JP6922090B2 - Manufacturing method of medium-high pressure corrosive foil for aluminum electrolytic capacitors - Google Patents
Manufacturing method of medium-high pressure corrosive foil for aluminum electrolytic capacitors Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/04—Etching of light metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/36—Alkaline compositions for etching aluminium or alloys thereof
Description
本発明は、アルミ電解コンデンサ用中高圧陽極箔の製造方法に関し、特にアルミ電解コンデンサ陽極箔の二段階焼鈍熱処理工程に関する。 The present invention relates to a method for producing a medium- and high-pressure anode foil for an aluminum electrolytic capacitor, and particularly to a two-step annealing heat treatment step for an aluminum electrolytic capacitor anode foil.
近年、アルミ電解コンデンサは、小型化、微型化に発展しつつあり、比較的小さい幅の切断及び比較的小さい直径の巻取等の製造要求を満たすように、アルミ電解コンデンサ用陽極箔の曲げ性能に対する要求が高まっている。現在、アルミ電解コンデンサ用中高圧腐食箔製造方法は、（１）前処理；（２）孔食；（３）リーマ腐食（reaming corrosion）；（４）後処理、洗浄；（５）焼鈍である。具体的に、水酸化ナトリウム溶液を利用し、中高圧電解コンデンサ用アルミニウム箔に対し、浸漬前処理を行い；前の工程で得られた陽極箔を、塩酸、硫酸混合溶液を用いて電流印加による孔食を行い；前の工程で得られた陽極箔を、塩酸、硫酸、リン酸溶液を用いて電流印加によるリーマ腐食を行い；前の工程で得られた陽極箔を、硝酸溶液に浸漬した後に、水道水による洗浄及び純水による洗浄を行い；前の工程で得られた陽極箔を、１５０℃のオーブン中に１２０ｓ保温し；前の工程で得られた陽極箔を、空気中で室温まで冷却する。 In recent years, aluminum electrolytic capacitors have been developed into miniaturization and miniaturization, and the bending performance of the anode foil for aluminum electrolytic capacitors so as to meet the manufacturing requirements such as cutting with a relatively small width and winding with a relatively small diameter. Is increasing. Currently, the methods for producing medium- and high-pressure corrosive foils for aluminum electrolytic capacitors are (1) pretreatment; (2) pitting corrosion; (3) reaming corrosion; (4) posttreatment, cleaning; and (5) annealing. .. Specifically, a sodium hydroxide solution was used to pre-immerse the aluminum foil for medium- and high-pressure electrolytic capacitors; the anode foil obtained in the previous step was subjected to current application using a mixed solution of hydrochloric acid and sulfuric acid. Pitting corrosion; the anode foil obtained in the previous step was reamer-corroded by applying an electric current using a hydrochloric acid, sulfuric acid, and phosphoric acid solution; the anode foil obtained in the previous step was immersed in a nitrate solution. Later, washing with tap water and washing with pure water is performed; the anode foil obtained in the previous step is kept warm in an oven at 150 ° C. for 120 s; the anode foil obtained in the previous step is kept at room temperature in air. Cool to.
従来の焼鈍過程では、通常１００〜２００℃の温度で保温し、乾燥の効果しか達成することができなかった。 In the conventional annealing process, the temperature is usually kept at a temperature of 100 to 200 ° C., and only the effect of drying can be achieved.
本発明の目的は、従来の腐食工程の基づき、焼鈍過程に対して改良を行い、二段階の異なる温度の窒素ガス保護の焼鈍熱処理を行い、アルミニウム金属の回復及び再結晶過程を利用し、電極箔の曲げ性能を向上させることにある。本発明により得られた腐食箔は、化成処理後、曲げ性能が２０％以上向上し、アルミ電解コンデンサに対する小型化に重要な促進作用を果たす。 An object of the present invention is to improve the annealing process based on the conventional corrosion process, perform annealing heat treatment for nitrogen gas protection at two different temperatures, utilize the recovery and recrystallization process of aluminum metal, and use the electrode. The purpose is to improve the bending performance of the foil. The corrosive foil obtained by the present invention has improved bending performance by 20% or more after chemical conversion treatment, and plays an important promoting action for miniaturization of aluminum electrolytic capacitors.
本発明の目的は、以下のような技術手段により実現される。 The object of the present invention is realized by the following technical means.
アルミ電解コンデンサ用中高圧腐食箔の製造方法の具体的ステップは以下のようである。 The specific steps of the method for manufacturing medium- and high-pressure corrosive foils for aluminum electrolytic capacitors are as follows.
Ａ.１ｗｔ％〜１０ｗｔ％水酸化ナトリウム溶液を用い、２０℃〜６０℃温度で中高圧電解コンデンサ用アルミニウム箔に対して浸漬前処理３０〜１２０ｓを行う。 A. Using a 1 wt% to 10 wt% sodium hydroxide solution, a dipping pretreatment of 30 to 120 s is performed on an aluminum foil for a medium- and high-pressure electrolytic capacitor at a temperature of 20 ° C to 60 ° C.
Ｂ.ステップＡで得られた陽極箔を１ｗｔ％〜５ｗｔ％塩酸、５ｗｔ％〜４０ｗｔ％硫酸混合溶液を用いて、２０℃〜９０℃温度で電流印加による孔食１２０〜６００ｓ行う。 B. The anode foil obtained in step A is subjected to pitting corrosion by applying a current at a temperature of 20 ° C. to 90 ° C. for 120 to 600 s using a mixed solution of 1 wt% to 5 wt% hydrochloric acid and 5 wt% to 40 wt% sulfuric acid.
Ｃ．ステップＢで得られた陽極箔を１ｗｔ％〜１０ｗｔ％塩酸、３ｗｔ％〜２０ｗｔ％硫酸、０.００５ｗｔ％〜０.０５ｗｔ％リン酸溶液を用いて、５０℃〜９５℃温度で電流印加によるリーマ腐食１２０〜６００ｓ行う。 C. The anode foil obtained in step B is reamered by applying a current at a temperature of 50 ° C. to 95 ° C. using a 1 wt% to 10 wt% hydrochloric acid, 3 wt% to 20 wt% sulfuric acid, and 0.005 wt% to 0.05 wt% phosphoric acid solutions. Corrosion is performed for 120 to 600 s.
Ｄ.ステップＣで得られた陽極箔を１ｗｔ％〜１０ｗｔ％硝酸溶液を用いて、２０℃〜６０℃温度で、３０〜１２０s浸漬した後、水道水による洗浄および純水による洗浄を行う。 D. The anode foil obtained in step C is immersed in a 1 wt% to 10 wt% nitric acid solution at a temperature of 20 ° C. to 60 ° C. for 30 to 120 s, and then washed with tap water and pure water.
Ｅ.ステップＤの処理により得られた陽極箔が昇温段階に進入し、昇温開始温度は室温であり、終了温度は一次定温温度であり、昇温速度は３０〜５０℃/ｓである。 E. The anode foil obtained by the treatment of step D enters the temperature rising stage, the temperature rise start temperature is room temperature, the end temperature is the primary constant temperature, and the temperature rise rate is 30 to 50 ° C./s. ..
Ｆ.ステップＥの処理により得られた陽極箔が一次定温段階に進入し、一次定温温度で一次窒素ガス保護の焼鈍処理を行い、保温温度は３００〜５００℃であり、保温時間は３０〜１２０ｓである。 F. The anode foil obtained by the treatment of step E enters the primary constant temperature stage, is annealed to protect the primary nitrogen gas at the primary constant temperature, the heat retention temperature is 300 to 500 ° C., and the heat retention time is 30 to 120 s. Is.
Ｇ.ステップＦの処理により得られた陽極箔が線形温度変化の段階に進入し、温度変化開始温度は一次保温温度であり、温度変化の終了温度は二次保温温度であり、温度変化の時間は５〜２０ｓである。 The anode foil obtained by the treatment of G. step F enters the stage of linear temperature change, the temperature change start temperature is the primary heat retention temperature, the end temperature of the temperature change is the secondary heat retention temperature, and the time of temperature change. Is 5 to 20 s.
Ｈ.ステップＧの処理により得られた陽極箔が二次定温段階に進入し、二次定温温度で二次窒素ガス保護の焼鈍処理を行い、保温温度は２５０〜３５０℃であり、二次保温温度は一次保温温度より低く、保温時間は３０〜１２０ｓである。 The anode foil obtained by the treatment of H. step G enters the secondary constant temperature stage, is annealed to protect the secondary nitrogen gas at the secondary constant temperature, and the heat retention temperature is 250 to 350 ° C., and the secondary heat retention is performed. The temperature is lower than the primary heat retention temperature, and the heat retention time is 30 to 120 s.
Ｉ.ステップＨの処理により得られた陽極箔を空気中で室温まで冷却させる。 I. The anode foil obtained by the treatment of step H is cooled to room temperature in air.
本発明は、従来技術に比べて以下のような利点がある。 The present invention has the following advantages over the prior art.
本発明は、従来の腐食工程に基づき、焼鈍過程に対して改良を行い、二段階の異なる温度での焼鈍熱処理を用いて、一次焼鈍温度が比較的に高く、二次焼鈍温度が一次焼鈍温度より低く、一次焼鈍が完成した後に、線形降温の過程を経て二次焼鈍過程に移行し、アルミニウム金属の回復及び再結晶の過程十分に利用し、アルミ電解コンデンサ用陽極箔の曲げ性能大幅に向上させる。 The present invention is based on the conventional corrosion process, is an improvement over the annealing process, and uses two steps of annealing heat treatment at different temperatures, the primary annealing temperature is relatively high, and the secondary annealing temperature is the primary annealing temperature. Lower, after the primary annealing is completed, it shifts to the secondary annealing process through the process of linear annealing, and the process of recovery and recrystallization of aluminum metal is fully utilized, and the bending performance of the anode foil for aluminum electrolytic capacitors is greatly improved. Let me.
本発明に係る実施例の目的、技術手段及び利点をより明確にするために、以下本発明の実施例における技術手段に対して、明確且つ十全な説明をするが、ここで説明する実施例は、本発明の一部の実施例に過ぎず、全部の実施例ではない。本発明の実施形態において説明する要素及び特徴は、一つまたは複数の他の実施形態において示す要素及び特徴と組み合わせ可能である。なお、目的を明確にするために、説明では、本発明に関連しない、当業者が熟知する部材及び処理の表示や記述を省略する。本発明に係る実施例に基づき、当業者の創造性作業をせず得られた全ての他の実施例も、本発明の保護範囲に属すものである。 In order to further clarify the purpose, technical means and advantages of the examples according to the present invention, the technical means in the examples of the present invention will be described below in a clear and thorough manner, but the examples described here will be described. Is only a part of the examples of the present invention, not all the examples. The elements and features described in the embodiments of the present invention can be combined with the elements and features shown in one or more other embodiments. In addition, in order to clarify the purpose, in the description, display and description of members and processes which are not related to the present invention and which are familiar to those skilled in the art are omitted. All other examples obtained based on the examples according to the present invention without the creativity work of those skilled in the art also belong to the scope of protection of the present invention.
アルミ電解コンデンサ用中高圧腐食箔の製造方法の具体的なステップは、以下のようである。 The specific steps of the method for manufacturing a medium-high pressure corrosive foil for an aluminum electrolytic capacitor are as follows.
（ａ）１ｗｔ％水酸化ナトリウム溶液を用いて、６０℃温度で中高圧電解コンデンサ用アルミニウム箔に対して浸漬前処理を１２０ｓ行う。 (A) Using a 1 wt% sodium hydroxide solution, a pre-immersion treatment is performed on an aluminum foil for a medium-high voltage electrolytic capacitor at a temperature of 60 ° C. for 120 seconds.
（ｂ）ステップ（ａ）で得られた陽極箔を１ｗｔ％塩酸、４０ｗｔ％硫酸混合溶液を用いて、９０℃温度で電流印加による孔食を６００ｓ行う。 (B) The anode foil obtained in step (a) is pitted by applying a current at a temperature of 90 ° C. using a mixed solution of 1 wt% hydrochloric acid and 40 wt% sulfuric acid for 600 seconds.
（ｃ）ステップ（ｂ）で得られた陽極箔を１ｗｔ％塩酸、３ｗｔ％硫酸、０.０５ｗｔ％リン酸溶液を用いて、９５℃温度で電流印加によるリーマ腐食を６００ｓ行う。 (C) The anode foil obtained in step (b) is subjected to reamer corrosion by applying a current at a temperature of 95 ° C. for 600 seconds using a 1 wt% hydrochloric acid, 3 wt% sulfuric acid, and 0.05 wt% phosphoric acid solution.
（ｄ）ステップ（ｃ）で得られた陽極箔を１ｗｔ％硝酸溶液を用いて、６０℃温度で１２０ｓ浸漬した後に、水道水による洗浄及び純水による洗浄を行う。 (D) The anode foil obtained in step (c) is immersed in a 1 wt% nitric acid solution at a temperature of 60 ° C. for 120 seconds, and then washed with tap water and pure water.
（ｅ）ステップ（ｄ）の処理により得られた陽極箔は、昇温速度が３０℃/ｓである昇温段階を経て、一次定温焼鈍温度に達する。 (E) The anode foil obtained by the treatment of step (d) reaches the primary constant temperature annealing temperature through a temperature raising step in which the temperature rising rate is 30 ° C./s.
（ｆ）ステップ（ｆ）の処理により得られた陽極箔に対して一次定温温度で一次窒素ガスの保護焼鈍処理を行い、保温温度３００℃、保温時間１２０ｓである。 (F) The anode foil obtained by the treatment of step (f) is subjected to protective annealing treatment of primary nitrogen gas at a primary constant temperature, and the heat retention temperature is 300 ° C. and the heat retention time is 120 s.
（ｇ）ステップ（ｆ）の処理により得られた陽極箔は、一次定温温度の線形温度から二次定温温度に変化し、温度変化時間は２０ｓである。 (G) The anode foil obtained by the treatment of step (f) changes from the linear temperature of the primary constant temperature to the secondary constant temperature, and the temperature change time is 20 s.
（ｈ）ステップ（ｇ）の処理により得られた陽極箔に対して二次定温温度で二次窒素ガス保護の焼鈍処理を行い、保温温度２５０℃、保温時間１２０ｓである。 (H) The anode foil obtained by the treatment of step (g) is annealed to protect the secondary nitrogen gas at a secondary constant temperature, and the heat retention temperature is 250 ° C. and the heat retention time is 120 s.
（ｉ）ステップ（ｈ）の処理により得られた陽極箔を空気中で室温まで冷却させる。 (I) The anode foil obtained by the treatment of step (h) is cooled to room temperature in air.
アルミ電解コンデンサ用中高圧腐食箔の製造方法の具体的なステップは、以下のようである。 The specific steps of the method for manufacturing a medium-high pressure corrosive foil for an aluminum electrolytic capacitor are as follows.
（ａ）２ｗｔ％水酸化ナトリウム溶液を用いて、２０℃温度で中高圧電解コンデンサ用アルミニウム箔に対して浸漬前処理を１００ｓ行う。 (A) Using a 2 wt% sodium hydroxide solution, a pre-immersion treatment is performed on an aluminum foil for a medium-high voltage electrolytic capacitor at a temperature of 20 ° C. for 100 seconds.
（ｂ）ステップ（ａ）で得られた陽極箔を２ｗｔ％塩酸、１０ｗｔ％硫酸混合溶液を用いて、７０℃温度で電流印加による孔食を５００ｓ行う。 (B) The anode foil obtained in step (a) is pitted by applying a current at a temperature of 70 ° C. using a mixed solution of 2 wt% hydrochloric acid and 10 wt% sulfuric acid for 500 s.
（ｃ）ステップ（ｂ）で得られた陽極箔を２ｗｔ％塩酸、５ｗｔ％硫酸、０.０１ｗｔ％リン酸溶液を用いて、８０℃温度で電流印加によるリーマ腐食を５００ｓ行う。 (C) The anode foil obtained in step (b) is subjected to reamer corrosion by applying a current at a temperature of 80 ° C. for 500 seconds using a 2 wt% hydrochloric acid, 5 wt% sulfuric acid, and 0.01 wt% phosphoric acid solution.
（ｄ）ステップ（ｃ）で得られた陽極箔を２ｗｔ％硝酸溶液を用いて、６０℃温度で１００ｓ浸漬した後に、水道水による洗浄及び純水による洗浄を行う。 (D) The anode foil obtained in step (c) is immersed in a 2 wt% nitric acid solution at a temperature of 60 ° C. for 100 seconds, and then washed with tap water and pure water.
（ｅ）ステップ（ｄ）の処理により得られた陽極箔は、昇温速度４０℃/ｓの昇温段階を経て、一次定温焼鈍温度に達する。 (E) The anode foil obtained by the treatment of step (d) reaches the primary constant temperature annealing temperature through the heating step of the heating rate of 40 ° C./s.
（ｆ）ステップ（ｅ）の処理により得られた陽極箔に対して一次定温温度下で一次窒素ガスの保護焼鈍処理を行うが、保温温度３５０℃、保温時間１００ｓである。 (F) The anode foil obtained by the treatment of step (e) is subjected to a protective annealing treatment of primary nitrogen gas under a primary constant temperature, and the heat retention temperature is 350 ° C. and the heat retention time is 100 s.
（ｇ）ステップ（ｆ）の処理により得られた陽極箔は、一次定温温度から二次定温温度に線形温度変化し、温度変化時間は１５ｓである。 (G) The anode foil obtained by the treatment of step (f) linearly changes in temperature from the primary constant temperature to the secondary constant temperature, and the temperature change time is 15 s.
（ｈ）ステップ（ｇ）の処理により得られた陽極箔に対して二次定温温度下で二次窒素ガス保護の焼鈍処理を行い、保温温度２８０℃、保温時間１００ｓである。 (H) The anode foil obtained by the treatment of step (g) is annealed to protect the secondary nitrogen gas under a secondary constant temperature, and the heat retention temperature is 280 ° C. and the heat retention time is 100 s.
（ｉ）ステップ（ｈ）の処理により得られた陽極箔を空気中で室温まで冷却させる。 (I) The anode foil obtained by the treatment of step (h) is cooled to room temperature in air.
アルミ電解コンデンサ用中高圧腐食箔の製造方法の具体的なステップは、以下のようである。 The specific steps of the method for manufacturing a medium-high pressure corrosive foil for an aluminum electrolytic capacitor are as follows.
（ａ）５ｗｔ％水酸化ナトリウム溶液を用いて、４０℃温度で中高圧電解コンデンサ用アルミニウム箔に対して浸漬前処理を１００ｓ行う。 (A) Using a 5 wt% sodium hydroxide solution, a pre-immersion treatment is performed on an aluminum foil for a medium-high voltage electrolytic capacitor at a temperature of 40 ° C. for 100 seconds.
（ｂ）ステップ（ａ）で得られた陽極箔を４ｗｔ％塩酸、２０ｗｔ％硫酸混合溶液を用いて、６０℃温度で電流印加による孔食を４００ｓ行う。 (B) The anode foil obtained in step (a) is pitted by applying a current at a temperature of 60 ° C. using a mixed solution of 4 wt% hydrochloric acid and 20 wt% sulfuric acid for 400 seconds.
（ｃ）ステップ（ｂ）で得られた陽極箔を５ｗｔ％塩酸、１０ｗｔ％硫酸、０.０３ｗｔ％リン酸溶液を用いて、７０℃温度で電流印加によるリーマ腐食を３００ｓ行う。 (C) The anode foil obtained in step (b) is subjected to reamer corrosion by applying a current at a temperature of 70 ° C. for 300 s using a 5 wt% hydrochloric acid, 10 wt% sulfuric acid, and 0.03 wt% phosphoric acid solution.
（ｄ）ステップ（ｃ）で得られた陽極箔を８ｗｔ％硝酸溶液を用いて、３０℃温度で６０ｓ浸漬した後に、水道水による洗浄及び純水による洗浄を行う。 (D) The anode foil obtained in step (c) is immersed in an 8 wt% nitric acid solution at a temperature of 30 ° C. for 60 seconds, and then washed with tap water and pure water.
（ｅ）ステップ（ｄ）の処理により得られた陽極箔は、昇温速度５０℃/ｓの昇温段階を経て、一次定温焼鈍温度に達する。 (E) The anode foil obtained by the treatment of step (d) reaches the primary constant temperature annealing temperature through the heating step of the heating rate of 50 ° C./s.
（ｆ）ステップ（ｅ）の処理により得られた陽極箔に対して一次定温温度で一次窒素ガスの保護焼鈍処理を行うが、保温温度４００℃、保温時間６０ｓである。 (F) The anode foil obtained by the treatment of step (e) is subjected to a protective annealing treatment of primary nitrogen gas at a primary constant temperature, and the heat retention temperature is 400 ° C. and the heat retention time is 60 s.
（ｇ）ステップ（ｆ）の処理により得られた陽極箔は、一次定温温度から二次定温温度に線形温度変化し、温度変化時間は１０ｓである。 (G) The anode foil obtained by the treatment of step (f) linearly changes in temperature from the primary constant temperature to the secondary constant temperature, and the temperature change time is 10 s.
（ｈ）ステップ（ｇ）の処理により得られた陽極箔に対して二次定温温度で二次窒素ガス保護の焼鈍処理を行い、保温温度３００℃、保温時間６０ｓである。 (H) The anode foil obtained by the treatment of step (g) is annealed to protect the secondary nitrogen gas at a secondary constant temperature, and the heat retention temperature is 300 ° C. and the heat retention time is 60 s.
（ｉ）ステップ（ｈ）の処理により得られた陽極箔を空気中で室温まで冷却させる。 (I) The anode foil obtained by the treatment of step (h) is cooled to room temperature in air.
アルミ電解コンデンサ用中高圧腐食箔の製造方法の具体的なステップは、以下のようである。 The specific steps of the method for manufacturing a medium-high pressure corrosive foil for an aluminum electrolytic capacitor are as follows.
（ａ）１０ｗｔ％水酸化ナトリウム溶液を用いて、２０℃℃温度で中高圧電解コンデンサ用アルミニウム箔に対して浸漬前処理を９０ｓ行う。 (A) Using a 10 wt% sodium hydroxide solution, a pre-immersion treatment is performed on an aluminum foil for a medium-high voltage electrolytic capacitor at a temperature of 20 ° C. for 90 seconds.
（ｂ）ステップ（ａ）で得られた陽極箔を５ｗｔ％塩酸、４０ｗｔ％硫酸混合溶液を用いて、２０℃温度で電流印加による孔食を１２０ｓ行う。 (B) The anode foil obtained in step (a) is pitted by applying a current at a temperature of 20 ° C. using a mixed solution of 5 wt% hydrochloric acid and 40 wt% sulfuric acid for 120 s.
（c）ステップ（ｂ）で得られた陽極箔を１０ｗｔ％塩酸、２０ｗｔ％硫酸、０.０５ｗｔ％リン酸溶液を用いて、５０℃温度で電流印加によるリーマ腐食を１２０ｓ行う。 (C) The anode foil obtained in step (b) is subjected to reamer corrosion by applying a current at a temperature of 50 ° C. for 120 s using a solution of 10 wt% hydrochloric acid, 20 wt% sulfuric acid and 0.05 wt% phosphoric acid.
（ｄ）ステップ（ｃ）で得られた陽極箔を１０ｗｔ％硝酸溶液を用いて２０℃温度で３０ｓ浸漬した後に、水道水による洗浄及び純水による洗浄を行う。 (D) The anode foil obtained in step (c) is immersed in a 10 wt% nitric acid solution at a temperature of 20 ° C. for 30 seconds, and then washed with tap water and pure water.
（ｅ）ステップ（ｄ）の処理により得られた陽極箔は、昇温速度５０℃/ｓの昇温段階を経て、一次定温焼鈍温度に達する。 (E) The anode foil obtained by the treatment of step (d) reaches the primary constant temperature annealing temperature through the heating step of the heating rate of 50 ° C./s.
（ｆ）ステップ（ｅ）の処理により得られた陽極箔に対して一次定温温度で一次窒素ガス保護の焼鈍処理を行うが、保温温度５００℃、保温時間３０ｓである。 (F) The anode foil obtained by the treatment of step (e) is annealed to protect the primary nitrogen gas at a primary constant temperature, and the heat retention temperature is 500 ° C. and the heat retention time is 30 s.
（ｇ）ステップ（ｆ）の処理により得られた陽極箔は、一次定温温度から二次定温温度に線形温度変化し、温度変化時間は５ｓである。 (G) The anode foil obtained by the treatment of step (f) linearly changes in temperature from the primary constant temperature to the secondary constant temperature, and the temperature change time is 5 s.
（ｈ）ステップ（ｇ）の処理より得られた陽極箔に対して二次定温温度で二次窒素ガス保護の焼鈍処理を行うが、保温温度は一次温度の３５０℃より低く、保温時間は３０ｓである。 (H) The anode foil obtained from the treatment of step (g) is annealed to protect the secondary nitrogen gas at a secondary constant temperature, but the heat retention temperature is lower than the primary temperature of 350 ° C. and the heat retention time is 30 s. Is.
（ｉ）ステップ（ｈ）の処理により得られた陽極箔を空気中で室温まで冷却させる。 (I) The anode foil obtained by the treatment of step (h) is cooled to room temperature in air.
本発明の腐食電極箔と従来技術の工程による腐食電極箔を生産ラインにおいて化成した後、比較結果は、以下のようである（化成条件：アジピン酸アンモニウム槽液，曲げ試験のチャックの半径は１.０ｍｍである）。 After chemicalizing the corroded electrode foil of the present invention and the corroded electrode foil by the process of the prior art in the production line, the comparison result is as follows (chemical conditions: ammonium adipate bath liquid, chuck radius of bending test is 1). It is .0 mm).
比較結果より、本発明の腐食工程により得られた腐食電極箔の化成後の曲げ性能が顕著に向上し、従来の腐食工程に比較して２０％％以上向上していることがわかる。 From the comparison results, it can be seen that the bending performance of the corroded electrode foil obtained by the corrosion process of the present invention after chemical conversion is remarkably improved, and is improved by 20% or more or more as compared with the conventional corrosion process.
なお、以上により本発明の及びその利点について説明したが、特許請求の範囲により限定される本発明の思想を超えない範囲で各種置換や変化を行うことができることは理解されるべきである。また、本発明の範囲は、明細書で説明した過程、設備、手段、方法及びステップの具体的実施例に限定されるものではない。当業者であれば、本発明に基づき、ここで説明する実施例と基本的に同じ機能又はそれと基本的に同じ結果を果たす、従来及び将来開発される過程、設備、手段、方法又はステップを使用することができる。そのため添付する特許請求の範囲は、その範囲内においてこのような過程、設備、手段、方法又はステップを含む。 Although the present invention and its advantages have been described above, it should be understood that various substitutions and changes can be made without exceeding the idea of the present invention limited by the claims. Moreover, the scope of the present invention is not limited to specific examples of the processes, equipment, means, methods and steps described herein. Those skilled in the art will use conventional and future developed processes, equipment, means, methods or steps based on the present invention that perform essentially the same functions or results as those described herein. can do. Therefore, the appended claims include such processes, equipment, means, methods or steps within the scope.
Claims (5)
（Ａ）１ｗｔ％〜１０ｗｔ％水酸化ナトリウム溶液を用いて、２０℃〜６０℃温度で中高圧電解コンデンサ用アルミニウム箔に対して３０〜１２０sの浸漬前処理を行い、
（Ｂ）ステップＡで得られた陽極箔を１ｗｔ％〜５ｗｔ％塩酸、５ｗｔ％〜４０ｗｔ％硫酸混合溶液を用いて、２０℃〜９０℃温度で電流印加による孔食を１２０〜６００ｓ行い、
（Ｃ）ステップＢで得られた陽極箔を１ｗｔ％〜１０ｗｔ％塩酸、３ｗｔ％〜２０ｗｔ％硫酸、０.００５ｗｔ％〜０.０５ｗｔ％リン酸溶液を用いて、５０℃〜９５℃温度で電流印加によるリーマ腐食を１２０〜６００ｓ行い、
（Ｄ）ステップＣで得られた陽極箔を１ｗｔ％〜１０ｗｔ％硝酸溶液を用いて、２０℃〜６０℃温度で３０〜１２０ｓ浸漬した後、水道水による洗浄及び純水による洗浄を行い、
（Ｅ）ステップＤの処理により得られた陽極箔を昇温段階に進入させ、昇温開始温度は室温であり、終了温度は一次定温温度であり、昇温速度は３０〜５０℃/ｓであり、
（Ｆ）ステップＥの処理により得られた陽極箔を一次定温段階に進入させ、保温温度?３００〜５００℃、保温時間３０〜１２０ｓであり、一次定温温度で一次窒素ガス保護の焼鈍処理を行い、
（Ｇ）ステップＦの処理により得られた陽極箔を線形温度変化段階に進入させ、温度変化の開始温度は一次保温温度であり、温度変化の終了温度は二次保温温度であり、温度変化時間は５〜２０ｓであり、
（Ｈ）ステップＧの処理より得られた陽極箔を二次定温段階に進入させ、二次定温温度で二次窒素ガス保護の焼鈍処理を行い、保温温度は２５０〜３５０℃であり、二次保温温度は一次保温温度より低く、保温時間は３０〜１２０ｓであり、
（Ｉ）ステップＨの処理により得られた陽極箔を空気中で室温まで冷却させる
ステップを含むことを特徴とするアルミ電解コンデンサ用中高圧腐食箔の製造方法。 A method for producing a medium- and high-pressure corrosive foil for an aluminum electrolytic capacitor, wherein the method is specifically:
(A) Using a 1 wt% to 10 wt% sodium hydroxide solution, a 30 to 120 s dip pretreatment was performed on an aluminum foil for a medium- and high-pressure electrolytic capacitor at a temperature of 20 ° C to 60 ° C.
(B) The anode foil obtained in step A is pitted by applying a current at a temperature of 20 ° C. to 90 ° C. using a mixed solution of 1 wt% to 5 wt% hydrochloric acid and 5 wt% to 40 wt% sulfuric acid for 120 to 600 s.
(C) The anode foil obtained in step B is currented at a temperature of 50 ° C. to 95 ° C. using a 1 wt% to 10 wt% hydrochloric acid, 3 wt% to 20 wt% sulfuric acid, and 0.005 wt% to 0.05 wt% phosphoric acid solutions. Reamer corrosion by application is performed for 120 to 600 s,
(D) The anode foil obtained in step C is immersed in a 1 wt% to 10 wt% nitric acid solution at a temperature of 20 ° C. to 60 ° C. for 30 to 120 seconds, and then washed with tap water and pure water.
(E) The anode foil obtained by the treatment in step D is brought into the temperature raising stage, the temperature rise start temperature is room temperature, the end temperature is the primary constant temperature, and the temperature rise rate is 30 to 50 ° C./s. can be,
(F) The anode foil obtained by the treatment of step E is allowed to enter the primary constant temperature stage, and the heat retention temperature is 300 to 500 ° C. and the heat retention time is 30 to 120 s, and the primary nitrogen gas protection is annealed at the primary constant temperature. ,
(G) The anode foil obtained by the treatment of step F is brought into the linear temperature change stage, the start temperature of the temperature change is the primary heat retention temperature, the end temperature of the temperature change is the secondary heat retention temperature, and the temperature change time. Is 5 to 20 s
(H) The anode foil obtained from the treatment in step G is brought into the secondary constant temperature stage, annealed to protect the secondary nitrogen gas at the secondary constant temperature, and the heat retention temperature is 250 to 350 ° C., which is secondary. The heat retention temperature is lower than the primary heat retention temperature, and the heat retention time is 30 to 120 s.
(I) A method for producing a medium- and high-pressure corrosive foil for an aluminum electrolytic capacitor, which comprises a step of cooling the anode foil obtained by the treatment of step H to room temperature in air.
The heating rate in step E is 30 to 50 ° C./s, the primary heat retention temperature in step F is 500 ° C., the heat retention time is 30 s, and the temperature change time in step G is 5 s. The method for producing a medium- and high-pressure corrosive foil for an aluminum electrolytic capacitor according to claim 1, wherein the secondary heat retention temperature in step H is 350 ° C. and the heat retention time is 30 s.
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