WO2014163202A1 - 固体電解コンデンサの製造方法 - Google Patents
固体電解コンデンサの製造方法 Download PDFInfo
- Publication number
- WO2014163202A1 WO2014163202A1 PCT/JP2014/060023 JP2014060023W WO2014163202A1 WO 2014163202 A1 WO2014163202 A1 WO 2014163202A1 JP 2014060023 W JP2014060023 W JP 2014060023W WO 2014163202 A1 WO2014163202 A1 WO 2014163202A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- conductive polymer
- conjugated conductive
- electrolytic capacitor
- dispersion
- solid electrolytic
- Prior art date
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- 150000003216 pyrazines Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000002053 thietanyl group Chemical group 0.000 description 1
- 125000001730 thiiranyl group Chemical group 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical group S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical group C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- 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
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
-
- 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
Definitions
- the present invention relates to a method for manufacturing a solid electrolytic capacitor and a solid electrolytic capacitor obtained by the manufacturing method.
- Solid electrolytic capacitors are known to be manufactured by forming a dielectric oxide film on a metal surface by anodic oxidation, and bringing this into contact with a solid electrolyte.
- Solid electrolytic using a conductive polymer as the solid electrolyte is known as a solid electrolytic capacitor.
- Capacitors have been proposed. Aluminum, tantalum, niobium and the like are known as examples of the metal covered with the dielectric oxide film formed by anodic oxidation.
- conjugated conductive polymers such as polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene, poly (p-phenylene-vinylene), polyacene, polythiophene vinylene and their derivatives. It has been.
- a technique of doping a conjugated conductive polymer using a polyanion such as polystyrene sulfonic acid as a counter anion of the conjugated conductive polymer is known.
- a solid electrolyte is formed by chemical oxidative polymerization of a monomer solution and an oxidant solution for obtaining a conductive polymer on a dielectric oxide film formed on a metal surface having a valve action. Or formed by electrolytic polymerization. Further, a method of forming by applying a conductive polymer aqueous solution or suspension has been proposed.
- Patent Document 1 discloses a step of forming a first solid electrolyte layer by impregnating a capacitor element with a conductive polymer dispersed aqueous solution in which conductive polymer fine particles are dispersed, and the first solid electrolyte layer.
- a second solid electrolyte layer is formed by impregnating the surface of the substrate individually with a solution containing a heterocyclic monomer and a solution containing an oxidizing agent or by impregnating a mixed solution containing a heterocyclic monomer and an oxidizing agent.
- a manufacturing method comprising the steps is disclosed.
- a conductive polymer layer is formed as a solid electrolyte layer by chemical polymerization of a polymerizable monomer on a capacitor element in which a dielectric oxide film is formed on the surface of a sintered body obtained by sintering valve metal powder.
- Patent Document 3 requires that the viscosity of a poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid (commonly known as PEDOT-PSS) dispersion be reduced in order to impregnate a capacitor with a conductive polymer.
- PEDOT-PSS polystyrene sulfonic acid
- the present invention can suppress an increase in viscosity during polymerization of a conjugated conductive polymer, and the conjugated conductive polymer has good conductivity, high impregnation properties, and coating properties. It is an object of the present invention to provide a solid electrolytic capacitor manufacturing method and a solid electrolytic capacitor capable of manufacturing a solid electrolytic capacitor having excellent capacitor characteristics with high productivity.
- the present inventors solved the above problem by manufacturing a solid electrolytic capacitor using a conjugated conductive polymer-containing dispersion containing seed particles protected by a polyanion. I found that I could do it. That is, the present invention relates to the following 1 to 13.
- the manufacturing method of the solid electrolytic capacitor which has the following process.
- a dispersion medium containing a monomer for obtaining a conjugated conductive polymer and seed particles protected by a polyanion as a protective colloid the monomer is polymerized to obtain a conjugated conductive polymer-containing dispersion.
- a dispersion of seed particles protected by a polyanion as a protective colloid is further added.
- the monomer for obtaining the conjugated conductive polymer is at least selected from pyrrole which may have a substituent, aniline which may have a substituent, and thiophene which may have a substituent. 7.
- R 1 and R 2 each independently represents a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 18 carbon atoms, or an optionally substituted carbon number. 1 to 18 alkoxy group or an optionally substituted alkylthio group having 1 to 18 carbon atoms, or a substituent in which R 1 and R 2 are bonded to each other to form a ring
- a sulfur atom-containing heterocycle having 2 to 10 carbon atoms which may have a group, or a sulfur atom and oxygen atom-containing heterocycle having 2 to 10 carbon atoms which may have a substituent is shown.
- a solid electrolytic capacitor obtained by the production method according to any one of 1 to 12 above.
- a conjugated conductive polymer-containing dispersion containing protective colloidal seed particles can be synthesized without increasing the viscosity of the dispersion during polymerization, and the above dispersion is used.
- the impregnation and coating properties of the porous anode body on which the dielectric oxide film is formed are excellent, the productivity of the solid electrolytic capacitor is excellent, and the conjugated system conductivity and the porous property are excellent. Since the anode body has high impregnation properties, a solid electrolytic capacitor having excellent capacitor characteristics can be produced.
- the method for producing the solid electrolytic capacitor of the present invention includes: In a dispersion medium containing a monomer for obtaining a conjugated conductive polymer and seed particles protected by a polyanion as a protective colloid, the monomer is polymerized to obtain a conjugated conductive polymer-containing dispersion.
- Obtaining step Attaching the conjugated conductive polymer-containing dispersion to the surface of a porous anode body having at least an anode body made of a valve metal and a dielectric coating formed on the surface of the anode body; and the porosity Removing a part or all of the dispersion medium from the conjugated conductive polymer-containing dispersion adhering to the anode body to form a solid electrolyte layer; It is characterized by having.
- the step of obtaining a conjugated conductive polymer-containing dispersion includes the above-mentioned monomer in a dispersion medium containing a monomer for obtaining a conjugated conductive polymer and seed particles protected by a polyanion. Is a step of polymerizing the conjugated conductive polymer.
- the conjugated conductive polymer-containing dispersion in the present invention comprises particles containing seed particles protected by a polyanion as a protective colloid and a conjugated conductive polymer (hereinafter sometimes simply referred to as “conductive polymer”).
- the “conductive polymer-containing particles” may be a dispersion (conductive polymer-containing dispersion) dispersed in a dispersion medium.
- a polyanion is coordinated on the surface of the seed particle so as to be a protective colloid, and the conjugated conductive polymer is doped with the polyanion.
- thickening during polymerization can be suppressed.
- the polyanion and the conjugated conductive polymer can be re-coordinated, and the conductivity is sufficiently developed.
- the conjugated conductive polymer is not particularly limited as long as the main chain is an organic polymer having a ⁇ -conjugated system.
- Examples of the conjugated conductive polymer include polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof.
- polypyrroles, polythiophenes and polyanilines are preferable, and polythiophenes are more preferable.
- preferred conjugated conductive polymers include polypyrroles such as polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propyl). Pyrrole), poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4) -Dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole) , Poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butene Shipiroru), poly (3-hexyloxy-pyrrole), poly (3-methyl-4-he
- Polythiophenes include polythiophene, poly (3-methylthiophene), poly (3-hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3- Dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene) ), Poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3- Butoxythiophene), poly (3-hexyloxythiophene), poly (3 Heptyloxythiophene), poly (3-
- polyanilines examples include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid).
- polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene), poly (3-methoxythiophene) and poly (3,4-ethylenedioxythiophene) have high conductivity.
- poly (3,4-ethylenedioxythiophene) [commonly known as PEDOT] is more preferable because it has higher conductivity and excellent heat resistance.
- PEDOT copolymer of 3,4-ethylenedioxythiophene and another monomer (for example, pyrrole).
- the content of the portion derived from 3,4-ethylenedioxythiophene in the PEDOT copolymer is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably Is 100% by mass.
- the conjugated conductive polymer can be used alone or in combination of two or more.
- the total amount of PEDOT and PEDOT copolymer in the conjugated conductive polymer is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and still more preferably 100% by mass. It is.
- the alkyl group, aryl group, heteroaryl group, alkoxy group and alkylthio group may be substituted with a carboxyl group, a hydroxyl group, a halogen atom or a cyano group. Two or more substituents may be condensed to form a ring.
- the monomer examples include pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3 -Dodecylpyrrole, 3,4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutyl Pyrrole, 3-hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole;
- a compound represented by the following formula (I) is preferably included, and a compound represented by the following formula (II) may be included. More preferably, 3,4-ethylenedioxythiophene is further included.
- R 1 and R 2 are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 18 carbon atoms, or an optionally substituted carbon number. 1 to 18 alkoxy group or an optionally substituted alkylthio group having 1 to 18 carbon atoms, or a substituent in which R 1 and R 2 are bonded to each other to form a ring
- a sulfur atom-containing heterocycle having 2 to 10 carbon atoms which may have a group, or a sulfur atom and oxygen atom-containing heterocycle having 2 to 10 carbon atoms which may have a substituent is shown.
- R 1 and R 2 are bonded to each other to form a ring
- R 1 and R 2 are bonded to each other to form a ring together with two carbons in the thiophene skeleton of formula (I).
- the number of carbon atoms in the ring formed by bonding R 1 and R 2 to each other includes two carbons in the thiophene skeleton.
- the substituent include an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heteroaryl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an alkylthio having 1 to 18 carbon atoms.
- the alkyl group, aryl group, heteroaryl group, alkoxy group and alkylthio group may be substituted with a carboxyl group, a hydroxyl group, a halogen atom or a cyano group.
- Two or more substituents may be condensed to form a ring.
- oxygen atom-containing heterocycle examples include an oxirane ring, an oxetane ring, a furan ring, a hydrofuran ring, a pyran ring, a pyrone ring, a dioxane ring, and a trioxane ring.
- sulfur atom-containing heterocycle examples include thiirane ring, thietane ring, thiophene ring, thiane ring, thiopyran ring, thiopyrylium ring, benzothiopyran ring, dithiane ring, dithiolane ring, and trithiane ring.
- Examples of the sulfur atom and oxygen atom-containing heterocycle include an oxathiolane ring and an oxathian ring.
- the content of the compound represented by the formula (I) in the total amount of the monomers for obtaining this conjugated conductive polymer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably Is 90% by mass or more, more preferably 100% by mass.
- R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent, or R 3 and R 4 are bonded to each other.
- R 1 and R 2 are bonded to each other to form a ring means that “R 1 and R 2 are bonded to each other to form a ring together with two carbons in the thiophene skeleton of formula (II).
- the number of carbon atoms in the ring formed by bonding R 1 and R 2 to each other includes two carbons in the thiophene skeleton.
- R 3 and R 4 are preferably a C 3-6 oxygen atom-containing heterocyclic ring which may have a substituent, in which R 3 and R 4 are bonded to each other to form a ring.
- a substituent for said oxygen atom containing heterocyclic ring, a dioxane ring, a trioxane ring, etc. are mentioned, Preferably it is a dioxane ring.
- the substituent include an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heteroaryl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an alkylthio having 1 to 18 carbon atoms.
