JPS6294913A - Manufacture of toroidal 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 1] The present invention relates to a method of manufacturing a wound electrolytic capacitor having a novel configuration.

[Technical aspects of the invention and its problems] In general, dry type thin electrolytic capacitors have a pair of positive and negative sides made of aluminum foil, for example! A pair of lead-out terminals also made of aluminum are connected to the hook, and the pair of anode and cathode foil phases are connected to each other.
It is wound up with a substrate interposed therebetween, then impregnated with a driving electrolyte, 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, and is an important component in a dry type cylindrical electrolytic capacitor. However, the commonly used spacer is kraft paper, but the kraft paper has a density of 0.3 to O, BQ/cm3.
And the density is relatively high, also! Since &IN is flattened, the apparent resistivity increases and the tan δ characteristics are impaired, and the thickness of kraft paper is 3 due to paper-making technology issues.
It has a thickness of 0 μ7n or more, which prevents it 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 properties. However, manila paper is several times more expensive than kraft paper, and in addition, it has poor strength after paper making. In order to withstand the capacitor manufacturing process (particularly the winding process), it is necessary to use a capacitor with a thickness of 40 μm or more, which continues to be an impediment to miniaturization. Furthermore, since a liquid driving electrolyte is used, there is a limit to the improvement of tan δ characteristics, and roughly liquid driving electrolytes increase resistivity at low temperatures, resulting in extremely poor low-temperature characteristics, making them difficult to use over a wide temperature range. Not only did it have problems that needed to be solved in practice, such as a lack of reliability, but it also had a problem with poor frequency characteristics because the lead terminal was stitched in the middle of the anode and cathode foils.

Therefore, in recent years, for example, Japanese Patent Application Laid-open No. 58-17609,
JP-A-58-191414 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 made of isoquinoline, N-ethylisoquinoline, N-n-butylisoquinoline, quinoline substituted with a hydrocarbon group at the N position, isoquinoline, or pyridine have been proposed to have improved properties. However, electrolytic capacitors using such TCNQ complex salts are generally used by melting and impregnating these TCNQ complex salts, but since the TCNQ complex salts are heated during melting and impregnation, the conductivity of the TCNQ complex salts tends to change. There is a problem with the tan δ characteristics, and since the lead terminal is inserted in the middle of the winding as in the past, the characteristics at high frequencies are poor.Furthermore, because a spacer is used, there is a
There were still problems to be solved, such as a wide range of 50μTrL) and a large equivalent series resistance. Furthermore, 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 very good.

[Object of the Invention] The present invention has been made in view of the above points, and it solves the above problems at once and provides a wound layer electrolysis device with a novel configuration that provides stable closing performance even when used in a wide temperature range. The object of the present invention is to provide a method for manufacturing a capacitor.

[Summary of the Invention] The method for manufacturing a wound electrolytic capacitor of the present invention is to vacuum-deposit a valve metal on one side and both sides of an insulator to form a valve metal film, and then deposit the valve metal film on the surface of the metal film. A TCNQ complex salt is vacuum-deposited on the anodic oxide film produced in 1 to form an organic semiconductor film, and a metal is vacuum-deposited on the paid semiconductor to form a cathode electrode film. This device is characterized in that an electrode lead-out portion is formed at one end of the turn.

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

That is, as shown in FIG. 2, for example, polyester, triacetate, tetrafluoroethylene, polycarbonate, etc.
To 1, insulators such as plastic snack film or plastic deck sheet made of polyamide, polyimide, etc.
), one end is left as a margin (2) and aluminum metal is vacuum-deposited to form a valve metal film (3).
The valve metal film (3) is anodized to form the valve metal pA(
3) An anodic oxide film (4) is formed on the surface, and then the margin part (2) is formed on the surface of the anodic Vi oxide film (4) excluding the end face located on the opposite side of the margin part (2). For example, 2,2'-bipyridinium (TCNQ), 2,4-hydroxy-N-penzylanilinium (TCNQ>
, 4-7 Minnow 2.3.5.6 1 Te 1 ~ La Methyanilinium (TCNQ) 2, Viridinium (TC
NQ>, 4-cyano-N-methyl-pyridenium (
TCNQ), N-E ethylquinolinium (TC
NQ)2, N-(2-phenythyl)quinolinium (T
A TCNQ complex salt such as CNQ)2 is vacuum deposited to form a structured semiconductor film (5). Next, the organic semiconductor film (5
) is vacuum-deposited with a metal such as silver, copper, or gold on the surface excluding the end surface located on the opposite side of the surface margin (2) to form a cathode electrode film (6), and then form a basic element (7). obtain.

Then, the basic element (7) is wound as shown in Fig. 1, and both end faces are coated with silver or copper paste and dried, or a metal such as zinc, aluminum or solder is coated with metal such as zinc, aluminum or solder. ), and the electrode lead-out part (8
) to which an external terminal (9) is attached and housed in a case or coated with resin or the like to form an exterior (not shown).

According to the method for manufacturing the wound electrolytic capacitor configured as described above, the above-mentioned T
Since the CN Q #ff salt is used, vacuum evaporation is easy, and unlike conventional melt impregnation, it is not heated, so the conductivity is high and the tan6 characteristics are good.
CNQ complex salt has a small change in resistivity due to temperature changes, and since it does not use a substrate, the resistance between the anode and cathode can be reduced, so it can be used in a wide temperature range from low to high temperatures.
There are few changes in nδ characteristics, changes in capacitance, and changes in leakage and current characteristics.Furthermore, unlike conventional models, the element shape is non-inductive, so impedance characteristics at high frequencies are significantly improved. It has the advantage of producing 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 vacuum-depositing aluminum metal on one side of a polyester film was
A voltage of i oov was applied in a 10% ammonium adipate aqueous solution to perform anodization, and 2,2-bipyridinium (TCNQ) 2 was applied at a temperature of 150°C on the anodic oxide film formed on the surface of the aluminum film by the anodic oxidation. Vacuum deposition was performed for 5 minutes to form an organic semiconductor film with a thickness of 5 μm, and then Ag was vacuum deposited on the organic semiconductor film to a thickness of 5 μm.
A basic element having the structure shown in Fig. 2, which can form a cathode electrode film of 10 m, is wound and AQ paste is applied to both end faces.
A wound type electrolytic capacitor (A) with a rating of 25WV, DC-0, 1μF, which is dried to form an electrode lead-out part, a lead-out terminal is welded to the electrode lead-out part, and an epoxy resin is coated as an exterior structure.Reference example N
- Melt-impregnated with TCNQ complex salt of n-probylisonoquinoline, metal case exterior tocitenal rating 25'WV, DC
-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 ra change rate and tan δ with respect to temperature in the above embodiment <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. 3 to 5, and the results of investigating the frequency-impedance characteristics were as shown in FIG. 6.

As is clear from FIGS. 3 to 6, Example (A) is more stable than Reference Example ([3) in all characteristics, and has particularly excellent impedance characteristics at high frequencies. demonstrated its excellent effectiveness.

In the above embodiments, aluminum metal is used to form the valve metal film, but similar effects can be obtained using other valve metals such as tantalum, titanium, and niobium. In addition, in each of the above embodiments, the basic element configuration is exemplified in which the valve metal film, the sensitive semiconductor film, and the cathode electrode film are formed only on one side of the insulator. It goes without saying that even if you do this, the same effect will be obtained by 1q.

[Effect of the invention 1] According to the present invention, a spacer is abolished and stable characteristics are obtained by using a new TCNQ complex salt as an organic semiconductor film, which is a completely conventional structure that goes beyond the framework of existing electrolytic capacitor structures. It is possible to obtain a method for producing a highly practical volume homomorphic electrolytic capacitor (l) consisting of a highly practical value.

[Brief explanation of drawings]

1 and 2 relate to one embodiment of the present invention; FIG. 1 is a front sectional view showing a wound type electrolytic capacitor, FIG. 2 is a perspective view showing basic elements constituting FIG. 1, and FIG. 4 is a temperature-tan δ characteristic curve, FIG. 5 is a temperature-leakage current characteristic curve, and FIG. 6 is a frequency-impedance characteristic curve. (1)・・・Insulator (2)・・・・・・
Margin area (3)...Valve action metal membrane (4)...
...Anodized film (5) ...Organic semiconductor film
(6)...Cathode electrode film (7)...Basic element (8)...Sfi electrode extraction part 14th edition Applicant Nagai Electronics Industrial Cooperative Association Figure 1 Figure 5 Figure 6 Procedures Amendment (voluntary) 1. Indication of the case 1985 Patent Application No. 235934 26 Name of the invention Method for manufacturing rolled electrolytic condenser 3. Person making the amendment Relationship to the case Patent applicant Address: 1960 Toki 13, Nagai City, Yamagata Prefecture, Nagai (
0238) 84-4403 Postal code 999-05 Name Nagai Electronic Industrial Cooperative Association Details as per the attached sheet 1. Name of the invention Method for manufacturing a wound electrolytic capacitor 2. Claims (1) Insulating material means for forming a valve metal film by vacuum-depositing a valve metal on both surfaces; means for forming an anodic oxide film on the surface of the metal film;
a means for vacuum-depositing a complex salt to form an organic semiconductor film; a means for vacuum-depositing a metal on the IjIa semiconductor to form a negative KA electrode film to form a basic element; A method for manufacturing a wound electrolytic capacitor, characterized in that a means for forming an electrode lead-out portion is used in combination with a means for forming an electrode lead-out portion. (2) Claim No. 1 characterized in that the insulator is made of a plastic film or a plastic sheet 1 to 1.
) Method of manufacturing the wound type electrolytic capacitor described in section 2. (3) 1'C,NQ It salt is 2,2'-bipyridinium (TCNQ>, 4-hydroxy-N
-penzylanilinium (TCNQ) 2,4-amino-
2,3,5,6-tetramethylanilinium (TCNQ
), pyridinium (TCNQ), 4-cyano-Nmethyl-pyridinium (TCNQ), N-
■The volume described in claim (1) or claim (2), characterized in that it consists of tilquinolinium (TCNQ>, N-(2-phenedyyl)quinolinium (-rCNQ) 2) Method for manufacturing a wound electrolytic capacitor. 3. Detailed description of the invention [Technical field of the invention 1 The present invention relates to a method for manufacturing a wound electrolytic capacitor having a novel configuration. [Technical background of the invention and its problems] In general, dry type thin electrolytic capacitors are made by connecting a pair of anode and cathode foils made of aluminum foil to a pair of lead terminals also made of aluminum, winding the anode and cathode foils with a spacer interposed between them, and then driving the capacitor. The spacer is impregnated with an electrolytic solution, stored in a case, and the opening of the case is sealed.Generally, the purpose of interposing a spacer is to connect a pair of positive and negative I41f+
These are insulation isolation J3 between the two phases H and retention of the driving electrolyte, which are important structural requirements in a dry cylindrical lightning reactor. However, the commonly used spacer is kraft paper, but the kraft paper has a density of 0.3 to 0.
．． The density is relatively high at 80/cm", and the cross-sectional shape of the fibers that make up kraft paper is flat, so the apparent resistivity becomes large, which deteriorates the tan δ property. In addition, kraft paper has problems in papermaking technology. The thickness of the capacitor is over 30 μm, and it cannot be made any thinner, which is a factor that hinders miniaturization.There is a risk of capacitor destruction due to overcurrent of 1 F, application of reverse voltage, etc., and there is a risk of continuous combustion due to 1 to 4 ignition. Therefore, there is a current tendency to use low-density 7-Ni 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, in order to maintain the strength after paper making to withstand the capacitor manufacturing process (particularly the winding process), it is necessary to use a sheet with a thickness of 40 μm rL or more, which remains an impediment to miniaturization. Furthermore, since a liquid driving electrolyte is used, there is a limit to the improvement of tan δ characteristics.Furthermore, liquid driving electrolytes tend to increase resistivity at low temperatures, resulting in extremely poor low-temperature characteristics, making them difficult to use over a wide temperature range. Not only did it have problems that needed to be solved in practice, such as a lack of reliability, but it also had the problem of poor frequency characteristics because the lead terminal was stitched in the middle of the positive and negative poles. In recent years, for example, Japanese Patent Application Laid-Open No. 17609/1983,
JP-A-58-191414 or JP-A-59-6
As disclosed in Publication No. 3604, instead of the driving electrolyte, N-n-propyl (or N-iso-propyl)
TCN consisting of isoquinoline, N-ethylisoquinoline, N-'-butylisoquinoline, quinoline substituted with a hydrocarbon group at the N position, isoquinoline or pyridine, etc.
A Q complex salt with improved properties has been proposed as a solid electrolyte. However, electrolytic capacitors I made using such TCNQ complex salts are generally made using these TCNQ complex salts.
Q complex salt is used by melting and impregnating it, but TCNQ♀11 is heated for a long time when melting and impregnating TCNQ complex salt.
If the conductivity of the salt decreases, there is a problem with the J' tan δ characteristics, and since the lead terminal is inserted in the middle of the winding as before, the characteristics at high frequencies are poor, so it is necessary to use a spacer. Therefore, there were still problems to be solved, such as the distance between the anode and cathode (approximately 40 to 50 μm) and the large series resistance. Furthermore, the TCNQ complex salt disclosed in the above-mentioned publication was not only difficult to deposit by complex salt deposition, but also had the problem that its temperature characteristics were not so good. [Objective of the Invention 1] The present invention has been made in view of the above points, and it solves the above problems at once, and has a novel structure that can be used in a wide temperature range and has stable quality (!1). The purpose of this invention is to provide a method for manufacturing a wound type electrolytic capacitor. [Summary of the Invention 1 The method for manufacturing a wound type electrolytic capacitor of the present invention is to provide a method for manufacturing a wound type electrolytic capacitor by applying a valve metal to one or both sides of an insulator under vacuum. A valve metal film is formed by vapor deposition, then a TCNQ complex salt is vacuum-deposited on the anodic oxide film formed on the surface of the metal film to form an organic semiconductor film, and a metal is vacuum-deposited on the organic semiconductor film. This method is characterized in that after forming a cathode electrode film and obtaining a basic element, the basic element is wound and electrode extension parts are formed on both end faces. [Embodiments of the Invention] Hereinafter, one embodiment of the present invention will be described. An example will be explained in detail. 1. As shown in FIG. 2, for example, polyester,
Triacetate, Te1-Rough [10 Ethylene, polycarbonate, polyamide, polyimide, etc., are insulators (1) such as plastic films or sheets. Aluminum metal is vacuum-deposited on one side of the insulating material (1) with one end left as a margin (2) to form a valve. After forming the metal film (3), the valve metal film (3) is anodized to form an arsenic anodic acid film (4) on the surface of the valve metal film (3), and then the anode For example, 2.2'-bipyridinium (TCNQ) 2.4 is applied from the surface of the oxide film (4) excluding the end surface located on the opposite side of the margin section (2) to the surface of the margin section (2).
-Hydroxy-N-penzylanilini 1 cum (TC
NQ), 4-amino-2,3,5,6-titramedylanilinium (TCNQ>2, pyridinium (T
CNQ), 4-cyano-Nmethyl-pyridinium (TCNQ) 2, N-ethylquinolinium (
An organic semiconductor film (5) is formed by depositing a TCNQ complex salt such as TCNQ), N-(2-)1Nedyl)quinolinium (TCNQ)2, or the like. Next, a cathode electrode film (6) is formed by vacuum-depositing a metal such as silver, copper, or gold on the surface of the organic semiconductor film (5) excluding the end face located on the opposite side of the margin (2). Then, basic element (1) is obtained. Then, the basic element (7) is wound as shown in FIG.
Apply silver or copper paste to both end faces and dry or metallize with metal such as zinc, aluminum or solder to form an electrode lead-out part (8), and connect an external terminal (9) to the electrode lead-out part (8). It is either mounted in a case, or coated with resin or the like to form an exterior (not shown). According to the method for manufacturing the wound positive electrolytic condenser constructed as described above, the above-described T
Because the CNQ complex salt is a complex salt, vacuum bonding 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 resistivity due to changes in the complex salt is small, and since sub-V is not used, the resistance between the anode and cathode can be reduced, so it can be used at a wide range of temperature UvA from low to high temperatures. 33, there are few changes in tan δ characteristics, changes in capacitance, and changes in leakage current characteristics, and furthermore, since the shape of the follower element is non-inductive compared to the conventional example, the impedance characteristics at high frequencies are significantly improved. It has the advantage of producing many outstanding 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 μ7n formed by vacuum vapor deposition of aluminum metal on one side of a polyester film was anodized by applying a voltage of 100 V in a 10% aqueous solution of ammonium adipate, and the aluminum film was formed by the anodization. On the anodic oxide skin IjIA generated on the surface, 2,2
'-Bipyridinium (TCNQ>28 temperature 150℃,
An organic semiconductor film with a thickness of 5 μm was formed by vacuum deposition for 5 minutes, and then ACI was vacuum deposited on the organic semiconductor to form a negative 14 electrode film with a thickness of 5 μm, as shown in Figure 2. A basic element consisting of the following configuration is wound, AQ paste is applied to both end faces, dried to form an electrode lead-out part, a lead-out terminal is welded to the electrode lead-out part, and the exterior structure is coated with epoxy resin, rated at 25WV0. .1μF wound type electrolytic capacitor (A). Reference Example After roughening the surface of aluminum foil, manila paper was interposed as a smoother between the anode foil on which a 4[N] conversion film was formed and the cathode foil on which the surface of the aluminum foil was roughened.
- Molten and impregnated with TCNQ button salt of n-probylisonoquinoline to form a metal case exterior! 825WV0.
1μF electrolytic capacitor (1B). The lead terminal in (B) above has a structure in which the anode and cathode foils are stitched and drawn out. Therefore, 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),
Roughly speaking, the results of investigating the leakage current were as shown in FIGS. 3 to 5, and the results of investigating the frequency-impedance characteristics were as shown in FIG. 6. As is clear from FIGS. 3 to 6, Example (A) is more stable than Reference Example (8) in all characteristics.
In particular, J3 had excellent inbuilt-dance characteristics at high frequencies, demonstrating the excellent effects of the present invention. A3 In the above embodiment, aluminum metal is used to form the valve metal film, but it is possible to obtain the same effect by using other valve metals such as tantalum, titanium, niobium, etc. can. Furthermore, in each of the above embodiments, the basic element configuration has been described by way of example in which the valve metal film, the fi compensation semiconductor film, and the cathode/electrode film are formed only on one side of the insulator. It goes without saying that the same effect as b can be obtained in this way. [Effect of the invention 1 According to the present invention, a completely new configuration beyond the framework of existing electrolytic capacitor configurations is achieved in which stable characteristics are obtained by abolishing the substrate 4) and using a new TCNQ complex salt as an organic semiconductor film. A method for manufacturing a wound electrolytic capacitor of high practical value can be obtained. 4.Fi of drawings! 111i Description FIGS. 1 and 2 relate to one embodiment of the present invention.
Figure 2 is a top view showing a well-wound electrolytic capacitor.
Figure 3 is a temperature-capacitance change rate characteristic curve diagram, Figure 4 is a hot water temperature-tanδ characteristic curve diagram, and Figure 5 is a temperature-leakage current characteristic curve diagram. , FIG. 6 is a frequency-impedance characteristic curve diagram. (1)・・・Insulator (2)・・・・・・
Margin area (3)...Valve action metal membrane (4)...
...Anodized film (5) ...Organic semiconductor film
(6)...Cathode electrode film (1)...Basic element (8)...Patent for electrode lead-out portion
Applicant Nagai Electronics Industrial Cooperative Association

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.
means for vacuum-depositing a complex salt to form an organic semiconductor film; means for vacuum-depositing a metal on the organic semiconductor film to form a cathode electrode film to obtain a basic element; 1. A method for manufacturing a wound electrolytic capacitor, comprising means for forming a wound electrolytic capacitor. (2) Claim (1) characterized in that the insulator is made of a plastic film or a plastic sheet.
A method for manufacturing a wound type electrolytic capacitor as described in . (3) TCNQ complex salt is 2,2'-bipyridinium (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, N-E ethylquinolinium (TCNQ)_2, N-
A method for manufacturing a wound electrolytic capacitor according to claim (1) or claim (2), characterized in that it is made of (2-phenythyl)quinolinium (TCNQ)_2.