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
  • H01G9/004—Details
  • H01G9/022—Electrolytes; Absorbents
  • H01G9/025—Solid electrolytes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
  • C08F212/36—Divinylbenzene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
  • C08K5/1565—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
  • C08K5/357—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/14—Copolymers of styrene with unsaturated esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/24—Electrically-conducting paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/124—Intrinsically conductive polymers
  • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/0029—Processes of manufacture
  • H01G9/0036—Formation of the solid electrolyte layer
• • 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
  • H01G9/15—Solid electrolytic capacitors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
  • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
  • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
  • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/14—Side-groups
  • C08G2261/142—Side-chains containing oxygen
  • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
• • 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
  • C08G2261/79—Post-treatment doping
  • C08G2261/794—Post-treatment doping with polymeric dopants
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
  • H10K10/10—Organic capacitors or resistors having potential barriers

Definitions

• the present invention relates to a dispersion containing a conjugated conductive polymer, as well as a solid electrolytic capacitor using the same and a method for producing the same.
• Solid electrolytic capacitors generally have a structure in which valve metals such as aluminum, tantalum, and niobium are used as anode and cathode foils, with a solid electrolyte between them.
• valve metals such as aluminum, tantalum, and niobium
• cathode foils with a solid electrolyte between them.
• the solid electrolyte is typically a conjugated conductive polymer such as polypyrrole, polyaniline, or polythiophene.
• Solid electrolytic capacitors are used in electronic devices because they can reduce equivalent series resistance (ESR) in the high frequency range. Furthermore, with the recent trend towards electrification of cars, development of solid electrolytic capacitors for automotive use is progressing. In particular, for capacitors intended for vehicle electronic control devices, there is a demand for further reduction in ESR in order to increase output through electronic control.
• ESR equivalent series resistance
• a known method for forming a solid electrolyte using a conductive polymer is, for example, to impregnate an electrolytic capacitor element with a monomer solution and an oxidizer solution for obtaining a conductive polymer, and then to perform oxidative polymerization or electrolytic polymerization within the electrolytic capacitor element (see, for example, Patent Document 1).
• the present invention has been made in consideration of these circumstances, and aims to provide a conductive polymer-containing dispersion that can reduce the ESR of solid electrolytic capacitors, and a method for producing the same. Another aim of the present invention is to provide a solid electrolytic capacitor with a lower ESR.
• the present invention is based on the discovery that the ESR of a solid electrolytic capacitor manufactured using a conductive polymer-containing dispersion is reduced when the conductive polymer-containing dispersion contains a cyclic ether compound having a specific structure.
• a conductive polymer-containing dispersion liquid comprising a conjugated conductive polymer (A), a polyanion (B), a hydroxyl group-containing cyclic ether compound (C) represented by any one of the following formulas (1) to (5), and a dispersion medium (D).
• R 11 to R 16 , R 21 to R 28 , R 31 to R 38 , R 41 to R 44 , and R 51 to R 56 are each independently a hydrogen atom; a hydroxyl group; an alkyl group having 1 to 8 carbon atoms which may be substituted with a hydroxyl group, a cyano group, or an amino group; a cycloalkenyl group having 5 or 6 carbon atoms; a phenyl group which may be substituted with a hydroxyl group, an amino group, a cyano group, or a formyl group; an acetyl group; an acetoacetyl group; an allyl group; an acryloyl group; a pyridyl group; an alkylsulfonyl group which may be substituted with a hydroxyl group; or a formyl group.
• R 61 and R 62 are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted alkoxy group having 1 to 18 carbon atoms, or an optionally substituted alkylthio group having 1 to 18 carbon atoms; or, formed by bonding R 61 and R 62 to each other, an optionally substituted alicyclic ring having 3 to 10 carbon atoms, an optionally substituted aromatic ring having 6 to 10 carbon atoms, an optionally substituted oxygen atom-containing heterocyclic ring having 2 to 10 carbon atoms, an optionally substituted sulfur atom-containing heterocyclic ring having 2 to 10 carbon atoms, or an optionally substituted sulfur atom- and oxygen atom-containing heterocyclic ring having 2 to 10 carbon atoms.
• the alkaline compound (F) is at least one selected from the group consisting of morpholine, 4-ethylmorpholine, and 4-(2-hydroxyethyl)morpholine.
• a method for producing a solid electrolytic capacitor comprising the steps of: depositing the conductive polymer-containing dispersion according to any one of [1] to [10] on a porous anode body made of a valve metal having a dielectric film on its surface; and then removing the dispersion medium (D) to form a solid electrolyte layer.
• a solid electrolytic capacitor having a solid electrolyte layer on a porous anode body made of a valve metal having a dielectric coating on a surface thereof, the solid electrolyte layer containing a conjugated conductive polymer (A), a polyanion (B), and a hydroxyl group-containing cyclic ether compound (C) represented by any one of the following formulas (1) to (5):
• R 11 to R 16 , R 21 to R 28 , R 31 to R 38 , R 41 to R 44 , and R 51 to R 56 are each independently a hydrogen atom; a hydroxyl group; an alkyl group having 1 to 8 carbon atoms which may be substituted with a hydroxyl group, a cyano group, or an amino group; a cycloalkenyl group having 5 or 6 carbon atoms; a phenyl group which may be substituted with a hydroxyl group, an amino group, a cyano group, or a
• the present invention provides a conductive polymer-containing dispersion that can reduce the ESR of a solid electrolytic capacitor, and a method for producing the same.
• the present invention also provides a solid electrolytic capacitor with a lower ESR.
• the term “optionally substituted” means that the group may be substituted or may not be substituted (unsubstituted).
• the term “class” attached to the name of a compound means a group of compounds containing the compound structure, including compounds having a substituent.
• polypyrroles refer to a group of compounds containing a polypyrrole structure.
• (Meth)acrylic acid is a general term for acrylic acid and methacrylic acid.
• (meth)acrylate is a general term for acrylate and methacrylate
• (meth)acryloyl is a general term for acryloyl and methacryloyl.
• ethylenically unsaturated bond refers to an ethylenically unsaturated bond having radical polymerizability, unless otherwise specified.
• ethylenically unsaturated monomer refers to a compound having an ethylenically unsaturated bond and used to form a polymer.
• the "polymer component” refers to the conjugated conductive polymer (A), the polyanion (B), and the polymer (E), and when the conductive polymer-containing dispersion does not contain the polymer (E), it refers to the conjugated conductive polymer (A) and the polyanion (B).
• a numerical range indicated using “to” indicates a range including the numerical values described before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper limit or lower limit of a numerical range in a certain stage can be arbitrarily combined with the upper limit or lower limit of a numerical range in another stage. In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with a value shown in the examples.
• the conductive polymer-containing dispersion comprises a conjugated conductive polymer (A), a polyanion (B), and a compound represented by the following formulas (1) to
• the dispersion medium (D) includes a hydroxyl group-containing cyclic ether compound (C) represented by any one of the following formulas (5):
• the conductive polymer-containing dispersion of this embodiment is preferably a conductive polymer-containing dispersion used for producing a solid electrolytic capacitor (conductive polymer-containing dispersion for a solid electrolytic capacitor).
