JP6468059B2 - Sn-plated steel sheet and method for producing Sn-plated steel sheet - Google Patents

Sn-plated steel sheet and method for producing Sn-plated steel sheet Download PDF

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JP6468059B2
JP6468059B2 JP2015094002A JP2015094002A JP6468059B2 JP 6468059 B2 JP6468059 B2 JP 6468059B2 JP 2015094002 A JP2015094002 A JP 2015094002A JP 2015094002 A JP2015094002 A JP 2015094002A JP 6468059 B2 JP6468059 B2 JP 6468059B2
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山中 晋太郎
晋太郎 山中
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Nippon Steel Corp
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Description

本発明は、Snめっき鋼板及びSnめっき鋼板の製造方法に関するものである。   The present invention relates to a Sn-plated steel sheet and a method for producing a Sn-plated steel sheet.

錫(Sn)めっき鋼板は、「ブリキ」としてよく知られており、飲料缶や食缶などの缶用途その他に、広く用いられている。これは、Snが人体に安全であり、かつ、美麗な金属であることによる。このSnめっき鋼板は、主に電気めっき法によって製造される。これは、比較的高価な金属であるSnの使用量を必要最小限の量に制御するには、溶融めっき法よりも電気めっき法が有利であることによる。Snめっき鋼板は、めっき後、又は、めっき後の加熱溶融処理により美麗な金属光沢が付与された後に、6価クロム酸塩の溶液を用いた電解処理や浸漬処理などのクロメート処理によって、Snめっき上にクロメート皮膜が施されることが多い。このクロメート皮膜の効果は、Snめっき表面の酸化を抑えることによる外観の黄変の防止や、塗装されて使用される場合における酸化Snの凝集破壊による塗膜密着性の劣化の防止、耐硫化黒変性の向上、などである。   Tin (Sn) plated steel sheets are well known as “tinplate” and are widely used for cans such as beverage cans and food cans. This is because Sn is safe for the human body and is a beautiful metal. This Sn-plated steel sheet is manufactured mainly by an electroplating method. This is because the electroplating method is more advantageous than the hot dipping method in order to control the amount of Sn, which is a relatively expensive metal, to the minimum necessary amount. Sn-plated steel sheet is Sn-plated by chromate treatment such as electrolytic treatment and immersion treatment using hexavalent chromate solution after plating or after a beautiful metallic luster is imparted by heat-melt treatment after plating. A chromate film is often applied on top. The effect of this chromate film is to prevent yellowing of the appearance by suppressing the oxidation of the Sn plating surface, to prevent deterioration of the adhesion of the coating film due to cohesive failure of oxidized Sn when coated and used, and sulfide black Improvement of denaturation, etc.

一方、近年、環境や安全に対する意識の高まりから、最終製品に6価クロムが含まれないのみならず、クロメート処理自体を行わないことが求められている。しかしながら、クロメート皮膜がないSnめっき鋼板は、上述の如く、酸化Snの成長によって外観が黄変したり、塗膜密着性が劣化したり、また、耐硫化黒変性が劣化したりする。   On the other hand, in recent years, due to increasing awareness of the environment and safety, not only hexavalent chromium is not included in the final product but also the chromate treatment itself is not required. However, as described above, the Sn-plated steel sheet having no chromate film is yellowed in appearance due to the growth of oxidized Sn, the adhesion of the coating film is deteriorated, and the resistance to sulfur blackening is deteriorated.

このため、クロメート皮膜に替わる皮膜処理をしたSnめっき鋼板が、いくつか提案されている。   For this reason, several Sn-plated steel sheets that have been subjected to film treatment instead of chromate films have been proposed.

例えば、以下の特許文献1では、リン酸イオンとシランカップリング剤とを含有する溶液を用いた処理によって、PとSiを含む皮膜を形成させたSnめっき鋼板が提案されており、以下の特許文献2では、リン酸アルミニウムを含む溶液を用いた処理によって、Al及びPと、Ni、Co、Cuの少なくとも1種と、シランカップリング剤との反応物を含む皮膜を形成させたSnめっき鋼板が提案されている。また、以下の特許文献3では、Snめっき上にZnめっきをした後にZn単独めっき層が消失するまで加熱処理を施す、クロメート皮膜を有さないSnめっき鋼板の製造方法が提案されている。更に、以下の特許文献4では、ジルコニウム、リン酸、フェノール樹脂等を含む化成処理皮膜を有する容器用鋼板が提案されている。   For example, in the following Patent Document 1, an Sn-plated steel sheet in which a film containing P and Si is formed by a treatment using a solution containing a phosphate ion and a silane coupling agent has been proposed. In Reference 2, an Sn-plated steel sheet in which a film containing a reaction product of Al and P, at least one of Ni, Co, and Cu and a silane coupling agent is formed by treatment with a solution containing aluminum phosphate. Has been proposed. Patent Document 3 below proposes a method for producing a Sn-plated steel sheet having no chromate film, in which heat treatment is performed until the Zn single plating layer disappears after Zn plating is performed on Sn plating. Furthermore, in the following Patent Document 4, a steel plate for containers having a chemical conversion treatment film containing zirconium, phosphoric acid, a phenol resin and the like is proposed.

