JP2001155966A - Method of manufacturing capacitor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a capacitor having high attaining ratio for capacity and satisfactory characteristic by having a capacitor element with a conductive polymer minute particle dispersion solution, a polymerizing monomer, an oxidizing solution or a mixed solution impregnated fully, while the capacitor element is made up of aluminum anode electrode foil and cathode electrode turned with a separator in-between. SOLUTION: A mixed solution 25 is fed under decompressed or pressurized conditions and is passed through from a lower edge side 9 to upper edge side 8 of a capacitor element 7, to impregnate the capacitor element 7. Then, the capacitor with high attaining ration for capacitor, and advantages in loss or impedance characteristics can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a small and large-capacity capacitor using a conductive polymer.

[0002]

2. Description of the Related Art In recent years, with the digitization of electric equipment,
As for the capacitor, a capacitor having a small size, a large capacity, and a low impedance in a high frequency region is required.

Hitherto, many capacitors have been proposed in which a conductive polymer having high electric conductivity is used as the electrolyte of the capacitor to reduce the impedance in a high frequency range.

Japanese Patent Application Laid-Open No. 2-15611 discloses a conductive polymer comprising aluminum having a dielectric film and 3,4-ethylenedioxythiophene as a repeating unit and p-toluenesulfonic acid anion as a dopant. A capacitor formed by chemical polymerization has been proposed. 3,4
A solution obtained by dissolving ethylenedioxythiophene monomer and an oxidizing agent in a solvent is applied to an oxidized aluminum electrode, and then the solvent is removed at room temperature or by heating, and the conductive polymer layer is formed by a chemical polymerization reaction. A process is described for forming, then washing off excess oxidant from the conductive polymer layer with water and finally drying to obtain a capacitor.

[0005] The Abstracts of the 58th Annual Meeting of the Electrochemical Society of Japan, pages 251 to 252 (1991), describe that a dielectric consisting of an electrodeposited polyimide thin film was formed on an etched aluminum foil, followed by chemical polymerization and electrolytic polymerization. Accordingly, a large-capacity film capacitor in which a conductive polymer layer is sequentially formed and used as an electrode has been proposed.

Further, Japanese Patent Application Laid-Open No. 9-293639 discloses a mixed solution obtained by mixing 3,4-ethylenedioxythiophene and an oxidizing agent, in which an anode electrode foil and a cathode electrode foil are separated by glass paper. A solid electrolytic capacitor has been proposed in which polyethylene dioxythiophene produced by a polymerization reaction in a mixed solution impregnated into a capacitor element wound through a separator and permeated into a separator is retained by a separator as an electrolyte layer. I have. Using ferric p-toluenesulfonate as the oxidizing agent and ethylene glycol as the solvent,
The capacitor element impregnated with the mixed solution is heated at 25 ° C to 1 ° C.
A method of producing a conductive polymer layer made of polyethylene dioxythiophene by a polymerization reaction by leaving it at a temperature of 00 ° C., washing with water, an organic solvent, etc., and finally drying to obtain a capacitor. It has been described.

Further, Japanese Patent Application Laid-Open No. Hei 6-325988 discloses that a capacitor element made of a tantalum sintered body is impregnated with a mixed solution obtained by mixing a cooled pyrrole monomer and an oxidizing agent, and then is cooled in air at 25 ° C. There has been proposed a production method in which polymerization is carried out.

[0008]

However, a capacitor in which an anode electrode foil and a cathode electrode foil are wound in a cylindrical solution through a separator in a mixed solution obtained by mixing a polymerizable monomer solution and an oxidizing agent solution. When the mixed solution is impregnated inside the capacitor element by reducing the pressure after immersing the element, when the air inside the capacitor element expands due to the reduced pressure and is released to the outside, and when the reduced pressure is stopped and returned to atmospheric pressure Then, the mixed solution is impregnated inside the capacitor element. If the pressure is reduced and then returned to the atmospheric pressure, air is likely to remain inside the capacitor element and the mixed solution cannot be sufficiently impregnated, so that a dense conductive polymer layer cannot be formed inside the capacitor element. However, there is a problem that a high capacity achievement rate and excellent capacitor characteristics cannot be obtained.

[0009] In addition, there are cases where bubbles are easily generated when the pressure is reduced,
If hydrogen peroxide is used as the oxidizing agent and oxygen gas is likely to be generated when the pressure is reduced, the mixed solution cannot be sufficiently impregnated only by reducing the pressure, so that a dense conductive polymer layer is formed inside the capacitor element. However, there was a problem that a high capacity achievement ratio and excellent capacitor characteristics could not be obtained because of the inability to form the capacitor.

An object of the present invention is to solve the above-mentioned problems of the prior art and to obtain a capacitor having a high capacity achievement ratio and excellent capacitor characteristics.

[0011]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and a first method for manufacturing a capacitor according to the present invention provides a mixed solution obtained by mixing a polymerizable monomer solution and an oxidizing agent solution. A step of preparing a capacitor element in which an anode electrode foil and a cathode electrode foil each having a dielectric layer formed thereon are wound via a separator, and opposing from one end face side of the capacitor element by decompression or pressurization. Supplying the mixed solution so as to pass through the end face side of the capacitor element to impregnate the capacitor element with the mixed solution; and
And forming a conductive polymer layer by a chemical polymerization reaction between the conductive polymer layer and the oxidizing agent.

A capacitor element in which an anode electrode foil and a cathode electrode foil each having a dielectric layer formed thereon are wound via a separator has an upper end face and a lower end face through which the inside and the outside of the capacitor element communicate. If the mixed solution is supplied to the capacitor element by impregnating the mixed solution by supplying the mixed solution from one end face of the capacitor element to the opposite end face by reducing or increasing the pressure, the air inside the capacitor element is blown to the other end face. Since the mixed solution is impregnated while being extruded from, air hardly remains inside the capacitor element, and the mixed solution can be sufficiently impregnated, so that the conductive polymer layer can be formed densely inside the capacitor element. A capacitor having a high capacity achievement ratio and excellent in loss characteristics and impedance characteristics can be obtained.

A second method of manufacturing a capacitor according to the present invention comprises a step of preparing a mixed solution obtained by mixing a polymerizable monomer solution and an oxidizing agent solution, and a step of preparing an anode electrode foil and a cathode electrode foil having a dielectric layer formed thereon. A step of preparing a capacitor element wound through a separator; and supplying the mixed solution so that the capacitor element is removed from one end face side to the opposite end face side by decompression or pressurization. Impregnating the mixed solution with pressure, impregnating the capacitor element with the mixed solution under pressure, and forming a conductive polymer layer by a chemical polymerization reaction between the polymerizable monomer and the oxidizing agent. This is a configuration having:

The mixed solution is supplied so that the mixed solution is discharged from one end face of the capacitor element to the opposite end face by decompression or pressurization, so that the mixed solution is impregnated in the capacitor element, and then the mixed solution is added to the capacitor element. In the case of pressure impregnation, the mixed solution is impregnated while extruding the air inside the capacitor element from the other end face side, so that air hardly remains in the capacitor element, and the mixed solution can be sufficiently impregnated. Further, by impregnating the mixed solution under pressure, it is possible to more sufficiently impregnate the portion where the mixed solution was not impregnated, for example, deep into the etching pit of the anode electrode foil. Since the polymer layer can be formed densely, a capacitor with a high capacity achievement ratio and excellent in loss characteristics and impedance characteristics can be obtained.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION
A step of preparing a mixed solution by mixing a polymerizable monomer solution and an oxidizing agent solution, and preparing a capacitor element by winding an anode electrode foil and a cathode electrode foil on each of which a dielectric layer is formed via a separator. A step of supplying the mixed solution so as to pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization to impregnate the capacitor element with the mixed solution; and Forming a conductive polymer layer by a chemical polymerization reaction between the capacitor and the oxidizing agent.