- the alkyl group, aryl group, heteroaryl group, alkoxy group and alkylthio group may be substituted with a carboxyl group, a hydroxyl group, a halogen atom or a cyano group. Two or more substituents may be condensed to form a ring.
- the content of the compound represented by the formula (II) in the total amount of the monomers for obtaining this conjugated conductive polymer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably Is 90% by mass or more, more preferably 100% by mass.
- the seed particles used in the present invention are not limited as long as they are protective colloidalized with a polyanion in a dispersion medium.
- a homopolymer or copolymer obtained by polymerizing an ethylenically unsaturated monomer is used. Particles.
- the ethylenically unsaturated monomer may be any monomer having at least one polymerizable vinyl group, for example, (meth) acrylic acid esters having a linear, branched or cyclic alkyl chain, Aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, heterocyclic vinyl compounds such as vinylpyrrolidone, hydroxyalkyl (meth) acrylates, dialkylaminoalkyl (meth) acrylates, vinyl esters represented by vinyl acetate and vinyl alkanoates , Monoolefins (ethylene, propylene, butylene, isobutylene, etc.), conjugated diolefins (butadiene, isoprene, chloroprene, etc.), ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids (acrylic acid, methacrylic acid, crotonic acid, itacone) Acid, maleic acid, fumaric acid, etc.), acrylonite
- These ethylenically unsaturated monomers may be used singly or in combination of two or more. These ethylenically unsaturated monomers are preferably at least one of the above aromatic vinyl compounds and (meth) acrylic acid esters. When these ethylenically unsaturated monomers contain an aromatic vinyl compound, the aromatic vinyl compound is preferably contained in an amount of 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 90 to 100% by mass. . Of the aromatic vinyl compounds, styrene is preferably used.
- the (meth) acrylic acid esters are preferably 50 to 100% by mass, more preferably 70 to 100% by mass, Preferably 90 to 100% by mass is contained.
- the (meth) acrylates at least one of methyl (meth) acrylate and tert-butyl (meth) acrylate is preferable, and at least one of methyl methacrylate and tert-butyl methacrylate is more preferable. More preferred is methyl methacrylate.
- These ethylenically unsaturated monomers are preferably at least one of styrene, methyl methacrylate and tert-butyl methacrylate.
- epoxy group-containing ⁇ , ⁇ -ethylenically unsaturated compounds such as glycidyl (meth) acrylate, hydrolyzable alkoxysilyl group-containing ⁇ such as vinyltriethoxysilane and ⁇ -methacryloxypropyltrimethoxysilane , ⁇ -ethylenically unsaturated compounds, polyfunctional vinyl compounds (ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, divinylbenzene, diallyl phthalate, etc.)
- An ⁇ , ⁇ -ethylenically unsaturated compound containing a carbonyl group which is introduced into a homopolymer or a copolymer and crosslinked itself or in combination with an ethylenically unsaturated compound component having an active hydrogen group
- Crosslinkable monomers such as those containing keto groups It is introduced into a homopolymer or
- the water resistance, moisture resistance, and heat resistance of the conjugated conductive polymer can be improved by introducing the crosslinkable monomer into the homopolymer or copolymer.
- the crosslinkable monomer divinylbenzene is more preferable.
- the content of the crosslinking agent monomer in the homopolymer or copolymer is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, further preferably 5 to 15% by mass, and still more preferably 8 to 12%. % By mass.
- the polyanion used in the present invention is a polymer having an anionic group.
- the anionic group include a group composed of sulfonic acid or a salt thereof, a group composed of phosphoric acid or a salt thereof, a monosubstituted phosphate group, a group composed of a carboxylic acid or a salt thereof, a monosubstituted sulfate group.
- a strongly acidic group is preferable, a group consisting of sulfonic acid or a salt thereof, a group consisting of phosphoric acid or a salt thereof is more preferable, and a group consisting of sulfonic acid or a salt thereof is more preferable.
- the anionic group may be directly bonded to the polymer main chain or may be bonded to the side chain.
- the anionic group is preferably bonded to the end of the side chain.
- the polyanion may have a substituent other than the anionic group.
- substituents include alkyl group, hydroxy group, alkoxy group, phenol group, cyano group, phenyl group, hydroxyphenyl group, ester group, halogeno group, alkenyl group, imide group, amide group, amino group, oxycarbonyl group, A carbonyl group etc. are mentioned. Among these, an alkyl group, a hydroxy group, a cyano group, a phenol group, and an oxycarbonyl group are preferable, and an alkyl group, a hydroxy group, and a cyano group are more preferable.
- the substituent may be directly bonded to the polymer main chain or may be bonded to the side chain. When the substituent is bonded to the side chain, the substituent is preferably bonded to the end of the side chain in order to perform each function of the substituent.
- the alkyl group that can be substituted in the polyanion can be expected to increase the solubility and dispersibility in the dispersion medium, the compatibility with the conjugated conductive polymer, the dispersibility, and the like.
- the alkyl group include a chain alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group; a cyclopropyl group, Examples thereof include cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group.
- the cyano group and hydroxyphenyl group that can be substituted in the polyanion can be expected to have an effect of increasing the compatibility with the conjugated conductive polymer, the solubility in the dispersion medium, and the heat resistance.
- the cyano group is bonded directly to the polymer main chain, bonded to the terminal of the alkyl group having 1 to 7 carbon atoms bonded to the polymer main chain, or terminal of the alkenyl group having 2 to 7 carbon atoms bonded to the polymer main chain. Those bonded to are preferred.
- the oxycarbonyl group that can be substituted in the polyanion is preferably an alkyloxycarbonyl group, an aryloxycarbonyl group, or an alkyloxycarbonyl group or an aryloxycarbonyl group having another functional group directly bonded to the polymer main chain.
- the polymer main chain of the polyanion is not particularly limited.
- examples of the polymer main chain include polyalkylene, polyimide, polyamide, and polyester. Of these, polyalkylene is preferable from the viewpoint of synthesis and availability.
- Polyalkylene is a polymer composed of repeating units of ethylenically unsaturated monomers.
- the polyalkylene may have a carbon-carbon double bond in the main chain.
- Examples of polyalkylene include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, poly (3,3,3-trifluoropropylene), polyacrylonitrile, polyacrylate, polymethacrylate, polystyrene, polybutadiene, poly And isoprene.
- polyimides examples include pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2,3,3-tetracarboxydiphenyl ether dianhydride, 2,2- [4,4 Examples include those obtained by polycondensation reaction of acid anhydrides such as' -di (dicarboxyphenyloxy) phenyl] propane dianhydride and diamines such as oxydianiline, paraphenylenediamine, metaphenylenediamine, and benzophenonediamine. .
- polyamide examples include polyamide 6, polyamide 6,6, polyamide 6,10 and the like.
- polyester examples include polyethylene terephthalate and polybutylene terephthalate.
- polystyrene sulfonic acid examples include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, and poly (2-acrylamide). -2-methylpropanesulfonic acid), polyisoprenesulfonic acid and the like. These may be homopolymers or two or more types of copolymers.
- polystyrene sulfonic acid polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polyacrylic acid butyl sulfonic acid are preferable, and polystyrene sulfonic acid [commonly known as PSS] is more preferable.
- PSS polystyrene sulfonic acid
- Polyanions especially polymers with sulfonic acid groups, can mitigate the thermal decomposition of conjugated conductive polymers and improve the dispersibility of the monomers in the dispersion medium to obtain conjugated conductive polymers. And function as a dopant for the conjugated conductive polymer.
- the polyanion used in the present invention has a weight average molecular weight of preferably 1,000 to 1,000,000, more preferably 5,000 to 300,000, still more preferably 8,000 to 200,000, still more preferably. 9,000-150,000.
- weight average molecular weight is in this range, the solubility of the polyanion in the dispersion medium and the doping of the polyanion to the conjugated conductive polymer are good.
- a weight average molecular weight is measured as a polystyrene conversion molecular weight using gel permeation chromatography.
- the polyanion may have the above properties selected from commercially available products, or may be obtained by synthesis by a known method.
- Examples of the method for synthesizing polyanions include the method described in Houben-Weyl, “Methoden der derorganischen Chemle” Vol. .
- the total amount of polyanions used is determined by the anionic group in the polyanion being conjugated.
- the amount is preferably 0.25 to 30 mol, more preferably 0.8 to 25 mol, still more preferably 1 to 10 mol, and still more preferably 2 to 1 mol of the monomer for obtaining a conductive polymer.
- the amount is ⁇ 5 mol.
- the amount of polyanion used in 100 parts by mass of the conjugated conductive polymer in this step is preferably 10 to 30,000 parts by mass, more preferably 50 to 25,000 parts by mass, and still more preferably 100 to 1,000. Part by mass, more preferably 200 to 500 parts by mass.
- the seed particles are those that are protective colloidalized with a polyanion in a dispersion medium, and a dispersion of the protective colloidalized seed particles dispersed in the dispersion medium can be produced as a resin emulsion.
- the polymerization reaction of the resin emulsion is a radical polymerization reaction, and is performed by any one of a batch type, a semi-continuous type, and a continuous type using an atmospheric pressure reactor or a pressure resistant reactor.
- the ethylenically unsaturated monomer and the polyanion are dissolved, emulsified or dispersed in a dispersion medium in advance, respectively, and the polyanion-containing liquid is mixed with the ethylenically unsaturated monomer. It is preferable to polymerize by adding a saturated monomer solution continuously or intermittently.
- the reaction temperature is usually 10 to 100 ° C., but is generally 30 to 90 ° C., preferably 60 to 90 ° C.
- the reaction time is not particularly limited, and may be appropriately adjusted according to the amount of each component used, the type of polymerization initiator, the reaction temperature, and the like.
- polyanion which is a protective colloid, contributes to the stability of the emulsion particles. It may be added. What is necessary is just to adjust suitably the kind and usage-amount of an emulsifier and an aliphatic amine according to various conditions including the usage-amount of a polyanion, and a composition of an ethylenically unsaturated monomer.
- emulsifiers used in such radical polymerization reactions include alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, polyoxyalkylene alkyl sulfates, and polyoxyalkylene alkyl phosphates.
- Nonionic surfactants such as anionic emulsifiers such as esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, and the like.
- Aliphatic amines include primary amines such as octylamine, laurylamine, myristylamine, stearylamine and oleylamine, secondary amines such as dioctylamine, dilaurylamine, distearylamine and dioleylamine, N, N-dimethyllauryl Amines, N, N-dimethylmyristylamine, N, N-dimethylpalmitylamine, N, N-dimethylstearylamine, N.N. And tertiary amines such as N-dimethylbehenylamine, N, N-dimethyloleylamine, N-methyldidecylamine and N-methyldioleylamine. You may use an emulsifier and an aliphatic amine individually by 1 type or in combination of 2 or more types.
- water-soluble polymers such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and polyvinyl pyrrolidone may be used in combination as long as the characteristics of the resulting conjugated conductive polymer are not impaired.
- the dispersion medium is an aqueous medium, and includes water or a mixed solvent of water and a water-soluble solvent.
- the proportion of the water-soluble solvent in the mixed solvent is preferably 0 to 30% by mass. When the proportion of the water-soluble solvent is 30% by mass or less, the polymerization stability of the synthetic resin emulsion tends to be improved.