• R 11 to R 16 , R 21 to R 28 , R 31 to R 38 , R 41 to R 44 , and R 51 to R 56 are each independently a hydrogen atom; a hydroxyl group; an alkyl group having 1 to 8 carbon atoms which may be substituted with a hydroxyl group, a cyano group, or an amino group; a cycloalkenyl group having 5 or 6 carbon atoms; a phenyl group which may be substituted with a hydroxyl group, an amino group, a cyano group, or a formyl group; an acetyl group; an acetoacetyl group; an allyl group; an acryloyl group; a pyridyl group; an alkylsulfonyl group which may be substituted with a hydroxyl group; or a formyl group.
• a solid electrolytic capacitor with low ESR can be manufactured.
• the conductive polymer-containing dispersion of this embodiment may further contain a polymer (E), an alkaline compound (F), and other additives, which will be described later.
• the total content of the conjugated conductive polymer (A), the polyanion (B), the hydroxyl group-containing cyclic ether compound (C), and the dispersion medium (D) in the conductive polymer-containing dispersion is preferably 80 to 100 mass%, more preferably 85 to 100 mass%, and even more preferably 90 to 100 mass%.
• the dispersion does not contain any polymer other than the conjugated conductive polymer (A) and the polyanion (B).
• a composite particle (1) containing a conjugated conductive polymer (A) and a polyanion (B) is formed.
• the total content of the conjugated conductive polymer (A) and the polyanion (B) in the conductive polymer-containing dispersion is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1 to 10% by mass, from the viewpoints of the effect of reducing the ESR of the solid electrolytic capacitor, the viscosity of the conductive polymer-containing dispersion that is easy to handle, and the dispersibility of the composite particles (1).
• the conductive polymer-containing dispersion may further contain a polymer (E) in addition to the conjugated conductive polymer (A), the polyanion (B), the hydroxyl group-containing cyclic ether compound (C) and the dispersion medium (D).
• E conjugated conductive polymer
• B polyanion
• C hydroxyl group-containing cyclic ether compound
• D dispersion medium
• the composite particle (2) containing the conjugated conductive polymer (A), the polyanion (B), and the polymer (E) may be contained in the conductive polymer-containing dispersion.
• the composite particle (1) described above may be contained in the conductive polymer-containing dispersion together with the composite particle (2).
• the structure of the composite particle (2) contained in the conductive polymer-containing dispersion is not particularly limited, but it is preferable that the polymer (E) forms an inner domain of the composite particle (2) and the polyanion (B) coordinates with the polymer (E) to form an outer domain of the composite particle (2), so that a part or all of the domain of the polymer (E) is covered with the conjugated conductive polymer (A) and the polyanion (B).
• the total content of the conjugated conductive polymer (A), the polyanion (B), the hydroxyl group-containing cyclic ether compound (C), the dispersion medium (D), and the polymer (E) in the conductive polymer-containing dispersion is preferably 80 to 100 mass%, more preferably 85 to 100 mass%, and further preferably 90 to 100 mass%.
• the total content of the conjugated conductive polymer (A), polyanion (B) and polymer (E) in the conductive polymer-containing dispersion is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1 to 10% by mass, from the viewpoints of the effect of reducing the ESR of the solid electrolytic capacitor, the viscosity of the conductive polymer-containing dispersion that is easy to handle, and the dispersibility of the composite particles (2).
• the conjugated conductive polymer (A) is not particularly limited as long as it is an organic polymer compound having a ⁇ -conjugated system in the main chain.
• the conjugated conductive polymer may be used alone or in combination of two or more kinds.
• the conjugated conductive polymer (A) may be a homopolymer of a monomer described later, which is a structural unit of the conjugated conductive polymer (A), or a copolymer of two or more kinds of monomers. Since the conductive polymer-containing dispersion of this embodiment contains a polyanion (B) that functions as a dopant, the conjugated conductive polymer (A) does not need to have a self-doping function.
• the content of the conjugated conductive polymer (A) in 100% by mass of the polymer component contained in the conductive polymer-containing dispersion of this embodiment is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 15 to 50% by mass, from the viewpoints of the dispersion stability of the conductive polymer-containing dispersion and the reduction in ESR of the solid electrolytic capacitor manufactured using the conductive polymer-containing dispersion.
• conjugated conductive polymer (A) examples include polypyrroles, polythiophenes, polyisothianaphthenes, polyacetylenes, polyphenylenes, polyphenylenevinylenes, polyanilines, polyacenes, polythiophenevinylenes, and copolymers thereof.
• polypyrroles, polythiophenes, and polyanilines are preferred, and polythiophenes are more preferred.
• the conjugated conductive polymer (A) preferably has a substituent such as an alkyl group, a carboxy group, a sulfo group, an alkoxy group, a hydroxyl group or a cyano group.
• polypyrroles include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), 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-butoxypyrrole), poly(3-hexyloxypyrrole), poly(3-methyl-4-hexy
• 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-hexyloxythiophen
• polyanilines examples include polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), poly(3-anilinesulfonic acid), etc.
• the conjugated conductive polymer (A) is preferably polypyrrole, polythiophene, poly(N-methylpyrrole), poly(3-methylthiophene), poly(3-methoxythiophene), or poly(3,4-ethylenedioxythiophene) from the viewpoint of high electrical conductivity, and more preferably poly(3,4-ethylenedioxythiophene) from the viewpoint of excellent heat resistance.
• the monomer for obtaining the conjugated conductive polymer (A), i.e., the monomer that is the constituent unit of the conjugated conductive polymer (A), preferably contains one or more compounds selected from the group consisting of pyrroles, anilines, and thiophenes.
• the compound may have a substituent X, and examples of the substituent X 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, an alkylthio group having 1 to 18 carbon atoms, a carboxy group, a hydroxyl group, a halogen atom, and a cyano group. Two or more of these substituents X may be bonded to each other by condensation or the like to form a ring.
• alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, and alkylthio groups may have a further substituent Y, such as a carboxy group, a hydroxyl group, a halogen atom, and a cyano group.
• Examples of monomers that serve as constituent units of the conjugated conductive polymer (A) 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-carboxybutylpyrrole, 3-hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyl pyrroles such as oxypyrrole, 3-methyl-4-hexyloxypyrrole, and 3-methyl-4-hexyloxypyrrole; thiophene, 3-methylthiophene
• the monomer that constitutes the conjugated conductive polymer (A) preferably contains a thiophene compound represented by the following formula (6) from the viewpoint of obtaining a conjugated conductive polymer with high conductivity.
• the compound represented by formula (6) may be used alone or in combination of two or more kinds.
• R 61 and R 62 are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted alkoxy group having 1 to 18 carbon atoms, or an optionally substituted alkylthio group having 1 to 18 carbon atoms; or, formed by bonding R 61 and R 62 to each other, an optionally substituted alicyclic ring having 3 to 10 carbon atoms, an optionally substituted aromatic ring having 6 to 10 carbon atoms, an optionally substituted oxygen atom-containing heterocyclic ring having 2 to 10 carbon atoms, an optionally substituted sulfur atom-containing heterocyclic ring having 2 to 10 carbon atoms, or an optionally substituted sulfur atom- and oxygen atom-containing heterocyclic ring having 2 to 10 carbon atoms.
• the substituent to be used here examples include a carboxy group, a hydroxyl group, a halogen atom, and a cyano group.
• the oxygen atom-containing heterocycle preferably contains 1 to 3 oxygen atoms constituting the ring, and examples thereof 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.
