JP2004197123A - Colored surface treated steel sheet - Google Patents
Colored surface treated steel sheet Download PDFInfo
- Publication number
- JP2004197123A JP2004197123A JP2002364188A JP2002364188A JP2004197123A JP 2004197123 A JP2004197123 A JP 2004197123A JP 2002364188 A JP2002364188 A JP 2002364188A JP 2002364188 A JP2002364188 A JP 2002364188A JP 2004197123 A JP2004197123 A JP 2004197123A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- colored surface
- plated steel
- treated
- treated steel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、半田性に優れた有色の表面処理皮膜をめっき鋼板に形成させてなる着色表面処理鋼板に関する。
【０００２】
【従来の技術】
近年、金属容器、電子部品基板、家電機器シャーシ、キャビネットなどの用途に適用する表面処理鋼板においては、装飾的観点から、黒色、白色、灰色などの無彩色、赤色、青色、黄色、緑色、茶色、ピンク色などの彩色に着色した表面処理皮膜を有する着色表面処理鋼板が用いられるようになってきている。これらの用途に用いられる表面処理鋼板は、所定の形状に成形加工した後の接着が必要な箇所、または他の部品や部材との接着に半田付けが行われる場合があるが、従来の着色表面処理鋼板においては着色した有色の表面処理皮膜の半田濡れ性が不良であり、半田付けが必要とされる用途に適用することができなかった。
【０００３】
従来技術として、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が開示されている（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。
【０００４】
また、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開示されている（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。
【０００５】
本出願に関する先行技術文献情報として次のものがある。
【０００６】
【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
【０００７】
【発明が解決しようとする課題】
本発明は、半田付けが可能な優れた半田濡れ性を有する着色表面処理鋼板を提供することを目的とする。
【０００８】
【課題を解決するための手段】
上記課題を解決するために本発明の着色表面処理鋼板は、めっき鋼板上にメニスコグラフ法による半田濡れ性が１０秒未満である有色の表面処理皮膜を形成したことを特徴とする。
【０００９】
さらに、本発明の着色表面処理鋼板においては、
めっき鋼板が、鋼板上に亜鉛層を形成させてなるめっき鋼板、または
めっき鋼板が、鋼板上に錫層を形成させてなるめっき鋼板、または
めっき鋼板が、鋼板上に亜鉛−錫合金層を形成させてなるめっき鋼板、またはめっき鋼板が、鋼板上に鋼板側から順に錫層と亜鉛層の二層めっき層を形成させてなるめっき鋼板、または
めっき鋼板が、鋼板上に鋼板側から順に亜鉛層と錫層の二層めっき層を形成させてなるめっき鋼板、または
めっき鋼板が、鋼板上に銅層を形成させてなるめっき鋼板、または
めっき鋼板が、鋼板上にニッケル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。
【００１０】
さらに、本発明の着色表面処理鋼板においては、
有色の表面処理皮膜が、着色顔料を含有させた水系ウレタン樹脂を塗布し乾燥してなる皮膜であることを特徴とし、さらに
この水系ウレタン樹脂に、さらに防錆剤と水分散性シリカを含有させたり、その上にさらに酸化防止剤を含有させてなることを特徴する。
【００１１】
さらに、本発明の着色表面処理鋼板においては、
有色の表面処理皮膜が、着色顔料と水溶化ロジンを含有させた水系アクリル樹脂を塗布し乾燥してなる皮膜であることを特徴とし、さらに
この水系アクリル樹脂に、さらに防錆剤、および水分散性シリカを含有させたり、その上にさらに酸化防止剤を含有させてなることを特徴する。
【００１２】
さらに、本発明の着色表面処理鋼板においては、前記着色顔料が黒色顔料であることを特徴とする。
【００１３】
【発明の実施の形態】
本発明においては、半田濡れ性に優れる水系ウレタン樹脂や水溶化ロジンを含有する水系アクリル樹脂、またはこれらの樹脂にさらに防錆剤、水分散性シリカ、酸化防止剤などを含有させた樹脂に、無彩色や彩色の着色顔料をさらに含有させ、めっき鋼板に塗布し乾燥させて有色の表面処理皮膜を形成させることより、メニスコグラフ法による半田濡れ性が１０秒未満の優れた半田濡れ性を有し、かつ色彩が鮮明で装飾性に優れた着色表面処理鋼板が得られた。