- the water-soluble solvent include alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone, glycols such as ethylene glycol and propylene glycol, ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether, and the like. .
- the polymerization initiator used in radical polymerization known and conventional ones can be used.
- the polymerization initiator include inorganic peroxides such as hydrogen peroxide, persulfuric acid, ammonium persulfate, potassium persulfate, and sodium persulfate, organic peroxides such as benzoyl peroxide and t-butyl hydroperoxide, Azo compounds such as 2,2′-azobisisobutyronitrile and 4,4′-azobis (4-cyanovaleric acid) are preferred, inorganic peroxides are preferred, and at least ammonium persulfate and potassium persulfate are preferred. One is more preferable, and potassium persulfate is more preferable.
- these polymerization initiators may be combined with sodium sulfoxylate formaldehyde, ascorbic acids, sulfites, tartaric acid or salts thereof, iron (II) sulfate, or the like for redox polymerization.
- chain transfer agents such as alcohol and mercaptans, as needed.
- the amount of the ethylenically unsaturated monomer used is preferably 10 to 100 parts by weight, more preferably 20 to 90 parts by weight, with respect to 100 parts by weight of the polyanion used in the production of the protective colloidal seed particles.
- the amount is preferably 30 to 70 parts by mass, and more preferably 35 to 50 parts by mass.
- the amount of the ethylenically unsaturated monomer used is 10 parts by mass or more, the proportion of the conjugated conductive polymer is relatively small, and the effect of suppressing the increase in viscosity during polymerization is easily obtained.
- the amount is more than 100 parts by mass, the stability of the protective colloidal seed particles is improved.
- the particle diameter d50 (50% median diameter on a volume basis) of the seed particles that are converted into protective colloid and dispersed in the dispersion medium is preferably 0.01 to 10 ⁇ m, more preferably 0.05. ⁇ 1 ⁇ m, more preferably 0.1 to 0.8 ⁇ m.
- the particle size distribution of the seed particles can be measured using a Microtrac UPA type particle size distribution measuring device manufactured by Nikkiso Co., Ltd.
- the particle size d50 dispersed in the seed particle dispersion medium is 0.01 ⁇ m or more, the dispersibility of the seed particles is improved, and when it is 10 ⁇ m or less, particle sedimentation is suppressed.
- Polymer polymerization Polymerization of the monomer for obtaining the conjugated conductive polymer is carried out in a dispersion medium containing the monomer for obtaining the conjugated conductive polymer and seed particles protected as a colloid with a polyanion. .
- a dispersion (resin emulsion) of a seed particle protected by colloid with the monomer, polyanion, and if necessary Additives are added to the dispersion medium to obtain a dispersion containing the monomer and protective colloidal seed particles (hereinafter sometimes simply referred to as a monomer liquid).
- the monomer solution may be prepared by a powerful stirring device such as a homogenizer, but it is preferably performed by ultrasonic irradiation.
- the ultrasonic irradiation energy is not particularly limited as long as a uniform monomer liquid can be obtained.
- the ultrasonic irradiation is preferably performed at a power consumption of 5 to 500 W / L (liter) and an irradiation time of 0.1 to 10 hours / L (liter).
- the power consumption is more preferably 100 to 500 W / L, further preferably 200 to 500 W / L, and still more preferably 200 to 400 W / L.
- the irradiation time is more preferably 0.5 to 8 hours / L, still more preferably 1 to 6 hours / L, still more preferably 2 to 5 hours / L.
- a conjugated conductive polymer formed during the polymerization is contained in a dispersion medium containing a monomer for obtaining a conjugated conductive polymer before the start of polymerization and seed particles protected by a polyanion as a protective colloid.
- a conjugated conductive polymer formed during the polymerization is contained in a dispersion medium containing a monomer for obtaining a conjugated conductive polymer before the start of polymerization and seed particles protected by a polyanion as a protective colloid.
- a part of the same predetermined amount of polyanion as that used for the protective colloid formation of the seed particles can be contained.
- the polyanion can be added to the monomer solution and dissolved, emulsified or dispersed in the monomer solution.
- the amount of the polyanion before the start of the polymerization is 5 to 99 of the total amount excluding the protective colloid of the polyanion seed particles to be used. % By weight is preferred, 10 to 90% by weight is more preferred, and 20 to 80% by weight is even more preferred.
- the dispersion medium used for monomer polymerization is not particularly limited as long as it can disperse a conjugated conductive polymer composed of a conjugated conductive polymer and seed particles protected by a polyanion as a protective colloid. However, the same type as that used for the seed particle dispersion is preferred.
- dispersion medium examples include water; amides such as N-vinylpyrrolidone, hexamethylphosphortriamide, N-vinylformamide, and N-vinylacetamide; phenols such as cresol, phenol, and xylenol; dipropylene glycol, 1,3 -Polyhydric alcohols such as butylene glycol, 1,4-butylene glycol, diglycerin, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol Carbonate compounds such as ethylene carbonate and propylene carbonate; dioxane, diethyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether 3-methyl-2-heterocyclic compounds such as oxazolidinone; ether
- solvents can be used alone or in combination of two or more.
- a dispersion medium containing 1 to 100% by weight of water, more preferably 50 to 100% by weight of water, still more preferably 80 to 100% by weight of water, and still more preferably 90 to 90% of water. It is more preferable to include 100% by mass, and it is more preferable to use water alone.
- the amount of the dispersion medium used is preferably 1 to 50,000 parts by mass with respect to a total of 100 parts by mass of the monomer for obtaining the conjugated conductive polymer and the seed particles protected by the polyanion as a protective colloid.
- the amount is preferably 50 to 10,000 parts by mass, more preferably 1,000 to 5,000 parts by mass, and still more preferably 2,000 to 3,500 parts by mass. If the amount of the dispersion medium used is too small, the viscosity of the dispersion tends to increase. If the amount of the dispersion medium used is too large, the operation for removing the dispersion medium from the dispersion requires time and the productivity of the solid electrolytic capacitor tends to decrease.
- ⁇ Oxidant> In the polymerization of the above monomers, for example, when producing a dispersion containing polypyrroles or polythiophenes as a conjugated conductive polymer, the polymerization is started by bringing the temperature to a predetermined temperature in the presence of an oxidizing agent.
- peroxodisulfuric acid ammonium peroxodisulfate (ammonium persulfate), peroxodisulfate such as sodium peroxodisulfate (sodium persulfate), potassium peroxodisulfate (potassium persulfate); metals such as boron trifluoride Halogen compounds; transition metal compounds such as ferric chloride, ferric sulfate and cupric chloride; metal oxides such as silver oxide and cesium oxide; peroxides such as hydrogen peroxide and ozone; benzoyl peroxide and the like Organic peroxides; oxygen and the like.
- peroxodisulfuric acid and peroxodisulfate are preferred, peroxodisulfate is more preferred, and at least one of ammonium peroxodisulfate (ammonium persulfate) and sodium peroxodisulfate (sodium persulfate) is more preferred. Sodium (sodium persulfate) is even more preferred.
- the said oxidizing agent can be used individually by 1 type or in combination of 2 or more types.
- the content of the oxidizing agent with respect to 100 parts by mass of the monomer for obtaining the conjugated conductive polymer is preferably 50 to 500 parts by mass, more preferably 100 to 300 parts by mass, and further preferably 150 to 250 parts by mass. It is.
- an oxidation catalyst may be used.
- the oxidation catalyst iron p-toluenesulfonate is preferable.
- the content of the oxidation catalyst with respect to 100 parts by mass of the monomer for obtaining the conjugated conductive polymer is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, and further preferably 5 to 10 parts by mass. It is.
- the polymerization temperature in the polymerization of the monomer is usually 5 to 80 ° C., preferably 10 to 60 ° C., more preferably 15 to 40 ° C.
- the temperature during polymerization is within this range, polymerization can be carried out at an appropriate reaction rate, increase in viscosity can be suppressed, and production of a dispersion containing a conjugated conductive polymer can be performed stably and economically.
- the conjugated conductive polymer obtained tends to have a high conductivity.
- polymerization can be managed by using a well-known heater and a cooler. Moreover, you may superpose
- the step of obtaining the conjugated conductive polymer-containing dispersion it is preferable to disperse the conjugated conductive polymer to be produced during the polymerization of the monomer.
- This dispersion treatment can be performed by a powerful stirring device such as a homogenizer, but is preferably performed by ultrasonic irradiation.
- the ultrasonic irradiation energy is not particularly limited as long as aggregation of the conjugated conductive polymer can be suppressed.
- the ultrasonic irradiation is preferably performed at a power consumption of 5 to 500 W / L, more preferably 100 to 500 W / L, and still more preferably 200 to 500 W / L, until the end of the reaction.
- a dispersion of seed particles that are made into a protective colloid with a polyanion during polymerization of the monomer.
- the amount of the protective colloidal seed particle dispersion added during the polymerization is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, based on the total amount of the protective colloidal seed particle dispersion used. 25 to 50% by mass is more preferable, and 30 to 45% by mass is even more preferable.
- ⁇ Addition of polyanion> you may further add the polyanion used in order to make a seed particle into protective colloid in the middle of polymerization of a monomer.
- the amount of polyanion added during the polymerization is preferably 0 to 90% by mass, more preferably 20 to 70% by mass, based on the total amount of polyanions used.
- an additive can be added to the monomer liquid or the conjugated conductive polymer-containing dispersion obtained in this step.
- the additive is not particularly limited as long as it can be mixed with the conjugated conductive polymer and the seed particles protected by colloid with a polyanion.
- the additives include water-soluble polymer compounds, water-dispersible compounds, alkaline compounds, surfactants, antifoaming agents, coupling agents, antioxidants, electrical conductivity improvers, and the like.
- An agent can be used individually by 1 type or in combination of 2 or more types.
- the water-soluble polymer compound is a water-soluble polymer having a cationic group or a nonionic group in the main chain or side chain of the polymer.
- Specific examples of the water-soluble polymer compound include, for example, polyoxyalkylene, water-soluble polyurethane, water-soluble polyester, water-soluble polyamide, water-soluble polyimide, water-soluble polyacryl, water-soluble polyacrylamide, polyvinyl alcohol, polyacrylic acid and the like. Is mentioned. Of these, polyoxyalkylene is preferred.
- polyoxyalkylene examples include diethylene glycol, triethylene glycol, oligopolyethylene glycol, triethylene glycol monochlorohydrin, diethylene glycol monochlorohydrin, oligoethylene glycol monochlorohydrin, triethylene glycol monobromohydrin, diethylene glycol monobromhydrin, Oligoethylene glycol monobromohydrin, polyethylene glycol, glycidyl ethers, polyethylene glycol glycidyl ethers, polyethylene oxide, triethylene glycol / dimethyl ether, tetraethylene glycol / dimethyl ether, diethylene glycol / dimethyl ether, diethylene glycol / diethyl ether / diethylene glycol Dibutyl ether, dipropylene glycol, tripropylene glycol, polypropylene glycol, polypropylene dioxide, polyoxyethylene alkyl ethers, polyoxyethylene glycerol fatty acid esters, polyoxyethylene fatty acid amides.
- a water-dispersible compound is a compound in which a part of a low hydrophilic compound is substituted with a highly hydrophilic functional group, or a compound having a highly hydrophilic functional group adsorbed around a low hydrophilic compound (For example, emulsion etc.), which is dispersed without being precipitated in water.
- Specific examples include polyesters, polyurethanes, acrylic resins, silicone resins, and emulsions of these polymers.
- the water-soluble polymer compound and the water-dispersible compound can be used alone or in combination of two or more. When a water-soluble polymer compound and a water-dispersible compound are added, the viscosity of the dispersion containing the conjugated conductive polymer can be adjusted, and the coating performance can be improved.
- the total amount is preferably 1 to 100 parts by mass with respect to a total of 100 parts by mass of the conjugated conductive polymer and the seed particles protected with a polyanion.
- the amount is 4000 parts by mass, more preferably 50 to 2000 parts by mass.
- alkaline compound known inorganic alkaline compounds and organic alkaline compounds can be used.
- the inorganic alkaline compound include ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia and the like.
- the organic alkaline compound include aromatic amines, aliphatic amines, and alkali metal alkoxides.
- nitrogen-containing heteroaryl ring compounds are preferred.
- the nitrogen-containing heteroaryl ring compound is a nitrogen-containing heterocyclic compound that exhibits aromaticity.
- the nitrogen atom contained in the heterocycle has a conjugated relationship with other atoms.
- the nitrogen-containing heteroaryl ring compound include pyridines, imidazoles, pyrimidines, pyrazines, and triazines. Of these, pyridines, imidazoles, and pyrimidines are preferable from the viewpoint of solvent solubility and the like.
- Surfactants include anionic surfactants such as carboxylates, sulfonates, sulfates and phosphates; cationic surfactants such as amine salts and quaternary ammonium salts; carboxybetaines and aminocarboxylic acids Examples include amphoteric surfactants such as salts and imidazolium betaines; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, ethylene glycol fatty acid esters, and polyoxyethylene fatty acid amides.
- Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone resin.
- examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, saccharides, vitamins and the like.
- the electrical conductivity improver is not particularly limited as long as it increases the electrical conductivity of the dispersion containing the conjugated conductive polymer.
- Examples of the electrical conductivity improver include compounds containing an ether bond such as tetrahydrofuran; compounds containing a lactone group such as ⁇ -butyrolactone and ⁇ -valerolactone; caprolactam, N-methylcaprolactam, N, N-dimethylacetamide, N -Compounds containing amide or lactam groups such as methylacetamide, N, N-dimethylformamide, N-methylformamide, N-methylformanilide, N-methylpyrrolidone, N-octylpyrrolidone, pyrrolidone; tetramethylenesulfone, dimethylsulfoxide, etc.
- Sulfone compounds or sulfoxide compounds comprising sugars or saccharide derivatives such as sucrose, glucose, fructose and lactose; sugar alcohols such as sorbitol and mannitol; imides such as succinimide and maleimide
- a furan derivative such as 2-furancarboxylic acid or 3-furancarboxylic acid
- a dialcohol or polyalcohol such as ethylene glycol, propylene glycol, glycerin, diethylene glycol, or triethylene glycol;
- tetrahydrofuran, N-methylformamide, N-methylpyrrolidone, ethylene glycol, propylene glycol, glycerin, dimethyl sulfoxide, and sorbitol are preferable from the viewpoint of improving electrical conductivity, and ethylene glycol, propylene glycol, and glycerin are more preferable.
- An electrical conductivity improver can be used individually by 1 type or in combination of 2 or more types.
- the solid content concentration of the conjugated conductive polymer-containing dispersion thus obtained is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, still more preferably 2 to 8% by mass, Even more preferably, it is 3 to 5% by mass.
- the polyanion is coordinated on the surface of the seed particles, whereby the particle size of the conjugated conductive polymer can be controlled and the viscosity increase during polymerization can be suppressed. Can do.
- the conjugated conductive polymer can be coordinated to the polyanion which is a dopant in the conjugated conductive polymer, and conductivity is exhibited.
- the production method of the present invention has at least the conjugated conductive polymer-containing dispersion obtained in the above-described step, an anode body made of a valve metal, and a dielectric film formed on the surface of the anode body.
- the solid electrolytic capacitor of the present invention can use, for example, a porous electrode obtained by sintering a valve metal powder having a high surface area, or a porous film obtained by etching a valve metal foil.
- valve metal examples include Al, Be, Bi, Mg, Ge, Hf, Nb, Sb, Si, Sn, Ta, Ti, V, W, and Zr, and alloys of at least one of these metals with other elements. Or a compound is mentioned. Among these, an electrode material composed of a valve metal of aluminum, niobium, or tantalum is preferable.
- a porous electrode made of a valve metal is formed into a porous anode body by forming a dielectric oxide film on the surface by, for example, anodization.
- the porous electrode can be anodized, for example, by applying a voltage in a phosphoric acid solution to form a dielectric oxide film.
- the magnitude of the formation voltage can be determined by the thickness of the dielectric oxide film and the withstand voltage of the capacitor.
- a preferable formation voltage is 1 to 800V, more preferably 1 to 300V.
- the production method of the present invention removes a part or all of the dispersion medium from the conjugated conductive polymer-containing dispersion adhering to the porous anode body obtained in the above-described step, thereby forming a solid electrolyte layer.
- the method for removing the dispersion medium is preferably performed by heat treatment from the viewpoint of efficiency, and is desirably performed in a range in which the conjugated conductive polymer is not deteriorated by oxygen.
- the heating conditions can be determined by the boiling point and volatility of the dispersion medium.
- the heating is preferably performed at room temperature to 300 ° C., preferably 50 to 200 ° C., more preferably 80 to 150 ° C.
- the heat treatment time is preferably 5 seconds to several hours.
- a hot plate, an oven, or a hot air dryer can be used.
- the reaction may be performed under reduced pressure in order to perform the heat treatment quickly in the atmosphere.
- the process of attaching the above-mentioned dispersion liquid, and the process of forming a solid electrolyte layer once or twice or more you may repeat the process of attaching the above-mentioned dispersion liquid, and the process of forming a solid electrolyte layer once or twice or more. Further, each time the dispersion is attached, heat treatment may be performed to remove a part or all of the dispersion medium, or the dispersion may be continuously attached a plurality of times and finally the dispersion medium may be removed. Further, after removing a part or all of the dispersion medium contained in the attached dispersion liquid, an arbitrary electrolytic solution may be impregnated.
- the physical properties of the dispersions in Examples and Comparative Examples were measured as follows.
- (1) Solid content concentration The solid content concentration in the dispersion was measured by weighing about 2 g of the dispersion obtained in each example into a sample container, and allowed to stand in a dryer at 105 ° C for 1 hour, and then in the sample container. The mass of the sample was measured, and the mass after drying relative to the mass before drying, that is, [mass after drying / mass before drying] was calculated as the solid content concentration.
- Viscosity The viscosity of the dispersion during the polymerization is a B-type viscometer at 25 ° C. Measurements were made using two rotors.
- Example 1 Production of seed particles protected by polyanions While stirring 1000 g of a 22 mass% aqueous solution of sodium polystyrene sulfonate (trade name Polynus PS-5, weight average molecular weight: about 120,000, manufactured by Tosoh Organic Chemical Co., Ltd.) in a nitrogen atmosphere, the temperature was raised to 80 ° C.
- sodium polystyrene sulfonate trade name Polynus PS-5, weight average molecular weight: about 120,000, manufactured by Tosoh Organic Chemical Co., Ltd.
- the ion exchange resin After adding 1500 ml of cation exchange resin and 1500 ml of anion exchange resin to the obtained reaction liquid and stirring for 12 hours, the ion exchange resin is separated by filtration, and a dispersion of seed particles protected by colloid with polyanion (polystyrene emulsion) Got.
- the d50 particle diameter of the seed particles in the obtained polystyrene emulsion was 0.46 ⁇ m.
- a cation exchange resin and 300 ml of an anion exchange resin are added to the obtained reaction solution, and the reaction solution is stirred for 12 hours, thereby converting unreacted monomers, an oxidizing agent and an oxidation catalyst into an ion exchange resin. Adsorbed.
- the ion exchange resin is separated by filtration, and a conjugated conductive polymer comprising seed particles (polystyrene emulsion) protected with polystyrene sulfonic acid and poly (3,4-ethylenedioxythiophene) doped with the polystyrene sulfonic acid.
- a coalescence-containing dispersion (1-1) was obtained.
- a porous anode body having a dielectric oxide film on its surface used for the solid electrolytic capacitor in the present invention was produced in accordance with the method disclosed in Japanese Patent Application Laid-Open No. 2011-77257. That is, a porous anode body in which a dielectric oxide film having niobium pentoxide was formed on the anode body surface using niobium powder for a capacitor was produced.
- This porous anode body had a capacitance of 22 ⁇ F in 30% sulfuric acid in accordance with the method described in the non-patent document “EIAJ standard RC2361A (revised in February 2000)”.
- the porous anode body obtained by the above method was impregnated with the dispersion liquid (1-1) for 1 minute in an atmosphere at 25 ° C. and then dried with a hot air dryer at 105 ° C. Next, a carbon paste was applied to the porous anode body and dried so as not to contact the anode lead terminal, and further, a silver paste was applied and dried to make contact with the cathode.
- the obtained solid electrolytic capacitor was measured for capacitance ( ⁇ F) at 120 Hz and equivalent series resistance [ESR] ( ⁇ ) at 100 kHz using an LCR meter. Table 4 shows the measurement results.
- a porous anode body having a dielectric oxide film on its surface was produced in the same manner as in Example 1.
- Example 2 Formation of porous anode body having dielectric oxide film on surface and adhesion of dispersion
- Example 1 a porous anode body having a dielectric oxide film on its surface was formed.
- the dispersion liquid (2-1) was prepared in the same manner as in Example 1 except that the above dispersion anode (1) was used instead of the dispersion liquid (1-1).
- the obtained solid electrolytic capacitor was measured for capacitance ( ⁇ F) at 120 Hz and equivalent series resistance [ESR] ( ⁇ ) at 100 kHz using an LCR meter. The measurement results are shown in Table 2.
- Dispersions (2-2) and (2-3) containing poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid doped therein were used in the same manner as in Example 1 except that the formulation shown in Table 2 was used.
- Tables 2 to 3 show the results of measuring the physical properties of the obtained dispersions (2-2) and (2-3) by the methods described above.
- Example 2 Formation of porous anode body having dielectric oxide film on surface and adhesion of dispersion
- a porous anode body having a dielectric oxide film on its surface was formed.
- a dispersion was performed in the same manner as in Example 1 except that the dispersions (2-2) and (2-3) were used instead of the dispersion (1-1). Liquids (2-2) and (2-3) were adhered to the porous anode body to obtain a solid electrolytic capacitor.
- Table 4 shows the measurement results of the obtained solid electrolytic capacitor.
- the conjugated conductive polymer-containing dispersion containing the protective colloidal seed particles of Example 1 can be produced without increasing the viscosity during polymerization.
