JP3810743B2 - Post-treated plated steel sheet - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は半田めっき鋼板に係わり、特に半田の濡れ性、経時性、切断端面の耐食性を向上させるめっきおよび後処理を施した後処理めっき鋼板に関する。
【０００２】
【従来の技術】
一般に半田付けの可能な錫めっき鋼板、鉛−錫めっき鋼板、銅めっき鋼板、亜鉛めっき鋼板などのめっき鋼板は、使用される環境にさらされた際にめっきの外観が変化し、赤錆が発生することがある。さらに、めっき鋼板は所定の形状に切断して使用されるため、切断端面は鋼素地が露出し、切断端面から赤錆が発生し、表面に伝播することが多い。そのため、これらのめっき鋼板においては経時した際の酸化膜の成長による半田性の低下や赤錆の発生を抑制する後処理方法が求められている。また、最近の電子部品の分野においては、基板となるめっき鋼板などの耐食性の劣化を防止するため、塩素を含有する腐食性の強い活性なフラックスの使用が拒否される傾向にあり、塩素を含有しないフラックスを用いた場合においても半田の濡れ性に優れる材料が求められている。塩素を含まない弱活性または非活性のフラックスを使用した場合は、半田はめっき鋼板に付着するものの、めっき鋼板上を均一に濡らすまでに長時間を要し、半田の濡れ性に劣り、その傾向はめっき鋼板の経時の増大にともなって顕著となる。
【０００３】
従来の公知技術として、鋼板上に錫めっきを施し、次いで錫めっき上に亜鉛めっきを施し、選択的にさらに亜鉛めっき上にクロメート処理を施したものである（例えば特許文献１参照。）。このめっき鋼板は、クロメート処理を施さない場合は長期間経時させた場合に耐食性が十分ではなく、腐食生成物の皮膜が生成することにより、半田濡れ性も劣化するおそれがある。また、クロメート処理を施すと高耐食性を付与することができるが、処理皮膜が安定であり、用途によっては十分な半田濡れ性が得られないこともある。
【０００４】
また、鋼板上に錫めっきを施し、次いで錫めっき上に亜鉛、ニッケル、コバルトのいずれか１種以上を主成分とするめっき、または亜鉛、ニッケル、コバルトのいずれか１種以上に錫、鉄、鉛、銅のいずれか１種以上を含有してなる、錫の標準電極電位より卑な電位を示す合金めっきを施した、半田用二層めっき鋼板を開示している（例えば特許文献２参照。）。このめっき鋼板はクロメート処理皮膜のような耐食性に優れた保護皮膜層を有していないため、耐食性が十分ではなく、腐食生成物の皮膜が生成することにより、半田濡れ性も劣化するおそれがある。
【０００５】
さらに、片面が耐錆性と耐ホイスカー性に優れ、他面が耐錆性と溶接性に優れた電子機器部品用表面処理鋼板を開示している（例えば特許文献３参照。）。この表面処理鋼板は、片面にＮｉめっき、またはＮｉめっきとその上にＳｎめっき、またはＮｉめっきとＺｎめっきを施し、他面にＮｉめっき、その上にＳｎ、その上にＺｎめっきを施し、加熱処理を施して片面上に、Ｎｉ−Ｆｅ合金、またはＮｉ−Ｆｅ合金とＮｉ−Ｓｎ合金、またはＮｉ−Ｆｅ合金とＮｉ−Ｚｎ合金を形成させ、他面にＳｎ−Ｚｎ合金、Ｚｎ−Ｎｉ合金、Ｓｎ−Ｎｉ合金、Ｆｅ−Ｎｉ合金を形成させ、さらに両面にクロメート皮膜を形成して構成される。この表面処理鋼板は目的とする片面における耐錆性と耐ホイスカー性、他面における耐錆性と溶接性には優れているものの、両面のめっき層上に安定なクロメート皮膜を形成させているため、用途によっては必要とされる十分な半田濡れ性が得られない場合がある。
【０００６】
また、Ｚｎめっき鋼板またはＺｎ合金めっき鋼板上にアクリル樹脂、ポリエステル樹脂又はウレタン樹脂からなる水分散性または水溶性有機樹脂とＣｒ６＋イオンと、ロジンアミン塩とを含む水溶液を用いて表面塗膜を形成した半田用のめっき鋼板が提案されている（例えば特許文献４参照。）が、めっき層に半田の成分であるＳｎが含まれていないために、用途によっては必要とされる十分な半田濡れ性が得られない場合がある。
【０００７】
さらに、ハンダ性に優れたＳｎ−Ｚｎ合金めっき皮膜を有する基体を、Ｔｉ、Ｖ、Ｍｎ、Ｚｒ、Ｍｏ、Ｗ及びＳｉの群から選択される少なくとも１種の金属の塩または酸素酸塩及び無機酸イオンを含有する水溶液に接触させることを特徴とする、Ｓｎ−Ｚｎ合金めっき皮膜上にクロムフリー皮膜を形成させ方法、およびこのクロムフリー皮膜上に耐食性を向上させるためのオーバーコート処理を施す方法が提案されている（例えば特許文献５参照。）。このクロムフリー皮膜やクロムフリー皮膜上に形成させたオーバーコートはＳｎ−Ｚｎ合金に対して高耐食性を付与することはできるが、その安定さ故に、特に塩素を含まない弱活性または非活性のフラックスを使用した場合の半田性に乏しい欠点を有している。
さらに、鋼板上にＳｎ−Ｚｎ合金層、または表面にＮｉめっきまたはＦｅ−Ｎｉ拡散層のいずれかからなる表面処理層を形成させた表面処理鋼板上にＳｎ−Ｚｎ合金層を形成させ、これらのＳｎ−Ｚｎ合金層上にリン酸マグネシウムを主体とする無機皮膜を形成させてなる環境対応型電子部品用表面処理鋼板が提案されている（例えば特許文献６参照。）。このリン酸マグネシウムを主体とする無機皮膜もＳｎ−Ｚｎ合金に対して高耐食性を付与することはできるが、その安定さ故に、特に塩素を含まない弱活性または非活性のフラックスを使用した場合の半田性に乏しい欠点を有している。
【０００８】
【特許文献１】
特公昭５３−４７２１６号公報
【特許文献２】
特開昭６３−２７７７８６号公報
【特許文献３】
特開平３−２９１３８６号公報
【特許文献４】
特開平９−２３４４２１号公報
【特許文献５】
特開２００２−０５３９７５号公報
【特許文献６】
特開２００２−２４９８８５号公報
【０００９】
【発明が解決しようとする課題】
本発明は、めっき鋼板を半田付けする際に、塩素を含有しないフラックスを使用した場合においても、半田の濡れ性に優れ、特に経時しても半田の濡れ性が劣化せず、しかも切断端面に赤錆が発生しにくい、耐食性に優れためっきおよび後処理皮膜を形成させた後処理めっき鋼板を提供するものである。
【００１０】
【課題を解決するための手段】
上記課題を解決する本発明の後処理めつき鋼板は、鋼板上に錫めっき量が３〜２０ｇ／ｍ ２ である錫めっきを施し、その上層に亜鉛めっき量が０．０１〜７ｇ／ｍ ２ である亜鉛めっきを施し、さらにその上層に、水系アクリル樹脂を１００〜８００ｇ／Ｌ、アミン塩を含んだ化合物、あるいはスチレン・無水マレイン酸共重合体のどちらか一方もしくは両方からなる防錆剤を１０〜１００ｇ／Ｌ、水溶化ロジンを５０〜６００ｇ／Ｌ、表面にアルミニウムをコーティングした粒径１００ｎｍ以下の水分散性シリカを１０〜２００ｇ／Ｌ、フェノール系および／またはトリス（２，４−ジ−tert−ブチルフェニル）フォスファイトあるいはテトラキス（２，４−ジ−tert−ブチルフェニル）［１，１−ビフェニル］−４，４’−ジイルビスフォスフォナイトからなる酸化防止剤を１〜１００ｇ／Ｌ含有してなるめっき鋼板用後処理液を、乾燥厚みが０．０５〜１０μｍとなるように塗布乾燥してなる後処理めっき鋼板であり、または
鋼板上に錫めっき量が３〜２０ｇ／ｍ ２ である錫めっきを施し、その上層に亜鉛めっき量が０．０１〜７ｇ／ｍ ２ である亜鉛めっきを施し、さらにその上層に、水系ウレタン樹脂を１００〜９００ｇ／Ｌ、アミン塩を含んだ化合物、あるいはスチレン・無水マレイン酸共重合体のどちらか一方もしくは両方からなる防錆剤を１０〜１００ｇ／Ｌ、表面にアルミニウムをコーティングした粒径１００ｎｍ以下の水分散性シリカを１０〜４００ｇ／Ｌ、フェノール系および／またはトリス（２，４−ジ−tert−ブチルフェニル）フォスファイトあるいはテトラキス（２，４−ジ−tert−ブチルフェニル）［１，１−ビフェニル］−４，４’−ジイルビスフォスフォナイトからなる酸化防止剤を０．５〜１００ｇ／Ｌ含有してなるめっき鋼板用後処理液を、乾燥厚みが０．０５〜１０μｍとなるように塗布乾燥してなる後処理めっき鋼板である。
これらのいずれかの後処理めっき鋼板において、鋼板上に錫めっきを施し、その上層に亜鉛めっきを施した後、めっき鋼板に錫の溶融温度以上の加熱処理を施してなること、または、
鋼板上に錫めっきを施し、次いでめっき鋼板に錫の溶融温度以上の加熱処理を施した後、その上層に亜鉛めっきを施してなることが好ましい。
【００１１】
【発明の実施の形態】
本発明に係るめっき鋼板は、鋼板上に錫めっきとその上に亜鉛めっきを施し、選択的にめっき鋼板を錫の溶融温度以上に加熱した後、水系アクリル樹脂を１００〜８００ｇ／Ｌ、防錆剤を１０〜１００ｇ／Ｌ、水溶化ロジンを５０〜６００ｇ／Ｌ、水分散性シリカを１０〜２００ｇ／Ｌ、酸化防止剤を０．５〜１００ｇ／Ｌ含有する水系アクリル樹脂を主成分とする後処理液、または水系ウレタン樹脂を１００〜９００ｇ／Ｌ、防錆剤を１０〜１００ｇ／Ｌ、水分散性シリカを１０〜４００ｇ／Ｌ、酸化防止剤を０．５〜１００ｇ／Ｌを含有する水系ウレタン樹脂を主成分とするめっき鋼板用後処理液のいずれかを、乾燥厚みが０．０５〜１０μｍになるように塗布し乾燥処理することによって、後処理めっき鋼板とするものである。この後処理めっき鋼板は、無塩素系フラックスを使用しても半田性に優れ、経時しても、あるいは加熱しても半田の濡れ性が劣化せず、また耐食性、耐酸化性にも優れ、さらに切断端面の赤錆の発生の抑制効果も優れる。
【００１２】
以下、本発明を詳細に説明する。
本発明の後処理めっき鋼板は、鋼板上に錫めっきを施し、その上に亜鉛めっきを施し、選択的にめっき鋼板を錫の溶融温度以上に加熱しためっき鋼板に、半田性を向上させる後処理皮膜を形成させたものである。鋼板上に直接形成させる錫めっき層は、公知の電気めっき法を用いて３〜２０ｇ／ｍ２のめっき量で形成させることが好ましい。３ｇ／ｍ２未満の場合は、錫めっきを施し、その上に亜鉛めっきを施し、次いで錫の溶融温度以上に加熱した場合、錫が鋼板や亜鉛めっき層に熱拡散し、全ての錫が鉄−錫合金、亜鉛−錫合金、または鉄−錫−亜鉛合金のいずれかの形成に消費されて殆どのフリー錫が失われ、半田性が劣化してしまう。錫めっき量の増加にともなって耐食性が向上するが、２０ｇ／ｍ２を超えてめっきしても耐食性の向上効果は飽和し、経済的ではなくなる。
【００１３】
鋼板上に上記のようにして錫めっき層を形成させた後、その上に亜鉛めっき層を形成させる。亜鉛めっき層も公知の電気めっき法を用いて形成させるが、めっき量は用途によって変動させる。良好な半田性が特に求められる用途では、０．０１〜０．０５ｇ／ｍ２のめっき量が好ましい。０．０１ｇ／ｍ２未満である場合は、長期間計時した場合に錫のホイスカーが発生し、電子部品回路などに適用された場合、ホイスカーが他のリード線などの導電部材と接触して短絡事故を引き起こす恐れがある。一方、０．０５ｇ／ｍ２を超えると、特に良好な半田性を必要とする用途において、十分な半田性が得られない。
【００１４】
良好な半田性を必要とし、なおかつめっき鋼板の切断端面の赤錆の発生が嫌われる用途においては、亜鉛めっき量は０．０５ｇ／ｍ２を超え、０．７ｇ／ｍ２以下であることが好ましい。０．０５ｇ／ｍ２以下では赤錆の発生の抑制効果に乏しく、０．７ｇ／ｍ２を超えると良好な半田性の発現にやや乏しくなる。上記の用途以外で、適度の半田性と良好な耐赤錆性が求められる用途では、０．７ｇ／ｍ２を超え、７ｇ／ｍ２以下であることが好ましい。７ｇ／ｍ２を超えると良好な半田性が得られにくくなる。
【００１５】
上記のようにして鋼板上に錫めっき層とさらにその上に亜鉛めっき層を形成させためっき鋼板は、そのまま以下に示す後処理皮膜を形成させて本発明の後処理めっき鋼板としてもよいが、めっき鋼板を錫の溶融温度以上に加熱し、鋼板と錫めっき層の界面、および錫めっき層と亜鉛めっき層の界面に鉄−錫合金、亜鉛−錫合金、または鉄−錫−亜鉛合金を形成させてもよい。これらの合金層を形成させることにより、鋼板と錫めっき層、および錫めっき層と亜鉛めっき層との密着性が向上する。また、亜鉛めっき層が薄い場合は、めっき鋼板の最表面において亜鉛に錫が合金化され、半田性が向上する。また錫が合金化することにより、耐ホイスカー性も向上する。
【００１６】
上記のようにして得られるめっき鋼板に、以下のようにして半田性を向上させるための後処理皮膜を形成させる。本発明の半田性を向上させる後処理皮膜としては、水系アクリル樹脂を主成分とする後処理液（以下、Ａ液という）を用いたものと、水系ウレタン樹脂を主成分とする後処理液（以下、Ｂ液という）を用いたものとがある。まずＡ液による後処理皮膜について説明する。
Ａ液において、水系アクリル樹脂は、カルボン酸を有するアクリル系モノマーの重合体または共重合体であり、特に水溶液重合、エマルジョン重合などの重合法を限定するものではない。しかし、水系アクリル樹脂の酸価（樹脂１ｇ中に含まれる遊離脂肪酸を中和するのに要する水酸化カリウムのミリグラム数）は、１５０以下であることが好ましい。濃度として、１００〜８００ｇ／Ｌの範囲が好ましい。１００ｇ／Ｌ未満では半田性向上の効果がなく、耐食性も低下する。一方，８００ｇ／Ｌを越えると半田性向上の効果が飽和し、水溶化ロジンと混ぜ合わせた場合に粘度が高くなり、ゲル化する恐れがあり、好ましくない。
【００１７】
Ａ液において、添加する水溶性ロジンは５０〜６００ｇ／Ｌの範囲で添加する必要がある。水溶化ロジンは、ロジンの主成分であるアビエチン酸分子内のカルボン酸基をアミン塩などにより中和し、ロジン石鹸とする方法により得られる。５０ｇ／Ｌ未満では経時後の半田濡れ性が不十分であり、６００ｇ／Ｌを越えると高粘度となり、ゲル化しやすく、塗布が困難になるので、好ましくない。
【００１８】
Ａ液において、添加する防錆剤は、クロムを含まないものを添加するのが良い。クロムを含まない以外は特に限定されないが、アミンを含んだ化合物、あるいはスチレン・無水マレイン酸共重合体のどちらか一方もしくは両方を含んだものを適用できる。アミンを含んだ化合物としては、具体的には、有機アミン石けんの単独あるいは混合したものを使用する。有機アミン石けんにはドテシルアミン、オレオイルイミダゾリン、アミノプロピル牛脂アミン、ロジンアミンが含まれ、アミンはカルボン酸などと造塩して使用することが出来る。スチレン・無水マレイン酸共重合体としては、スチレン・無水マレイン酸共重合アルキルエステル・アンモニウム塩が好ましい。添加量としては１０〜１００ｇ／Ｌであることが好ましい。１０ｇ／Ｌ未満では、耐食性向上に効果が認められず、１００ｇ／Ｌを越えると耐食性向上効果は極めて良好であるが、液の粘度が上昇して塗布が困難になるので好ましくない。
【００１９】
Ａ液において、添加する水分散性シリカは、耐食性、めっき鋼板の皮膜硬度を向上させ耐疵付き性を向上させるものであり、１０〜２００ｇ／Ｌの範囲で添加することが好ましい。１０ｇ／Ｌ未満では耐食性を向上させることができない。２００ｇ／Ｌを超えると半田濡れ性が著しく低下する。半田濡れ性を重要視する場合には、めっき鋼板に付着した量を１０〜１００ｍｇ／ｍ２の範囲とすることが好ましい。より半田濡れ性を重要視する場合には、１０〜５０ｍｇ／ｍ２の範囲とする。水分散性シリカとしては特に限定するものではないが、シリカ表面にアルミニウムをコーティングしたものは分散作用が優れており、特に好適に適用できる。シリカの粒径としては小さいものが好ましく、１００ｎｍ以下であることが好ましく、６０ｎｍ以下のものは特に分散作用が優れている。 シリカは一般的には濡れ性を阻害するが、１００ｎｍ以下の超微粒子にすることによって、半田濡れ性を阻害することなく、耐食性、めっき鋼板皮膜硬度を向上させ耐疵付き性を向上させることができる。
【００２０】
本発明のＡ液および後記するＢ液に添加する酸化防止剤は、半田濡れ性の経時による低下の主原因と考えられていためっき鋼板のめっき層表面の酸化防止のためではなく、めっき層の酸化を抑制するためにめっき層上に施す上記の樹脂層の酸化を抑制するために添加される。この用途に適用する酸化防止剤としては、硫黄系酸化防止剤などもあるが、フェノール系酸化防止剤またはリン系酸化防止剤が好ましく、両者を併用してもよい。添加量としては０．５〜１００ｇ／Ｌであることが好ましい。０．５ｇ／Ｌ未満では、耐酸化性向上に効果が認められず、１００ｇ／Ｌを越えると液の粘度が上昇して塗布が困難になるので好ましくない。
【００２１】
次に、Ｂ液による後処理皮膜について説明する。Ｂ液において、水系ウレタン樹脂は特に限定されるものではないが、高強度を有する方が耐食性に効果がある。濃度として、１００〜９００ｇ／Ｌの範囲が好ましい。１００ｇ／Ｌ未満では耐食性が不十分であり、９００ｇ／Ｌを越えると半田濡れ性が悪くなる。また、防錆剤は、Ａ液の場合と同様に、クロムを含まない以外は特に限定されないが、アミンを含んだ化合物も適用できる。具体的には、有機アミン石けんの単独あるいは混合したものを使用する。有機アミン石けんにはドテシルアミン、オレオイルイミダゾリン、アミノプロピル牛脂アミン、ロジンアミンが含まれ、アミンはカルボン酸などと造塩して使用することが出来る。スチレン・無水マレイン酸共重合体としては、スチレン・無水マレイン酸共重合アルキルエステル・アンモニウム塩が好ましい。添加量は１０〜１００ｇ／Ｌであることが好ましく、１０ｇ／Ｌ未満では、耐食性向上に効果が認められず、１００ｇ／Ｌを越えると耐食性向上効果は極めて良好であるが、半田性が低下するので好ましくない。
【００２２】
Ｂ液においては、水分散性シリカは、Ａ液と同様の目的で添加されるが、１０〜２００ｇ／Ｌの範囲で添加することが好ましい。１０ｇ／Ｌ未満では耐食性を向上させることができない。４００ｇ／Ｌを超えると半田濡れ性が著しく低下する。半田濡れ性を重要視する場合には、めっき鋼板に付着した量を１０〜１５０ｍｇ／ｍ２の範囲とすることが好ましい。より半田濡れ性を重要視する場合には、１０〜８０ｍｇ／ｍ２の範囲とする。水分散性シリカとしてはＡ液において用いたものと同様のものを用いることが好ましい。
【００２３】
また、酸化防止剤についても、Ａ液の場合と同様に、フェノール系酸化防止剤またはリン系酸化防止剤が好ましく、両者を併用してもよい。添加量についてもＡ液の場合と同様の理由から、０．５〜１００ｇ／Ｌであることが好ましい。
【００２４】
上記Ａ液およびＢ液のｐＨは３〜１０の範囲が適当である。ｐＨが３未満の場合は処理液の安定性が不良であり、１０を越えても好ましくない。より長期間処理液が安定して使用するには、ｐＨ６〜９の範囲が好ましい。
【００２５】
上記のＡ液またはＢ液を、前記のめっき鋼板の片面あるいは両面に塗布する。この場合、表裏面で塗布膜厚を変えても良い。塗布する方法としては、浸漬法、ロールコート法、カーテンフローコート法、スプレーコート法など、公知の方法で良く、特に限定されるものではない。しかし、両面塗布を行う場合、本処理液が水系であることを活かして、連続めっきラインの後工程において、浸漬・絞りによる塗布を行う方法が容易で経済的である。
【００２６】
Ａ液またはＢ液は、乾燥後の膜厚が０．０５〜１０μｍとなるように塗布する。Ａ液またはＢ液を塗布しためっき鋼板は、後処理皮膜を成膜させるために乾燥する。皮膜の厚みが０．０５μｍ未満では、十分な半田性、耐指紋性が得られないばかりでなく、耐食性が著しく劣る。１０μｍを越えると特性向上の効果が飽和し、コストメリットがなくなる。
【００２７】
【実施例】
以下、実施例および比較例にて本発明を具体的に説明する。
１．実施例１（試料番号１〜１０）
焼鈍および調質圧延を施した鋼板（板厚０．５ｍｍ）をめっき原板として、アルカリ脱脂、および硫酸酸洗による清浄化処理を行った後、電気めっき法を用いて錫めっき層とその上に亜鉛めっき層を表１に示すめっき量で形成させた。一部の試料については、錫めっき層を形成させた後に錫の溶融温度以上に加熱し急冷した後、亜鉛めっき層を形成させた。また他の一部の試料については、錫めっき層を形成させ、次いで亜鉛めっき層を形成させた後、錫の溶融温度以上に加熱した後、急冷し、めっき番号Ａ〜Ｊのめっき鋼板を作製した。これらのめっき鋼板の両面に、浸漬・絞り法、スプレーコート法あるいはロールコート法により表２に示す試料作成条件でめっき鋼板用後処理液を塗布した後、９０℃の温度で乾燥し、試料番号１〜１３の試料を作製した。このようにして得られた試料番号１〜１３の試料について、下記の特性評価を行い、表４にその評価結果を示した。
【００２８】
２.実施例２（試料番号１４〜２３）
実施例１の場合と同様にして得られた表１に示すめっき番号Ａ〜Ｊで示すめっき鋼板の両面に、浸漬・絞り法、スプレーコート法あるいはロールコート法により表３に示す試料作成条件でめっき鋼板用後処理液を塗布した後、９０℃の温度で乾燥し、試料番号１４〜２３の試料を作製した。このようにして得られた試料番号１４〜２３の試料について、下記の特性評価を行い、表４にその評価結果を示した。
【００２９】
[特性評価]
１）半田濡れ性：
すなわち、メニスコグラフ法（ＭＩＬ−ＳＴＤ−８８３Ｂ）により、ＳＯＬＤＥＲＣＨＥＣＫＥＲ（ＭＯＤＥＬ ＳＡＴ−５０００、ＲＨＥＳＣＡ製）を使用し、上記の供試材から切り出した幅１０ｍｍのサンプルを、実施例１の場合は塩素を含まない非活性フラックス（ＮＡ−２００、タムラ化研製）に浸漬し、実施例２の場合は塩素を含まない弱活性フラックス（ラピックスＲＭＡ、日本半田工業製）に浸漬し、その後２５０℃に保持した半田浴（ＪＩＳ Ｚ ３２８２：Ｈ６０Ａ）に前記のフラックスを塗布したサンプルを浸漬速度２ｍｍ／秒で、２ｍｍ浸漬させ、半田が濡れるまでの時間ゼロクロスタイムを測定し、下記に示す基準で半田濡れ性を評価した。濡れ時間は短い程半田付け性に優れることを示す。なお、試験は試料作製直後と恒温恒湿（６０℃、９５％ＲＨ）で５００時間経時後の二通りで行った。×以外を合格範囲とした。
◎：３秒未満、○：３〜５秒未満、△：５〜１０秒未満、×：１０秒以上
【００３０】
２）耐食性（耐端面赤錆性）：
実施例１および実施例２の試料から４０ｍｍ×８０ｍｍの大きさの供試材を切り出し、ＪＩＳ Ｚ ２３７１に準じて塩水噴霧試験を４８時間行い、赤錆の発生程度を肉眼観察し、下記に示す基準で耐食性を評価した。×以外を合格範囲とした。
◎：赤錆の発生なし、○：端面の５０％未満の部分で赤錆の発生が認められる、△：端面の５０〜８０％の部分で赤錆発生、×：端面の８０％を超える部分で赤錆発生
【００３１】
３）耐ホイスカー性：
実施例１および実施例２の試料から３０ｍｍ×３０ｍｍの大きさの供試材を切り出し、温度：８５℃、湿度：８５％ＲＨの高温高湿の雰囲気中で３０日間暴露した後のホイスカーの発生状況を走査電子顕微鏡を用い、１５００倍の倍率で観察し、下記の基準で耐ホイスカー性を評価した。
◎：ホイスカーの発生は認められない。
○：１０μｍ未満の長さのホイスカーがわずかに発生しているのが認められる。
△：１０〜３０μｍの長さのホイスカーが発生しているのが認められる。
×：３０μｍを超える長さのホイスカーが発生しているのが認められる。
◎および○を合格範囲とした。
【００３２】
その結果、表４に示すように、本発明の実施例１及び実施例２の後処理めっき鋼板は、何れも半田濡れ性、特に経時後の半田濡れ性、および耐食性の項目において良好な性状を示した。
【００３３】
【表１】
【表２】
【表３】
【表４】
【発明の効果】
以上のように、本発明によれば、めっき鋼板を半田付けする際に、塩素を含有しない非活性フラックスを使用した場合においても、半田の濡れ性に優れ、特に半田の濡れ性が経時しても劣化しない耐酸化性に優れ、しかも切断端面の赤錆発生抑制効果に優れた耐食性を有し、且つ耐疵付き性に優れた皮膜が得られるめっき及び後処理皮膜を形成させた後処理めっき鋼板を得ることが可能となった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a solder-plated steel sheet, and more particularly to a post-processed plated steel sheet that has been subjected to plating and post-treatment to improve solder wettability, aging, and corrosion resistance of a cut end surface.
[0002]
[Prior art]
In general, plated steel sheets such as tin-plated steel sheets, lead-tin-plated steel sheets, copper-plated steel sheets, and galvanized steel sheets that can be soldered change the appearance of plating when exposed to the environment in which they are used, resulting in red rust. Sometimes. Furthermore, since the plated steel sheet is used after being cut into a predetermined shape, the steel base is exposed at the cut end face, and red rust is often generated from the cut end face and propagates to the surface. Therefore, in these plated steel sheets, there is a need for a post-treatment method that suppresses the deterioration of solderability and red rust due to the growth of an oxide film over time. Also, in the recent electronic component field, in order to prevent the deterioration of corrosion resistance of plated steel sheets used as substrates, the use of highly corrosive active flux containing chlorine tends to be rejected and contains chlorine. There is a demand for a material having excellent solder wettability even when a non-flux is used. When weakly active or inactive flux that does not contain chlorine is used, the solder adheres to the plated steel sheet, but it takes a long time to evenly wet the plated steel sheet, resulting in poor solder wettability. Becomes prominent with the aging of the plated steel sheet.
[0003]
As a conventional publicly known technique, tin plating is performed on a steel plate, then zinc plating is performed on the tin plating, and further, chromate treatment is further performed on the zinc plating (see, for example, Patent Document 1). When the chromate treatment is not performed, the plated steel sheet does not have sufficient corrosion resistance when aged for a long period of time, and a corrosion product film may be formed, which may deteriorate solder wettability. Further, when chromate treatment is performed, high corrosion resistance can be imparted, but the treated film is stable, and depending on the application, sufficient solder wettability may not be obtained.
[0004]
In addition, tin plating is performed on the steel plate, and then the plating mainly containing any one or more of zinc, nickel, and cobalt on the tin plating, or tin, iron, and any one or more of zinc, nickel, and cobalt, A two-layer plated steel sheet for solder is disclosed, which contains at least one of lead and copper and is plated with an alloy having a lower potential than the standard electrode potential of tin (see, for example, Patent Document 2). ). Since this plated steel sheet does not have a protective coating layer with excellent corrosion resistance like the chromate-treated coating, the corrosion resistance is not sufficient, and the formation of a corrosion product coating may also deteriorate solder wettability. .
[0005]
Furthermore, the surface-treated steel sheet for electronic device components which one side was excellent in rust resistance and whisker resistance, and the other side was excellent in rust resistance and weldability is disclosed (for example, refer patent document 3). This surface-treated steel sheet is Ni-plated on one side, or Ni-plated and Sn-plated on it, or Ni-plated and Zn-plated, Ni-plated on the other side, Sn on it, Zn-plated on it, and heated A Ni—Fe alloy, or a Ni—Fe alloy and a Ni—Sn alloy, or a Ni—Fe alloy and a Ni—Zn alloy are formed on one surface, and a Sn—Zn alloy and a Zn—Ni alloy are formed on the other surface. Sn-Ni alloy and Fe-Ni alloy are formed, and a chromate film is formed on both sides. This surface-treated steel sheet is excellent in rust resistance and whisker resistance on one side, and on the other side, but has a stable chromate film on the plating layers on both sides. Depending on the application, the required solder wettability may not be obtained.
[0006]
Also, a surface coating film is formed on a Zn-plated steel sheet or Zn alloy-plated steel sheet using an aqueous solution containing a water-dispersible or water-soluble organic resin made of acrylic resin, polyester resin, or urethane resin, Cr 6+ ions, and a rosinamine salt. Although a plated steel sheet for soldering has been proposed (see, for example, Patent Document 4), since the plating layer does not contain Sn, which is a component of solder, sufficient solder wettability required for some applications May not be obtained.
[0007]
Furthermore, a substrate having a Sn—Zn alloy plating film excellent in solderability is formed by using at least one metal salt or oxyacid salt selected from the group consisting of Ti, V, Mn, Zr, Mo, W, and Si, and an inorganic salt. A method of forming a chromium-free film on a Sn—Zn alloy plating film, and a method of applying an overcoat treatment for improving corrosion resistance, characterized by contacting with an aqueous solution containing acid ions Has been proposed (see, for example, Patent Document 5). Although this chromium-free film or an overcoat formed on the chromium-free film can impart high corrosion resistance to the Sn—Zn alloy, it is a weakly active or inactive flux that does not contain chlorine, because of its stability. Has the disadvantage of poor solderability.
Furthermore, an Sn—Zn alloy layer is formed on a surface-treated steel sheet in which a Sn—Zn alloy layer is formed on the steel plate, or a surface treatment layer made of either Ni plating or Fe—Ni diffusion layer is formed on the surface. A surface-treated steel sheet for an environmentally friendly electronic component in which an inorganic film mainly composed of magnesium phosphate is formed on a Sn—Zn alloy layer has been proposed (see, for example, Patent Document 6). This inorganic film mainly composed of magnesium phosphate can also give high corrosion resistance to the Sn—Zn alloy, but due to its stability, particularly when a weakly active or inactive flux containing no chlorine is used. It has the disadvantage of poor solderability.
[0008]
[Patent Document 1]
Japanese Patent Publication No. 53-47216 [Patent Document 2]
Japanese Patent Laid-Open No. 63-277786 [Patent Document 3]
JP-A-3-291386 [Patent Document 4]
JP-A-9-234421 [Patent Document 5]
Japanese Patent Laid-Open No. 2002-053975 [Patent Document 6]
Japanese Patent Laid-Open No. 2002-249885
[Problems to be solved by the invention]
The present invention is excellent in solder wettability even when using a flux containing no chlorine when soldering a plated steel sheet, and the solder wettability is not deteriorated even with lapse of time. It is an object of the present invention to provide a post-treated plated steel sheet in which red rust is hardly generated and plating and post-treatment film having excellent corrosion resistance are formed.
[0010]
[Means for Solving the Problems]
To solve the above problems aftertreatment plated steel sheet of the present invention, tin plating amount subjected to tin plating is 3 to 20 g / m 2 on the steel sheet, galvanized amount thereon is 0.01~7g / m 2 A rust preventive agent comprising either one or both of a water-based acrylic resin 100 to 800 g / L, a compound containing an amine salt, and a styrene / maleic anhydride copolymer is further applied to the upper layer. 10 to 100 g / L, 50 to 600 g / L of water-soluble rosin, 10 to 200 g / L of water-dispersible silica having a particle size of 100 nm or less coated with aluminum on the surface, phenolic and / or tris (2,4-di- -Tert-butylphenyl) phosphite or tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphos It is a post-processed plated steel sheet obtained by applying and drying a post-treatment liquid for a plated steel sheet containing 1 to 100 g / L of an antioxidant composed of lonite so that the dry thickness is 0.05 to 10 μm, or A tin plating amount of 3 to 20 g / m 2 is applied to the top, a zinc plating amount of 0.01 to 7 g / m 2 is applied to the upper layer, and an aqueous urethane resin is applied to the upper layer. 100 to 900 g / L, 10 to 100 g / L of a rust inhibitor composed of either or both of a compound containing an amine salt and a styrene / maleic anhydride copolymer, and a particle size of 100 nm or less with aluminum coated on the surface 10 to 400 g / L of a water dispersible silica, phenolic and / or tris (2,4-di-tert-butylphenyl) phosphite or tetrakis Plated steel sheet containing 0.5 to 100 g / L of an antioxidant comprising bis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite This is a post-treated plated steel sheet obtained by coating and drying the post-treatment liquid for use so that the dry thickness becomes 0.05 to 10 μm.
In any one of these post-treated plated steel sheets, tin plating is performed on the steel sheet, and after galvanizing the upper layer, the plated steel sheet is subjected to heat treatment at a temperature higher than the melting temperature of tin, or
It is preferable that the steel plate is subjected to tin plating, and then the plated steel plate is subjected to heat treatment at a temperature equal to or higher than the melting temperature of tin, and then the upper layer is subjected to galvanization.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The plated steel sheet according to the present invention is tin-plated on the steel sheet and galvanized thereon, and after selectively heating the plated steel sheet above the melting temperature of tin, the water-based acrylic resin is 100 to 800 g / L, rust-proof. Main component is water-based acrylic resin containing 10 to 100 g / L of agent, 50 to 600 g / L of water-soluble rosin, 10 to 200 g / L of water-dispersible silica, and 0.5 to 100 g / L of antioxidant. 100-900 g / L of post-treatment liquid or water-based urethane resin, 10-100 g / L of rust inhibitor, 10-400 g / L of water-dispersible silica, 0.5-100 g / L of antioxidant A post-processed plated steel sheet is obtained by applying and drying one of the post-treatment liquids for a plated steel sheet containing a water-based urethane resin as a main component so that the dry thickness is 0.05 to 10 μm. This post-treated plated steel sheet is excellent in solderability even when a chlorine-free flux is used, solder wettability does not deteriorate even with aging or heating, and excellent in corrosion resistance and oxidation resistance. Furthermore, the effect of suppressing the occurrence of red rust on the cut end face is also excellent.
[0012]
Hereinafter, the present invention will be described in detail.
The post-processed plated steel sheet of the present invention is a post-process that improves the solderability of a plated steel sheet obtained by performing tin plating on the steel sheet, applying galvanization thereon, and selectively heating the plated steel sheet above the melting temperature of tin. A film is formed. The tin plating layer formed directly on the steel plate is preferably formed with a plating amount of 3 to 20 g / m 2 using a known electroplating method. In the case of less than 3 g / m 2 , tin plating is applied, and then galvanization is performed thereon. Then, when heating is performed at a temperature higher than the melting temperature of tin, tin is thermally diffused into the steel plate or the galvanized layer, and all tin is iron -Most of the free tin is lost due to the formation of either a tin alloy, a zinc-tin alloy, or an iron-tin-zinc alloy, and solderability deteriorates. Corrosion resistance improves as the tin plating amount increases, but even if plating exceeds 20 g / m 2 , the effect of improving corrosion resistance is saturated and is not economical.
[0013]
After forming a tin plating layer on a steel plate as described above, a galvanization layer is formed thereon. The galvanized layer is also formed using a known electroplating method, but the plating amount is varied depending on the application. In applications where good solderability is particularly required, a plating amount of 0.01 to 0.05 g / m 2 is preferable. If it is less than 0.01 g / m 2 , tin whiskers are generated when time is measured for a long period of time, and when applied to electronic component circuits, the whisker contacts other conductive members such as lead wires and shorts. May cause an accident. On the other hand, if it exceeds 0.05 g / m 2 , sufficient solderability cannot be obtained in applications that require particularly good solderability.
[0014]
Requires good solderability, in yet applications where red rust cut end surface of the plated steel sheet is disliked, it is preferable galvanized amount is greater than 0.05 g / m 2, is 0.7 g / m 2 or less . If it is 0.05 g / m 2 or less, the effect of suppressing the occurrence of red rust is poor, and if it exceeds 0.7 g / m 2 , it will be somewhat poor in expressing good solderability. In applications other than the above applications where moderate solderability and good red rust resistance are required, it is preferably more than 0.7 g / m 2 and 7 g / m 2 or less. When it exceeds 7 g / m 2 , it is difficult to obtain good solderability.
[0015]
The plated steel sheet in which the tin plating layer and the galvanized layer are further formed on the steel sheet as described above may be used as the post-processed plated steel sheet of the present invention by directly forming the post-treatment film shown below. The plated steel sheet is heated above the melting temperature of tin to form an iron-tin alloy, zinc-tin alloy, or iron-tin-zinc alloy at the interface between the steel sheet and the tin plating layer and at the interface between the tin plating layer and the zinc plating layer. You may let them. By forming these alloy layers, the adhesion between the steel plate and the tin plating layer and between the tin plating layer and the galvanization layer is improved. Further, when the galvanized layer is thin, tin is alloyed with zinc on the outermost surface of the plated steel sheet, and solderability is improved. In addition, whisker resistance is improved by alloying tin.
[0016]
A post-treatment film for improving solderability is formed on the plated steel sheet obtained as described above. As the post-treatment film for improving the solderability of the present invention, a post-treatment liquid mainly composed of an aqueous acrylic resin (hereinafter referred to as A liquid) and a post-treatment liquid mainly composed of an aqueous urethane resin ( Hereinafter referred to as “Liquid B”). First, the post-treatment film with the liquid A will be described.
In the liquid A, the water-based acrylic resin is a polymer or copolymer of an acrylic monomer having a carboxylic acid, and does not particularly limit a polymerization method such as aqueous solution polymerization or emulsion polymerization. However, the acid value of the water-based acrylic resin (the number of milligrams of potassium hydroxide required to neutralize the free fatty acid contained in 1 g of the resin) is preferably 150 or less. The concentration is preferably in the range of 100 to 800 g / L. If it is less than 100 g / L, there is no effect of improving solderability, and the corrosion resistance is also lowered. On the other hand, if it exceeds 800 g / L, the effect of improving solderability is saturated, and when mixed with water-soluble rosin, the viscosity becomes high and gelation may occur, which is not preferable.
[0017]
In the liquid A, it is necessary to add the water-soluble rosin to be added in the range of 50 to 600 g / L. The water-solubilized rosin is obtained by a method in which a rosin soap is obtained by neutralizing a carboxylic acid group in an abietic acid molecule, which is the main component of rosin, with an amine salt or the like. If it is less than 50 g / L, the solder wettability after the lapse of time is insufficient, and if it exceeds 600 g / L, the viscosity becomes high, the gel tends to gel, and the coating becomes difficult.
[0018]
In the liquid A, it is preferable to add a rust inhibitor that does not contain chromium. Although it does not specifically limit except not containing chromium, the compound containing either one or both of the compound containing an amine and a styrene-maleic anhydride copolymer is applicable. As the compound containing an amine, specifically, an organic amine soap alone or a mixture thereof is used. Organic amine soaps include dodecylamine, oleoyl imidazoline, aminopropyl tallow amine, and rosin amine, and the amine can be used by salt formation with carboxylic acid or the like. The styrene / maleic anhydride copolymer is preferably a styrene / maleic anhydride copolymer alkyl ester / ammonium salt. The addition amount is preferably 10 to 100 g / L. If it is less than 10 g / L, no effect is observed in improving the corrosion resistance, and if it exceeds 100 g / L, the effect of improving the corrosion resistance is very good, but it is not preferable because the viscosity of the liquid increases and application becomes difficult.
[0019]
In the liquid A, the water-dispersible silica to be added improves the corrosion resistance and the film hardness of the plated steel sheet and improves the scratch resistance, and is preferably added in the range of 10 to 200 g / L. If it is less than 10 g / L, corrosion resistance cannot be improved. When it exceeds 200 g / L, the solder wettability is remarkably lowered. When importance is attached to the solder wettability, the amount adhering to the plated steel sheet is preferably in the range of 10 to 100 mg / m 2 . If the solder wettability is more important, the range is 10 to 50 mg / m 2 . The water-dispersible silica is not particularly limited, but silica coated with aluminum on the silica surface has an excellent dispersing action and can be particularly preferably applied. The particle diameter of silica is preferably small, preferably 100 nm or less, and those having 60 nm or less are particularly excellent in dispersing action. Silica generally inhibits wettability, but by making ultrafine particles of 100 nm or less, corrosion resistance and plated steel film hardness can be improved and scratch resistance can be improved without inhibiting solder wettability. it can.
[0020]
The antioxidant added to the A liquid of the present invention and the B liquid described later is not for preventing the oxidation of the plated layer surface of the plated steel sheet, which was considered to be the main cause of the decrease in solder wettability with time, It is added to suppress oxidation of the resin layer applied on the plating layer in order to suppress oxidation. Antioxidants applied to this application include sulfur-based antioxidants, but phenol-based antioxidants or phosphorus-based antioxidants are preferred, and both may be used in combination. The addition amount is preferably 0.5 to 100 g / L. If it is less than 0.5 g / L, the effect for improving the oxidation resistance is not recognized, and if it exceeds 100 g / L, the viscosity of the liquid rises and application becomes difficult.
[0021]
Next, the post-treatment film with the B liquid will be described. In the liquid B, the water-based urethane resin is not particularly limited, but having higher strength is more effective in corrosion resistance. The concentration is preferably in the range of 100 to 900 g / L. If it is less than 100 g / L, the corrosion resistance is insufficient, and if it exceeds 900 g / L, solder wettability deteriorates. Further, the rust preventive agent is not particularly limited except that it does not contain chromium, as in the case of the liquid A, but a compound containing an amine can also be applied. Specifically, organic amine soap used alone or in combination is used. Organic amine soaps include dodecylamine, oleoyl imidazoline, aminopropyl tallow amine, and rosin amine, and the amine can be used by salt formation with carboxylic acid or the like. The styrene / maleic anhydride copolymer is preferably a styrene / maleic anhydride copolymer alkyl ester / ammonium salt. The addition amount is preferably 10 to 100 g / L, and if it is less than 10 g / L, no effect is observed in improving the corrosion resistance, and if it exceeds 100 g / L, the effect of improving the corrosion resistance is very good, but the solderability is lowered. Therefore, it is not preferable.
[0022]
In the liquid B, the water-dispersible silica is added for the same purpose as the liquid A, but is preferably added in the range of 10 to 200 g / L. If it is less than 10 g / L, corrosion resistance cannot be improved. When it exceeds 400 g / L, the solder wettability is remarkably lowered. When importance is attached to solder wettability, it is preferable that the amount adhered to the plated steel sheet is in the range of 10 to 150 mg / m 2 . If the solder wettability is more important, the range is 10 to 80 mg / m 2 . As the water-dispersible silica, it is preferable to use the same silica as used in the liquid A.
[0023]
Moreover, also about antioxidant, a phenolic antioxidant or phosphorus antioxidant is preferable similarly to the case of A liquid, and you may use both together. The addition amount is preferably 0.5 to 100 g / L for the same reason as in the case of the liquid A.
[0024]
The pH of the liquid A and liquid B is suitably in the range of 3-10. If the pH is less than 3, the stability of the treatment solution is poor, and exceeding 10 is not preferable. In order to use the treatment solution stably for a longer period of time, a pH range of 6 to 9 is preferable.
[0025]
Said A liquid or B liquid is apply | coated to the one or both surfaces of the said plated steel plate. In this case, the coating film thickness may be changed on the front and back surfaces. The application method may be a known method such as a dipping method, a roll coating method, a curtain flow coating method, or a spray coating method, and is not particularly limited. However, when performing double-sided coating, taking advantage of the fact that this treatment liquid is water-based, a method of performing coating by dipping and drawing in the subsequent process of the continuous plating line is easy and economical.
[0026]
Liquid A or liquid B is applied so that the film thickness after drying is 0.05 to 10 μm. The plated steel sheet to which the liquid A or the liquid B is applied is dried to form a post-treatment film. When the thickness of the film is less than 0.05 μm, sufficient solderability and fingerprint resistance cannot be obtained, and corrosion resistance is remarkably deteriorated. If it exceeds 10 μm, the effect of improving the characteristics is saturated and the cost merit is lost.
[0027]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
1. Example 1 (Sample Nos. 1 to 10)
An annealing and temper rolled steel sheet (thickness 0.5 mm) is used as the plating base, and after alkali degreasing and cleaning treatment with sulfuric acid pickling, the electroplating method is used to form the tin plating layer and the top The galvanized layer was formed with the plating amount shown in Table 1. About some samples, after forming the tin plating layer, it heated more than the melting temperature of tin and quenched, and then formed the galvanization layer. For some other samples, after forming a tin plating layer and then forming a galvanization layer, heating to a temperature equal to or higher than the melting temperature of tin and then rapidly cooling to produce plated steel sheets with plating numbers A to J did. After applying the post-treatment liquid for the plated steel sheet on both surfaces of these plated steel sheets by the dipping / drawing method, spray coating method or roll coating method under the sample preparation conditions shown in Table 2, the sample is dried at a temperature of 90 ° C. Samples 1 to 13 were prepared. The samples having the sample numbers 1 to 13 thus obtained were subjected to the following characteristic evaluation. Table 4 shows the evaluation results.
[0028]
2. Example 2 (Sample Nos. 14 to 23)
On both surfaces of the plated steel sheet indicated by the plating numbers A to J shown in Table 1 obtained in the same manner as in Example 1, the sample preparation conditions shown in Table 3 by immersion / drawing method, spray coating method or roll coating method were used. After apply | coating the post-processing liquid for plating steel plates, it dried at the temperature of 90 degreeC and produced the sample of sample numbers 14-23. The samples having sample numbers 14 to 23 thus obtained were evaluated for the following characteristics. Table 4 shows the evaluation results.
[0029]
[Characteristic evaluation]
1) Solder wettability:
That is, according to the meniscograph method (MIL-STD-883B), a sample having a width of 10 mm cut out from the above-mentioned test material using SOLDERCHECKER (MODEL SAT-5000, manufactured by RHESCA) is used. Solder immersed in a non-active flux (NA-200, manufactured by Tamura Chemical Co., Ltd.), and in the case of Example 2, immersed in a weakly active flux not containing chlorine (Lapics RMA, manufactured by Nippon Solder Industries, Ltd.), and then maintained at 250 ° C. A sample coated with the above flux in a bath (JIS Z 3282: H60A) is immersed at 2 mm / sec for 2 mm, the time until the solder gets wet is measured, and the zero cross time is measured, and the solder wettability is evaluated according to the following criteria. did. A shorter wetting time indicates better solderability. Note that the test was performed in two ways, immediately after sample preparation and at a constant temperature and humidity (60 ° C., 95% RH) for 500 hours. Except for ×, the acceptable range.
A: Less than 3 seconds, O: Less than 3-5 seconds, Δ: Less than 5-10 seconds, X: More than 10 seconds
2) Corrosion resistance (red face rust resistance):
Samples having a size of 40 mm × 80 mm were cut out from the samples of Example 1 and Example 2, and subjected to a salt spray test according to JIS Z 2371 for 48 hours. The degree of occurrence of red rust was visually observed, and the criteria shown below The corrosion resistance was evaluated. Except for ×, the acceptable range.
◎: No red rust, ○: Red rust is observed in less than 50% of the end face, △: Red rust occurs in 50 to 80% of the end face, ×: Red rust occurs in more than 80% of the end face [0031]
3) Whisker resistance:
Generation of whiskers after cutting 30 mm × 30 mm specimens from the samples of Example 1 and Example 2 and exposing them for 30 days in a high temperature and high humidity atmosphere of temperature: 85 ° C. and humidity: 85% RH The situation was observed using a scanning electron microscope at a magnification of 1500 times, and whisker resistance was evaluated according to the following criteria.
A: No whisker is observed.
○: It is recognized that whiskers having a length of less than 10 μm are slightly generated.
(Triangle | delta): It is recognized that the whisker of 10-30 micrometers in length has generate | occur | produced.
X: It is recognized that whiskers having a length exceeding 30 μm are generated.
◎ and ○ were accepted.
[0032]
As a result, as shown in Table 4, each of the post-treated plated steel sheets of Example 1 and Example 2 of the present invention has good properties in terms of solder wettability, particularly solder wettability after aging, and corrosion resistance. Indicated.
[0033]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
【The invention's effect】
As described above, according to the present invention, when soldering a plated steel sheet, even when a non-active flux containing no chlorine is used, the solder wettability is excellent. Post-treated plated steel sheet that is excellent in oxidation resistance that does not deteriorate, and has a corrosion resistance excellent in the effect of suppressing the occurrence of red rust on the cut end face, and a plating and post-treatment film capable of obtaining a film with excellent scratch resistance It became possible to get.
Claims (4)
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| EP1844111B1 (en) | 2005-01-28 | 2008-10-29 | Basf Se | Preparation and method for applying corrosion protection layers |
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| JPS5192739A (en) * | 1975-02-13 | 1976-08-14 | Tairyukaseito taisumatsujiseino suguretadenkiburiki | |
| JPH0645902B2 (en) * | 1987-03-13 | 1994-06-15 | 東洋鋼鈑株式会社 | Post-treatment method for plated steel sheet |
| JPH04314890A (en) * | 1991-04-15 | 1992-11-06 | Nikko Kyodo Co Ltd | Liquid and method for surface treatment |
| JP3192084B2 (en) * | 1996-03-04 | 2001-07-23 | 東洋鋼鈑株式会社 | Coated steel sheet and subsequent treatment method |
| JPH106074A (en) * | 1996-06-20 | 1998-01-13 | Harima Chem Inc | Solder paste composition |
| AU4319097A (en) * | 1996-09-20 | 1998-04-14 | Toyo Kohan Co. Ltd. | Post-treating solution of plated steel sheet having improved solderability, post-treated plate and method of production thereof |
| JPH11144994A (en) * | 1997-11-06 | 1999-05-28 | Oji Paper Co Ltd | Zinc evaporation base material for capacitor and manufacture thereof |
| JP3836273B2 (en) * | 1998-06-02 | 2006-10-25 | 東洋鋼鈑株式会社 | Method for producing a surface-treated metal plate excellent in workability, scratch resistance and corrosion resistance |
| JP4007736B2 (en) * | 1998-12-16 | 2007-11-14 | 新日本製鐵株式会社 | Chromium-free organically coated galvanized steel |
| JP3857866B2 (en) * | 2000-02-29 | 2006-12-13 | 日本ペイント株式会社 | Non-chromate metal surface treatment agent, surface treatment method and treated painted steel |
| JP2001288584A (en) * | 2000-03-31 | 2001-10-19 | Nippon Steel Corp | Surface-treated metallic sheet excellent in abrasion resistance and press galling resistance |
| JP2002212757A (en) * | 2001-01-11 | 2002-07-31 | Sumitomo Metal Ind Ltd | Galvanized steel sheet having excellent corrosion resistance after working and production method therefor |
| JP3908912B2 (en) * | 2001-02-22 | 2007-04-25 | 新日本製鐵株式会社 | Surface-treated steel sheet for environmentally friendly electronic components with excellent solder wettability, rust resistance, and whisker resistance |
| JP4812955B2 (en) * | 2001-03-26 | 2011-11-09 | 株式会社クラレ | anti-rust |
| JP3702193B2 (en) * | 2001-04-06 | 2005-10-05 | 新日本製鐵株式会社 | Non-delaminating lubricated galvanized steel sheet with excellent corrosion resistance after machining |
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