【００１４】
有色の表面処理皮膜を形成させるめっき鋼板のめっき層としては、亜鉛、錫、銅、ニッケル、ビスマスなどの純金属の単層、またはこれらの純金属を２層以上重ねて形成させた複層のめっき層、亜鉛−錫、亜鉛−銅、亜鉛−ニッケル、亜鉛−アルミニウム、亜鉛−鉄あるいは亜鉛−コバルトなどの亜鉛合金、錫−ニッケル、錫−銅あるいは錫−鉄などの錫合金、銅−ベリリウムや銅−ニッケルなどの銅合金などの合金めっき層など、用途に応じて選択可能である。鋼板上へのめっき層の形成は、溶融めっき、または電気めっきなどを適宜選択することができる。めっき層を形成させた鋼板は、そのままめっき層上に下記の有色の表面処理皮膜を形成させる基板としてのめっき鋼板としてもよいが、めっき層を形成させた後加熱して、単層のめっき層を溶融させて光輝化したり、また複層めっきのめっき層を溶融させて合金化して単層の合金層としたり、めっき層同士または鋼板とめっき層の間でそれぞれの金属を固相拡散させるなどして、表面処理皮膜を形成させる基板としてのめっき鋼板としてもよい。
【００１５】
次いで、これらの金属からなるめっき層を形成させためっき鋼板上に、着色顔料を含有させた表面処理皮膜を形成させる。表面処理皮膜としては、水系ウレタン樹脂または水溶化ロジンを含有させた水系アクリル樹脂を用いることが好ましい。これらの水系樹脂の濃度としては、１００〜９００ｇ／ｌの範囲であることが好ましい。着色顔料としては有機系、無機系のいずれも適用可能であり、黒色、白色などの無彩色、赤色、青色、黄色などの彩色の顔料を１種または２種以上添加して好みの色を発色させる。樹脂中へ添加する量は樹脂の固形分に対して１〜５０重量％であることが好ましい。含有量が１重量％未満では色によっては色調の鮮明性に乏しく、５０重量％を超えるとハンダ性が不良となり、また耐食性が著しく低下する。より好ましい添加量は３〜３０重量％である。
【００１６】
上記の着色顔料を含有させた水系ウレタン樹脂または水溶化ロジンを含有させた水系アクリル樹脂に、さらに防錆剤、水分散性シリカを含有させてめっき鋼板の耐食性を向上させ、その上さらに酸化防止剤などを含有させることにより、半田濡れ性を向上させることができる。水系ウレタン樹脂を用いる場合、防錆剤としては、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。上記の濃度の樹脂液に添加する量は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。
【００１７】
水分散性シリカは、上記の濃度の樹脂液に１０〜４００ｇ／ｌ添加するのが好ましい。１０ｇ／ｌ未満では、耐食性の向上に効果がなく、４００ｇ／ｌを越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、シリコンとして１０〜４００ｍｇ／ｍ2 の範囲にするのが好ましい。より半田濡れ性を重要視する場合は、１０〜１００ｍｇ／ｍ2 の範囲が好ましい。水分散性シリカとしては、シリカの表面にアルミニウムをコーティングしたものが分散作用を有しており、特に好ましい。シリカの粒径としては、分散性の点で小さい方が好ましく、１００ｎｍ以下、より好ましくは６０ｎｍ以下である。
【００１８】
上記のように着色顔料を含有させ、さらに防錆剤と水分散性シリカを含有させた水系ウレタン樹脂に、またさらに酸化防止剤を含有させることにより、半田濡れ性を向上させることができる。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。
【００１９】
水系アクリル樹脂を用いる場合、防錆剤としては、水系ウレタン樹脂に用いたものと同様の有機アミン石けんの単独あるいは混合したものを、水系ウレタン樹脂の場合と同様の添加量で上記の濃度の樹脂液に添加する。
【００２０】
水溶性ロジンは、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てロジン石鹸とする方法により得られたものを、特に経時後の半田濡れ性を向上させるために水系アクリル樹脂中に含有させる。上記の樹脂液中に５０〜６００ｇ／ｌの範囲で添加するのが好ましい。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。
【００２１】
水分散性シリカは、水系ウレタン樹脂に用いたのと同様のものを、上記の濃度の樹脂液に１０〜２００ｇ／ｌ添加するのが好ましい。１０ｇ／ｌ未満では、耐食性の向上に効果がなく、２００ｇ／ｌを越えると、半田濡れ性が著しく低下する。
【００２２】
上記のように着色顔料を含有させ、さらに防錆剤と水分散性シリカ、さらに水溶性ロジンを含有させた水系アクリル樹脂に、またさらに酸化防止剤を含有させることにより、半田濡れ性を向上させることができる。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。
【００２３】