特開2004−60052号公報Japanese Patent Laid-Open No. 2004-60052 特開2011−174172号公報JP 2011-174172 A 特開昭63−290292号公報JP-A 63-290292 特開2007−284789号公報JP 2007-284789 A

しかしながら、上記特許文献1〜特許文献4で提案されているSnめっき鋼板やその製造方法では、経時による酸化Snの成長を十分に抑制することができず、耐黄変性や塗膜密着性の確保が不十分なだけでなく、耐硫化黒変性が劣るといった問題があった。   However, the Sn-plated steel sheet proposed in Patent Documents 1 to 4 and its manufacturing method cannot sufficiently suppress the growth of oxidized Sn over time, and ensure yellowing resistance and coating film adhesion. There is a problem that not only is insufficient, but the sulfur blackening resistance is inferior.

そこで、本発明は、上記問題に鑑みてなされたものであり、本発明の目的とするところは、従来のクロメート処理を行うことなく、耐黄変性、塗膜密着性、耐硫化黒変性に優れる、Snめっき鋼板及びSnめっき鋼板の製造方法を提供することにある。   Therefore, the present invention has been made in view of the above problems, and the object of the present invention is excellent in yellowing resistance, coating film adhesion, and sulfurization blackening resistance without performing conventional chromate treatment. It is providing the manufacturing method of Sn plating steel plate and Sn plating steel plate.

上記課題を解決するために、本発明者が鋭意検討した結果、Snめっき鋼板の表面に、NiとZnとを主体とするZn−Niめっき層を形成させることで、クロメート処理を行わずに、耐黄変性、塗膜密着性、耐硫化黒変に優れるSnめっき鋼板を実現可能である旨に想到した。
上記知見に基づき完成された本発明の要旨は、以下の通りである。
In order to solve the above-mentioned problems, the present inventors diligently studied, and by forming a Zn-Ni plating layer mainly composed of Ni and Zn on the surface of the Sn-plated steel sheet, without performing chromate treatment, The inventors have conceived that an Sn-plated steel sheet excellent in yellowing resistance, coating film adhesion, and sulfide blackening resistance can be realized.
The summary of this invention completed based on the said knowledge is as follows.

(1)鋼板の少なくとも片面に、SnをSn換算量として片面当たり2.8g/m以上15g/m以下含有するSnめっき層が形成されたSnめっき鋼板上に、質量%で、Niを5%以上75%以下含有し、残部がZn及び不純物からなるZn−Niめっき層が、片面当たり0.05g/m以上0.5g/m以下の付着量で形成された、Snめっき鋼板。
(2)前記Zn−Niめっき層におけるNi含有率が、質量%で、10%以上55%以下である、(1)に記載のSnめっき鋼板。
(3)前記Zn−Niめっき層におけるNi含有率が、質量%で、10%以上30%以下である、(1)又は(2)に記載のSnめっき鋼板。
(4)前記Snめっき層と前記鋼板との間に、SnとFeとの合金層を有する、(1)〜(3)の何れか1項に記載のSnめっき鋼板。
(5)鋼板の少なくとも片面に、SnをSn換算量として片面当たり2.8g/m以上15g/m以下含有するSnめっき層が形成されたSnめっき鋼板を、NiイオンとZnイオンとを含み、Niイオン濃度が質量%で20%以上95%以下であり、かつ、NiイオンとZnイオンの合計が50kg/m以上250kg/m以下である水溶液中で、電流密度0.1A/dm以上150A/dm以下の条件で電解する、Snめっき鋼板の製造方法。
(6)鋼板の少なくとも片面に、SnをSn換算量として片面当たり2.8g/m以上15g/m以下含有するSnめっき層と、当該Snめっき層と鋼板との間に位置するSnとFeとの合金層と、が形成されたSnめっき鋼板を、NiイオンとZnイオンとを含み、Niイオン濃度が質量%で20%以上95%以下であり、かつ、NiイオンとZnイオンの合計が50kg/m以上250kg/m以下である水溶液中で、電流密度0.1A/dm以上150A/dm以下の条件で電解する、Snめっき鋼板の製造方法。

(1) On at least one side of a steel sheet , Sn is formed on a Sn-plated steel sheet on which an Sn plating layer containing Sn in an amount of 2.8 g / m 2 or more and 15 g / m 2 or less per side is formed in terms of mass%. the Ni containing 5% or more than 75%, the balance being Zn-Ni plated layer consisting of Zn and impurities, formed by two or more 0.5 g / m 2 or less of coating weight per side 0.05 g / m, Sn plated steel sheet.
(2) The Sn-plated steel sheet according to (1), wherein the Ni content in the Zn-Ni plated layer is 10% to 55% by mass.
(3) The Sn-plated steel sheet according to (1) or (2), wherein the Ni content in the Zn—Ni plating layer is 10% by mass or more and 30% or less.
(4) The Sn-plated steel sheet according to any one of (1) to (3), which has an alloy layer of Sn and Fe between the Sn-plated layer and the steel sheet.
(5) on at least one surface of the steel sheet, the S n, the Sn plated steel sheet Sn plating layer is formed containing 2.8 g / m 2 or more 15 g / m 2 or less per one side as Sn in terms of weight, Ni ions and Zn In an aqueous solution containing Ni and having a Ni ion concentration of 20% to 95% by mass and a total of Ni ions and Zn ions of 50 kg / m 3 to 250 kg / m 3. electrolysis in .1A / dm 2 or more 150A / dm 2 the following conditions, the production method of the Sn-plated steel sheet.
(6) At least on one side of the steel sheet , Sn is contained between 2.8 g / m 2 and 15 g / m 2 or less as Sn equivalent amount, and between the Sn plating layer and the steel sheet. The Sn-plated steel sheet on which the alloy layer of Sn and Fe is formed contains Ni ions and Zn ions, the Ni ion concentration is 20% to 95% by mass, and the Ni ions and Zn total ion in aqueous solution is less than 50 kg / m 3 or more 250 kg / m 3, to electrolysis at a current density of 0.1 a / dm 2 or more 150A / dm 2 the following conditions, the production method of the Sn-plated steel sheet.

