JP4912914B2 - Capacitor and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a capacitor having a low ESR and a high withstand voltage. <P>SOLUTION: The capacitor 10 comprises a positive electrode 11 composed of a porous body of valve metal, a dielectric layer 12 formed through surface oxidation of the positive electrode 11, and a solid electrolytic layer 13 formed on the surface of the dielectric layer 12 wherein the solid electrolytic layer 13 contains a &pi; conjugated system conductive polymer, polyanion and ion conductive compound. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to capacitors such as aluminum electrolytic capacitors, tantalum electrolytic capacitors, niobium electrolytic capacitors, and methods for producing these capacitors.

In recent years, with the digitization of electronic devices, capacitors used in electronic devices are required to reduce impedance (equivalent series resistance) in a high frequency region. Conventionally, so-called functional capacitors (hereinafter abbreviated as “capacitors”) in which an oxide film of a valve metal such as aluminum, tantalum, or niobium is used as a dielectric have been used to meet this requirement.
As shown in Patent Document 1, this capacitor has an anode made of a porous body of valve metal, a dielectric layer formed by oxidizing the surface of the anode, a conductive solid electrolyte layer, and a carbon layer. And a cathode having a silver layer or the like laminated thereon. As the solid electrolyte layer, a conductive film containing a π-conjugated conductive polymer may be used.

As a method for forming a conductive film containing a π-conjugated conductive polymer, an electrolytic layer in which a conductive layer made of manganese oxide is formed in advance on the surface of the porous body of the valve metal, and then this is used as an electrode for polymerization. A chemical method (see Patent Document 3) in which a legal method (see Patent Document 2) and a precursor monomer constituting a π-conjugated conductive polymer using an oxidizing agent are polymerized are widely known.
As a method for forming a conductive film other than the electrolytic polymerization method and the chemical oxidation polymerization method, for example, in Patent Document 4, aniline is chemically oxidatively polymerized while coexisting with a polyanion having a sulfo group, a carboxyl group, etc. Has been proposed, and a polyaniline aqueous solution is applied and dried to form a coating film. In this method, it is said that a highly conductive film can be easily formed.
JP 2003-37024 A JP-A-63-158829 JP 63-173313 A JP-A-7-105718

However, when the method for forming a conductive film described in Patent Documents 2 to 4 is applied when forming the solid electrolyte layer of the capacitor, there arises a problem that the withstand voltage of the capacitor is lowered. In addition, the electrolytic polymerization method described in Patent Document 2 is complicated because the conductive layer made of manganese oxide is formed, and the manganese oxide has low conductivity, so that the highly conductive π-conjugated conductivity is high. There was a problem that the effect of using a polymer was weakened.
In the chemical oxidative polymerization method described in Patent Document 3, the polymerization time is long, and in order to ensure the thickness of the film, it must be repeatedly polymerized, and the formation efficiency of the conductive film is low. Compared with the conductivity, it was low. If the conductivity of the capacitor is low, there arises a problem that the equivalent series resistance (hereinafter, equivalent series resistance is referred to as ESR) increases.
An object of the present invention is to provide a capacitor with low ESR and high withstand voltage. It is another object of the present invention to provide a capacitor manufacturing method that can easily manufacture a capacitor with low ESR and high withstand voltage.

The present invention includes the following configurations.
[1] In a capacitor comprising an anode made of a porous body of valve metal, a dielectric layer formed by oxidizing the anode surface, and a solid electrolyte layer formed on the surface of the dielectric layer,
The solid electrolyte layer includes a π-conjugated conductive polymer, a polyanion, an ion conductive compound, and an alkaline compound, and the ion conductive compound is a compound having a structure represented by the following chemical formula (I) Capacitor.
(I)-(RO) _n-
(In formula (I), R represents one or more selected from the group consisting of substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, and substituted or unsubstituted phenylene. N is 4 to 2,000. Is an integer. )
[2 ] The capacitor according to [ 1 ], wherein the ion conductive compound is a compound represented by the following chemical formula (II).
(II) X- (RO) _n -Y
(In the formula (II), R represents one or more selected from the group consisting of substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, and substituted or unsubstituted phenylene. X represents a hydrogen atom or a hydroxyl group. Substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted glycidyl group, substituted or unsubstituted (meth) acryloyl Represents one or more selected from the group consisting of a group, a substituted or unsubstituted oxycarbonyl group, Y represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl One or more selected from the group consisting of a group, a substituted or unsubstituted glycidyl group, a substituted or unsubstituted (meth) acryloyl group, and a substituted or unsubstituted carbonyl group To .n is an integer of 4 to 2,000.)
[ 3 ] The solid electrolyte layer is a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxyl groups, a compound having two or more carboxyl groups, one or more hydroxyl groups, and one or more carboxyl groups. [1] or [2] further containing one or more conductivity improvers selected from the group consisting of a compound having an amide group, a compound having an amide group, a compound having an imide group, a lactam compound, and a compound having a glycidyl group . The capacitor described.

[ 4 ] The dielectric layer surface formed by oxidizing the surface of the anode made of a porous body of the valve metal contains a π-conjugated conductive polymer, a polyanion, an ion conductive compound, and a solvent at 25 ° C. attaching a conductive polymer solution having a pH of 4 to 13 ;
Dielectric layer surface to the conductive polymer solution was deposited possess and drying the,
A method for producing a capacitor, wherein the ion conductive compound is a compound having a structure represented by the following chemical formula (I) :
(I)-(RO) _n-
(In formula (I), R represents one or more selected from the group consisting of substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, and substituted or unsubstituted phenylene. N is 4 to 2,000. Is an integer.)

The capacitor of the present invention has a low ESR and a high withstand voltage.
According to the capacitor manufacturing method of the present invention, a capacitor having a low ESR and a high withstand voltage can be easily manufactured.

<Capacitor>
An embodiment of the capacitor of the present invention will be described.
FIG. 1 is a diagram illustrating a configuration of a capacitor according to the present embodiment. The capacitor 10 of this embodiment includes an anode 11 made of a porous body of valve metal, a dielectric layer 12 formed by oxidizing the surface of the anode 11, and a solid electrolyte layer formed on the surface of the dielectric layer 12. 13 and a cathode 14 are schematically configured.

(anode)
Examples of the valve metal forming the anode 11 include aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, and antimony. Of these, aluminum, tantalum, and niobium are preferable.
Specific examples of the anode 11 include those obtained by etching an aluminum foil to increase the surface area and then oxidizing the surface, or oxidizing the surface of a sintered body of tantalum particles and niobium particles into pellets. Can be mentioned. The surface of the anode 11 thus oxidized is uneven.

(Dielectric layer)
The dielectric layer 12 is obtained by, for example, forming the surface of the anode 11 by anodic oxidation in an electrolytic solution such as a diammonium adipate aqueous solution. Therefore, as shown in FIG. 1, the dielectric layer 12 is along the uneven surface of the anode 11.

(Solid electrolyte layer)
The solid electrolyte layer 13 is a layer containing a π-conjugated conductive polymer, a polyanion, and an ion conductive compound as essential components. The thickness of the solid electrolyte layer 13 is preferably 1 to 100 μm.

[Π-conjugated conductive polymer]
The π-conjugated conductive polymer can be used as long as the main chain is an organic polymer having a π-conjugated system. Examples thereof include polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of easy polymerization and stability in air, polypyrroles, polythiophenes and polyanilines are preferred.
Even if the π-conjugated conductive polymer remains unsubstituted, sufficient conductivity can be obtained. However, in order to further increase the conductivity, an alkyl group, a carboxyl group, a sulfo group, an alkoxyl group, a hydroxyl group, a cyano group It is preferable to introduce a functional group such as a group into the π-conjugated conductive polymer.

  Specific examples of such π-conjugated conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), Poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly ( 3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole), poly (3-methoxypyrrole), polythiophene, poly (3-methylthiophene), Poly (3-hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-de Ruthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly ( 3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly ( 3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4 Dimethoxythiophene), poly (3,4-ethylenedioxythiophene) , Poly (3,4-propylenedioxythiophene), poly (3,4-butenedioxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl -4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene), polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), poly ( 3-anilinesulfonic acid) and the like.

  Among them, from one or two kinds selected from polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene), poly (3-methoxythiophene), and poly (3,4-ethylenedioxythiophene). The (co) polymer is preferably used from the viewpoints of resistance and reactivity. Furthermore, polypyrrole and poly (3,4-ethylenedioxythiophene) are more preferable from the viewpoint of higher conductivity and improved heat resistance.

[Polyanion]
The polyanion is a homopolymer or copolymer selected from substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted polyester And having a structural unit having an anionic group. Moreover, you may have a structural unit which does not have an anion group as needed.
The polyanion not only solubilizes the π-conjugated conductive polymer in a solvent, but also functions as a dopant for the π-conjugated conductive polymer.