上記のようにして得られた何れかの樹脂液を、上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よい。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、公知の方法を用いることができる。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、連続めっき工程の後工程において、浸漬・絞りによる塗布を行う方法が容易で経済的である。これらのいずれかの塗布方法を用いて塗布した後、乾燥させてめっき鋼板上に有色の表面処理皮膜を形成させ、着色表面処理鋼板とする。乾燥後の皮膜厚さは０．０５〜１０μｍであることが好ましい。皮膜の厚みが０．０５μｍ未満の場合は、十分な半田濡れ性が得られない。また、手指で触れた場合に指紋が付きやすく、耐食性が著しく劣る。１０μｍを越える場合は、これらの特性向上の効果が飽和し、コストメリットがなくなる。
【００２４】
このようにして得られる本発明の着色表面処理鋼板は、以下に示すメニスコグラフ法（ＭＩＬ−ＳＴＤ−８８３Ｂ）による半田濡れ性が１０秒未満であることが好ましい。メニスコグラフ法による半田濡れ性が１０秒を超える場合は、加熱溶融した半田が着色表面処理鋼板の表面に十分に広がらず、半田付けする相手材との十分な接着力が得られない。メニスコグラフ法による半田濡れ性の測定は、以下のようにして行う。すなわち、ＳＯＬＤＥＲＣＨＥＣＫＥＲ（ＭＯＤＥＬ ＳＡＴ−５０００、ＲＨＥＳＣＡ製）を使用し、上記の着色表面処理鋼板から切り出した幅１０ｍｍのサンプルをフラックスに浸漬し、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、半田濡れ性（秒）とする。
【００２５】
【実施例】
以下、実施例により本発明を具体的に説明する。
【００２６】
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両面に、表２に示す黄、黒、赤系の着色顔料を含有する樹脂液を浸漬・絞り法を用いて塗布した後、９０℃の温度で乾燥し、試料番号１〜２０の試料を作製し、下記の特性評価を行い、表３にその評価結果を示した。
【００２７】
【表１】
【表２】
【表３】
[特性評価]
１）半田濡れ性：
ＳＯＬＤＥＲＣＨＥＣＫＥＲ（ＭＯＤＥＬ ＳＡＴ−５０００、ＲＨＥＳＣＡ製）を用い、メニスコグラフ法（ＭＩＬ−ＳＴＤ−８８３Ｂ）により評価した。すなわち、試料番号１〜２０の試料から幅１０ｍｍの試片を切り出し、表３に示すように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試片を浸漬速度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２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
【００３１】
２）色彩鮮明性：
試料番号１〜２０の試料について分光測色計（ＭＯＤＥＬ：ＣＭ−３５００ｄ、ミノルタ（株）製）を用い、Ｌ値、ａ値、ｂ値を測定し、それぞれの測定値が表４に示すそれぞれの値の範囲内にあるものを合格基準とし○で示した。合格基準をはずれる値のものを不合格として×で示した。
【００３２】
【表４】
３）耐食性：
試料番号１〜２０の試料について、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。
○：赤錆の発生は認められない。
△：試料表面の一部にわずかな赤錆の発生が認められる。
×：試料全面に赤錆の発生が認められる。
【００３４】
４）耐ホイスカー性：
試料番号１〜２０の試料から３０ｍｍ角の試片を切り出し、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て１５００倍の倍率で観察し、下記の評価基準で耐ホイスカー性を評価した。◎および○を合格範囲とした。
◎：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。
【００３５】
表３に示すように、本発明の試料は何れも、半田濡れ性、特に経時後の半田濡れ性、色彩鮮明性、耐食性、および耐ホイスカー性の項目の何れにおいても良好な性状を示した。
【００３６】
【発明の効果】
以上のように、本発明の着色表面処理鋼板は、無彩色や彩色の着色顔料を含有させた水系ウレタン樹脂や水溶化ロジンを含有させた水系アクリル樹脂、またはこれらの樹脂にさらに防錆剤、水分散性シリカを添加し、さらに、酸化防止剤を添加してなる樹脂液をめっき鋼板に塗布し乾燥させることにより、有色の表面処理皮膜を形成させてたものである。そのため、本発明の着色表面処理鋼板は、メニスコグラフ法による半田濡れ性が１０秒未満の優れた半田濡れ性を有し、色彩が鮮明で装飾性にも優れ、かつ耐食性にも優れたものとなる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a colored surface-treated steel sheet formed by forming a colored surface-treated film having excellent solderability on a plated steel sheet.