以上説明したように本発明によれば、従来のクロメート処理を行うことなく、耐黄変性、塗膜密着性、耐硫化黒変性に優れるSnめっき鋼板及びSnめっき鋼板の製造方法を提供することが可能となる。   As described above, according to the present invention, it is possible to provide a Sn-plated steel sheet and a method for producing a Sn-plated steel sheet that are excellent in yellowing resistance, coating film adhesion, and sulfurization blackness resistance without performing conventional chromate treatment. It becomes possible.

試験例でのめっき浴組成とめっき中Ni含有率を図示したグラフ図である。It is the graph which illustrated the plating bath composition and Ni content rate during plating in a test example. 試験例での△b*に及ぼすめっき中Ni含有率の影響を図示したグラフ図である。It is the graph which illustrated the influence of Ni content in plating which has on (DELTA) b * in a test example. 試験例でのめっき浴中Ni含有率に及ぼす電流密度の影響を示したグラフ図である。It is the graph which showed the influence of the current density which acts on Ni content rate in the plating bath in a test example.

以下に、本発明の好適な実施の形態について詳細に説明する。
以下で説明する本発明は、食缶、飲料缶などの缶用途その他に広く用いられるSnめっき鋼板と、かかるSnめっき鋼板の製造方法に関するものである。より詳細には、従来のクロメート処理を行うことなく、耐黄変性、塗膜密着性、耐硫化黒変性に優れるSnめっき鋼板及びSnめっき鋼板の製造方法に関するものである。
Hereinafter, preferred embodiments of the present invention will be described in detail.
The present invention described below relates to a Sn-plated steel sheet widely used for cans such as food cans and beverage cans, and a method for producing such a Sn-plated steel sheet. More specifically, the present invention relates to a Sn-plated steel sheet and a method for producing a Sn-plated steel sheet that are excellent in yellowing resistance, coating film adhesion, and sulfurization blackness resistance without performing conventional chromate treatment.

本実施形態に係るSnめっき鋼板は、鋼板の少なくとも片方の表面にSnめっき層の形成されたSnめっき鋼板の表面に、所定量のNiを含有し、残部がZn及び不純物からなるZn−Niめっき層が所定の付着量で形成されていることを特徴とする。   The Sn-plated steel sheet according to the present embodiment contains a predetermined amount of Ni on the surface of the Sn-plated steel sheet on which the Sn-plated layer is formed on at least one surface of the steel sheet, and the balance is Zn-Ni plating composed of Zn and impurities. The layer is formed with a predetermined adhesion amount.

より詳細には、本実施形態に係るSnめっき鋼板は、鋼板の少なくとも片面に、質量%で、SnをSn換算量として0.1g/m以上15g/m以下含有するSnめっき層が形成されたSnめっき鋼板上に、質量%で、Niを5%以上75%以下含有し、残部がZn及び不純物からなるZn−Niめっき層が、合計で0.05g/m以上0.5g/m以下の付着量で形成されている。 More specifically, in the Sn-plated steel sheet according to the present embodiment, an Sn plating layer containing 0.1 g / m 2 or more and 15 g / m 2 or less of Sn as a Sn equivalent amount is formed on at least one surface of the steel sheet. On the Sn-plated steel sheet, the Zn—Ni plating layer containing 5% or more and 75% or less of Ni and the balance of Zn and impurities is 0.05 g / m 2 or more and 0.5 g / m in total. It is formed with an adhesion amount of m 2 or less.

<鋼板について>
本実施形態に係るSnめっき鋼板に用いられる鋼板は、特に規定されるものではなく、一般的な容器用のSnめっき鋼板に用いられている鋼板であれば、任意のものを使用可能であり、例えば、低炭素鋼や極低炭素鋼などが挙げられる。また、用いる鋼板の製造方法や材質も特に規定されるものではなく、例えば、鋳造から熱間圧延、酸洗、冷間圧延、焼鈍、調質圧延等の工程を経て製造されたものを挙げることができる。
<About steel plates>
The steel plate used for the Sn-plated steel plate according to the present embodiment is not particularly defined, and any steel plate can be used as long as it is a steel plate used for a Sn-plated steel plate for general containers. For example, low carbon steel, ultra low carbon steel, etc. are mentioned. Also, the manufacturing method and material of the steel sheet to be used are not particularly specified, and examples include those manufactured through processes such as casting, hot rolling, pickling, cold rolling, annealing, temper rolling, etc. Can do.

