JP5492595B2 - Capacitor and manufacturing method thereof - Google Patents

Description

  The present invention relates to a capacitor such as an aluminum electrolytic capacitor, a tantalum electrolytic capacitor, a niobium electrolytic capacitor, and a method for manufacturing the same.

  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”) using an oxide film of a valve metal such as aluminum, tantalum, or niobium 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 technique using a conductive film containing such a π-conjugated system conductive polymer, in a capacitor including the solid electrolyte having the above-described configuration, the solid electrolyte is a π-conjugated system in which a nitrogen-containing aromatic cyclic compound is added. A composition comprising a composition containing a conductive polymer as an essential component has been proposed (Patent Document 2). The composition constituting the solid electrolyte contributes to lowering the equivalent series resistance (hereinafter referred to as ESR) of the capacitor and has a feature that the capacitor can be easily manufactured. In addition, a capacitor which is a composition containing a π-conjugated conductive polymer whose pH is adjusted to 3 to 13 by neutralizing the solid electrolyte is also proposed, and has a feature that the leakage current is small and the capacitance is large. (Patent Document 3)

  Further, a solid electrolyte for a capacitor in which a composition containing π-conjugated conductive polymer, polyether, and low resistance agent, which are neutralized and adjusted to pH 3 to 9, as essential components, is in direct contact with the outer dielectric layer is also proposed. (Patent Document 4). This composition is characterized in that, together with the low ESR and high capacity of the capacitor, it is possible to realize a high breakdown voltage device that could not be achieved by the conventional method for producing a solid electrolyte in electrolysis or chemical polymerization.

  Patent Documents 5 and 6 also disclose a technique using a π-conjugated conductive polymer as a solid electrolyte. As a specific example, the chemistry of conventional ethylenedioxythiophene (EDOT) is disclosed. There is no significant improvement over the performance obtained by polymerization.

  On the other hand, a technique using sorbitol and mannitol as a highly conductive agent for improving the conductivity of the solid electrolyte has been proposed (Cited document 7, Cited document 8). However, these techniques have a problem with respect to changes in capacitor characteristics in a high-temperature process such as solder reflow.

  In addition, in a solid electrolytic capacitor in which a solid electrolyte is formed by an in-situ polymerization method, a technique for reducing pressure increase due to moisture in surface mounting at a high temperature has been proposed (see Patent Document 9).

JP 2003-37024 A Japanese Patent Laid-Open No. 2006-100774 JP 2006-287182 A JP 2008-109065 A US Patent Application Publication No. 2007/0064376 US Patent Application Publication No. 2008/0005878 Special table 2009-508341 Special table 2009-508342 gazette JP 2001-148331 A

  The present invention is based on these inventions, and maintains the characteristics that the listed capacitance is large, the ESR is low, the leakage current is small, the withstand voltage is high, and the high temperature treatment process in the reflow process An object of the present invention is to provide a capacitor with little change in characteristics as a capacitor and improved heat resistance even after passing through and a method for manufacturing the same.

  In order to solve the above problems, according to one aspect of the present invention, an anode made of a porous body of valve metal, a dielectric layer formed by oxidizing the anode surface, and formed on the surface of the dielectric layer. The solid electrolyte layer includes a cationized conductive polymer (a), a polymer anion salt (b), or a polymer anion salt (b) and an anion salt (c). An oxidation inhibitor comprising at least one binder (d) selected from polyesters, polyurethanes, acrylics, epoxies, polyamides, polyacrylamides and silane coupling agents, and saccharides and / or sugar alcohols A solid electrolyte layer comprising a conductive polymer (a) and a polymer anion salt (b), or a conductive polymer (a), a polymer anion salt (b) and an a Based on 100 parts by weight of the on-salt (c), 10 to 200 parts by weight of binder (d), provides a capacitor comprising 50 parts by mass or more of the oxidation inhibiting component (e).

  According to another aspect of the present invention, the anode includes a valve metal porous body, a dielectric layer formed by oxidizing the anode surface, and a solid electrolyte layer formed on the surface of the dielectric layer. In the method for producing a capacitor, the solid electrolyte layer comprises a cationized conductive polymer (a), a polymer anion salt (b), a polymer anion salt (b) and an anion salt (c), polyesters, polyurethane One or more binders (d) selected from styrene, acrylics, epoxies, polyamides, polyacrylamides and silane coupling agents, and an oxidation-inhibiting component (e) comprising saccharides and / or sugar alcohols , A solvent, and the solid electrolyte layer comprises a conductive polymer (a) and a polymer anion salt (b), or a conductive polymer (a), a polymer anion salt (b) and an anion salt ( The conductive polymer solution containing 10 to 200 parts by weight of the binder (d) and 50 parts by weight or more of the oxidation-inhibiting component (e) and adjusted to pH 3 to 12 with respect to 100 parts by weight of the total amount of Provided is a method for producing a capacitor formed so as to contain 7% by mass or less of moisture (f) by dipping or coating and drying.

  The present invention makes it possible to maintain excellent characteristics such as a high capacitance, low ESR, and high withstand voltage of a capacitor, and to improve heat resistance.

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

  Next, an embodiment of the present invention will be described with reference to the drawings. In the following description of the drawings, the same or similar parts are denoted by the same or similar reference numerals. However, it should be noted that the drawings are schematic, and dimensions, ratios, and the like in the drawings are different from actual ones and should be determined in consideration of the following description.

  Further, the following embodiments exemplify configurations and methods for embodying the technical idea of the present invention, and the embodiments of the present invention specify the contents of the invention as follows. Not what you want to do. Various modifications can be made to the embodiment of the present invention within the scope of the claims.

<Capacitor>
One 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 includes a cationized conductive polymer (a) and a polymer anion salt (b), or a polymer anion salt (b) and an anion salt (c), polyesters, polyurethanes, acrylics, A solid electrolyte comprising one or more binders (d) selected from epoxies, polyamides, polyacrylamides and silane coupling agents, and an oxidation inhibitory component (e) comprising saccharides and / or sugar alcohols The layer is 10 to 10 parts by mass with respect to 100 parts by mass of the total amount of the conductive polymer (a) and the polymer anion salt (b), or the conductive polymer (a), the polymer anion salt (b) and the anion salt (c). It contains 200 parts by weight of the binder (d) and 50 parts by weight or more of the oxidation inhibitory component (e). The thickness of the solid electrolyte layer 13 is preferably 1 to 100 μm.

[Conductive polymer]
As the conductive polymer, any organic polymer having a π-conjugated main chain can be used. 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 conductive polymer is not substituted, sufficient conductivity can be obtained. However, in order to further improve the conductivity, an alkyl group, a carboxy group, a sulfo group, an alkoxy group, a hydroxy group, a cyano group, etc. It is preferable to introduce a functional group into the conductive polymer.

  Specific examples of such conductive polymers include polypyrrole, poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3-carboxypyrrole) , Poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole), poly (3 -Methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly 3-methyl-4-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole), poly (thiophene), poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propyl Thiophene), poly (3-butylthiophene), poly (3-hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene) , Poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly (3-hydride) Xylthiophene), 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-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene), poly (3,4 4-diheptyloxythiophene), poly (3,4-dioctyloxythiophene) ), Poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), Poly (3,4-butenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3-methyl-4-ethoxythiophene), 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), Examples include poly (2-aniline sulfonic acid), poly (3-aniline sulfonic 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 because they have higher conductivity and improved heat resistance.

