JP2006128403A - Solid electrolyte, solid electrolytic capacitor, and solid electrolytic capacitor manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid electrolyte capable of obtaining ample capacity emergence ratio, superior withstand voltage, and satisfactory aging yield, when constituting a solid electrolytic capacitor. <P>SOLUTION: The solid electrolyte contains a poly (3, 4-ethylenedioxythiophene) as a conductive high polymer compound, a proton donating high polymer compound, a soluble high polymer compound, and a dopant for enhancing the conductivity of the conductive high polymer compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a solid electrolyte, a solid electrolytic capacitor, and a method for manufacturing a solid electrolytic capacitor.

  In recent years, digitization, downsizing, and speeding up of electronic devices have been increasingly accelerated. Under such circumstances, an electrolytic capacitor that is one of the electronic components suitable for high frequency applications frequently used in various electronic devices is required to have a larger capacity and a lower impedance during high frequency operation than ever before. At the same time, there is a strong desire for operational stability, reliability, and a longer life.

  An electrolytic capacitor is generally composed of a so-called valve action metal layer made of aluminum, tantalum or the like, a dielectric layer made of an oxide film formed by anodizing the surface, an electrolyte layer, graphite, silver, or the like. It has a structure in which conductor layers are sequentially stacked.

  Such electrolytic capacitors are roughly classified into two types, liquid electrolytic capacitors and solid electrolytic capacitors, depending on the properties of the electrolyte material. The former includes an electrolyte layer containing a liquid electrolyte (electrolytic solution) as an electrolyte material, and the latter includes an electrolyte layer containing a solid electrolyte (complex salt, conductive polymer, etc.) as an electrolyte material. It is. Comparing these from the viewpoints of various characteristics, the former is inherently likely to cause deterioration over time due to leakage or evaporation (dry up) of the electrolyte, whereas the latter has almost no such fear.

  Based on these advantages, research and development of solid electrolytic capacitors has been actively carried out recently. In particular, from the viewpoint of leakage current value, impedance characteristics, heat resistance, etc., the focus of development and practical application is manganese dioxide and complex salts. There is a rapid shift from those using a conjugated conductive polymer in which an electron donating or electron withdrawing substance (dopant) is doped into polypyrrole, polythiophene, polyaniline or the like.

  By the way, in the electrolytic capacitor having the general configuration described above, the valve metal layer is usually roughened and widened to increase the capacity, and the surface thereof has a fine uneven shape. Therefore, the dielectric layer formed on the valve action metal layer has a fine uneven shape as well. The dielectric layer is subject to natural degradation, rapid temperature changes, electrical shock (overvoltage, reverse voltage, or excessive ripple current applied), physical shock that occurs when an electrolytic capacitor is left unloaded for a long period of time. Due to factors such as addition, there is a risk of significant damage leading to loss of the function. When such damage occurs, the electrolytic capacitor causes a phenomenon such as an increase in leakage current and a short circuit. Therefore, in order to prevent the occurrence of such a short circuit, it is desirable that the electrolytic capacitor has a function of repairing the damaged portion of the dielectric layer itself (hereinafter referred to as “self-repair function”).

  In this regard, in the liquid electrolytic capacitor using the above-described electrolytic solution or the like, the valve metal that appears (exposed) in the damaged portion comes into contact with the electrolytic solution. This electrolytic solution contains ionic molecules or compounds, and when a predetermined rated voltage is applied to the electrolytic capacitor, the valve action metal is oxidized by oxygen generated from the ionic molecules or compounds, and the dielectric The damaged part of the layer is regenerated. On the other hand, the solid electrolytic capacitor has essentially no self-repairing function as described above because the electrolyte has substantially no ionic conductivity. Therefore, when a very local damaged portion appears in the dielectric layer, a current path is formed there. Joule heat is generated locally due to the generation of current, which may cause part of the solid electrolyte to become non-conductive, resulting in interruption of the current path of the leakage current. In such a case, the current path cannot be completely interrupted, which may result in a short circuit.

Therefore, attempts have been made to impart a self-repairing function to a conductive polymer type solid electrolytic capacitor while maintaining its excellent characteristics and physical properties. For example, as an electrolyte, an electrolytic solution and a conductive polymer compound (See, for example, Patent Documents 1 and 2).
JP-A-11-283874 Japanese Patent Laid-Open No. 2000-21688

  However, as described above, the electrolytic capacitor using both the electrolytic solution and the conductive polymer compound is not different from the electrolytic type electrolytic capacitor in that the electrolytic solution is contained in the electrolyte, and is caused by leakage or evaporation of the electrolytic solution. However, it is difficult to sufficiently suppress the deterioration with time.

  Therefore, it is desired to give a self-repairing function to a solid electrolytic capacitor without including an electrolytic solution in the electrolyte.

  By the way, the solid electrolytic capacitor which does not contain electrolyte solution in electrolyte has the following faults besides the point of a self-repair function. That is, in a solid electrolytic capacitor, in order to realize a higher capacity, a conductive polymer compound is filled as much as possible in the roughened / expanded portion of the valve metal layer to bring it close to the theoretical capacity. However, it is difficult to completely fill, and particularly when an electrolyte layer made of a conductive polymer compound is formed by chemical oxidative polymerization, filling becomes more difficult to obtain a capacity close to the theoretical capacity, That is, there is a drawback that it is difficult to obtain a sufficient capacity appearance rate.

  In addition, the solid electrolytic capacitor is also required to have excellent voltage resistance. The withstand voltage can be improved by adding a self-healing function to the solid electrolytic capacitor, but in order to improve the withstand voltage by other methods, it is effective to increase the thickness of the dielectric layer. It is. However, when the thickness of the dielectric layer is increased, the capacity tends to decrease, and it is difficult to obtain excellent voltage resistance and sufficient capacity at the same time.

  Furthermore, in order to make a solid electrolytic capacitor usable at a predetermined rated voltage, it is necessary to perform an aging treatment. However, a solid electrolytic capacitor that does not have a self-healing function requires a high rated voltage. In addition, the dielectric layer is damaged during the aging treatment, so that a short circuit is likely to occur, and a sufficient aging yield cannot be obtained.

  Thus, it is difficult for a conventional solid electrolytic capacitor to obtain a sufficient capacity appearance rate, and since it does not have a self-repair function, it has excellent voltage resistance and sufficient aging yield. Had the problem of being difficult.

  The present invention has been made in view of the above-described problems of the prior art, and when a solid electrolytic capacitor is configured, it is possible to obtain a sufficient capacity appearance rate, an excellent withstand voltage, and a sufficient aging yield. An object of the present invention is to provide a solid electrolyte, a solid electrolytic capacitor provided with the solid electrolyte, and a method of manufacturing the solid electrolytic capacitor.

  In order to achieve the above object, the present invention provides poly (3,4-ethylenedioxythiophene) as a conductive polymer compound, a proton-donating polymer compound, a water-soluble polymer compound, and the conductive material. A solid electrolyte comprising: a dopant for increasing the conductivity of a polymer compound.

  Such a solid electrolyte contains a water-soluble polymer compound together with a proton-donating polymer compound. By using this water-soluble polymer compound as a medium, the dispersibility of the proton-donating polymer compound is dramatically improved. Excellent ion conductivity can be obtained. Further, the solid electrolyte contains the specific conductive polymer compound and a dopant for enhancing the conductivity, and can obtain excellent electronic conductivity. As a result, when the solid electrolyte of the present invention is used in a solid electrolytic capacitor, it is possible to obtain excellent voltage resistance and sufficient aging yield due to its excellent ionic conductivity and electronic conductivity. In addition, a sufficient capacity appearance rate can be obtained.

  Here, in the solid electrolyte of the present invention, the proton donating polymer compound is at least selected from the group consisting of polyfluoroethylene, polystyrene, poly (meth) acrylic acid, polyimide, polyethylene, polypropylene, polybutadiene, and derivatives thereof. It is preferable to have one as a main chain. The proton-donating polymer compound preferably has a side chain containing at least one group selected from the group consisting of a sulfonic acid group and a phosphoric acid group, and is a perfluoroalkyl containing a sulfonic acid group. Particularly preferred are those having an ether side chain.

  These proton donating polymer compounds have good dispersibility and can impart particularly excellent ion conductivity to the solid electrolyte. Therefore, when a solid electrolytic capacitor is configured using such a solid electrolyte, the solid electrolytic capacitor can obtain better voltage resistance, more sufficient aging yield, and more sufficient capacity appearance rate.

  From the viewpoint of obtaining the effect of the present invention more sufficiently, the content of the proton donating polymer compound in the solid electrolyte of the present invention is 0.01 to 50 parts by mass with respect to 100 parts by mass of the conductive polymer compound. It is preferable that

  In the solid electrolyte of the present invention, the water-soluble polymer compound is preferably at least one selected from the group consisting of polyvinyl alcohol and cellulose.

  Since these water-soluble polymer compounds function well as a medium for dispersing the proton-donating polymer compound, the dispersibility of the proton-donating polymer compound is improved, and the ionic conductivity is improved by the solid electrolyte. Can be granted. Therefore, when a solid electrolytic capacitor is configured using such a solid electrolyte, the solid electrolytic capacitor can obtain better voltage resistance, more sufficient aging yield, and more sufficient capacity appearance rate.

  In addition, from the viewpoint of obtaining the effect of the present invention more sufficiently, the content of the water-soluble polymer compound in the solid electrolyte of the present invention is 0.01 to 50 parts by mass with respect to 100 parts by mass of the conductive polymer compound. Preferably there is.

  Furthermore, in the solid electrolyte of the present invention, the dopant is preferably at least one selected from the group consisting of alkylbenzene sulfonic acid and salts thereof, alkylnaphthalene sulfonic acid and salts thereof, and phosphoric acid. Or a salt thereof is particularly preferred.

  These dopants can sufficiently increase the conductivity of the conductive polymer compound. Therefore, when a solid electrolytic capacitor is configured using a solid electrolyte containing such a dopant, the solid electrolytic capacitor can obtain a more sufficient capacity appearance rate.

  The present invention also provides a first electrode layer, a dielectric layer formed on the first electrode layer, a second electrode layer disposed opposite to the first electrode layer, and a first electrode And a solid electrolyte layer made of the solid electrolyte of the present invention disposed between the layer and the second electrode layer.

  Since this solid electrolytic capacitor includes the solid electrolyte layer made of the solid electrolyte of the present invention described above, it is possible to obtain excellent voltage resistance and sufficient aging yield and to obtain a sufficient capacity appearance rate. Can do.

  From the viewpoint of obtaining the effect of the present invention more sufficiently, in the solid electrolytic capacitor of the present invention, the first electrode layer is a layer made of a valve metal having a roughened or enlarged surface. Is preferred.

  The present invention further includes a monomer constituting the conductive polymer compound, a proton-donating polymer compound, a water-soluble polymer compound, water, and a dielectric layer formed on the first electrode layer. And a solid electrolyte layer forming step of forming a solid electrolyte layer by polymerizing the monomer in the monomer-containing composition, and a solid electrolyte. And a second electrode layer forming step of forming a second electrode layer by laminating a conductive member on the layer. A method for producing a solid electrolytic capacitor is provided.

  In such a method for producing a solid electrolytic capacitor, a monomer-containing composition for forming a solid electrolyte layer contains a proton-donating polymer compound and a water-soluble polymer compound together with the monomer. What has a composition is used. The monomer-containing composition contains water and alcohol as these solvents. Thus, in the above characteristic composition, by using water and alcohol in combination as a solvent, it becomes possible to sufficiently disperse the proton-donating polymer compound using the water-soluble polymer compound as a medium, and excellent ion It becomes possible to form a solid electrolyte layer having conductivity. Therefore, the solid electrolytic capacitor manufactured by the above-described method for manufacturing a solid electrolytic capacitor can obtain excellent voltage resistance and a sufficient aging yield, and a sufficient capacity appearance rate.

  Moreover, the manufacturing method of the solid electrolytic capacitor of this invention WHEREIN: Before implementing a solid electrolyte layer formation process, the surface of a valve action metal is roughened or expanded, and the 1st electrode layer which forms a 1st electrode layer It is preferable to further include a layer forming step and a dielectric layer forming step of forming a dielectric layer by oxidizing the roughened or widened portion of the first electrode layer.

  The first electrode layer formed by the first electrode layer formation step has a rough surface or is roughened to form a fine concavo-convex shape, so that high capacity can be realized. It becomes. In addition, the dielectric layer formed in the subsequent dielectric layer forming step has a fine uneven shape. Then, by forming the solid electrolyte layer on the dielectric layer by the above-described solid electrolyte layer forming step, the material constituting the solid electrolyte layer is sufficiently provided on the roughened or enlarged portion of the valve metal surface. Can be filled. Therefore, the solid electrolytic capacitor manufactured by the above-described method for manufacturing a solid electrolytic capacitor can obtain excellent voltage resistance and a sufficient aging yield, and a sufficient capacity appearance rate.

