JPS61270808A - Manufacture of laminated electrolytic capacitor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method of manufacturing a multilayer electrolytic capacitor having a novel configuration.

[Technical background of the invention and its problems] In general, a dry type thin electrolytic capacitor has a pair of anode and cathode foils made of, for example, aluminum foil connected to a pair of lead-out terminals also made of aluminum, and a connection between the pair of anode and cathode foils. A spanner is interposed between the coils and the coil is wound, and then impregnated with a driving electrolyte and housed in a case, and the opening of the case is sealed.

Generally, the purpose of interposing a spacer is to insulate and isolate a pair of anode and cathode foils and to retain a driving electrolyte, which is an important component in a dry type thin electrolytic capacitor. However, the commonly used spacer is kraft paper, but the kraft paper has a degree of 0.3 to 0.8 Gl/α3.
The density of kraft paper is relatively high, and since the fibers are flattened, the apparent resistivity increases, impairing the tan δ properties.Kraft paper has a thickness of 30 μm due to paper-making technology issues.
m or more, which prevents the capacitor from being made any thinner and hinders miniaturization.Furthermore, it has drawbacks such as the risk of ignition and continued combustion when the capacitor is destroyed by applied voltage or reverse voltage. Therefore, there is currently a trend to use low-density manila paper instead of kraft paper, which greatly contributes to improving tanδ characteristics, but manila paper is several times more expensive than kraft paper (in addition, it has a higher In order to withstand the capacitor manufacturing process (especially the winding process), the thickness must be 40 mm.
It is necessary to use a material having a diameter of μm or more, which is still an impediment to miniaturization. In addition, since a liquid driving electrolyte is used, there is a limit to the improvement of tanδ characteristics.Furthermore, liquid driving electrolytes have a specific resistance at low temperatures, resulting in extremely poor low-temperature characteristics, making them difficult to use over a wide temperature range. Not only did they have problems that needed to be resolved in practical use, such as a lack of reliability, but they also had problems with poor frequency characteristics because the element was wound and the lead terminal was inserted midway.

In recent years, for example, Japanese Patent Application Laid-open No. 17609/1983,
JP-A-58-191414M or JP-A-59-6
As disclosed in Publication No. 3604, instead of the driving electrolyte, N-n-propyl (or N-iso-propyl)
TCNQ complex salts consisting of isoquinoline, N-ethylisoquinoline, N-n-butylisoquinoline, quinoline substituted with a hydrocarbon group at the N position, isoquinoline, or lysine, etc., have been proposed to have improved properties. Therefore, electrolytic capacitors using such TCNQti salts are generally made of these TCNQ! The salt is used by melting and impregnating it, but the conductivity of the TCNQ complex salt tends to change because it is heated when melting and impregnating it (there is a problem with tan δ characteristics, and the element shape is the same as before, with the lead terminal being wound around Since it is a type that is inserted midway through the body, its characteristics at high frequencies are poor, and since it uses a spacer, the distance between the anode and cathode is wide (approximately 40 to 50 μm), and the equivalent series resistance is large.There are still problems that need to be solved. Moreover, the TCNQ complex salt disclosed in the above-mentioned publication was not only difficult to vacuum evaporate, but also had the problem that its temperature characteristics were not so good.

[Object of the Invention] The present invention has been made in view of the above points, and provides a multilayer electrolytic capacitor with a novel configuration that solves the above problems at once and provides stable performance characteristics even when used in a wide temperature range. The purpose of this invention is to provide a method for manufacturing.

[Summary of the Invention 1 The method for manufacturing a multilayer electrolytic capacitor of the present invention involves vacuum-depositing a valve metal on one or both sides of an insulator to form a valve metal film, and then anodizing the surface of the metal film. TCNQti salt is vacuum-deposited on the film to form an organic semiconductor film, and a metal paste is screen printed on the organic semiconductor film to form a cathode electrode film to obtain a basic element. A plurality of the basic elements are laminated and both end faces are formed. This feature is characterized in that an electrode lead-out portion is formed at the top.

[Embodiments of the invention] An embodiment of the present invention will be described in detail below.

That is, as shown in FIG. 2, one end is placed on one side of an insulating material (1) such as a plastic film sheet or a ceramic sheet made of polyester, triacetate, tetrafluoroethylene, polycarbonate, polyamide, polyimide, etc. as a margin. (2) Aluminum metal is vapor-deposited and valve action metal It! (3), the valve metal film (3) is anodized to form an anodic oxide film (4) on the surface of the valve metal film (3), and then the anodic oxide film (4) is For example, 2゜2'-biviridinium (TCNQ) 2,4-hydroxy-N-pen is applied onto the surface of the margin section (2) from the surface excluding the end surface located on the opposite side of the margin section (2). Zylanilinium (TCNQ>
, 4-amino-2,3,5,6-tetramethylanilinium (TCNQ), viridinium (
TCNQ), 4-cyano-N methyl-pyridenium (TCNQ), N-E ethylquinolinium (T
A TCNQ complex salt consisting of N-(2-phenythyl)quinolinium (TCNQ) 2 or the like is vacuum-deposited to form an organic semiconductor film (5). Next, a metal paste such as silver, copper or gold is screen printed on the surface of the organic semiconductor film (5) excluding the end surface located on the opposite side of the margin portion (2) to form the cathode electrode WA (6). Form basic elements (7
). Then, as shown in Figure 1, the basic element (7) is attached to the required number of units [1], and then silver or copper paste is applied to both end faces and dried, or metallized with metal such as zinc, aluminum or solder, and the electrodes are drawn out. forming part (8);
An external terminal (9) is attached to the electrode lead-out part (8), and the external terminal (9) is housed in a case or coated with resin or the like to form an exterior (not shown).

According to the method for manufacturing a multilayer electrolytic capacitor constructed as described above, the above-described T
Since CNQ complex salt is used, vacuum deposition is easy, and unlike conventional melt impregnation, heating is not required, resulting in high conductivity.
The TCNQ complex salt has good nδ characteristics, and the change in specific resistance due to temperature changes is small, and since no spacer is used, the resistance between the anode and cathode can be reduced, so it can be used in a wide temperature range from low temperatures to wet temperatures. In addition, there are few changes in tan δ characteristics, changes in capacitance, and changes in leakage current characteristics, and unlike conventional examples, the element shape is non-inductive, so impedance characteristics at high frequencies are significantly improved. It has the advantage of having excellent effects.

Next, an example of comparison between an embodiment of the present invention and a conventional reference example will be described.

Example The surface of an aluminum film with a thickness of 1 μm formed by vapor-depositing aluminum metal on one side of a polyester film was anodized by applying a voltage of i oov in a 10% aqueous solution of ammonium adipate. On the anodic oxide film formed in step 1, 2.2' to viridinium (TCNQ) 2 was vacuum-deposited at a temperature of 150°C for 5 minutes to form an organic semiconductor film with a thickness of 5 μm. Screen print Ag paste on top (
Screen mesh 200)L A plurality of basic elements having the configuration shown in FIG. 2, which can form a cathode electrode film with a thickness of 5 μm, are laminated, and Aq paste is applied to both end faces and dried to form an electrode extension part. , a rated 25WV made by welding a lead-out terminal to the electrode lead-out part and covering it with epoxy resin as an exterior structure.
, DC-0,1μF multilayer electrolytic capacitor (A)
Example: A coiled element with manila paper interposed as a spacer between an anode foil on which an anodized film was formed after roughening the surface of the aluminum foil and a cathode foil on which the surface of the aluminum foil was roughened was used.
- Rated 25WV, DC - melt-impregnated with TCNQ complex salt of n-probylisonoquinoline and used as a metal case exterior.
0.1 μF (7) Electrolytic capacitor (B) The lead terminal in (B) above has a structure in which the anode and cathode foils are stitched and drawn out.

However, the capacitance change rate and tan δ with respect to temperature of the above-mentioned Example (A) according to the present invention and the conventional reference example (B)
Furthermore, the results of investigating the leakage current were as shown in FIGS. 4 to 6, and the results of investigating the frequency-impedance characteristics were as shown in FIG. 7.

As is clear from FIGS. 4 to 7, Example (A) is more stable than Reference Example (8) in all characteristics.
It has particularly excellent impedance characteristics at high frequencies,
The excellent effects of the present invention were demonstrated.

Although the above embodiments have been described using aluminum metal for forming the valve metal film, similar effects can be obtained by using other valve metals such as tantalum, titanium, and niobium. . Furthermore, in the above embodiment, the basic elements of the required size are individually formed, and the basic elements are laminated individually. However, as shown in FIG. )
After laminating the required number of layers using
It will be more efficient to cut it to the required size in the direction of the arrow). Portions in FIG. 3 that are the same as those in FIG. 2 are given the same numbers and their explanations are omitted. Furthermore, in each of the above embodiments, the basic element configuration is exemplified in which the valve metal film, organic semiconductor film, and cathode electrode film are formed only on one side of the insulator. Needless to say, the same effect can be obtained.

[Effects of the Invention] According to the present invention, spacers are eliminated and 1. Furthermore, by using a novel TCNQ complex salt as an organic semiconductor film, a method for manufacturing a multilayer electrolytic capacitor of high practical value, which has a completely new configuration that goes beyond the framework of existing electrolytic capacitor configurations and has stable characteristics, is obtained. be able to.

[Brief explanation of the drawing]

1 and 2 relate to one embodiment of the present invention, in which FIG. 1 is a front sectional view showing an 81-layer electrolytic capacitor, FIG. 2 is a perspective view showing basic elements constituting FIG. 1, and FIG. 3 is a perspective view showing a basic element according to another embodiment of the present invention, FIG. 4 is a temperature-capacitance change rate characteristic curve, and FIG. 5 is a temperature-ta
nδ characteristic curve diagram, Figure 6 is a temperature-leakage current characteristic curve diagram,
FIG. 7 is a frequency-impedance characteristic curve diagram. (1)・・・・・・・・・Insulating material (2)・
...Margin area (3) ...Valve action metal membrane
(4)...Anodic oxide film (5)...Organic semiconductor film (6)...Cathode electrode film (7H1
1) Basic element (8) Electrode lead-out part patent application Marcon Electronics Co., Ltd. Highman Parts Co., Ltd. 2 Figure 6 N-gorge soft (H2) Figure 7 Procedural amendment written spontaneously) 1986
Field May 19th

Claims (3)

[Claims] (1) Means for vacuum-depositing a valve metal on one or both sides of an insulator to form a valve metal film, means for forming an anodized film on the surface of the metal film, and TCNQ on the oxide film.
A means for forming an organic semiconductor film by vacuum evaporating a complex salt, a means for screen printing a metal paste on the organic semiconductor film to form a cathode electrode film to obtain a basic element, and a means for laminating a plurality of the basic elements and forming electrodes on both end faces. 1. A method for manufacturing a multilayer electrolytic capacitor, comprising means for forming a lead-out portion. (2) The method for manufacturing a multilayer electrolytic capacitor according to claim (1), wherein the insulator is made of a plastic film, a plastic sheet, or a ceramic sheet. (3) TCNQ complex salt is 2,2'-biviridinium (T
CNQ)_2,4-hydroxy-N-benzylanilinium (TCNQ)_2,4-amino-2,3,5,
6-tetramethylanilinium (TCNQ)_2, pyridinium (TCNQ)_2, 4-cyano-N-methyl-
Pyridenium (TCNQ)_2, NE ethylquinolinium (TCNQ)_2, N-(2-phenythyl)quinolinium (TCNQ)_2 A method for manufacturing a multilayer electrolytic capacitor according to scope (2).