<Snめっき層について>
上記のような鋼板の少なくとも片面には、Snめっきが施されて、Snめっき層が形成される。かかるSnめっきによって、鋼板の耐食性は向上する。なお、本明細書における「Snめっき」とは、金属Snによるめっきだけでなく、金属Snに不純物が混入したものや、金属Snに微量元素が添加したものも含む。
<About Sn plating layer>
Sn plating is performed on at least one surface of the steel plate as described above to form a Sn plating layer. Such Sn plating improves the corrosion resistance of the steel sheet. In addition, “Sn plating” in this specification includes not only plating with metal Sn but also a metal Sn mixed with impurities and a metal Sn added with a trace element.

本実施形態に係るSnめっき層において、片面当たりのSn付着量は、Sn換算量として、0.1g/m以上15g/m以下とする。Snめっき層の片面当たりの付着量が、Sn換算量として0.1g/m未満では、耐食性に劣り、好ましくない。また、Snめっき層の片面当たりの付着量が、Sn換算量として15g/m超過では、Snによる耐食性の向上効果は十分であり、更なる増加は経済的な観点から好ましくない。なお、Snめっき層の片面当たりの付着量は、好ましくは、Sn換算量として0.9g/m以上14g/m以下である。 In the Sn plating layer according to the present embodiment, the Sn adhesion amount per one surface is 0.1 g / m 2 or more and 15 g / m 2 or less as the Sn conversion amount. If the adhesion amount per one side of the Sn plating layer is less than 0.1 g / m 2 as the Sn conversion amount, the corrosion resistance is inferior, which is not preferable. Moreover, if the adhesion amount per one side of Sn plating layer exceeds 15 g / m < 2 > as Sn conversion amount, the improvement effect of corrosion resistance by Sn will be enough, and the further increase is not preferable from an economical viewpoint. In addition, the adhesion amount per one side of the Sn plating layer is preferably 0.9 g / m 2 or more and 14 g / m 2 or less in terms of Sn.

ここで、上記の片面当たりのSnの付着量は、例えばJIS G 3303に記載された電解法や蛍光X線法によって測定された値とする。   Here, the adhesion amount of Sn per one surface is a value measured by, for example, an electrolytic method or a fluorescent X-ray method described in JIS G 3303.

[Snめっき層の形成方法]
また、Snめっきを鋼板表面に施す方法は、特に規定しないが、例えば公知の電気めっき法が好ましく、溶融したSnに鋼板を浸漬することでめっきする溶融法を用いてもよい。電気めっき法としては、例えば、周知のフェロスタン浴やハロゲン浴やアルカリ浴などを用いた電解法を利用することができる。
[Method of forming Sn plating layer]
The method of applying Sn plating to the surface of the steel sheet is not particularly defined, but for example, a known electroplating method is preferable, and a melting method of plating by immersing the steel sheet in molten Sn may be used. As the electroplating method, for example, an electrolysis method using a well-known ferrostan bath, halogen bath, alkali bath, or the like can be used.

なお、Snめっき後に、Snめっきの施された鋼板をSnの融点である231.9℃以上に加熱する、加熱溶融処理を施しても構わない。この加熱溶融処理によって、Snめっき鋼板の表面に光沢が出るとともに、Snめっきと鋼板の間に、SnとFeとの合金層が形成され、耐食性が更に向上する。   In addition, you may perform the heat-melting process which heats the steel plate in which Sn plating was given to 231.9 degreeC or more which is melting | fusing point of Sn after Sn plating. By this heat-melting treatment, the surface of the Sn-plated steel sheet becomes glossy, and an alloy layer of Sn and Fe is formed between the Sn plating and the steel sheet, thereby further improving the corrosion resistance.

<Zn−Niめっき層について>
本実施形態に係るSnめっき鋼板は、上記のようなSnめっき層を有するSnめっき鋼板の表面に、質量%で、Niを5%以上75%以下含有し、残部がZn及び不純物からなるZn−Niめっき層が、片面当たり、0.05g/m以上0.5g/m以下の付着量で形成される。
<About Zn-Ni plating layer>
The Sn-plated steel sheet according to the present embodiment contains 5% to 75% of Ni by mass% on the surface of the Sn-plated steel sheet having the Sn plating layer as described above, with the balance being Zn— consisting of Zn and impurities. Ni plating layer per one side is formed by 0.05 g / m 2 or more 0.5 g / m 2 or less of coating weight.

Niの含有率を5質量%以上75質量%以下とすることで、Zn−Niめっき層中に、熱力学的に安定なγ相(NiZn21主体)やα相(Znが固溶したNi)のいずれか又は両方が含まれるようになる。これらのNiとZnとからなるめっき層は、Snめっき表面を覆いSnめっき表面への酸素到達を抑制することで酸化Snの成長を抑制するとともに、ZnとNiとを含むめっきの一部がSnめっき中に取り込まれることでSn自体を酸化させ難くする効果があり、黄変や塗膜密着性、耐硫化黒変性を改善すると考えられる。 By making the Ni content 5% by mass or more and 75% by mass or less, thermodynamically stable γ phase (Ni 5 Zn 21 main component) or α phase (Zn is dissolved in the Zn—Ni plating layer). Ni) or both of them are included. These plating layers made of Ni and Zn cover the Sn plating surface and suppress the growth of Sn oxide by suppressing the arrival of oxygen to the Sn plating surface, and part of the plating containing Zn and Ni is Sn. It is considered that Sn itself is difficult to oxidize by being taken in during plating, and that yellowing, coating film adhesion, and resistance to sulfur blackening are improved.

Ni単独でも酸化Snの抑制効果はあるものの、Ni自体の色調により外観が黄みを増すだけでなく、塗膜密着性も低下し、更にNiS生成により黒変するため好ましくない。一方、Zn単独ではポーラスな酸化亜鉛が成長するため、酸化Snの抑制効果が不十分で、耐黄変性塗膜密着性に劣るため、好ましくない。   Although Ni alone has the effect of suppressing Sn oxidation, it is not preferable because not only the appearance increases yellow due to the color tone of Ni itself, but also the adhesion of the coating film decreases, and further blackening occurs due to NiS generation. On the other hand, when Zn alone is used, porous zinc oxide grows, so that the effect of suppressing Sn oxide is insufficient, and the adhesion to yellowing-resistant coating film is inferior.

Niの含有率が5質量%未満であると、η相(Zn)がZn−Niめっき層中に過剰に含まれるため、経時でZnが酸化し、塗膜密着性が劣化する。Niの含有率が75質量%超過であると、Niが過剰となりNiSを形成し易くなるため耐硫化黒変性に劣り、また、塗膜密着性も低下する。このため、Niの含有率は、質量%で5%以上75%とする必要がある。なお、Niの含有率の好ましい範囲は、10質量%以上55質量%以下であり、より好ましい範囲は、10質量%以上30質量%以下である。   When the Ni content is less than 5% by mass, the η phase (Zn) is excessively contained in the Zn—Ni plating layer, so that Zn is oxidized over time and the coating film adhesion deteriorates. If the Ni content exceeds 75% by mass, Ni becomes excessive and NiS is easily formed, so that it is inferior to sulfur blackening resistance and the coating film adhesion also decreases. For this reason, the content rate of Ni needs to be 5% or more and 75% by mass%. In addition, the preferable range of the content rate of Ni is 10 mass% or more and 55 mass% or less, and a more preferable range is 10 mass% or more and 30 mass% or less.

上記のNi、Znを主体とするZn−Niめっき層中には、不可避的な不純物、例えば、Fe、S、Na、K、Cl、F、Mg、Cr、Pbなどを含んでいても、特に問題はない。   The Zn—Ni plating layer mainly composed of Ni and Zn may contain inevitable impurities such as Fe, S, Na, K, Cl, F, Mg, Cr, and Pb. No problem.

上記のNi、Znを主体とするZn−Niめっき層の付着量は、0.05g/m以上0.5g/m以下である必要がある。Zn−Niめっき層の付着量が0.05g/m未満である場合には、Snめっき表面の被覆率の低下や、Zn−Niめっき層の一部のSnめっき層中への取り込みが少ないことによって、酸化Snの成長の抑制効果に劣る。一方、Zn−Niめっき層の付着量が0.5g/mを超過である場合には、本実施形態に係るSnめっき鋼板が塗装されて使用される場合の塗膜密着性が低下する。Zn−Niめっき層の付着量の好ましい範囲は、0.1g/m以上0.3g/m以下である。 Adhesion amount of Zn-Ni plated layer mainly above Ni, and Zn is required to be 0.05 g / m 2 or more 0.5 g / m 2 or less. When the adhesion amount of the Zn—Ni plating layer is less than 0.05 g / m 2 , the coverage of the Sn plating surface is reduced and a part of the Zn—Ni plating layer is not taken into the Sn plating layer. Therefore, the effect of suppressing the growth of Sn oxide is inferior. On the other hand, when the adhesion amount of the Zn—Ni plating layer is more than 0.5 g / m 2 , the coating film adhesion when the Sn-plated steel sheet according to the present embodiment is coated and used is lowered. A preferable range of the adhesion amount of the Zn—Ni plating layer is 0.1 g / m 2 or more and 0.3 g / m 2 or less.

上記のNi、Znを主体とするZn−Niめっき層の組成及び付着量は、本Zn−Niめっき層を表面に形成させたSnめっき鋼板を、例えば、硝酸などの酸性溶液に浸漬して溶解し、得られた溶解液を高周波誘導結合プラズマ(Inductively Coupled Plasma:ICP)発光分析法などの化学分析によって測定された値とする。   The composition and adhesion amount of the above Zn-Ni plating layer mainly composed of Ni and Zn are dissolved by, for example, immersing an Sn-plated steel sheet having the Zn-Ni plating layer formed on the surface thereof in an acidic solution such as nitric acid. Then, the obtained lysate is set to a value measured by a chemical analysis such as an inductively coupled plasma (ICP) emission analysis method.