[0002]
[Prior art]
In recent years, surface-treated steel sheets applied to applications such as metal containers, electronic component substrates, home appliance chassis, cabinets, etc., from the decorative point of view, achromatic colors such as black, white, gray, red, blue, yellow, green, brown Colored surface-treated steel sheets having a surface-treated film colored in a color such as pink have been used. The surface-treated steel sheet used for these applications may be soldered to the area that needs to be bonded after forming into a predetermined shape, or to be bonded to other parts or members. In the treated steel sheet, the colored and colored surface treatment film had poor solder wettability and could not be applied to applications requiring soldering.
[0003]
As a conventional technique, tin plating is applied to a steel sheet, and then zinc, nickel, and plating mainly containing at least one of cobalt, zinc, nickel, and tin are applied to at least one of zinc, nickel, and cobalt. 2. Description of the Related Art A two-layer plated steel sheet for solder has been disclosed which contains at least one of iron, lead, and copper, and has been subjected to alloy plating exhibiting a potential lower than the standard electrode potential of tin. 1). This plated steel sheet does not have a protective film layer having excellent corrosion resistance such as a chromate-treated film, so that the corrosion resistance is not sufficient, and the formation of a corrosion product film may deteriorate solder wettability. .
[0004]
Further, an Sn—Zn alloy layer is formed on a surface-treated steel sheet having a Sn—Zn alloy layer formed on a steel sheet, or a surface treatment layer formed of either Ni plating or an Fe—Ni diffusion layer formed on the surface thereof. There is disclosed an environment-friendly surface-treated steel sheet for an electronic component in which an inorganic film mainly composed of magnesium phosphate is formed on a Sn-Zn alloy layer (for example, see Patent Document 2). The inorganic coating mainly composed of magnesium phosphate can also impart high corrosion resistance to the Sn-Zn alloy, but because of its stability, particularly when a weakly active or inactive flux containing no chlorine is used. It has a disadvantage of poor solderability.
[0005]
Prior art document information on the present application includes the following.
[0006]
[Patent Document 1]
JP-A-63-277786 [Patent Document 2]
JP-A-2002-249885
[Problems to be solved by the invention]
An object of the present invention is to provide a colored surface-treated steel sheet having excellent solder wettability that can be soldered.
[0008]
[Means for Solving the Problems]
In order to solve the above problems, a colored surface-treated steel sheet according to the present invention is characterized in that a colored surface-treated film having a solder wettability of less than 10 seconds by a meniscograph method is formed on a plated steel sheet.
[0009]
Furthermore, in the colored surface-treated steel sheet of the present invention,
A plated steel sheet, a plated steel sheet formed by forming a zinc layer on a steel sheet, or a plated steel sheet formed by forming a tin layer on a steel sheet, or a plated steel sheet forms a zinc-tin alloy layer on a steel sheet A plated steel sheet, or a plated steel sheet, is formed by forming a two-layered coating layer of a tin layer and a zinc layer on the steel sheet in order from the steel sheet side, or a plated steel sheet is formed by sequentially forming a zinc layer on the steel sheet from the steel sheet side. A plated steel sheet formed by forming a two-layer plating layer of tin and a tin layer, or a plated steel sheet formed by forming a copper layer on a steel sheet, or a plated steel sheet formed by forming a nickel layer on a steel sheet It is a steel plate.
[0010]
Furthermore, in the colored surface-treated steel sheet of the present invention,
The colored surface treatment film is characterized by being a film obtained by applying and drying an aqueous urethane resin containing a coloring pigment, and further comprising a rust inhibitor and water-dispersible silica in the aqueous urethane resin. Or further containing an antioxidant thereon.
[0011]
Furthermore, in the colored surface-treated steel sheet of the present invention,
The colored surface treatment film is characterized by being a film formed by applying and drying an aqueous acrylic resin containing a color pigment and a water-soluble rosin, and further adding a rust preventive agent and an aqueous dispersion to the aqueous acrylic resin. It is characterized by containing a functional silica or further containing an antioxidant.
[0012]
Further, in the colored surface-treated steel sheet of the present invention, the colored pigment is a black pigment.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, a water-based urethane resin having excellent solder wettability, a water-based acrylic resin containing water-soluble rosin, or a resin further containing a rust inhibitor, water-dispersible silica, an antioxidant, and the like, By further containing an achromatic or colored coloring pigment, coating on a plated steel sheet and drying to form a colored surface treatment film, the solder wettability by the meniscograph method has excellent solder wettability of less than 10 seconds. Thus, a colored surface-treated steel sheet having a clear color and excellent decorativeness was obtained.
[0014]
As a plating layer of a plated steel sheet for forming a colored surface treatment film, a single layer of a pure metal such as zinc, tin, copper, nickel, bismuth, or a multilayer formed by laminating two or more layers of these pure metals is used. Plating layer, zinc alloy such as zinc-tin, zinc-copper, zinc-nickel, zinc-aluminum, zinc-iron or zinc-cobalt, tin alloy such as tin-nickel, tin-copper or tin-iron, copper-beryllium And an alloy plating layer of a copper alloy such as copper-nickel or the like can be selected according to the application. For the formation of the plating layer on the steel plate, hot-dip plating, electroplating or the like can be appropriately selected. The steel sheet on which the plating layer is formed may be a plated steel sheet as a substrate on which the following colored surface treatment film is formed on the plating layer as it is. Melting and brightening, or melting and alloying the plating layer of the multilayer plating to form a single alloy layer, or solid-phase diffusion of each metal between plating layers or between steel plate and plating layer, etc. Then, a plated steel sheet as a substrate on which the surface treatment film is formed may be used.
[0015]
Next, a surface treatment film containing a coloring pigment is formed on the plated steel sheet on which a plating layer made of these metals is formed. As the surface treatment film, it is preferable to use an aqueous urethane resin or an aqueous acrylic resin containing water-soluble rosin. The concentration of these aqueous resins is preferably in the range of 100 to 900 g / l. Both organic and inorganic coloring pigments can be used, and one or more colored pigments such as achromatic colors such as black and white, red, blue, and yellow are added to produce the desired color. Let it. The amount added to the resin is preferably 1 to 50% by weight based on the solid content of the resin. When the content is less than 1% by weight, the sharpness of the color tone is poor depending on the color, and when it exceeds 50% by weight, the solderability becomes poor and the corrosion resistance is remarkably reduced. A more preferable addition amount is 3 to 30% by weight.
[0016]
The aqueous urethane resin containing the above color pigment or the aqueous acrylic resin containing water-soluble rosin further contains a rust inhibitor and water-dispersible silica to improve the corrosion resistance of the plated steel sheet, and further prevent oxidation. By containing an agent or the like, solder wettability can be improved. When an aqueous urethane resin is used, as the rust preventive, an organic amine soap alone or as a mixture is used. Organic amine soaps include dotesylamine, oleoylimidazoline, aminopropyl tallowamine, and rosinamine, and amines can be used after forming a salt with carboxylic acid or the like. The styrene / maleic anhydride copolymer is preferably a styrene / maleic anhydride copolymerized alkyl ester / ammonium salt. The amount to be added to the resin solution having the above concentration is preferably from 10 to 100 g / l, and if it is less than 10 g / l, the effect of improving the corrosion resistance is not recognized. If it exceeds 100 g / l, the effect of improving the corrosion resistance is extremely good. However, it is not preferable because solderability is deteriorated.
[0017]
The water-dispersible silica is preferably added to the resin solution having the above concentration in an amount of 10 to 400 g / l. If it is less than 10 g / l, there is no effect on the improvement of corrosion resistance, and if it exceeds 400 g / l, the solder wettability is remarkably reduced. When importance is attached to solder wettability, it is preferable that the amount of silicon adhered to the plated steel sheet be in the range of 10 to 400 mg / m 2 as silicon. When the solder wettability is more important, the range is preferably 10 to 100 mg / m 2 . As water-dispersible silica, silica coated with aluminum on the surface has a dispersing action and is particularly preferable. The particle size of the silica is preferably small from the viewpoint of dispersibility, and is 100 nm or less, more preferably 60 nm or less.
[0018]
The solder wettability can be improved by adding a coloring pigment as described above, and further adding an antioxidant to the aqueous urethane resin containing a rust inhibitor and water-dispersible silica. Examples of the antioxidant include a sulfur-based antioxidant, and a phenol-based antioxidant or a phosphorus-based antioxidant is preferable, and both may be used in combination. The addition amount is preferably 0.5 to 100 g / l. If the amount is less than 0.5 g / l, no effect on improving the oxidation resistance is recognized, and if it exceeds 100 g / l, the viscosity of the liquid increases and coating becomes difficult.
[0019]
When using an aqueous acrylic resin, as the rust preventive, a single or a mixture of the same organic amine soaps as those used for the aqueous urethane resin, and a resin having the above concentration at the same addition amount as in the case of the aqueous urethane resin Add to the solution.
[0020]
Water-soluble rosin is obtained by a method in which a carboxylic acid group in abietic acid molecule, which is a main component of rosin, is neutralized with an amine salt or the like to obtain a rosin soap, and particularly, improves solder wettability after aging. For this purpose, it is contained in an aqueous acrylic resin. It is preferable to add 50 to 600 g / l to the above resin solution. If it is less than 50 g / l, the solder wettability after aging is insufficient, and if it exceeds 600 g / l, it becomes high in viscosity, gels easily, and application becomes difficult.
[0021]
The same water-dispersible silica as that used for the aqueous urethane resin is preferably added to the resin solution having the above concentration in an amount of 10 to 200 g / l. If it is less than 10 g / l, there is no effect on the improvement of corrosion resistance, and if it exceeds 200 g / l, the solder wettability is remarkably reduced.
[0022]
Include the coloring pigment as described above, further improve the solder wettability by adding an antioxidant to the water-based acrylic resin further containing a rust inhibitor and water-dispersible silica, and water-soluble rosin. be able to. Examples of the antioxidant include a sulfur-based antioxidant, and a phenol-based antioxidant or a phosphorus-based antioxidant is preferable, and both may be used in combination. The addition amount is preferably 0.5 to 100 g / l. If the amount is less than 0.5 g / l, no effect on improving the oxidation resistance is recognized, and if it exceeds 100 g / l, the viscosity of the liquid increases and coating becomes difficult.
[0023]
One of the resin liquids obtained as described above is applied to one or both surfaces of the plated steel sheet. In this case, the coating thickness may be changed on the front and back surfaces. Known methods such as a dipping method, a roll coating method, a curtain flow coating method, and a spray coating method can be used as the coating method. However, in the case of performing double-sided coating, it is easy and economical to carry out coating by immersion and drawing in the subsequent step of the continuous plating step, taking advantage of the fact that the treatment liquid is aqueous. After being applied using any of these application methods, it is dried to form a colored surface-treated film on the plated steel sheet to obtain a colored surface-treated steel sheet. The film thickness after drying is preferably 0.05 to 10 μm. If the thickness of the film is less than 0.05 μm, sufficient solder wettability cannot be obtained. In addition, when touched by a finger, a fingerprint is easily formed, and the corrosion resistance is extremely poor. If it exceeds 10 μm, the effect of improving these characteristics is saturated, and the cost advantage is lost.
[0024]
The colored surface-treated steel sheet of the present invention thus obtained preferably has a solder wettability of less than 10 seconds by the following meniscograph method (MIL-STD-883B). When the solder wettability by the meniscograph method exceeds 10 seconds, the solder melted by heating does not sufficiently spread on the surface of the colored surface-treated steel sheet, and a sufficient adhesive force with a partner material to be soldered cannot be obtained. The measurement of solder wettability by the meniscograph method is performed as follows. That is, using a SOLDERCHECKER (MODEL SAT-5000, manufactured by RHESCA), a sample having a width of 10 mm cut out from the colored surface-treated steel sheet is immersed in a flux, and then a solder bath (JIS Z 3282: H60A) maintained at 250 ° C. The sample coated with the above-mentioned flux was immersed at 2 mm / sec at a immersion speed of 2 mm, and the time until the solder was wetted was measured for zero cross time to determine the solder wettability (second).
[0025]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
[0026]
After using a steel sheet (plate thickness 0.5 mm) subjected to annealing and temper rolling as a plating base sheet and performing a cleaning treatment by alkali degreasing and sulfuric acid pickling, the metals or alloys shown in Table 1 are shown in Table 1. Plating was performed using a plating method at a plating amount shown in Table 1, and plated steel sheets indicated by plating numbers A to K were produced. A resin solution containing a yellow, black, and red color pigment shown in Table 2 was applied to both surfaces of these plated steel sheets by using a dipping and drawing method, and then dried at a temperature of 90 ° C. Twenty samples were prepared, and the following characteristics were evaluated. Table 3 shows the evaluation results.
[0027]
[Table 1]
[Table 2]
[Table 3]
[Characteristic evaluation]
1) Solder wettability:
The evaluation was performed by a meniscograph method (MIL-STD-883B) using SOLDERCHECKER (MODEL SAT-5000, manufactured by RESCA). That is, a 10 mm wide specimen was cut out from each of the sample numbers 1 to 20, and was immersed in a weakly active flux containing no chlorine (Lapix RMA, manufactured by Nippon Solder Industry) as shown in Table 3, and then kept at 250 ° C. A sample coated with the above flux was immersed in a solder bath (JIS Z 3282: H60A) at a immersion speed of 2 mm / sec for 2 mm, and the time until the solder was wet was measured. Was evaluated. The shorter the wetting time, the better the solderability. The test was performed in two ways: immediately after the preparation of the sample and after 500 hours of aging at a constant temperature and constant humidity (60 ° C., 95% RH). A value other than x was regarded as a pass range.
◎: less than 3 seconds ○: less than 3 to 5 seconds Δ: less than 5 to 10 seconds ×: 10 seconds or more
2) Color clarity:
Using a spectrophotometer (MODEL: CM-3500d, manufactured by Minolta Co., Ltd.), L value, a value, and b value were measured for the samples of sample numbers 1 to 20, and the respective measured values are shown in Table 4. Those within the range of the value of were shown as 合格 as acceptable criteria. A value out of the acceptance criteria was indicated by x as a failure.
[0032]
[Table 4]
3) Corrosion resistance:
The samples of Sample Nos. 1 to 20 were subjected to a salt spray test in accordance with JIS Z 2371 for 48 hours, and the degree of occurrence of red rust was visually observed, and the corrosion resistance was evaluated based on the following criteria. A value other than x was regarded as a pass range.
：: No occurrence of red rust is observed.
Δ: Slight red rust is observed on a part of the sample surface.
×: Red rust is observed on the entire surface of the sample.
[0034]
4) Whisker resistance:
Using a scanning electron microscope, a 30 mm square specimen was cut out from each of the sample numbers 1 to 20 and exposed to whiskers in a high-temperature and high-humidity atmosphere of 85 ° C. and 85% RH for 30 days. Whisker resistance was evaluated according to the following evaluation criteria. ◎ and ○ were regarded as acceptable ranges.
：: No whisker was observed.
：: Whiskers having a length of less than 10 μm are slightly generated.
Δ: Whiskers having a length of 10 to 30 μm are observed.
X: Whisker having a length exceeding 30 μm was observed.
[0035]
As shown in Table 3, all of the samples of the present invention exhibited favorable properties in the items of solder wettability, particularly, solder wettability after aging, color clarity, corrosion resistance, and whisker resistance.
[0036]
【The invention's effect】
As described above, the colored surface-treated steel sheet of the present invention is a water-based urethane resin containing an achromatic or colored coloring pigment or a water-based acrylic resin containing a water-soluble rosin, or a rust inhibitor to these resins. A colored surface-treated film is formed by applying a resin solution obtained by adding water-dispersible silica and further adding an antioxidant to a plated steel sheet and drying it. Therefore, the colored surface-treated steel sheet of the present invention has an excellent solder wettability of less than 10 seconds by a meniscograph method, a clear color, excellent decorativeness, and excellent corrosion resistance. .
Claims (15)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002364188A JP3828864B2 (en) | 2002-12-16 | 2002-12-16 | Colored surface-treated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002364188A JP3828864B2 (en) | 2002-12-16 | 2002-12-16 | Colored surface-treated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004197123A true JP2004197123A (en) | 2004-07-15 |
| JP3828864B2 JP3828864B2 (en) | 2006-10-04 |
Family
ID=32762128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002364188A Expired - Fee Related JP3828864B2 (en) | 2002-12-16 | 2002-12-16 | Colored surface-treated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3828864B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007147590A (en) * | 2005-11-04 | 2007-06-14 | Furukawa Electric Co Ltd:The | Metal material for electric/electronic component, and electric/electronic component using same |
| JP2007277624A (en) * | 2006-04-05 | 2007-10-25 | Toshiyuki Arai | Colored surface-treated metallic plate |
| KR100787720B1 (en) | 2006-07-24 | 2007-12-24 | 동부제강주식회사 | Cr-free color coating material for metal coated steel sheet and a process for producing cr-free color coated steel sheet using the coating material |
| CN102719162A (en) * | 2012-06-20 | 2012-10-10 | 浙江博星化工涂料有限公司 | Water-based artificial granite paint |
-
2002
- 2002-12-16 JP JP2002364188A patent/JP3828864B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007147590A (en) * | 2005-11-04 | 2007-06-14 | Furukawa Electric Co Ltd:The | Metal material for electric/electronic component, and electric/electronic component using same |
| JP2007277624A (en) * | 2006-04-05 | 2007-10-25 | Toshiyuki Arai | Colored surface-treated metallic plate |
| KR100787720B1 (en) | 2006-07-24 | 2007-12-24 | 동부제강주식회사 | Cr-free color coating material for metal coated steel sheet and a process for producing cr-free color coated steel sheet using the coating material |
| CN102719162A (en) * | 2012-06-20 | 2012-10-10 | 浙江博星化工涂料有限公司 | Water-based artificial granite paint |
| CN102719162B (en) * | 2012-06-20 | 2014-06-04 | 浙江博星化工涂料有限公司 | Water-based artificial granite paint |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3828864B2 (en) | 2006-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5661698B2 (en) | Hot-dip Zn-Al alloy-plated steel sheet | |
| JP6394843B1 (en) | Plated steel sheet | |
| JP3828864B2 (en) | Colored surface-treated steel sheet | |
| JP3503594B2 (en) | Hot-dip Zn-Al alloy coated steel sheet excellent in blackening resistance and method for producing the same | |
| JP2001214280A (en) | Sn SERIES AND Al SERIES PLATED STEEL SHEET COATED WITH Cr- FREE FILM EXCELLENT IN LUBRICITY | |
| JP4339669B2 (en) | Colored surface treatment aluminum plate | |
| JP5661699B2 (en) | Manufacturing method of resin-coated steel sheet | |
| JP3810743B2 (en) | Post-treated plated steel sheet | |
| JP5101250B2 (en) | Resin coated steel sheet | |
| JP3910912B2 (en) | Post-treated steel sheet | |
| JP3810742B2 (en) | Post-treatment liquid for plated steel sheet, post-treated plated steel sheet using the same, and method for producing the same | |
| JP2005139489A (en) | Steel sheet with color-treated surface and heat sink | |
| JP2004204244A (en) | Post-treatment liquid for plated steel sheet, post-treated plated steel sheet with the use of it, and manufacturing method therefor | |
| JP2642284B2 (en) | High strength and high ductility alloyed hot-dip galvanized steel sheet | |
| JPH08269733A (en) | Rust preventive steel sheet for fuel tank | |
| JPH0310089A (en) | Double-ply plated steel sheet for soldering | |
| JP3383124B2 (en) | Hot-dip aluminized steel sheet for building materials excellent in corrosion resistance after painting and method for producing the same | |
| JPS63277786A (en) | Two-ply plated steel sheet for soldering | |
| JP2005144895A (en) | Colored, surface-treated stainless steel plate and box | |
| JPH0536516B2 (en) | ||
| JPH0544006A (en) | Production of alloyed hot dip galvanized steel sheet having excellent workability and corrosion resistance | |
| JP3717114B2 (en) | Molten Sn-Zn plated steel sheet | |
| JP2003342758A (en) | Posttreatment liquid for plated steel sheet improving soldering property, posttreated steel and production method therefor | |
| JP5041770B2 (en) | Post-treated steel sheet | |
| JPS62192597A (en) | Plated steel sheet having superior powdering resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20041130 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060124 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060324 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060627 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060707 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 3828864 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100714 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20090309 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100714 Year of fee payment: 4 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: R3D02 |
|
| A072 | Dismissal of procedure [no reply to invitation to correct request for examination] |
Free format text: JAPANESE INTERMEDIATE CODE: A072 Effective date: 20090623 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100714 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110714 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120714 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130714 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |