JP3810742B2 - Post-treatment liquid for plated steel sheet, post-treated plated steel sheet using the same, and method for producing the same - Google Patents
Post-treatment liquid for plated steel sheet, post-treated plated steel sheet using the same, and method for producing the same Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明はめっき鋼板、特に半田めっき鋼板の後処理に係わり、半田の濡れ性、経時性、耐食性を向上させるめっき鋼板用後処理液、それを用いた後処理めっき鋼板、およびその製造方法に関する。
【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て酸化皮膜が成長し、場合によっては赤錆が発生することがある。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、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１参照。）。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。
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を開示している（例えば特許文献２参照。）。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。
【０００４】
【特許文献１】
特開昭６３−２７７７８６号公報
【特許文献２】
特開２００２−２４９８８５号公報
【０００５】
【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、しかも耐食性に優れた皮膜が得られるめっき鋼板用後処理液、およびこの後処理液をめっき鋼板に塗布し乾燥してなる後処理めっき鋼板およびその製造方法を提供するものである。
【０００６】
【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めっき鋼板用後処理液は、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、酸化防止剤を０．５〜１００ｇ／Ｌ含有してなり、ｐＨが３〜１０の範囲であることを特徴とするもの、または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、酸化防止剤を０．５〜１００ｇ／Ｌ含有してなり、ｐＨが３〜１０の範囲であることを特徴とするものである。
前記酸化防止剤は、フェノール系酸化防止剤および／またはリン系酸化防止剤であることが望ましい。
また、本発明の後処理めっき鋼板は、上記何れかのめっき鋼板用後処理液を、めっき鋼板に乾燥厚みが０．０５〜１０μｍとなるように塗布してなることを特徴とし、また、めっき鋼板が鋼板上に亜鉛めっき層、錫めっき層、亜鉛−錫合金めっき層、銅めっき層、ニッケルめっき層のいずれかのめっき層を形成させてなるめっき鋼板であることを特徴とするものである。
さらに、本発明の後処理めっき鋼板の製造方法は、上記何れかのめっき鋼板用後処理液を、鋼板上に亜鉛めっき層、錫めっき層、亜鉛−錫合金めっき層、銅めっき層、ニッケルめっき層のいずれかのめっき層を形成させてなるめっき鋼板に、乾燥厚みが０．０５〜１０μｍとなるように塗布し乾燥することを特徴とする。
【０００７】
【発明の実施の形態】
本発明に係るめっき鋼板用後処理液は、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である。そして、本発明に係る後処理めっき鋼板およびその製造方法は、このめっき鋼板用後処理液を、鋼板上に亜鉛めっき層、錫めっき層、亜鉛−錫合金めっき層、銅めっき層、ニッケルめっき層のいずれかのめっき層を形成させためっき鋼板に、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、また耐食性および耐酸化性にも優れる。
【０００８】
以下、実施例にて本発明を詳細に説明する。
本発明の水系アクリル樹脂を主成分とするめっき鋼板用後処理液において、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。
【０００９】
水溶化ロジンは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。
【００１０】
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、後処理皮膜に上記の水溶性ロジンを含ませない場合は処理液に１０〜４００ｇ／Ｌ添加するのが好ましい。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。後処理皮膜に水溶性ロジンを含ませる場合は処理液に１０〜２００ｇ／Ｌ添加するのが好ましい。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、Ｓｉとして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性に優れており、より好ましい。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。
【００１１】
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が適用できる。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デシルアミン、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。
【００１２】
本発明において、めっき鋼板用の後処理液に酸化防止剤を添加することにより、樹脂層の酸化および変質を抑制するとともに、めっき層の酸化も抑制し、経時した場合においても優れた半田濡れ性を確保することが可能である。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を超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。
【００１３】
一方、本発明の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を超えると半田濡れ性が悪くなる。また、防錆剤は、水系アクリル樹脂を主成分とするめっき鋼板用後処理液の場合と同様に、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デシルアミン、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、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。
【００１４】
また、酸化防止剤についても、水系アクリル樹脂を主成分とするめっき鋼板用後処理液の場合と同様に、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。添加量についても水系アクリル樹脂を主成分とするめっき鋼板用後処理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。
【００１５】
上記各めっき鋼板用後処理液の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。
【００１６】
上記のようにして得られた何れかのめっき鋼板用後処理液を、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・絞りによる塗布やロールコートなどを行う方法が容易で経済的である。
【００１７】
めっき鋼板用後処理液は、乾燥後の膜厚が０．０５〜１０μｍとなるように塗布する。めっき鋼板用後処理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。
【００１８】
めっき鋼板の仕様は特に限定されるものではない。溶融めっき、または電気めっきなど、いずれの手法を用いても十分な効果を有するめっきが得られる。また、銅めっき、ニッケルめっき、錫めっき、鉛−錫合金めっき、亜鉛めっき、亜鉛−ニッケル、亜鉛−アルミニウム、亜鉛−錫、亜鉛−鉄あるいは亜鉛−コバルトなどの亜鉛合金めっき、亜鉛−コバルト−モリブデン等からなる複合亜鉛めっき、または下層の錫と上層の亜鉛や、下層の亜鉛と上層の錫からなる二層めっきなどの複層めっきなど、鋼板上に施すめっきの種類も用途に応じて選択される。
【００１９】
【実施例】
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、表１に示す金属または合金を、表１に示すめっき法を用いて表１に示すめっき量でめっきし、めっき番号Ａ〜Ｋで示すめっき鋼板を作製した。これらのめっき鋼板の中から表２に示すめっき番号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１〜９の試料を作製した。比較例として、後処理を施さないめっきままのめっき鋼板を試料番号１０の試料とした。このようにして得られた試料番号１〜１０の試料について、下記の特性評価を行い、表３にその評価結果を示した。
【００２０】
また、めっき番号Ａ〜Ｋで示すめっき鋼板の中から表４に示すめっき番号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４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１１〜１９の試料を作製した。比較例として、後処理を施さないままのめっき鋼板を試料番号２０の試料とした。このようにして得られた試料番号１１〜２０の試料について、下記の特性評価を行い、表５にその評価結果を示した。
【００２１】
[特性評価]
１）半田濡れ性：
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
２）耐食性：
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、△：一部赤錆発生、×：全面に赤錆発生
【００２２】
その結果、表３及び表５に示すように、本発明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、本発明の酸化防止剤の効果が発揮された。一方、比較例のように、後処理液を施さないめっき鋼板においては、半田濡れ性、および耐食性の両方において性能が劣っていた。
【００２３】
【表１】
【表２】
【表３】
【表４】
【表５】
【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、しかも耐食性に優れた皮膜が得られるめっき鋼板用後処理液、およびこのめっき鋼板用後処理液をめっき鋼板に塗布し乾燥してなる後処理めっき鋼板およびその製造方法を提供することが可能となった。本発明のめっき鋼板用後処理液を塗布した後処理めっき鋼板は、塩素を含ま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、半田の濡れ性は経時しても劣ることがなく、また耐食性にも優れ、しかも皮膜が疵付き難いという特性を有している。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a post-treatment for a plated steel sheet, particularly a solder-plated steel sheet, and relates to a post-treatment solution for a plated steel sheet that improves solder wettability, aging, and corrosion resistance, a post-treated plated steel sheet using the same, and a method for manufacturing the same.
[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 the plating and grow an oxide film when exposed to the environment in which they are used. In some cases, red rust may occur. Therefore, there is a need for a post-treatment method that suppresses a decrease in solderability due to the growth of an oxide film over time in these plated steel sheets. 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 technique, tin plating is performed on a steel plate, and then tin plating is mainly performed on one or more of zinc, nickel, and cobalt, or tin is plated on one or more of zinc, nickel, and cobalt. Disclosed is a two-layer plated steel sheet for soldering, which is plated with an alloy having a base potential lower than the standard electrode potential of tin, containing at least one of iron, lead, and copper (for example, Patent Documents) 1). 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. .
A Sn—Zn alloy layer is formed on a surface-treated steel plate in which a Sn—Zn alloy layer on the steel plate or a surface treatment layer made of either Ni plating or Fe—Ni diffusion layer is formed on the surface, and these Sn— An environmentally-friendly surface-treated steel sheet for electronic parts, in which an inorganic film mainly composed of magnesium phosphate is formed on a Zn alloy layer, is disclosed (for example, see Patent Document 2). 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.
[0004]
[Patent Document 1]
JP 63-277786 A [Patent Document 2]
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 that does not contain chlorine when soldering a plated steel sheet, and in particular, the solder wettability does not deteriorate over time, and the corrosion resistance is excellent. It is intended to provide a post-treatment liquid for a plated steel sheet from which a coated film is obtained, a post-treated plated steel sheet obtained by applying this post-treatment liquid to a plated steel sheet and drying it, and a method for producing the same.
[0006]
[Means for Solving the Problems]
The post-treatment liquid for a plated steel sheet according to the present invention that solves the above-described problems comprises a water-based acrylic resin of 100 to 800 g / L, a compound containing an amine salt, or a styrene / maleic anhydride copolymer, or both. 10 to 100 g / L of rust inhibitor, 50 to 600 g / L of water-solubilized 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, and 0.5 to 0.5 antioxidant. 100 g / L Ri Na contain, what pH is equal to or in the range of 3 to 10, or a water-borne urethane resin 100~900g / L, compound containing an amine salt, or a styrene-maleic acid copolymer 10~100g a rust inhibitor consisting either or both of the polymer / L, particle size 100nm or less of water coated with aluminum on the surface Chisei silica 10 to 400 g / L, Ri Na contain 0.5 to 100 g / L of antioxidant, in which pH is equal to or in the range of 3-10.
The antioxidant is preferably a phenolic antioxidant and / or a phosphorus antioxidant.
Further, the post-treated plated steel sheet of the present invention is characterized in that any one of the above-described post-treatment liquids for plated steel sheet is applied to the plated steel sheet so that the dry thickness is 0.05 to 10 μm. The steel sheet is a plated steel sheet in which any one of a zinc plating layer, a tin plating layer, a zinc-tin alloy plating layer, a copper plating layer, and a nickel plating layer is formed on the steel plate. .
Furthermore, the manufacturing method of the post-treatment plated steel sheet of the present invention comprises any one of the above-described post-treatment liquids for a plated steel sheet, the zinc plating layer, tin plating layer, zinc-tin alloy plating layer, copper plating layer, nickel plating on the steel plate. It is characterized in that it is applied to a plated steel sheet formed with any one of the plating layers so that the dry thickness is 0.05 to 10 μm and dried.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The post-treatment liquid for a plated steel sheet according to the present invention is 100 to 800 g / L of an aqueous acrylic resin, 10 to 100 g / L of a rust inhibitor, 50 to 600 g / L of a water-soluble rosin, and 10 to 200 g of water-dispersible silica. / L, a post-treatment liquid mainly composed of an aqueous acrylic resin containing 0.5 to 100 g / L of an antioxidant, or an aqueous urethane resin of 100 to 900 g / L, an antirust agent of 10 to 100 g / L, water This is a post-treatment liquid for a plated steel sheet mainly composed of an aqueous urethane resin containing 10 to 400 g / L of dispersible silica and 0.5 to 100 g / L of an antioxidant. And the post-treatment plated steel sheet and the manufacturing method thereof according to the present invention are obtained by applying a post-treatment liquid for a plated steel sheet to a zinc plating layer, a tin plating layer, a zinc-tin alloy plating layer, a copper plating layer, a nickel plating layer on the steel plate. A post-processed plated steel sheet is obtained by applying and drying the plated steel sheet on which any one of the above plating layers is formed so as to have a dry thickness of 0.05 to 10 μm. This post-treated plated steel sheet is excellent in solderability even when a chlorine-free flux is used, and does not deteriorate the wettability of the solder even if it is aged or heated, and is excellent in corrosion resistance and oxidation resistance.
[0008]
Hereinafter, the present invention will be described in detail with reference to examples.
In the post-treatment solution for a plated steel sheet containing the aqueous acrylic resin as a main component of the present invention, the aqueous acrylic resin is a polymer or copolymer of an acrylic monomer having a carboxylic acid, and particularly a heavy polymer such as aqueous solution polymerization or emulsion polymerization. It does not limit the legality. 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.
[0009]
The water-solubilized rosin needs 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.
[0010]
Water dispersible silica improves corrosion resistance and film hardness of the plated steel sheet and improves scratch resistance. When the above-mentioned water-soluble rosin is not included in the post-treatment film, the treatment liquid is 10 to 400 g / L. It is preferable to add. 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 a water-soluble rosin is included in the post-treatment film, it is preferable to add 10 to 200 g / L to the treatment liquid. When importance is attached to solder wettability, it is preferable that the amount adhering to the plated steel sheet is in the range of 10 to 100 mg / m 2 as Si. 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 silica particle size is preferably small, preferably 100 nm or less, and particularly preferably 60 nm or less because of excellent dispersibility. 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.
[0011]
It is preferable to add a rust preventive 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. The amine can be used after 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.
[0012]
In the present invention, by adding an antioxidant to the post-treatment liquid for the plated steel sheet, the oxidation and deterioration of the resin layer are suppressed, and the oxidation of the plating layer is also suppressed. Can be secured. 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, an 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.
[0013]
On the other hand, in the post-treatment liquid for a plated steel sheet mainly composed of the aqueous urethane resin of the present invention, the aqueous 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, the solder wettability deteriorates. The rust preventive agent is not particularly limited except that it does not contain chromium, as in the case of a post-treatment liquid for a plated steel sheet containing a water-based acrylic resin as a main component, but an amine-containing compound 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. The amine can be used after 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 corrosion resistance. If it exceeds 100 g / L, the effect of improving corrosion resistance is very good, but the viscosity of the liquid increases. Therefore, it is not preferable because the coating becomes difficult.
[0014]
Moreover, also about antioxidant, the phenolic antioxidant or phosphorus antioxidant is preferable similarly to the case of the post-processing liquid for plated steel plates which has a water-based acrylic resin as a main component, and you may use both together. The addition amount is also preferably 0.5 to 100 g / L for the same reason as in the case of the post-treatment liquid for a plated steel sheet containing a water-based acrylic resin as a main component.
[0015]
The pH of the post-treatment liquid for each plated steel sheet 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.
[0016]
One of the post-treatment liquids for a plated steel sheet obtained as described above is applied to one side or both sides of the plated steel sheet. 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 aqueous, a method of performing coating by dipping / drawing, roll coating, etc. in the subsequent process of the continuous plating line is easy and economical.
[0017]
The post-treatment liquid for the plated steel sheet is applied so that the film thickness after drying is 0.05 to 10 μm. The plated steel sheet coated with the post-treatment liquid for the plated steel sheet 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.
[0018]
The specification of the plated steel sheet is not particularly limited. Plating having a sufficient effect can be obtained by using any method such as hot dipping or electroplating. Also, copper plating, nickel plating, tin plating, lead-tin alloy plating, zinc plating, zinc-nickel, zinc-aluminum, zinc-tin, zinc-iron or zinc-cobalt zinc alloy plating, zinc-cobalt-molybdenum Depending on the application, the type of plating to be applied to the steel sheet, such as composite galvanizing, etc., or multi-layer plating, such as lower layer tin and upper layer zinc, or two layer plating consisting of lower layer zinc and upper layer tin, is also selected. The
[0019]
【Example】
Table 1 shows the metals or alloys shown in Table 1 after performing annealing treatment and cleaning treatment by alkaline degreasing and sulfuric acid washing using a steel plate (plate thickness: 0.5 mm) subjected to annealing and temper rolling as a plating original plate. It plated with the plating amount shown in Table 1 using the plating method, and the plated steel plate shown by plating number AK was produced. From these plated steel sheets, a post-treatment solution for plated steel sheets was applied to both sides of the plated steel sheets having the plating numbers shown in Table 2 under the sample preparation conditions shown in Table 2 by dipping / drawing, spray coating, or roll coating. Then, it dried at the temperature of 90 degreeC and produced the sample of the sample numbers 1-9. As a comparative example, an as-plated steel sheet without post-treatment was used as a sample No. 10. The samples Nos. 1 to 10 thus obtained were evaluated for the following characteristics, and Table 3 shows the evaluation results.
[0020]
Moreover, on both surfaces of the plated steel plate having the plating number shown in Table 4 among the plated steel plates indicated by plating numbers A to K, the plated steel plate is subjected to the sample preparation conditions shown in Table 4 by dipping / drawing method, spray coating method or roll coating method. After applying the used post-treatment liquid, it was dried at a temperature of 90 ° C. to prepare samples Nos. 11 to 19. As a comparative example, a plated steel plate with no post-treatment was used as a sample No. 20. The samples Nos. 11 to 20 thus obtained were subjected to the following characteristic evaluation, and Table 5 shows the evaluation results.
[0021]
[Characteristic evaluation]
1) Solder wettability:
Using a SOLDERCHECKER (MODEL SAT-5000, manufactured by RHESCA) by a meniscograph method (MIL-STD-883B), a sample having a width of 10 mm cut out from the above-mentioned test material is not containing chlorine in the case of Example 1. Immerse in an active flux (NA-200, manufactured by Tamura Kaken). In the case of Example 2, a solder bath (Lapics RMA, manufactured by Nippon Solder Industries) that does not contain chlorine and then maintained at 250 ° C. A sample obtained by applying the above flux to JIS Z 3282: H60A) was immersed for 2 mm at an immersion speed of 2 mm / second, and the zero cross time until the solder was wet was measured, and the solder wettability was evaluated according to the following criteria. 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: 10 seconds or more 2) Corrosion resistance:
A salt spray test was conducted for 48 hours in accordance with JIS Z 2371, and the degree of red rust was visually observed, and the corrosion resistance was evaluated according to the criteria shown below. Except for ×, the acceptable range.
○: No red rust occurred, △: Partial red rust occurred, ×: Red rust occurred on the entire surface. [0022]
As a result, as shown in Table 3 and Table 5, all the post-treated plated steel sheets of the present invention showed good properties in terms of solder wettability, particularly solder wettability after time, and corrosion resistance. The effect of the antioxidant was demonstrated. On the other hand, as in the comparative example, the plated steel sheet not subjected to the post-treatment liquid was inferior in both solder wettability and corrosion resistance.
[0023]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
【The invention's effect】
As described above, according to the present invention, when soldering a plated steel sheet, even when a flux not containing chlorine is used, the solder wettability is excellent, and particularly, the solder wettability is deteriorated over time. A post-treatment liquid for a plated steel sheet that provides a coating with excellent oxidation resistance and corrosion resistance, and a post-treated plated steel sheet obtained by applying the post-treatment liquid for a plated steel sheet to a plated steel sheet and drying it, and a method for producing the same It became possible to provide. The post-treated plated steel sheet coated with the post-treatment liquid for the plated steel sheet of the present invention has excellent solder wettability even when using an inactive flux containing no chlorine, and the solder wettability is inferior even with time. In addition, the film has excellent corrosion resistance and has a characteristic that the film is hardly wrinkled.
Claims (6)
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| 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 |
| 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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