[Zn−Niめっき層の形成方法]
Snめっき鋼板の表面に位置する上記のNi、Znを主体とするZn−Niめっき層は、Niイオンと、Znイオンとを含む水溶液を利用した陰極電解によって、形成することができる。水溶液の種類は、特に規定するものではないが、周知の硫酸浴や塩化物浴を適用することが可能である。本実施形態に係るZn−Niめっきを形成する際には、NiイオンとZnイオンとを含み、かつ、Niイオン濃度が質量%で20%以上95%以下、かつ、NiイオンとZnイオンとの合計が50kg/m以上250kg/m以下である水溶液中で、液温25℃以上70℃以下、電流密度0.1A/dm以上100A/dm以下の条件で陰極電解する必要がある。この条件で陰極電解処理を実施することで、本発明の範囲の、鋼板の少なくとも片面に、質量%で、Snを0.1g/m以上15g/m以下を含有するSnめっき鋼板上に、質量%で、Niを5%以上75%以下含有し、残部がZn及び不純物からなるZn−Niめっき層を有するSnめっき鋼板を得ることができる。
[Method of forming Zn—Ni plating layer]
The Zn—Ni plating layer mainly composed of Ni and Zn located on the surface of the Sn-plated steel sheet can be formed by cathodic electrolysis using an aqueous solution containing Ni ions and Zn ions. The type of the aqueous solution is not particularly limited, but a well-known sulfuric acid bath or chloride bath can be applied. When forming the Zn—Ni plating according to the present embodiment, the Ni ion and the Zn ion are included, the Ni ion concentration is 20% to 95% by mass%, and the Ni ion and the Zn ion are mixed. Cathodic electrolysis is required in an aqueous solution having a total of 50 kg / m 3 or more and 250 kg / m 3 or less under conditions of a liquid temperature of 25 ° C. or more and 70 ° C. or less and a current density of 0.1 A / dm 2 or more and 100 A / dm 2 or less. . By carrying out cathodic electrolysis treatment under these conditions, on at least one surface of the steel sheet within the scope of the present invention, on a Sn-plated steel sheet containing 0.1 g / m 2 or more and 15 g / m 2 or less of Sn in mass%. In addition, it is possible to obtain a Sn-plated steel sheet having a Zn—Ni plating layer containing 5% to 75% Ni by mass and the balance being Zn and impurities.

めっき浴中のNiイオン濃度が20質量%未満である場合には、Zn−Niめっき層中のNiの含有率が5質量%未満となり、本発明の範囲を満たさない。また、めっき浴中のNiイオン濃度が95%超過である場合には、Zn−Niめっき層中のNi含有率が75質量%超過となり、本発明の範囲を満たさない。めっき浴中のNiイオン濃度の好ましい範囲は、30質量%以上90質量%以下であり、より好ましくは30質量%以上80%質量以下である。   When the Ni ion concentration in the plating bath is less than 20% by mass, the Ni content in the Zn—Ni plating layer is less than 5% by mass, which does not satisfy the scope of the present invention. Further, when the Ni ion concentration in the plating bath is over 95%, the Ni content in the Zn—Ni plating layer is over 75 mass%, which does not satisfy the scope of the present invention. A preferable range of the Ni ion concentration in the plating bath is 30% by mass or more and 90% by mass or less, and more preferably 30% by mass or more and 80% by mass or less.

また、NiイオンとZnイオンとの合計が50kg/m未満である場合には、Zn−Niめっきの付着効率に劣り、得られたZn−Niめっきも粗となり、性能に劣るため、好ましくない。また、NiイオンとZnイオンとの合計が250kg/m超過である場合には、沈殿物の生成等、液の安定性に劣り、得られためっきも粗くなり塗膜密着性に劣るため、好ましくない。 Moreover, when the sum of Ni ions and Zn ions is less than 50 kg / m 2 , the deposition efficiency of Zn—Ni plating is inferior, and the obtained Zn—Ni plating becomes rough and inferior in performance. . In addition, when the total of Ni ions and Zn ions is more than 250 kg / m 3 , the formation of precipitates and the like is inferior in stability of the liquid, and the obtained plating becomes rough and inferior in coating film adhesion. It is not preferable.

めっき浴の液温は、25℃以上70℃以下であることが好ましい。液温を25℃以上とすることで、液の安定性を更に向上させることが可能となる。液温が高い方がZn−Niめっきの付着効率は向上するが、液温が70℃超過である場合には、付着効率の向上効果は飽和する傾向にあり経済性の観点から好ましくなく、また、めっき浴からの水蒸気発生もあり、作業性の観点からも好ましくない。従って、めっき浴の液温は、25℃以上70℃以下であることが好ましい。なお、めっき浴の液温は、より好ましくは、35℃以上60℃以下である。   The liquid temperature of the plating bath is preferably 25 ° C. or higher and 70 ° C. or lower. By setting the liquid temperature to 25 ° C. or higher, the stability of the liquid can be further improved. The higher the liquid temperature, the better the deposition efficiency of Zn-Ni plating. However, if the liquid temperature exceeds 70 ° C, the effect of improving the adhesion efficiency tends to saturate, which is not preferable from the viewpoint of economy. Also, water vapor is generated from the plating bath, which is not preferable from the viewpoint of workability. Accordingly, the temperature of the plating bath is preferably 25 ° C. or higher and 70 ° C. or lower. The liquid temperature of the plating bath is more preferably 35 ° C. or higher and 60 ° C. or lower.

陰極電解する際の電流密度は、0.1A/dm以上100A/dm以下とする必要がある。電流密度が0.1A/dm未満である場合には、Zn−Niめっき層中のNi含有率が高くなり塗膜密着性や耐硫化黒変性に劣るだけでなく、Zn−Niめっきの付着効率が著しく小さく、本発明の範囲のZn−Niめっきを得ることが出来ない。一方、電流密度が150A/dm超過である場合には、めっきが粗となり塗膜密着性に劣り、好ましくない。陰極電解する際の電流密度は、好ましくは、1A/dm以上90A/dm以下である。 The current density at the time of cathodic electrolysis needs to be 0.1 A / dm 2 or more and 100 A / dm 2 or less. When the current density is less than 0.1 A / dm 2 , the Ni content in the Zn—Ni plating layer becomes high and the coating film adhesion and sulfur blackening resistance are not only inferior, but also the Zn—Ni plating adheres. The efficiency is remarkably small, and Zn—Ni plating within the range of the present invention cannot be obtained. On the other hand, when the current density exceeds 150 A / dm 2 , the plating becomes rough and the coating film adhesion is poor, which is not preferable. The current density during cathodic electrolysis is preferably 1 A / dm 2 or more and 90 A / dm 2 or less.