  Here, polyalkylene is a polymer whose main chain is composed of repeating methylene. For example, polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, poly (3,3,3-trifluoropropylene), polyacrylonitrile, polyacrylate, polystyrene and the like can be mentioned.

Polyalkenylene is a polymer composed of structural units containing one or more unsaturated bonds (vinyl groups) in the main chain. Among these, substituted or unsubstituted butenylene is preferable because of the interaction between the unsaturated bond and the π-conjugated conductive polymer and the ease of synthesis using substituted or unsubstituted butadiene as a starting material.
Specific examples of polyalkenylene include propenylene, 1-methylpropenylene, 1-butylpropenylene, 1-decylpropenylene, 1-cyanopropenylene, 1-phenylpropenylene, 1-hydroxypropenylene, 1-butenylene, 1-methyl-1-butenylene, 1-ethyl-1-butenylene, 1-octyl-1-butenylene, 1-pentadecyl-1-butenylene, 2-methyl-1-butenylene, 2-ethyl-1-butenylene, 2- Butyl-1-butenylene, 2-hexyl-1-butenylene, 2-octyl-1-butenylene, 2-decyl-1-butenylene, 2-dodecyl-1-butenylene, 2-phenyl-1-butenylene, 2-butenylene, 1-methyl-2-butenylene, 1-ethyl-2-butenylene, 1-octyl-2-butenylene 1-pentadecyl-2-butenylene, 2-methyl-2-butenylene, 2-ethyl-2-butenylene, 2-butyl-2-butenylene, 2-hexyl-2-butenylene, 2-octyl-2-butenylene, 2- Decyl-2-butenylene, 2-dodecyl-2-butenylene, 2-phenyl-2-butenylene, 2-propylenephenyl-2-butenylene, 3-methyl-2-butenylene, 3-ethyl-2-butenylene, 3-butyl 2-butenylene, 3-hexyl-2-butenylene, 3-octyl-2-butenylene, 3-decyl-2-butenylene, 3-dodecyl-2-butenylene, 3-phenyl-2-butenylene, 3-propylenephenyl- 2-butenylene, 2-pentenylene, 4-propyl-2-pentenylene, 4-butyl-2-pentenylene, 4-he Selected from sil-2-pentenylene, 4-cyano-2-pentenylene, 3-methyl-2-pentenylene, 4-ethyl-2-pentenylene, 3-phenyl-2-pentenylene, 4-hydroxy-2-pentenylene, hexenylene, etc. And polymers containing one or more structural units.

As polyimide, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-tetracarboxydiphenyl ether dianhydride, 2,2 ′-[ Examples include polyimides from anhydrides such as 4,4′-di (dicarboxyphenyloxy) phenyl] propane dianhydride and diamines such as oxydiamine, paraphenylenediamine, metaphenylenediamine, and benzophenonediamine.
Examples of the polyamide include polyamide 6, polyamide 6,6, polyamide 6,10 and the like.
Examples of the polyester include polyethylene terephthalate and polybutylene terephthalate.

When the polyanion has another substituent, examples of the substituent include an alkyl group, a hydroxyl group, an amino group, a cyano group, a phenyl group, a phenol group, an ester group, an alkoxyl group, and a carbonyl group. In view of solubility in a solvent, heat resistance, compatibility with a resin, and the like, an alkyl group, a hydroxyl group, a phenol group, and an ester group are preferable.
Alkyl groups can increase solubility and dispersibility in polar or nonpolar solvents, compatibility and dispersibility in resins, etc., and hydroxyl groups form hydrogen bonds with other hydrogen atoms and the like. It can be made easy and the solubility in an organic solvent, the compatibility with a resin, the dispersibility, and the adhesiveness can be increased. In addition, the cyano group and the hydroxyphenyl group can increase the compatibility and solubility in the polar resin, and can also increase the heat resistance.
Among the above substituents, an alkyl group, a hydroxyl group, an ester group, and a cyano group are preferable.

Examples of the alkyl group include chain alkyl groups such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, and dodecyl, and cycloalkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl. . In consideration of solubility in an organic solvent, dispersibility in a resin, steric hindrance, and the like, an alkyl group having 1 to 12 carbon atoms is more preferable.
Examples of the hydroxyl group include a hydroxyl group directly bonded to the main chain of the polyanion or a hydroxyl group bonded via another functional group. Examples of other functional groups include an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an amide group, and an imide group. Hydroxyl groups are substituted at the ends or in these functional groups. In these, the hydroxyl group couple | bonded with the terminal of the C1-C6 alkyl group couple | bonded with the principal chain is more preferable from the compatibility to resin and the solubility to an organic solvent.
Examples of the ester group include an alkyl ester group directly bonded to the main chain of the polyanion, an aromatic ester group, and an alkyl ester group or an aromatic ester group having another functional group interposed therebetween.
Examples of the cyano group include a cyano group directly bonded to the main chain of the polyanion, a cyano group bonded to the terminal of the alkyl group having 1 to 7 carbon atoms bonded to the main chain of the polyanion, and 2 carbon atoms bonded to the main chain of the polyanion. And a cyano group bonded to the terminal of the alkenyl group of ˜7.

  The anion group of the polyanion may be a functional group capable of undergoing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate group, A monosubstituted phosphate group, a phosphate group, a carboxyl group, a sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxyl group are more preferable.

Specific examples of the polyanion include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly (2-acrylamide- 2-methylpropanesulfonic acid), polyisoprenesulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, poly (2-acrylamido-2-methylpropane carboxylic acid), polyisoprene carboxylic acid, polyacrylic acid, etc. Can be mentioned.
These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
Among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polyacrylic acid butyl sulfonic acid are preferable. These polyanions can mitigate thermal decomposition of the π-conjugated conductive polymer.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

  The ratio of the π-conjugated conductive polymer and the polyanion in the solid electrolyte layer 13 is preferably 1 to 1,000 parts by mass of the π-conjugated conductive polymer with respect to 100 parts by mass of the polyanion. When the π-conjugated conductive polymer is less than 1 part by mass, the conductivity tends to be insufficient, and when it exceeds 1,000 parts by mass, the solvent solubility tends to be insufficient.

[Ion conductive compound]
The ion conductive compound in the present invention is a polymer having a repeating unit having an electron donating site (nucleophilic site) and exhibiting ion conductivity in the presence of an electrolyte. Examples of the electron donating moiety include a cyano group, an amino group, an amide group, and an imide group.
Further, an amide bond (—NH—CO—) and an ether bond (—O—) are also exemplified as the electron donating moiety.

Among the ion conductive compounds, a compound having a structure represented by the following chemical formula (I) in the molecule is preferable because the withstand voltage of the capacitor 10 becomes higher. The structure of chemical formula (I) may be in the main chain of the compound or in the side chain. A plurality of compounds may exist in the compound.
(I)-(RO) _n-

In formula (I), R represents one or more selected from the group consisting of substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, and substituted or unsubstituted phenylene.
Here, examples of the substituted or unsubstituted alkylene in R include ethylene, propylene, and butylene.
As substituted or unsubstituted alkenylene, propenylene, 1-methyl-propenylene, 1-butyl-propenylene, 1-decyl-propenylene, 1-cyano-propenylene, 1-phenyl-propenylene, 1-hydroxy-propenylene, 1-butenylene Etc.

  n is an integer of 1 to 2,000, preferably an integer of 3 to 1,000. When n is larger than 2,000, the compatibility of the ion conductive compound with the π-conjugated conductive polymer tends to be low, and it becomes difficult to form a uniform matrix.

Further, among the ion conductive compounds, since the withstand voltage of the capacitor 10 is particularly high, the ion conductive compound is preferably a compound represented by the following chemical formula (II).
(II) X- (RO) _n -Y
In formula (II), R represents one or more selected from the group consisting of substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, and substituted or unsubstituted phenylene. Alkylene and alkenylene are the same as in formula (I).
X is a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted glycidyl group, substituted Alternatively, it represents one or more selected from the group consisting of an unsubstituted (meth) acryloyl group and a substituted or unsubstituted oxycarbonyl group.
Y is a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted glycidyl group, substituted or unsubstituted (meth) acryloyl group, substituted Or it represents 1 or more types chosen from the group which consists of an unsubstituted carbonyl group.
Examples of the substituent when X and Y are substituted with a substituent include an alkyl group, a hydroxyl group, a vinyl group, an alkylaryl group, an acryloyl group, an amino group, and an amide group.

Here, examples of the substituted or unsubstituted alkylene in R include ethylene, propylene, and butylene.
As substituted or unsubstituted alkenylene, propenylene, 1-methyl-propenylene, 1-butyl-propenylene, 1-decyl-propenylene, 1-cyano-propenylene, 1-phenyl-propenylene, 1-hydroxy-propenylene, 1-butenylene Etc.
Examples of the alkyl group for X include a methyl group, an ethyl group, a propyl group, and a butyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Examples of the alkenyl group include a propenyl group and a butenyl group.
Examples of the aryl group include a phenyl group and a naphthyl group.