  The conductive polymer can be easily produced by chemical oxidative polymerization of a precursor monomer that forms the conductive polymer in a solvent in the presence of a suitable oxidizing agent, an oxidation catalyst, and a polymer anion described below.

[Precursor monomer]
The precursor monomer has a π-conjugated system in the molecule, and a π-conjugated system is formed in the main chain even when polymerized by the action of an appropriate oxidizing agent. Examples thereof include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.

  Specific examples of the precursor monomer include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxypyrrole, 3-methyl-4-carboxypyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3 -Ethylthiophene, 3-propylthiophene, -Butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3 -Cyanothiophene, 3-phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3 -Heptyloxythiophene, 3-octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxy Offene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene 3,4-didecyloxythiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3-methyl- 4-methoxythiophene, 3-methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, aniline, 2-methylaniline, 3-isobutylaniline, Examples include 2-aniline sulfonic acid and 3-aniline sulfonic acid.

[solvent]
The solvent used in the production of the conductive polymer is not particularly limited, and may be any solvent that can dissolve or disperse the precursor monomer and can maintain the oxidizing power of the oxidizing agent and the oxidation catalyst. . For example, polar solvents such as water, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylene phosphortriamide, acetonitrile, benzonitrile, cresol, phenol, xylenol, etc. Phenols, alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, hydrocarbons such as hexane, benzene and toluene, carboxylic acids such as formic acid and acetic acid, ethylene carbonate, propylene carbonate, etc. Carbonate compounds, ether compounds such as dioxane, diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether Chain ethers such as polypropylene glycol dialkyl ether, 3-methyl-2-oxazolidinone heterocyclic compounds such as, acetonitrile, glutarodinitrile, methoxy acetonitrile, propionitrile, nitrile compounds such as benzonitrile and the like. These solvents may be used alone, as a mixture of two or more kinds, or as a mixture with other organic solvents.

[moisture]
The solid electrolyte of this embodiment contains moisture. The presence of an appropriate amount of moisture can improve the capacitance and lower the ESR. This is presumably related to the fact that the solid electrolyte of this embodiment contains a large amount of polymer anions such as polystyrene sulfonic acid. A moisture content of 7% by mass or less can be preferably used. Preferably it is 5 mass% or less. 4 mass% or less is more preferable. If the moisture content is more than 7% by mass, the film quality of the solid electrolyte tends to be weak, the high temperature heat resistance of the solid electrolytic capacitor is deteriorated, and the electrostatic capacity and ESR are liable to deteriorate with long-term durability. Further, when the water content is 0.1% by mass or less, a decrease in capacitance is observed. In the present invention, if the water content is in the range of 0.1 to 7% by mass, it is possible to achieve both capacitance and ESR. Furthermore, the outstanding long-term durability can be expressed by adjusting the water content to 4% by mass or less.

  The adjustment of the amount of water in the solid electrolyte can be controlled by the drying conditions, the drying atmosphere, and the like. For example, the drying temperature can be performed in a temperature range of 100 to 300 ° C. In addition, the moisture content can be suitably adjusted even in a reduced pressure atmosphere.

[Oxidizing agent and oxidation catalyst]
The oxidizing agent and the oxidation catalyst are not particularly limited as long as they can oxidize the precursor monomer to obtain a conductive polymer. Examples thereof include ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate. Peroxodisulfate, ferric chloride, ferric sulfate, ferric nitrate, transition metal compounds such as cupric chloride, metal halides such as boron trifluoride, aluminum chloride, silver oxide, cesium oxide Metal oxides such as hydrogen peroxide and ozone, organic peroxides such as benzoyl peroxide, oxygen and the like.

[Polymer anion]
The polymer anion refers to a polymer having an anion group in the side chain of the polymer.

  The anionic group may be any functional group that can cause chemical oxidation doping to the conductive polymer. Among these, from the viewpoint of ease of production and stability, a monosubstituted sulfate group and a monosubstituted phosphate ester Group, phosphoric acid group, carboxy group, 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 carboxy group are more preferable.

  Examples of the polymer include substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted polyester, and copolymers thereof. , Comprising a structural unit having an anionic group, or comprising a structural unit having an anionic group and a structural unit having no anionic group.

  The anion group of the polymer anion functions as a dopant for the conductive polymer, and improves the conductivity and heat resistance of the conductive polymer.

  Specific examples of the polymer anion include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfonic acid, polyvinyl Examples thereof include carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, and polyacrylic acid. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.

  Of these, polystyrene sulfonic acid, polyacryl sulfonic acid, and polymethacryl sulfonic acid are preferable. Polyacrylsulfonic acid and polymethacrylsulfonic acid are excellent in heat resistance and environmental resistance because thermal decomposition of the π-conjugated conductive polymer component is relaxed by absorbing thermal energy and decomposing by itself.

  The degree of polymerization of the polymer anion 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.

  Examples of the method for producing a polymer anion include a method of directly introducing an anion group into a polymer having no anion group using an acid, a method of sulfonating a polymer having no anion group with a sulfonating agent, and an anion group containing The method of manufacturing by superposing | polymerizing a polymerizable monomer is mentioned.

  Examples of the method for producing an anion group-containing polymerizable monomer by polymerization include a method for producing an anion group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst. Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, kept at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, an anionic group-containing polymerizable monomer may be copolymerized with a polymerizable monomer having no anionic group.

  The oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the π-conjugated conductive polymer. When the obtained polymer is a polymer anion salt, it is preferably transformed into a polymer anion acid. Examples of the method for changing to an anionic acid include an ion exchange method using an ion exchange resin, an ultrafiltration method, and the like. Among these, an ultrafiltration method is preferable from the viewpoint of easy work.

  The anionic group-containing polymerizable monomer is one in which a part of the monomer is substituted with a mono-substituted sulfate group, a carboxy group, a sulfo group, etc., for example, a substituted or unsubstituted ethylene sulfonic acid compound, a substituted or unsubstituted Styrene sulfonic acid compound, substituted or unsubstituted acrylate sulfonic acid compound, substituted or unsubstituted methacrylate sulfonic acid compound, substituted or unsubstituted acrylamide sulfonic acid compound, substituted or unsubstituted cyclovinylene sulfonic acid compound, substituted or unsubstituted And a substituted or unsubstituted vinyl aromatic sulfonic acid compound.

Specifically, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, methallyl sulfonic acid and its salts, styrene sulfonic acid and its salts, methallyloxybenzene sulfonic acid and its salts, allyloxybenzene sulfonic acid and Salts thereof, α-methylstyrenesulfonic acid and salts thereof, acrylamide-t-butylsulfonic acid and salts thereof, 2-acrylamido-2-methylpropanesulfonic acid and salts thereof, cyclobutene-3-sulfonic acid and salts thereof, isoprenesulfone Acid and salts thereof, 1,3-butadiene-1-sulfonic acid and salts thereof, 1-methyl-1,3-butadiene-2-sulfonic acid and salts thereof, 1-methyl-1,3-butadiene-4-sulfone acid and salts thereof, ethyl acrylate sulfonic acid _(CH 2 CH-C _{OO- (CH 2) 2 -SO 3} H) and its salts, acrylic acid propyl sulfonic acid _{(CH 2 CH-COO- (CH} 2) 3 -SO 3 H) and its salts, acrylic acid -t- butyl sulfonic acid _{(CH 2 CH-COO-C} (CH 3) 2 CH 2 -SO 3 H) and its salts, acrylic acid -n- butyl sulfonic acid _{(CH 2 CH-COO- (CH} 2) 4 -SO 3 H) and its salts, allyl ethyl sulfonic acid _{(CH 2 CHCH 2 -COO- (CH} 2) 2 -SO 3 H) and its salts, allyl acid -t- butyl sulfonic acid _{(CH 2 CHCH 2 -COO-C} (CH 3 ) ₂ CH ₂ -SO ₃ H) and salts thereof, 4-pentenoic acid ethyl sulfonic acid _{(CH 2 CH (CH 2)} 2 -COO- (CH 2) 2 -SO 3 H) and its salts, 4 Pentenoic acid propyl sulfonic acid _{(CH 2 CH (CH 2)} 2 -COO- (CH 2) 3 -SO 3 H) and salts thereof, 4-pentenoic acid -n- butyl sulfonic acid _{(CH 2 CH (CH 2)} 2 _{-COO- (CH 2) 4 -SO 3} H) and salts thereof, 4-pentenoic acid -t- butyl sulfonic acid _{(CH 2 CH (CH 2)} 2 -COO-C (CH 3) 2 CH 2 -SO 3 H) and its salts, 4-pentenoic acid phenylene sulfonic acid _{(CH 2 CH (CH 2)} 2 -COO-C 6 H 4 -SO 3 H) and salts thereof, 4-pentenoic acid naphthalenesulfonic acid _(CH 2 CH ( _{CH 2) 2 -COO-C 10} H 8 -SO 3 H) and salts thereof, ethyl methacrylate sulfonic acid _{(CH 2 C (CH 3)} -COO- (CH 2) 2 -SO 3 H) and Salts, propyl methacrylate sulfonic acid _{(CH 2 C (CH 3)} -COO- (CH 2) 3 -SO 3 H) and its salts, methacrylic acid -t- butyl sulfonic acid _{(CH 2 C (CH 3)} - _{COO-C (CH 3) 2} CH 2 -SO 3 H) and its salts, methacrylic acid -n- butyl sulfonic acid _{(CH 2 C (CH 3)} -COO- (CH 2) 4 -SO 3 H) and its salts, methacrylic acid phenylene sulfonic acid _{(CH 2 C (CH 3)} -COO-C 6 H 4 -SO 3 H) and its salts, methacrylic acid naphthalenesulfonic acid _{(CH 2 C (CH 3)} -COO-C 10 H ₈ -SO 3 _H) and salts thereof, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, Li-2-acrylamido-2-methylpropanesulfonic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. Moreover, the copolymer containing 2 or more types of these may be sufficient.

  Examples of the polymerizable monomer having no anionic group include ethylene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, styrene, p-methylstyrene, p. -Ethylstyrene, p-butylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, α-methylstyrene, 2-vinylnaphthalene, 6-methyl-2-vinylnaphthalene, 1-vinylimidazole, vinylpyridine, Vinyl acetate, acrylaldehyde, acrylonitrile, N-vinyl-2-pyrrolidone, N-vinylacetamide, N-vinylformamide, N-vinylimidazole, acrylamide, N, N-dimethylacrylamide, acrylic acid, methyl acrylate, Ethyl acrylate, propyl acrylate, acrylic acid -Butyl, i-butyl acrylate, t-butyl acrylate, isooctyl acrylate, isononyl butyl acrylate, lauryl acrylate, allyl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, benzyl acrylate, acrylic Ethyl carbitol, phenoxyethyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, methoxybutyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i methacrylate -Butyl, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, methacrylic acid Benzyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acryloylmorpholine, vinylamine, N, N-dimethylvinylamine, N, N-diethylvinylamine, N, N-dibutylvinylamine, N, N-di -T-butylvinylamine, N, N-diphenylvinylamine, N-vinylcarbazole, vinyl alcohol, vinyl chloride, vinyl fluoride, methyl vinyl ether, ethyl vinyl ether, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 2-methylcyclohexene, vinylphenol, 1,3-butadiene, 1-methyl-1,3-butadiene, 2-methyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene, 1,2- Dimethyl , 3-butadiene, 1,3-dimethyl-1,3-butadiene, 1-octyl-1,3-butadiene, 2-octyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 2-phenyl -1,3-butadiene, 1-hydroxy-1,3-butadiene, 2-hydroxy-1,3-butadiene and the like.

  Solvent solubility can be controlled by copolymerizing these polymerizable monomers having no anionic group.

  The amount of the polymer anion in the conductive composite particles can be suitably used as long as the conductive polymer can be stably dissolved or dispersed in the solvent, and is not particularly limited. Preferably, the molar amount of the anion group in the polymer anion is in the range of 1 to 5 times the molar amount of the conductive polymer. Within this range, the conductive composite particles can achieve both high conductivity and stable dispersibility. When the amount is less than 1 times, the dispersibility tends to deteriorate, and when the amount is more than 5 times, the conductivity tends to decrease.

[Monomer anion]
The monomer anion has an anion group and functions as a conductive polymer dopant.

  As the organic carboxylic acid, aliphatic, aromatic, cycloaliphatic and the like containing one or more carboxy groups can be used. For example, formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, nitroacetic acid, And triphenylacetic acid.

  As the organic sulfonic acid, aliphatic, aromatic, cycloaliphatic or the like containing one or more sulfo groups, or a polymer containing sulfo groups can be used.

  As one containing one sulfo group, for example, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1 -Nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, 1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid, 2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfone Acid, trifluoroethanesulfonic acid, colistin methanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 2-amino-5-naphthol- 7-sulfonic acid, 3-aminopropanesulfone N-cyclohexyl-3-aminopropanesulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hex Tylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, 2, 4-dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid 4-amino-2-chlorotoluene-5-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-amino-5-methoxy-2-methylbenzenesulfonic acid, 2-amino-5-methyl Benzene-1-sulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4 -Acetamide-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, 4 -Amino-1-naphthalenesulfonic acid, 8-chloronaphthalene-1- Examples include sulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, anthraquinone sulfonic acid, and pyrene sulfonic acid. These metal salts can also be used.

  Examples of those containing two or more sulfo groups include ethanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, decanedisulfonic acid, o-benzenedisulfonic acid, m-benzenedisulfonic acid, p-benzenedisulfonic acid, and toluenedisulfonic acid. , Xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, dimethylbenzene disulfonic acid, diethylbenzene disulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 3,4-dihydroxy-1,3 Benzene disulfonic acid, naphthalene disulfonic acid, methyl naphthalene disulfonic acid, ethyl naphthalene disulfonic acid, pentadecyl naphthalene disulfonic acid, 3-amino-5-hydroxy-2,7-naphthalene disulfonic acid, 1- Cetamide-8-hydroxy-3,6-naphthalenedisulfonic acid, 2-amino-1,4-benzenedisulfonic acid, 1-amino-3,8-naphthalenedisulfonic acid, 3-amino-1,5-naphthalenedisulfonic acid, 8-Amino-1-naphthol-3,6-disulfonic acid, 4-amino-5-naphthol-2,7-disulfonic acid, 4-acetamido-4'-isothio-cyanotostilbene-2,2'-disulfonic acid 4-acetamido-4′-isothiocyanatostilbene-2,2′-disulfonic acid, 4-acetamido-4′-maleimidylstilbene-2,2′-disulfonic acid, naphthalenetrisulfonic acid, dinaphthylmethanedisulfone An acid, anthraquinone disulfonic acid, anthracene sulfonic acid, etc. are mentioned. These metal salts can also be used.

[PH adjuster]
The polymer anion salt and the monomer anion salt can be configured using a pH adjuster, and the pH is adjusted to 3 to 9. The pH adjustment may be appropriately performed using a pH adjuster. Examples of the pH adjuster include alkalis, amines, imidazoles, pyridines, and the like.

  Examples of the alkali include sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia. Examples of amines include aliphatic amines such as ethylamine, diethylamine, methylethylamine, and triethylamine, aromatic amines such as aniline, benzylamine, pyrrole, imidazole, and pyridine, or derivatives thereof, pyrrole, sodium methoxide, and the like. And metal alkoxides such as sodium alkoxide such as sodium ethoxide, potassium alkoxide and calcium alkoxide.

  Among these, weakly basic aliphatic amines, imidazoles, pyridines, and metal alkoxides are preferable.

  Specific examples of imidazoles and derivatives thereof include imidazole, 2-methylimidazole, 2-propylimidazole, 2-undecylimidazole, 2-phenylimidazole, N-methylimidazole, 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, dimethyl 4,5-imidazole dicarboxylate, benzimidazole, 2-aminobenz Imidazole, 2-amino-base lens imidazole-2-sulfonic acid, 2-amino-1-methyl-base lens imidazole, 2-hydroxy-base lens imidazole, 2- (2-pyridyl) base lens 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.

[Conductivity improver]
Since the solid electrolyte layer has higher conductivity, it is preferable to further contain a conductivity improver. Here, the conductivity improver interacts with the conductive polymer or the dopant of the conductive polymer to improve the electrical conductivity of the 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 hydroxy groups, a compound having two or more carboxy groups, 1 It is one or more compounds selected from the group consisting of compounds having one or more hydroxy groups and one or more carboxy groups, compounds having amide groups, compounds having imide groups, lactam compounds, and compounds having glycidyl groups. Is preferred. Moreover, it is preferable that this electroconductivity improvement agent is contained more than the total amount of a conductive polymer, a polymer anion salt, and / or an anion salt.

-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.

  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 hydroxy group, a carboxy 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- Lysine methanol, 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.

  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, alkyl group, hydroxy group, carboxy group, cyano group, phenyl group, phenol group, ester group, alkoxyl group, carbonyl group, etc. 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, preferably in the range of 0.5 to 30 mol, per 1 mol of the polymer anion and / or anion group unit of the anion. From the viewpoint of the physical properties and conductivity of the solid electrolyte layer 13, the range of 1 to 10 mol is particularly preferable. 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 and the polymer anion and / or the anion and the conductive polymer tends to be weak. , Conductivity may be insufficient. In addition, when the nitrogen-containing aromatic cyclic compound exceeds 100 mol, the content of the conductive polymer is reduced, and it is difficult to obtain sufficient conductivity, and the physical properties of the solid electrolyte layer 13 change. There is.

-Compound having two or more hydroxy groups Examples of the compound having two or more hydroxy groups include propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, diglycerin, isoprene glycol, di- Methylolpropionic acid, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, thiodiethanol, tartaric acid, D-glucaric acid, Polyhydric aliphatic alcohols such as glutaconic acid; polymeric alcohols such as polyvinyl alcohol and cellulose; 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 2,3-dihydroxy-1-pentadecylbenzene, 2, 4-jihi Roxyacetophenone, 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-dihydroxybenzoic acid, 1,4-hydroquinonesulfonic acid and its salts, 4,5-hydroxybenzene- 1,3-disulfonic acid and its 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-dihydroxynaphthoic acid, 1,4-dihydroxy-2-naphthoic acid phenyl ester, 4,5-dihydroxynaphthalene-2,7-disulfonic acid and Salts thereof, 1,8-dihydroxy-3,6-naphthalenedisulfonic acid and salts thereof, 6,7-dihydroxy-2-naphthalenesulfonic acid and salts thereof, 1,2,3-trihydroxybenzene (pyrogallol), 1, 2,4-trihydroxybenzene, 5-methyl-1,2,3-tri Hydroxybenzene, 5-ethyl-1,2,3-trihydroxybenzene, 5-propyl-1,2,3-trihydroxybenzene, trihydroxybenzoic acid, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzoaldehyde, tri Aromatics such as hydroxyanthraquinone, 2,4,6-trihydroxybenzene, tetrahydroxy-p-benzoquinone, tetrahydroxyanthraquinone, methyl garlic acid (methyl gallate), ethyl garlic acid (ethyl gallate), potassium hydroquinone sulfonate Compounds and the like.

  The content of the compound having two or more hydroxy groups is preferably in the range of 0.05 to 50 mol with respect to 1 mol of the anion group of the polymer anion and / or anion, A range is more preferable. If the content of the compound having two or more hydroxy groups is less than 0.05 mol relative to 1 mol of the polymer anion and / or anion group unit of the anion, conductivity and heat resistance may be insufficient. When the content of the compound having two or more hydroxy groups is more than 50 moles per mole of the polymer anion and / or anion group unit of the anion, the content of the conductive polymer in the solid electrolyte layer 13 However, it is difficult to obtain sufficient conductivity, and the physical properties of the solid electrolyte layer 13 may change.

-Compound having two or more carboxy groups Examples of the compound having two or more carboxy groups include 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, citric acid; phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride, 5-sulfoisophthalic acid, 5-hydroxyisophthalic acid, methyltetrahydroanhydride At least one aromatic ring such as phthalic acid, 4,4′-oxydiphthalic acid, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid An aromatic carboxylic acid compound having a carboxy group bonded thereto; Recall acid, oxy two acid, thio-diacetic acid, thiodipropionic acid, iminodiacetic acid, etc. imino acid are exemplified.

  The compound having two or more carboxy groups is preferably in the range of 0.1 to 30 mol, and in the range of 0.3 to 10 mol, with respect to 1 mol of the polymer anion and / or anion group unit of the anion. It is more preferable. When the content of the compound having two or more carboxy groups is less than 0.1 mol relative to 1 mol of the polymer anion and / or anion group unit of the anion, conductivity and heat resistance may be insufficient. When the content of the compound having two or more carboxy groups is more than 30 mol per mol of the polymer anion and / or anion group unit of the anion, the content of the conductive polymer in the solid electrolyte layer 13 is increased. As a result, it is difficult to obtain sufficient conductivity, and the physical properties of the solid electrolyte layer 13 may change.

-A compound having one or more hydroxy groups and one or more carboxy groups As a compound having one or more hydroxy groups and one or more carboxy 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 hydroxy groups and one or more carboxy groups is 1 to 5,000 parts by mass with respect to 100 parts by mass in total of the polymer anion salt and / or the anion salt and the conductive polymer. It is preferable that it is 50 to 500 parts by mass. When the content of the compound having one or more hydroxy groups and one or more carboxy groups is less than 1 part by mass, conductivity and heat resistance may be insufficient. In addition, when the content of the compound having one or more hydroxy groups and one or more carboxy groups is more than 5,000 parts by mass, the content of the conductive polymer in the solid electrolyte layer 13 is decreased, which is also sufficient. It is difficult to obtain high 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 preferably 50 to 500 parts by mass with respect to 100 parts by mass of the polymer anion salt and / or the anion salt and the conductive polymer. More preferred. 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 conductive polymer in the solid electrolyte layer 13 decreases, and it is difficult to obtain sufficient conductivity.

-Imide compound As an imide 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, and preferably 50 to 5,000 parts by mass with respect to 100 parts by mass in total of the conductive polymer and the polymer anion and / or anion. More preferred. If the amount of the imide compound added is less than the lower limit, the effect of adding the imide compound is reduced, which is not preferable. Moreover, when the said upper limit is exceeded, since the electroconductive fall resulting from the electroconductive polymer density | concentration fall will arise, 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.

-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.

-Organic solvent Moreover, when a part of organic solvent remains in the solid electrolyte layer 13, it functions as a conductive improvement agent. 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 -Multivalents such as butylene glycol, glycerin, diglycerin, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol Aliphatic alcohols, carbonate compounds such as ethylene carbonate and propylene carbonate, ether compounds such as dioxane and diethyl ether, chain ethers such as dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether and polypropylene glycol dialkyl ether, 3- Examples include heterocyclic compounds such as methyl-2-oxazolidinone, and nitrile compounds such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, and benzonitrile. These solvents may be used alone or as a mixture of two or more.

-Ether compound Among the conductivity improvers, an ether compound represented by the following chemical formula (I) is preferable because the withstand voltage of the capacitor 10 becomes higher.

(I) X- (RO) _n -Y
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.

  X represents one or more selected from the group consisting of a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted aryl group. Represent.

  Y represents one or more selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted aryl group.

  Examples of the substituent in the case where X and Y are substituted with a substituent include an alkyl group, a hydroxy 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.

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

  Specific examples of the polymer represented by the chemical formula (I) include diethylene glycol, triethylene glycol, oligopolyethylene glycol, triethylene glycol monochlorohydrin, diethylene glycol monochlorohydrin, oligoethylene glycol monochlorohydrin, triethylene glycol monobromide. Dorin, diethylene glycol monobromohydrin, oligoethylene glycol monobromohydrin, polyethylene glycol, polyether, glycidyl ethers, polyethylene glycol glycidyl ethers, polyethylene oxide, triethylene glycol monobutyl ether, triethylene glycol monoethyl ether, triethylene glycol monomethyl Ether, tetraethylene glycol monobutyl ether Etc., Triethylene glycol / dimethyl ether, tetraethylene glycol / dimethyl ether, diethylene glycol / dimethyl ether, diethylene glycol / diethyl ether / diethylene glycol / dibutyl ether, dipropylene glycol, tripropylene glycol, polypropylene glycol, polypropylene dioxide, polyoxyethylene alkyl ether, poly Examples thereof include oxyethylene glycerin fatty acid ester and polyoxyethylene fatty acid amide.

  The content of the ether compound is preferably 1 to 10,000 parts by mass, and preferably 50 to 1,500 parts by mass with respect to 100 parts by mass in total of the conductive polymer and the polymer anion salt and / or anion salt. It is more preferable that When the content of the ether compound is less than 1 part by mass, the withstand voltage of the capacitor 10 may not be increased. When the content exceeds 10,000 parts by mass, the conductivity of the solid electrolyte layer 13 is decreased, and the ESR of the capacitor 10 is decreased. Tend to be higher.

[Binder]
One or more binders used in this embodiment can be added from polyesters, polyurethanes, acrylics, epoxies, polyamides, polyacrylamides, and silane coupling agents.

  The binder is not particularly limited as long as it is compatible or mixed and dispersed with the conductive polymer or polymer anion and / or anion, 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.

  The silane coupling agent is a compound represented by the following chemical formula (I).

Formula _(I) X 3 -Si-Y
In formula (I), X represents an alkoxyl group or a halogen atom. Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Y is one or more selected from the group consisting of a substituted or unsubstituted vinyl group, epoxy group, styryl group, methacryloxy group, acryloxy group, amino group, ureido group, chloropropyl group, mercapto group, sulfide group, and isocyanate group. Represents a group of

  Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Methyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (amino Til) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl- N- (1,3-dimethylethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3 -Ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysila And the like.

  The addition amount is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the conductive polymer and the polymer anion salt and / or the composite conductor of the anion salt.

[Oxidation inhibiting component]
Examples of the oxidation inhibitory component used in the present embodiment include saccharides, sugar alcohols, polyhydroxys and the like.

  Specific examples include sugars and sugar derivatives such as sucrose, glucose, lactose, maltose, and xylose; sugar alcohols such as sorbitol, xylitol, erythritol, mannitol, dipentaerythritol, and pentaerythritol.

  Among them, mannitol, erythritol, pentaerythritol, dipentaerythritol, xylose, and glucose are superior in heat resistance from their melting points.

  The amount added is preferably 10 to 10,000 parts by weight, and more preferably 50 to 1,000 parts by weight with respect to 100 parts by weight of the composite conductor of conductive polymer and polymer anion salt and / or anion salt. . 100-400 mass parts is the most preferable from a viewpoint of the electroconductivity and film forming property of a solid electrolyte composition.

  When the addition amount is less than 10 parts by mass, it is difficult to obtain desired heat resistance performance. On the other hand, when the addition amount exceeds 10,000 parts by mass, the conductivity of the solid electrolyte composition tends to deteriorate, and it is not preferable because it does not dissolve in the solvent.

[Electrolyte]
If necessary, an electrolytic solution may also be used. The electrolytic solution is not particularly limited as long as it has high conductivity, and a known electrolyte is dissolved in a known solvent.

  Examples of the solvent in the electrolytic solution 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, aminoethanol, aminopropanediol, 3-amino-1-propanol, etc. ), Secondary amines (dimethylamine, diethylamine, dipropy Amine, methylethylamine, diphenylamine, iminodiethanol, ethylaminopropanol, etc.), tertiary amine (trimethylamine, triethylamine, tripropylamine, triphenylamine, 1,8-diazabicyclo (5,4,0) -undecene-7, nitrilo Ethanol, etc.), tetraalkylammonium (tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, dimethyldiethylammonium, etc.) and the like. The addition amount is not particularly limited.

(Separator)
As the separator 15 used in the solid electrolytic capacitor of the present embodiment, known natural fibers and artificial fibers can be preferably used. There is no particular limitation here.

(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.

  The solid electrolyte layer 13 of the capacitor 10 described above includes one or more binders selected from polyesters, polyurethanes, acrylics, epoxies, polyamides, polyacrylamides, and silane coupling agents, saccharides, and / or An oxidation inhibitory component comprising sugar alcohols is used. With such a composition of the solid electrolyte layer 13, the capacitor of this embodiment has excellent characteristics such as a large capacitance, a low ESR, a small leakage current, and a high withstand voltage, and further a reflow process. The heat resistance is also improved with little change in characteristics as a capacitor even after a high temperature treatment process.

<Capacitor manufacturing method>
Next, a method for manufacturing the capacitor 10 will be described.

  The method of manufacturing a capacitor according to this embodiment includes a capacitor intermediate dielectric layer 12 having an anode 11 made of a porous body of valve metal and an oxide film dielectric layer 12 formed by oxidizing the surface of the anode 11. In this method, a conductive polymer solution is applied or immersed on the side surface, and the solid electrolyte layer 13 is formed in direct contact therewith.

  The conductive polymer solution in this production method has a polymer anion and / or monomer anion adjusted to pH 3 to 9 and a conductive polymer, a melting point of 80 ° C. or higher and lower than 280 ° C., and has 4 or more hydroxyl groups in the molecule. An aliphatic compound and a solvent are included. Moreover, it is not restricted to this range, It is also preferable to set it as pH 3-12.

  To prepare a conductive polymer solution, first, a precursor monomer such as unsubstituted aniline, pyrrole, or thiophene that forms a conductive polymer is added to a solution obtained by dissolving a polymer anion in a solvent. . Next, an oxidizing agent is added to polymerize the monomer, and then the excess oxidizing agent and monomer are separated and purified to obtain a conductive polymer solution.

  The solvent contained in the conductive polymer solution is not particularly limited. For example, alcohol solvents such as methanol, ethanol, isopropanol (IPA), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DMF) Amide solvents such as methyl ethyl ketone (MEK), acetone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, toluene, xylene and water. These may be used alone or in combination. Among these, from the viewpoint of environmental protection in recent years, water and alcohol solvents having a low environmental load are preferable.

  Examples of the method for applying the conductive polymer solution include known methods such as coating, dipping, and spraying. Examples of the drying method include known methods such as hot air drying.

  After the solid electrolyte layer 13 is formed, the cathode metal layer 14 can be formed by a known technique in which the cathode metal layer 14 is formed with a carbon paste or a silver paste, or the cathode electrode is opposed via a separator. .

  The manufacturing method described above forms the solid electrolyte layer 13 by applying and drying a conductive polymer solution, so that the process is simple, suitable for mass production, and low cost.

  The solid electrolyte layer 13 may be formed by chemical oxidative polymerization or electrolytic polymerization if the simplicity of the process and cost are not taken into consideration.

  In chemical oxidative polymerization, a precursor monomer solution such as substituted or unsubstituted aniline, pyrrole, or thiophene that forms a conductive polymer, and an oxidant solution are prepared, and a capacitor intermediate is alternately immersed in the capacitor. A conductive polymer is formed on the dielectric layer side surface of the intermediate. As the oxidizing agent, those similar to the above production method can be used.

  The dopant may be dissolved in the monomer solution or the oxidant solution at the same time, or after the conductive polymer is formed, a solution in which the dopant is dissolved in the solvent may be permeated into the conductive polymer and added.

  In electropolymerization, first, a precursor monomer such as unsubstituted aniline, pyrrole, or thiophene that forms a conductive polymer is added to a solvent such as acetonitrile, and a conductive layer is formed on the surface of the electrolytic cell to which a dopant is added as an electrolyte. The formed capacitor intermediate is charged as an electrode. Then, polymerization is performed by applying a voltage higher than the oxidation potential of the precursor monomer to form a conductive polymer on the dielectric layer of the capacitor intermediate.

  In the solid electrolyte layer 13, the conductive polymer is often formed as particles having a particle diameter of 1 to 500 nm. For this reason, the conductive polymer does not reach the deepest part of the fine voids on the surface of the dielectric layer of the capacitor intermediate, and it may be difficult to draw out the capacitance. From this, it is preferable to replenish the capacity by forming a solid electrolyte layer 13 and then infiltrating an electrolyte as necessary.

  Drying conditions are not particularly limited here, and are preferably equal to or higher than the boiling point of the main solvent. More preferably, it is 120 ° C. or higher. If the drying temperature is too low, the residual solvent may increase, which is not preferable.

  In the capacitor manufacturing method described above, the solid electrolyte layer 13 of the capacitor 10 uses an aliphatic compound having a melting point of 40 ° C. or higher and 280 ° C. or lower and having four or more hydroxyl groups in the molecule. The capacitor manufactured by such a method has excellent characteristics such as large capacitance, low ESR, small leakage current, and high withstand voltage, and also has a high temperature treatment process in the reflow process. As a result, the heat resistance is improved. Moreover, the method of this embodiment has the characteristics that a process is simple and productivity is high.

  The capacitor and the manufacturing method thereof according to the present invention are not limited to the above-described embodiment. 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 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 first and second embodiments will be described.

[First Embodiment]
(1) Preparation of conductive polymer solution (Preparation Example 1) Preparation of conductive polymer solution (I) 14.2 g of 3,4-ethylenedioxythiophene and 42.6 g of 2,000 ml of ion-exchanged water Of polystyrene sulfonic acid (mass average molecular weight; about 300,000) was mixed at 20 ° C.

  While maintaining the mixed solution thus obtained at 20 ° C. and stirring, 29.64 g of ammonium persulfate and 8.0 g of ferric sulfate oxidation catalyst solution dissolved in 200 ml of ion-exchanged water were added. The reaction was stirred for an hour.

  The resulting reaction solution was dialyzed to remove impure ions, ion-exchanged, and a solution containing about 1.6% by mass of polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) (hereinafter referred to as PEDOT-PSS). A solution).

  And imidazole was added to 100 g of this PEDOT-PSS solution, and the conductive polymer raw material solution (A) of pH 7 was obtained. To 100 g of this conductive polymer raw material solution, 3.2 g of polyethylene glycol having a molecular weight of 1000, 3.2 g of pentaerythritol, and 1.6 g of polyester are mixed and dispersed to obtain a conductive polymer solution (I). It was.

(Preparation Example 2) Preparation of Conductive Polymer Solution (II) Imidazole was added to 100 g of the PEDOT-PSS solution in Preparation Example 1 to obtain a pH 5 conductive polymer raw material solution (B). 4.8 g of triethylene glycol monobutyl ether, 3.2 g of xylitol, 4.8 g of pentaerythritol, and 0.8 g of polyester are mixed and dispersed in 100 g of this conductive polymer raw material solution to obtain a conductive polymer solution. (II) was obtained.

Preparation Example 3 Preparation of Conductive Polymer Solution (III) Imidazole was added to 100 g of the PEDOT-PSS solution in Preparation Example 1 to obtain a conductive polymer raw material solution (C) having a pH of 10. To 100 g of this conductive polymer raw material solution, 0.8 g of hydroxyethyl acrylate, 0.8 g of pentaerythritol, 0.8 g of maltose, and 0.48 g of polyester are mixed and dispersed to obtain a conductive polymer solution (III )

(Preparation Example 4) Preparation of Conductive Polymer Solution (IV) To 100 g of the conductive polymer raw material solution (A) in Preparation Example 1, 3.2 g of polyethylene glycolose having a molecular weight of 1000, 1.6 g of pentaerythritol, 0.8 g 8 g of a silane coupling agent was mixed and dispersed to obtain a conductive polymer solution (IV).

(Preparation Example 5) Preparation of Conductive Polymer Solution (V) 4.8 g of pentaerythritol and 0.16 g of silane coupling agent were mixed with 100 g of the conductive polymer raw material solution (B) in Preparation Example 2. And dispersed to obtain a conductive polymer solution (V).

(Preparation Example 6) Preparation of Conductive Polymer Solution (VI) To 100 g of the conductive polymer raw material solution (C) in Preparation Example 3, 0.8 g of hydroxyethyl acrylate, 3.2 g of erythritol, 1.44 g of polyester 0.16 g of a silane coupling agent was mixed and dispersed to obtain a conductive polymer solution (VI).

Preparation Example 7 Preparation of Conductive Polymer Solution (VII) To 100 g of the conductive polymer raw material solution (A) in Preparation Example 1, 3.2 g of polyethylene glycol having a molecular weight of 1000, 3.2 g of mannitol, 1.6 g Polyester and 1.6 g of a silane coupling agent were mixed and dispersed to obtain a conductive polymer solution (VII).

(Preparation Example 8) Preparation of Conductive Polymer Solution (VIII) To 100 g of the conductive polymer raw material solution (B) in Preparation Example 2, 4.8 g of triethylene glycol monobutyl ether, 0.96 g of mannitol, 0.48 g Were mixed and dispersed to obtain a conductive polymer solution (VIII).

(Preparation Example 9) Preparation of Conductive Polymer Solution (IX) To 100 g of the conductive polymer raw material solution (C) in Preparation Example 3, 0.8 g of hydroxyethyl acrylate, 0.96 g of xylitol, 0.48 g of polyester Were mixed and dispersed to obtain a conductive polymer solution (IX).

(Preparation Example 10) Preparation of Conductive Polymer Solution (X) To 100 g of the conductive polymer raw material solution (A) in Preparation Example 1, 3.2 g of polyethylene glycol having a molecular weight of 1000, 0.48 g of sorbitol, 1.6 g Of xylose and 0.48 g of polyester were mixed and dispersed to obtain a conductive polymer solution (X).

(Preparation Example 11) Preparation of Conductive Polymer Solution (XI) To 100 g of the conductive polymer raw material solution (B) in Preparation Example 2, 4.8 g of triethylene glycol monobutyl ether, 4.8 g of glucose, 0.48 g Were mixed and dispersed to obtain a conductive polymer solution (XI).

(Preparation Example 12) Preparation of Conductive Polymer Solution (XII) To 100 g of the conductive polymer raw material solution (A) in Preparation Example 1, 3.2 g of polyethylene glycol having a molecular weight of 1000, 3.2 g of xylitol, 4.0 g Were mixed and dispersed to obtain a conductive polymer solution (XII).

(Preparation Example 13) Preparation of Conductive Polymer Solution (XIII) To 100 g of the conductive polymer raw material solution (B) in Preparation Example 2, 4.8 g of triethylene glycol monobutyl ether, 0.16 g of pentaerythritol, 0. 08 g of a silane coupling agent was mixed and dispersed to obtain a conductive polymer solution (XIII).

(Preparation Example 14) Preparation of Conductive Polymer Solution (XIV) To 100 g of the conductive polymer raw material solution (C) in Preparation Example 3, 0.8 g of hydroxyacrylate, 0.16 g of xylitol and 0.096 g of polyester were added. It mixed and disperse | distributed and the conductive polymer solution (XIV) was obtained.

(Preparation Example 15) Preparation of Conductive Polymer Solution (XV) To 100 g of the conductive polymer raw material solution (A) in Preparation Example 1, 3.2 g of polyethylene glycol having a molecular weight of 1000 is mixed, dispersed, and conductive. A polymer solution (XV) was obtained.

(2) Manufacture of capacitor Etched aluminum foil formed by connecting a positive electrode lead terminal to etched aluminum foil (anode foil) and then applying a voltage of 102 V in a 10% by mass aqueous solution of diammonium adipate to form (oxidize it) (Anode foil) and aluminum cathode foil were wound into a cylindrical shape via a cellulose separator to obtain a capacitor element.

(3) Evaluation of water content In a petri dish having a diameter of about 10 cm, 3 g of the conductive polymer solution used in the following Examples 12 to 24 and Comparative Examples 6 to 7 were weighed, and Examples 12 to 24 and Comparative Examples 6 to 7 were prepared for measurement of moisture content of each solid electrolyte (composition) obtained by drying the conductive polymer solution.

  The produced solid electrolyte was measured using a coulometric titration-type moisture measuring device (CA-100 type) manufactured by Mitsubishi Chemical Corporation with the expelling temperature set to 150 ° C.

Example 1
The capacitor element obtained by manufacturing the capacitor was immersed in the conductive polymer solution (I) prepared in Preparation Example 1 under reduced pressure, and then dried by a hot air dryer at 150 ° C. for 30 minutes. Further, the immersion in the conductive polymer solution (I) was repeated twice to form a solid electrolyte layer between the dielectric layer and the cathode.

  Next, the capacitor element on which the solid electrolyte layer was formed was loaded in an aluminum case and sealed with a sealing rubber.

  Next, in the applying process, a direct current voltage of 60 V was applied between the anode and the cathode in an atmosphere at 105 ° C. for 60 minutes to obtain a capacitor.

  About the produced capacitor, the initial value of the electrostatic capacity in 120 Hz and the ESR in 100 kHz was measured using LCZ meter 2345 (made by NF circuit design block company).

In addition, after the initial value measurement, the ratio of the destroyed element was obtained after the acceleration test in the pressure cooker (temperature 121 ° C., pressure 2 atm, humidity 100%, charging time 100 h). The results are shown in Table 1. Note that ESR is an index of impedance.

  In addition, the addition amount in Table 1 is a ratio when the solid content of PEDOT-PSS is 100.

(Examples 2 to 11)
Instead of conductive polymer solution (I), conductive polymer solution (II), conductive polymer solution (III), conductive polymer solution (IV), conductive polymer solution (V), conductive Polymer solution (VI), conductive polymer solution (VII), conductive polymer solution (VIII), conductive polymer solution (IX)), conductive polymer solution (X), conductive polymer solution ( XI), except that Example 2, Example 3, Example 4, Example 5, Example 6, Example 7, Example 8, Example 9, Example 9, The capacitors of Example 10 and Example 11 were produced. Further, the capacitance, ESR, and pressure cooker breakdown rate were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Examples 1-4)
Instead of the conductive polymer solution (I), a conductive polymer solution (XII), a conductive polymer solution (XIII), a conductive polymer solution (XIV), or a conductive polymer solution (XV) was used. Except for this, capacitors of Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 were produced in the same manner as Example 1. Further, the capacitance, ESR, and pressure cooker breakdown rate were measured in the same manner as in Example 1. The results are shown in Table 1.

[Second Embodiment]
(1) Preparation of conductive polymer solution (Preparation Example 16) Preparation of conductive polymer solution (XVI) 42.6 g in 14.2 g of 3,4-ethylenedioxythiophene and 2,000 ml of ion-exchanged water Of polystyrene sulfonic acid (mass average molecular weight; about 300,000) was mixed at 20 ° C.

  While maintaining the mixed solution thus obtained at 20 ° C. and stirring, 29.64 g of ammonium persulfate and 8.0 g of ferric sulfate oxidation catalyst solution dissolved in 200 ml of ion-exchanged water were added. The reaction was stirred for an hour.

  The resulting reaction solution is dialyzed to remove impure ions, and then ion-exchanged to contain a conductive complex of about 1.6% by mass of polystyrene sulfonic acid and poly (3,4-ethylenedioxythiophene). A solution (hereinafter referred to as a PEDOT-PSS solution) was obtained.

