JP2009010330A - Method for manufacturing anode foil for aluminum electrolytic capacitor - Google Patents
Method for manufacturing anode foil for aluminum electrolytic capacitor Download PDFInfo
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- JP2009010330A JP2009010330A JP2008080103A JP2008080103A JP2009010330A JP 2009010330 A JP2009010330 A JP 2009010330A JP 2008080103 A JP2008080103 A JP 2008080103A JP 2008080103 A JP2008080103 A JP 2008080103A JP 2009010330 A JP2009010330 A JP 2009010330A
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- 239000011888 foil Substances 0.000 title claims abstract description 58
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003990 capacitor Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title abstract description 20
- 238000005530 etching Methods 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 19
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 238000005406 washing Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000005452 bending Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 3
- 239000010731 rolling oil Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- -1 aluminum ions Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- ing And Chemical Polishing (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
本発明はアルミニウム電解コンデンサ（以下、電解コンデンサと称す）に用いられる陽極箔の製造方法に関し、特に中高圧用の電解コンデンサ用陽極箔の製造方法に関するものである。 The present invention relates to a method for producing an anode foil used for an aluminum electrolytic capacitor (hereinafter referred to as an electrolytic capacitor), and more particularly to a method for producing an anode foil for a medium-high voltage electrolytic capacitor.
近年、電解コンデンサの小形化、コストダウンへの要望がますます高まり、電解コンデンサ用陽極箔（以下、陽極箔と称す）の単位面積当たりの静電容量を高める技術にはより一層の進歩が求められている。 In recent years, there has been an increasing demand for electrolytic capacitor miniaturization and cost reduction, and further progress is required in technology for increasing the capacitance per unit area of anode foil for electrolytic capacitors (hereinafter referred to as anode foil). It has been.
陽極箔の静電容量を高める、すなわち実効表面積を拡大するには、酸性溶液中で化学的または電気化学的にエッチングを行う方法が採られている。
また、中高圧用に使用される陽極箔のエッチング工程は、汚れや自然酸化皮膜、圧延油などを取り除く前処理工程を経て、トンネル状のエッチングピット（以下、ピットと称す）を形成する第１エッチング工程と、そのピットを陽極酸化電圧に適した孔径まで拡大する第２エッチング工程に分割して行うのが主流となっており、特に第１エッチング工程において、いかに多くのトンネルピットを分散させて生成させることができるかが重要となる。
In order to increase the capacitance of the anode foil, that is, to increase the effective surface area, a method of chemically or electrochemically etching in an acidic solution is employed.
In addition, the etching process of the anode foil used for medium and high pressure is a first process for forming tunnel-like etching pits (hereinafter referred to as pits) through a pretreatment process for removing dirt, natural oxide film, rolling oil, and the like. The mainstream is to divide the etching process into a second etching process that expands the pits to a hole diameter suitable for the anodic oxidation voltage. In particular, in the first etching process, how many tunnel pits are dispersed. Whether it can be generated is important.
そのために、アルミニウム原箔表層に濃縮した微量不純物を付着させ、ピット発生の基点とする手法が一般的となっているが、濃縮度合が不均一となってしまうのが欠点であった。
その解決策として、酸性またはアルカリ性の水溶液に浸漬処理を行い、その後アルミニウムよりも自然電極電位の高い金属イオンを含む酸性溶液中でカソード電流を印加して原箔表面にピット発生基点となる金属イオンを均一に付着させるという製造方法が提案されている（例えば、特許文献１参照）。
For this reason, a method of attaching a small amount of concentrated impurities to the surface layer of the aluminum foil and using it as a starting point of pit generation has become common, but it has been a disadvantage that the degree of concentration becomes uneven.
As a solution, a metal ion that becomes a pit generation base point on the surface of the original foil by immersing it in an acidic or alkaline aqueous solution and then applying a cathode current in an acidic solution containing a metal ion having a higher natural electrode potential than aluminum. There has been proposed a manufacturing method for uniformly attaching (see, for example, Patent Document 1).
しかしながら、特許文献１に開示の方法では、アルミニウム箔を、金属イオンを含有した酸性水溶液中に浸漬すると、アルミニウム箔表面に金属イオンが吸着する量が増大せず、金属イオンを吸着させるのにカソード電流印加工程が必要となる場合がある。このときには生産コスト高となる上、通常、直後の第１エッチング工程でアノード電流印加が必要となるため、設備面の煩雑化につながってしまう。 However, in the method disclosed in Patent Document 1, when the aluminum foil is immersed in an acidic aqueous solution containing metal ions, the amount of metal ions adsorbed on the surface of the aluminum foil does not increase, and the cathode is used to adsorb metal ions. A current application step may be required. In this case, the production cost is high, and normally, an anode current needs to be applied in the first etching step immediately after that, which leads to complicated facilities.
本発明は、この問題を解決するものであり、簡易な方法でピット発生点を均一に制御して高容量の電解コンデンサ用陽極箔を安価に製造できる方法を提供することを目的とするものである。 The present invention is to solve this problem, and an object of the present invention is to provide a method for producing a high-capacity electrolytic capacitor anode foil at a low cost by uniformly controlling pit generation points by a simple method. is there.
上記課題を解決するため、本発明では、アルミニウム箔にトンネル状ピットを発生させる第１エッチング工程と、第１エッチング工程で発生したピットの孔径を拡大するための第２エッチング工程とを有する電解コンデンサ用陽極箔の製造方法において、前記第１エッチング工程の前に、前記アルミニウム箔を第１前処理液に浸漬する第１前処理と、該アルミニウム箔を金属イオンを含むアルカリ性の第２前処理液に浸漬する第２前処理とを有することを特徴とする。 In order to solve the above-mentioned problem, in the present invention, an electrolytic capacitor having a first etching step for generating tunnel-like pits in an aluminum foil and a second etching step for expanding the hole diameter of the pits generated in the first etching step In the method for manufacturing an anode foil, a first pretreatment for immersing the aluminum foil in a first pretreatment liquid and an alkaline second pretreatment liquid containing metal ions before the first etching step. And a second pretreatment immersed in the substrate.
本発明において、前記第２前処理液として、水酸化ナトリウム、炭酸ナトリウム、ケイ酸ナトリウムのうち少なくとも１種を含むアルカリ性溶液に、Ｚｎ、Ｓｎ、Ｔｉ、Ｃｕ、Ｂｉ、Ｐｂ、Ｍｇのうち少なくとも１種の金属塩を混合した溶液を用い、かつ、第２前処理液の液温が８０℃以上であることが好ましい。 In the present invention, as the second pretreatment liquid, an alkaline solution containing at least one of sodium hydroxide, sodium carbonate, and sodium silicate is used, and at least one of Zn, Sn, Ti, Cu, Bi, Pb, and Mg. It is preferable to use a solution in which seed metal salts are mixed and the liquid temperature of the second pretreatment liquid is 80 ° C. or higher.
本発明において、前記第２前処理工程と第１エッチング工程との間に乾燥処理工程を有することが好ましい。 In the present invention, it is preferable to have a drying treatment step between the second pretreatment step and the first etching step.
本発明において、前記乾燥処理の温度は２５〜１００℃であることが好ましい。 In this invention, it is preferable that the temperature of the said drying process is 25-100 degreeC.
本発明では、第１前処理において、リン酸および硝酸を含む酸性の第１前処理液によってアルミニウム箔の表面濃縮不純物を取り除きながら表面を活性化させ、第２前処理において、金属イオンを含むアルカリ性の第２前処理液に浸漬することにより、アルミニウム箔表面が中和された後、箔表面がアルカリ性雰囲気になるため、アルミニウムイオンと金属イオンの電位差を利用する金属イオンの吸着を効率的に行わせることができるとともに、分布が均一で、かつ長さの揃ったピットを発生させることができ、その結果、単位面積あたりの静電容量が高いエッチング箔を得ることができると考えられる。 In the present invention, in the first pretreatment, the surface is activated while removing the surface concentrated impurities of the aluminum foil with the acidic first pretreatment liquid containing phosphoric acid and nitric acid, and in the second pretreatment, the alkali containing metal ions is activated. After the surface of the aluminum foil is neutralized by dipping in the second pretreatment liquid, the foil surface becomes an alkaline atmosphere, so that the metal ions are efficiently adsorbed using the potential difference between the aluminum ions and the metal ions. It is considered that pits having uniform distribution and uniform length can be generated, and as a result, an etching foil having a high capacitance per unit area can be obtained.
また、本発明の電解コンデンサ用陽極箔の製造方法によれば、前記第２前処理は、カソード電流印加ではなく、処理液への浸漬処理が行われるため、安価で簡易な設備によってピット発生のための金属塩をより均一にアルミニウム箔表面に付着させることができる。
これにより単位面積あたりの静電容量が高いエッチング箔を提供することができ、電解コンデンサの小形化に寄与することができる。
Further, according to the method for manufacturing an anode foil for an electrolytic capacitor of the present invention, the second pretreatment is not cathodic current application, but is immersed in a treatment solution, so that pits are generated by inexpensive and simple equipment. Therefore, the metal salt can be more uniformly attached to the surface of the aluminum foil.
As a result, an etching foil having a high capacitance per unit area can be provided, which can contribute to downsizing of the electrolytic capacitor.
また、本発明では、第２前処理後に水洗することなくそのまま乾燥処理を行うことにより、アルミニウム箔表面に金属イオンが付着するために、さらなるピット分布の均一化が進むので、単位面積あたりの静電容量がより高いエッチング箔を得ることができると考えられる。 In the present invention, since the metal ions adhere to the surface of the aluminum foil by performing the drying process without washing with water after the second pretreatment, the pit distribution is further uniformized. It is considered that an etching foil having a higher electric capacity can be obtained.
以下、実施例に基づいて本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described based on examples.
［実施例１］
純度９９．９９％、厚さ１１０μｍの高純度軟質アルミニウム箔を使用し、第１前処理として、リン酸１０．０ｍｏｌ／Ｌ、硝酸１．０ｍｏｌ／Ｌの混合溶液（第１処理液）にアルミニウム箔を１５秒間浸漬した。その際の液温は７０℃である。
[Example 1]
A high-purity soft aluminum foil having a purity of 99.99% and a thickness of 110 μm is used. As a first pretreatment, aluminum is added to a mixed solution (first treatment liquid) of 10.0 mol / L phosphoric acid and 1.0 mol / L nitric acid. The foil was immersed for 15 seconds. The liquid temperature in that case is 70 degreeC.
次に、第２前処理として、Ｐｂイオン（３０ｐｐｍ）を含む０．０１ｍｏｌ／Ｌの水酸化ナトリウム水溶液（第２処理液）を８０℃に加熱し、その溶液にアルミニウム箔を６０秒間浸漬した。 Next, as a second pretreatment, a 0.01 mol / L sodium hydroxide aqueous solution (second treatment liquid) containing Pb ions (30 ppm) was heated to 80 ° C., and an aluminum foil was immersed in the solution for 60 seconds.
十分な水洗を行った後、第１エッチング工程として、硫酸３．０ｍｏｌ／Ｌ、塩化アルミニウム１．０ｍｏｌ／Ｌの混合溶液を７５℃に加熱し、該溶液中で、上記のアルミニウム箔に電流密度０．２Ａ／ｃｍ２、電気量１８Ｃ／ｃｍ２にて、直流電流を印加する処理を行った。 After sufficient water washing, as a first etching step, a mixed solution of sulfuric acid 3.0 mol / L and aluminum chloride 1.0 mol / L is heated to 75 ° C., and the current density is applied to the aluminum foil in the solution. A treatment for applying a direct current was performed at 0.2 A / cm 2 and an electric quantity of 18 C / cm 2 .
続いて、第２エッチング工程として、塩酸０．５０ｍｏｌ／Ｌ、塩化アルミニウム１．０ｍｏｌ／Ｌの混合溶液を８５℃に加熱し、上記のエッチング箔を１５分間浸漬してピットの孔径拡大を行い、水洗、脱塩素処理を施し、エッチング箔試料を作製した。 Subsequently, as a second etching step, a mixed solution of hydrochloric acid 0.50 mol / L and aluminum chloride 1.0 mol / L is heated to 85 ° C., and the etching foil is immersed for 15 minutes to expand the pit hole diameter, Washing with water and dechlorination were performed to prepare an etching foil sample.
［実施例２〜４］第２前処理液の浸漬温度比較
第２前処理液の温度を７０、９０、１００℃の範囲で変更した以外は、実施例１と同様の方法でエッチング箔試料を作製した。
[Examples 2 to 4] Comparison of immersion temperature of second pretreatment liquid Etching foil samples were prepared in the same manner as in Example 1 except that the temperature of the second pretreatment liquid was changed in the range of 70, 90, and 100 ° C. Produced.
（比較例１）
第２前処理を行わない以外は、実施例１と同様の方法でエッチング箔試料を作製した。
(Comparative Example 1)
An etching foil sample was produced in the same manner as in Example 1 except that the second pretreatment was not performed.
（比較例２）
上記の第１前処理、第２前処理の代わりに、自然酸化皮膜や圧延油を取り除くための公知の前処理（０．５ｍｏｌ／Ｌのリン酸水溶液に３分間浸漬）のみを行い、第１および第２前処理を行わない以外は、実施例１と同様の方法でエッチング箔試料を作製した。
(Comparative Example 2)
Instead of the first pretreatment and the second pretreatment, only a known pretreatment for removing a natural oxide film and rolling oil (immersion in a 0.5 mol / L phosphoric acid aqueous solution for 3 minutes) is performed. An etching foil sample was prepared in the same manner as in Example 1 except that the second pretreatment was not performed.
（比較例３）
上記の第１前処理を、自然酸化皮膜や圧延油を取り除くための公知の前処理条件である０．５ｍｏｌ／Ｌのリン酸水溶液への３分間浸漬を行う以外は、実施例１と同様の方法でエッチング箔試料を作製した。
(Comparative Example 3)
The first pretreatment is the same as in Example 1 except that the first pretreatment is performed for 3 minutes in a 0.5 mol / L phosphoric acid aqueous solution, which is a known pretreatment condition for removing the natural oxide film and rolling oil. The etching foil sample was produced by the method.
（比較例４）
上記の第１前処理を、１０．０ｍｏｌ／Ｌのリン酸水溶液のみで行う以外は、実施例１と同様の方法でエッチング箔試料を作製した。
(Comparative Example 4)
An etching foil sample was prepared in the same manner as in Example 1 except that the first pretreatment was performed only with a 10.0 mol / L phosphoric acid aqueous solution.
（比較例５）
上記の第１前処理を、１．０ｍｏｌ／Ｌの硝酸水溶液のみで行う以外は、実施例１と同様の方法でエッチング箔試料を作製した。
(Comparative Example 5)
An etching foil sample was prepared in the same manner as in Example 1 except that the first pretreatment was performed only with a 1.0 mol / L nitric acid aqueous solution.
［実施例５〜１０］第２前処理液の含有金属塩比較
上記の実施例１において、第２前処理液の含有する金属塩を、Ｐｂの代わりに、Ｚｎ、Ｓｎ、Ｔｉ、Ｃｕ、Ｂｉ、Ｍｇとしたものについても、実施例１と同様の方法でエッチング箔試料を作製した。なお、金属イオン濃度はいずれも３０ｐｐｍとした。
[Examples 5 to 10] Comparison of metal salt contained in second pretreatment liquid In Example 1 above, the metal salt contained in the second pretreatment liquid was replaced by Zn, Sn, Ti, Cu, Bi instead of Pb. Etching foil samples were prepared by the same method as in Example 1 for Mg. The metal ion concentration was 30 ppm.
［実施例１１、１２］第２前処理液のアルカリ性液種の比較
上記の実施例１において、第２前処理液のアルカリ性液種を水酸化ナトリウムの代わりに炭酸ナトリウム、ケイ酸ナトリウムを用いた水溶液（濃度は何れも０．０２ｍｏｌ／Ｌ）（実施例１１、１２）についても、実施例１と同様の方法でエッチング箔試料を作製した。
[Examples 11 and 12] Comparison of alkaline liquid type of second pretreatment liquid In Example 1 above, sodium carbonate and sodium silicate were used as the alkaline liquid type of the second pretreatment liquid instead of sodium hydroxide. Etching foil samples were prepared in the same manner as in Example 1 for aqueous solutions (both concentrations were 0.02 mol / L) (Examples 11 and 12).
［実施例１ａ〜１ｅ］第２前処理後、水洗なしで乾燥（温度）の比較
上記の実施例１において、第２前処理後、水洗なしでそのまま乾燥処理を行った。なお、乾燥処理温度は各々、２５、４５、８０、１００、１２０℃とした以外は、実施例１と同様の方法でエッチング箔試料を作製した。
[Examples 1a to 1e] Comparison of drying (temperature) without washing with water after the second pretreatment In Example 1, the drying treatment was performed as it was without washing with water after the second pretreatment. In addition, the etching foil sample was produced by the method similar to Example 1 except the drying process temperature having been 25, 45, 80, 100, and 120 degreeC, respectively.
［実施例５ｂ〜１０ｂ］第２前処理液の含有金属塩、水洗なしで乾燥（温度変更）の比較
上記の実施例５〜１０において、第２前処理後、水洗なしでそのまま、乾燥処理温度４５℃、乾燥時間５分間で乾燥処理を行った以外は、実施例５〜１０と同様の方法でエッチング箔試料を作製した。
[Examples 5b to 10b] Comparison of the metal salt contained in the second pretreatment liquid and drying (temperature change) without washing In the above Examples 5 to 10, the drying treatment temperature was maintained without washing after the second pretreatment. Etching foil samples were prepared in the same manner as in Examples 5 to 10 except that the drying treatment was performed at 45 ° C. and a drying time of 5 minutes.
上記の実施例１〜１２、１ａ〜１ｅ、５ｂ〜１０ｂ、比較例１〜５のエッチング箔試料について、濃度１００ｇ／Ｌ、液温９０℃のホウ酸水溶液中で４００Ｖ化成を行い、各試料について静電容量と、折曲強度（φ１．０ｍｍ、２．５Ｎ荷重、折曲角度９０度の条件下で１往復を４回とする）を測定した。その結果を表１に示す。 For the etching foil samples of Examples 1 to 12, 1a to 1e, 5b to 10b, and Comparative Examples 1 to 5, 400V conversion was performed in a boric acid aqueous solution having a concentration of 100 g / L and a liquid temperature of 90 ° C. Capacitance and bending strength (φ1.0 mm, 2.5N load, bending angle 90 °, one round trip was set to 4 times) were measured. The results are shown in Table 1.
［第２前処理液への浸漬有無、第１前処理液への浸漬有無比較］ 実施例１、比較例１、２
実施例１と比較例１とを比較すると、表１の結果から分かるように、第１前処理のみで第２前処理を行わない場合、ピット発生点となる不純物が取り除かれた状態であるため、正常なエッチングが行われず静電容量が、大幅に低下し、また、折曲強度も低下した。よって、第２前処理が必須であることが分かる。
また、比較例２のように、第１および第２前処理を行わない場合、ピット発生点となる不純物が残存するが、均一に分布していないため、静電容量が若干低下し、折曲強度が低下した。
[Comparison of presence / absence of immersion in second pretreatment liquid and presence / absence of immersion in first pretreatment liquid] Example 1, Comparative Examples 1 and 2
When Example 1 and Comparative Example 1 are compared, as can be seen from the results in Table 1, when the second pretreatment is not performed with only the first pretreatment, the impurities that are the pit generation points are removed. As a result, normal etching was not performed, and the capacitance was greatly lowered, and the bending strength was also lowered. Therefore, it turns out that the second pretreatment is essential.
In addition, as in Comparative Example 2, when the first and second pretreatments are not performed, impurities that become pit generation points remain, but since the impurities are not uniformly distributed, the capacitance is slightly lowered and bending is caused. The strength decreased.
［第１前処理の条件比較］ 実施例１、比較例３〜５
実施例１と比較例３とを比較すると、表１の結果から分かるように、リン酸および硝酸を含む第１前処理液による第１前処理を行わず、０．５ｍｏｌ／Ｌのリン酸水溶液のみで行う比較例３の場合、アルミニウム箔の表面濃縮不純物の除去、表面の活性化が不十分になると考えられる。
よって、比較例３の場合、アルミニウム箔表面の不純物の除去、表面活性化が不十分なため、第２前処理において、金属イオンを含むアルカリ性の第２前処理液に浸漬したとき、アルミニウムイオンと金属イオンの電位差を利用する金属イオンの吸着を効率的に行わせることができなくなる。それ故、ピットの分布が不均一で、かつ長さが不揃いとなり、正常なエッチングが行われず、静電容量が低下し、また、折曲強度も低下している。
また、上記の第１前処理を、１０．０ｍｏｌ／Ｌのリン酸水溶液のみで行う場合（比較例４）、または、１．０ｍｏｌ／Ｌの硝酸水溶液のみで行う場合（比較例５）、上記比較例３よりは若干改善されるが、それでもやはり、静電容量低下、折曲強度低下を十分に抑えることができなかった。
従って、リン酸および硝酸を含む酸性の第１前処理液による第１前処理は、アルミニウム箔表面の濃縮不純物の除去、表面の活性化を十分に行わせ、第２前処理の効果を得る上で、必須条件となる。
[Comparison of Conditions for First Pretreatment] Example 1 and Comparative Examples 3 to 5
When Example 1 and Comparative Example 3 are compared, as can be seen from the results in Table 1, the 0.5 mol / L phosphoric acid aqueous solution is not used without performing the first pretreatment with the first pretreatment liquid containing phosphoric acid and nitric acid. In the case of Comparative Example 3 performed only with this, it is considered that the removal of surface concentrated impurities and the activation of the surface of the aluminum foil are insufficient.
Therefore, in the case of Comparative Example 3, since the removal of impurities on the surface of the aluminum foil and the surface activation are insufficient, in the second pretreatment, when immersed in an alkaline second pretreatment liquid containing metal ions, aluminum ions and Adsorption of metal ions utilizing the potential difference of metal ions cannot be performed efficiently. Therefore, the distribution of pits is not uniform and the lengths are not uniform, normal etching is not performed, the capacitance is lowered, and the bending strength is also lowered.
Moreover, when performing said 1st pre-processing only with 10.0 mol / L phosphoric acid aqueous solution (Comparative Example 4), or when performing only with 1.0 mol / L nitric acid aqueous solution (Comparative Example 5), the said Although it is slightly improved as compared with Comparative Example 3, it was still impossible to sufficiently suppress the decrease in capacitance and the decrease in bending strength.
Therefore, the first pretreatment with the acidic first pretreatment liquid containing phosphoric acid and nitric acid sufficiently removes the concentrated impurities on the surface of the aluminum foil and activates the surface to obtain the effect of the second pretreatment. This is a necessary condition.
［第２前処理液への浸漬温度比較］ 実施例１〜４
表１に示す実施例１〜４の結果から明らかなように、実施例１〜４は比較例１〜５と比較し静電容量は同等以上で折曲強度が向上している。さらに、第２前処理液への浸漬温度は８０℃以上の場合、静電容量、折曲強度ともに大きく向上しており、より好ましい。８０℃以上にすることで、金属塩がアルミニウム箔へ均一に分散し、吸着するためと考えられる。
[Comparison of immersion temperature in second pretreatment liquid] Examples 1 to 4
As is clear from the results of Examples 1 to 4 shown in Table 1, Examples 1 to 4 have a capacitance equal to or higher than that of Comparative Examples 1 to 5 and have improved bending strength. Furthermore, when the immersion temperature in the second pretreatment liquid is 80 ° C. or higher, both the capacitance and the bending strength are greatly improved, which is more preferable. It is considered that the metal salt is uniformly dispersed and adsorbed on the aluminum foil when the temperature is 80 ° C. or higher.
［他の実施例比較］ 実施例１、５〜１０、１１、１２
上記実施例では、第２前処理液に水酸化ナトリウムとＰｂを使用したが、アルカリ性物質を炭酸ナトリウム、ケイ酸ナトリウムに変更した場合も、上記と同様の効果が得られた（実施例１、１１、１２）。
また、Ｐｂの代わりにＺｎ、Ｓｎ、Ｔｉ、Ｃｕ、Ｂｉ、Ｍｇの何れか１種を混合しても、上記と同様の効果が得られた（実施例１、５〜１０）。
さらに、Ｐｂ、Ｚｎ、Ｓｎ、Ｔｉ、Ｃｕ、Ｂｉ、Ｍｇの中から複数種混合しても、同様の効果が得られた。
そして、前記第２前処理のアルカリ性として、水酸化ナトリウム、炭酸ナトリウム、ケイ酸ナトリウムを複数種混合した場合も、同様の効果が得られた。
[Comparison of Other Examples] Examples 1, 5 to 10, 11, 12
In the said Example, although sodium hydroxide and Pb were used for the 2nd pre-processing liquid, the effect similar to the above was acquired when the alkaline substance was changed into sodium carbonate and sodium silicate (Example 1, 11, 12).
Further, even when any one of Zn, Sn, Ti, Cu, Bi, and Mg was mixed instead of Pb, the same effects as described above were obtained (Examples 1, 5 to 10).
Furthermore, the same effect was obtained even when plural kinds of Pb, Zn, Sn, Ti, Cu, Bi, and Mg were mixed.
And the same effect was acquired also when multiple types of sodium hydroxide, sodium carbonate, and sodium silicate were mixed as alkalinity of the said 2nd pretreatment.
［第２前処理後、水洗なしで乾燥（温度）の比較］ 実施例１ａ〜１ｅ
実施例１と実施例１ａ〜１ｅの結果から分かるように、水洗なしで乾燥処理を行った場合、水洗ありの場合よりも、さらに静電容量が増加している。
ここで、実施例１ａ〜１ｅの結果から分かるように、乾燥処理は２５〜１００℃で行うのが好適である。１２０℃で行っても、静電容量、折曲強度にさらなる改善効果はみられず、また、２５℃以下では乾燥に時間を要するため、乾燥処理は２５〜１００℃で行うことが望ましい。
[Comparison of drying (temperature) after the second pretreatment without washing with water] Examples 1a to 1e
As can be seen from the results of Example 1 and Examples 1a to 1e, when the drying treatment is performed without water washing, the capacitance is further increased as compared with the case with water washing.
Here, as can be seen from the results of Examples 1a to 1e, the drying process is preferably performed at 25 to 100 ° C. Even if it is performed at 120 ° C., no further improvement effect is observed in the capacitance and bending strength, and it takes time for drying at 25 ° C. or lower.
［第２前処理液の含有金属塩、水洗なしで乾燥（温度）の比較］実施例５〜１０、実施例５ｂ〜１０ｂ
上記の実施例５〜１０と、実施例５ｂ〜１０ｂとを比較すると、第２前処理液の含有する金属塩を、Ｐｂの代わりに、Ｚｎ、Ｓｎ、Ｔｉ、Ｃｕ、Ｂｉ、Ｍｇとしたものについても上記と同様、水洗なしで乾燥処理を行った場合の方が、水洗ありの場合よりも、静電容量が増加している。
[Comparison of metal salt contained in second pretreatment liquid, drying without washing with water (temperature)] Examples 5 to 10, Examples 5b to 10b
When the above Examples 5 to 10 and Examples 5b to 10b are compared, the metal salt contained in the second pretreatment liquid is Zn, Sn, Ti, Cu, Bi, Mg instead of Pb. Similarly to the above, the electrostatic capacity increases when the drying treatment is performed without washing, as compared with the case with washing.
Claims (4)
前記第１エッチング工程の前に、
前記アルミニウム箔をリン酸および硝酸を含む酸性の第１前処理液に浸漬する第１前処理と、
該アルミニウム箔を金属イオンを含むアルカリ性の第２前処理液に浸漬する第２前処理とを行う工程を有することを特徴とするアルミニウム電解コンデンサ用陽極箔の製造方法。 In the method for producing an anode foil for an aluminum electrolytic capacitor, comprising: a first etching step for generating tunnel-like pits in the aluminum foil; and a second etching step for expanding the hole diameter of the pits generated in the first etching step.
Before the first etching step,
A first pretreatment of immersing the aluminum foil in an acidic first pretreatment liquid containing phosphoric acid and nitric acid;
A method for producing an anode foil for an aluminum electrolytic capacitor, comprising a step of performing a second pretreatment of immersing the aluminum foil in an alkaline second pretreatment liquid containing metal ions.
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| CN103280327A (en) * | 2013-05-16 | 2013-09-04 | 陶荣燕 | Method for preparing high dielectric constant electrode foil |
| JP2015079913A (en) * | 2013-10-18 | 2015-04-23 | ニチコン株式会社 | Method for manufacturing electrode foil for electrolytic capacitor |
| DE102016107489B4 (en) | 2015-09-02 | 2023-11-09 | Mitsubishi Electric Corporation | Dither power supply control method and dither power supply control apparatus |
| WO2023236572A1 (en) * | 2022-06-09 | 2023-12-14 | 南通海星电子股份有限公司 | Preparation process for polyimide-aluminum composite foil |
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