JP2000100666A - Manufacture of solid electrolytic capacitor, and solid electrolytic capacitor manufactured thereby - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the formation of a conductive high polymer layer on an anode lead wire, by not soaking the face having the anode lead wire in at least monomer solution when soaking it in monomer solution. SOLUTION: Tantalum powder is press-molded into specified form on the anode lead wire 2 consisting of tantalum, and then it is baked to form a porous body, and the anode is oxidated in phosphoric acid aqueous solution, thus a dielectric oxide film layer is made on the surface of the porous body to make an anode body 1. Next, the anode body 1 is soaked halfway in monomer solution 3, with is side having the anode lead wire 2 up side, and then is pulled up. Then, the anode body 1 is soaked wholly in oxidizer solution, and then is pulled up and is kept in atmosphere at a specified temperature. A chain of operations of soaking it in this oxidizer solution 4 are repeated for specified times, and then it is subjected to chemical oxidative polymerizing reaction, and then it is washed and dried. The above operation is repeated a specified number of times to form a conductive high polymer layer. By this method, the formation of the conductive high polymer layer on the anode lead wire is prevented.

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 solid electrolytic capacitor using a conductive polymer layer as a solid electrolyte, and a solid electrolytic capacitor manufactured by using the method.

[0002]

2. Description of the Related Art In recent years, with the digitization of electronic equipment, excellent high-frequency characteristics of solid electrolytic capacitors used for the same have been demanded.

A solid electrolytic capacitor using a conductive polymer layer as a solid electrolyte has an anode body made of a valve metal having a dielectric oxide film layer formed on the surface thereof, on which a conductive polymer layer is formed. It is obtained by doing.

[0004] In the first conventional method of manufacturing a solid electrolytic capacitor, a conductive polymer layer is formed by mixing a monomer solution and an oxidizing agent solution as shown in US Patent No. 4,697,001. The porous body is obtained by alternately immersing the porous body in the monomer solution and the oxidizing agent solution, and the previously immersed solution, for example, the monomer solution is contained inside the porous body and immersed in the other solution, for example, the oxidizing agent solution. A conductive polymer layer was polymerized inside the body.

[0005]

However, in this manufacturing method, since the monomer solution is contained inside the anode body and immersed in the oxidizing agent solution, the reaction starts from the contact interface and the entire pores inside the anode body become conductive. It is difficult to form a polymer layer, and when the monomer solution is immersed in the oxidant solution, the monomer solution flows out and diffuses into the oxidant solution and reacts outside the anode body. There was a problem that the yield of adhesion to the body was low.

The present invention solves the above problems,
A method of manufacturing a solid electrolytic capacitor capable of uniformly and densely forming a conductive polymer layer up to a pore portion inside an anode body and preventing formation of a conductive polymer layer on an anode lead wire, and a method of manufacturing the same It is an object of the present invention to provide a solid electrolytic capacitor manufactured by using the method.

[0007]

According to the present invention, in order to achieve the above object, at least the surface having the anode lead-out line is not immersed in the monomer solution when immersed in the monomer solution.

According to this manufacturing method, the conductive polymer layer can be uniformly and densely formed up to the pores inside the anode body, and the formation of the conductive polymer layer on the anode lead wire can be prevented. .

[0009]

DETAILED DESCRIPTION OF THE INVENTION The invention according to claim 1 of the present invention comprises a valve action metal having an anode lead wire and having a dielectric oxide film layer having a conductive polymer layer on the surface. A step of immersing the anode body in a monomer solution containing a monomer with the surface having the anode lead-out line of the anode body facing upward, a step of pulling up the anode body from the monomer solution, and a step of immersing the anode body in an oxidant solution containing an oxidant And a step of sequentially pulling up the anode body from the oxidant solution,
In the method for manufacturing a solid electrolytic capacitor for forming the conductive polymer layer on the dielectric oxide film layer, when immersing in the monomer solution, the surface having the anode lead wire is not immersed in at least the monomer solution, Since the whole anode body is not immersed in the monomer solution, the monomer solution is retained throughout the anode body by capillary action, making it difficult to hold air in the pores inside the anode body, and ensuring uniform and dense conductivity even in the pores. The molecular layer can be formed, and even if the entire anode body is immersed in an oxidizing agent solution, a conductive polymer is not formed on a release material such as Teflon attached to the base of the anode lead wire, and this process is repeated. This also has the effect of preventing the formation of a conductive polymer layer on the anode lead-out line without rising over the Teflon to the anode lead-out line.

According to a second aspect of the present invention, there is provided an anode body comprising a valve metal having an anode lead wire and having a dielectric oxide film layer having a conductive polymer layer on a surface thereof. A step of immersing the anode body in a monomer solution containing a monomer with the surface having a lead line as an upper surface, a step of pulling up the anode body from the monomer solution, and a step of immersing the anode body in an oxidant solution containing an oxidant, In the method of manufacturing a solid electrolytic capacitor for forming the conductive polymer layer on the dielectric oxide film layer through a step of sequentially pulling up the anode body from the oxidizing agent solution, when immersing in a monomer solution, a predetermined immersion position Immersion at a speed of 1 mm / sec or less. If immersion at a speed of 1 mm / sec or less, it becomes easier to hold air in the pores inside the anode body.
It is preferable that the immersion is performed at a speed of not more than c, so that it is difficult to hold air in the pores inside the anode body, and it is possible to prevent the liquid from waving and to precisely control the immersion position.

