JP4379005B2 - Method for producing tin-based plated steel sheet having Si-containing chemical conversion film - Google Patents
Method for producing tin-based plated steel sheet having Si-containing chemical conversion film Download PDFInfo
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- JP4379005B2 JP4379005B2 JP2003159448A JP2003159448A JP4379005B2 JP 4379005 B2 JP4379005 B2 JP 4379005B2 JP 2003159448 A JP2003159448 A JP 2003159448A JP 2003159448 A JP2003159448 A JP 2003159448A JP 4379005 B2 JP4379005 B2 JP 4379005B2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Description
【０００１】
【発明の属する技術分野】
この発明は、DI缶、食缶、飲料缶などに使用される缶用錫めっき鋼板および家電製品のシャーシーや部品ケース等に用いられる半田付け性を要求される錫系めっき鋼板に関するものであって、特に、表面にＰとSiを含有する化成皮膜を有する錫系めっき鋼板の製造方法に関するものである。
【０００２】
【従来の技術】
缶用表面処理鋼板として、従来からぶりきと称される錫めっき鋼板が、また、家電用の半田付けできる鋼板としてPb−Sn合金めっき鋼板が広く用いられており、かかる錫系めっき鋼板は、通常、めっき表面に、重クロム酸やクロム酸などの６価のクロム化合物を含有する水溶液中に浸漬もしくはこの溶液中で電解あるいは塗布することによってクロメート皮膜を形成させるのが一般的であり、このクロメート皮膜によって、錫系めっき層表面の錫酸化物の成長を防止している。
【０００３】
しかし、錫系めっき鋼板に重クロム酸やクロム酸などの６価のクロム酸化物を含有する水溶液中に浸漬処理または電解処理を施すか、あるいは錫系めっき鋼板の表面に水溶液を塗布する場合、作業環境上の安全性確保および廃水処理に多大な費用を要するだけでなく、万が一、事故等でクロメート処理液が漏洩した場合には環境に大きな被害を及ぼす危険性が大きい。昨今の環境問題から、クロムを規制する動きが各分野で進行しており、前記錫系めっき鋼板においてもクロムを使わない化成処理の必要性が増大している。
【０００４】
缶用錫めっき鋼板のクロメート処理に代わる化成処理に関する技術としては、例えば、特許文献１に、りん酸系溶液中で錫めっき鋼板を陰極として直流電解することにより、錫めっき鋼板上にCrを含有しない化成皮膜を形成した錫めっき鋼板の表面処理法が開示されており、また、特許文献２には、化成皮膜中にＰもしくはＰとAlを含有させて、Crを含有しない化成皮膜を錫めっき層表面に施したシームレス缶用電気めっきぶりきが開示されている。
【０００５】
しかしながら、塗料密着性、耐食性などの性能を総合的に見た場合、上掲公報に記載された化成皮膜はいずれも、従来の重クロム酸やクロム酸を含有する溶液によって形成したクロメート皮膜に比べると上記性能が十分に得られているとはいえない。
【０００６】
本発明者らは、ＰとSiを含有する化成処理を施すことによって従来クロメート処理と同等以上の性能が得られる技術を見いだし、かかる技術を、既に出願した特許文献３〜６において提案した。
【０００７】
しかし、十分な性能を得るためには、化成皮膜中のSi量を安定して確保する必要があるが、公知の浸漬法ではSi量のバラツキが大きく、安定したSi量を含有する化成皮膜を得ることが困難であった。特に、３ｍｇ／ｍ２以上のSi量を、より好ましくは５ｍｇ／ｍ２以上のSi量を短時間で安定して確保することが困難であった。
【０００８】
【特許文献１】
特公昭55−24516号公報
【特許文献２】
特公平1-32308号公報
【特許文献３】
特開2002−206191号公報
【特許文献４】
特開2002−275643号公報
【特許文献５】
特開2002−275657号公報
【特許文献６】
特開2002−206191号公報
【０００９】
【発明が解決しようとする課題】
この発明の目的は、錫系めっき層の上層に形成される化成皮膜中に、その皮膜特性を向上させる作用を有するものの環境上の問題から望ましくないとされるCrを含有させることなく、諸特性を満足させるＰとSiを含有する化成皮膜を安定して得ることができる、Si含有化成皮膜を有する錫系めっき鋼板の製造方法を提供することにある。
【００１０】
【課題を解決しようとするための手段】
以下にこの発明をさらに詳細に説明する。
錫系めっき層の上層に、ＰとSiを含有する化成皮膜を安定して形成させる方法として、特に、３ｍｇ／ｍ２以上のSi量を、より好ましくは５ｍｇ／ｍ２以上のSi量を安定して得られる製造方法を鋭意研究を重ねた結果、りん酸イオンとシランカップリング剤を含有する化成処理液に錫系めっき鋼板を浸漬または該化成処理液を塗布し、化成処理液が鋼板のめっき層上に存在した状態で該鋼板を80〜200℃に加熱して乾燥させることにより、前記シランカップリング剤のアルコキシシリル基が加水分解したシラノール基と、めっき層表面のＯＨ基との脱水縮合反応が生じるように化成皮膜を形成し、次いで該化成皮膜上に残存する未反応のシランカップリング剤やリン酸イオンを除去するために水洗した後、再度乾燥させる方法により、短時間で安定して化成皮膜が得られることを新規に見いだした。
【００１１】
ここで、前記化成処理液は、Sn、FeおよびNiから選択される１種の金属塩をさらに含有することが好ましい。
また、前記化成処理液は、酸化剤、エッチング剤から選ばれる１種をさらに含有することが好ましい。
更に、前記化成処理液に界面活性剤を含有させると、加熱乾燥時の鋼板上での化成処理液の膜がより均一となり安定した化成皮膜が得られるのでより好適である。
【００１２】
【発明の実施の形態】
以下にこの発明の構成を詳細に説明する。
この発明でいう「錫系めっき鋼板」とは、鋼板の片面または両面に錫を含むめっき層を有するものである。錫を含むめっき層としては、Snと、Ni、Fe、Zn、BiおよびCuのうちから選んだ１種または２種以上を含有する合金層、あるいは金属錫層と、該金属錫層と鋼板との間に形成した、FeおよびNiのうちから選んだ１種または２種を含有する錫合金層の中間層との２層からなるめっき層等が挙げられるが、特に限定されるものではない。
【００１３】
また、前記中間層には、Fe−Ni合金層と、該Fe−Ni合金層の上面に形成したFe−Sn−Ni合金層の２層からなる場合も本発明に含まれる。このとき、Fe−Ni合金層は、Ni／（Fe＋Ni）質量比が0.02〜0.50の範囲であることが好ましい。Ni／（Fe＋Ni）質量比が0.02未満だと、Fe−Sn合金主体の四角柱状の結晶からなり、隙間部分が多く耐食性が低下するのに加えて、シラン皮膜も連続的に形成されにくくなるため塗料密着性の向上効果が小さいからである。一方、Ni／（Fe＋Ni）質量比が0.50を超えると、Fe−Sn−Ni合金の結晶状態が疎となり、鋼板自体の耐食性が劣化するとともに、シラン皮膜も緻密に形成されないため、塗料密着性の向上効果が小さいからである。なお、鋼板と、錫を含有するめっき層の間にニッケルめっき等の下地めっきを適宜施したものも本発明に含まれる。
【００１４】
ＰとSiを含有させた化成皮膜の形成方法としては、例えば、りん酸系化成処理によって行うことが好ましく、この場合、化成処理液中のＰの供給源としては、りん酸イオン換算で１〜80g/lのりん酸、りん酸ナトリウム、りん酸アルミニウム、りん酸カリウム等の金属塩、および／または、１水素りん酸塩など使用することがより好適である。なお、本発明でいうリン酸イオンとは、具体的にはオルトリン酸イオン（ＰＯ４ ３−）を意味する。
【００１５】
なお、化成処理液中のりん酸イオン換算の好適範囲を１〜80g/lとした理由は、１g/l未満だと、塗料密着性と耐食性が劣るからであり、一方、80g/lを超えると、化成皮膜に欠陥が生じやすくなり、塗料密着性や耐食性が低下するからであり、加えて、未反応のりん酸が残存し塗料密着性が低下する場合もあるからである。
【００１６】
化成処理液中には、Siの供給源としてはシランカップリング剤を用いる。シランカップリング剤の一般化学式は、Ｘ−Si−ＯＲ２ｏｒ３（ＯＲ：アルコキシ基）であり、アルコキシシリル基（Si−ＯＲ）が水により加水分解されてシラノール基を生成し、金属表面のＯＨ基との脱水縮合反応により密着する。化成処理液のｐＨは1.5〜5.5の範囲にすることが好ましい。すなわち、化成処理液のｐＨを1.5〜5.5の範囲に調整すれば、シランカップリング剤を化成処理液中に均一に溶解することができる。
【００１７】
尚、シランカップリング剤としては、３-メタクリロキシプロピルトリメトキシシラン、２-（３，４-エポキシシクロヘキシル）エチルトリメトキシシラン、３-グリシドキシプロピルトリメトキシシラン、Ｎ-２-（アミノエチル）３-アミノプロピルトリメトキシシラン、Ｎ-２（アミノエチル）３-アミノプロピルメチルジメトキシシラン、３-アミノプロピルトリエトキシシラン、Ｎ-フェニル-３-アミノプロピルトリメトキシシラン、３-メルカプトプロピルメトキシシラン、３-クロロプロピルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２-メトキシエトキシ）シラン、アミノ基の存在する、Ｎ-２（アミノエチル）３-アミノプロピルトリメトキシシラン、Ｎ-２-（アミノエチル）３-アミノプロピルメチルジメトキシシラン、３‐アミノプロピルトリエトキシシランなどが使用できるが、特にシランカップリング剤の一般化学式におけるＸ-Si-ＯＲ２ or ３のＸにエポキシ基が存在する２-（３，４-エポキシシクロヘキシル）エチルトリメトキシシランや３−グリシドキシプロピルトリメトキシシランが好適である。
【００１８】
尚、化成処理液には、Sn、Fe、Niの金属塩、例えば、SnCl2、FeCl2、NiCl2、SnSO4、FeSO4、NiSO4などの金属塩を適宜添加することができる。この場合には、促進剤として塩素酸ナトリウム、亜硝酸塩などの酸化剤、フッ素イオンなどのエッチング剤を適宜添加してもよい。
【００１９】
また、化成処理液の均一処理性を向上させる目的で、ラウリル硫酸ナトリウム、アセチレングリコールなどの界面活性剤を適宜添加することがより好適である。
【００２０】
錫系めっきされた鋼板は、前記化成処理液に40〜80℃で１〜５秒間浸漬後、ロール等で適当な厚さの化成処理液の膜になるように絞った後、化成処理液が鋼板上に存在した状態で該鋼板を80〜200℃に加熱して乾燥させる。この加熱乾燥工程において、前述したアルコキシシリル基（Si−ＯＲ）の加水分解したシラノール基と金属表面のＯＨ基とが脱水縮合反応が促進されるため、化成皮膜形成が安定して行われるのである。浸漬処理だけでは脱水縮合反応が遅いため、３ｍｇ／ｍ２以上の皮膜中のSi量を得ることは困難であり、より好ましい５ｍｇ／ｍ２以上の皮膜中のSi量を得ることは無論困難である。
【００２１】
加熱は、化成処理液が鋼板上に存在したままで行う必要があり、このため、通常、工業的に行われている熱風を吹き付ける加熱方法は好ましくなく、赤外線加熱、誘導加熱、輻射加熱が好適である。
【００２２】
加熱温度は、鋼板温度として80〜200℃とする必要がある。80℃未満では、前記脱水縮合反応の速度が遅く、化成皮膜形成が不安定となり、十分なSi量が得られないからであり、また、200℃を超えると、脱水縮合反応は十分早く進むが、錫系めっき表面での錫の酸化が起こるばかりでなく、加熱エネルギーを過剰に消費するので好ましくない。
【００２３】
化成処理液を加熱乾燥させた後は、直ちに水洗し、未反応のシランカップリング剤やりん酸イオンを洗い落とす。未反応のシランカップリング剤やりん酸イオンが表面に残存していると、耐食性が劣るので、必ず水洗除去する必要がある。水洗後の乾燥は通常の熱風乾燥を行えば良い。
【００２４】
なお、めっき層上への化成処理液の膜の形成は、上述した浸漬処理で行う代わりに、鋼板上の液の膜厚制御が容易なロールコーターを用いて化成処理液を塗布する方法によって行っても良い。
【００２５】
以上のことから、本発明では、錫系めっき表面に、ＰおよびSiを含有する化成皮膜を安定して形成することに成功したのである。
【００２６】
次にこの発明に従う具体的な製造方法の一例を説明する。
冷延鋼板にSnめっきを施した後、錫の融点（231.9℃）以上の温度で加熱溶融(リフロー)処理を行い、Fe−Sn合金層（中間層）と金属Sn層（上層）の２層からなる錫系めっき層を形成させ、引き続き、浸漬処理によって化成処理を行う。尚、リフロー処理後に表面に生成した錫酸化物を除去するため、15g/lの炭酸ナトリウム水溶液中で１C/dm2の陰極処理を行ってもよい。
【００２７】
化成処理液としては、リン酸イオン換算で１〜80g/lのリン酸、錫イオン換算で0.001〜10g/lの塩化第一錫、0.1〜1.0 g/lの塩素酸ナトリウムを含有し、さらにシランカップリング剤を0.5〜20.0 mass％添加した水溶液を用いる。
【００２８】
化成処理の条件は、温度を40〜80℃、処理（浸漬）時間を1〜5秒とすることが好ましい。化成処理後の錫めっき鋼板は、リンガーロールで絞って化成処理液の膜を所定の膜厚に制御し、赤外線加熱装置により該鋼板を110℃に加熱し乾燥させ、その後、直ちに水洗し、35〜90℃の温風で乾燥する。
【００２９】
尚、上述したところは、この発明の実施形態の一例を示したにすぎず、請求の範囲において種々の変更を加えることができる。
【００３０】
【実施例】
次に、この発明の実施例について以下で詳細に説明する。
実施例１〜８
板厚0.1〜2.0 ｍｍの低炭素鋼または極低炭素鋼からなる冷延鋼板の両面に、表１に示すめっき構成の錫系めっき層を片面当り10ｇ／ｍ２の付着量で形成した後、表２に示す３種類の化成処理液Ａ〜Ｃから選んだ表１に示す化成処理液を用いて浸漬あるいはロール塗布を行い、加熱乾燥後、直ちに水洗し、温風乾燥することにより、化成皮膜を形成した。化成皮膜形成のため加熱乾燥させるときの加熱方法および加熱温度についても表１に示す。
【００３１】
比較例１〜４
尚、比較のため、化成皮膜の形成方法がこの発明の適正範囲外である製造方法でも錫系めっき鋼板を製造した。
【００３２】
【表１】
【表２】
（化成皮膜の評価）
実施例および比較例の各錫系めっき鋼板について、化成皮膜中のＰおよびSi量の測定を蛍光Ｘ線による表面分析により行った。表１にそれらの評価結果を示す。
【００３５】
（耐食性の評価）
実施例および比較例の各錫系めっき鋼板について、塩水噴霧試験（JIS Z 2371準拠）を24時間行い、赤錆発生面積率（％）で耐食性を評価した。表１にその評価結果を示す。
【００３６】
表１の評価結果から明らかなように、実施例1〜８はいずれも、化成皮膜中のSi量は安定して３ｍｇ／ｍ２以上であり、良好な耐食性を示し、より好ましい５ｍｇ／ｍ２以上の範囲ではさらに良好な耐食性を示した。一方、比較例１〜３はいずれも、化成皮膜中のSi量が３ｍｇ／ｍ２未満であり、実用レベルにないことがわかる。
【００３７】
【発明の効果】
この発明は、錫系めっき層の上層に形成される化成皮膜中に、その皮膜特性を向上させる作用を有するものの環境上の問題から望ましくないとされるCrを含有させることなく、諸特性を満足させるＰとSiを含有する化成皮膜を安定して得ることができる、Si含有化成皮膜を有する錫系めっき鋼板の製造方法の提供が可能になった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a tin-plated steel sheet for cans used in DI cans, food cans, beverage cans and the like, and a tin-based plated steel sheet required for solderability to be used for a chassis or a component case of a home appliance. In particular, the present invention relates to a method for producing a tin-based plated steel sheet having a chemical conversion film containing P and Si on the surface.
[0002]
[Prior art]
As a surface-treated steel sheet for cans, a tin-plated steel sheet conventionally referred to as tinplate, and a Pb-Sn alloy-plated steel sheet is widely used as a solderable steel sheet for home appliances. Usually, it is common to form a chromate film on the plating surface by dipping in an aqueous solution containing a hexavalent chromium compound such as dichromic acid or chromic acid, or by electrolysis or coating in this solution. The chromate film prevents the growth of tin oxide on the surface of the tin-based plating layer.
[0003]
However, when the tin-plated steel sheet is subjected to immersion treatment or electrolytic treatment in an aqueous solution containing hexavalent chromium oxide such as dichromic acid or chromic acid, or when the aqueous solution is applied to the surface of the tin-plated steel sheet, Not only does it cost a lot of money to ensure safety in the work environment and wastewater treatment, but in the unlikely event that the chromate treatment liquid leaks due to an accident or the like, there is a great risk of serious damage to the environment. Due to recent environmental problems, movements to regulate chromium are progressing in various fields, and the need for chemical conversion treatment without using chromium is increasing even in the tin-based plated steel sheet.
[0004]
As a technology regarding chemical conversion treatment instead of chromate treatment of tin-plated steel sheets for cans, for example, Patent Document 1 contains Cr on tin-plated steel sheets by direct current electrolysis using a tin-plated steel sheet as a cathode in a phosphoric acid solution. The surface treatment method of the tin plating steel plate which formed the chemical conversion film which does not carry out is disclosed, and patent document 2 makes P or P, and Al contain in a chemical conversion film, and tin-plates the chemical conversion film which does not contain Cr An electroplating tin for seamless cans applied to the surface of the layer is disclosed.
[0005]
However, when performance such as paint adhesion and corrosion resistance is viewed comprehensively, all of the chemical conversion films described in the above publications are compared with conventional chromate films formed by a solution containing dichromic acid or chromic acid. It cannot be said that the above performance is sufficiently obtained.
[0006]
The inventors of the present invention have found a technique in which performance equivalent to or higher than that of a conventional chromate treatment can be obtained by performing a chemical conversion treatment containing P and Si, and proposed such a technology in Patent Documents 3 to 6 already filed.
[0007]
However, in order to obtain sufficient performance, it is necessary to stably secure the amount of Si in the chemical conversion film. However, in the known immersion method, there is a large variation in the amount of Si, and a chemical conversion film containing a stable amount of Si is required. It was difficult to get. In particular, it has been difficult to stably secure an Si amount of 3 mg / m 2 or more, more preferably an Si amount of 5 mg / m 2 or more in a short time.
[0008]
[Patent Document 1]
Japanese Patent Publication No.55-24516 [Patent Document 2]
Japanese Patent Publication No. 1-332308 [Patent Document 3]
JP 2002-206191 A [Patent Document 4]
JP 2002-275643 A [Patent Document 5]
JP 2002-275657 A [Patent Document 6]
Japanese Patent Laid-Open No. 2002-206191
[Problems to be solved by the invention]
An object of the present invention is to provide various properties without adding Cr, which is not desirable due to environmental problems, although it has an effect of improving the coating properties in the chemical conversion coating formed on the upper layer of the tin-based plating layer. It is providing the manufacturing method of the tin-plated steel plate which has Si and a chemical conversion film which can obtain stably the chemical conversion film containing P and Si which satisfies these.
[0010]
[Means for solving problems]
The present invention is described in further detail below.
As a method for stably forming a chemical conversion film containing P and Si on the upper layer of the tin-based plating layer, particularly an amount of Si of 3 mg / m 2 or more, more preferably an amount of Si of 5 mg / m 2 or more is stable. As a result of diligent research on the production method obtained, the tin-plated steel sheet is immersed in or coated with a chemical conversion treatment solution containing phosphate ions and a silane coupling agent. the Rukoto dried by heating steel sheet to 80 to 200 ° C. in a state that existed in the plating layer, alkoxysilyl group of the silane coupling agent is a silanol group by hydrolysis, the OH groups of the plating layer surface A chemical conversion film is formed so as to cause a dehydration condensation reaction , and then washed with water to remove unreacted silane coupling agent and phosphate ions remaining on the chemical conversion film , and then dried again in a short time. Cheap It was newly found that a chemical conversion film can be obtained.
[0011]
Here, it is preferable that the said chemical conversion liquid further contains 1 type of metal salt selected from Sn, Fe, and Ni.
Moreover, it is preferable that the said chemical conversion liquid further contains 1 type chosen from an oxidizing agent and an etching agent.
Furthermore, it is more preferable to add a surfactant to the chemical conversion treatment liquid because the film of the chemical conversion treatment liquid on the steel sheet during heat drying becomes more uniform and a stable chemical conversion film can be obtained.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The configuration of the present invention will be described in detail below.
The “tin-plated steel sheet” in the present invention has a plating layer containing tin on one or both surfaces of the steel sheet. As a plating layer containing tin, Sn, an alloy layer containing one or more selected from Ni, Fe, Zn, Bi and Cu, or a metal tin layer, the metal tin layer and a steel plate, There are, but not limited to, a plating layer composed of two layers with an intermediate layer of a tin alloy layer containing one or two selected from Fe and Ni formed between the two.
[0013]
Further, the present invention includes a case where the intermediate layer is composed of two layers of an Fe—Ni alloy layer and an Fe—Sn—Ni alloy layer formed on the upper surface of the Fe—Ni alloy layer. At this time, the Fe—Ni alloy layer preferably has a Ni / (Fe + Ni) mass ratio in the range of 0.02 to 0.50. When the Ni / (Fe + Ni) mass ratio is less than 0.02, it consists of a square columnar crystal mainly composed of Fe-Sn alloy, and there are many gaps and corrosion resistance is lowered. This is because the effect of improving paint adhesion is small. On the other hand, if the Ni / (Fe + Ni) mass ratio exceeds 0.50, the crystalline state of the Fe-Sn-Ni alloy becomes sparse, the corrosion resistance of the steel sheet itself deteriorates, and the silane film is not formed densely, so that the paint adhesion This is because the improvement effect is small. It should be noted that the present invention includes a steel plate and a plating layer containing tin appropriately subjected to base plating such as nickel plating.
[0014]
As a method for forming a chemical conversion film containing P and Si, for example, it is preferable to carry out by a phosphoric acid-based chemical conversion treatment. In this case, as a supply source of P in the chemical conversion treatment liquid, More preferably, 80 g / l of phosphoric acid, sodium phosphate, aluminum phosphate, potassium phosphate and other metal salts and / or monohydrogen phosphate are used. In addition, the phosphate ion as used in the field of this invention specifically means an orthophosphate ion (PO 4 3− ).
[0015]
The reason why the preferable range in terms of phosphate ion in the chemical conversion solution is 1 to 80 g / l is that if it is less than 1 g / l, the paint adhesion and the corrosion resistance are inferior, whereas it exceeds 80 g / l. This is because defects are likely to occur in the chemical conversion film, and paint adhesion and corrosion resistance are lowered. In addition, unreacted phosphoric acid may remain and paint adhesion may be lowered.
[0016]
In the chemical conversion solution, a silane coupling agent is used as a Si supply source. The general chemical formula of the silane coupling agent is X-Si- OR2or3 (OR: alkoxy group), where the alkoxysilyl group (Si-OR) is hydrolyzed with water to produce a silanol group, and the OH group on the metal surface It adheres by dehydration condensation reaction. The pH of the chemical conversion solution is preferably in the range of 1.5 to 5.5. That is, the silane coupling agent can be uniformly dissolved in the chemical conversion treatment liquid by adjusting the pH of the chemical conversion treatment liquid to a range of 1.5 to 5.5.
[0017]
As the silane coupling agent, 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-2- (aminoethyl) ) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethoxysilane 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane with amino group, N-2- (amino Ethyl) 3-aminopropylmethyldimethoxysilane Although 3-aminopropyltriethoxysilane, etc. silane can be used, in particular there are epoxy groups X of X-Si-OR 2 or 3 in the general formula of the silane coupling agent 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane and 3-glycidoxypropyltrimethoxysilane are preferred.
[0018]
Note that a metal salt of Sn, Fe, Ni, for example, a metal salt such as SnCl 2 , FeCl 2 , NiCl 2 , SnSO 4 , FeSO 4 , and NiSO 4 can be appropriately added to the chemical conversion solution. In this case, an oxidizing agent such as sodium chlorate or nitrite, or an etching agent such as fluorine ion may be added as an accelerator.
[0019]
Further, for the purpose of improving the uniform processability of the chemical conversion treatment liquid, it is more preferable to appropriately add a surfactant such as sodium lauryl sulfate or acetylene glycol.
[0020]
After the tin-plated steel sheet is immersed in the chemical conversion treatment solution at 40 to 80 ° C. for 1 to 5 seconds and then squeezed with a roll or the like to form a film of a chemical conversion treatment solution having an appropriate thickness, The steel sheet is heated to 80 to 200 ° C. and dried while existing on the steel sheet. In this heating and drying step, the dehydration condensation reaction is promoted between the hydrolyzed silanol group of the alkoxysilyl group (Si-OR) and the OH group on the metal surface, so that the formation of the chemical conversion film is stably performed. . Since the dehydration condensation reaction is slow only by the dipping treatment, it is difficult to obtain the Si amount in the film of 3 mg / m 2 or more, and of course, it is difficult to obtain the more preferable Si amount in the film of 5 mg / m 2 or more. is there.
[0021]
Heating needs to be performed while the chemical conversion treatment solution is still present on the steel sheet. For this reason, a heating method in which hot air is blown industrially is not preferable, and infrared heating, induction heating, and radiation heating are preferable. It is.
[0022]
The heating temperature needs to be 80 to 200 ° C. as the steel plate temperature. If it is less than 80 ° C., the rate of the dehydration condensation reaction is slow, the formation of the conversion film becomes unstable, and a sufficient amount of Si cannot be obtained. If it exceeds 200 ° C., the dehydration condensation reaction proceeds sufficiently quickly. This is not preferable because not only oxidation of tin on the surface of the tin-based plating occurs, but also excessive heating energy is consumed.
[0023]
After the chemical conversion solution is heated and dried, it is immediately washed with water to wash off unreacted silane coupling agent and phosphate ions. If unreacted silane coupling agent or phosphate ions remain on the surface, the corrosion resistance is inferior and must be washed away with water. What is necessary is just to perform normal hot-air drying after drying with water.
[0024]
In addition, formation of the film of the chemical conversion treatment liquid on the plating layer is performed by a method of applying the chemical conversion treatment liquid using a roll coater that can easily control the film thickness of the liquid on the steel plate, instead of performing the above-described immersion treatment. May be.
[0025]
From the above, the present invention succeeded in stably forming a chemical conversion film containing P and Si on the surface of the tin-based plating.
[0026]
Next, an example of a specific manufacturing method according to the present invention will be described.
After Sn plating is applied to the cold-rolled steel sheet, it is heated and melted (reflowed) at a temperature equal to or higher than the melting point of tin (231.9 ° C), and two layers of Fe-Sn alloy layer (intermediate layer) and metal Sn layer (upper layer) Then, a tin-based plating layer is formed, followed by chemical conversion treatment by dipping treatment. In order to remove tin oxide formed on the surface after the reflow treatment, a cathode treatment of 1 C / dm 2 may be performed in a 15 g / l sodium carbonate aqueous solution.
[0027]
The chemical conversion treatment solution contains 1 to 80 g / l phosphoric acid in terms of phosphate ions, 0.001 to 10 g / l stannous chloride in terms of tin ions, 0.1 to 1.0 g / l sodium chlorate, and An aqueous solution to which 0.5 to 20.0 mass% of a silane coupling agent is added is used.
[0028]
The conditions for the chemical conversion treatment are preferably a temperature of 40 to 80 ° C. and a treatment (immersion) time of 1 to 5 seconds. The tin-plated steel sheet after the chemical conversion treatment is squeezed with a ringer roll to control the film of the chemical conversion treatment liquid to a predetermined film thickness, and the steel sheet is heated to 110 ° C. by an infrared heating device and dried, and then immediately washed with water. Dry with warm air of ~ 90 ° C.
[0029]
The above description only shows an example of the embodiment of the present invention, and various modifications can be made within the scope of the claims.
[0030]
【Example】
Next, embodiments of the present invention will be described in detail below.
Examples 1-8
After forming a tin-based plating layer having a plating configuration shown in Table 1 on both sides of a cold-rolled steel plate made of low-carbon steel or ultra-low-carbon steel having a thickness of 0.1 to 2.0 mm with an adhesion amount of 10 g / m 2 per side, Chemical conversion coating is performed by dipping or roll coating using the chemical conversion treatment liquid shown in Table 1 selected from the three types of chemical conversion liquids A to C shown in Table 2, followed by heat drying, followed by water washing and hot air drying. Formed. Table 1 also shows the heating method and heating temperature when heating and drying for forming the chemical conversion film.
[0031]
Comparative Examples 1-4
For comparison, a tin-plated steel sheet was also manufactured by a manufacturing method in which the method for forming the chemical conversion film is outside the proper range of the present invention.
[0032]
[Table 1]
[Table 2]
(Evaluation of chemical conversion film)
About each tin-type plated steel plate of an Example and a comparative example, the measurement of the amount of P and Si in a chemical conversion film was performed by the surface analysis by a fluorescent X ray. Table 1 shows the evaluation results.
[0035]
(Evaluation of corrosion resistance)
About each tin-plated steel plate of an Example and a comparative example, the salt spray test (JIS Z 2371 conformity) was done for 24 hours, and corrosion resistance was evaluated by red rust generation | occurrence | production area ratio (%). Table 1 shows the evaluation results.
[0036]
As is clear from the evaluation results in Table 1, in all of Examples 1 to 8, the Si amount in the chemical conversion film is stably 3 mg / m 2 or more, exhibits good corrosion resistance, and is more preferably 5 mg / m 2. In the above range, better corrosion resistance was exhibited. On the other hand, all of Comparative Examples 1 to 3 show that the amount of Si in the chemical conversion film is less than 3 mg / m 2, which is not at a practical level.
[0037]
【The invention's effect】
This invention satisfies various properties without containing Cr, which is not desirable due to environmental problems, although it has the effect of improving the coating properties in the chemical conversion coating formed on the upper layer of the tin-based plating layer. It has become possible to provide a method for producing a tin-based plated steel sheet having a Si-containing chemical conversion film that can stably obtain a chemical conversion film containing P and Si.
Claims (5)
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| JP2003159448A JP4379005B2 (en) | 2002-06-05 | 2003-06-04 | Method for producing tin-based plated steel sheet having Si-containing chemical conversion film |
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| JP2003159448A JP4379005B2 (en) | 2002-06-05 | 2003-06-04 | Method for producing tin-based plated steel sheet having Si-containing chemical conversion film |
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| US8147983B2 (en) | 2005-10-20 | 2012-04-03 | Jfe Steel Corporation | Tin-plated steel sheet |
| JP5651280B2 (en) * | 2007-02-23 | 2015-01-07 | Ｊｆｅスチール株式会社 | Surface-treated galvanized steel sheet with excellent corrosion resistance and surface appearance after continuous high-speed press forming and method for producing the same |
| CN102803561A (en) | 2010-03-23 | 2012-11-28 | 新日本制铁株式会社 | Steel sheet for container and method for producing same |
| US8133594B2 (en) | 2010-06-04 | 2012-03-13 | Nippon Steel Corporation | Steel sheet for container use |
| JP6806152B2 (en) | 2016-05-24 | 2021-01-06 | 日本製鉄株式会社 | Sn-based alloy plated steel sheet |
| WO2017204265A1 (en) | 2016-05-24 | 2017-11-30 | 新日鐵住金株式会社 | Sn-plated steel sheet |
| JP6870731B2 (en) | 2017-04-13 | 2021-05-12 | 日本製鉄株式会社 | Manufacturing method of Sn-plated steel sheet and Sn-plated steel sheet |
| US11598009B2 (en) | 2018-03-01 | 2023-03-07 | Nippon Steel Corporation | Sn-plated steel sheet and method for manufacturing Sn-plated steel sheet |
| CN114829675B (en) | 2019-12-19 | 2024-03-08 | 日本制铁株式会社 | Sn-based plated steel sheet |
| CN111172524B (en) * | 2020-01-19 | 2021-07-06 | 东北大学 | Preparation method and use method of environment-friendly nano plating solution for tin plate |
| CN115315541B (en) | 2020-03-26 | 2023-10-24 | 日本制铁株式会社 | Sn-based plated steel sheet |
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