JP2001297950A - Method of manufacturing anode foil for aluminum electrolytic capacitor - Google Patents
Method of manufacturing anode foil for aluminum electrolytic capacitorInfo
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- JP2001297950A JP2001297950A JP2000114884A JP2000114884A JP2001297950A JP 2001297950 A JP2001297950 A JP 2001297950A JP 2000114884 A JP2000114884 A JP 2000114884A JP 2000114884 A JP2000114884 A JP 2000114884A JP 2001297950 A JP2001297950 A JP 2001297950A
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- acid
- foil
- aqueous solution
- etching
- aluminum foil
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はアルミ電解コンデン
サの陽極箔に用いられるアルミ電解コンデンサ用陽極箔
の製造方法に関し、特に中高圧用のアルミ電解コンデン
サ用陽極箔の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an anode foil for an aluminum electrolytic capacitor used for an anode foil of an aluminum electrolytic capacitor, and more particularly to a method for producing an anode foil for an aluminum electrolytic capacitor for medium and high pressures.
【０００２】[0002]
【従来の技術】近年、電子機器の小型化、高信頼性化に
伴い、アルミ電解コンデンサに対するユーザからのニー
ズも小型化が強く要望されており、そのためにアルミ電
解コンデンサ用陽極箔も従来以上に単位面積当たりの静
電容量を高める必要が生じている。2. Description of the Related Art In recent years, with the miniaturization and high reliability of electronic devices, there has been a strong demand from users for miniaturization of aluminum electrolytic capacitors. There is a need to increase the capacitance per unit area.
【０００３】一般的なアルミ電解コンデンサは、アルミ
ニウム箔をエッチングによって実効表面積を拡大させた
表面に陽極酸化により誘電体酸化皮膜を形成した陽極箔
とアルミニウム箔をエッチングによって実効表面積を拡
大させた陰極箔とをセパレータを介して巻回することに
よりコンデンサ素子を構成し、このコンデンサ素子に駆
動用電解液を含浸させるとともに、このコンデンサ素子
を金属ケース内に封止することにより構成されている。A general aluminum electrolytic capacitor is composed of an anode foil having a dielectric oxide film formed by anodic oxidation on a surface having an effective surface area increased by etching an aluminum foil and a cathode foil having an effective surface area enlarged by etching an aluminum foil. Are wound through a separator to form a capacitor element, and the capacitor element is impregnated with a driving electrolyte, and the capacitor element is sealed in a metal case.
【０００４】この種のアルミ電解コンデンサにおいて、
その静電容量を高める或いは小形化を図るには、陽極箔
の実効表面積を拡大し単位面積当たりの静電容量を高め
ることが必要不可欠になっており、陽極箔の実効表面積
を拡大させるエッチング技術の開発が盛んに行われてい
る。In this type of aluminum electrolytic capacitor,
In order to increase the capacitance or reduce the size, it is essential to increase the effective surface area of the anode foil and increase the capacitance per unit area. Etching technology to increase the effective surface area of the anode foil Is being actively developed.
【０００５】上記陽極箔のエッチング方法は、硫酸、硝
酸、燐酸、蓚酸などの皮膜を形成する酸を添加した塩化
物水溶液中で化学的あるいは電気化学的に行われている
が、中高圧用に使用される陽極箔のエッチング方法は、
基本的にはエッチングピット（以下、ピットと称す）を
生成させる前段エッチング工程と、このピットを使用電
圧に適した径まで拡大する後段エッチング工程とからな
る方法で、いかに数多くのピットを生成させて効率よく
ピットの径を拡大させるかが重要なポイントとなってい
る。The above-mentioned method of etching the anode foil is performed chemically or electrochemically in a chloride aqueous solution to which an acid for forming a film such as sulfuric acid, nitric acid, phosphoric acid, and oxalic acid is added. The etching method of the anode foil used is
Basically, a method consisting of a pre-etching step for generating etching pits (hereinafter referred to as pits) and a post-etching step for expanding the pits to a diameter suitable for the operating voltage is used to generate a number of pits. An important point is to effectively increase the pit diameter.
【０００６】陽極箔の実効表面積を拡大する技術は、例
えば、特開平９−１８０９６６号公報に記載された技術
のように、直流電流を流して電気化学的にエッチングす
る前段エッチング工程と、塩酸、硫酸または硝酸のうち
１種類以上を含む溶液中で交流電流を流してエッチング
する後段エッチング工程を行うことにより、陽極箔の実
効表面積の拡大と機械的強度の向上を図ることができる
と記載されている。As a technique for increasing the effective surface area of the anode foil, for example, as in a technique described in Japanese Patent Application Laid-Open No. 9-180966, a pre-etching step of electrochemically etching by flowing a direct current, It is described that by performing a subsequent etching step in which an alternating current is passed in a solution containing at least one of sulfuric acid and nitric acid to perform etching, the effective surface area of the anode foil and the mechanical strength can be improved. I have.
【０００７】また、特開平６−１７６９７６号公報に記
載された技術は、前段エッチング工程の途中に熱処理を
施すことにより、ピットの分散性が良くなり陽極箔の実
効表面積を拡大することができると記載されている。Further, the technique described in Japanese Patent Application Laid-Open No. 6-176976 discloses that by performing a heat treatment during the pre-etching step, the dispersibility of the pits is improved and the effective surface area of the anode foil can be increased. Has been described.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、上記従
来の陽極箔のエッチング方法において、前段エッチング
工程は皮膜を形成させる酸を添加してエッチングしてい
ることから、前段エッチング工程後にアルミニウム箔の
表面に不均一の薄い皮膜が形成されてしまうので、後段
エッチング工程でのピット径の拡大が不均一になり、ア
ルミニウム箔の表面も溶解してしまうので、陽極箔の実
効表面積の拡大を図りにくいばかりでなく、機械的強度
も弱くなるという課題を有していた。However, in the above-described conventional method for etching an anode foil, since the pre-etching step involves etching by adding an acid for forming a film, the surface of the aluminum foil is etched after the pre-etching step. Since a non-uniform thin film is formed, the expansion of the pit diameter in the subsequent etching process becomes non-uniform, and the surface of the aluminum foil also dissolves, so it is difficult to increase the effective surface area of the anode foil. In addition, there was a problem that the mechanical strength was weakened.
【０００９】また、上記特開平９−１８０９６６号公報
に記載の技術は、後段エッチング工程を塩酸、硫酸また
は硝酸のうち一種類以上を含む溶液中で交流電流を流し
てエッチングすることにより、アルミニウム箔の表面の
溶解を減少させて陽極箔の実効表面積を拡大することが
できると記載されているが、後段エッチング工程に交流
電流を用いると、直流電流を用いたときよりもエッチン
グ時間が長くなってしまい、生産効率が悪くなり、ま
た、前段エッチング工程で直流電流を用い、後段エッチ
ング工程で交流電流を用いることは生産設備が煩雑にな
ってしまうという課題を有していた。[0009] The technique described in Japanese Patent Application Laid-Open No. 9-180966 discloses an aluminum foil by performing a subsequent etching step in a solution containing at least one of hydrochloric acid, sulfuric acid and nitric acid by flowing an alternating current. It is described that the effective surface area of the anode foil can be increased by reducing the dissolution of the surface of the anode foil, but if an alternating current is used in the subsequent etching step, the etching time becomes longer than when using a direct current. As a result, the production efficiency is deteriorated, and the use of a direct current in the first etching step and the use of the alternating current in the second etching step has a problem that the production equipment becomes complicated.
【００１０】さらに、特開平６−１７６９７６号公報に
記載された技術も、前段エッチング工程の途中に熱処理
を施すことによりピットの分散性は良くなるが、後段エ
ッチング工程で硫酸イオンを含む水溶液で化学エッチン
グをするので、原箔ロット間での溶解性の差（ばらつ
き）の影響を受けやすく、均一なピット径の拡大ができ
ないため、陽極箔の実効表面積の拡大をすることが困難
であるという課題を有していた。In the technique described in Japanese Patent Application Laid-Open No. 6-176976, the dispersibility of the pits is improved by performing a heat treatment in the middle of the first etching step. Since the etching is performed, it is susceptible to the difference (variation) in solubility between the original foil lots, and the uniform pit diameter cannot be increased. Therefore, it is difficult to increase the effective surface area of the anode foil. Had.
【００１１】本発明はこのような従来の課題を解決し、
実効表面積の拡大を図り、機械的強度が強くて単位面積
当たりの静電容量の高い陽極箔を得ることができるアル
ミ電解コンデンサ用陽極箔の製造方法を提供することを
目的とするものである。The present invention solves such a conventional problem,
It is an object of the present invention to provide a method for manufacturing an anode foil for an aluminum electrolytic capacitor capable of increasing an effective surface area and obtaining an anode foil having high mechanical strength and high capacitance per unit area.
【００１２】[0012]
【課題を解決するための手段】上記課題を解決するため
に本発明は、以下の製造方法を有するものである。In order to solve the above problems, the present invention has the following manufacturing method.
【００１３】本発明の請求項１に記載の発明は、特に前
段エッチング工程と後段エッチング工程の間に、アルミ
ニウム箔の表面の皮膜を溶解させる酸性水溶液に浸漬す
る第１の中間処理工程と、アルミニウム箔の表面に皮膜
を生成させる水溶液に浸漬する第２の中間処理工程を設
けた製造方法としたもので、この方法により、第１の中
間処理としてアルミニウム箔の表面の皮膜を溶解する酸
性水溶液中に浸漬することにより、前段エッチング工程
後のアルミニウム箔の表面の不均一の皮膜が除去され、
アルミニウム箔の表面を活性化することができる。その
後、第２の中間処理によって活性化したアルミニウム箔
の表面に均一な皮膜を生成することができるものであ
る。この皮膜により、引き続き行う後段エッチング工程
においてアルミニウム箔の表面の溶解を阻害することが
できるため、ピットの壁面が優先的にエッチングされ、
効率よくピット径を拡大することができることから、実
効表面積の拡大を図ることができ、機械的強度が強くて
単位面積当たりの静電容量の高い陽極箔を得ることがで
きるものである。[0013] The invention according to claim 1 of the present invention comprises a first intermediate treatment step of dipping in an acidic aqueous solution for dissolving a film on the surface of an aluminum foil, particularly between a first etching step and a second etching step; A production method provided with a second intermediate treatment step of immersing in an aqueous solution for forming a film on the surface of the foil. In this method, as a first intermediate treatment, an acidic aqueous solution dissolving the film on the surface of the aluminum foil is used. By immersion in, the uneven film on the surface of the aluminum foil after the pre-etching step is removed,
The surface of the aluminum foil can be activated. Thereafter, a uniform film can be formed on the surface of the aluminum foil activated by the second intermediate treatment. With this film, the dissolution of the surface of the aluminum foil can be inhibited in the subsequent etching step, so that the wall surfaces of the pits are preferentially etched,
Since the pit diameter can be efficiently increased, the effective surface area can be increased, and an anode foil having high mechanical strength and high capacitance per unit area can be obtained.
【００１４】また、請求項２に記載の発明は、特に、第
１の中間処理に用いるアルミニウム箔の表面に皮膜を生
成しない酸性水溶液が塩酸、フッ酸、硝酸のうちから選
択された少なくとも１種類の酸性水溶液を用いた製造方
法とするもので、この方法によりアルミニウム箔の表面
の不均一な皮膜を除去し、アルミニウム箔の表面を活性
化することができるという作用を有する。The invention according to claim 2 is characterized in that the acidic aqueous solution which does not form a film on the surface of the aluminum foil used for the first intermediate treatment is at least one selected from hydrochloric acid, hydrofluoric acid and nitric acid. The production method using an acidic aqueous solution of (1) has an effect of removing a non-uniform film on the surface of the aluminum foil and activating the surface of the aluminum foil.
【００１５】また、請求項３に記載の発明は、特に、第
２の中間処理に用いるアルミニウム箔の表面に皮膜を生
成する水溶液として硫酸、クロム酸、リン酸、ほう酸の
うちから選択された少なくとも１種類の無機酸水溶液ま
たはシュウ酸、クエン酸、コハク酸、マロン酸のうちか
ら選択された少なくとも１種類の有機酸水溶液を用いた
製造方法とするもので、この方法により、活性化された
アルミニウム箔の表面に均一な皮膜を生成することがで
きるという作用効果を有する。[0015] The invention according to claim 3 provides, in particular, at least one selected from among sulfuric acid, chromic acid, phosphoric acid and boric acid as an aqueous solution for forming a film on the surface of the aluminum foil used for the second intermediate treatment. The production method uses one kind of an inorganic acid aqueous solution or at least one kind of an organic acid aqueous solution selected from oxalic acid, citric acid, succinic acid, and malonic acid. This has the effect that a uniform film can be formed on the surface of the foil.
【００１６】[0016]
【発明の実施の形態】以下、本発明の実施の形態につい
て詳細に説明する。Embodiments of the present invention will be described below in detail.
【００１７】本発明の前段エッチング工程は、アルミニ
ウム箔の表面を如何に密度を高めて均一にピットを生成
させるかが重要となる。このためには、塩酸水溶液もし
くはその水溶液に蓚酸、硫酸、リン酸、硼酸からなる酸
またはその塩の少なくとも１種類を添加したエッチング
液で電気化学的にエッチングを行うようにする。In the pre-etching step of the present invention, it is important how to increase the density on the surface of the aluminum foil to uniformly generate pits. For this purpose, the etching is performed electrochemically using an aqueous solution of hydrochloric acid or an etching solution obtained by adding at least one kind of an acid composed of oxalic acid, sulfuric acid, phosphoric acid, boric acid or a salt thereof to the aqueous solution.
【００１８】この塩酸水溶液の濃度は２〜１５％の範囲
が好ましく、濃度が２％未満では充分なピットを得るこ
とができず、１５％を越えるとアルミニウム箔の表面の
溶解が起きてしまう。好適な範囲は４〜１２％である。The concentration of the aqueous hydrochloric acid solution is preferably in the range of 2 to 15%. If the concentration is less than 2%, sufficient pits cannot be obtained. If the concentration exceeds 15%, the surface of the aluminum foil will be dissolved. The preferred range is 4-12%.
【００１９】また、蓚酸、硫酸、リン酸、硼酸からなる
酸またはその塩の少なくとも１種類を添加することでピ
ット生成密度をより高めることができる。この添加量と
しては０．１〜１５％の範囲が好ましい。The pit formation density can be further increased by adding at least one kind of acid composed of oxalic acid, sulfuric acid, phosphoric acid and boric acid or a salt thereof. This addition amount is preferably in the range of 0.1 to 15%.
【００２０】上記エッチング液の温度もピット生成に重
要な影響を及ぼす。温度が５０℃未満ではピット生成密
度が少なく、一方、１００℃を越えるとアルミニウム箔
の表面の溶解が起きるので、エッチング液の温度は５０
〜１００℃の範囲が好ましい。The temperature of the etchant also has an important effect on pit formation. If the temperature is lower than 50 ° C., the pit formation density is low, while if it is higher than 100 ° C., the surface of the aluminum foil is dissolved.
The range of -100 ° C is preferred.
【００２１】次に、中間処理は、アルミニウム箔の表面
の皮膜を溶解させる酸性水溶液に浸漬する第１の中間処
理工程と、アルミニウム箔の表面に皮膜を生成させる水
溶液に浸漬する第２の中間処理工程とを有するものであ
る。Next, the intermediate treatment includes a first intermediate treatment step of dipping in an acidic aqueous solution for dissolving the film on the surface of the aluminum foil, and a second intermediate treatment step of dipping in an aqueous solution for forming a film on the surface of the aluminum foil. And a process.
【００２２】上記第１の中間処理工程は、前段エッチン
グ工程後のアルミニウム箔の表面の不均一の皮膜を除去
し、アルミニウム箔の表面を活性化するものである。In the first intermediate treatment step, the non-uniform film on the surface of the aluminum foil after the pre-etching step is removed, and the surface of the aluminum foil is activated.
【００２３】この第１の中間処理工程は、塩酸、フッ
酸、硝酸のうちから選択された少なくとも１種類の酸性
水溶液が用いられ、酸性水溶液の酸濃度は２〜１０％の
範囲が好ましい。酸濃度が２％未満では十分な皮膜の除
去が行われず、１０％を越えるとアルミニウム箔の表面
が溶解してしまう。また、この酸性水溶液の温度は、５
０〜９０℃の範囲が好ましい。In the first intermediate treatment step, at least one kind of acidic aqueous solution selected from hydrochloric acid, hydrofluoric acid and nitric acid is used, and the acidic aqueous solution preferably has an acid concentration of 2 to 10%. If the acid concentration is less than 2%, the film is not sufficiently removed, and if it exceeds 10%, the surface of the aluminum foil is dissolved. The temperature of the acidic aqueous solution is 5
A range from 0 to 90C is preferred.
【００２４】上記第２の中間処理工程は、アルミニウム
箔の表面に皮膜を生成させるもので、硫酸、クロム酸、
リン酸、ほう酸の無機酸またはシュウ酸、クエン酸、コ
ハク酸、マロン酸の有機酸のうちから選択された少なく
とも１種類の水溶液を用いることができる。In the second intermediate treatment step, a film is formed on the surface of the aluminum foil, and sulfuric acid, chromic acid,
At least one aqueous solution selected from inorganic acids of phosphoric acid and boric acid or organic acids of oxalic acid, citric acid, succinic acid and malonic acid can be used.
【００２５】この第２の中間処理工程で用いる水溶液の
濃度は、０．５〜５％の範囲が好ましい。また水溶液の
温度は無機酸水溶液で４０〜７０℃、有機酸水溶液で５
０〜９０℃の範囲が好ましい。The concentration of the aqueous solution used in the second intermediate treatment step is preferably in the range of 0.5 to 5%. The temperature of the aqueous solution is 40 to 70 ° C. for an inorganic acid aqueous solution, and 5 to
A range from 0 to 90C is preferred.
【００２６】なお、第２の中間処理において、皮膜を生
成させる水溶液がアルカリ性水溶液や中性水溶液では、
第２の中間処理後に生成する皮膜は均一ではあるがアル
ミニウム箔の表面だけでなくピット壁面も厚い皮膜で覆
ってしまうので、引き続き行うピット径の拡大ができに
くくなってしまう。従って、第２の中間処理工程は皮膜
を生成させることができる酸性の水溶液を用いなければ
ならない。In the second intermediate treatment, if the aqueous solution for forming the film is an alkaline aqueous solution or a neutral aqueous solution,
Although the film formed after the second intermediate treatment is uniform, not only the surface of the aluminum foil but also the pit wall surface is covered with a thick film, so that it is difficult to continuously increase the pit diameter. Therefore, the second intermediate treatment step must use an acidic aqueous solution capable of forming a film.
【００２７】次に、後段エッチング工程は、前段エッチ
ング工程でできたピットをアルミニウム箔の表面の溶解
を抑えてピットの径拡大を行うものである。この後段エ
ッチング工程に用いられるエッチング液は、硫酸、硝酸
のいずれかに蓚酸、燐酸、クロム酸、酢酸、リン酸、ク
エン酸、硼酸の少なくとも１種類以上を添加したエッチ
ング液が好ましく、またこのエッチング液の濃度は０．
１〜５．０％の範囲が好ましい。濃度が０．１％未満で
はアルミニウム箔の表面の溶解が起こり、５．０％を越
えるとアルミニウム箔の表面に酸化皮膜が形成されすぎ
てピットの径拡大が起こりにくくなる。Next, in the post-etching step, the diameter of the pits formed in the pre-etching step is increased by suppressing the dissolution of the surface of the aluminum foil. The etchant used in the subsequent etching step is preferably an etchant obtained by adding at least one of oxalic acid, phosphoric acid, chromic acid, acetic acid, phosphoric acid, citric acid, and boric acid to either sulfuric acid or nitric acid. The concentration of the solution is 0.
A range of 1 to 5.0% is preferred. When the concentration is less than 0.1%, the surface of the aluminum foil is dissolved, and when the concentration exceeds 5.0%, an oxide film is excessively formed on the surface of the aluminum foil, and it is difficult for the pit diameter to increase.
【００２８】このエッチング液中でエッチングすること
により、アルミニウム箔中の不純物や粒界の影響による
表面溶解を抑えてピット径の拡大と均一化を図ることが
できるので、実効表面積の拡大ができ、単位面積当たり
の静電容量の高い陽極箔を得ることができるものであ
る。By performing etching in this etching solution, it is possible to suppress the surface melting due to the influence of impurities and grain boundaries in the aluminum foil and to enlarge and uniform the pit diameter, so that the effective surface area can be increased. An anode foil having a high capacitance per unit area can be obtained.
【００２９】（実施例１）純度９９．９８％、厚み１０
０μｍのアルミニウム箔を用い、液温８５℃の酸性水溶
液（塩酸濃度１０％、硫酸濃度１０％）中に浸漬し、電
流密度２０Ａ／ｄｍ2の直流電流を２５０秒印加して前
段エッチング工程を行った。(Example 1) Purity 99.98%, thickness 10
A 0 μm aluminum foil was immersed in an acidic aqueous solution (hydrochloric acid concentration 10%, sulfuric acid concentration 10%) at a liquid temperature of 85 ° C., and a direct current having a current density of 20 A / dm 2 was applied for 250 seconds to perform a pre-etching step. Was.
【００３０】次に、中間処理として液温８０℃、濃度５
％の塩酸水溶液中に６０秒浸漬する第１の中間処理を行
った後、液温４０℃、濃度０．５％の硫酸水溶液中に６
０秒浸漬する第２の中間処理を行った。Next, a liquid temperature of 80.degree.
After performing the first intermediate treatment of immersing in a 60% aqueous hydrochloric acid solution for 60 seconds, the solution was immersed in a 0.5% aqueous sulfuric acid solution at 40 ° C.
A second intermediate treatment of immersion for 0 seconds was performed.
【００３１】次に、後段エッチング工程として液温７０
℃、濃度３％の硝酸水溶液中に浸漬し、かつ電流密度１
０Ａ／ｄｍ2の直流電流を６００秒印加してピット拡大
工程を行い、最後に脱Ｃｌ処理として液温５０℃、濃度
１０％の硝酸水溶液中で１分間洗浄してエッチングされ
た陽極箔を作製した。Next, a liquid temperature of 70 is used as a subsequent etching step.
Immersed in a 3% aqueous nitric acid solution at a
A pit enlarging step is performed by applying a direct current of 0 A / dm 2 for 600 seconds, and finally, as a Cl removal treatment, the anode foil is washed by washing in a 10% nitric acid aqueous solution at a liquid temperature of 50 ° C. for 1 minute to produce an etched anode foil. did.
【００３２】（実施例２）上記実施例１において、第１
の中間処理で用いた塩酸の代わりに液温７０℃、濃度１
０％の硝酸水溶液を用い、第２の中間処理で用いた硫酸
の代わりに液温５０℃、濃度１％のリン酸水溶液を用い
た以外は実施例１と同様にしてエッチングされた陽極箔
を作製した。(Embodiment 2) In Embodiment 1 described above, the first
Liquid temperature 70 ° C, concentration 1 instead of hydrochloric acid used in the intermediate treatment of
An anode foil etched in the same manner as in Example 1 except that a 0% aqueous nitric acid solution was used, and a sulfuric acid aqueous solution having a liquid temperature of 50 ° C. and a concentration of 1% was used instead of the sulfuric acid used in the second intermediate treatment. Produced.
【００３３】（実施例３）上記実施例１において、第１
の中間処理で用いた塩酸の代わりに液温５０℃、濃度２
％の弗酸を用い、第２の中間処理で用いた硫酸の代わり
に液温７０℃、濃度３％のほう酸水溶液を用いた以外は
実施例１と同様にしてエッチングされた陽極箔を作製し
た。(Embodiment 3) In the first embodiment, the first
Liquid temperature 50 ° C, concentration 2 instead of hydrochloric acid used in the intermediate treatment of
Anode foil was etched in the same manner as in Example 1 except that a sulfuric acid solution having a liquid temperature of 70 ° C. and a concentration of 3% was used instead of sulfuric acid used in the second intermediate treatment. .
【００３４】（実施例４）上記実施例１において、第２
の中間処理で用いた硫酸の代わりに液温６０℃、濃度２
％のクロム酸水溶液を用いた以外は実施例１と同様にし
てエッチングされた陽極箔を作製した。(Embodiment 4) In the first embodiment, the second
Liquid temperature 60 ° C, concentration 2 instead of sulfuric acid used in the intermediate treatment of
An etched anode foil was prepared in the same manner as in Example 1 except that an aqueous solution of chromic acid was used.
【００３５】（実施例５）上記実施例１において、第２
の中間処理で用いた硫酸の代わりに液温５０℃、濃度３
％のクエン酸水溶液を用いた以外は実施例１と同様にし
てエッチングされた陽極箔を作製した。(Embodiment 5) In the first embodiment, the second
Liquid temperature 50 ° C, concentration 3 instead of sulfuric acid used in the intermediate treatment of
An etched anode foil was prepared in the same manner as in Example 1 except that a 1% aqueous citric acid solution was used.
【００３６】（実施例６）上記実施例１において、第２
の中間処理で用いた硫酸の代わりに液温７０℃、濃度４
％のシュウ酸水溶液を用いた以外は実施例１と同様にし
てエッチングされた陽極箔を作製した。(Embodiment 6) In the first embodiment, the second
Liquid temperature 70 ° C, concentration 4
Anode foil was etched in the same manner as in Example 1 except that an aqueous oxalic acid solution was used.
【００３７】（実施例７）上記実施例１において、第２
の中間処理で用いた硫酸の代わりに液温８０℃、濃度５
％のマロン酸水溶液を用いた以外は実施例１と同様にし
てエッチングされた陽極箔を作製した。(Embodiment 7) In the first embodiment, the second
Liquid temperature 80 ° C, concentration 5
Anode foils were etched in the same manner as in Example 1 except that a 1% aqueous malonic acid solution was used.
【００３８】（実施例８）上記実施例１において、第２
の中間処理で用いた硫酸の代わりに液温９０℃、濃度５
％のコハク酸水溶液を用いた以外は実施例１と同様にし
てエッチングされた陽極箔を作製した。(Eighth Embodiment) In the first embodiment, the second
Liquid temperature 90 ° C, concentration 5 instead of sulfuric acid used in the intermediate treatment of
Anode foil was etched in the same manner as in Example 1 except that an aqueous succinic acid solution was used.
【００３９】（比較例）上記実施例１において、第１の
中間処理と第２の中間処理を実施しないようにしてエッ
チングされた陽極箔を作製した。(Comparative Example) An anode foil was produced in the same manner as in Example 1 except that the first intermediate treatment and the second intermediate treatment were not performed.
【００４０】上記した本発明の実施例１〜８および比較
例のエッチングされた陽極箔について、液温９０℃、濃
度８％のほう酸水溶液中で５００Ｖ化成を行い、それら
の各試料について静電容量と折曲げ強度（φ１．０ｍ
ｍ、５０ｇ荷重、折曲げ角度９０度の条件下で１往復を
１回とする）を測定した。その結果を（表１）に示す。The etched anode foils of Examples 1 to 8 of the present invention and the comparative example were subjected to a chemical conversion at 500 V in an aqueous solution of boric acid having a liquid temperature of 90 ° C. and a concentration of 8%. And bending strength (φ1.0m
m, a load of 50 g, and a bending angle of 90 °, one reciprocation is defined as one time). The results are shown in (Table 1).
【００４１】[0041]
【表１】 [Table 1]
【００４２】（表１）から明らかなように、本発明の実
施例１〜４による陽極箔は、第２の中間処理に無機酸水
溶液を用いることにより、比較例と比べて静電容量が高
く機械的強度も強い陽極箔を得ることができる。As is clear from Table 1, the anode foils according to Examples 1 to 4 of the present invention have a higher capacitance than the comparative example by using an inorganic acid aqueous solution for the second intermediate treatment. An anode foil having high mechanical strength can be obtained.
【００４３】また、上記実施例５〜８による陽極箔は、
第２の中間処理に有機酸水溶液を用いても、比較例と比
べて静電容量が高く機械的強度も強い陽極箔を得ること
ができる。The anode foils according to Examples 5 to 8 were
Even when an organic acid aqueous solution is used for the second intermediate treatment, an anode foil having a higher capacitance and a higher mechanical strength than the comparative example can be obtained.
【００４４】[0044]
【発明の効果】以上のように本発明のアルミ電解コンデ
ンサ用陽極箔の製造方法によれば、アルミニウム箔を電
解エッチングしてピットを生成させる前段エッチング工
程と、上記前段エッチング工程により生成されたピット
を拡大する後段エッチング工程とからなるアルミ電解コ
ンデンサ用電極箔の製造方法であって、前段エッチング
工程と後段エッチング工程の間に、アルミニウム箔の表
面の皮膜を溶解させる酸性水溶液に浸漬する第１の中間
処理工程と、アルミニウム箔の表面に皮膜を生成させる
水溶液に浸漬する第２の中間処理工程を設けた製造方法
としたもので、この方法により、第１の中間処理として
アルミニウム箔の表面の皮膜を溶解する酸性水溶液中に
浸漬することにより、前段エッチング工程後のアルミニ
ウム箔の表面の不均一の皮膜が除去され、アルミニウム
箔の表面を活性化することができる。その後、第２の中
間処理によって活性化したアルミニウム箔の表面に均一
な皮膜を生成することができるものである。この皮膜に
より、引き続き行う後段エッチング工程においてアルミ
ニウム箔の表面の溶解を阻害することができるため、ピ
ットの壁面が優先的にエッチングされ、効率よくピット
径を拡大することができることから、機械的強度が強く
て、単位面積当たりの静電容量の高い電極箔を得ること
ができるものである。As described above, according to the method for manufacturing an anode foil for an aluminum electrolytic capacitor of the present invention, a pre-etching step of forming pits by electrolytically etching an aluminum foil, and a pit formed by the above-mentioned pre-etching step. A method for producing an electrode foil for an aluminum electrolytic capacitor, comprising: a first etching step of enlarging a first step of immersing in an acidic aqueous solution that dissolves a film on the surface of the aluminum foil between the first and second etching steps. A manufacturing method comprising an intermediate treatment step and a second intermediate treatment step of immersing in an aqueous solution for forming a film on the surface of the aluminum foil. According to this method, a film on the surface of the aluminum foil is formed as a first intermediate treatment. By immersing the aluminum foil in an acidic aqueous solution that dissolves One film is removed, it is possible to activate the surface of the aluminum foil. Thereafter, a uniform film can be formed on the surface of the aluminum foil activated by the second intermediate treatment. With this film, the dissolution of the surface of the aluminum foil can be inhibited in the subsequent etching step, so that the wall surfaces of the pits are preferentially etched, and the pit diameter can be efficiently increased, so that the mechanical strength is reduced. It is possible to obtain an electrode foil which is strong and has a high capacitance per unit area.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２３Ｆ 1/20 Ｃ２３Ｆ 1/20 Ｃ２３Ｇ 1/12 Ｃ２３Ｇ 1/12 Ｃ２５Ｆ 3/04 Ｃ２５Ｆ 3/04 Ｂ Ｈ０１Ｇ 9/055 Ｈ０１Ｇ 9/04 ３３７ 9/00 9/24 Ｂ (72)発明者 吉村 義仁 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 武石 信弘 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 鳥居 健 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 Ｆターム(参考） 4K026 AA09 AA21 BA08 BB10 CA16 CA18 CA22 CA26 CA38 DA03 EA06 EA07 EB04 4K053 PA10 PA11 PA13 QA01 RA05 RA16 RA17 RA19 SA06 TA01 TA15 TA16 TA20 ZA10 4K057 WA05 WB05 WC05 WC10 WD05 WE02 WE03 WN02 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C23F 1/20 C23F 1/20 C23G 1/12 C23G 1/12 C25F 3/04 C25F 3/04 B H01G 9 / 055 H01G 9/04 337 9/00 9/24 B (72) Inventor Yoshihito Yoshimura 1006 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Nobuhiro Takeishi 1006 Kadoma, Kadoma, Kadoma, Osaka Inside Matsushita Electric Industrial Co., Ltd. QA01 RA05 RA16 RA17 RA19 SA06 TA01 TA15 TA16 TA20 ZA10 4K057 WA05 WB05 WC05 WC10 WD05 WE02 WE03 WN02
Claims (3)
ットを生成させる前段エッチング工程と、上記前段エッ
チング工程により生成されたピットを拡大する後段エッ
チング工程とからなるアルミ電解コンデンサ用陽極箔の
製造方法であって、前段エッチング工程と後段エッチン
グ工程の間に、アルミニウム箔の表面の皮膜を溶解させ
る酸性水溶液に浸漬する第１の中間処理工程と、アルミ
ニウム箔の表面に皮膜を生成させる水溶液に浸漬する第
２の中間処理工程を設けたアルミ電解コンデンサ用陽極
箔の製造方法。1. A method of manufacturing an anode foil for an aluminum electrolytic capacitor, comprising: a pre-etching step of electrolytically etching an aluminum foil to form pits; and a post-etching step of enlarging the pits generated by the pre-etching step. A first intermediate treatment step of dipping in an acidic aqueous solution that dissolves a film on the surface of the aluminum foil between a first etching step and a second etching step, and a second intermediate treatment of dipping in an aqueous solution for forming a film on the surface of the aluminum foil. A method for producing an anode foil for an aluminum electrolytic capacitor provided with an intermediate treatment step.
酸のうちから選択された少なくとも１種類の酸性水溶液
を用いて行う請求項１に記載のアルミ電解コンデンサ用
陽極箔の製造方法。2. The method for producing an anode foil for an aluminum electrolytic capacitor according to claim 1, wherein the first intermediate treatment step is performed using at least one kind of an acidic aqueous solution selected from hydrochloric acid, hydrofluoric acid and nitric acid.
リン酸、ほう酸のうちから選択された少なくとも１種類
の無機酸水溶液またはシュウ酸、クエン酸、コハク酸、
マロン酸のうちから選択された少なくとも１種類の有機
酸水溶液を用いて行う請求項１に記載のアルミ電解コン
デンサ用陽極箔の製造方法。3. The method according to claim 2, wherein the second intermediate treatment step comprises sulfuric acid, chromic acid,
Phosphoric acid, aqueous solution of at least one inorganic acid selected from boric acid, or oxalic acid, citric acid, succinic acid,
The method for producing an anode foil for an aluminum electrolytic capacitor according to claim 1, wherein the method is performed using at least one kind of an organic acid aqueous solution selected from malonic acid.
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|---|---|---|---|
| JP2000114884A JP3582451B2 (en) | 2000-04-17 | 2000-04-17 | Manufacturing method of anode foil for aluminum electrolytic capacitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000114884A JP3582451B2 (en) | 2000-04-17 | 2000-04-17 | Manufacturing method of anode foil for aluminum electrolytic capacitor |
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| JP3582451B2 JP3582451B2 (en) | 2004-10-27 |
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| JP2005015916A (en) * | 2003-06-03 | 2005-01-20 | Showa Denko Kk | Method of producing aluminum material for electrolytic capacitor electrode, aluminum material for electrolytic capacitor electrode, method of producing electrode material for electrolytic capacitor and aluminum electrolytic capacitor |
| JP2008258232A (en) * | 2007-03-31 | 2008-10-23 | Nippon Chemicon Corp | Electrode material for electrolytic capacitor |
| JP2015079913A (en) * | 2013-10-18 | 2015-04-23 | ニチコン株式会社 | Method for manufacturing electrode foil for electrolytic capacitor |
| CN109183053A (en) * | 2018-09-18 | 2019-01-11 | 山东龙口三元铝材有限公司 | A kind of flexibility treatment fluid and its method for handling pull ring material |
| CN112133563A (en) * | 2020-09-29 | 2020-12-25 | 新疆众和股份有限公司 | Six-stage formation process of high-capacity low-leakage medium-voltage anode foil |
-
2000
- 2000-04-17 JP JP2000114884A patent/JP3582451B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015916A (en) * | 2003-06-03 | 2005-01-20 | Showa Denko Kk | Method of producing aluminum material for electrolytic capacitor electrode, aluminum material for electrolytic capacitor electrode, method of producing electrode material for electrolytic capacitor and aluminum electrolytic capacitor |
| JP2008258232A (en) * | 2007-03-31 | 2008-10-23 | Nippon Chemicon Corp | Electrode material for electrolytic capacitor |
| JP2015079913A (en) * | 2013-10-18 | 2015-04-23 | ニチコン株式会社 | Method for manufacturing electrode foil for electrolytic capacitor |
| CN109183053A (en) * | 2018-09-18 | 2019-01-11 | 山东龙口三元铝材有限公司 | A kind of flexibility treatment fluid and its method for handling pull ring material |
| CN112133563A (en) * | 2020-09-29 | 2020-12-25 | 新疆众和股份有限公司 | Six-stage formation process of high-capacity low-leakage medium-voltage anode foil |
| CN112133563B (en) * | 2020-09-29 | 2021-08-03 | 新疆众和股份有限公司 | Six-stage formation process of high-capacity low-leakage medium-voltage anode foil |
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|---|---|
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