  Moreover, it is preferable that the manufacturing method of the solid electrolytic capacitor of this invention further has the post-processing process which performs an aging process, after implementing a 2nd electrode layer formation process.

  Here, the aging process is a process for enabling the solid electrolytic capacitor to be used at a predetermined rated voltage as described above, and a voltage is gradually applied to the solid electrolytic capacitor at a predetermined temperature and a predetermined humidity. It is a process to apply. That is, by performing such an aging treatment, a solid electrolytic capacitor that can be used at a rated voltage can be obtained.

  In the method for producing a solid electrolytic capacitor of the present invention, the monomer used for the monomer-containing composition is preferably 3,4-ethylenedioxythiophene.

  When such a monomer is polymerized, poly (3,4-ethylenedioxythiophene) as a conductive polymer compound is generated. Then, the solid electrolyte layer is formed by including the poly (3,4-ethylenedioxythiophene), the proton-donating polymer compound, and the water-soluble polymer compound. A large capacity appearance rate can be obtained.

  Furthermore, in the method for producing a solid electrolytic capacitor of the present invention, the proton donating polymer compound used in the monomer-containing composition is polyfluoroethylene, polystyrene, poly (meth) acrylic acid, polyimide, polyethylene, polypropylene, polybutadiene. And at least one selected from the group consisting of these derivatives as the main chain. The proton-donating polymer compound preferably has a side chain containing at least one group selected from the group consisting of a sulfonic acid group and a phosphoric acid group, and is a perfluoroalkyl containing a sulfonic acid group. Particularly preferred are those having an ether side chain.

  These proton donating polymer compounds have good dispersibility and can impart particularly excellent ion conductivity to the solid electrolyte layer. Therefore, the obtained solid electrolytic capacitor can obtain better voltage resistance, more sufficient aging yield, and more sufficient capacity appearance rate.

  In the method for producing a solid electrolytic capacitor of the present invention, the water-soluble polymer compound used in the monomer-containing composition is preferably at least one selected from the group consisting of polyvinyl alcohol and cellulose.

  Since these water-soluble polymer compounds function well as a medium for dispersing the proton-donating polymer compound, the dispersibility of the proton-donating polymer compound is improved, and the ionic conductivity is improved by the solid electrolyte layer. Can be granted. Therefore, the obtained solid electrolytic capacitor can obtain better voltage resistance, more sufficient aging yield, and more sufficient capacity appearance rate.

  Furthermore, in the manufacturing method of the solid electrolytic capacitor of this invention, it is preferable that a monomer containing composition further contains the oxidizing agent for oxidatively polymerizing the said monomer. By containing an oxidizing agent in the monomer-containing composition, a uniform solution soaks into the surface-expanded portion, and as a result, a uniform polymer is formed.

  Furthermore, in the method for producing a solid electrolytic capacitor of the present invention, it is preferable that the monomer-containing composition further includes a dopant for increasing the conductivity of the conductive polymer compound. The dopant is preferably at least one selected from the group consisting of alkylbenzenesulfonic acid and salts thereof, alkylnaphthalenesulfonic acid and salts thereof, and phosphoric acid, and is paratoluenesulfonic acid or salts thereof. Is particularly preferred.

  By using the monomer-containing composition containing these dopants, the conductivity of the conductive polymer compound can be sufficiently increased in the solid electrolyte layer. Therefore, the obtained solid electrolytic capacitor can obtain a more sufficient capacity appearance rate.

  ADVANTAGE OF THE INVENTION According to this invention, when a solid electrolytic capacitor is comprised, the solid electrolyte which can acquire sufficient capacity | capacitance appearance rate, the outstanding voltage resistance, and sufficient aging yield can be provided.

  In addition, according to the present invention, it is possible to provide a solid electrolytic capacitor having a sufficient capacity appearance rate, excellent voltage resistance, and a sufficient aging yield.

  Furthermore, according to the present invention, it is possible to provide a method for manufacturing a solid electrolytic capacitor capable of manufacturing a solid electrolytic capacitor having a sufficient capacity appearance rate, an excellent withstand voltage, and a sufficient aging yield.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, the same code | symbol is attached | subjected to the same element and the overlapping description is abbreviate | omitted. The positional relationship such as up, down, left and right is based on the positional relationship in the drawing.

[Solid electrolytic capacitor]
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the solid electrolytic capacitor of the present invention. As shown in FIG. 1, the solid electrolytic capacitor 1 has a configuration in which a solid electrolytic capacitor element 18 to which an anode lead-out line 8 and a cathode lead-out line 10 are connected is covered with a resin mold layer 16. An external anode terminal 12 and an external cathode terminal 14 are connected to the anode lead-out line 8 and the cathode lead-out line 10, respectively. In the solid electrolytic capacitor element 18, the dielectric layer 4 is provided between the electrodes 2 (first electrode layers) and the electrodes 6 that are alternately arranged at a constant interval.

  FIG. 2 is a cross-sectional view schematically showing the main part of the solid electrolytic capacitor 1, and shows the state in which the electrode 2, the dielectric layer 4, the electrode 6 and the resin mold layer 16 are laminated in more detail. . In FIG. 2, the solid electrolytic capacitor 1 has a configuration in which an electrode 2, a dielectric layer 4, a solid electrolyte layer 20, and conductor layers 22 and 24 are sequentially laminated. Thus, the electrode 26 (second electrode layer) is composed of the conductor layers 22 and 24, and the electrode 6 is composed of the solid electrolyte layer 20 and the electrode 26.

(anode)
The electrode 2 functions as an anode in the solid electrolytic capacitor 1. The surface is subjected to a roughening or widening process to form a fine concavo-convex shape, thereby increasing the surface area and increasing the capacity of the solid electrolytic capacitor 1. The material constituting the electrode 2 is not particularly limited as long as it is generally used for an electrolytic capacitor. A metal is mentioned. Among these, aluminum or tantalum is relatively preferably used. The thickness of the electrode 2 is usually preferably about 1 to 500 μm.

(Dielectric layer)
The dielectric layer 4 is formed so as to cover the surface of the electrode 2 along the irregular shape. The dielectric layer 4 is usually formed of a metal oxide film having electrical insulation (for example, an aluminum oxide film when the electrode 2 is aluminum), and is easily formed by oxidizing the surface layer portion of the electrode 2 by a predetermined method. Is done. The thickness of the dielectric layer 4 is usually 1 nm to 1 μm.

  The dielectric layer 4 tends to be easily damaged by cracking, chipping, or missing due to thermal or physical damage in the process of oxidizing the electrode 2 or after the solid electrolytic capacitor 1 is completed or used. When such a crack or the like develops, there is a possibility that the damaged portion 30 may partially occur so that the electrode 2 and the solid electrolyte layer 20 communicate with each other. When this happens, the insulation between the two is hindered, and in some cases, a short circuit occurs. On the other hand, in the present invention, the damaged portion 30 is filled or covered with the repair portion 32 made of an oxide of the valve action metal constituting the electrode 2. As described above, when the damaged portion 30 is generated in the dielectric layer 4, the repair portion 32 is formed in the dielectric layer 4.

(cathode)
The solid electrolyte layer 20 is a layer made of the solid electrolyte of the present invention, and is formed so as to fill in the recesses along the dielectric layer 4 on the fine uneven surface of the electrode 2 formed by surface enlargement. The thickness of the solid electrolyte layer 20 is desirably a thickness that can cover the uneven surface, and is preferably about 1 to 100 μm, for example. The solid electrolyte constituting the solid electrolyte layer 20 includes a conductive polymer compound, a proton-donating polymer compound, a water-soluble polymer compound, and a dopant for increasing the conductivity of the conductive polymer compound. It contains.

  The solid electrolyte layer 20 includes a proton-donating polymer compound and a water-soluble polymer compound together with the conductive polymer compound and its dopant. When the solid electrolytic capacitor 1 is configured using the solid electrolyte layer 20 containing such a proton-donating polymer compound, the proton-donating polymer compound functions as an oxidizing species or is unavoidably present in the surroundings. Or it is thought that it functions as a metal oxidation reaction catalyst by oxygen.

  Therefore, when the oxide film constituting the dielectric layer 4 is damaged due to thermal shock or physical or chemical impact, the electrolyte layer 4 becomes an anode (for example, a valve action metal layer) at the damaged portion. The anode comes into contact, and the anode is oxidized by the above-described oxidation action or catalytic action, so that the oxide film can be regenerated. Thereby, the insulating property of the dielectric layer 4 is recovered and maintained. That is, the solid electrolytic capacitor 1 including the above-described solid electrolyte layer 20 can exhibit a self-repair function without containing an electrolytic solution.

  The solid electrolyte layer 20 contains a water-soluble polymer compound together with the proton-donating polymer compound. By using this water-soluble polymer compound as a medium, the dispersibility of the proton-donating polymer compound can be improved. It can be improved dramatically and excellent ionic conductivity can be obtained. Furthermore, the solid electrolyte layer 20 contains the specific conductive polymer compound and a dopant for increasing the conductivity, and can obtain excellent electronic conductivity. Therefore, the solid electrolytic capacitor 1 exhibits an excellent self-repairing function due to the excellent ionic conductivity of the solid electrolyte layer 20, can obtain excellent voltage resistance and sufficient aging yield, A sufficient capacity appearance rate can be obtained due to the excellent ion conductivity and electronic conductivity of the electrolyte layer 20.

  Here, at least poly (3,4-ethylenedioxythiophene) is used as the conductive polymer compound, but in addition to this, a polymer compound usually used as the conductive polymer compound can be used in combination. . For example, polyaniline, polypyrrole, polythiophene, polyfuran, and derivatives thereof can be used, and two or more of these may be used in combination.

  The proton donating polymer compound is a so-called proton conducting polymer compound capable of donating protons (moving protons freely). This proton-donating polymer compound is, for example, a compound in which a side chain containing a functional group capable of donating protons (hereinafter referred to as “proton-donating functional group”) is bonded to a polymer skeleton as a main chain. .

  Examples of the polymer skeleton as the main chain include polyfluoroethylene, polystyrene, poly (meth) acrylic acid (polyacrylic acid or polymethacrylic acid), polyimide, polyethylene, polypropylene, polybutadiene, and derivatives thereof.

  Examples of the proton-donating functional group include a sulfonic acid group, a phosphoric acid group, and a carboxyl group, and among these, a sulfonic acid group or a phosphoric acid group that is a relatively strong acid group is more preferable.

  As those having the above-described polymer skeleton and proton-donating functional group, polyfluoroethylene, polystyrene, poly (meth) acrylic acid, polyimide and derivatives thereof having sulfonic acid groups bonded thereto, and phosphoric acid groups are bonded. Poly (meth) acrylic acid and its derivatives are preferably used.

  As the proton-donating polymer compound, those having a perfluoroalkyl ether side chain containing a sulfonic acid group are more preferable, and polyfluoroethylene having a perfluoroalkyl ether side chain containing a sulfonic acid group and derivatives thereof are particularly preferable. preferable. This type of polyfluoroethylene is preferably a copolymer having fluoroethylene having a perfluoroalkyl ether side chain having a sulfonic acid group at the terminal and tetrafluoroethylene as a monomer unit, specifically, For example, the compound which has a repeating unit represented by following formula (1) is mentioned.

  In formula (1), p is approximately 3 to 20, preferably 5 to 15, q is approximately 1 to 1000, preferably 1 to 500, m is approximately 1 to 5, preferably 1 to 3, and n is approximately 1 to 1. 5, preferably an integer from 1 to 3.

  In addition, the content of the proton-donating polymer compound in the solid electrolyte layer 20 is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the conductive polymer compound, and 0.1 to 45 parts by mass. More preferably, it is more preferably 0.2 to 40 parts by mass. In addition, content here is a value based on the preparation amount at the time of forming the solid electrolyte layer 20, ie, the material input amount at the time of producing | generating a conductive polymer compound. When the content is less than 0.01 parts by mass, the self-repair function tends to be insufficient as compared with the case where the content is within the above range. On the other hand, when the content exceeds 50 parts by mass, various characteristics (capacity, leakage current value, impedance characteristics, heat resistance, etc.) as a solid electrolytic capacitor are reduced as compared with the case where the content is within the above range. Tend.

  In the solid electrolyte layer 20, in addition to the above proton-donating polymer compound, a sulfonic acid compound such as sulfosalicylic acid, a phosphate compound such as urea phosphate, mono-n-butoxyethyl phosphate, maleic Carboxylic acid compounds such as acid, benzoic acid, p-nitrobenzoic acid, phthalic acid, and hydroxycarboxylic acid may be added. These additions tend to improve the self-repair function.

  The water-soluble polymer compound retains water and can disperse the proton-donating polymer compound, and examples thereof include polyvinyl alcohol and cellulose.

  The content of the water-soluble polymer compound in the solid electrolyte layer 20 is preferably 0.01 to 50 parts by mass, and preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the conductive polymer compound. Is more preferable, and 0.2 to 40 parts by mass is particularly preferable. The content of the water-soluble polymer compound is the same as the content of the proton-donating polymer compound described above, the amount charged when the solid electrolyte layer 20 is formed, that is, when the conductive polymer compound is generated. The value is based on the material input. When the content of the water-soluble polymer compound is less than 0.01 part by mass, the self-repair function tends to be insufficient as compared with the case where the content is in the above range. On the other hand, when the content exceeds 50 parts by mass, various characteristics (capacity, leakage current value, impedance characteristics, heat resistance, etc.) as a solid electrolytic capacitor are reduced as compared with the case where the content is within the above range. Tend.

  The dopant is for increasing the conductivity of the conductive polymer compound. For example, the alkylbenzene sulfonic acid and its salt (for example, sodium paratoluene sulfonate), the alkyl naphthalene sulfonic acid and its salt (for example, isopropyl naphthalene). Sodium sulfonate) and phosphoric acid.

  As a material of the conductor layers 22 and 24 constituting the electrode 26 formed on the solid electrolyte layer 20, for example, carbon or metal can be used. As the conductor layer 22, carbon, and as the conductor layer 24 are used. Silver can be used. The electrode 26 is not limited to the two-layer structure of the conductor layers 22 and 24, and may be composed of three or more layers.

  The anode lead-out line 8, the cathode lead-out line 10, the external anode terminal 12 and the external cathode terminal 14 are used for energizing the solid electrolytic capacitor element 18. For example, all of them are iron (Fe) or copper (Cu ) And the like, and materials obtained by plating these conductive materials (for example, tin (Sn) plating or tin lead (SnPb) plating).

  The resin mold layer 16 constitutes the exterior of the solid electrolytic capacitor 1 and is made of, for example, an insulating resin material such as an epoxy resin.

[Method of manufacturing solid electrolytic capacitor]
Next, a method for manufacturing the solid electrolytic capacitor 1 having the above configuration will be described below.

  FIG. 3 is a flowchart showing an example of a procedure for manufacturing the solid electrolytic capacitor 1 of the present invention. As shown in FIG. 3, first, the electrode 2 is formed by roughening or expanding the surface of the valve metal (first electrode layer member) by chemical or electrochemical etching (step S11; First electrode layer forming step). Next, the surface of the electrode 2 (roughened or enlarged portion) is anodized to produce an oxide film, and the dielectric layer 4 is formed (step S12; dielectric layer forming step). Specifically, the anodic oxidation at this time can be performed by immersing the electrode 2 in a chemical conversion solution and applying a constant voltage with the electrode 2 as a positive electrode. The applied voltage can be appropriately determined according to the thickness of the oxide film to be formed, and is usually set to a voltage of about several volts to several hundred volts. Furthermore, as the chemical conversion solution, a buffer solution such as ammonium borate, ammonium phosphate, or organic acid ammonium can be preferably used, and an aqueous solution of ammonium adipate that is an organic acid ammonium is particularly preferable.

  When forming the electrode 2, for example, as described above, an untreated valve metal that has not been roughened or enlarged is used, and the valve metal is roughened or roughened. A surface-treated valve metal that has been subjected to surface roughening or surface enlargement processing in advance may be applied separately, or may be roughened or subjected to surface expansion processing in order to save time and effort. May be used. When the dielectric layer 4 is formed on the electrode 2, for example, the electrode 2 on which the oxide film is partially formed is used, and the electrode 2 is cut to form no oxide film. The dielectric layer 4 may be formed so as to cover the entire periphery of the electrode 2 by separately forming an oxide film on the cut surface after exposing the surface (cut surface).

  In parallel with step S11 or step S12, the monomer constituting the conductive polymer compound described above, the proton donating polymer compound described above, the water-soluble polymer compound described above, and water and alcohol as a solvent. Are mixed to prepare a monomer-containing composition (step S13). Here, as alcohol used for a solvent, ethanol, butanol, etc. are mentioned, for example, These are used individually or in combination of 2 or more types.

  Examples of the monomer include aniline, pyrrole, thiophene, furan, and derivatives thereof. By polymerizing these, conductive polymers such as polyaniline, polypyrrole, polythiophene, polyfuran, and derivatives thereof. A compound can be obtained. In order to produce poly (3,4-ethylenedioxythiophene) as the conductive polymer compound, it is preferable to use 3,4-ethylenedioxythiophene as the monomer.

  Next, the dielectric layer 4 is formed by immersing the electrode 2 having the dielectric layer 4 formed on the surface in the monomer-containing composition or applying the monomer-containing composition to the electrode 2. A monomer-containing composition is adhered on the top (step S14). Furthermore, the monomer contained in the monomer-containing composition attached on the dielectric layer 4 is polymerized by, for example, chemical oxidation polymerization to form the solid electrolyte layer 20 on the dielectric layer 4 (step S15). A solid electrolyte layer forming step).

  Chemical oxidative polymerization can be performed by bringing an oxidant solution obtained by dissolving an oxidant in a solvent such as water into contact with the electrode 2 to which the monomer-containing composition is attached. Examples of a method for bringing both into contact include a method in which the electrode 2 is immersed in an oxidant solution, a method in which the oxidant solution is applied to the electrode 2, and the like. Examples of the oxidizing agent used for polymerization include halides such as iodine and bromine, metal halides such as silicon pentafluoride, protonic acids such as sulfuric acid, oxygen compounds such as sulfur trioxide, sulfates such as cerium sulfate, Examples thereof include persulfates such as sodium sulfate, peroxides such as hydrogen peroxide, and iron salts such as iron paratoluate. Further, the chemical oxidative polymerization of the monomer can be carried out by including the oxidant in the monomer-containing composition without separately using such an oxidant solution.

  It is preferable that at least one of the monomer-containing composition and the oxidant solution contains a dopant for increasing the conductivity of the conductive polymer compound. As this dopant, what was illustrated previously in description of the solid electrolytic capacitor 1 can be used. In addition, what has a function as a dopant may be used as said oxidizing agent, and while using the oxidizing agent which has this function, you may use a dopant further. Examples of the material having both functions of an oxidant and a dopant include iron salts as exemplified above as a dopant such as iron paratoluenesulfonate.

  In addition, when the solvent contained in the monomer-containing composition volatilizes and dissipates to the outside with the polymerization reaction of the monomer, an operation for removing this solvent is not particularly required. If it does not volatilize sufficiently, it is desirable to remove the solvent before or after step S15 as necessary (solvent removal step).

  The content of the proton-donating polymer compound in the monomer-containing composition is preferably 0.01 to 50 parts by mass, and 0.1 to 45 parts by mass with respect to 100 parts by mass of the monomer. Is more preferable, and it is still more preferable that it is 0.2-40 mass parts. When the content is less than 0.01 parts by mass, the self-repair function of the obtained solid electrolytic capacitor tends to be insufficient as compared with the case where the content is in the above range. On the other hand, when the content exceeds 50 parts by mass, various characteristics (capacity, leakage current value, impedance characteristics, heat resistance, etc.) of the obtained solid electrolytic capacitor are reduced as compared with the case where the content is within the above range. Tend to.

  The content of the water-soluble polymer compound in the monomer-containing composition is preferably 0.01 to 50 parts by mass, and preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the monomer. More preferred is 0.2 to 40 parts by mass. When the content is less than 0.01 parts by mass, the self-repair function of the obtained solid electrolytic capacitor tends to be insufficient as compared with the case where the content is in the above range. On the other hand, when the content exceeds 50 parts by mass, various characteristics (capacity, leakage current value, impedance characteristics, heat resistance, etc.) of the obtained solid electrolytic capacitor are reduced as compared with the case where the content is within the above range. Tend to.

  Next, a conductive member (second electrode layer member) is laminated on the solid electrolyte layer 20 to form the electrode 26 (step S16; second electrode layer forming step). Lamination is performed by, for example, applying a paste made of a conductive member on the solid electrolyte layer 20 to form the conductor layer 22, and further applying a paste made of a different conductive member thereon. This can be done by forming the conductor layer 24. Specifically, for example, after applying and drying a carbon paste on the solid electrolyte layer 20, the conductor layers 22 and 24 can be formed by applying and drying a silver paste.

  After forming the solid electrolytic capacitor element 18 in this way, the anode lead-out line 8 and the cathode lead-out line 10 are connected to the electrodes. Subsequently, after covering the entire solid electrolytic capacitor element 18 with the resin mold layer 16 so that a part of each lead wire is exposed to the outside, the anode lead wire 8 and the cathode lead wire 10 are respectively connected to the external anode terminal 12 and the external lead wire 10. The solid electrolytic capacitor 1 is obtained by connecting the cathode terminal 14 (step S17). Then, it is preferable to perform an aging process further (step S18; post-processing process). The aging treatment can be performed by applying a constant voltage to the external anode terminal 12 and the external cathode terminal 14 of the solid electrolytic capacitor 1, thereby completing the manufacture of the solid electrolytic capacitor 1.

  In the method for producing the solid electrolytic capacitor 1 of the present invention described above, the monomer-containing composition for forming the solid electrolyte layer 20 contains a proton donating polymer compound. Here, it is considered that the proton-donating polymer compound functions as an oxidizing species or as a metal oxidation reaction catalyst by water or oxygen unavoidably present in the surroundings. Therefore, when the oxide film constituting the dielectric layer 4 is damaged by thermal shock or physical or chemical impact, the solid electrolyte layer 20 is brought into contact with the valve action metal layer at the damaged portion. Thus, the valve action metal is oxidized by the above-described oxidation action or catalytic action, and the oxide film can be regenerated. As a result, the insulation of the dielectric layer 4 is restored and maintained, and the resulting solid electrolytic capacitor 1 can exhibit a self-repairing function.

  Furthermore, the monomer-containing composition contains a water-soluble polymer compound, and water and alcohol as solvents. Thus, by using water and alcohol in combination as a solvent, it becomes possible to sufficiently disperse the proton-donating polymer compound using the water-soluble polymer compound as a medium, and roughening or expanding the surface of the valve metal. It is possible to sufficiently fill these parts with the formed parts. Thereby, the obtained solid electrolytic capacitor 1 can obtain an excellent self-repairing function, can obtain excellent voltage resistance and sufficient aging yield, and can obtain a sufficient capacity appearance rate.

  Further, in the solid electrolytic capacitor 1 having such properties, the electrode 2 is anodized again in the post-processing step in which the above-described aging treatment is performed, and generation of a new damaged portion 30 on the dielectric layer 4 is suppressed. It is considered that the repair portion 32 is efficiently formed in the damaged portion 30 of the dielectric layer 4 generated during the manufacture of the solid electrolytic capacitor 1.

  Therefore, when the aging process of step S18 is performed, even if the dielectric layer 4 has a defect, it can be efficiently repaired. Regardless of the presence or absence of such an aging treatment, the dielectric layer 4 may be damaged even during use of the solid electrolytic capacitor 1 as described above, and the leakage current may undesirably increase. Also in this case, the damaged portion 30 of the dielectric layer 4 is self-repaired by the metal oxidizing ability or oxidation catalytic ability of the solid electrolyte. Therefore, the solid electrolytic capacitor 1 can achieve excellent voltage resistance and a sufficient capacity appearance rate at a high level.

  In the present embodiment, an example of the structure and manufacturing method of the chip-type solid electrolytic capacitor 1 having the layer structure shown in FIG. 1 has been described. However, the solid electrolytic capacitor of the present invention is not limited to this. 2 may have a single layer structure as shown in FIG. 2, or may be a wound solid electrolytic capacitor formed by winding such a layer structure.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

Example 1
An electrolytic capacitor was manufactured through the following procedure. That is, first, an aluminum foil (3.5 mm × 6.5 mm) that has been subjected to a surface enlargement treatment is prepared as an anode, and a portion (anode portion) that should become an anode and a portion that should form a cathode (cathode) on the surface of the aluminum foil. The insulator for partitioning these was formed in the position which should partition with the formation part. After this aluminum foil is immersed in an aqueous solution of ammonium adipate as a chemical conversion solution, a voltage of 6 V is applied to the aluminum foil to advance the anodic oxidation reaction, whereby a dielectric comprising an aluminum oxide film on the surface of the aluminum foil A layer was formed.

