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WO2025009460A1 - Condensateur électrolytique - Google Patents

Condensateur électrolytique Download PDF

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Publication number
WO2025009460A1
WO2025009460A1 PCT/JP2024/023318 JP2024023318W WO2025009460A1 WO 2025009460 A1 WO2025009460 A1 WO 2025009460A1 JP 2024023318 W JP2024023318 W JP 2024023318W WO 2025009460 A1 WO2025009460 A1 WO 2025009460A1
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group
carboxylic acid
electrolytic capacitor
carbonyl group
compound
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Japanese (ja)
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博之 有馬
彬人 中村
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/035—Liquid electrolytes, e.g. impregnating materials
    • 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
    • H01G9/145—Liquid electrolytic capacitors
    • 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

  • This disclosure relates to electrolytic capacitors.
  • electrolytic capacitors that include an anode body with a dielectric layer, a conductive polymer that covers at least a portion of the dielectric layer, and an electrolyte are considered promising.
  • the conductive polymer includes, for example, a conjugated polymer and a dopant.
  • the electrolyte is a liquid component such as a nonaqueous solvent or a solution in which a solute is dissolved in a nonaqueous solvent.
  • Patent Document 1 proposes an electrolyte solution for use in an electrolytic capacitor having an anode with a dielectric oxide film, a cathode, a separator disposed between the anode and the cathode, and a conductive polymer and electrolyte solution held by the separator, the electrolyte solution containing a solvent containing at least one selected from the group consisting of ethylene glycol, polyethylene glycol, and derivatives thereof, and a solute containing at least one selected from the group consisting of a dicarboxylic acid having a hydroxyl group at the ⁇ -position, a polycarboxylic acid having a hydroxyl group at the ⁇ -position, and salts thereof.
  • Patent Document 2 proposes a solid electrolytic capacitor having a capacitor element in which an anode foil and a cathode foil are wound with a separator therebetween, the capacitor element having a solid electrolyte layer, and voids in the capacitor element being filled with an electrolyte solution, the electrolyte solution containing an ammonium salt of an aliphatic carboxylic acid as a solute and a polyhydric alcohol as a solvent, and the amount of the solute acid added to the solvent is 0.6 mol/kg or less.
  • Patent Document 3 proposes a conductive polymer hybrid aluminum electrolytic capacitor having a capacitor element in which an anode electrode foil and a cathode electrode foil on which an aluminum dielectric oxide film is formed are wound with a separator interposed therebetween, the conductive polymer layer being formed on the dielectric oxide film, and an electrolyte solution, the electrolyte solution containing a solute and a solvent, the solvent containing diethylene glycol and/or triethylene glycol, and the solute containing a salt of a long-chain dibasic carboxylic acid (dicarboxylic acid) having 12 or more carbon atoms and an amine having a boiling point of 150°C or higher.
  • a conductive polymer hybrid aluminum electrolytic capacitor having a capacitor element in which an anode electrode foil and a cathode electrode foil on which an aluminum dielectric oxide film is formed are wound with a separator interposed therebetween, the conductive polymer layer being formed on the dielectric oxide film, and an electrolyte solution, the electrolyt
  • Electrolytes containing carboxylic acids or carboxylic acid salts, such as those described in Patent Documents 4 to 6, are also known as electrolytes for electrolytic capacitors.
  • conductive polymers for example, high conductivity is achieved when a conjugated polymer is doped with a dopant.
  • the liquid component contains an acid component, it is expected that de-doping of the dopant is suppressed and the high conductivity of the conductive polymer is maintained.
  • it is actually difficult to suppress the decrease in conductivity of the conductive polymer over time when the electrolytic capacitor is used, and it may be difficult to suppress an increase in ESR.
  • a first aspect of the present disclosure includes a capacitor element and a liquid component
  • the capacitor element includes an anode body having a dielectric layer on a surface thereof, and a conductive polymer covering at least a portion of the dielectric layer
  • the liquid component includes an acid component and a solvent
  • the acid component includes a first carboxylic acid compound having a first moiety and a second moiety each
  • the first site has a first carboxy group including a first carbonyl group, a second carbonyl group, and a linking group linking the first carbonyl group and the second carbonyl group
  • the present invention relates to an electrolytic capacitor, wherein the second portion includes a heteroatom bonded to the second carbonyl group and a hydrocarbon group having two or more carbon atoms bonded to the heteroatom.
  • a second aspect of the present disclosure includes a capacitor element and a liquid component
  • the capacitor element includes an anode body having a dielectric layer on a surface thereof, and a conductive polymer covering at least a portion of the dielectric layer
  • the liquid component includes an acid component, a base component, and a solvent
  • the acid component includes a first carboxylic acid compound having a first site; the first site has a first carboxy group including a first carbonyl group, a second carbonyl group, and a linking group linking the first carbonyl group and the second carbonyl group
  • the present invention relates to an electrolytic capacitor, wherein the base component includes at least one selected from the group consisting of an amine, a quaternary ammonium compound, and an amidinium compound.
  • FIG. 1 is a schematic cross-sectional view of an electrolytic capacitor according to an embodiment of the present disclosure.
  • 2 is a schematic diagram showing a portion of a capacitor element of the electrolytic capacitor of FIG. 1 in an expanded form.
  • the ESR of the electrolytic capacitor is greatly affected by the ionic conductivity of the liquid components and the state of electrical connection of the components of the electrolytic capacitor.
  • the resistance of the conductive polymer tends to be high compared to the cathode extraction layer or anode body that constitutes the cathode body. Therefore, as mentioned above, the conductivity of the conductive polymer greatly affects the ESR. And, as mentioned above, the conductive polymer deteriorates as the electrolytic capacitor is used, so in order to maintain high conductivity, it is important to stabilize the conductive polymer.
  • an electrolytic capacitor contains a conductive polymer and a liquid component
  • the liquid component greatly affects the state of the conductive polymer (including conductivity, stability, etc.).
  • the mechanism by which the liquid component affects the ESR of the electrolytic capacitor is completely different from that of electrolytic capacitors that contain conductive polymers and liquid components.
  • An electrolytic capacitor includes a capacitor element and a liquid component, the capacitor element includes an anode body having a dielectric layer on a surface thereof, and a conductive polymer covering at least a portion of the dielectric layer,
  • the liquid component includes an acid component and a solvent, the acid component includes a first carboxylic acid compound having a first moiety and a second moiety each; the first site has a first carboxy group including a first carbonyl group, a second carbonyl group, and a linking group linking the first carbonyl group and the second carbonyl group,
  • the second portion includes a heteroatom bonded to the second carbonyl group and a hydrocarbon group having two or more carbon atoms bonded to the heteroatom.
  • the first carboxylic acid compound included in the liquid component may be referred to as a first carboxylic acid compound A.
  • the liquid component may further contain a base component.
  • the dissociation property of the acid component is enhanced, and it is easy to obtain a higher conductivity of the conductive polymer.
  • An electrolytic capacitor according to a second aspect of the present disclosure includes a capacitor element and a liquid component, the capacitor element includes an anode body having a dielectric layer on a surface thereof, and a conductive polymer covering at least a portion of the dielectric layer,
  • the liquid component includes an acid component, a base component, and a solvent, the acid component includes a first carboxylic acid compound having a first site; the first site has a first carboxy group including a first carbonyl group, a second carbonyl group, and a linking group linking the first carbonyl group and the second carbonyl group,
  • the base component includes at least one selected from the group consisting of an amine, a quaternary ammonium compound, and an amidinium compound.
  • the first carboxylic acid compound contained in the liquid component may be referred to as a first carboxylic acid compound B.
  • first carboxylic acid compound A and the first carboxylic acid compound B may be collectively referred to as the first carboxylic acid compound.
  • the liquid component contains an acid component that includes a first carboxylic acid compound, which can reduce the change over time in the ESR (in other words, the increase over time) that occurs with use of the electrolytic capacitor.
  • the reason why the change over time in the ESR is reduced is thought to be as follows.
  • the second carbonyl group of the first carboxylic acid compound is likely to coordinate to the cationic portion of the conductive polymer due to the charge bias, and the conductive polymer can be stabilized.
  • the first carboxy group is likely to be in close proximity to the conductive polymer, and the conductive polymer can be stabilized. Due to such stabilizing action of the second carbonyl group and the first carboxy group, when the electrolytic capacitor is used, the progress of dedoping from the conductive polymer is suppressed, and the deterioration of the conductive polymer is suppressed, and high conductivity is maintained. Therefore, it is considered that the change in ESR over time is reduced.
  • the first carboxylic acid compound A having the second portion a hydrocarbon group having two or more carbon atoms is bonded to the second carbonyl group via a heteroatom, which is advantageous because the withstand voltage characteristics are further improved.
  • the first carboxylic acid compound B is combined with a more stable base component, which makes it easier to maintain the dissociated state and easier to maintain the higher repairability of the dielectric coating.
  • the first carboxylic acid compound easily forms an appropriate coating on the surface of the dielectric layer on the surface of the anode body. This coating improves the film repairability of the dielectric layer, making it possible to keep leakage current low even when the electrolytic capacitor is used for a long period of time. Furthermore, the action of the first carboxylic acid compound suppresses deterioration of the conductive polymer over time, making it possible to maintain a state in which many liquid components are retained in the conductive polymer near the dielectric layer. This is also thought to improve the film repairability of the dielectric layer. In addition, the ease with which the dielectric layer is repaired also ensures high voltage resistance.
  • the equivalent ratio of the base component to the first carboxylic acid compound may be 0.5 or more and 10 or less. In this case, a high degree of dissociation of the first carboxylic acid compound can be ensured. In addition, corrosion of the electrode can be suppressed, and high voltage resistance can be easily ensured.
  • the first carboxylic acid compound may have a second moiety including a heteroatom bonded to the second carbonyl group and a hydrocarbon group bonded to the heteroatom (the hydrocarbon group having two or more carbon atoms in the above (Technology 1)).
  • the heteroatom may be an oxygen atom or a nitrogen atom.
  • the first moiety can be easily introduced into the first carboxylic acid compound via the oxygen atom or nitrogen atom.
  • the second site may contain a residue of a hydroxy compound or a residue of an amine compound.
  • the first site can be easily introduced into the first carboxylic acid compound via an oxygen atom or an amino group.
  • the second moiety may contain a residue of a polyol.
  • the polyol may be an alkylene glycol, a polyalkylene glycol or a monoether thereof.
  • the first moiety can be easily introduced into the first carboxylic acid compound via an oxygen atom.
  • the number of carbon atoms in the main chain connecting the first carbon atom of the first carbonyl group and the second carbonyl group in the linking group may be 1 to 4.
  • the first carboxy group is likely to take a stabilized structure when ionized, and the surroundings of the conductive polymer are likely to be kept acidic.
  • the linking group may contain a non-aromatic cyclic divalent group or an aromatic divalent group.
  • the solubility of the first carboxylic acid compound in the solvent and the affinity for the dielectric layer are easily adjusted.
  • the first carboxy group is easily stabilized and the positions of the second carbonyl group and the first carboxy group are easily fixed, so the pH of the liquid component tends to be lower.
  • the main chain in the linking group that links the first carbon atom of the first carbolic group and the second carbon atom of the second carbonyl group may be an aliphatic divalent group.
  • the function of the liquid component to repair the dielectric layer can be enhanced, and the effect of reducing leakage current can be further enhanced.
  • the aliphatic divalent group has a first substituent
  • the aliphatic divalent group may have a monovalent aliphatic hydrocarbon group having 6 or more carbon atoms as at least one of the first substituents.
  • the effect of suppressing esterification of the first carboxy group is enhanced, and it is easy to ensure higher conductivity of the conductive polymer.
  • the voltage resistance of the electrolytic capacitor can be further improved.
  • the aliphatic divalent group may have the monovalent aliphatic hydrocarbon group at the ⁇ -position of the first carbonyl group.
  • the steric hindrance of the aliphatic hydrocarbon group further enhances the effect of suppressing esterification of the first carboxy group, and fluctuations in ESR can be further suppressed.
  • the acid component may further contain a second carboxylic acid compound different from the first carboxylic acid compound.
  • the first carboxylic acid compound in addition to making it easier to reduce the pH of the liquid component, the first carboxylic acid compound can ensure a certain degree of voltage resistance while further reducing the change in ESR over time.
  • the ratio of the first carboxylic acid compound to the acid component may be 20 mass% or more. In this case, the change in ESR over time can be further suppressed. In addition, it is easy to ensure higher voltage resistance.
  • the liquid component contained in the electrolytic capacitor includes an acid component and a solvent.
  • the acid component includes a first carboxylic acid compound.
  • the first carboxylic acid compound has one first site.
  • the first site has a first carboxy group containing a first carbonyl group, a second carbonyl group, and a linking group linking these carbonyl groups.
  • the linking group linking the first carbonyl group and the second carbonyl group may be referred to as a first linking group.
  • the first carboxy group and the second carbonyl group of the first site improve the stability of the conductive polymer and maintain high conductivity, thereby reducing the change over time in the ESR of the electrolytic capacitor.
  • the action of the first carboxylic acid compound enhances the film repairability of the dielectric layer, making it possible to suppress an increase in leakage current even after long-term use and ensure high voltage resistance.
  • the presence of the first linking group creates a certain amount of distance between the second carbonyl group and the first carbonyl group or the first carboxy group. This is thought to result in the first carboxylic acid compound having relatively high stability. This makes it easier for the first carboxylic acid compound to act on the conductive polymer, which is thought to be advantageous in terms of the stability and high conductivity of the conductive polymer.
  • the first carboxy group may be in any of the following forms: free form, salt form, anion form, or form interacting with a conductive polymer (e.g., complexed).
  • a conductive polymer e.g., complexed
  • the first carboxy group includes all of these forms.
  • the first carboxylic acid compound may have one second site.
  • the second site includes a heteroatom (hereinafter sometimes referred to as the first heteroatom) and a hydrocarbon group bonded to the first heteroatom.
  • the first heteroatom is bonded to the second carbonyl group in the first site.
  • the hydrocarbon group bonded to the first heteroatom also includes a hydrocarbon group having a substituent (a fourth substituent described below).
  • the first carboxylic acid compound includes, for example, a compound represented by the following formula (I):
  • X1 is a first carbonyl group
  • X2 is a second carbonyl group
  • Y1 is a first carboxy group
  • R1 is a first linking group
  • X3 is a heteroatom (first heteroatom)
  • R2 is a monovalent organic group containing a hydrocarbon group which may have a substituent (fourth substituent)
  • R3 is a hydrogen atom or a substituent (seventh substituent described later)
  • Z1 is a first moiety
  • Z2 is a second moiety.
  • the structures of the first linking group (R 1 in formula (I)) and the second site (Z 2 in formula (I)) are not particularly limited as long as they do not inhibit the action of the first carboxy group and the second carbonyl group on the conductive polymer.
  • the first site may be, for example, a residue of a polycarboxylic acid or an acid anhydride thereof.
  • polycarboxylic acids include dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids (particularly, dicarboxylic acids).
  • the second site is a residue of a compound (e.g., a hydroxy compound, an amine compound) that can be linked to a polycarboxylic acid or an acid anhydride thereof.
  • a compound e.g., a hydroxy compound, an amine compound
  • the first site is a residue of a polycarboxylic acid (particularly, a dicarboxylic acid) or an acid anhydride thereof.
  • the first linking group (for example, R 1 in formula (I)) may have a main chain and a substituent (including a side chain) bonded to the main chain, or may be composed of only the main chain (corresponding to the case where no substituent is present).
  • the substituent (including a side chain) bonded to the main chain may be referred to as the first substituent.
  • the main chain connects the carbon atom (first carbon atom) of the first carbonyl group and the carbon atom (second carbon atom) of the second carbonyl group.
  • the main chain is a linear portion that includes at least carbon atoms, and the first carbon atom and the second carbon atom are not included in the main chain.
  • the first substituent is not included in the main chain.
  • the main chain also includes a case where the number of carbon atoms in the main chain is 1 (for example, a methylene group, a methylene group having a first substituent, a group having a methylene group and a hetero atom (second hetero atom) described later (oxymethylene group, oxymethylene group having a first substituent, etc.)).
  • the chain having the fewest number of atoms (carbon atoms, second heteroatoms, etc.) constituting the chain is the main chain.
  • the first substituent may further have a substituent (second substituent).
  • the main chain may be a hydrocarbon chain or may contain a second heteroatom.
  • the second heteroatom includes at least one selected from the group consisting of oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms.
  • the main chain may contain one second heteroatom, or may contain two or more.
  • the main chain may be linear or may form part of a ring structure.
  • the main chain may form part of at least one ring structure selected from the group consisting of non-aromatic rings and aromatic rings. These rings may be hydrocarbon rings or may be heterocycles containing a heteroatom (third heteroatom). These rings may be bridged rings or condensed rings.
  • the third heteroatom contained in the heterocycle may be at least one selected from the group consisting of oxygen atoms, sulfur atoms, and nitrogen atoms.
  • the heterocycle may contain one third heteroatom, or may contain two or more third heteroatoms. When the third heteroatom contained in the heterocycle constitutes the main chain, the third heteroatom is the second heteroatom.
  • Examples of the heterocycle include divalent groups corresponding to the heterocycle groups described for the first substituent described below, and the description of the heterocycle of the first substituent can be referred to.
  • the first linking group is a 1,1-dimethylethane-1,2-diyl group
  • 1,2-ethylene groups constitute the main chain, except for the two methyl groups corresponding to the substituents.
  • the first carbonyl group and the second carbonyl group are bonded to the 1- and 2-positions of cyclohexane, respectively, the chain of carbon atoms at the 1st and 2nd positions of cyclohexane becomes the main chain, and the number of carbon atoms in the main chain is 2.
  • the first linking group is a cyclohexane-1,2-diyl group.
  • the first linking group is a 2-norbornene-5,6-diyl group
  • the chain of carbon atoms at the 5th and 6th positions of the norbornene ring becomes the main chain, and the number of carbon atoms in the main chain is 2.
  • the first linking group is a 1,2-phenylene group
  • the chain of carbon atoms at the 1st and 2nd positions of the benzene ring becomes the main chain, and the number of carbon atoms in the main chain is 2.
  • an alkylene group, an alkenylene group, etc. are preferable.
  • the main chain may be an oxyalkylene group or a polyoxyalkylene group. These groups constituting the main chain may form part of a ring structure.
  • the number of carbon atoms in the main chain may be 1 or more and 10 or less, 1 or more and 6 or less, or 1 or more and 4 or less.
  • the number of carbon atoms in the main chain is preferably 1 or more and 4 or less, and may be 2 or more and 4 or less.
  • the distance between the first carboxy group and the second carbonyl group is relatively short, so that the first carboxy group is likely to take a stabilized structure when ionized, and the surroundings of the conductive polymer are likely to be kept acidic. This suppresses deterioration of the conductive polymer, and further enhances the effect of maintaining high conductivity.
  • the first linking group may include a cyclic divalent group (such as a non-aromatic cyclic divalent group or an aromatic divalent group).
  • the cyclic divalent group may be a divalent hydrocarbon ring group or a divalent heterocyclic group.
  • the first linking group includes a cyclic divalent group, it is easy to adjust the solubility of the first carboxylic acid compound in the solvent and the affinity for the dielectric layer.
  • the first linking group has a cyclic divalent group, the first carboxyl group is easily stabilized and the positions of the second carbonyl group and the first carboxyl group are easily fixed with the bulkiness of the ring. Therefore, the pH of the liquid component tends to be low, and the conductive polymer is easily stabilized.
  • the first linking group may include a non-aromatic or aromatic divalent hydrocarbon ring group (cyclohexane-1,2-diyl, 2-norbornene-5,6-diyl, 1,2-phenylene, etc.), or a non-aromatic or aromatic divalent heterocyclic group.
  • the cyclic divalent group (such as a non-aromatic cyclic divalent group or an aromatic divalent group) may further have a substituent (third substituent).
  • the first linking group may have a structure in which a non-aromatic cyclic divalent group or an aromatic divalent group is bonded to an aliphatic divalent group.
  • the aliphatic divalent group constitutes a part of the main chain of the first linking group.
  • the first linking group may have a structure in which one non-aromatic cyclic divalent group or an aromatic divalent group is bonded to one aliphatic divalent group.
  • the first linking group may have a structure in which one non-aromatic cyclic divalent group or an aromatic divalent group is bonded to one aliphatic divalent group.
  • the first linking group may have a structure in which one non-aromatic cyclic divalent group or an aromatic divalent group is bonded to each bond of the divalent group.
  • the aliphatic divalent group portion may have a first substituent.
  • the main chain of the first linking group is an aliphatic divalent group.
  • the function of the liquid component to repair the dielectric layer can be enhanced, and the effect of reducing leakage current when a high voltage is applied is further enhanced.
  • the aliphatic divalent group may have a first substituent.
  • Examples of the first substituent carried by the main chain of the first linking group include a hydrocarbon group, a heterocyclic group, an R 4a -O- group (such as an alkoxy group), an R 4b -O-C( ⁇ O)- group (such as an alkoxycarbonyl group), an R 4c -C( ⁇ O)- group (such as an acyl group), a carboxy group, a hydroxy group, and a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.).
  • the first substituent is usually a monovalent group.
  • Each of R 4a , R 4b, and R 4c can be a hydrocarbon group.
  • the hydrocarbon group as the first substituent, and the hydrocarbon groups as R 4a , R 4b and R 4c may be saturated or unsaturated.
  • these hydrocarbon groups include non-aromatic hydrocarbon groups (aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, etc.), aromatic hydrocarbon groups, etc.
  • the aliphatic hydrocarbon groups may be linear or branched.
  • Examples of the aliphatic hydrocarbon groups include alkyl groups and unsaturated aliphatic hydrocarbon groups (alkenyl groups, dienyl groups, trienyl groups, etc.).
  • alkyl groups examples include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, hexyl groups, heptyl groups, n-octyl groups, 2-ethylhexyl groups, nonyl groups, decyl groups, undecyl groups, lauryl groups (dodecyl groups), myristyl groups, etc.
  • Examples of the unsaturated aliphatic hydrocarbon group include a vinyl group, an allyl group, a hexenyl group, a 2-octenyl group, a 2,4,6-trimethylnonan-2-en-1-yl group, a decenyl group, a dodecenyl group (including a 2-dodecenyl group and a tetrapropenyl group), and a tetradecenyl group.
  • the number of carbon atoms in the aliphatic hydrocarbon group may be 1 or more, or 6 or more.
  • the number of carbon atoms in the aliphatic hydrocarbon group may be 12 or less, 8 or less, or 5 or less.
  • the number of carbon atoms in the aliphatic hydrocarbon group (monovalent aliphatic hydrocarbon group) may be 1 or more and 12 or less, 1 or more and 8 or less, 1 or more and 5 or less, or 6 or more and 12 or less.
  • Examples of the alicyclic hydrocarbon group include a cycloalkyl group (such as a cyclohexyl group), a cycloalkenyl group (such as a cyclohexenyl group), a cycloalkadienyl group (such as a cyclopentadienyl group), and a bridged cyclic hydrocarbon group (such as a norbornyl group, a norbornenyl group, and a dicyclopentadienyl group).
  • the number of carbon atoms in the alicyclic hydrocarbon group may be 5 or more and 16 or less, 5 or more and 12 or less, or 5 or more and 10 or less.
  • aromatic hydrocarbon group examples include an aryl group (such as a phenyl group and a naphthyl group).
  • the number of carbon atoms in the aromatic hydrocarbon group may be 6 or more and 14 or less, or 6 or more and 10 or less.
  • the heterocyclic group as the first substituent is a monovalent heterocyclic group containing a heteroatom (fourth heteroatom) as a constituent atom of the ring.
  • the fourth heteroatom may be, for example, at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom.
  • the heterocyclic group may contain one fourth heteroatom, or may contain two or more fourth heteroatoms.
  • the heterocyclic group may be saturated or unsaturated.
  • the heterocyclic group may be non-aromatic or aromatic.
  • the heterocyclic group may be, for example, 5 to 14 members, or 5 to 10 members.
  • heterocyclic groups include oxygen-containing ring groups (furanyl group, tetrahydrofuranyl group, etc.), sulfur-containing ring groups (thiophene-3-yl group, etc.), and nitrogen-containing ring groups (pyrrolidinyl group, piperidinyl group, pyridyl group, morpholinyl group, etc.).
  • this aliphatic divalent group may have a monovalent aliphatic hydrocarbon group having 6 or more carbon atoms as at least one of the first substituents.
  • the main chain of the first linking group may be an aliphatic divalent group, and at least one of the first substituents may have a monovalent aliphatic hydrocarbon group having 6 or more carbon atoms. In these cases, the voltage resistance of the electrolytic capacitor can be further improved.
  • the effect of lowering the pH of the liquid component is relatively low, and the first carboxy group tends to be easily esterified.
  • the first substituents is an aliphatic hydrocarbon group having 6 or more carbon atoms, the effect of suppressing esterification is enhanced, and higher conductivity of the conductive polymer can be ensured.
  • the first linking group has the first substituent at the ⁇ -position of the first carbonyl group.
  • the first linking group has an aliphatic hydrocarbon group having 6 or more carbon atoms as the first substituent at the ⁇ -position of the first carbonyl group
  • the steric hindrance of this group further enhances the effect of suppressing esterification of the first carboxy group. Therefore, the action of the first carboxylic acid compound on the conductive polymer is maintained, and the effect of suppressing fluctuations in ESR is enhanced.
  • the ⁇ -position of the first carbonyl group may have two first substituents.
  • the ⁇ -position of the first carbonyl group may have a first substituent such as a tert-butyl group or a cyclic group (alicyclic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, etc.).
  • the ⁇ -position of the first carbonyl group may have an alkyl group (e.g., an alkyl group having 1 to 3 carbon atoms) having a cyclic group (e.g., an alicyclic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, etc.) as a second substituent as a first substituent at the ⁇ -position of the first carbonyl group.
  • an alkyl group e.g., an alkyl group having 1 to 3 carbon atoms
  • a cyclic group e.g., an alicyclic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, etc.
  • the number of first substituents in the first linking group is, for example, 1 or more.
  • the upper limit of the number of first substituents in the first linking group is not particularly limited and may be determined according to the chain length of the main chain.
  • the number of first substituents may be 6 or less, or may be 3 or less.
  • examples of the second substituent include at least one selected from the group consisting of hydrocarbon groups other than the first substituent and groups (or atoms) other than hydrocarbon groups among the groups (or atoms) exemplified as the first substituent.
  • examples of the second substituent include at least one selected from the group consisting of groups (or atoms) other than heterocyclic groups among the groups (or atoms) exemplified as the first substituent.
  • the third substituent can be selected from the substituents exemplified for the first or second substituent.
  • polycarboxylic acids corresponding to the first site include succinic acid, succinic acids having an alkyl group or an alkenyl group as the first substituent (2,2-dimethylsuccinic acid, 2-n-butylsuccinic acid, 2-n-octylsuccinic acid, 2-n-dodecylsuccinic acid, 2-(2'-octenyl)succinic acid, 2-(2'-dodecenyl)succinic acid, etc.), polycarboxylic acids having an alicyclic hydrocarbon group as the first substituent (2-n-cyclohexylsuccinic acid, etc.), polycarboxylic acids having an aromatic hydrocarbon group as the first substituent (2-phenylsuccinic acid, etc.), and polycarboxylic acids in which the first linking group contains a cyclic divalent group (1,2-cyclohexanedicarboxylic acid, 5-norbornene-2,3-dicarbox
  • the second site (e.g., Z2 in formula (I)) includes, for example, a first heteroatom (e.g., X3 in formula (I)) bonded to the second carbonyl group of the first site, and a hydrocarbon group (first hydrocarbon group) bonded to the first heteroatom.
  • This first hydrocarbon group also includes a hydrocarbon group having a substituent (fourth substituent).
  • the second site may include a first heteroatom and a monovalent organic group including the first hydrocarbon group bonded to the first heteroatom.
  • This organic group also includes an organic group having a fourth substituent on the first hydrocarbon group, and a substituent (fifth substituent) other than the fourth substituent.
  • the first heteroatom e.g., X3 in formula (I)
  • the first heteroatom bonded to the second carbonyl group in the first site may be an oxygen atom, a nitrogen atom, or a sulfur atom.
  • the second portion includes a first hydrocarbon group (including a hydrocarbon group having a fourth substituent, described below) bonded to the first heteroatom.
  • the number of carbon atoms in the first hydrocarbon group may be 1 or more, or may be 2 or more.
  • the number of carbon atoms in the hydrocarbon group is 2 or more.
  • the second site may be a residue of a hydroxy compound, a residue of an amine compound, or a residue of a mercapto compound.
  • the first heteroatom is an oxygen atom or a sulfur atom.
  • the number of bonds j of X 3 is 2 and k is 0. Therefore, the -X 3 (-R 3 ) k- group in formula (I) is -O- or -S-.
  • the second site is a residue of an amine compound, the first heteroatom is a nitrogen atom.
  • the number of bonds j of X 3 is 3 and k is 1. Therefore, the -X 3 (-R 3 ) k- group in formula (I) is represented by a -N(-R 3 )- group.
  • the >X 3 -R 3 group corresponds to an amino group.
  • the amino group includes, for example, >N-R 3 and >NH.
  • the first moiety can be easily introduced into the first carboxylic acid compound by an ester bond or an amide bond, which is preferable.
  • the second moiety contains a residue of a hydroxy compound or a residue of an amine compound.
  • the second site may be a residue of a polyol compound or a residue of a polyamine compound.
  • the second site may be a residue of a polythiol compound.
  • the residue of one hydroxyl group of the polyol compound, the residue of one amino group of the polyamine compound, and the residue of one mercapto group of the polythiol compound correspond to the -X 3 (-R 3 )k- group.
  • the remaining hydroxyl group, amino group, or mercapto group may be a fourth substituent of the hydrocarbon group bonded to the first heteroatom (for example, X 3 in formula (I)), or may be a fifth substituent of the organic group containing a hydrocarbon group bonded to the first heteroatom.
  • R 3 may be a hydrogen atom.
  • the seventh substituent may be a hydrocarbon group (e.g., an alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group).
  • the number of carbon atoms of the alkyl group of the seventh substituent may be 1 to 10, 1 to 6, or 1 to 4.
  • the organic group may be a chain group or may include a ring structure.
  • the ring structure may constitute a part of the main chain of the organic group.
  • the organic group may include a heteroatom (fifth heteroatom) in the main chain.
  • the main chain may be saturated or unsaturated.
  • the fifth heteroatom may be at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom.
  • the main chain may have one fifth heteroatom, or may have two or more fifth heteroatoms.
  • the number of fifth heteroatoms in the main chain may be four or less.
  • the fifth heteroatom may be different from the first heteroatom, but when it is the same as the first heteroatom, molecular design or synthesis is relatively easy. All of the two or more fifth heteroatoms may be the same as the first heteroatom.
  • the organic group may have a main chain and at least one of a fourth substituent and a fifth substituent bonded to the main chain.
  • the main chain is a linear portion containing at least a carbon atom (more specifically, at least a carbon atom contained in the first hydrocarbon group).
  • the fourth and fifth substituents are not included in the main chain.
  • the main chain also includes a case where the main chain has one carbon atom (for example, a methyl group, a methyl group having a fourth substituent).
  • the main chain containing a fifth heteroatom may include, for example, a polyoxyalkylene group or a group corresponding to a polyalkyleneamine. When the polyoxyalkylene group has a hydroxy group at its terminal, the hydroxy group corresponds to the fifth substituent.
  • the oxygen atom of the ether and the linear portion of the hydrocarbon group bonded to this oxygen atom are included in the main chain.
  • the group corresponding to a polyalkyleneamine has an amino group -NH 2 at its terminal, this amino group corresponds to the fifth substituent.
  • a hydrocarbon group is bonded to an amino group, the nitrogen atom of the amino group and the straight-chain portion (the portion with the largest number of carbon atoms) of the hydrocarbon group bonded to this nitrogen atom are included in the main chain.
  • a part of the main chain has a ring structure (cyclic group)
  • there are multiple chains that constitute the organic group in this case, the chain with the smallest number of atoms (carbon atoms, fifth heteroatoms, etc.) that constitute the chain constitutes at least a part of the main chain.
  • the ring structure may be saturated or unsaturated.
  • the fourth and fifth substituents can each further have a substituent (sixth substituent).
  • the sixth substituent can be selected from the substituents exemplified as the second substituent, and the like.
  • the total number of these substituents can be 1 or more, 1 to 6, or 1 to 4.
  • Examples of the hydroxy compound corresponding to the second site include monohydroxy compounds and polyols.
  • Examples of the monohydroxy compounds include aliphatic alcohols (such as alkyl alcohols and alkenyl alcohols), alicyclic alcohols, aromatic hydroxy compounds, and alkylene oxide adducts of these hydroxy compounds.
  • Examples of the aliphatic alcohols include n-hexanol, n-octanol, n-decanol, isodecanol, 2-decenol, and 2-dodecenol.
  • the number of carbon atoms in the aliphatic alcohol may be 1 to 20, 6 to 16, or 8 to 14.
  • Examples of the alicyclic alcohols include hexanol, hexenol, and norbornan-2-ol.
  • the alicyclic alcohol may be monocyclic or polycyclic (condensed or crosslinked).
  • the alicyclic alcohol also includes alkyl alcohols having an alicyclic group (C 1-4 alcohols having an alicyclic group such as cyclohexylmethanol and cyclohexylethanol).
  • the alicyclic group portion of the alicyclic alcohol may be 5 to 12-membered, or 5 to 10-membered.
  • Examples of aromatic hydroxy compounds include phenol, methylphenol, naphthol, and the like. The number of carbon atoms in the aromatic ring of the aromatic hydroxy compound may be 6 to 14, or 6 to 10.
  • Examples of aromatic hydroxy compounds also include alkyl alcohols having an aryl group, such as benzyl alcohol and phenethyl alcohol (e.g., C 6-14 aryl-C 1-4 alky
  • polyols examples include aliphatic polyols (alkane polyols, alkenediols, etc.), alicyclic polyols, aromatic polyols, and alkylene oxide adducts of these polyols, and polyalkylene glycols.
  • alkane polyols examples include alkane diols (ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 2-ethyl-1,3-hexanediol, 1,9-nonanediol, 2-butyl-2-ethyl-1,3-propanediol, etc.), glycerin, polyglycerin (diglycerin, triglycerin, tetraglycerin, etc.), trimethylolpropane, sugars or sugar alcohols (mannitol, erythritol, xylitol, pentaerythritol, etc.).
  • alkane diols ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanedi
  • the number of carbon atoms in the alkane polyol may be 1 or more and 12 or less, or 1 or more and 10 or less (or 9 or less). Within these ranges, the number of carbon atoms may be 2 or more.
  • Examples of the alkene diol include 1,4-dihydroxybutan-2-ene.
  • the number of carbon atoms of the alkene diol may be, for example, 2 or more and 12 or less, or 2 or more and 10 or less (or 9 or less).
  • Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and the like. Examples of the polyalkylene glycol include poly(C 2-4 alkylene glycol).
  • the number of repetitions of the oxyalkylene group is 2 or more, may be 2 or more and 10 or less, or may be 2 or more and 6 or less.
  • Specific examples of the polyethylene glycol include diethylene glycol and triethylene glycol.
  • Specific examples of the polypropylene glycol include dipropylene glycol and tripropylene glycol.
  • Specific examples of the polytrimethylene glycol include di(trimethylene glycol) and tri(trimethylene glycol).
  • Alicyclic polyols include polyhydroxycycloalkanes (polyhydroxycycloalkanes having 5 to 10 carbon atoms, such as dihydroxycyclohexane and trihydroxycyclohexane), polyhydroxycycloalkenes (polyhydroxycycloalkenes having 5 to 10 carbon atoms, such as dihydroxycyclohexene), and poly(hydroxyalkyl)cycloalkanes (poly(hydroxyC 1-4 alkyl)C 5-10 cycloalkanes) such as cyclohexanedimethanol.
  • Aromatic polyols include dihydroxybenzene, biphenol, bisphenol, and poly(hydroxyalkyl)arenes (poly(hydroxyC 1-4 alkyl)C 6-10 arenes) such as xylylene glycol.
  • alkylene oxide adduct examples include compounds (excluding the above polyalkylene glycols) in which one or more alkylene oxides ( C2-4 alkylene oxides such as ethylene oxide and propylene oxide) are added per hydroxy group to the hydroxy group of the above monohydroxy compound or polyol.
  • alkylene oxides C2-4 alkylene oxides such as ethylene oxide and propylene oxide
  • the number of alkylene oxides added per hydroxy group is, for example, 6 or less, and may be 4 or less, or 3 or less.
  • the lower limit and upper limit of the number of alkylene oxides can be combined in any desired manner.
  • the first moiety is introduced into one hydroxy group of the polyol.
  • the remaining hydroxy groups of the polyol may be free, etherified, esterified, salted, protected, interacting or bonding with components present in the formation process, or interacting or bonding with other components contained in the electrolytic capacitor.
  • the second moiety may be a residue of a mono C 1-4 alkyl ether of a poly C 2-4 alkylene glycol (e.g., a residue of triethylene glycol monomethyl ether, a residue of tripropylene glycol monomethyl ether, a residue of tri(trimethylene glycol) monomethyl ether, etc.).
  • the second moiety contains a residue of a polyol.
  • the polyol is preferably an alkylene glycol, a polyalkylene glycol, or a monoether thereof. It is also preferable that the second moiety is a residue of a monohydroxy compound (such as an aliphatic alcohol).
  • Examples of the amine compound corresponding to the second site include monoamines and polyamines.
  • at least one amino group is preferably an amino group having active hydrogen (>NH, -NH 2 ).
  • Examples of the monoamine include aliphatic amines (alkylamines such as methylamine, ethylamine, n-hexylamine, n-octylamine, n-decylamine, and isodecylamine; alkenylamines such as allylamine, 1-amino-2-hexene, 1-amino-2-decene, and 2-amino-2-decene), alicyclic amines (cyclohexylamine, 1-norbornylamine, and 2-cyclohexylethylamine), aromatic amines (aniline, benzylamine, and the like), and cyclic monoamines (pyrrolidine, piperidine, and morpholine, and the like).
  • the number of carbon atoms of the aliphatic amine may be 1 or more and 20 or less, 6 or more and 16 or less, or 8 or more and 14 or less.
  • the alicyclic group portion of the alicyclic amine may be 5 to 12 members, or 5 to 10 members.
  • the number of carbon atoms in the aromatic ring of the aromatic amine may be 6 to 14, or 6 to 10.
  • the aromatic amine also includes alkylamines having an aryl group such as benzylamine (C 6-14 aryl-C 1-4 alkylamine, etc.).
  • the cyclic monoamine may be 5 to 12 members, or 5 to 10 members.
  • polyamines corresponding to the second portion include aliphatic polyamines, polyalkylene polyamines, alicyclic polyamines, aromatic polyamines, and cyclic polyamines.
  • aliphatic polyamines include alkylenediamines (ethylenediamine, 1,4-diaminobutane, N,N'-dialkylalkylenediamines, etc.), triaminoalkanes, and tetraaminoalkanes.
  • alkylenediamines include C2-6 alkylenediamines (e.g., C2-4 alkylenediamines).
  • N,N'-dialkylalkylenediamines examples include N,N'-dialkylethylenediamines such as N,N'-dialkyl- C1-6 alkyl- C2-6 alkylenediamines (e.g., N,N'-di- C1-4 alkyl- C2-4 alkylenediamines).
  • Specific examples of N,N'-dialkylalkylenediamines include N,N'-diethylethylenediamine, N,N'-diisopropylethylenediamine, and N,N'-di-t-butylethylenediamine.
  • the carbon number of the aliphatic polyamine may be 1 or more and 10 or less, or 2 or more and 6 or less.
  • Examples of the alicyclic polyamine include polyaminocycloalkanes (polyamino C 5-10 cycloalkanes such as diaminocyclohexane, etc.), polyaminocycloalkenes (polyamino C 5-10 cycloalkenes such as diaminocyclohexene, etc.), and the like.
  • Examples of the aromatic polyamine include polyaminoarenes (polyamino C 6-10 arenes such as 1,4-phenylenediamine and triaminobenzene, etc.), and the like.
  • Examples of the cyclic amine include compounds having an -NH group and at least one -NH group or -NH 2 group.
  • cyclic amines examples include cyclic amines (cytosine, guanine, adenine, etc.) and cyclic polyamines (piperazine, thymine, uracil, etc.) having an amino group as a substituent.
  • the cyclic amine may be 5 to 12 members, or 5 to 10 members.
  • the liquid component may contain, for example, as the first carboxylic acid compound, at least one compound selected from the group consisting of a compound represented by the following formula (Ia) and a compound represented by the following formula (Ib).
  • R 1a to R 1f are each independently a hydrogen atom or a first substituent
  • n1 and n2 correspond to the number of repetitions of a methylene chain which may have a first substituent.
  • Ring Z 1a is a cyclic divalent group (such as a non-aromatic cyclic divalent group or an aromatic divalent group) contained in the first linking group.
  • R 3a is a third substituent possessed by ring Z 1a
  • m1 corresponds to the number of third substituents in ring Z 1a .
  • R 2 , R 3 , X 3 , and k are the same as those in formula (I).)
  • Formula (Ia) corresponds to the case where the main chain of the first linking group is an aliphatic divalent group in formula (I).
  • n1 is an integer of 0 or more, and may be an integer of 1 or more.
  • (n1+1) and (n2+1) each correspond to the number of carbon atoms in the main chain in the first linking group described above.
  • Each of n1 and n2 may be, for example, 1 to 5 or 1 to 3.
  • n1 is 2 or more, at least two of R 1c bonded to each carbon atom of the main chain may be the same, or all may be different.
  • n1 is 2 or more, at least two of R 1d bonded to each carbon atom of the main chain may be the same, or all may be different.
  • n2 is 2 or more, at least two of R 1e (or R 1f ) bonded to each carbon atom of the main chain may be the same, or all may be different.
  • the compound of formula (Ia) preferably has at least a first substituent at the ⁇ -position of the first carbonyl group.
  • at least one of R 1a and R 1b is a first substituent.
  • at least one of the first substituents that can be sterically hindered, in addition to an aliphatic hydrocarbon group having 6 or more carbon atoms is present at the ⁇ -position of the first carbonyl group.
  • one of R 1a and R 1b may be an aliphatic hydrocarbon group having 6 or more carbon atoms or a first substituent that can be sterically hindered, and the other may be a hydrogen atom.
  • each of R 1c and R 1d may be a hydrogen atom or a first substituent regardless of the number of n1, but each of R 1c and R 1d may be a hydrogen atom.
  • each of R 1e and R 1f may be a hydrogen atom or a first substituent regardless of the number of n2, but each of R 1e and R 1f may be a hydrogen atom.
  • Formula (Ib) corresponds to the case where the first linking group contains a divalent cyclic group (such as a non-aromatic cyclic divalent group or an aromatic divalent group) in formula (I).
  • n2 is an integer of 0 or more. The value obtained by adding the minimum number of carbon atoms between the two bonds of ring Z 1a to n2 corresponds to the number of carbon atoms in the main chain in the first linking group described above.
  • n2 may be, for example, 0 to 4 or 0 to 2.
  • at least two of R 1e (or R 1f ) bonded to each carbon atom of the main chain may be the same, or all may be different.
  • m1 which corresponds to the number of the third substituents, is an integer of 0 or more.
  • the upper limit of the number of the third substituents can be selected according to the number of members of ring Z 1a .
  • ring Z 1a has multiple third substituents R 3a , at least two of the multiple R 3a may be the same, or all of them may be different.
  • the compound represented by formula (Ib) may be, for example, a compound represented by the following formula (ib):
  • ring Z 1b is a cyclic divalent group (non-aromatic cyclic divalent group or aromatic divalent group) contained in the first connecting group.
  • R 1e and R 1f , n2, R 3a , m1, R 2 , R 3 , X 3 , and k are the same as above.
  • (n2+2) corresponds to the number of carbon atoms in the main chain of the first linking group.
  • the second moiety R 2 -X 3 (-R 3 ) k - can be described with reference to the above description of the second moiety.
  • the second moiety may be, for example, a monovalent group represented by any one of the following (iia) to (iid). In these divalent groups, * indicates a bond to the second carbonyl group.
  • the second moiety is a residue of a monohydroxy compound (such as an aliphatic alcohol) or a residue of a monoamine compound (such as an aliphatic amine).
  • the second moiety represented by formula (iia) corresponds to the residue of the polyol (diol, etc.) described above.
  • the second moieties represented by formulae (iib) to (iid) correspond to the residue of the polyamine compound described above.
  • R 2a may be a chain group or a group containing a ring structure.
  • R 2a may have at least one of the fourth and fifth substituents described above.
  • Formulae (iic) and (iid) are groups corresponding to the cyclic amine described above.
  • R 2a may contain one or more oxygen atoms.
  • the second moiety having R 2a include a second moiety containing a residue of polyalkylene glycol (or a polyoxyalkylene group).
  • R 2a may have one or more nitrogen atoms (or an amino group >N-R 6 ).
  • the second moiety having R 2a include a second moiety containing a residue of polyalkylene amine (or a group corresponding to polyalkylene amine).
  • R 6 may be a hydrogen atom or a substituent (eighth substituent).
  • the eighth substituent may be selected from the examples of the seventh substituent.
  • R 5a1 , R 5b1 and R 5b2 are each independently a hydrogen atom or a fifth substituent.
  • Ring Z 2a and ring Z 2b correspond to the ring structure (specifically, a nitrogen-containing ring) contained in the second portion.
  • R 5c1 and R 5c2 are each independently a fourth or fifth substituent possessed by ring Z 2a and ring Z 2b .
  • p1 indicating the number of substituents R 5c1 and q1 indicating the number of substituents R 5c2 are each an integer of 0 or more. The upper limit of p1 and q1 may be determined according to the number of members of ring Z 2a and ring Z 2b , respectively.
  • the acid component may contain one type of first carboxylic acid compound or a combination of two or more types.
  • the acid component may further include a second carboxylic acid compound different from the first carboxylic acid compound.
  • the acid component includes the second carboxylic acid compound, the pH of the liquid component can be further reduced. Since the decrease in the conductivity of the conductive polymer is further suppressed, the change in ESR over time can be further reduced.
  • the second carboxylic acid compound may be a carboxylic acid other than the first carboxylic acid compound, a carboxylic acid anhydride, a coordination compound of a carboxylic acid, or a carboxylic acid compound having two or more first sites (second carboxylic acid compound B).
  • a second carboxylic acid compound other than second carboxylic acid compound B may be referred to as second carboxylic acid compound A.
  • the carboxylic acid may be an aliphatic carboxylic acid or an aromatic carboxylic acid.
  • the aromatic carboxylic acid include aromatic hydroxy acids (benzoic acid, salicylic acid, etc.), aromatic polycarboxylic acids (phthalic acid, pyromellitic acid, etc.), and sulfoaromatic carboxylic acids (p-sulfobenzoic acid, 3-sulfophthalic acid, 5-sulfosalicylic acid, etc.).
  • the coordination compounds include coordination compounds having at least one central atom selected from the group consisting of boron, aluminum, and silicon, and an acid having a carbonyloxy bond bonded to this central atom. Specific examples of the coordination compounds include borodisalicylic acid, borodisalic acid, borodiglycolic acid, and borodigallic acid.
  • the second carboxylic acid compound B includes, for example, two or more first sites and a second linking group that links the second carbonyl groups of these first sites.
  • the second linking group may include a heteroatom (such as an oxygen atom, a nitrogen atom, or a sulfur atom) that is bonded to the second carbonyl group. This heteroatom portion can be expressed in the same manner as -X 3 (-R 3 ) k - in the formula (I) of the first carboxylic acid compound, and the explanation for the first carboxylic acid compound can be referred to.
  • the second linking group may be a residue of a polyol or a residue of a polyamine compound.
  • a part of the hydroxyl group of the polyol or a part of the amino group of the polyamine compound may not be bonded to the first site.
  • the hydroxyl group or amino group that is not bonded to the first site may be in a free form, may form an ester bond, an ether bond, an amide bond, or the like, or may form a salt.
  • each hydroxyl group or each amino group that is not bonded to the first site may be protected, may interact or bond with a component present in the production process, or may interact or bond with other components contained in the electrolytic capacitor.
  • the explanation of the first and second parts of the first carboxylic acid compound (polyol, polyamine compound, fourth to eighth substituents, etc.) can be referred to.
  • the second carboxylic acid compound B include diesters of alkylene glycol or polyalkylene glycol and polycarboxylic acid (or its acid anhydride), polyamides of polyamine and polycarboxylic acid (diamide of ethylenediamine and 2-octenylsuccinic acid, diamide of N,N'-(2'-propyl)ethylenediamine and 2-octenylsuccinic acid, diamide of piperazine and 2-octenylsuccinic acid, etc.).
  • diester examples include esters of alkylene glycol and dicarboxylic acid or its acid anhydride (diesters of ethylene glycol and succinic acid, diesters of ethylene glycol and 2-octenylsuccinic acid, diesters of ethylene glycol and 1,2-cyclohexanedicarboxylic acid, diesters of ethylene glycol and phthalic acid, etc.), and esters of polyalkylene glycol and dicarboxylic acid or its acid anhydride (diesters of triethylene glycol and 2-octenylsuccinic acid, diesters of tri(trimethylene glycol) and 2-octenylsuccinic acid, etc.).
  • the second carboxylic acid compound B is not limited to these.
  • the acid component may contain one or more types of second carboxylic acid compounds.
  • aromatic carboxylic acids phthalic acid, salicylic acid, benzoic acid, etc.
  • the above-mentioned coordination compounds borodisalicylic acid, borodisalicylic acid, borodiglycolic acid, etc.
  • phthalic acid, salicylic acid, borodisalicylic acid, etc. are preferred, and among these, phthalic acid, salicylic acid, borodisalicylic acid, etc. are preferred.
  • the acid component may contain one or more types of second carboxylic acid compounds A.
  • the acid component may contain one or more types of second carboxylic acid compounds B.
  • the carboxy group and other acid groups (sulfonic acid group, phosphoric acid group, phosphonic acid group, etc.) of the second carboxylic acid compound may each be in any of the following forms: free form, salt form, anion form, or form interacting (complexed, etc.) with the conductive polymer.
  • the carboxy group and other acid groups of the second carboxylic acid compound each include all of these forms.
  • the acid component may include an acid other than the first carboxylic acid compound and the second carboxylic acid compound.
  • examples of such other acids include acids having a carbonyloxy bond other than carboxylic acid (oxocarbonic acid, Meldrum's acid, etc.) or a coordination compound thereof, phenolic compounds (picric acid, p-nitrophenol, pyrogallol, catechol, etc.) or a coordination compound thereof, sulfur-containing acids (sulfuric acid, sulfonic acids (aromatic sulfonic acids, etc.), oxyaromatic sulfonic acids (phenol-2-sulfonic acid, etc.), etc.), compounds having a sulfonylimide bond, boron-containing acids (boric acid, halogenated boric acids (tetrafluoroboric acid, etc.), or partial esters thereof), phosphorus-containing acids (phosphoric acid, halogenated phosphoric acids (hexafluorophosphoric acid, etc.), phosphorus-containing
  • Compounds with sulfonylimide bonds include saccharin, 1,2-benzenedisulfonimide, cyclohexafluoropropane-1,3-bis(sulfonyl)imide, 4-methyl-N-[(4-methylphenyl)sulfonyl]benzenesulfonamide, dibenzenesulfonimide, trifluoromethanesulfonanilide, N-[(4-methylphenyl)sulfonyl]acetamide, benzenesulfonanilide, and N,N'-diphenylsulfamide.
  • the above-mentioned coordination compounds include, for example, coordination compounds having at least one central atom selected from the group consisting of boron, aluminum, and silicon, and an acid or phenolic compound having a carbonyloxy bond bonded to this central atom.
  • coordination compounds include borodicatechol and borodipyrogallol.
  • the acid component may contain one or more of the above acids.
  • the ratio of the first carboxylic acid compound in the acid component may be 20% by mass or more, or may be 33% by mass or more. In this case, the effect of suppressing the change in ESR over time is further enhanced. In addition, it is easy to ensure higher voltage resistance.
  • the ratio of the first carboxylic acid compound in the acid component is 100% by mass or less, and from the viewpoint of easy to ensure higher voltage resistance and improving the film repairability of the dielectric layer, it may be 80% by mass or less. These lower and upper limits can be combined arbitrarily.
  • the mass ratio of the second carboxylic acid compound to the first carboxylic acid compound may be 0/100 or more and 80/20 or less, or 20/80 or more and 67/33 or less.
  • the mass ratio is in this range, the action of the first carboxylic acid compound is easily exerted, and the effect of reducing the change in ESR over time is enhanced while maintaining high voltage resistance.
  • the mass ratio of the second carboxylic acid compound B to the first carboxylic acid compound may be 0/100 or more and less than 50/50, 0.1/99.9 or more and 30/70 or less, or 1/99 or more and 20/80 or less. When the mass ratio is in such a range, the voltage resistance can be further improved.
  • the concentration of the first carboxylic acid compound contained in the liquid component may be 1% by mass or more and 30% by mass or less, or 1% by mass or more and 20% by mass or less. From the viewpoint of further reducing the change in ESR over time, the concentration of the first carboxylic acid compound is preferably 1% by mass or more and 14% by mass or less, and more preferably 2% by mass or more and 12% by mass or less.
  • the liquid component may further include an oligomer component of the second carboxylic acid compound B.
  • the oligomer component includes an oligomer having a carboxy group
  • the oligomer is included in the second carboxylic acid compound.
  • the oligomer has, for example, a repeating structure of a first portion and a second linking group.
  • the second linking group is a residue of a polyol compound
  • the oligomer has a structure in which a polycarboxylic acid or its acid anhydride corresponding to the first portion and a polyol compound are alternately linked by ester bonds.
  • the oligomer When the second linking group is a residue of a polyamine compound, the oligomer has a structure in which a polycarboxylic acid or its acid anhydride corresponding to the first portion and a polyamine compound are alternately linked by amide bonds.
  • the oligomer component may include one type of oligomer, or may include two or more oligomers having different structures or chain lengths.
  • the liquid component may further include a base component.
  • a base component In this case, the dissociation property of the acid component such as the first carboxylic acid compound is enhanced, and the acid group such as the carboxy group can be easily reacted with the conductive polymer. Therefore, it is easy to obtain a higher conductivity of the conductive polymer.
  • the base component examples include ammonia, amines (specifically, primary amines, secondary amines, and tertiary amines), quaternary ammonium compounds, and amidinium compounds.
  • the liquid component may contain one type of base component, or two or more types.
  • the amine may be aliphatic, aromatic, or heterocyclic.
  • the amine include dialkylamines (such as diethylamine), trialkylamines (such as trimethylamine, ethyldimethylamine, triethylamine (TEA), tri-n-butylamine (TBA), dimethyl-n-octylamine (DMOA)), alkylenediamines (such as ethylenediamine), aromatic amines (such as aniline), and heterocyclic amines (such as pyrrolidine, imidazole compounds (such as imidazole (Imd), 1,2,3,4-tetramethylimidazolinium), pyridine (Pyr), 4-dimethylaminopyridine, and diazabicycloundecene (DBU)).
  • Each of the aromatic amines and heterocyclic amines may be monocyclic or polycyclic (such as condensed rings or bridged rings).
  • the quaternary ammonium compounds include am
  • the liquid component may contain the base component in a free form, in a cationic form, or in a salt form. All of these forms may be referred to as the base component.
  • the equivalent ratio of the first carboxylic acid compound to the base component may be 0.5 or more and 10 or less, 1.0 or more and 9.0 or less, or 1.3 or more and 8.9 or less. In this case, a high degree of dissociation of the first carboxylic acid compound can be ensured, and corrosion of the electrode can be suppressed. In addition, high voltage resistance can be easily ensured.
  • the equivalent ratio of the first carboxylic acid compound to the base component is the ratio of (the total number of carboxy groups per molecule of the first carboxylic acid compound)/(the total number of moles of OH- that can be generated per molecule of the base component).
  • the equivalent ratio of the acid component to the base component may be 0.5 or more and 15 or less, or 1.0 or more and 10 or less.
  • the equivalent ratio of the acid component/base component may be selected from the above numerical range described for the equivalent ratio of the first carboxylic acid compound/base component.
  • the equivalent ratio of the acid component to the base component is the ratio of (the total number of acid groups per one molecule of the acid component)/(the total number of moles of OH -- that can be generated per one molecule of the base component).
  • the solvent contained in the liquid component may be a non-aqueous solvent.
  • the non-aqueous solvent include a sulfone compound, a lactone compound, a carbonate compound, and an alcohol compound.
  • the liquid component may contain one type of non-aqueous solvent or a combination of two or more types of non-aqueous solvents.
  • sulfone compounds include cyclic sulfone compounds (such as sulfolane (SL)) and sulfoxide compounds (such as dimethyl sulfoxide and diethyl sulfoxide).
  • Lactone compounds include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone.
  • Carbonate compounds include linear carbonates (such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate), cyclic carbonates (such as ethylene carbonate, propylene carbonate, and fluoroethylene carbonate).
  • alcohol compounds include monohydric alcohols and polyhydric alcohols.
  • polyhydric alcohols include glycol compounds (alkylene glycols (ethylene glycol (EG), propylene glycol, etc.), polyalkylene glycols (polyethylene glycol (PEG), polypropylene glycol, etc.)), glycerin compounds (glycerin, polyglycerin, etc.), sugar alcohol compounds, and alkylene oxide adducts of these compounds (ethylene oxide adducts, polyethylene oxide adducts, etc.).
  • glycol compounds alkylene glycols (ethylene glycol (EG), propylene glycol, etc.), polyalkylene glycols (polyethylene glycol (PEG), polypropylene glycol, etc.)
  • glycerin compounds glycerin, polyglycerin, etc.
  • sugar alcohol compounds and alkylene oxide adducts of these compounds (ethylene oxide adducts, polyethylene oxide adducts, etc.).
  • the non-aqueous solvent preferably contains at least a glycol compound.
  • the non-aqueous solvent may contain a glycol compound and a sulfone compound (such as a cyclic sulfone compound such as SL), and may also contain a polyalkylene glycol (such as PEG) in addition to these.
  • the liquid component may contain alkali metal ions (sodium ions, potassium ions, etc.). However, it is preferable that the concentration of alkali metal ions in the liquid component is low. It is also preferable that the liquid component does not contain alkali metal ions. In this case, the liquid component may contain alkali metal ions at or below the detection limit.
  • the concentration of alkali metal ions in the liquid component may be 100 ppm or less, or 50 ppm or less, by mass.
  • the capacitor element included in the electrolytic capacitor includes an anode body having a dielectric layer on a surface thereof, and a conductive polymer that covers at least a portion of the dielectric layer.
  • the conductive polymer constitutes at least a portion of a cathode body of the capacitor element.
  • the cathode body may further include a cathode extraction layer (e.g., a cathode foil).
  • the anode body may contain a valve metal, an alloy containing a valve metal, a compound containing a valve metal, etc. These materials may be used alone or in combination of two or more.
  • the valve metal include aluminum, tantalum, niobium, and titanium.
  • Anode foil is suitable as the anode body. It is preferable that the anode body has a porous portion with pores at least on the surface layer.
  • Anode bodies other than anode foil include porous sintered bodies or porous molded bodies of particles containing valve metal.
  • Anode foils having a porous portion can be obtained, for example, by roughening the surface of a substrate (such as a foil-shaped or plate-shaped substrate) containing a valve metal.
  • the roughening can be performed by etching (for example, electrolytic etching or chemical etching).
  • the dielectric layer is formed by anodizing the valve metal on the surface of the anode body.
  • the anodization is performed, for example, by chemical conversion treatment.
  • the dielectric layer is formed, for example, so as to cover at least a portion of the surface of the anode body.
  • the dielectric layer contains an oxide of the valve metal.
  • the dielectric layer when tantalum is used as the valve metal, the dielectric layer contains Ta2O5 , and when aluminum is used as the valve metal, the dielectric layer contains Al2O3 .
  • the dielectric layer is not limited to this and may be any material that functions as a dielectric.
  • the dielectric layer is usually formed on the surface of the anode body.
  • the dielectric layer is formed on the surface of the porous part of the anode body, it is formed along the inner wall surfaces of the holes in the porous part and the depressions (pits) on the surface of the anode body.
  • the conductive polymer includes, for example, a conjugated polymer and a dopant.
  • the conductive polymer may cover at least a part of the dielectric layer. This embodiment includes a case where the conductive polymer is in contact with at least a part of the dielectric layer.
  • the capacitor element includes an anode foil and a cathode foil
  • the conductive polymer may be interposed between these foils.
  • the conductive polymer may be impregnated into a separator interposed between the anode foil and the cathode foil.
  • the conductive polymer may be in contact with at least a part of the cathode foil in addition to at least a part of the dielectric layer.
  • the conductive polymer may constitute a layer.
  • the conductive polymer is sometimes called a solid electrolyte.
  • the conductive polymer constitutes at least a part of the cathode body in the electrolytic capacitor.
  • the conductive polymer may further include an additive as necessary.
  • Conjugated polymers include known conjugated polymers used in electrolytic capacitors, such as ⁇ -conjugated polymers.
  • Conjugated polymers include, for example, polymers having a basic skeleton of polypyrrole, polythiophene, polyaniline, polyfuran, polyacetylene, polyphenylene, polyphenylenevinylene, polyacene, and polythiophenevinylene.
  • the above polymers may contain at least one monomer unit constituting the basic skeleton.
  • the above polymers include homopolymers, copolymers of two or more monomers, and derivatives thereof (such as substitutes having a substituent).
  • polythiophenes include poly(3,4-ethylenedioxythiophene) (PEDOT).
  • the conjugated polymer may be used alone or in combination of two or more types.
  • the weight average molecular weight (Mw) of the conjugated polymer is not particularly limited and is, for example, 1,000 or more and 1,000,000 or less.
  • the weight average molecular weight (Mw) is a value calculated as polysaccharide measured by gel permeation chromatography (GPC). GPC is usually measured using a polyhydroxymethacrylate gel column and an aqueous sodium nitrate solution as the mobile phase.
  • the dopant may be a relatively low molecular anion or a polymer anion.
  • the anion include sulfate ion, nitrate ion, phosphate ion, borate ion, organic sulfonate ion, and carboxylate ion.
  • Compounds that generate these anions are used as dopants.
  • dopants that generate sulfonate ions include aromatic sulfonic acid compounds (such as paratoluenesulfonic acid and naphthalenesulfonic acid).
  • the aromatic sulfonic acid compound may have at least one group selected from the group consisting of a carboxy group and a hydroxy group.
  • polymeric anions examples include polyvinyl sulfonic acid, polystyrene sulfonic acid (PSS), polyallylsulfonic acid, polyacrylic sulfonic acid, polymethacrylic sulfonic acid, poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, polyester sulfonic acid (such as aromatic polyester sulfonic acid), phenolsulfonic acid novolac resin, and polyacrylic acid.
  • the polymeric anion may be a polymer of a single monomer, a copolymer of two or more monomers, or a substituted product having a substituent.
  • polyanions derived from polystyrene sulfonic acid are preferred.
  • dopants are merely examples and are not limited to these.
  • One dopant may be used alone, or two or more dopants may be used in combination.
  • the conductive polymer may be formed, for example, by carrying out at least one of chemical polymerization and electrolytic polymerization of a precursor of a conjugated polymer on a dielectric layer in the presence of a dopant.
  • a conductive polymer e.g., a layer of a conductive polymer
  • the conductive polymer used in these solutions or dispersions can be obtained by polymerizing a precursor of a conjugated polymer in the presence of a dopant.
  • precursors of conjugated polymers include raw monomers of conjugated polymers, and oligomers and prepolymers in which multiple molecular chains of raw monomers are linked together. One type of precursor may be used, or two or more types may be used in combination.
  • the Mw of the dopant is not particularly limited and is, for example, 1,000 or more and 1,000,000 or less.
  • the amount of dopant contained in the conductive polymer is, for example, 10 parts by mass or more and 1,000 parts by mass or less, and may be 20 parts by mass or more and 500 parts by mass or less, relative to 100 parts by mass of the conjugated polymer.
  • the cathode extraction layer may include, for example, a first layer covering at least a part of the conductive polymer.
  • the cathode extraction layer may include a first layer and a second layer covering the first layer.
  • Examples of the first layer include a layer containing conductive particles, metal foil (cathode foil), and the like.
  • Examples of the conductive particles include at least one selected from conductive carbon and metal powder.
  • the cathode extraction layer may be formed of a layer containing conductive carbon (such as graphite) as the first layer (also referred to as a carbon layer) and a layer containing metal powder or metal foil as the second layer. When a metal foil is used as the first layer, the cathode extraction layer may be formed of this metal foil.
  • the cathode extraction layer may be formed by a known method depending on the layer configuration.
  • the layer containing metal powder as the second layer can be formed, for example, by laminating a composition containing metal powder onto the surface of the first layer.
  • a second layer can be, for example, a metal paste layer (such as a silver paste layer) formed using a composition containing metal powder such as silver particles and a resin (binder resin).
  • the resin can be a thermosetting resin such as an imide resin or an epoxy resin, or a thermoplastic resin.
  • the type of metal is not particularly limited, but it is preferable to use a valve metal such as aluminum, tantalum, or niobium, or an alloy containing a valve metal. If necessary, the surface of the metal foil may be roughened.
  • the surface of the metal foil may be provided with a chemical conversion coating, or may be provided with a coating of a metal (heterogeneous metal) different from the metal constituting the metal foil, or a nonmetal.
  • heterogeneous metals and nonmetals include metals such as titanium and nonmetals such as carbon (e.g., conductive carbon).
  • the coating of the dissimilar metal or nonmetal may be the first layer, and the metal foil may be the second layer.
  • a separator may be disposed between the cathode body (e.g., cathode foil) and the anode body (e.g., anode foil).
  • the separator is not particularly limited, and may be, for example, a nonwoven fabric containing fibers of cellulose, polyethylene terephthalate, vinylon, or polyamide (e.g., aliphatic polyamide, aromatic polyamide such as aramid).
  • the conductive polymer may be impregnated into the separator.
  • the conductive polymer may be interposed between the anode body (e.g., anode foil) and the cathode body (e.g., cathode foil) and may be in contact with at least a portion of the dielectric layer and at least a portion of the cathode body.
  • the combination of the conductive polymer with a liquid component containing a first carboxylic acid compound allows the conductive polymer to maintain high conductivity, so that even in these embodiments, a decrease in ESR can be suppressed.
  • the electrolytic capacitor may be a wound type, and may be either a chip type or a laminate type.
  • the electrolytic capacitor has at least one capacitor element.
  • the electrolytic capacitor may have a plurality of capacitor elements.
  • the electrolytic capacitor may have a laminate of two or more capacitor elements, or may have two or more wound type capacitor elements.
  • the configuration or number of the capacitor elements may be selected according to the type or use of the electrolytic capacitor.
  • one end of the cathode lead is electrically connected to the cathode extraction layer.
  • One end of the anode lead is electrically connected to the anode body.
  • the other end of the anode lead and the other end of the cathode lead are each drawn out from the exterior body or case.
  • the other end of each lead exposed from the exterior body or case is used for solder connection with the board on which the electrolytic capacitor is to be mounted.
  • Each lead may be a lead wire or a lead frame.
  • FIG. 1 is a schematic cross-sectional view of an electrolytic capacitor according to this embodiment
  • FIG. 2 is a schematic view of a portion of a capacitor element of the electrolytic capacitor in an expanded form.
  • the electrolytic capacitor of the present disclosure is not limited to the following embodiments.
  • the components of the following embodiments may be arbitrarily combined with at least one of the above (Technology 1) to (Technology 14) of the solid electrolytic capacitor of the present disclosure, or may be arbitrarily combined with at least one of the above (Technology 1) to (Technology 14) and the components described above.
  • the electrolytic capacitor for example, comprises a capacitor element 10, a bottomed case 101, a sealing member 102 that closes the opening of the bottomed case 101, a seat plate 103 that covers the sealing member 102, lead wires 104A, 104B, and lead tabs 105A, 105B.
  • the bottomed case 10 contains the capacitor element 10 and a liquid component (not shown). The vicinity of the open end of the bottomed case 101 is drawn inward, and the open end is curled so as to be crimped to the sealing member 102.
  • the lead wires 104A, 104B are led out from the sealing member 102 and pass through the seat plate 103.
  • the lead tabs 105A, 105B connect the lead wires 104A, 104B to the electrodes of the capacitor element 10, respectively.
  • Capacitor element 10 is, for example, a wound body as shown in FIG. 2.
  • the wound body includes anode foil 11 connected to lead tab 105A, cathode foil 12 connected to lead tab 105B, and separator 13.
  • Anode foil 11 and cathode foil 12 are wound via separator 13.
  • the outermost periphery of the wound body is fixed by stop tape 14. Note that FIG. 2 shows the wound body in a partially unfolded state before the outermost periphery is secured.
  • a dielectric layer (not shown) is formed on at least a portion of the surface of the anode foil 11.
  • a separator 13 and a conductive polymer (not shown) are interposed between the anode foil 11 and the cathode foil 12.
  • the conductive polymer is in contact with at least a portion of the dielectric layer.
  • the conductive polymer is also in contact with at least a portion of the cathode foil 12.
  • the conductive polymer and the separator are impregnated with a liquid component.
  • First carboxylic acid compound X1 was prepared according to the following procedure. 2-Octenylsuccinic anhydride (50 mmol) and ethylene glycol (250 mmol) were mixed and reacted for 15 hours at 110° C. under a nitrogen atmosphere. The end point of the reaction was determined by the acid value. In this manner, an ethylene glycol solution of the first carboxylic acid compound X1 was produced. The structure of the obtained first carboxylic acid compound X1 was confirmed by liquid chromatography mass spectrometry (LC/MS) (ion source: ESI ⁇ ).
  • LC/MS liquid chromatography mass spectrometry
  • Production Example 2 Succinic anhydride was used instead of 2-octenylsuccinic acid, and the reaction was carried out for 6 hours at a reaction temperature of 100° C. Except for this, an ethylene glycol solution of the first carboxylic acid compound X2 was produced in the same manner as in Production Example 1.
  • Examples 1 to 14 and Comparative Examples 1 to 7 A wound-type electrolytic capacitor (rated voltage 25 V, rated capacitance 330 ⁇ F) was produced by the following procedure and evaluated.
  • An aluminum foil having a thickness of 100 ⁇ m was subjected to an etching treatment to roughen the surface of the aluminum foil. Then, a dielectric layer was formed on the surface of the aluminum foil by chemical conversion treatment. The chemical conversion treatment was performed by immersing the aluminum foil in an ammonium adipate solution and applying a voltage thereto. Then, the aluminum foil was cut into a size of 8 mm long x 120 mm wide to prepare an anode body.
  • An anode lead tab and a cathode lead tab were connected to the anode body and the cathode body, and the anode body and the cathode body were wound with the lead tabs interposed therebetween.
  • An anode lead wire and a cathode lead wire were connected to the ends of the lead tabs protruding from the wound body, respectively.
  • the wound body was then subjected to a chemical conversion treatment again to form a dielectric layer on the cut end of the anode body.
  • the ends of the outer surface of the wound body were fixed with a winding stop tape to produce the wound body.
  • the reaction solution obtained was dialyzed to remove unreacted monomers and excess oxidizing agent, and a polymer dispersion containing poly(3,4-ethylenedioxythiophene) doped with PSS (PEDOT/PSS) as a conductive polymer was obtained.
  • the Mw of the polymer dopant is a value measured under the conditions described above.
  • the capacitor element was immersed in the liquid component and placed in a reduced pressure atmosphere (40 kPa) for 5 minutes to allow the liquid component to be impregnated into the capacitor element.
  • the capacitor element impregnated with the liquid component was placed inside a bottomed case with the lead wires positioned on the open side of the bottomed case.
  • a sealing member (elastic material containing butyl rubber as a rubber component) formed so that the lead wires could pass through was placed above the capacitor element.
  • the bottomed case was then drawn near the open end, and the open end was then curled to adhere to the sealing member. In this way, the capacitor element and liquid component were sealed inside the bottomed case.
  • An electrolytic capacitor as shown in Figure 1 was completed by placing a seat plate on the curled portion. A total of 40 electrolytic capacitors were made for each example.
  • the produced electrolytic capacitors were aged at 130°C for two hours while the rated voltage was applied.
  • the electrolytic capacitors prepared as described above were evaluated as follows. (1) Capacitance change ( ⁇ cap) and ESR change ( ⁇ ESR) The capacitance at a frequency of 120 Hz and the ESR value at a frequency of 100 kHz of the 20 electrolytic capacitors after the aging treatment were measured using an LCR meter in an environment of 20° C. Then, the average values of the measured values of the 20 electrolytic capacitors (initial capacitance value: c0 (F), initial ESR value: r0 ( ⁇ )) were calculated.
  • a high-temperature load test (accelerated test) was conducted. That is, the rated voltage was applied to the electrolytic capacitor for 750 hours at a temperature of 145°C.
  • the average capacitance value (c1 (F)) and ESR value (r1 ( ⁇ )) after the accelerated test were determined in the same manner as for the initial capacitance value and initial ESR value.
  • the acid components used in the liquid components are shown in Table 1.
  • the evaluation results of each electrolytic capacitor are shown in Table 2.
  • A1 to A14 are examples, and B1 to B7 are comparative examples.
  • the ⁇ ESR is significantly smaller, at 2.10 or less, compared to B1 to B7, and the fluctuation of ESR due to the accelerated test is kept small.
  • the main chain of the first carboxylic acid compound used in A1 to A8 and A11 to A14 can be said to be an aliphatic chain, but the ⁇ ESR can be significantly reduced compared to B4 to B7, which use an aliphatic dicarboxylic acid.
  • the leakage current after the accelerated test was kept relatively small, and a larger capacitance was obtained after the accelerated test compared to the comparative example.
  • the electrolytic capacitor of the examples maintains excellent capacitor performance even after the accelerated test, and has excellent reliability.
  • the electrolytic capacitor of the present disclosure can be used as a hybrid electrolytic capacitor.
  • the change in ESR over time can be reduced.
  • the increase in leakage current over time can be suppressed, and high voltage resistance can be ensured. Therefore, the electrolytic capacitor of the present disclosure is particularly suitable for various applications requiring high reliability or long life.
  • the applications of the electrolytic capacitor are not limited to these.
  • Electrolytic capacitor 101 Case with bottom 102: Sealing member 103: Seat plate 104A, 104B: Lead wire 105A, 105B: Lead tab 10: Capacitor element 11: Anode foil 12: Cathode foil 13: Separator 14: Stop tape

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Abstract

La présente invention concerne un condensateur électrolytique qui comprend un élément de condensateur et un composant liquide. L'élément de condensateur comprend : un corps d'anode dont la surface est recouverte d'une couche diélectrique ; et un polymère électroconducteur qui recouvre au moins une partie de la couche diélectrique. Le composant liquide comprend un composant acide et un solvant. Le composant acide comprend un premier composé d'acide carboxylique qui a une première partie et une seconde partie. La première partie comprend un premier groupe carboxy qui contient un premier groupe carbonyle, un second groupe carbonyle et un groupe de liaison qui relie le premier groupe carbonyle et le second groupe carbonyle l'un à l'autre. La seconde partie comprend un hétéroatome qui est lié au second groupe carbonyle et un groupe hydrocarboné qui possède au moins deux atomes de carbone et qui est lié à l'hétéroatome.
PCT/JP2024/023318 2023-07-06 2024-06-27 Condensateur électrolytique Pending WO2025009460A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08255731A (ja) * 1995-03-15 1996-10-01 Nichicon Corp 電解コンデンサ駆動用電解液
JP2004128275A (ja) * 2002-10-03 2004-04-22 Nichicon Corp 電解コンデンサの駆動用電解液及び電解コンデンサ
WO2017026378A1 (fr) * 2015-08-12 2017-02-16 日本ケミコン株式会社 Condensateur électrolytique solide et procédé pour la fabrication d'un condensateur électrolytique solide
JP2019102791A (ja) * 2017-11-29 2019-06-24 三洋化成工業株式会社 電解コンデンサ用電解液及び電解コンデンサ
JP2020202362A (ja) * 2019-06-04 2020-12-17 阪本薬品工業株式会社 コンデンサ電解液用の改質剤、ならびにそれを用いた電解液及び電解コンデンサ
JP2022017716A (ja) * 2020-07-14 2022-01-26 ニチコン株式会社 電解コンデンサの製造方法
WO2023054502A1 (fr) * 2021-09-30 2023-04-06 日本ケミコン株式会社 Condensateur électrolytique solide
JP2023138354A (ja) * 2022-03-16 2023-10-02 三洋化成工業株式会社 ハイブリッド型電解コンデンサ用電解液及びハイブリッド型電解コンデンサ
WO2024010063A1 (fr) * 2022-07-06 2024-01-11 パナソニックＩｐマネジメント株式会社 Condensateur électrolytique

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08255731A (ja) * 1995-03-15 1996-10-01 Nichicon Corp 電解コンデンサ駆動用電解液
JP2004128275A (ja) * 2002-10-03 2004-04-22 Nichicon Corp 電解コンデンサの駆動用電解液及び電解コンデンサ
WO2017026378A1 (fr) * 2015-08-12 2017-02-16 日本ケミコン株式会社 Condensateur électrolytique solide et procédé pour la fabrication d'un condensateur électrolytique solide
JP2019102791A (ja) * 2017-11-29 2019-06-24 三洋化成工業株式会社 電解コンデンサ用電解液及び電解コンデンサ
JP2020202362A (ja) * 2019-06-04 2020-12-17 阪本薬品工業株式会社 コンデンサ電解液用の改質剤、ならびにそれを用いた電解液及び電解コンデンサ
JP2022017716A (ja) * 2020-07-14 2022-01-26 ニチコン株式会社 電解コンデンサの製造方法
WO2023054502A1 (fr) * 2021-09-30 2023-04-06 日本ケミコン株式会社 Condensateur électrolytique solide
JP2023138354A (ja) * 2022-03-16 2023-10-02 三洋化成工業株式会社 ハイブリッド型電解コンデンサ用電解液及びハイブリッド型電解コンデンサ
WO2024010063A1 (fr) * 2022-07-06 2024-01-11 パナソニックＩｐマネジメント株式会社 Condensateur électrolytique

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