According to this method, the mixed solution is supplied so that the mixed solution escapes from one end face of the capacitor element to the opposite end face by decompression or pressurization, and the mixed solution is impregnated into the capacitor element. The mixed solution is impregnated while extruding air from the other end side,
Since air hardly remains inside the capacitor element and the mixed solution can be sufficiently impregnated, a conductive polymer layer can be densely formed inside the capacitor element by a chemical polymerization reaction, so that the capacity achievement rate is high. Thus, a capacitor having excellent loss characteristics and impedance characteristics can be realized.

Here, thiophene, pyrrole, aniline or a derivative thereof is used as the polymerizable monomer.

The solvent for the polymerizable monomer solution includes water, methanol, ethanol, isopropanol, and the like.
Examples thereof include butanol and a mixture thereof, but may be a stock solution of a polymerizable monomer without using a solvent.

Examples of the oxidizing agent include ferric alkyl benzene sulfonate, ferric naphthalene sulfonate, ferric alkyl naphthalene sulfonate, ferric anthraquinone sulfonate, ammonium persulfate and hydrogen peroxide. Preferably, ferric naphthalenesulfonate is used.

As the solvent for the oxidizing agent solution, water, methanol, ethanol, isopropanol, butanol, or a mixture thereof can be used.

Here, an anode electrode foil and a cathode electrode foil are subjected to an etching treatment on a valve metal such as an aluminum foil, a tantalum foil, a niobium foil and a titanium foil, and a dielectric layer is further formed on the anode electrode foil. Is used.

As the separator, manila paper, kraft paper, synthetic fiber paper, synthetic fiber nonwoven fabric made of polyamide, polypropylene, polyethylene, polyethylene terephthalate or the like, glass paper or the like is used.

For reducing the pressure, a pressure reducing pump, a cylinder or the like is used.

For pressurization, a gas cylinder, a compressor, a cylinder and the like are used.

According to a second aspect of the present invention, there is provided a process for preparing a polymerizable monomer solution and an oxidizing agent solution, and connecting an anode electrode foil and a cathode electrode foil on each of which a dielectric layer is formed via a separator. Winding the capacitor element, and supplying the polymerizable monomer solution and the oxidizing agent solution so that the capacitor element is removed from one end face side to the opposite end face side by decompression or pressurization. Production of a capacitor having a step of impregnating an element with the polymerizable monomer solution and the oxidizing agent solution, and a step of forming a conductive polymer layer by a chemical polymerization reaction between the polymerizable monomer and the oxidizing agent. Is the way.

According to this method, a polymerizable monomer solution and an oxidizing agent solution are supplied so that the polymerizable monomer solution and the oxidizing agent solution are discharged from one end face side to the opposite end face side by decompression or pressurization.
Since the capacitor element is impregnated with the polymerizable monomer solution and the oxidizing agent solution, the polymerizable monomer solution and the oxidizing agent solution are impregnated while the air inside the capacitor element is pushed out from the other end face side, and the inside of the capacitor element is impregnated. Since air hardly remains and the polymerizable monomer solution and the oxidizing agent solution can be sufficiently impregnated, the conductive polymer layer can be densely formed inside the capacitor element by a chemical polymerization reaction, so that the capacity achievement rate can be improved. And a capacitor having high loss characteristics and excellent impedance characteristics can be realized.

According to a third aspect of the present invention, there is provided a process for preparing a dispersion of fine conductive polymer particles, and winding an anode electrode foil and a cathode electrode foil having a dielectric layer formed thereon through a separator. Preparing the capacitor element by supplying the conductive polymer fine particle dispersion so as to pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization. A step of impregnating a molecular fine particle dispersion, a step of performing heat treatment on the capacitor element to form a conductive polymer fine particle layer, and a step of preparing a mixed solution obtained by mixing a polymerizable monomer solution and an oxidizing agent solution, A step of supplying the mixed solution so as to pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization to impregnate the capacitor element with the mixed solution; Sex monomer - by chemical polymerization reaction between said oxidizing agent is a method of manufacturing the capacitor and a step of forming a conductive polymer layer.

According to this method, the conductive polymer fine particle dispersion is supplied from one end face side to the opposite end face side of the capacitor element by decompression or pressurization, and the conductive polymer fine particle dispersion is supplied to the capacitor element. So that
The conductive polymer fine particle dispersion is impregnated while extruding the air inside the capacitor element from the other end surface side, so that air hardly remains inside the capacitor element, and the conductive polymer fine particle dispersion can be sufficiently impregnated. Therefore, heat treatment can be performed to form a conductive polymer fine particle layer at a high coverage inside the capacitor element.

Next, the mixed solution is supplied so that the mixed solution is impregnated with the mixed solution so as to pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization. The mixed solution is impregnated while extruding from the other end face side, air is hardly left inside the capacitor element, and the mixed solution can be sufficiently impregnated, so that the conductive polymer layer is formed inside the capacitor element by a chemical polymerization reaction. It can be formed densely. Since the conductive polymer fine particle layer as a base layer is formed at a high coverage inside the capacitor element and the conductive polymer layer can be densely formed thereon, the capacity achievement rate is high and the loss characteristics are high. And a capacitor having excellent impedance characteristics.

Here, the conductive polymer fine particles of the conductive polymer fine particle dispersion include polythiophene, polypyrrol,
Polyaniline or a derivative thereof is used.

According to a fourth aspect of the present invention, there is provided a method for preparing a mixed solution by mixing a polymerizable monomer solution and an oxidizing agent solution, and comprising the steps of: A step of preparing a capacitor element by winding it through a separator; and supplying the mixed solution so as to pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization. A step of impregnating the mixed solution, a step of impregnating the capacitor element with the mixed solution, and a step of forming a conductive polymer layer by a chemical polymerization reaction between the polymerizable monomer and the oxidizing agent. This is a method for manufacturing a capacitor having:

According to this method, the mixed solution is supplied so as to pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization, and the mixed solution is impregnated in the capacitor element. The mixed solution is impregnated while extruding air from the other end side,
Air hardly remains inside the capacitor element, and the mixed solution can be sufficiently impregnated.

Further, by impregnating the mixed solution by pressurizing, the place where the mixed solution was not impregnated,
For example, since the deep portion of the etching pit of the anode electrode foil can be more sufficiently impregnated, the conductive polymer layer can be densely formed inside the capacitor element by a chemical polymerization reaction. A capacitor having excellent loss characteristics and impedance characteristics can be realized.

According to a fifth aspect of the present invention, there is provided a process for preparing a polymerizable monomer solution and an oxidizing agent solution, and connecting the anode electrode foil and the cathode electrode foil each having the dielectric layer formed thereon through a separator. Winding the capacitor element, and supplying the polymerizable monomer solution and the oxidizing agent solution so that the capacitor element is removed from one end face side to the opposite end face side by decompression or pressurization. Impregnating the element with the polymerizable monomer solution and the oxidizing agent solution; impregnating the capacitor element with at least one of the polymerizable monomer solution and the oxidizing agent solution; And forming a conductive polymer layer by a chemical polymerization reaction of-with the oxidizing agent.

According to this method, the polymerizable monomer solution and the oxidizing agent solution are supplied such that the polymerizable monomer solution and the oxidizing agent solution are discharged from one end face of the capacitor element to the opposite end face by decompression or pressurization.
Since the capacitor element is impregnated with the polymerizable monomer solution and the oxidizing agent solution, the polymerizable monomer solution and the oxidizing agent solution are impregnated while the air inside the capacitor element is pushed out from the other end face side, and the inside of the capacitor element is impregnated. Air hardly remains, and the polymerizable monomer solution and the oxidizing agent solution can be sufficiently impregnated.

Further, by impregnating at least one of the polymerizable monomer solution and the oxidizing agent solution by pressurizing, the portion where the polymerizable monomer solution and the oxidizing agent solution were not impregnated, for example, the anode electrode foil Since the deep portion of the etching pit can be more sufficiently impregnated, the conductive polymer layer can be formed densely inside the capacitor element by a chemical polymerization reaction, so that the capacity achievement rate is high, and the loss characteristics and impingement property are reduced. A capacitor with excellent dance characteristics can be realized.

According to a sixth aspect of the present invention, there is provided a process for preparing a dispersion of fine conductive polymer particles, and winding an anode electrode foil and a cathode electrode foil having a dielectric layer formed thereon through a separator. Preparing the capacitor element by supplying the conductive polymer fine particle dispersion liquid from one end face side to the opposite end face side of the capacitor element by decompression or pressurization, and supplying the conductive element to the capacitor element. A step of impregnating the polymer fine particle dispersion, a step of impregnating the capacitor element with the conductive polymer fine particle dispersion, and a step of performing a heat treatment on the capacitor element to form a conductive polymer fine particle layer. Preparing a mixed solution in which a polymerizable monomer solution and an oxidizing agent solution are mixed; and mixing the mixed solution so that the mixed solution is removed from one end face of the capacitor element to the opposite end face by decompression or pressurization. Supplying a liquid, a step of impregnating the capacitor element with the mixed solution, a step of impregnating the capacitor element with the mixed solution, and a chemical polymerization reaction between the polymerizable monomer and the oxidizing agent, Forming a conductive polymer layer.

According to this method, the conductive polymer fine particle dispersion is supplied from one end face side of the capacitor element to the opposite end face side by decompression or pressurization, and the conductive polymer fine particle dispersion is supplied to the capacitor element. So that
The conductive polymer fine particle dispersion is impregnated while extruding the air inside the capacitor element from the other end surface side, so that air hardly remains inside the capacitor element, and the conductive polymer fine particle dispersion can be sufficiently impregnated. .

Further, by impregnating the conductive polymer fine particle dispersion by pressurizing, the portion where the conductive polymer fine particle dispersion was not impregnated, for example, more deeply into the etching pit of the anode electrode foil. Since it can be impregnated, the conductive polymer fine particle layer can be formed at a high coverage inside the capacitor element by performing a heat treatment.

Next, the mixed solution is supplied so that the mixed solution is impregnated with the mixed solution so that the mixed solution is discharged from one end face of the capacitor element to the opposite end face by decompression or pressurization. Is pushed out from the other end face side, and the mixed solution is impregnated, so that air hardly remains inside the capacitor element, and the mixed solution can be sufficiently impregnated.

Further, by impregnating the mixed solution by pressurizing, the place where the mixed solution was not impregnated,
For example, since the deep portion of the etching pit of the anode electrode foil can be more sufficiently impregnated, the conductive polymer layer can be formed densely inside the capacitor element by a chemical polymerization reaction. Since the conductive polymer fine particle layer as a base layer is formed at a high coverage inside the capacitor element and the conductive polymer layer can be densely formed thereon, the capacity achievement rate is high and the loss characteristics are high. And a capacitor having excellent impedance characteristics.

Further, a mixed solution obtained by cooling the polymerizable monomer solution and the oxidizing agent solution and mixing the cooled polymerizable monomer solution and the oxidizing agent solution may be used.

A conductive polymer fine particle dispersion, a polymerizable monomer solution,
In order to facilitate the impregnation with the oxidizing agent solution or the mixed solution, it is preferable to fill a large opening that passes from one end face side to the opposite end face side of the capacitor element.

In order to supply a conductive polymer fine particle dispersion, a polymerizable monomer solution, an oxidizing agent solution or a mixed solution so as to pass from one end face side to the opposite end face side of the capacitor element. As described, it is preferable to fix the side surface of the capacitor element.

Further, the dielectric layer may be an oxide film of a valve metal.

Also, the dielectric layer may be a polymer film.

It is preferable that the polymer is a polyimide or a copolymer of acrylic acid, methacrylic acid and styrene.

Hereinafter, each embodiment of the present invention will be described in detail.

(Embodiment 1) Hereinafter, a first embodiment of the present invention will be described with reference to FIGS. 1A is an external view of a capacitor element, and FIG. 1B is an enlarged view of the inside of the capacitor element.

As the anode electrode foil 1, an aluminum-etched foil 2 provided with a dielectric layer 3 on both sides by anodic oxidation was cut into a size of 5 mm in width and 216 mm in length. The cathode electrode foil 4 has a width of 5 mm and a length of 26 mm.
A 2 mm aluminum etched foil was used.

Next, the anode electrode foil 1 and the cathode electrode foil 4 were
It is wound through a separator 5 made of manila paper having a thickness of 40 μm, and stopped by a stopping tape 6 to obtain a capacitor element 7. The external dimensions of the wound capacitor element 7 used here are about 9 mm in diameter, and the upper end face 8 and the lower end face 9
Has a dimension between both end faces of about 6 mm. An anode lead wire 10 and a cathode lead wire 11 are previously connected to the anode electrode foil 1 and the cathode electrode foil 4 via an anode lead tab 12 and a cathode lead tab 13, respectively. And protrudes from the upper end surface 8.

Next, the cut surface when the anode electrode foil 1 was formed and the anode lead tab 12 were anodized. Anode lead wire 10 is supported, and capacitor element 7 is heated to 70 ° C.
In a 3% aqueous solution of ammonium adipate. First, the voltage is increased from 0 to 10.2 V at a speed of 10 mV / sec, and then a constant voltage of 10.2 V is applied for 60 minutes.
A dielectric layer was formed on the cut surface and the anode lead tab 12 by anodic oxidation. After washing with running deionized water for 10 minutes, drying was performed at 105 ° C. for 5 minutes.

This configuration was regarded as a capacitor, and the capacity in a chemical conversion solution was measured to be 670 μF.

Next, the portion where the anode electrode foil 1, the cathode electrode foil 4 and the separator 5 of the capacitor element 7 are to be wound, and the anode lead tab 12 and the cathode lead tab 13 are connected. An epoxy adhesive was applied to a large opening extending from the lower end surface 9 of the portion to the upper end surface 8 to seal the opening.

Next, description will be made with reference to FIG. In FIG. 2, (a) shows a schematic view of the impregnation jig, and (b) shows an enlarged view around the capacitor element.

The wire mesh 16 is fixed to the support pipe 18 with an adhesive. The wire mesh 16 has an anode lead of the capacitor element 7.
A hole for passing the lead wire 10 and the cathode lead wire 11 is provided,
In addition, one having an open eye so that a liquid could be passed was used. An opening 20 was provided at the other end of the support pipe 18. The support pipe 18, the packing 21, and the connection pipe 22 are fixed to the lid 19 with an adhesive. A cylinder 23 is connected to the connection pipe 22. After inserting the capacitor element 7 into the wire net 16, the tape 17 was wound around the side face 15 of the capacitor element 7 and the support pipe 18, and the side face 15 was fixed, and the capacitor element 7 was attached.

A polymerizable monomer, pyrrol, and a surfactant, sodium triisopropylnaphthalenesulfonate, were put in water, and the monomer was dissolved by stirring with a stirrer.
Prepare a solution. Next, β-naphthalenesulfonic acid and hydrogen peroxide are put in water, and stirred with a stirrer to prepare a dissolved oxidizing agent solution. A mixed solution 25 is prepared by mixing a monomer solution and an oxidizing agent solution. At this time, the mixed solution 25
4 mol / l of pyrrole, 0.01 mol / l of sodium triisopropylnaphthalenesulfonate,
It was prepared to have a concentration of 1 mol / l of hydrogen peroxide and 1.4 mol / l of β-naphthalenesulfonic acid.

The mixed solution 25 is put in the glass bottle 26. Capacitor element 7 attached to support pipe 18
Is immersed in the mixed solution 25. The lid 19 is pressed from above and the piston 24 is pushed in, and the compressed air enters the glass bottle 26 through the connecting pipe 22 and the mixed solution 25 is pressurized. The pressurized mixed solution 25 enters from the lower side 9 of the end face of the capacitor element 7 and
Is impregnated inside. At this time, the mixed solution 25 was supplied by pushing the piston 24 until a part of the mixed solution 25 came out from the opposite upper end portion 8 side.

A conductive polymer layer 14 made of polypyrrole was formed inside the capacitor element 7 by a chemical polymerization reaction.

20 seconds after the impregnation with the mixed solution 25, the capacitor element 7 is taken out and immersed in deionized water previously placed in a glass bottle. Lid 1
9 is pressed from above, and the piston 24 is pushed in and pressurized,
From the lower end surface 9 side of the capacitor element 7 to the opposite upper end surface 8
The condenser element 7 is washed by supplying deionized water so as to pass to the side. Next, the capacitor element 7 is washed in the same manner using ethanol as an organic solvent. Then, it was placed in an oven and dried at 120 ° C. for 60 minutes.

A series of steps from impregnation to drying was repeated four times until a predetermined amount of the conductive polymer layer 14 was formed inside the capacitor element 7.

After the formation of the conductive polymer layer 14, the capacitor element 7 is housed in a bottomed cylindrical aluminum case, the opening of which is sealed with a rubber plate, and an aging treatment is performed. Completed 10 capacitors. 1 kHz
The capacitance at z, the loss factor, and the impedance at 100 kHz were each measured. The average values are shown in (Table 1).

According to the present embodiment, the mixed solution is supplied so as to be released from one end face of the capacitor element to the opposite end face by pressurization, and the mixed solution is impregnated in the capacitor element. The mixed solution is impregnated while extruding the air inside from the other end face, and air is hardly left inside the capacitor element, and the mixed solution can be sufficiently impregnated. Since the molecular layer can be formed densely, the capacity achievement rate is high as shown in (Table 1).
A capacitor excellent in loss characteristics and impedance characteristics can be obtained.

[0064]

[Table 1]

Comparative Example 1 As Comparative Example 1, a capacitor was manufactured in the same manner as in Embodiment 1, except that the impregnation conditions and the cleaning conditions were changed. The impregnation of the mixed solution was performed as follows without using an impregnation jig. The capacitor element is immersed in the mixed solution in the glass bottle. The glass bottle was placed in a bell jar, and when the pressure reached 15 mmHg using a vacuum pump, the pressure was stopped and the pressure was returned to the atmospheric pressure, so that the mixed solution was impregnated. Further, the cleaning was changed so that the immersion cleaning with deionized water was performed for 15 minutes and the immersion cleaning with ethanol was performed for 15 minutes without using the impregnation jig.

The results of measuring the characteristics are shown in the above (Table 1).

In Comparative Example 1, air is likely to remain inside the capacitor element only by reducing the pressure and then returning to the atmospheric pressure. In particular, oxygen gas is generated when the pressure is reduced because hydrogen peroxide is used as the oxidizing agent. As a result, impregnation of the mixed solution is hindered, and the mixed solution cannot be sufficiently impregnated. Therefore, since a dense conductive polymer layer cannot be formed inside the capacitor element, as shown in Table 1, The capacity achievement ratio was low, and the loss characteristics and impedance characteristics were poor.

As is clear from the comparison between Comparative Example 1 and Embodiment 1 in (Table 1), in Embodiment 1,
By supplying the mixed solution so that the capacitor element is released from one end face side to the opposite end face side by pressurization and sufficiently impregnating the mixed solution into the capacitor element, the capacity achievement rate is high, the loss characteristic and the impedance are improved. It was found that a capacitor having excellent characteristics was obtained.

(Embodiment 2) Hereinafter, a second embodiment of the present invention will be described with reference to FIG.

The capacitor element 7 was the same as that of the first embodiment, and was used with a seal.

Next, description will be made with reference to FIG. In FIG. 3, (a) shows a schematic view of the impregnation jig, and (b) shows an enlarged view around the capacitor element. Wire mesh 28 is a support pipe 29
Is fixed with an adhesive. A connection pipe 33 is fixed to the other end of the support pipe 29 with an adhesive 32. The support pipe 29 is fixed to the lid 30 with an adhesive. Lid 30
Was provided with a through hole 31. A cylinder 34 is connected to the connection pipe 33. After inserting the capacitor element 7 into the wire mesh 28, the tape 27 was wound around the side face 15 of the capacitor element 7 and the support pipe 29, and the side face 15 was fixed, and the capacitor element 7 was attached.

8 mol / l of a polymerizable monomer, pyrrol, is placed in a solvent of methanol, and stirred with a stirrer to prepare a dissolved monomer solution 36. Next, 0.8 mol / l of ferric naphthalenesulfonate is put in a solvent of methanol and stirred with a stirrer to prepare an oxidizing agent solution 37 dissolved therein.

The monomer solution 36 is placed in a glass bottle 38. The capacitor element 7 attached to the support pipe 29 is immersed in the monomer solution 36. When the lid 30 is pressed from above and the piston 35 is pulled, the air in the support pipe 29 is drawn into the cylinder 34 through the connection pipe 33, and the pressure in the support pipe 29 is reduced. Due to the reduced pressure, the monomer solution 36 enters from the lower end face 9 side of the capacitor element 7 and is impregnated inside the capacitor element 7. At this time, the piston 35 was pulled to supply the monomer solution 36 until a part of the monomer solution 36 came out of the opposite end face upper portion 8 side.

Next, the oxidizing agent solution 37 was impregnated into the capacitor element 7 in the same manner as described above.

A conductive polymer layer 14 made of polypyrrole was formed inside the capacitor element 7 by a chemical polymerization reaction.

Thirty seconds after the impregnation with the oxidizing agent solution 37, the tape 27 is removed, the capacitor element 7 is removed from the impregnation jig, and immersion cleaning with ethanol for 15 minutes and immersion cleaning with deionized water. For 10 minutes. Then, it was placed in an oven and dried at 120 ° C. for 60 minutes.

A series of steps from impregnation to drying was repeated six times until a predetermined amount of the conductive polymer layer 14 was formed inside the capacitor element 7.

After the formation of the conductive polymer layer 14, the capacitor element 7 is housed in a bottomed cylindrical aluminum case, the opening of which is sealed with a rubber plate, and an aging treatment is performed. Completed 10 capacitors. The same characteristic evaluation as in the first embodiment was performed, and the average values thereof are shown in (Table 1).

According to the present embodiment, the polymerizable monomer solution and the oxidizing agent solution are supplied from one end face side of the capacitor element to the opposite end face side under reduced pressure, and the polymerizable monomer solution is supplied to the capacitor element. Since the solution and the oxidant solution are impregnated, the polymerizable monomer solution and the oxidant solution are impregnated while extruding the air inside the capacitor element from the other end face side, so that air hardly remains inside the capacitor element, Since the monomer solution and the oxidizing agent solution can be sufficiently impregnated, the conductive polymer layer can be densely formed inside the capacitor element by a chemical polymerization reaction.
As shown in Table 1, it is possible to obtain a capacitor having a high capacity achievement ratio and excellent loss characteristics and impedance characteristics.

(Embodiment 3) Hereinafter, a third embodiment of the present invention will be described.

The capacitor element was the same as that of the first embodiment except that the separator was changed from manila paper to a non-woven fabric of polyamide, and used was a capped one.

The conductive polymer particles of poly (3,4-ethylenedioxythiophene) (PEDOT), the dopant of polystyrenesulfonic acid, the surfactant, the binder and the solvent were water, and the active ingredient was 3.9. A conductive polymer fine particle dispersion in a weight% was used.

Using the impregnation jig as in the first embodiment,
The conductive polymer fine particle dispersion was supplied so as to be released from one end face side to the opposite end face side of the capacitor element by pressurization, and the capacitor element was impregnated with the conductive polymer fine particle dispersion.

Next, the capacitor element impregnated with the conductive polymer fine particle dispersion was removed from the impregnating jig, placed in an oven, and subjected to a heat treatment at 140 ° C. for 10 minutes. A polymer fine particle layer was formed.

A monomer solution of a stock solution of 3,4-ethylenedioxythiophene (EDOT) of a polymerizable monomer is prepared. Next, ferric naphthalene sulfonate is placed in methanol, and stirred with a stirrer to prepare a dissolved oxidizing agent solution. A mixed solution prepared by mixing a monomer solution and an oxidizing agent solution is prepared. At this time, when the mixed solution is used, EDOT
1.6 mol / l, ferric naphthalene sulfonate 0.8
It was prepared to have a concentration of mol / l.

As in the first embodiment, using an impregnation jig,
The mixed solution was supplied so as to be released from one end face side to the opposite end face side of the capacitor element by pressurization, and the capacitor element was impregnated with the mixed solution.

The capacitor element impregnated with the mixed solution was removed from the impregnating jig and placed in an oven at 40 ° C. for 30 minutes.
Heat treatment was performed at 85 ° C. for 30 minutes. A conductive polymer layer made of PEDOT was formed inside the capacitor element by a chemical polymerization reaction.

Next, immersion cleaning with ethanol was performed for 15 minutes, and immersion cleaning with deionized water was performed for 10 minutes. Then, it was placed in an oven and dried at 120 ° C. for 60 minutes.

After the formation of the conductive polymer layer, the capacitor element is housed in a bottomed cylindrical aluminum case, the opening of which is sealed with a rubber plate, and an aging treatment is performed.
A total of 10 capacitors were completed. Embodiment 1
The characteristics were evaluated in the same manner as described above, and their average values are shown in (Table 1).

According to the present embodiment, the conductive polymer fine particle dispersion is supplied from one end face of the capacitor element to the opposite end face by pressurization, and the conductive polymer fine particle is supplied to the capacitor element. Since the dispersion liquid is impregnated, the conductive polymer fine particle dispersion liquid is impregnated while extruding the air inside the capacitor element from the other end face side, so that air hardly remains inside the capacitor element, and the conductive polymer fine particle dispersion liquid Can be sufficiently impregnated, so that the conductive polymer fine particle layer can be formed at a high coverage inside the capacitor element by performing a heat treatment. Next, the mixed solution is supplied so as to be released from one end face side of the capacitor element to the opposite end face side by pressurization, and the mixed solution is impregnated into the capacitor element, so that the air inside the capacitor element is removed from the other end face. Since the mixed solution is impregnated while extruding from the side, air hardly remains inside the capacitor element, and the mixed solution can be sufficiently impregnated, so that the conductive polymer layer is densely formed inside the capacitor element by a chemical polymerization reaction. Can be. As shown in (Table 1), a conductive polymer fine particle layer as a base layer is formed at a high coverage inside the capacitor element, and the conductive polymer layer can be formed densely thereon. A capacitor having a high capacity achievement ratio and excellent in loss characteristics and impedance characteristics can be obtained.

Comparative Example 2 As Comparative Example 2, except that the conditions for impregnation of the conductive polymer fine particle dispersion and the mixed solution were changed.
A capacitor was manufactured in the same manner as in the third embodiment. The impregnation of the conductive polymer fine particle dispersion was performed as follows without using an impregnation jig. The capacitor element is immersed in the conductive polymer fine particle dispersion in the glass bottle. Place the glass bottle in the bell jar and use a vacuum pump for 30m
When the pressure reached mHg, the pressure was stopped and the pressure was returned to the atmospheric pressure, so that the dispersion of the conductive polymer fine particles was impregnated. The impregnation of the mixed solution was performed as follows without using an impregnation jig. The capacitor element is immersed in the mixed solution in the glass bottle. The glass bottle was placed in a bell jar, and when the pressure reached 15 mmHg using a vacuum pump, the pressure was stopped and the pressure was returned to the atmospheric pressure, so that the mixed solution was impregnated.

The results of measuring the characteristics are shown in the above (Table 1).

In Comparative Example 2, air is likely to remain inside the capacitor element only by reducing the pressure and then returning to the atmospheric pressure, and the conductive polymer fine particle dispersion or mixed solution cannot be sufficiently impregnated. Since it is impossible to form a conductive polymer fine particle layer having a high coverage and a dense conductive polymer layer inside, the capacity achievement ratio is low as shown in Table 1 and the loss characteristics and impedance are low. Characteristics were bad.

As is clear from the comparison between Comparative Example 2 and Embodiment 3 in (Table 1), in Embodiment 3,
A conductive polymer fine particle dispersion or mixed solution is supplied so as to be released from one end face of the capacitor element to the opposite end face by pressurization, and the capacitor element is sufficiently impregnated with the conductive polymer fine particle dispersion or mixed solution. As a result, it was found that a capacitor with a high capacity achievement ratio and excellent in loss characteristics and impedance characteristics was obtained.

(Embodiment 4) Hereinafter, a fourth embodiment of the present invention will be described with reference to FIG. In FIG.
(A) is a schematic view of an impregnation jig, and (b) is an enlarged view around a capacitor element.

The capacitor element was the same as that in the first embodiment, and was used with a seal.

The polymerizable monomer, pyrrole, is placed in methanol, and the monomer solution dissolved by stirring with a stirrer is placed in a thermostat at -30 ° C. and cooled. Next, ferric naphthalene sulfonate is placed in methanol, and the oxidizing agent solution dissolved by stirring with a stirrer is placed in a -30 ° C. constant temperature bath and cooled. A mixed solution 55 obtained by mixing a monomer solution and an oxidizing agent solution is prepared. At this time, the mixture was prepared to have a concentration of 1.4 mol / l of pyrrole and 0.8 mol / l of ferric naphthalenesulfonate as a mixed solution.

As in the first embodiment, using an impregnation jig,
The mixed solution 55 is supplied so as to be released from the lower end surface 9 side of the capacitor element 7 to the upper end surface 8 side opposite thereto by pressurization.
The mixed solution 55 was impregnated in the capacitor element 7.

Next, after closing the opening 50 with the closing rubber plate 57, the piston 54 was pushed in, and compressed air was introduced into the glass bottle 56 via the connecting pipe 52, and the mixed solution 55 was pressurized. The pressurized mixed solution 55 enters the lower end 9 of the capacitor element 7 and enters the capacitor element 7.
Is impregnated inside. At this time, since the opening 50 of the support pipe 48 is closed, the mixed solution 55 can be impregnated by applying a pressure of several hundred kPa.

A conductive polymer layer made of polypyrrole was formed inside the capacitor element 7 by a chemical polymerization reaction.

30 seconds after the impregnation with the mixed solution 55, the tape 47 is removed, the capacitor element 7 is removed from the impregnating jig, the immersion cleaning with ethanol is performed for 15 minutes, and the immersion cleaning with deionized water is performed. It was applied for 10 minutes. Then, it was placed in an oven and dried at 120 ° C. for 60 minutes.

A series of steps from impregnation to drying was repeated five times until a predetermined amount of the conductive polymer layer was formed inside the capacitor element 7.

After the formation of the conductive polymer layer, the capacitor element 7 is housed in a cylindrical aluminum case having a bottom, the opening thereof is sealed with a rubber plate, and an aging treatment is performed. Ten capacitors were completed. The same characteristic evaluation as in the first embodiment was performed, and the average values thereof are shown in (Table 1).

According to the present embodiment, the mixed solution is supplied so as to be released from one end face of the capacitor element to the opposite end face by pressurization, and the mixed solution is impregnated into the capacitor element. The mixed solution is impregnated while extruding the air inside from the other end face side, so that air hardly remains in the capacitor element, and the mixed solution can be sufficiently impregnated. Further, by impregnating the mixed solution under pressure, where the mixed solution was not impregnated, for example, in the deep portion of the etching pit of the anode electrode foil,
Since the impregnation can be performed more sufficiently, the conductive polymer layer can be densely formed inside the capacitor element by a chemical polymerization reaction, so that the capacity achievement rate is high as shown in (Table 1) and the loss characteristic is high. And a capacitor having excellent impedance characteristics can be obtained.

(Embodiment 5) Hereinafter, a fifth embodiment of the present invention will be described.

The capacitor element was the same as that of the first embodiment, and was used with a seal.

A monomer solution prepared by putting 6 mol / l of a polymerizable monomer and 0.03 mol / l of sodium triisopropylnaphthalenesulfonate as a surfactant in water and stirring with a stirrer to dissolve the monomer solution. Prepare Next, 3 mol / l of β-naphthalenesulfonic acid and 1.5 mol / l of hydrogen peroxide are put in water, and stirred with a stirrer to prepare a dissolved oxidizing agent solution.

As in the first embodiment, using an impregnation jig,
A monomer solution was supplied so as to be released from one end face side to the opposite end face side of the capacitor element by pressurization, and the capacitor element was impregnated with the monomer solution.

Next, an oxidizing agent solution is supplied by using an impregnating jig in the same manner as in the first embodiment so that the oxidizing agent solution is released from one end face side to the opposite end face side by pressurization. The oxidant solution was impregnated.

Next, the impregnating jig is used to cover the opening of the support pipe with a closing rubber plate, and then the piston is pushed in, and the oxidizing agent solution is impregnated into the capacitor element by applying pressure. did.

A conductive polymer layer made of polypyrrole was formed inside the capacitor element by a chemical polymerization reaction.

20 seconds after the impregnation with the oxidizing agent solution,
The tape was removed and the capacitor element was removed from the impregnation jig, and immersion cleaning with deionized water was performed for 15 minutes, and immersion cleaning with ethanol was performed for 10 minutes. Then, it was placed in an oven and dried at 120 ° C. for 60 minutes.

A series of steps from impregnation to drying was repeated six times until a predetermined amount of the conductive polymer layer was formed inside the capacitor element.

After the formation of the conductive polymer layer, the capacitor element was housed in a bottomed cylindrical aluminum case, and the opening was sealed with a rubber plate, followed by aging.
A total of 10 capacitors were completed. Embodiment 1
The characteristics were evaluated in the same manner as described above, and their average values are shown in (Table 1).

According to the present embodiment, the polymerizable monomer solution and the oxidizing agent solution are supplied from one end face of the capacitor element to the opposite end face by pressurization, and the polymerizable monomer solution is supplied to the capacitor element. -Since the solution and the oxidizing agent solution are impregnated, the polymerizable monomer solution and the oxidizing agent solution are impregnated while the air inside the capacitor element is pushed out from the other end side, so that air hardly remains inside the capacitor element, and It is possible to sufficiently impregnate the acidic monomer solution and the oxidizing agent solution. Further, by impregnating the oxidizing agent solution by applying pressure, it is possible to more sufficiently impregnate the portion where the polymerizable monomer solution and the oxidizing agent solution have not been impregnated, for example, into the deep etching pit of the anode electrode foil. So
Since the conductive polymer layer can be densely formed inside the capacitor element by the chemical polymerization reaction, a capacitor having a high capacity achievement ratio and excellent loss characteristics and impedance characteristics as shown in Table 1 can be obtained. Obtainable.

(Embodiment 6) Hereinafter, a sixth embodiment of the present invention will be described.

The capacitor element was the same as that of the first embodiment except that the separator was changed from manila paper to a non-woven fabric made of polyamide, and a sealing element was used.

A conductive polymer fine particle dispersion containing 3.9% by weight of an active ingredient was prepared by using PEDOT conductive polymer fine particles, polystyrenesulfonic acid dopant, surfactant, binder and solvent as water. Was.

Using the impregnation jig as in the first embodiment,
The conductive polymer fine particle dispersion was supplied so as to be released from one end face side to the opposite end face side of the capacitor element by pressurization, and the capacitor element was impregnated with the conductive polymer fine particle dispersion.

Next, the opening of the support pipe was closed with a closing rubber plate using an impregnating jig in the same manner as in the fourth embodiment, and then the piston was pushed in. The capacitor element was impregnated.

Next, the capacitor element impregnated with the conductive polymer fine particle dispersion was removed from the impregnating jig, placed in an oven, and subjected to a heat treatment at 140 ° C. for 10 minutes. A polymer fine particle layer was formed.

Next, the polymerizable monomer, pyrrole, was placed in methanol and stirred with a stirrer to dissolve the monomer.
The solution is cooled by placing it in a thermostat at −30 ° C. Next, ferric naphthalene sulfonate is placed in methanol, and the oxidizing agent solution dissolved by stirring with a stirrer is placed in a -30 ° C. constant temperature bath and cooled. A mixed solution prepared by mixing a monomer solution and an oxidizing agent solution is prepared. At this time, the mixture was prepared to have a concentration of 1.4 mol / l of pyrrole and 0.8 mol / l of ferric naphthalenesulfonate as a mixed solution.

Using the impregnation jig as in the first embodiment,
The mixed solution was supplied so as to be released from one end face side to the opposite end face side of the capacitor element by pressurization, and the capacitor element was impregnated with the mixed solution.

Next, as in the fourth embodiment, the opening of the support pipe was covered with a closing rubber plate using an impregnating jig, the piston was pushed in, and the mixed solution was impregnated into the capacitor element by pressurization. .

30 seconds after the impregnation with the mixed solution, the tape was removed and the capacitor element was removed from the impregnation jig.
It was left at room temperature for 30 minutes.

A conductive polymer layer made of polypyrrole was formed inside the capacitor element by a chemical polymerization reaction.

Next, immersion cleaning with ethanol was performed for 15 minutes, and immersion cleaning with deionized water was performed for 10 minutes. Then, it was placed in an oven and dried at 120 ° C. for 60 minutes.

After the formation of the conductive polymer layer, the capacitor element 7 is housed in a bottomed cylindrical aluminum case, the opening of which is closed with a rubber plate, and an aging treatment is performed. Ten capacitors were completed. The same characteristic evaluation as in the first embodiment was performed, and the average values thereof are shown in (Table 1).

According to the present embodiment, the conductive polymer fine particle dispersion is supplied from one end face of the capacitor element to the opposite end face by pressurization, and the conductive polymer fine particle is supplied to the capacitor element. Since the dispersion liquid is impregnated, the conductive polymer fine particle dispersion liquid is impregnated while extruding the air inside the capacitor element from the other end face side, so that air hardly remains inside the capacitor element, and the conductive polymer fine particle dispersion liquid Can be sufficiently impregnated. Further, by impregnating the conductive polymer fine particle dispersion by pressurizing, the portion where the conductive polymer fine particle dispersion was not impregnated, for example, more deeply impregnating the etching pit of the anode electrode foil. Therefore, the conductive polymer fine particle layer can be formed at a high coverage inside the capacitor element by performing a heat treatment. Next, the mixed solution is supplied so as to be released from one end face side of the capacitor element to the opposite end face side by pressurization, and the mixed solution is impregnated into the capacitor element. The mixed solution is impregnated while being pushed out from the side, so that air hardly remains inside the capacitor element, and the mixed solution can be sufficiently impregnated. Further, by impregnating the mixed solution under pressure, it is possible to more sufficiently impregnate the portion where the mixed solution was not impregnated, for example, deep into the etching pit of the anode electrode foil. A conductive polymer layer can be densely formed inside. As shown in (Table 1), a conductive polymer fine particle layer as a base layer is formed at a high coverage inside the capacitor element, and the conductive polymer layer can be formed densely thereon. A capacitor having a high capacity achievement ratio and excellent in loss characteristics and impedance characteristics can be obtained.

(Embodiment 7) Hereinafter, a seventh embodiment of the present invention will be described.

In this embodiment, a capacitor was completed in the same manner as in Embodiment 1, except that a high-molecular polyimide was used as the dielectric layer instead of the anodic oxide film. The steps before the dielectric layer is changed to polyimide and before the sealing is performed will be described below.

A dielectric layer made of polyimide is provided on both sides of the aluminum-etched foil by electrodeposition. First, biphenyltetracarboxylic dianhydride and p-phenylenediamine were reacted in N-methylpyrrolidone by refluxing nitrogen to obtain a polyamic acid. This polyamic acid is N, N
-Diluted in dimethylamide and added triethylamine to obtain a polyamic acid salt solution. Then, methanol was added to adjust to finally contain 0.15% of polyamic acid to prepare an electrodeposition solution.

An aluminum-etched foil is immersed in the electrodeposition solution, and this is used as an anode.
A voltage of V was applied to electrodeposit the polyamic acid film. Thereafter, the mixture was heated at 250 ° C. for 1 hour to polyimide the polyamic acid. This electrodeposition and heating were repeated three times to form a dielectric layer made of polyimide.

The aluminum-etched foil provided with the dielectric layer was cut into a size of 5 mm in width and 216 mm in length and used as an anode electrode foil. In addition, the cathode electrode foil has a width of 5 m.
m, an aluminum etched foil having a length of 262 mm was used.

Next, the anode electrode foil and the cathode electrode foil are wound via a separator made of manila paper having a thickness of 40 μm, and stopped by a winding tape to obtain a capacitor element. The anode electrode foil and the cathode electrode foil should be
The lead wire and the cathode lead wire are connected via an anode lead tab and a cathode lead tab, and protrude from the upper end face.

Next, while supporting the anode lead wire, the capacitor element is immersed in the same electrodeposition solution as described above. The anode foil was used as an anode, and a voltage of 12 V was applied between the anode and the separated electrode to electrodeposit a polyamic acid film. Thereafter, the mixture was heated at 250 ° C. for 1 hour to polyimide the polyamic acid. In this way, a dielectric layer made of polyimide was formed on the cut surface when the anode electrode foil was formed and the anode lead tab.

This structure was regarded as a capacitor, and the capacity of a chemical conversion solution consisting of an aqueous solution of adipic acid was measured.
It was 0 μF.

The characteristics were evaluated in the same manner as in the first embodiment, and their average values are shown in Table 1. According to the present embodiment, even when a polymer polyimide is used for the dielectric layer, as shown in Table 1, a film capacitor having a high capacity achievement ratio and excellent loss characteristics and impedance characteristics is obtained. Was realized.

Embodiment 8 Hereinafter, an eighth embodiment of the present invention will be described.

In this embodiment, a capacitor is completed in the same manner as in Embodiment 1 except that a polymer of acrylic acid, methacrylic acid and styrene is used as the dielectric layer instead of the anodic oxide film. Was. The steps before the dielectric layer is changed to a copolymer of acrylic acid, methacrylic acid and styrene and before the sealing is performed will be described below.

A dielectric layer made of a copolymer of acrylic acid, methacrylic acid and styrene is provided on both sides of the aluminum-etched foil by electrodeposition. First, the composition of the electrodeposition solution used was
The solid content is 10% by weight, deionized water is 86% by weight, and butyl cellosolve is 4% by weight. The solid content therein has a molecular weight of about 3
A mixture of a copolymer of acrylic acid, methacrylic acid and styrene and a benzoquanamine-based resin in a ratio of 7: 3 was used, and 50% of the carboxylic acid groups were neutralized with trimethylamine in order to disperse the mixture in the electrodeposition solution. .

An aluminum-etched foil was immersed in the electrodeposition solution, and this was used as an anode. A voltage was applied between the electrode and a separately provided electrode until the voltage reached 5 V at a current density of 0.3 mA / cm ^2. Current electrodeposition was performed, and then constant voltage electrodeposition was performed at 5 V for 15 minutes.

Next, washing with deionized water at 80 ° C.
After the heat treatment was performed for 0 minutes, heat treatment was performed at 180 ° C. for 30 minutes to cause a cross-linking reaction with the benzoguanamine-based resin. These series of processes were repeated three times to form a dielectric layer.

The aluminum-etched foil provided with the dielectric layer was cut into a size of 5 mm in width and 216 mm in length and used as an anode electrode foil. In addition, the cathode electrode foil has a width of 5 m.
m, an aluminum etched foil having a length of 262 mm was used.

Next, the anode electrode foil and the cathode electrode foil are wound through a separator made of manila paper having a thickness of 40 μm, and stopped by a winding tape to obtain a capacitor element. The anode electrode foil and the cathode electrode foil should be
The lead wire and the cathode lead wire are connected via an anode lead tab and a cathode lead tab, and protrude from the upper end face.

Next, while supporting the anode lead wire, the capacitor element is immersed in the same electrodeposition solution as described above. A voltage is applied between the anode electrode foil as an anode and a separately provided electrode, a constant current electrodeposition is performed at a current density of 0.3 mA / cm ² until the voltage reaches 5 V, and a constant voltage is further applied at 5 V for 15 minutes. Electrodeposition was performed. Next, washing with deionized water at 80 ° C. is performed for 20 minutes.
After performing the heat treatment at 180 ° C. for 30 minutes, a cross-linking reaction with the benzoguanamine-based resin was performed. In this way, a dielectric layer made of a copolymer of acrylic acid, methacrylic acid and styrene was formed on the cut surface when the anode electrode foil was formed and on the tab for the anode lead.

[0147] This structure was regarded as a capacitor, and the capacity in a chemical conversion solution consisting of an aqueous solution of adipic acid was measured.
It was 40 μF.

The same characteristic evaluation as in the first embodiment was performed, and the average values thereof are shown in (Table 1).

According to the present embodiment, even when a polymer of acrylic acid, methacrylic acid and styrene of a polymer is used as the dielectric layer, the capacity achievement ratio is high as shown in (Table 1). It was found that a film capacitor having excellent loss characteristics and impedance characteristics could be realized.

In the first to eighth embodiments,
As the solvent for the polymerizable monomer solution, the oxidizing agent solution or the mixed solution, the case of methanol and water has been described, but ethanol, isopropanol, butanol, and other solvents,
And various mixed systems can also be applied, and the present invention is not limited to the type.

In the first to eighth embodiments,
Although the case where pyrrole and 3,4-ethylenedioxythiophene are used as the polymerizable monomer has been described, aniline or another polymerizable monomer that can be a conductive polymer can be applied, and the type is limited. Not done.

In the first to eighth embodiments,
Although the case where poly (3,4-ethylenedioxythiophene) is used as the conductive polymer fine particles in the conductive polymer fine particle dispersion has been described, polythiophene, polypyrrol, polyaniline, or a derivative thereof can also be used. , But is not limited to that type.

In the first to eighth embodiments,
As the polymer to be the dielectric layer, polyimide and a case of using a copolymer of acrylic acid, methacrylic acid, and styrene have been described, but any other polymer material that can form a thin film can be used. However, the invention is not limited to that type.

In the first to eighth embodiments,
Although only the case where the valve metal is aluminum has been described, other materials such as tantalum, zirconium, niobium, hafnium and titanium, and intermetallic compounds thereof can also be used.

In the first to eighth embodiments,
The case where the oxidizing agent is hydrogen peroxide and ferric naphthalenesulfonate has been described, but ferric alkylbenzene sulfonate, ferric alkylnaphthalene sulfonate, ferric anthraquinone sulfonate, ammonium persulfate, and other oxidizing agents It can also be used and the invention is not limited to that type.

In the first to eighth embodiments,
Although the case where an air cylinder is used as a means for applying pressure and pressure reduction has been described, a pressure reduction pump, a gas cylinder, a compressor, and the like may be used, and the present invention is not limited to such means.

In the first to eighth embodiments,
A conductive polymer fine particle dispersion, a polymerizable monomer solution,
Although the case where the oxidizing agent solution or the mixed solution is supplied has been described, the configuration may be such that the oxidizing agent solution or the mixed solution is supplied so as to pass from the upper end surface to the lower end surface.

Further, in the embodiment, the case where the impregnation is performed by applying a pressure of several hundred kPa from the lower side of the end face of the capacitor element has been described, but the impregnation is performed by applying the pressure from the upper side of the end face or from both sides of the end face. Is also good.

In the first to eighth embodiments,
A large opening that extends from the lower part of the end face to the upper part of the end face of the part where the anode electrode foil, cathode electrode foil, and separator of the capacitor element starts to be wound, and the part where the anode lead tab and the cathode lead tab are connected. In the description above, the case where an epoxy adhesive is applied as a seal is described. However, in the part where the winding is started, a resin molded product is inserted or a part where the tab for the anode lead and the tab for the cathode lead are connected. In this case, the tabs for the anode lead and the cathode lead may be changed so as not to have a large opening, and the present invention is not limited to this as long as the large opening can be narrowed or closed. It is not limited to.

[0160]

As described above, according to the present invention, a conductive polymer fine particle dispersion, a polymerizable monomer solution, or the like is formed so as to be released from one end face side to the opposite end face side of the capacitor element by decompression or pressurization. By supplying the oxidizing agent solution or the mixed solution and impregnating the capacitor element, it is possible to obtain an advantageous effect that a capacitor achievement ratio is high and a capacitor excellent in loss characteristics and impedance characteristics can be obtained.

Also, a conductive polymer fine particle dispersion, a polymerizable monomer solution, an oxidizing agent solution, or a mixed solution is supplied so as to pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization. Then, the capacitor element is impregnated, and then the capacitor element is impregnated with a conductive polymer fine particle dispersion, a polymerizable monomer solution, an oxidizing agent solution, or a mixed solution, so that the capacity achievement rate is high, the loss characteristic and the impedance are improved. -An advantageous effect that a capacitor having excellent dance characteristics can be obtained.

[Brief description of the drawings]

FIG. 1 is an external perspective view of a capacitor element according to Embodiment 1 of the present invention.

FIG. 2 is a cross-sectional view of the impregnation jig according to the first embodiment of the present invention.

FIG. 3 is a cross-sectional view of an impregnation jig according to Embodiment 2 of the present invention.

FIG. 4 is a sectional view of an impregnation jig according to a fourth embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Anode electrode foil 2 Aluminum etched foil 3 Dielectric layer 4 Cathode electrode foil 5 Separator 6 Winding tape 7 Capacitor element 8 Upper end face 9 Lower end face 10 Anode lead wire 11 Cathode lead wire 12 Anode Lead tab 13 Cathode lead tab 14 Conductive polymer layer 15 Side surface 16, 46 Wire mesh 17, 27, 47 Tape 18, 28, 48 Support pipe 19, 30, 49 Lid 20, 50 Opening 21, 51 Packing 22, 33, 52 Connecting pipe 23, 34, 53 Cylinder 24, 35, 54 Piston 25, 55 Mixed solution 26, 38, 56 Glass bottle 31 Through hole 32 Adhesive 36 Monomer solution 37 Oxidant solution 57 Closure Rubber plate

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hiroki Kusanagi 3-10-1 Higashi-Mita, Tama-ku, Kawasaki City, Kanagawa Prefecture Inside Matsushita Giken Co., Ltd. (72) Inventor Yasue Matsuya 3 Higashi-Mita, Tama-ku, Kawasaki City, Kanagawa Prefecture Matsushita Giken Co., Ltd.

Claims (12)

[Claims] 1. A step of mixing a polymerizable monomer solution and an oxidizing agent solution to prepare a mixed solution, and winding an anode electrode foil and a cathode electrode foil having a dielectric layer formed thereon through a separator. A step of preparing a capacitor element, supplying the mixed solution so as to pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization, and impregnating the capacitor element with the mixed solution, Forming a conductive polymer layer by a chemical polymerization reaction between the polymerizable monomer and the oxidizing agent. 2. A step of preparing a polymerizable monomer solution and an oxidizing agent solution, and a step of preparing a capacitor element by winding an anode electrode foil and a cathode electrode foil each having a dielectric layer formed thereon through a separator. Supplying the polymerizable monomer solution and the oxidizing agent solution such that the polymerizable monomer solution and the oxidizing agent solution pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization, and the polymerizable monomer solution is supplied to the capacitor element. A method for manufacturing a capacitor, comprising: a step of impregnating the oxidizing agent solution; and a step of forming a conductive polymer layer by a chemical polymerization reaction between the polymerizable monomer and the oxidizing agent. 3. A step of preparing a dispersion liquid of conductive polymer fine particles, and a step of preparing a capacitor element by winding an anode electrode foil and a cathode electrode foil each having a dielectric layer formed thereon through a separator. Supplying the conductive polymer fine particle dispersion so as to pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization, and impregnating the capacitor element with the conductive polymer fine particle dispersion. Subjecting the capacitor element to a heat treatment to form a conductive polymer fine particle layer; preparing a mixed solution of a polymerizable monomer solution and an oxidizing agent solution; and Supplying the mixed solution so as to pass from one end surface side to the opposite end surface side to impregnate the capacitor element with the mixed solution; and
Forming a conductive polymer layer by a chemical polymerization reaction of the capacitor with the oxidizing agent. 4. A process of preparing a mixed solution by mixing a polymerizable monomer solution and an oxidizing agent solution, and winding an anode electrode foil and a cathode electrode foil having a dielectric layer formed thereon through a separator. A step of preparing a capacitor element, supplying the mixed solution so as to pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization, and impregnating the capacitor element with the mixed solution, A method for manufacturing a capacitor, comprising: a step of impregnating the capacitor element with the mixed solution under pressure; and a step of forming a conductive polymer layer by a chemical polymerization reaction between the polymerizable monomer and the oxidizing agent. 5. A step of preparing a polymerizable monomer solution and an oxidizing agent solution, and a step of preparing a capacitor element by winding an anode electrode foil and a cathode electrode foil having a dielectric layer formed thereon through a separator. Supplying the polymerizable monomer solution and the oxidizing agent solution such that the polymerizable monomer solution and the oxidizing agent solution pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization, and the polymerizable monomer solution is supplied to the capacitor element. Impregnating the oxidizing agent solution, pressurizing and impregnating the capacitor element with at least one of the polymerizable monomer solution and the oxidizing agent solution, and chemically polymerizing the polymerizable monomer and the oxidizing agent. Forming a conductive polymer layer by a reaction. 6. A step of preparing a dispersion of conductive polymer fine particles, and a step of winding an anode electrode foil and a cathode electrode foil having a dielectric layer formed thereon through a separator to prepare a capacitor element. A step of supplying the conductive polymer fine particle dispersion so as to pass from one end face side to the opposite end face side of the capacitor element by pressure reduction or pressurization, and impregnating the capacitor element with the conductive polymer fine particle dispersion liquid. And a step of impregnating the capacitor element with the conductive polymer fine particle dispersion, a step of performing heat treatment on the capacitor element to form a conductive polymer fine particle layer, a polymerizable monomer solution and an oxidizing agent. A step of preparing a mixed solution obtained by mixing the solutions,
A step of supplying the mixed solution so as to pass from one end face side to the opposite end face side of the capacitor element by decompression or pressurization, and impregnating the capacitor element with the mixed solution; and A method for producing a capacitor, comprising: a step of impregnating under pressure; and a step of forming a conductive polymer layer by a chemical polymerization reaction between the polymerizable monomer and the oxidizing agent. 7. The method according to claim 1, wherein the polymerizable monomer solution and the oxidant solution are cooled, and the cooled polymerizable monomer solution and the oxidant solution are mixed to prepare a mixed solution. 7. The method for manufacturing a capacitor according to any one of items 4 and 6. 8. The method of manufacturing a capacitor according to claim 1, wherein a large opening extending from one end face side to the opposite end face side of the capacitor element is filled. 9. The method for manufacturing a capacitor according to claim 1, wherein a side surface of the capacitor element is fixed. 10. The method according to claim 1, wherein the dielectric layer is an oxide film of a valve metal. 11. The method according to claim 1, wherein the dielectric layer is a polymer film. 12. A polymer film comprising a polyimide or a copolymer of acrylic acid, methacrylic acid and styrene.
12. The method for manufacturing a capacitor according to any one of claims 11 to 11.