• the sulfur atom-containing heterocycle preferably has 1 to 3 nitrogen atoms constituting the ring, and examples thereof include a thiirane ring, a thietane ring, a thiophene ring, a thiane ring, a thiopyran ring, a thiopyrylium ring, a benzothiopyran ring, a dithiane ring, a dithiolane ring, and a trithiane ring.
• the heterocycle containing a sulfur atom and an oxygen atom preferably contains 1 to 3 sulfur atoms and oxygen atoms in total, and examples thereof include an oxathiolane ring and an oxathiane ring.
• the content of the compound represented by formula (6) in the monomers that form the constituent units of the conjugated conductive polymer (A) is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and even more preferably 100% by mass, from the viewpoints of uniformity and good conductivity of the conjugated conductive polymer (A).
• the monomer that constitutes the conjugated conductive polymer (A) is preferably a compound represented by the following formula (7) among the compounds represented by formula (6), and more preferably contains 3,4-ethylenedioxythiophene.
• R 71 and R 72 each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted oxygen atom-containing heterocycle having 3 to 6 carbon atoms formed by bonding together R 71 and R 72 .
• R 71 and R 72 are preferably an optionally substituted oxygen atom - containing heterocycle having 3 to 6 carbon atoms formed by bonding together .
• the oxygen atom-containing heterocycle preferably has 1 to 3 oxygen atoms constituting the ring, and examples thereof include a dioxane ring and a trioxane ring, and a dioxane ring is preferred.
• the oxygen atom-containing heterocycle is preferably unsubstituted.
• the substituent to be substituted here is the same as the above-mentioned substituent Y, and examples thereof include a carboxy group, a hydroxyl group, a halogen atom, and a cyano group.
• the polyanion (B) is a polymer having two or more anionic groups. It functions as a dopant for the conjugated conductive polymer (A).
• the polyanion (B) is coordinated to the outside of the polymer (E) that forms a domain inside, and is considered to act as a protective colloid.
• the content of the polyanion (B) in 100 mass% of the polymer component contained in the conductive polymer-containing dispersion of this embodiment is preferably 30 to 95 mass%, more preferably 40 to 90 mass%, and even more preferably 50 to 85 mass%, from the viewpoints of stability in the conductive polymer-containing dispersion and a decrease in ESR of a solid electrolytic capacitor produced using the conductive polymer-containing dispersion.
• the content of the polyanion (B) is preferably 45 to 1900 parts by mass, more preferably 70 to 900 parts by mass, and further preferably 100 to 500 parts by mass, based on 100 parts by mass of the conjugated conductive polymer (A).
• the anionic group examples include a group consisting of sulfonic acid or its salt, a group consisting of phosphoric acid or its salt, a mono-substituted phosphate ester group, a group consisting of carboxylic acid or its salt, and a mono-substituted sulfate ester group.
• a strongly acidic group is preferred, a group consisting of sulfonic acid or its salt, a group consisting of phosphoric acid or its salt, and a group consisting of sulfonic acid or its salt are more preferred, and a group consisting of sulfonic acid or its salt are even more preferred.
• the polyanion (B) is preferably a polymer having two or more groups consisting of sulfonic acid or its salt.
• the salt include sodium, potassium, magnesium, calcium, and ammonium salts.
• the anionic group may be bonded to the main chain or to the side chain of the polymer constituting the polyanion (B).
• the anionic group is bonded to the side chain, it is preferable that the anionic group is bonded to the end of the side chain from the viewpoint of obtaining a high doping effect for the conjugated conductive polymer (A).
• the anionic group may be bonded directly to the main chain, or may be bonded via another structure.
• the anionic group is preferably bonded via a benzene ring, and in this case, it is more preferable that the anionic group is bonded at the para position to the main chain.
• the polyanion (B) may have a substituent other than the anionic group.
• the substituent may be bonded to the main chain or to the side chain of the polymer constituting the polyanion (B). When the substituent is bonded to the side chain, it is preferable that the substituent is bonded to the end of the side chain from the viewpoint of exerting the properties of the substituent.
• the main chain structure of the polymer constituting the polyanion (B) is not particularly limited, but from the standpoint of synthesis and availability, for example, polyalkylene such as polyethylene is preferred.
• polyanion (B) a compound having a group consisting of sulfonic acid or a salt thereof as an anionic group is preferred, as described above, in order to improve the dispersibility in the dispersion medium (D) of the monomer that is a constituent unit of the conjugated conductive polymer (A).
• polyanions having a group consisting of sulfonic acid include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyethyl acrylate sulfonic acid, polybutyl acrylate sulfonic acid, poly(2-acrylamide-2-methylpropane sulfonic acid), polyisoprene sulfonic acid, and copolymers thereof, etc.
• polystyrene sulfonic acid polyisoprene sulfonic acid, polyethyl acrylate sulfonic acid, and polybutyl acrylate sulfonic acid are preferred, with polystyrene sulfonic acid being more preferred.
• the polyanion (B) contained in the conductive polymer-containing dispersion and the polyanion used in the production process of the conductive polymer-containing dispersion may have the same structure or different structures (e.g., different cations are bonded, etc.).
• sodium polystyrene sulfonate is preferably used as the polyanion from the viewpoint of water solubility, etc., and may be converted to polystyrene sulfonic acid by ion exchange or the like in a subsequent desalting process.
• the polyanion (B) can be produced by a known production method, for example, as described in JP-A-2005-76016, or a commercially available product can be used.
• the hydroxyl group-containing cyclic ether compound (C) in this embodiment is a hydroxyl group-containing compound represented by any one of the following formulas (1) to (5).
• R 11 to R 16 , R 21 to R 28 , R 31 to R 38 , R 41 to R 44 , and R 51 to R 56 each independently represent a hydrogen atom; a hydroxyl group; an alkyl group having 1 to 8 carbon atoms which may be substituted with a hydroxyl group, a cyano group, or an amino group; a cycloalkenyl group having 5 or 6 carbon atoms; a phenyl group which may be substituted with a hydroxyl group, an amino group, a cyano group, or a formyl group; an acetyl group; an acetoacetyl group; an allyl group; an acryloyl group; a pyridyl group; an alkylsulfonyl group which may be substituted with a hydroxyl group; or a formyl group.
• R 11 and R 12 are a hydrogen atom or an alkyl group, and at least one of R 13 to R 16 is a hydroxyalkyl group, with the remainder being a hydrogen atom.
• R 21 and R 22 are a hydrogen atom or an alkyl group, and at least one of R 23 to R 28 is a hydroxyalkyl group, with the remainder being a hydrogen atom.
• R 31 and R 32 are a hydrogen atom or an alkyl group, and at least one of R 33 to R 38 is a hydroxyalkyl group, with the remainder being a hydrogen atom.
• R 41 and R 42 are a hydrogen atom or an alkyl group, and at least one of R 43 to R 44 is a hydroxyalkyl group, with the remainder being a hydrogen atom.
• R 51 and R 52 are a hydrogen atom or an alkyl group, and at least one of R 53 to R 56 is a hydroxyalkyl group, with the remainder being a hydrogen atom.
• the hydroxyl-containing cyclic ether compound (C) improves the conductivity of the conductive polymer-containing dispersion and acts to reduce the ESR of the solid electrolytic capacitor manufactured using the conductive polymer-containing dispersion.
• the reason why the ESR of the solid electrolytic capacitor is further reduced is not clear, but it is speculated that the structure of the hydroxyl-containing cyclic ether compound (C) has some advantageous effect on further improving the conductivity of the conductive path formed by the conductive polymer-containing dispersion containing the conjugated conductive polymer (A) and the polyanion (B), thereby reducing the ESR of the solid electrolytic capacitor.
• hydroxyl group-containing cyclic ether compound (C) from the viewpoint of reducing the ESR of the solid electrolytic capacitor, a compound having a carbonyl group is preferred, and a compound in which the carbon atom forming the cyclic structure has a carbonyl group is more preferred.
• the hydroxyl-containing cyclic ether compound (C) has a higher boiling point and a lower polarity than chain glycol compounds such as ethylene glycol and propylene glycol, and therefore the dispersion stability of the conductive polymer-containing dispersion is easily maintained.
• the hydroxyl-containing cyclic ether compound (C) having two oxygen atoms forming a ring structure has a higher boiling point than cyclic ether compounds having one oxygen atom forming a ring structure such as tetrahydrofuran and tetrahydropyran, and has a hydroxyl group, so that the dispersion stability of the conductive polymer-containing dispersion is easily maintained.
• the hydroxyl group-containing cyclic ether compound (C) may have one or more hydroxyl groups.
• the hydroxyl group may or may not be directly bonded to a carbon atom constituting the ring.
• hydroxyl group-containing cyclic ether compound (C) represented by formula (1) include 1,3-dioxolane-2-ol, 1,3-dioxolane-2-methanol, 1,3-dioxolane-2-ethanol, 1,3-dioxolane-4-ol, 1,3-dioxolane-4-methanol, 1,3-dioxolane-4-ethanol, 2,2-dimethyl-1,3-dioxolane-4-ol, 2,2-dimethyl-1,3-dioxolane-4-methanol, and 2,2-dimethyl-1,3-dioxolane-4-ethanol.
• hydroxyl group-containing cyclic ether compound (C) represented by formula (2) include 1,3-dioxane-2-ol, 1,3-dioxane-4-ol, 1,3-dioxane-5-ol, 1,3-dioxane-2-methanol, 1,3-dioxane-4-methanol, 1,3-dioxane-5-methanol, 1,3-dioxane-2-ethanol, 1,3-dioxane-4-ethanol, 1,3-dioxane-5-ethanol, and 2-phenyl-1,3-dioxane-5-ol.
• hydroxyl group-containing cyclic ether compound (C) represented by formula (3) include 1,4-dioxane-2-ol, 1,4-dioxane-2-methanol, 1,4-dioxane-2-ethanol, 1,4-dioxane-2,3-diol, and 1,4-dioxane-2,5-diol.
• hydroxyl-containing cyclic ether compound (C) represented by formula (4) include 4-hydroxy-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2-one, and 4-(2-hydroxyethyl)-1,3-dioxolan-2-one.
• hydroxyl-containing cyclic ether compound (C) represented by formula (5) include 5-hydroxy-1,3-dioxan-2-one, 5-hydroxymethyl-1,3-dioxan-2-one, and 5-(2-hydroxyethyl)-1,3-dioxan-2-one.
• the hydroxyl group-containing cyclic ether compound (C) is preferably at least one selected from the group consisting of 2,2-dimethyl-1,3-dioxolane-4-methanol, 4-hydroxymethyl-1,3-dioxolane-2-one, 2,2-dimethyl-1,3-dioxolane-4-ethanol, and 1,3-dioxan-5-ol.
• the content of the hydroxyl group-containing cyclic ether compound (C) is, from the viewpoint of effectively reducing the stability of the conductive polymer-containing dispersion and the ESR of the solid electrolytic capacitor, preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, even more preferably 4 to 30 parts by mass, still more preferably 10 to 25 parts by mass, and particularly preferably 15 to 25 parts by mass, per part by mass of the total amount of the polymer components contained in the polymer-containing dispersion.
• the content of the hydroxyl group-containing cyclic ether compound (C) in the conductive polymer-containing dispersion is preferably 0.5 to 50 mass%, more preferably 3 to 40 mass%, even more preferably 6 to 30 mass%, still more preferably 12 to 30 mass%, and particularly preferably 20 to 30 mass%.
• the dispersion medium (D) of the conductive polymer-containing dispersion of the present embodiment is not particularly limited, but is preferably capable of maintaining the conductive polymer-containing dispersion more efficiently and with high dispersion stability.
• the dispersion medium (D) is preferably capable of dissolving or dispersing the hydroxyl group-containing cyclic ether compound (C), more preferably capable of dissolving, and even more preferably capable of dissolving all of the hydroxyl group-containing cyclic ether compound (C) contained in the conductive polymer-containing dispersion.
• dispersion medium (D) examples include water; amides such as N-vinylpyrrolidone, hexamethylphosphortriamide, N-vinylformamide, and N-vinylacetamide; phenols such as cresol, phenol, and xylenol; polyhydric alcohols such as dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, diglycerin, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and neopentyl glycol; carbonate compounds such as ethylene carbonate and propylene carbonate; ethers such as dioxane, diethyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, and polypropylene glycol dialkyl ether; heterocyclic compounds such as 3-methyl-2-ox
• the dispersion medium (D) may be one type alone or two or more types in combination. Among these, from the viewpoint of good dispersion stability and ease of production of the conductive polymer-containing dispersion liquid, it is preferable that the dispersion medium contains 1 to 99 mass% water, more preferably contains 50 to 99 mass% water, and even more preferably contains only water.
• the content of the dispersion medium (D) in the conductive polymer-containing dispersion is preferably 30 to 98% by mass, more preferably 45 to 97% by mass, and even more preferably 60 to 94% by mass, from the viewpoint of the desired viscosity and dispersion stability of the conductive polymer-containing dispersion.
• the polymer (E) is a polymer other than the conjugated conductive polymer (A) and the polyanion (B), and is a polymer that is insoluble in the dispersion medium (D).
• the content of the polymer (E) in 100 mass% of the polymer component contained in the conductive polymer-containing dispersion of the present embodiment is preferably 0 to 50 mass%, more preferably 0 to 40 mass%, and even more preferably 0 to 25 mass%, from the viewpoints of the dispersion stability of the conductive polymer-containing dispersion and the decrease in ESR of a solid electrolytic capacitor produced using the conductive polymer-containing dispersion.
• the polymer (E) is not particularly limited, but for example, a polymer containing a structural unit derived from an ethylenically unsaturated monomer is preferable, and a polymer consisting of a structural unit derived from an ethylenically unsaturated monomer is more preferable.
• the polymer (E) is preferably a nonionic polymer, and more preferably consists of a hydrocarbon.
• the polymer (E) may include either a homopolymer or a copolymer, or both.
• the polymer (E) may be one type alone or two or more types in combination, and may be either crystalline or amorphous, and is preferably amorphous.
• the polymer (E) may also have a crosslinked structure.
