JP4021922B1 - Method for producing aluminum foil for electrolytic capacitor electrode - Google Patents
Method for producing aluminum foil for electrolytic capacitor electrode Download PDFInfo
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- JP4021922B1 JP4021922B1 JP2006308814A JP2006308814A JP4021922B1 JP 4021922 B1 JP4021922 B1 JP 4021922B1 JP 2006308814 A JP2006308814 A JP 2006308814A JP 2006308814 A JP2006308814 A JP 2006308814A JP 4021922 B1 JP4021922 B1 JP 4021922B1
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 26
- 239000011888 foil Substances 0.000 title claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000003990 capacitor Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000137 annealing Methods 0.000 claims abstract description 27
- 238000005097 cold rolling Methods 0.000 claims abstract description 16
- 238000005098 hot rolling Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 238000005096 rolling process Methods 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 8
- 238000005530 etching Methods 0.000 abstract description 33
- 229910052733 gallium Inorganic materials 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000000866 electrolytic etching Methods 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 229910018131 Al-Mn Inorganic materials 0.000 description 2
- 229910018182 Al—Cu Inorganic materials 0.000 description 2
- 229910018461 Al—Mn Inorganic materials 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 1
- 239000001741 Ammonium adipate Substances 0.000 description 1
- 235000019293 ammonium adipate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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Abstract
【課題】エッチング性および信頼性に優れ、無電解エッチングが可能な電解コンデンサ電極用アルミニウム箔を提供する。
【解決手段】質量％で、Ｓｉ：０．０１〜０．３０％、Ｆｅ：０．０１〜０．３０％、Ｎｉ：０．００５１〜０．０５％を含有し、さらに所望によりＺｎ、Ｓｎ、Ｉｎ、Ｇａの内、少なくとも１種以上を合計で０．００３０〜０．１０％含有し、残部がＡｌと不可避不純物からなる組成を有し、熱間圧延後の冷間圧延における圧下率が７５％以上９８％未満の板厚を有するアルミニウム合金圧延材に、３００℃から５００℃の中間焼鈍を施して電解コンデンサ電極用アルミニウム箔とする。無電解においてもエッチング時に均一なピットを高密度に形成することが可能になり、高静電容量及び高信頼性を兼ね備えた電解コンデンサ電極を低コストで製造することが可能になる。
【選択図】図１Disclosed is an aluminum foil for an electrolytic capacitor electrode which is excellent in etching property and reliability and can be electrolessly etched.
SOLUTION: In mass%, Si: 0.01 to 0.30%, Fe: 0.01 to 0.30%, Ni: 0.0051 to 0.05%, and further Zn, Sn if desired In addition, at least one of In and Ga is contained in a total amount of 0.0030 to 0.10%, and the balance has a composition composed of Al and inevitable impurities, and the reduction ratio in cold rolling after hot rolling is An aluminum alloy rolled material having a plate thickness of 75% or more and less than 98% is subjected to intermediate annealing at 300 ° C. to 500 ° C. to obtain an aluminum foil for electrolytic capacitor electrodes. Even in the case of non-electrolysis, uniform pits can be formed at high density during etching, and an electrolytic capacitor electrode having both high capacitance and high reliability can be manufactured at low cost.
[Selection] Figure 1
Description
この発明は、電解コンデンサの電極として用いる際にエッチングが施される電解コンデンサ電極用アルミニウム箔の製造方法に関するものであり、特に陰極用のアルミニウム箔の製造方法に好適である。 The present invention relates to a method for producing an aluminum foil for an electrolytic capacitor electrode that is etched when used as an electrode for an electrolytic capacitor, and is particularly suitable for a method for producing an aluminum foil for a cathode.
