JP2004088069A - Manufacturing method of aluminum material for electrolytic capacitor electrode, aluminum anode material for the same, and manufacturing method of electrode material for electrolytic capacitor - Google Patents
Manufacturing method of aluminum material for electrolytic capacitor electrode, aluminum anode material for the same, and manufacturing method of electrode material for electrolytic capacitor Download PDFInfo
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Abstract
Description
【０００１】
【発明の属する技術分野】
この発明は、電解コンデンサ用アルミニウム材の製造方法、電解コンデンサ電極用アルミニウム陽極材、電解コンデンサ用電極材の製造方法及びアルミニウム電解コンデンサに関する。
【０００２】
なお、この明細書において「アルミニウム」の語はその合金を含む意味で用い、アルミニウム材には箔と板およびこれらを用いた成形体が含まれる。
【０００３】
【従来の技術及び課題】
アルミニウム電解コンデンサ用電極材として一般に用いられているアルミニウム材は、大きな表面積を有して単位面積当たりの静電容量の大きいものであることが要求されるため、電気化学的あるいは化学的エッチング処理を施して、アルミニウム材の実効面積を拡大することが行われている。
【０００４】
さらに、この実効面積の増大を目的として、エッチング孔をより多く、太くすることに関して材料の組成、製造工程、エッチング方法等種々の面から研究がなされている。
【０００５】
例えば、直流エッチング法でトンネル状ピットを生成させる電解コンデンサ用アルミニウム材の製造において、通常は、（１００）面の結晶方位を発達させるために、５００℃前後の温度にて不活性雰囲気もしくは真空中で最終焼鈍することが行われている。なお、最終焼鈍とは、仕上げ冷間圧延の後もしくは仕上げ冷間圧延、洗浄の後に実施する工程である。
【０００６】
最終焼鈍時にアルミニウム材の表面に結晶性酸化物粒子が生成された場合、電解エッチング時に結晶周辺からエッチピットが生じることが非特許文献１、非特許文献２で述べられており、その結晶性酸化物粒子をアルミニウム材の表面に生成させることは静電容量の向上に寄与すると考えられる。
【０００７】
しかしながら、前述したように、最終焼鈍の一般的雰囲気である不活性ガス雰囲気もしくは真空雰囲気では、雰囲気中の酸素が極微量であるため、最終焼鈍を実施しても結晶化しにくい。逆に酸化雰囲気中で高温焼鈍すると酸化皮膜が厚くなり、エッチピットの均一性が低下する。
【０００８】
アルミニウム材の表面に結晶を多く析出させる方法として、最終焼鈍前に蒸気または湿った空気をアルミニウム材表面に吹き付ける方法、大気中において２００℃程度の温度で加熱する方法、加熱された水またはアミン水溶液中にアルミニウム材を浸漬するいわゆるベーマイト処理方法などにより水和処理皮膜を形成する方法が知られている（特許文献１）。
【０００９】
水和処理皮膜はその後の最終焼鈍により結晶性酸化物がアルミニウム材の表面に析出しやすいものの、Ａｌ−ＯＨ基を表面に多く有するため、コイルの状態や単板を重ねた状態でバッチ焼鈍した場合に密着しやすいという問題があった。また、大気中において２００℃程度の温度で加熱する方法では、再現性良く目的の酸化膜を得るためには水蒸気量の制御等精確な雰囲気制御が必要であり、アルミニウム箔表面が目的の温度に達するのに時間がかかるという欠点があった。
【００１０】
また、特許文献２には、酸素または水分を含む酸化性雰囲気中における連続最終焼鈍によりγ―Ａｌ２Ｏ３を析出させる技術が公開されているが、最終焼鈍時間が短時間であるが故に、γ―Ａｌ２Ｏ３の析出が不十分な恐れがあった。
【００１１】
【非特許文献１】
福岡潔、大澤伸夫、本居徹也，軽金属学会第９５回秋季大会講演概要ｐ．２ ６５（１９９８）、
【００１２】
【非特許文献２】
大澤伸夫，福岡潔；表面技術，５０［７］，６４３（１９９９）
【００１３】
【特許文献１】
特公昭５８−３４９２６号公報
【００１４】
【特許文献２】
特開昭６３−１１６４１７号公報
この発明は、このような技術背景に鑑みてなされたものであって、精確な雰囲気制御を要することなく、短時間で処理でき、その後の最終焼鈍により十分なエッチングピットの核となる結晶性酸化物等の物質を生成でき、エッチング特性に優れた電解コンデンサ電極用アルミニウム材の製造方法、電解コンデンサ電極用アルミニウム陽極材、電解コンデンサ用電極材の製造方法及びアルミニウム電解コンデンサを提供することを課題とする。
【００１５】
【課題を解決するための手段】
本発明は以下の手段を提供する。
（１）アルミニウムスラブに熱間圧延及び冷間圧延を順次実施してアルミニウム材とした後、このアルミニウム材を加熱体との接触により加熱し、その後焼鈍する事を特徴とする電解コンデンサ電極用アルミニウム材の製造方法。
（２）さらに加熱体との接触前あるいは接触後の少なくともどちらかにおいて、アルミニウム材を洗浄する工程を含むことを特徴とする前項１に記載の電解コンデンサ電極用アルミニウム材の製造方法。
（３）アルミニウムスラブに熱間圧延及び冷間圧延を順次実施してアルミニウム材とした後、このアルミニウム材を洗浄し、次いで乾燥しあるいは乾燥することなく、アルミニウム材を加熱体との接触により加熱し、その後焼鈍することを特徴とする電解コンデンサ電極用アルミニウム材の製造方法。
（４）アルミニウムスラブに熱間圧延及び冷間圧延を順次実施してアルミニウム材とした後、このアルミニウム材を加熱体との接触により加熱し、さらに洗浄し、次いで乾燥しあるいは乾燥することなく、その後焼鈍することを特徴とする電解コンデンサ電極用アルミニウム材の製造方法。
（５）加熱体の表面温度が８０〜４００℃、アルミニウム材と加熱体との接触時間が０．００１〜３０秒である請求項１ないし前項４のいずれかに記載の電解コンデンサ電極用アルミニウム材の製造方法。
（６）焼鈍がアルミニウム実体温度４６０〜６００℃にて不活性ガス雰囲気中で行われる前項１ないし前項４のいずれかに記載の電解コンデンサ電極用アルミニウム材の製造方法。
（７）アルミニウム実体温度が５００〜５８０℃である請求項６に記載の電解コンデンサ電極用アルミニウム材の製造方法。
（８）加熱体が熱ロールである前項１ないし前項４のいずれかに記載の電解コンデンサ電極用アルミニウム材の製造方法。
（９）加熱体との接触後、アルミニウム材を冷却する前項１ないし前項４のいずれかに記載の電解コンデンサ電極用アルミニウム材の製造方法。
（１０）アルミニウム材の冷却を冷却ロールとの接触により行う前項９に記載の電解コンデンサ電極用アルミニウム材の製造方法。
（１１）洗浄に用いる洗浄液が有機溶剤である前項２ないし前項１０のいずれかに記載の電解コンデンサ電極用アルミニウム材の製造方法。
（１２）有機溶剤がＣｎＨ２ｎ＋１ＯＨ（ｎ＝１〜１０の自然数）で表されるアルコール、シクロヘキサノール（Ｃ６Ｈ１１０Ｈ）、１，２−エタンジオール（ＨＯＣＨ２ＣＨ２ＯＨ）、１，２−プロパンジオール（ＣＨ３ＣＨ（ＯＨ）ＣＨ２ＯＨ）、１，３−プロパンジオール（ＨＯＣＨ２ＣＨ２ＣＨ２ＯＨ）、ＣｎＨ２ｎ＋２（ｎ＝５〜１５の自然数）で表されるアルカン系炭化水素、シクロヘキサン、Ｒ１ＣＯＲ２（Ｒ１およびＲ２：脂肪族炭化水素基であり、Ｒ１とＲ２の炭素数の合計が８以下）で表されるケトン、シクロヘシサノン（Ｃ６Ｈ１０Ｏ）、Ｒ１−Ｏ−Ｒ２（Ｒ１およびＲ２：脂肪族炭化水素基であり、Ｒ１とＲ２の炭素数の合計が８以下）で表されるエーテル、２−メトキシエタノール（ＣＨ３ＯＣＨ２ＣＨ２ＯＨ）、２−エトキシエタノール（ＣＨ３ＣＨ２ＯＣＨ２ＣＨ２ＯＨ）、２−ブトキシエタノール（ＣＨ３ＣＨ２ＣＨ２ＣＨ２ＯＣＨ２ＣＨ２ＯＨ） ２−（２−エトキシ）エトキシエタノール（ＣＨ３ＣＨ２ＯＣＨ２ＣＨ２ＯＣＨ２ＣＨ２ＯＨ）、ＣＨ３ＣＯＯＲ（Ｒ：炭素数１〜５である脂肪族炭化水素基）で表される酢酸エステル、トルエンキシレンから選ばれた１種または２種以上の混合物である前項１１に記載の電解コンデンサ電極用アルミニウム材の製造方法。
（１３）洗浄に用いる洗浄液が水に界面活性剤を添加したものである前項２ないし前項１０のいずれかに記載の電解コンデンサ電極用アルミニウム材の製造方法。
（１４）界面活性剤が、Ｒ−ＯＳＯ３Ｎａ（Ｒ＝炭素数８〜１８の飽和炭化水素基もしくは二重結合を一つ有する不飽和炭化水素基）で表されるアニオン界面活性剤（硫酸エステル塩）、Ｒ−ＳＯ３Ｎａ（Ｒ＝炭素数８〜１８の飽和炭化水素基もしくは二重結合を一つ有する不飽和炭化水素基）もしくはＲ−ＳＯ３Ｎａ（Ｒ：アルキル基が炭素数８〜１４の飽和炭化水素基もしくは二重結合を一つ有する不飽和炭化水素基であるアルキルベンジル基）で表されるアニオン界面活性剤（スルホン酸塩）、Ｒ−Ｎ＋（ＣＨ３）３・Ｃｌ− （Ｒ＝炭素数８〜１６の飽和炭化水素基）で表されるカチオン界面活性剤（第４級アンモニウム塩）、Ｒ−Ｏ−（−ＣＨ２ＣＨ２Ｏ）ｎＨ（Ｒ＝炭素数８〜１６の飽和炭化水素基もしくは二重結合を一つ有する不飽和炭化水素基、ｎ＝６〜１４）またはＲ−Ｏ−（−ＣＨ２ＣＨ２Ｏ）ｎＨ（Ｒ＝アルキル基が炭素数８〜１２の飽和炭化水素基もしくは二重結合を一つ有する不飽和炭化水素基であるアルキルフェニル基、ｎ＝６〜１４）で表されるポリエチレングリコール型非イオン界面活性剤のうちから選ばれた１種または複数のアニオン界面活性剤の混合物、複数のカチオン界面活性剤の混合物、複数の非イオン界面活性剤の混合物、１種以上のアニオン界面活性剤と１種以上の非イオン界面活性剤の混合物、１種以上のカチオン界面活性剤と１種以上の非イオン界面活性剤の混合物である前項１３に記載の電解コンデンサ電極用アルミニウム材の製造方法。
（１５）洗浄後の乾燥温度が２００℃以下である前項３または前項４に記載の電解コンデンサ電極用アルミニウム材の製造方法。
（１６）洗浄後の乾燥温度が９０℃以下である前項１５に記載の電解コンデンサ電極用アルミニウム材の製造方法。
（１７）アルミニウム純度９９．９％以上である前項１ないし前項１６のいずれかに記載の電解コンデンサ電極用アルミニウム材の製造方法。
（１８）前項１ないし前項１７のいずれかに記載の製造方法によって製造された電解コンデンサ用アルミニウム陽極材。
（１９）中圧用または高圧用である前項１８に記載の電解コンデンサ用アルミニウム陽極材。
（２０）前項１ないし前項１７のいずれかに記載の製造方法によって製造されたアルミニウム材に、焼鈍後、エッチングを実施することを特徴とする電解コンデンサ用電極材の製造方法。
（２１）エッチングが直流エッチングである前項２０に記載の電解コンデンサ用電極材の製造方法。
（２１）電極材として、前項２０または前項２１に記載の製造方法によって製造されたアルミニウム電極材が用いられていることを特徴とするアルミニウム電解コンデンサ。
【００１６】
上述のように、この発明は、アルミニウムスラブに熱間圧延及び冷間圧延を順次実施してアルミニウム材としたのち、このアルミニウム材を加熱体との接触により加熱し、その後焼鈍することを特徴とする。
【００１７】
即ち、冷間圧延以降の工程において、加熱体との接触によりアルミニウム材を加熱することによりその後の焼鈍によりエッチピット核となり得る物質をアルミニウム材表面に析出させる。加熱方法として接触加熱を用いるのは、加熱体表面により、均一に短時間でアルミニウム材表面を目的の温度に到達させることが出来るため制御が比較的容易で、しかも急速且つ短時間で加熱できるため雰囲気の影響を少なくできるからである。
【００１８】
電解コンデンサ用アルミニウム材の製造において、従来一般に（１００）面の結晶方位を発達させるために、４５０〜６００℃の温度範囲で不活性雰囲気もしくは真空中で最終焼鈍を実施しているが、結晶性酸化物等エッチピットの核となりうる物質が十分生成しない。そこで、最終焼鈍前に接触加熱により急速加熱することによって、最終焼鈍時に結晶性酸化物微粒子等エッチピットの核となり得る物質の生成を促進させる。
【００１９】
ここでエッチピットの核となり得る物質は、結晶性酸化物のみならず、非晶質でも密度の高いものあるいは厚いもの、非晶質の中に結晶性酸化物や金属アルミニウムが含まれるものが含まれる。また、結晶性酸化物の種類としてはγ−Ａｌ２Ｏ３をはじめとするＡｌ２Ｏ３、ベーマイトをはじめとするＡｌＯＯＨ、アルミニウム以外の含有金属（例えばＭｇ、Ｐｂ、Ｃｕ等）との複合酸化物などがあるが、金属酸化物あるいは金属水酸化物等に特に限定されるものではない。
【００２０】
このようなアルミニウム材表面の酸化皮膜の中で他の場所と特性が異なるものが生成されれば、エッチング時にエッチピットの核となりうると考えられ、最終焼鈍前に急速加熱することにより、焼鈍時に結晶や結晶に転移する前の状態の非晶質、非晶質の中に結晶や金属アルミニウムが含まれる物質が生成し、これらがエッチピット核となると推定される。
【００２１】
急速加熱の方法として加熱体との接触加熱を用いるのは、前述したように、極短時間でアルミニウム材表面を目的の温度に到達させることができ生産性に優れる、短時間に加熱できるため雰囲気の影響を受けにくい、アルミニウム材表面に接触する加熱体表面の温度が均一であればアルミニウムコイルの幅方向・長手方向に均一な酸化膜が形成できるというような利点を有するためである。
【００２２】
以下に、電解コンデンサ用アルミニウム材の製造方法を説明する。
【００２３】
アルミニウム材の純度は電解コンデンサ用に使用される範囲であれば特に限定されないが、純度９９．９％以上のものが好ましく、特に９９．９５％以上が好ましい。なお、本発明においてアルミニウム材の純度は１００％からＦｅ，Ｓｉ， Ｃｕ， Ｍｎ， Ｃｒ， Ｚｎ， ＴｉおよびＧａの合計濃度（％）を差し引いた値とする。
【００２４】
アルミニウム材の製造は、限定はされないが、アルミニウム材料の溶解成分調整・スラブ鋳造、均熱処理、熱間圧延、冷間圧延、仕上冷間圧延（低圧下圧延）、接触加熱の順に実施される。アルミニウム材の（１００）面積率が９０％以上であることが好ましく、アルミニウム材のエッチング条件との関係で、アルミニウム材の製造工程条件は適宜変更される。なお、圧延工程の途中において、前工程の圧延により生じたアルミニウム材の結晶組織の歪みを解消する目的で焼鈍（中間焼鈍と称す）を実施しても良い。また、中間焼鈍以前の工程でアルミニウム表面の不純物や油分を除去する目的で洗浄を行ってもよい。
【００２５】
中間焼鈍以前の工程で用いる洗浄液は特に限定されないが、アルカリ水溶液、酸水溶液、有機溶剤等が用いられる。
【００２６】
圧延工程を終了したアルミニウム材は、表面に油分が存在するため、必要に応じ、最終焼鈍前であって後述する接触加熱前あるいは接触加熱後の少なくともどちらかで洗浄を行うことが好ましい。このような洗浄を行うことで、接触加熱の効果がより発揮され、大きな静電容量が得られる。
【００２７】
圧延終了後洗浄を行うことなく接触加熱を行い大きい摩耗粉などがアルミニウム材表面に付着している場合には、洗浄により除去することが好ましい。
【００２８】
前記接触加熱前あるいは接触加熱後の洗浄に用いられる洗浄液は、脱脂を目的とすることから、有機溶剤や水に界面活性剤を添加したものを用いることができる。
【００２９】
有機溶剤としては、アルミニウムを溶解しない物質を用いることができ、例として、アルコール、ジオール、トルエン・キシレン等の芳香族炭化水素、アルカン系炭化水素、シクロヘキサン、ケトン、エーテル、エステル、石油製品等があげられるが、特に限定されるものではない。
【００３０】
上記アルコールの例としては、メタノール（ＣＨ３ＯＨ）、エタノール（Ｃ２Ｈ５ＯＨ）、１−プロパノール（ＣＨ３ＣＨ２ＣＨ２ＯＨ）、２−プロパノール（ＣＨ３ＣＨ２（ＯＨ）ＣＨ３）、１−ブタノール（ＣＨ３ＣＨ２ＣＨ２ＣＨ２ＯＨ）、２−ブタノール（ＣＨ３ＣＨ２ＣＨ２（ＯＨ）ＣＨ３）、１−ペンタノール（ＣＨ３ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨ）、２−ペンタノール（ＣＨ３ＣＨ２ＣＨ２ＣＨ２（ＯＨ）ＣＨ３）等が挙げられ、ＣｎＨ２ｎ＋１ＯＨ（ｎ＝１〜１０の自然数）で表されるものが好ましい。また、シクロヘキサノール等の脂乾炭化水素類も用いることが出来る。
【００３１】
上記ジオールの例としては１，２−エタンジオール（ＨＯＣＨ２ＣＨ２ＯＨ）、１，２−プロパンジオール（ＣＨ３ＣＨ（ＯＨ）ＣＨ２ＯＨ）、１，３−プロパンジオール（ＨＯＣＨ２ＣＨ２ＣＨ２ＯＨ）等が例示できる。
【００３２】
上記アルカン系炭化水素の例としては、ペンタン（Ｃ５Ｈ１２）、ヘキサン（Ｃ６Ｈ１４）、ヘプタン（Ｃ７Ｈ１６）、オクタン（Ｃ８Ｈ１８）、ノナン（Ｃ９Ｈ２０）、デカン（Ｃ１０Ｈ２２）等が挙げられＣｎＨ２ｎ＋２（ｎ＝５〜１５の自然数）で表されるものが好ましい。またシクロヘキサン等脂乾式炭化水素の適用も可能である。
【００３３】
上記ケトンの例としてはアセトン（ＣＨ３ＣＯＣＨ３）、２−ブタノン（ＣＨ３ＣＯＣ２Ｈ５）、３−ペンタノン（ＣＨ３ＣＨ２ＣＯＣＨ２ＣＨ３）、３−メチル−２−ブタノン（ＣＨ３ＣＯＣＨ（ＣＨ３）２）等が例示でき、Ｒ１ＣＯＲ２（Ｒ１およびＲ２：脂肪族炭化水素基であり、Ｒ１とＲ２の炭素数の合計が８以下）で表されるものが好ましい。また、シクロヘキサノン（Ｃ６Ｈ１０Ｏ）等環状ケトンを用いても良い。
【００３４】
上記エーテルの例としては、Ｒ１−Ｏ−Ｒ２（Ｒ１およびＲ２：脂肪族炭化水素基であり、Ｒ１とＲ２の炭素数の合計が８以下）で表される物質、２−メトキシエタノール（ＣＨ３ＯＣＨ２ＣＨ２ＯＨ）、２−エトキシエタノール（ＣＨ３ＣＨ２ＯＣＨ２ＣＨ２ＯＨ）、２−ブトキシエタノール（ＣＨ３ＣＨ２ＣＨ２ＣＨ２ＯＣＨ２ＣＨ２ＯＨ） ２−（２−エトキシ）エトキシエタノール（ＣＨ３ＣＨ２ＯＣＨ２ＣＨ２ＯＣＨ２ＣＨ２ＯＨ）、等のグリコールエーテルも含まれる。
【００３５】
上記エステルの例としては、ＣＨ３ＣＯＯＲ（Ｒ：炭素数１〜５である脂肪族炭化水素基）で表される酢酸エステルが例示できる。
【００３６】
上記石油製品の例としては、工業ガソリン（ＪＩＳ Ｋ ２２０１）、自動車ガソリン（ＪＩＳ Ｋ ２２０２）、航空ガソリン（ＪＩＳ Ｋ ２２０６）、灯油（ＪＩＳ Ｋ ２２０３）、軽油（ＪＩＳ Ｋ２２０４）、航空ガソリン（ＪＩＳ Ｋ ２２０６）、石油エーテル（ＪＩＳ Ｋ ８５９３）、石油ベンジン（ＪＩＳ Ｋ ８５９４）、リグロイン（ＪＩＳ Ｋ ８９３７）、ケロシン等が挙げられる。
【００３７】
上記有機溶剤としては、複数の有機溶剤を混合して用いても良く、水と混合し得る有機溶剤の場合は必要に応じて水と混合して用いても良い。
【００３８】
一方、上記洗浄に用いる、水に界面活性剤を添加した洗浄液中に含まれる界面活性剤としては、アニオン界面活性剤、カチオン界面活性剤、非イオン性界面活性剤を用いることが出来る。
【００３９】
アニオン界面活性剤としては、硫酸エステル塩、スルホン酸塩を用いることができる。
【００４０】
上記硫酸エステル塩としては、Ｒ−ＯＳＯ３Ｎａ（Ｒ＝炭素数８〜１８のの飽和炭化水素基もしくは二重結合を一つ有する不飽和炭化水素基）を利用でき、具体的にはドデシル硫酸ナトリウム（Ｃ１２Ｈ２５ＯＳＯ３Ｎａ）、ヘキサデシル硫酸ナトリウム（Ｃ１６Ｈ３３ＯＳＯ３Ｎａ）、ステアリル硫酸ナトリウム（Ｃ１８Ｈ３７ＯＳＯ３Ｎａ）、オレイル硫酸ナトリウム（Ｃ１８Ｈ３５ＯＳＯ３Ｎａ）等が例示できる。
【００４１】
上記スルホン酸塩はＲ−ＳＯ３Ｎａ（Ｒ＝炭素数８〜１８の飽和炭化水素基もしくは二重結合を一つ有する不飽和炭化水素基）もしくはドデシルベンゼンスルホン酸ナトリウム（Ｃ１２Ｈ２５−Ｃ６Ｈ４−ＳＯ３Ｎａ）等のＲ−ＳＯ３Ｎａ（Ｒ：アルキル基が炭素数８〜１４の飽和炭化水素基もしくは二重結合を一つ有する不飽和炭化水素基であるアルキルベンジル基）で表されるものを用いることができる。
【００４２】
カチオン界面活性剤としては、Ｒ−Ｎ＋（ＣＨ３）３・Ｃｌ− （Ｒ＝炭素数８〜１６の飽和炭化水素基）で表される第４級アンモニウム塩を用いることができる。
【００４３】
非イオン性界面活性剤としては、Ｒ−Ｏ−（−ＣＨ２ＣＨ２Ｏ）ｎＨ（Ｒ＝炭素数８〜１６の飽和炭化水素基もしくは二重結合を一つ有する不飽和炭化水素基、ｎ＝６〜１４）またはＲ−Ｏ−（−ＣＨ２ＣＨ２Ｏ）ｎＨ（Ｒ＝アルキル基が炭素数８〜１２の飽和炭化水素基もしくは二重結合を一つ有する不飽和炭化水素基であるアルキルフェニル基、ｎ＝６〜１４）で表されるポリエチレングリコール型非イオン界面活性剤を例示できる。なおｎが上記範囲より多いものが非イオン性界面活性剤中に５０％以下のモル比で含まれていても良い。
【００４４】
また、上記界面活性剤の少なくとも１種類以上を水に添加し洗浄液として用いることができる。界面活性剤の炭素数が上記範囲より少ない界面活性剤が５０％以下のモル比で添加されていても良い。なお、アニオン界面活性剤とカチオン界面活性剤を水中で混合させると沈殿が生成するため、混合はさけることが好ましい。
【００４５】
界面活性剤の添加濃度は特に規定されないが、洗浄効果を発揮させるために臨界ミセル濃度以上であることが好ましい。
【００４６】
上記洗浄工程において、洗浄液として用いる有機溶剤もしくは界面活性剤水溶液とアルミニウム材の接触方法としては特に限定されないが、浸漬、洗浄液表面へのアルミニウム材の接触、スプレー等が挙げられる。
【００４７】
また、アルミニウム材表面の油分や摩耗粉をより除去する目的で、洗浄液とアルミニウム材との接触中にアルミニウム材をブラシもしくはスポンジと接触させさらにこすっても良い。
【００４８】
洗浄工程において、洗浄液とアルミニウム材との接触時間は特に限定されるものではないが、０．５秒以上１０分以下であることが好ましい。洗浄液とアルミニウム材の接触時間が０．５秒未満では洗浄が不十分であり、１０分より長く接触させても洗浄効果が飽和に達する。洗浄液の液温は有機溶剤の場合は５〜６０℃、水に界面活性剤を添加した洗浄液の場合は５〜８０℃であることが好ましい。洗浄液の液温が下限未満の場合には洗浄力が不十分であり、上限より高い温度で洗浄しても洗浄力は飽和に達する。
【００４９】
アルミニウム材の洗浄後、必要に応じて乾燥しても良い。乾燥方法として、例えば、空気中加熱、不活性雰囲気加熱、真空加熱を用いることができる。空気中で乾燥する場合の雰囲気温度は２００℃以下、乾燥時間は１０分以下であることが好ましい。乾燥温度が２００℃より高くなるかもしくは加熱時間が１０分より長くなると、酸化膜が成長しすぎてエッチング特性が低下する恐れがあるからである。
【００５０】
圧延終了後のアルミニウム材または圧延終了後さらに洗浄を施したアルミニウム材は、その後の焼鈍によりエッチピットの核を多く生成させるために接触加熱される。加熱手段は、熱ロール、加熱ベルト、加熱板など接触加熱が可能なものであれば良いが、簡便で連続的に接触加熱を行いうる点で熱ロールが望ましい。
また、片面ずつ加熱しても良く、表裏面の一方のみを加熱してもよい。加熱体の加熱表面の材質としては、ステンレス、メッキ、セラミックス、テフロン樹脂（登録商標）、シリコーン樹脂等自由に選択できるが、アルミニウム材の表面酸化膜が加熱体の表面に凝着しない物質が好ましい。
【００５１】
アルミニウム材に接触させる加熱体の表面温度は８０〜４００℃が好ましい。加熱体の表面温度が８０℃未満では、加熱が不十分となり、接触加熱後に行う焼鈍時の結晶性酸化物微粒子等エッチピットの核となり得る物質の生成が不十分となる恐れがある。一方、４００℃より高くなると、酸化膜が厚くなりすぎ、冷却時に皺が発生し、操業上の問題が生じる恐れがある。特に好ましい加熱体表面温度は１００〜３５０℃である。さらに好ましい加熱体表面温度は１６０〜２９０℃である。
【００５２】
アルミニウム材表面と加熱体表面との接触時間は０．００１〜３０秒とするのが好ましい。接触時間が０．００１秒未満では、アルミニウム材表面を充分加熱することができず、やはりエッチピット核となり得る物質の生成が不十分になる恐れがある。一方、３０秒より長くすると、酸化膜が厚くなりすぎエッチピットが発生しにくくなる恐れがある。特に好ましい接触時間は、０．０１〜１０秒である。さらに好ましい接触時間は０．１〜７秒である。
【００５３】
加熱体の表面温度及び接触時間は、接触前のアルミニウム材表面の酸化膜の特性を考慮して適宜選択すればよい。接触加熱雰囲気は特に限定されず、特別な雰囲気制御も必要なく空気中で実施できる。
【００５４】
加熱体として熱ロールを用いた加熱装置の一例としては、アルミニウム材の表裏面を目的の温度で接触加熱するために、少なくとも２個の熱ロールを配置した装置が挙げられる。アルミニウム材を熱ロール等で接触加熱した後のアルミニウム材の巻き取り時に皺が生じる場合には、熱ロールなどによる加熱後１個もしくは複数個の冷却ロール等の冷却体を通過させ、アルミニウム材を冷却させてから巻き取る構成としても良い。特に、冷却体として冷却ロールを用いることで、簡便にかつ連続的に冷却を行うことができる。また、熱ロールなどによりアルミニウム材を目的の接触加熱温度に加熱する前に、別の熱ロールを用いて、目的の接触加熱温度より低い温度にアルミニウム材の温度を予備的に上げておいてもよい。
【００５５】
接触加熱後、要すれば前述した洗浄を行った後、エッチピットの核となり得る物質の生成を促進させるとともに、アルミニウム材の結晶組織の方位を（１００）方位に整えてエッチング特性を向上させることを主目的として最終焼鈍がなされる。
【００５６】
なお、最終圧延後最終焼鈍前に、上述した工程以外の他の工程例えばアルミニウム材コイルを分割するためのスリット工程等を実施しても良いことは勿論である。
【００５７】
最終焼鈍においては、前工程である接触加熱工程でアルミニウム材に形成された酸化膜の厚さを最終焼鈍工程で増大させ過ぎて、エッチング核となり得る可能性を消去させないように、最終焼鈍後の酸化皮膜の合計厚さがハンターホール法（Ｍ．Ｓ．Ｈｕｎｔｅｒ ａｎｄ Ｐ． Ｆｏｗｌｅ， Ｊ． Ｅｌｅｃｔｒｏｃｈｅｍ． Ｓｏｃ．， １０１［９］， ４８３（１９５４）参照）による厚さで２．５〜５．０ｎｍとなるように最終焼鈍を実施するのが好ましい。また、最終焼鈍後のアルミニウム材の（１００）面積率は９０％以上が好ましい。
【００５８】
この最終焼鈍における処理雰囲気は特に限定されるものではないが、酸化皮膜の厚さを増大させすぎないように、水分および酸素の少ない雰囲気中で加熱するのが好ましい。具体的には、アルゴン、窒素などの不活性ガス中あるいは０．１Ｐａ以下の真空中で加熱することが好ましい。
【００５９】
最終焼鈍の方法は特に限定されるものではなく、コイルに巻き取った状態でバッチ焼鈍しても良く、コイルを巻き戻し連続焼鈍した後コイルに巻き取っても良く、バッチ焼鈍と連続焼鈍の少なくともどちらかを複数回行っても良い。
【００６０】
最終焼鈍時の温度、時間は特に限定されるものではないが、例えばコイルの状態でバッチ焼鈍を行う場合は、アルミニウム実体温度４６０〜６００℃にて、１０分〜５０時間焼鈍するのが好ましい。アルミニウム実体温度が４６０℃未満、時間が１０分未満では、酸化皮膜中のエッチピットの核と成り得る物質の生成が十分ではなく、その分散状態が疎となりすぎて、結晶をエッチング核とするエッチング時の拡面効果が期待できない恐れがあり、（１００）面の結晶方位の発達も不十分となる恐れがあるからである。逆に６００℃を越えて焼鈍すると、コイルでバッチ焼鈍する場合はアルミニウム材が密着を起こし易くなり、また５０時間を超えて焼鈍してもエッチングによる面積拡大効果は飽和し、却って熱エネルギーコストの増大を招く。特に好ましい温度は、アルミニウム実体温度で５００〜５８０℃、時間は２０分〜４０時間である。
【００６１】
また、最終焼鈍の昇温速度・パターンは特に限定されず、一定速度で昇温させても良く、昇温、温度保持を繰り返しながらステップ昇温・冷却させても良く、焼鈍工程にてアルミニウム実体温度４６０〜６００℃の温度域で合計１０分〜５０時間焼鈍されれば良い。なお、最終焼鈍後に得られる電解コンデンサ電極用アルミニウム材の厚さは特に規定されることはない。
【００６２】
最終焼鈍を終了したアルミニウム材には、拡面積率向上のためエッチング処理を実施する。エッチング処理条件は特に限定されないが、好ましくは直流エッチング法を採用するのが良い。直流エッチング法によって、前記最終焼鈍において生成が促進されたエッチピットの核となる部分において、深く太くエッチングされ、多数のトンネル状ピットが生成され、高静電容量が実現される。
【００６３】
エッチング処理後、望ましくは化成処理を行って陽極材とするのが良く、特に、中圧用および高圧用の電解コンデンサ電極材として用いるのが良い。もとより、陰極材として用いることを妨げるものではない。
【００６４】
上記のような陽極材及び／または陰極材を電極材として用いることにより、アルミニウム電解コンデンサが構成される。この電解コンデンサでは、電極材の拡面率が増大しているため、大きな静電容量を有するものとなる。
【００６５】
なお、静電容量の測定は、化成処理されたエッチド箔について、例えば８０ｇ／Ｌのホウ酸アンモニウム、３０℃中で、白金板を対極として１２０Ｈｚにて測定する等、常法に従って行えばよい。
【００６６】
この発明のコンデンサは、実施例のものに限定されることはない。
【００６７】
【実施例】
以下に本発明の実施例および比較例を示す。
［実施例１〜１２及び比較例１〜３］
（実施例１）
厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を用意した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた後、表面温度が２００℃のステンレス製加熱板２枚の間にアルミニウム材を挟み、２秒間空気中で接触加熱させた。接触加熱後のアルミニウム材を重ねた状態で、アルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（実施例２）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた後、表面温度が２５０℃のステンレス製加熱板２枚の間にアルミニウム材を挟み、２秒間空気中で接触加熱させた。接触加熱後のアルミニウム材を重ねた状態で、アルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（実施例３）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた後、表面温度が２００℃のステンレス製加熱板２枚の間にアルミニウム材を挟み、２秒間空気中で接触加熱させた。接触加熱後のアルミニウム材を重ねた状態で、アルゴン雰囲気下でアルミニウム材の実体温度を室温から５６０℃まで５０℃／ｈで昇温させた後、５６０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（実施例４）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた後、表面温度が２００℃のステンレス製加熱板２枚の間にアルミニウム材を挟み、１秒間空気中で接触加熱させた。接触加熱後のアルミニウム材を重ねた状態で、アルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（実施例５）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた。次に、表面温度２００℃に設定した熱ロール（表面に硬質クロムメッキを施したもの）２本を用意し、１本目の熱ロールにアルミニウム材表面を１秒間接触させた後、続けて２本目の熱ロールにアルミニウム材裏面を１秒間接触させることにより接触加熱を行った。接触加熱後のアルミニウム材を重ねた状態で、アルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後５４０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（実施例６）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた。次に、表面温度が９０℃のステンレス製加熱板２枚の間にアルミニウム材を挟み、１秒間空気中で接触加熱させた。接触加熱後のアルミニウム材を重ねた状態で、アルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（実施例７）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた。次に、表面温度３８０℃に設定した熱ロール（表面に硬質クロムメッキを施したもの）２本を用意し、１本目の熱ロールにアルミニウム材表面を０．１秒間接触させた後、続けて２本目の熱ロールにアルミニウム材裏面を０．１秒間接触加熱させることにより接触加熱を行った。接触加熱後のアルミニウム材を重ねた状態で、アルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（実施例８）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた。次に、表面温度２５０℃に設定した熱ロール（表面に硬質クロムメッキを施したもの）２本を用意し、１本目の熱ロールにアルミニウム材表面を０．００５秒間接触させた後、続けて２本目の熱ロールにアルミニウム材裏面を０．００５秒間接触させることにより接触加熱を行った。接触加熱後のアルミニウム材を重ねた状態で、アルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（実施例９）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた後、表面温度が１５０℃のステンレス製加熱板２枚の間にアルミニウム材を挟み、３０秒間空気中で接触加熱させた。接触加熱後のアルミニウム材を重ねた状態で、アルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（実施例１０）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた後、表面温度が２００℃のステンレス製加熱板２枚の間にアルミニウム材を挟み、２秒間空気中で接触加熱させた。接触加熱後のアルミニウム材を重ねた状態で、アルゴン雰囲気下でアルミニウム材の実体温度を室温から４８０℃まで５０℃／ｈで昇温させた後、４８０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（実施例１１）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた後、表面温度が２００℃のステンレス製加熱板２枚の間にアルミニウム材を挟み、２秒間空気中で接触加熱させた。接触加熱後のアルミニウム材を重ねた状態で、アルゴン雰囲気下でアルミニウム材の実体温度を室温から５８０℃まで５０℃／ｈで昇温させた後、５８０℃にて２４時間保持させ、次いで冷却させたのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（実施例１２）
接触加熱後に、表面温度が１０℃のステンレス板の間にアルミニウム材を１０秒間挟み冷却させる工程を含むこと以外は、実施例１と同様にして電解コンデンサ用高純度アルミニウム材を得た。
（比較例１）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた後、重ねた状態でアルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（比較例２）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた後、重ねた状態でアルゴン雰囲気下でアルミニウム材の実体温度を室温から４８０℃まで５０℃／ｈで昇温させた後、４８０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
（比較例３）
実施例１と同じく、厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を作製した。得られたアルミニウム材をアルカン系炭化水素に２秒間浸漬し、９０℃にて１分間空気中で乾燥させた後、重ねた状態でアルゴン雰囲気下でアルミニウム材の実体温度を室温から５８０℃まで５０℃／ｈで昇温させた後、５８０℃にて２４時間保持させ、次いで冷却したのち炉出しし、電解コンデンサ用高純度アルミニウム材を得た。
上記実施例および比較例で得られたアルミニウム材を酸に浸漬した後、塩酸−硫酸水溶液で電解エッチングしたのち、さらに酸溶液に浸漬することによりピット径を太くしエッチド箔を得た。得られたエッチド箔を、化成電圧２７０ＶにてＥＩＡＪ規格に従い化成処理し、静電容量測定用サンプルとした。
【００６８】
実施例および比較例の接触加熱条件、焼鈍時のアルミニウム材の実態温度、静電容量評価を表１に示す。静電容量評価は、比較例１を１００とした時の値を示す。
【００６９】
【表１】
上記表１からわかるように、実施例では、焼鈍前に加熱板または熱ロールを用いて接触加熱を行うことにより、接触加熱を行わない比較例１〜３と較べて静電容量の向上が見られる。
［実施例１３〜１３０及び比較例４］
表２及び表３に示す有機溶剤および表４に示す水に界面活性剤を添加したものを洗浄液として用意した。
【００７１】
【表２】
【表３】
【表４】
（実施例１３）
厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材に対し、表２のＡ１液に２秒間浸漬した後、空気中で９０℃にて６０秒間乾燥した。次に、アルミニウム材を表面温度が２００℃のステンレス製加熱板２枚の間に挟み、２秒間接触加熱を行った。
【００７５】
次いで、接触加熱後のアルミニウム材を重ねた状態でアルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却した後炉出しし、電解コンデンサ電極用アルミニウム材を得た。
（実施例１４〜８８）
実施例１３と同じ厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を、表５〜表８の工程の条件で洗浄・乾燥した後、アルミニウム材を表面温度が２００℃のステンレス製加熱板２枚の間に挟み、２秒間接触加熱を行った。なお実施例５３〜８２では、アルミニウム材が洗浄液に浸漬されている間ブラシをアルミニウム材表面に接触させ摺動した。
【００７６】
接触加熱後のアルミニウム材を重ねた状態でアルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却した後炉出しし、電解コンデンサ電極用アルミニウム材を得た。
（実施例８９〜９６）
実施例１３と同じ厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を２００℃のステンレス製加熱板２枚の間に挟み、２秒間接触加熱を行った。
【００７７】
次に、表８の工程３の条件にて洗浄・乾燥した。なお、アルミニウム材が洗浄液に浸漬されている間ブラシをアルミニウム材表面に接触させ摺動した。
【００７８】
洗浄・乾燥後のアルミニウム材を重ねた状態でアルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却した後炉出しし、電解コンデンサ電極用アルミニウム材を得た。
（実施例９７〜１０２）
実施例１３と同じ厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を、表８の工程１の条件にて洗浄・乾燥した後、アルミニウム材を表面温度が２００℃のステンレス製加熱板２枚の間に挟み、２秒間接触加熱を行った。次に、接触加熱後のアルミニウム材を表８の工程３の条件で洗浄・乾燥した。
【００７９】
工程３の条件で洗浄・乾燥したアルミニウム材を重ねた状態でアルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却した後炉出しし、電解コンデンサ電極用アルミニウム材を得た。
（実施例１０３〜１０７）
実施例１３と同じ厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を、表８の工程の条件で洗浄・乾燥した後、アルミニウム材を表面温度が２００℃のステンレス製加熱板２枚の間に挟み、２秒間接触加熱を行った。
【００８０】
接触加熱後のアルミニウム材を重ねた状態でアルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却した後炉出しし、電解コンデンサ電極用アルミニウム材を得た。
（実施例１０８〜１１１）
実施例１３と同じ厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を２００℃のステンレス製加熱板２枚の間に挟み、２秒間接触加熱を行った。次に、表８及び表９の工程３の条件にて洗浄・乾燥した。なお、アルミニウム材が洗浄液に浸漬されている間ブラシをアルミニウム材表面に接触させ摺動した。
【００８１】
洗浄・乾燥後のアルミニウム材を重ねた状態でアルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却した後炉出しし、電解コンデンサ電極用アルミニウム材を得た。
（実施例１１２〜１２８）
実施例１３と同じ厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材に対し、表９の工程１の条件での洗浄・乾燥、表９の工程２の条件での接触加熱を施した。
【００８２】
接触加熱後のアルミニウム材を重ねた状態でアルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却した後炉出しし、電解コンデンサ電極用アルミニウム材を得た。
（実施例１２９）
実施例１３と同じ厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材を２００℃のステンレス製加熱板２枚の間に挟み、２秒間接触加熱を行った。接触加熱後のアルミニウム材を重ねた状態でアルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却した後炉出しし、電解コンデンサ電極用アルミニウム材を得た。
（実施例１３０）
熱ロールでの接触加熱後に表面温度２５℃の冷却ロールにアルミニウム材を接触させる工程を含む事以外は、実施例１２４と同様にして電解コンデンサ電極用アルミニウム材を得た。
（比較例４）
実施例１３と同じ厚さ１１０μｍに圧延された純度９９．９９％のアルミニウム材をアルゴン雰囲気下でアルミニウム材の実体温度を室温から５４０℃まで５０℃／ｈで昇温させた後、５４０℃にて２４時間保持させ、次いで冷却した後炉出しし、電解コンデンサ電極用アルミニウム材を得た。
上記実施例１３〜１３０および比較例４で得られたアルミニウム材をＨＣｌ １．０ｍｏｌ・ｄｍ−３とＨ２ＳＯ４ ３．５ｍｏｌ・ｄｍ−３を含む液温７５℃の水溶液に浸漬した後、電流密度０．２Ａ／ｃｍ２で電解処理を施した。電解処理後の箔をさらに前記組成の塩酸―硫酸混合水溶液に９０℃にて３６０秒浸漬し、ピット径を太くしエッチド箔を得た。得られたエッチド箔を化成電圧２７０ＶにてＥＩＡＪ規格に従い化成処理した静電容量測定用サンプルとした。各サンプルについて測定した静電容量を、比較例４を１００とした場合の相対値にて表５〜表９に示す。
【００８３】
【表５】
【表６】
【表７】
【表８】
【表９】
上記表９の実施例１２９と比較例４との比較により、最終焼鈍を行う前に接触加熱を行うことにより静電容量が向上する。また、実施例１３〜１１１と実施例１２９の比較により接触加熱前後の少なくともどちらかで洗浄を行うことによりさらに静電容量が向上することが分かる。
【００８９】
また、実施例１０３〜１１１により、洗浄後の乾燥温度が２００℃以下であると静電容量が向上し、９０℃以下ではさらに静電容量が高い。
【００９０】
【発明の効果】
この発明は、上述の次第で、冷間圧延後に加熱体との接触によりアルミニウム材を加熱した後焼鈍することにより、箔表面にエッチピット核となりうる物質が多く析出したエッチング特性に優れた電解コンデンサ用アルミニウム材を製造することができる。特に、加熱方法として接触加熱を用いるから、均一に短時間でアルミニウム材表面を目的の温度に到達させることができるため、温度制御が比較的容易で、しかも急速かつ短時間で加熱できるため雰囲気の影響を少なくできる。従って、この電解コンデンサ用アルミニウム材をエッチングすることにより、前記エッチピットの核となりうる物質の存在位置において、効果的にエッチングが行われ、その結果拡面率を向上でき、ひいては静電容量の増大した電解コンデンサ電極材となし得、結果として大きな静電容量を有するアルミニウム電解コンデンサを得ることができる。
【００９１】
また、加熱体との接触前あるいは接触後の少なくともどちらかにおいて、アルミニウム材を洗浄することにより、さらに静電容量の増大効果が得られる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing an aluminum material for an electrolytic capacitor, an aluminum anode material for an electrolytic capacitor electrode, a method for producing an electrode material for an electrolytic capacitor, and an aluminum electrolytic capacitor.
[0002]
In this specification, the term "aluminum" is used to include its alloy, and the aluminum material includes a foil, a plate, and a molded article using these.
[0003]
[Prior art and problems]
Aluminum materials generally used as electrode materials for aluminum electrolytic capacitors are required to have a large surface area and a large capacitance per unit area. In this case, the effective area of the aluminum material is increased.
[0004]
Further, for the purpose of increasing the effective area, studies have been made on various aspects such as a material composition, a manufacturing process, an etching method, and the like, in order to increase and increase the size of an etching hole.
[0005]
For example, in the production of an aluminum material for an electrolytic capacitor in which tunnel-like pits are generated by a DC etching method, usually, in order to develop the crystal orientation of the (100) plane, an inert atmosphere or a vacuum is used at a temperature of about 500 ° C. The final annealing is performed. The final annealing is a step performed after finish cold rolling or after finish cold rolling and washing.
[0006]
It is described in Non-Patent Documents 1 and 2 that when crystalline oxide particles are generated on the surface of an aluminum material during final annealing, etch pits are formed from the periphery of the crystal during electrolytic etching. It is considered that the generation of the material particles on the surface of the aluminum material contributes to the improvement of the capacitance.
[0007]
However, as described above, in an inert gas atmosphere or a vacuum atmosphere, which is a general atmosphere for final annealing, since the amount of oxygen in the atmosphere is extremely small, it is difficult to crystallize even if the final annealing is performed. Conversely, when annealing at a high temperature in an oxidizing atmosphere, the oxide film becomes thicker, and the uniformity of the etch pits is reduced.
[0008]
As a method of precipitating a lot of crystals on the surface of the aluminum material, a method of blowing steam or moist air to the surface of the aluminum material before final annealing, a method of heating at a temperature of about 200 ° C. in the atmosphere, a heated water or amine aqueous solution A method of forming a hydration treatment film by a so-called boehmite treatment method in which an aluminum material is immersed therein is known (Patent Document 1).
[0009]
The hydrated coating film was subjected to batch annealing in a coil state or in a state where veneers were stacked, although the crystalline oxide was likely to precipitate on the surface of the aluminum material by the subsequent final annealing, but had many Al-OH groups on the surface. In such a case, there is a problem that it is easy to adhere. In addition, in the method of heating at a temperature of about 200 ° C. in the air, accurate atmosphere control such as control of the amount of water vapor is required in order to obtain a target oxide film with good reproducibility. There was the disadvantage that it took time to reach.
[0010]
Patent Document 2 discloses that γ-Al is obtained by continuous final annealing in an oxidizing atmosphere containing oxygen or moisture. 2 O 3 Although a technique for precipitating γ-Al has been disclosed, since the final annealing time is short, γ-Al 2 O 3 There was a risk that the precipitation of insufficiency was insufficient.
[0011]
[Non-patent document 1]
Kiyoshi Fukuoka, Nobuo Osawa, Tetsuya Motoi, Outline of the 95th Autumn Meeting of the Japan Institute of Light Metals p. 265 (1998),
[0012]
[Non-patent document 2]
Nobuo Osawa, Kiyoshi Fukuoka; Surface Technology, 50 [7], 643 (1999)
[0013]
[Patent Document 1]
JP-B-58-34926
[0014]
[Patent Document 2]
JP-A-63-116417
The present invention has been made in view of such technical background, and can be performed in a short time without requiring precise atmosphere control, and can be sufficiently crystallized by the final annealing to be a core of etching pits. And a method for producing an aluminum material for an electrolytic capacitor electrode, an aluminum anode material for an electrolytic capacitor electrode, a method for producing an electrode material for an electrolytic capacitor, and an aluminum electrolytic capacitor. I do.
[0015]
[Means for Solving the Problems]
The present invention provides the following means.
(1) Aluminum for an electrolytic capacitor electrode characterized in that hot rolling and cold rolling are sequentially performed on an aluminum slab to form an aluminum material, and this aluminum material is heated by contact with a heating body and then annealed. The method of manufacturing the material.
(2) The method for producing an aluminum material for an electrolytic capacitor electrode according to the above item 1, further comprising a step of cleaning the aluminum material before or after contact with the heating element.
(3) After hot rolling and cold rolling are sequentially performed on the aluminum slab to form an aluminum material, the aluminum material is washed, and then dried or heated without being dried, by contact with a heating body. And then annealing. A method for producing an aluminum material for an electrolytic capacitor electrode.
(4) After hot rolling and cold rolling are sequentially performed on an aluminum slab to form an aluminum material, the aluminum material is heated by contact with a heating body, further washed, and then dried or without drying. A method for producing an aluminum material for an electrode of an electrolytic capacitor, which is followed by annealing.
(5) The aluminum material for an electrolytic capacitor electrode according to any one of (1) to (4), wherein the surface temperature of the heating element is 80 to 400 ° C., and the contact time between the aluminum material and the heating element is 0.001 to 30 seconds. Manufacturing method.
(6) The method for producing an aluminum material for an electrolytic capacitor electrode according to any one of the above (1) to (4), wherein the annealing is performed in an inert gas atmosphere at a substantial aluminum temperature of 460 to 600 ° C.
(7) The method for producing an aluminum material for an electrolytic capacitor electrode according to claim 6, wherein the actual aluminum temperature is 500 to 580 ° C.
(8) The method for producing an aluminum material for an electrolytic capacitor electrode according to any one of the above items 1 to 4, wherein the heating body is a heat roll.
(9) The method for producing an aluminum material for an electrolytic capacitor electrode according to any one of the above (1) to (4), wherein the aluminum material is cooled after contact with the heating element.
(10) The method for producing an aluminum material for an electrolytic capacitor electrode according to the above (9), wherein the aluminum material is cooled by contact with a cooling roll.
(11) The method for producing an aluminum material for an electrolytic capacitor electrode according to any one of (2) to (10) above, wherein the cleaning liquid used for cleaning is an organic solvent.
(12) The organic solvent is C n H 2n + 1 An alcohol represented by OH (n is a natural number of 1 to 10), cyclohexanol (C 6 H 11 0H), 1,2-ethanediol (HOCH 2 CH 2 OH), 1,2-propanediol (CH 3 CH (OH) CH 2 OH), 1,3-propanediol (HOCH) 2 CH 2 CH 2 OH), C n H 2n + 2 Alkane hydrocarbon represented by (n = natural number of 5 to 15), cyclohexane, R 1 COR 2 (R 1 And R 2 : An aliphatic hydrocarbon group, wherein the total number of carbon atoms of R1 and R2 is 8 or less); 6 H 10 O), R 1 -OR 2 (R 1 And R 2 : An aliphatic hydrocarbon group, R 1 And R 2 An ether represented by the formula: 2-methoxyethanol (CH 3 OCH 2 CH 2 OH), 2-ethoxyethanol (CH 3 CH 2 OCH 2 CH 2 OH), 2-butoxyethanol (CH 3 CH 2 CH 2 CH 2 OCH 2 CH 2 OH) 2- (2-ethoxy) ethoxyethanol (CH 3 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH), CH 3 12. The aluminum for an electrolytic capacitor electrode according to the above item 11, which is one or a mixture of two or more selected from an acetate ester represented by COOR (R: an aliphatic hydrocarbon group having 1 to 5 carbon atoms) and toluene xylene. The method of manufacturing the material.
(13) The method for producing an aluminum material for an electrode of an electrolytic capacitor according to any one of (2) to (10) above, wherein the cleaning liquid used for cleaning is obtained by adding a surfactant to water.
(14) The surfactant is R-OSO 3 Anionic surfactant (sulfate ester) represented by Na (R = saturated hydrocarbon group having 8 to 18 carbon atoms or unsaturated hydrocarbon group having one double bond), R-SO 3 Na (R = a saturated hydrocarbon group having 8 to 18 carbon atoms or an unsaturated hydrocarbon group having one double bond) or R-SO 3 An anionic surfactant (sulfonate) represented by Na (R: an alkyl group wherein the alkyl group is a saturated hydrocarbon group having 8 to 14 carbon atoms or an unsaturated hydrocarbon group having one double bond); RN + (CH 3 ) 3 ・ Cl − (R = saturated hydrocarbon group having 8 to 16 carbon atoms), a cationic surfactant (quaternary ammonium salt), R—O — (— CH 2 CH 2 O) n H (R = a saturated hydrocarbon group having 8 to 16 carbon atoms or an unsaturated hydrocarbon group having one double bond, n = 6 to 14) or R—O — (— CH 2 CH 2 O) n H (R = alkylphenyl group wherein the alkyl group is a saturated hydrocarbon group having 8 to 12 carbon atoms or an unsaturated hydrocarbon group having one double bond, n = 6 to 14) A mixture of one or more anionic surfactants selected from ionic surfactants, a mixture of a plurality of cationic surfactants, a mixture of a plurality of nonionic surfactants, one or more anionic surfactants, 14. The method for producing an aluminum material for an electrolytic capacitor electrode according to the above item 13, wherein the mixture is a mixture of one or more nonionic surfactants, a mixture of one or more cationic surfactants and one or more nonionic surfactants.
(15) The method for producing an aluminum material for an electrolytic capacitor electrode according to the above (3) or (4), wherein the drying temperature after the washing is 200 ° C. or lower.
(16) The method for producing an aluminum material for an electrolytic capacitor electrode according to the above (15), wherein the drying temperature after the washing is 90 ° C. or less.
(17) The method for producing an aluminum material for an electrolytic capacitor electrode according to any one of the above (1) to (16), which has an aluminum purity of 99.9% or more.
(18) An aluminum anode material for an electrolytic capacitor manufactured by the manufacturing method according to any one of the above items 1 to 17.
(19) The aluminum anode material for electrolytic capacitors according to the above item 18, which is for medium pressure or high pressure.
(20) A method for producing an electrode material for an electrolytic capacitor, characterized in that the aluminum material produced by the production method according to any one of (1) to (17) is annealed and then etched.
(21) The method for producing an electrode material for an electrolytic capacitor according to the above item 20, wherein the etching is a DC etching.
(21) An aluminum electrolytic capacitor, wherein an aluminum electrode material manufactured by the manufacturing method described in the above item 20 or 21 is used as the electrode material.
[0016]
As described above, the present invention is characterized in that after hot rolling and cold rolling are sequentially performed on an aluminum slab to form an aluminum material, the aluminum material is heated by contact with a heating body, and then annealed. I do.
[0017]
That is, in a step after the cold rolling, the aluminum material is heated by contact with a heating body, and a substance that can become an etch pit nucleus is precipitated on the aluminum material surface by subsequent annealing. The contact heating is used as the heating method because the surface of the aluminum material can reach the target temperature uniformly and in a short time by the surface of the heating element, so that the control is relatively easy, and the heating can be performed quickly and in a short time. This is because the influence of the atmosphere can be reduced.
[0018]
In the production of aluminum materials for electrolytic capacitors, final annealing is conventionally performed in an inert atmosphere or in a vacuum in a temperature range of 450 to 600 ° C. in order to develop a crystal orientation of the (100) plane. A substance that can serve as a nucleus of an etch pit such as an oxide is not sufficiently generated. Therefore, by performing rapid heating by contact heating before final annealing, the generation of a substance that can be a nucleus of etch pits such as crystalline oxide fine particles during final annealing is promoted.
[0019]
Here, the substance which can be a core of the etch pit includes not only a crystalline oxide but also an amorphous substance having a high density or a thick substance, and an amorphous substance containing a crystalline oxide or metallic aluminum. It is. Further, as the kind of the crystalline oxide, γ-Al 2 O 3 And other Al 2 O 3 And a composite oxide with a metal other than aluminum, such as boehmite and AlOOH, and aluminum (eg, Mg, Pb, Cu, etc.), but is not particularly limited to a metal oxide or a metal hydroxide.
[0020]
If such an oxide film on the surface of the aluminum material has a characteristic different from that of other places, it may be considered as a nucleus of an etch pit at the time of etching. It is presumed that a crystal or a non-crystalline amorphous state before the transition to the crystal is generated, and a substance containing the crystal or the metal aluminum in the amorphous is generated, and these become the etch pit nuclei.
[0021]
As described above, contact heating with a heating element is used as a rapid heating method because, as described above, the aluminum material surface can reach the target temperature in a very short time and is excellent in productivity. This is because if the temperature of the surface of the heating element in contact with the surface of the aluminum material is uniform and the temperature of the surface of the heating member is uniform, it is possible to form a uniform oxide film in the width and length directions of the aluminum coil.
[0022]
Hereinafter, a method for producing an aluminum material for an electrolytic capacitor will be described.
[0023]
The purity of the aluminum material is not particularly limited as long as it is in a range used for an electrolytic capacitor, but the purity is preferably 99.9% or more, particularly preferably 99.95% or more. In the present invention, the purity of the aluminum material is a value obtained by subtracting the total concentration (%) of Fe, Si, Cu, Mn, Cr, Zn, Ti and Ga from 100%.
[0024]
The production of the aluminum material is not limited, but is carried out in the order of adjustment of the melting component of the aluminum material, slab casting, soaking, hot rolling, cold rolling, finishing cold rolling (low-reduction rolling), and contact heating. The (100) area ratio of the aluminum material is preferably 90% or more, and the manufacturing process conditions of the aluminum material are appropriately changed depending on the etching conditions of the aluminum material. In the middle of the rolling process, annealing (referred to as intermediate annealing) may be performed in order to eliminate the distortion of the crystal structure of the aluminum material caused by the rolling in the preceding process. Cleaning may be performed in a step before the intermediate annealing in order to remove impurities and oil on the aluminum surface.
[0025]
The cleaning liquid used in the step before the intermediate annealing is not particularly limited, but an aqueous alkali solution, an aqueous acid solution, an organic solvent, or the like is used.
[0026]
Since the aluminum material after the rolling step has an oily component on its surface, it is preferable to wash the aluminum material before final annealing and at least before or after contact heating as described below, if necessary. By performing such cleaning, the effect of contact heating is more exerted, and a large capacitance can be obtained.
[0027]
After the completion of rolling, contact heating is performed without performing washing, and when large wear powder or the like is attached to the surface of the aluminum material, it is preferable to remove the aluminum powder by washing.
[0028]
As the cleaning liquid used for cleaning before or after the contact heating, for the purpose of degreasing, a cleaning liquid obtained by adding a surfactant to an organic solvent or water can be used.
[0029]
As the organic solvent, a substance that does not dissolve aluminum can be used.Examples include alcohols, diols, aromatic hydrocarbons such as toluene and xylene, alkane hydrocarbons, cyclohexane, ketones, ethers, esters, and petroleum products. Although it is mentioned, it is not particularly limited.
[0030]
Examples of the alcohol include methanol (CH 3 OH), ethanol (C 2 H 5 OH), 1-propanol (CH 3 CH 2 CH 2 OH), 2-propanol (CH 3 CH2 (OH) CH 3 ), 1-butanol (CH 3 CH 2 CH 2 CH 2 OH), 2-butanol (CH 3 CH 2 CH 2 (OH) CH 3 ), 1-pentanol (CH 3 CH 2 CH 2 CH 2 CH 2 OH), 2-pentanol (CH 3 CH 2 CH 2 CH 2 (OH) CH 3 ) And the like; n H 2n + 1 Those represented by OH (n is a natural number of 1 to 10) are preferred. Also, fat-dried hydrocarbons such as cyclohexanol can be used.
[0031]
Examples of the above diol include 1,2-ethanediol (HOCH 2 CH 2 OH), 1,2-propanediol (CH 3 CH (OH) CH 2 OH), 1,3-propanediol (HOCH) 2 CH 2 CH 2 OH) and the like.
[0032]
Examples of the alkane hydrocarbon include pentane (C 5 H 12 ), Hexane (C 6 H 14 ), Heptane (C 7 H 16 ), Octane (C 8 H 18 ), Nonane (C 9 H 20 ), Decane (C 10 H 22 ) Etc. and C n H 2n + 2 (N = natural number of 5 to 15) is preferable. It is also possible to use a fat-based hydrocarbon such as cyclohexane.
[0033]
Acetone (CH 3 COCH 3 ), 2-butanone (CH 3 COC 2 H 5 ), 3-pentanone (CH 3 CH 2 COCH 2 CH 3 ), 3-methyl-2-butanone (CH 3 COCH (CH 3 ) 2 ) Can be exemplified. 1 COR 2 (R 1 And R 2 : An aliphatic hydrocarbon group, wherein the total number of carbon atoms of R1 and R2 is 8 or less). In addition, cyclohexanone (C 6 H 10 O) You may use cyclic ketones, such as.
[0034]
Examples of the above ethers include R 1 -OR 2 (R 1 And R 2 : An aliphatic hydrocarbon group, R 1 And R 2 A total of 8 or less), 2-methoxyethanol (CH 3 OCH 2 CH 2 OH), 2-ethoxyethanol (CH 3 CH 2 OCH 2 CH 2 OH), 2-butoxyethanol (CH 3 CH 2 CH 2 CH 2 OCH 2 CH 2 OH) 2- (2-ethoxy) ethoxyethanol (CH 3 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH), etc. are also included.
[0035]
Examples of the above ester include CH 3 An acetate ester represented by COOR (R: an aliphatic hydrocarbon group having 1 to 5 carbon atoms) can be exemplified.
[0036]
Examples of the petroleum products include industrial gasoline (JIS K 2201), automobile gasoline (JIS K 2202), aviation gasoline (JIS K 2206), kerosene (JIS K 2203), light oil (JIS K 2204), and aviation gasoline (JIS K 2204). 2206), petroleum ether (JIS K 8593), petroleum benzine (JIS K 8594), ligroin (JIS K 8937), kerosene and the like.
[0037]
As the organic solvent, a plurality of organic solvents may be mixed and used, and in the case of an organic solvent that can be mixed with water, the organic solvent may be mixed with water as necessary.
[0038]
On the other hand, as the surfactant contained in the cleaning liquid obtained by adding a surfactant to water used for the above-mentioned cleaning, an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used.
[0039]
Sulfate and sulfonate can be used as the anionic surfactant.
[0040]
Examples of the sulfate ester salt include R-OSO 3 Na (R = a saturated hydrocarbon group having 8 to 18 carbon atoms or an unsaturated hydrocarbon group having one double bond) can be used. Specifically, sodium dodecyl sulfate (C 12 H 25 OSO 3 Na), sodium hexadecyl sulfate (C 16 H 33 OSO 3 Na), sodium stearyl sulfate (C 18 H 37 OSO 3 Na), sodium oleyl sulfate (C 18 H 35 OSO 3 Na) and the like.
[0041]
The sulfonate is R-SO 3 Na (R = a saturated hydrocarbon group having 8 to 18 carbon atoms or an unsaturated hydrocarbon group having one double bond) or sodium dodecylbenzenesulfonate (C 12 H 25 -C 6 H 4 -SO 3 R-SO such as Na) 3 Na (R: an alkyl benzyl group in which the alkyl group is a saturated hydrocarbon group having 8 to 14 carbon atoms or an unsaturated hydrocarbon group having one double bond) can be used.
[0042]
As the cationic surfactant, RN + (CH 3 ) 3 ・ Cl − A quaternary ammonium salt represented by (R = saturated hydrocarbon group having 8 to 16 carbon atoms) can be used.
[0043]
Non-ionic surfactants include RO-(-CH 2 CH 2 O) n H (R = a saturated hydrocarbon group having 8 to 16 carbon atoms or an unsaturated hydrocarbon group having one double bond, n = 6 to 14) or R—O — (— CH 2 CH 2 O) n H (R = alkylphenyl group wherein the alkyl group is a saturated hydrocarbon group having 8 to 12 carbon atoms or an unsaturated hydrocarbon group having one double bond, n = 6 to 14) An ionic surfactant can be exemplified. A compound in which n is larger than the above range may be contained in the nonionic surfactant in a molar ratio of 50% or less.
[0044]
Further, at least one of the above surfactants can be added to water and used as a cleaning liquid. A surfactant in which the number of carbon atoms of the surfactant is smaller than the above range may be added in a molar ratio of 50% or less. In addition, when an anionic surfactant and a cationic surfactant are mixed in water, a precipitate is formed. Therefore, it is preferable to avoid mixing.
[0045]
The concentration of the surfactant to be added is not particularly limited, but is preferably equal to or higher than the critical micelle concentration in order to exert a cleaning effect.
[0046]
In the above-mentioned washing step, the method of contacting the aluminum material with the organic solvent or the aqueous surfactant solution used as the washing liquid is not particularly limited, and examples include immersion, contact of the aluminum material with the surface of the washing liquid, and spraying.
[0047]
Further, for the purpose of further removing oil and abrasion powder on the surface of the aluminum material, the aluminum material may be brought into contact with a brush or a sponge during the contact between the cleaning liquid and the aluminum material, and further rubbed.
[0048]
In the cleaning step, the contact time between the cleaning liquid and the aluminum material is not particularly limited, but is preferably 0.5 seconds or more and 10 minutes or less. If the contact time between the cleaning liquid and the aluminum material is less than 0.5 seconds, the cleaning is insufficient, and even if the cleaning liquid is contacted for more than 10 minutes, the cleaning effect reaches saturation. The temperature of the cleaning solution is preferably 5 to 60 ° C. for an organic solvent, and 5 to 80 ° C. for a cleaning solution obtained by adding a surfactant to water. When the temperature of the cleaning liquid is lower than the lower limit, the cleaning power is insufficient, and the cleaning power reaches saturation even when the temperature is higher than the upper limit.
[0049]
After washing the aluminum material, it may be dried if necessary. As a drying method, for example, heating in air, heating in an inert atmosphere, and vacuum heating can be used. When drying in the air, the ambient temperature is preferably 200 ° C. or less, and the drying time is preferably 10 minutes or less. If the drying temperature is higher than 200 ° C. or the heating time is longer than 10 minutes, the oxide film may grow too much and the etching characteristics may be deteriorated.
[0050]
The aluminum material after the completion of the rolling or the aluminum material further cleaned after the completion of the rolling is contact-heated in order to generate a large number of etch pit nuclei by subsequent annealing. The heating means may be a heating roll, a heating belt, a heating plate or any other means capable of contact heating, but a heating roll is desirable in that simple and continuous contact heating can be performed.
In addition, heating may be performed on one surface at a time, or only one of the front and back surfaces may be heated. The material of the heating surface of the heating element can be freely selected from stainless steel, plating, ceramics, Teflon resin (registered trademark), silicone resin, and the like, but a substance that does not cause the surface oxide film of the aluminum material to adhere to the surface of the heating element is preferable. .
[0051]
The surface temperature of the heating element brought into contact with the aluminum material is preferably from 80 to 400C. If the surface temperature of the heating body is less than 80 ° C., the heating becomes insufficient, and there is a possibility that the generation of a substance that can be a nucleus of an etch pit, such as crystalline oxide fine particles, during annealing performed after the contact heating becomes insufficient. On the other hand, when the temperature is higher than 400 ° C., the oxide film becomes too thick, and wrinkles occur during cooling, which may cause operational problems. A particularly preferred heating element surface temperature is 100 to 350 ° C. A more preferred heating element surface temperature is 160 to 290 ° C.
[0052]
The contact time between the surface of the aluminum material and the surface of the heating element is preferably 0.001 to 30 seconds. If the contact time is less than 0.001 second, the surface of the aluminum material cannot be sufficiently heated, and there is a possibility that the generation of a substance that may become an etch pit nucleus may become insufficient. On the other hand, if the time is longer than 30 seconds, the oxide film may be too thick, and it may be difficult to generate etch pits. Particularly preferred contact times are from 0.01 to 10 seconds. A more preferred contact time is 0.1 to 7 seconds.
[0053]
The surface temperature and the contact time of the heating element may be appropriately selected in consideration of the characteristics of the oxide film on the surface of the aluminum material before the contact. The contact heating atmosphere is not particularly limited, and the heating can be performed in the air without any special atmosphere control.
[0054]
As an example of a heating device using a heat roll as a heating element, a device in which at least two heat rolls are arranged in order to contact-heat the front and back surfaces of an aluminum material at a target temperature is exemplified. If wrinkles occur during winding of the aluminum material after the aluminum material has been contact-heated with a hot roll or the like, the aluminum material is heated by a hot roll or the like, and then passed through a cooling body such as one or more cooling rolls to remove the aluminum material. It is good also as a structure wound up after cooling. In particular, by using a cooling roll as a cooling body, cooling can be performed easily and continuously. Also, before heating the aluminum material to the desired contact heating temperature with a heat roll or the like, the temperature of the aluminum material may be preliminarily raised to a temperature lower than the desired contact heating temperature using another heat roll. Good.
[0055]
After the contact heating, if necessary, after the above-described cleaning, the generation of a substance that can be a nucleus of an etch pit is promoted, and the crystal structure of the aluminum material is oriented in the (100) direction to improve etching characteristics. The final annealing is performed for the main purpose.
[0056]
It is needless to say that after the final rolling and before the final annealing, other steps other than the above-described steps, for example, a slit step for dividing the aluminum material coil may be performed.
[0057]
In the final annealing, the thickness of the oxide film formed on the aluminum material in the contact heating step, which is the previous step, is excessively increased in the final annealing step, so that the possibility of becoming an etching nucleus is not erased. The total thickness of the oxide film is determined by the Hunter Hall method (MS Hunter and P. Fowle, J. Electrochem. Soc., 101 [9], 483 (1954)), it is preferable to carry out the final annealing so as to have a thickness of 2.5 to 5.0 nm. The (100) area ratio of the aluminum material after the final annealing is preferably 90% or more.
[0058]
The treatment atmosphere in the final annealing is not particularly limited, but it is preferable to heat in an atmosphere with a small amount of moisture and oxygen so that the thickness of the oxide film is not excessively increased. Specifically, it is preferable to heat in an inert gas such as argon or nitrogen or in a vacuum of 0.1 Pa or less.
[0059]
The method of final annealing is not particularly limited, and may be batch-annealed in a state of being wound on a coil, may be wound on a coil after rewinding and continuously annealing the coil, and at least batch annealing and continuous annealing may be performed. Either one may be performed multiple times.
[0060]
Although the temperature and time during the final annealing are not particularly limited, for example, when performing batch annealing in the state of a coil, it is preferable to perform annealing at an aluminum body temperature of 460 to 600 ° C for 10 minutes to 50 hours. If the aluminum substance temperature is less than 460 ° C. and the time is less than 10 minutes, the generation of a substance that can become a nucleus of an etch pit in the oxide film is not sufficient, and the dispersion state becomes too sparse to perform etching with the crystal as an etching nucleus. This is because there is a possibility that the widening effect at the time cannot be expected, and the development of the crystal orientation of the (100) plane may be insufficient. Conversely, if annealing is performed at a temperature exceeding 600 ° C., when batch annealing is performed with a coil, the aluminum material is likely to adhere to each other. Even when annealing is performed for more than 50 hours, the effect of area expansion by etching is saturated, and the heat energy cost is reduced. Causes an increase. A particularly preferred temperature is 500 to 580 ° C. at a substantial aluminum temperature, and the time is 20 minutes to 40 hours.
[0061]
Further, the heating rate / pattern of the final annealing is not particularly limited, and the temperature may be raised at a constant rate, or the temperature may be raised and cooled while repeating the temperature raising and the temperature holding. The annealing may be performed in a temperature range of 460 to 600 ° C. for a total of 10 minutes to 50 hours. The thickness of the aluminum material for an electrolytic capacitor electrode obtained after the final annealing is not particularly limited.
[0062]
The aluminum material that has been subjected to the final annealing is subjected to an etching process to improve the area expansion ratio. The etching conditions are not particularly limited, but preferably a direct current etching method is used. By the DC etching method, a deep and thick etching is performed in a portion serving as a nucleus of the etch pit whose generation is promoted in the final annealing, a large number of tunnel-like pits are generated, and a high capacitance is realized.
[0063]
After the etching treatment, it is preferable to perform a chemical conversion treatment to obtain an anode material, and it is particularly preferable to use it as an electrode material for medium and high pressure electrolytic capacitors. Of course, this does not preclude the use as a cathode material.
[0064]
By using the anode material and / or the cathode material as described above as an electrode material, an aluminum electrolytic capacitor is formed. This electrolytic capacitor has a large capacitance because the surface area of the electrode material is increased.
[0065]
The capacitance may be measured in accordance with a conventional method with respect to the etched foil subjected to the chemical conversion treatment, for example, by measuring in 80 g / L ammonium borate at 30 ° C. at 120 Hz using a platinum plate as a counter electrode.
[0066]
The capacitor of the present invention is not limited to the embodiment.
[0067]
【Example】
Hereinafter, examples and comparative examples of the present invention will be described.
[Examples 1 to 12 and Comparative Examples 1 to 3]
(Example 1)
An aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was prepared. The obtained aluminum material was immersed in an alkane-based hydrocarbon for 2 seconds, dried in air at 90 ° C. for 1 minute, and then sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C. Contact heating was performed in air for 2 seconds. In a state where the aluminum materials after the contact heating were stacked, the actual temperature of the aluminum material was increased from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then maintained at 540 ° C. for 24 hours, and then cooled. Thereafter, the furnace was taken out of the furnace to obtain a high-purity aluminum material for an electrolytic capacitor.
(Example 2)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in air, and then sandwiched between two stainless steel heating plates having a surface temperature of 250 ° C. Contact heating was performed in air for 2 seconds. In a state where the aluminum materials after the contact heating were stacked, the actual temperature of the aluminum material was increased from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then maintained at 540 ° C. for 24 hours, and then cooled. Thereafter, the furnace was taken out of the furnace to obtain a high-purity aluminum material for an electrolytic capacitor.
(Example 3)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane-based hydrocarbon for 2 seconds, dried in air at 90 ° C. for 1 minute, and then sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C. Contact heating was performed in air for 2 seconds. In a state where the aluminum materials after the contact heating were stacked, the actual temperature of the aluminum material was raised from room temperature to 560 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then maintained at 560 ° C. for 24 hours, and then cooled. Thereafter, the furnace was taken out of the furnace to obtain a high-purity aluminum material for an electrolytic capacitor.
(Example 4)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane-based hydrocarbon for 2 seconds, dried in air at 90 ° C. for 1 minute, and then sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C. Contact heating was performed in air for 1 second. In a state where the aluminum materials after the contact heating were stacked, the actual temperature of the aluminum material was increased from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then maintained at 540 ° C. for 24 hours, and then cooled. Thereafter, the furnace was taken out of the furnace to obtain a high-purity aluminum material for an electrolytic capacitor.
(Example 5)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane-based hydrocarbon for 2 seconds and dried at 90 ° C. for 1 minute in the air. Next, two hot rolls (hard chrome plated on the surface) set at a surface temperature of 200 ° C. are prepared, and the surface of the aluminum material is brought into contact with the first hot roll for 1 second, and then the second hot roll is formed. The contact heating was performed by bringing the aluminum material back surface into contact with the heat roll for 1 second. In a state where the aluminum materials after the contact heating are stacked, the actual temperature of the aluminum material is increased from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then maintained at 540 ° C. for 24 hours, and then cooled. The furnace was taken out to obtain a high-purity aluminum material for an electrolytic capacitor.
(Example 6)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane-based hydrocarbon for 2 seconds and dried at 90 ° C. for 1 minute in the air. Next, an aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 90 ° C., and contact heating was performed in air for 1 second. In a state where the aluminum materials after the contact heating were stacked, the actual temperature of the aluminum material was increased from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then maintained at 540 ° C. for 24 hours, and then cooled. Thereafter, the furnace was taken out of the furnace to obtain a high-purity aluminum material for an electrolytic capacitor.
(Example 7)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane-based hydrocarbon for 2 seconds and dried at 90 ° C. for 1 minute in the air. Next, two hot rolls (hard chrome plated on the surface) set at a surface temperature of 380 ° C. were prepared, and the surface of the aluminum material was brought into contact with the first hot roll for 0.1 second. Contact heating was performed by contact heating the back surface of the aluminum material to the second heat roll for 0.1 second. In a state where the aluminum materials after the contact heating were stacked, the actual temperature of the aluminum material was increased from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then maintained at 540 ° C. for 24 hours, and then cooled. Thereafter, the furnace was taken out of the furnace to obtain a high-purity aluminum material for an electrolytic capacitor.
(Example 8)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane-based hydrocarbon for 2 seconds and dried at 90 ° C. for 1 minute in the air. Next, two hot rolls (hard chrome plated on the surface) set at a surface temperature of 250 ° C. were prepared, and the surface of the aluminum material was brought into contact with the first hot roll for 0.005 seconds. Contact heating was performed by bringing the back surface of the aluminum material into contact with the second heat roll for 0.005 seconds. In a state where the aluminum materials after the contact heating were stacked, the actual temperature of the aluminum material was increased from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then maintained at 540 ° C. for 24 hours, and then cooled. Thereafter, the furnace was taken out of the furnace to obtain a high-purity aluminum material for an electrolytic capacitor.
(Example 9)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in air, and then sandwiched between two stainless steel heating plates having a surface temperature of 150 ° C. Contact heating was performed in air for 30 seconds. In a state where the aluminum materials after the contact heating were stacked, the actual temperature of the aluminum material was increased from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then maintained at 540 ° C. for 24 hours, and then cooled. Thereafter, the furnace was taken out of the furnace to obtain a high-purity aluminum material for an electrolytic capacitor.
(Example 10)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane-based hydrocarbon for 2 seconds, dried in air at 90 ° C. for 1 minute, and then sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C. Contact heating was performed in air for 2 seconds. In a state where the aluminum materials after the contact heating were stacked, the actual temperature of the aluminum material was raised from room temperature to 480 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then the temperature was maintained at 480 ° C. for 24 hours, and then cooled. Thereafter, the furnace was taken out of the furnace to obtain a high-purity aluminum material for an electrolytic capacitor.
(Example 11)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane-based hydrocarbon for 2 seconds, dried in air at 90 ° C. for 1 minute, and then sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C. Contact heating was performed in air for 2 seconds. In the state where the aluminum materials after the contact heating are stacked, the actual temperature of the aluminum material is increased from room temperature to 580 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then maintained at 580 ° C. for 24 hours, and then cooled. After that, it was taken out of the furnace to obtain a high-purity aluminum material for an electrolytic capacitor.
(Example 12)
After the contact heating, a high-purity aluminum material for an electrolytic capacitor was obtained in the same manner as in Example 1, except that a process of sandwiching and cooling the aluminum material between stainless steel plates having a surface temperature of 10 ° C. for 10 seconds was included.
(Comparative Example 1)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane-based hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in the air, and then, in an overlapped state, the actual temperature of the aluminum material was changed from room temperature to 540 ° C. under an argon atmosphere. After the temperature was raised at a rate of ° C./h, the temperature was maintained at 540 ° C. for 24 hours, then cooled and then taken out of the furnace to obtain a high-purity aluminum material for an electrolytic capacitor.
(Comparative Example 2)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane-based hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in the air, and then, in an overlapped state, the actual temperature of the aluminum material was changed from room temperature to 480 ° C. under an argon atmosphere. After the temperature was raised at a rate of ° C./h, the temperature was kept at 480 ° C. for 24 hours, and then cooled, and then the furnace was taken out to obtain a high-purity aluminum material for electrolytic capacitors.
(Comparative Example 3)
As in Example 1, an aluminum material having a purity of 99.99% and rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane-based hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in the air, and then, in an overlapping state, the actual temperature of the aluminum material was changed from room temperature to 580 ° C. in an argon atmosphere. After the temperature was raised at a rate of ° C./h, the temperature was maintained at 580 ° C. for 24 hours, then cooled and then taken out of the furnace to obtain a high-purity aluminum material for an electrolytic capacitor.
After immersing the aluminum materials obtained in the above Examples and Comparative Examples in an acid, electrolytic etching with an aqueous hydrochloric acid-sulfuric acid solution, and then further immersing in an acid solution to increase the pit diameter to obtain an etched foil. The obtained etched foil was subjected to a chemical conversion treatment at a chemical conversion voltage of 270 V in accordance with the EIAJ standard to obtain a capacitance measurement sample.
[0068]
Table 1 shows the contact heating conditions, the actual temperature of the aluminum material at the time of annealing, and the capacitance evaluation of the examples and the comparative examples. The capacitance evaluation shows a value when Comparative Example 1 is set to 100.
[0069]
[Table 1]
As can be seen from Table 1 above, in the examples, by performing contact heating using a heating plate or a heating roll before annealing, the improvement in capacitance was observed as compared with Comparative Examples 1 to 3 in which contact heating was not performed. Can be
[Examples 13 to 130 and Comparative Example 4]
A cleaning solution was prepared by adding a surfactant to an organic solvent shown in Tables 2 and 3 and water shown in Table 4.
[0071]
[Table 2]
[Table 3]
[Table 4]
(Example 13)
The aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was immersed in the solution A1 in Table 2 for 2 seconds, and then dried in air at 90 ° C. for 60 seconds. Next, the aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C., and contact heating was performed for 2 seconds.
[0075]
Next, the body temperature of the aluminum material is raised from room temperature to 540 ° C. at a rate of 50 ° C./h in an argon atmosphere with the aluminum materials after the contact heating being piled up, and then held at 540 ° C. for 24 hours, and then cooled. Then, it was taken out of the furnace to obtain an aluminum material for an electrolytic capacitor electrode.
(Examples 14 to 88)
After washing and drying the aluminum material having a purity of 99.99% rolled to the same thickness as in Example 13 and having a thickness of 110 μm under the conditions of the steps shown in Tables 5 to 8, the aluminum material was heated with stainless steel having a surface temperature of 200 ° C. Contact heating was performed for 2 seconds between two plates. In Examples 53 to 82, while the aluminum material was immersed in the cleaning liquid, the brush was brought into contact with the surface of the aluminum material and slid.
[0076]
The temperature of the aluminum material is raised from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere in a state where the aluminum materials after the contact heating are stacked, and then the temperature is maintained at 540 ° C. for 24 hours, and then cooled. The furnace was taken out to obtain an aluminum material for an electrolytic capacitor electrode.
(Examples 89 to 96)
An aluminum material having a purity of 99.99% and rolled to the same thickness as in Example 13 and having a thickness of 110 μm was sandwiched between two stainless steel heating plates at 200 ° C. and subjected to contact heating for 2 seconds.
[0077]
Next, it was washed and dried under the conditions of step 3 in Table 8. While the aluminum material was immersed in the cleaning liquid, the brush was slid in contact with the surface of the aluminum material.
[0078]
After the washed and dried aluminum materials are stacked, the actual temperature of the aluminum materials is increased from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then maintained at 540 ° C. for 24 hours, and then cooled. After the furnace was removed, an aluminum material for an electrolytic capacitor electrode was obtained.
(Examples 97 to 102)
After washing and drying the aluminum material having a purity of 99.99% rolled to the same thickness as in Example 13 and having a thickness of 110 μm under the conditions of Step 1 in Table 8, the aluminum material was heated with a stainless steel heating plate having a surface temperature of 200 ° C. Contact heating was performed for 2 seconds while sandwiching between two sheets. Next, the aluminum material after the contact heating was washed and dried under the conditions of step 3 in Table 8.
[0079]
In a state where the aluminum materials washed and dried under the condition of step 3 are stacked, the actual temperature of the aluminum material is increased from room temperature to 540 ° C. at 50 ° C./h under an argon atmosphere, and then maintained at 540 ° C. for 24 hours. Then, after cooling, the furnace was taken out to obtain an aluminum material for an electrolytic capacitor electrode.
(Examples 103 to 107)
After washing and drying the aluminum material having a purity of 99.99% rolled to the same thickness as in Example 13 and having a thickness of 110 μm under the conditions of the steps shown in Table 8, the aluminum material was heated to two stainless steel heating plates having a surface temperature of 200 ° C. , And contact heating was performed for 2 seconds.
[0080]
The temperature of the aluminum material is raised from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere in a state where the aluminum materials after the contact heating are stacked, and then the temperature is maintained at 540 ° C. for 24 hours, and then cooled. The furnace was taken out to obtain an aluminum material for an electrolytic capacitor electrode.
(Examples 108 to 111)
An aluminum material having a purity of 99.99% and rolled to the same thickness as in Example 13 and having a thickness of 110 μm was sandwiched between two stainless steel heating plates at 200 ° C. and subjected to contact heating for 2 seconds. Next, cleaning and drying were performed under the conditions of Step 3 in Tables 8 and 9. While the aluminum material was immersed in the cleaning liquid, the brush was slid in contact with the surface of the aluminum material.
[0081]
After the washed and dried aluminum materials are stacked, the actual temperature of the aluminum materials is increased from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then maintained at 540 ° C. for 24 hours, and then cooled. After the furnace was removed, an aluminum material for an electrolytic capacitor electrode was obtained.
(Examples 112 to 128)
The aluminum material having a purity of 99.99% rolled to the same thickness of 110 μm as in Example 13 was subjected to washing and drying under the conditions of step 1 in Table 9 and contact heating under the conditions of step 2 of Table 9. .
[0082]
The temperature of the aluminum material is raised from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere in a state where the aluminum materials after the contact heating are overlapped, and then held at 540 ° C. for 24 hours, and then cooled. The furnace was taken out to obtain an aluminum material for an electrolytic capacitor electrode.
(Example 129)
An aluminum material having a purity of 99.99% and rolled to the same thickness as in Example 13 and having a thickness of 110 μm was sandwiched between two stainless steel heating plates at 200 ° C., and contact heating was performed for 2 seconds. The temperature of the aluminum material is raised from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere in a state where the aluminum materials after the contact heating are overlapped, and then held at 540 ° C. for 24 hours, and then cooled. The furnace was taken out to obtain an aluminum material for an electrolytic capacitor electrode.
(Example 130)
An aluminum material for an electrode of an electrolytic capacitor was obtained in the same manner as in Example 124 except that a step of contacting the aluminum material with a cooling roll having a surface temperature of 25 ° C. after contact heating with a hot roll was included.
(Comparative Example 4)
An aluminum material having a purity of 99.99%, which was rolled to the same thickness as in Example 13 and having a thickness of 110 μm, was heated from room temperature to 540 ° C. at a rate of 50 ° C./h under an argon atmosphere, and then heated to 540 ° C. For 24 hours, and then cooled and then taken out of the furnace to obtain an aluminum material for an electrolytic capacitor electrode.
The aluminum materials obtained in Examples 13 to 130 and Comparative Example 4 were combined with 1.0 mol · dm of HCl. -3 And H 2 SO 4 3.5mol · dm -3 Immersed in an aqueous solution having a liquid temperature of 75 ° C. containing a current density of 0.2 A / cm 2 Was subjected to electrolytic treatment. The foil after the electrolytic treatment was further immersed in a hydrochloric acid-sulfuric acid mixed aqueous solution of the above composition at 90 ° C. for 360 seconds to increase the pit diameter to obtain an etched foil. The obtained etched foil was used as a sample for capacitance measurement which was subjected to a chemical conversion treatment at a formation voltage of 270 V according to the EIAJ standard. The capacitance measured for each sample is shown in Tables 5 to 9 as relative values when Comparative Example 4 is set to 100.
[0083]
[Table 5]
[Table 6]
[Table 7]
[Table 8]
[Table 9]
According to the comparison between Example 129 in Table 9 and Comparative Example 4, the capacitance is improved by performing the contact heating before performing the final annealing. Further, a comparison between Examples 13 to 111 and Example 129 reveals that the capacitance is further improved by performing the cleaning before and / or after the contact heating.
[0089]
Further, according to Examples 103 to 111, when the drying temperature after washing is 200 ° C. or less, the capacitance is improved, and when the drying temperature is 90 ° C. or less, the capacitance is even higher.
[0090]
【The invention's effect】
According to the present invention, an electrolytic capacitor having excellent etching characteristics, in which a lot of substances that can become etch pit nuclei are deposited on a foil surface by heating and annealing an aluminum material by contact with a heating body after cold rolling, as described above. For manufacturing aluminum materials. In particular, since contact heating is used as the heating method, the surface of the aluminum material can reach the target temperature uniformly and in a short time, so that the temperature control is relatively easy, and the heating can be performed quickly and in a short time. The effect can be reduced. Therefore, by etching the aluminum material for an electrolytic capacitor, etching is effectively performed at a position where a substance that can be a nucleus of the etch pit is present, and as a result, the area coverage can be improved, and the capacitance can be increased. The electrode material of the present invention can be obtained as a result, and as a result, an aluminum electrolytic capacitor having a large capacitance can be obtained.
[0091]
Further, by washing the aluminum material at least before or after contact with the heating element, an effect of further increasing the capacitance can be obtained.
Claims (22)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003111747A JP2004088069A (en) | 2002-07-05 | 2003-04-16 | Manufacturing method of aluminum material for electrolytic capacitor electrode, aluminum anode material for the same, and manufacturing method of electrode material for electrolytic capacitor |
| AT03719219T ATE497630T1 (en) | 2002-04-25 | 2003-04-25 | METHOD FOR PRODUCING ALUMINUM MATERIAL FOR AN ELECTRODE OF AN ELECTROLYTIC CAPACITOR, ALUMINUM MATERIAL FOR AN ELECTRODE OF AN ELECTROLYTIC CAPACITOR AND METHOD FOR PRODUCING ELECTRODE MATERIAL FOR AN ELECTROLYTIC CAPACITOR |
| DE60335943T DE60335943D1 (en) | 2002-04-25 | 2003-04-25 | METHOD FOR PRODUCING ALUMINUM MATERIAL FOR AN ELECTRODE OF AN ELECTROLYTIC CONDENSER, ALUMINUM MATERIAL FOR AN ELECTRODE OF AN ELECTROLYTIC CONDENSER AND METHOD FOR PRODUCING ELECTRODE MATERIAL FOR AN ELECTROLYTIC CONDENSER |
| EP03719219A EP1498513B9 (en) | 2002-04-25 | 2003-04-25 | Process for producing aluminum material for electrolytic capacitor electrode, aluminum material for electrolytic capacitor electrode and process for producing electrode material for electrolytic capacitor |
| AU2003235941A AU2003235941A1 (en) | 2002-04-25 | 2003-04-25 | Process for producing aluminum material for electrolytic capacitor electrode, aluminum material for electrolytic capacitor electrode and process for producing electrode material for electrolytic capacitor |
| CN03809123.2A CN1646731A (en) | 2002-04-25 | 2003-04-25 | Process for producing aluminum material for electrolytic capacitor electrode, aluminum material for electrolytic capacitor electrode and process for producing electrode material for electrolytic capac |
| PCT/JP2003/005384 WO2003091482A1 (en) | 2002-04-25 | 2003-04-25 | Process for producing aluminum material for electrolytic capacitor electrode, aluminum material for electrolytic capacitor electrode and process for producing electrode material for electrolytic capacitor |
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| JP2002196867 | 2002-07-05 | ||
| JP2003111747A JP2004088069A (en) | 2002-07-05 | 2003-04-16 | Manufacturing method of aluminum material for electrolytic capacitor electrode, aluminum anode material for the same, and manufacturing method of electrode material for electrolytic capacitor |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004006685A (en) * | 2002-04-25 | 2004-01-08 | Showa Denko Kk | Method of manufacturing aluminum material for electrode of electrolytic capacitor, method of manufacturing electrode material for electrolytic capacitor, and aluminum electrolytic capacitor |
| JP2006210894A (en) * | 2004-12-27 | 2006-08-10 | Showa Denko Kk | Manufacturing method, aluminum material for electrolytic capacitor electrode, anode material for aluminum electrolytic capacitor, and the aluminum electrolytic capacitor of aluminum material for electrolytic capacitor electrode |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004006685A (en) * | 2002-04-25 | 2004-01-08 | Showa Denko Kk | Method of manufacturing aluminum material for electrode of electrolytic capacitor, method of manufacturing electrode material for electrolytic capacitor, and aluminum electrolytic capacitor |
| JP4498682B2 (en) * | 2002-04-25 | 2010-07-07 | 昭和電工株式会社 | The manufacturing method of the aluminum material for electrolytic capacitor electrodes, the manufacturing method of the electrode material for electrolytic capacitors, and an aluminum electrolytic capacitor. |
| JP2006210894A (en) * | 2004-12-27 | 2006-08-10 | Showa Denko Kk | Manufacturing method, aluminum material for electrolytic capacitor electrode, anode material for aluminum electrolytic capacitor, and the aluminum electrolytic capacitor of aluminum material for electrolytic capacitor electrode |
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