WO2023127826A1 - 電解コンデンサおよび電解コンデンサ用液状成分 - Google Patents

電解コンデンサおよび電解コンデンサ用液状成分 Download PDF

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Publication number
WO2023127826A1
WO2023127826A1 PCT/JP2022/048000 JP2022048000W WO2023127826A1 WO 2023127826 A1 WO2023127826 A1 WO 2023127826A1 JP 2022048000 W JP2022048000 W JP 2022048000W WO 2023127826 A1 WO2023127826 A1 WO 2023127826A1
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Prior art keywords
antioxidant
group
electrolytic capacitor
liquid component
component
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English (en)
French (fr)
Japanese (ja)
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雄一郎 椿
達治 青山
佳津代 齊藤
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to US18/723,795 priority Critical patent/US20250046528A1/en
Priority to CN202280085928.7A priority patent/CN118435303A/zh
Priority to JP2023571029A priority patent/JPWO2023127826A1/ja
Publication of WO2023127826A1 publication Critical patent/WO2023127826A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H01G9/0036—Formation of the solid electrolyte layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—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
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/08—Housing; Encapsulation
    • H01G9/10—Sealing, e.g. of lead-in wires
    • 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
    • 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
    • H01G9/151—Solid electrolytic capacitors with wound foil electrodes

Definitions

  • the present disclosure relates to electrolytic capacitors and liquid components for electrolytic capacitors.
  • Electrolytic capacitors As a small-sized, large-capacity, low-ESR (equivalent series resistance) capacitor, an electrolytic capacitor comprising an anode body having a dielectric layer formed thereon and a conductive polymer covering at least a portion of the dielectric layer is considered promising. There is Conductive polymers are sometimes called solid electrolytes. Electrolytic capacitors may also contain a liquid component such as an electrolytic solution.
  • Patent Document 1 describes an electrolytic capacitor comprising an organic solvent, a solute, and an additive, the acid component of the solute having an organic acid and an inorganic acid, and the acid component being contained in an excess molar ratio relative to the base component. It is proposed to use a driving electrolyte. The document also proposes adding an antioxidant to the electrolyte.
  • Electrolytic capacitors may be exposed to high temperatures during reflow, or used in high temperature environments depending on the application.
  • electrolytic capacitors are sometimes used in high-temperature environments such as in or near engine compartments of vehicles (such as automobiles). Therefore, electrolytic capacitors are required to have high heat resistance.
  • an electrolytic capacitor that includes a container having an opening, a capacitor element housed in the container, and a sealing body that seals the opening,
  • the capacitor element includes an anode body having a dielectric layer on its surface, and a conductive polymer covering a portion of the dielectric layer,
  • the sealing body contains an elastic polymer,
  • An antioxidant component is present in a space closed by the container and the sealing body,
  • the antioxidant component relates to an electrolytic capacitor containing a first antioxidant that does not have a boiling point or has a boiling point of 320° C. or higher.
  • Another aspect of the present disclosure includes a non-aqueous solvent and an antioxidant component dissolved in the non-aqueous solvent,
  • the non-aqueous solvent contains at least an alcoholic solvent,
  • the antioxidant component contains a first antioxidant that has no boiling point or a boiling point of 320 ° C. or higher, It relates to liquid components for electrolytic capacitors.
  • the heat resistance of electrolytic capacitors can be improved.
  • FIG. 1 is a cross-sectional schematic diagram of an electrolytic capacitor according to an embodiment of the present disclosure
  • FIG. 2 is a schematic diagram in which a part of a capacitor element of the electrolytic capacitor of FIG. 1 is developed;
  • an electrolytic capacitor may have a structure in which a capacitor element and a liquid component such as an electrolytic solution are housed in a container having an opening, and the opening is sealed with a sealing body containing an elastic polymer.
  • elastic polymers have high sealing properties, they do not have sufficient heat resistance and become brittle due to oxidation deterioration in high-temperature environments, and the sealing function of the sealing body tends to deteriorate.
  • non-aqueous solvents especially alcohol-based solvents
  • non-aqueous solvents contained in the liquid components are absorbed by the sealing material. Deterioration of the body may progress more easily.
  • the sealing member deteriorates, cracks or cracks occur, making it easier for air to enter the inside of the electrolytic capacitor.
  • the oxidative deterioration of the conductive polymer and the oxidative deterioration of the sealer are more likely to proceed.
  • non-aqueous solvents such as alcohol-based solvents tend to evaporate.
  • the electrolytic capacitor of the present disclosure includes a container having an opening, a capacitor element housed in the container, and a sealing body that seals the opening.
  • the capacitor element includes an anode body having a dielectric layer on its surface, and a conductive polymer covering a portion of the dielectric layer.
  • the sealing member contains an elastic polymer.
  • An antioxidant component is present in the space enclosed by the container and the sealing member.
  • the antioxidant component includes a first antioxidant that has no boiling point or a boiling point of 320° C. or higher.
  • an antioxidant hereinafter sometimes referred to as a primary antioxidant
  • the first antioxidant itself is easily reduced and readily reacts with radicals generated with the involvement of oxygen.
  • the first antioxidant does not have a boiling point or has a boiling point of 320° C. or higher, it is less likely to vaporize or decompose even if the electrolytic capacitor is exposed to high temperatures. Therefore, the first antioxidant exists inside the electrolytic capacitor and reacts with the radicals generated with the involvement of oxygen to inactivate them, resulting in a deterioration reaction of the conductive polymer with the involvement of oxygen or deterioration of the sealant. reaction can be suppressed.
  • the oxidizing action of the antioxidant component may be deactivated by the component contained in the conductive polymer or liquid component.
  • the antioxidant component contains a first antioxidant with relatively high stability, so that deactivation of the antioxidant component is suppressed.
  • the effect of the antioxidant component that suppresses can be effectively exhibited.
  • the liquid component contains at least a non-aqueous solvent containing an alcohol solvent, so that the effect of suppressing deactivation of the antioxidant component is maintained. Therefore, an increase in ESR or a decrease in capacity when the electrolytic capacitor is exposed to high temperatures is suppressed. In other words, the heat resistance of the electrolytic capacitor can be improved.
  • the antioxidant component exists inside the electrolytic capacitor in a state where it can come into contact with radicals generated with the involvement of oxygen.
  • the antioxidant component is often in contact with the liquid component.
  • the liquid component may contain an antioxidant component.
  • the antioxidant component may be dissolved or dispersed in the liquid component, or may be contained in a state in which it is immiscible with the liquid component (eg, in a solid or liquid state). At least part of the first antioxidant may be present in an undissolved state in the liquid component.
  • a portion of the antioxidant component e.g., a portion of the first antioxidant
  • the remainder e.g., the remainder of the first antioxidant
  • the incompatible antioxidant is floating in the liquid component or It may be present in the liquid component (in other words, in contact with the liquid component) in a submerged state.
  • the solid electrolyte layer containing the conductive polymer may contain an antioxidant component.
  • the electrolytic capacitor may include a solid electrolyte layer that includes the conductive polymer and partially covers the dielectric layer.
  • the solid electrolyte layer may contain the first antioxidant.
  • the conductive polymer may include a conjugated polymer and a dopant.
  • the electrolytic capacitor may further contain a liquid component.
  • the liquid component may contain a non-aqueous solvent, and the non-aqueous solvent may contain at least an alcoholic solvent. At least part of the first antioxidant may be present in a state not dissolved in the liquid component.
  • the liquid component for electrolytic capacitors of the present disclosure includes a non-aqueous solvent and an antioxidant component dissolved in the non-aqueous solvent.
  • the non-aqueous solvent contains at least an alcoholic solvent.
  • the antioxidant component includes a first antioxidant that has no boiling point or a boiling point of 320° C. or higher.
  • the concentration of the first antioxidant in the liquid component for an electrolytic capacitor may be 0.1% by mass or more and 50% by mass or less.
  • the alcohol solvent is at least one selected from the group consisting of alkylene glycol having 2 to 6 carbon atoms and glycerin (first alcohol-based solvent).
  • the ratio of the alcohol solvent to the non-aqueous solvent may be 5% by mass or more and 100% by mass or less.
  • the first antioxidant is at least one selected from the group consisting of a hydroxy group, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. may contain.
  • the first antioxidant is selected from the group consisting of at least a phenolic antioxidant IA having a phenolic hydroxy group and a phosphorus antioxidant. At least one selected may be included.
  • the phenolic antioxidant IA contains (a) one or more phenolic hydroxy groups, an alkyl group having 1 to 4 carbon atoms and 1 carbon atom in the aromatic ring. and at least one selected from the group consisting of 4 alkoxy groups; and (c) one or more phenolic hydroxy groups on the aromatic ring, in which a hydrogen atom is bonded to at least one carbon atom adjacent to the carbon atom having and at least one selected from the group consisting of phenolic antioxidants having no substituents on the aromatic ring.
  • the first antioxidant may include at least a phenolic antioxidant Ia having two or more phenolic hydroxy groups.
  • the first antioxidant may contain at least a hindered phenol compound.
  • the electrolytic capacitor and the liquid component for the electrolytic capacitor of the present disclosure including the above (1) to (16), will be described in more detail below. At least one of the above (1) to (16) may be combined with at least one of the elements described below within a technically consistent range.
  • antioxidant component refers to a component that has the effect of inactivating radicals generated with the involvement of oxygen.
  • Antioxidant components include components commonly referred to as antioxidants, as well as antidegradants, antiaging agents, radical chain inhibitors, peroxide decomposers, chain initiation inhibitors, light stabilizers, heat stabilizers (or Also included are components called heat resistant stabilizers), metal deactivators, ultraviolet absorbers, weather stabilizers, and the like.
  • the antioxidant component contains at least the first antioxidant.
  • the boiling point is 320°C or higher, and may be 350°C or higher or 400°C or higher.
  • the upper limit of the boiling point of the first antioxidant is not particularly limited, and may be 800° C. or lower, for example.
  • the first antioxidant is less likely to volatilize, transpire, or sublimate in the electrolytic capacitor.
  • the boiling point of the antioxidant is used as a reference, but antioxidants that are as difficult to volatilize, transpire, or sublime as antioxidants with a boiling point of 320 ° C. or higher, such as Antioxidants that do not have a boiling point shall also be included in the first antioxidant.
  • Such antioxidants more particularly have no boiling point, are in a liquid or solid state at 320°C, and have a decomposition temperature above 320°C (e.g., above 350°C or above 400°C). ).
  • the antioxidant component may include a first antioxidant and a second antioxidant other than the first antioxidant.
  • the second antioxidant has a boiling point of less than 320°C.
  • Each antioxidant contains, for example, at least one selected from the group consisting of hydroxy groups, nitrogen atoms, oxygen atoms, sulfur atoms and phosphorus atoms.
  • antioxidants include phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, benzimidazole antioxidants, carotenoid compounds, water-soluble vitamins (vitamin B or its derivatives, vitamin C or its derivatives, etc.), glutathione, sesamin, melatonin, and flavonoid compounds.
  • Flavonoid compounds also include glycosides, prenylated flavonoids, O-methoxylated flavonoids, and the like. From the viewpoint of many compounds having relatively low boiling points and low thermal stability, the first antioxidant (or antioxidant component) does not contain vitamin A, vitamin D, vitamin K or derivatives thereof (specifically is below the detection limit).
  • Phenolic antioxidants have phenolic hydroxy groups.
  • a phenolic antioxidant having a phenolic hydroxy group may be referred to as a phenolic antioxidant IA.
  • phenolic antioxidants IA include monophenolic antioxidants and polyphenolic antioxidants.
  • Polyphenolic antioxidants include, for example, compounds containing ring structures containing aromatic rings with phenolic hydroxy groups. Such compounds contain two or more phenolic hydroxy groups in one molecule. Such compounds include, for example, compounds having a structure in which two or more ring structures containing an aromatic ring having a phenolic hydroxy group are bonded via a single bond or a linking group (first linking group). be.
  • One of the aromatic rings contained in the compound may have one phenolic hydroxy group or two or more phenolic hydroxy groups.
  • the upper limit of the number of phenolic hydroxy groups in one aromatic ring can be selected according to the size of the aromatic ring, and is, for example, 5 or less, may be 4 or less, or 3 or less, or 2 or less.
  • the upper limit of the number of phenolic hydroxy groups contained in one molecule can be selected according to the size of the molecule, and is, for example, 20 or less, may be 14 or less, 10 or less, or 6 or less. may be
  • the ring structure may be an aromatic ring or a condensed ring of an aromatic ring and a non-aromatic ring.
  • Each of the aromatic ring and the non-aromatic ring may be either a hydrocarbon ring or a heterocyclic ring.
  • the non-aromatic ring may be a bridged ring.
  • the aromatic ring includes aromatic hydrocarbon rings having 6 to 20 carbon atoms (eg, 6 to 14 or 6 to 10) (benzene, naphthalene, phenanthrene, anthracene, etc.), 5- to 20-membered (eg, 6- to 14-membered) aromatic heterocycles (furan, pyrrole, thiophene, imidazole, pyridine, pyrazine, quinoline, indole, benzimidazole, benzotriazole, purine, etc.).
  • Condensed rings of aromatic rings and non-aromatic rings include chromene, chromone, chroman, coumarin, 4H-chromen-4-one, carbazole and the like.
  • Non-aromatic rings include alicyclic hydrocarbon rings having 5 to 14 carbon atoms (eg, 5 to 10) (cyclopentane, cyclohexane, cyclooctane, etc.), 6 to 20 carbon atoms (eg, 6 to 14) bridged cyclic hydrocarbon rings (norbornane, norbornene, dicyclopentadiene, etc.), 5- to 20-membered (e.g., 6- to 14-membered) non-aromatic heterocycles (tetrahydrofuran, dioxolane, dioxane, pyrrolidine, piperidine, morpholine, thiazine, etc.).
  • the heterocyclic ring includes, for example, a ring structure containing at least one heteroatom as a ring-constituting atom.
  • heteroatoms include at least one selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms.
  • a chain linking group may be linear or branched.
  • Polyvalent groups include divalent groups, trivalent groups, tetravalent groups, and the like.
  • the aromatic ring may be selected from the aromatic rings exemplified for the ring structures above.
  • the non-aromatic ring may be selected from the non-aromatic rings exemplified for the ring structures above.
  • polyvalent groups containing aromatic rings include aromatic polyvalent groups (phenylene group, naphthylene group, etc.) and Ar(--R 1a --)m groups.
  • Ar represents a ring structure containing an aromatic ring
  • m represents the number of —R 1a — groups
  • Ar has and represents an integer of 2 or more
  • R 1a represents an alkylene group.
  • polyvalent groups containing non-aromatic rings include polyvalent groups corresponding to non-aromatic rings (cyclohexanediyl group, dicyclopentanediyl group, etc.) and Cy(-R 1b -)n groups. be done. Cy represents a non-aromatic ring, n is the number of —R 1b — groups Cy has and is an integer of 2 or more, and R 1b represents an alkylene group.
  • R 1c to R 1i represents an alkylene group
  • R 2a represents a divalent hydrocarbon group (a divalent aromatic hydrocarbon group such as a phenylene group, a divalent alicyclic hydrocarbon group such as a cyclohexanediyl group). hydrogen group, alkylene group, etc.).
  • the first linking group is not limited to these.
  • alkylene groups represented by R 1a to R 1i and R 2a each have, for example, 1 to 10 carbon atoms, 1 to 6 or 1 to 4 carbon atoms.
  • the number of carbon atoms in the polyvalent group corresponding to alkene is, for example, 2-10, and may be 2-6 or 2-4.
  • Each of m and n is, for example, 4 or less, and may be 3 or less.
  • Aliphatic hydrocarbon and alkylene groups may be linear or branched.
  • Ar(--R 1a -)m group at least two of R 1a may be the same or all may be different.
  • Ar(--R 1a -)m groups include, for example, polyvalent groups in which two or three methylene groups are bonded to a benzene ring.
  • Examples of the Cy(--R 1b -)n group include trivalent groups in which methylene groups are bonded to three nitrogen atoms of cyclohexanedimethylene and isocyanuric acid.
  • Compounds containing a ring structure containing an aromatic ring having a phenolic hydroxy group also include compounds containing a substituent (first substituent) other than a phenolic hydroxy group.
  • the first substituent may have on at least one of the ring structure containing the aromatic ring and the first linking group.
  • R 2b represents a monovalent group corresponding to a hydrocarbon group or a heterocycle.
  • the position of this hydroxy group is usually on at least one of the first linking group and the non-aromatic ring contained in the ring structure.
  • the hydrocarbon group for the first substituent or R 2b include aromatic hydrocarbon groups (aryl groups having 6 to 14 carbon atoms such as phenyl group), alicyclic hydrocarbon groups (cycloalkyl groups having 5 to 10 carbon atoms, groups (such as cyclohexyl groups), bridged cyclic hydrocarbon groups having 6 to 20 carbon atoms (such as norbornyl groups), and aliphatic hydrocarbon groups (such as alkyl groups and alkenyl groups). Aliphatic hydrocarbon groups may be linear or branched.
  • the number of carbon atoms in the alkyl group is, for example, 1 to 20, may be 1 to 16 or 1 to 10, may be 1 to 6 or 1 to 4, or may be 1 to 3.
  • Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hexyl, 2-ethylhexyl, decyl, tetradecyl, octadecyl.