[0011] The invention according to claim 3 is based on claim 1.
Or, after pulling up from the monomer solution described in 2, the monomer solution is not retained in the outermost layer of the anode body, so that the amount of the monomer solution flowing out and diffused into the oxidant solution is suppressed, and the contamination of the oxidant solution is reduced. It has the effect of being able to.

The invention described in claim 4 is the same as the invention described in claim 3.
When the anode body is pulled up from the monomer solution described above, the anode body is pulled up at a speed of 1 mm / sec or less until the anode body is completely pulled up from the monomer solution. When the anode body is pulled up at a speed of 1 mm / sec or more, the monomer solution is held in the outermost layer of the anode body. When immersed in the oxidizing agent solution, the monomer solution of the outermost layer of the anode body flows out and diffuses into the oxidizing agent solution, thereby contaminating the oxidizing agent solution and hindering the efficient use of the monomer solution. It is preferable to pull up at the following speed, and since the monomer solution is not held in the outermost layer of the anode body, it has an effect that the monomer solution can be used with high efficiency.

The invention described in claim 5 is the third invention.
After pulling up the anode body from the monomer solution described, the anode body is brought into contact with a porous body having an affinity lower than the affinity of the anode body for the monomer solution, and the attached solution of the outermost layer of the anode body is removed. By having the anode body contact a porous body having an affinity lower than the affinity of the anode body for the monomer solution, the monomer solution contained inside the anode body is not removed, and the anode body is removed. This has the effect that only the monomer solution attached to the outermost layer can be removed.

[0014] The invention according to claim 6 is the first invention.
Or when immersing in the oxidizing solution according to 2, the surface having the anode lead-out line is at least immersed in the oxidizing solution,
This has an effect that a conductive polymer layer can be sufficiently formed on the surface having the anode lead-out line.

The invention described in claim 7 is the first invention.
Or, when immersing in the oxidizing agent solution described in 2, the immersion is performed at a speed of 50 mm / sec or more to a predetermined immersion position.
When immersed at a speed of m / sec or less, waviness of the liquid surface tends to occur, and when immersed at a speed of 1 mm / sec or less, the waviness of the liquid surface can be prevented. It is preferable that the immersion is performed at a speed of 50 mm / sec or more because the amount of outflow and diffusion into the oxidizing agent solution before immersion increases, and the distribution of adhesion formation of the conductive polymer layer to the anode body occurs. This has the effect of preventing ripples on the liquid surface and suppressing the amount of the monomer solution contained in the anode body flowing out and diffused into the oxidizing agent solution.

The invention described in claim 8 is the first invention.
Or, when immersing in the oxidizing agent solution described in 2 above, immersion at a speed of 1 mm / sec or less up to 1/4 from the lower surface of the anode body, then 1 m
It is immersed to a predetermined immersion position at a speed of not less than m / sec. Since it is immersed up to 1/4 from the lower surface of the anode body at a speed of 1 mm / sec or less, the liquid surface can be prevented from waving and then 1 mm / sec. Even when immersed to a predetermined immersion position at a speed of more than sec, no waving of the liquid surface occurs, the immersion position can be precisely controlled, and the monomer solution contained inside the anode body is This has the effect of reducing the amount of outflow and diffusion.

The invention according to claim 9 is the first invention.
Or when immersed in the oxidant solution according to 2, after immersion from the lower surface of the anode body to 1/4 at a speed of 1 to 50 mm / sec,
It is characterized in that it is held in place for less than 1 sec, and is immersed again at a speed of 1 mm / sec or more to a predetermined immersion position,
When immersed at a speed of 1 to 50 mm / sec from the lower surface of the anode body to 1/4, even if the liquid surface undulates, 1 /
Ripple can be suppressed by holding it in place for less than 1 sec at a position of less than 4 and then, even if immersed at a speed of 1 mm / sec or more, no undulation of the liquid surface occurs and the immersion position is precisely controlled. This has the effect that the amount of the monomer solution contained in the anode body can be suppressed from flowing out and diffusing into the oxidizing agent solution.

According to a tenth aspect of the present invention, there is provided a conductive polymer comprising a step of sequentially lifting the anode body according to any one of the first to ninth aspects from the oxidizing agent solution and holding the anode body for a predetermined time. It forms a layer and has the effect of further increasing the filling of pores inside the anode body.

Further, in the invention according to claim 11, when the anode body is pulled up from the oxidant solution according to claim 1 or 2, it takes 50 mm until the anode body is completely pulled up from the oxidant solution.
When the wire is pulled up at a speed of 50 mm / sec or less, the amount of the oxidant solution taken out is small, so that the oxidant solution is not easily held on the anode body, and the conductive polymer layer is formed on the anode body. 50mm because it is difficult to form on the top
It is preferable to pull up at a speed of at least / sec. Thereby, the oxidizing agent solution can be brought out to the maximum, the oxidizing agent solution is held above the anode body, and the conductive polymer layer can be formed on the anode body.

The invention according to a twelfth aspect of the present invention is directed to the anode of the anode body comprising a valve action metal provided with an anode lead wire and having a dielectric oxide film layer having a conductive polymer layer on the surface. A step of immersing the anode body in an oxidant solution containing an oxidant with the surface having the lead line as an upper surface, a step of pulling up the anode body from the oxidant solution, and a step of immersing the anode body in a monomer solution containing a monomer, In a method for manufacturing a solid electrolytic capacitor in which the conductive polymer layer is formed on the dielectric oxide film layer through a step of sequentially pulling up the anode body from the monomer solution, when the anode body is immersed in an oxidizing agent solution, The surface having the wire is at least not immersed in the oxidizing agent solution, and even if this process is repeated, the conductive material on the anode wire does not go over the Teflon to the anode wire. It has the effect of preventing formation of the layer.

