JP2002359162A - Solid electrolytic capacitor containing board and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid electrolytic capacitor which comprises a foil-like valve metal base having a roughed surface with an insulative oxide film formed thereon, has an insulative oxide film, a solid polymer electrolyte layer and conductor layers formed one above another on the metal base and is suited to be contained in a circuit board. SOLUTION: The solid electrolytic capacitor comprises a foil-like valve metal base 2 having a roughed surface with an insulative oxide film formed thereon. The capacitor has at least an insulative oxide film 9, a solid polymer electrolyte layer 11 and conductor layers 12, 13 formed one above another on the metal base 2. A foil-like lead electrode metal base 3 has a near-one-end portion bonded to a near-one-end portion of the metal base 2 having the roughed surface with the insulative oxide film formed thereon to form a bond zone 4 in the form of a metal-to-metal electric connection. The capacitor has an anode electrode 1 with the metal base 2 having a substantially smooth surface region 5 at least on a portion adjacent to the bond zone 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid electrolytic capacitor and a printed circuit board having the solid electrolytic capacitor incorporated therein, and a method for producing the same. A foil-shaped valve metal substrate with a film formed thereon, an insulating oxide film, a solid polymer electrolyte layer and a conductor layer on the foil-shaped valve metal substrate,
The present invention relates to a solid electrolytic capacitor formed sequentially, a solid electrolytic capacitor suitable for being incorporated in a circuit board, a printed circuit board having the solid electrolytic capacitor incorporated therein, and a method of manufacturing the same.

[0002]

2. Description of the Related Art Electrolytic capacitors include aluminum, titanium, brass, nickel,
Using a metal such as tantalum, a so-called valve metal for the anode, anodizing the surface of the valve metal to form an insulating oxide film, then forming an electrolyte layer that substantially functions as a cathode, and further forming graphite or It is formed by providing a conductive layer such as silver as a cathode.

For example, an aluminum electrolytic capacitor uses a porous aluminum foil having an increased specific surface area as an anode by etching, and impregnates an electrolytic solution between an aluminum oxide layer formed on the surface of the anode and a cathode foil. It is configured by providing a separator paper.

[0004] In general, the life of an electrolytic capacitor using an electrolytic solution for an electrolyte layer between an insulating oxide film and a cathode is determined by leakage from the sealing portion and evaporation of the electrolytic solution. On the other hand, a solid electrolytic capacitor using a solid electrolyte made of a metal oxide or an organic compound does not have such a problem and is preferable.

A typical solid electrolyte composed of a metal oxide used for a solid electrolytic capacitor is manganese dioxide. On the other hand, a solid electrolyte composed of an organic compound used for a solid electrolytic capacitor is disclosed in, for example, 52-79255 and JP-A-58-19141.
No. 4,7,7,8,8-tetracyanooxydimethane (TCNQ) complex salt.

[0006] In recent years, as the power supply circuit of electronic equipment has become higher in frequency, the capacitors used have been required to have performances corresponding thereto. However, a solid electrolyte layer made of manganese dioxide or a TCNQ complex salt has been required. The solid electrolytic capacitor used had the following problems.

The solid electrolyte layer made of manganese dioxide is
In general, it is formed by repeating the thermal decomposition of manganese nitrate. The insulating oxide film as a dielectric is formed by the heat applied during the thermal decomposition or by the oxidizing action of the NOx gas generated during the thermal decomposition. If the solid electrolyte layer is made of manganese dioxide, the leakage current value will be large,
There is a problem that various characteristics of the finally obtained solid electrolytic capacitor tend to be low. When manganese dioxide is used as the solid electrolyte,
There is also a problem that the impedance of the solid electrolytic capacitor is increased.

On the other hand, the TCNQ complex salt has an electric conductivity of 1 S /
cm or less, there was a problem that it was not possible to sufficiently meet the current demand for lowering the impedance of electrolytic capacitors. In addition, TCN
The Q complex salt has a low adhesion to an insulating oxide film and has a low thermal stability when fixed with solder and a low thermal stability over time. It has been pointed out that capacitors cannot provide sufficient reliability. In addition, the TCNQ complex salt is expensive, and the solid electrolytic capacitor using the TCNQ complex salt as a solid electrolyte has a problem that the cost is high.

[0009] Manganese dioxide or TCNQ complex salt is
In order to solve these problems when used as a solid electrolyte and obtain a solid electrolytic capacitor having more excellent characteristics, the production cost is relatively low, and the adhesion with the insulating oxide film is relatively good. It has been proposed to use a highly conductive polymer compound having excellent thermal stability as a solid electrolyte.

For example, Japanese Patent No. 2725553 discloses that
A solid electrolytic capacitor in which polyaniline is formed by chemical oxidation polymerization on an insulating oxide film on the surface of an anode is disclosed.

Japanese Patent Publication No. 8-31400 discloses that it is difficult to form a high-strength conductive polymer film on an insulating oxide film on the surface of an anode only by a chemical oxidation polymerization method. Because the insulating oxide film on the anode surface is an electric conductor, it is impossible or extremely difficult to form an electrolytic polymerized film directly on the insulating oxide film on the anode surface by electrolytic polymerization. To form a metal or manganese dioxide thin film on the insulating oxide film,
We have proposed a solid electrolytic capacitor in which a conductive polymer film such as polypyrrole, polythiophene, polyaniline, or polyfuran is formed on a thin film of metal or manganese dioxide by electrolytic polymerization.

Further, Japanese Patent Publication No. 4-74853 discloses a solid electrolytic capacitor in which a conductive polymer film such as polypyrrole, polythiophene, polyaniline or polyfuran is formed on an insulating oxide film by chemical oxidation polymerization. ing.

On the other hand, with the demand for smaller and thinner electronic devices, electronic components are required to be further reduced in size and higher in performance. Is required. In particular, the thickness of the IC card is 1 m
m or less, the thickness of the portable personal computer is 20
mm or less, which is extremely thin, so that electronic components mounted thereon and wiring boards on which the electronic components are mounted are required to be formed with a thickness of several mm to several hundred microns. .

However, since the above-mentioned solid electrolytic capacitors are all manufactured as a single component and mounted on a wiring board via a solder layer, the electronic components are sufficiently integrated and highly integrated. There was a problem that the density could not be increased.

Japanese Patent Application Laid-Open No. 2-54510 and Japanese Patent No. 2950587 disclose a solid electrolytic capacitor.
As with the resistance function of the wiring board and the conductive pattern, the circuit board is formed in advance integrally with the board, and a plurality of solid electrolytic capacitors are formed on a single board. Is proposed to reduce the thickness of the device.

That is, Japanese Patent Application Laid-Open No. 2-54510 discloses that a pattern of a foil-shaped valve metal substrate such as an aluminum foil having an ability to form an electric conductor and an insulating oxide film is formed on an insulating substrate. The surface of the pattern 1
In some or several places, an insulating oxide film layer, a conductive polymer layer of a heterocyclic compound and a conductor layer, in order, to form a solid electrolytic capacitor built-in substrate, and discloses a method of manufacturing On both surfaces, a pattern of an electric conductor and a valve metal substrate having an ability to form an insulating oxide film is formed, and an insulating oxide film layer and a heterocyclic compound are formed at one or several places on the surface of the pattern of the valve metal substrate. A conductive polymer layer and a conductor layer are sequentially formed, a solid electrolytic capacitor built-in substrate is manufactured, and then a solid electrolytic capacitor built-in substrate is laminated to disclose a solid electrolytic capacitor built-in substrate having a multilayer structure. . JP-A-2-55410
According to the publication, a solid electrolytic capacitor using a conductive polymer, like a resistor layer and a conductive pattern of a circuit board,
By forming them integrally with the board in advance, it is not necessary to mount individual capacitors on the circuit board, and it is possible to realize high-density electronic components and to improve electrical characteristics such as noise reduction. It is said that it can be improved.

On the other hand, Japanese Patent No. 2950587 discloses that a dielectric layer, an electrolyte layer and a conductor layer are sequentially formed on both sides of a plate-shaped anode body, that is, a plate-shaped valve metal base, and each conductor layer is formed. , A capacitor terminal is formed, a capacitor element is formed, and a printed circuit board having a desired wiring pattern is joined to both surfaces of the capacitor element thus formed via a resin layer to form a solid electrolytic capacitor. A capacitor is disclosed. According to Japanese Patent No. 2950587, even a solid electrolyte that is mechanically fragile is protected by the printed circuit boards arranged on both sides, so that a highly reliable solid electrolytic capacitor can be obtained. By forming a desired wiring pattern on a printed circuit board in advance, it is said that other electronic components can be easily mounted on the printed circuit board.

[0018]

In such an electric wiring board with a built-in solid electrolytic capacitor, a lead electrode for connecting the solid electrolytic capacitor to another electronic component to be mounted on the substrate is provided with an insulating material serving as an anode. When connecting to a foil-shaped valve metal substrate having a capability of forming a conductive oxide film is indispensable, but simply connecting a metal conductor such as copper to the foil-shaped valve metal substrate to form a lead electrode Has a problem that desired capacitor characteristics cannot be obtained.

That is, in order to obtain a large capacitance, the solid electrolytic capacitor is formed by roughening (enlarging) a foil-shaped valve metal base so as to increase the surface area of the valve metal base.
In addition, a foil-shaped valve metal base of a desired size is cut out from a foil-shaped sheet of a valve metal such as aluminum having an insulating oxide film formed thereon such as aluminum oxide, and the insulating oxidation of the roughened foil-shaped valve metal is performed. A solid polymer electrolyte layer serving as a cathode is formed on the film, and a conductive layer such as a carbon paste layer and a silver paste layer is further provided on the solid polymer electrolyte layer serving as a cathode to form a cathode lead electrode. In order to form a lead electrode of the anode, the insulating oxide film formed on the surface of the roughened foil-shaped valve metal substrate is removed, and a metal conductor such as copper is formed. It is necessary to connect by ultrasonic welding, cold welding (cold welding) or the like so that the metal is electrically connected and joined to the valve metal base. Since the lead electrode is thus formed and the foil-shaped valve metal base is cut out from the valve metal sheet, an insulating oxide film is not formed on the edge portion of the foil-shaped valve metal base,
If the insulating oxide film is not formed on the edge of the foil-shaped valve metal substrate, the metal portion of the valve metal substrate comes into contact with the solid polymer electrolyte layer and does not function as a solid electrolytic capacitor. It is indispensable to form an insulating oxide film on the edge of the foil-shaped valve metal base.

However, an anode body in which a metal conductor such as copper is joined to a foil-shaped valve metal base having a surface roughened by ultrasonic welding, cold welding (cold welding), or the like, When immersing in a chemical solution such as ammonium adipate contained in a conductive container such as a stainless steel beaker and connecting a metal conductor such as copper to the positive electrode and connecting the conductive container to the negative electrode to perform anodization In addition, when a metal conductor such as copper comes into contact with the chemical conversion solution, current continues to flow, and as a result, the metal conductor such as copper is corroded, and an insulating oxide film cannot be formed on the edge portion of the valve metal base. There is a problem, and when only the foil-shaped valve metal substrate whose surface has been subjected to surface roughening treatment is immersed in a chemical conversion solution and anodized, the surface of the foil-shaped valve metal substrate is roughened. Alms Because of this, the chemical conversion solution reaches the metal conductor such as copper due to the capillary phenomenon, similarly, the current continues to flow, the metal conductor such as copper is corroded, and the edge of the foil-shaped valve metal base has an insulating property. There was a problem that an oxide film could not be formed.

Such a problem is caused by providing an electrode on the edge of the foil-shaped valve metal base where the insulating oxide film is not formed, before joining the metal conductor such as copper to the foil-shaped valve metal base, and forming an anode. By oxidizing and forming an insulating oxide film on the edge portion of the valve metal substrate, it is theoretically possible to solve the problem, but in general, the thickness of the foil sheet of the valve metal substrate such as aluminum is Since it is on the order of 100 microns, it is extremely difficult to provide an electrode on the edge portion of the foil-shaped valve metal substrate where the insulating oxide film is not formed and to perform anodizing treatment. There is a problem that it is not possible to obtain a solid electrolytic capacitor suitable for performing the above.

Therefore, the present invention provides a foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon,
A solid electrolytic capacitor in which an insulating oxide film, a solid polymer electrolyte layer and a conductor layer are sequentially formed on a foil-shaped valve metal substrate, and the solid electrolytic capacitor and the solid state suitable for being incorporated in a circuit board. An object of the present invention is to provide a substrate with a built-in electrolytic capacitor and a method for manufacturing the same.

[0023]

Means for Solving the Problems The present inventor has made intensive studies in order to achieve the object of the present invention, and as a result, has found that a foil-like lead electrode has An area near one end of the metal base is joined so that the metal is electrically connected to form a joint, and the foil-shaped valve metal base is at least in a portion adjacent to the joint.
It has been found that by configuring the anode electrode of the solid electrolytic capacitor to have a substantially smooth surface area, it is possible to achieve the above object of the present invention.

That is, an object of the present invention is to provide a foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon, and at least an insulating oxide film formed on the foil-shaped valve metal substrate. , The solid polymer electrolyte layer and the conductor layer,
The formed solid electrolytic capacitor, wherein the surface is roughened, and an area near one end of a foil-shaped valve metal base on which an insulating oxide film is formed is provided in an area near one end of a foil-shaped lead electrode metal base. Are joined so that the metals are electrically connected to form a joint, and the foil-shaped valve metal base is
This is achieved by a solid electrolytic capacitor comprising an anode electrode having a substantially smooth surface area at least in a part adjacent to the joint.