  And imidazole was added to 100 g of this PEDOT-PSS solution, and the conductive polymer raw material solution (MB) of pH 7 was obtained. In 100 g of this conductive polymer raw material solution, 4.8 g of hydroxyethyl acrylate and 4.8 g of pentaerythritol were mixed and dispersed to obtain a conductive polymer solution (XVI).

(Preparation Example 17) Preparation of Conductive Polymer Solution (XVII) 4.8 g of hydroxyethyl acrylate was mixed and dispersed in the conductive polymer raw material solution (MB) in Preparation Example 16 to obtain a conductive polymer solution ( XVII).

(Preparation Example 18) Preparation of Conductive Polymer Solution (XVIII) 4.8 g of pentaerythritol was mixed and dispersed in 100 g of the conductive polymer raw material solution (MB) in Preparation Example 16 to obtain a conductive polymer solution ( XVIII) was obtained.

(2) Manufacture of capacitor Etched aluminum foil formed by connecting a positive electrode lead terminal to etched aluminum foil (anode foil) and then applying a voltage of 102 V in a 10% by mass aqueous solution of diammonium adipate to form (oxidize it) (Anode foil) and aluminum cathode foil were wound into a cylindrical shape through a cellulose separator to obtain a capacitor.

(3) Evaluation of water content In a petri dish having a diameter of about 10 cm, 3 g of the conductive polymer solution used in the following Examples 12 to 14 and Comparative Examples 5 and 6 were weighed, respectively. 14 and Comparative Examples 5 and 6 were prepared for measurement of moisture content of each solid electrolyte (composition) obtained by drying the conductive polymer solution.

  The produced solid electrolyte was measured using a coulometric titration-type moisture measuring device (CA-100 type) manufactured by Mitsubishi Chemical Corporation with the expelling temperature set to 150 ° C.

(Withstand voltage evaluation)
The produced solid electrolytic capacitor was boosted at a rate of 50 V to 0.5 V / second using a stabilized DC power supply at room temperature, and the voltage value when the current value reached 100 mA was defined as a withstand voltage.

(Example 12)
The capacitor obtained by manufacturing the capacitor was immersed in the conductive polymer solution (XVI) prepared in Preparation Example 17 under reduced pressure, and then dried by a hot air dryer at 125 ° C. for 30 minutes. Further, the immersion in the conductive polymer solution (XVI) was repeated twice to form a solid electrolyte layer between the dielectric layer and the cathode.

  Next, a capacitor in which a solid electrolyte layer was formed was loaded in an aluminum case and sealed with a sealing rubber.

  Next, in the application step, a direct current voltage of 60 V was applied between the anode and the cathode in an atmosphere at 150 ° C. for 60 minutes to obtain a solid electrolytic capacitor.

  About the produced capacitor, the electrostatic capacitance in 120 Hz and the initial value of ESR in 100 kHz were measured using LCR meter 2345 (made by NF circuit design block company). The results are shown in Table 2. Note that ESR is an index of impedance.

In an atmosphere of 150 ° C., a 50 V DC voltage was applied between the anode and the cathode for 500 hours to evaluate the heat resistance of the solid electrolytic capacitor. Table 2 shows the rate of change from the initial value of the capacitance. High temperature evaluation was performed by leaving it in an atmosphere of 260 ° C. for 3 minutes.

  In addition, the addition amount in Table 2 is a ratio when the solid content of PEDOT-PSS is 100. In addition, the capacitance can be less than 40, ESR can be 25 or less, and the capacitance change rate can be 10% or more.

(Examples 13 and 14)
The solid electrolysis of Example 13 and Example 14 was carried out in the same manner as in Example 12 except that drying in a hot air dryer at 125 ° C. for 30 minutes in Example 12 was performed at 150 ° C., 30 minutes, 180 ° C. and 30 minutes. A capacitor was produced.

  In the same manner as in Example 12, the capacitance, ESR, and heat resistance were measured. The results are shown in Table 2.

(Comparative Examples 5 and 6)
Using the conductive polymer solution (XVII) (Comparative Example 5) and the conductive polymer solution (XVIII) (Comparative Example 6), respectively, it was dried at 100 ° C. for 30 minutes in the same manner as in Example 12. The solid electrolytic capacitors of Comparative Example 5 and Comparative Example 6 were produced.

  Moreover, it carried out similarly to Example 12, and measured the electrostatic capacitance, ESR, and heat resistance. The results are shown in Table 2.

[Other embodiments]
As described above, the present invention has been described by the embodiments and examples. However, it should be understood that the descriptions and drawings constituting a part of this disclosure are exemplary and limit the present invention. Absent. From this disclosure, various alternative embodiments, examples and operational techniques will be apparent to those skilled in the art.

  As described above, the present invention includes various embodiments not described herein.

  The invention of the capacitor and the manufacturing method thereof according to the present application can be used for various electronic devices including digital devices.

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

Claims (6)

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 is
A cationized conductive polymer (a);
A polymer anion salt (b), or a polymer anion salt (b) and an anion salt (c);
A binder (d) of polyesters or silane coupling agents;
Pentaerythritol,
A conductivity improver;
And the solid electrolyte layer has a total amount of 100 parts by mass of the conductive polymer (a) and the polymer anion salt (b), or the conductive polymer (a), the polymer anion salt (b), and the anion salt (c). against it, 30 to 100 parts by weight of the polyesters or 10 to 100 parts by weight of the silane coupling agents of the binder (d), viewed contains more than 50 parts by weight of pentaerythritol,
Furthermore, a capacitor, characterized in including Mukoto 1.2 wt% to 1.8 wt% or less of moisture of the solid electrolyte (f).   The conductivity improver is selected from a compound having an amide group, a compound having an imide group, a lactam compound, a compound having a glycidyl group, and an acrylic compound, and the conductivity improver is selected from the conductive polymer (a) and the compound. 2. The capacitor according to claim 1, wherein the capacitor is contained in a larger amount than the total amount of the polymer anion salt (b), or the conductive polymer (a), the polymer anion salt (b), and the anion salt (c).   The capacitor according to claim 1, wherein the solid electrolyte layer is in contact with the dielectric layer.   The capacitor according to claim 1, further comprising a separator between the anode and the cathode. In a method of manufacturing 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 is
A cationized conductive polymer (a);
A polymer anion salt (b), or a polymer anion salt (b) and an anion salt (c);
A binder (d) of polyesters or silane coupling agents;
Pentaerythritol,
A conductivity improver;
A solvent,
The solid electrolyte layer is composed of 100 parts by mass of the total amount of the conductive polymer (a) and the polymer anion salt (b) or the conductive polymer (a), the polymer anion salt (b) and the anion salt (c). A conductive polymer solution containing 30 to 100 parts by weight of a polyester or 10 to 100 parts by weight of a silane coupling agent (d) and 50 parts by weight or more of pentaerythritol and adjusted to pH 3 to 12. A method for producing a capacitor, wherein the capacitor is formed so as to contain 1.2% by mass or more and 1.8% by mass or less of moisture (f) by dipping or coating and drying. The method for manufacturing a capacitor according to claim 5 , wherein the drying is performed in an atmosphere of 150 ° C. or higher.

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