  Specific examples of the polymer represented by the chemical formula (I) and the chemical formula (II) include diethylene glycol, triethylene glycol, oligopolyethylene glycol, triethylene glycol monochlorohydrin, diethylene glycol monochlorohydrin, oligoethylene glycol monochlorohydrin, Triethylene glycol monobromohydrin, diethylene glycol monobromohydrin, oligoethylene glycol monobromhydrin, polyethylene glycol, polyether, polyethylene oxide, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether diethylene glycol・ Dibutyl ether, dipropylene Recall, tripropylene glycol, polypropylene glycol, polypropylene dioxide, polyoxyethylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid amide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butoxyethyl methacrylate , N-butoxyethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, n-butoxyethyl acrylate, n-butoxyethylene glycol acrylate, methoxytriethylene glycol acrylate Rate, methoxy polyethylene glycol Monofunctional (meth) acrylate compounds such as polyacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) ) Bifunctional (meth) acrylate compounds such as acrylate, glycerin di (meth) acrylate, ethylene glycol diglycidyl ether, glycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycidyl ether, Tripropylene glycidyl ether, polypropylene glycidyl ether, glycerin diglycidyl ether Examples include ricidyl ethers, 2-methacryloyloxyethyl succinic acid, glycidyl methacrylate, trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, and the like. It is done.

  Specific examples of the ion conductive compound other than the polymer represented by the chemical formula (I) and the chemical formula (II) include, for example, polyvinylpyrrolidone composed of a monomer unit having an amide bond, and a monomer having an amide group Examples include polyacrylamide, polyvinyl acetamide, polyamide, polyimide, polyamic acid, polyacrylonitrile, polysilamine, polyvinyl alcohol, and the like composed of body units.

  The ion conductive compound may be cross-linked as necessary. The crosslinking method is not particularly limited, and a known method can be applied. For example, when the ion conductive compound has a (meth) acryloyl group, it can be crosslinked by reacting (meth) acryloyl groups with each other using a radical generator such as an azo compound or a peroxide.

  As content of an ion conductive compound, it is preferable that it is 1-1000 mass parts with respect to a total of 100 mass parts of (pi) conjugated system conductive polymer and a polyanion, and is 50-1500 mass parts. It is more preferable. When the content of the ion conductive compound is less than 1 part by mass, the withstand voltage of the capacitor 10 may not increase. When the content exceeds 10,000 parts by mass, the conductivity of the solid electrolyte layer 13 decreases, and the capacitor 10 ESR tends to be high.

[Conductivity improver]
Since the solid electrolyte layer 13 has higher conductivity, it is preferable to further contain a conductivity improver. Here, the conductivity improver interacts with the dopant of the π-conjugated conductive polymer or the π-conjugated conductive polymer to improve the electrical conductivity of the π-conjugated conductive polymer.
As the conductivity improver, since the conductivity of the solid electrolyte layer 13 is further improved, a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxyl groups, a compound having two or more carboxyl groups, 1 It is at least one compound selected from the group consisting of compounds having one or more hydroxyl groups and one or more carboxyl groups, compounds having amide groups, compounds having imide groups, lactam compounds, and compounds having glycidyl groups. Is preferred.

-Nitrogen-containing aromatic cyclic compound A nitrogen-containing aromatic cyclic compound has an aromatic ring containing at least one nitrogen atom, and the nitrogen atom in the aromatic ring is in the aromatic ring. It has a conjugated relationship with other atoms. In order to become a conjugated relationship, the nitrogen atom and other atoms form an unsaturated bond. Alternatively, even if the nitrogen atom does not directly form an unsaturated bond with another atom, it may be adjacent to the other atom that forms the unsaturated bond. This is because an unshared electron pair existing on a nitrogen atom can form a pseudo conjugate relationship with an unsaturated bond formed between other atoms.
The nitrogen-containing aromatic cyclic compound preferably has both a nitrogen atom having a conjugated relationship with another atom and a nitrogen atom adjacent to the other atom forming the unsaturated bond.

Examples of such nitrogen-containing aromatic cyclic compounds include pyridines and derivatives thereof containing one nitrogen atom, imidazoles and derivatives thereof containing two nitrogen atoms, pyrimidines and derivatives thereof, and pyrazines. And derivatives thereof, triazines containing three nitrogen atoms, and derivatives thereof. From the viewpoint of solvent solubility and the like, pyridines and derivatives thereof, imidazoles and derivatives thereof, and pyrimidines and derivatives thereof are preferable.
The nitrogen-containing aromatic cyclic compound may be one in which a substituent such as an alkyl group, a hydroxyl group, a carboxyl group, a cyano group, a phenyl group, a phenol group, an ester group, an alkoxyl group, or a carbonyl group is introduced into the ring. It may be good or not introduced. The ring may be polycyclic.

  Specific examples of pyridines and derivatives thereof include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, N-vinylpyridine, 2,4-dimethylpyridine, 2,4. , 6-trimethylpyridine, 3-cyano-5-methylpyridine, 2-pyridinecarboxylic acid, 6-methyl-2-pyridinecarboxylic acid, 4-pyridinecarboxaldehyde, 4-aminopyridine, 2,3-diaminopyridine, 2 , 6-diaminopyridine, 2,6-diamino-4-methylpyridine, 4-hydroxypyridine, 4-pyridinemethanol, 2,6-dihydroxypyridine, 2,6-pyridinedimethanol, methyl 6-hydroxynicotinate, 2 -Hydroxy-5-pyridinemethanol, ethyl 6-hydroxynicotinate, 4-pi Ginmethanol, 4-pyridineethanol, 2-phenylpyridine, 3-methylquinoline, 3-ethylquinoline, quinolinol, 2,3-cyclopentenopyridine, 2,3-cyclohexanopyridine, 1,2-di (4- Pyridyl) ethane, 1,2-di (4-pyridyl) propane, 2-pyridinecarboxaldehyde, 2-pyridinecarboxylic acid, 2-pyridinecarbonitrile, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, Examples include 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, and 3-pyridinesulfonic acid.

  Specific examples of imidazoles and derivatives thereof include imidazole, 2-methylimidazole, 2-propylimidazole, 2-undecylimidazole, 2-phenylimidazole, N-methylimidazole, N-vinylimidazole, and N-allylimidazole. 1- (2-hydroxyethyl) imidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 4,5-imidazole dicarboxylic acid, 4,5-imidazole dicarboxylic acid Dimethyl, benzimidazole, 2-aminobenzimidazole, 2-aminobenzimidazole-2-sulfonic acid, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole, 2- (2-pyridyl) benzene And imidazole.

  Specific examples of pyrimidines and derivatives thereof include 2-amino-4-chloro-6-methylpyrimidine, 2-amino-6-chloro-4-methoxypyrimidine, 2-amino-4,6-dichloropyrimidine, 2-amino-4,6-dihydroxypyrimidine, 2-amino-4,6-dimethylpyrimidine, 2-amino-4,6-dimethoxypyrimidine, 2-aminopyrimidine, 2-amino-4-methylpyrimidine, 4,6 -Dihydroxypyrimidine, 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,4,6-triaminopyrimidine, 2,4-dimethoxypyrimidine, 2,4,5-trihydroxypyrimidine, 2,4-pyrimidinediol, etc. Is mentioned.

  Specific examples of the pyrazines and derivatives thereof include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5-methylpyrazinecarboxylic acid, pyrazineamide, 5 -Methylpyrazineamide, 2-cyanopyrazine, aminopyrazine, 3-aminopyrazine-2-carboxylic acid, 2-ethyl-3-methylpyrazine, 2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, 2, Examples include 3-diethylpyrazine.

  Specific examples of triazines and derivatives thereof include 1,3,5-triazine, 2-amino-1,3,5-triazine, 3-amino-1,2,4-triazine, and 2,4-diamino. -6-phenyl-1,3,5-triazine, 2,4,6-triamino-1,3,5-triazine, 2,4,6-tris (trifluoromethyl) -1,3,5-triazine, 2,4,6-tri-2-pyridine-1,3,5-triazine, 3- (2-pyridine) -5,6-bis (4-phenylsulfonic acid) -1,2,4-triazine disodium 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine, 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine-ρ, ρ′- Disodium disulphonate, 2-hydroxy-4,6-dichloro -1,3,5-triazine and the like.

Since a non-shared electron pair exists in the nitrogen atom in the nitrogen-containing aromatic cyclic compound, a substituent or a proton is easily coordinated or bonded on the nitrogen atom. When a substituent or proton is coordinated or bonded to a nitrogen atom, it tends to have a cationic charge on the nitrogen atom. Here, since the nitrogen atom and other atoms have a conjugated relationship, the cation charge generated by the coordination or bonding of a substituent or a proton on the nitrogen atom is contained in the nitrogen-containing aromatic ring. Once diffused, it will exist in a stable form.
For this reason, in the nitrogen-containing aromatic cyclic compound, a substituent may be introduced into the nitrogen atom to form a nitrogen-containing aromatic cyclic compound cation. Further, a salt may be formed by combining the cation and the anion. Even if it is a salt, the same effect as a nitrogen-containing aromatic cyclic compound which is not a cation is exhibited.
Examples of the substituent introduced into the nitrogen atom of the nitrogen-containing aromatic cyclic compound include a hydrogen atom, an alkyl group, a hydroxyl group, a carboxyl group, a cyano group, a phenyl group, a phenol group, an ester group, an alkoxyl group, and a carbonyl group. Is mentioned. As the kind of the substituent, the substituent shown above can be introduced.

  The content of the nitrogen-containing aromatic cyclic compound is preferably in the range of 0.1 to 100 mol, more preferably in the range of 0.5 to 30 mol, with respect to 1 mol of the anion group unit of the polyanion. The range of 1 to 10 mol is particularly preferable from the viewpoint of the physical properties and conductivity of the solid electrolyte layer 13. When the content of the nitrogen-containing aromatic cyclic compound is less than 0.1 mol, the interaction between the nitrogen-containing aromatic cyclic compound, the polyanion and the conjugated conductive polymer tends to be weak, and the conductivity May be insufficient. In addition, when the nitrogen-containing aromatic cyclic compound exceeds 100 moles, the content of the conjugated conductive polymer decreases, and it is difficult to obtain sufficient conductivity, and the physical properties of the solid electrolyte layer 13 change. There are things to do.

-Compound having two or more hydroxyl groups Examples of the compound having two or more hydroxyl groups include propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, diglycerin, D-glucose, D-glucitol, isoprene glycol, dimethylolpropionic acid, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol Polyhydric aliphatic alcohols such as dipentaerythritol, thiodiethanol, glucose, tartaric acid, D-glucaric acid, glutaconic acid;
Polymer alcohols such as polyvinyl alcohol, cellulose, polysaccharides, sugar alcohols;
1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 2,3-dihydroxy-1-pentadecylbenzene, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,4-dihydroxybenzophenone, 2,6 -Dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 2,4'-dihydroxydiphenylsulfone, 2,2 ', 5,5'-tetrahydroxydiphenylsulfone, 3,3', 5,5 '-Tetramethyl-4,4'-dihydroxydiphenylsulfone, hydroxyquinonecarboxylic acid and its salts, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6- Dihydroxybenzoic acid, 3,5-di Droxybenzoic acid, 1,4-hydroquinonesulfonic acid and its salts, 4,5-hydroxybenzene-1,3-disulfonic acid and its salts, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6- Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene-2,6-dicarboxylic acid, 1,6-dihydroxynaphthalene-2,5-dicarboxylic acid, 1,5-dihydroxy Naphthoic acid, 1,4-dihydroxy-2-naphthoic acid phenyl ester, 4,5-dihydroxynaphthalene-2,7-disulfonic acid and its salts, 1,8-dihydroxy-3,6-naphthalenedisulfonic acid and its salts, 6,7-Dihydroxy-2-naphthalenesulfonic acid and its 1,2,3-trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene, 5-methyl-1,2,3-trihydroxybenzene, 5-ethyl-1,2,3-tri Hydroxybenzene, 5-propyl-1,2,3-trihydroxybenzene, trihydroxybenzoic acid, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzaldehyde, trihydroxyanthraquinone, 2,4,6-trihydroxybenzene, tetra Examples thereof include aromatic compounds such as hydroxy-p-benzoquinone, tetrahydroxyanthraquinone, methyl garlic acid (methyl gallate), ethyl garlic acid (ethyl gallate), and potassium hydroquinone sulfonate.

  The content of the compound having two or more hydroxyl groups is preferably in the range of 0.05 to 50 mol and more preferably in the range of 0.3 to 10 mol with respect to 1 mol of the anion group unit of the polyanion. More preferred. When the content of the compound having two or more hydroxyl groups is less than 0.05 mol with respect to 1 mol of the anion group unit of the polyanion, conductivity and heat resistance may be insufficient. In addition, when the content of the compound having two or more hydroxyl groups is more than 50 mol with respect to 1 mol of the anion group unit of the polyanion, the content of the π-conjugated conductive polymer in the solid electrolyte layer 13 is small. Thus, it is difficult to obtain sufficient conductivity, and the physical properties of the solid electrolyte layer 13 may change.

When a compound having two or more hydroxyl groups is included as the conductivity improver, the conductivity of the solid electrolyte layer 13 can be further increased for the following reason.
The π-conjugated conductive polymer in the solid electrolyte layer 13 is in a highly oxidized state, and a part of the π-conjugated conductive polymer is easily oxidized and deteriorated by heat or the like. Therefore, it is considered that radicals are generated and the deterioration proceeds due to radical chains. However, it is presumed that a compound having two or more hydroxyl groups can block the radical chain by radical scavenging of the hydroxyl groups and suppress the progress of deterioration, and as a result, the conductivity becomes higher.

・ Compounds having two or more carboxyl groups As compounds having two or more carboxyl groups, maleic acid, fumaric acid, itaconic acid, citraconic acid, malonic acid, 1,4-butanedicarboxylic acid, succinic acid, tartaric acid, Aliphatic carboxylic acid compounds such as adipic acid, D-glucaric acid, glutaconic acid and citric acid;
Phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride, 5-sulfoisophthalic acid, 5-hydroxyisophthalic acid, methyltetrahydrophthalic anhydride, 4,4'-oxydiphthalic acid, biphenyltetracarboxylic dianhydride, benzophenone tetra Aromatic carboxylic acid compounds in which at least one carboxyl group is bonded to an aromatic ring, such as carboxylic dianhydride, naphthalene dicarboxylic acid, trimellitic acid, pyromellitic acid; diglycolic acid, oxydibutyric acid Thiodiacetic acid, thiodibutyric acid, iminodiacetic acid, iminobutyric acid and the like.

  The compound having two or more carboxyl groups is preferably in the range of 0.1 to 30 mol, more preferably in the range of 0.3 to 10 mol, relative to 1 mol of the anion group unit of the polyanion. When the content of the compound having two or more carboxyl groups is less than 0.1 mol relative to 1 mol of the anion group unit of the polyanion, conductivity and heat resistance may be insufficient. In addition, when the content of the compound having two or more carboxyl groups is more than 30 mol with respect to 1 mol of the anion group unit of the polyanion, the content of the π-conjugated conductive polymer in the solid electrolyte layer 13 is decreased. However, it is difficult to obtain sufficient conductivity, and the physical properties of the solid electrolyte layer 13 may change.

・ Compounds having one or more hydroxyl groups and one or more carboxyl groups As compounds having one or more hydroxyl groups and one or more carboxyl groups, tartaric acid, glyceric acid, dimethylolbutanoic acid, dimethylolpropanoic acid , D-glucaric acid, glutaconic acid and the like.

  The content of the compound having one or more hydroxyl groups and one or more carboxyl groups is preferably 1 to 5,000 parts by mass with respect to 100 parts by mass in total of the polyanion and the π-conjugated conductive polymer. 50 to 500 parts by mass is more preferable. When the content of the compound having one or more hydroxyl groups and one or more carboxyl groups is less than 1 part by mass, conductivity and heat resistance may be insufficient. Further, when the content of the compound having one or more hydroxyl groups and one or more carboxyl groups is more than 5,000 parts by mass, the content of the π-conjugated conductive polymer in the solid electrolyte layer 13 is decreased. Again, it is difficult to obtain sufficient conductivity.

Amide Compound A compound having an amide group is a monomolecular compound having an amide bond represented by —CO—NH— (the CO moiety is a double bond) in the molecule. That is, as the amide compound, for example, a compound having functional groups at both ends of the bond, a compound in which a cyclic compound is bonded to one end of the bond, urea and urea derivatives in which the functional groups at both ends are hydrogen Etc.
Specific examples of amide compounds include acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-fluamide, formamide, N-methylformamide, propionamide , Propioluamide, butyramide, isobutylamide, methacrylamide, palmitoamide, stearylamide, oleamide, oxamide, glutaramide, adipamide, cinnamamide, glycolamide, lactamide, glyceramide, tartaramide, citrulamide, glyoxylamide, plubuamide, acetoacetamide, Dimethylacetamide, benzylamide, anthranilamide, ethylenediamine Laacetamide, diacetamide, triacetamide, dibenzamide, tribenzamide, rhodanine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea, 1,3-dimethylurea, 1,3-diethylurea and These derivatives are mentioned.

  The molecular weight of the amide compound is preferably 46 to 10,000, more preferably 46 to 5,000, and particularly preferably 46 to 1,000.

  The content of the amide compound is preferably 1 to 5,000 parts by mass and more preferably 50 to 500 parts by mass with respect to 100 parts by mass in total of the polyanion and the π-conjugated conductive polymer. When the content of the amide compound is less than 1 part by mass, conductivity and heat resistance may be insufficient. On the other hand, when the content of the amide compound exceeds 5,000 parts by mass, the content of the π-conjugated conductive polymer in the solid electrolyte layer 13 decreases, and it is difficult to obtain sufficient conductivity.

-Imide compound As an amide compound, since electroconductivity becomes higher, the monomolecular compound (henceforth an imide compound) which has an imide bond is preferable. Examples of the imide compound include phthalimide and phthalimide derivatives, succinimide and succinimide derivatives, benzimide and benzimide derivatives, maleimide and maleimide derivatives, naphthalimide and naphthalimide derivatives from the skeleton.

Moreover, although an imide compound is classified into an aliphatic imide, an aromatic imide, etc. by the kind of functional group of both terminal, an aliphatic imide is preferable from a soluble viewpoint.
Furthermore, the aliphatic imide compound is classified into a saturated aliphatic imide compound having an unsaturated bond between carbons in the molecule and an unsaturated aliphatic imide compound having an unsaturated bond between carbons in the molecule.
The saturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and is a compound in which both R ¹ and R ² are saturated hydrocarbons. Specifically, cyclohexane-1,2-dicarboximide, allantoin, hydantoin, barbituric acid, alloxan, glutarimide, succinimide, 5-butylhydantoic acid, 5,5-dimethylhydantoin, 1-methylhydantoin, 1,5 , 5-trimethylhydantoin, 5-hydantoin acetic acid, N-hydroxy-5-norbornene-2,3-dicarboximide, glutarimide, semicarbazide, α, α-dimethyl-6-methylsuccinimide, bis [2- (succinimideoxy) Carbonyloxy) ethyl] sulfone, α-methyl-α-propylsuccinimide, cyclohexylimide and the like.
The unsaturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and one or both of R ¹ and R ² are one or more unsaturated bonds. Specific examples are 1,3-dipropylene urea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, 1,8-bis. Maleimide octane, N-carboxyheptylmaleimide and the like can be mentioned.

  The molecular weight of the imide compound is preferably 60 to 5,000, more preferably 70 to 1,000, and particularly preferably 80 to 500.

  The content of the imide compound is preferably 10 to 10,000 parts by mass, more preferably 50 to 5,000 parts by mass with respect to 100 parts by mass in total of the π-conjugated conductive polymer and the polyanion. . If the addition amount of the amide compound and the imide compound is less than the lower limit, the effect of the addition of the amide compound and the imide compound is lowered, which is not preferable. Moreover, when the said upper limit is exceeded, since the electroconductive fall resulting from the fall of (pi) conjugated system conductive polymer concentration will occur, it is unpreferable.

-Lactam compound A lactam compound is an intramolecular cyclic amide of aminocarboxylic acid, and a part of the ring is -CO-NR- (R is hydrogen or an arbitrary substituent). However, one or more carbon atoms in the ring may be replaced with an unsaturated or heteroatom.
Examples of the lactam compound include pentano-4-lactam, 4-pentanelactam-5-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidinone, hexano-6-lactam, 6-hexane lactam and the like.

  The content of the lactam compound is preferably 10 to 10,000 parts by mass and more preferably 50 to 5,000 parts by mass with respect to 100 parts by mass in total of the π-conjugated conductive polymer and the polyanion. . If the amount of the lactam compound added is less than the lower limit, the effect of the addition of the lactam compound is reduced, which is not preferable. Moreover, when the said upper limit is exceeded, since the electroconductive fall resulting from the fall of (pi) conjugated system conductive polymer concentration will occur, it is unpreferable.

-Compound having glycidyl group Examples of the compound having glycidyl group include ethyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl phenyl ether, bisphenol A, diglycidyl ether, acrylic Examples thereof include glycidyl compounds such as acid glycidyl ether and methacrylic acid glycidyl ether.

  The content of the compound having a glycidyl group is preferably 10 to 10,000 parts by mass and more preferably 50 to 5000 parts by mass with respect to 100 parts by mass in total of the π-conjugated conductive polymer and the polyanion. preferable. When the amount of the compound having a glycidyl group is less than the lower limit, the effect of adding the compound having a glycidyl group is undesirably reduced. Moreover, when the said upper limit is exceeded, since the electroconductive fall resulting from the fall of (pi) conjugated system conductive polymer concentration will occur, it is unpreferable.

-Organic solvent Moreover, when one part organic solvent remains in the solid electrolyte layer 13, it functions as an electroconductivity improver. Examples of the organic solvent that can be a conductivity improver include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylene phosphortriamide, N-vinylpyrrolidone, Polar solvents such as N-vinylformamide and N-vinylacetamide, phenols such as cresol, phenol and xylenol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4 -Butylene glycol, glycerin, diglycerin, D-glucose, D-glucitol, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanedio , Polyhydric aliphatic alcohols such as neopentyl glycol, carbonate compounds such as ethylene carbonate and propylene carbonate, ether compounds such as dioxane and diethyl ether, dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc. Chain ethers, heterocyclic compounds such as 3-methyl-2-oxazolidinone, nitrile compounds such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, and benzonitrile. These solvents may be used alone or as a mixture of two or more.

  Such a conductivity improver can form a hydrogen bond between the polyanion and the π-conjugated conductive polymer, or bring the π-conjugated conductive polymers close to each other by the interaction between these compounds. it can. As a result, energy required for hopping, which is an electrical conduction phenomenon between π-conjugated conductive polymers, is reduced, and thus the overall electrical resistance is reduced and the electrical conductivity is further improved.

[Dopant]
The solid electrolyte layer 13 may contain a dopant other than the polyanion in order to further improve the conductivity of the π-conjugated conductive polymer.
Examples of other dopants include halogen compounds, Lewis acids, proton acids, and the like. Specifically, organic acids such as organic carboxylic acids and organic sulfonic acids, organic cyano compounds, fullerenes, hydrogenated fullerenes, fullerene hydroxides, Examples thereof include carboxylic acid fullerene and sulfonic acid fullerene.

Examples of organic acids include alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl naphthalene disulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, naphthalene disulfonic acid, naphthalene trisulfonic acid, dinaphthylmethane disulfonic acid, Examples include organic sulfonic acid compounds such as anthraquinone sulfonic acid, anthraquinone disulfonic acid, anthracene sulfonic acid, and pyrene sulfonic acid, and organic carboxylic acid compounds such as acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, and malonic acid. It is done. These metal salts can also be used.
As the organic cyano compound, a compound having two or more cyano groups in a conjugated bond can be used. Examples include tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, dichlorodicyanobenzoquinone (DDQ), tetracyanoquinodimethane, and tetracyanoazanaphthalene.

  The content of the dopant compound is preferably 10 to 10,000 mol parts, and more preferably 30 to 3,000 mol parts with respect to 100 mol parts of the π-conjugated conductive polymer. If the addition amount of the dopant compound is less than the lower limit value, the effect due to the addition of the dopant compound is reduced, which is not preferable. Moreover, when the said upper limit is exceeded, since the electroconductive fall resulting from the fall of (pi) conjugated system conductive polymer concentration will occur, it is unpreferable.

[Binder resin]
The solid electrolyte layer 13 may contain a binder resin in order to adjust film formability, film strength, and the like.
The binder resin is not particularly limited as long as it is compatible or mixed and dispersible with the π-conjugated conductive polymer or polyanion, and may be a thermosetting resin or a thermoplastic resin. For example, polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyimides such as polyimide and polyamideimide, polyamides such as polyamide 6, polyamide 6,6, polyamide 12 and polyamide 11, polyvinylidene fluoride, polyvinyl fluoride, poly Fluorine resin such as tetrafluoroethylene, ethylenetetrafluoroethylene copolymer, polychlorotrifluoroethylene, polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, vinyl resin such as polyvinyl chloride, epoxy resin, xylene resin, aramid resin, Examples include polyurethane, polyurea, melamine resin, phenolic resin, polyether, acrylic resin, and copolymers thereof.
In addition, a water-soluble polymer or a water-dispersible polymer is preferable because the compatibility between the π-conjugated conductive polymer and the polyanion is excellent. Both the water-soluble polymer and the water-dispersible polymer have hydrophilic groups. Examples of the hydrophilic group include —CO—, —COOM, —CONR—, —OH, —NR ₂ , —O—, —SO ₃ M, and a salt containing these groups (R is a hydrogen atom or An organic group, M is a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary amine, etc.);

  The content of the binder resin is preferably 1 to 50,000 parts by mass, more preferably 10 to 1,000 parts by mass with respect to 100 parts by mass in total of the π-conjugated conductive polymer and the polyanion. . If the amount of the binder resin added is less than the lower limit value, the effect of the binder resin addition is not preferable. Moreover, when the said upper limit is exceeded, since the electroconductive fall resulting from the fall of (pi) conjugated system conductive polymer concentration will occur, it is unpreferable.

(cathode)
The cathode 14 is composed of a layer of carbon, silver, aluminum or the like, for example.
When the cathode 14 is made of carbon, silver or the like, it can be formed from a conductive paste containing a conductor such as carbon or silver. Moreover, when the cathode 14 is comprised with aluminum, it consists of aluminum foil.

Since the solid electrolyte layer 13 of the capacitor 10 described above contains an ion conductive compound, the conductivity is high. Therefore, the ESR of the capacitor 10 can be lowered.
The ion conductive compound in the solid electrolyte layer 13 is attached or coordinated to the metal oxide constituting the dielectric layer 12 to form a layer of the ion conductive compound on a part of the metal oxide surface. This layer is considered to serve as a buffer that suppresses the speed of electrons or ions moving between the electrodes by the electric field. It is considered that the withstand voltage of the capacitor 10 can be increased because the movement speed of the electrons or ions can be suppressed to prevent the anode 11 or the cathode 14 from being damaged by the collision.
It is considered that the defective portion of the dielectric layer 12 is oxidized and repaired when an electric field is applied to the capacitor 10. In the present invention, since the ion conductive compound in the solid electrolyte layer 13 becomes an oxygen supply source during oxidation, the dielectric layer 12 can be easily repaired. This is also considered to be a factor that increases the withstand voltage of the capacitor 10.

<Capacitor manufacturing method>
Next, a method for manufacturing the capacitor 10 will be described.
In the method of manufacturing the capacitor 10 according to this embodiment, a conductive intermediate is formed on the surface of the capacitor intermediate body having the anode 11 and the dielectric layer 12 of the oxide film formed by oxidizing the surface of the anode 11. Apply and attach polymer solution.
The conductive polymer solution used at this time contains a π-conjugated conductive polymer, a polyanion, an ion conductive compound, and a solvent as essential components.

Examples of the solvent include water and / or an organic solvent.
Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylene phosphortriamide, N-vinylpyrrolidone, N-vinylformamide, N- Polar solvents such as vinylacetamide, phenols such as cresol, phenol, xylenol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, di Glycerin, D-glucose, D-glucitol, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentylglyco Polyhydric aliphatic alcohols such as ruthenium, ketones such as acetone and methyl ethyl ketone, hydrocarbons such as hexane, benzene and toluene, carboxylic acids such as formic acid and acetic acid, carbonate compounds such as ethylene carbonate and propylene carbonate, dioxane and diethyl Ether compounds such as ether, chain ethers such as dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, heterocyclic compounds such as 3-methyl-2-oxazolidinone, acetonitrile, glutarodinitrile, methoxy Examples thereof include nitrile compounds such as acetonitrile, propionitrile, and benzonitrile. These solvents may be used alone or as a mixture of two or more.

  The content of the organic solvent is preferably 1 to 10,000 parts by mass and more preferably 50 to 3,000 parts by mass with respect to 100 parts by mass in total of the polyanion and the π-conjugated conductive polymer. .

If necessary, other additives may be added to the conductive polymer solution in order to improve the coating property and stability of the conductive polymer solution, the properties of the solid electrolyte layer 13, and the like. The additive is not particularly limited as long as it can be mixed with a π-conjugated conductive polymer and a polyanion. For example, a surfactant, an antifoaming agent, a coupling agent, an antioxidant, and the like can be used.
Surfactants include anionic surfactants such as carboxylates, sulfonates, sulfates and phosphates; cationic surfactants such as amine salts and quaternary ammonium salts; carboxybetaines and aminocarboxylic acids Examples include amphoteric surfactants such as salts and imidazolium betaines; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, ethylene glycol fatty acid esters, and polyoxyethylene fatty acid amides.
Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone resin.
Examples of the coupling agent include silane coupling agents having a vinyl group, an amino group, an epoxy group, a methacryl group, and the like.
Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, saccharides, vitamins and the like.

The conductive polymer solution preferably has a pH of 3 to 13 at 25 ° C, more preferably 5 to 11. If the pH of the conductive polymer solution is 3 or more, corrosion of the dielectric layer 12 by the conductive polymer solution can be prevented. However, if the pH exceeds 13, the conductivity of the π-conjugated conductive polymer tends to decrease, which is not preferable.
In order to adjust the pH of the conductive polymer solution to 3 to 13, an alkaline compound may be added. As the alkaline compound, known inorganic alkali compounds and organic alkali compounds can be used. Examples of the inorganic alkali compound include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia and the like.
As the organic alkali compound, a nitrogen-containing aromatic cyclic compound (aromatic amine), an aliphatic amine, a metal alkoxide, or the like can be suitably used.
Examples of the nitrogen-containing aromatic cyclic compound include those described above.
Examples of the aliphatic amine compound include aliphatic amines such as dimethylamine and diethylamine, and aromatic amines such as imidazole, 2-methylimidazole, 1-hydroxyethylimidazole, 2,6-pyridinedimethanol, and 2-pyridinecarboxylic acid. Examples thereof include sodium alkoxides such as compounds, sodium methoxide and sodium ethoxide, potassium alkoxides and calcium alkoxides.

In order to obtain a conductive polymer solution, for example, first, a precursor monomer that forms a π-conjugated conductive polymer is chemically oxidatively polymerized in a solvent in the presence of a polyanion to form a π-conjugated conductive polymer. A solution containing a complex in which a polyanion is complexed is prepared.
Next, an ion conductive compound and optional components such as a conductivity improver and an alkaline compound are added to the solution containing the composite to obtain a conductive polymer solution.

  Examples of the method for attaching the conductive polymer solution to the surface of the dielectric layer 12 include known methods such as coating, dipping, and spraying.

Next, the conductive polymer solution attached to the dielectric layer 12 is dried to form the solid electrolyte layer 13. Examples of the drying method include known methods such as room temperature drying, hot air drying, and far-infrared drying. In this drying, not all of the organic solvent in the conductive polymer solution is necessarily removed, and some of the organic solvent may be included in the solid electrolyte layer 13.
Next, a carbon paste, a silver paste, or the like is applied on the solid electrolyte layer 13 to form the cathode 14 to obtain the capacitor 10.

In the method of manufacturing the capacitor 10 described above, a conductive polymer solution containing a π-conjugated conductive polymer is attached to the dielectric layer 12, and the attached conductive polymer solution is dried to form the solid electrolyte layer 13. Therefore, the process is simple and the productivity is high.
Further, since the solid electrolyte layer 13 is formed from a conductive polymer solution containing an ion conductive compound, the conductivity of the solid electrolyte layer 13 is high, the ESR of the capacitor 10 is low, and the withstand voltage of the capacitor 10 is also high. .

In addition, the capacitor | condenser and its manufacturing method of this invention are not limited to embodiment example mentioned above. For example, in the capacitor of the present invention, as shown in FIG. 2, a separator 15 can be provided between the dielectric layer 12 and the cathode 14 as necessary. Examples of the capacitor in which the separator 15 is provided between the dielectric layer 12 and the cathode 14 include a wound capacitor.
Examples of the separator 15 include a sheet (including a nonwoven fabric) made of polyvinyl alcohol, polyester, polyethylene, polystyrene, polypropylene, polyimide, polyamide, polyvinylidene fluoride, and the like, a glass fiber nonwoven fabric, and the like.
The density of the separator 15 is preferably in the range of 0.1 to 1 g / cm ^3, and more preferably in the range of 0.2 to 0.8 g / cm ^3.
When the separator 15 is provided, a method of forming the cathode 14 by impregnating the separator 15 with a carbon paste or a silver paste can be applied.

In the capacitor of the present invention, an electrolytic solution can be used as necessary. The electrolytic solution is not particularly limited as long as the electric conductivity is high, and examples thereof include a well-known electrolyte dissolved in a well-known electrolyte solution.
Examples of the electrolyte solution solvent include alcohol solvents such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, and glycerin, lactone solvents such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone, Examples thereof include amide solvents such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide and N-methylpyrrolidinone, nitrile solvents such as acetonitrile and 3-methoxypropionitrile, water and the like.
Examples of the electrolyte include adipic acid, glutaric acid, succinic acid, benzoic acid, isophthalic acid, phthalic acid, terephthalic acid, maleic acid, toluic acid, enanthic acid, malonic acid, formic acid, 1,6-decanedicarboxylic acid, 5,6 -Decane dicarboxylic acid such as decanedicarboxylic acid, octane dicarboxylic acid such as 1,7-octane dicarboxylic acid, organic acid such as azelaic acid and sebacic acid, or boric acid, polyhydric alcohol of boric acid obtained from boric acid and polyhydric alcohol Complex compounds, inorganic acids such as phosphoric acid, carbonic acid and silicic acid are used as anionic components, and primary amines (methylamine, ethylamine, propylamine, butylamine, ethylenediamine, etc.), secondary amines (dimethylamine, diethylamine, dipropylamine, Methylethylamine, diphenylamine, etc.), tertiary amine (trimethyl) Amine, triethylamine, tripropylamine, triphenylamine, 1,8-diazabicyclo (5,4,0) -undecene-7), tetraalkylammonium (tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, Examples thereof include electrolytes containing methyltriethylammonium, dimethyldiethylammonium, etc.) as cationic components.