Further, in the present invention, a substantially smooth surface refers to a surface which has been smoothed to such an extent that a liquid cannot proceed due to capillary action.

According to the present invention, a region near one end of the foil-shaped lead electrode metal base is joined to a region near one end of the foil-shaped valve metal base so that the metal is electrically connected. Thus, a joint is formed, and the foil-shaped valve metal base has a substantially smooth surface area at least in a portion adjacent to the joint. In the case where an insulating oxide film is formed on an edge portion where the insulating oxide film is not formed, the chemical conversion solution proceeds along the roughened surface of the foil-shaped valve metal base by capillary action. Also, the chemical conversion solution does not reach the foil-shaped lead electrode metal substrate beyond the substantially smooth surface area of the foil-shaped valve metal substrate, and therefore, the foil-shaped valve metal having a roughened surface. Anodization is completed when an insulating oxide film is formed on the metal substrate. Since an insulating oxide film can be formed on the edge of the foil-shaped valve metal base as desired, the foil-shaped lead electrode metal base can be connected to other electronic components mounted on the circuit board. By providing such a contact, a solid electrolytic capacitor having desired electric characteristics can be built in the circuit board.

Further, when a solid polymer electrolyte layer is formed by chemical oxidative polymerization on the entire surface of a foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon, a solution containing a raw material monomer is used. And the oxidant solution, by capillary action,
Through the foil-shaped valve metal substrate whose surface is not roughened, it reaches the foil-shaped conductive metal, reacts with the conductive metal, and may be short-circuited. When forming the electrolyte layer, the electrolytic solution containing the raw material monomer and the supporting electrolyte reaches the foil-shaped conductive metal through the foil-shaped valve metal substrate whose surface is not roughened by capillary action. In some cases, a short-circuit occurred due to the reaction with the conductive metal.
In the vicinity of the joint, because it has a substantially smooth surface, a solution containing a raw material monomer or an oxidizing agent solution, or
Capable of reliably preventing the electrolyte solution containing the raw material monomer and supporting electrolyte from reaching the foil-shaped conductive metal via the foil-shaped valve metal substrate whose surface is not roughened by capillary action become.

In a preferred embodiment of the present invention, the foil-shaped lead metal base is formed of a conductive metal base.

In a further preferred aspect of the present invention, the area near one end of the foil-shaped valve metal base and the area near one end of the foil-shaped conductive metal base are ultrasonically welded or cold welded. Are joined by

In another preferred embodiment of the present invention, the foil-shaped lead electrode substrate includes a foil-shaped valve metal substrate having an unroughened surface and a conductive metal substrate capable of being soldered. The surface is roughened, in an area near one end of the foil-shaped valve metal base on which an insulating oxide film is formed,
As one end near area of the foil-shaped valve metal base whose surface is not roughened, the valve metals are electrically connected,
An area near one end of the foil-shaped conductive metal base, to which solder connection is possible, is electrically connected to a metal in an area near the other end of the foil-shaped valve metal base which is joined and the surface of which is not roughened. It is joined so that it is connected to.

According to another preferred embodiment of the present invention,
Between a foil-shaped valve metal substrate having a roughened surface and functioning as an anode having an insulating oxide film formed thereon and a conductive metal substrate provided with contacts to other electronic components mounted on a circuit board In addition, since a foil-shaped valve metal base whose surface is not roughened is interposed, the chemical conversion solution reaches the conductive metal base such as copper, and the conductive metal base such as copper is corroded. Can be more reliably prevented,
A solid electrolytic capacitor having desired electrical characteristics can be manufactured and built into a circuit board.

In a further preferred embodiment of the present invention, the surface of the foil-shaped valve metal base on which the surface is roughened and on which an insulating oxide film is formed, and the surface near one end are not roughened. An area near one end of the foil-shaped valve metal base is joined by ultrasonic welding or cold pressure welding,
The area near the other end of the foil-shaped valve metal base whose surface is not roughened and the area near the one end of the foil-shaped conductive metal base are joined by ultrasonic welding or cold pressure welding. ing.

[0033] In a preferred embodiment of the present invention, the substantially smooth surface is applied to the roughened surface of the foil-shaped valve metal base in the vicinity of the joint by a pressure treatment, a rolling treatment, It is formed by performing a smoothing process selected from the group consisting of a cutting process and a calendering process.

In another preferred embodiment of the present invention, the foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon is roughened except for a part of the surface. The surface of the unexposed foil-shaped valve metal base is formed by roughening the surface, and the substantially smooth surface area is formed by the partial surface.

[0035] In a preferred embodiment of the present invention, the substantially smooth surface is provided on the foil-shaped valve metal base at least at a portion adjacent to the joint portion over the entire circumference of the foil-shaped valve metal base. A region is formed.

According to a preferred embodiment of the present invention, a substantially smooth surface area is formed on the foil-shaped valve metal base near the joint over the entire circumference of the foil-shaped valve metal base. It is possible to more reliably prevent the chemical solution from reaching the conductive metal substrate such as copper and corroding the conductive metal substrate such as copper, and to provide a solid electrolytic capacitor having desired electrical characteristics. It can be manufactured and built into a circuit board.

The object of the present invention is also to provide a foil-shaped valve metal base having a roughened surface and an insulating oxide film formed thereon,
A solid electrolytic capacitor in which at least an insulating oxide film, a solid polymer electrolyte layer and a conductor layer are sequentially formed on the foil-shaped valve metal substrate, wherein the surface is roughened, and the insulating oxide film is formed. The area near one end of the foil-shaped lead electrode metal base is joined to the area near one end of the foil-shaped valve metal base on which is formed so that the metal is electrically connected. At least one solid electrolytic capacitor having an anode electrode having a substantially smooth surface area at least in a portion adjacent to the joint, wherein the foil-shaped valve metal base is formed on one surface of an insulating substrate; The present invention is achieved by a substrate having a built-in solid electrolytic capacitor, wherein the substrate is mounted on a substrate.

In a preferred embodiment of the present invention, at least one wiring pattern is formed on the other surface of the insulating substrate.

In a preferred embodiment of the present invention, at least one electronic component is mounted on the other surface of the insulating substrate.

In a preferred embodiment of the present invention, the substrate with a built-in solid electrolytic capacitor further comprises, in addition to the first insulating substrate, a second insulating substrate facing the first insulating substrate. A capacitor is integrally mounted between one surface of the first insulating substrate and one surface of the second insulating substrate.

According to a preferred embodiment of the present invention, the substrate with a built-in solid electrolytic capacitor further includes, in addition to the first insulating substrate, a second insulating substrate facing the first insulating substrate. Since it is integrally attached between one surface of the first insulating substrate and one surface of the second insulating substrate, an electronic component including a solid electrolytic capacitor,
It can be mounted on a substrate with a built-in solid electrolytic capacitor with high integration and high density.

In a preferred embodiment of the present invention, at least one wiring pattern is formed on the other surface of the second insulating substrate.

In a further preferred aspect of the present invention, a through-hole is formed at a position corresponding to the anode electrode on at least one of the first insulating substrate and the second insulating substrate.

According to a further preferred embodiment of the present invention, a through hole is formed at a position corresponding to the anode electrode of at least one of the first insulating substrate and the second insulating substrate. Thus, the anode electrode of the solid electrolytic capacitor can be easily electrically connected to the wiring pattern formed on at least one of the first insulating substrate and the second insulating substrate.

In a further preferred aspect of the present invention, a through hole is formed at a position corresponding to a cathode electrode of the solid electrolytic capacitor of at least one of the first insulating substrate and the second insulating substrate. ing.

According to a further preferred embodiment of the present invention, at least one of the first insulating substrate and the second insulating substrate has a through hole formed at a position corresponding to the cathode electrode of the solid electrolytic capacitor. Therefore, it is possible to easily electrically connect the cathode electrode of the solid electrolytic capacitor to a wiring pattern formed on at least one of the first insulating substrate and the second insulating substrate via the through hole. .

In a further preferred aspect of the present invention, at least one electronic component is mounted on at least one of the other surfaces of the first insulating substrate and the second insulating substrate.

In a further preferred aspect of the present invention, the first insulating substrate, the second insulating substrate and the solid electrolytic capacitor are integrated by a resin.

[0049] In a further preferred aspect of the present invention, through the through holes formed in at least one of the first insulating substrate and the second insulating substrate,
The at least one wiring pattern is electrically connected to an anode electrode of the solid electrolytic capacitor.

In a further preferred aspect of the present invention, the through hole is filled with a conductive resin, and the conductive resin electrically connects the cathode electrode of the solid electrolytic capacitor to the at least one wiring pattern. Have been.

[0051] In a preferred embodiment of the present invention, the solid electrolytic capacitor is housed in a substantially closed space formed by the first insulating substrate and the second insulating substrate.

In the present invention, a substantially closed space means a closed space except that the space is connected to the outside by a through hole or the like.

According to a preferred embodiment of the present invention, the substrate with a built-in solid electrolytic capacitor has a first insulating substrate and a second insulating substrate facing each other, and a second insulating substrate of the first insulating substrate. A solid electrolytic capacitor fixed on the surface, wherein the solid electrolytic capacitor is housed in a substantially closed space formed by the first insulating substrate and the second insulating substrate. When fabricating the built-in substrate, no excessive pressure is applied to the solid electrolytic capacitor, and therefore, the insulating oxide film formed on the surface of the valve metal base is broken by the pressure applied during fabrication, and the anode is crushed. When the valve metal substrate acting as a contact and the solid polymer electrolyte layer are in contact and energized,
There is no possibility that a short circuit occurs, and the flatness of the substrate with a built-in solid electrolytic capacitor can be improved.

In a preferred embodiment of the present invention, the first insulating substrate and the second insulating substrate are adhered to each other with an adhesive of the same material as the insulating substrate and the second insulating substrate.

According to a preferred embodiment of the present invention, the first insulating substrate and the second insulating substrate are bonded by the same material as the first insulating substrate and the second insulating substrate. Even when used for a long time, the first insulating substrate and the second insulating substrate do not peel off, and the reliability of the substrate with a built-in solid electrolytic capacitor can be improved.

In a preferred embodiment of the present invention, the first insulating substrate is formed by a flat substrate and a frame-shaped substrate fixed to the flat substrate around the solid electrolytic capacitor. Have been.

In a further preferred aspect of the present invention, the first insulating substrate is a flat substrate and a frame fixed to the flat substrate along a peripheral portion of the flat substrate. And the substrate.

According to a further preferred aspect of the present invention, the first insulating substrate is a flat substrate and a frame-like fixed to the flat substrate along the periphery of the flat substrate. The solid electrolytic capacitor is housed in a substantially closed space formed by the flat substrate and the frame-shaped substrate when the solid electrolytic capacitor built-in substrate is manufactured. Because you can
No excessive pressure is applied to the solid electrolytic capacitor,
Therefore, when the insulating oxide film formed on the surface of the valve metal substrate is broken by the pressure applied during fabrication, the valve metal substrate acting as an anode comes into contact with the solid polymer electrolyte layer, and the current flows. In addition, there is no possibility that a short circuit occurs.

In a further preferred aspect of the present invention, the frame-shaped substrate is fixed to the plate-shaped substrate by an adhesive made of the same material as the frame-shaped substrate.

According to the preferred embodiment of the present invention, since the frame-shaped substrate is fixed to the plate-shaped substrate by the same material as the frame-shaped substrate and the adhesive of the frame-shaped substrate, the frame-shaped substrate can be used for a long time. Even when used, the flat substrate and the frame substrate are not separated, and the reliability of the substrate with a built-in solid electrolytic capacitor can be improved.

[0061] In a preferred embodiment of the present invention, the first insulating substrate includes a flat substrate portion and a frame-shaped substrate portion located around the solid electrolytic capacitor.

[0062] In a further preferred aspect of the present invention, the first insulating substrate includes a plate-shaped substrate portion and a frame-shaped substrate portion located at a peripheral portion of the plate-shaped substrate portion. .

According to a further preferred embodiment of the present invention, the first insulating substrate includes a flat substrate portion and a frame-shaped substrate portion located at a peripheral portion of the flat substrate portion,
Therefore, when manufacturing the substrate with a built-in solid electrolytic capacitor, the solid electrolytic capacitor can be accommodated in a substantially closed space formed by the flat substrate portion and the frame-shaped substrate portion. No excessive pressure is applied to the electrolytic capacitor, and therefore, the insulating oxide film formed on the surface of the valve metal substrate is broken by the pressure applied at the time of fabrication, and the valve metal substrate acting as an anode and When the polymer electrolyte layer comes into contact and is energized,
There is no risk of short circuit.

In a preferred embodiment of the present invention, the second insulating substrate is formed in a flat plate shape.

In a preferred embodiment of the present invention, the second insulating substrate is a flat substrate and the flat substrate is located at a position where the second insulating substrate can be joined to the frame-shaped substrate of the first insulating substrate. And a frame-shaped substrate fixed to the substrate.

According to a preferred embodiment of the present invention, the second insulating substrate is fixed to the flat substrate at a position where the second insulating substrate can be joined to the flat substrate and the frame substrate of the first insulating substrate. Therefore, when producing a substrate with a built-in solid electrolytic capacitor, the solid electrolytic capacitor, the flat substrate of the first insulating substrate and the frame-shaped substrate fixed to this Since it can be accommodated in a substantially closed space formed between the flat substrate of the second insulating substrate and the frame-shaped substrate fixed thereto,
No excessive pressure is applied to the solid electrolytic capacitor,
Therefore, when the insulating oxide film formed on the surface of the valve metal substrate is broken by the pressure applied during fabrication, the valve metal substrate acting as an anode comes into contact with the solid polymer electrolyte layer, and the current flows. In addition, there is no possibility that a short circuit occurs.

