductive auxiliary liquid (2) 50 g of phthalic acid, 5 g of nitrophenol and 5 g of polyethylene glycol diglycidyl ether are added to 500 g of ethylene glycol in a 1 L beaker equipped with a stirrer, and further ethylamine is added. After adjusting to pH 6, the conductive auxiliary liquid (2) was prepared by stirring for 24 hours.
- this conductive auxiliary liquid (2) When the conductivity of this conductive auxiliary liquid (2) was measured at 25 ° C. with a conductivity measuring instrument (F-55) manufactured by Horiba, Ltd., the conductivity of this conductive auxiliary liquid (2) was It was 0.5 mS / cm.
- this conductive auxiliary liquid (3) When the conductivity of this conductive auxiliary liquid (3) was measured under the condition of 25 ° C. with a conductivity meter (F-55) manufactured by Horiba, Ltd., the conductivity of this conductive auxiliary liquid (3) was It was 0.6 mS / cm.
- Example 134 Etching the surface of the aluminum foil, immersing the etched aluminum foil in a 12% aqueous ammonium solution, applying a voltage of 130 V to the aluminum foil in the aqueous ammonium solution, and applying an aluminum oxide film on the surface of the aluminum foil
- a dielectric layer is formed to form an anode, a lead terminal is attached to the anode, a lead terminal is attached to a cathode made of aluminum foil, and the anode with the lead terminal and the cathode are wound through a separator.
- a capacitor element for producing a wound aluminum electrolytic capacitor having a set ESR of 30 m ⁇ or less, a set capacitance of 30 ⁇ F or more, a set leakage current of 100 ⁇ A or less, and a set breakdown voltage of 65 V or more was produced.
- the capacitor element was immersed in a monomer solution prepared by adding 70 ml of ethanol to 30 ml of a mixed solution in which 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene were mixed at a mass ratio of 4: 6, After pulling up, it was dried at 50 ° C. for 10 minutes. Thereafter, the capacitor element was immersed in 100 ml of the oxidizing agent / dopant solution of Example 61 and pulled up, and then heated at 50 ° C. for 30 hours and at 180 ° C.
- the capacitor element is immersed in the conductive auxiliary liquid (1), After being pulled up, it was packaged with an exterior material to produce a wound aluminum electrolytic capacitor of Example 134.
- Example 135 A wound aluminum electrolytic capacitor of Example 135 was manufactured in the same manner as in Example 134 except that the conductive auxiliary liquid (2) was used instead of the conductive auxiliary liquid (1).
- Example 136 A wound aluminum electrolytic capacitor of Example 136 was manufactured in the same manner as in Example 134 except that the conductive auxiliary liquid (3) was used instead of the conductive auxiliary liquid (1).
- Example 137 The wound aluminum electrolytic capacitor of Example 137 was the same as Example 134 except that the oxidant / dopant solution of Example 66 was used instead of the oxidant / dopant solution of Example 61. Manufactured.
- Example 138 A wound aluminum electrolytic capacitor of Example 138 was produced in the same manner as in Example 137 except that the conductive auxiliary liquid (2) was used instead of the conductive auxiliary liquid (1).
- Example 139 A wound aluminum electrolytic capacitor of Example 139 was manufactured in the same manner as in Example 137 except that the conductive auxiliary liquid (3) was used instead of the conductive auxiliary liquid (1).
- Example 134 is the same as Example 134 except that 100 ml of the oxidizing agent / dopant solution of Comparative Example 3 was used instead of 100 ml of the oxidizing agent / dopant solution of Example 61, and the operation of immersing in the conductive auxiliary liquid (1) was not performed. The same operation was performed to produce a wound aluminum electrolytic capacitor of Comparative Example 9.
- Example 134 is the same as Example 134, except that 100 ml of the oxidizing agent / dopant solution of Comparative Example 4 was used instead of 100 ml of the oxidizing agent / dopant solution of Example 61, and the operation of immersing in the conductive auxiliary liquid (1) was not performed. The same operation was performed to manufacture a wound aluminum electrolytic capacitor of Comparative Example 10.
- the capacitors of Examples 134 to 139 have an ESR of 21 to 23 m ⁇ , satisfy a set ESR of 30 m ⁇ or more, a capacitance of 34 to 35 ⁇ F, and a set electrostatic capacity of 30 ⁇ F or more.
- the oxidizing agent and dopant for conductive polymer manufacture which can manufacture the conductive polymer suitable for manufacturing the electrolytic capacitor with few leakage currents, and its solution can be provided, and those It is possible to provide a conductive polymer suitable for manufacturing an electrolytic capacitor with low leakage current using any of the above, and to provide an electrolytic capacitor with low leakage current using the conductive polymer as an electrolyte .
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Abstract
Description
すなわち、上記コンデンサ素子を本発明の酸化剤兼ドーパント溶液とモノマー(チオフェンまたはその誘導体)との混合物に浸漬し、引き上げた後(取り出した後)、室温または加熱下でモノマーを重合させてチオフェンまたはその誘導体の重合体をポリマー骨格とする導電性高分子からなる電解質層を形成した後、その電解質層を有するコンデンサ素子を外装材で外装して、巻回型アルミニウム電解コンデンサを製造する。
この導電性高分子製造用酸化剤兼ドーパント溶液(以下、簡略化して、「酸化剤兼ドーパント溶液」という場合がある)の調製(1)では、実施例1~30の酸化剤兼ドーパント溶液および比較例1の酸化剤兼ドーパント溶液について示す。これら実施例1~30の酸化剤兼ドーパント溶液は後記の実施例31~60のタンタル電解コンデンサの製造にあたって使用するものであり、比較例1の酸化剤兼ドーパント溶液は後記の比較例2のタンタル電解コンデンサの製造にあたって使用するものである。
5.7kgのナフタレンスルホン酸第二鉄(鉄とナフタレンスルホン酸とのモル比1:2.70)が溶解したエタノール溶液(水分含有量1%)を10kg調製した。
5.7kgのナフタレンスルホン酸第二鉄が溶解したエタノール溶液10kgに代えて、4.7kgのナフタレンスルホン酸第二鉄(鉄とナフタレンスルホン酸とのモル比1:2.70)と1kgのメタンスルホン酸第二鉄(鉄とメタンスルホン酸とのモル比1:2.70)とが溶解したエタノール溶液(水分含有量1%)10kgを用いた以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
5.7kgのナフタレンスルホン酸第二鉄が溶解したエタノール溶液10kgに代えて、4.7kgのパラトルエンスルホン酸第二鉄(鉄とパラトルエンスルホン酸とのモル比1:2.70)と1kgのメタンスルホン酸第二鉄(鉄とメタンスルホン酸とのモル比1:2.70)とが溶解したエタノール溶液(水分含有量1%)10kgを用いた以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
5.7kgのナフタレンスルホン酸第二鉄が溶解したエタノール溶液10kgに代えて、4.7kgのナフタレンスルホン酸第二鉄(鉄とナフタレンスルホン酸とのモル比1:2.70)と1kgのパラトルエンスルホン酸第二鉄(鉄とパラトルエンスルホン酸とのモル比1:2.70)とが溶解したエタノール溶液(水分含有量1%)10kgを用いた以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gに代えて、リン酸トリブチル300gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例5の酸化剤兼ドーパント溶液におけるリン酸トリブチルの添加量は、ナフタレンスルホン酸第二鉄に対して5.26%である。
リン酸ジブチル300gに代えて、リン酸ジブチル500gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例6の酸化剤兼ドーパント溶液におけるリン酸ジブチルの添加量は、ナフタレンスルホン酸第二鉄に対して8.77%である。
リン酸ジブチル300gに代えて、リン酸ジブチル100gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例7の酸化剤兼ドーパント溶液におけるリン酸ジブチルの添加量は、ナフタレンスルホン酸第二鉄に対して1.75%である。
リン酸ジブチル300gに代えて、リン酸200gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例8の酸化剤兼ドーパント溶液におけるリン酸の添加量は、ナフタレンスルホン酸第二鉄に対して3.51%である。
リン酸ジブチル300gに代えて、亜リン酸200gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例9の酸化剤兼ドーパント溶液における亜リン酸の添加量は、ナフタレンスルホン酸第二鉄に対して3.51%である。
リン酸ジブチル300gに代えて、亜リン酸ジブチル300gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例10の酸化剤兼ドーパント溶液における亜リン酸ジブチルの添加量は、ナフタレンスルホン酸第二鉄に対して5.26%である。
リン酸ジブチル300gに代えて、亜リン酸トリブチル300gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例11の酸化剤兼ドーパント溶液における亜リン酸トリブチルの添加量は、ナフタレンスルホン酸第二鉄に対して5.26%である。
リン酸ジブチル300gに代えて、ホウ酸200gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例12の酸化剤兼ドーパント溶液におけるホウ酸の添加量は、ナフタレンスルホン酸第二鉄に対して3.51%である。
リン酸ジブチル300gに代えて、ホウ酸トリブチル200gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例13の酸化剤兼ドーパント溶液におけるホウ酸トリブチルの添加量は、ナフタレンスルホン酸第二鉄に対して3.51%である。
リン酸ジブチル300gに代えて、リン酸ジエチルヘキシル300gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例14の酸化剤兼ドーパント溶液におけるリン酸ジエチルヘキシルの添加量は、ナフタレンスルホン酸第二鉄に対して5.26%である。
リン酸ジブチル300gに代えて、ジチオリン酸200gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例15の酸化剤兼ドーパント溶液におけるジチオリン酸の添加量は、ナフタレンスルホン酸第二鉄に対して3.51%である。
リン酸ジブチル300gに代えて、ジチオリン酸ジエチルヘキシル200gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例16の酸化剤兼ドーパント溶液におけるジチオリン酸ジエチルヘキシルの添加量は、ナフタレンスルホン酸第二鉄に対して3.51%である。
リン酸ジブチル300gに代えて、チオリン酸200gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例17の酸化剤兼ドーパント溶液におけるチオリン酸の添加量は、ナフタレンスルホン酸第二鉄に対して3.51%である。
リン酸ジブチル300gに代えて、チオリン酸ジエチル300gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例18の酸化剤兼ドーパント溶液におけるチオリン酸ジエチルの添加量は、ナフタレンスルホン酸第二鉄に対して5.26%である。
リン酸ジブチル300gに代えて、リン酸ジメチル200gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例19の酸化剤兼ドーパント溶液におけるリン酸ジメチルの添加量は、ナフタレンスルホン酸第二鉄に対して3.51%である。
リン酸ジブチル300gに代えて、リン酸ジエチル200gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例20の酸化剤兼ドーパント溶液におけるリン酸ジエチルの添加量は、ナフタレンスルホン酸第二鉄に対して3.51%である。
リン酸ジブチル300gに代えて、リン酸ジプロピル250gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例21の酸化剤兼ドーパント溶液におけるリン酸ジプロピルの添加量は、ナフタレンスルホン酸第二鉄に対して4.39%である。
リン酸ジブチル300gに代えて、リン酸ジベンジル570gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例22の酸化剤兼ドーパント溶液におけるリン酸ジベンジルの添加量は、ナフタレンスルホン酸第二鉄に対して10.00%である。