- the obtained dispersion exhibits a high impregnation property to the porous anode body, the solid electrolytic capacitor excellent in capacitor characteristics in Example 1 having a larger capacitance than that of Comparative Example 1 and having a small equivalent series resistance. was gotten. Therefore, it can be seen from Example 1 that according to the present invention, a solid electrolytic capacitor having excellent capacitor characteristics can be manufactured with high productivity.
- Comparative Example 1 is inferior in productivity because the viscosity at the time of polymerization becomes very large, and the solid electrolytic capacitor using the obtained dispersion is inferior in capacitor characteristics as compared with Example 1.
- PS-1 weight average molecular weight 50,000
- PS-5 weight average molecular weight 120,000
- Example 3 since the polymerization initiator (ammonium persulfate) was used instead of the polymerization initiator (potassium persulfate) of Example 1, the capacitance and equivalent series resistance were slightly inferior to those of Example 1, Capacitor characteristics superior to those of the comparative example.
- the solid electrolytic capacitor has capacitor characteristics regardless of whether styrene, methyl methacrylate, or tert-butyl methacrylate is used as the ethylenically unsaturated monomer that is a constituent of the seed particles. Is excellent.
- Example 7 the amount of styrene, which is a constituent component of the seed particles, is halved compared to Example 1, but the capacitor characteristics are as excellent as in Example 1.
- a porous anode body on which a dielectric oxide film is formed can be obtained. Since the impregnation and coating properties are good, the productivity of solid electrolytic capacitors is excellent, and the above dispersion exhibits good conductivity and high impregnation into the porous anode. It can be manufactured and is industrially useful.
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Abstract
Description
陽極酸化による誘電体酸化被膜で被われる金属の例として、アルミニウム、タンタル、ニオブ等が知られている。
また、固体電解コンデンサに用いられる導電性高分子として、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセチレン、ポリフェニレン、ポリ(p-フェニレン-ビニレン)、ポリアセン、ポリチオフェンビニレンおよびその誘導体等の共役系導電性重合体が知られている。また、上記共役系導電性重合体の対アニオンとしてポリスチレンスルホン酸等のポリアニオンを用い、共役系導電性重合体をドープする技術が知られている。
例えば、特許文献1には、コンデンサ素子に導電性高分子の微粒子を分散させた導電性高分子分散水溶液を含浸させて第1の固体電解質層を形成する工程と、この第1の固体電解質層の表面に、複素環式モノマーを含有する溶液と酸化剤を含有する溶液を個々に含浸又は複素環式モノマーと酸化剤を含有する混合溶液を含浸することにより第2の固体電解質層を形成する工程とを具備した製造方法が開示されている。
特許文献2には、弁金属粉末を焼結してなる焼結体の表面に誘電体酸化皮膜を形成したコンデンサ素子に、固体電解質層として重合性モノマーの化学重合により導電性高分子層を形成した後、このコンデンサ素子を導電性高分子溶液に浸漬、又は導電性高分子溶液を塗布し、乾燥させることにより、化学重合による導電性高分子層の上にさらに厚く導電性高分子層を形成する方法が開示されている。
特許文献3には、導電性ポリマーをコンデンサ内部へ含浸させるために、ポリ(3,4-エチレンジオキシチオフェン)-ポリスチレンスルホン酸〔通称PEDOT-PSS〕分散液の低粘度化を必要としており、超音波照射を用いた重合を実施することを特徴とするプロセスが提案されている。
ところで、導電性重合体は分散媒中で凝集しやすく、導電性重合体を含む分散液は反応時に高粘度になることがある。高粘度の分散液は工業的な取扱いが不便である。また、固体電解コンデンサへの適用のために、より高い導電性と含浸性および塗布性が、導電性重合体含有分散液に求められている。
すなわち、本発明は下記1~13に関する。
共役系導電性重合体を得るための単量体と、ポリアニオンにより保護コロイド化されたシード粒子とを含む分散媒中で、上記単量体を重合して共役系導電性重合体含有分散液を得る工程、
弁金属からなる陽極体と、該陽極体表面に形成された誘電体被膜とを少なくとも有する多孔性陽極体の表面に、上記共役系導電性重合体含有分散液を付着させる工程、及び
上記多孔性陽極体に付着した共役系導電性重合体含有分散液から、分散媒の一部又は全部を除去し、固体電解質層を形成する工程。
2. 前記シード粒子が、エチレン性不飽和単量体を重合して得られる単独重合体又は共重合体である、前記1に記載の固体電解コンデンサの製造方法。
3. 前記ポリアニオンにより保護コロイド化されたシード粒子のd50粒子径が、0.01~10μmである、請求項1又は2に記載の固体電解コンデンサの製造方法。
4. 前記共役系導電性重合体含有分散液を得る工程において、前記単量体の重合の途上に、ポリアニオンにより保護コロイド化されたシード粒子の分散液をさらに添加する、前記1~3のいずれかに記載の固体電解コンデンサの製造方法。
5. 前記共役系導電性重合体含有分散液を得る工程において、前記単量体の重合の途上で、生成する共役系導電性重合体を分散処理する、前記1~4のいずれかに記載の固体電解コンデンサの製造方法。
6. 前記分散処理を超音波照射によって行う、前記5に記載の固体電解コンデンサの製造方法。
7. 前記共役系導電性重合体を得るための単量体が、置換基を有してもよいピロール、置換基を有してもよいアニリン、および置換基を有してもよいチオフェンから選ばれる少なくとも1つである、前記1~6のいずれかに記載の固体電解コンデンサの製造方法。
8. 前記共役系導電性重合体を得るための単量体が、下記式(I)で表される化合物を含むものである、前記1~6のいずれかに記載の固体電解コンデンサの製造方法。
9. 前記ポリアニオンがスルホン酸基を有するポリマーである、前記1~8のいずれかに記載の固体電解コンデンサの製造方法。
10. 前記ポリアニオン中のアニオン基が、前記共役系導電性重合体を得るための単量体1モルに対し、0.25~30モルである、前記1~9のいずれかに記載の固体電解コンデンサの製造方法。
11. 前記共役系導電性重合体含有分散液を得る工程において、
前記分散媒が水を含み、
前記重合がペルオキソ二硫酸およびその塩から選ばれる少なくとも一つの酸化剤を用いて行われる、前記1~10のいずれかに記載の固体電解コンデンサの製造方法。
12. 前記共役系導電性重合体含有分散液が、エチレングリコール、プロピレングリコールおよびグリセリンから選ばれる少なくとも1つの電気伝導率向上剤を含む、前記1~11のいずれかに記載の固体電解コンデンサの製造方法。
13. 前記1~12のいずれかに記載の製造方法で得られる固体電解コンデンサ。
共役系導電性重合体を得るための単量体と、ポリアニオンにより保護コロイド化されたシード粒子とを含む分散媒中で、上記単量体を重合して共役系導電性重合体含有分散液を得る工程、
弁金属からなる陽極体と、該陽極体表面に形成された誘電体被膜とを少なくとも有する多孔性陽極体の表面に、上記共役系導電性重合体含有分散液を付着させる工程、及び
上記多孔性陽極体に付着した共役系導電性重合体含有分散液から、分散媒の一部又は全部を除去し、固体電解質層を形成する工程、
を有することを特徴とする。
共役系導電性重合体含有分散液を得る工程は、共役系導電性重合体を得るための単量体と、ポリアニオンにより保護コロイド化されたシード粒子とを含む分散媒中で、上記単量体を重合して共役系導電性重合体を得る工程である。
本発明における共役系導電性重合体含有分散液は、ポリアニオンにより保護コロイド化されたシード粒子と共役系導電性重合体(以下、単に「導電性重合体」ということがある)とを含む粒子(以下、「導電性重合体含有粒子」ということがある)が、分散媒中に分散した分散液(導電性重合体含有分散液)である。
上記共役系導電性重合体含有粒子において、シード粒子の表面にポリアニオンが保護コロイドとなるように配位し、このポリアニオンによって共役系導電性重合体がドープされる。
シード粒子にドーパントであるポリアニオンを配位させることで、重合時の増粘を抑制することができる。さらにシード粒子表面にポリアニオンが配位することで、ポリアニオンと共役系導電性重合体との再配位が可能となり導電性が十分に発現される。
共役系導電性重合体は、主鎖がπ共役系で構成されている有機高分子であれば特に限定されない。共役系導電性重合体としては、例えば、ポリピロール類、ポリチオフェン類、ポリアセチレン類、ポリフェニレン類、ポリフェニレンビニレン類、ポリアニリン類、ポリアセン類、ポリチオフェンビニレン類、およびこれらの共重合体等が挙げられる。これらの中でも、ポリピロール類、ポリチオフェン類およびポリアニリン類が好ましく、ポリチオフェン類がより好ましい。また、共役系導電性重合体は、アルキル基、カルボキシル基、スルホン酸基、アルコキシル基、ヒドロキシル基、シアノ基等の置換基を有するものが高い導電性が得られる点で好ましい。