  In the above-described embodiment, the cathode is provided. However, when the solid electrolyte layer is used as the cathode, the cathode is not necessarily provided separately. In that case, the anode can be prevented from being damaged by the present invention, and the withstand voltage can be increased.

  Hereinafter, the present invention will be described in more detail with reference to examples. The pH in the following examples is a value measured at 25 ° C.

Example 1
(1) Preparation of conductive polymer solution 14.2 g (0.1 mol) of 3,4-ethylenedioxythiophene and 27.5 g (0.15 mol) of polystyrene sulfonic acid (2,000 ml of ion-exchanged water) (Molecular weight; about 150,000) was mixed at 20 ° C.
29.64 g (0.13 mol) of ammonium persulfate and 8.0 g (0.02 mol) of ferric sulfate dissolved in 200 ml of ion-exchanged water were kept at 20 ° C. while stirring the mixed solution thus obtained. The oxidation catalyst solution was added and stirred for 3 hours to react.
The resulting reaction solution was dialyzed to remove unreacted monomers, oxidizing agent, and oxidation catalyst, and a solution containing about 1.5% by mass of polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) (hereinafter, This was referred to as a complex solution).
Then, after stirring, 0.36 g of 25% by mass of ammonia water was added to 100 g of this composite solution, and then 4.5 g of polyethylene glycol 200 (number average molecular weight; 200, n of chemical formula (I) was 3 to 3). 4) was added to obtain a conductive polymer solution having a pH of 8.5.

(2) Manufacture of capacitor After connecting the anode lead terminal to the etched aluminum foil (anode foil), a voltage of 100 V was applied in an aqueous solution of 10% by mass of diammonium adipate to form (oxidize) the aluminum foil. A dielectric layer was formed on the surface to obtain a capacitor intermediate.
Next, a counter aluminum cathode foil with a cathode lead terminal welded to the anode foil of the capacitor intermediate was laminated via a cellulose separator, and this was wound up to obtain a capacitor element.
After immersing this capacitor element in the conductive polymer solution prepared in (1) under reduced pressure, the process of drying for 10 minutes with a 120 ° C. hot air dryer is repeated three times on the dielectric layer side surface of the capacitor intermediate. A solid electrolyte layer was formed.
Next, the capacitor was fabricated by sealing the aluminum case with a capacitor element on which a solid electrolyte layer was formed and a sealing rubber.
About the produced capacitor, the initial value of the electrostatic capacitance in 120 Hz and the equivalent series resistance (ESR) in 100 kHz was measured using LCZ meter 2345 (made by NF circuit design block company).
Further, the withstand voltage of the capacitor was measured as follows. A DC voltage was applied to both electrodes, the voltage was increased at a rate of 0.2 V / sec, the voltage when the current value reached 0.4 A was measured, and the voltage was taken as the withstand voltage.
These measurement results are shown in Table 1.

(Example 2)
To 100 g of the composite solution of Example 1, 3.0 g of 1- (2-hydroxyethylimidazole) was added instead of 0.36 g of 25 mass% aqueous ammonia, and the amount of polyethylene glycol 200 was changed to 9.0 g. A capacitor was fabricated in the same manner as in Example 1 except that. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Example 3)
To 100 g of the composite solution of Example 1, 3.0 g of imidazole was added instead of 0.36 g of 25% by mass ammonia water, and 7.5 g of polyethylene glycol 6000 (several instead of 4.5 g of polyethylene glycol 200) A capacitor was produced in the same manner as in Example 1 except that 6,000 was added and the average molecular weight was 6,000 and n in the chemical formula (I) was 130 to 140). And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

Example 4
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25 mass% ammonia water, and 7.5 g of polyethylene glycol 400 (instead of 4.5 g of polyethylene glycol 200). A capacitor was fabricated in the same manner as in Example 1 except that the number average molecular weight: 400 and n in the chemical formula (I) was 7 to 9) were added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Example 5)
After adding 3 mass% sodium hydroxide to 100 g of the composite solution of Example 1 to adjust the pH to 7.5, 7.5 g of polyethylene glycol 400 was added to prepare a conductive polymer solution. A capacitor was produced in the same manner as in Example 1 except that this conductive polymer solution was used. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Example 6)
A capacitor was produced in the same manner as in Example 1 except that 7.5 g of polyethylene glycol 400 was added to 100 g of the composite solution of Example 1 instead of 4.5 g of polyethylene glycol 200. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Examples 7 to 16)
After adding 0.36 g of 25 mass% aqueous ammonia to 100 g of the composite solution of Example 1, 6.0 g of polyethylene glycol 600 is added, and in Example 7, 4.5 g of ethylene glycol is added. 8 is 4.5 g glycerin, Example 9 is 6.0 g tetraethylene glycol dimethyl ether, Example 10 is 4.5 g ethylene glycol diglycidyl ether, Example 11 is 4.5 g acrylic glycidyl ether, Examples 12 is 2.5 g trihydroxybenzene, Example 13 is 3.0 g triammonium 4-sulfoisophthalate, Example 14 is ammonium adipate, Example 15 is 4.5 g maleimide, Example 16 is 6. Same as Example 1 except that 0 g N, N-dimethylacrylamide was added. To prepare a capacitor to. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Examples 17 and 18)
After adding 0.36 g of 25 mass% ammonia water to 100 g of the complex solution of Example 1, 6.0 g of polyethylene glycol 600 is added, and in Example 17, 7.5 g of dimethylacetamide is added. In No. 18, a capacitor was produced in the same manner as in Example 1 except that 4.5 g of N-vinylpyrrolidone was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Example 19)
After adding 0.36 g of 25 mass% ammonia water to 100 g of the complex solution of Example 1, 7.5 g of polyethylene glycol 20000 (number average molecular weight; 20,000, n in the chemical formula (I) is 450 to 470. ) Was added in the same manner as in Example 1 except that the above was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Examples 20 and 21)
After adding 0.36 g of 25 mass% ammonia water to 100 g of the complex solution of Example 1, in Example 20, 7.5 g of polyethylene glycol 700 (number average molecular weight; 700, n of chemical formula (I) is 14) In Example 21, except that 7.5 g of polypropylene glycol 3000 (number average molecular weight; 3,000, n in chemical formula (I) is 50) was added in the same manner as in Example 1. Was made. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Example 22)
A capacitor was obtained in the same manner as in Example 1 except that 0.36 g of 25 mass% ammonia water was added to 100 g of the composite solution of Example 1 and then 3.0 g of polyvinylpyrrolidone and 4.5 g of maleimide were added. Was made. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Example 23)
After adding 0.36 g of 25 mass% ammonia water to 100 g of the composite solution of Example 1, 3.0 g of polyethylene oxide (number average molecular weight; 3,000, n in chemical formula (I) is 65 to 70) A capacitor was fabricated in the same manner as in Example 1 except that was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Example 24)
After adding 0.36 g of 25 mass% ammonia water to 100 g of the composite solution of Example 1, 3.0 g of polyethylene oxide (number average molecular weight; 3,000, n in chemical formula (I) is 65 to 70) A capacitor was produced in the same manner as in Example 1 except that 4.5 g of ethylene glycol was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Example 25)
The same as Example 1 except that 0.36 g of 25 mass% ammonia water was added to 100 g of the complex solution of Example 1, and then 3.0 g of polyacrylamide (number average molecular weight; 6,500) was added. Thus, a capacitor was produced. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Example 26)
Example 1 with the exception that 7.5 g of polyethylene glycol (number average molecular weight; 600) was added to 100 g of the complex solution of Example 1 after adding 25 mass% ammonia water to adjust the pH to 4. A capacitor was produced in the same manner. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Example 27)
This was carried out except that 10% by weight sodium hydroxide was added to 100 g of the complex solution of Example 1 to adjust the pH to 12.5, and then 7.5 g of polyethylene glycol (number average molecular weight; 600) was added. A capacitor was produced in the same manner as in Example 1. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 1.

(Example 28)
A conductive polymer solution having a pH of 8.5 was obtained in the same manner as in Example 1 except that 9 g of dipropylene glycol was added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 29)
A conductive polymer solution having a pH of 8.5 was obtained in the same manner as in Example 1 except that 9 g of polypropylene glycol 700 was added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 30)
A conductive polymer solution having a pH of 8.5 was obtained in the same manner as in Example 1 except that 9 g of polypropylene glycol 2000 was added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 31)
A conductive polymer solution having a pH of 8.5 was obtained in the same manner as in Example 1 except that 9 g of polypropylene glycol 3000 was added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 32)
A conductive polymer solution having a pH of 8.5 was obtained in the same manner as in Example 1 except that 6 g of Epolite 40E (manufactured by Kyoeisha Chemical Co., Ltd.) was added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200. It was. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 33)
A conductive polymer solution having a pH of 8.5 was obtained in the same manner as in Example 1 except that 6 g of Epolite 100E (manufactured by Kyoeisha Chemical) was added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200. It was. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 34)
A conductive polymer solution having a pH of 8.5 was obtained in the same manner as in Example 1 except that 6 g of Epolite 200E (manufactured by Kyoeisha Chemical Co., Ltd.) was added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200. It was. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 35)
A conductive polymer solution having a pH of 8.5 was obtained in the same manner as in Example 1 except that 6 g of EPOLIGHT 400E (manufactured by Kyoeisha Chemical Co., Ltd.) was added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200. It was. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 36)
A conductive polymer solution having a pH of 8.5 was obtained in the same manner as in Example 1 except that 6 g of EPOLITE 80MF (manufactured by Kyoeisha Chemical Co., Ltd.) was added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200. It was. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 37)
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25 mass% ammonia water, and 9 g of light acrylate MTG-A (instead of 4.5 g of polyethylene glycol 200). A capacitor was produced in the same manner as in Example 1 except that Kyoeisha Chemical) was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 38)
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25% by mass ammonia water, and 9 g of light acrylate 130-A (instead of 4.5 g of polyethylene glycol 200). A capacitor was produced in the same manner as in Example 1 except that Kyoeisha Chemical) was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 39)
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25 mass% ammonia water, and 9 g of light acrylate 3EG-A (instead of 4.5 g of polyethylene glycol 200). A capacitor was produced in the same manner as in Example 1 except that Kyoeisha Chemical) was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 40)
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25 mass% ammonia water, and 9 g of light acrylate 4EG-A (instead of 4.5 g of polyethylene glycol 200). A capacitor was produced in the same manner as in Example 1 except that Kyoeisha Chemical) was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 41)
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25% by mass ammonia water, and 9 g of light acrylate 14EG-A (instead of 4.5 g of polyethylene glycol 200). A capacitor was produced in the same manner as in Example 1 except that Kyoeisha Chemical) was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 42)
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25% by mass ammonia water, and 9 g of light ester G (Kyoeisha Chemical Co., Ltd.) instead of 4.5 g of polyethylene glycol 200. A capacitor was produced in the same manner as in Example 1 except that the product was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 43)
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25 mass% ammonia water, and 9 g of light ester 2EG (Kyoeisha Chemical Co., Ltd.) instead of 4.5 g of polyethylene glycol 200. A capacitor was produced in the same manner as in Example 1 except that the product was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 44)
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25 mass% ammonia water, and 9 g of light ester 4EG (Kyoeisha Chemical Co., Ltd.) instead of 4.5 g of polyethylene glycol 200. A capacitor was produced in the same manner as in Example 1 except that the product was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 45)
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25 mass% ammonia water, and 9 g of light ester 9EG (Kyoeisha Chemical Co., Ltd.) instead of 4.5 g of polyethylene glycol 200. A capacitor was produced in the same manner as in Example 1 except that the product was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 46)
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25 mass% ammonia water, and 9 g of light ester 14EG (Kyoeisha Chemical Co., Ltd.) instead of 4.5 g of polyethylene glycol 200. A capacitor was produced in the same manner as in Example 1 except that the product was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 47)
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25% by mass ammonia water, and 9 g of light ester G-101P (instead of 4.5 g of polyethylene glycol 200). A capacitor was produced in the same manner as in Example 1 except that Kyoeisha Chemical) was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 48)
To 100 g of the composite solution of Example 1, 3.0 g of vinylimidazole was added instead of 0.36 g of 25% by mass ammonia water, and 9 g of hydroxyethyl acrylate was added instead of 4.5 g of polyethylene glycol 200. A capacitor was fabricated in the same manner as in Example 1 except that. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 49)
The same procedure as in Example 1 was performed except that 6 g of a silane coupling agent (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 g of polyethylene glycol 400 were added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200. Thus, a conductive polymer solution having a pH of 8.5 was obtained. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 50)
The same procedure as in Example 1 was performed except that 6 g of a silane coupling agent (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 g of polyethylene glycol 400 were added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200. Thus, a conductive polymer solution having a pH of 8.5 was obtained. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 51)
In the same manner as in Example 1, except that 3 g of polyurethane (D6300 manufactured by Dainichi Seika Co., Ltd.) and 3 g of polyethylene glycol 400 were added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200, the pH was 8.5. A conductive polymer solution was obtained. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 52)
In the same manner as in Example 1 except that 3 g of polyurethane (D4080 manufactured by Dainichi Seika Co., Ltd.) and 3 g of polyethylene glycol 400 were added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200, pH 8.5 A conductive polymer solution was obtained. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 53)
In the same manner as in Example 1, except that 3 g of polyurethane (R967 manufactured by Enomoto Kasei Co., Ltd.) and 3 g of polyethylene glycol 400 were added to 100 g of the complex solution instead of 4.5 g of polyethylene glycol 200, the pH of the solution was 8.5. A conductive polymer solution was obtained. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Example 54)
In the same manner as in Example 1, except that 3 g of polyurethane (Z-105 manufactured by Kyoyo Chemical Co., Ltd.) and 3 g of polyethylene glycol 400 were added to 100 g of the composite solution instead of 4.5 g of polyethylene glycol 200, pH 8. 5 conductive polymer solution was obtained. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Comparative Example 1)
A capacitor was fabricated in the same manner as in Example 1 except that the ion conductive compound was not added to the complex solution of Example 1 and that it was used as it was as a conductive polymer solution. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Comparative Example 2)
A capacitor was produced in the same manner as in Example 1 except that 0.36 g of 25 mass% ammonia water was added to 100 g of the composite solution of Example 1 and no ion conductive compound was added. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

(Comparative Example 3)
Example 1 is the same as Example 1 except that 0.36 g of 25% by mass ammonia water was added to 100 g of the complex solution of Example 1, 2.5 g of trihydroxybenzene was added, and no ion conductive compound was added. A capacitor was produced in the same manner. And it carried out similarly to Example 1, and measured the electrostatic capacitance, ESR, and withstand voltage. The measurement results are shown in Table 2.

The capacitors of Examples 1 to 54 including the solid electrolyte layer containing the π-conjugated conductive polymer, the polyanion, and the ion conductive compound had high withstand voltage and low ESR. In addition, the capacitance was sufficiently secured.
The capacitors of Comparative Examples 1 to 3 including the solid electrolyte layer containing the π-conjugated conductive polymer and the polyanion but not containing the ion conductive compound had low withstand voltage and high ESR.

It is sectional drawing which shows one example of embodiment in the capacitor | condenser of this invention. It is a perspective view which shows the other embodiment example in the capacitor | condenser of this invention.

Explanation of symbols

  10 Capacitor 11 Anode 12 Dielectric Layer 13 Solid Electrolyte Layer 14 Cathode 15 Separator

Claims (4)

In a capacitor comprising an anode made of a porous body of valve metal, a dielectric layer formed by oxidizing the anode surface, and a solid electrolyte layer formed on the surface of the dielectric layer,
The solid electrolyte layer includes a π-conjugated conductive polymer, a polyanion, an ion conductive compound, and an alkaline compound, and the ion conductive compound is a compound having a structure represented by the following chemical formula (I) Capacitor.
(I)-(RO) _n-
(In formula (I), R represents one or more selected from the group consisting of substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, and substituted or unsubstituted phenylene. N is 4 to 2,000. Is an integer.) The capacitor according to claim 1 , wherein the ion conductive compound is a compound represented by the following chemical formula (II).
(II) X- (RO) _n -Y
(In the formula (II), R represents one or more selected from the group consisting of substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, and substituted or unsubstituted phenylene. X represents a hydrogen atom or a hydroxyl group. Substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted glycidyl group, substituted or unsubstituted (meth) acryloyl Represents one or more selected from the group consisting of a group, a substituted or unsubstituted oxycarbonyl group, Y represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl One or more selected from the group consisting of a group, a substituted or unsubstituted glycidyl group, a substituted or unsubstituted (meth) acryloyl group, and a substituted or unsubstituted carbonyl group To .n is an integer of 4 to 2,000.) The solid electrolyte layer has a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxyl groups, a compound having two or more carboxyl groups, a compound having one or more hydroxyl groups and one or more carboxyl groups 1 or 2 further comprising one or more conductivity improvers selected from the group consisting of a compound having an amide group, a compound having an imide group, a lactam compound, and a compound having a glycidyl group. The capacitor described. The dielectric layer surface formed by oxidizing the surface of the anode made of a porous body of valve metal contains a π-conjugated conductive polymer, a polyanion, an ion conductive compound, and a solvent, and has a pH of 4 at 25 ° C. Attaching a conductive polymer solution that is ~ 13 ;
Dielectric layer surface to the conductive polymer solution was deposited possess and drying the,
A method for producing a capacitor, wherein the ion conductive compound is a compound having a structure represented by the following chemical formula (I) :
(I)-(RO) _n-
(In formula (I), R represents one or more selected from the group consisting of substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, and substituted or unsubstituted phenylene. N is 4 to 2,000. Is an integer.)

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