According to a thirteenth aspect of the present invention, there is provided an anode body comprising a valve action metal having an anode lead wire and having a dielectric oxide film layer having a conductive polymer layer on the surface. A step of immersing the anode body in an oxidant solution containing an oxidant with the surface having the lead line as an upper surface, a step of pulling up the anode body from the oxidant solution, and a step of immersing the anode body in a monomer solution containing a monomer, In the method of manufacturing a solid electrolytic capacitor for forming the conductive polymer layer on the dielectric oxide film layer through a step of sequentially pulling up the anode body from the monomer solution, when immersing in an oxidizing agent solution, It is immersed at a speed of 1 mm / sec or less to the position, making it difficult to hold air in the pores inside the anode body, preventing the liquid from waving, and precisely controlling the immersion position. To.

Further, according to a fourteenth aspect of the present invention, the outermost layer of the anode body does not hold the oxidant solution after being pulled up from the oxidant solution of the twelfth or thirteenth aspect. This has the effect of suppressing the amount of outflow and diffusion into the oxidizing agent solution and reducing the contamination of the oxidizing agent solution.

According to a fifteenth aspect of the present invention, when the anode body is pulled up from the oxidant solution, the anode body is pulled up at a speed of 1 mm / sec or less until the anode body is completely pulled up from the oxidant solution. Since the monomer solution is not suppressed in the outermost layer of the anode body, it has an effect that the monomer solution can be used with high efficiency.

According to a sixteenth aspect of the present invention, after the anode body is pulled up from the oxidant solution according to the fourteenth aspect, the porous body has an affinity lower than the affinity of the anode body for the oxidant solution. Contacting the anode body with the body, and having a step of removing the attached solution of the outermost layer of the anode body, without removing the monomer solution contained inside the anode body, only the monomer solution attached to the outermost layer of the anode body It has the effect of being able to be removed.

According to a seventeenth aspect of the present invention, at the time of immersion in the monomer solution according to the twelfth or thirteenth aspect, at least the surface having the anode lead-out line is immersed in the monomer solution. It has an effect that a polymer layer can be sufficiently formed on the surface.

In the invention according to claim 18, when immersing in the monomer solution according to claim 12 or 13, at least the surface having the anode lead-out line is immersed in the monomer solution. This has the effect of preventing the monomer solution contained in the anode body from flowing out and diffusing into the oxidant solution.

[0027] According to a nineteenth aspect of the present invention, in the immersion in the monomer solution according to the twelfth or thirteenth aspect, the immersion is performed at a speed of 1 mm / sec or less at first to 1/4 from the lower surface of the anode body. It immerses to a predetermined immersion position at a speed of 1 mm / sec or more, so that immersion can be precisely controlled and the amount of monomer solution contained in the anode body flowing out and diffused into the oxidizing agent solution is suppressed. Has the effect of being able to

According to a twentieth aspect of the present invention, when immersing in the monomer solution according to the twelfth or thirteenth aspect, the immersion is performed at a rate of 1 to 50 mm / sec to 最初 from the lower surface of the anode body first. , Held in place for less than 1 sec, again 1 mm / s
It is immersed to a predetermined immersion position at a speed of ec or more, so that the immersion position can be precisely controlled and the amount of monomer solution contained inside the anode body flowing out and diffused into the oxidizing agent solution is suppressed It has the effect of being able to.

According to a twenty-first aspect of the present invention, there is provided an electroconductive polymer layer comprising a step of successively holding the anode body according to any one of the twelfth to twentieth aspects from the monomer solution and holding the anode body for a predetermined time. Which has the effect of further increasing the ability to fill the pores inside the anode body.

According to a twenty-second aspect of the present invention, when the anode body is pulled up from the monomer solution according to the twenty-first aspect, the anode body is pulled up at a speed of 50 mm / sec or more until the anode body is completely pulled up from the oxidizing agent solution. The oxidant solution is held on the upper part, and the conductive polymer layer can be formed on the upper part of the anode body.

According to a twenty-third aspect of the present invention, the porous body according to the fifth or sixteenth aspect is made of a flexible material or a fibrous material. In order to prevent the destruction of the conductive polymer and the dielectric oxide film formed on the substrate, it has the effect of forming a porous body made of a flexible material or a fiber material.

According to a twenty-fourth aspect of the present invention, the valve action metal according to any one of the first to twenty-third aspects is at least one selected from the group consisting of tantalum and aluminum. It has an effect that formation of a polymer layer can be prevented.

According to a twenty-fifth aspect of the present invention, there is provided a solid electrolytic capacitor manufactured by using the method for manufacturing a solid electrolytic capacitor according to any one of the first to twenty-fourth aspects, wherein the high conductivity is provided on the anode lead wire. This has the effect of providing a solid electrolytic capacitor that prevents formation of a molecular layer.

Hereinafter, embodiments of the present invention will be described. (Embodiment 1) FIG. 1 is a view for explaining a main part of a method for manufacturing a solid electrolytic capacitor according to a first embodiment of the present invention.

In FIG. 1, 1 is an anode body and 2 is an anode body 1.
The reference numeral 3 denotes a monomer solution, and 4 denotes an oxidant solution.