リン酸ジブチル300gに代えて、リン酸ジフェニル250gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例23の酸化剤兼ドーパント溶液におけるリン酸ジフェニルの添加量は、ナフタレンスルホン酸第二鉄に対して4.39%である。
リン酸ジブチル300gに代えて、亜リン酸ジメチル200gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例24の酸化剤兼ドーパント溶液における亜リン酸ジメチルの添加量は、ナフタレンスルホン酸第二鉄に対して3.51%である。
リン酸ジブチル300gに代えて、亜リン酸ジエチル200gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例25の酸化剤兼ドーパント溶液における亜リン酸ジエチルの添加量は、ナフタレンスルホン酸第二鉄に対して3.51%である。
リン酸ジブチル300gに代えて、亜リン酸ジプロピル250gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例26の酸化剤兼ドーパント溶液における亜リン酸ジプロピルの添加量は、ナフタレンスルホン酸第二鉄に対して4.39%である。
リン酸ジブチル300gに代えて、亜リン酸ジベンジル350gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例27の酸化剤兼ドーパント溶液における亜リン酸ジベンジルの添加量は、ナフタレンスルホン酸第二鉄に対して6.14%である。
リン酸ジブチル300gに代えて、亜リン酸ジフェニル300gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例28の酸化剤兼ドーパント溶液における亜リン酸ジフェニルの添加量は、ナフタレンスルホン酸第二鉄に対して5.26%である。
リン酸ジブチル300gに代えて、リン酸エチル250gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例29の酸化剤兼ドーパント溶液におけるリン酸エチルの添加量は、ナフタレンスルホン酸第二鉄に対して4.39%である。
リン酸ジブチル300gに代えて、亜リン酸エチル250gを添加した以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この実施例30の酸化剤兼ドーパント溶液における亜リン酸エチルの添加量は、ナフタレンスルホン酸第二鉄に対して4.39%である。
リン酸ジブチル300gを添加しなかった以外は、すべて実施例1と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
実施例31
このタンタル電解コンデンサのコンデンサ素子としては定格電圧が16Vで、ESRが20mΩ以下、静電容量が150μF以上、漏れ電流が100μA以下になるよう設計したタンタル焼結体を用いた。
上記実施例1の酸化剤兼ドーパント溶液に代えて、実施例2~30および比較例1の酸化剤兼ドーパント溶液をそれぞれ別々に用い、それ以外は実施例31と同様の操作を行って、それぞれの酸化剤兼ドーパント溶液を用いた実施例32~60および比較例2のタンタル電解コンデンサを製造した。
HEWLETT PACKARD社製のLCRメーター(4284A)を用い、25℃の条件下で、100kHzで測定する。
静電容量:
HEWLETT PACKARD社製のLCRメーター(4284A)を用い、25℃の条件下で、120Hzで測定する。
漏れ電流:
コンデンサに、25℃で16Vの電圧を60秒間印加した後、デジタルオシロスコープにて漏れ電流を測定する。
この導電性高分子製造用酸化剤兼ドーパント溶液(以下、簡略化して、「酸化剤兼ドーパント溶液」という場合がある)の調製(2)では、実施例61~91の酸化剤兼ドーパント溶液および比較例3~4の酸化剤兼ドーパント溶液について示す。これらの酸化剤兼ドーパント溶液は、後記の実施例92~122および比較例5~6の巻回型アルミニウム電解コンデンサの製造にあたって使用するものである。
5.7kgのナフタレンスルホン酸第二鉄(鉄とナフタレンスルホン酸とのモル比1:2.70)が溶解したエタノール溶液(水分含有量1%)を10kg調製した。
5.7kgのナフタレンスルホン酸第二鉄が溶解したエタノール溶液10kgに代えて、4.7kgのナフタレンスルホン酸第二鉄(鉄とナフタレンスルホン酸とのモル比1:2.70)と1kgのメタンスルホン酸第二鉄(鉄とメタンスルホン酸とのモル比1:2.70)とが溶解したエタノール溶液(水分含有量1%)10kgを用いた以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
5.7kgのナフタレンスルホン酸第二鉄が溶解したエタノール溶液10kgに代えて、4.7kgのパラトルエンスルホン酸第二鉄(鉄とパラトルエンスルホン酸とのモル比1:2.70)と1kgのメタンスルホン酸第二鉄(鉄とメタンスルホン酸とのモル比1:2.70)とが溶解したエタノール溶液(水分含有量1%)10kgを用いた以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した
5.7kgのナフタレンスルホン酸第二鉄が溶解したエタノール溶液10kgに代えて、4.7kgのナフタレンスルホン酸第二鉄(鉄とナフタレンスルホン酸とのモル比1:2.70)と1kgのパラトルエンスルホン酸第二鉄(鉄とパラトルエンスルホン酸とのモル比1:2.70)とが溶解したエタノール溶液(水分含有量1%)10kgを用いた以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、リン酸ジエチルヘキシル300gとクレジルグリシジルエーテル1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、リン酸ジエチルヘキシル300gとメタクリル酸グリシジル1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、リン酸ジエチルヘキシル300gとメタクリル酸グリシジル500gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン500gとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gに代えて、リン酸ジブチル500gを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gに代えて、リン酸ジブチル100gを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gに代えて、リン酸200gを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gに代えて、亜リン酸200gを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gに代えて、亜リン酸ジブチル300gを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gに代えて、亜リン酸トリブチル300gを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gに代えて、ホウ酸200gを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、リン酸トリブチル300gとメタクリル酸グリシジル1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgに代えて、ジチオリン酸200gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、ジチオリン酸ジエチルヘキシル200gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgに代えて、チオリン酸200gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、チオリン酸ジエチル300gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、リン酸ジメチル200gと3-グリシドキシプロピルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、リン酸ジエチル200gと信越化学株式会社製のエポキシポリシロキサン「X-41-1053」(商品名)1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、リン酸ジプロピル250gと信越化学株式会社製のエポキシポリシロキサン「X-41-1056」(商品名)1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、リン酸ジベンジル570gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、リン酸ジフェニル250gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、亜リン酸ジメチル200gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、亜リン酸ジエチル200gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、亜リン酸ジプロピル250gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、亜リン酸ジベンジル350gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、亜リン酸ジフェニル300gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、リン酸エチル250gと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
リン酸ジブチル300gとグリセリンジグリシジルエーテル1kgとに代えて、亜リン酸エチル250と2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1kgとを添加した以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。
濃度が57%のナフタレンスルホン酸第二鉄(鉄とナフタレンスルホン酸とのモル比1:2.70)のエタノール溶液(水分含有量1%)を10kg調製して、これを比較例3の酸化剤兼ドーパント溶液とした。なお、この比較例3の酸化剤兼ドーパント溶液は巻回型アルミニウム電解コンデンサの製造に際して使用するものであるが、その組成は前記比較例1の酸化剤兼ドーパント溶液と同じものであり、この比較例3の酸化剤兼ドーパント溶液と、実施例61の酸化剤兼ドーパント溶液とを対比すると、この比較例3の酸化剤兼ドーパント溶液には、リン酸ジブチルが添加されておらず、グリセリンジグリシジルエーテルも添加されていない。
リン酸ジブチル300gを添加しなかった以外は、すべて実施例61と同様の操作を行って、酸化剤兼ドーパント溶液を調製した。この比較例4の酸化剤兼ドーパント溶液は、実施例61の酸化剤兼ドーパント溶液と同様に、グリセリンジグリシジルエーテルがナフタレンスルホン酸第二鉄に対して17.54%添加されているが、リン酸ジブチルは添加されていない。
実施例92
この実施例92では、実施例61の酸化剤兼ドーパント溶液を用いて導電性高分子を製造し、その導電性高分子を電解質として用いて巻回型アルミニウム電解コンデンサを製造する例を示す。
上記実施例61の酸化剤兼ドーパント溶液に代えて、実施例62~91および比較例3~4の酸化剤兼ドーパント溶液をそれぞれ別々に用い、それ以外は実施例92と同様の操作を行って、それぞれの酸化剤兼ドーパント溶液を用いた実施例93~122および比較例5~6の巻回型アルミニウム電解コンデンサを製造した。
この巻回型アルミニウム電解コンデンサの評価(2)では、前記の巻回型アルミニウム電解コンデンサの評価(1)の場合とはモノマーを変えて製造した実施例123~125の巻回型アルミニウム電解コンデンサのコンデンサ特性について示す。
3,4-エチレンジオキシチオフェンとブチル化エチレンジオキシチオフェンとを質量比4:6で混合したモノマー混合液に代えて、モノマーとしてブチル化エチレンジオキシチオフェンのみを用いた以外は、すべて実施例92と同様の操作を行って、実施例123の巻回型アルミニウム電解コンデンサを製造した。
3,4-エチレンジオキシチオフェンとブチル化エチレンジオキシチオフェンとを質量比4:6で混合したモノマー混合液に代えて、モノマーとしてブチル化エチレンジオキシチオフェンのみを用いた以外は、すべて実施例97と同様の操作を行って、実施例124の巻回型アルミニウム電解コンデンサを製造した。
3,4-エチレンジオキシチオフェンとブチル化エチレンジオキシチオフェンとを質量比4:6で混合したモノマー混合液に代えて、モノマーとしてブチル化エチレンジオキシチオフェンのみを用いた以外は、すべて実施例98と同様の操作を行って、実施例125の巻回型アルミニウム電解コンデンサを製造した。
実施例61の酸化剤兼ドーパント溶液に代えて、比較例3の酸化剤兼ドーパント溶液を用いた以外は、実施例123と同様の操作を行って、比較例7の巻回型アルミニウム電解コンデンサを製造した。
実施例61の酸化剤兼ドーパント溶液に代えて、比較例4の酸化剤兼ドーパント溶液を用いた以外は、実施例123と同様の操作を行って、比較例8の巻回型アルミニウム電解コンデンサを製造した。
前記の実施例31~60では、本発明の実施例1~30の酸化剤兼ドーパント溶液を用いて、コンデンサ素子に、いわゆる「その場重合」により導電性高分子層を形成し、それを電解質とするタンタル電解コンデンサを製造し、その特性評価を〔タンタル電解コンデンサでの評価(1)〕として示したが、この〔タンタル電解コンデンサでの評価(2)〕では、コンデンサ素子に、まず、本発明の実施例1の酸化剤兼ドーパント溶液を用いて、いわゆる「その場重合」により導電性高分子層を形成して第1の電解質層とし、さらに、その第1の電解質層上にπ共役系導電性高分子の分散液を用いて形成した導電性高分子層を第2の電解質層または第2および第3の電解質層として製造したタンタル電解コンデンサについての特性評価を示す。
内容積が2Lの攪拌機付きセパラブルフラスコに1Lの純水を入れ、そこにスチレンスルホン酸ナトリウム170gとアクリル酸ヒドロキシエチル30gとを添加した。そして、その溶液に酸化剤として過硫酸アンモニウムを1g添加して、スチレンスルホン酸とアクリル酸ヒドロキシエチルとの重合反応を12時間行った。この重合反応後の反応液を限外濾過装置〔ザルトリウス社製Vivaflow200(商品名)、分子量分画5万〕で処理して、液中の遊離の低分子成分を除去し、水を加えて濃度3%に調整した。
3%スルホン化ポリエステル〔互応化学工業社製プラスコートZ-561(商品名)、重量平均分子量27,000〕水溶液200gを内容積1Lのビーカーに入れ、過硫酸アンモニウム2gを添加した後、スターラーで攪拌して溶解した。次いで、硫酸第二鉄の40%水溶液0.4gを添加し、攪拌しながら、その中に3,4-エチレンジオキシチオフェン3mLをゆっくり滴下し、24時間かけて、3,4-エチレンジオキシチオフェンの重合を行った。
この実施例126のタンタル電解コンデンサ用のコンデンサ素子としては、定格電圧が16Vで、ESRが20mΩ以下、静電容量が150μF以上、漏れ電流が100μA以下になるよう設計したタンタル焼結体を用いた。
実施例126と同様のコンデンサ素子に、実施例126と同様に、実施例1の酸化剤兼ドーパントの希釈溶液を用い、3,4-エチレンジオキシチオフェンとブチル化エチレンジオキシチオフェンとを質量比4:6で混合したモノマー混合物を重合して製造した導電性高分子からなる第1の電解質層を形成した。
この巻回型アルミニウム電解コンデンサでの評価(3)では、リン酸エステルや亜リン酸エステルなどの無機酸エステル系添加剤をモノマーと混合し、そのモノマーと無機酸エステル系添加剤との混合物を電解コンデンサの製造工程中に有機スルホン酸第二鉄溶液と混合してモノマーの存在下で、本発明の導電性高分子製造用酸化剤兼ドーパント溶液に該当する有機スルホン酸第二鉄とリン酸エステルや亜リン酸エステルなどの無機酸エステル系添加剤とを含む導電性高分子製造用酸化剤兼ドーパント溶液を構成し、その導電性高分子製造用酸化剤ドーパント溶液でモノマーを重合して導電性高分子からなる電解質層を形成する工程を経て、巻回型アルミニウム電解コンデンサを製造して、その特性を評価する。
アルミニウム箔の表面をエッチング処理し、そのエッチング処理後のアルミニウム箔を12%アンモニウム水溶液中に浸漬し、そのアンモニウム水溶液中のアルミニウム箔に75Vの電圧を印加してアルミニウム箔の表面にアルミニウムの酸化被膜からなる誘電体層を形成して陽極とし、その陽極にリード端子を取り付け、また、アルミニウム箔からなる陰極にリード端子を取り付け、それらのリード端子付き陽極と陰極とをセパレータを介して巻回して、設定ESRが30mΩ以下で、設定静電容量が50μF以上で、設定漏れ電流が100μA以下で、設定破壊電圧が50V以上で、素子内部の空隙体積が0.1mlの巻回型アルミニウム電解コンデンサ製造用のコンデンサ素子を準備した。
3.9kgのナフタレンスルホン酸第二鉄(鉄とナフタレンスルホン酸とのモル比1:2.70)が溶解したエタノール溶液(水分含有量1%)を9.32kg調製した。
3,4-エチレンジオキシチオフェンとブチル化エチレンジオキシチオフェンとを質量比4:6で混合したモノマー混合物20mlに対して、リン酸ジフェニル4ml(これはリン酸ジフェニルの質量として3.04gに相当する)とを添加してモノマー溶液を調製した。
リン酸ジブチルに代えて、亜リン酸ジブチルを用いた以外は、すべて実施例128と同様の操作を行って、実施例131の巻回型アルミニウム電解コンデンサを製造した。
リン酸ジエチルヘキシルに代えて、亜リン酸ジエチルヘキシルを用いた以外は、すべて実施例129と同様の操作を行って、実施例132の巻回型アルミニウム電解コンデンサを製造した、
リン酸ジフェニルに代えて、亜リン酸ジフェニルを用いた以外は、すべて実施例130と同様の操作を行って、実施例133の巻回型アルミニウム電解コンデンサを製造した。
この巻回型アルミニウム電解コンデンサでの評価(4)では、本発明の導電性高分子製造用酸化剤兼ドーパント溶液を用いて合成した導電性高分子からなる電解質と、導電性補助液とを併用した巻回型アルミニウム電解コンデンサを製造し、その特性を評価する。
撹拌装置付き1Lビーカー内に入れたγ-ブチロラクトン500gに50gのヒドロキシベンゼンカルボン酸と5gのニトロ安息香酸(つまり、ニトロベンゼンカルボン酸)と1gの3-グリシドキシプロピルトリメトキシシランとを添加し、さらにエチルアミンを添加することでpH4に調整した後、24時間撹拌することによって導電性補助液(1)を調製した。
撹拌装置付き1Lビーカー内に入れたエチレングリコール500gに50gのフタル酸と5gのニトロフェノールと5gのポリエチレングリコールジグリシジルエーテルとを添加し、さらにエチルアミンを添加することでpH6に調整した後、24時間撹拌することによって導電性補助液(2)を調製した。
撹拌装置付き1Lビーカー内に入れたエチレングリコール500gに50gのフタル酸と5gのニトロ安息香酸と100gのリン酸トリブチルと2gのポリエチレングリコール400と5gのポリシロキサンとを添加し、さらにジエチルアミンを添加することでpH3に調整した後、24時間撹拌することによって導電性補助液(3)を調製した。
アルミニウム箔の表面をエッチング処理し、そのエッチング処理後のアルミニウム箔を12%アンモニウム水溶液中に浸漬し、そのアンモニウム水溶液中のアルミニウム箔に130Vの電圧を印加してアルミニウム箔の表面にアルミニウムの酸化被膜からなる誘電体層を形成して陽極とし、その陽極にリード端子を取り付け、また、アルミニウム箔からなる陰極にリード端子を取り付け、それらのリード端子付き陽極と陰極とをセパレータを介して巻回して、設定ESRが30mΩ以下で、設定静電容量が30μF以上、設定漏れ電流が100μA以下、設定破壊電圧が65V以上の巻回型アルミニウム電解コンデンサ製造用のコンデンサ素子を作製した。
導電性補助液(1)に代えて、導電性補助液(2)を用いた以外は、すべて実施例134と同様の操作を行って、実施例135の巻回型アルミニウム電解コンデンサを製造した。
導電性補助液(1)に代えて、導電性補助液(3)を用いた以外は、すべて実施例134と同様の操作を行って、実施例136の巻回型アルミニウム電解コンデンサを製造した。
実施例61の酸化剤兼ドーパント溶液に代えて、実施例66の酸化剤兼ドーパント溶液を用いた以外は、すべて実施例134と同様の操作を行って、実施例137の巻回型アルミニウム電解コンデンサを製造した。
導電性補助液(1)に代えて、導電性補助液(2)を用いた以外は、実施例137と同様の操作を行って、実施例138の巻回型アルミニウム電解コンデンサを製造した。
導電性補助液(1)に代えて、導電性補助液(3)を用いた以外は、実施例137と同様の操作を行って、実施例139の巻回型アルミニウム電解コンデンサを製造した。
実施例61の酸化剤兼ドーパント溶液100mlに代えて、比較例3の酸化剤兼ドーパント溶液100mlを用い、導電性補助液(1)に浸漬する操作を行わなかった以外は、すべて実施例134と同様の操作を行って、比較例9の巻回型アルミニウム電解コンデンサを製造した。
実施例61の酸化剤兼ドーパント溶液100mlに代えて、比較例4の酸化剤兼ドーパント溶液100mlを用い、導電性補助液(1)に浸漬する操作を行わなかった以外は、すべて実施例134と同様の操作を行って、比較例10の巻回型アルミニウム電解コンデンサを製造した。
Claims (12)
- 有機スルホン酸第二鉄と、リン酸、リン酸エステル、亜リン酸、亜リン酸エステル、ホウ酸、ホウ酸エステル、チオリン酸、チオリン酸エステル、ジチオリン酸およびジチオリン酸エステルよりなる群から選ばれる少なくとも1種とを含むことを特徴とする導電性高分子製造用酸化剤兼ドーパント。
- さらにグリシジル基を有する化合物またはその開環化合物を含む請求項1記載の導電性高分子製造用酸化剤兼ドーパント。
- 有機スルホン酸第二鉄における鉄に対する有機スルホン酸のモル比が1:3より有機スルホン酸が少ない請求項1または2記載の導電性高分子製造用酸化剤兼ドーパント。
- リン酸、リン酸エステル、亜リン酸、亜リン酸エステル、ホウ酸、ホウ酸エステル、チオリン酸、チオリン酸エステル、ジチオリン酸およびジチオリン酸エステルよりなる群から選ばれる少なくとも1種の添加量が、有機スルホン酸第二鉄に対して質量基準で1~100%である請求項1~3のいずれかに記載の導電性高分子製造用酸化剤兼ドーパント。
- 請求項1~4のいずれかに記載の導電性高分子製造用酸化剤兼ドーパントが20~70質量%の濃度で水、アルコールまたは水とアルコールとの混合液に溶解していることを特徴とする導電性高分子製造用酸化剤兼ドーパント溶液。
- 請求項1~4のいずれかに記載の導電性高分子製造用酸化剤兼ドーパントを用いてチオフェンまたはその誘導体、ピロールまたはその誘導体およびアニリンおよびその誘導体よりなる群から選ばれる少なくとも1種のモノマーを酸化重合して製造したことを特徴とする導電性高分子。
- 請求項5記載の導電性高分子製造用酸化剤兼ドーパント溶液を用いてチオフェンまたはその誘導体、ピロールまたはその誘導体およびアニリンおよびその誘導体よりなる群から選ばれる少なくとも1種のモノマーを酸化重合して製造したことを特徴とする導電性高分子。
- チオフェンの誘導体が、3,4-エチレンジオキシチオフェンとアルキル化エチレンジオキシチオフェンとの混合物である請求項8記載の導電性高分子。
- 請求項6~9のいずれかに記載の導電性高分子を電解質として用いたことを特徴とする電解コンデンサ。
- 請求項6~9のいずれかに記載の導電性高分子と、ポリマーアニオンをドーパントとするπ共役系導電性高分子の分散液から得られた導電性高分子とを電解質として用いたことを特徴とする電解コンデンサ。
- さらに、沸点が150℃以上の高沸点有機溶剤または沸点が150℃以上の高沸点有機溶剤とヒドロキシル基またはカルボキシル基を少なくとも1つ有する芳香族系化合物とを含有する導電性補助液を含む請求項10または11記載の電解コンデンサ。
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