• Examples of ethylenically unsaturated monomers from which the structural units of polymer (E) are derived include (meth)acrylates having linear, branched or cyclic alkyl groups; aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; heterocyclic vinyl compounds such as vinylpyrrolidone; hydroxyalkyl (meth)acrylates; dialkylaminoalkyl (meth)acrylates such as 2-ethylhexyl (meth)acrylate; vinyl esters such as vinyl acetate and vinyl alkanoate; monoolefins such as ethylene, propylene, butylene and isobutylene; conjugated diolefins such as butadiene, isoprene and chloroprene; ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid; vinyl cyanide compounds such as
• the polymer (E) may have a crosslinked structure.
• the crosslinked structure may be a structure derived from a compound having a plurality of independent ethylenically unsaturated bonds.
• a plurality of independent ethylenically unsaturated bonds refers to a plurality of ethylenically unsaturated bonds that do not form a conjugated diene with each other.
• the crosslinked structure may be formed, for example, by a polymer having a first reactive functional group and a crosslinking agent having a plurality of second reactive functional groups that react with the first reactive functional group, or may be formed by reacting a polymer having both a first reactive functional group and a second reactive functional group intramolecularly or intermolecularly.
• a crosslinked copolymer By forming a crosslinked copolymer, the water resistance, moisture resistance, heat resistance, etc. of the solid electrolyte using this are likely to be improved.
• the content of structural units forming a crosslinked structure in 100 mass% of polymer (E) is preferably 50 mass% or less, more preferably 30 mass% or less, and even more preferably 15 mass% or less.
• the total content of the structural units forming a crosslinked structure and the structural units derived from the crosslinking agent in 100% by mass of the polymer (E) is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 15% by mass or less.
• Examples of compounds that form crosslinked structures include epoxy group-containing ⁇ , ⁇ -ethylenically unsaturated compounds such as glycidyl (meth)acrylate; hydrolyzable alkoxysilyl group-containing ⁇ , ⁇ -ethylenically unsaturated compounds such as vinyl triethoxysilane and ⁇ -methacryloxypropyl trimethoxysilane; and polyfunctional vinyl compounds such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, allyl (meth)acrylate, divinylbenzene, and diallyl phthalate.
• epoxy group-containing ⁇ , ⁇ -ethylenically unsaturated compounds such as glycidyl (meth)acrylate
• hydrolyzable alkoxysilyl group-containing ⁇ , ⁇ -ethylenically unsaturated compounds such as vinyl triethoxysilane and ⁇ -methacryloxypropyl trimethoxysilane
• crosslinkable monomers such as carbonyl group-containing ⁇ , ⁇ -ethylenically unsaturated compounds (those containing ketone groups) may be combined with polyhydrazine compounds (especially those having two or more hydrazide groups such as oxalic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, and polyacrylic acid hydrazide) to crosslink.
• polyhydrazine compounds especially those having two or more hydrazide groups such as oxalic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, and polyacrylic acid hydrazide
• the polymer (E) is preferably obtained as a dispersion containing the polymer (E) dispersed in a dispersion medium, and more preferably in the form of an emulsion.
• the particles contained in the dispersion containing the polymer (E) have a 50% volume cumulative particle size (d 50 ) of preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 1 ⁇ m, even more preferably 0.1 to 0.8 ⁇ m, and still more preferably 0.3 to 0.6 ⁇ m, from the viewpoints of dispersion stability and suppression of sedimentation.
• the d50 can be determined by the method described in the Examples below.
• the polymer (E) can be produced by radical polymerization reaction in a normal pressure or pressure-resistant reactor, and the production method may be any of batch, semi-continuous, and continuous. It is preferable to produce it by emulsion polymerization, which is a method of continuously or intermittently adding a raw material liquid containing an ethylenically unsaturated monomer to a polyanion-containing liquid and polymerizing it. According to emulsion polymerization, a polyanion is coordinated to the polymer (E), and a composite particle (2) having a structure in which a polyanion domain is formed outside the domain of the polymer (E) can be efficiently obtained.
• the polyanion used here may have the same structure as the polyanion (B), or may have a different structure (e.g., a different cation is bound thereto).
• the amount of the ethylenically unsaturated monomer used in the synthesis of polymer (E) is preferably 10 to 100 parts by mass, more preferably 20 to 90 parts by mass, and even more preferably 30 to 80 parts by mass, per 100 parts by mass of polyanion, from the viewpoints of suppressing thickening of the dispersion containing polymer (E) and improving dispersion stability.
• the dispersion medium used in the synthesis of the polymer (E) is preferably an aqueous medium, more preferably 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 30 mass% or less from the viewpoint of the dispersion stability of the particles during the polymerization reaction.
• the dispersion medium used in the synthesis of the polymer (E) may be the same component as the dispersion medium (D) contained in the conductive polymer-containing dispersion liquid, or may be a different component.
• water-soluble solvent examples include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone; glycols such as ethylene glycol and propylene glycol; and ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether.
• the content of the dispersion medium in the dispersion liquid containing polymer (E) is preferably 30 to 99% by mass, more preferably 50 to 95% by mass, and even more preferably 70 to 90% by mass, from the viewpoint of the dispersion stability of the dispersion liquid containing polymer (E).
• the polyanion contributes to the dispersion stability of the dispersion containing polymer (E).
• additives such as emulsifiers and aliphatic amines may be added to the dispersion containing polymer (E) as necessary.
• the type and amount of additives are appropriately adjusted depending on the content and composition of the ethylenically unsaturated monomer and polyanion.
• the emulsifier and aliphatic amine contained in the dispersion containing polymer (E) may be one type alone or two or more types.
• emulsifiers include anionic surfactants such as alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, polyoxyalkylene alkyl sulfates, and polyoxyalkylene alkyl phosphates; and nonionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, polyoxyalkylene fatty acid esters, and polyoxyalkylene sorbitan fatty acid esters.
• anionic surfactants such as alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, polyoxyalkylene alkyl sulfates, and polyoxyalkylene alkyl phosphates
• nonionic surfactants such as polyoxyal
• Aliphatic amines include, for example, primary amines such as octylamine, laurylamine, myristylamine, stearylamine, and oleylamine; secondary amines such as dioctylamine, dilaurylamine, distearylamine, and dioleylamine; and tertiary amines such as N,N-dimethyllaurylamine, N,N-dimethylmyristylamine, N,N-dimethylpalmitylamine, N,N-dimethylstearylamine, N,N-dimethylbehenylamine, N,N-dimethyloleylamine, N-methyldidecylamine, and N-methyldioleylamine.
• primary amines such as octylamine, laurylamine, myristylamine, stearylamine, and oleylamine
• secondary amines such as dioctylamine, dilaurylamine
• water-soluble polymers such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and polyvinylpyrrolidone may be included within a range that does not impair the properties of the conductive polymer-containing dispersion of this embodiment.
• Examples of the polymerization initiator for the radical polymerization reaction to obtain the polymer (E) include inorganic peroxides such as hydrogen peroxide, persulfuric acid, ammonium persulfate, potassium persulfate, and sodium persulfate; organic peroxides such as benzoyl peroxide and tert-butyl hydroperoxide; and azo compounds such as 2,2'-azobisisobutyronitrile and 4,4'-azobis(4-cyanovaleric acid).
• inorganic peroxides such as hydrogen peroxide, persulfuric acid, ammonium persulfate, potassium persulfate, and sodium persulfate
• organic peroxides such as benzoyl peroxide and tert-butyl hydroperoxide
• azo compounds such as 2,2'-azobisisobutyronitrile and 4,4'-azobis(4-cyanovaleric acid).
• polymerization initiators may be combined with sodium sulfoxylate formaldehyde, ascorbic acids, sulfites, tartaric acid or a salt thereof, iron(II) sulfate, and the like to carry out redox polymerization. Furthermore, chain transfer agents such as alcohols and mercaptans may be used as necessary.
• the reaction temperature in the radical polymerization reaction is preferably 10 to 100° C., more preferably 30 to 90° C.
• the reaction time is not particularly limited and is appropriately adjusted depending on the amount of raw materials, the type of polymerization initiator, the reaction temperature, etc.
• the reaction product obtained by the radical polymerization reaction is preferably desalted in order to ensure the quality stability of the dispersion containing polymer (E).
• the method of desalting is not particularly limited, and any known method can be used, such as dialysis, centrifugation washing, and ion exchange using ion exchange resins.
• the alkaline compound is not particularly limited, and organic or inorganic alkaline compounds can be used.
• the alkaline compound (F) may be used alone or in combination of two or more kinds.
• morpholinopropyl amine examples include 4-(2-morpholinoethoxy)aniline, 4-(4-pyridyl)morpholine, 4-aminomorpholine, 4-(2-hydroxypropyl)morpholine, 4-(2-hydroxyethyl)morpholine, 4-(3-hydroxypropyl)morpholine, 2-hydroxy-3-morpholinopropanesulfonic acid, 2-morpholinoethanesulfonic acid, 3-morpholinopropanesulfonic acid, 4-acetylmorpholine, 4-acetoacetylmorpholine, 4-acryloylmorpholine, 4-allylmorpholine, phenylmorpholine, ethyl 3-(morpholino)propionate, 4-formylmorpholine, 4-(4-formylphenyl)morpholine, and salts thereof.
• inorganic alkaline compounds examples include ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, etc.
• the conductive polymer-containing dispersion of the present embodiment may contain other additives that do not fall under any of the conjugated conductive polymer (A), the polyanion (B), the hydroxyl group-containing cyclic ether compound (C), the dispersion medium (D), the polymer (E), and the alkaline compound (F).
• the type and content of the other additives are not particularly limited. Examples of the other additives include water-soluble polymer compounds, water-dispersible compounds, surfactants, antifoaming agents, coupling agents, antioxidants, etc.
• the other additives may be used alone or in combination of two or more.
• the water-soluble polymer compound and the water-dispersible compound can adjust the viscosity of the conductive polymer-containing dispersion and improve the coating performance.
• the total content of the water-soluble polymer compound and the water-dispersible compound is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and even more preferably 3 to 30 parts by mass, per part by mass of the polymer component contained in the conductive polymer-containing dispersion.
• water-soluble polymeric compound examples include polyoxyalkylenes, water-soluble polyurethanes, water-soluble polyesters, water-soluble polyamides, water-soluble polyimides, water-soluble polyacrylics, water-soluble polyacrylamides, polyvinyl alcohols, polyacrylic acids, etc.
• polyoxyalkylenes are preferred.
• polyoxyalkylenes examples include oligopolyethylene glycol, triethylene glycol monochlorohydrin, diethylene glycol monochlorohydrin, oligoethylene glycol monochlorohydrin, triethylene glycol monobromohydrin, diethylene glycol monobromohydrin, 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 glycerin fatty acid esters, and polyoxyethylene fatty acid amides.
• the water-dispersible compound is preferably one that disperses in water without precipitating, for example, by substituting a portion of a compound having low hydrophilicity with a functional group having high hydrophilicity.
• examples of the water-dispersible compound include polyester, polyurethane, acrylic resin, silicone resin, and compounds obtained by modifying these by introducing functional groups, etc. Also included are block copolymers and graft copolymers of acrylic resin and polyester or polyurethane.
• surfactant examples include anionic surfactants such as carboxylates, sulfonates, sulfate salts, and phosphate salts; cationic surfactants such as amine salts and quaternary ammonium salts; amphoteric surfactants such as carboxybetaine, aminocarboxylate salts, and imidazolium betaine; and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, ethylene glycol fatty acid esters, and polyoxyethylene fatty acid amides.
• the defoaming agent examples include silicone resin, polydimethylsiloxane, and silicone oil.
• antioxidant examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, vitamins, and the like.
• the conductive polymer-containing dispersion of this embodiment can be produced, for example, by polymerizing a monomer that is a structural unit of the conjugated conductive polymer (A) in a raw material liquid (1) containing a monomer and a polyanion that are structural units of the conjugated conductive polymer (A), and adding a hydroxyl group-containing cyclic ether compound (C).
• the raw material liquid (1) may contain a polymer (E).
• An alkaline compound (F) and other additives may be added as desired.
• the polymer (E) may form a complex with a polyanion, or may form a complex in which the polyanion is coordinated outside the domain of the polymer (E).
• the polymer (E) may also be added as the above-mentioned polymer (E)-containing dispersion.
• the polyanion used in the production process of the conductive polymer-containing dispersion may have the same structure as the polyanion (B) contained in the conductive polymer-containing dispersion, or may have a different structure (e.g., a cation is bonded thereto).
• the monomers that are the constituent units of the conjugated conductive polymer (A) are dissolved, emulsified or dispersed in the raw material liquid (1).
• the raw material liquid (1) can be prepared, for example, by stirring with a stirrer such as a homomixer or homogenizer, or by ultrasonic irradiation, etc.
• a polyanion may be added from the viewpoint of suppressing aggregation of particles in the raw material liquid (1).
• the raw material liquid (1) may contain a composite particle (2) that is a complex in which a polyanion is coordinated to the outside of the domain of the polymer (E) and an additionally added polyanion.
• the additionally added polyanion may be the same as or a different component from the polyanion that forms a complex with the polymer (E), but is preferably the same.
• the amount of the polyanion to be additionally added is preferably 99% by mass or less, more preferably 10 to 90% by mass, even more preferably 30 to 80% by mass, and still more preferably 40 to 70% by mass, based on 100% by mass of the total polyanion in the raw material liquid (1).
• the total content of polyanions in the raw material liquid (1) is preferably an amount of 0.25 to 30 moles of anionic groups per mole of monomer that is a constituent unit of the conjugated conductive polymer (A), more preferably 0.5 to 25 moles, and even more preferably 0.8 to 20 moles, from the viewpoint of dispersion stability of the conductive polymer-containing dispersion and reduction in ESR of a solid electrolytic capacitor manufactured using the conductive polymer-containing dispersion.
• Examples of the dispersion medium in the raw material liquid (1) include water; amides such as N-vinylpyrrolidone, hexamethylphosphoramide, N-vinylformamide, and N-vinylacetamide; phenols such as cresol, phenol, and xylenol; polyhydric alcohols such as dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, diglycerin, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and neopentyl glycol; carbonates such as ethylene carbonate and propylene carbonate; ethers such as dioxane, diethyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, and polypropylene glycol dialkyl ether; heterocyclic compounds such as 3-methyl-2-
• the dispersion medium may be used alone or in combination of two or more kinds.
• the dispersion medium preferably contains water.
• the content of water in 100% by mass of the dispersion medium is preferably 1% by mass or more, more preferably 50% by mass or more, and even more preferably 100% by mass.
• the dispersion medium in the raw material liquid (1) preferably has the same components as the dispersion medium (D) of the conductive polymer-containing dispersion.
• the content of the dispersion medium in the raw material liquid (1) is preferably 1 to 99.9% by mass, more preferably 10 to 99% by mass, and even more preferably 30 to 98% by mass, from the viewpoint of appropriate viscosity and reactivity during the polymerization reaction.
• the polymerization reaction for synthesizing the conjugated conductive polymer (A) is preferably carried out in the presence of an oxidizing agent.
• the oxidizing agent include peroxodisulfuric acid, peroxodisulfate salts such as ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate; metal halide compounds such as boron trifluoride; transition metal compounds such as iron chloride (III), iron sulfate (III), and copper chloride (II); metal oxides such as silver oxide and cesium oxide; peroxides such as hydrogen peroxide and ozone; organic peroxides such as benzoyl peroxide; and oxygen.
• the oxidizing agent may be used alone or in combination of two or more.
• the amount of the oxidizing agent used is preferably 50 to 1500 parts by mass, more preferably 70 to 1000 parts by mass, and even more preferably 100 to 500 parts by mass, relative to 100 parts by mass of the monomer that is a constituent unit of the conjugated conductive polymer (A), from the viewpoint of appropriately promoting the polymerization reaction.
• the temperature in the polymerization reaction is preferably 5 to 80°C, more preferably 10 to 60°C, and even more preferably 15 to 40°C, from the viewpoint of achieving an appropriate reaction rate and suppressing an increase in the viscosity of the reaction liquid.
• the temperature may be changed as appropriate depending on the progress of the reaction.
• the polymerization reaction is preferably carried out with stirring from the viewpoint of preventing aggregation of particles in the reaction liquid.
• the stirring method is not particularly limited, and examples include a method of circulating and stirring the reaction liquid using a high-shear mixer, etc.
• the method for producing the solid electrolytic capacitor of the present embodiment includes a step of depositing the conductive polymer-containing dispersion of the present embodiment described above onto a porous anode body made of a valve metal having a dielectric coating on its surface, and then removing the dispersion medium (D) from the dispersion liquid deposited on the porous anode body to form a solid electrolyte layer.
• a solid electrolyte layer using the conductive polymer-containing dispersion liquid of this embodiment through such a process, a solid electrolytic capacitor having a low ESR can be suitably manufactured.
• valve metals include aluminum, beryllium, bismuth, magnesium, germanium, hafnium, niobium, antimony, silicon, tin, tantalum, titanium, vanadium, tungsten, zirconium, and alloys or compounds containing at least one of these metals.
• aluminum, niobium, and tantalum are preferred from the viewpoint of versatility.
• a porous anode body can be produced by forming a dielectric coating on the surface of a porous valve metal.
• Porous valve metals can be obtained, for example, by sintering a valve metal powder with a high specific surface area, or by etching a valve metal foil.
• the dielectric film can be formed as a dielectric oxide film on the surface of the porous valve metal, for example, by anodizing the porous valve metal in a phosphate solution.
• the formation voltage in the anodization is set according to the thickness of the dielectric oxide film and the withstand voltage of the capacitor, and is preferably 1 to 800 V, more preferably 1 to 500 V, and even more preferably 1 to 300 V.
• the conductive polymer-containing dispersion can be applied to the porous anode body by, for example, coating, spraying, immersion, or other methods.
• the method of immersing the porous anode body in the conductive polymer-containing dispersion is preferred because it allows the conductive polymer-containing dispersion to penetrate and adhere evenly throughout the porous anode body.
• the impregnation may be performed under reduced pressure.
• the conductive polymer-containing dispersion When the conductive polymer-containing dispersion is immersed in the porous anode body to adhere to it, the conductive polymer-containing dispersion is usually impregnated into the porous anode body at a temperature of about 10 to 35°C for about 10 seconds to 10 minutes, although this depends on the type and viscosity of the dispersion medium (D) of the conductive polymer-containing dispersion.
• the dispersion medium (D) is preferably removed by heating and drying the porous anode body to which the conductive polymer-containing dispersion liquid is attached.
• the heating conditions are appropriately set in consideration of the boiling point and volatility of the dispersion medium (D) and the oxidative deterioration of the polymer component, and the heat treatment is usually performed at room temperature to 300° C., preferably 40 to 250° C., and more preferably 50 to 200° C. for 5 seconds to several hours.
• the heating device for example, a hot plate, an oven, a hot air dryer, etc. can be used, and from the viewpoint of drying efficiency, drying may be performed under reduced pressure.
• the removal of the dispersion medium (D) mentioned here does not only mean that the dispersion medium (D) is completely absent, but also that some of the dispersion medium may remain within a range that does not interfere with the production of the solid electrolytic capacitor.
• the above steps may be repeated.
• the solid electrolyte layer formed in the above step may be impregnated with any electrolyte solution.
• the electrolyte solution to be impregnated into the solid electrolyte layer include polar organic solvents that may contain salts.
• a protic solvent can be used, and examples thereof include monohydric alcohols such as ethanol, propanol, butanol, pentanol, hexanol, cyclobutanol, cyclopentanol, cyclohexanol, and benzyl alcohol; and polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, methyl cellosolve, ethyl cellosolve, methoxypropylene glycol, dimethoxypropanol, and alkylene oxide adducts of polyethylene glycol and polyoxyethylene glycerin, and oxyalcohol compounds.
• monohydric alcohols such as ethanol, propanol, butanol, pentanol, hexanol, cyclobutanol, cyclopentanol, cyclohexanol, and benzyl alcohol
• polyhydric alcohols such as ethylene glyco
• aprotic solvents can also be used as the polar organic solvent.
• the solvent include sulfones such as dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, sulfolane, 3-methyl sulfolane, and 2,4-dimethyl sulfolane; amides such as N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, and hexamethylphosphoric amide; lactones and cyclic amides such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, N-methyl-2-pyrrolidone, ethylene carbonate, propylene carbonate, butylene carbonate, and isobut
• acids that can form salts include carboxylic acids such as oxalic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, benzoic acid, toluic acid, enanthic acid, malonic acid, 1,6-decanedicarboxylic acid, 1,7-octanedicarboxylic acid, azelaic acid, resorcylic acid, phloroglucinic acid, gallic acid, gentisic acid, protocatechuic acid, pyrocatechuic acid, trimellitic acid, and pyromellitic acid; and organic acids such as sulfonic acids.
• carboxylic acids such as oxalic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic
• boric acid examples include boric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, carbonic acid, and silicic acid.
• boron complexes such as borodisalicylic acid, borodisalic acid, borodiglycolic acid, borodimalonic acid, borodisuccinic acid, borodiadipic acid, borodiazelaic acid, borodibenzoic acid, borodimaleic acid, borodilactic acid, borodimalic acid, boroditartaric acid, borodicitric acid, borodiphthalic acid, borodi(2-hydroxy)isobutyric acid, borodiresorcylic acid, borodimethylsalicylic acid, borodinaphthoic acid, borodimandelic acid, and borodi(3-hydroxy)propionic acid.
• the electrolyte may contain additives.
• additives include complex compounds of boric acid and polysaccharides such as mannitol and sorbitol; complex compounds of boric acid and polyhydric alcohols; boric acid esters; nitro compounds such as o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, o-nitrophenol, m-nitrophenol, p-nitrophenol, and p-nitrobenzyl alcohol; and phosphate esters. These may be used alone or in combination of two or more.
