JP5338823B2 - Surface-treated steel sheet and manufacturing method thereof - Google Patents
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本発明は、耐錆性、耐食性に優れ、さらに皮膜の経時安定性(黄変性、塗料密着性)にも優れる表面処理鋼板およびその製造方法に関し、特に電解クロム酸処理鋼板(ティンフリースチール、以下TFS)代替のCrフリー鋼板として好適な表面処理鋼板およびその製造方法に関する。 The present invention relates to a surface-treated steel sheet excellent in rust resistance and corrosion resistance, and also excellent in film stability over time (yellowing, paint adhesion) and a method for producing the same. The present invention relates to a surface-treated steel sheet suitable as an alternative Cr-free steel sheet and a manufacturing method thereof.
鋼板表面に金属CrとCr酸化物を有するTFSは、塗装前の一次防錆性と塗料密着性に優れる性質を有することから、特に塗装缶用の下地鋼板として広く使用されている。TFSはその製造過程で6価のCrを含む水溶液にて電解処理が施される。電解処理にて形成される皮膜は0価と3価のCrのみであり、電解処理後は水や湯洗浄を行うことから、6価のCrは皮膜に含有されない。しかしながらCrを含有する処理液を使用することから、排水処理、排気処理等の環境負荷対応設備費用が今後さらに増加することが懸念され、また製品は0価と3価のCrのみであってもCrに対するイメージから一般的に敬遠される可能性もある。ますます環境問題がクローズアップされる今後は、皮膜中にCrを含まない脱Cr化製品(Crフリー鋼板)への要求が高まると考えられる。 TFS having metal Cr and Cr oxide on the steel sheet surface is widely used as a base steel sheet for coating cans because it has excellent primary rust prevention properties and paint adhesion before coating. TFS is subjected to electrolytic treatment with an aqueous solution containing hexavalent Cr in the manufacturing process. The film formed by the electrolytic treatment is only 0-valent and trivalent Cr, and after the electrolytic treatment, washing with water or hot water is performed, so hexavalent Cr is not contained in the film. However, since a treatment liquid containing Cr is used, there is a concern that the cost of equipment for environmental loads such as wastewater treatment and exhaust treatment will increase further in the future, and even if the product is only zero-valent and trivalent Cr There is also the possibility of being generally shunned from the image of Cr. In the future, when environmental problems are increasingly being raised, it is considered that there is an increasing demand for de-Cr products that do not contain Cr in the coating (Cr-free steel plates).
TFS代替のCrフリー鋼板として、特許文献1〜3等がある。特許文献1は、鋼板上にリン酸塩層を有する皮膜構造を有する。鋼板上に化成処理皮膜のみの場合、金属めっきに比べバリア効果が低いためか、耐錆性や耐食性が劣る問題がある。化成処理の主流であるクロメートでさえも化成処理皮膜単独では缶用鋼板としての性能を十分満足しないため、下層に金属Cr層を有する皮膜構造を有する。したがって、特許文献1に開示された技術も耐錆性や耐食性を満足するものでは無かった。 Patent Documents 1 to 3 and the like are available as Cr-free steel plates instead of TFS. Patent Document 1 has a film structure having a phosphate layer on a steel plate. In the case of only the chemical conversion treatment film on the steel plate, there is a problem that the rust resistance and the corrosion resistance are inferior because the barrier effect is lower than the metal plating. Even chromate, which is the mainstream of chemical conversion treatment, has a film structure having a metal Cr layer in the lower layer because the chemical conversion treatment film alone does not sufficiently satisfy the performance as a steel plate for cans. Therefore, the technique disclosed in Patent Document 1 does not satisfy rust resistance and corrosion resistance.
一方、特許文献2は、鋼板上にSn、Zn、Niから選ばれた少なくとも1種の金属と鉄との合金層とその上層にシランカップリング剤処理層とさらにその上層に熱可塑性ポリエステル樹脂層を有する鋼板をプレス成形した缶である。これはプレス成形に耐えうるポリエステルフィルムとの密着性に優れた下地皮膜層としてシランカップリング処理層を有する。シランカップリング処理薬剤は高価であり、TFS代替としてプレス加工しない場合や塗装缶の場合にはかなりのコストアップになってしまい、実用的でない。また食品用途として従来使用されたことのない皮膜層を有する場合、食品用缶としての適正を判断するための試験の費用と時間を必要とする。 On the other hand, Patent Document 2 discloses an alloy layer of at least one metal selected from Sn, Zn, and Ni on a steel plate, a silane coupling agent-treated layer on the upper layer, and a thermoplastic polyester resin layer on the upper layer. It is the can which press-formed the steel plate which has this. This has a silane coupling treatment layer as an undercoat layer having excellent adhesion to a polyester film that can withstand press molding. The silane coupling treatment chemical is expensive, and it is not practical because the cost is considerably increased when it is not pressed as a substitute for TFS or in the case of a paint can. Moreover, when it has the film layer which has not been used conventionally for food use, the cost and time of the test for judging the appropriateness as a food can are required.
また、特許文献3は、鋼板上にFe−Ni拡散層とその上層にNi層、さらにその上層にNi−Sn合金層と最上層に0.1mg/m2以上10mg/m2以下の非合金化金属Sn層を有する皮膜構造を有する。非合金化金属Sn層を有する場合、その表層にSn酸化物皮膜が形成される。Sn酸化物皮膜は脆くて凝集破壊を起こしやすいため、塗膜剥離の原因となりやすい。また経時によりSn酸化物皮膜量は増加し、塗料密着性が劣化するだけでなく、表面が黄変する問題も引き起こす。そのため、従来の錫めっき鋼板ではSn層上にクロメート処理やリン酸塩処理等の化成処理を施すことによって、Sn酸化物を還元させたり、それ以上酸化物皮膜が形成されにくいようにしている。特許文献3もクロメート処理皮膜やリン酸塩処理皮膜を有しない場合は、経時により塗料密着性の劣化や外観の黄変を生じるといった問題を生じる。 Further, Patent Document 3, Ni layer and its upper Fe-Ni diffusion layer on the steel sheet, further Ni-Sn alloy layer and the top layer to 0.1 mg / m 2 or more 10 mg / m 2 or less of unalloyed thereon It has a film structure having a metallized Sn layer. When it has a non-alloyed metal Sn layer, a Sn oxide film is formed in the surface layer. Since the Sn oxide film is brittle and easily causes cohesive failure, it tends to cause peeling of the coating film. Also, the amount of Sn oxide film increases with time, which not only deteriorates the paint adhesion, but also causes the problem of yellowing of the surface. For this reason, in conventional tin-plated steel sheets, the Sn layer is subjected to chemical conversion treatment such as chromate treatment or phosphate treatment to reduce Sn oxide or prevent the formation of an oxide film any more. Patent Document 3 also has a problem that when it does not have a chromate-treated film or a phosphate-treated film, the paint adhesion deteriorates over time and the appearance yellows.
一方、Sn付着量を低減した溶接缶用薄めっきぶりきに関する技術として特許文献4〜6等がある。 On the other hand, there are Patent Documents 4 to 6 and the like as techniques relating to thin plating tin plating for welding cans with reduced Sn adhesion amount.
特許文献4はSnめっきをSn−Ni合金めっきとして皮膜形成し、非合金化Snを低減しようとするものである。NiによりSnの合金化を促進しようとするものであり、価格の高いNiめっき量を多く必要としてコスト高になるだけでなく、Sn−Ni合金めっきだけでは充分な塗料密着性や耐食性が得られないため、クロメート処理を施す必要があり、Crフリー鋼板とはならないものであった。 Patent Document 4 intends to reduce Sn non-alloyed Sn by forming a film as Sn-Ni alloy plating. It is intended to promote alloying of Sn with Ni. Not only does it require a large amount of expensive Ni plating, but the cost is high, and sufficient paint adhesion and corrosion resistance can be obtained with Sn-Ni alloy plating alone. Therefore, it was necessary to perform chromate treatment, and it was not a Cr-free steel plate.
特許文献5は、缶外面側はSnを完全に合金化するものであるが、缶内面には合金化していない金属Snを残存させクロメート処理を施すものである。TFS代替に見合うコストと塗料密着性を有し尚且つCrフリー鋼板を達成したものでは無い。 In Patent Document 5, Sn is completely alloyed on the outer surface side of the can, but metal Sn which is not alloyed is left on the inner surface of the can and subjected to chromate treatment. It does not achieve a Cr-free steel sheet that has cost and paint adhesion suitable for TFS substitution.
特許文献6はFe−Sn合金層とその上層にNiめっき層を有するものである。Niめっきを単独めっき層として最表層に有するため、傷や欠陥部、端面等鋼板のFeが露出された部分と電位差を生じ局部的に鉄が溶解し耐錆性や耐食性が劣る。 Patent document 6 has a Fe-Sn alloy layer and a Ni plating layer on it. Since Ni is plated on the outermost layer as a single plating layer, a potential difference is generated between the exposed portions of the steel plate such as scratches, defects, and end faces, and iron is locally dissolved, resulting in poor rust resistance and corrosion resistance.
本発明の課題は、耐錆性、耐食性に優れ、さらに皮膜の経時安定性(黄変性、塗料密着性)にも優れる表面処理鋼板およびその製造方法を提供することである。 An object of the present invention is to provide a surface-treated steel sheet that is excellent in rust resistance and corrosion resistance, and also excellent in the temporal stability of the film (yellowing and paint adhesion) and a method for producing the same.
また、本発明の課題は、TFS代替のCrフリー鋼板として食品缶用途にも使用できる表面処理鋼板およびその製造方法を提供することである。 Moreover, the subject of this invention is providing the surface treatment steel plate which can be used also for a food can use as Cr free steel plate of TFS substitution, and its manufacturing method.
本発明者らはTFS代替のCrフリー鋼板としてまず、従来技術の特許文献1のように鋼板上に種々の化成処理皮膜を形成させることを試みた。しかしながら化成処理皮膜はその上層の有機樹脂皮膜層や下層の金属層との密着性に優れることはあっても耐錆性や耐食性が劣ることがわかった。酸素や水分のバリア性という観点からはやはり酸化物よりも金属が優れており、少量でも金属めっき層を有することで飛躍的に耐錆性や耐食性が向上することがわかった。特に湿潤環境にさらされず、塗料の一次密着性しか要求されない化粧缶等のような缶については、高価な薬剤を使用したり、食品用缶として実績の無い薬剤を使用する必要が無く、既存設備を使用してTFS代替のCrフリー鋼板の製造が可能となった。また新規な薬剤処理が追加されないため、コスト面や安全性についての検証の問題点も解決できた。 The present inventors first tried to form various chemical conversion coatings on a steel sheet as disclosed in Patent Document 1 of the prior art as a Cr-free steel sheet as a substitute for TFS. However, it was found that the chemical conversion treatment film is inferior in rust resistance and corrosion resistance even though it has excellent adhesion to the upper organic resin film layer and the lower metal layer. From the standpoint of oxygen and moisture barrier properties, metals are still superior to oxides, and even with a small amount, it has been found that rust resistance and corrosion resistance are dramatically improved by having a metal plating layer. For cans such as makeup cans that are not particularly exposed to wet environments and require only primary adhesion of paint, there is no need to use expensive drugs or use unproven drugs as food cans. It became possible to manufacture Cr-free steel plates instead of TFS. In addition, since no new chemical treatment was added, the problem of verification of cost and safety could be solved.
さらに、本発明者らは、ぶりきや薄目付けぶりきのCrフリー化成処理も検討した。皮膜としては、錫めっき層は従来のぶりきや薄目付けぶりきと同じ皮膜で表層のクロメート皮膜をCrフリー化成処理皮膜にした。その結果錫めっき量が少ない程、塗料密着性が良好で経時による表面黄変の問題が少なくなることがわかった。このことから、TFS代替のCrフリー技術(鋼板)として、鋼板表面に合金化していない金属Snを有しない全合金化錫めっき層を設けることを想到し、本発明に至った。 Furthermore, the present inventors also examined Cr-free chemical conversion treatment for tinplate and thin tinplate. As the coating, the tin plating layer was the same coating as conventional tinting and thin tinting, and the surface chromate coating was changed to a Cr-free chemical conversion coating. As a result, it was found that the smaller the tin plating amount, the better the paint adhesion and the less the problem of surface yellowing over time. From this, as a Cr-free technique (steel plate) alternative to TFS, it was conceived that an all-alloyed tin plating layer having no metal Sn not alloyed was provided on the surface of the steel plate, and the present invention was achieved.
本発明の要旨は以下に記載するとおりである。 The gist of the present invention is as described below.
(1)鋼板の少なくとも片面にFe−Sn合金層を有し、該Fe−Sn合金層上の非合金化Sn量が0.1mg/m2未満であることを特徴とする表面処理鋼板(第1発明)。 (1) A surface-treated steel sheet having a Fe—Sn alloy layer on at least one surface of the steel sheet, and the amount of non-alloyed Sn on the Fe—Sn alloy layer being less than 0.1 mg / m 2 1 invention).
(2)鋼板の少なくとも片面にFe−Ni合金層を有し、該Fe−Ni合金層上にFe−Ni−Sn合金層を有し、該Fe−Ni−Sn合金層上の非合金化Sn量が0.1mg/m2未満であることを特徴とする表面処理鋼板(第2発明)。 (2) Fe-Ni alloy layer on at least one surface of the steel sheet, Fe-Ni-Sn alloy layer on the Fe-Ni alloy layer, and non-alloyed Sn on the Fe-Ni-Sn alloy layer A surface-treated steel sheet characterized in that the amount is less than 0.1 mg / m 2 (second invention).
(3)前記Fe−Sn合金層または前記Fe−Ni−Sn合金層の片面あたりのSn付着量が0.01〜1.0g/m2であることを特徴とする(1)または(2)記載の表面処理鋼板(第3発明)。 (3) The amount of Sn deposited per one side of the Fe—Sn alloy layer or the Fe—Ni—Sn alloy layer is 0.01 to 1.0 g / m 2 (1) or (2) The surface-treated steel sheet according to the description (third invention).
(4)冷延鋼板に焼鈍、調質圧延したのち、片面あたりのSn付着量が0.01〜1.0g/m2となるようにSnめっき処理を施し、その後加熱溶融処理を施して非合金化Sn量を0.1mg/m2未満とすることを特徴とする表面処理鋼板の製造方法(第4発明)。 (4) After annealing and temper rolling the cold-rolled steel sheet, Sn plating treatment is performed so that the Sn adhesion amount per side becomes 0.01 to 1.0 g / m 2, and then heat melting treatment is applied to the non-coated steel sheet. A method for producing a surface-treated steel sheet, characterized in that the amount of alloyed Sn is less than 0.1 mg / m 2 (fourth invention).
(5)冷延鋼板の両面にNiめっき処理、焼鈍、調質圧延を順次施したのち、片面あたりのSn付着量が0.01〜1.0g/m2となるようにSnめっき処理を施し、その後加熱溶融処理を施して非合金化Sn量を0.1mg/m2未満とすることを特徴とする表面処理鋼板の製造方法(第5発明)。 (5) Ni plating treatment, annealing, and temper rolling are sequentially performed on both surfaces of the cold-rolled steel sheet, and then Sn plating treatment is performed so that the Sn adhesion amount per one surface becomes 0.01 to 1.0 g / m 2. , then heating and melting processes performed by a method for producing a surface-treated steel sheet, characterized in that the unalloyed Sn content is less than 0.1 mg / m 2 (fifth aspect).
(6)加熱溶融処理を施して非合金化Sn量を0.1mg/m2未満としたのち、電解質水溶液中で1〜10C/dm2の陰極電解処理を施すことを特徴とする(4)または(5)記載の表面処理鋼板の製造方法(第6発明)。 (6) Heat-melting treatment is performed to make the amount of non-alloyed Sn less than 0.1 mg / m 2, and then cathodic electrolysis treatment of 1 to 10 C / dm 2 is performed in an aqueous electrolyte solution (4) Or the manufacturing method (6th invention) of the surface treatment steel plate as described in (5).
本発明によれば、耐錆性、耐食性に優れ、さらに皮膜の経時安定性(黄変性、塗料密着性)にも優れる表面処理鋼板が得られる。本発明の表面処理鋼板は、Crを全く使用しない皮膜を有する鋼板であり、食品缶用鋼板として使用された場合も安全である。 According to the present invention, it is possible to obtain a surface-treated steel sheet that is excellent in rust resistance and corrosion resistance, and also excellent in the temporal stability of the film (yellowing and paint adhesion). The surface-treated steel sheet of the present invention is a steel sheet having a coating that does not use Cr at all, and is safe even when used as a steel sheet for food cans.
本発明の表面処理鋼板は、(1)鋼板の少なくとも片面にFe−Sn合金層を有し、該Fe−Sn合金層上の非合金化Sn量が0.1mg/m2未満である(第1発明)、または(2)鋼板の少なくとも片面にFe−Ni合金層を有し、該Fe−Ni合金層上にFe−Ni−Sn合金層を有し、該Fe−Ni−Sn合金層上の非合金化Sn量が0.1mg/m2未満である(第2発明)。 The surface-treated steel sheet of the present invention has (1) an Fe—Sn alloy layer on at least one surface of the steel sheet, and the amount of non-alloyed Sn on the Fe—Sn alloy layer is less than 0.1 mg / m 2 (first 1 invention), or (2) an Fe—Ni alloy layer on at least one surface of a steel sheet, an Fe—Ni—Sn alloy layer on the Fe—Ni alloy layer, and the Fe—Ni—Sn alloy layer The amount of non-alloyed Sn is less than 0.1 mg / m 2 (second invention).
第1発明の表面処理鋼板は、鋼板の少なくとも片面にFe−Sn合金層を有することで耐錆性と耐食性に優れる作用を奏する。また、Fe−Sn合金層上の非合金化Sn量を0.1mg/m2未満とすることにより、塗料密着性に優れ、経時による塗料密着性の劣化や外観の劣化の無い鋼板が得られる。 The surface-treated steel sheet according to the first aspect of the invention has an effect of being excellent in rust resistance and corrosion resistance by having a Fe—Sn alloy layer on at least one surface of the steel sheet. Further, by setting the amount of non-alloyed Sn on the Fe—Sn alloy layer to less than 0.1 mg / m 2 , a steel sheet having excellent paint adhesion and having no deterioration in paint adhesion or appearance over time can be obtained. .
第1発明の表面処理鋼板は、冷延鋼板に焼鈍、調質圧延したのち、片面あたりのSn付着量が0.01〜1.0g/m2となるようにSnめっき処理を施し、その後加熱溶融処理することによって製造される。Fe−Sn合金層は加熱溶融処理で形成される。Snめっきは一般的に使用されているフィロスタン浴、ハロゲン浴、MSA浴等を用いて行えば良い。 The surface-treated steel sheet of the first invention is annealed and temper-rolled on a cold-rolled steel sheet, and then Sn-plated so that the Sn adhesion amount on one side becomes 0.01 to 1.0 g / m 2 and then heated. Manufactured by melt processing. The Fe—Sn alloy layer is formed by heat melting treatment. Sn plating may be performed using a generally used philostane bath, halogen bath, MSA bath or the like.
加熱溶融処理は、めっきした金属Snを非合金化Sn量が0.1mg/m2未満となるように錫融点以上の温度に加熱保持する加熱溶融処理を施す。具体的には抵抗加熱法又は高周波加熱法により加熱する。 The heat melting treatment is performed by heating and holding the plated metal Sn at a temperature equal to or higher than the melting point of tin so that the amount of non-alloyed Sn is less than 0.1 mg / m 2 . Specifically, heating is performed by a resistance heating method or a high frequency heating method.
非合金化Sn量を0.1mg/m2未満とすることにより、塗料密着性に優れ、経時による塗料密着性の劣化や外観の劣化の無い鋼板が得られる。ここでいう非合金化Sn量が0.1mg/m2未満とは、JIS G 3303−1969の付属書に規定される電解はく離法によるぶりきのすず付着量試験方法において、電位−時間曲線において合金化していない表面すずの溶解による停滞電位が無く、直ちに合金すず溶解電位が現れる場合を指す。 By setting the amount of non-alloyed Sn to less than 0.1 mg / m 2 , a steel sheet having excellent paint adhesion and having no deterioration in paint adhesion or appearance over time can be obtained. Here, the amount of non-alloyed Sn is less than 0.1 mg / m 2 in the potential-time curve in the tin tin adhesion amount test method by the electrolytic peeling method defined in the appendix of JIS G 3303-1969. This refers to the case where there is no stagnation potential due to the dissolution of the non-alloyed surface tin, and the tin alloy dissolution potential immediately appears.
Snめっき付着量は片面あたり0.01〜1.0g/m2とすることが好ましい。0.01g/m2未満ではめっきによる耐錆性、耐食性の効果が現れないことがあるためである。1.0g/m2超では加熱溶融処理で非合金化Sn量を0.1mg/m2未満にすることが難しいためである。また高速製造性の観点からは、Sn付着量は少な目のほうが望ましく、0.01〜0.5g/m2が好ましい。 The Sn plating adhesion amount is preferably 0.01 to 1.0 g / m 2 per side. If it is less than 0.01 g / m 2 , the effects of rust resistance and corrosion resistance by plating may not appear. This is because if it exceeds 1.0 g / m 2 , it is difficult to make the amount of non-alloyed Sn less than 0.1 mg / m 2 by heat melting treatment. Further, from the viewpoint of high-speed productivity, it is desirable that the Sn adhesion amount is small, and 0.01 to 0.5 g / m 2 is preferable.
第2発明の表面処理鋼板は、鋼板の少なくとも片面にFe−Ni合金層を有し、該Fe−Ni合金層上にFe−Ni−Sn合金層を有することで、耐食性、塗料密着性、耐錆性に優れる。すなわち、Fe−Ni−Sn合金層は緻密な構造であるために薄くてもピンホールが少なく耐食性に優れた性質を有する。また合金層にNiを含有することにより、塗料密着性も向上する。この理由は定かではないが、おそらく最表層に形成される酸化物の形態に何らかの影響を及ぼすものと考えられる。 The surface-treated steel sheet of the second invention has an Fe—Ni alloy layer on at least one surface of the steel sheet, and has an Fe—Ni—Sn alloy layer on the Fe—Ni alloy layer, thereby providing corrosion resistance, paint adhesion, Excellent rusting property. That is, since the Fe—Ni—Sn alloy layer has a dense structure, even if it is thin, it has few pinholes and has excellent corrosion resistance. Moreover, paint adhesion is also improved by containing Ni in the alloy layer. The reason for this is not clear, but it is thought that it probably has some influence on the form of the oxide formed on the outermost layer.
NiはFe−Ni合金層として鋼板表面に存在することによって、Feの電位をやや貴な方向にシフトし、Feの溶出速度すなわち腐食速度を低減させる。一方、Niが単独のNiめっき層として残存する場合は、逆に貴なNiとFeあるいはFe−Ni合金との間に電位差を生じ、Feの溶解を促進させるからである。 Ni exists as a Fe—Ni alloy layer on the surface of the steel sheet, thereby shifting the Fe potential in a slightly noble direction and reducing the elution rate of Fe, that is, the corrosion rate. On the other hand, when Ni remains as a single Ni plating layer, on the contrary, a potential difference is generated between noble Ni and Fe or an Fe-Ni alloy to promote the dissolution of Fe.
第2発明の表面処理鋼板は、冷延鋼板の両面にNiめっき処理、片面あたりのSn付着量が0.01〜1.0g/m2となるようにSnめっき処理を施し、その後加熱溶融処理することによって製造される。Fe−Ni−Sn合金層は加熱溶融処理で形成される。 The surface-treated steel sheet of the second invention is Ni-plated on both surfaces of the cold-rolled steel sheet, Sn-plated so that the Sn adhesion amount per side is 0.01 to 1.0 g / m 2, and then heat-melted. Manufactured by doing. The Fe—Ni—Sn alloy layer is formed by heat melting treatment.
焼鈍および調質圧延をNiめっき処理後Snめっき処理前に行っても良いし、焼鈍および調質圧延後Niめっき処理とSnめっき処理を続けて行っても良い。Niめっき処理、焼鈍、調質圧延を順次施したのち、Snめっき処理を施すことがNiが鋼中により深く拡散するため、耐錆性の点から好ましい。 The annealing and temper rolling may be performed after the Ni plating process and before the Sn plating process, or the Ni plating process and the Sn plating process may be performed continuously after the annealing and temper rolling. It is preferable from the viewpoint of rust resistance that Ni is diffused deeper into the steel after the Ni plating treatment, annealing, and temper rolling are sequentially performed.
Niめっき処理方法は限定されない。一般的に用いられるワット浴、硫酸浴、スルファミン酸浴などを用いることができる。 The Ni plating method is not limited. Commonly used watt baths, sulfuric acid baths, sulfamic acid baths and the like can be used.
Niめっき付着量は片面あたり0.002〜0.1g/m2が好ましい。Niめっき付着量が0.002g/m2未満の場合は上記に記載したような緻密な合金層が形成されなくなり、耐食性向上効果が得られなくなる。一方Niめっき付着量が0.1g/m2を超えた場合は、最終工程後もNiめっきが単独のNiめっき層として不必要に残存してしまい、コスト高になるだけではなく、却って耐食性を劣化させる。 The Ni plating adhesion amount is preferably 0.002 to 0.1 g / m 2 per side. When the Ni plating adhesion amount is less than 0.002 g / m 2, the dense alloy layer as described above is not formed, and the corrosion resistance improvement effect cannot be obtained. On the other hand, when the Ni plating adhesion amount exceeds 0.1 g / m 2 , the Ni plating remains unnecessarily as a single Ni plating layer even after the final process, which not only increases the cost but also improves the corrosion resistance. Deteriorate.
焼鈍は、鋼板を還元性雰囲気中で連続焼鈍処理することが好ましい。還元性雰囲気としては特に制限されず、例えばN2とH2の混合雰囲気等が挙げられる。また焼鈍温度は、650℃〜750℃で30秒〜10分間行われる。調質圧延は伸び率が1.5〜2%の処理を行うことが好ましい。 For annealing, it is preferable that the steel sheet is continuously annealed in a reducing atmosphere. The reducing atmosphere is not particularly limited, and examples thereof include a mixed atmosphere of N 2 and H 2 . The annealing temperature is 650 ° C. to 750 ° C. for 30 seconds to 10 minutes. In the temper rolling, it is preferable to perform a treatment with an elongation of 1.5 to 2%.
加熱溶融処理ではめっきした金属Snを非合金化Sn量が0.1mg/m2未満となるように加熱し、合金化する。非合金化Sn量を0.1mg/m2未満とすることにより、塗料密着性に優れ、経時による塗料密着性の劣化や外観の劣化の無い鋼板が得られる。 In the heat melting treatment, the plated metal Sn is heated and alloyed so that the amount of non-alloyed Sn is less than 0.1 mg / m 2 . By setting the amount of non-alloyed Sn to less than 0.1 mg / m 2 , a steel sheet having excellent paint adhesion and having no deterioration in paint adhesion or appearance over time can be obtained.
Snめっき付着量は、前述のとおり片面あたり0.01〜1.0g/m2とすることが好ましい。0.01g/m2未満ではめっきによる耐錆性、耐食性の効果が現れにくいためである。1.0g/m2超ではFe−Sn合金にさらにNiが入った場合、加熱溶融処理時に金属Snをはじいて島状金属Snを形成しやすいため、非合金化Sn量を0.1mg/m2未満とするのが非常に困難となりやすく、合金化するための加熱処理コストがかかる上、それ以上の耐錆性、耐食性効果が得られない傾向にある。 As described above, the Sn plating adhesion amount is preferably 0.01 to 1.0 g / m 2 per side. This is because if it is less than 0.01 g / m 2 , the effects of rust resistance and corrosion resistance due to plating are difficult to appear. If it exceeds 1.0 g / m 2 , when Ni is further contained in the Fe—Sn alloy, it is easy to form the metal Sn by repelling the metal Sn during the heat-melting treatment, so the amount of non-alloyed Sn is 0.1 mg / m 2. It tends to be very difficult to make it less than 2, and heat treatment costs are required for alloying, and further rust resistance and corrosion resistance effects tend not to be obtained.
上述の各表面処理鋼板の製造方法において、加熱溶融処理後に電解質水溶液中で陰極処理することがさらに好ましい。これによって塗料密着性をさらに向上させることができる。Snめっき後すぐに金属Sn表面にはSn酸化物皮膜が形成され、さらに加熱溶融処理時には合金化が下地鉄との界面から進み、表面は金属Snが高温状態にさらされるため、さらにSn酸化物皮膜が形成される。加熱溶融処理後に電解質水溶液中で陰極処理することによってSn酸化物皮膜を還元し、塗料密着性をさらに向上させることができる。電解質水溶液は、めっき層が溶解しないことや耐食性等に悪影響を及ぼさないことが好ましく、例えばNa2CO3水溶液やNaHCO3水溶液などの中性〜弱アルカリ性水溶液が好適に使用できる。陰極処理は1〜10C/dm2程度で行う。 In the method for producing each surface-treated steel sheet, it is more preferable to perform a cathode treatment in an aqueous electrolyte solution after the heat-melting treatment. As a result, the paint adhesion can be further improved. Immediately after Sn plating, a Sn oxide film is formed on the surface of the metal Sn, and during the heat-melting process, alloying proceeds from the interface with the underlying iron, and the surface is exposed to high-temperature metal Sn. A film is formed. The Sn oxide film can be reduced by cathodic treatment in an aqueous electrolyte solution after the heat-melting treatment, and the paint adhesion can be further improved. The electrolyte aqueous solution preferably does not dissolve the plating layer and does not adversely affect the corrosion resistance. For example, a neutral to weak alkaline aqueous solution such as a Na 2 CO 3 aqueous solution or a NaHCO 3 aqueous solution can be suitably used. Cathodic treatment is carried out at about 1 to 10C / dm 2.
本発明で用いる冷延鋼板(めっき原板)は、公知のめっき原板を使用できる。板厚も特に限定されないが、例えば0.12〜0.60mmのものを使用できる。 As the cold-rolled steel plate (plating original plate) used in the present invention, a known plating original plate can be used. The plate thickness is not particularly limited, but for example, a thickness of 0.12 to 0.60 mm can be used.
上述の本発明の表面処理鋼板は、耐錆性、耐食性に優れ、さらに経時による表面の黄変、塗料密着性低下の問題がなく、また、この表面処理鋼板は、Crを全く使用しない皮膜を有する鋼板であり、環境対応商品としての付加価値を高めることができるだけでなく、食品缶用鋼板として使用された場合も安全である。 The above-described surface-treated steel sheet of the present invention is excellent in rust resistance and corrosion resistance, and has no problem of surface yellowing and paint adhesion deterioration with time, and this surface-treated steel sheet has a coating that does not use any Cr. This steel plate not only increases the added value as an environmentally friendly product, but is also safe when used as a steel plate for food cans.
本発明の表面処理鋼板の製造過程ではCrを含有する処理液を全く使用しないことや他の化成処理薬剤も使用しないことにより、排水処理、排気処理等の環境負荷対応が簡便になる。 In the manufacturing process of the surface-treated steel sheet of the present invention, it is easy to deal with environmental loads such as waste water treatment and exhaust treatment by not using any treatment liquid containing Cr or using any other chemical conversion treatment chemical.
以下に本発明を実施例に基づき具体的に説明する。なお、実施例では冷延鋼板の両面に以下に示す製法による処理を施した。 The present invention will be specifically described below based on examples. In addition, in the Example, the process by the manufacturing method shown below was given to both surfaces of the cold-rolled steel plate.
(製法A)冷間圧延後のめっき原板(厚さ0.2mm)を電解脱脂した後、後述する(a)浴を用いてNiめっきを行い、10vol%H2+90%volN2雰囲気中で700℃で焼鈍し、Niめっきを拡散浸透させた。この鋼板を伸び率1.5%の調質圧延を行った後、脱脂、酸洗を行い、後述する(b)浴を用いてSnめっきした。引き続きSnの融点以上の温度に加熱保持する加熱溶融処理した。
(製法B)冷間圧延後焼鈍、調質圧延を施しためっき原板(厚さ0.2mm)をアルカリ電解脱脂、硫酸酸洗した後(a)浴を用いてNiめっきを施し、さらに後述する(c)浴を用いてSnめっきを施し、Snの融点以上の温度に加熱保持する加熱溶融処理した。
(Process A) After electrolytic degreasing plating original plate (thickness 0.2 mm) after cold rolling, subjected to Ni plating using later-described (a) bath, with 10vol% H 2 + 90% volN 2 atmosphere 700 Annealing was performed at 0 ° C. to diffuse and infiltrate the Ni plating. The steel sheet was subjected to temper rolling with an elongation of 1.5%, then degreased and pickled, and Sn-plated using a bath (b) described later. Subsequently, a heating and melting treatment was carried out by heating and holding at a temperature higher than the melting point of Sn.
(Manufacturing method B) After carrying out the annealing after cold rolling and the temper-rolling plating board (thickness 0.2mm), alkaline electrolytic degreasing and sulfuric acid washing (a) Ni plating is performed using a bath, and it mentions later. (C) Sn plating was performed using a bath, and a heat melting treatment was performed by heating and holding at a temperature equal to or higher than the melting point of Sn.
(製法C)冷間圧延後焼鈍、調質圧延を施しためっき原板(厚さ0.2mm)をアルカリ電解脱脂、硫酸酸洗した後(b)浴を用いてSnめっきを施し、Snの融点以上の温度に加熱保持する加熱溶融処理した。
(製法D)冷間圧延後のめっき原板(厚さ0.2mm)を電解脱脂した後、(a)浴を用いてNiめっきを行い、10vol%H2+90vol%N2雰囲気中で700℃で焼鈍し、Niめっきを拡散浸透させた。この鋼板を伸び率1.5%の調質圧延を行った後、脱脂、酸洗を行い、(b)浴を用いてSnめっきした。引き続きSnの融点以上の温度に加熱保持する加熱溶融処理し、さらに30g/lの炭酸水素ナトリウム水溶液中で5C/dm2の陰極電解処理を行った。
(Manufacturing method C) An alkaline electrolytic degreasing and sulfuric acid-washed plating original plate (thickness 0.2 mm) subjected to annealing and temper rolling after cold rolling (b) Sn plating using a bath, melting point of Sn The heating and melting treatment was performed by heating and holding at the above temperature.
(Procedure D) After electrolytic degreasing plating original plate (thickness 0.2 mm) after cold rolling, subjected to Ni plating using (a) bath at 700 ° C. with 10vol% H 2 + 90vol% N 2 atmosphere Annealing was performed and Ni plating was diffused and infiltrated. The steel sheet was subjected to temper rolling with an elongation of 1.5%, then degreased and pickled, and (b) Sn plated using a bath. Subsequently, a heating and melting treatment was performed by heating and holding at a temperature equal to or higher than the melting point of Sn, and a 5 C / dm 2 cathode electrolysis treatment was performed in a 30 g / l aqueous sodium hydrogen carbonate solution.
(製法E)冷間圧延後焼鈍、調質圧延を施しためっき原板(厚さ0.2mm)を電解脱脂した後、(a)浴を用いてNiめっきを行い、10vol%H2+90vol%N2雰囲気中で700℃で焼鈍し、Niめっきを拡散浸透させた。この鋼板を伸び率1.5%の調質圧延を行った後、脱脂、酸洗を行い、(b)浴を用いてSnめっきした。
(製法F)冷間圧延後焼鈍、調質圧延を施しためっき原板(厚さ0.2mm)をアルカリ電解脱脂、硫酸酸洗した後、後述する(d)浴に5秒浸漬して0.5g/m2のリン酸亜鉛皮膜を形成した。
(Process E) after after cold rolling annealing, it is plated subjected to temper rolling (thickness 0.2 mm) was electrolytically degreased, subjected to Ni plating using (a) bath, 10vol% H 2 + 90vol% N Annealing was performed at 700 ° C. in two atmospheres to diffuse and infiltrate the Ni plating. The steel sheet was subjected to temper rolling with an elongation of 1.5%, then degreased and pickled, and (b) Sn plated using a bath.
(Manufacturing method F) After carrying out the alkaline electrolytic degreasing and the sulfuric acid pickling, the plating original plate (thickness 0.2mm) which annealed and temper-rolled after cold rolling was immersed in the below-mentioned (d) bath for 5 second, and 0. A 5 g / m 2 zinc phosphate coating was formed.
(製法G)冷間圧延後焼鈍、調質圧延を施しためっき原板(厚さ0.2mm)をアルカリ電解脱脂、硫酸酸洗した後(b)浴を用いてSnめっきを施し、Snの融点以上の温度に加熱保持する加熱溶融処理した。引き続き後述する(e)液を塗布後到達板温100℃で乾燥した。 (Manufacturing method G) The plating base plate (thickness 0.2 mm) subjected to annealing and temper rolling after cold rolling is subjected to alkaline electrolytic degreasing and sulfuric acid washing (b), Sn plating is performed using a bath, and the melting point of Sn The heating and melting treatment was performed by heating and holding at the above temperature. Subsequently, the liquid (e) described later was applied and dried at an ultimate plate temperature of 100 ° C.
(a)〜(e)浴の組成は下記の通りである。
(a)浴(Niめっき浴)
硫酸ニッケル 250g/l
塩化ニッケル 45g/l
ほう酸 30g/l
(b)浴(Snめっき浴)
Sn2+ 20g/l
遊離メタンスルホン酸 25g/l
光沢剤 適量
酸化防止剤 適量
(c)浴(Snめっき浴)
硫酸第一錫 55g/l
フェノールスルホン酸(65%) 35g/l
光沢剤 適量
The compositions of the (a) to (e) baths are as follows.
(A) Bath (Ni plating bath)
Nickel sulfate 250g / l
Nickel chloride 45g / l
Boric acid 30g / l
(B) Bath (Sn plating bath)
Sn 2+ 20 g / l
Free methanesulfonic acid 25g / l
Brightener Suitable amount Antioxidant Suitable amount (c) Bath (Sn plating bath)
Stannous sulfate 55g / l
Phenolsulfonic acid (65%) 35g / l
Appropriate amount of brightener
(d)浴(リン酸Zn浴)
Znイオン 4g/l
Niイオン 1g/l
Mn2+イオン 0.5g/l
PO4 3−イオン 10g/l
NO3 −イオン 適量
(e)液(シランカップリング剤水溶液)
3−アミノプロピルトリエトキシシラン 15g/l
(D) Bath (Zn phosphate bath)
Zn ion 4g / l
Ni ion 1g / l
Mn 2+ ion 0.5 g / l
PO 4 3- ion 10g / l
NO 3 - ions qs (e) solution (silane coupling agent aqueous solution)
3-aminopropyltriethoxysilane 15g / l
以下に得られた鋼板の試験方法を述べる。
1)全Niめっき量
蛍光X線分析により予め付着量既知のサンプルを測定して得た検量線を用いて求めた。
A test method for the obtained steel sheet will be described below.
1) Total Ni plating amount It calculated | required using the analytical curve obtained by measuring the sample with known adhesion amount beforehand by fluorescent X-ray analysis.
2)Sn合金めっき量、非合金化金属Sn量
JIS G 3303−1969付属書の電解はく離法を用いて求めた。
2) Sn alloy plating amount, non-alloyed metal Sn amount It was determined using the electrolytic stripping method of JIS G 3303-1969 appendix.
3)Tピール試験(塗料密着性試験)
2枚の試料表面にそれぞれエポキシ・フェノール系塗料を50mg/dm2となるように塗装し、鋼板温度として210℃で10分焼付けた後、塗装面同士をナイロンフィルムを挟んで向かい合わせにしてホットプレスにて圧着し、これを5mm幅の試験片に分割し引張り試験片を作成した。向かい合って接着された鋼板の接着強度を引張り試験機にて測定した。引張り強度が2.5kg/5mm以上を◎、1.5kg/5mm以上2.5kg/5mm未満を○、1.0kg/5mm以上1.5kg/5mm未満を△、1.0kg/5mm未満を×とした。
3) T peel test (paint adhesion test)
After coating the two sample surfaces with epoxy / phenolic paint to 50 mg / dm 2 and baking at 210 ° C. for 10 minutes as the steel plate temperature, the coated surfaces face each other with a nylon film between them. Crimping was performed with a press, and this was divided into 5 mm wide test pieces to prepare tensile test pieces. The adhesion strength of the steel plates bonded face to face was measured with a tensile tester. Tensile strength of 2.5 kg / 5 mm or more is ◎, 1.5 kg / 5 mm or more and less than 2.5 kg / 5 mm is ◯, 1.0 kg / 5 mm or more and less than 1.5 kg / 5 mm is △, and less than 1.0 kg / 5 mm is × It was.
4)鉄溶出試験(耐食性試験)
試料表面にそれぞれエポキシ・フェノール系塗料を50mg/dm2となるように塗装し、鋼板温度として210℃で10分焼付けた後、4cm×8cmのサイズに切り出し、裏面と端面をシールした。塗装面にカッターにて地鉄に達するまでのカット(4cm長さ)を2本入れ(クロスカット)、1.5mass%NaCl水溶液と1.5mass%クエン酸水溶液を同量ずつ混合した試験液80mlに浸漬し、55℃で4日間経過した後取り出して鉄溶出量を測定した。鉄溶出量が0.06g/l以下を○、0.06g/l超0.2g/l未満を△、0.2g/l以上を×とした。
4) Iron dissolution test (corrosion resistance test)
An epoxy / phenolic paint was applied to the sample surface to 50 mg / dm 2 and baked at 210 ° C. for 10 minutes as a steel plate temperature, then cut into a size of 4 cm × 8 cm, and the back and end surfaces were sealed. Put two cuts (4cm length) until reaching the base iron with a cutter on the painted surface (cross cut), and mix 80ml of 1.5mass% NaCl aqueous solution and 1.5mass% citric acid aqueous solution. After 4 days at 55 ° C., it was taken out and the amount of iron elution was measured. The amount of iron elution was 0.06 g / l or less, ◯, more than 0.06 g / l and less than 0.2 g / l, Δ, and 0.2 g / l or more, x.
5)耐錆性試験
裏面および端面をシールした50×100mmの試験片を、温度60℃、相対湿度70%の雰囲気中で経時させ、2週間後に取り出して観察し、評価した。錆発生個数0個を◎、1〜10個を○、11〜50個を△、51個以上を×とした。
5) Rust Resistance Test A 50 × 100 mm test piece with the back and end surfaces sealed was aged in an atmosphere at a temperature of 60 ° C. and a relative humidity of 70%, taken out after 2 weeks, observed, and evaluated. The number of occurrences of rust was 0, 、 1, 1-10 were ◯, 11-50 were △, and 51 or more were x.
6)耐黄変性試験
温度60℃、相対湿度70%の雰囲気中で経時させ、10日後に取り出してハンターLab系を測定した。b値が5以下を○、5超〜7未満を△、7以上を×とした。
6) Yellowing resistance test Aged in an atmosphere at a temperature of 60 ° C. and a relative humidity of 70%, and taken out after 10 days to measure the Hunter Lab system. A b value of 5 or less was evaluated as ○, a value of more than 5 to less than 7 as Δ, and a value of 7 or more as x.
結果を表1に示した。
また、表1中、評価欄の食品実績は、皮膜が食品用途で使用実績があるか否かを評価したもので、○は使用実績があるもの、×は使用実績がないものである。
The results are shown in Table 1.
In Table 1, the food performance in the evaluation column is an evaluation of whether or not the film has been used in food applications, where ◯ indicates that there is a usage record and × indicates that there is no use record.
本発明例No.1〜6は、塗料密着性、耐黄変性、耐錆性、耐食性に優れ、缶用素材としての性能を満足している。合金SnめっきのなされていないNo.10は、耐錆性と耐食性は良好であるが、塗料密着性と耐黄変性が劣っていた。No.7〜9は耐錆性と耐食性は良好であるが、表層に合金化していない金属Sn層を有するため、塗料密着性と耐黄変性が劣っていた。No.11は塗料密着性には優れるものの、金属めっき層を有さないため耐食性と耐錆性が劣った。No.12は塗料密着性、耐食性、耐錆性には優れるが食品缶用皮膜としての実績が無く、コストアップとなるため、直ちに食品缶用途に適用することはできない。 Invention Example No. Nos. 1 to 6 are excellent in paint adhesion, yellowing resistance, rust resistance and corrosion resistance, and satisfy performance as a can material. No. No alloy Sn-plated No. 10 had good rust resistance and corrosion resistance, but was inferior in paint adhesion and yellowing resistance. No. 7 to 9 had good rust resistance and corrosion resistance, but had a non-alloyed metal Sn layer on the surface layer, and therefore the paint adhesion and yellowing resistance were inferior. No. Although No. 11 was excellent in paint adhesion, it was inferior in corrosion resistance and rust resistance because it did not have a metal plating layer. No. No. 12 is excellent in paint adhesion, corrosion resistance, and rust resistance, but has no track record as a film for food cans and increases costs, so it cannot be immediately applied to food can applications.
本発明の表面処理鋼板は、耐錆性、耐食性、塗料密着性および耐黄変性に優れるので、これらの性能が要求される用途分野、例えば塗装下地鋼板として、化粧缶等の一般缶や家電製品、事務用品等の用途分野に利用することができる。 Since the surface-treated steel sheet of the present invention is excellent in rust resistance, corrosion resistance, paint adhesion and yellowing resistance, it can be used in application fields where these performances are required, for example, general cans such as makeup cans and home appliances as coated base steel sheets. It can be used in application fields such as office supplies.
本発明の表面処理鋼板は、容器用鋼板として使用されているTFS等のCrを含有する皮膜を有する表面処理鋼板代替のCrフリー鋼板として、菓子缶や海苔缶などのドライパック食品缶にも好適に使用される。 The surface-treated steel sheet of the present invention is suitable for dry-pack food cans such as confectionery cans and laver cans as a Cr-free steel sheet as a substitute for surface-treated steel sheets having a film containing Cr such as TFS used as a steel sheet for containers. Used for.
本発明の表面処理鋼板は、本発明の表面処理鋼板を製造する方法として利用することができる。 The surface-treated steel sheet of the present invention can be used as a method for producing the surface-treated steel sheet of the present invention.
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