  • the number of carbon atoms in the alkenyl group is, for example, 2-10, and may be 2-6 or 2-4.
  • Specific examples of alkenyl groups include vinyl and allyl.
  • a monovalent group corresponding to a heterocycle may be 5- to 14-membered or 5- to 10-membered.
  • the first substituent or the monovalent group corresponding to the hydrocarbon group or heterocycle as R2b may further have a substituent (second substituent).
  • the second substituent include a hydroxy group, an amino group, an alkylamino group, a dialkylamino group, a carboxyl group, and an alkoxycarbonyl group.
  • the number of carbon atoms in the alkyl of the alkylamino group or dialkylamino group is, for example, 1 to 20, may be 1 to 16 or 1 to 10, may be 1 to 6 or 1 to 4, may be 1 to 3 may be used.
  • the number of carbon atoms of the alkoxycarbonyl group as the second substituent may be, for example, 2 to 20, may be 2 to 17, may be 2 to 15 or 2 to 11, may be 2 to 7 or 2 to It may be 5, or it may be 2-4.
  • the second substituent may be an alkyl group (having 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms or 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms).
  • the number of first substituents in the compound can be selected according to the size of the compound, and may be 1-14, 1-10, or 1-6.
  • the number of second substituents may be, for example, 1-10 or 1-6.
  • first substituents may be the same or all may be different.
  • secondary substituents may be the same or may all be different.
  • the type and number of substituents on the aromatic ring having a phenolic hydroxy group contribute to the solubility and oxidation stability of the phenolic antioxidant IA in liquid components.
  • the aromatic ring includes at least one phenolic hydroxy group, and at least one of the first substituents selected from the group consisting of an alkyl group and an alkoxy group. may have a substituent of When each of the alkyl group and the alkoxy group has 1 to 4 carbon atoms (preferably 1 to 3 carbon atoms), the solubility in liquid components tends to increase.
  • alkyl groups include methyl, ethyl, n-propyl, isopropyl and tert-butyl groups.
  • alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy and tert-butoxy groups.
  • the aromatic ring does not have an alkyl group or an alkoxy group.
  • the stability of the antioxidant tends to increase.
  • the aromatic ring may not have any substituent other than the phenolic hydroxy group.
  • the solubility in liquid components tends to increase.
  • the solubility in the liquid component tends to increase. Therefore, when a liquid component containing a dissolved first antioxidant is used in an electrolytic capacitor, it is preferable to select the phenolic antioxidant IA in consideration of these factors.
  • phenolic antioxidant IA examples include, for example, (a) an aromatic ring having at least one (one or two or more) phenolic hydroxy group and ) and at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 4 carbon atoms (preferably 1 to 3), and (b) at least one (1 a phenolic antioxidant having one or more phenolic hydroxy groups, and a hydrogen atom bonded to at least one of the carbon atoms adjacent to the carbon atom having the phenolic hydroxy group, and (c) selected from the group consisting of phenolic antioxidants having at least one (one or more) phenolic hydroxy group on the aromatic ring and no other substituents on the aromatic ring At least one kind is mentioned. These antioxidants may have two or more phenolic hydroxy groups. Moreover, in these antioxidants, the number of hydroxy groups including the phenolic hydroxy group may be 2 or more.
  • Amine antioxidants include aromatic amine antioxidants, amine-ketone antioxidants, and hindered amine compounds.
  • Examples of phosphorus antioxidants include phosphite compounds.
  • Sulfur-based antioxidants include sulfur-containing acids, esters or salts of sulfur-containing acids, isothiocyanate compounds, thioether-based antioxidants, and the like.
  • Examples of carotenoid compounds include at least one selected from the group consisting of lutein, zeaxanthin, canthaxanthin, fucoxanthin, astaxanthin, antheraxanthin, and violaxanthin.
  • Examples of vitamin B or derivatives thereof include vitamin B2 or derivatives thereof, such as at least one selected from the group consisting of riboflavin and esters or salts thereof.
  • vitamin C or derivatives thereof include at least one selected from the group consisting of ascorbic acid (such as L-ascorbic acid), erythorbic acid, esters thereof (such as L-ascorbic acid palmitate), and salts thereof. is mentioned.
  • at least one selected from the group consisting of 1,8-cineole, ⁇ -pinene, camphor, and borneol may be used as a rosemary extract-based antioxidant.
  • Primary antioxidants also include flavonoid compounds that do not have phenolic hydroxy groups.
  • flavonoid compounds include at least one selected from the group consisting of flavones [zapotin, cerrosillin, sinensetin, tangeretin, nobiletin, etc.] and flavonols (3-hydroxyflavone, natsudaidyne, etc.).
  • the first antioxidant contains a hindered phenol compound.
  • a hindered phenol compound is a phenol compound having a hindered group in an aromatic ring.
  • a hindered group includes a tertiary or quaternary carbon atom (especially a quaternary carbon atom) attached to an aromatic ring. Examples of such hindered groups include hindered alkyl groups. Hindered alkyl groups include isopropyl group, sec-butyl group, tert-butyl group, tert-pentyl group (tert-amyl group), ⁇ -methylbenzyl group, ⁇ , ⁇ -dimethylbenzyl group and the like.
  • the phenol compound may have one or more of these hindered groups.
  • the phenolic compound has more than one hindered group, at least two may be the same or all may be different.
  • monophenolic antioxidants include, for example, aryl ester compounds having a phenolic hydroxy group, Trolox, normelatonin, ferulic acid, and gingerol.
  • aryl ester compound having a phenolic hydroxy group in addition to the phenolic hydroxy group at the aryl site, a compound which may have at least one selected from the group consisting of an alkyl group and an alkoxy group, such as octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionate.
  • aryl ester compounds having a phenolic hydroxy group when used by dissolving in a liquid component, compounds in which the number of carbon atoms in the alkyl or alkoxy group in the aryl moiety is 1 to 4 (preferably 1 to 3). , compounds having no alkyl group or alkoxy group in the aryl moiety, and compounds having two or more hydroxy groups including phenolic hydroxy groups are preferred.
  • a ring structure containing an aromatic ring having a phenolic hydroxy group is a compound having a structure in which two or more are bonded via a single bond or a first linking group.
  • polyphenolic antioxidants as the first antioxidant, a ring structure containing an aromatic ring having a phenolic hydroxy group is a compound having a structure in which two or more are bonded via a single bond or a first linking group.
  • polyphenol antioxidants as the first antioxidant include, for example, hydroxytyrosol, pinocembrin, pinobanksin, protocatechuic acid, curcumin, rosemary extract antioxidants (carnosol, caffeic acid, etc.), 2, 5-di-tert-butyl hydroquinone, 2,5-di-tert-amyl hydroquinone, gallic acid, propyl gallate, polyhydroxycinnamic acid derivatives (chlorogenic acid, caffeic acid, etc.), dopamine, adrenaline, noradrenaline, carnosine acids, ursolic acid.
  • Phenolic antioxidants include flavonoid compounds having phenolic hydroxy groups (including glycosides), isoflavonoid compounds having phenolic hydroxy groups (including glycosides), and neoflavonoid compounds having phenolic hydroxy groups. , a biflavonoid compound having a phenolic hydroxy group, an aurone compound having a phenolic hydroxy group, and the like may also be used.
  • Such compounds include flavones having a phenolic hydroxy group [primretin, chrysin, dectochrysin, primethin, avigenin, acacetin, genquanin, echioidinin, baicalein, oroxylon, negretein, norwogonin, geraldone ( geraldone, tithonine, luteolin, 6-hydroxyltheolin, chrysoeriol, diosmetin, pilloin, veltin, noraltocalpetin, altocalpetin, scutellarein, hispizurin, solbifolin, pecto linarigenin, cirsimaritin, mikanin, isoscutellarein, zapotinin, alnetin, tricetin, tricin, corymbosin, nepetin, pedalitin, nodifloretin ), cirsiliol, oivatilin, si
  • phenolic antioxidant IA rosemary extract-based antioxidants (rosmarinic acid, luteolin, etc.), gnetin C, quebrazic acid, resveratrol, etc. may be used.
  • polyphenol compounds which may have at least one selected from the group consisting of an alkyl group and an alkoxy group in an aromatic ring (aryl site) having a phenolic hydroxy group may be used.
  • aryl site aromatic ring
  • polyphenol compounds when used by dissolving in a liquid component, a compound having an alkyl group or an alkoxy group having 1 to 4 carbon atoms (preferably 1 to 3) in the aryl moiety, an alkyl group and A compound having no alkoxy group, a compound having two or more hydroxy groups including a phenolic hydroxy group, and the like are preferred.
