JPH0574663A - Manufacture of electrode foil for aluminum electrolytic capacitor - Google Patents
Manufacture of electrode foil for aluminum electrolytic capacitorInfo
- Publication number
- JPH0574663A JPH0574663A JP3261063A JP26106391A JPH0574663A JP H0574663 A JPH0574663 A JP H0574663A JP 3261063 A JP3261063 A JP 3261063A JP 26106391 A JP26106391 A JP 26106391A JP H0574663 A JPH0574663 A JP H0574663A
- Authority
- JP
- Japan
- Prior art keywords
- foil
- immersed
- minutes
- aqueous solution
- boric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
(57)【要約】
【目的】より高い静電容量が得られることができるよう
にしたアルミニウム電解コンデンサ用電極箔の製造方法
を提供すること。
【構成】エッチングされたアルミニウム箔を高温の純水
中に所定時間浸漬してボイル処理した後、リン酸または
リン酸塩水溶液中に浸漬し、続いて少なくともカルボン
酸またはその塩を含有するホウ酸水溶液中にそのアルミ
ニウム箔を浸漬して陽極酸化する。(57) [Abstract] [Purpose] To provide a method of manufacturing an electrode foil for an aluminum electrolytic capacitor, which is capable of obtaining a higher capacitance. [Structure] After the etched aluminum foil is immersed in high temperature pure water for a predetermined time to boil it, it is immersed in phosphoric acid or an aqueous solution of phosphate, and then boric acid containing at least carboxylic acid or its salt. The aluminum foil is immersed in an aqueous solution and anodized.
Description
【０００１】[0001]
【産業上の利用分野】本発明はアルミニウム電解コンデ
ンサ用電極箔の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an electrode foil for aluminum electrolytic capacitors.
【０００２】[0002]
【従来の技術】一般に、この種の電極箔は次のようにし
て製造されている。先ず、エッチングされ、かつ純水中
でボイル処理されたアルミニウム箔を用意し、このアル
ミニウム箔をリン酸やホウ酸などの水溶液中において一
定の電圧を印加して所望の厚さの酸化皮膜を生成させ
る。そして、酸またはアルカリ水溶液中に浸漬する減極
処理および数１００℃の高温雰囲気中に数分間放置する
熱処理工程を行なう。これら化成処理、減極処理、熱処
理は通常数回繰り返される。2. Description of the Related Art Generally, this type of electrode foil is manufactured as follows. First, prepare an aluminum foil that has been etched and boiled in pure water, and apply a constant voltage to this aluminum foil in an aqueous solution of phosphoric acid or boric acid to form an oxide film of the desired thickness. Let Then, a depolarization process of immersing in an acid or alkali aqueous solution and a heat treatment process of leaving it in a high temperature atmosphere of several 100 ° C. for several minutes are performed. These chemical conversion treatment, depolarization treatment, and heat treatment are usually repeated several times.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、この方
法では静電容量を高めるのに限度があり、最近とみに要
望されている、より一層の小形かつ高容量化に応えるこ
とができない。However, this method has a limit in increasing the electrostatic capacity, and it is not possible to meet the recent demand for smaller size and higher capacity.
【０００４】本発明はこのような事情に鑑みなされたも
ので、より高い静電容量が得られることができるように
したアルミニウム電解コンデンサ用電極箔の製造方法を
提供することにある。The present invention has been made in view of the above circumstances, and an object thereof is to provide a method of manufacturing an electrode foil for an aluminum electrolytic capacitor, which is capable of obtaining a higher electrostatic capacity.
【０００５】[0005]
【課題を解決するための手段】上記した目的を達成する
ために、請求項１においては、エッチングされたアルミ
ニウム箔を高温の純水中に所定時間浸漬してボイル処理
した後、リン酸またはリン酸塩水溶液中に浸漬し、続い
て少なくともカルボン酸またはその塩を含有するホウ酸
水溶液中にそのアルミニウム箔を浸漬して陽極酸化する
ことを特徴としている。In order to achieve the above-mentioned object, in the first aspect of the present invention, the etched aluminum foil is immersed in high temperature pure water for a predetermined time and boiled, and then phosphoric acid or phosphorus is added. It is characterized in that the aluminum foil is immersed in an aqueous acid salt solution, and subsequently, the aluminum foil is anodized in a boric acid aqueous solution containing at least a carboxylic acid or a salt thereof.
【０００６】また請求項２では、エッチングされたアル
ミニウム箔を高温の純水中に所定時間浸漬してボイル処
理した後、リン酸またはリン酸塩水溶液中に浸漬し、続
いて本化成工程を行ない、さらに再化成工程を行なうア
ルミニウム電解コンデンサ用電極箔の製造方法におい
て、上記再化成工程では少なくともカルボン酸またはそ
の塩を含有するホウ酸水溶液を用いて陽極酸化を行なう
ことを特徴としている。According to a second aspect of the present invention, the etched aluminum foil is immersed in high temperature pure water for a predetermined period of time to be boiled, and then immersed in an aqueous solution of phosphoric acid or a phosphoric acid salt. In the method for manufacturing an electrode foil for an aluminum electrolytic capacitor, which further includes a re-formation step, the re-formation step is characterized in that anodic oxidation is performed using an aqueous boric acid solution containing at least a carboxylic acid or a salt thereof.
【０００７】さらに請求項３においては、エッチングさ
れたアルミニウム箔を高温の純水中に所定時間浸漬して
ボイル処理した後、リン酸またはリン酸塩水溶液中に浸
漬し、続いて本化成工程を行ない、さらに再化成工程を
行なうアルミニウム電解コンデンサ用電極箔の製造方法
において、上記本化成工程および上記再化成工程のいず
れにおいても、少なくとも一度はカルボン酸またはその
塩を含むホウ酸水溶液中で化成することを特徴としてい
る。Further, according to a third aspect of the present invention, the etched aluminum foil is immersed in high temperature pure water for a predetermined period of time to be boiled, and then immersed in an aqueous solution of phosphoric acid or a phosphoric acid salt. In the method for producing an electrode foil for an aluminum electrolytic capacitor, which further comprises a re-formation step, in both the main formation step and the re-formation step, formation is performed at least once in a boric acid aqueous solution containing a carboxylic acid or a salt thereof. It is characterized by
【０００８】本化成および再化成は、必要に応じて数回
繰り返されるが、その場合、例えば最初にアルミニウム
箔をホウ酸水溶液中に浸漬し、所定時間電圧を印加して
第１の陽極酸化（本化成処理）を行ない、必要に応じて
減極処理を行なった後、引き続きそのアルミニウム箔を
カルボン酸またはその塩を含有するホウ酸水溶液中に浸
漬し、所定時間電圧を印加して第２の陽極酸化（再化成
処理）を行なう。これとは反対に上記の第１の陽極酸化
工程と第２の陽極酸化工程とを入れ替えてもよい。This chemical conversion and re-chemical conversion are repeated several times as needed. In this case, for example, the aluminum foil is first immersed in an aqueous boric acid solution, and a voltage is applied for a predetermined time to carry out the first anodic oxidation ( After performing this chemical conversion treatment) and performing depolarization treatment as needed, the aluminum foil is subsequently immersed in a boric acid aqueous solution containing a carboxylic acid or a salt thereof, and a voltage is applied for a predetermined time to produce a second Anodize (reformation treatment). On the contrary, the first anodic oxidation process and the second anodic oxidation process may be interchanged.
【０００９】ここで使用されるカルボン酸としては、例
えばコハク酸、グルタル酸、アジピン酸、ピメリン酸、
スベリン酸、アゼライン酸、セバシン酸などの脂肪族飽
和ジカルボン酸や、クエン酸、酒石酸、リンゴ酸、乳
酸、グリコール酸、グリセリン酸などの脂肪族オキシカ
ルボン酸、フマル酸、マレイン酸、シトラコン酸などの
脂肪族不飽和ジカルボン酸、フタル酸、ニトロフタル
酸、テトラヒドロフタル酸などの環状ジカルボン酸、ポ
リアクリル酸、ポリメタアクリル酸、ポリエチレンスル
ホン酸、ポリスチレンスルホン酸などの高分子酸などを
使用できる。また、その塩としては例えばこれらのアン
モニウム塩や第１〜３級アミン塩、第４級アンモニウム
塩などを使用できる。上記高分子酸またはその塩の分子
量は２００〜１０００００、溶解のし易さを考慮する
と、一般に分子量は４００〜４００００が好ましい。本
発明においては、カルボン酸またはその塩に代えて、そ
の前駆体を適宜用いてもよい。この場合の前駆体として
は、酸アミド、エステル、酸無水物などが例示される。Examples of the carboxylic acid used here include succinic acid, glutaric acid, adipic acid, pimelic acid,
Such as aliphatic saturated dicarboxylic acids such as suberic acid, azelaic acid and sebacic acid, and aliphatic oxycarboxylic acids such as citric acid, tartaric acid, malic acid, lactic acid, glycolic acid and glyceric acid, fumaric acid, maleic acid and citraconic acid. Cyclic dicarboxylic acids such as aliphatic unsaturated dicarboxylic acids, phthalic acid, nitrophthalic acid, and tetrahydrophthalic acid, and polymeric acids such as polyacrylic acid, polymethacrylic acid, polyethylenesulfonic acid, and polystyrenesulfonic acid can be used. As the salt, for example, these ammonium salts, primary to tertiary amine salts, quaternary ammonium salts and the like can be used. The molecular weight of the above-mentioned polymeric acid or its salt is preferably 200 to 100,000, and in view of easiness of dissolution, the molecular weight is generally preferably 400 to 40,000. In the present invention, a precursor thereof may be appropriately used instead of the carboxylic acid or salt thereof. Examples of the precursor in this case include acid amide, ester, and acid anhydride.
【００１０】上記カルボン酸またはその塩を含有するホ
ウ酸水溶液のｐＨは３〜９、好ましくは４．５〜７に設
定される。このホウ酸水溶液中におけるカルボン酸また
はその塩の濃度は０．００２〜１．０ｗｔ％、液温は７
０〜１００℃が好適である。また、ホウ酸の濃度は０．
５〜１０ｗｔ％が好ましい。The pH of the aqueous boric acid solution containing the carboxylic acid or its salt is set to 3 to 9, preferably 4.5 to 7. The concentration of the carboxylic acid or its salt in this aqueous boric acid solution is 0.002-1.0 wt% and the liquid temperature is 7
0-100 degreeC is suitable. Further, the concentration of boric acid is 0.
5 to 10 wt% is preferable.
【００１１】本化成後に、減極処理、熱処理および再陽
極酸化処理（再化成）が少なくとも１回実施される。そ
の場合、再化成には本化成と同様にカルボン酸またはそ
の塩を含有するホウ酸水溶液を用いることが好ましく、
これによれば、従来法に比べて静電容量が約５％以上増
大する。なお、減極処理にはｐＨ７〜９で液温７０℃の
アンモニア水（濃度０．００１〜０．２ｗｔ％）、また
はｐＨ４〜８のリン酸水溶液（濃度０．１〜８ｗｔ％）
などが用いられ、その浸漬時間は１〜５分間であること
が好ましい。After this formation, depolarization treatment, heat treatment and re-anodizing treatment (reformation) are performed at least once. In that case, it is preferable to use an aqueous boric acid solution containing a carboxylic acid or a salt thereof for the re-chemical conversion,
According to this, the capacitance is increased by about 5% or more as compared with the conventional method. For the depolarization treatment, ammonia water having a pH of 7 to 9 and a liquid temperature of 70 ° C. (concentration of 0.001 to 0.2 wt%) or a phosphoric acid aqueous solution of pH 4 to 8 (concentration of 0.1 to 8 wt%)
Etc. are used, and the immersion time is preferably 1 to 5 minutes.
【００１２】[0012]
【実施例】［実施例１］ （Ａ）先ず、純度９９．９９％で厚さ１００μｍのアル
ミニウムエッチング箔を用意した。この場合、そのエッ
チング倍率はエッチングしていない平坦箔に対して２０
倍である。EXAMPLES Example 1 (A) First, an aluminum etching foil having a purity of 99.99% and a thickness of 100 μm was prepared. In this case, the etching rate is 20 for flat foil that is not etched.
Double.
【００１３】（Ｂ）このアルミニウムエッチング箔を液
温９８℃以上の純水中で１５分間ボイル処理した。(B) This aluminum etching foil was boiled for 15 minutes in pure water having a liquid temperature of 98 ° C. or higher.
【００１４】（Ｃ）ボイル処理したアルミニウムエッチ
ング箔を液温５０℃、１．７ｗｔ％のリン酸水溶液に５
分間浸漬処理した。(C) The boiled aluminum etching foil was immersed in a 1.7 wt% phosphoric acid aqueous solution at a liquid temperature of 50 ° C.
Immersion treatment was performed for a minute.
【００１５】（Ｄ）次に、純水１リットルにホウ酸２０
ｇを溶解しアジピン酸アンモニウム０．１ｇを添加して
なる液温８５℃のホウ酸水溶液中にアルミニウムエッチ
ング箔を浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流
し、化成電圧を１５０Ｖまで上昇させ、同電圧を１０分
間印加して１回目の本化成を行なった。(D) Next, 1 liter of pure water was added with 20 parts of boric acid.
The aluminum etching foil is immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C., which is obtained by dissolving 0.1 g of ammonium adipate and adding 0.1 g of ammonium adipate, and applying a current having a current density of 10 mA / cm 2 to increase the formation voltage to 150 V. The same voltage was applied for 10 minutes to perform the first main chemical conversion.
【００１６】（Ｅ）引き続き、同アルミニウムエッチン
グ箔を同じく純水１リットルにホウ酸２０ｇを溶解しア
ジピン酸アンモニウム０．１ｇを添加してなる液温８５
℃のホウ酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃｍ
2 の電流を流し、化成電圧を２５０Ｖまで上昇させ、同
電圧を１０分間印加して２回目の本化成を行なった。(E) Subsequently, the aluminum etching foil was dissolved in 1 liter of pure water, 20 g of boric acid was dissolved, and 0.1 g of ammonium adipate was added to the solution.
Immersed in boric acid aqueous solution at ℃, current density 10mA / cm
A current of 2 was passed to raise the formation voltage to 250 V, and the same voltage was applied for 10 minutes to perform the second main formation.
【００１７】（Ｆ）さらに、３回目の本化成として、同
アルミニウムエッチング箔を純水１リットルにホウ酸２
０ｇを溶解しアジピン酸アンモニウム０．１ｇを添加し
てなる液温８５℃のホウ酸水溶液中に浸漬し、電流密度
１０ｍＡ／ｃｍ2 の電流を流し、化成電圧を３８０Ｖま
で上昇させ、同電圧を４０分間印加した。(F) Further, as the third main chemical conversion, the same aluminum etching foil was added to 1 liter of pure water and 2 parts of boric acid.
It is immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C., in which 0 g is dissolved and 0.1 g of ammonium adipate is added, and a current having a current density of 10 mA / cm 2 is applied to increase the formation voltage to 380 V. It was applied for 40 minutes.
【００１８】（Ｇ）本化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(G) The aluminum etching foil after the chemical conversion was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes for depolarization treatment.
【００１９】（Ｈ）５００℃の加熱雰囲気中で２分間熱
処理した。(H) Heat treatment was performed in a heating atmosphere of 500 ° C. for 2 minutes.
【００２０】（Ｉ）上記（Ｄ）と同じ条件の水溶液、す
なわち純水１リットルにホウ酸２０ｇを溶解しアジピン
酸アンモニウム０．１ｇを添加してなる液温８５℃のホ
ウ酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃｍ2 の電
流を流し、化成電圧を３８０Ｖまで上昇させ、同電圧を
１３分間印加して１回目の再化成を行なった。(I) Immersion in an aqueous solution of boric acid at a liquid temperature of 85 ° C., which is obtained by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.1 g of ammonium adipate to the solution under the same conditions as in (D) above. Then, a current having a current density of 10 mA / cm 2 was passed, the formation voltage was raised to 380 V, and the same voltage was applied for 13 minutes to perform the first re-formation.
【００２１】（Ｊ）再化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(J) The aluminum etching foil after reforming was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes for depolarization treatment.
【００２２】（Ｋ）５００℃の加熱雰囲気中で２分間熱
処理した。(K) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【００２３】（Ｌ）引き続き、上記（Ｉ）と同じ条件で
２回目の再化成を行なった。(L) Subsequently, the second re-formation was carried out under the same conditions as the above (I).
【００２４】（Ｍ）水洗いし、乾燥させて化成箔の静電
容量を測定したところ、０．９２２μＦ／ｃｍ2 であっ
た。(M) After washing with water and drying, the capacitance of the formed foil was measured and found to be 0.922 μF / cm 2 .
【００２５】（Ｎ）この化成箔（１５ｍｍ×２７０ｍ
ｍ）を陽極とし、一方、純度９９．２％で厚さ２０μ
ｍ、エッチング倍率５０倍のアルミニウム箔（１５ｍｍ
×３００ｍｍ）を陰極とし、セパレータを介して巻回し
て、コンデンサ素子を作成した。そして、このコンデン
サ素子に電解液を含浸させ、ケース内に封入し、定格２
５０Ｖ３７μＦの電解コンデンサを作成したところ、そ
の静電容量は４０．７μＦであった。(N) This formed foil (15 mm × 270 m)
m) as an anode, while the purity is 99.2% and the thickness is 20μ.
m, aluminum foil with an etching magnification of 50 times (15 mm
× 300 mm) was used as a cathode and wound with a separator interposed therebetween to form a capacitor element. Then, this capacitor element is impregnated with an electrolytic solution and sealed in a case, and the rating 2
When a 50V 37 μF electrolytic capacitor was prepared, its electrostatic capacity was 40.7 μF.
【００２６】なお、上記工程（Ｌ）と工程（Ｍ）との間
に、液温３０℃、８５ｗｔ％のリン酸水溶液であって、
アンモニア水でｐＨ６．５に調整した溶液に４分間浸漬
処理を行なう工程を介在させてもよい。この工程を追加
した電解コンデンサは例えば１０５℃、１０００時間の
高温貯蔵試験における製品の漏れ電流による劣化を防止
できる。Between the step (L) and the step (M), an aqueous solution of phosphoric acid having a liquid temperature of 30 ° C. and 85 wt%,
A step of performing a dipping treatment for 4 minutes in a solution adjusted to pH 6.5 with aqueous ammonia may be interposed. The electrolytic capacitor added with this step can prevent deterioration due to leakage current of the product in a high temperature storage test at 105 ° C. for 1000 hours.
【００２７】［実施例２］ （Ａ）先ず、純度９９．９９％で厚さ１００μｍのアル
ミニウムエッチング箔を用意した。この場合、そのエッ
チング倍率はエッチングしていない平坦箔に対して２０
倍である。Example 2 (A) First, an aluminum etching foil having a purity of 99.99% and a thickness of 100 μm was prepared. In this case, the etching rate is 20 for flat foil that is not etched.
Double.
【００２８】（Ｂ）このアルミニウムエッチング箔を液
温９８℃以上の純水中で１５分間ボイル処理した。(B) This aluminum etching foil was boiled for 15 minutes in pure water having a liquid temperature of 98 ° C. or higher.
【００２９】（Ｃ）ボイル処理したアルミニウムエッチ
ング箔を液温５０℃、１．７ｗｔ％のリン酸水溶液に５
分間浸漬処理した。(C) The boiled aluminum etching foil was immersed in a 1.7 wt% phosphoric acid aqueous solution at a liquid temperature of 50 ° C.
Immersion treatment was performed for a minute.
【００３０】（Ｄ）次に、純水１リットルにホウ酸２０
ｇを溶解しクエン酸アンモニウム０．１ｇを添加してな
る液温８５℃のホウ酸水溶液中にアルミニウムエッチン
グ箔を浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流
し、化成電圧を１５０Ｖまで上昇させ、同電圧を１０分
間印加して１回目の本化成を行なった。(D) Next, 1 liter of pure water was added with 20 parts of boric acid.
The aluminum etching foil is immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C. obtained by dissolving g and adding 0.1 g of ammonium citrate, and applying a current having a current density of 10 mA / cm 2 to increase the formation voltage to 150 V. The same voltage was applied for 10 minutes to perform the first main chemical conversion.
【００３１】（Ｅ）引き続き、同アルミニウムエッチン
グ箔を同じく純水１リットルにホウ酸２０ｇを溶解しク
エン酸アンモニウム０．１ｇを添加してなる液温８５℃
のホウ酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃｍ2
の電流を流し、化成電圧を２５０Ｖまで上昇させ、同電
圧を１０分間印加して２回目の本化成を行なった。(E) Subsequently, 20 g of boric acid was dissolved in 1 liter of pure water and 0.1 g of ammonium citrate was added to the aluminum etching foil, and the liquid temperature was 85 ° C.
Current density of 10 mA / cm 2
Was applied to increase the formation voltage to 250 V, and the same voltage was applied for 10 minutes to perform the second main formation.
【００３２】（Ｆ）さらに、３回目の本化成として、同
アルミニウムエッチング箔を純水１リットルにホウ酸２
０ｇを溶解しクエン酸アンモニウム０．１ｇを添加して
なる液温８５℃のホウ酸水溶液中に浸漬し、電流密度１
０ｍＡ／ｃｍ2 の電流を流し、化成電圧を３８０Ｖまで
上昇させ、同電圧を４０分間印加した。(F) Further, as the third main chemical conversion, the same aluminum etching foil was added to 1 liter of pure water and 2 parts of boric acid.
It is immersed in an aqueous boric acid solution having a liquid temperature of 85 ° C., which is obtained by dissolving 0 g and adding 0.1 g of ammonium citrate, and the current density is 1
A current of 0 mA / cm 2 was passed to raise the formation voltage to 380 V, and the same voltage was applied for 40 minutes.
【００３３】（Ｇ）本化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(G) The aluminum etching foil after this chemical conversion was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes for depolarization treatment.
【００３４】（Ｈ）５００℃の加熱雰囲気中で２分間熱
処理した。(H) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【００３５】（Ｉ）上記（Ｄ）と同じ条件の水溶液、す
なわち純水１リットルにホウ酸２０ｇを溶解しクエン酸
アンモニウム０．１ｇを添加してなる液温８５℃のホウ
酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流
を流し、化成電圧を３８０Ｖまで上昇させ、同電圧を１
３分間印加して１回目の再化成を行なった。(I) Immersion in an aqueous solution of the same conditions as in the above (D), that is, in a boric acid aqueous solution having a liquid temperature of 85 ° C. prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.1 g of ammonium citrate. Then, a current having a current density of 10 mA / cm 2 is passed to raise the formation voltage to 380 V, and the same voltage is set to 1
The first re-formation was performed by applying for 3 minutes.
【００３６】（Ｊ）再化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(J) The aluminum etching foil after the re-formation was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes for depolarization treatment.
【００３７】（Ｋ）５００℃の加熱雰囲気中で２分間熱
処理した。(K) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【００３８】（Ｌ）引き続き、上記（Ｉ）と同じ条件で
２回目の再化成を行なった。(L) Subsequently, the second re-formation was carried out under the same conditions as in (I) above.
【００３９】（Ｍ）水洗いし、乾燥させて化成箔の静電
容量を測定したところ、０．９３５μＦ／ｃｍ2 であっ
た。(M) After washing with water and drying, the capacitance of the formed foil was measured and found to be 0.935 μF / cm 2 .
【００４０】（Ｎ）この化成箔（１５ｍｍ×２７０ｍ
ｍ）を陽極として、実施例１と同様、定格２５０Ｖ３７
μＦの電解コンデンサを作成したところ、その静電容量
は４１．２μＦであった。(N) This formed foil (15 mm × 270 m)
m) as an anode, similarly to Example 1, rated 250V37
When a μF electrolytic capacitor was created, its capacitance was 41.2 μF.
【００４１】［実施例３］ （Ａ）先ず、純度９９．９９％で厚さ１００μｍのアル
ミニウムエッチング箔を用意した。この場合、そのエッ
チング倍率はエッチングしていない平坦箔に対して２０
倍である。Example 3 (A) First, an aluminum etching foil having a purity of 99.99% and a thickness of 100 μm was prepared. In this case, the etching rate is 20 for flat foil that is not etched.
Double.
【００４２】（Ｂ）このアルミニウムエッチング箔を液
温９８℃以上の純水中で１５分間ボイル処理した。(B) This aluminum etching foil was boiled in pure water at a liquid temperature of 98 ° C. or higher for 15 minutes.
【００４３】（Ｃ）ボイル処理したアルミニウムエッチ
ング箔を液温５０℃、１．７ｗｔ％のリン酸水溶液に５
分間浸漬処理した。(C) The boiled aluminum etching foil was immersed in a 1.7 wt% phosphoric acid aqueous solution at a liquid temperature of 50 ° C.
Immersion treatment was performed for a minute.
【００４４】（Ｄ）次に、純水１リットルにホウ酸２０
ｇを溶解しフタル酸０．１ｇを添加してなる液温８５℃
のホウ酸水溶液中にアルミニウムエッチング箔を浸漬
し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、化成電圧
を１５０Ｖまで上昇させ、同電圧を１０分間印加して１
回目の本化成を行なった。(D) Next, 1 liter of pure water was added with 20 parts of boric acid.
Liquid temperature of 85 ℃
The aluminum etching foil was dipped in the boric acid aqueous solution described above, a current density of 10 mA / cm 2 was applied, the formation voltage was raised to 150 V, and the same voltage was applied for 10 minutes to obtain 1
The second time this formation was performed.
【００４５】（Ｅ）引き続き、同アルミニウムエッチン
グ箔を同じく純水１リットルにホウ酸２０ｇを溶解しフ
タル酸０．１ｇを添加してなる液温８５℃のホウ酸水溶
液中に浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流
し、化成電圧を２５０Ｖまで上昇させ、同電圧を１０分
間印加して２回目の本化成を行なった。(E) Subsequently, the aluminum etching foil was immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C. prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.1 g of phthalic acid to obtain a current density. A current of 10 mA / cm 2 was passed to raise the formation voltage to 250 V, and the same voltage was applied for 10 minutes to perform the second main formation.
【００４６】（Ｆ）さらに、３回目の本化成として、同
アルミニウムエッチング箔を純水１リットルにホウ酸２
０ｇを溶解しフタル酸０．１ｇを添加してなる液温８５
℃のホウ酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃｍ
2 の電流を流し、化成電圧を３８０Ｖまで上昇させ、同
電圧を４０分間印加した。(F) Further, as the third chemical conversion, the same aluminum etching foil was added to 1 liter of pure water and 2 parts of boric acid.
A liquid temperature of 85, prepared by dissolving 0 g and adding 0.1 g of phthalic acid.
Immersed in boric acid aqueous solution at ℃, current density 10mA / cm
A current of 2 was passed to raise the formation voltage to 380 V, and the same voltage was applied for 40 minutes.
【００４７】（Ｇ）本化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(G) The aluminum etching foil after the chemical conversion was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes for depolarization treatment.
【００４８】（Ｈ）５００℃の加熱雰囲気中で２分間熱
処理した。(H) Heat treatment was performed in a heating atmosphere of 500 ° C. for 2 minutes.
【００４９】（Ｉ）上記（Ｄ）と同じ条件の水溶液、す
なわち純水１リットルにホウ酸２０ｇを溶解しフタル酸
０．１ｇを添加してなる液温８５℃のホウ酸水溶液中に
浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、化成
電圧を３８０Ｖまで上昇させ、同電圧を１３分間印加し
て１回目の再化成を行なった。(I) Immersion in an aqueous solution of the same conditions as in the above (D), that is, in a boric acid aqueous solution having a liquid temperature of 85 ° C. prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.1 g of phthalic acid. Then, a current having a current density of 10 mA / cm 2 was passed, the formation voltage was raised to 380 V, and the same voltage was applied for 13 minutes to perform the first re-formation.
【００５０】（Ｊ）再化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(J) The aluminum etching foil after re-formation was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes to perform depolarization treatment.
【００５１】（Ｋ）５００℃の加熱雰囲気中で２分間熱
処理した。(K) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【００５２】（Ｌ）引き続き、上記（Ｉ）と同じ条件で
２回目の再化成を行なった。(L) Subsequently, the second re-formation was performed under the same conditions as in (I) above.
【００５３】（Ｍ）水洗いし、乾燥させて化成箔の静電
容量を測定したところ、０．９１５μＦ／ｃｍ2 であっ
た。(M) After washing with water and drying, the capacitance of the formed foil was measured and found to be 0.915 μF / cm 2 .
【００５４】（Ｎ）この化成箔（１５ｍｍ×２７０ｍ
ｍ）を陽極として、実施例１と同様、定格２５０Ｖ３７
μＦの電解コンデンサを作成したところ、その静電容量
は４０．４μＦであった。(N) This formed foil (15 mm × 270 m)
m) as an anode, similarly to Example 1, rated 250V37
When a μF electrolytic capacitor was created, its capacitance was 40.4 μF.
【００５５】［実施例４］ （Ａ）先ず、純度９９．９９％で厚さ１００μｍのアル
ミニウムエッチング箔を用意した。この場合、そのエッ
チング倍率はエッチングしていない平坦箔に対して２０
倍である。Example 4 (A) First, an aluminum etching foil having a purity of 99.99% and a thickness of 100 μm was prepared. In this case, the etching rate is 20 for flat foil that is not etched.
Double.
【００５６】（Ｂ）このアルミニウムエッチング箔を液
温９８℃以上の純水中で１５分間ボイル処理した。(B) The aluminum etching foil was boiled for 15 minutes in pure water having a liquid temperature of 98 ° C. or higher.
【００５７】（Ｃ）ボイル処理したアルミニウムエッチ
ング箔を液温５０℃、１．７ｗｔ％のリン酸水溶液に５
分間浸漬処理した。(C) The boiled aluminum etching foil was immersed in a 1.7 wt% phosphoric acid aqueous solution at a liquid temperature of 50 ° C.
Immersion treatment was performed for a minute.
【００５８】（Ｄ）次に、純水１リットルにホウ酸２０
ｇを溶解しフマル酸０．１ｇを添加してなる液温８５℃
のホウ酸水溶液中にアルミニウムエッチング箔を浸漬
し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、化成電圧
を１５０Ｖまで上昇させ、同電圧を１０分間印加して１
回目の本化成を行なった。(D) Next, 1 liter of pure water was added with 20 parts of boric acid.
liquid temperature of 85 ° C. which is obtained by dissolving 0.1 g of fumaric acid
The aluminum etching foil was dipped in the boric acid aqueous solution described above, a current density of 10 mA / cm 2 was applied, the formation voltage was raised to 150 V, and the same voltage was applied for 10 minutes to obtain 1
The second time this formation was performed.
【００５９】（Ｅ）続いて、同アルミニウムエッチング
箔を同じく純水１リットルにホウ酸２０ｇを溶解しフマ
ル酸０．１ｇを添加してなる液温８５℃のホウ酸水溶液
中に浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、
化成電圧を２５０Ｖまで上昇させ、同電圧を１０分間印
加して２回目の本化成を行なった。(E) Subsequently, the same aluminum etching foil was immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C., which was prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.1 g of fumaric acid. Applying a current of density 10mA / cm 2 ,
The formation voltage was raised to 250 V, and the same voltage was applied for 10 minutes to perform the second main formation.
【００６０】（Ｆ）さらに、３回目の本化成として、同
アルミニウムエッチング箔を純水１リットルにホウ酸２
０ｇを溶解しフマル酸０．１ｇを添加してなる液温８５
℃のホウ酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃｍ
2 の電流を流し、化成電圧を３８０Ｖまで上昇させ、同
電圧を４０分間印加した。(F) Further, as the third main chemical conversion, the same aluminum etching foil was added to 1 liter of pure water and 2 parts of boric acid.
A liquid temperature of 85, prepared by dissolving 0 g of fumaric acid and adding 0.1 g of fumaric acid.
Immersed in boric acid aqueous solution at ℃, current density 10mA / cm
A current of 2 was passed to raise the formation voltage to 380 V, and the same voltage was applied for 40 minutes.
【００６１】（Ｇ）本化成後のアルミニウムエッチング
箔を液温７０℃、ｐＨ７〜９に調整したアンモニア水に
３分間浸漬し、減極処理を行なった。(G) The aluminum etching foil after the chemical conversion was immersed in ammonia water adjusted to a liquid temperature of 70 ° C. and pH 7 to 9 for 3 minutes to perform depolarization treatment.
【００６２】（Ｈ）５００℃の加熱雰囲気中で２分間熱
処理した。(H) Heat treatment was performed in a heating atmosphere of 500 ° C. for 2 minutes.
【００６３】（Ｉ）上記（Ｄ）と同じ条件の水溶液、す
なわち純水１リットルにホウ酸２０ｇを溶解しフマル酸
０．１ｇを添加してなる液温８５℃のホウ酸水溶液中に
浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、化成
電圧を３８０Ｖまで上昇させ、同電圧を１３分間印加し
て１回目の再化成を行なった。(I) Immersion in an aqueous solution of the same conditions as in the above (D), that is, an aqueous boric acid solution having a liquid temperature of 85 ° C. prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.1 g of fumaric acid. Then, a current having a current density of 10 mA / cm 2 was passed, the formation voltage was raised to 380 V, and the same voltage was applied for 13 minutes to perform the first re-formation.
【００６４】（Ｊ）再化成後のアルミニウムエッチング
箔を液温７０℃、ｐＨ７〜９に調整したアンモニア水に
３分間浸漬し、減極処理を行なった。(J) The aluminum etching foil after re-formation was immersed in ammonia water adjusted to a liquid temperature of 70 ° C. and pH 7 to 9 for 3 minutes to perform depolarization treatment.
【００６５】（Ｋ）５００℃の加熱雰囲気中で２分間熱
処理した。(K) Heat treatment was performed for 2 minutes in a heating atmosphere of 500 ° C.
【００６６】（Ｌ）引き続き、上記（Ｉ）と同じ条件で
２回目の再化成を行なった。(L) Subsequently, the second re-formation was carried out under the same conditions as the above (I).
【００６７】（Ｍ）水洗いし、乾燥させて化成箔の静電
容量を測定したところ、０．９１４μＦ／ｃｍ2 であっ
た。(M) After washing with water and drying, the capacitance of the formed foil was measured and found to be 0.914 μF / cm 2 .
【００６８】（Ｎ）この化成箔（１５ｍｍ×２７０ｍ
ｍ）を陽極として、実施例１と同様、定格２５０Ｖ３７
μＦの電解コンデンサを作成したところ、その静電容量
は４０．３μＦであった。(N) This formed foil (15 mm × 270 m)
m) as an anode, similarly to Example 1, rated 250V37
When a μF electrolytic capacitor was created, its capacitance was 40.3 μF.
【００６９】［実施例５］ （Ａ）先ず、純度９９．９９％で厚さ１００μｍのアル
ミニウムエッチング箔を用意した。この場合、そのエッ
チング倍率はエッチングしていない平坦箔に対して２０
倍である。Example 5 (A) First, an aluminum etching foil having a purity of 99.99% and a thickness of 100 μm was prepared. In this case, the etching rate is 20 for flat foil that is not etched.
Double.
【００７０】（Ｂ）このアルミニウムエッチング箔を液
温９８℃以上の純水中で１５分間ボイル処理した。(B) This aluminum etching foil was boiled for 15 minutes in pure water having a liquid temperature of 98 ° C. or higher.
【００７１】（Ｃ）ボイル処理したアルミニウムエッチ
ング箔を液温５０℃、１．７ｗｔ％のリン酸水溶液に５
分間浸漬処理した。(C) The boiled aluminum etching foil was immersed in a 1.7 wt% phosphoric acid aqueous solution at a liquid temperature of 50 ° C.
Immersion treatment was performed for a minute.
【００７２】（Ｄ）次に、純水１リットルにホウ酸２０
ｇを溶解しフマル酸０．１ｇを添加してなる液温８５℃
のホウ酸水溶液中にアルミニウムエッチング箔を浸漬
し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、化成電圧
を１５０Ｖまで上昇させ、同電圧を１０分間印加して１
回目の本化成を行なった。(D) Next, 1 liter of pure water was added with 20 parts of boric acid.
liquid temperature of 85 ° C. which is obtained by dissolving 0.1 g of fumaric acid
The aluminum etching foil was dipped in the boric acid aqueous solution described above, a current density of 10 mA / cm 2 was applied, the formation voltage was raised to 150 V, and the same voltage was applied for 10 minutes to obtain 1
The second time this formation was performed.
【００７３】（Ｅ）引き続き、同アルミニウムエッチン
グ箔を同じく純水１リットルにホウ酸２０ｇを溶解しフ
マル酸０．１ｇを添加してなる液温８５℃のホウ酸水溶
液中に浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流
し、化成電圧を２５０Ｖまで上昇させ、同電圧を１０分
間印加して２回目の本化成を行なった。(E) Subsequently, the aluminum etching foil was immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C., which was prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.1 g of fumaric acid. A current of 10 mA / cm 2 was passed to raise the formation voltage to 250 V, and the same voltage was applied for 10 minutes to perform the second main formation.
【００７４】（Ｆ）さらに、３回目の本化成として、同
アルミニウムエッチング箔を純水１リットルにホウ酸２
０ｇを溶解しフマル酸０．１ｇを添加してなる液温８５
℃のホウ酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃｍ
2 の電流を流し、化成電圧を３８０Ｖまで上昇させ、同
電圧を４０分間印加した。(F) Further, as the third main chemical conversion, the same aluminum etching foil was added to 1 liter of pure water and 2 parts of boric acid.
A liquid temperature of 85, prepared by dissolving 0 g of fumaric acid and adding 0.1 g of fumaric acid.
Immersed in boric acid aqueous solution at ℃, current density 10mA / cm
A current of 2 was passed to raise the formation voltage to 380 V, and the same voltage was applied for 40 minutes.
【００７５】（Ｇ）本化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(G) The aluminum etching foil after this chemical conversion was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes to perform depolarization treatment.
【００７６】（Ｈ）５００℃の加熱雰囲気中で２分間熱
処理した。(H) Heat treatment was performed in a heating atmosphere of 500 ° C. for 2 minutes.
【００７７】（Ｉ）純水１リットルにホウ酸２０ｇを溶
解しホウ酸アンモニウム０．５ｇを添加してなる液温８
５℃のホウ酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃ
ｍ2の電流を流し、化成電圧を３８０Ｖまで上昇させ、
同電圧を１３分間印加して１回目の再化成を行なった。(I) A liquid temperature of 8 g prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.5 g of ammonium borate.
Immersed in 5 ° C aqueous boric acid solution, current density 10mA / c
Apply a current of m 2 to raise the formation voltage to 380V,
The same voltage was applied for 13 minutes to perform the first re-formation.
【００７８】（Ｊ）再化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(J) The aluminum etching foil after re-formation was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes to perform depolarization treatment.
【００７９】（Ｋ）５００℃の加熱雰囲気中で２分間熱
処理した。(K) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【００８０】（Ｌ）引き続き、上記（Ｉ）と同じ条件で
２回目の再化成を行なった。(L) Subsequently, the second re-formation was carried out under the same conditions as the above (I).
【００８１】（Ｍ）水洗いし、乾燥させて化成箔の静電
容量を測定したところ、０．９２７μＦ／ｃｍ2 であっ
た。(M) After washing with water and drying, the capacitance of the formed foil was measured and found to be 0.927 μF / cm 2 .
【００８２】（Ｎ）この化成箔（１５ｍｍ×２７０ｍ
ｍ）を陽極として、実施例１と同様、定格２５０Ｖ３７
μＦの電解コンデンサを作成したところ、その静電容量
は４０．９μＦであった。(N) This formed foil (15 mm × 270 m)
m) as an anode, similarly to Example 1, rated 250V37
When a μF electrolytic capacitor was created, its capacitance was 40.9 μF.
【００８３】［実施例６］ （Ａ）先ず、純度９９．９９％で厚さ１００μｍのアル
ミニウムエッチング箔を用意した。この場合、そのエッ
チング倍率はエッチングしていない平坦箔に対して２０
倍である。Example 6 (A) First, an aluminum etching foil having a purity of 99.99% and a thickness of 100 μm was prepared. In this case, the etching rate is 20 for flat foil that is not etched.
Double.
【００８４】（Ｂ）このアルミニウムエッチング箔を液
温９８℃以上の純水中で１５分間ボイル処理した。(B) This aluminum etching foil was boiled in pure water at a liquid temperature of 98 ° C. or higher for 15 minutes.
【００８５】（Ｃ）ボイル処理したアルミニウムエッチ
ング箔を液温５０℃、１．７ｗｔ％のリン酸水溶液に５
分間浸漬処理した。(C) The boiled aluminum etching foil was immersed in a 1.7 wt% phosphoric acid aqueous solution at a liquid temperature of 50 ° C.
Immersion treatment was performed for a minute.
【００８６】（Ｄ）次に、水１リットルにホウ酸２０ｇ
を溶解しフマル酸０．１ｇを添加してなる液温８５℃の
ホウ酸水溶液中にアルミニウムエッチング箔を浸漬し、
電流密度１０ｍＡ／ｃｍ2 の電流を流し、化成電圧を１
５０Ｖまで上昇させ、同電圧を１０分間印加して１回目
の本化成を行なった。(D) Next, 20 g of boric acid was added to 1 liter of water.
Is dissolved and 0.1 g of fumaric acid is added, and the aluminum etching foil is immersed in an aqueous boric acid solution having a liquid temperature of 85 ° C.,
Applying a current with a current density of 10 mA / cm 2 at a formation voltage of 1
The voltage was raised to 50 V and the same voltage was applied for 10 minutes to perform the first main chemical conversion.
【００８７】（Ｅ）引き続き、同アルミニウムエッチン
グ箔を同じく純水１リットルにホウ酸２０ｇを溶解しフ
マル酸０．１ｇを添加してなる液温８５℃のホウ酸水溶
液中に浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流
し、化成電圧を２５０Ｖまで上昇させ、同電圧を１０分
間印加して２回目の本化成を行なった。(E) Subsequently, the same aluminum etching foil was immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C. prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.1 g of fumaric acid to obtain a current density. A current of 10 mA / cm 2 was passed to raise the formation voltage to 250 V, and the same voltage was applied for 10 minutes to perform the second main formation.
【００８８】（Ｆ）さらに、３回目の本化成として、同
アルミニウムエッチング箔を純水１リットルにホウ酸２
０ｇを溶解しフマル酸０．１ｇを添加してなる液温８５
℃のホウ酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃｍ
2 の電流を流し、化成電圧を３８０Ｖまで上昇させ、同
電圧を４０分間印加した。(F) Further, as the third chemical conversion, the same aluminum etching foil was added to 1 liter of pure water and 2 parts of boric acid.
A liquid temperature of 85, prepared by dissolving 0 g of fumaric acid and adding 0.1 g of fumaric acid.
Immersed in boric acid aqueous solution at ℃, current density 10mA / cm
A current of 2 was passed to raise the formation voltage to 380 V, and the same voltage was applied for 40 minutes.
【００８９】（Ｇ）本化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(G) The aluminum etching foil after this chemical conversion was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes to perform depolarization treatment.
【００９０】（Ｈ）５００℃の加熱雰囲気中で２分間熱
処理した。(H) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【００９１】（Ｉ）上記（Ｄ）と同じ条件の水溶液、す
なわち純水１リットルにホウ酸２０ｇを溶解しフマル酸
０．１ｇを添加してなる液温８５℃のホウ酸水溶液中に
浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、化成
電圧を３８０Ｖまで上昇させ、同電圧を１３分間印加し
て１回目の再化成を行なった。(I) Immersion in an aqueous solution of the same conditions as in (D) above, that is, in a boric acid aqueous solution having a liquid temperature of 85 ° C. prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.1 g of fumaric acid. Then, a current having a current density of 10 mA / cm 2 was passed, the formation voltage was raised to 380 V, and the same voltage was applied for 13 minutes to perform the first re-formation.
【００９２】（Ｊ）再化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(J) The deoxidized aluminum etching foil was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes to perform depolarization treatment.
【００９３】（Ｋ）５００℃の加熱雰囲気中で２分間熱
処理した。(K) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【００９４】（Ｌ）引き続き、純水１リットルにホウ酸
２０ｇを溶解しホウ酸アンモニウム０．５ｇを添加して
なる液温８５℃のホウ酸水溶液中に浸漬し、電流密度１
０ｍＡ／ｃｍ2 の電流を流し、化成電圧を３８０Ｖまで
上昇させ、同電圧を１３分間印加して２回目の再化成を
行なった。(L) Subsequently, 20 g of boric acid was dissolved in 1 liter of pure water and 0.5 g of ammonium borate was added, and the sample was immersed in an aqueous boric acid solution having a liquid temperature of 85 ° C. to obtain a current density of 1
A current of 0 mA / cm 2 was flown to raise the formation voltage to 380 V, and the same voltage was applied for 13 minutes to perform the second formation again.
【００９５】（Ｍ）水洗いし、乾燥させて化成箔の静電
容量を測定したところ、０．９１８μＦ／ｃｍ2 であっ
た。(M) After washing with water and drying, the capacitance of the formed foil was measured and found to be 0.918 μF / cm 2 .
【００９６】（Ｎ）この化成箔（１５ｍｍ×２７０ｍ
ｍ）を陽極として、実施例１と同様、定格２５０Ｖ３７
μＦの電解コンデンサを作成したところ、その静電容量
は４０．５μＦであった。(N) This formed foil (15 mm × 270 m)
m) as an anode, similarly to Example 1, rated 250V37
When a μF electrolytic capacitor was created, its capacitance was 40.5 μF.
【００９７】［実施例７］ （Ａ）先ず、純度９９．９９％で厚さ１００μｍのアル
ミニウムエッチング箔を用意した。この場合、そのエッ
チング倍率はエッチングしていない平坦箔に対して２０
倍である。Example 7 (A) First, an aluminum etching foil having a purity of 99.99% and a thickness of 100 μm was prepared. In this case, the etching rate is 20 for flat foil that is not etched.
Double.
【００９８】（Ｂ）このアルミニウムエッチング箔を液
温９８℃以上の純水中で１５分間ボイル処理した。(B) This aluminum etching foil was boiled for 15 minutes in pure water at a liquid temperature of 98 ° C. or higher.
【００９９】（Ｃ）ボイル処理したアルミニウムエッチ
ング箔を液温５０℃、１．７ｗｔ％のリン酸水溶液に５
分間浸漬処理した。(C) The boiled aluminum etching foil was immersed in a 1.7 wt% phosphoric acid aqueous solution at a liquid temperature of 50 ° C.
Immersion treatment was performed for a minute.
【０１００】（Ｄ）次に、純水１リットルにホウ酸２０
ｇを溶解しフマル酸０．１ｇを添加してなる液温８５℃
のホウ酸水溶液中にアルミニウムエッチング箔を浸漬
し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、化成電圧
を１５０Ｖまで上昇させ、同電圧を１０分間印加して１
回目の本化成を行なった。(D) Next, 1 liter of pure water was added with 20 parts of boric acid.
liquid temperature of 85 ° C. which is obtained by dissolving 0.1 g of fumaric acid and adding 0.1 g of fumaric acid
The aluminum etching foil was immersed in the boric acid aqueous solution described above, and a current having a current density of 10 mA / cm 2 was applied to increase the formation voltage to 150 V, and the same voltage was applied for 10 minutes to obtain 1
The second time this formation was performed.
【０１０１】（Ｅ）続いて、同アルミニウムエッチング
箔を同じく純水１リットルにホウ酸２０ｇを溶解しフマ
ル酸０．１ｇを添加してなる液温８５℃のホウ酸水溶液
中に浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、
化成電圧を２５０Ｖまで上昇させ、同電圧を１０分間印
加して２回目の本化成を行なった。(E) Subsequently, the aluminum etching foil was immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C. prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.1 g of fumaric acid. Applying a current of density 10mA / cm 2 ,
The formation voltage was raised to 250 V, and the same voltage was applied for 10 minutes to perform the second main formation.
【０１０２】（Ｆ）さらに、３回目の本化成として、同
アルミニウムエッチング箔を純水１リットルにホウ酸２
０ｇを溶解しホウ酸アンモニウム０．１ｇを添加してな
る液温８５℃のホウ酸水溶液中に浸漬し、電流密度１０
ｍＡ／ｃｍ2 の電流を流し、化成電圧を３８０Ｖまで上
昇させ、同電圧を４０分間印加した。(F) Further, as the third main chemical conversion, the aluminum etching foil was mixed with 1 liter of pure water and 2 parts of boric acid.
It was immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C., which was obtained by dissolving 0 g and adding 0.1 g of ammonium borate to obtain a current density of
A current of mA / cm 2 was passed, the formation voltage was raised to 380 V, and the same voltage was applied for 40 minutes.
【０１０３】（Ｇ）本化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(G) The aluminum etching foil after this chemical conversion was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes to perform depolarization treatment.
【０１０４】（Ｈ）５００℃の加熱雰囲気中で２分間熱
処理した。(H) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【０１０５】（Ｉ）純水１リットルにホウ酸２０ｇを溶
解しホウ酸アンモニウム０．５ｇを添加してなる液温８
５℃のホウ酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃ
ｍ2の電流を流し、化成電圧を３８０Ｖまで上昇させ、
同電圧を１３分間印加して１回目の再化成を行なった。(I) A liquid temperature of 8 g prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.5 g of ammonium borate.
Immersed in 5 ° C aqueous boric acid solution, current density 10mA / c
Apply a current of m 2 to raise the formation voltage to 380V,
The same voltage was applied for 13 minutes to perform the first re-formation.
【０１０６】（Ｊ）再化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(J) The aluminum etching foil after re-chemical conversion was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes for depolarization treatment.
【０１０７】（Ｋ）５００℃の加熱雰囲気中で２分間熱
処理した。(K) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【０１０８】（Ｌ）引き続き、上記（Ｉ）と同じ条件で
２回目の再化成を行なった。(L) Subsequently, the second re-formation was carried out under the same conditions as in (I) above.
【０１０９】（Ｍ）水洗いし、乾燥させて化成箔の静電
容量を測定したところ、０．９２０μＦ／ｃｍ2 であっ
た。(M) After washing with water and drying, the capacitance of the formed foil was measured and found to be 0.920 μF / cm 2 .
【０１１０】（Ｎ）この化成箔（１５ｍｍ×２７０ｍ
ｍ）を陽極として、実施例１と同様、定格２５０Ｖ３７
μＦの電解コンデンサを作成したところ、その静電容量
は４０．６μＦであった。(N) This formed foil (15 mm × 270 m)
m) as an anode, similarly to Example 1, rated 250V37
When a μF electrolytic capacitor was created, its capacitance was 40.6 μF.
【０１１１】［実施例８］ （Ａ）先ず、純度９９．９９％で厚さ１００μｍのアル
ミニウムエッチング箔を用意した。この場合、そのエッ
チング倍率はエッチングしていない平坦箔に対して２０
倍である。Example 8 (A) First, an aluminum etching foil having a purity of 99.99% and a thickness of 100 μm was prepared. In this case, the etching rate is 20 for flat foil that is not etched.
Double.
【０１１２】（Ｂ）このアルミニウムエッチング箔を液
温９８℃以上の純水中で１５分間ボイル処理した。(B) This aluminum etching foil was boiled in pure water at a liquid temperature of 98 ° C. or higher for 15 minutes.
【０１１３】（Ｃ）ボイル処理したアルミニウムエッチ
ング箔を液温５０℃、１．７ｗｔ％のリン酸水溶液に５
分間浸漬処理した。(C) The boiled aluminum etching foil was immersed in a 1.7 wt% phosphoric acid aqueous solution at a liquid temperature of 50 ° C.
Immersion treatment was performed for a minute.
【０１１４】（Ｄ）次に、純水１リットルにホウ酸２０
ｇを溶解しフマル酸０．１ｇを添加してなる液温８５℃
のホウ酸水溶液中にアルミニウムエッチング箔を浸漬
し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、化成電圧
を１５０Ｖまで上昇させ、同電圧を１０分間印加して１
回目の本化成を行なった。(D) Next, 1 liter of pure water was added with 20 parts of boric acid.
liquid temperature of 85 ° C. which is obtained by dissolving 0.1 g of fumaric acid
The aluminum etching foil was immersed in the boric acid aqueous solution described above, and a current having a current density of 10 mA / cm 2 was applied to increase the formation voltage to 150 V, and the same voltage was applied for 10 minutes to obtain 1
The second time this formation was performed.
【０１１５】（Ｅ）引き続き、同アルミニウムエッチン
グ箔を同じく純水１リットルにホウ酸２０ｇを溶解しホ
ウ酸アンモニウムを０．５ｇを添加してなる液温８５℃
のホウ酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃｍ2
の電流を流し、化成電圧を２５０Ｖまで上昇させ、同電
圧を１０分間印加して２回目の本化成を行なった。(E) Subsequently, the same aluminum etching foil was prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.5 g of ammonium borate to a liquid temperature of 85 ° C.
Current density of 10 mA / cm 2
Was applied to increase the formation voltage to 250 V, and the same voltage was applied for 10 minutes to perform the second main formation.
【０１１６】（Ｆ）さらに、３回目の本化成として、同
アルミニウムエッチング箔を純水１リットルにホウ酸２
０ｇを溶解しホウ酸アンモニウム０．５ｇを添加してな
る液温８５℃のホウ酸水溶液中に浸漬し、電流密度１０
ｍＡ／ｃｍ2 の電流を流し、化成電圧を３８０Ｖまで上
昇させ、同電圧を４０分間印加した。(F) Further, as the third chemical conversion, the same aluminum etching foil was added to 1 liter of pure water and 2 parts of boric acid.
It was immersed in an aqueous boric acid solution having a liquid temperature of 85 ° C. prepared by dissolving 0 g and adding 0.5 g of ammonium borate to obtain a current density of 10
A current of mA / cm 2 was passed, the formation voltage was raised to 380 V, and the same voltage was applied for 40 minutes.
【０１１７】（Ｇ）本化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(G) The aluminum etching foil after the present chemical conversion was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes for depolarization treatment.
【０１１８】（Ｈ）５００℃の加熱雰囲気中で２分間熱
処理した。(H) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【０１１９】（Ｉ）純水１リットルにホウ酸２０ｇを溶
解しホウ酸アンモニウム０．５ｇを添加してなる液温８
５℃のホウ酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃ
ｍ2の電流を流し、化成電圧を３８０Ｖまで上昇させ、
同電圧を１３分間印加して１回目の再化成を行なった。(I) A liquid temperature of 8 g prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.5 g of ammonium borate.
Immersed in 5 ° C aqueous boric acid solution, current density 10mA / c
Apply a current of m 2 to raise the formation voltage to 380V,
The same voltage was applied for 13 minutes to perform the first re-formation.
【０１２０】（Ｊ）再化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(J) The aluminum etching foil after re-chemical conversion was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes for depolarization treatment.
【０１２１】（Ｋ）５００℃の加熱雰囲気中で２分間熱
処理した。(K) Heat treatment was performed in a heating atmosphere of 500 ° C. for 2 minutes.
【０１２２】（Ｌ）引き続き、上記（Ｉ）と同じ条件で
２回目の再化成を行なった。(L) Subsequently, the second re-formation was carried out under the same conditions as the above (I).
【０１２３】（Ｍ）水洗いし、乾燥させて化成箔の静電
容量を測定したところ、０．９１５μＦ／ｃｍ2 であっ
た。(M) After washing with water and drying, the capacitance of the formed foil was measured and found to be 0.915 μF / cm 2 .
【０１２４】（Ｎ）この化成箔（１５ｍｍ×２７０ｍ
ｍ）を陽極として、実施例１と同様、定格２５０Ｖ３７
μＦの電解コンデンサを作成したところ、その静電容量
は４０．４μＦであった。(N) This formed foil (15 mm × 270 m)
m) as an anode, similarly to Example 1, rated 250V37
When a μF electrolytic capacitor was created, its capacitance was 40.4 μF.
【０１２５】［実施例９］ （Ａ）先ず、純度９９．９９％で厚さ１００μｍのアル
ミニウムエッチング箔を用意した。この場合、そのエッ
チング倍率はエッチングしていない平坦箔に対して２０
倍である。Example 9 (A) First, an aluminum etching foil having a purity of 99.99% and a thickness of 100 μm was prepared. In this case, the etching rate is 20 for flat foil that is not etched.
Double.
【０１２６】（Ｂ）このアルミニウムエッチング箔を液
温９８℃以上の純水中で１５分間ボイル処理した。(B) This aluminum etching foil was boiled in pure water at a liquid temperature of 98 ° C. or higher for 15 minutes.
【０１２７】（Ｃ）ボイル処理したアルミニウムエッチ
ング箔を液温５０℃、１．７ｗｔ％のリン酸水溶液に５
分間浸漬処理した。(C) The boiled aluminum etching foil was immersed in a 1.7 wt% phosphoric acid aqueous solution at a liquid temperature of 50 ° C.
Immersion treatment was performed for a minute.
【０１２８】（Ｄ）次に、純水１リットルにホウ酸２０
ｇを溶解しポリアクリル酸アンモニウム（分子量４００
０）０．５ｇを添加してなる液温８５℃のホウ酸水溶液
中にアルミニウムエッチング箔を浸漬し、電流密度１０
ｍＡ／ｃｍ2 の電流を流し、化成電圧を１５０Ｖまで上
昇させ、同電圧を１０分間印加して１回目の本化成を行
なった。(D) Next, 1 liter of pure water was added with 20 parts of boric acid.
g to dissolve ammonium polyacrylate (molecular weight 400
0) The aluminum etching foil was immersed in an aqueous boric acid solution having a liquid temperature of 85 ° C. to which 0.5 g was added to obtain a current density of 10
A current of mA / cm 2 was flown to raise the formation voltage to 150 V, and the same voltage was applied for 10 minutes to perform the first main formation.
【０１２９】（Ｅ）続いて、同アルミニウムエッチング
箔を同じく純水１リットルにホウ酸２０ｇを溶解しポリ
アクリル酸アンモニウム（分子量４０００）０．５ｇを
添加してなる液温８５℃のホウ酸水溶液中に浸漬し、電
流密度１０ｍＡ／ｃｍ2 の電流を流し、化成電圧を２５
０Ｖまで上昇させ、同電圧を１０分間印加して２回目の
本化成を行なった。(E) Subsequently, the same aluminum etching foil was prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.5 g of ammonium polyacrylate (molecular weight 4000) at a liquid temperature of 85 ° C. in boric acid. It is immersed in the solution, a current density of 10 mA / cm 2 is applied, and the formation voltage is set to 25.
The voltage was increased to 0 V, and the same voltage was applied for 10 minutes to perform the second main chemical conversion.
【０１３０】（Ｆ）さらに、３回目の本化成として、同
アルミニウムエッチング箔を純水１リットルにホウ酸２
０ｇを溶解しポリアクリル酸アンモニウム（分子量４０
００）０．５ｇを添加してなる液温８５℃のホウ酸水溶
液中に浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流
し、化成電圧を３８０Ｖまで上昇させ、同電圧を４０分
間印加した。(F) Further, as the third chemical conversion, the same aluminum etching foil was added to 1 liter of pure water and 2 parts of boric acid.
Dissolve 0 g of ammonium polyacrylate (molecular weight 40
00) 0.5 g was immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C., a current having a current density of 10 mA / cm 2 was passed, the formation voltage was increased to 380 V, and the same voltage was applied for 40 minutes.
【０１３１】（Ｇ）本化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(G) The aluminum etching foil after this chemical conversion was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes to perform depolarization treatment.
【０１３２】（Ｈ）５００℃の加熱雰囲気中で２分間熱
処理した。(H) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【０１３３】（Ｉ）純水１リットルにホウ酸２０ｇを溶
解しポリアクリル酸アンモニウム（分子量４０００）
０．５ｇを添加してなる液温８５℃のホウ酸水溶液中に
浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、化成
電圧を３８０Ｖまで上昇させ、同電圧を１３分間印加し
て１回目の再化成を行なった。(I) Ammonium polyacrylate (molecular weight 4000) was prepared by dissolving 20 g of boric acid in 1 liter of pure water.
It is immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C. to which 0.5 g is added, a current having a current density of 10 mA / cm 2 is applied, the formation voltage is increased to 380 V, and the same voltage is applied for 13 minutes for the first time. Was reformed.
【０１３４】（Ｊ）再化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(J) The aluminum etching foil after re-formation was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes for depolarization treatment.
【０１３５】（Ｋ）５００℃の加熱雰囲気中で２分間熱
処理した。(K) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【０１３６】（Ｌ）引き続き、上記（Ｉ）と同じ条件で
２回目の再化成を行なった。(L) Subsequently, the second re-formation was carried out under the same conditions as the above (I).
【０１３７】（Ｍ）水洗いし、乾燥させて化成箔の静電
容量を測定したところ、０．９２３μＦ／ｃｍ2 であっ
た。(M) After washing with water and drying, the capacitance of the chemical conversion foil was measured and found to be 0.923 μF / cm 2 .
【０１３８】（Ｎ）この化成箔（１５ｍｍ×２７０ｍ
ｍ）を陽極として、実施例１と同様、定格２５０Ｖ３７
μＦの電解コンデンサを作成したところ、その静電容量
は４０．８μＦであった。(N) This formed foil (15 mm × 270 m)
m) as an anode, similarly to Example 1, rated 250V37
When a μF electrolytic capacitor was created, its capacitance was 40.8 μF.
【０１３９】［比較例１］ （ａ）先ず、純度９９．９９％で厚さ１００μｍのアル
ミニウムエッチング箔を用意した。この場合、そのエッ
チング倍率はエッチングしていない平坦箔に対して２０
倍である。Comparative Example 1 (a) First, an aluminum etching foil having a purity of 99.99% and a thickness of 100 μm was prepared. In this case, the etching rate is 20 for flat foil that is not etched.
Double.
【０１４０】（ｂ）このアルミニウムエッチング箔を液
温９８℃以上の純水中で１５分間ボイル処理した。(B) This aluminum etching foil was boiled in pure water at a liquid temperature of 98 ° C. or higher for 15 minutes.
【０１４１】（ｃ）次に、純水１リットルにホウ酸２０
ｇを溶解しホウ酸アンモニウムを０．５ｇ添加してなる
液温８５℃のホウ酸水溶液中にアルミニウムエッチング
箔を浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、
化成電圧を１５０Ｖまで上昇させ、同電圧を１０分間印
加して１回目の本化成を行なった。(C) Next, 1 liter of pure water was added with 20 parts of boric acid.
g of aluminum and 0.5 g of ammonium borate are added, the aluminum etching foil is immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C., and a current having a current density of 10 mA / cm 2 is applied,
The formation voltage was raised to 150 V, and the same voltage was applied for 10 minutes to perform the first main formation.
【０１４２】（ｄ）引き続き、同アルミニウムエッチン
グ箔を同じく純水１リットルにホウ酸２０ｇを溶解しホ
ウ酸アンモニウム０．５ｇを添加してなる液温８５℃中
に浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流し、化
成電圧を２５０Ｖまで上昇させ、同電圧を１０分間印加
して２回目の本化成を行なった。(D) Subsequently, the aluminum etching foil was immersed in a liquid temperature of 85 ° C. in which 20 g of boric acid was dissolved in 1 liter of pure water and 0.5 g of ammonium borate was added, and the current density was 10 mA / cm. A current of 2 was passed to raise the formation voltage to 250 V, and the same voltage was applied for 10 minutes to perform the second main formation.
【０１４３】（ｅ）さらに、３回目の本化成として、同
アルミニウムエッチング箔を純水１リットルにホウ酸２
０ｇを溶解しホウ酸アンモニウム０．５ｇを添加してな
る液温８５℃のホウ酸水溶液中に浸漬し、電流密度１０
ｍＡ／ｃｍ2 の電流を流し、化成電圧を３８０Ｖまで上
昇させ、同電圧を４０分間印加した。(E) Further, as the third main chemical conversion, the same aluminum etching foil was added to 1 liter of pure water and 2 parts of boric acid.
It was immersed in an aqueous boric acid solution having a liquid temperature of 85 ° C. prepared by dissolving 0 g and adding 0.5 g of ammonium borate to obtain a current density of 10
A current of mA / cm 2 was passed, the formation voltage was raised to 380 V, and the same voltage was applied for 40 minutes.
【０１４４】（ｆ）本化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(F) The aluminum etching foil after the present chemical conversion was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes for depolarization treatment.
【０１４５】（ｇ）５００℃の加熱雰囲気中で２分間熱
処理した。(G) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【０１４６】（ｈ）純水１リットルにホウ酸２０ｇを溶
解しホウ酸アンモニウム０．５ｇを添加してなる液温８
５℃中に浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を流
し、化成電圧を３８０Ｖまで上昇させ、同電圧を１３分
間印加して１回目の再化成を行なった。(H) A liquid temperature of 8 g prepared by dissolving 20 g of boric acid in 1 liter of pure water and adding 0.5 g of ammonium borate.
It was immersed in 5 ° C., a current having a current density of 10 mA / cm 2 was passed, the formation voltage was increased to 380 V, and the same voltage was applied for 13 minutes to perform the first re-formation.
【０１４７】（ｉ）再化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(I) The aluminum etching foil after re-formation was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes to perform depolarization treatment.
【０１４８】（ｊ）５００℃の加熱雰囲気中で２分間熱
処理した。(J) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【０１４９】（ｋ）引き続き、上記（ｈ）と同じ条件で
２回目の再化成を行なった。(K) Subsequently, the second re-formation was carried out under the same conditions as in (h) above.
【０１５０】（ｌ）水洗いし、乾燥させて化成箔の静電
容量を測定したところ、０．８４９μＦ／ｃｍ2 であっ
た。(L) After washing with water and drying, the capacitance of the formed foil was measured and found to be 0.849 μF / cm 2 .
【０１５１】（ｍ）この化成箔（１５ｍｍ×２７０ｍ
ｍ）を陽極として、実施例１と同様、定格２５０Ｖ３７
μＦの電解コンデンサを作成したところ、その静電容量
は３７．５μＦであった。(M) This formed foil (15 mm × 270 m)
m) as an anode, similarly to Example 1, rated 250V37
When a μF electrolytic capacitor was created, its capacitance was 37.5 μF.
【０１５２】［比較例２］ （ａ）先ず、純度９９．９９％で厚さ１００μｍのアル
ミニウムエッチング箔を用意した。この場合、そのエッ
チング倍率はエッチングしていない平坦箔に対して２０
倍である。Comparative Example 2 (a) First, an aluminum etching foil having a purity of 99.99% and a thickness of 100 μm was prepared. In this case, the etching rate is 20 for flat foil that is not etched.
Double.
【０１５３】（ｂ）このアルミニウムエッチング箔を液
温９８℃以上の純水中で１５分間ボイル処理した。(B) This aluminum etching foil was boiled for 15 minutes in pure water at a liquid temperature of 98 ° C. or higher.
【０１５４】（ｃ）次に、純水１リットルにホウ酸２０
ｇを溶解しアジピン酸アンモニウムを０．１ｇを添加し
てなる液温８５℃のホウ酸水溶液中にアルミニウムエッ
チング箔を浸漬し、電流密度１０ｍＡ／ｃｍ2 の電流を
流し、化成電圧を１５０Ｖまで上昇させ、同電圧を１０
分間印加して１回目の本化成を行なった。(C) Next, 1 liter of pure water was added with 20 parts of boric acid.
g of aluminum and 0.1 g of ammonium adipate were added, and the aluminum etching foil was immersed in a boric acid aqueous solution at a liquid temperature of 85 ° C., and a current density of 10 mA / cm 2 was applied to increase the formation voltage to 150 V. The same voltage to 10
The voltage was applied for a minute to perform the first chemical conversion.
【０１５５】（ｄ）引き続き、同アルミニウムエッチン
グ箔を同じく純水１リットルにホウ酸２０ｇを溶解しア
ジピン酸アンモニウムを０．１ｇを添加してなる液温８
５℃のホウ酸水溶液中に浸漬し、電流密度１０ｍＡ／ｃ
ｍ2 の電流を流し、化成電圧を２５０Ｖまで上昇させ、
同電圧を１０分間印加して２回目の本化成を行なった。(D) Subsequently, 20 g of boric acid was dissolved in 1 liter of pure water and 0.1 g of ammonium adipate was added to the aluminum etching foil, and the liquid temperature was 8
Immersed in 5 ° C aqueous boric acid solution, current density 10mA / c
Apply a current of m 2 to raise the formation voltage to 250V,
The same voltage was applied for 10 minutes to perform the second main chemical conversion.
【０１５６】（ｅ）さらに、３回目の本化成として、同
アルミニウムエッチング箔を純水１リットルにホウ酸２
０ｇを溶解しアジピン酸アンモニウムを０．１ｇを添加
してなる液温８５℃のホウ酸水溶液中に浸漬し、電流密
度１０ｍＡ／ｃｍ2 の電流を流し、化成電圧を３８０Ｖ
まで上昇させ、同電圧を４０分間印加した。(E) Further, as the third chemical conversion, the same aluminum etching foil was added to 1 liter of pure water and 2 parts of boric acid.
It is immersed in a boric acid aqueous solution having a liquid temperature of 85 ° C., in which 0 g is dissolved and 0.1 g of ammonium adipate is added, and a current having a current density of 10 mA / cm 2 is applied, and a formation voltage is 380 V.
And the same voltage was applied for 40 minutes.
【０１５７】（ｆ）本化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(F) The aluminum etching foil after the chemical conversion was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes to perform depolarization treatment.
【０１５８】（ｇ）５００℃の加熱雰囲気中で２分間熱
処理した。(G) Heat treatment was performed for 2 minutes in a heating atmosphere at 500 ° C.
【０１５９】（ｈ）純水１リットルにホウ酸２０ｇを溶
解しアジピン酸アンモニウムを０．１ｇ添加してなる液
温８５℃のホウ酸水溶液中に浸漬し、電流密度１０ｍＡ
／ｃｍ2 の電流を流し、化成電圧を３８０Ｖまで上昇さ
せ、同電圧を１３分間印加して１回目の再化成を行なっ
た。(H) 20 g of boric acid was dissolved in 1 liter of pure water, and 0.1 g of ammonium adipate was added, and the sample was immersed in an aqueous boric acid solution having a liquid temperature of 85 ° C. to obtain a current density of 10 mA.
/ Cm 2 of current was passed, the formation voltage was raised to 380 V, and the same voltage was applied for 13 minutes to perform the first re-formation.
【０１６０】（ｉ）再化成後のアルミニウムエッチング
箔を液温７０℃、３．５ｗｔ％のリン酸水溶液に３分間
浸漬し、減極処理を行なった。(I) The aluminum etching foil after re-formation was immersed in a 3.5 wt% phosphoric acid aqueous solution at a liquid temperature of 70 ° C. for 3 minutes for depolarization treatment.
【０１６１】（ｊ）５００℃の加熱雰囲気中で２分間熱
処理した。(J) Heat treatment was performed in a heating atmosphere at 500 ° C. for 2 minutes.
【０１６２】（ｋ）引き続き、上記（ｈ）と同じ条件で
２回目の再化成を行なった。(K) Subsequently, the second re-formation was performed under the same conditions as in (h) above.
【０１６３】（ｌ）水洗いし、乾燥させて化成箔の静電
容量を測定したところ、０．８８４μＦ／ｃｍ2 であっ
た。(L) After washing with water and drying, the capacitance of the formed foil was measured and found to be 0.884 μF / cm 2 .
【０１６４】（ｍ）この化成箔（１５ｍｍ×２７０ｍ
ｍ）を陽極として、実施例１と同様、定格２５０Ｖ３７
μＦの電解コンデンサを作成したところ、その静電容量
は３９．０μＦであった。(M) This formed foil (15 mm × 270 m)
m) as an anode, similarly to Example 1, rated 250V37
When a μF electrolytic capacitor was created, its capacitance was 39.0 μF.
【０１６５】上記各実施例および各比較例で得られた化
成箔の箔の静電容量と、その化成箔を用いて試作した電
解コンデンサ（製品）の静電容量を表にまとめると表１
および表２のようになる。The capacitances of the foils of the chemical conversion foils obtained in each of the above Examples and Comparative Examples and the capacitances of the electrolytic capacitors (products) prototyped using the chemical conversion foils are summarized in Table 1.
And it becomes like Table 2.
【０１６６】[0166]
【表１】 [Table 1]
【０１６７】[0167]
【表２】 [Table 2]
【０１６８】比較例１に示すようにホウ酸水溶液中にて
化成した箔の静電容量は０．８４９μＦ／ｃｍ2 であ
る。次に、比較例２に示すようにカルボン酸またはその
箔を含有するホウ酸水溶液中にて化成した箔の静電容量
は０．８８４μＦ／ｃｍ2 で、比較例１より４．１％の
静電容量の向上を図ることができる。次に、本発明に係
るようにリン酸またはリン酸塩水溶液中に浸漬した後
に、カルボン酸またはその塩を含有するホウ酸水溶液中
にて化成した箔の静電容量は、例えば実施例１による
と、０．９２２μＦ／ｃｍ2 で比較例１より８．９％の
静電容量の向上を図ることができ、さらには比較例２よ
り４．３％の静電容量を図ることができる。As shown in Comparative Example 1, the capacitance of the foil formed in the boric acid aqueous solution is 0.849 μF / cm 2 . Next, as shown in Comparative Example 2, the capacitance of the foil formed in an aqueous solution of boric acid containing carboxylic acid or its foil was 0.884 μF / cm 2, which was 4.1% less than that of Comparative Example 1. The electric capacity can be improved. Next, the capacitance of the foil formed in an aqueous solution of boric acid containing a carboxylic acid or a salt thereof after being immersed in an aqueous solution of phosphoric acid or a phosphate according to the present invention is, for example, according to Example 1. With 0.922 μF / cm 2 , the capacitance can be improved by 8.9% as compared with Comparative Example 1, and further by 4.3% as compared with Comparative Example 2.
【０１６９】[0169]
【発明の効果】以上にて説明したように、本発明によれ
ば、エッチングされたアルミニウム箔を純水でボイルし
た後、リン酸またはリン酸塩水溶液中に浸漬し、続いて
本化成および再化成するにあたって、少なくともそのい
ずれかの工程において、カルボン酸もしくはその塩を含
有するホウ酸水溶液中で化成するようにしたことによ
り、静電容量の高い電極箔が製造される。As described above, according to the present invention, the etched aluminum foil is boiled with pure water and then immersed in an aqueous solution of phosphoric acid or a phosphoric acid salt. At the time of formation, at least one of the steps is performed in an aqueous solution of boric acid containing a carboxylic acid or a salt thereof to form an electrode foil having a high capacitance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 羽賀 昇 神奈川県藤沢市辻堂新町２丁目２番１号 エルナ−株式会社内 (72)発明者 佐々木 幹夫 東京都千代田区丸の内二丁目１番２号 旭 硝子株式会社内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Noboru Haga 2-2-1 Tsujido Shinmachi, Fujisawa-shi, Kanagawa Elna Co., Ltd. (72) Inventor Mikio Sasaki 2-1-2 Marunouchi, Chiyoda-ku, Tokyo Asahi Glass Co., Ltd.
Claims (3)
純水中に所定時間浸漬してボイル処理した後、リン酸ま
たはリン酸塩水溶液中に浸漬し、続いて少なくともカル
ボン酸またはその塩を含有するホウ酸水溶液中にそのア
ルミニウム箔を浸漬して陽極酸化することを特徴とする
アルミニウム電解コンデンサ用電極箔の製造方法。1. An etched aluminum foil is dipped in high temperature pure water for a predetermined time to be boiled, then dipped in an aqueous solution of phosphoric acid or a phosphate, and subsequently containing at least a carboxylic acid or a salt thereof. A method for producing an electrode foil for an aluminum electrolytic capacitor, which comprises immersing the aluminum foil in a boric acid aqueous solution and anodizing the same.
純水中に所定時間浸漬してボイル処理した後、リン酸ま
たはリン酸塩水溶液中に浸漬し、続いて本化成工程を行
ない、さらに再化成工程を行なうアルミニウム電解コン
デンサ用電極箔の製造方法において、上記再化成工程で
は少なくともカルボン酸またはその塩を含有するホウ酸
水溶液を用いて陽極酸化を行なうことを特徴とするアル
ミニウム電解コンデンサ用電極箔の製造方法。2. The etched aluminum foil is immersed in high temperature pure water for a predetermined time to boil it, and then immersed in an aqueous solution of phosphoric acid or a phosphoric acid salt. In the method for producing an electrode foil for an aluminum electrolytic capacitor, which comprises performing the step, in the re-forming step, anodization is performed using an aqueous boric acid solution containing at least a carboxylic acid or a salt thereof. Production method.
純水中に所定時間浸漬してボイル処理した後、リン酸ま
たはリン酸塩水溶液中に浸漬し、続いて本化成工程を行
ない、さらに再化成工程を行なうアルミニウム電解コン
デンサ用電極箔の製造方法において、上記本化成工程お
よび上記再化成工程のいずれにおいても、少なくとも一
度はカルボン酸またはその塩を含むホウ酸水溶液中で化
成することを特徴とするアルミニウム電解コンデンサ用
電極箔の製造方法。3. The etched aluminum foil is immersed in high temperature pure water for a predetermined time for boil treatment, then immersed in an aqueous solution of phosphoric acid or a phosphate, followed by the main chemical conversion step, and further re-chemical conversion. In the method for producing an electrode foil for an aluminum electrolytic capacitor, which comprises performing the step, in both the main chemical conversion step and the rechemical conversion step, chemical conversion is performed at least once in a boric acid aqueous solution containing a carboxylic acid or a salt thereof. Manufacturing method of electrode foil for aluminum electrolytic capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3261063A JP2727823B2 (en) | 1991-09-12 | 1991-09-12 | Method for producing electrode foil for aluminum electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3261063A JP2727823B2 (en) | 1991-09-12 | 1991-09-12 | Method for producing electrode foil for aluminum electrolytic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0574663A true JPH0574663A (en) | 1993-03-26 |
| JP2727823B2 JP2727823B2 (en) | 1998-03-18 |
Family
ID=17356566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3261063A Expired - Fee Related JP2727823B2 (en) | 1991-09-12 | 1991-09-12 | Method for producing electrode foil for aluminum electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2727823B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09162081A (en) * | 1995-12-08 | 1997-06-20 | Nichicon Corp | Method for chemically converting electrode foil for electrolytic capacitor |
| JP2003124068A (en) * | 2001-10-10 | 2003-04-25 | Showa Denko Kk | Anode foil for capacitor, method for manufacturing anode foil and solid electrolytic capacitor using anode foil |
| JP2005200715A (en) * | 2004-01-16 | 2005-07-28 | Nichicon Corp | Method for manufacturing anode foil in aluminum electrolytic capacitor |
| JP2007036048A (en) * | 2005-07-28 | 2007-02-08 | Nichicon Corp | Manufacturing method of electrode foil for aluminum electrolytic capacitor |
| JP2007311681A (en) * | 2006-05-22 | 2007-11-29 | Nichicon Corp | Method of manufacturing electrode foil of electrolytic capacitor |
| JP2009170861A (en) * | 2008-01-11 | 2009-07-30 | Young Joo Oh | Metal capacitor and its manufacturing method |
| WO2015075921A1 (en) * | 2013-11-20 | 2015-05-28 | パナソニックＩｐマネジメント株式会社 | Electrolytic capacitor and manufacturing method for same |
| JP2018039977A (en) * | 2016-09-01 | 2018-03-15 | 株式会社豊田自動織機 | Ion-conductive material |
| CN109402700A (en) * | 2018-11-01 | 2019-03-01 | 青海瑞合铝箔有限公司 | A kind of improved Waste Acid From Hua Cheng Foil manufacturing process |
| JP2019201128A (en) * | 2018-05-17 | 2019-11-21 | 日本軽金属株式会社 | Manufacturing method of electrode for aluminum electrolytic capacitor |
| CN113774456A (en) * | 2021-08-20 | 2021-12-10 | 扬州宏远电子股份有限公司 | A kind of double chemical forming process method and aluminum foil for starting AC corrosion foil |
-
1991
- 1991-09-12 JP JP3261063A patent/JP2727823B2/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09162081A (en) * | 1995-12-08 | 1997-06-20 | Nichicon Corp | Method for chemically converting electrode foil for electrolytic capacitor |
| JP2003124068A (en) * | 2001-10-10 | 2003-04-25 | Showa Denko Kk | Anode foil for capacitor, method for manufacturing anode foil and solid electrolytic capacitor using anode foil |
| JP2005200715A (en) * | 2004-01-16 | 2005-07-28 | Nichicon Corp | Method for manufacturing anode foil in aluminum electrolytic capacitor |
| JP2007036048A (en) * | 2005-07-28 | 2007-02-08 | Nichicon Corp | Manufacturing method of electrode foil for aluminum electrolytic capacitor |
| JP2007311681A (en) * | 2006-05-22 | 2007-11-29 | Nichicon Corp | Method of manufacturing electrode foil of electrolytic capacitor |
| JP2009170861A (en) * | 2008-01-11 | 2009-07-30 | Young Joo Oh | Metal capacitor and its manufacturing method |
| WO2015075921A1 (en) * | 2013-11-20 | 2015-05-28 | パナソニックＩｐマネジメント株式会社 | Electrolytic capacitor and manufacturing method for same |
| JPWO2015075921A1 (en) * | 2013-11-20 | 2017-03-16 | パナソニックＩｐマネジメント株式会社 | Electrolytic capacitor and manufacturing method thereof |
| US10026559B2 (en) | 2013-11-20 | 2018-07-17 | Panasonic Intellectual Property Management Co., Ltd. | Electrolytic capacitor and manufacturing method for same |
| JP2018039977A (en) * | 2016-09-01 | 2018-03-15 | 株式会社豊田自動織機 | Ion-conductive material |
| JP2019201128A (en) * | 2018-05-17 | 2019-11-21 | 日本軽金属株式会社 | Manufacturing method of electrode for aluminum electrolytic capacitor |
| WO2019220690A1 (en) * | 2018-05-17 | 2019-11-21 | 日本軽金属株式会社 | Method for manufacturing electrode for aluminum electrolytic capacitors |
| CN109402700A (en) * | 2018-11-01 | 2019-03-01 | 青海瑞合铝箔有限公司 | A kind of improved Waste Acid From Hua Cheng Foil manufacturing process |
| CN113774456A (en) * | 2021-08-20 | 2021-12-10 | 扬州宏远电子股份有限公司 | A kind of double chemical forming process method and aluminum foil for starting AC corrosion foil |
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|---|---|
| JP2727823B2 (en) | 1998-03-18 |
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