The method for manufacturing a solid electrolytic capacitor according to the first embodiment of the present invention, as shown in FIG.
Tantalum powder is press-molded into a predetermined shape on the anode lead wire 2 made of tantalum, and then baked to obtain 1.4 mm × 3.0 mm ×
An anode body 1 is obtained by forming a 3.8 mm porous body and anodizing it in a phosphoric acid aqueous solution at an applied voltage of 30 V to form a dielectric oxide film layer on the surface of the porous body.

Next, as shown in FIG. 1 (b), the anode body 1 in which the dielectric oxide film layer was formed on the monomer solution 3 kept at 5 ° C. was provided with the anode lead wire 2 at a speed of 10 mm / sec. The surface is immersed in half with the surface facing upward, and as shown in FIG. 1 (c), after 5 minutes, pulled up at a speed of 0.1 mm / sec.

Thereafter, as shown in FIG. 1 (d), when immersing in the oxidizing agent solution 4, as shown in FIG. 1 (e), 100 mm / sec to a predetermined immersion position where the entire anode body 1 is immersed. Immersion at a speed of 10 seconds after 10 seconds as shown in FIG.
It is pulled up at a speed of 0 mm / sec and kept in an atmosphere of 5 ° C. for 5 minutes. A series of operations of dipping in this oxidizing agent solution 4
The process is repeated once, and then kept in an atmosphere at 45 ° C. for 10 minutes to cause a chemical oxidation polymerization reaction. Thereafter, the substrate is washed with pure water at 80 ° C. and dried at 105 ° C. for 5 minutes. The above operation is repeated eight times to form a conductive polymer layer.

On the other hand, a conventional manufacturing method is shown for comparison. Until a dielectric oxide film layer is formed, it is manufactured in the same manner as in the first embodiment of the present invention. Next, the anode body on which the dielectric oxide film was formed was immersed in a monomer solution maintained at 5 ° C. at a speed of 10 mm / sec to a predetermined immersion position where the entire anode body was immersed, and after 5 minutes at a speed of 10 mm / sec. Pull up. Thereafter, when immersing in the oxidizing agent solution, the anode body is immersed at a speed of 10 mm / sec to a predetermined immersion position where the entire anode body is immersed, and after 10 seconds, pulled up at a speed of 10 mm / sec.
For 5 minutes. A series of operations of dipping in the oxidizing agent solution is repeated four times, and thereafter, the substrate is kept in an atmosphere at 45 ° C. for 10 minutes to cause a chemical oxidation polymerization reaction. Then 8
Wash with pure water at 0 ° C. and dry at 105 ° C. for 5 minutes. The above operation is repeated eight times to form a conductive polymer layer.

The obtained capacitor element according to the first embodiment of the present invention and the conventional capacitor element are formed by forming a carbon layer 5 and a silver paint layer 6 on a conductive polymer layer as shown in FIG. And 8 were provided and covered with a resin 9 to obtain a solid electrolytic capacitor, and the capacitance and short circuit occurrence rate at 120 Hz and 100 kHz were measured.

As a result, the conventional solid electrolytic capacitor has a capacitance at 120 Hz of 160 μF (capacitance appearance rate is 91%) and a capacitance at 100 kHz of 140 μF.
F and the short circuit occurrence rate is 20%,
The solid electrolytic capacitor obtained in the first embodiment of the present invention has a capacitance at 120 Hz of 164 μF (capacity appearance rate is 94%) and a capacitance at 100 kHz of 143 μF.
F, and the short-circuit occurrence rate was 0%. As a result, the manufacturing method according to the first embodiment of the present invention can uniformly and densely form the conductive polymer layer up to the pores inside the anode body, and form the conductive polymer layer on the anode lead wire. Is preventing. Therefore, the capacitance appearance rate at 120 Hz is improved as compared with the conventional manufacturing method, and the short circuit occurrence rate can be reduced.

In the first embodiment of the present invention and the conventional monomer solution, 10 vol.
1% pyrrole as a monomer in an aqueous solution containing 1%
mol / l, and an oxidizing agent solution was prepared by adding 0.25 mol / l of ferric sulfate as an oxidizing agent to an aqueous solution containing 10 vol% of isopropyl alcohol, and alkylnaphthalenesulfonic acid ions as a dopant in the form of a Na salt. To give a concentration of 0.03 mol / l. Further, the monomer is not limited to pyrrole, and the oxidizing agent is not limited to ferric sulfate.

In the first embodiment of the present invention, when immersing in the monomer solution, the immersion is performed at 10 mm / sec.
It is not limited to that. Further, although the surface having the anode lead-out line is immersed in half with the surface having the anode lead-out line facing upward, the surface having the anode lead-out line may be at least immersed in the monomer solution. Also, the speed of immersion in the oxidizing agent solution is set to 100 mm / sec.
However, the immersion may be performed at a speed of 50 mm / sec or more.

In the first embodiment of the present invention, the monomer solution is pulled up at a speed of 0.1 mm / sec.
The same operation and effect can be obtained by removing the monomer solution attached to the outermost layer of the anode body by bringing the anode body into contact with the porous body after being pulled up at an arbitrary speed. At this time, the material of the porous body may be any material having a lower affinity than the affinity of the anode body for the monomer solution, but the conductive polymer and the dielectric oxide film formed on the outermost layer of the anode body may be destroyed. In order to prevent this, a flexible material or a fiber material is preferable. As a result, the monomer solution contained inside the anode body is not removed.

Further, in the first embodiment of the present invention,
Although the case of immersion in the oxidizing agent solution after immersion in the monomer solution has been described, it goes without saying that the same operation and effect can be obtained even when immersing in the monomer solution after immersing in the oxidizing agent solution. Further, in the first embodiment of the present invention, the valve action metal is tantalum, but may be aluminum.

(Embodiment 2) FIG. 3 is a view for explaining a main part of a method for manufacturing a solid electrolytic capacitor according to a second embodiment of the present invention.

In FIG. 3, the same components as those in FIG. 1 are denoted by the same reference numerals. In the method for manufacturing a solid electrolytic capacitor according to the second embodiment of the present invention, when the solid electrolytic capacitor is immersed in the monomer solution 3, as shown in FIG.
The manufacturing method is the same as the manufacturing method shown in the first embodiment of the present invention except that the entire anode body 1 is immersed at a rate of / sec.

The obtained capacitor element according to the second embodiment of the present invention is obtained as a solid electrolytic capacitor in the same manner as in the first embodiment of the present invention.
The capacitance at 0 kHz and the short-circuit occurrence rate were measured.

As a result, the capacitance at 120 Hz was 163
μF (capacitance appearance rate was 93%), the capacitance at 100 kHz was 144 μF, and the short-circuit occurrence rate was 10%.

Thus, according to the manufacturing method of the second embodiment of the present invention, a conductive polymer layer can be uniformly and densely formed up to the pores inside the anode body. Also, since the liquid is prevented from waving, the immersion position can be precisely controlled. Therefore, the capacitance appearance rate at 120 Hz is improved as compared with the conventional manufacturing method, and the short circuit occurrence rate can be reduced.

Incidentally, the monomer solution and the oxidizing agent solution according to the second embodiment of the present invention have the same liquid composition as the first embodiment of the present invention. Further, the monomer is the first compound of the present invention.
The embodiment is not limited to pyrrole, and the oxidizing agent is not limited to ferric sulfate.

In the second embodiment of the present invention, the immersion speed in the monomer solution is 0.1 mm / sec.
What is necessary is just to immerse at a speed of 1 mm / sec or less. Although the immersion speed in the oxidizing agent solution is set to 100 mm / sec, the immersion speed may be 50 mm / sec or more as in the first embodiment of the present invention.

In the second embodiment of the present invention, the monomer solution was pulled up at a rate of 0.1 mm / sec.
Similar to the first embodiment of the present invention, the same operation and effect can be obtained even if the anode body is brought into contact with the porous body to remove the monomer solution attached to the outermost layer of the anode body after being pulled up at an arbitrary speed as in the first embodiment of the present invention. Having. At this time, the material of the porous body may be any material having a lower affinity than the affinity of the anode body for the monomer solution as in the first embodiment of the present invention, but is formed on the outermost layer of the anode body. In order to prevent the destruction of the conductive polymer and the dielectric oxide film, a flexible material or a fiber material is preferable.
As a result, the monomer solution contained inside the anode body is not removed.

Further, in the second embodiment of the present invention,
Although the case of immersion in the oxidizing agent solution after immersion in the monomer solution has been described, the same effect is obtained even in the case of immersing in the monomer solution after immersing in the oxidizing agent solution as in the first embodiment of the present invention. Needless to say, it has an effect.
Further, in the second embodiment of the present invention, the valve action metal is tantalum, but may be aluminum as in the first embodiment of the present invention.

(Embodiment 3) FIG. 4 is a view for explaining a main part of a method for manufacturing a solid electrolytic capacitor according to a third embodiment of the present invention.

In FIG. 4, the same components as those in FIG. 1 are denoted by the same reference numerals. In the method for manufacturing a solid electrolytic capacitor according to the third embodiment of the present invention, as shown in FIG.
The method is the same as the manufacturing method shown in the first embodiment of the present invention, except that the surface having the anode lead-out line 2 is immersed at a rate of / sec and the surface is up to half.

The obtained capacitor element according to the third embodiment of the present invention is obtained as a solid electrolytic capacitor in the same manner as in the first embodiment of the present invention.
The capacitance at 0 kHz and the short-circuit occurrence rate were measured.

As a result, the capacitance at 120 Hz was 167
μF (capacitance appearance rate was 95%), the capacitance at 100 kHz was 146 μF, and the short-circuit occurrence rate was 0%.

As a result, the conductive polymer layer can be formed uniformly and densely up to the pores inside the anode body as compared with the manufacturing methods of the first and second embodiments of the present invention, and the conductive polymer layer can be formed on the anode lead wire. The formation of a conductive polymer layer is prevented. Therefore, the capacitance appearance rate at 120 Hz is improved and the short circuit occurrence rate can be reduced as compared with the manufacturing methods of the first and second embodiments of the present invention.

Incidentally, the monomer solution and the oxidizing agent solution according to the third embodiment of the present invention have the same liquid composition as that of the first embodiment of the present invention. Further, the monomer is the first compound of the present invention.
The embodiment is not limited to pyrrole, and the oxidizing agent is not limited to ferric sulfate.

Further, in the third embodiment of the present invention, when immersing in the monomer solution, the immersion is performed by half with the surface having the anode lead-out line as the upper surface. Similarly, it is sufficient that at least the surface having the anode lead line is not immersed in the monomer solution. Although the immersion speed in the monomer solution is set to 0.1 mm / sec, the immersion speed may be 1 mm / sec or less as in the second embodiment of the present invention.
Further, the immersion speed in the oxidizing agent solution was set to 100 mm / sec, but the immersion speed may be 50 mm / sec or more.