  • the tert-butyl group is an alkyl group having 1 to 3 carbon atoms (especially a methyl group, an ethyl group, etc.) or a Compounds substituted with 1 to 3 alkoxy groups (especially methoxy groups, ethoxy groups, etc.), compounds without tert-butyl groups, or these compounds further having two or more phenolic hydroxy groups, etc.
  • it is suitable for use by dissolving it in a liquid component.
  • phenolic antioxidants IA may be used singly or in combination of two or more.
  • aromatic amine-based antioxidants include, for example, aromatic amine compounds having a plurality of aromatic rings.
  • a plurality of aromatic rings may be linked via —NH— or a linking group (second linking group).
  • the aromatic ring can be selected from the aromatic rings described for the phenolic antioxidants, and is preferably an aromatic hydrocarbon ring (such as an aromatic hydrocarbon ring having 6 to 14 carbon atoms such as benzene and naphthalene).
  • the second linking group can be selected from examples of the first linking group, and is preferably a polyvalent group corresponding to an aliphatic hydrocarbon, an alkylene group, or the like. These carbon atoms are, for example, 1-10, and may be 1-6 or 1-4.
  • the amino group bonded to the aromatic ring contained in the aromatic amine compound may be bonded to a group other than the aromatic ring (such as a group corresponding to a non-aromatic ring or an aliphatic hydrocarbon group).
  • groups include alicyclic hydrocarbon groups and aliphatic hydrocarbon groups exemplified for the first substituent, as well as organic sulfonyl groups ( --SO.sub.2 -- R.sub.3 ).
  • R 3 include the aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and aliphatic hydrocarbon groups exemplified for the first substituent.
  • the aromatic amine compound may have one or more substituents (third substituents).
  • Examples of the third substituent include groups other than the hydrocarbon groups exemplified for the first substituent.
  • the aromatic amine compound has two or more third substituents, at least two may be the same or all may be different.
  • the aromatic amine compound may have an aryl site (a phenol site, a hindered phenol site, etc.) having a phenolic hydroxy group.
  • aromatic amine compounds examples include N-phenyl-1-naphthylamine, di(alkylphenyl)amine (4,4'-dioctylphenylamine, etc.), 4,4'-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine.
  • p-(p-toluenesulfonylamido)diphenylamine N,N'-di-2-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'-isopropyl -p-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine is.
  • amine-ketone antioxidants are 2,2,4-trimethyl-1,2-dihydroquinoline polymer (in other words, reaction product of diphenylamine and acetone) and acetylcysteine.
  • Hindered amine compounds include compounds having a piperidyl group having a plurality of alkyl groups (alkyl groups having 1 to 3 carbon atoms such as methyl groups), such as tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl ) butane-1,2,3,4-tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, 1,2, 3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] Tetra
  • the aryl moiety may have, in addition to a phenolic hydroxy group, at least one selected from the group consisting of an alkyl group and an alkoxy group.
  • ester compounds for example, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-butyl-2-(4-hydroxy-3,5-di-tert-butylbenzyl)propanediate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate].
  • piperidyl ester compounds having an aryl moiety having a phenolic hydroxy group when used by dissolving in a liquid component, the alkyl group or alkoxy group having 1 to 4 carbon atoms (preferably 1 to 3 ), compounds having no alkyl group or alkoxy group, compounds having two or more hydroxy groups including phenolic hydroxy groups, and the like are preferable.
  • the piperidyl ester compound which may have at least one selected from the group consisting of an alkyl group and an alkoxy group in addition to a phenolic hydroxy group at the aryl moiety the above compound having a tert-butyl group is used.
  • the tert-butyl group is an alkyl group having 1 to 3 carbon atoms (especially methyl group, ethyl group, etc.) or an alkoxy group having 1 to 3 carbon atoms (especially methoxy group, ethoxy group) etc.), compounds that do not have a tert-butyl group, or these compounds that further have two or more phenolic hydroxy groups, are particularly suitable for use by dissolving in a liquid component. ing.
  • Amine-based antioxidants as the first antioxidant may be used singly or in combination of two or more.
  • the phosphite compound as the phosphorus antioxidant of the first antioxidant include aromatic phosphite compounds (e.g., aryl phosphite compounds, arylene bisphosphite compounds), aliphatic phosphite compounds [alkyl phosphite compounds (e.g. trialkylphosphite compounds such as trioctylphosphite, tri(2-ethylhexyl)phosphite, triisodecylphosphite), alkenylphosphite compounds (e.g. trialkenylphosphite compounds such as trioleylphosphite) ), etc.], which are cyclic phosphite compounds.
  • aromatic phosphite compounds e.g., aryl phosphite compounds, arylene bisphosphite compounds
  • aliphatic phosphite compounds alkyl phosphite compounds (e.g.
  • an aryl phosphite compound that may have at least one selected from the group consisting of an alkyl group, an alkoxy group, and a hydroxy group (phenolic hydroxy group) at the aryl moiety [e.g., tris (nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tri-o-tolylphosphite, triphenylphosphite] and the like.
  • a hydroxy group phenolic hydroxy group
  • the arylene bisphosphite compound is an arylene bisphosphite compound that may have at least one selected from the group consisting of an alkyl group, an alkoxy group, and a hydroxy group (phenolic hydroxy group) at the arylene moiety [e.g. , tetra-C 12-15 alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite)] and the like.
  • Cyclic phosphite compounds include bisarylene-alkylphosphite compounds and aryloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane compounds.
  • the bisarylene-alkylphosphite compound has at least one selected from the group consisting of an alkyl group, an alkoxy group and a hydroxy group (phenolic hydroxy group) at the bisarylene moiety.
  • bisarylene-alkylphosphite compounds eg, 2,2′-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexylphosphite] that may be used.
  • the aryloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane compound has an alkyl group, an alkoxy group, and a hydroxy group (phenolic hydroxy group) at the aryl moiety of the aryloxy group.
  • the tert-butyl group is an alkyl group having 1 to 3 carbon atoms (especially a methyl group, an ethyl group, etc.) or a Compounds substituted with 1 to 3 alkoxy groups (especially methoxy groups, ethoxy groups, etc.), compounds without tert-butyl groups, or these compounds further having two or more phenolic hydroxy groups, etc.
  • Phosphorus-based antioxidants as the first antioxidant may be used singly or in combination of two or more.
  • sulfur-based antioxidants of the first antioxidant examples include laurylthiopropionic acid.
  • Esters or salts of sulfur-containing acids include dilauryl thiopropionate, sulfurous acid, sulfites (sodium, potassium, calcium, ammonium, sodium bisulfite, etc.), pyrosulfites, and the like.
  • Thioether antioxidants include 2,2-bis ⁇ [3-(dodecylthio)-1-oxopropoxy]methyl ⁇ propane-1,3-diylbis[3-(dodecylthio)propionate], di(tridecyl)3 , 3′-thiodipropionate, and the like.
  • Sulfur-based antioxidants as the first antioxidant may be used singly or in combination of two or more.
  • benzimidazole-based antioxidants include, for example, imidazole dipeptides (carnosine, anserine, balenine, etc.).
  • the benzimidazole-based antioxidants as the first antioxidant may be used singly or in combination of two or more.
  • the first antioxidants at least one selected from the group consisting of phenol-based antioxidants and phosphorus-based antioxidants may be used.
  • the phenol-based antioxidant and the amine-based antioxidant react with the peroxy radicals even if the peroxy radicals are generated by oxygen in the capacitor element, thereby effecting the chain reaction of radicals. can be effectively suppressed. Therefore, at least one first antioxidant selected from the group consisting of phenol antioxidants and amine antioxidants may be used.
  • phenol-based antioxidants are less likely to cause unexpected side reactions than amine-based antioxidants, are available in many types, and are readily available. Therefore, it is preferable to use at least the phenolic antioxidant IA.
  • Phenolic antioxidant IA and other first antioxidants (specifically, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, benzimidazole antioxidants and vitamin C or its at least one first antioxidant selected from the group consisting of derivatives).
  • first antioxidants IA in particular, phenolic antioxidants having two or more phenolic hydroxy groups (sometimes referred to as phenolic antioxidant Ia) have high reactivity with peroxy radicals. Therefore, the first antioxidant more preferably contains at least the phenolic antioxidant Ia. Further, when the first antioxidant contains at least a hindered phenol compound, a higher effect is obtained. At least part of the phenolic antioxidant Ia may be a hindered phenol compound.
  • examples of monophenolic antioxidants include 2,6-tert-butyl-4-methylphenol, butylhydroxyanisole, sesamol, and ⁇ -tocopherol.
  • Polyphenolic antioxidants include catechol, hydroquinone, resorcinol, urushiol, pyrogallol and the like.
  • Amine antioxidants include 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline and the like.
  • examples of benzimidazole antioxidants include 2-mercaptobenzimidazole and 2-mercaptomethylbenzimidazole.
  • Phosphorus antioxidants include tri-p-tolylphosphite and trihexylphosphite. Secondary antioxidants also include citric acid and the like.
  • the ratio of the first antioxidant to the antioxidant component is preferably as high as possible.
  • the ratio of the first antioxidant to the antioxidant component is 100% by mass or less.
  • the antioxidant component may consist of only the first antioxidant.
  • the mass ratio of the first antioxidant to the conductive polymer is, for example, 0.01 or more and 300 or less, and may be 0.05 or more and 100 or less. , 0.1 or more and 20 or less, or 0.1 or more and 10 or less, or 1 or more and 10 or less, or 1.5 or more and 8 or less.
  • the mass ratio is in such a range, it is possible to easily secure a higher deterioration suppressing effect of the conductive polymer, and in addition, it is possible to suppress the leakage current and reduce the occurrence of internal short circuits.
  • the mass ratio may be 0.1 or more and 8 or less, 0.3 or more and 8 or less, or 1 or more and 6 or less.
  • the conductive polymer may contain a conjugated polymer and a dopant.
  • the molar ratio of the first antioxidant to the total monomer units of the conjugated polymer is, for example, 0.1 to 200 or less, 0.5 to 100 or less (or 50 or less), 1 or more (or 2 or more) and 50 or less, 2 or more (or 3 or more) and 40 or less, or 2 or more and 10 or less.
  • the above molar ratio may be 1 or more and 30 or less, or 2 or more and 25 or less.
  • the molar ratio may be the ratio of the number of moles of the first antioxidant to the total number of moles of the raw material monomers of the conjugated polymer.
  • the mass ratio of the first antioxidant to the conjugated polymer is, for example, 0.1 or more and 200 or less, and may be 0.5 or more and 100 or less. , 1 or more (or 2 or more) and 50 or less, 2 or more (or 3 or more) and 40 or less, or 2 or more and 25 or less (or 10 or less).
  • the mass ratio may be 1 or more and 20 or less, 1 or more and 15 or less, or 3 or more and 15 or less.
  • the mass ratio is within this range, the effect of suppressing deterioration of the conjugated polymer is further enhanced, leakage current can be suppressed, and the occurrence of internal short circuits can be reduced.
  • the concentration of the first antioxidant in the liquid component is, for example, 0.1% by mass or more and 50% by mass or less, may be 0.1% by mass or more and 20% by mass or less, or is 0.5% by mass or more. (or 1% by mass or more) may be 10% by mass or less.
  • concentration of the first antioxidant is within such a range, the effect of suppressing deterioration of the conductive polymer and the sealant is further enhanced, and a high repair effect of the dielectric layer is easily ensured, thereby reducing leakage current. It can be kept low, and the occurrence of internal short circuits can be reduced.
  • Analysis of the antioxidant present in the electrolytic capacitor is performed, for example, by the following procedure.
  • the electrolytic capacitor is disassembled, and if it contains a liquid component, all the liquid component is collected and the mass (M 0 ) is measured. If there is an undissolved component in the liquid component, this component is also collected, dried under reduced pressure, and the mass (M 1 ) is measured.
  • the sampled liquid component is qualitatively analyzed by high performance liquid chromatography-mass spectrometry (HPLC-MS) or gas chromatography-mass spectrometry (GC-MS) to identify the antioxidant contained in the liquid component.
  • HPLC-MS high performance liquid chromatography-mass spectrometry
  • GC-MS gas chromatography-mass spectrometry
  • GC-MS is used for antioxidants with a boiling point of less than 500°C
  • HPLC-MS is used for antioxidants with a boiling point of 500°C or higher.
  • a calibration curve is prepared using the same antioxidant as the identified antioxidant, and the concentration of the antioxidant contained in the liquid component is determined. From this concentration and the mass M 0 , the mass (M 2 ) of the antioxidant dissolved in the entire liquid component is determined.
  • a sample obtained by dissolving all of the dried components that are not dissolved in the liquid component in a solvent is qualitatively analyzed by HPLC-MS or GC-MS to identify the antioxidant.
  • the mass of inhibitor (M 3 ) is the mass of antioxidant present in the electrolytic capacitor.
  • the mass of the first antioxidant present in the electrolytic capacitor is determined according to the above as the first antioxidant. Analyzes are performed at least three times and averaged. Using the mass obtained in this manner, the mass ratio to the conductive polymer, conjugated polymer, elastic polymer, or non-aqueous solvent (alkylene glycol, etc.) in the liquid component is determined.
  • the number of moles of the first antioxidant present in the electrolytic capacitor is obtained from the identification result of the first antioxidant and the mass of the first antioxidant present in the electrolytic capacitor.
  • the electrolytic capacitor of the present disclosure may contain liquid components.
  • the liquid component contains a non-aqueous solvent.
  • the non-aqueous solvent contains at least an alcoholic solvent.
  • the liquid component may contain the above antioxidant component in a dissolved or dispersed state.
  • the present disclosure also includes liquid components for electrolytic capacitors that include a non-aqueous solvent and an antioxidant component dissolved in the non-aqueous solvent.
  • at least a portion of the first antioxidant may be present in the electrolytic capacitor without being dissolved in the liquid component.
  • the first antioxidant can easily spread throughout the inside of the electrolytic capacitor, and oxygen can be generated near the conductive polymer and the sealant. It is easy to inactivate the radicals that are involved and generated, and the effect of suppressing deterioration is more likely to be obtained.
  • antioxidant component contained in the liquid component you can refer to the explanation of the antioxidant component above.
  • the composition of the liquid component other than the antioxidant component will be described in more detail below.
  • Non-aqueous solvent contains at least an alcoholic solvent.
  • the non-aqueous solvent may contain an alcoholic solvent (first solvent) and another solvent (second solvent).
  • first solvent an alcoholic solvent
  • second solvent another solvent
  • the second solvent include sulfone compounds, lactone compounds, carbonate compounds, and the like.
  • the liquid component may contain one type of non-aqueous solvent, or may contain two or more types in combination.
  • Alcohol solvents include monohydric alcohols and polyhydric alcohols.
  • the alcohol-based solvent may contain at least a polyhydric alcohol from the viewpoint of easily obtaining high repairability of the dielectric layer.
  • Polyhydric alcohols include glycol compounds, glycerin compounds, sugar alcohol compounds, and the like.
  • the liquid component may contain one kind or two or more kinds of alcohol solvents.
  • the alcohol-based solvent contains at least an alkylene glycol having 2 to 6 carbon atoms (hereinafter sometimes referred to as first alkylene glycol) and glycerin. It preferably contains at least one selected from the group consisting of (hereinafter sometimes referred to as a primary alcoholic solvent).
  • first alkylene glycol alkylene glycol
  • glycerin glycerin
  • a primary alcoholic solvent a primary alcoholic solvent
  • the presence of the first antioxidant in the electrolytic capacitor prevents the conductive polymer and sealing even when the liquid component contains the first alcoholic solvent.
  • the oxidative deterioration of the body can be effectively suppressed, and high heat resistance can be secured.
  • the antioxidant component contains a phenolic antioxidant IA
  • the liquid component contains an acid component
  • the hydroxy group contained in the phenolic antioxidant IA may be esterified and rendered inactive.
  • the antioxidant component contains the phenol-based antioxidant IA
  • the liquid component contains an alcohol-based solvent such as a primary alcohol-based solvent, which facilitates the reaction between the alcohol-based solvent and the acid component.
  • the activity of the anti-oxidant IA is easily maintained, and it becomes easy to ensure high heat resistance.
  • the first alkylene glycol examples include ethylene glycol (EG), propylene glycol (PG), trimethylene glycol, tetramethylene glycol and the like.
  • the first alkylene glycol may have 2 to 4 carbon atoms, or may have 2 or 3 carbon atoms.
  • the non-aqueous solvent may contain the first alkylene glycol alone or in combination of two or more.
  • the non-aqueous solvent preferably contains at least ethylene glycol as an alcoholic solvent.
  • the non-aqueous solvent may contain ethylene glycol and at least one selected from alkylene glycols having 3 or more and 6 or less carbon atoms.
  • the non-aqueous solvent may contain at least one selected from primary alkylene glycols (or primary alcoholic solvents) and at least one selected from other alcoholic solvents.
  • the mass ratio of the first antioxidant dissolved in the liquid component (especially the phenolic antioxidant IA) to the first alkylene glycol (or first alcoholic solvent) is, for example, 0.005 or more and 2 or less, may be 0.01 or more and 0.7 or less, or may be 0.03 or more and 0.5 or less .
  • first antioxidant/first alkylene Glycol (or first alcoholic solvent) is, for example, 0.005 or more and 2 or less, may be 0.01 or more and 0.7 or less, or may be 0.03 or more and 0.5 or less .
  • Glycol compounds other than the first alkylene glycol include alkylene glycols having 6 or more carbon atoms (referred to as second alkylene glycols), polyalkylene glycols, and alkylene oxide adducts of polyhydric alcohols.
  • second alkylene glycol examples include alkylene glycols having 6 to 10 carbon atoms such as dihydroxyoctane and dihydroxydecane.
  • Polyalkylene glycols include poly-C 2-4 alkylene glycols (eg, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol (PEG), etc.) and the like.
  • alkylene oxide adducts of polyhydric alcohols examples include C 2-3 alkylene oxide adducts of polyhydric alcohols (ethylene oxide adducts, etc.), and poly-C 2-3 alkylene oxide adducts of polyhydric alcohols ( polyethylene oxide adducts, etc.) are also included.
  • polyhydric alcohols to which alkylene oxides are added include alkylene glycols having 4 or more carbon atoms, trimethylolpropane, and sugar alcohols (glycerin, erythritol, mannitol, pentaerythritol, etc.).
  • the number of repeating oxyalkylene units in the polyalkylene glycol is, for example, 2 or more and 600 or less, may be 2 or more and 10 or less, or may be more than 10 and 600 or less (eg, 100 or more and 600 or less).
  • the number of alkylene oxide units in the alkylene oxide adduct may be 1 or more, and the total number of alkylene oxide units may be 2 or more.
  • the total number of repeating alkylene oxide units in the alkylene oxide adduct may be 2 or more and 50 or less, or may be 2 or more and 20 or less.
  • Glycerin compounds include glycerin and polyglycerin (diglycerin, triglycerin, etc.). The number of repeating glycerin units in polyglycerin is, for example, 2 or more and 20 or less, and may be 2 or more and 10 or less.
  • Sugar alcohol compounds include sugar alcohols (erythritol, mannitol, pentaerythritol, etc.).
  • the ratio of the alcohol-based solvent to the non-aqueous solvent is, for example, 5% by mass or more and 100% by mass or less, may be 10% by mass or more (or 20% by mass or more) 100% by mass, or 10% by mass or more and 80% by mass. It may be no more than mass % (or no more than 50 mass %), or no less than 20 mass % and no more than 50 mass %.
  • the ratio of the first alcoholic solvent or the first alkylene glycol (especially ethylene glycol) to the non-aqueous solvent may be within such a range.
  • the ratio of the alcohol solvent such as the first alcohol solvent or the first alkylene glycol (ethylene glycol, etc.) is within such a range, the effect of the first antioxidant is more likely to be exhibited, and higher heat resistance can be obtained. easy to get.
  • an antioxidant component containing at least one selected from the group consisting of a phenolic antioxidant IA and a phosphorus antioxidant (especially a phenolic antioxidant IA) the first alcoholic solvent or It is preferable that the ratio of the alcohol-based solvent such as the first alkylene glycol (such as ethylene glycol) is within the above range.
  • sulfone compounds include sulfolane (SL), dimethylsulfoxide and diethylsulfoxide.
  • Lactone compounds include ⁇ -butyrolactone (GBL), ⁇ -valerolactone and the like.
  • Carbonate compounds include dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, ethylene carbonate, propylene carbonate and fluoroethylene carbonate.
  • the non-aqueous solvent may contain the second solvent alone or in combination of two or more.
  • Qualitative and quantitative analysis of each solvent in the non-aqueous solvent can be performed using liquid components and utilizing GC-MS analysis.
  • concentration of the first alkylene glycol (or first alcoholic solvent) in the liquid component is determined, and from this concentration and the mass of the entire liquid component, the amount of the first alkylene glycol (or first alcoholic solvent) contained in the entire liquid component is determined.
  • Mass is required. From this mass and the mass of the first antioxidant, the mass ratio of the first antioxidant/first alkylene glycol (or first alcoholic solvent) is determined.
  • GC-MS analysis may be performed under the following conditions.
  • Apparatus GCMS-QP2010 (manufactured by Shimadzu Corporation) Sample volume: 1 ⁇ L Column: DB-WAX (length 30 m, inner diameter 0.25 mm, film thickness of adsorbent 0.25 ⁇ m, heat resistance upper limit temperature 260 ° C.) Heating flow: Hold 1 min at 50°C ⁇ Raise temperature to 250°C at 10°C/min ⁇ Hold at 250°C for 20 min Ion beam source temperature setting: 200°C Interface temperature: 250°C
  • the liquid component may contain a solute.
  • solutes include acid components, base components, and the like.
  • the liquid component preferably contains at least an acid component.
  • the acid component in the liquid component suppresses the dedoping phenomenon of the dopant and stabilizes the conductivity of each polymer component. Further, even when the conductive polymer component is dedoped with the dopant, the site of the dedoping trace is re-doped with the acid component of the liquid component, so that the ESR is easily maintained at a low level.
  • the liquid component contains an acid component and the antioxidant component contains the phenolic antioxidant IA, the phenolic antioxidant IA may be easily deactivated.
  • the liquid component contains an alcohol-based solvent such as a primary alcohol-based solvent, the activity of the phenolic antioxidant IA can be maintained, and higher heat resistance can be ensured.
  • acid components include acids having a carbonyloxy bond (carboxylic acid, oxocarbonic acid, Meldrum's acid, etc.), acids having a carbonyloxy bond, coordination compounds of phenolic compounds, phenolic compounds (picric acid, p-nitrophenol , pyrogallol, catechol, etc.), sulfur-containing acids (sulfuric acid, sulfonic acid (aromatic sulfonic acid, etc.), oxyaromatic sulfonic acid (phenol-2-sulfonic acid, etc.), etc.), compounds having a sulfonylimide bond, boron-containing acids (such as boric acid, halogenated boric acid (such as tetrafluoroboric acid), or partial esters thereof), phosphorus-containing acids (such as phosphoric acid, halogenated phosphoric acid (such as hexafluorophosphoric acid), phosphonic acid, phosphinic acid, or These partial esters, etc.), nitrogen-
  • carboxylic acid examples include aliphatic carboxylic acid, aromatic carboxylic acid (including sulfoaromatic carboxylic acid (p-sulfobenzoic acid, 3-sulfophthalic acid, 5-sulfosalicylic acid, etc.)) and the like.
  • Aromatic carboxylic acids in particular, aromatic hydroxy acids (benzoic acid, salicylic acid, etc.), aromatic polycarboxylic acids (phthalic acid, pyromellitic acid, etc.) are preferred because of their high stability.
  • Compounds having a sulfonylimide bond 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, N,N'-diphenylsulfamide and the like.
  • the coordination compound examples include coordination compounds in which at least one central atom selected from the group consisting of boron, aluminum and silicon is bonded to the central atom with an acid having a carbonyloxy bond.
  • Specific examples of coordination compounds include borodisalicylic acid, borodisoxalic acid, borodiglycolic acid, borodigallic acid, borodicatechol, and borodipyrogallol.
  • the liquid component may contain one type of acid component, or may contain two or more types.
  • aromatic carboxylic acids phthalic acid, salicylic acid, benzoic acid, etc.
  • the above coordination compounds borodisalicylic acid, borodisoxalic acid, borodiglycolic acid, etc.
  • Salicylic acid and the like are preferred.
  • the acid component may be contained in the liquid component in a free form, an anion form, or a salt form. All these forms are sometimes referred to as an acid component.
  • the liquid component may contain a base component together with the acid component.
  • the base component neutralizes at least a portion of the acid component. Therefore, corrosion of the electrode due to the acid component can be suppressed while increasing the concentration of the acid component.
  • the liquid component may contain one or more base components.
  • Amines may be aliphatic, aromatic, or heterocyclic.
  • Amines include, for example, trimethylamine, diethylamine, ethyldimethylamine, triethylamine, ethylenediamine, aniline, pyrrolidine, imidazole (such as 1,2,3,4-tetramethylimidazolinium), and 4-dimethylaminopyridine.
  • imidazole such as 1,2,3,4-tetramethylimidazolinium
  • 4-dimethylaminopyridine such as 1,2,3,4-tetramethylimidazolinium
  • Examples of quaternary ammonium compounds include amidine compounds (including imidazole compounds).
  • the liquid component may contain the base component in free form, cation form, or salt form. All these forms are sometimes referred to as base components.
  • the molar ratio of the total amount of the acid component to the base component may be, for example, 0.5 or more (or 1 or more) and 50 or less, or 1.1 or more (or 1.5 or more). It may be 20 or less. From the viewpoint of suppressing dedoping and easily ensuring high conductivity of the conductive polymer, the acid component may be used in an excess amount relative to the base component.
  • the pH of the liquid component may be 1 or more and 4 or less, or may be 1 or more and 3.5 or less.
  • the concentration of the solute in the liquid component is 0.1% by mass or more and 25% by mass or less from the viewpoint of ensuring high dissociation of the solute in the liquid component and easily obtaining high film repairability of the dielectric layer. 0.5% by mass or more and 25% by mass or less (or 15% by mass or less).
  • concentration of the acid component is determined in terms of the free acid, not the anion or salt.
  • concentrations of base components are determined in terms of free base, not cations or salts.
  • the capacitor element contains a conductive polymer.
  • a capacitor element usually includes at least an anode body having a dielectric layer on its surface and a conductive polymer covering a portion of the dielectric layer.
  • the conductive polymer may form a solid electrolyte layer.
  • the anode body can contain a valve action metal, an alloy containing a valve action metal, a compound containing a valve action metal, and the like. These materials can be used singly or in combination of two or more. For example, aluminum, tantalum, niobium, and titanium are preferably used as valve metals.
  • An anode body having a porous surface can be obtained, for example, by roughening the surface of a base material (such as a foil-like or plate-like base material) containing a valve action metal by etching or the like.
  • the anode body may be a molded body of particles containing a valve metal or a sintered body thereof. Note that the sintered body has a porous structure.
  • the dielectric layer is formed by anodizing the valve action metal on the surface of the anode body by chemical conversion treatment or the like.
  • the dielectric layer may be formed so as to cover at least part of the anode body.
  • a dielectric layer is usually formed on the surface of the anode body. Since the dielectric layer is formed on the porous surface of the anode body, it is formed along the inner wall surfaces of the holes and depressions (pits) on the surface of the anode body.
  • the dielectric layer contains an oxide of a valve metal.
  • the dielectric layer contains Ta 2 O 5 when tantalum is used as the valve metal, and the dielectric layer contains Al 2 O 3 when aluminum is used as the valve metal.
  • the dielectric layer is not limited to this, and may be any material as long as it functions as a dielectric.
  • the dielectric layer is formed along the surface of the anode body (including the inner walls of the pores).
  • a conductive polymer includes, for example, a conjugated polymer and a dopant.
  • a conductive polymer is attached so as to cover a portion of the dielectric layer.
  • the conductive polymer adhered to the surface of the dielectric layer may constitute a layer (sometimes referred to as a solid electrolyte layer).
  • the conductive polymer constitutes at least part of the cathode body in the electrolytic capacitor.
  • the conductive polymer may further contain additives as needed.
  • Conjugated polymers include known conjugated polymers used in electrolytic capacitors, such as ⁇ -conjugated polymers.
  • Conjugated polymers include, for example, polymers having polypyrrole, polythiophene, polyaniline, polyfuran, polyacetylene, polyphenylene, polyphenylenevinylene, polyacene, and polythiophenevinylene as a basic skeleton.
  • the above polymer may contain at least one type of monomer unit that constitutes the basic skeleton.
  • the above polymers also include homopolymers, copolymers of two or more monomers, and derivatives thereof (substituents having substituents, etc.).
  • polythiophenes include poly(3,4-ethylenedioxythiophene) and the like.
  • Conjugated polymers may be used singly or in combination of two or more.
  • the weight average molecular weight (Mw) of the conjugated polymer is not particularly limited, but is, for example, 1,000 or more and 1,000,000 or less.
  • the weight average molecular weight (Mw) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC). GPC is usually measured using a polystyrene gel column and water/methanol (volume ratio 8/2) as a mobile phase.
  • dopant examples include relatively low-molecular-weight anions and polymeric anions. Examples of anions include sulfate, nitrate, phosphate, borate, organic sulfonate, carboxylate and the like. Compounds that generate these anions are used as dopants. Dopants that generate sulfonate ions include, for example, paratoluenesulfonic acid and naphthalenesulfonic acid.
  • polymeric anions examples include polyvinylsulfonic acid, polystyrenesulfonic acid, polyallylsulfonic acid, polyacrylsulfonic acid, polymethacrylsulfonic acid, poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprenesulfonic acid, polyester sulfonic acids (such as aromatic polyester sulfonic acids), phenolsulfonic acid novolak resins and polyacrylic acids.
  • the polymeric anion may be a polymer of a single monomer, a copolymer of two or more monomers, or a substituent having a substituent. Among them, polyanions derived from polystyrene sulfonic acid are preferred.
  • dopants are merely examples and are not limited to these.
  • a dopant may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the conductive polymer may be formed, for example, by subjecting a conjugated polymer precursor to at least one of chemical polymerization and electrolytic polymerization on the dielectric layer in the presence of a dopant. Alternatively, it may be formed by bringing a solution in which a conductive polymer is dissolved or a dispersion in which a conductive polymer is dispersed into contact with the dielectric layer.
  • the conductive polymer used in these solutions or dispersions can be obtained by polymerizing a conjugated polymer precursor in the presence of a dopant.
  • precursors of conjugated polymers include starting monomers for conjugated polymers, oligomers and prepolymers in which a plurality of molecular chains of starting monomers are linked. One type of precursor may be used, or two or more types may be used in combination.
  • the amount of the dopant contained in the conductive polymer is, for example, 10 to 1000 parts by mass, and may be 20 to 500 parts by mass or 50 to 200 parts by mass with respect to 100 parts by mass of the conjugated polymer.
  • the solid electrolyte layer may contain an antioxidant component containing the first antioxidant.
  • the antioxidant component dissolved in the liquid component penetrates into the solid electrolyte layer, so that the solid electrolyte layer may contain the antioxidant component, but the solid electrolyte layer is formed.
  • an antioxidant component may be included. Both of these may be employed.
  • the solid electrolyte layer may be formed, for example, by chemical polymerization or electrolytic polymerization using a polymerization liquid containing an antioxidant component.
  • the solid electrolyte layer may be formed using a solution or dispersion containing a conductive polymer together with an antioxidant component.
  • Analysis of the conductive polymer contained in the electrolytic capacitor is performed by the following procedure. First, the electrolytic capacitor is disassembled, the capacitor element is taken out, and the surface is polished to expose the surface of the conductive polymer (solid electrolyte). All the exposed conductive polymer is scraped off and dried under reduced pressure. A predetermined amount is sampled from the dried sample, and the sample sample can be used for analysis of the conductive polymer by H 1 -NMR. The antioxidant component contained in the solid electrolyte layer can also be analyzed by H 1 -NMR in the same manner as in the case of conductive polymers.
  • a metal foil may be used for the cathode body as well as for the anode body.
  • the type of metal is not particularly limited, it is preferable to use a valve-acting metal such as aluminum, tantalum, or niobium, or an alloy containing a valve-acting 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 (dissimilar metal) different from the metal constituting the metal foil (dissimilar metal) or a non-metal coating. Examples of dissimilar metals and non-metals include metals such as titanium and non-metals such as carbon.
  • a separator When a metal foil is used as the cathode body, a separator may be arranged between the metal foil and the anode body.
  • the separator is not particularly limited, and for example, a nonwoven fabric containing fibers of cellulose, polyethylene terephthalate, vinylon, polyamide (eg, aromatic polyamide such as aliphatic polyamide and aramid) may be used.
  • the electrolytic capacitor may be of wound type, chip type or laminated type.
  • An electrolytic capacitor may have at least one capacitor element, and may have a plurality of capacitor elements.
  • an electrolytic capacitor may comprise a stack of two or more capacitor elements, or may comprise two or more wound capacitor elements. The configuration or number of capacitor elements may be selected according to the type or application of the electrolytic capacitor.
  • the material of the container for example, metals such as aluminum, stainless steel, copper, iron and brass, or alloys thereof can be used.
  • the shape of the container is not particularly limited as long as it can contain the capacitor element and the liquid component.
  • the sealing member is not particularly limited as long as it seals the opening of the container.
  • the present disclosure by allowing the first antioxidant to be present in the electrolytic capacitor, even when the electrolytic capacitor is exposed to high temperatures, deterioration of the sealant containing the elastic polymer can be suppressed, and high heat resistance can be obtained. Therefore, the present disclosure is particularly suitable when using a sealant containing an elastic polymer.
  • the sealant may further contain a cross-linking agent for cross-linking the elastic polymer, an additive, and the like.
  • An insulating elastic polymer is used as the elastic polymer.
  • elastic polymers include butyl rubber, isoprene rubber, silicone rubber, fluororubber, ethylene propylene rubber, chlorosulfonated polyethylene rubber (hypalon rubber, etc.), and the like.
  • the sealant may contain one type of elastic polymer, or may contain two or more types in combination.
  • the ratio of the elastic polymer in the sealing member is, for example, 10% by mass or more, and may be 20% by mass or more.
  • the sealant is likely to deteriorate in a high-temperature environment. Even in such a case, deterioration of the elastic polymer can be suppressed by using the liquid component, and high heat resistance of the electrolytic capacitor can be ensured.
  • the proportion of the elastic polymer is preferably 50% by mass or less or 40% by mass or less.
  • the ratio of the elastic polymer is the ratio of the elastic polymer containing the cross-linking agent.
  • the elastic polymer that constitutes the sealing body is usually crosslinked with a crosslinking agent.
  • a crosslinking agent selected from the group consisting of phenol resins (alkylphenol resin oligomers, etc.) and peroxides (organic peroxides, etc.), It is especially suitable for applications that require high heat resistance.
  • phenol resins alkylphenol resin oligomers, etc.
  • peroxides organic peroxides, etc.
  • additives include reinforcing agents (such as carbon such as carbon black), antioxidants, anti-aging agents, cross-linking agents, cross-linking accelerators, dispersing aids, modifiers, vulcanizing agents, vulcanizing aids, and at least one selected from the group consisting of processing aids.
  • Qualitative and quantitative analysis of the elastic polymer contained in the sealant can be obtained, for example, by the following procedures. First, the sealing body is dried under reduced pressure for 1 hour, and the mass of the sealing body is measured. Next, the sealing body is cut out to prepare a sample, and the mass is measured. The sample is subjected to at least one of H 1 -NMR and infrared absorption spectroscopy to identify components (elastic polymer, etc.) contained in the sealant. Samples can also be subjected to quantitative analysis using thermogravimetric analysis (TG or TGA). From the mass of the obtained elastic polymer and the mass of the first antioxidant, the mass ratio of the first antioxidant/elastic polymer is determined.
  • TG or TGA thermogravimetric analysis
  • the electrolytic capacitor of the present disclosure will be described more specifically based on the embodiments.
  • the electrolytic capacitor of the present disclosure is not limited to the following embodiments.
  • FIG. 1 is a schematic cross-sectional view of an electrolytic capacitor according to this embodiment
  • FIG. 2 is a schematic diagram showing a part of a capacitor element of the same electrolytic capacitor.
  • the electrolytic capacitor includes, for example, a capacitor element 10, a bottomed case 101 that accommodates the capacitor element 10 and a liquid component (not shown), a sealing member 102 that closes the opening of the bottomed case 101, and a seat plate that covers the sealing member 102. 103 , lead wires 104 A and 104 B extending from the sealing member 102 and penetrating the seat plate 103 , and lead tabs 105 A and 105 B connecting the lead wires and the electrodes of the capacitor element 10 .
  • 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 capacitor element 10 is, for example, a wound body as shown in FIG.
  • the wound body includes anode body 11 connected to lead tab 105A, cathode body 12 connected to lead tab 105B, and separator 13 .
  • a conductive polymer layer (solid electrolyte layer) (not shown) is formed on anode body 11 . At least the conductive polymer layer (solid electrolyte layer) of capacitor element 10 may be impregnated with a liquid component.
  • FIG. 2 shows a partially unfolded state before stopping the outermost circumference of the wound body.
  • An aluminum foil having a thickness of 100 ⁇ m was subjected to an etching treatment to roughen the surface of the aluminum foil. After that, a dielectric layer was formed on the surface of the aluminum foil by chemical conversion treatment.
  • the chemical conversion treatment was carried out by immersing an aluminum foil in an ammonium adipate solution and applying a voltage of 60 V thereto. After that, the aluminum foil was cut 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 via a separator while winding the lead tab.
  • An anode lead wire and a cathode lead wire were connected to the ends of each lead tab protruding from the wound body.
  • the produced wound body was subjected to chemical conversion treatment again to form a dielectric layer on the cut end of the anode body. Next, the ends of the outer surface of the wound body were fixed with a winding stop tape to produce a wound body.
  • a mixed solution was prepared by dissolving 3,4-ethylenedioxythiophene (EDOT) and polystyrene sulfonic acid (PSS, weight average molecular weight of 100,000) as a dopant in ion-exchanged water. While stirring the mixed solution, iron (III) sulfate (oxidizing agent) dissolved in ion-exchanged water was added to carry out a polymerization reaction. After the reaction, the resulting reaction solution is dialyzed to remove unreacted monomers and excess oxidizing agent, and a polymer dispersion containing polyethylenedioxythiophene (PEDOT/PSS) doped with about 5% by mass of PSS ( A liquid mixture) was obtained.
  • EDOT 3,4-ethylenedioxythiophene
  • PSS polystyrene sulfonic acid
  • a disk-shaped elastic member containing butyl rubber was used, which was obtained by kneading a butyl polymer, a peroxide-based cross-linking agent, and an additive, and molding the mixture using a mold.
  • additives a reinforcing material (carbon black), a cross-linking accelerator, a dispersing aid (stearic acid), a hindered phenol antioxidant, and a modifier (silane coupling agent) were used. The amount of each component used was adjusted so that the content of butyl rubber, which is an elastic polymer in the sealant, was 30% by mass.
  • the solid electrolytic capacitor was subjected to reflow treatment in a 260°C environment for 3 minutes.
  • the electrolytic capacitor was housed in a constant temperature bath of 145° C. atmosphere, and an accelerated test was performed by keeping the rated voltage applied for 5000 hours.
  • the capacitance and ESR were measured in a 20° C. environment in the same manner as the initial capacitance and ESR, and the average value of 20 solid electrolytic capacitors (capacitance after accelerated test: c1 , ESR after the accelerated test: r1).
  • Table 1 shows the evaluation results.
  • A1 to A9 are examples, and B1 to B2 are comparative examples.
  • Examples 1-9 and Comparative Examples 1-2 do not have much difference in initial ESR and capacitance values.
  • the rate of decrease in capacitance was large, and the rate of change in ESR was large. (B1 and B2).
  • A1 using the first antioxidant both the rate of decrease in capacitance and the rate of change in ESR after the accelerated test are suppressed as compared to B1 and B2.
  • a liquid component was prepared in the same manner as for electrolytic capacitor A1, except that no antioxidant was used.
  • a capacitor element was impregnated with a liquid component in the same manner as in the electrolytic capacitor A1, except that the obtained liquid component was used.
  • the amount of antioxidant shown in Table 2 was placed in the case, and then the capacitor element impregnated with the liquid component was placed.
  • the amount (% by mass) of the first antioxidant shown in Table 2 means the ratio of the first antioxidant to the total amount of the liquid component and the first antioxidant.
  • the electrolytic capacitor was completed in the same manner as the electrolytic capacitor A1, and was subjected to aging treatment. Evaluation similar to the above was performed using the obtained electrolytic capacitor. After the evaluation, when the electrolytic capacitor was disassembled and the bottom of the case was checked, at least part of the antioxidant remained without being dissolved in the liquid component.
  • Table 2 The results are shown in Table 2.
  • A10 to A19 are Examples.
  • Table 2 also shows the results of A1 and B1.
  • Electrolytic capacitors A20 and B3>> In forming the solid electrolyte layer, an antioxidant was added to the liquid mixture at the concentration shown in Table 3. A solid electrolyte layer was formed using the resulting liquid mixture. Also, no liquid component (electrolyte) was used. Except for these, the electrolytic capacitor was completed in the same manner as the electrolytic capacitor A1, and was subjected to aging treatment. Evaluation similar to the above was performed using the obtained electrolytic capacitor.
  • the rate of decrease in capacitance is remarkably large, and the rate of change in ESR is also significantly increased (B6 ). That is, in A21, by using the first antioxidant and using a non-aqueous solvent containing an alcohol solvent, deactivation of the first antioxidant is suppressed even in a high temperature environment, and the conductive polymer or the sealing material It is considered that the deterioration of the first antioxidant
  • a liquid component was prepared in the same manner as for the electrolytic capacitor A21, except that the first antioxidant shown in Table 5 or Table 6 was used in an amount such that the concentration shown in Table 5 or Table 6 was obtained.
  • An electrolytic capacitor was completed and subjected to aging treatment in the same manner as the electrolytic capacitor A1, except that the obtained liquid component was used. Evaluation similar to the above was performed using the obtained electrolytic capacitor.
  • Table 5 The results are shown in Table 5 or Table 6.
  • Table 5 or 6 A29 to A38 are examples.
  • Tables 5 and 6 also show the results of A21 and B4.
  • the electrolytic capacitor of the present disclosure and the liquid component for an electrolytic capacitor of the present disclosure are suitable for use in hybrid electrolytic capacitors. Electrolytic capacitors are particularly suitable for applications that require high heat resistance. However, the liquid component for electrolytic capacitors and the uses of electrolytic capacitors are not limited to these.
  • Electrolytic capacitor 101 Bottomed case 102: Sealing body 103: Seat plate 104A, 104B: Lead wire 105A, 105B: Lead tab 10: Capacitor element 11: Anode body 12: Cathode body 13: Separator 14: Winding tape

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