In another preferred embodiment of the present invention, the second insulating substrate is provided at a position where the second insulating substrate can be joined to the flat substrate and the frame-shaped substrate portion of the first insulating substrate. And a frame-shaped substrate fixed to the substrate.

According to another preferred embodiment of the present invention,
The second insulating substrate has a flat substrate and a frame-shaped substrate fixed to the flat substrate at a position where the second insulating substrate can be joined to the frame-shaped substrate portion of the first insulating substrate. ,
When manufacturing a substrate with a built-in solid electrolytic capacitor, the solid electrolytic capacitor is formed by a flat substrate portion of the first insulating substrate and a frame-shaped substrate portion integrally formed therewith, and a flat substrate portion of the second insulating substrate. Can be accommodated in a substantially closed space formed between the solid-state substrate and the frame-shaped substrate fixed thereto, so that no excessive pressure is applied to the solid electrolytic capacitor, and therefore, When the insulating oxide film formed on the surface of the valve metal substrate is broken by the pressure applied during fabrication, the valve metal substrate acting as an anode and the solid polymer electrolyte layer come into contact with each other, There is no risk of short circuit.

In a preferred embodiment of the present invention, the frame-shaped substrate is fixed to the plate-shaped substrate by an adhesive made of the same material as the frame-shaped substrate.

According to a preferred embodiment of the present invention, the frame-shaped substrate is fixed to the plate-shaped substrate by the flat-plate-shaped substrate and an adhesive of the same material as that of the frame-shaped substrate. Even when used, the flat substrate and the frame substrate are not separated, and the reliability of the substrate with a built-in solid electrolytic capacitor can be improved.

In a preferred embodiment of the present invention, the second insulating substrate is formed of a flat substrate portion and a frame-shaped portion of the first insulating substrate located at a position capable of being joined to the frame-shaped substrate. It has a substrate part.

According to a preferred embodiment of the present invention, the second insulating substrate has a flat substrate portion and a frame-shaped substrate portion located at a position where the second insulating substrate can be joined to the frame-shaped substrate of the first insulating substrate. Therefore, when manufacturing the substrate with a built-in solid electrolytic capacitor, the solid electrolytic capacitor, a flat substrate of the first insulating substrate and a frame-shaped substrate fixed thereto,
The solid electrolytic capacitor can be accommodated in a substantially closed space formed between the flat substrate portion of the second insulating substrate and the frame-shaped substrate portion formed integrally therewith. No excessive pressure is applied to the valve metal substrate, and therefore, the insulating oxide film formed on the surface of the valve metal base is
There is no danger that a short circuit will occur when the valve metal substrate, which is broken down and acts as an anode, comes into contact with the solid polymer electrolyte layer due to the pressure applied at the time of fabrication, and is energized.

In another preferred embodiment of the present invention, the second insulating substrate is located at a position where the second insulating substrate can be joined to the flat substrate and the frame-shaped substrate of the first insulating substrate. A frame-shaped substrate is provided.

According to another preferred embodiment of the present invention,
The second insulating substrate includes a flat substrate portion and a frame-shaped substrate portion located at a position that can be joined to the frame-shaped substrate portion of the first insulating substrate. When manufacturing a solid electrolytic capacitor, a flat substrate portion of the first insulating substrate and a frame-shaped substrate portion formed integrally therewith, and a flat substrate portion of the second insulating substrate and Since the solid electrolytic capacitor can be accommodated in a substantially closed space formed between the solid electrolytic capacitor and a frame-shaped substrate portion formed integrally with the solid electrolytic capacitor, excessive pressure is not applied to the solid electrolytic capacitor. When the insulating oxide film formed on the surface of the valve metal substrate is broken by the pressure applied during fabrication, the valve metal substrate acting as an anode and the solid polymer electrolyte layer come into contact with each other, There is no risk of short circuit

In a preferred embodiment of the present invention, the second insulating substrate is formed by a flat substrate and a frame substrate fixed to the flat substrate around the solid electrolytic capacitor. The first insulating substrate is formed in a flat plate shape.

According to a preferred embodiment of the present invention, the second insulating substrate is formed by a flat substrate and a frame-shaped substrate fixed to the flat substrate around the solid electrolytic capacitor, The first insulating substrate is formed in a flat plate shape.Therefore, when manufacturing a substrate with a built-in solid electrolytic capacitor, the solid electrolytic capacitor is formed by a flat first insulating substrate and a flat plate of the second insulating substrate. The solid electrolytic capacitor can be accommodated in a substantially closed space formed by the shape-like substrate and the frame-like substrate fixed thereto, so that no excessive pressure is applied to the solid electrolytic capacitor, and therefore, the valve metal The insulating oxide film formed on the surface of the substrate,
There is no danger that a short circuit will occur when the valve metal substrate, which is broken down and acts as an anode, comes into contact with the solid polymer electrolyte layer due to the pressure applied at the time of fabrication, and is energized.

In a further preferred aspect of the present invention, the frame-shaped substrate of the second insulating substrate is fixed to the plate-shaped substrate along a peripheral portion of the plate-shaped substrate.

In a preferred embodiment of the present invention, the frame-shaped substrate is fixed to the plate-shaped substrate by an adhesive made of the same material as the frame-shaped substrate.

In another preferred embodiment of the present invention, the second insulating substrate includes a plate-shaped substrate portion and a frame-shaped substrate portion located around the solid electrolytic capacitor. Is formed in a flat plate shape.

According to another preferred embodiment of the present invention,
The second insulating substrate includes a flat substrate portion and a frame-shaped substrate portion positioned around the solid electrolytic capacitor, and the first insulating substrate is formed in a flat shape, and When manufacturing the capacitor built-in substrate, a solid electrolytic capacitor is formed by a flat first insulating substrate, a flat substrate of the second insulating substrate and a frame-shaped substrate integrally formed therewith. Since the solid electrolytic capacitor can be accommodated in a substantially closed space, no excessive pressure is applied to the solid electrolytic capacitor, and therefore, an insulating oxide film formed on the surface of the valve metal base is added during production. The valve metal substrate, which is broken by the applied pressure and acts as an anode, and the solid polymer electrolyte layer are in contact with each other, and there is no possibility that a short circuit will occur when electricity is supplied.

In a further preferred aspect of the present invention, the frame-shaped substrate portion of the second insulating substrate is located at a peripheral edge of the plate-shaped substrate portion.

The object of the present invention is also to provide a foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon,
A method for manufacturing a solid electrolytic capacitor in which at least an insulating oxide film, a solid polymer electrolyte layer and a conductor layer are sequentially formed on the foil-shaped valve metal substrate, wherein the surface is roughened, The region near one end of the foil-shaped valve metal substrate on which the conductive oxide film is formed and the region near one end of the foil-shaped lead electrode metal substrate are joined so that metal is electrically connected. Forming a joined portion to form a joined body of the foil-shaped valve metal substrate and the foil-shaped lead electrode metal substrate; and joining the foil-shaped valve metal substrate and the foil-shaped lead electrode metal substrate. The body is immersed in a chemical conversion solution of the foil-shaped valve metal substrate, a voltage is applied to the joined body, anodizing treatment is performed, and an insulating oxide film is formed on at least an edge portion of the valve metal substrate. And anodizing treatment of the foil-shaped valve metal On the entire surface of the body, forming a solid polymer electrolyte layer, the solid polymer electrolyte layer,
Applying a conductive paste and drying to form a conductive layer, further comprising, prior to the step of forming the insulating oxide film, at least the foil-shaped valve metal adjacent to the joint portion Subjecting the roughened surface of the substrate to a smoothing treatment to form a substantially smooth surface area, wherein only the portion of the foil-shaped valve metal substrate excluding the substantially smooth surface is removed. This is achieved by a method for manufacturing a solid electrolytic capacitor, characterized by immersing in a chemical conversion solution and performing anodizing treatment to form an insulating oxide film on at least an edge portion of the valve metal substrate.

The object of the present invention is also to provide a foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon,
A method for manufacturing a solid electrolytic capacitor in which at least an insulating oxide film, a solid polymer electrolyte layer, and a conductor layer are sequentially formed on the foil-shaped valve metal substrate, wherein the surface is roughened. The region near one end of the foil-shaped valve metal substrate and the region near one end of the conductive metal substrate are joined so that the metal is electrically connected to form a joint, and the foil is formed. Forming a joined body of the valve-shaped valve metal base and the foil-shaped lead electrode metal base; and performing a roughening treatment on the surface of the foil-shaped valve metal base excluding a portion adjacent to the joint. Part of the part of the foil-shaped valve metal substrate that has not been subjected to the surface roughening treatment, and the part that has been subjected to the surface roughening treatment, the foil-shaped valve metal substrate is immersed in a chemical conversion solution, A voltage is applied to the joined body to perform an anodic oxidation treatment, and at least the valve metal substrate Forming a solid polymer electrolyte layer on the entire surface of the foil-shaped valve metal substrate that has been subjected to anodizing treatment; Applying a conductive paste on the electrolyte layer and drying to form a conductor layer.

The object of the present invention is also to provide a foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon,
A method for manufacturing a substrate with a built-in solid electrolytic capacitor including at least one solid electrolytic capacitor in which at least an insulating oxide film, a solid polymer electrolyte layer, and a conductor layer are sequentially formed on the foil-shaped valve metal substrate. The area near one end of the foil-shaped valve metal base on which the surface is roughened and the insulating oxide film is formed, and the area near one end of the foil-shaped lead electrode metal base are electrically connected between the metals. Forming a joined portion by joining together so as to be electrically connected, and forming a joined body of the foil-shaped valve metal base and the foil-shaped lead electrode metal base; and the foil-shaped valve metal base. And a bonded body of the foil-shaped lead electrode metal base, the foil-shaped valve metal base is immersed in a chemical conversion solution, a voltage is applied to the bonded body, and anodizing treatment is performed. At least on the edge,
A step of forming an insulating oxide film, and a step of forming a solid polymer electrolyte layer on the entire surface of the foil-shaped valve metal substrate that has been subjected to anodic oxidation, and, on the solid polymer electrolyte layer, Applying a conductive paste and drying to form a conductor layer and produce at least one solid electrolytic capacitor; and at least one solid electrolytic capacitor,
Attaching to one surface of an insulating substrate, and prior to the step of forming the insulating oxide film, a roughened surface of the foil-shaped valve metal base at least adjacent to the joint portion Applying a smoothing treatment to form a substantially smooth surface area, and immersing only the portion of the foil-shaped valve metal substrate excluding the substantially smooth surface in a chemical conversion solution, thereby performing anodization. This is achieved by a method for manufacturing a substrate with a built-in solid electrolytic capacitor, characterized by performing a treatment and forming an insulating oxide film on at least an edge portion of the valve metal base.

The object of the present invention is also to provide a foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon,
A method for manufacturing a substrate with a built-in solid electrolytic capacitor including at least one solid electrolytic capacitor in which at least an insulating oxide film, a solid polymer electrolyte layer, and a conductor layer are sequentially formed on the foil-shaped valve metal substrate. Then, a region near one end of the foil-shaped valve metal base whose surface is not roughened and a region near one end of the conductive metal base are joined so that metal is electrically connected. Forming a joint, and forming a joined body of the foil-shaped valve metal base and the foil-shaped lead electrode metal base, and the foil-shaped valve metal base excluding a portion adjacent to the joint. Performing a surface roughening treatment on the surface of the foil-shaped valve metal base, a part of the part that has not been subjected to the surface roughening treatment, and a part that has been subjected to the surface roughening treatment, A valve metal substrate is immersed in a chemical conversion solution, and a voltage is applied to the joined body. Applying an anodizing treatment to form an insulating oxide film on at least an edge portion of the valve metal base; and forming a solid high-level material on the entire surface of the anodized foil-shaped valve metal base. Forming a molecular electrolyte layer, applying a conductive paste on the solid polymer electrolyte layer, and drying to form a conductive layer;
A method for producing a solid electrolytic capacitor built-in substrate, comprising: a step of producing two solid electrolytic capacitors; and a step of attaching the at least one solid electrolytic capacitor to one surface of an insulating substrate. .

In a preferred embodiment of the present invention, at least one wiring pattern is formed on the other surface of the insulating substrate to manufacture a substrate with a built-in solid electrolytic capacitor.

In a preferred embodiment of the present invention, at least one electronic component is mounted on the other surface of the insulating substrate to manufacture a substrate with a built-in solid electrolytic capacitor.

In a preferred embodiment of the present invention, a second insulating substrate is used in addition to the first insulating substrate, and one surface of the second insulating substrate faces the solid electrolytic capacitor. As a result, the solid electrolytic capacitor is fixed between the first insulating substrate and the second insulating substrate to manufacture a substrate with a built-in solid electrolytic capacitor.

[0089] In a preferred embodiment of the present invention, at least one surface of the second insulating substrate is provided on the other surface.
By forming one wiring pattern, a substrate with a built-in solid electrolytic capacitor is manufactured.

In a further preferred aspect of the present invention, a through hole is formed in at least one of the first insulating substrate and the second insulating substrate at a position corresponding to the anode electrode. A substrate with a built-in electrolytic capacitor is manufactured.

In a further preferred aspect of the present invention, a through hole is formed at a position corresponding to a cathode electrode of the solid electrolytic capacitor of at least one of the first insulating substrate and the second insulating substrate. As a result, a substrate with a built-in solid electrolytic capacitor is manufactured.

