JP2007227770A - Manufacturing method of anode foil for electrolytic capacitor - Google Patents

Manufacturing method of anode foil for electrolytic capacitor Download PDF

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JP2007227770A
JP2007227770A JP2006048621A JP2006048621A JP2007227770A JP 2007227770 A JP2007227770 A JP 2007227770A JP 2006048621 A JP2006048621 A JP 2006048621A JP 2006048621 A JP2006048621 A JP 2006048621A JP 2007227770 A JP2007227770 A JP 2007227770A
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anode foil
electrolytic capacitor
etching
cleaning
producing
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JP4690221B2 (en
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Takeshi Ichikawa
武志 市川
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Nichicon Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of manufacturing an anode foil for an electrolytic capacitor with high capacity by removing sulfate ions preventing efficient hole diameter expansion in an etching process. <P>SOLUTION: The manufacturing method of the anode foil for the electrolytic capacitor includes a pre-treatment process for removing a surface oxide film of aluminum foil, a first stage etching process for generating a tunnelling pit using an etching liquid containing sulphuric acid, and a second stage etching process for expanding a hole diameter of the pit generated in the process. A cleaning process for removing the sulfate ions is arranged between the first stage and the second stage etching processes. The above-mentioned cleaning process consists of 3 stages of a first deionized water cleaning, an alkali cleaning, and a second deionized water cleaning. An immersion treatment by an alkaline solution (0.0005-0.002 mol/L) containing at least one type among sodium hydroxide, sodium carbonate, and sodium silicate is performed in the alkali cleaning process. A sulfate ion content of the deionized water in the second deionized water cleaning process is set to be 0.05 ppm or less. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明はアルミニウム電解コンデンサ（以下、電解コンデンサと称す）に用いられる陽極箔の製造方法であり、特に中高圧用の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。   The present invention relates to a method for producing an anode foil used for an aluminum electrolytic capacitor (hereinafter referred to as an electrolytic capacitor), and particularly relates to a method for producing an anode foil for an electrolytic capacitor for medium to high pressure.

電解コンデンサの静電容量を高めるには、その構成要素の１つとして用いられる陽極箔の実効表面積を拡大することにより、陽極箔の単位面積当たりの静電容量を高める必要がある。   In order to increase the capacitance of the electrolytic capacitor, it is necessary to increase the capacitance per unit area of the anode foil by expanding the effective surface area of the anode foil used as one of its constituent elements.

陽極箔の実効表面積を拡大するには、硫酸、塩酸、硝酸、リン酸、シュウ酸の中から１種類以上を溶解した水溶液中で化学的または電気化学的にエッチングを行う方法が採られている。
また、中高圧用に使用される陽極箔のエッチング工程は、トンネル状のエッチングピット（以下、ピットと称す）を形成する第１段エッチングと、そのピットを目標とする電圧に適した孔径まで拡大する第２段エッチングに分割して行うのが主流となっており、多数の分散性の良いピットを生成させ、効率よくピットの孔径を拡大させることができる。 In order to increase the effective surface area of the anode foil, a method of chemically or electrochemically etching in an aqueous solution in which at least one of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and oxalic acid is dissolved is employed. .
In addition, the etching process of the anode foil used for medium and high pressures is the first stage etching for forming tunnel-like etching pits (hereinafter referred to as pits), and the pits are expanded to a hole diameter suitable for the target voltage. It is the mainstream to divide into the second-stage etching, and it is possible to generate a large number of pits with good dispersibility and efficiently expand the hole diameter of the pits.

第１段エッチング工程でのピット発生については、アルミニウム箔中の微量元素の利用やエッチング液組成、エッチング条件の変更等、様々な方法により、ピット密度の増加やピット分散性の向上が図られている（例えば非特許文献１参照）。
永田伊佐也、「電解液陰極アルミニウム電解コンデンサ」、日本蓄電器工業株式会社、平成９年２月２４日、第２版、Ｐ２２９−２４１ Regarding the generation of pits in the first-stage etching process, the pit density is increased and the pit dispersibility is improved by various methods such as the use of trace elements in the aluminum foil, the composition of the etchant, and the etching conditions. (For example, refer nonpatent literature 1).
Isaya Nagata, “Electrolyte Cathode Aluminum Electrolytic Capacitor”, Nippon Electric Storage Industrial Co., Ltd., February 24, 1997, Second Edition, P229-241

第２段エッチング工程においては、孔径拡大を行う際に所定の間隔で印加する電流を遮断する休止状態を間欠的に設けるようにすることでピット深さ方向で均一な孔径拡大を行う方法が採られている（例えば特許文献１参照）。
特開平１１−３０７３９９号公報 In the second-stage etching process, a method of uniformly expanding the hole diameter in the pit depth direction is adopted by intermittently providing a resting state that interrupts the current applied at a predetermined interval when the hole diameter is expanded. (See, for example, Patent Document 1).
JP-A-11-307399

上記の２段階エッチングにおいて、第１段エッチング工程で硫酸を溶解したエッチング液を使用すると、第１段エッチング終了後、エッチング箔の表面から深部にかけて硫酸イオンが付着する。
上記の硫酸イオンは、第２段エッチング工程で孔径拡大する際、均一な孔径拡大の妨げになり、静電容量の低下をもたらすため、第１段エッチング工程後にこれを除去する効果的な方法が求められていた。 In the above-described two-stage etching, when an etching solution in which sulfuric acid is dissolved in the first-stage etching process is used, sulfate ions adhere from the surface of the etching foil to the deep portion after the completion of the first-stage etching.
When the above-mentioned sulfate ion enlarges the hole diameter in the second-stage etching step, it interferes with the uniform hole diameter enlargement and causes a decrease in the capacitance. Therefore, an effective method for removing this after the first-stage etching step is an effective method. It was sought after.

本発明は、第１段エッチング工程後に、エッチング表面から深部にかけて付着した硫酸イオンを除去することにより、第２段エッチング工程にて効率的な孔径拡大を行い、単位面積当たりの静電容量をより高めることができる電極箔を提供するものである。
すなわち、アルミニウム箔の表面酸化皮膜を除去する前処理工程と、硫酸を含んだエッチング液を使用し、トンネル状ピットを発生させる第１段エッチング工程と、該工程で発生したピットの孔径を拡大するための第２段エッチング工程とを有する電解コンデンサ用陽極箔の製造方法において、
第１段エッチング工程と第２段エッチング工程との間に、硫酸イオンを除去する洗浄工程を設けたことを特徴とする電解コンデンサ用陽極箔の製造方法である。 In the present invention, after the first stage etching step, sulfate ions adhering from the etching surface to the deep part are removed, thereby efficiently expanding the hole diameter in the second stage etching step, thereby further increasing the capacitance per unit area. An electrode foil that can be increased is provided.
That is, a pretreatment process for removing the surface oxide film of the aluminum foil, a first stage etching process for generating tunnel-like pits using an etching solution containing sulfuric acid, and a hole diameter of the pits generated in the process is expanded. In the manufacturing method of the anode foil for electrolytic capacitors having the second stage etching step for
A method for producing an anode foil for an electrolytic capacitor, characterized in that a cleaning step for removing sulfate ions is provided between the first step etching step and the second step etching step.

また、第１段エッチングに使用するエッチング液が、硫酸に、塩酸、硝酸、リン酸、シュウ酸のうち少なくとも１種類を溶解してなることを特徴とする電解コンデンサ用陽極箔の製造方法である。   The method for producing an anode foil for an electrolytic capacitor is characterized in that an etching solution used for the first stage etching is obtained by dissolving at least one of hydrochloric acid, nitric acid, phosphoric acid, and oxalic acid in sulfuric acid. .

さらに、上記洗浄工程が、第１の純水洗浄工程、アルカリ洗浄工程、第２の純水洗浄工程の３段からなることを特徴とする電解コンデンサ用陽極箔の製造方法である。   Further, the method for producing an anode foil for an electrolytic capacitor is characterized in that the cleaning step comprises three stages of a first pure water cleaning step, an alkali cleaning step, and a second pure water cleaning step.

そして、第２の純水洗浄工程において、純水の硫酸イオン含有量が０．０５ｐｐｍ以下であることを特徴とする電解コンデンサ用陽極箔の製造方法である。   And in the 2nd pure water washing process, the sulfate ion content of pure water is 0.05 ppm or less, It is a manufacturing method of the anode foil for electrolytic capacitors characterized by the above-mentioned.

また、上記アルカリ洗浄工程が、水酸化ナトリウム、炭酸ナトリウム、ケイ酸ナトリウムのうち少なくとも１種類を含むアルカリ性溶液への浸漬処理にて行われることを特徴とする電解コンデンサ用陽極箔の製造方法である。   The alkaline cleaning step is a method for producing an anode foil for an electrolytic capacitor, wherein the alkaline cleaning step is performed by an immersion treatment in an alkaline solution containing at least one of sodium hydroxide, sodium carbonate, and sodium silicate. .

さらに、上記アルカリ性溶液の濃度が、０．０００５〜０．００２ｍｏｌ/Ｌであることを特徴とする電解コンデンサ用陽極箔の製造方法である。   Furthermore, it is the manufacturing method of the anode foil for electrolytic capacitors characterized by the density | concentration of the said alkaline solution being 0.0005-0.002 mol / L.

そして、上記アルカリ洗浄工程におけるアルカリ性溶液への浸漬温度が、３５〜６０℃であることを特徴とする電解コンデンサ用陽極箔の製造方法である。   And the immersion temperature in the alkaline solution in the said alkali washing process is 35-60 degreeC, It is a manufacturing method of the anode foil for electrolytic capacitors characterized by the above-mentioned.

また、上記アルカリ洗浄工程におけるアルカリ性溶液への浸漬時間が、１５〜６０秒であることを特徴とする電解コンデンサ用陽極箔の製造方法である。   In the method for producing an anode foil for an electrolytic capacitor, the immersion time in the alkaline solution in the alkali cleaning step is 15 to 60 seconds.

本発明の電解コンデンサ用陽極箔の製造方法によれば、第１段エッチング工程（トンネルピット発生工程）と、第２段エッチング工程（化成電圧に応じた孔径までピットを拡大する工程）との間に、純水洗浄工程、アルカリ洗浄工程、純水洗浄工程の３段からなる、硫酸イオン除去のための洗浄工程を設けることにより、効率的な孔径拡大を行うことができ、陽極箔の静電容量を向上させることができる。   According to the method for producing an anode foil for an electrolytic capacitor of the present invention, between the first-stage etching step (tunnel pit generation step) and the second-stage etching step (step of expanding pits to the hole diameter corresponding to the formation voltage). In addition, by providing a cleaning process for removing sulfate ions consisting of three stages of a pure water cleaning process, an alkali cleaning process, and a pure water cleaning process, the pore diameter can be increased efficiently, and the electrostatic capacity of the anode foil can be increased. Capacity can be improved.

以下、本発明の実施例について詳述する。   Examples of the present invention will be described in detail below.

［実施例１、４、１３、１５、１６］アルカリ性溶液の濃度比較
純度９９．９９％、厚さ１１０μｍの高純度軟質アルミニウム箔を、１ｍｏｌ/Ｌのリン酸溶液に１分間浸漬して前処理を行った。
次に、第１段エッチング工程として、硫酸３．０ｍｏｌ／Ｌ、塩化アルミニウム１．０ｍｏｌ／Ｌの混合溶液を７５℃に加熱し、該溶液中で、上記のアルミニウム箔に電流密度０．２Ａ／ｃｍ２、電気量１８Ｃ／ｃｍ２にて、直流電流を印加し、第１段エッチングを行った。
第１段エッチング後、硫酸イオン含有量０．０５ｐｐｍ以下の純水を注水した純水洗浄槽中で３分間浸漬洗浄を行い、その後、０．０００３〜０．００３ｍｏｌ／Ｌ、４５℃の水酸化ナトリウム水溶液に１５秒間浸漬した後、再度、硫酸イオン含有量が０．０５ｐｐｍ以下の純水に浸漬し、３分間洗浄を行った。
続いて、第２段エッチング工程として、塩酸０．５０ｍｏｌ／Ｌ、塩化アルミニウム１．０ｍｏｌ／Ｌの混合溶液を８５℃に加熱し、上記の洗浄を終えたエッチング箔を１５分間浸漬してピットの孔径拡大を行い、水洗、脱塩素処理を施し、エッチング箔試料を作製した。 [Examples 1, 4, 13, 15, 16] Concentration comparison of alkaline solution Pretreatment by immersing a high-purity soft aluminum foil having a purity of 99.99% and a thickness of 110 μm in a 1 mol / L phosphoric acid solution for 1 minute Went.
Next, as a first stage etching step, a mixed solution of sulfuric acid 3.0 mol / L and aluminum chloride 1.0 mol / L is heated to 75 ° C., and the current density is 0.2 A / First-stage etching was performed by applying a direct current at cm 2 and an electric quantity of 18 C / cm 2 .
After the first stage etching, immersion cleaning is performed for 3 minutes in a pure water cleaning tank into which pure water having a sulfate ion content of 0.05 ppm or less is poured, and then 0.0003 to 0.003 mol / L, hydroxylated at 45 ° C. After dipping in a sodium aqueous solution for 15 seconds, it was again dipped in pure water having a sulfate ion content of 0.05 ppm or less and washed for 3 minutes.
Subsequently, as the second stage etching step, a mixed solution of hydrochloric acid 0.50 mol / L and aluminum chloride 1.0 mol / L was heated to 85 ° C., and the etching foil after the above cleaning was immersed for 15 minutes to remove pits. The pore size was expanded, washed with water and dechlorinated, to prepare an etching foil sample.

［実施例５、６、８、１１、１２］アルカリ性溶液への浸漬温度比較
水酸化ナトリウム水溶液の濃度を０．００１ｍｏｌ／Ｌ、浸漬時間を３０秒に固定し、浸漬温度を３０〜７０℃の範囲で変更した以外は、実施例１と同様の方法でエッチング箔試料を作製した。 [Examples 5, 6, 8, 11, 12] Comparison of immersion temperature in alkaline solution The concentration of the aqueous sodium hydroxide solution was fixed to 0.001 mol / L, the immersion time was fixed to 30 seconds, and the immersion temperature was 30 to 70 ° C. An etching foil sample was prepared in the same manner as in Example 1 except that the range was changed.

［実施例４、７〜１０］アルカリ性溶液への浸漬時間比較
水酸化ナトリウム水溶液の濃度を０．００１ｍｏｌ／Ｌに固定し、浸漬時間を１０〜７０秒の範囲で変更した以外は、実施例１と同様の方法でエッチング箔試料を作製した。 [Examples 4 and 7 to 10] Comparison of immersion time in alkaline solution Example 1 except that the concentration of the sodium hydroxide aqueous solution was fixed at 0.001 mol / L and the immersion time was changed in the range of 10 to 70 seconds. Etching foil samples were prepared in the same manner as described above.

［実施例２、３、１４］
上記実施例以外に、水酸化ナトリウム水溶液の濃度を０．０００５ｍｏｌ／Ｌ、浸漬温度を４５℃に固定し、浸漬時間を３０、６０秒としたもの（実施例２、３）、水酸化ナトリウム水溶液の濃度を０．００２ｍｏｌ／Ｌ、水酸化ナトリウム水溶液の濃度を０．００１ｍｏｌ／Ｌ、浸漬温度を６０℃、浸漬時間を６０秒としたもの（実施例１４）についてもエッチング箔試料を作製した。 [Examples 2, 3, and 14]
In addition to the above examples, the concentration of the sodium hydroxide aqueous solution was 0.0005 mol / L, the immersion temperature was fixed at 45 ° C., and the immersion time was 30 to 60 seconds (Examples 2 and 3). Etching foil samples were also prepared for those having a concentration of 0.002 mol / L, a sodium hydroxide aqueous solution concentration of 0.001 mol / L, an immersion temperature of 60 ° C., and an immersion time of 60 seconds (Example 14).

［実施例１７］純水中の硫酸イオン濃度比較
純水洗浄工程の純水中の硫酸イオン濃度を０．１０ｐｐｍとした以外は、実施例８と同様の方法でエッチング箔試料を作製した。 [Example 17] Comparison of sulfate ion concentration in pure water Etching foil samples were prepared in the same manner as in Example 8 except that the sulfate ion concentration in pure water in the pure water washing step was changed to 0.10 ppm.

［実施例１８、１９］アルカリの種類による比較
アルカリ洗浄に用いるアルカリの種類を、炭酸ナトリウム、ケイ酸ナトリウム（一例としてオルトケイ酸ナトリウム）とした以外は、実施例８と同様の方法でエッチング箔試料を作製した。 [Examples 18 and 19] Comparison by type of alkali Etching foil sample in the same manner as in Example 8 except that the type of alkali used for alkali cleaning was sodium carbonate or sodium silicate (sodium orthosilicate as an example). Was made.

（比較例１）
上記の第１の純水洗浄とアルカリ洗浄を行わず、硫酸イオン含有量０．０５ｐｐｍ以下の純水にて３分間洗浄を行った以外は、実施例１と同様の方法でエッチング箔試料を作製した。 (Comparative Example 1)
An etching foil sample was prepared in the same manner as in Example 1 except that the first pure water cleaning and the alkali cleaning were not performed, and cleaning was performed for 3 minutes with pure water having a sulfate ion content of 0.05 ppm or less. did.

（比較例２）
上記の洗浄（純水洗浄−アルカリ洗浄−純水洗浄）を行わなかった以外は、実施例１と同様の方法でエッチング箔試料を作製した。 (Comparative Example 2)
An etching foil sample was prepared in the same manner as in Example 1 except that the above cleaning (pure water cleaning-alkali cleaning-pure water cleaning) was not performed.

上記の実施例１〜１９、および比較例１、２のエッチング箔試料について、洗浄工程後（第２段エッチング工程前）のエッチング箔に残留する硫酸イオン量を測定した。測定にはＤｉｏｎｅｘ社製イオンクロマトグラフィーＤＸ−１２０を用いた。その結果を表１〜３に示す。
また、上記のエッチング箔試料（第２段エッチング工程終了後のもの）について、濃度１００ｇ／Ｌ、液温９０℃のホウ酸水溶液中で５４０Ｖ化成を行い、各試料の静電容量をＬＣＲメータにて測定した。その結果を表１〜３に示す。 For the etching foil samples of Examples 1 to 19 and Comparative Examples 1 and 2, the amount of sulfate ions remaining on the etching foil after the cleaning process (before the second stage etching process) was measured. The ion chromatography DX-120 made from Dionex was used for the measurement. The results are shown in Tables 1-3.
Moreover, about said etching foil sample (after the 2nd step etching process completion), 540V chemical conversion is performed in boric acid aqueous solution with a density | concentration of 100 g / L and a liquid temperature of 90 degreeC, and the electrostatic capacitance of each sample is set to an LCR meter. Measured. The results are shown in Tables 1-3.

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［アルカリ性溶液の濃度比較］実施例１、４、１３、１５、１６
表１から明らかなように、水酸化ナトリウム水溶液の濃度は、０．０００５〜０．００２ｍｏｌ／Ｌの範囲が好適である。０．０００３ｍｌ／Ｌでは、洗浄効果が十分でなく硫酸イオンが残留するため、静電容量が低下し（実施例１５）、０．００３ｍｌ／Ｌでは、水酸化ナトリウムによる過溶解や皮膜形成が起こり、静電容量が低下する傾向がある（実施例１６）。 [Concentration comparison of alkaline solution] Examples 1, 4, 13, 15, 16
As apparent from Table 1, the concentration of the sodium hydroxide aqueous solution is preferably in the range of 0.0005 to 0.002 mol / L. At 0.0003 ml / L, the cleaning effect is not sufficient and sulfate ions remain, so the capacitance decreases (Example 15). At 0.003 ml / L, overdissolution and film formation by sodium hydroxide occur. There is a tendency for the capacitance to decrease (Example 16).

［アルカリ性溶液への浸漬温度比較］実施例５、６、８、１１、１２
表１から明らかなように、水酸化ナトリウム水溶液への浸漬温度は、３５〜６０℃の範囲が好適である。３０℃では、洗浄効果が十分でなく硫酸イオンが残留するため、静電容量が低下し（実施例５）、７０℃では、水酸化ナトリウムによる過溶解や皮膜形成が起こり、静電容量が低下する傾向がある（実施例１２）。 [Comparison of immersion temperature in alkaline solution] Examples 5, 6, 8, 11, 12
As is apparent from Table 1, the immersion temperature in the aqueous sodium hydroxide solution is preferably in the range of 35 to 60 ° C. At 30 ° C., the cleaning effect is not sufficient, and sulfate ions remain, resulting in a decrease in capacitance (Example 5). At 70 ° C., overdissolution and film formation by sodium hydroxide occur, resulting in a decrease in capacitance. (Example 12).

［アルカリ性溶液への浸漬時間比較］実施例４、７〜１０
表１から明らかなように、水酸化ナトリウム水溶液への浸漬時間は、１５〜６０秒の範囲が好適である。１０秒では、洗浄効果が十分でなく硫酸イオンが残留するため、静電容量が低下する（実施例７）。また、７０秒としても、硫酸イオンの除去効果は６０秒の場合と変わらないので、工数がかかる（実施例１０）。 [Comparison of immersion time in alkaline solution] Examples 4, 7 to 10
As apparent from Table 1, the immersion time in the aqueous sodium hydroxide solution is preferably in the range of 15 to 60 seconds. In 10 seconds, the cleaning effect is not sufficient and sulfate ions remain, so that the capacitance decreases (Example 7). Moreover, even if it is 70 seconds, since the removal effect of a sulfate ion is not different from the case of 60 seconds, a man-hour is required (Example 10).

［純水洗浄液の硫酸イオン濃度比較］実施例１７
表１から明らかなように、純水洗浄液の硫酸イオン濃度が０．１０ｐｐｍでは、硫酸イオンが多すぎるため、静電容量が低下してしまう。よって、硫酸イオン濃度は０．０５ｐｐｍ以下とするのが適当である。 [Comparison of sulfate ion concentration in pure water cleaning solution] Example 17
As is clear from Table 1, when the sulfuric acid ion concentration of the pure water cleaning liquid is 0.10 ppm, the amount of sulfuric acid ions is too large, and thus the capacitance decreases. Therefore, it is appropriate that the sulfate ion concentration is 0.05 ppm or less.

［アルカリの種類による比較］実施例１８、１９
表２、３から明らかなように、アルカリ洗浄に用いるアルカリの種類を、炭酸ナトリウム、ケイ酸ナトリウムとした場合も、水酸化ナトリウムを使用した実施例８と同様の効果が得られることが分かる。 [Comparison by type of alkali] Examples 18 and 19
As is apparent from Tables 2 and 3, it is understood that the same effect as in Example 8 using sodium hydroxide can be obtained even when the type of alkali used for alkali cleaning is sodium carbonate or sodium silicate.

上記のアルカリ洗浄を行わず、硫酸イオン含有量０．０５ｐｐｍ以下の純水にて３分間洗浄した比較例１、上記のアルカリ洗浄および純水洗浄を行わなかった比較例２は、いずれも、硫酸イオンが多量残留するため、静電容量が低下した。   Comparative Example 1 in which the above alkaline cleaning was not performed, and cleaning was performed for 3 minutes with pure water having a sulfate ion content of 0.05 ppm or less, and Comparative Example 2 in which the above alkaline cleaning and pure water cleaning were not performed were both sulfuric acid Since a large amount of ions remained, the capacitance decreased.

なお、上記実施例１９では、ケイ酸ナトリウムとして、オルトケイ酸ナトリウムを使用したが、これ以外に、メタケイ酸ナトリウム、二ケイ酸ナトリウム、四ケイ酸ナトリウムを一種または複数種合わせて使用することもできる。   In Example 19, sodium orthosilicate was used as sodium silicate, but in addition to this, sodium metasilicate, sodium disilicate, and sodium tetrasilicate can be used alone or in combination. .

また、上記実施例では第２の純水洗浄槽中の硫酸イオン濃度を０．０５ｐｐｍ以下としたが、第１の純水洗浄を浸漬とする場合、洗浄槽中の硫酸イオンを０．０５ｐｐｍ以下とすれば、箔に付着してアルカリ洗浄槽へ持ち込まれる硫酸イオンが減少するので、より好ましい。   Moreover, in the said Example, although the sulfate ion density | concentration in a 2nd pure water washing tank was 0.05 ppm or less, when making a 1st pure water washing | cleaning into immersion, the sulfate ion in a washing tank is 0.05 ppm or less. This is more preferable because sulfate ions adhering to the foil and brought into the alkali cleaning tank are reduced.

Claims (8)

アルミニウム箔の表面酸化皮膜を除去する前処理工程と、硫酸を含んだエッチング液を使用し、トンネル状ピットを発生させる第１段エッチング工程と、該工程で発生したピットの孔径を拡大するための第２段エッチング工程とを有する電解コンデンサ用陽極箔の製造方法において、
第１段エッチング工程と第２段エッチング工程との間に、硫酸イオンを除去する洗浄工程を設けたことを特徴とする電解コンデンサ用陽極箔の製造方法。 A pretreatment process for removing the surface oxide film on the aluminum foil, a first-stage etching process for generating tunnel-like pits using an etching solution containing sulfuric acid, and for expanding the hole diameter of the pits generated in the process In the method of manufacturing an anode foil for an electrolytic capacitor having a second stage etching step,
A method for producing an anode foil for an electrolytic capacitor, wherein a cleaning step for removing sulfate ions is provided between the first step etching step and the second step etching step. 第１段エッチング工程に使用するエッチング液が、硫酸に、塩酸、硝酸、リン酸、シュウ酸のうち少なくとも１種類を溶解してなることを特徴とする請求項１に記載の電解コンデンサ用陽極箔の製造方法。   2. The anode foil for an electrolytic capacitor according to claim 1, wherein an etching solution used in the first stage etching step is obtained by dissolving at least one of hydrochloric acid, nitric acid, phosphoric acid, and oxalic acid in sulfuric acid. Manufacturing method. 上記洗浄工程が、第１の純水洗浄工程、アルカリ洗浄工程、第２の純水洗浄工程の３段からなることを特徴とする請求項１に記載の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 electrolytic capacitor according to claim 1, wherein the cleaning step includes three stages of a first pure water cleaning step, an alkali cleaning step, and a second pure water cleaning step. 第２の純水洗浄工程において、純水の硫酸イオン含有量が０．０５ｐｐｍ以下であることを特徴とする請求項３に記載の電解コンデンサ用陽極箔の製造方法。   The method for producing an anode foil for an electrolytic capacitor according to claim 3, wherein the sulfate ion content of pure water is 0.05 ppm or less in the second pure water cleaning step. 上記アルカリ洗浄工程が、水酸化ナトリウム、炭酸ナトリウム、ケイ酸ナトリウムのうち少なくとも１種類を含むアルカリ性溶液への浸漬処理にて行われることを特徴とする請求項３に記載の電解コンデンサ用陽極箔の製造方法。   The said alkaline washing | cleaning process is performed by the immersion process in the alkaline solution containing at least 1 sort (s) among sodium hydroxide, sodium carbonate, and sodium silicate, The anode foil for electrolytic capacitors of Claim 3 characterized by the above-mentioned. Production method. 上記アルカリ性溶液の濃度が、０．０００５〜０．００２ｍｏｌ/Ｌであることを特徴とする請求項５に記載の電解コンデンサ用陽極箔の製造方法。   6. The method for producing an anode foil for an electrolytic capacitor according to claim 5, wherein the concentration of the alkaline solution is 0.0005 to 0.002 mol / L. 上記アルカリ洗浄工程におけるアルカリ性溶液への浸漬温度が、３５〜６０℃であることを特徴とする請求項５に記載の電解コンデンサ用陽極箔の製造方法。   6. The method for producing an anode foil for an electrolytic capacitor according to claim 5, wherein the immersion temperature in the alkaline solution in the alkali cleaning step is 35 to 60 ° C. 6. 上記アルカリ洗浄工程におけるアルカリ性溶液への浸漬時間が、１５〜６０秒であることを特徴とする請求項５に記載の電解コンデンサ用陽極箔の製造方法。   6. The method for producing an anode foil for an electrolytic capacitor according to claim 5, wherein the immersion time in the alkaline solution in the alkali cleaning step is 15 to 60 seconds.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101026664B1 (en) 2008-10-15 2011-04-04 한국제이씨씨(주) ETCHANT MANUFACTURING METHOD BY AC ELECTROLYTIC ETCHING BASED ON HCl WITH ETHYLENE GLYCOL AND PROPYLENE GLYCOL ADDITIVES
CN114540932A (en) * 2022-03-02 2022-05-27 南通海星电子股份有限公司 Process method for improving uniformity of electrode foil pores

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Publication number Priority date Publication date Assignee Title
JPH043409A (en) * 1990-04-20 1992-01-08 Elna Co Ltd Method of etching aluminum foil for electrolytic capacitor
JP2005264288A (en) * 2004-03-22 2005-09-29 Matsushita Electric Ind Co Ltd Method for manufacturing etched foil for aluminum electrolytic capacitor, the etched foil, and chemical foil thereof

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
JPH043409A (en) * 1990-04-20 1992-01-08 Elna Co Ltd Method of etching aluminum foil for electrolytic capacitor
JP2005264288A (en) * 2004-03-22 2005-09-29 Matsushita Electric Ind Co Ltd Method for manufacturing etched foil for aluminum electrolytic capacitor, the etched foil, and chemical foil thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101026664B1 (en) 2008-10-15 2011-04-04 한국제이씨씨(주) ETCHANT MANUFACTURING METHOD BY AC ELECTROLYTIC ETCHING BASED ON HCl WITH ETHYLENE GLYCOL AND PROPYLENE GLYCOL ADDITIVES
CN114540932A (en) * 2022-03-02 2022-05-27 南通海星电子股份有限公司 Process method for improving uniformity of electrode foil pores
CN114540932B (en) * 2022-03-02 2023-09-08 南通海星电子股份有限公司 Technological method for improving uniformity of electrode foil hole forming

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