電解コンデンサの陰極に用いられるアルミニウム箔としては、純Ａｌ系と合金系（主にＡｌ−Ｃｕ系、Ａｌ−Ｍｎ系）が用いられている。このうち純Ａｌ系は、不純物が少なく、信頼性は高いが、溶解性が低いため、電解エッチングが採用されており、コストが高いという課題を有している。一方、合金系は不純物が多く信頼性が低いとされている。例えば、Ａｌ−Ｃｕ系（例えば、特許文献１参照）は、Ｃｕの含有によりエッチング性を向上させるものの、コンデンサに組み込んだ際に、電解液中に溶出したＣｕが析出し、短絡などの安全上（信頼性）の問題が発生する。また、Ａｌ−Ｍｎ系（例えば、特許文献２）は、Ｍｎの含有によりエッチング性を向上させるものの、エッチング時に溶出したＭｎを含有するエッチング液の廃液処理上の問題（環境問題）が発生する。ただし、これら合金系は、溶解性が高いため、無電解エッチングが可能であり、コストの低い製造方法の採用が可能である。
したがって、信頼性重視の観点からは純Ａｌ系が選定され、コスト重視の観点では合金系が選定されている。
Accordingly, a pure Al system is selected from the viewpoint of emphasizing reliability, and an alloy system is selected from the viewpoint of emphasizing cost.
ところで最近では、コンデンサが使用される製品の全体的な品質レベルの向上に伴い、コンデンサに対しても信頼性が重視されるようになり、電極用に使用されるアルミニウム箔も信頼性の高い純Ａｌ系が主流になる傾向にある。しかし、上記したように従来の純Ａｌ系アルミニウム箔は電解エッチングが必要であるためコスト高になるという問題点を有している。このため低コスト化が可能な無電解エッチングが可能な純Ａｌ系アルミニウム箔の開発要求が強くなっている。
これに対し、本願発明者らは、純Ａｌ系ベースにＮｉなどを添加することにより無電解エッチングを可能にしたアルミニウム箔を提案している。しかし、当該アルミニウム箔は、エッチングが圧延目の凹凸に集中し易く、結果的に未エッチ領域がスジ状に残存し、均一性不良や外観不良の問題が発生している。
Recently, with the improvement of the overall quality level of products in which capacitors are used, reliability has become more important for capacitors, and aluminum foil used for electrodes is also highly reliable. Al type tends to become mainstream. However, as described above, the conventional pure Al-based aluminum foil has a problem of high cost because it requires electrolytic etching. For this reason, there is an increasing demand for development of pure Al-based aluminum foil that can be electrolessly etched at a lower cost.
On the other hand, the present inventors have proposed an aluminum foil that enables electroless etching by adding Ni or the like to a pure Al base. However, in the aluminum foil, the etching tends to concentrate on the unevenness of the rolling line, and as a result, the unetched region remains in a streak shape, causing problems such as poor uniformity and poor appearance.
本発明は、上記事情を背景としてなされたものであり、無電解エッチングにおいても均一性の高いエッチングが可能であり、したがってコストが安く、且つ信頼性の高いアルミニウム箔の製造方法を提供することを目的とする。 The present invention has been made against the background of the above circumstances, and provides a method for manufacturing an aluminum foil that is capable of highly uniform etching even in electroless etching, and thus is low in cost and high in reliability. Objective.
すなわち、本発明のうち、第１の発明の電解コンデンサ電極用アルミニウム箔の製造方法は、質量％で、Ｓｉ：０．０１〜０．３０％、Ｆｅ：０．０１〜０．３０％、Ｎｉ：０．００５１〜０．０５％を含有し、残部がＡｌと不可避不純物からなる組成を有し、熱間圧延後の冷間圧延における圧下率が７５％以上９８％未満の板厚を有するアルミニウム合金圧延材に、３００℃から５００℃の中間焼鈍を施すことを特徴とする。 That is, the manufacturing method of the aluminum foil for electrolytic capacitor electrodes according to the first aspect of the present invention is mass%, Si: 0.01 to 0.30%, Fe: 0.01 to 0.30%, Ni : Aluminum containing 0.0051 to 0.05%, with the balance being Al and inevitable impurities, and having a plate thickness of 75% or more and less than 98% in the cold rolling after hot rolling The alloy rolled material is subjected to intermediate annealing at 300 ° C. to 500 ° C.
第２の発明の電解コンデンサ電極用アルミニウム箔の製造方法は、質量％で、Ｓｉ：０．０１〜０．３０％、Ｆｅ：０．０１〜０．３０％、Ｎｉ：０．００５１〜０．０５％と、Ｚｎ、Ｓｎ、Ｉｎ、Ｇａの内、少なくとも１種以上を合計で０．００３０〜０．１０％含有し、残部がＡｌと不可避不純物からなる組成を有し、熱間圧延後の冷間圧延における圧下率が７５％以上９８％未満の板厚を有するアルミニウム合金圧延材に、３００℃から５００℃の中間焼鈍を施すことを特徴とする。 The manufacturing method of the aluminum foil for electrolytic capacitor electrodes of 2nd invention is the mass%, Si: 0.01-0.30%, Fe: 0.01-0.30%, Ni: 0.0051-0. 05%, containing at least one of Zn, Sn, In, and Ga in a total amount of 0.0030 to 0.10%, with the balance being composed of Al and inevitable impurities, after hot rolling An aluminum alloy rolled material having a sheet thickness of 75% or more and less than 98% in cold rolling is subjected to intermediate annealing at 300 ° C. to 500 ° C.
本発明によれば、適切な圧下率で圧延がなされた状態の冷間圧延材に中間焼鈍を行って、さらに冷間圧延を行うことで、エッチングに寄与する元素を表面に濃化させて表層でのエッチング性を向上させることができる。該アルミニウム箔を無電解エッチングする際にも、未エッチング光沢がなく、均一にエッチングピットを形成することができる。
以下に、本発明で規定するアルミニウム箔の成分限定理由および製造条件について説明する。
According to the present invention, intermediate annealing is performed on a cold-rolled material in a state of being rolled at an appropriate reduction rate, and further cold rolling is performed to concentrate the elements contributing to etching on the surface, thereby forming a surface layer. Etching property can be improved. Even when the aluminum foil is subjected to electroless etching, the etching pits can be uniformly formed without any unetched gloss.
The reasons for limiting the components of aluminum foil and the production conditions defined in the present invention will be described below.
Ｓｉ：０．０１〜０．３０％
Ｓｉはエッチングの起点となる析出物を形成させる。ただし、０．０１％未満では、Ｓｉの絶対量が少なく、その作用が十分発揮されない。一方、０．３０％を越えると、析出が進行し、過溶解となり、エッテング形態が不均一になり、静電容量が低下する。このため、Ｓｉ含有量を上記範囲に定める。なお、同様の理由で、Ｓｉ含有量の下限を０．０２％、上限を０．１５％とするのが望ましい。
Si: 0.01-0.30%
Si forms precipitates that serve as starting points for etching. However, if it is less than 0.01%, the absolute amount of Si is small, and its action is not sufficiently exhibited. On the other hand, if it exceeds 0.30%, precipitation proceeds and overdissolution occurs, the etching form becomes non-uniform, and the capacitance decreases. For this reason, Si content is defined to the said range. For the same reason, it is desirable that the lower limit of the Si content is 0.02% and the upper limit is 0.15%.
Ｆｅ：０．０１〜０．３０％
Ｆｅはエッチングの起点となる析出物を形成させ、また強度を高める作用がある。ただし、０．０１％未満ではＦｅ絶対量が少なく、その作用が十分発揮されない。また、高純度化のためにコストアップとなる。一方、０．３０％を越えると析出が進行し、過溶解となり、エッチング形態が不均一になり、静電容量が低下する。このため、Ｆｅ含有量を上記範囲に定める。なお、同様の理由で、Ｆｅ含有量の下限を０．０２％、上限を０．１５％とするのが望ましい。
Fe: 0.01 to 0.30%
Fe has the effect of forming precipitates as starting points for etching and increasing the strength. However, if it is less than 0.01%, the absolute amount of Fe is small, and its action is not sufficiently exhibited. In addition, the cost increases due to high purity. On the other hand, if it exceeds 0.30%, precipitation proceeds and overdissolution occurs, the etching form becomes uneven, and the capacitance decreases. For this reason, Fe content is defined to the said range. For the same reason, it is desirable that the lower limit of the Fe content is 0.02% and the upper limit is 0.15%.
Ｎｉ：０．００５１〜０．０５％
ＮｉはＡｌ−（Ｎｉ、Ｆｅ）系の析出物を形成する。これらは、電位的に貴であり、バルクとの間で局部電池反応を起こし、エッチング性を向上させる。ただし、０．００５１％未満では十分な数のＡｌ−（Ｎｉ、Ｆｅ）系の析出物が得られず、分散が不十分の為、不均一なエッチング形態となる。一方、０．０５％超では、大きな析出物が形成され易くなり、エッチングにより粗大なピットが発生し、好ましくない。このため、Ｎｉ含有量を上記範囲に定める。なお、同様の理由で、Ｎｉ含有量の下限を０．００７５％、上限を０．０３％とするのが望ましい。
Ni: 0.0051 to 0.05%
Ni forms an Al- (Ni, Fe) -based precipitate. These are noble in potential, cause a local cell reaction with the bulk, and improve the etching property. However, if it is less than 0.0051%, a sufficient number of Al— (Ni, Fe) -based precipitates cannot be obtained and the dispersion is insufficient, resulting in a non-uniform etching pattern. On the other hand, if it exceeds 0.05%, large precipitates are easily formed, and coarse pits are generated by etching, which is not preferable. For this reason, Ni content is defined to the said range. For the same reason, it is desirable that the lower limit of the Ni content is 0.0075% and the upper limit is 0.03%.
Ｚｎ、Ｓｎ、Ｇａ、Ｉｎの内、少なくとも１種以上：合計０．００３０〜０．１０％
これら元素はＮｉ同様に中間焼鈍により表層へ濃化し、バルク表層の電位を卑にするので所望により含有させる。これにより、表層において貴であるＡｌ−（Ｎｉ、Ｆｅ）系析出物と卑であるバルクとの電位差が増大し、特に表層において溶解性が増大し、表面の末エッチ光沢が改善され、均一なエッチングがなされる。上記含有量が０．００３０％未満であると、上記効果が不十分となり、０．１０％を超えると不純物量が多くなり過ぎ、過溶解となる。このため上記元素の合計含有量を上記範囲に定める。なお、同様の理由で下限を０．００５０％、上限を０．０５％とするのが望ましい。
At least one or more of Zn, Sn, Ga, and In: 0.0030 to 0.10% in total
Like Ni, these elements are concentrated in the surface layer by intermediate annealing, and the potential of the bulk surface layer is reduced, so that they are contained as desired. As a result, the potential difference between the Al- (Ni, Fe) -based precipitates that are noble on the surface layer and the bulk that is base is increased, in particular, the solubility is increased on the surface layer, the surface end etch gloss is improved, and uniform Etching is performed. When the content is less than 0.0030%, the above effect is insufficient, and when it exceeds 0.10%, the amount of impurities is excessively increased and excessive dissolution occurs. Therefore, the total content of the above elements is set within the above range. For the same reason, it is desirable that the lower limit is 0.0050% and the upper limit is 0.05%.
中間焼鈍：３００〜５００℃
Ｎｉは３００℃以上の熱処理により表層へ濃化する。したがって、適温の中間焼鈍によりＮｉが表層に濃化し適度な析出が起こり、エッチング性を向上させる。この中間焼鈍の温度が３００℃未満であると、温度が不十分なため、Ｎｉの濃化が起こらない。一方、５００℃超えると、Ｎｉが表層に濃化し過ぎ、必要以上のＮｉの析出が起こり過溶解を引き起すので、中間焼鈍における加熱温度を３００〜５００℃で行う。なお、中間焼鈍は、通常はバッチ炉において行うことができ、その際に保持時間は例えば１〜９時間とすることができる。１時間以上の保持によってＮｉの表層への濃化を確実に行うことができる。一方、保持時間が９時間を超えるとＮｉの濃化と共に過度な析出が起こり、過溶解を引き起こすので、上記保持時間が望ましい。
Intermediate annealing: 300-500 ° C
Ni is concentrated in the surface layer by heat treatment at 300 ° C. or higher. Therefore, Ni is concentrated on the surface layer by intermediate annealing at an appropriate temperature, and appropriate precipitation occurs, thereby improving the etching property. If the temperature of this intermediate annealing is less than 300 ° C., the temperature is insufficient and Ni concentration does not occur. On the other hand, when the temperature exceeds 500 ° C., Ni is excessively concentrated on the surface layer, and Ni is excessively precipitated to cause over-dissolution. Therefore, the heating temperature in the intermediate annealing is performed at 300 to 500 ° C. In addition, intermediate annealing can be normally performed in a batch furnace, and the holding time can be 1 to 9 hours, for example. Concentration to the surface layer of Ni can be reliably performed by holding for 1 hour or more. On the other hand, if the holding time exceeds 9 hours, excessive precipitation occurs with concentration of Ni and causes overdissolution, so the above holding time is desirable.
圧下率：７５〜９８％未満
中間焼鈍までの冷間圧延は、Ｎｉを表面へ濃化させる為の駆動力となる。ただし、この圧下率が７５％未満であると、圧下率が低く駆動力が不十分となり、Ｎｉの表層濃縮が十分になされない。一方、圧下率が９８％以上になると、中間焼鈍後の圧下率が少なくなり、十分な強度が確保できない。したがって、上記中間焼鈍前の熱間圧延後の圧下率を上記範囲に定める。
Reduction ratio: less than 75 to 98% Cold rolling until intermediate annealing provides a driving force for concentrating Ni on the surface. However, when the rolling reduction is less than 75%, the rolling reduction is low and the driving force becomes insufficient, and the Ni surface layer is not sufficiently concentrated. On the other hand, when the rolling reduction is 98% or more, the rolling reduction after the intermediate annealing decreases, and sufficient strength cannot be ensured. Therefore, the reduction ratio after hot rolling before the intermediate annealing is set in the above range.
以上、説明したように本発明の電解コンデンサ電極用アルミニウム箔の製造方法によれば、質量％で、Ｓｉ：０．０１〜０．３０％、Ｆｅ：０．０１〜０．３０％、Ｎｉ：０．００５１〜０．０５％を含有し、さらに所望によりＺｎ、Ｓｎ、Ｉｎ、Ｇａの内、少なくとも１種以上を０．００３０〜０．１０％含有し、残部がＡｌと不可避不純物からなる組成を有し、熱間圧延後の冷間圧延における圧下率が７５％以上９８％未満の板厚を有するアルミニウム合金圧延材に、３００℃から５００℃の中間焼鈍を施すので、表面層に適度に濃化された元素によりエッチングが均一になされ、無電解エッチングにおいても未エッチング部が生じない良好なエッチングが可能になる。この結果、コストが低く、かつ信頼性の高い電解コンデンサ電極用アルミニウム箔を得ることができる。 As described above, according to the method for producing an aluminum foil for electrolytic capacitor electrodes of the present invention, Si: 0.01 to 0.30%, Fe: 0.01 to 0.30%, Ni: A composition containing 0.0051 to 0.05%, further containing 0.0030 to 0.10% of Zn, Sn, In, or Ga as desired, and the balance of Al and inevitable impurities. The aluminum alloy rolled material having a thickness of 75% or more and less than 98% in the cold rolling after hot rolling is subjected to an intermediate annealing of 300 ° C. to 500 ° C. Etching is made uniform by the concentrated elements, and good etching without unetched portions is possible even in electroless etching. As a result, an aluminum foil for electrolytic capacitor electrodes with low cost and high reliability can be obtained.
以下に、本発明の一実施形態を図１に基づいて説明する。
本発明の合金組成に調整したアルミニウム合金は、半連続鋳造などによる常法などにより溶製する（工程１）。本発明としては特にその溶製方法が特定されるものではない。得られた合金鋳塊は、５５０℃以上、１時間以上の均質化処理（工程２）を行うのが望ましい。該均質化処理は、適宜の加熱炉などを用いて行うことができ、加熱方法、加熱手段が特に限定されるものではない。均質化処理後のアルミニウム合金に対しては、常法により熱間圧延を行うことができる。熱間圧延前（工程４）には、アルミニウム合金に対し均熱する（工程３）こともでき、例えば５３０℃以上に加熱する。熱間圧延における条件は本発明としては特に限定をされるものではない。熱間圧延後に、箔圧延を含む冷間圧延を行う。
Below, one Embodiment of this invention is described based on FIG.
The aluminum alloy adjusted to the alloy composition of the present invention is melted by a conventional method such as semi-continuous casting (step 1). In the present invention, the melting method is not particularly specified. The obtained alloy ingot is desirably subjected to a homogenization treatment (step 2) at 550 ° C. or higher for 1 hour or longer. The homogenization treatment can be performed using an appropriate heating furnace or the like, and the heating method and heating means are not particularly limited. The aluminum alloy after the homogenization treatment can be hot-rolled by a conventional method. Before hot rolling (step 4), the aluminum alloy can be soaked (step 3), for example, heated to 530 ° C. or higher. The conditions in the hot rolling are not particularly limited as the present invention. After hot rolling, cold rolling including foil rolling is performed.
冷間圧延に際しては中間焼鈍を必須で行う。この中間焼鈍前に、７５％以上、９８％未満の圧下率で冷間圧延（工程５）を行っておく。中間焼鈍（工程６）は、３００〜５００℃の加熱温度を条件にして１〜９時間の保持時間により行うことができる。中間焼鈍は、既知の焼鈍炉などを用いて行うことができ、本発明としては中間焼鈍を行う装置の構成が特に限定されるものではない。中間焼鈍後は、最終厚さの箔にまで冷間圧延（工程７）を行う。中間焼鈍後の圧下率は本発明としては特に限定をしないが、例えば７０〜９９％の圧下率とすることができる。
上記冷間圧延によって、例えば数十μｍから１００μｍ程度のアルミニウム箔を得ることができるが、本発明としては最終品としてのアルミニウム箔の厚さが特に限定されるものではない。
In the case of cold rolling, intermediate annealing is essential. Before this intermediate annealing, cold rolling (step 5) is performed at a rolling reduction of 75% or more and less than 98%. The intermediate annealing (step 6) can be performed with a holding time of 1 to 9 hours on the condition of a heating temperature of 300 to 500 ° C. The intermediate annealing can be performed using a known annealing furnace, and the configuration of the apparatus for performing the intermediate annealing is not particularly limited as the present invention. After the intermediate annealing, cold rolling (step 7) is performed to a final thickness foil. Although the rolling reduction after intermediate annealing is not particularly limited as the present invention, it can be, for example, a rolling reduction of 70 to 99%.
An aluminum foil having a thickness of, for example, several tens to 100 μm can be obtained by the cold rolling, but the thickness of the aluminum foil as a final product is not particularly limited in the present invention.
上記各工程を経て得られたアルミニウム箔には、その後、熱処理を施すことなく、エッチング処理（工程８）がなされる。なお、冷間圧延終了後に熱処理を行うと、回復や再結晶が起こり、強度低下を引き起こすため、冷間圧延後に熱処理を施さないのが望ましい。
エッチング工程は塩酸を主体とする電解液や塩酸を含まない（１０００ｐｐｍ以下）電解液を用いた電解エッチングや無電解エッチングにより行うことができる。コスト面では無電解エッチングが有利である。
エッチング処理においては、ピットが高密度で均一に形成され、未エッチング部が生じることなく高い粗面化率が得られる。この箔を化成処理し、必要な耐電圧を得た後、常法により電解コンデンサに電極として組み込むことにより静電容量の高いコンデンサが得られる。本発明としては化成処理の方法が特に限定されるものではない。
The aluminum foil obtained through the above steps is then subjected to an etching treatment (step 8) without being subjected to heat treatment. If heat treatment is performed after the end of cold rolling, recovery or recrystallization occurs and causes a decrease in strength. Therefore, it is desirable not to perform heat treatment after cold rolling.
The etching step can be performed by electrolytic etching or electroless etching using an electrolytic solution mainly composed of hydrochloric acid or an electrolytic solution not containing hydrochloric acid (1000 ppm or less). In terms of cost, electroless etching is advantageous.
In the etching process, the pits are uniformly formed with high density, and a high roughening rate can be obtained without generating an unetched portion. This foil is subjected to a chemical conversion treatment to obtain a necessary withstand voltage, and then a capacitor having a high capacitance is obtained by incorporating it as an electrode in an electrolytic capacitor by a conventional method. In the present invention, the chemical conversion treatment method is not particularly limited.
本発明は電解コンデンサの陰極として使用するのが好適であるが、本発明としてはこれに限定されるものではなく、例えば化成電圧の低い電解コンデンサの陽極としても使用することができる。 The present invention is preferably used as a cathode of an electrolytic capacitor. However, the present invention is not limited to this, and for example, it can also be used as an anode of an electrolytic capacitor having a low formation voltage.
次に、本発明の実施例を説明する。
表１に示す組成（残部Ａｌおよびその他の不純物）において、常法によりアルミニウム合金鋳塊を溶製し、該アルミニウム合金鋳塊に対し、５６０℃×６時間で均質化処理を行った。該鋳塊を５３０℃×４時間で均熱処理した後、熱間圧延で板厚７ｍｍに仕上げた後、表１に示す圧下率で冷間圧延を行い、その後、表１に示す条件で中間焼鈍を行った。その後、最終板厚５０μｍに冷間圧延をして供試材を得た。
Next, examples of the present invention will be described.
In the composition shown in Table 1 (the balance Al and other impurities), an aluminum alloy ingot was melted by a conventional method, and the aluminum alloy ingot was homogenized at 560 ° C. for 6 hours. The ingot is soaked at 530 ° C. for 4 hours, finished to a thickness of 7 mm by hot rolling, then cold-rolled at the reduction shown in Table 1, and then subjected to intermediate annealing under the conditions shown in Table 1. Went. Thereafter, cold rolling was performed to a final thickness of 50 μm to obtain a test material.
上記供試材を、
第１段階：６Ｍ−ＨＣｌ＋０．５Ｍ−Ｈ３ＰＯ４、５０℃×６０ｓｅｃ
第２段階：２Ｍ−ＨＣｌ＋１．５Ｍ−Ｈ３ＰＯ４、４０℃×１８０ｓｅｃ
の条件でエッチング処理した後、８５℃のアジピン酸アンモニウム溶液中で３Ｖ化成後、静電容量を測定した。静電容量は、供試材Ｎｏ．１の静電容量を１００とした相対評価により行った。これらの結果を表１に示した。
表１から明らかなように、本発明の供試材では、高い静電容量と高い強度とが得られている。一方、比較例は、組成と、中間焼鈍前の圧下率、中間焼鈍の温度条件のいずれかが発明の範囲外であることにより、静電容量、強度ともに本発明材よりも劣っている。
The above test materials
First stage: 6M-HCl + 0.5M-H 3 PO 4 , 50 ° C. × 60 sec
Second stage: 2M-HCl + 1.5M-H 3 PO 4 , 40 ° C. × 180 sec
After performing the etching process under the conditions of 3V in the ammonium adipate solution at 85 ° C., the capacitance was measured. The electrostatic capacity is the test material No. The relative evaluation was performed with a capacitance of 1 as 100. These results are shown in Table 1.
As is clear from Table 1, the test material of the present invention has high capacitance and high strength. On the other hand, the comparative example is inferior to the material of the present invention in terms of both capacitance and strength because any one of the composition, the rolling reduction before intermediate annealing, and the temperature conditions of intermediate annealing are out of the scope of the invention.
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