[0092] In a further preferred aspect of the present invention, at least one electronic component is mounted on at least one of the other surfaces of the first insulating substrate and the second insulating substrate, and a solid electrolytic capacitor is provided. A built-in substrate is manufactured.

In a further preferred embodiment of the present invention, a substrate with a built-in solid electrolytic capacitor is manufactured by integrating the first insulating substrate, the second insulating substrate, and the solid electrolytic capacitor with a resin. .

[0094] In a further preferred aspect of the present invention, through the through holes formed in at least one of the first insulating substrate and the second insulating substrate,
By electrically connecting the at least one wiring pattern to the anode electrode of the solid electrolytic capacitor, a substrate with a built-in solid electrolytic capacitor is manufactured.

In a further preferred aspect of the present invention, the through hole is filled with a conductive resin, and the cathode electrode of the solid electrolytic capacitor and the at least one wiring pattern are electrically connected by the conductive resin. By doing so, a substrate with a built-in solid electrolytic capacitor is manufactured.

[0096] In a further preferred aspect of the present invention, the anode is connected to the anode electrode of the solid electrolytic capacitor via the through hole formed in one of the first insulating substrate and the second insulating substrate. The electronic component mounted on one of the one insulating substrate and the second insulating substrate is connected to manufacture a substrate with a built-in solid electrolytic capacitor.

In the present invention, the valve metal substrate is formed of a metal or alloy selected from the group consisting of a metal having an ability to form an insulating oxide film and an alloy thereof. Preferred valve metals include one metal selected from the group consisting of aluminum, tantalum, titanium, niobium, and zirconium, or alloys of two or more metals. Of these, aluminum and tantalum are particularly preferred. The anode electrode is formed by processing these metals or alloys into a foil shape.

In the present invention, the material of the conductive metal is not particularly limited as long as it is a metal or an alloy having conductivity, but preferably, solder connection is possible, and particularly, copper, brass, or the like can be used. , Nickel, zinc and chromium, it is preferable to select from one kind of metal or an alloy of two or more kinds of metals. Among these, electrical properties, workability in later steps, cost, etc. In light of the above, copper is most preferably used.

In the present invention, the solid polymer electrolyte layer comprises
Contains a conductive polymer compound, preferably, the surface is roughened by chemical oxidation polymerization or electrolytic oxidation polymerization,
It is formed on a foil-shaped valve metal substrate on which an insulating oxide film is formed.

When the solid polymer electrolyte layer is formed by chemical oxidation polymerization, specifically, the surface of the solid polymer electrolyte layer is roughened, for example, as follows.
It is formed on a foil-shaped valve metal substrate on which an insulating oxide film is formed.

First, a solution containing 0.001 to 2.0 mol / l of an oxidizing agent, or a solution containing only 0.001 to 2.0 mol / l on only a foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon. A solution to which a compound giving a dopant species is added is uniformly deposited by a method such as coating or spraying.

Then, preferably, at least 0.01
A solution containing mol / liter of the raw material monomer of the conductive polymer compound or the raw material monomer of the conductive polymer compound itself is brought into direct contact with the insulating oxide film formed on the surface of the foil-shaped valve metal base. As a result, the raw material monomer is polymerized, the conductive polymer compound is synthesized, and the solid polymer electrolyte layer made of the conductive polymer compound is formed on the insulating oxide film formed on the surface of the foil-shaped valve metal base. It is formed.

In the present invention, the conductive polymer compound contained in the solid polymer electrolyte layer includes a substituted or unsubstituted π-conjugated heterocyclic compound, a conjugated aromatic compound, and a heteroatom-containing conjugated aromatic compound. Preferably, a compound selected from the group consisting of a starting monomer is used.Among these, a conductive polymer compound using a substituted or unsubstituted π-conjugated heterocyclic compound as a starting monomer is preferable. Conductive polymer compounds selected from the group consisting of polyaniline, polypyrrole, polythiophene, polyfuran, and derivatives thereof, particularly polyaniline, polypyrrole, and polyethylenedioxythiophene are preferably used.

In the present invention, specific examples of the raw material monomer of the conductive polymer compound preferably used for the solid polymer electrolyte layer include unsubstituted aniline, alkylaniline, alkoxyaniline, haloaniline, o-phenylenediamine , 2,6-dialkylanilines,
2,5-dialkoxyanilines, 4,4′-diaminodiphenyl ether, pyrrole, 3-methylpyrrole,
3-ethylpyrrole, 3-propylpyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene,
3,4-ethylenedioxythiophene and the like can be mentioned.

In the present invention, the oxidizing agent used in the chemical oxidative polymerization is not particularly limited, but examples thereof include halides such as iodine, bromine and bromine iodide, silicon pentafluoride, and antimony pentafluoride. Metal halides such as silicon tetrafluoride, phosphorus pentachloride, phosphorus pentafluoride, aluminum chloride, molybdenum chloride, protic acids such as sulfuric acid, nitric acid, fluorosulfuric acid, trifluoromethanesulfuric acid, chlorosulfuric acid, sulfur trioxide, nitrogen dioxide Oxygen compounds such as sodium persulfate, potassium persulfate, ammonium persulfate and other persulfates, hydrogen peroxide, potassium permanganate,
Peroxides such as peracetic acid and difluorosulfonyl peroxide are used as oxidizing agents.

In the present invention, if necessary, an oxidizing agent
Compounds that provide the added dopant species include, for example,
For example, LiPF₆, LiAsF₆, NaPF₆, KPF
₆, KAsF₆Anions such as hexafluorolineani
On, hexafluoroarsenic anion, where the cation is
Alkali metal clicks such as titanium, sodium and potassium
Salt that is on, LiBF₄, NaBF₄, NH₄B
F₄, (CH₃)₄NBF ₄, (N-C₄H₉)₄NB
F₄Tetrafluoroboron salt compounds such as p-toluenesulfur
Honic acid, p-ethylbenzenesulfonic acid, P-hydroxy
Sibenzenesulfonic acid, dodecylbenzenesulfonic acid,
Methylsulfonic acid, dodecylsulfonic acid, benzenesulfur
Sulfonic acids such as sulfonic acid and β-naphthalenesulfonic acid
Or its derivatives, sodium butylnaphthalenesulfonate
, Sodium 2,6-naphthalenedisulfonic acid, tol
Sodium ene sulfonate, tetra toluene sulfonate
Sulfonic acid such as butyl ammonium or its derivative
Salt, ferric chloride, ferric bromide, cupric chloride, pickup
Metal halides such as copper, hydrochloric acid, hydrogen bromide, iodide water
Sulfuric acid, phosphoric acid, nitric acid or their alkali metals
Salt, alkaline earth metal salt or ammonium salt, persalt
Perhalic acid such as elemental acid, sodium perchlorate or
Hydrohalic acids such as salts thereof, inorganic acids or salts thereof,
Acetic, oxalic, formic, butyric, succinic, lactic, citric
Acid, phthalic acid, maleic acid, benzoic acid, salicylic acid,
Mono or dicarboxylic acids such as cotinic acid, aromatic hetero
Halogenated cyclic carboxylic acid, trifluoroacetic acid, etc.
Carboxylic acids such as carboxylic acids and their salts
Can be mentioned.

In the present invention, the compound capable of providing these oxidizing agents and dopant species is used in the form of a suitable solution dissolved in water, an organic solvent or the like. The solvents may be used alone or as a mixture of two or more. The mixed solvent is also effective in increasing the solubility of the compound giving the dopant species. As the mixed solvent, those having compatibility between the solvents and those having compatibility with the compound capable of providing the oxidizing agent and the dopant species are preferable. Specific examples of the solvent include organic amides, sulfur-containing compounds, esters, and alcohols.

On the other hand, when the solid polymer electrolyte layer is formed on a foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon by electrolytic oxidation polymerization, a known method is used. The solid polymer electrolyte layer is formed by immersing the conductive underlayer in the electrolyte containing the raw material monomer of the conductive polymer compound and the supporting electrolyte together with the counter electrode, using the conductive underlayer as the working electrode, and supplying an electric current. You.

Specifically, first, a thin conductive underlayer is formed on a foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon, preferably by chemical oxidation polymerization. It is formed. The thickness of the conductive underlayer is controlled by controlling the number of polymerizations under certain polymerization conditions. The number of polymerizations is determined by the type of the raw material monomer.

The conductive underlayer may be made of any one of a metal, a metal oxide having conductivity, and a conductive polymer compound, but is preferably made of a conductive polymer compound. As a raw material monomer for forming the conductive underlayer, a raw material monomer used for chemical oxidative polymerization can be used, and the conductive polymer compound contained in the conductive underlayer is a solid polymer formed by chemical oxidative polymerization. This is the same as the conductive polymer compound contained in the polymer electrolyte layer.

When ethylene dioxythiophene or pyrrole is used as a raw material monomer for forming the conductive underlayer, the conductive polymer produced when the polymer solid electrolyte layer is formed only by chemical oxidation polymerization is used. 10% of the total amount
The conductive underlayer may be formed by converting the number of polymerizations so that the conductive polymer is formed under a condition of about 30% (weight ratio).

Thereafter, the conductive underlayer is immersed in an electrolytic solution containing a raw material monomer of the conductive polymer compound and a supporting electrolyte together with the counter electrode, using the conductive underlayer as a working electrode, and a current is supplied to the conductive underlayer. A solid polymer electrolyte layer is formed thereon.

Various additives can be added to the electrolytic solution, if necessary, in addition to the raw material monomer of the conductive polymer compound and the supporting electrolyte.

The conductive polymer compound that can be used for the solid polymer electrolyte layer is the same as the conductive polymer compound used for the conductive underlayer and, therefore, the conductive polymer compound used for chemical oxidation polymerization. And a conductive polymer compound using a compound selected from the group consisting of a substituted or unsubstituted π-conjugated heterocyclic compound, a conjugated aromatic compound and a heteroatom-containing conjugated aromatic compound as a raw material monomer is preferable. Of these, a conductive polymer compound using a substituted or unsubstituted π-conjugated heterocyclic compound as a starting monomer is preferable, and further selected from the group consisting of polyaniline, polypyrrole, polythiophene, polyfuran, and derivatives thereof. Conductive polymer compounds, in particular, polyaniline, polypyrrole, and polyethylenedioxythiophene are preferred. Used well.

The supporting electrolyte is selected according to the monomer and the solvent to be combined. Specific examples of the supporting electrolyte include, for example, basic compounds such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, and carbonate. Sodium, sodium hydrogen carbonate, etc., as acidic compounds, sulfuric acid, hydrochloric acid, nitric acid, hydrogen bromide, perchloric acid, trifluoroacetic acid, sulfonic acid, etc., and as salts, sodium chloride, sodium bromide, iodide Potassium, potassium chloride, potassium nitrate, sodium periodate, sodium perchlorate, lithium perchlorate, ammonium iodide,
Ammonium chloride, boron tetrafluoride compound, tetramethylammonium chloride, tetraethylammonium chloride, tetramethylammonium bromide,
Examples thereof include tetraethylammonium bromide, tetraethylammonium perchloride, tetrabutylammonium perchloride, tetramethylammonium, D-toluenesulfonic acid chloride, triethylamine polydisalicylate, and 10-sodium camphorsulfonate.

In the present invention, the dissolution concentration of the supporting electrolyte may be set so as to obtain a desired current density.
Although not particularly limited, it is generally set in the range of 0.05 to 1.0 mol / liter.

In the present invention, the solvent used in the electrolytic oxidation polymerization is not particularly limited.
Water, a protic solvent, an aprotic solvent, or a mixed solvent obtained by mixing two or more of these solvents can be appropriately selected. As the mixed solvent, those having compatibility between the solvents and those having compatibility with the monomer and the supporting electrolyte can be preferably used.

Specific examples of the protic solvent used in the present invention include formic acid, acetic acid, propionic acid, methanol, ethanol, n-propanol, isopropanol, tert-butyl alcohol, methyl cellosolve, and the like.
Examples thereof include diethylamine and ethylenediamine.

Specific examples of the aprotic solvent include methylene chloride, 1,2-dichloroethane, carbon disulfide, acetonitrile, acetone, propylene carbonate, nitromethane, nitrobenzene, ethyl acetate, diethyl ether, tetrahydrofuran, dimethoxyethane, and the like. Dioxane, N, N-dimethylacetamide, N,
N-dimethylformamide, pyridine, dimethylsulfoxide and the like can be mentioned.

In the present invention, by electrolytic oxidation polymerization,
When the solid polymer electrolyte layer is formed, any of the constant voltage method, the constant current method, and the potential sweep method may be used. In the process of electrolytic oxidation polymerization, the conductive polymer compound can be polymerized by a combination of the constant voltage method and the constant current method. The current density is not particularly limited, but may be up to 500 mA /
cm ² .

In the present invention, at the time of chemical oxidation polymerization or electrolytic oxidation polymerization, as disclosed in JP-A-2000-100665, it is also possible to polymerize a conductive polymer compound while irradiating ultrasonic waves. In the case where the conductive polymer compound is polymerized while being irradiated with ultrasonic waves, it is possible to improve the film quality of the obtained solid polymer electrolyte layer.

In the present invention, the maximum thickness of the solid polymer electrolyte layer is not particularly limited, as long as it can completely fill the irregularities on the anode electrode surface formed by etching or the like. Generally, 5 to 1
It is about 00 μm.

In the present invention, the solid electrolytic capacitor is
Further, on the solid polymer electrolyte layer, a conductor layer functioning as a cathode is provided, and as the conductor layer, a graphite paste layer and a silver paste layer can be provided,
The graphite paste layer and the silver paste layer can be formed by a screen printing method, a spray coating method, or the like. Although the cathode of the solid electrolytic capacitor can be formed only by the silver paste layer, when the graphite paste layer is formed, compared with the case where the cathode of the solid electrolytic capacitor is formed only by the silver paste layer, the silver paste layer is formed. Migration can be prevented.

In forming a graphite paste layer and a silver paste layer as a cathode, a portion corresponding to a foil-shaped valve metal substrate on which a roughening treatment is performed using a metal mask and an insulating oxide film is formed is used. The graphite paste layer and the silver paste layer are formed only on the portion corresponding to the foil-shaped valve metal substrate on which the removed portion is masked and subjected to a surface roughening treatment and on which an insulating oxide film is formed.

In the present invention, the solid electrolytic capacitor is
One surface is fixed to the other surface side of one insulating substrate having at least one wiring pattern formed thereon, or
Each is fixed between the other surfaces of a pair of opposing insulating substrates having at least one wiring pattern formed on one surface.

In the present invention, the material of the insulating substrate is not particularly limited, but it can be formed of a resin such as a phenol resin, a polyimide resin, an epoxy resin, or a polyester resin having good adhesiveness and solvent resistance. Furthermore, not only organic materials, but also inorganic materials
An insulating substrate may be formed, and a metal oxide-based substrate such as an alumina substrate can also be used as the insulating substrate of the present invention.

[0127]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in detail with reference to the accompanying drawings.

FIG. 1 is a schematic plan view of an anode electrode of a solid electrolytic capacitor according to a preferred embodiment of the present invention, and FIG. 2 is a schematic sectional view taken along line AA.

In this embodiment, aluminum is used as the valve metal having the ability to form an insulating oxide film. As shown in FIGS. 1 and 2, the anode electrode 1 of the solid electrolytic capacitor according to this embodiment is A foil-like aluminum substrate 2 having a roughened surface (enlarged surface) and an aluminum oxide film as an insulating oxide film formed on the surface, and a foil-like copper substrate 3 as a metal conductor constituting a lead electrode It has.

As shown in FIGS. 1 and 2, the anode electrode according to this embodiment has a roughened surface,
One end region of the foil-shaped copper substrate 3 is connected to one end region of the foil-shaped aluminum substrate 2 having an aluminum oxide film formed on the surface by ultrasonic welding so that the metal is electrically connected. , And a welded joint 4 is formed.

As shown in FIGS. 1 and 2, the roughened surface area of the foil-like aluminum substrate 2 adjacent to the weld joint 4 is smoothed over the entire circumference, and is substantially smooth. A smoothing region 5 having a surface is formed.
In this embodiment, the roughened surface of the foil-shaped aluminum substrate 2 is pressed by a hand press,
The smoothed area 5 is formed.

Even if the smoothing region 5 is formed before joining the foil-shaped aluminum substrate 2 and the foil-shaped copper substrate 3,
It may be formed after the aluminum substrate 2 and the foil-shaped copper substrate 3 are joined.

In forming the anode electrode, first, a foil-shaped aluminum substrate 2 of a predetermined size having a roughened surface and an aluminum oxide film formed on the surface is cut out of an aluminum foil sheet, and the foil-shaped aluminum substrate is cut. The copper base 3 and the copper base 3 are overlapped so that the end regions having a predetermined area overlap each other.

Next, the edge region of the foil-shaped copper substrate 3 and the edge region of the foil-shaped aluminum substrate 2 which are overlapped with each other are joined by ultrasonic welding to form a welded joint 4. Is done. By joining the foil-like copper base 3 and the foil-like aluminum base 2 by ultrasonic welding, the aluminum oxide film is removed and the foil-like copper base 3 is electrically connected between the metals. The end region and the end region of the foil-shaped aluminum substrate 2 are joined. Here, the areas of the end regions of the foil-shaped copper base 3 and the end regions of the foil-shaped aluminum base 2 overlapping each other are determined so that the joint has a predetermined strength.

In the anode electrode 1 thus formed, since the foil-like aluminum base 2 constituting the dielectric is cut out from the aluminum foil sheet, an aluminum oxide film is formed on the edge thereof. In order to use it as an anode electrode of a solid electrolytic capacitor, a foil-shaped aluminum substrate 2 having a roughened surface is required.
It is necessary to form an aluminum oxide film by anodization on the edge portion of.

FIG. 3 is a schematic sectional view showing an anodic oxidation method for forming an aluminum oxide film on the edge of a foil-shaped aluminum substrate 2.

As shown in FIG. 3, only a portion of the foil-shaped aluminum substrate 2 excluding the smoothing region 5 is immersed in a chemical conversion solution 8 composed of an aqueous solution of ammonium adipate accommodated in a stainless beaker 7. Thus, the anode electrode 1 is set, and a voltage is applied using the foil-shaped copper base 4 as an anode and the stainless beaker 7 as a cathode.

The operating voltage can be appropriately determined according to the thickness of the aluminum oxide film to be formed.
When an aluminum oxide film having a film thickness of m to 1 μm is formed, it is usually set to several volts to about 20 volts.

As a result, the anodization is started, and the chemical conversion solution 8 rises due to the capillary phenomenon because the surface of the foil-shaped aluminum substrate 2 is roughened. The surface of the aluminum substrate 2 is smoothed over the entire circumference and the smoothed region 5 is formed, so that the surface of the foil-shaped aluminum substrate 2 and the surface of the foil-shaped copper substrate 3 are roughened. It does not rise beyond the joint, so that the chemical conversion solution 8 is reliably prevented from coming into contact with the foil-like copper substrate 3 constituting the lead electrode, and the surface including the edge portion has a foil-like aluminum substrate. An aluminum oxide film is formed only on the entire surface of No. 2.

The surface of the anode electrode 1 thus formed is roughened, and the cathode electrode is formed by a known method on the entire surface of the foil-shaped aluminum substrate 2 on which the aluminum oxide film is formed. An electrolytic capacitor is created.

FIG. 4 is a schematic sectional view of a solid electrolytic capacitor.

As shown in FIG. 4, the solid electrolytic capacitor 10 has a foil-shaped aluminum substrate 2 having an anode electrode 1 having a roughened surface and an aluminum oxide film formed thereon.
Is provided with a cathode electrode 14 composed of a solid polymer electrolyte layer 11, a graphite paste layer 12, and a silver paste layer 13.

The solid polymer electrolyte layer 11 containing a conductive polymer compound is formed on the entire surface of the foil-shaped aluminum substrate 2 on which the surface of the anode electrode 1 has been roughened and on which an aluminum oxide film has been formed. Formed by oxidative polymerization.

The graphite paste layer 12 and the silver paste layer 13 are formed on the solid polymer electrolyte layer 11 by a screen printing method or a spray coating method.

The solid electrolytic capacitor 1 thus produced
Numeral 0 is fixed between the pair of insulating substrates and built in the printed circuit board to form a solid electrolytic capacitor built-in printed circuit board.

FIG. 5 is a schematic sectional view of a printed circuit board with a built-in solid electrolytic capacitor.

As shown in FIG. 5, the printed circuit board 20 with a built-in solid electrolytic capacitor includes a first insulating substrate 21 and a second insulating substrate 22 facing each other. The solid electrolytic capacitor 10 is provided between the solid electrolytic capacitor 10 and the substrate 22.

A bank 23 whose height is larger than the thickness of the solid electrolytic capacitor 10 is formed on the first insulating substrate 21 along two opposing sides.
The solid electrolytic capacitor 10 is positioned at a predetermined position on one surface of the first insulating substrate 21 between the banks 23, and is fixed by an adhesive 29.

In the present embodiment, the bank 23 is formed by punching a substrate made of the same material as the first insulating substrate 21 and the second insulating substrate 22 so that a portion having a predetermined area is left around the periphery thereof. Then, a frame-shaped substrate is formed, and the frame-shaped substrate is fixed to the first insulating substrate using an adhesive of the same material as the first insulating substrate 21 and the second insulating substrate 22. Have been.

On the other surface of the first insulating substrate 21, a wiring pattern 24 is formed.
A plurality of through holes 25 are formed.

When the solid electrolytic capacitor 10 is positioned at a predetermined position on the first insulating substrate 21 and is fixed on the first insulating substrate 21 by the adhesive 29, the resin 2
6 is poured into the second insulating substrate 22 so as to contact the bank 23 formed on the first insulating substrate 21.
Is covered.

A wiring pattern 27 is formed on the upper surface of the second insulating substrate 22, and a plurality of through holes 28 are also formed in the second insulating substrate 22.

The resin 26 includes a plurality of through holes 25 formed in the first insulating substrate 21 and the second insulating substrate 22.
Is poured so as not to block the plurality of through holes 28 formed in the solid electrolytic capacitor 1.
0 is integrated with and fixed to the first insulating substrate 21 and the second insulating substrate 22, and the first insulating substrate 21 and the second insulating substrate 22 are bonded using the same material as the first insulating substrate 21 and the second insulating substrate 22. The insulating substrate 21 and the second insulating substrate 22 are bonded to form the printed circuit board 20 with a built-in solid electrolytic capacitor.

Further, electronic components 30 are mounted on the lower surface of the first insulating substrate 21 and the upper surface of the second insulating substrate 22, and the contacts are electrically connected to the wiring patterns 24 and 27.

The first insulating substrate 21 and the second insulating substrate 22 are located at positions corresponding to the foil-shaped copper base 4 of the anode electrode 1 of the solid electrolytic capacitor 10 and at the cathode electrode 14 respectively.
Are provided at positions corresponding to. The anode electrode 1 and the cathode electrode 14 of the solid electrolytic capacitor 10 can be visually confirmed through the through holes 25 and 28. ing.

The anode electrode 1 of the solid electrolytic capacitor 10 is connected to the first insulating substrate 21 through the through holes 25 and 28.
And the wiring pattern 27 formed on the second insulating substrate 22 is electrically connected to the wiring pattern formed on the first insulating substrate 21. It is electrically connected to the pattern 24 or the wiring pattern 27 formed on the second insulating substrate 22.

In FIG. 5, the wiring pattern 24 formed on the first insulating substrate 21 and the solid electrolytic capacitor 10
Is electrically connected to the foil-shaped copper base 4 constituting the anode electrode 1 by a solder 31 through a through-hole 25, while a wiring pattern 24 formed on the first insulating substrate 21 is formed. The cathode electrode 14 of the solid electrolytic capacitor 10 is connected to the conductive resin 32 filled in the through hole 28.
Indicates an example of electrical connection.

According to this embodiment, at the time of the anodic oxidation treatment,
Since the surface of the foil-shaped aluminum substrate 2 is roughened, the chemical conversion solution 8 rises by capillary action.
The roughened surface area adjacent to the weld joint 4 of the foil-shaped aluminum substrate 2 is smoothed over the entire circumference,
Since the smoothed region 5 having a substantially smooth surface is formed, the foil-shaped aluminum substrate 2 and the foil-shaped copper substrate 3
Therefore, it does not rise beyond the junction with the aluminum alloy, and therefore, the conversion solution 8 is applied to the foil-like copper base 3 constituting the lead electrode.
Can reliably be prevented from contacting with each other, and the aluminum oxide film can be formed only on the entire surface of the aluminum substrate 2 whose surface including the edge portion is a foil. By providing a contact with another electronic component mounted on the circuit board on the copper substrate 3 in the shape of a solid, it is possible to incorporate a solid electrolytic capacitor having desired electrical characteristics into the circuit board.

Further, according to the present embodiment, the first insulating substrate 22 is provided with the bank 23, and when manufacturing the printed circuit board 20 with a built-in solid electrolytic capacitor, the solid electrolytic capacitor 10 is connected to the first insulating substrate 21. Is housed in a substantially closed space formed by the bank 23 and the second insulating substrate 22.
With the solid electrolytic capacitor 10 and the first insulating substrate 21
When integrated with the solid electrolytic capacitor, excessive pressure is not applied to the solid electrolytic capacitor, so that the aluminum oxide film formed on the surface of the foil-shaped aluminum substrate 2 is broken, and aluminum acting as an anode and solid high The contact with the molecular electrolyte layer 11 and the occurrence of a short circuit during energization can be reliably prevented.

FIG. 6 is a schematic plan view of an anode electrode of a solid electrolytic capacitor according to another preferred embodiment of the present invention, and FIG. 7 is a schematic sectional view taken along the line BB.

In this embodiment, aluminum is used as the valve metal having the ability to form an insulating oxide film. As shown in FIGS. 6 and 7, the anode 41 of the solid electrolytic capacitor according to this embodiment is A foil-shaped aluminum substrate 42 having a roughened surface (increased surface) and having an aluminum oxide film as an insulating oxide film formed on the surface;
Foil-shaped aluminum substrate 43 whose surface is not roughened
And a foil-shaped copper base 44 as a metal conductor constituting a lead electrode.

As shown in FIGS. 6 and 7, in this embodiment, a foil-like aluminum substrate 42 having a roughened surface and an aluminum oxide film formed on the surface is provided.
The one end region of the foil-shaped aluminum base 43 whose surface is not roughened is joined by ultrasonic welding so that the valve metals are electrically connected to each other,
Further, one end region of the foil-shaped copper base 44 is electrically connected to the metal by ultrasonic welding at the other end region of the foil-shaped aluminum base 43 whose surface is not roughened. So that the two weld joints 45, 46
Are formed.