  Subsequently, 3,4-ethylenedioxythiophene (trade name: BAYTRON (registered trademark) M, manufactured by Bayel) as a monomer constituting the conductive polymer compound, 0.9 g of iron paratoluenesulfonate ( Product name: BAYTRON (registered trademark) C-B50, manufactured by Bayel) 10.81 g, polyfluoroethylene solution having a perfluoroalkyl ether side chain containing a sulfonic acid group as a proton-donating polymer (trade name: Nafion ( (Registered trademark) solution SE20192, manufactured by Dupont) 0.045 g, polyvinyl alcohol as a water-soluble polymer (trade name: Kuraray Poval PVA403, manufactured by Kuraray Co., Ltd.) 0.108 g, and 3.76 g of water are mixed, and a single amount A solution of the body containing composition was prepared. In this solution, when the content of BAYTRON (registered trademark) M is 100 parts by mass, the content of Nafion (registered trademark) as a solid content is 1 part by mass, and the content of polyvinyl alcohol is 12 parts by mass. there were. The aluminum foil on which the dielectric layer was formed was immersed in this solution for 1 minute and then pulled up and left in the air for 30 minutes with the monomer-containing composition attached thereto. Thereby, the monomer in the monomer containing composition adhering to aluminum foil was oxidatively polymerized. The aluminum foil was then washed with running water for 15 minutes and dried at 100 ° C. for 5 minutes. This polymerization process from immersion to drying was repeated three times to form a solid electrolyte layer having a thickness of 1 μm on the dielectric layer.

  Next, a carbon paste layer as a conductor layer is applied to a thickness of 3 μm on the solid electrolyte layer, and a silver paste layer as a conductor layer is further applied to a thickness of 20 μm on the carbon paste layer. did. This formed the cathode which consists of a carbon paste layer and a silver paste layer. Thus, a capacitor element having a structure in which the anode, the dielectric layer, the solid electrolyte layer, and the cathode were laminated in this order was obtained.

  Thereafter, a conductive cathode lead was connected to the cathode side using a conductive adhesive, and a conductive anode lead was connected to the anode side with a resistance welding machine. And the solid electrolytic capacitor was produced by covering the circumference | surroundings of a capacitor | condenser element so that an anode lead and a cathode lead may be partially exposed with an epoxy resin, and forming a resin mold layer.

(Examples 2 to 4)
In the preparation of the monomer-containing composition solution, the blending amount of a polyfluoroethylene solution having a perfluoroalkyl ether side chain containing a sulfonic acid group (trade name: Nafion (registered trademark) solution SE20192, manufactured by Dupont) was carried out. In Example 2, 0.225 g (5 parts by mass of Nafion (registered trademark) solid content with respect to 100 parts by mass of BAYTRON (registered trademark) M), and in Example 3, 0.45 g (BAYTRON (registered trademark) M100 parts by mass) On the other hand, Nafion (registered trademark) solid content 10 parts by mass), in Example 4, 0.675 g (BAYTRON (registered trademark) M 100 parts by mass, Nafion (registered trademark) solids content 15 parts by mass) Produced solid electrolytic capacitors of Examples 2 to 4 in the same manner as Example 1.

(Examples 5-7)
In the preparation of the monomer-containing composition solution, the blending amount of a polyfluoroethylene solution having a perfluoroalkyl ether side chain containing a sulfonic acid group (trade name: Nafion (registered trademark) solution SE20192, manufactured by Dupont) was set to 0.00. In Example 5, the blending amount of polyvinyl alcohol (trade name: Kuraray Poval PVA403, manufactured by Kuraray Co., Ltd.) in 225 g (BAYTRON (registered trademark) M100 parts by mass with Nafion (registered trademark) solid content of 5 parts by mass) Is 0.009 g (1 part by mass with respect to 100 parts by mass of BAYTRON (registered trademark) M100). In Example 6, 0.045 g (5 parts by mass with respect to 100 parts by mass of BAYTRON (registered trademark) M100). Is 0.18 g (20 parts by mass for 100 parts by mass of BAYTRON (registered trademark) M) Except for using in the same manner as in Example 1 to prepare a solid electrolytic capacitor of Examples 5-7.

(Comparative Example 1)
In the preparation of the monomer-containing composition solution, a polyfluoroethylene solution having a perfluoroalkyl ether side chain containing a sulfonic acid group (trade name: Nafion (registered trademark) solution SE20192, manufactured by Dupont) and polyvinyl alcohol (trade name) : Kuraray Poval PVA403 (manufactured by Kuraray Co., Ltd.) was prepared, and a solid electrolytic capacitor of Comparative Example 1 was produced in the same manner as in Example 1 except that 2.63 g of butanol was added instead of 3.76 g of water.

(Evaluation of capacity appearance rate)
Regarding the cathode forming portion (3.5 mm × 4.5 mm) of the aluminum foil that has been subjected to the surface enlargement treatment that constitutes the solid electrolytic capacitors of Examples 1 to 7 and Comparative Example 1, the theoretical capacity was previously set before forming the solid electrolyte layer. Have been measured. That is, each aluminum foil was immersed in an electrolytic solution (ammonium adipate aqueous solution), and a theoretical capacity was measured at a frequency of 120 Hz using an LCR meter 4284A manufactured by HEWLETT PACKARD.

On the other hand, about the solid electrolytic capacitor of Examples 1-7 and the comparative example 1, the electrostatic capacitance was measured by IMPANDANCE / GAIN-PHASE ANALYZER 4194A made from HEWLETT PACKARD, respectively. From the electrostatic capacity as the solid electrolytic capacitor and the theoretical capacity measured in advance, the capacity appearance rate (%) was obtained by the following formula.
Capacity appearance rate = (capacitance as solid electrolytic capacitor / theoretical capacity) × 100
The results are shown in Table 1.

(Evaluation of aging yield)
100 solid electrolytic capacitors of Examples 1 to 7 and Comparative Example 1 were prepared, and aging treatment was performed on them as follows. That is, an aging process is performed by gradually applying a voltage to the solid electrolytic capacitor in an environment of a temperature of 100 to 150 ° C. and a humidity of 60 to 90% RH, and finally applying a voltage according to the foil to be used. Went. The ratio of those that were not short-circuited by this aging treatment was determined, and this was evaluated as the aging yield (%). The results are shown in Table 1.

(Evaluation of withstand voltage)
For each of the solid electrolytic capacitors of Examples 1 to 7 and Comparative Example 1, ten pieces were prepared that were not short-circuited by performing the aging treatment. A voltage is gradually applied to these solid electrolytic capacitors at a rate of 0 to 100 mV / second, and the voltage (V) at the point where the current rises (where the current begins to flow rapidly) is taken as the withstand voltage. It was measured. The results are shown in Table 1. In addition, the value of withstand voltage in the table is an average value of 10 measured values.

  As is apparent from the results shown in Table 1, according to the solid electrolytic capacitors (Examples 1 to 7) of the present invention, superior voltage resistance and sufficient aging compared to the solid electrolytic capacitor of Comparative Example 1. It was confirmed that the yield and sufficient capacity appearance rate were obtained. In addition, since the outstanding voltage resistance and sufficient aging yield were obtained, it is thought that the solid electrolytic capacitor of Examples 1-7 has a self-repair function.

It is a schematic cross section which shows one Embodiment of the solid electrolytic capacitor of this invention. It is sectional drawing which shows typically the principal part of the solid electrolytic capacitor 1 shown in FIG. It is a flowchart which shows an example of the procedure which manufactures the solid electrolytic capacitor of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Solid electrolytic capacitor, 2 ... Electrode (1st electrode layer), 4 ... Dielectric layer (dielectric), 6 ... Electrode, 8 ... Anode lead-out wire, 10 ... Cathode lead-out wire, 12 ... External anode terminal, 14 DESCRIPTION OF SYMBOLS ... External cathode terminal, 16 ... Resin mold layer, 18 ... Solid electrolytic capacitor element, 20 ... Solid electrolyte layer, 22, 24 ... Conductor layer, 26 ... Electrode (second electrode layer), 30 ... Damaged part, 32 ... Repair department.

Claims (23)

  Poly (3,4-ethylenedioxythiophene) as a conductive polymer compound, a proton-donating polymer compound, a water-soluble polymer compound, and a dopant for increasing the conductivity of the conductive polymer compound; A solid electrolyte comprising:   The proton donating polymer compound has at least one selected from the group consisting of polyfluoroethylene, polystyrene, poly (meth) acrylic acid, polyimide, polyethylene, polypropylene, polybutadiene, and derivatives thereof as a main chain. The solid electrolyte according to claim 1, wherein the solid electrolyte is present.   The solid according to claim 1 or 2, wherein the proton-donating polymer compound has a side chain containing at least one group selected from the group consisting of a sulfonic acid group and a phosphoric acid group. Electrolytes.   The solid electrolyte according to any one of claims 1 to 3, wherein the proton-donating polymer compound has a perfluoroalkyl ether side chain containing a sulfonic acid group.   5. The content of the proton-donating polymer compound is 0.01 to 50 parts by mass with respect to 100 parts by mass of the conductive polymer compound. 5. The solid electrolyte according to 1.   The solid electrolyte according to any one of claims 1 to 5, wherein the water-soluble polymer compound is at least one selected from the group consisting of polyvinyl alcohol and cellulose.   The content of the water-soluble polymer compound is 0.01 to 50 parts by mass with respect to 100 parts by mass of the conductive polymer compound, according to any one of claims 1 to 6. The solid electrolyte described.   The said dopant is at least 1 sort (s) selected from the group which consists of alkylbenzenesulfonic acid and its salt, alkylnaphthalenesulfonic acid and its salt, and phosphoric acid, The any one of Claims 1-7 characterized by the above-mentioned. The solid electrolyte according to item.   The solid electrolyte according to any one of claims 1 to 8, wherein the dopant is para-toluenesulfonic acid or a salt thereof. A first electrode layer;
A dielectric layer formed on the first electrode layer;
A second electrode layer disposed opposite the first electrode layer;
A solid electrolyte layer made of the solid electrolyte according to any one of claims 1 to 9 disposed between the first electrode layer and the second electrode layer;
A solid electrolytic capacitor comprising:   11. The solid electrolytic capacitor according to claim 10, wherein the first electrode layer is a layer made of a valve metal having a roughened or enlarged surface. On the dielectric layer formed on the first electrode layer, a monomer constituting the conductive polymer compound, a proton-donating polymer compound, a water-soluble polymer compound, water, alcohol, A solid electrolyte layer forming step of forming a solid electrolyte layer by polymerizing the monomer in the monomer-containing composition;
A second electrode layer forming step of forming a second electrode layer by laminating a conductive member on the solid electrolyte layer;
A method for producing a solid electrolytic capacitor, comprising:   Before performing the solid electrolyte layer forming step, the first electrode layer forming step of forming the first electrode layer by roughening or expanding the surface of the valve metal, and the first electrode layer The method for producing a solid electrolytic capacitor according to claim 12, further comprising a dielectric layer forming step of forming a dielectric layer by oxidizing the roughened or widened portion.   The method for producing a solid electrolytic capacitor according to claim 12, further comprising a post-treatment step of performing an aging treatment after the second electrode layer forming step.   The method for producing a solid electrolytic capacitor according to any one of claims 12 to 14, wherein the monomer is 3,4-ethylenedioxythiophene.   The proton donating polymer compound has at least one selected from the group consisting of polyfluoroethylene, polystyrene, poly (meth) acrylic acid, polyimide, polyethylene, polypropylene, polybutadiene, and derivatives thereof as a main chain. It exists, The manufacturing method of the solid electrolytic capacitor as described in any one of Claims 12-15 characterized by the above-mentioned.   The proton-donating polymer compound has a side chain containing at least one group selected from the group consisting of a sulfonic acid group and a phosphoric acid group. The manufacturing method of the solid electrolytic capacitor as described in any one of Claims.   The production of the solid electrolytic capacitor according to any one of claims 12 to 17, wherein the proton donating polymer compound has a perfluoroalkyl ether side chain containing a sulfonic acid group. Method.   The method for producing a solid electrolytic capacitor according to any one of claims 12 to 18, wherein the water-soluble polymer compound is at least one selected from the group consisting of polyvinyl alcohol and cellulose. .   The method for producing a solid electrolytic capacitor according to any one of claims 12 to 19, wherein the monomer-containing composition further includes an oxidizing agent for oxidizing and polymerizing the monomer. .   21. The solid electrolytic capacitor according to any one of claims 12 to 20, wherein the monomer-containing composition further includes a dopant for increasing the conductivity of the conductive polymer compound. Production method.   The method for producing a solid electrolytic capacitor according to claim 21, wherein the dopant is at least one selected from the group consisting of alkylbenzene sulfonic acid and its salt, alkyl naphthalene sulfonic acid and its salt, and phosphoric acid. . The method for producing a solid electrolytic capacitor according to claim 21 or 22, wherein the dopant is p-toluenesulfonic acid or a salt thereof.

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