• the method for producing a solid electrolytic capacitor of this embodiment can be carried out in the conventional manufacturing process for solid electrolytic capacitors by using the conductive polymer-containing dispersion of this embodiment and changing the manufacturing conditions as necessary. Therefore, according to the method for producing a solid electrolytic capacitor of this embodiment, it is possible to produce a solid electrolytic capacitor with a lower ESR than conventional ones while suppressing increases in manufacturing costs, without requiring major equipment changes to the conventional manufacturing process for solid electrolytic capacitors.
• the solid electrolytic capacitor of this embodiment has a solid electrolyte layer on a porous anode body made of a valve metal having a dielectric film on its surface, and the solid electrolyte layer contains a conjugated conductive polymer (A), a polyanion (B), and a hydroxyl-containing cyclic ether compound (C) represented by any one of the above formulas (1) to (5).
• a solid electrolytic capacitor having such a configuration has a low ESR.
• Such a solid electrolytic capacitor can be suitably manufactured by the method for manufacturing a solid electrolytic capacitor according to the present embodiment described above.
• the solid electrolyte layer may contain the above-mentioned electrolytic solution.
• Solid content concentration The solid content concentration was calculated by weighing out about 10 g of a dispersion sample, heating it for 30 minutes at a temperature 10° C. higher than the boiling point of the dispersion medium with the highest boiling point among the dispersion mediums contained therein using an infrared moisture meter ("FD-720", Kett Electric Laboratory Co., Ltd.), and calculating the evaporation residue as the solid content.
• the heating conditions are 110° C. for 30 minutes.
• pH of the composite particle-containing liquid was measured with a pH meter ("HM-30G", manufactured by DKK-TOA Corporation; 25° C.).
• Example 1 ⁇ Production of Dispersion Containing Polymer (E1)> A raw material solution (a) was prepared by mixing with stirring 86 g of styrene, 49 g of 2-ethylhexyl acrylate, 15 g of divinylbenzene, and 500 g of a 22 mass % aqueous solution of sodium polystyrene sulfonate ("Polinas (registered trademark) PS-5", manufactured by Tosoh Finechem Corporation; Mw approximately 120,000; the same applies hereinafter) (110 g of sodium polystyrene sulfonate).
• Polystyrene sulfonate Polystyrene sulfonate
• a high-pressure homogenizer manufactured by Niro Soavi; 400 bar (40 MPa
• Dispersion liquid (3) was desalted by ion exchange using 125.6 mL of a cation exchange resin and 109.9 mL of an anion exchange resin for 3 hours to obtain dispersion liquid (4) containing a conductive polymer (pH 1.9, solid content concentration 1.65% by mass).
• Examples 2 to 6, Comparative Examples 1 and 2 Each conductive polymer-containing dispersion was produced in the same manner as in Example 1, except that the 2,2-dimethyl-1,3-dioxolane-4-methanol used in Example 1 was changed to the (cyclic) ether compound or amount shown in Examples 2 to 6 and Comparative Examples 1 and 2 in Table 1.
• Example 7 In a 1 L polyethylene container, 63.0 g of a 12 mass % aqueous solution of sodium polystyrene sulfonate (7.56 g of sodium polystyrene sulfonate) and 225.7 g of pure water were mixed with stirring at 32° C. To this, 2.80 g of 3,4-ethylenedioxythiophene was added, and emulsified and mixed for 30 minutes in a homomixer to prepare a raw material liquid (1-2) (total content of sodium polystyrene sulfonate: 2.0 mol of sodium sulfonate groups per 1 mol of 3,4-ethylenedioxythiophene). In Example 1, the raw material liquid (1-1) was changed to the raw material liquid (1-2), and the steps after the step of producing the conjugated conductive polymer (A1) were carried out in the same manner as in Example 1 to produce a conductive polymer-containing dispersion.
• Example 8 to 12 Each conductive polymer-containing dispersion was produced in the same manner as in Example 7, except that the 2,2-dimethyl-1,3-dioxolane-4-methanol used in Example 7 was changed to the (cyclic) ether compound or amount shown in Examples 8 to 12 and Comparative Examples 3 and 4 in Table 1.
• the hydroxyl group-containing cyclic ether compounds used in Examples 1 to 12 are as follows: 2,2-Dimethyl-1,3-dioxolane-4-methanol is a compound in which, in the formula (1), R 11 and R 12 are methyl groups, R 13 is a hydroxymethyl group, and R 14 to R 16 are hydrogen atoms.
• 4-Hydroxymethyl-1,3-dioxolan-2-one is a compound in which R 41 is a hydroxymethyl group, and R 42 to R 44 are hydrogen atoms in the formula (4).
• 2,2-Dimethyl-1,3-dioxolane-4-ethanol is a compound in which, in the formula (1), R 11 and R 12 are methyl groups, R 13 is a hydroxyethyl group, and R 14 to R 16 are hydrogen atoms.
• 1,3-Dioxane-5-ol is a compound in which, in formula (2), R 21 and R 22 are hydrogen atoms, R 23 , R 24 , R 26 to R 28 are hydrogen atoms, and R 25 is a hydroxyl group.
• solid electrolytic capacitors were produced as follows. A porous anode body of an aluminum electrolytic capacitor element (withstand voltage 35 V, design capacity 400 ⁇ F) was immersed in the conductive polymer-containing dispersion liquid for 5 minutes at 25° C. in an air atmosphere, and then dried at 120° C. for 30 minutes in a hot air dryer ("ST-110", manufactured by Espec Corporation) to obtain a solid electrolytic capacitor in which a solid electrolyte layer was formed on the surface of the dielectric oxide film of the porous anode body.
• ST-110 hot air dryer
• ESR equivalent series resistance

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Power Engineering (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Electrochemistry (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Manufacturing & Machinery (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Physics & Mathematics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=91588528

Family Applications (2)

Family Applications After (1)

Country Status (7)

Families Citing this family (1)

Citations (5)

Family Cites Families (16)

• 2023
  • 2023-12-18 JP JP2024566025A patent/JPWO2024135579A1/ja active Pending
  • 2023-12-18 US US18/839,518 patent/US12278061B1/en active Active
  • 2023-12-18 CN CN202380083748.XA patent/CN120303353A/zh active Pending
  • 2023-12-18 JP JP2024547415A patent/JPWO2024135580A1/ja active Pending
  • 2023-12-18 KR KR1020247027629A patent/KR20240131455A/ko not_active Withdrawn
  • 2023-12-18 EP EP23906940.4A patent/EP4640769A1/en active Pending
  • 2023-12-18 KR KR1020257019117A patent/KR20250102098A/ko active Pending
  • 2023-12-18 WO PCT/JP2023/045174 patent/WO2024135579A1/ja not_active Ceased
  • 2023-12-18 CN CN202380022921.5A patent/CN118742614A/zh active Pending
  • 2023-12-18 WO PCT/JP2023/045175 patent/WO2024135580A1/ja not_active Ceased
  • 2023-12-20 TW TW112149656A patent/TW202432739A/zh unknown
  • 2023-12-20 TW TW112149653A patent/TW202432697A/zh unknown

Patent Citations (5)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events