As shown in FIGS. 6 and 7, the roughened surface area of the foil-shaped aluminum substrate 42 adjacent to the welded joint 46 is pressed by a hand press over the entire circumference. , And a smoothed region 47 having a substantially smooth surface is formed.

In forming the anode electrode 41, first,
A foil-shaped copper substrate 44 which is to constitute a lead electrode cut to a predetermined size, and a foil-shaped aluminum substrate 43 which is cut out from an aluminum foil sheet into a predetermined size and whose surface is not roughened are respectively formed by a predetermined size. The areas are superimposed such that the end regions overlap each other.

Next, the end region of the foil-like copper base 44 overlapped with the foil-like aluminum base 43
Are joined by ultrasonic welding to form a welded joint 45. Aluminum foil substrate 4
Even if an aluminum oxide film is formed on the surface of the aluminum foil 3, the foil-like copper base is removed by ultrasonic welding so that the aluminum oxide film is removed and the metal is electrically connected. The end region of 44 and the end region of the foil-shaped aluminum base 43 are joined. Here, the areas of the end regions of the foil-shaped copper base body 44 and the end regions of the foil-shaped aluminum base body 43 that overlap each other are determined so that the joint has a predetermined strength.

Thereafter, a foil-shaped aluminum substrate 42 of a predetermined size having a roughened surface and an aluminum oxide film formed on the surface is cut out of the aluminum foil sheet, and a foil-shaped copper substrate 44 and a foil-shaped copper substrate 44 are cut out. Aluminum base 43
The joined body is overlapped with a foil-shaped aluminum base 43 whose surface is not roughened so that end regions of a predetermined area overlap each other.

Next, an end region of the foil-shaped aluminum substrate 42 having the surfaces superposed on each other roughened and having an aluminum oxide film formed on the surface, and a foil-shaped aluminum substrate having an unroughened surface. The end region of the base 43 is joined by ultrasonic welding to form a weld joint 4
6 is generated. Here, by joining by ultrasonic welding, the aluminum oxide film formed on the surface of the foil-shaped aluminum substrate 42 is removed, and the surface is roughened so that the aluminum pure metal is electrically connected. The end region of the unplated foil-shaped aluminum substrate 43 and the end region of the foil-shaped aluminum substrate 42 having a roughened surface are joined. Here, the area of the end region of the foil-shaped aluminum base 43 and the area of the end region of the foil-shaped aluminum base 42 overlapping each other are determined so that the joint has a predetermined strength.

The anode electrode 41 thus formed is obtained by cutting a foil-shaped aluminum base 42 having a roughened surface constituting a dielectric and an aluminum oxide film on the surface from an aluminum foil sheet. Because
An aluminum oxide film is not formed on the edge of the foil-like aluminum base 42 whose surface is roughened by anodic oxidation to be used as an anode electrode of a solid electrolytic capacitor. It is necessary to form an aluminum oxide film.

FIG. 8 is a schematic cross-sectional view showing an anodic oxidation method for forming an aluminum oxide film on the edge of a foil-shaped aluminum substrate 42 having a roughened surface.

As shown in FIG. 8, a foil-like aluminum substrate 42 was placed in a chemical conversion solution 49 comprising an aqueous solution of ammonium adipate housed in a stainless steel beaker 48.
The anode electrode 41 is set so that only the portion excluding the portion where the smoothing region 47 is formed is immersed, and a voltage is applied using the foil-shaped copper base 44 as an anode and the stainless beaker 48 as a cathode. You.

The operating voltage can be appropriately determined according to the thickness of the aluminum oxide film to be formed.
When an aluminum oxide film having a film thickness of m to 1 μm is formed, it is usually set to several volts to about 20 volts.

As a result, anodic oxidation is started, and the chemical conversion solution 49 rises due to the capillary phenomenon due to the roughened surface of the foil-shaped aluminum substrate 42, but the foil formation near the weld joint 46 is increased. A smoothing region 47 is formed over the entire surface of the aluminum substrate 42 in the shape of a foil, and the surface of the aluminum substrate 43 in the form of foil interposed between the copper substrate 44 in the shape of a foil is roughened. Therefore, the formation solution 49 does not rise beyond the welded joint 47 between the foil-shaped aluminum substrate 42 having a roughened surface and the foil-shaped aluminum substrate 43 having a non-roughened surface. Therefore, the chemical conversion solution 49 is reliably prevented from coming into contact with the foil-like copper substrate 44 constituting the lead electrode, and the foil-like aluminum substrate 42 having a roughened surface including an edge portion is provided. Only the entire surface, the aluminum oxide film is formed.

The surface of the anode electrode 41 thus formed is roughened, and the entire surface of the foil-shaped aluminum substrate 42 on which the aluminum oxide film is formed is covered with the embodiment shown in FIGS. Similarly, a cathode electrode including a solid polymer electrolyte layer, a graphite paste layer, and a silver paste layer is formed, and a solid electrolytic capacitor is manufactured.

The obtained solid electrolytic capacitor is fixed to an insulating substrate and provided with predetermined wiring in the same manner as in the embodiment shown in FIGS. 1 to 5 to produce a printed circuit board with a built-in solid electrolytic capacitor. You.

In this embodiment, the anode electrode 41 of the solid electrolytic capacitor has one end region of a foil-shaped aluminum base 42 having a roughened surface and an aluminum oxide film formed on the surface, and a roughened surface. One end region of the non-surfaced foil-shaped aluminum substrate 43 is joined by ultrasonic welding so that the valve metals are electrically connected to each other, and the surface of the foil-shaped aluminum substrate is not roughened. The other end region of the base member 43 and the one end region of the foil-shaped copper base member 44 are joined and formed by ultrasonic welding so that the metals are electrically connected to each other. Joint 46 between aluminum and aluminum base 43
The roughened surface area of the foil-shaped aluminum substrate 42 adjacent to the surface is pressed and smoothed by a hand press over the entire circumference thereof, and the smoothed area has a substantially smoothed surface. 47 are formed.

Therefore, the foil-like aluminum substrate 42
Is subjected to an anodizing treatment, a foil-like aluminum substrate 42
Surface is roughened, by capillary action,
Although the chemical conversion solution 49 rises, a smoothing region 47 is formed over the entire surface of the foil-shaped aluminum substrate 42 adjacent to the welded joint 46, and furthermore, a gap between the aluminum substrate 42 and the foil-shaped copper substrate 44. Aluminum substrate 4 interposed between
3 is not roughened, the foil-shaped aluminum base 43 and the foil-shaped copper base 4 whose surfaces are not roughened.
Therefore, the chemical solution 49 can be more reliably prevented from coming into contact with the foil-like copper base 43 constituting the lead electrode, and the edge portion does not rise. Since the aluminum oxide film can be formed only on the entire surface of the foil-like aluminum substrate 42 whose surface is roughened, the aluminum-containing film is mounted on the foil-like copper substrate 43 constituting a lead electrode and mounted on a circuit board. By providing a contact with another electronic component to be formed, a solid electrolytic capacitor having desired electric characteristics can be built in the circuit board.

[0177]

EXAMPLES In order to further clarify the effects of the present invention, examples and comparative examples are given below.

Example 1 A solid electrolytic capacitor having a solid polymer electrolyte layer was manufactured as follows.

From a copper foil sheet having a thickness of 60 μm, 0.5 c
From a 100 μm-thick aluminum foil sheet having a size of m × 1 cm and a copper foil cut out and having an aluminum oxide film formed thereon and subjected to a surface roughening treatment, a 1 cm ×
Aluminum foil was cut out at a size of 1.5 cm and overlapped so that the areas near one end overlapped by 3 mm. The part where the areas near one end overlapped was made by Emerson Japan Inc. A 40 kHz-ultrasonic welding machine was used to join and electrically connect to form a joined body of copper foil and aluminum foil.

Thereafter, a pressure of 10 kg / cm ² was applied to the roughened surface area having a width of 5 mm including the joint of the joined body of the copper foil and the aluminum foil and the area of the aluminum foil adjacent to the joint by a hand press. To smooth the roughened surface over the entire width of the aluminum foil,
A smoothed area was formed.

Further, the thus obtained conjugate was placed in an aqueous solution of ammonium adipate adjusted to a pH of 6.0 at a concentration of 7% by weight, below the portion where the two-part mixed type epoxy resin was applied. Was set in an aqueous solution of ammonium adipate so that the aluminum foil was immersed.
At this time, the copper foil was not brought into contact with the aqueous solution of ammonium adipate.

The bonded body was used as an anode, and the formation current density was 50
The surface of an aluminum foil immersed in an aqueous solution of ammonium adipate was oxidized under the conditions of a current of 100 mA / cm ² and a formation voltage of 35 volts to form an aluminum oxide film, thereby producing an anode electrode.

Next, the prepared anode electrode was pulled up from an aqueous solution of ammonium adipate, and a solid polymer electrolyte layer made of polypyrrole was formed on the surface of the aluminum foil on which the anode electrode was roughened by chemical oxidation polymerization. Was formed.

Here, the solid polymer electrolyte layer composed of polypyrrole was prepared by distilling and purifying 0.1 mol / l of a pyrrole monomer, 0.1 mol / l of sodium alkylnaphthalenesulfonate and 0.05 mol / l of sulfuric acid. The anode electrode was set so that only the aluminum foil was immersed in an ethanol-water mixed solution cell containing iron (III), and the mixture was stirred for 30 minutes to allow the chemical oxidative polymerization to proceed. , Repeated, generated. As a result, a solid polymer electrolyte layer having a maximum thickness of about 50 μm was formed.

Further, a carbon paste was applied to the surface of the solid polymer electrolyte layer thus obtained, and a silver paste was applied to the surface of the carbon paste to form a cathode electrode, thereby producing a solid electrolytic capacitor. did.

On the other hand, two glass cloth-containing epoxy resin insulating substrates each having a thickness of 1 mm and a size of 2 cm × 4.5 cm, each having a copper foil having a thickness of 18 μm adhered to both sides thereof, were prepared as follows. ,Got ready.

On the copper foil surface, in order to form an electric circuit,
An unnecessary portion of the copper foil was chemically etched to form a predetermined wiring pattern. However, all the copper foil on the substrate surface on the side where the solid electrolytic capacitor was to be fixed was chemically etched and removed.

Further, through holes are formed at the positions of the glass cloth-containing epoxy resin insulating substrate corresponding to the anode electrode and the cathode electrode of the solid electrolytic capacitor to be incorporated, respectively, and the through hole and the etched copper foil are formed. A 3 μm nickel plating was applied on the pattern by electroless plating, and a 0.08 μm gold plating was further applied thereon.

Through holes for various electronic components to be mounted were further formed on a glass cloth-containing epoxy resin insulating substrate.

On the other hand, a 100 μm thick substrate made of the same glass cloth-containing epoxy resin as
The substrate was processed into a size of × 4.5 cm, and the inner portion was removed by punching, leaving a region of 3 mm width around the processed substrate, to produce a bank forming substrate.

Further, two 50 μm-thick epoxy prepregs made of the same glass cloth-containing epoxy resin as the two substrates were processed into a size of 2 cm × 4.5 cm, and an area of 3 mm width was formed around the processed substrates. The inner part was removed by punching, leaving behind.

[0192] The bank-formed substrate from which the inner portion was removed by punching and the surface from which one of the copper foils of the glass-cloth-containing epoxy resin insulating substrate was removed were processed to a thickness of 50 µm as described above. Through one of the epoxy prepregs, and using a vacuum hot press device under pressure and reduced pressure for 40 minutes.
Hold at 175 ° C and cure the epoxy prepreg,
The glass cloth-containing epoxy resin insulating substrate and the substrate from which the inner portion was removed were fixed to obtain an insulating substrate having a concave space.

On the surface of the two glass cloth-containing epoxy resin insulating substrates from which the other copper foil was removed, the anode electrode and the cathode electrode of the solid electrolytic capacitor were positioned at positions corresponding to the through holes formed in the insulating substrate. To be located at
The solid electrolytic capacitor was fixed using a silicone adhesive.

Next, on a glass cloth-containing epoxy resin insulating substrate to which a solid electrolytic capacitor is fixed, a glass cloth-containing epoxy resin insulating substrate having a concave space formed on one surface is processed as described above. Thickness 50μ
Through the other epoxy prepreg, the solid electrolytic capacitor was overlapped and closely attached so as to be accommodated in the concave space.

The two insulated substrates thus adhered were held at 175 ° C. for 40 minutes under pressure and reduced pressure using a vacuum hot press device, and the epoxy prepreg was cured to cure the two substrates. Between the glass cloth-containing epoxy resin insulating substrates.

After cooling the glass cloth-containing epoxy resin insulating substrate, the glass cloth-containing epoxy resin insulating substrate is formed on the surface of the glass cloth-containing epoxy resin insulating substrate via through holes formed in each of the glass cloth-containing epoxy resin insulating substrates. The wiring pattern and the lead electrode and the cathode electrode made of copper foil of the anode electrode of the built-in solid electrolytic capacitor were electrically connected by solder to obtain a printed circuit board # 1 with a built-in solid electrolytic capacitor.

The electrical characteristics of the thus-obtained printed circuit board sample # 1 with a built-in solid electrolytic capacitor were measured with an impedance analyzer 4294 manufactured by Agilent Technologies.
A was evaluated using A.

As a result, the capacitance at 120 Hz was 8
4.0 μF and an ESR at 100 kHz of 20 mΩ
Met. The leakage current (5 minute value) when a voltage of 10 V was applied at room temperature was 0.10 μA.

Further, the printed circuit board sample # 1 with a built-in solid electrolytic capacitor was left under a constant temperature condition of 125 ° C., and the electrical characteristics were evaluated in exactly the same manner.
The capacitance at 20 Hz is 83.9 μF and 100 k
The ESR at Hz was 22 mΩ. In addition, at room temperature,
Leakage current when applying a voltage of 10 volts (5-minute value)
Was 0.13 μA.

Example 2 The surface roughened over the entire width of the aluminum foil by applying a pressure of 10 kg / cm ² by hand press to the roughened surface area of 5 mm width including the area of the aluminum foil. Instead of forming a smoothed region, a roughened surface region having a width of 5 mm including a joint portion of the joined body of the copper foil and the aluminum foil and a region of the aluminum foil adjacent to the joined portion is provided by Emerson Japan. 0.5 kg / cm ² by a horn having a cedar pattern connected to a 40 kHz ultrasonic welding machine manufactured by Branson Division.
Pressure, and continuously irradiate ultrasonic waves to smooth the roughened surface over the entire width of the aluminum foil,
A solid electrolytic capacitor was manufactured in exactly the same manner as in Example 1 except that a smoothing region was formed.

Further, two glass cloth-containing epoxy resin insulating substrates were manufactured in exactly the same manner as in Example 1.

On the other hand, two substrates each made of the same glass cloth-containing epoxy resin as the substrate and having a thickness of 100 μm were processed into dimensions of 2 cm × 4.5 cm, and an area of 3 mm width was formed around the processed substrate. The inside portion was removed by punching to leave two substrates for bank formation.

Next, three 50 μm-thick epoxy prepregs made of the same glass cloth-containing epoxy resin as the substrate were processed into dimensions of 2 cm × 4.5 cm, respectively, leaving a 3 mm wide area around the processed substrate. Then, the inner portion was removed by punching to produce a first epoxy prepreg, a second epoxy prepreg, and a third epoxy prepreg.

[0204] One of the bank-formed substrates from which the inside portion has been removed by punching and the surface from which one of the copper foils of the glass-cloth-containing epoxy resin insulating substrate has been removed are subjected to the above-processed thickness process. Adhere through one of the 50 μm first epoxy prepregs and hold at 175 ° C. for 40 minutes under pressure and reduced pressure using a vacuum hot press machine to cure the epoxy prepreg and A cloth-containing epoxy resin insulating substrate;
One of the bank forming substrates was fixed to obtain a first insulating substrate having a concave space.

In the same manner, the other of the bank forming substrate punched out and the inner portion thereof was removed, and the other surface of the glass cloth-containing epoxy resin insulating substrate from which the other copper foil had been removed were brought together as described above. Closely adhere to the other of the processed 50 μm thick second epoxy prepreg, hold at 175 ° C. for 40 minutes under pressure and reduced pressure using a vacuum hot press apparatus, and cure the epoxy prepreg. Thus, the glass cloth-containing epoxy resin insulating substrate and the other substrate for bank formation were fixed to obtain a second insulating substrate having a concave space.

In the thus obtained recessed space of the first insulating substrate, the silicone is placed so that the anode electrode and the cathode electrode of the solid electrolytic capacitor are located at positions corresponding to the through holes formed in the insulating substrate. Using a system adhesive,
The solid electrolytic capacitor was fixed.

Next, on the first insulating substrate to which the solid electrolytic capacitor was fixed, the second insulating substrate was interposed with the third epoxy prepreg having a thickness of 50 μm processed as described above, The spaces are opposed to each other, and the solid electrolytic capacitors are overlapped so as to be accommodated in the concave space,
Closely attached.

The first and second insulating substrates thus adhered to each other are heated at 175 ° C. for 40 minutes under pressure and reduced pressure using a vacuum hot press.
, And the epoxy prepreg was cured to fix the space between the first insulating substrate and the second insulating substrate.

After cooling the first insulating substrate and the second insulating substrate, the first insulating substrate and the second insulating substrate are formed on the surface of the substrate via through holes formed in the first insulating substrate and the second insulating substrate, respectively. The wiring pattern and the lead electrode and the cathode electrode made of copper foil of the anode electrode of the built-in solid electrolytic capacitor are electrically connected by solder to obtain a printed circuit board # 2 with a built-in solid electrolytic capacitor. Was.

The electrical characteristics of the thus-obtained printed circuit board sample # 2 with a built-in solid electrolytic capacitor were measured using an impedance analyzer 4294 manufactured by Agilent Technologies.
A was evaluated using A.

As a result, the capacitance at 120 Hz was 8
2.0 μF, ESR at 100 kHz is 40 mΩ
Met. The leakage current (5 minute value) when a voltage of 10 V was applied at room temperature was 0.15 μA.

Further, the printed board sample # 2 with a built-in solid electrolytic capacitor was allowed to stand under a constant temperature condition of 125 ° C., and its electrical characteristics were evaluated in exactly the same manner. At 0 μF, 100
The ESR at kHz was 43.0 mΩ, and the leakage current (5-minute value) when a voltage of 10 volts was applied at room temperature was 0.17 μA.

Example 3 A copper foil having a size of 0.5 cm × 1 cm was cut out from a copper foil sheet having a thickness of 60 μm, and an aluminum foil sheet having a thickness of 100 μm that had not been subjected to surface roughening was cut out.
Aluminum foil was cut out to a size of 1 cm x 1.5 cm and overlapped so that the areas near one end overlapped each other by 3 mm. The part where the areas near one end overlapped was joined by the Emerson Japan Inc. Branson Division And electrically connected by a 40 kHz-ultrasonic welding machine manufactured by Co., Ltd. to form a joined body of copper foil and aluminum foil.

Next, the width 5 including the region of the aluminum foil forming the joint portion of the joined body of the copper foil and the aluminum foil was used.
In a known manner, the surface area other than the surface area of the aluminum foil having a thickness of 0.1 mm is electrochemically subjected to an etching treatment,
It was roughened and its surface area was enlarged.

Thereafter, the joined body thus obtained was subjected to an etching treatment in an aqueous solution of ammonium adipate adjusted to a pH of 6.0 at a concentration of 7% by weight to have a roughened surface. The aluminum foil was set in an aqueous solution of ammonium adipate so that it was completely immersed. At this time, the copper foil was not brought into contact with the aqueous solution of ammonium adipate.

The bonded body was used as an anode, and the formation current density was 50
The surface of an aluminum foil immersed in an aqueous solution of ammonium adipate was oxidized under the conditions of a current of 100 mA / cm ² and a formation voltage of 35 volts to form an aluminum oxide film, thereby producing an anode electrode.

Using the anode electrode thus manufactured, a solid electrolytic capacitor was manufactured in exactly the same manner as in Example 1.

Further, two glass cloth-containing epoxy resin insulating substrates were manufactured in exactly the same manner as in Example 1.

[0219] The surface of the glass cloth-containing epoxy resin insulating substrate from which one copper foil was removed was placed 3 m wide around the substrate.
m, leaving the inner part to a depth of 0.3 mm,
After cutting, the area around the substrate was reduced to 0.
A first insulating substrate in which a concave space having a depth of 3 mm was formed was obtained.

Next, 50 μm thick epoxy prepregs made of the same glass cloth-containing epoxy resin as the substrate were processed into dimensions of 2 cm × 4.5 cm, leaving a 3 mm wide area around the processed substrate. The inner part was removed by stamping.

The anode electrode and the cathode electrode of the solid electrolytic capacitor are located at positions corresponding to the through holes formed in the first insulating substrate in the recessed space of the first insulating substrate subjected to the cutting process. Thus, the solid electrolytic capacitor was fixed using a silicone adhesive.

The first insulating substrate having the solid electrolytic capacitor fixed in the recessed space was punched out to a thickness of 5 mm.
An epoxy prepreg of 0 μm was overlaid, and a second glass cloth-containing epoxy resin insulating substrate was overlaid thereon and brought into close contact therewith.

The first and second insulating substrates thus adhered to each other were heated at 175 ° C. for 40 minutes under pressure and reduced pressure using a vacuum hot press.
, And the epoxy prepreg was cured to fix the space between the first insulating substrate and the second insulating substrate.

After cooling the first insulating substrate and the second insulating substrate, the first insulating substrate and the second insulating substrate are formed on the surface of the substrate via through holes formed in the first insulating substrate and the second insulating substrate, respectively. The lead pattern and the cathode electrode made of copper foil of the anode electrode of the built-in solid electrolytic capacitor are electrically connected by solder to obtain a printed circuit board # 3 with a built-in solid electrolytic capacitor. Was.

The electrical characteristics of the thus obtained printed circuit board sample # 3 with a built-in solid electrolytic capacitor were measured using an impedance analyzer 4294 manufactured by Agilent Technologies.
A was evaluated using A.

As a result, the capacitance at 120 Hz was 8
0.5 μF, ESR at 100 kHz is 35 mΩ
Met. The leakage current (5 minute value) when a voltage of 10 V was applied at room temperature was 0.15 μA.

Further, printed circuit board sample # 2 with a built-in solid electrolytic capacitor was left under a constant temperature condition of 125 ° C., and its electrical characteristics were evaluated in the same manner. At 0 μF, 100
The ESR at kHz was 30.5 mΩ, and the leakage current (5-minute value) when a voltage of 10 V was applied at room temperature was 0.20 μA.

Comparative Example A copper foil having a size of 0.5 cm × 1 cm was cut out from a copper foil sheet having a thickness of 60 μm, an aluminum oxide film was formed, and the surface was roughened to a thickness of 100 μm.
From the aluminum foil sheet of m, the aluminum foil was cut out at a size of 1 cm × 1.5 cm and overlapped so that the regions near one end overlapped by 3 mm, and the portions where the regions near one end overlapped each other,
Emerson Japan Co., Ltd. Branson Business Headquarters 40kHz
It was joined and electrically connected by a z-ultrasonic welding machine to form a joined body of copper foil and aluminum foil.

Furthermore, at a concentration of 7% by weight, a pH of 6.0
It was set in an aqueous solution of ammonium adipate such that only the aluminum foil of the joined body obtained in this way was immersed in the aqueous solution of ammonium adipate adjusted as described above. At this time, the copper foil was not brought into contact with the aqueous solution of ammonium adipate.

The copper foil portion is used as a current supply port, the joint side is used as an anode, and the formation current density is 50 to 100 mA / c.
The surface of the aluminum foil immersed in an aqueous solution of ammonium adipate was oxidized under conditions of m ² and a formation voltage of 35 volts to form an aluminum oxide film, thereby producing an anode electrode.

After the formation of the aluminum oxide film, the joined body of the copper foil and the aluminum foil was observed. As a result, it was found that the portion of the copper foil serving as the current supply port was corroded and deteriorated.
In particular, the alteration at the joint was remarkable.

Using the joined body of the aluminum foil and the copper foil on each of which the aluminum oxide film was formed, Example 1 was used.
A solid electrolytic capacitor was fabricated in exactly the same manner as described above, and a printed circuit board sample # 4 with a built-in solid electrolytic capacitor was fabricated.

The electrical characteristics of the thus-obtained printed circuit board sample # 4 with a built-in solid electrolytic capacitor were measured with an impedance analyzer 4294 manufactured by Agilent Technologies.
A was evaluated using A.

As a result, in order to evaluate the leakage current, 10
When a voltage of volt was applied, a short circuit occurred and the solid electrolytic capacitor was damaged.

According to Examples 1 to 3 and Comparative Example, the roughened surface of the surface area including the surface area of the aluminum foil forming the joint between the copper foil and the aluminum foil was obtained.
Printed circuit board samples # 1 and 2 with a built-in solid electrolytic capacitor according to the present invention using a solid electrolytic capacitor produced using an anode electrode having an aluminum oxide film formed thereon by smoothing and anodizing, and copper foil and aluminum The surface area of the aluminum foil other than the area including the area of the aluminum foil forming the joint with the foil is subjected to a roughening treatment, and the surface area of the roughened aluminum foil is anodized. Thus, the printed circuit board sample # 3 with a built-in solid electrolytic capacitor according to the present invention using the solid electrolytic capacitor produced using the anode electrode on which the aluminum oxide film was formed has the capacitance characteristics
Although the SR characteristics and leakage current characteristics are good, a solid electrolytic capacitor produced using an anode electrode with an aluminum oxide film formed by anodic oxidation without smoothing the aluminum foil surface is used. It was found that the printed circuit board sample # 4 with a built-in solid electrolytic capacitor according to the comparative example had no function as a solid electrolytic capacitor.

The present invention is not limited to the above-described embodiments and examples, and various modifications can be made within the scope of the invention described in the claims. It goes without saying that it is included.

For example, in the above-described embodiment, the foil-shaped aluminum substrates 2 and 42 whose surfaces are roughened are subjected to a smoothing treatment so that the foil-shaped aluminum substrates 2 and Although the smoothing regions 5 and 47 are formed in 42, the foil-like aluminum substrate whose surface is not roughened is joined to a conductive metal substrate such as a foil-like copper substrate, and then a joining portion is included. The foil-shaped aluminum substrate may be roughened to leave an end region, thereby forming a region having a smooth surface.

Further, in each of the above embodiments, aluminum is used as the valve metal bases 2, 42, 43. Instead of aluminum, aluminum alloy or tantalum, titanium, niobium, zirconium or The valve metal bases 2, 42, and 43 can also be formed from these alloys and the like.

In the above embodiment, foil-like copper is used as the metal conductor to form the lead electrode. Instead of copper, a copper alloy, brass, nickel, zinc, chromium or copper is used. These alloys can also form metal conductors.

Furthermore, in the embodiment shown in FIGS. 1 to 5, the foil-like aluminum base 2 and the foil-like copper base 3 are joined by ultrasonic welding. Instead, cold welding (cold welding)
May be joined to form a joint.

Similarly, in the embodiment shown in FIG. 6 to FIG. 8, the foil-shaped aluminum substrate 42 having a roughened surface and the aluminum While joining by welding, the aluminum base 43 whose surface is not roughened and the foil-like copper base 44 are joined by ultrasonic welding. Both of these joints, or one of them, are joined together. Instead of ultrasonic welding, cold welding (cold welding)
May be joined to form a joint.

In the above embodiment, the solid electrolytic capacitor 10 is sandwiched between the first insulating substrate 21 and the second insulating substrate 22 to produce the printed circuit board 20 with a built-in solid electrolytic capacitor. The solid electrolytic capacitor 10 can be fixed on an insulating substrate to produce a printed circuit board 20 with a built-in solid electrolytic capacitor.

Further, in the above embodiment, the plurality of electronic components 30 are mounted on both the surface of the first insulating substrate 21 and the surface of the second insulating substrate 22. It is not always necessary to mount it.

In the above embodiment, the electronic components 30 are mounted on both the surface of the first insulating substrate 21 and the surface of the second insulating substrate 22. The electronic component 30 may be mounted on only one of the surfaces of the second insulating substrate 22.

Further, in the above embodiment, a plurality of wiring patterns are formed on the surface of the first insulating substrate 21 and the surface of the second insulating substrate 22, respectively. It is not always necessary to form a plurality of wiring patterns on the front surface and the surface of the second insulating substrate 22, and it is sufficient that at least one wiring pattern is formed.

In the above embodiment, a plurality of through holes 25 and 28 are formed in the first insulating substrate 21 and the second insulating substrate 22, respectively. It is not always necessary to form a plurality of through holes 25, 28 in each of the two insulating substrates 22, but it is sufficient that at least one through hole 25, 28 is formed in each.

Further, in the embodiment shown in FIG. 5, the banks 23 are formed on the first insulating substrate 21. However, the banks 23 may be formed on the second insulating substrate 22.

In the embodiment shown in FIG. 5, a substrate made of the same material as the first insulating substrate 21 and the second insulating substrate 22 is formed so that a portion having a predetermined area is left around the periphery thereof. Punching to form a frame-shaped substrate, and fixing the frame-shaped substrate to the first insulating substrate using an adhesive of the same material as the first insulating substrate 21 and the second insulating substrate 22; Thus, the bank 23 can be formed integrally with the first insulating substrate 21 by cutting the first insulating substrate 21 or the like. And both the second insulating substrate 22
The bank can be integrally formed by cutting or the like.

Furthermore, in the embodiment shown in FIG. 5, the first insulating substrate 21 has a bank along its two opposing sides, the height of which is larger than the thickness of the solid electrolytic capacitor 10. 23 are formed, but the bank 2
It is not always necessary to form 3 and a spacer may be used instead. Alternatively, the first insulating substrate 21 and the second insulating substrate 22 may be simply sandwiched by the resin 26 with the solid electrolytic capacitor 10 interposed therebetween. They may be integrated so as to be separated from each other.

Further, in the embodiment shown in FIGS. 1 to 5, the roughened surface area adjacent to the welded joint 4 of the foil-shaped aluminum base 2 is formed by hand pressing over the entire circumference thereof. , Pressurized, smoothed,
In the embodiment shown in FIGS. 6 to 8 in which the smoothing region 5 is formed, the surface region adjacent to the welding joint 46 of the foil-shaped aluminum substrate 42 on which the aluminum oxide film is formed is the surface region thereof. The entire surface is pressed and smoothed by a hand press to form a smoothed region 47. The smoothed regions 5, 47 are formed of at least the foil-like aluminum adjacent to the weld joints 4, 46. It may be formed on the bases 2 and 42, and further, the foil-like aluminum bases 2 and 4 forming the weld joints 4 and 46.
2 may be formed.

[0251]

According to the present invention, a foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon, and an insulating oxide film and a solid polymer formed on the foil-shaped valve metal substrate. It is possible to provide a solid electrolytic capacitor in which an electrolyte layer and a conductor layer are sequentially formed, and a solid electrolytic capacitor and a solid electrolytic capacitor built-in substrate suitable for being built in a circuit board, and a method for manufacturing the same. Become.

[Brief description of the drawings]

FIG. 1 is a schematic plan view of an anode electrode of a solid electrolytic capacitor according to a preferred embodiment of the present invention.

FIG. 2 is a schematic sectional view taken along the line AA of FIG. 1;

FIG. 3 is a schematic cross-sectional view showing an anodic oxidation method for forming an aluminum oxide film on an edge of a foil-shaped aluminum substrate.

FIG. 4 is a schematic sectional view of a solid electrolytic capacitor.

FIG. 5 is a schematic sectional view of a printed circuit board with a built-in solid electrolytic capacitor.

FIG. 6 is a schematic plan view of an anode electrode of a solid electrolytic capacitor according to another preferred embodiment of the present invention.

FIG. 7 is a schematic sectional view taken along the line BB of FIG. 6;

FIG. 8 is a schematic cross-sectional view showing an anodic oxidation method for forming an aluminum oxide film on an edge portion of a foil-shaped aluminum substrate having a roughened surface.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Anode electrode 2 Foil-shaped aluminum base 3 Foil-shaped copper base 4 Weld joint 5 Smoothing area 7 Stainless beaker 8 Chemical conversion solution 10 Solid electrolytic capacitor 11 Solid polymer electrolyte layer 12 Graphite paste layer 13 Silver paste layer 14 Cathode electrode Reference Signs List 20 Printed board with built-in solid electrolytic capacitor 21 First insulating substrate 22 Second insulating substrate 23 Bank of first insulating substrate 24 Wiring pattern 25 Through hole 26 Resin 27 Wiring pattern 28 Through hole 29 Adhesive 30 Electronic component 31 Solder 32 Conductive resin 41 Anode electrode 42 Foil-shaped aluminum base having a roughened surface 43 Foil-shaped aluminum base not having a roughened surface 44 Foil-shaped copper base 45 Welded joint 46 Welded joint 47 Smooth Chemical area 48 Stainless beaker 49 Chemical conversion solution

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Noriyoshi Nanba 1-13-1, Nihonbashi, Chuo-ku, Tokyo Inside TDK Corporation

Claims (16)

[Claims] 1. A foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon, and at least an insulating oxide film, a solid polymer electrolyte layer, The conductor layer is a solid electrolytic capacitor formed sequentially, and a foil-like lead electrode is provided in a region near one end of a foil-like valve metal base having a roughened surface and an insulating oxide film formed thereon. An area near one end of the metal base is joined so that the metal is electrically connected to form a joint,
At least one solid electrolytic capacitor having an anode electrode having a substantially smooth surface area is attached to one surface of an insulating substrate, wherein the foil-shaped valve metal substrate has at least a portion adjacent to the joint. A substrate with a built-in solid electrolytic capacitor. 2. The solid electrolytic capacitor built-in substrate according to claim 1, wherein said foil-shaped lead electrode metal substrate is formed of a conductive metal substrate. 3. The foil-shaped lead electrode substrate includes a foil-shaped valve metal substrate having a non-roughened surface and a conductive metal substrate, and the surface is roughened to form an insulating oxide film. In the region near one end of the foil-shaped valve metal substrate, the region near one end of the foil-shaped valve metal substrate, whose surface is not roughened, is electrically connected between valve metals. The metal is electrically connected to the area near the other end of the foil-shaped valve metal base, which is joined and the surface of which is not roughened, to the area near the other end of the foil-shaped conductive metal base. 2. The substrate with a built-in solid electrolytic capacitor according to claim 1, further comprising an anode electrode joined as described above. 4. The foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon is a foil-shaped valve metal substrate which is not roughened except for a part of the surface. 4. The built-in solid electrolytic capacitor according to claim 1, wherein the surface is formed by roughening the surface, and the substantially smooth surface region is formed by the partial surface. substrate. 5. The solid electrolytic capacitor built-in substrate according to claim 1, wherein at least one wiring pattern is formed on the other surface of said insulating substrate. 6. In addition to the insulating substrate, further comprising a second insulating substrate facing the insulating substrate, wherein the solid electrolytic capacitor includes one surface of the insulating substrate and one surface of the second insulating substrate. The substrate with a built-in solid electrolytic capacitor according to any one of claims 1 to 5, wherein the substrate is integrally mounted between the surfaces. 7. The substrate with a built-in solid electrolytic capacitor according to claim 6, wherein at least one wiring pattern is formed on the other surface of the second insulating substrate. 8. The substantially smooth surface area is applied to a roughened surface of the foil-shaped valve metal base near the joint by pressing, rolling, cutting and calendering. A smoothing process selected from the group consisting of
The solid electrolytic capacitor built-in substrate according to any one of claims 1 to 7, wherein the substrate is formed. 9. At least in a portion adjacent to the joint, the substantially smooth surface area is formed on the foil-shaped valve metal base over the entire circumference of the foil-shaped valve metal base. The substrate with a built-in solid electrolytic capacitor according to claim 1. 10. A foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon, and at least an insulating oxide film, a solid polymer electrolyte layer, What is claimed is: 1. A method for manufacturing a substrate with a built-in solid electrolytic capacitor, in which a conductive layer includes at least one solid electrolytic capacitor sequentially formed, the foil-shaped valve having a roughened surface and an insulating oxide film formed thereon. A region near one end of the metal substrate and a region near one end of the foil-shaped lead electrode metal substrate are joined so that metal is electrically connected to form a joint, and the foil-shaped Forming a joined body of the valve metal base and the foil-shaped lead electrode metal base; and forming the joined body of the foil-shaped valve metal base and the foil-shaped lead electrode metal base. Is immersed in a chemical conversion solution, and a voltage is applied to the joined body. Performing an anodizing treatment to form an insulating oxide film on at least an edge portion of the valve metal base; and forming a solid on the entire surface of the anodized foil-shaped valve metal base. A step of forming a polymer electrolyte layer, a step of applying a conductive paste on the solid polymer electrolyte layer, and drying to form a conductor layer, and forming at least one solid electrolytic capacitor; Attaching at least one solid electrolytic capacitor to one surface of an insulating substrate, further comprising, prior to the step of forming the insulating oxide film, at least the foil-shaped valve metal adjacent to the joint portion A step of subjecting the roughened surface of the substrate to a smoothing process to form a substantially smooth surface area, and excluding the substantially smooth surface area of the foil-shaped valve metal base. Only A method for manufacturing a substrate with a built-in solid electrolytic capacitor, characterized in that the substrate is immersed in a chemical conversion solution, anodized, and an insulating oxide film is formed on at least an edge portion of the valve metal substrate. 11. A smoothing process selected from the group consisting of a pressing process, a rolling process, a cutting process, and a calendering process is performed on the roughened surface of the foil-shaped valve metal base near the joint. 11. The method of manufacturing a substrate with a built-in solid electrolytic capacitor according to claim 10, wherein the substrate is formed to form the substantially smooth surface region. 12. A flattening process is performed on at least the roughened surface of the foil-shaped valve metal substrate adjacent to the joining portion over the entire periphery of the foil-shaped valve metal substrate, The method for manufacturing a substrate with a built-in solid electrolytic capacitor according to claim 10 or 11, wherein a smooth surface region is formed. 13. A foil-shaped valve metal substrate having a roughened surface and an insulating oxide film formed thereon, and at least an insulating oxide film, a solid polymer electrolyte layer, A method for manufacturing a solid electrolytic capacitor built-in substrate in which a conductor layer sequentially includes at least one solid electrolytic capacitor formed therein, the surface of which is near one end of a foil-shaped valve metal substrate whose surface is not roughened. The region and the region near one end of the conductive metal substrate,
Joining to form a joint so that the metals are electrically connected, forming a joined body of the foil-shaped valve metal base and the foil-shaped lead electrode metal base; and Performing a surface roughening process on the surface of the foil-shaped valve metal base except for a portion adjacent to the surface of the foil-shaped valve metal base; a portion of the foil-shaped valve metal base not subjected to the surface roughening process; The portion subjected to the chemical treatment, the foil-shaped valve metal substrate, immersed in a chemical conversion solution, applying a voltage to the joined body, performing an anodizing treatment, at least the edge portion of the valve metal substrate, A step of forming an insulating oxide film; a step of forming a solid polymer electrolyte layer on the entire surface of the foil-shaped valve metal substrate that has been subjected to anodizing; and a step of forming a solid polymer electrolyte layer on the solid polymer electrolyte layer. A conductive paste is applied and dried to form a conductive layer, and at least one solid state electrode is formed. Producing a dissolving capacitor; and attaching the solid electrolytic capacitor to at least one surface on one side.
On the other surface of the insulating substrate on which one wiring pattern is formed,
A method for manufacturing a substrate with a built-in solid electrolytic capacitor, comprising a step of attaching. 14. The method according to claim 14, further comprising:
The method for manufacturing a substrate with a built-in solid electrolytic capacitor according to any one of claims 10 to 13, wherein at least one wiring pattern is formed. 15. In addition to the insulating substrate, a second insulating substrate is used, and one surface of the second insulating substrate is
The solid electrolytic capacitor according to any one of claims 10 to 14, wherein the solid electrolytic capacitor is fixed between the first insulating substrate and the second insulating substrate so as to face the solid electrolytic capacitor. A method for manufacturing a substrate with a built-in solid electrolytic capacitor as described in the above. 16. The method according to claim 15, further comprising forming at least one wiring pattern on the other surface of the second insulating substrate.