In the third embodiment of the present invention, the monomer solution was pulled up at a rate of 0.1 mm / sec.
Similar to the second embodiment of the present invention, the same operation and effect can be obtained by removing the monomer solution attached to the outermost layer of the anode body by bringing the anode body into contact with the porous body after lifting at an arbitrary speed as in the second embodiment of the present invention. Was confirmed. At this time, the material of the porous body may be any material having a lower affinity than the affinity of the anode body for the monomer solution as in the first embodiment of the present invention, but is formed on the outermost layer of the anode body. In order to prevent the destruction of the conductive polymer and the dielectric oxide film, a flexible material or a fiber material is preferable. As a result, the monomer solution contained inside the anode body is not removed.

Further, in the third embodiment of the present invention,
Although the case of immersion in the oxidizing agent solution after immersion in the monomer solution has been described, the same effect is obtained even in the case of immersing in the monomer solution after immersing in the oxidizing agent solution as in the first embodiment of the present invention. Needless to say, it has an effect.
Further, in the third embodiment of the present invention, the valve metal is tantalum, but may be aluminum as in the first embodiment of the present invention.

(Embodiment 4) FIG. 5 is a view for explaining a main part of a method for manufacturing a solid electrolytic capacitor according to a fourth embodiment of the present invention.

In FIG. 5, the same components as those in FIG. 1 are denoted by the same reference numerals. The method for manufacturing a solid electrolytic capacitor according to the fourth embodiment of the present invention is shown in FIG.
As shown in the figure, except that the anode body 1 is immersed in the oxidizing agent solution 4 at a rate of 0.1 mm / sec to 1/4 of the anode body 1 and then immersed at a predetermined immersion position where the entire anode body 1 is immersed at 50 mm / sec. This is the same as the manufacturing method shown in the first embodiment of the present invention.

The obtained capacitor element according to the fourth embodiment of the present invention is obtained by a method similar to that of the first embodiment of the present invention.
The capacitance at 0 kHz and the short-circuit occurrence rate were measured.

As a result, the capacitance at 120 Hz was 166.
μF (capacitance appearance rate was 95%), the capacitance at 100 kHz was 144 μF, and the short-circuit occurrence rate was 0%.

Thus, the same operation and effect as those of the third embodiment of the present invention can be obtained. The monomer solution and the oxidizing agent solution according to the fourth embodiment of the present invention have the same liquid composition as the first embodiment of the present invention. Also, the monomer is
Like the first embodiment of the present invention, it is not limited to pyrrole, and the oxidizing agent is not limited to ferric sulfate.

Further, in the fourth embodiment of the present invention, when immersion in the monomer solution, the immersion is performed by half with the surface having the anode lead-out line as the upper surface. Similarly, it is sufficient that at least the surface having the anode lead line is not immersed in the monomer solution. Although the immersion speed in the monomer solution is set to 0.1 mm / sec, the immersion speed may be 1 mm / sec or less as in the second embodiment of the present invention.
The anode body 1 was immersed in an oxidizing agent solution at a rate of 0.1 mm / sec to 1/4 of the anode body 1 and then immersed at 50 mm / sec to a predetermined immersion position where the entire anode body 1 was immersed.
It may be immersed at 1/4 from the lower surface of the anode body at the following speed, and then immersed at a speed of 1 mm / sec or more.

In the fourth embodiment of the present invention, the monomer solution was pulled up at a rate of 0.1 mm / sec.
Similar to the second embodiment of the present invention, the same operation and effect can be obtained by removing the monomer solution attached to the outermost layer of the anode body by bringing the anode body into contact with the porous body after lifting at an arbitrary speed as in the second embodiment of the present invention. Was confirmed. At this time, the material of the porous body may be any material having a lower affinity than the affinity of the anode body for the monomer solution as in the first embodiment of the present invention, but is formed on the outermost layer of the anode body. In order to prevent the destruction of the conductive polymer and the dielectric oxide film, a flexible material or a fiber material is preferable. As a result, the monomer solution contained inside the anode body is not removed.

Further, in the fourth embodiment of the present invention,
Although the case of immersion in the oxidizing agent solution after immersion in the monomer solution has been described, the same effect is obtained even in the case of immersing in the monomer solution after immersing in the oxidizing agent solution as in the first embodiment of the present invention. Needless to say, it has an effect.
Further, in the fourth embodiment of the present invention, the valve action metal is tantalum, but may be aluminum as in the first embodiment of the present invention.

(Embodiment 5) FIG. 6 is a view for explaining a main part of a method for manufacturing a solid electrolytic capacitor according to a fifth embodiment of the present invention.

In FIG. 6, the same components as those in FIG. 1 are denoted by the same reference numerals. FIG. 6E shows a method for manufacturing a solid electrolytic capacitor according to the fifth embodiment of the present invention.
As shown in the figure, after immersing the anode body 1 in the oxidizing agent solution 4 at a speed of 10 mm / sec to 1/4 of the anode body 1, holding the same for 0.5 sec, and immersing the entire anode body 1 again at 50 mm / sec. The method is the same as the manufacturing method shown in the first embodiment of the present invention except that the immersion position is immersed to the immersion position.

The obtained capacitor element in the fifth embodiment of the present invention can be obtained as a solid electrolytic capacitor in the same manner as in the first embodiment of the present invention.
The capacitance at 0 kHz and the short-circuit occurrence rate were measured.

As a result, the capacitance at 120 Hz was 167
μF (capacitance appearance rate was 95%), the capacitance at 100 kHz was 145 μF, and the short circuit occurrence rate was 0%.

The monomer solution and the oxidizing agent solution according to the fifth embodiment of the present invention have the same liquid compositions as those of the first embodiment of the present invention. Further, the monomer is not limited to pyrrole as in the first embodiment of the present invention, and the oxidizing agent is not limited to ferric sulfate.

Further, in the fifth embodiment of the present invention, when immersion in the monomer solution, the immersion is performed by half with the surface having the anode lead-out line as the upper surface. Similarly, it is sufficient that at least the surface having the anode lead line is not immersed in the monomer solution. Although the immersion speed in the monomer solution is set to 0.1 mm / sec, the immersion speed may be 1 mm / sec or less as in the second embodiment of the present invention.
Also, the anode body 1 is heated at a speed of 10 mm / sec to the oxidant solution.
After immersion to / 4, it was held in place for 0.5 sec, and immersed again at 50 mm / sec. However, after immersion to 1/4 from the lower surface of the anode body at a speed of 1 mm / sec or more, in place for less than 1 sec It may be held and immersed again at a speed of 1 mm / sec or more.

In the fifth embodiment of the present invention, the monomer solution was pulled up at a rate of 0.1 mm / sec.
Similar to the first embodiment of the present invention, the same operation and effect can be obtained even if the anode body is brought into contact with the porous body to remove the monomer solution attached to the outermost layer of the anode body after being pulled up at an arbitrary speed as in the first embodiment of the present invention. Was confirmed. At this time, the material of the porous body may be any material having a lower affinity than the affinity of the anode body for the monomer solution as in the first embodiment of the present invention, but is formed on the outermost layer of the anode body. In order to prevent the destruction of the conductive polymer and the dielectric oxide film, a flexible material or a fiber material is preferable. As a result, the monomer solution contained inside the anode body is not removed.

Further, in the fifth embodiment of the present invention,
Although the case of immersion in the oxidizing agent solution after immersion in the monomer solution has been described, the same effect is obtained even in the case of immersing in the monomer solution after immersing in the oxidizing agent solution as in the first embodiment of the present invention. Needless to say, it has an effect.
Further, in the fifth embodiment of the present invention, the valve action metal is tantalum, but may be aluminum as in the first embodiment of the present invention.

[0080]

As described above, the present invention has an effect that formation of a conductive polymer layer on an anode lead wire can be prevented.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a main part of a method for manufacturing a solid electrolytic capacitor according to a first embodiment of the present invention.

FIG. 2 is a sectional view of the solid electrolytic capacitor.

FIG. 3 is a diagram illustrating a main part of a method for manufacturing a solid electrolytic capacitor according to a second embodiment of the present invention.

FIG. 4 is a diagram illustrating a main part of a method for manufacturing a solid electrolytic capacitor according to a third embodiment of the present invention.

FIG. 5 is a diagram illustrating a main part of a method for manufacturing a solid electrolytic capacitor according to a fourth embodiment of the present invention.

FIG. 6 is a diagram illustrating a main part of a method for manufacturing a solid electrolytic capacitor according to a fifth embodiment of the present invention.

[Explanation of symbols]

 Reference Signs List 1 anode body 2 anode lead wire 3 monomer solution 4 oxidizing agent solution

Continued on front page (72) Inventor Emiko Igaki 1006 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. Chiharu Hayashi 1006 Kadoma Kadoma, Kadoma City, Osaka Prefecture (72) Inside the Matsushita Electric Industrial Co., Ltd. 1006 Kadoma Matsushita Electric Industrial Co., Ltd.

Claims (25)

[Claims] 1. An anode body comprising a valve action metal having an anode lead wire and having a dielectric oxide film layer having a conductive polymer layer on the surface, the surface having the anode lead wire facing upward. A step of immersing the anode body in a monomer solution containing a monomer, a step of pulling the anode body out of the monomer solution, a step of immersing the anode body in an oxidant solution containing an oxidant, and pulling up the anode body from the oxidant solution Through the steps sequentially, in a method of manufacturing a solid electrolytic capacitor for forming the conductive polymer layer on the dielectric oxide film layer,
A method for producing a solid electrolytic capacitor, characterized in that at least the surface having the anode lead-out line is not immersed in the monomer solution when immersed in the monomer solution. 2. An anode body comprising a valve action metal having an anode lead wire and having a dielectric oxide film layer having a conductive polymer layer on the surface, with the surface having the anode lead wire facing upward. A step of immersing the anode body in a monomer solution containing a monomer, a step of pulling the anode body out of the monomer solution, a step of immersing the anode body in an oxidant solution containing an oxidant, and pulling up the anode body from the oxidant solution Through the steps sequentially, in a method of manufacturing a solid electrolytic capacitor for forming the conductive polymer layer on the dielectric oxide film layer,
When immersed in the monomer solution, 1mm /
A method for manufacturing a solid electrolytic capacitor, characterized by immersing at a speed of not more than sec. 3. The method for producing a solid electrolytic capacitor according to claim 1, wherein the monomer solution is not held in the outermost layer of the anode body after being pulled up from the monomer solution. 4. When the anode body is completely lifted out of the monomer solution, it takes 1 mm.
4. The method for manufacturing a solid electrolytic capacitor according to claim 3, wherein the pulling is performed at a speed of not more than / sec. 5. After the anode body is pulled out of the monomer solution, the anode body is brought into contact with a porous body having an affinity lower than the affinity of the anode body for the monomer solution, and the adhesion solution of the outermost layer of the anode body is 4. The method for manufacturing a solid electrolytic capacitor according to claim 3, further comprising the step of removing the solid electrolytic capacitor. 6. The method for producing a solid electrolytic capacitor according to claim 1, wherein when immersing in the oxidizing solution, at least a surface having an anode lead wire is immersed in the oxidizing solution. 7. The method for producing a solid electrolytic capacitor according to claim 1, wherein when immersing in the oxidizing agent solution, immersion is performed at a speed of 50 mm / sec or more to a predetermined immersion position. 8. When immersing in an oxidizing agent solution, the immersion is performed at a speed of 1 mm / sec or less up to 1/4 from the lower surface of the anode body.
3. The method for manufacturing a solid electrolytic capacitor according to claim 1, wherein the immersion is performed to a predetermined immersion position at a speed of not less than m / sec. 9. When immersing in an oxidizing agent solution, after immersing at a rate of 1 to 50 mm / sec from the lower surface of the anode body to 1/4,
2. The method according to claim 1, wherein the holding is performed in place for less than 1 sec, and the dipping is performed again at a speed of 1 mm / sec or more to a predetermined dipping position.
Or a method for manufacturing a solid electrolytic capacitor according to item 2. 10. The conductive polymer layer according to claim 1, wherein a step of holding the anode body from the oxidizing agent solution for a predetermined time and sequentially forming the conductive polymer layer is performed. Manufacturing method of solid electrolytic capacitor. 11. When the anode body is pulled out of the oxidant solution, the anode body is completely removed from the oxidant solution by 50 mm.
11. The method for manufacturing a solid electrolytic capacitor according to claim 10, wherein the pulling is performed at a speed of not less than / sec. 12. An anode body comprising a valve action metal having an anode lead wire and having a dielectric oxide film layer having a conductive polymer layer on the surface, the surface having the anode lead wire facing upward. A step of immersing the anode body in an oxidant solution containing an oxidant; a step of pulling up the anode body from the oxidant solution; a step of immersing it in a monomer solution containing a monomer; and pulling up the anode body from the monomer solution. In a method for manufacturing a solid electrolytic capacitor in which the conductive polymer layer is formed on the dielectric oxide film layer through successive steps, when immersing in an oxidizing solution, the surface having the anode lead-out line is at least an oxidizing solution. A method for manufacturing a solid electrolytic capacitor, characterized in that the capacitor is not immersed in a capacitor. 13. An anode body comprising a valve action metal having an anode lead wire and having a dielectric oxide film layer having a conductive polymer layer on the surface, the surface having the anode lead wire facing upward. A step of immersing the anode body in an oxidant solution containing an oxidant; a step of pulling up the anode body from the oxidant solution; a step of immersing it in a monomer solution containing a monomer; and pulling up the anode body from the monomer solution. In a method for manufacturing a solid electrolytic capacitor in which the conductive polymer layer is formed on the dielectric oxide film layer through successive steps, when immersing in an oxidizing agent solution, 1 mm to a predetermined immersion position.
A method for producing a solid electrolytic capacitor, characterized by immersing at a rate of not more than / sec. 14. The method for manufacturing a solid electrolytic capacitor according to claim 12, wherein the oxidant solution is not held in the outermost layer of the anode body after being pulled up from the oxidant solution. 15. When the anode body is pulled up from the oxidizing agent solution, 1 mm / mm
2. The method according to claim 1, wherein the lifting is performed at a speed of not more than sec.
5. The method for manufacturing a solid electrolytic capacitor according to item 4. 16. After pulling up the anode body from the oxidant solution, the anode body is brought into contact with a porous body having an affinity lower than that of the anode body for the oxidant solution, and the anode body outermost layer The method for manufacturing a solid electrolytic capacitor according to claim 14, further comprising a step of removing the adhered solution. 17. The method for producing a solid electrolytic capacitor according to claim 12, wherein, when immersed in the monomer solution, at least the surface having the anode lead-out line is immersed in the monomer solution. 18. The method for producing a solid electrolytic capacitor according to claim 12, wherein when immersing in the monomer solution, immersion is performed at a speed of 50 mm / sec or more to a predetermined immersion position. 19. When immersed in the monomer solution, the immersion is performed at a speed of 1 mm / sec or less up to 1/4 from the lower surface of the anode body, and then immersed to a predetermined immersion position at a speed of 1 mm / sec or more. 14. The method for manufacturing a solid electrolytic capacitor according to claim 12 or 13. 20. When immersed in the monomer solution, the immersion is performed at a rate of 1 to 50 mm / sec from the lower surface of the anode body to 1/4, then held in place for less than 1 sec, and again at a speed of 1 mm / sec or more. 14. The method for manufacturing a solid electrolytic capacitor according to claim 12, wherein the immersion is performed up to the immersion position. 21. The solid according to claim 12, wherein a conductive polymer layer is formed by sequentially performing a step of holding the anode body from the monomer solution for a predetermined time after the anode body is pulled out of the monomer solution. Manufacturing method of electrolytic capacitor. 22. When the anode body is completely lifted out of the oxidizing agent solution when it is pulled out of the monomer solution, the distance between the anode body and the oxidizing agent solution is 50 mm / mm.
3. The method of claim 2, wherein the lifting is performed at a speed of at least sec.
2. The method for manufacturing a solid electrolytic capacitor according to 1. 23. The method according to claim 5, wherein the porous body is made of a flexible material or a fiber material. 24. The valve metal according to claim 1, wherein the valve action metal is at least one selected from tantalum and aluminum.
3. The method for manufacturing a solid electrolytic capacitor according to any one of the above items 3. 25. A solid electrolytic capacitor produced by using the method for producing a solid electrolytic capacitor according to claim 1. Description: