WO2014155419A1 - 導電性高分子微粒子分散体の製造方法およびその導電性高分子微粒子分散体を用いた電解コンデンサの製造方法 - Google Patents
導電性高分子微粒子分散体の製造方法およびその導電性高分子微粒子分散体を用いた電解コンデンサの製造方法 Download PDFInfo
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- 239000006185 dispersion Substances 0.000 title claims abstract description 105
- 239000003990 capacitor Substances 0.000 title claims description 56
- 229920001940 conductive polymer Polymers 0.000 title claims description 47
- 238000000034 method Methods 0.000 title description 11
- 239000002245 particle Substances 0.000 title 2
- 239000007800 oxidant agent Substances 0.000 claims abstract description 64
- -1 iron ions Chemical class 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052742 iron Inorganic materials 0.000 claims abstract description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 229920000447 polyanionic polymer Polymers 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 35
- 230000001590 oxidative effect Effects 0.000 claims abstract description 29
- 239000002019 doping agent Substances 0.000 claims abstract description 24
- 229920000123 polythiophene Polymers 0.000 claims abstract description 20
- 229930192474 thiophene Natural products 0.000 claims abstract description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 44
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 44
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 44
- 239000010419 fine particle Substances 0.000 claims description 43
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 239000007784 solid electrolyte Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 150000003577 thiophenes Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 31
- 239000000463 material Substances 0.000 description 27
- 239000012153 distilled water Substances 0.000 description 26
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 24
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 24
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 159000000014 iron salts Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GOTHKCARNFTUSW-UHFFFAOYSA-N 2-decylthiophene Chemical compound CCCCCCCCCCC1=CC=CS1 GOTHKCARNFTUSW-UHFFFAOYSA-N 0.000 description 1
- NZSSXTMHSXMZBL-UHFFFAOYSA-N 3-butoxythiophene Chemical compound CCCCOC=1C=CSC=1 NZSSXTMHSXMZBL-UHFFFAOYSA-N 0.000 description 1
- KPOCSQCZXMATFR-UHFFFAOYSA-N 3-butylthiophene Chemical compound CCCCC=1C=CSC=1 KPOCSQCZXMATFR-UHFFFAOYSA-N 0.000 description 1
- RDEGOEYUQCUBPE-UHFFFAOYSA-N 3-ethoxythiophene Chemical compound CCOC=1C=CSC=1 RDEGOEYUQCUBPE-UHFFFAOYSA-N 0.000 description 1
- SLDBAXYJAIRQMX-UHFFFAOYSA-N 3-ethylthiophene Chemical compound CCC=1C=CSC=1 SLDBAXYJAIRQMX-UHFFFAOYSA-N 0.000 description 1
- IUUMHORDQCAXQU-UHFFFAOYSA-N 3-heptylthiophene Chemical compound CCCCCCCC=1C=CSC=1 IUUMHORDQCAXQU-UHFFFAOYSA-N 0.000 description 1
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 1
- HGDGACBSGVRCSM-UHFFFAOYSA-N 3-methoxy-4-methylthiophene Chemical compound COC1=CSC=C1C HGDGACBSGVRCSM-UHFFFAOYSA-N 0.000 description 1
- RFSKGCVUDQRZSD-UHFFFAOYSA-N 3-methoxythiophene Chemical compound COC=1C=CSC=1 RFSKGCVUDQRZSD-UHFFFAOYSA-N 0.000 description 1
- UUHSVAMCIZLNDQ-UHFFFAOYSA-N 3-nonylthiophene Chemical compound CCCCCCCCCC=1C=CSC=1 UUHSVAMCIZLNDQ-UHFFFAOYSA-N 0.000 description 1
- WQYWXQCOYRZFAV-UHFFFAOYSA-N 3-octylthiophene Chemical compound CCCCCCCCC=1C=CSC=1 WQYWXQCOYRZFAV-UHFFFAOYSA-N 0.000 description 1
- QZNFRMXKQCIPQY-UHFFFAOYSA-N 3-propylthiophene Chemical compound CCCC=1C=CSC=1 QZNFRMXKQCIPQY-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- FREONMIBRAAMGB-UHFFFAOYSA-L COC1=C(C=CC=C1)S(=O)(=O)[O-].[Fe+2].COC1=C(C=CC=C1)S(=O)(=O)[O-] Chemical compound COC1=C(C=CC=C1)S(=O)(=O)[O-].[Fe+2].COC1=C(C=CC=C1)S(=O)(=O)[O-] FREONMIBRAAMGB-UHFFFAOYSA-L 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Chemical group 0.000 description 1
- 229920002125 Sokalan® Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical group CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- AWRGYUYRFKKAID-UHFFFAOYSA-L iron(2+);phenylmethanesulfonate Chemical compound [Fe+2].[O-]S(=O)(=O)CC1=CC=CC=C1.[O-]S(=O)(=O)CC1=CC=CC=C1 AWRGYUYRFKKAID-UHFFFAOYSA-L 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Chemical group 0.000 description 1
- 229920001444 polymaleic acid Chemical group 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
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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
- H01G9/0029—Processes of manufacture
- H01G9/0036—Formation of the solid electrolyte layer
-
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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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
- H01G9/02—Diaphragms; Separators
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- 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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- 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
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/055—Etched foil electrodes
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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
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- H—ELECTRICITY
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- 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
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- 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
- H01G9/151—Solid electrolytic capacitors with wound foil electrodes
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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
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- 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
- C08G2261/3223—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
-
- 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
- C08G2261/70—Post-treatment
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- H—ELECTRICITY
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- 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
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
Definitions
- the present invention relates to a method for producing a conductive polymer fine particle dispersion applied to an antistatic agent, an electrolyte for an electrolytic capacitor, a display element, and the like, and an electrolytic capacitor using the conductive polymer fine particle dispersion obtained by this production method It relates to the manufacturing method.
- a dopant is a substance for developing conductivity. In addition to this high conductivity, it is chemically and physically stable, so it is used in antistatic agents and display elements. It has also been proposed to use it as a solid electrolyte material for electrolytic capacitors.
- a method for producing a conductive polymer having such a ⁇ -conjugated structure a method is known in which a monomer is oxidatively polymerized using an oxidizing agent in the state where a dopant is present.
- a monomer is oxidatively polymerized using an oxidizing agent in the state where a dopant is present.
- polystyrenesulfonic acid is used as a dopant
- poly3,4-ethylenedioxythiophene doped with polystyrenesulfonic acid and having high conductivity can be prepared.
- the poly 3,4-ethylenedioxythiophene prepared by this method is in the form of fine particles dispersed in water. That is, according to the above method, a conductive polymer fine particle dispersion can be prepared (for example, Patent Document 1).
- the method for producing a conductive polymer fine particle dispersion according to the present invention includes the following steps.
- a monomer dispersion is prepared by dispersing at least one monomer selected from thiophenes and derivatives thereof and at least one polyanion selected from polyanions as a dopant in a solvent containing water as a main component. Step to do.
- a conductive polythiophene dispersion doped with a polyanion is prepared by mixing the monomer dispersion and an oxidant containing a first oxidant that generates iron ions in a solvent to oxidatively polymerize the monomer. Step to do.
- the concentration of the trivalent iron ion in the conductive polythiophene dispersion doped with the polyanion at the time when the oxidative polymerization reaction of the monomer is completed is 3 parts by weight or more and 30 parts by weight with respect to 100 parts by weight of the polythiophene. Or less.
- the conductive polymer fine particle dispersion can be prepared without impairing mass productivity.
- conductive polythiophene doped with a polyanion suitable for a solid electrolyte of an electrolytic capacitor is dispersed in water as fine particles.
- ESR equivalent series resistance value
- FIG. 1 is a partially cutaway perspective view showing an outline of an electrolytic capacitor using a conductive polymer fine particle dispersion prepared by a manufacturing method according to an embodiment of the present invention.
- FIG. 2 is a partial cross-sectional view of the capacitor element in the electrolytic capacitor shown in FIG.
- the conductive polymer can be obtained by removing the solvent component from the conductive polymer fine particle dispersion obtained by the conventional method as described above.
- ESR may be increased depending on the method and conditions for forming the conductive polymer film. Therefore, in order to employ the conductive polymer fine particle dispersion having a ⁇ -conjugated structure as the solid electrolyte of the electrolytic capacitor, it is necessary to make the conductive polymer fine particle dispersion suitable for the solid electrolyte of the electrolytic capacitor.
- FIG. 1 is a partially cutaway perspective view showing an outline of an electrolytic capacitor using a conductive polymer fine particle dispersion prepared by a manufacturing method according to an embodiment of the present invention.
- FIG. 2 is a partial cross-sectional view of the capacitor element in the electrolytic capacitor shown in FIG.
- the electrolytic capacitor includes a capacitor element 10, a metal case 14, and a sealing material 13.
- the case 14 accommodates the capacitor element 10, and the sealing material 13 seals the opening of the case 14.
- the case 14 and the sealing material 13 constitute an exterior body that seals the capacitor element 10.
- the capacitor element 10 includes an anode 1 and a cathode 2, and a separator 4 and a solid electrolyte layer 5 interposed therebetween.
- the anode 1 is produced by roughening the surface of an aluminum foil by etching and forming a dielectric oxide film layer 3 on this surface by chemical conversion treatment.
- the cathode 2 is also made of an aluminum foil whose surface is roughened by etching.
- Lead terminals 11 and 12 shown in FIG. 1 are connected to the anode 1 and the cathode 2, respectively. The lead terminals 11 and 12 penetrate the sealing material 13 and are drawn to the outside.
- the anode 1 and the cathode 2 are wound through a separator 4 between them to form a capacitor element 10.
- the capacitor element 10 is impregnated with a conductive polymer fine particle dispersion, which will be described later, and the solvent component is removed by drying, whereby a conductive polymer solid electrolyte layer 5 is formed between the anode 1 and the cathode 2. .
- a dispersion is prepared by dispersing at least one monomer selected from thiophenes and derivatives thereof and at least one polyanion selected from polyanions as a dopant in a solvent containing water as a main component.
- the dispersion is mixed with an oxidizing agent containing a first oxidizing agent that generates iron ions in a solvent to oxidatively polymerize the monomer.
- a conductive polythiophene dispersion doped with a polyanion is prepared.
- Monomeric thiophenes and derivatives thereof have a ⁇ -conjugated structure.
- monomers include thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-nonylthiophene, 3- Examples include decylthiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-methyl-4-methoxythiophene, 3,4-ethylenedioxythiophene, benzothiophene, and benzodithiophene.
- 3,4-ethylenedioxythiophene is particularly preferable because of an appropriate polymerization rate and excellent heat resistance of the polymer.
- polyanions used as the dopant examples include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyacryl sulfonic acid, polyacrylamide tertiary butyl sulfonic acid, polyacrylic acid, polymethacrylic acid, polymaleic acid and copolymers having these structural units, or Examples of these polyanions include ammonium salts, lithium salts, sodium salts, and the like. Among them, polystyrene sulfonic acid is particularly preferable because of good dispersibility and excellent heat resistance. These polyanions may be used in combination of two or more.
- the weight average molecular weight of the polyanions is preferably from 10,000 to 400,000, more preferably from 30,000 to 200,000, particularly preferably from 50,000 to 100,000.
- the number average molecular weight of the polyanions is preferably 1,000 or more and 300,000 or less, more preferably 10,000 or more and 150,000 or less, and particularly preferably 20,000 or more and 100,000 or less.
- Examples of the first oxidizing agent that generates iron ions in a solvent include iron salts of inorganic acids such as iron (III) chloride, iron (III) sulfate, and iron (III) nitrate, iron methoxybenzenesulfonate, iron toluenesulfonate, and the like. And iron salts of organic acids.
- iron (III) sulfate is particularly preferable because an appropriate polymerization rate can be obtained and a polymer having excellent heat resistance can be obtained.
- ferric sulfate iron (III) sulfate is referred to as ferric sulfate.
- hydrogen peroxide, persulfate, permanganate, benzoyl peroxide, ozone, etc. can be used as the second oxidant that is used in combination with the first oxidant and does not generate iron ions in the solvent.
- ammonium persulfate is particularly preferable because an appropriate polymerization rate can be obtained, a polymer excellent in heat resistance can be obtained, storage stability is excellent, and handling is easy.
- the water used as the solvent is preferably ion-exchanged water or distilled water with a low impurity content.
- the solvent is mainly composed of water.
- the main component means that it contains impurities such as traces, additives, etc., for example, 95% or more is water.
- a monomer and a polyanion are simultaneously added to water charged in a container while applying a share using a disperser to prepare a dispersion.
- the monomer and the polyanion are sequentially added to the water charged in the container while applying a share using a disperser to prepare a dispersion.
- a monomer and a polyanion are charged into water charged in a container, and then a dispersion is prepared by sharing using a disperser.
- a disperser a homomixer, a high-pressure homogenizer, or the like can be used.
- the dispersion time can be shortened compared to the case where the monomer and polyanion are sequentially added.
- the monomer may be introduced after the introduction of the polyanion.
- water may be partially added to the container before the monomer or polyanion is added, and then divided into a plurality of times as appropriate during dispersion.
- the purpose of this operation is to disperse the monomer having a ⁇ -conjugated structure, which is difficult to adjust to water, into fine particles and dispersed in water, and the method is not limited thereto.
- the polyanion is solid or has a high viscosity, it is dissolved or diluted in water and added as an aqueous solution.
- the ratio of the monomer and water is preferably 9 parts by weight or more with respect to 1 part by weight of the monomer. If the proportion of water is smaller than this, the viscosity of the dispersion becomes too high during the polymerization, and there is a possibility that a homogeneous conductive polymer fine particle dispersion cannot be obtained.
- the ratio of the polyanion to the monomer is preferably 1 part by weight or more and 5 parts by weight or less with respect to 1 part by weight of the monomer. If the polyanion is less than 1 part by weight relative to 1 part by weight of the monomer, the conductivity of the resulting conductive polymer will be low. Moreover, even if the ratio of the polyanion exceeds 5 parts by weight with respect to 1 part by weight of the monomer, the conductivity of the obtained conductive polymer is hardly improved. Therefore, if considering the material cost, 5 parts by weight or less is preferable.
- oxidative polymerization of monomers An oxidant is added to this dispersion while applying a share to the dispersion prepared as described above using a disperser.
- the oxidizing agent is solid or has a high viscosity, it is dissolved or diluted in water and added as an aqueous solution.
- the dispersed monomer is oxidatively polymerized to form fine particles of a polymer (hereinafter referred to as polythiophene).
- a dispersion of polythiophene having a polyanion as a dopant can be prepared by continuing the share by the disperser until the polymerization is completed even after the addition of the oxidizing agent.
- the monomer may be oxidatively polymerized by introducing the dispersion and the oxidizing agent into separate apparatuses. That is, the method is not particularly limited as long as the dispersion and the oxidizing agent are mixed and subjected to oxidative polymerization.
- the temperature of the dispersion and the dispersion is preferably 5 ° C. or higher and 10 ° C. or lower. By controlling to this temperature range, the reaction rate becomes moderate.
- polymerization is 3 to 30 weight part with respect to 100 weight part of polythiophene.
- the selection of materials and the amount used, dispersion conditions, polymerization conditions and the like are adjusted as appropriate.
- a conductive polymer fine particle dispersion in which conductive polythiophene is dispersed can be prepared.
- This polythiophene is doped with a polyanion and is suitable for a solid electrolyte of an electrolytic capacitor. That is, by using this polythiophene as a solid electrolyte, an electrolytic capacitor having a small equivalent series resistance value (ESR) and a long life can be produced.
- ESR equivalent series resistance value
- Example 5 (Examples 1 to 5) First, 3,4-ethylenedioxythiophene as a monomer having a ⁇ -conjugated structure is charged into distilled water charged into a container, and then a 29.5% aqueous solution of polystyrene sulfonic acid is charged as a polyanion. Then, a dispersion of 3,4-ethylenedioxythiophene is prepared by applying a shear for 10 minutes with a homomixer.
- Example 1 The ratio of each material used in Example 1 is as follows: 3,4-ethylenedioxythiophene 14.2 parts by weight, polystyrene sulfonic acid 30.5 parts by weight, ferric sulfate 8.5 parts by weight, ammonium persulfate 29.8 Parts by weight and 5240 parts by weight of distilled water.
- the ratio of each material used in Example 2 is 8.3 parts by weight of ferric sulfate and 4176 parts by weight of distilled water in Example 1 above.
- the ratio of each material used in Example 3 is 3.7 parts by weight of ferric sulfate and 348 parts by weight of distilled water in Example 1 above.
- the ratio of each material used in Example 4 is 2.8 parts by weight of ferric sulfate and 136 parts by weight of distilled water in Example 1 above.
- the ratio of each material used in Example 5 is 2.8 parts by weight of ferric sulfate and 116 parts by weight of distilled water in Example 1 above. The rest is the same as in Example 1.
- poly3,4-ethylenedioxythiophene having polystyrene sulfonic acid as a dopant is dispersed in the solvent.
- concentration of trivalent iron ions in this dispersion is measured by capillary electrophoresis.
- the ratio (concentration) of trivalent iron ions to 100 parts by weight of poly3,4-ethylenedioxythiophene is 3.0 parts by weight in Example 1, 3.1 parts by weight in Example 2, and 3 in Example 3. 0.0 parts by weight, 3.1 parts by weight in Example 4, and 3.0 parts by weight in Example 5.
- the ratio of trivalent iron ions to 100 parts by weight of the dispersion at this time is 0.007 parts by weight in Example 1, 0.01 parts by weight in Example 2, 0.111 parts by weight in Example 3, In Example 4, it is 0.190 weight part, and in Example 5, it is 0.233 weight part.
- the ratio of trivalent iron ions to 100 parts by weight of poly3,4-ethylenedioxythiophene is around 3 parts by weight, and trivalent iron ions to 100 parts by weight of the dispersion. The ratio of is different.
- Example 6 to 10 The conductive polymer fine particle dispersions of Examples 6 to 10 are prepared under the same conditions as in Example 1 by changing the ratio of each material used.
- the ratio of each material used in Example 6 is 25.1 parts by weight of ferric sulfate and 17660 parts by weight of distilled water in Example 1 above.
- the ratio of each material used in Example 7 is 25.0 parts by weight of ferric sulfate and 14111 parts by weight of distilled water in Example 1.
- the ratio of each material used in Example 8 is 13.0 parts by weight of ferric sulfate and 1337 parts by weight of distilled water in Example 1.
- the ratio of each material used in Example 9 is 10.1 parts by weight of ferric sulfate and 627 parts by weight of distilled water in Example 1.
- the ratio of each material used in Example 10 is 11.0 parts by weight of ferric sulfate and 562 parts by weight of distilled water in Example 1. The rest is the same as in Example 1.
- the ratio (concentration) of trivalent iron ions with respect to 100 parts by weight of poly3,4-ethylenedioxythiophene using polystyrene sulfonic acid as a dopant after polymerization was 9.4 parts by weight in Example 6, and in Example 7, 10.2 parts by weight, Example 8 is 10.1 parts by weight, Example 9 is 10.0 parts by weight, and Example 10 is 10.5 parts by weight.
- the ratio of trivalent iron ions to 100 parts by weight of the dispersion at this time is 0.008 parts by weight in Example 6, 0.010 parts by weight in Example 7, 0.105 parts by weight in Example 8, In Example 9, it is 0.200 part by weight, and in Example 10, it is 0.224 part by weight.
- the ratio of trivalent iron ions to 100 parts by weight of poly3,4-ethylenedioxythiophene is around 10 parts by weight, and trivalent iron ions to 100 parts by weight of the dispersion. The ratio of is different.
- Example 11 to 15 The conductive polymer fine particle dispersions of Examples 11 to 15 are prepared under the same conditions as in Example 1 by changing the ratio of each material used.
- the ratio of each material used in Example 11 is 76.2 parts by weight of ferric sulfate and 53144 parts by weight of distilled water in Example 1 above.
- the ratio of each material used in Example 12 is 75.8 parts by weight of ferric sulfate and 42495 parts by weight of distilled water in Example 1 above.
- the ratio of each material used in Example 13 is 38.0 parts by weight of ferric sulfate and 4160 parts by weight of distilled water in Example 1.
- the ratio of each material used in Example 14 is 29.4 parts by weight of ferric sulfate and 2030 parts by weight of distilled water in Example 1.
- the ratio of each material used in Example 15 is 29.7 parts by weight of ferric sulfate and 1837 parts by weight of distilled water in Example 1 above. The rest is the same as in Example 1.
- the ratio (concentration) of trivalent iron ions with respect to 100 parts by weight of poly3,4-ethylenedioxythiophene using polystyrene sulfonic acid as a dopant after the completion of polymerization was 30.0 parts by weight in Example 11, and in Example 12, 29.8 parts by weight, Example 13 is 29.6 parts by weight, Example 14 is 29.8 parts by weight, and Example 15 is 30.0 parts by weight.
- the ratio of trivalent iron ions to 100 parts by weight of the dispersion at this time is 0.007 parts by weight in Example 11, 0.010 parts by weight in Example 12, 0.110 parts by weight in Example 13, In Example 14, it is 0.198 part by weight, and in Example 15, it is 0.225 part by weight.
- the ratio of trivalent iron ions to 100 parts by weight of poly3,4-ethylenedioxythiophene is around 30 parts by weight, and trivalent iron ions to 100 parts by weight of the dispersion. The ratio of is different.
- Example 16 to 18 In Examples 16 to 18, the ratio of each material used was 14.2 parts by weight of 3,4-ethylenedioxythiophene, 30.5 parts by weight of polystyrene sulfonic acid, 13.0 parts by weight of ferric sulfate, 29 per ammonium sulfate. 8 parts by weight and 1337 parts by weight of distilled water. That is, the ratio of the material is the same as in Example 8.
- Example 16 ferric sulfate and ammonium persulfate added immediately after the addition of ferric sulfate were added in four equal portions. That is, immediately after the 1/4 amount of ferric sulfate used in Example 8 was added, the same 1/4 amount of ammonium persulfate was added. The same operation is performed after 5 minutes. Repeat this operation two more times.
- Example 17 ferric sulfate and ammonium persulfate are added in approximately equal portions each twice. That is, immediately after the 1 ⁇ 2 amount of the ferric sulfate used in Example 8 was added, the 1 ⁇ 2 amount of ammonium persulfate was also added. The same operation is performed after 15 minutes.
- Example 18 the interval between the two inputs in Example 17 is 30 minutes.
- a conductive polymer fine particle dispersion is prepared under the same conditions as in Example 1 except for these conditions.
- the ratio (concentration) of trivalent iron ions with respect to 100 parts by weight of poly3,4-ethylenedioxythiophene using polystyrene sulfonic acid as a dopant after the polymerization was completed was 10.3 parts by weight in Example 16, and in Example 17 10.3 parts by weight, and in Example 18, 10.5 parts by weight.
- the ratio of trivalent iron ions to 100 parts by weight of the dispersion at this time is 0.113 parts by weight in Example 16, 0.101 parts by weight in Example 17, and 0.110 parts by weight in Example 18. is there.
- Example 19 In Example 19, the proportion of each material used was 14.2 parts by weight of 3,4-ethylenedioxythiophene, 30.5 parts by weight of polystyrene sulfonic acid, 13.2 parts by weight of ferric sulfate, and 29.8 ammonium persulfate. Parts by weight and 1337 parts by weight of distilled water. That is, the ratio of the material is almost the same as in Example 8.
- ferric sulfate is added immediately after ammonium persulfate is added. That is, the order of adding ferric sulfate and ammonium persulfate is reversed. Except for these, a conductive polymer fine particle dispersion is prepared under the same conditions as in Example 1.
- the concentration of trivalent iron ions in the poly3,4-ethylenedioxythiophene dispersion using polystyrenesulfonic acid as a dopant after polymerization in Example 19 was 100 parts by weight of poly3,4-ethylenedioxythiophene. The amount is 10.1 parts by weight. Moreover, the trivalent iron ion with respect to 100 weight part of dispersions at this time is 0.1 weight part.
- Example 20 A conductive polymer fine particle dispersion is prepared under the same conditions as in Example 1 except that 8.5 parts by weight of ferric chloride is used as the first oxidizing agent instead of ferric sulfate.
- the concentration of trivalent iron ions with respect to 100 parts by weight of poly3,4-ethylenedioxythiophene using polystyrene sulfonic acid as a dopant after polymerization is 3.1 parts by weight.
- the trivalent iron ion with respect to 100 weight part of dispersions at this time is 0.008 weight part.
- Example 21 A conductive polymer fine particle dispersion is prepared under the same conditions as in Example 1 except that 30 parts by weight of sodium persulfate is used in place of ammonium persulfate as the second oxidizing agent.
- concentration of trivalent iron ions with respect to 100 parts by weight of poly3,4-ethylenedioxythiophene using polystyrene sulfonic acid as a dopant after polymerization is 3.0 parts by weight.
- the trivalent iron ion with respect to 100 weight part of dispersions at this time is 0.008 weight part.
- Example 22 As a first oxidizing agent, 8.5 parts by weight of ferric chloride is used instead of ferric sulfate, and as a second oxidizing agent, 30 parts by weight of sodium persulfate is used instead of ammonium persulfate. Other than this, a conductive polymer fine particle dispersion is prepared under the same conditions as in Example 1. The concentration of trivalent iron ions with respect to 100 parts by weight of poly3,4-ethylenedioxythiophene using polystyrene sulfonic acid as a dopant after polymerization is 3.0 parts by weight. Moreover, the trivalent iron ion with respect to 100 weight part of dispersions at this time is 0.007 weight part.
- Comparative Examples 1 to 3 In Comparative Example 1, the ratio of each material used was 14.2 parts by weight of 3,4-ethylenedioxythiophene, 30.5 parts by weight of polystyrene sulfonic acid, 7.0 parts by weight of ferric sulfate, and 29.8 ammonium persulfate. Parts by weight and 4887 parts by weight of distilled water. In the comparative example 2, in the said comparative example 1, it is 3.5 weight part of ferric sulfate and 320 weight part of distilled water. In the comparative example 3, in the said comparative example 1, it is 2.3 weight part of ferric sulfate and 104 weight part of distilled water. A conductive polymer fine particle dispersion is prepared in the same manner as in Example 1 except for these conditions.
- the ratio (concentration) of trivalent iron ions with respect to 100 parts by weight of poly3,4-ethylenedioxythiophene using polystyrene sulfonic acid as a dopant after the completion of polymerization was 2.7 parts by weight in Comparative Example 1, Comparative Example 2, In Comparative Example 3, it is 2.8 parts by weight.
- the ratio of trivalent iron ions to 100 parts by weight of the dispersion at this time is 0.008 parts by weight in Comparative Example 1, 0.112 parts by weight in Comparative Example 2, and 0.220 parts by weight in Comparative Example 3. is there.
- Comparative Examples 4 to 6 In Comparative Example 4, the ratio of each material used was 14.2 parts by weight of 3,4-ethylenedioxythiophene, 30.5 parts by weight of polystyrene sulfonic acid, 78.7 parts by weight of ferric sulfate, and 29.8 parts of ammonium persulfate. Parts by weight and 56703 parts by weight of distilled water. In the comparative example 5, in the said comparative example 4, they are 39.5 weight part of ferric sulfate and 4443 weight part of distilled water. In the comparative example 6, in the said comparative example 1, they are 30.0 weight part of ferric sulfate and 1964 weight part of distilled water. A conductive polymer fine particle dispersion is prepared in the same manner as in Example 1 except for these conditions.
- the ratio (concentration) of trivalent iron ions with respect to 100 parts by weight of poly3,4-ethylenedioxythiophene using polystyrene sulfonic acid as a dopant after the polymerization was completed was 30.6 parts by weight in Comparative Example 4 and in Comparative Example 5 32.0 parts by weight, and in Comparative Example 6 it is 32.2 parts by weight.
- the ratio of trivalent iron ions to 100 parts by weight of the dispersion at this time is 0.007 parts by weight in Comparative Example 4, 0.100 parts by weight in Comparative Example 5, and 0.220 parts by weight in Comparative Example 6. is there.
- the conductive polymer fine particle dispersions according to the examples and comparative examples obtained by the above procedure contain poly 3,4-ethylenedioxythiophene having polystyrene sulfonic acid as a dopant. Therefore, the obtained conductive polymer fine particle dispersion is washed and filtered with distilled water, and then the concentration of poly3,4-ethylenedioxythiophene is adjusted to 2.5%. Capacitor element 10 is impregnated with this dispersion to form solid electrolyte layer 5 to produce a wound electrolytic capacitor with a rated voltage of 35 V and a capacitance of 47 ⁇ F.
- the amount of trivalent iron ions in the dispersion at the time when the polymerization was completed was 3 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of poly 3,4-ethylenedioxythiophene. ing. Of these, the yield of poly3,4-ethylenedioxythiophene is close to 90%. Moreover, the ESR of electrolytic capacitors produced using these conductive polymer fine particle dispersions is a target of 35 m ⁇ or less.
- the amount of trivalent iron ions with respect to 100 parts by weight of the poly 3,4-ethylenedioxythiophene dispersion is 0.01 parts by weight. As described above, it is 0.20 part by weight or less.
- the ESR of the electrolytic capacitor is smaller than those in Examples 1, 5, 6, 10, 11, and 15.
- the concentration of trivalent iron ions in the conductive polythiophene dispersion doped with polyanions is 0.01 parts by weight or more and 0.20 parts by weight or less with respect to 100 parts by weight of the polythiophene dispersion. It is preferable to become. As a result, the ESR of the electrolytic capacitor can be further reduced.
- the ESR of the electrolytic capacitor was smaller than in the other examples. That is, the ESR of the electrolytic capacitor according to Examples 16, 17, and 18 is smaller than the ESR of the electrolytic capacitor according to Example 8 having the smallest ESR.
- Example 8 the oxidizing agent is charged all at once. In this case, since the polymerization reaction is fast, a relatively large amount of polymer having a short chain length is generated. On the other hand, in Examples 16, 17, and 18, the oxidizing agent is divided and introduced. This slows the polymerization reaction and reduces the number of polymers with a short chain length compared to batch injection. As a result, it is considered that the resistance component due to the resistance between the polymer chains decreases and the ESR becomes small. Thus, it is preferable to divide the oxidizing agent into a plurality of times and add it to the dispersion. Thereby, the ESR of the electrolytic capacitor can be further reduced.
- the ESR of the electrolytic capacitor is smaller in Examples 17 and 18 in which the number of times the oxidant is divided into the dispersion liquid and added twice is smaller than that in Example 16. Yes. Therefore, it is preferable to add the oxidizing agent to the dispersion in two portions. Thereby, the ESR of the electrolytic capacitor can be further reduced.
- Example 18 in which the interval between the first oxidant addition and the second oxidant addition was 30 minutes, the ESR of the electrolytic capacitor was further reduced as compared with Examples 16 and 17. Although the results are not shown, it has been confirmed that the ESR of the electrolytic capacitor does not become so small even if the interval of the oxidant input is longer than 30 minutes. Therefore, the ESR of the electrolytic capacitor can be further reduced by setting the interval between the first oxidant and the second oxidant to 30 minutes or more.
- Example 19 in which ferric sulfate as the first oxidant was added after adding ammonium persulfate as the second oxidant, the ESR of the electrolytic capacitor was smaller than that in Example 8.
- the first oxidizing agent including ferric sulfate has a strong oxidizing action, and the polymerization reaction proceeds quickly. For this reason, a relatively large amount of polymer having a short chain length is produced.
- the oxidizing action of the second oxidizing agent including ammonium persulfate is relatively mild. By adding this ammonium persulfate first, the polymerization reaction proceeds without causing an initial rapid polymerization reaction. As a result, it is considered that the polymer having a short chain length is reduced and the ESR of the electrolytic capacitor is reduced. However, when only ammonium persulfate is used as the oxidizing agent, the polymerization reaction becomes extremely slow.
- the first oxidizing agent and the second oxidizing agent in combination rather than using them alone. It is more preferable that the first oxidant is added after the second oxidant is added. Thereby, the ESR of the electrolytic capacitor can be further reduced.
- Example 1 ferric sulfate that allows the polymerization reaction to proceed faster and ammonium persulfate that causes the polymerization reaction to proceed more slowly than ferric sulfate are used as an oxidizing agent.
- Example 20 to 22 in Example 1, at least one of ferric sulfate and ammonium persulfate is replaced with the same amount of another oxidizing agent having a different polymerization reaction rate.
- the ESR of the electrolytic capacitor is larger than that of Example 1 although it is a slight difference. Although the reason is not clear, it is considered that Example 1 has a reaction rate that provides an optimum polymer chain length as a solid electrolyte of the electrolytic capacitor.
- the oxidizing agent includes at least ferric sulfate as the first oxidizing agent and ammonium persulfate as the second oxidizing agent used in combination with the first oxidizing agent.
- Comparative Examples 1 to 3 the amount of trivalent iron ions with respect to 100 parts by weight of poly3,4-ethylenedioxythiophene is less than 3 parts by weight.
- the ESR of the electrolytic capacitor is low to some extent, it is not lower than 35 m ⁇ .
- the yield of poly3,4-ethylenedioxythiophene using polystyrene sulfonic acid as a dopant is remarkably low at 50% or less.
- Comparative Examples 4 to 6 the amount of trivalent iron ions with respect to 100 parts by weight of poly3,4-ethylenedioxythiophene exceeds 30 parts by weight. In Comparative Examples 4 to 6, although the yield of poly3,4-ethylenedioxythiophene using polystyrene sulfonic acid as a dopant was 90% or more, the ESR of the electrolytic capacitor greatly exceeded 35 m ⁇ . .
- a winding type solid electrolytic capacitor using an aluminum foil as an electrode has been described as an example.
- the conductive polymer fine particle dispersion obtained by the manufacturing method of the present embodiment includes a wound solid electrolytic capacitor having a valve metal foil other than aluminum as an electrode, a laminated electrolytic capacitor, and an anode body made of a valve metal.
- the present invention can also be applied to an electrolytic capacitor using a sintered body, or a hybrid type electrolytic capacitor using an electrolyte together with a solid electrolyte.
- Examples 1 to 22 are examples for explaining the invention, and are not limited thereto.
- the present invention is useful for an electrolytic capacitor using a conductive polymer fine particle dispersion.
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Abstract
Description
まず、容器に投入した蒸留水に、π共役構造を有するモノマーとして、3,4-エチレンジオキシチオフェンを投入し、次いでポリアニオンとしてポリスチレンスルホン酸の29.5%水溶液を投入する。その後、ホモミキサーで10分間シェアをかけて、3,4-エチレンジオキシチオフェンの分散液を調製する。
使用する各材料の割合を変更して実施例1と同じ条件で実施例6~10の導電性高分子微粒子分散体を調製する。
使用する各材料の割合を変更して実施例1と同じ条件で実施例11~15の導電性高分子微粒子分散体を調製する。
実施例16~18では、使用する各材料の割合を3,4-エチレンジオキシチオフェン14.2重量部、ポリスチレンスルホン酸30.5重量部、硫酸第二鉄13.0重量部、過硫酸アンモニウム29.8重量部、蒸留水1337重量部である。すなわち、材料の割合は実施例8と同じである。
実施例19では、使用する各材料の割合を3,4-エチレンジオキシチオフェン14.2重量部、ポリスチレンスルホン酸30.5重量部、硫酸第二鉄13.2重量部、過硫酸アンモニウム29.8重量部、蒸留水1337重量部である。すなわち、材料の割合は実施例8とほぼ同じである。実施例19では過硫酸アンモニウムを投入した直後に硫酸第二鉄を投入する。すなわち硫酸第二鉄、過硫酸アンモニウムの投入順を逆にする。これら以外は、実施例1と同じ条件で導電性高分子微粒子分散体を調製する。
第1酸化剤として、硫酸第二鉄に代えて塩化第二鉄を8.5重量部用いる以外は実施例1と同じ条件で導電性高分子微粒子分散体を調製する。重合終了後のポリスチレンスルホン酸をドーパントとするポリ3,4-エチレンジオキシチオフェン100重量部に対する三価の鉄イオンの濃度は3.1重量部である。また、このときの分散体100重量部に対する三価の鉄イオンは、0.008重量部である。
第2酸化剤として、過硫酸アンモニウムに代えて過硫酸ナトリウムを30重量部用いる以外は実施例1と同じ条件で導電性高分子微粒子分散体を調製する。重合終了後のポリスチレンスルホン酸をドーパントとするポリ3,4-エチレンジオキシチオフェン100重量部に対する三価の鉄イオンの濃度は3.0重量部である。また、このときの分散体100重量部に対する三価の鉄イオンは、0.008重量部である。
第1酸化剤として、硫酸第二鉄に代えて塩化第二鉄を8.5重量部用い、第2酸化剤として、過硫酸アンモニウムに代えて過硫酸ナトリウムを30重量部用いる。これ以外は実施例1と同じ条件で導電性高分子微粒子分散体を調製する。重合終了後のポリスチレンスルホン酸をドーパントとするポリ3,4-エチレンジオキシチオフェン100重量部に対する三価の鉄イオンの濃度は3.0重量部である。また、このときの分散体100重量部に対する三価の鉄イオンは、0.007重量部である。
比較例1では、使用する各材料の割合を3,4-エチレンジオキシチオフェン14.2重量部、ポリスチレンスルホン酸30.5重量部、硫酸第二鉄7.0重量部、過硫酸アンモニウム29.8重量部、蒸留水4887重量部である。比較例2では、上記比較例1において、硫酸第二鉄3.5重量部、蒸留水320重量部である。比較例3では、上記比較例1において、硫酸第二鉄2.3重量部、蒸留水104重量部である。これらの条件以外は実施例1と同じにして導電性高分子微粒子分散体を調製する。
比較例4では、使用する各材料の割合を3,4-エチレンジオキシチオフェン14.2重量部、ポリスチレンスルホン酸30.5重量部、硫酸第二鉄78.7重量部、過硫酸アンモニウム29.8重量部、蒸留水56703重量部である。比較例5では、上記比較例4において、硫酸第二鉄39.5重量部、蒸留水4443重量部である。比較例6では、上記比較例1において、硫酸第二鉄30.0重量部、蒸留水1964重量部である。これらの条件以外は実施例1と同じにして導電性高分子微粒子分散体を調製する。
2 陰極
3 誘電体酸化皮膜層
4 セパレータ
5 固体電解質層
10 コンデンサ素子
11,12 リード端子
13 封口材
14 ケース
Claims (8)
- チオフェン類およびその誘導体から選ばれた少なくとも一つのモノマーと、ドーパントとしてポリアニオン類から選ばれた少なくとも一つのポリアニオンとを、水を主成分とする溶媒中に分散させて分散液を調製するステップと、
前記分散液と、前記溶媒中で鉄イオンを生じる第1酸化剤を含む酸化剤とを混合して前記モノマーを酸化重合させることにより、前記ポリアニオンがドープされた導電性のポリチオフェン微粒子分散体を調製するステップと、を備え、
前記モノマーの酸化重合反応が終了した時点の、前記ポリアニオンがドープされた導電性のポリチオフェン分散体中の三価の鉄イオンの濃度を、前記ポリチオフェン100重量部に対して、3重量部以上、30重量部以下である、
導電性高分子微粒子分散体の製造方法。 - 前記ポリアニオンがドープされた導電性のポリチオフェン分散体中の三価の鉄イオンの濃度が、前記分散体100重量部に対して、0.01重量部以上、0.20重量部以下である、
請求項1に記載の導電性高分子微粒子分散体の製造方法。 - 前記酸化剤が、前記第1酸化剤としての硫酸鉄(III)と、前記第1酸化剤と併用する第2酸化剤としての過硫酸アンモニウムとを含む、
請求項1、2のいずれか一項に記載の導電性高分子微粒子分散体の製造方法。 - 前記酸化剤を、前記分散液に複数回に分割して混合する、
請求項1~3のいずれか一項に記載の導電性高分子微粒子分散体の製造方法。 - 前記酸化剤を、前記分散液に2回に分割して混合する、
請求項4に記載の導電性高分子微粒子分散体の製造方法。 - 1回目の前記酸化剤の混合と2回目の前記酸化剤の混合の間隔が30分以上である、
請求項5に記載の導電性微粒子分散体の製造方法。 - 前記酸化剤は、前記第1酸化剤と併用され、前記溶媒中で鉄イオンを生じない第2酸化剤をさらに含み、前記第2酸化剤を前記分散液と混合した後に、前記第1酸化剤を混合させる、
請求項1に記載の導電性高分子微粒子分散体の製造方法。 - 陽極と、陰極と、前記陽極と陰極との間に介在するセパレータとを有するコンデンサ素子に、請求項1~7のいずれか一項に記載の製造方法により調製された導電性高分子微粒子分散体を含浸するステップと、
前記導電性高分子微粒子分散体に含まれる溶媒成分を除去して、前記陽極と前記陰極との間に導電性高分子の固体電解質層を形成するステップと、を備えた、
電解コンデンサの製造方法。
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