これらの中でも、ポリピロール、ポリチオフェン、ポリ(N-メチルピロール)、ポリ(3-メチルチオフェン)、ポリ(3-メトキシチオフェン)およびポリ(3,4-エチレンジオキシチオフェン)が、導電性が高い点から好ましい。特に、ポリ(3,4-エチレンジオキシチオフェン)〔通称PEDOT〕は、導電性がより高い上に、耐熱性に優れる点からより好ましい。また、3,4-エチレンジオキシチオフェンと他の単量体(例えばピロール)との共重合体(PEDOT共重合体)であってもよい。このPEDOT共重合体中における3,4-エチレンジオキシチオフェンに由来する部分の含有量は、好ましくは70質量%以上、より好ましくは80質量%以上、さらに好ましくは90質量%以上、よりさらに好ましくは100質量%である。
共役系導電性重合体は、1種単独で又は2種以上を組み合わせて用いることができる。共役系導電性重合体中における、PEDOT及びPEDOT共重合体の合計量は、好ましくは70質量%以上、より好ましくは80質量%以上、さらに好ましくは90質量%以上、よりさらに好ましくは100質量%である。
共役系導電性重合体を得るための単量体としては、置換基を有してもよいピロール、置換基を有してもよいアニリン、および置換基を有してもよいチオフェンから選ばれる少なくとも1つが好ましく用いられる。置換基としては例えば、炭素数1~18のアルキル基、炭素数6~10のアリール基、炭素数5~10のヘテロアリール基、炭素数1~18のアルコキシ基、炭素数1~18のアルキルチオ基、カルボキシル基、ヒドロキシル基、ハロゲン原子およびシアノ基が挙げられる。なお、上記アルキル基、アリール基、ヘテロアリール基、アルコキシ基およびアルキルチオ基は、カルボキシル基、水酸基、ハロゲン原子又はシアノ基で置換されていてもよい。また2つ以上の置換基が縮合して環を形成していてもよい。
アニリン、2-メチルアニリン、3-イソブチルアニリン、2-アニリンスルホン酸、3-アニリンスルホン酸等が挙げられる。
共役系導電性重合体を得るための単量体は、1種単独で又は2種以上を組み合わせて用いることができる。
置換基としては例えば、炭素数1~18のアルキル基、炭素数6~10のアリール基、炭素数5~10のヘテロアリール基、炭素数1~18のアルコキシ基、炭素数1~18のアルキルチオ基、カルボキシル基、ヒドロキシル基、ハロゲン原子およびシアノ基が挙げられる。なお、上記アルキル基、アリール基、ヘテロアリール基、アルコキシ基およびアルキルチオ基は、カルボキシル基、水酸基、ハロゲン原子又はシアノ基で置換されていてもよい。また2つ以上の置換基が縮合して環を形成していてもよい。
上記イオウ原子含有複素環としては、チイラン環、チエタン環、チオフェン環、チアン環、チオピラン環、チオピリリウム環、ベンゾチオピラン環、ジチアン環、ジチオラン環、トリチアン環等が挙げられる。
上記イオウ原子および酸素原子含有複素環としては、オキサチオラン環、オキサチアン環等が挙げられる。
この共役系導電性重合体を得るための単量体の全量中における、式(I)で表される化合物の含有量は、好ましくは70質量%以上、より好ましくは80質量%以上、さらに好ましくは90質量%以上、よりさらに好ましくは100質量%である。
R3およびR4は、好ましくはR3とR4とが互いに結合して環を形成した、置換基を有してもよい炭素数3~6の酸素原子含有複素環である。上記酸素原子含有複素環としては、ジオキサン環、トリオキサン環等が挙げられ、好ましくはジオキサン環である。置換基としては例えば、炭素数1~18のアルキル基、炭素数6~10のアリール基、炭素数5~10のヘテロアリール基、炭素数1~18のアルコキシ基、炭素数1~18のアルキルチオ基、カルボキシル基、ヒドロキシル基、ハロゲン原子およびシアノ基が挙げられる。なお、上記アルキル基、アリール基、ヘテロアリール基、アルコキシ基およびアルキルチオ基は、カルボキシル基、水酸基、ハロゲン原子又はシアノ基で置換されていてもよい。また2つ以上の置換基が縮合して環を形成していてもよい。
この共役系導電性重合体を得るための単量体の全量中における、式(II)で表される化合物の含有量は、好ましくは70質量%以上、より好ましくは80質量%以上、さらに好ましくは90質量%以上、よりさらに好ましくは100質量%である。
本発明に用いるシード粒子は、分散媒中でポリアニオンによって保護コロイド化されるものであればよく、好ましい例として、エチレン性不飽和単量体を重合して得られる単独重合体又は共重合体の粒子が挙げられる。
これらエチレン性不飽和単量体は、上記芳香族ビニル化合物及び(メタ)アクリル酸エステル類の少なくとも1種であることが好ましい。
これらエチレン性不飽和単量体が芳香族ビニル化合物を含む場合は、上記芳香族ビニル化合物を好ましくは50~100質量%、より好ましくは70~100質量%、さらに好ましくは90~100質量%含む。また芳香族ビニル化合物の中でも、スチレンを用いることが好ましい。
また、これらエチレン性不飽和単量体が(メタ)アクリル酸エステル類を含む場合は、上記(メタ)アクリル酸エステル類を好ましくは50~100質量%、より好ましくは70~100質量%、さらに好ましくは90~100質量%含む。また(メタ)アクリル酸エステル類の中でも、(メタ)アクリル酸メチル及び(メタ)アクリル酸tert-ブチルの少なくとも1種が好ましく、メタクリル酸メチル及びメタクリル酸tert-ブチルの少なくとも1種がより好ましく、メタクリル酸メチルがさらに好ましい。
これらエチレン性不飽和単量体は、スチレン、メタクリル酸メチル及びメタクリル酸tert-ブチルの少なくとも1種が好ましい。
単独重合体又は共重合体中における架橋剤モノマーの含有量は、好ましくは1~30質量%、より好ましくは3~20質量%、さらに好ましくは5~15質量%、よりさらに好ましくは8~12質量%である。
本発明に用いられるポリアニオンは、アニオン性基を有するポリマーである。アニオン性基としては、スルホン酸又はその塩からなる基、リン酸又はその塩からなる基、一置換リン酸エステル基、カルボン酸又はその塩からなる基、一置換硫酸エステル基等が挙げられる。これらのうち、強酸性基が好ましく、スルホン酸又はその塩からなる基、リン酸又はその塩からなる基がより好ましく、スルホン酸又はその塩からなる基がさらに好ましい。アニオン性基はポリマー主鎖に直接結合していてもよいし、側鎖に結合していてもよい。側鎖にアニオン性基が結合している場合、ドープ効果をより顕著に果たすので、アニオン性基は側鎖の末端に結合していることが好ましい。
ポリエステルとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート等が挙げられる。
ポリアニオン、特にスルホン酸基を有するポリマーは、共役系導電性重合体の熱分解を緩和することができ、共役系導電性重合体を得るための単量体の分散媒中での分散性を向上させ、さらに共役系導電性重合体のドーパントとして機能する。
また、本工程における共役系導電性重合体100質量部に対するポリアニオンの使用量は、好ましくは10~30,000質量部、より好ましくは50~25,000質量部、さらに好ましくは100~1,000質量部、よりさらに好ましくは200~500質量部である。
ポリアニオンの使用量が多すぎると共役系導電性重合体の導電性が低下する傾向があり、ポリアニオンの使用量が少なすぎると共役系導電性重合体の分散媒中での分散性が低下する傾向がある。
シード粒子は、分散媒中でポリアニオンによって保護コロイド化されるものであり、分散媒中に分散した保護コロイド化されたシード粒子の分散液は、樹脂エマルジョンとして製造することができる。
反応温度は、通常、10~100℃で行われるが、30~90℃が一般的であり、60~90℃が好ましい。反応時間は、特に制限されることはなく、各成分の使用量、重合開始剤の種類および反応温度等に応じて適宜調整すればよい。
乳化剤および脂肪族アミンは、1種単独又は2種以上を組み合わせて使用してもよい。
保護コロイド化されて、分散媒中に分散しているシード粒子の粒径のd50(体積基準での50%メジアン径)は、0.01~10μmであることが好ましく、より好ましくは0.05~1μmで、さらに好ましくは0.1~0.8μmである。シード粒子の粒子径分布は、日機装(株)製、マイクロトラックUPA型粒度分布測定装置にて測定できる。シード粒子の分散媒中に分散している粒径のd50が0.01μm以上だとシード粒子の分散性が向上し、10μm以下であると粒子沈降が抑制される。
共役系導電性重合体を得るための単量体の重合は、共役系導電性重合体を得るための単量体と、ポリアニオンにより保護コロイド化されたシード粒子とを含む分散媒中で行われる。
〈単量体液〉
共役系導電性重合体を得るための単量体を分散媒中で重合するためには、該単量体、ポリアニオンにより保護コロイド化されたシード粒子の分散液(樹脂エマルジョン)および必要に応じて添加剤を分散媒に添加し、単量体と保護コロイド化されたシード粒子とを含む分散液(以下、単に単量体液と称すことがある)を得る。
上記単量体液の調製は、ホモジナイザー等の強力な撹拌装置によって行ってもよいが、超音波照射によって行うことが好ましい。超音波照射エネルギーは、均一な単量体液が得られるのであれば、特に限定されない。超音波照射は、消費電力5~500W/L(リットル)で、照射時間0.1~10時間/L(リットル)行うことが好ましい。当該消費電力は、より好ましくは100~500W/L、さらに好ましくは200~500W/L、よりさらに好ましくは200~400W/Lである。当該照射時間は、より好ましくは0.5~8時間/L、さらに好ましくは1~6時間/L、よりさらに好ましくは2~5時間/Lである。
上記ポリアニオンは単量体液に添加し、溶解、乳化又は分散させることによって、単量体液に含有させることができる。単量体液に、保護コロイド化されたシード粒子の分散液以外にポリアニオンを含有させる場合、その重合開始前におけるポリアニオンの量は、使用するポリアニオンのシード粒子の保護コロイドを除いた総量の5~99質量%が好ましく、10~90質量%がより好ましく、20~80質量%がさらに好ましい。
単量体の重合に用いられる分散媒は、共役系導電性重合体とポリアニオンにより保護コロイド化されたシード粒子とからなる共役系導電性重合体を分散させることができるものであれば特に限定されないが、シード粒子の分散液に用いたのと同じ種類のものが好ましい。
分散媒として、例えば、水;N-ビニルピロリドン、ヘキサメチルホスホルトリアミド、N-ビニルホルムアミド、N-ビニルアセトアミド等のアミド類;クレゾール、フェノール、キシレノール等のフェノール類;ジプロピレングリコール、1,3-ブチレングリコール、1,4-ブチレングリコール、ジグリセリン、イソプレングリコール、ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、1,9-ノナンジオール、ネオペンチルグリコール等の多価アルコール類;エチレンカーボネート、プロピレンカーボネート等のカーボネート化合物;ジオキサン、ジエチルエーテル、プロピレングリコールジアルキルエーテル、ポリエチレングリコールジアルキルエーテル、ポリプロピレングリコールジアルキルエーテル等のエーテル類;3-メチル-2-オキサゾリジノン等の複素環化合物;アセトニトリル、グルタロジニトリル、メトキシアセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル類等が挙げられる。
これら溶媒は、1種単独で又は2種以上を組み合わせて用いることができる。これらのうち、水を1~100質量%含む分散媒を用いることが好ましく、より好ましくは水を50~100質量%、さらに好ましくは水を80~100質量%、よりさらに好ましくは水を90~100質量%含むことがより好ましく、水を単独で用いることがさらに好ましい。
上記単量体の重合において、例えば、ポリピロール類やポリチオフェン類を共役系導電性重合体として含む分散液を製造する場合、酸化剤の存在下に所定の温度にすることによって重合が開始される。
酸化剤としては、ペルオキソ二硫酸;ペルオキソ二硫酸アンモニウム(過硫酸アンモニウム)、ペルオキソ二硫酸ナトリウム(過硫酸ナトリウム)、ペルオキソ二硫酸カリウム(過硫酸カリウム)等のペルオキソ二硫酸塩;三フッ化ホウ素等の金属ハロゲン化合物;塩化第二鉄、硫酸第二鉄、塩化第二銅等の遷移金属化合物;酸化銀、酸化セシウム等の金属酸化物;過酸化水素、オゾン等の過酸化物;過酸化ベンゾイル等の有機過酸化物;酸素等が挙げられる。これらのうちペルオキソ二硫酸及びペルオキソ二硫酸塩が好ましく、ペルオキソ二硫酸塩がより好ましく、ペルオキソ二硫酸アンモニウム(過硫酸アンモニウム)及びペルオキソ二硫酸ナトリウム(過硫酸ナトリウム)の少なくとも1種がさらに好ましく、ペルオキソ二硫酸ナトリウム(過硫酸ナトリウム)がよりさらに好ましい。
上記酸化剤は、1種単独で又は2種以上を組み合わせて用いることができる。
共役系導電性重合体を得るための単量体100質量部に対する、酸化剤の含有量は、好ましくは50~500質量部、より好ましくは100~300質量部、さらに好ましくは150~250質量部である。
<酸化触媒>
上記単量体の重合において、酸化触媒を用いても良い。酸化触媒としては、p-トルエンスルホン酸鉄が好ましい。
共役系導電性重合体を得るための単量体100質量部に対する、酸化触媒の含有量は、好ましくは1~20質量部、より好ましくは3~15質量部、さらに好ましくは5~10質量部である。
上記単量体の重合における重合時の温度は通常、5~80℃であり、好ましくは10~60℃であり、より好ましくは15~40℃である。
重合時の温度をこの範囲内にすると、適度な反応速度で重合を行うことができ、粘度の上昇を抑えることができ、共役系導電性重合体を含む分散液の製造を安定的に且つ経済的な時間で行うことができ、且つ得られる共役系導電性重合体の導電率が高くなる傾向がある。重合時の温度は、公知のヒータやクーラを用いることにより管理することができる。また必要に応じ、上記範囲内で温度を変化させながら重合を行ってもよい。
共役系導電性重合体含有分散液を得る工程においては、上記単量体の重合の途上で、生成する共役系導電性重合体を分散処理することが好ましい。
この分散処理は、ホモジナイザー等の強力な撹拌装置によって行うこともできるが、超音波照射によって行うことが好ましい。この分散処理によって、長い主鎖を有する共役系導電性重合体の凝集を抑制することができる。超音波照射エネルギーは、共役系導電性重合体の凝集を抑制することができる限り、特に限定されない。超音波照射は、好ましくは消費電力5~500W/L、より好ましくは100~500W/L、さらに好ましくは200~500W/Lで、反応終了時まで行うことが好ましい。
また、単量体の重合の途上に、ポリアニオンにより保護コロイド化されたシード粒子の分散液をさらに添加することが好ましい。単量体の重合の途上で、所定量の保護コロイド化されたシード粒子の分散液の一部をさらに添加することで、重合時の反応液の増粘を抑制でき撹拌混合効率の向上や製造装置への負荷を低減することができる。
重合途上に添加する保護コロイド化されたシード粒子の分散液の量は、使用する保護コロイド化されたシード粒子の分散液の総量の10~90質量%が好ましく、20~70質量%がより好ましく、25~50質量%がさらに好ましく、30~45質量%がよりさらに好ましい。
また、単量体の重合の途上に、シード粒子を保護コロイド化するために用いるポリアニオンをさらに添加してもよい。単量体の重合の途上で、所定量のポリアニオンの一部をさらに添加することで重合時の反応液の増粘を抑制でき撹拌混合効率の向上や製造装置への負荷を低減することができる。
重合途上に添加するポリアニオンの量は、使用するポリアニオンの総量の0~90質量%が好ましく、20~70質量%がより好ましい。
上記単量体液、又は本工程によって得られる共役系導電性重合体含有分散液に、必要に応じて添加剤を添加することができる。
上記添加剤は、共役系導電性重合体およびポリアニオンにより保護コロイド化されたシード粒子と混合しうるものであれば特に制限されない。上記添加剤としては、例えば、水溶性高分子化合物、水分散性化合物、アルカリ性化合物、界面活性剤、消泡剤、カップリング剤、酸化防止剤、電気伝導率向上剤等が挙げられ、これら添加剤は、1種単独で又は2種以上を組み合わせて用いることができる。
水溶性高分子化合物および水分散性化合物は、1種単独で又は2種以上を組み合わせて用いることができる。水溶性高分子化合物および水分散性化合物を添加すると、共役系導電性重合体を含む分散液の粘度調節ができたり、塗布性能を向上させたりすることができる。
窒素含有ヘテロアリール環化合物としては、ピリジン類、イミダゾール類、ピリミジン類、ピラジン類、トリアジン類等が挙げられる。これらのうち、溶媒溶解性等の観点から、ピリジン類、イミダゾール類、ピリミジン類が好ましい。
酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、糖類、ビタミン類等が挙げられる。
上述の共役系導電性重合体含有分散液を得る工程では、シード粒子表面にポリアニオンが配位することで、共役系導電性重合体の粒径が制御でき、重合時の増粘を抑制することができる。また、共役系導電性重合体においてドーパントであるポリアニオンへの共役系導電性重合体の配位が可能となり、導電性が発現される。
また、本発明の製造方法は、前述の工程で得られた共役系導電性重合体含有分散液を、弁金属からなる陽極体と、該陽極体表面に形成された誘電体被膜とを少なくとも有する多孔性陽極体の表面に付着させる工程を有する。
本発明の固体電解コンデンサは、例えば、高表面積を有する弁金属粉末を焼結してなる多孔性の電極、あるいは、弁金属箔をエッチングし得られる多孔性膜を電極とすることができる。
上記弁金属としては、Al、Be、Bi、Mg、Ge、Hf、Nb、Sb、Si、Sn、Ta、Ti、V、WおよびZr、ならびにこれらの金属の少なくとも1つと他の元素との合金又は化合物が挙げられる。中でもアルミニウム、ニオブ、又はタンタルの弁金属から構成される電極材料が好ましい。
上記多孔性電極は、例えばリン酸溶液中で電圧を印加することにより陽極酸化され、誘電体酸化被膜を形成することができる。誘電体酸化被膜の厚さやコンデンサの耐電圧により、化成電圧の大きさを決めることができる。好ましい化成電圧は1~800Vであり、より好ましくは1~300Vである。
浸漬時間は、通常10秒~5分間程度であり、共役系導電性重合体含有分散液の温度は分散媒の種類にもよるが通常10~35℃程度である。
また、本発明の製造方法は、前述の工程で得られた多孔性陽極体に付着した共役系導電性重合体含有分散液から、分散媒の一部又は全部を除去し、固体電解質層を形成する工程を有する。
分散媒の除去方法は、効率性の点で加熱処理によって行うことが好ましく、共役系導電性重合体の酸素による劣化のない範囲で行うことが望ましい。加熱条件は、分散媒の沸点や揮発性により決めることができる。
加熱条件として例えば、室温~300℃まで、好ましくは50~200℃、より好ましくは80~150℃で除去することが好ましい。加熱処理時間は5秒~数時間が好ましい。
加熱処理には、例えば、ホットプレート、オーブン、熱風乾燥機を用いることができる。大気下、もしくは加熱処理を迅速に行うために減圧下で行ってもよい。
また、分散液を付着させるごとに加熱処理を行い、分散媒を一部又は全部除去してもよく、又は複数回分散液を連続で付着させ、最後に分散媒を除去してもよい。
さらに、付着させた分散液に含まれる分散媒を一部はたは全部除去した後に、任意の電解液を含浸させてもよい。
(1)固形分濃度
分散液中の固形分濃度は、各例で得られた分散液を試料容器におよそ2g秤量し、105℃の乾燥機中に1時間静置した後、試料容器中の試料の質量を測定し、乾燥前の質量に対する乾燥後の質量、すなわち〔乾燥後質量/乾燥前質量〕を固形分濃度として算出した。
(2)粘度
重合中の分散液の粘度は、25℃においてB型粘度計で、No.2のローターを用いて測定した。
(3)pH
各例で得られた分散液のpHは、25℃においてpHメーター(東亜ディーケーケー(株)製、型式HM-30G)を用いて測定した
(4)電導度
各例で得られた分散液100gを撹拌しながら、該分散液にアンモニア水を添加した。次いで、エチレングリコール10gを添加し、pH4.5の変性分散液を得た。JIS K 7194に準じて、pH調整された分散液をガラス板上に流涎し、100℃にて熱風乾燥させて厚さ10μmの膜を形成させた。該膜の導電率をロレスタ(三菱化学(株)社製)により測定した。
(5)シード粒子の粒径
日機装(株)製マイクロトラックUPA型粒度分布測定装置により測定した。
(6)ポリスチレンスルホン酸ナトリウムの重量平均分子量
ゲル浸透クロマトグラフィーを用いて測定を行った。なお、測定には昭和電工(株)製の「Shodex GPC 101」(カラム OHPak SB-806M HQ)を用い、測定条件はカラム温度40℃、溶出液は水、溶出速度1ml/分とした。標準ポリスチレン換算分子量(Mw)で表示した。
(ポリアニオンによって保護コロイド化されたシード粒子の製造)
ポリスチレンスルホン酸ナトリウム(東ソー有機化学(株)製、商品名ポリナスPS-5、重量平均分子量:約120,000)22質量%水溶液1000gを窒素雰囲気化で撹拌しながら、80℃に昇温した。この溶液に、過硫酸カリウム2gを添加し、一方、スチレン135gとジビニルベンゼン15gとポリスチレンスルホン酸ナトリウム(同上)22質量%水溶液500gからなる単量体乳化物および2.5質量%の過硫酸カリウム水溶液40gを、それぞれ、2時間、2.5時間かけて滴下した。滴下終了後2時間80℃を維持した後に室温まで冷却した。得られた反応液に陽イオン交換樹脂1500mlおよび陰イオン交換樹脂1500mlを添加し、12時間撹拌したのち、イオン交換樹脂をろ別して、ポリアニオンによって保護コロイド化されたシード粒子の分散液(ポリスチレンエマルジョン)を得た。得られたポリスチレンエマルジョン中の、シード粒子のd50粒子径は0.46μmであった。
イオン交換水579.94g、上記ポリスチレンエマルジョン(不揮発分28.0質量%)71.15gおよびp-トルエンスルホン酸鉄(III)6水和物2質量%水溶液36.05gを27℃にて混ぜ合わせた。この溶液に、超音波分散機((株)ギンセン製、製品名GSD1200AT)を用い、消費電力300W/Lの条件で、27℃にて超音波を照射しながら3,4-エチレンジオキシチオフェン8.57gを添加し混ぜ合わせた。
得られた混合液に27℃にて撹拌翼による撹拌と超音波照射とをしながらペルオキソ二硫酸ナトリウム18.0gを添加して重合反応を開始させた。次いで、予め仕込んだものと同じポリスチレンエマルジョン47.8g、イオン交換水237.9gを混合し、4時間かけて滴下した。その後、27℃にて4時間撹拌翼による撹拌と超音波照射とをしながら反応させた。
反応終了後、得られた反応液に陽イオン交換樹脂300mlおよび陰イオン交換樹脂300mlを添加して、反応液を12時間撹拌することによって、未反応モノマー、酸化剤および酸化触媒をイオン交換樹脂に吸着させた。該イオン交換樹脂をろ別して、ポリスチレンスルホン酸によって保護コロイド化されたシード粒子(ポリスチレンエマルジョン)及び上記ポリスチレンスルホン酸によりドーピングされたポリ(3,4-エチレンジオキシチオフェン)からなる共役系導電性重合体含有分散液(1-1)を得た。
得られた分散液(1-1)の各物性を上述の方法により測定したところ、固形分濃度が4.2質量%、pHが1.9、電導度が93S/cmであった。また、分散液(1-1)の製造における重合時の各時間における粘度を表3に示す。
本発明における固体電解コンデンサに用いる、誘電体酸化被膜を表面に有する多孔性陽極体は、特開2011-77257号公報に開示の方法にならい製造した。すなわち、コンデンサ用ニオブ粉末を用い、陽極体表面に五酸化二ニオブを有する誘電体酸化被膜が形成された多孔性陽極体を作製した。
この多孔性陽極体は、非特許文献「EIAJ規格RC2361A(2000年2月改正)」に記載の方法に準拠した30%硫酸中での静電容量は、22μFであった。
25℃の大気下で、上記方法で得られた多孔性陽極体を、上記分散液(1-1)に1分間含浸させた後、105℃の熱風乾燥機で乾燥した。次いで陽極リード端子に接触させないように多孔性陽極体にカーボンペーストを塗布、乾燥させ、さらに、陰極の接点をとるために銀ペーストを塗布、乾燥させた。
得られた固体電解コンデンサの120Hzでの静電容量(μF)および100kHzでの等価直列抵抗〔ESR〕(Ω)を、LCRメーターを用いて測定した。測定結果を表4に示す。
(ポリアニオンによって保護コロイド化されたシード粒子の製造)
表1の配合にしたこと以外は実施例1と同様にして、ポリアニオンによって保護コロイド化されたシード粒子の分散液(ポリスチレンエマルジョン)を得た。得られたポリスチレンエマルジョン中の、シード粒子のd50粒子径は表1に示す。
表1の配合にしたこと以外は実施例1と同様にして、ポリスチレンスルホン酸によって保護コロイド化されたシード粒子(ポリスチレンエマルジョン)及び上記ポリスチレンスルホン酸によりドーピングされたポリ(3,4-エチレンジオキシチオフェン)からなる共役系導電性重合体含有分散液(1-2)~(1-8)を得た。
得られた分散液(1-2)~(1-8)の各物性を上述の方法により測定した。その結果を表2及び表3に示す。
実施例1と同様にして多孔性陽極体を作製した。
分散液(1-1)を分散液(1-2)~(1-8)に変えたこと以外は実施例と同様にして、固体電解コンデンサを製造し、実施例1と同様の測定を行った。その測定結果を表4に示す。
(ポリアニオンによって保護コロイド化されたシード粒子を含まない共役系導電性重合体含有分散液の製造)
イオン交換水593.24g、ポリスチレンスルホン酸(東ソー有機化学(株)製、商品名ポリナスPS-50、重量平均分子量:約230,000)22質量%水溶液58.44gおよびp-トルエンスルホン酸鉄(III)6水和物2質量%水溶液36.05gを27℃にて混ぜ合わせた。この溶液に、超音波分散機((株)ギンセン製、製品名GSD1200AT)を用い、消費電力300W/Lの条件で、27℃にて超音波を照射しながら3,4-エチレンジオキシチオフェン8.57gを添加し混ぜ合わせた。
得られた混合液に27℃にて撹拌翼による撹拌と超音波照射とをしながらペルオキソ二硫酸ナトリウム18.0gを添加して重合反応を開始させた。次いで、予め仕込んだものと同じポリスチレンスルホン酸水溶液39.0g、イオン交換水246.8gを混合し、4時間かけて滴下した。その後、27℃にて4時間撹拌翼による撹拌と超音波照射とをしながら反応させた。
反応終了後、得られた反応液に陽イオン交換樹脂300mlおよび陰イオン交換樹脂300mlを添加して、反応液を12時間撹拌することによって、未反応モノマー、酸化剤および酸化触媒をイオン交換樹脂に吸着させた。該イオン交換樹脂をろ別して、ポリ(3,4-エチレンジオキシチオフェン)とそれにドープされたポリスチレンスルホン酸を含む分散液を得た。
得られた分散液(2-1)の各物性を上述の方法により測定したところ、固形分濃度が3.0質量%、pHが1.9、電導度が102S/cmであった。また、重合時の各時間における粘度を表1に示す。
実施例1と同様に、誘電体酸化被膜を表面に有する多孔性陽極体の形成を行った。
次に上記多孔性陽極体を用いて、分散液(1-1)の代わりに上記分散液(2-1)を用いた以外は実施例1と同様の方法で、分散液(2-1)を多孔性陽極体に付着させ固体電解コンデンサを得た。
得られた固体電解コンデンサの120Hzでの静電容量(μF)および100kHzでの等価直列抵抗〔ESR〕(Ω)を、LCRメーターを用いて測定した。測定結果を表2に示す。
(ポリアニオンによって保護コロイド化されたシード粒子を含まない共役系導電性重合体含有分散液の製造)
表2の配合にしたこと以外は比較例1と同様にして、ポリ(3,4-エチレンジオキシチオフェン)とそれにドープされたポリスチレンスルホン酸を含む分散液を得た。得られたポリスチレンエマルジョン中の、シード粒子のd50粒子径は表1に示す。
表2の配合にしたこと以外は実施例1と同様にして、ポリ(3,4-エチレンジオキシチオフェン)とそれにドープされたポリスチレンスルホン酸を含む分散液(2-2)及び(2-3)を得た。
得られた分散液(2-2)及び(2-3)の各物性を上述の方法により測定した結果を、表2~3に示す。
実施例1と同様に、誘電体酸化被膜を表面に有する多孔性陽極体の形成を行った。
次に上記多孔性陽極体を用いて、分散液(1-1)の代わりに上記分散液(2-2)及び(2-3)を用いた以外は実施例1と同様の方法で、分散液(2-2)及び(2-3)を多孔性陽極体に付着させ固体電解コンデンサを得た。
得られた固体電解コンデンサの測定結果を表4に示す。
一方、比較例1では、重合時の粘度が非常に大きくなることから生産性に劣り、また得られた分散液を用いた固体電解コンデンサは、実施例1に比べコンデンサ特性に劣ることがわかる。
実施例2では、実施例1のポリアニオン(PS-5,重量平均分子量120,000)に変えてPS-1(重量平均分子量50,000)を用いているため、反応時の粘度が実施例1と比べると増加しているが良好に抑制されており、また実施例1と比べて静電容量が高く、等価直列抵抗も低く、コンデンサ特性に優れている。
実施例3では、実施例1の重合開始剤(過硫酸カリウム)に変えて重合開始剤(過硫酸アンモニウム)を用いているため、静電容量及び等価直列抵抗が実施例1よりも若干劣るが、比較例よりも優れたコンデンサ特性を有する。
実施例4~6に示すとおり、シード粒子の構成成分であるエチレン性不飽和単量体として、スチレン、メタクリル酸メチル、及びメタクリル酸tert-ブチルのいずれを用いても、固体電解コンデンサはコンデンサ特性に優れている。
実施例7では、シード粒子の構成成分であるスチレンの量を実施例1の半分にしているが、実施例1と同等に優れたコンデンサ特性を有する。
Claims (13)
- 下記工程を有する固体電解コンデンサの製造方法。
共役系導電性重合体を得るための単量体と、ポリアニオンにより保護コロイド化されたシード粒子とを含む分散媒中で、上記単量体を重合して共役系導電性重合体含有分散液を得る工程、
弁金属からなる陽極体と、該陽極体表面に形成された誘電体被膜とを少なくとも有する多孔性陽極体の表面に、上記共役系導電性重合体含有分散液を付着させる工程、及び
上記多孔性陽極体に付着した共役系導電性重合体含有分散液から、分散媒の一部又は全部を除去し、固体電解質層を形成する工程。 - 前記シード粒子が、エチレン性不飽和単量体を重合して得られる単独重合体又は共重合体である、請求項1に記載の固体電解コンデンサの製造方法。
- 前記ポリアニオンにより保護コロイド化されたシード粒子のd50粒子径が、0.01~10μmである、請求項1又は2に記載の固体電解コンデンサの製造方法。
- 前記共役系導電性重合体含有分散液を得る工程において、前記単量体の重合の途上に、ポリアニオンにより保護コロイド化されたシード粒子の分散液をさらに添加する、請求項1~3のいずれかに記載の固体電解コンデンサの製造方法。
- 前記共役系導電性重合体含有分散液を得る工程において、前記単量体の重合の途上で、生成する共役系導電性重合体を分散処理する、請求項1~4のいずれかに記載の固体電解コンデンサの製造方法。
- 前記分散処理を超音波照射によって行う、請求項5に記載の固体電解コンデンサの製造方法。
- 前記共役系導電性重合体を得るための単量体が、置換基を有してもよいピロール、置換基を有してもよいアニリン、および置換基を有してもよいチオフェンから選ばれる少なくとも1つである、請求項1~6のいずれかに記載の固体電解コンデンサの製造方法。
- 前記共役系導電性重合体を得るための単量体が、下記式(I)で表される化合物を含むものである、請求項1~6のいずれかに記載の固体電解コンデンサの製造方法。
- 前記ポリアニオンがスルホン酸基を有するポリマーである、請求項1~8のいずれかに記載の固体電解コンデンサの製造方法。
- 前記ポリアニオン中のアニオン基が、前記共役系導電性重合体を得るための単量体1モルに対し、0.25~30モルである、請求項1~9のいずれかに記載の固体電解コンデンサの製造方法。
- 前記共役系導電性重合体含有分散液を得る工程において、
前記分散媒が水を含み、
前記重合がペルオキソ二硫酸およびその塩から選ばれる少なくとも一つの酸化剤を用いて行われる、請求項1~10のいずれかに記載の固体電解コンデンサの製造方法。 - 前記共役系導電性重合体含有分散液が、エチレングリコール、プロピレングリコールおよびグリセリンから選ばれる少なくとも1つの電気伝導率向上剤を含む、請求項1~11のいずれかに記載の固体電解コンデンサの製造方法。
- 請求項1~12のいずれかに記載の製造方法で得られる固体電解コンデンサ。
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WO2019130677A1 (ja) | 2017-12-25 | 2019-07-04 | 昭和電工株式会社 | 固体電解コンデンサ製造用分散液組成物及び固体電解コンデンサの製造方法 |
US11721493B2 (en) | 2017-12-25 | 2023-08-08 | Showa Denko K.K. | Liquid dispersion composition for solid electrolytic capacitor production |
JP7071834B2 (ja) | 2018-02-09 | 2022-05-19 | 信越ポリマー株式会社 | キャパシタ及びその製造方法、並びに導電性高分子分散液 |
JP2019140249A (ja) * | 2018-02-09 | 2019-08-22 | 信越ポリマー株式会社 | キャパシタ及びその製造方法、並びに導電性高分子分散液 |
US11031187B2 (en) | 2018-03-30 | 2021-06-08 | Showa Denko K.K. | Method of manufacturing solid electrolytic capacitor, and method of manufacturing dispersion containing conjugated electrically conductive polymer |
KR20200122402A (ko) | 2018-03-30 | 2020-10-27 | 쇼와 덴코 가부시키가이샤 | 고체 전해 콘덴서의 제조 방법, 및 공액계 도전성 중합체를 함유하는 분산액의 제조 방법 |
WO2019189257A1 (ja) | 2018-03-30 | 2019-10-03 | 昭和電工株式会社 | 固体電解コンデンサの製造方法、及び共役系導電性重合体を含有する分散液の製造方法 |
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US20160055981A1 (en) | 2016-02-25 |
TWI620216B (zh) | 2018-04-01 |
CN105051847A (zh) | 2015-11-11 |
US9640325B2 (en) | 2017-05-02 |
CN105051847B (zh) | 2018-01-16 |
TW201505056A (zh) | 2015-02-01 |
KR101782434B1 (ko) | 2017-09-28 |
KR20150124981A (ko) | 2015-11-06 |
JPWO2014163202A1 (ja) | 2017-02-16 |
JP6539913B2 (ja) | 2019-07-10 |
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