続いて、実施例及び比較例を示しながら、本発明に係るSnめっき鋼板及びSnめっき鋼板の製造方法について、具体的に説明する。なお、以下に示す実施例は、あくまでも本発明に係るSnめっき鋼板及びSnめっき鋼板の製造方法の一例にすぎず、本発明に係るSnめっき鋼板及びSnめっき鋼板の製造方法が下記の例に限定されるものではない。   Then, the manufacturing method of Sn plating steel plate and Sn plating steel plate concerning the present invention is explained concretely, showing an example and a comparative example. In addition, the Example shown below is only an example of the manufacturing method of Sn plating steel plate and Sn plating steel plate which concerns on this invention, and the manufacturing method of Sn plating steel plate and Sn plating steel plate which concerns on this invention is limited to the following example. Is not to be done.

(試験例)
<試験材の作製>
板厚0.2mmの低炭素冷延鋼板を、前処理として電解アルカリ脱脂、水洗、希硫酸浸漬酸洗、水洗した後、フェノールスルホン酸浴を用いて電気Snめっきを施した。一部の試験材は、Snめっき層の付着量を変化させた。また、電気Snめっき後に加熱溶融処理をした試験材も作製した。このように作製したSnめっき鋼板を、表1〜表6に示すNi及びZnの組成の水溶液中で陰極電解し、Ni、Znを主体とするZn−Niめっき層をSnめっき層の表面に形成した。なお、表1〜表5においては、硫酸浴から陰極電解処理をし、表6においては、塩化物浴から陰極電解処理をした。
(Test example)
<Production of test material>
A low carbon cold-rolled steel sheet having a thickness of 0.2 mm was subjected to electrolytic alkaline degreasing, water washing, dilute sulfuric acid immersion acid washing, and water washing as pretreatment, and then subjected to electric Sn plating using a phenolsulfonic acid bath. Some of the test materials changed the amount of Sn plating layer deposited. Moreover, the test material which carried out the heat-melt process after electric Sn plating was also produced. The thus-prepared Sn-plated steel sheet is subjected to cathodic electrolysis in an aqueous solution having the composition of Ni and Zn shown in Tables 1 to 6, and a Zn—Ni plating layer mainly composed of Ni and Zn is formed on the surface of the Sn plating layer. did. In Tables 1 to 5, cathodic electrolysis was performed from a sulfuric acid bath, and in Table 6, cathodic electrolysis was performed from a chloride bath.

<Ni、Zn組成及び付着量の測定>
このように作製したSnめっき鋼板の表面におけるNi、Znの組成及び付着量は、Snめっき鋼板を10%硝酸に浸漬して、Ni、Znを含む層を溶解し、得られた溶解液をICP発光分析により分析することで求めた。なお、Snめっき層の付着量は、上記の蛍光X線分析により測定した。
<Measurement of Ni and Zn composition and adhesion amount>
The composition and adhesion amount of Ni and Zn on the surface of the Sn-plated steel sheet produced in this way were determined by immersing the Sn-plated steel sheet in 10% nitric acid to dissolve the layer containing Ni and Zn, and the obtained solution was ICP. It was determined by analyzing by luminescence analysis. In addition, the adhesion amount of Sn plating layer was measured by said fluorescent X ray analysis.

<耐黄変性>
耐黄変性は、上記<試験材の作製>に記載の方法で作製したSnめっき鋼板を、40℃、相対湿度80%の雰囲気中に4週間載置する湿潤試験を行い、湿潤試験前後における色差b*値の変化量△b*を求めて、評価した。△b*が1以下であれば◎とし、1超過2以下であれば○とし、2超過であれば×とし、◎と○を合格と評価した。b*は、市販の色差計であるスガ試験機製SC−GV5を用いて測定し、b*の測定条件は、光源C、全反射、測定径30mmである。
<Yellow resistance>
Yellowing resistance is a color difference between before and after the wet test, in which a Sn-plated steel sheet prepared by the method described in <Preparation of Test Material> is placed in an atmosphere of 40 ° C. and 80% relative humidity for 4 weeks. b * value change Δb * was determined and evaluated. When Δb * was 1 or less, ◎, when 1 exceeded 2 or less, ○, when 2 exceeded, ×, and ◎ and ○ were evaluated as acceptable. b * is measured using SC-GV5 manufactured by Suga Test Instruments, which is a commercially available color difference meter. The measurement conditions for b * are light source C, total reflection, and measurement diameter of 30 mm.

<塗膜密着性>
塗膜密着性は、上記<試験材の作製>に記載の方法で作製したSnめっき鋼板を、<耐黄変性>に記載の方法で湿潤試験した後、表面に、市販の缶用エポキシ樹脂塗料を乾燥重量で7g/m塗布し、200℃で10分焼き付け、24時間室温に置いた後、鋼板表面に達する傷を碁盤目状に入れ(3mm間隔で縦横7本ずつの傷)、その部位のテープ剥離試験をして評価した。テープ貼り付け部位の塗膜が全て剥離していなければ◎とし、碁盤目の傷部周囲で塗膜剥離が認められれば○とし、碁盤目の枡内に塗膜剥離が認められれば×とし、◎と○を合格とした。なお、試験は、上記<耐黄変性>に記載の湿潤試験をした試験材と、していない試験材の両方に対して実施した。
<Coating film adhesion>
For coating film adhesion, a Sn-plated steel sheet produced by the method described in <Preparation of Test Material> was subjected to a wet test by the method described in <Yellow Resistance>, and then a commercially available epoxy resin coating for cans was formed on the surface. Was applied at a dry weight of 7 g / m 2, baked at 200 ° C. for 10 minutes, and left at room temperature for 24 hours. Then, scratches reaching the surface of the steel sheet were put in a grid pattern (scratches of 7 vertical and horizontal at 3 mm intervals) The tape peeling test of the part was performed and evaluated. ◎ if all of the coating film on the tape application site is not peeled off, ◯ if the coating film peeling is observed around the scratched part of the grid, and x if coating film peeling is observed in the grid of the grid. ◎ and ○ were accepted. The test was conducted on both the test material subjected to the wet test described in the above <yellowing resistance> and the test material not subjected to the wet test.

<耐硫化黒変性>
耐硫化黒変性は、上記<塗膜密着性>に記載の方法で作製及び湿潤試験したSnめっき鋼板の表面に、市販の缶用エポキシ樹脂塗料を乾燥重量で7g/m塗布した後、200℃で10分焼き付け、24時間室温に置いた後、所定のサイズに切断し、リン酸二水素ナトリウムを0.3%、リン酸水素ナトリウムを0.7%、L−システイン塩酸塩を0.6%からなる水溶液中に浸漬し、密封容器中で121℃・60分のレトルト処理を行い、試験後の外観から評価した。試験前後で外観の変化が全く認められなければ◎とし、僅かに(10%以下)黒変が認められれば○とし、試験面の10%超過の領域に黒変が認められれば×とし、◎と○を合格とした。
<Sulfur black resistance>
Anti-sulfur blackening resistance was measured by applying a commercially available epoxy resin coating for cans to a surface of a Sn-plated steel sheet prepared and wet-tested by the method described in <Coating film adhesion> above, after applying 7 g / m 2 by dry weight. After baking at room temperature for 10 minutes and leaving at room temperature for 24 hours, it was cut into a predetermined size, 0.3% sodium dihydrogen phosphate, 0.7% sodium hydrogen phosphate, and 0.1% L-cysteine hydrochloride. It was immersed in a 6% aqueous solution, subjected to a retort treatment at 121 ° C. for 60 minutes in a sealed container, and evaluated from the appearance after the test. ◎ if there is no change in appearance before and after the test, ◯ if there is a slight (10% or less) blackening, and x if there is blackening in an area exceeding 10% of the test surface. And ○ passed.

<塗装後耐食性>
塗装後耐食性は、上記<塗膜密着性>に記載の方法で作製及び湿潤試験したSnめっき鋼板の表面に、市販の缶用エポキシ樹脂塗料を乾燥重量で7g/m塗布した後、200℃で10分焼き付け、24時間室温に置いた後、所定のサイズに切断し、市販のトマトジュースに60℃で7日間浸漬した後の、錆の発生有無を目視にて評価した。錆が全く認められなければ○とし、錆が認められれば×とし、○を合格とした。
<Corrosion resistance after painting>
Corrosion resistance after coating was measured at 200 ° C. after applying a commercially available epoxy resin coating for cans at a dry weight of 7 g / m 2 on the surface of the Sn-plated steel sheet prepared and wet-tested by the method described in <Coating Film Adhesion> above. After being baked for 10 minutes and left at room temperature for 24 hours, it was cut into a predetermined size, and the presence or absence of rust was visually evaluated after being dipped in commercial tomato juice at 60 ° C. for 7 days. When rust was not recognized at all, it was evaluated as ◯, when rust was observed, it was evaluated as x, and ◯ was regarded as acceptable.

<めっき浴安定性>
めっき浴安定性は、<試験材の作製>に記載のめっき浴を24時間放置した後の外観を目視観察し、濁りや沈殿が認められた場合を×とし、透明で濁りや沈殿が認められなかった場合を○とした。
<Plating bath stability>
The plating bath stability is determined by visually observing the appearance after leaving the plating bath described in <Preparation of test material> for 24 hours, and when turbidity or precipitation is observed, it is x, and transparent, turbidity or precipitation is observed. The case where it did not exist was marked as ◯.

以下に示す表1〜表6は、Ni、Znを主体とするZn−Niめっき層を表面に有するSnめっき鋼板の作製条件とその組成及び付着量の結果、並びに、耐黄変性、塗膜密着性、耐硫化黒変性及びめっき浴安定性の評価結果である。   Tables 1 to 6 below show the preparation conditions of Sn-plated steel sheet having a Zn—Ni plating layer mainly composed of Ni and Zn, results of the composition and adhesion amount, yellowing resistance, and coating adhesion. It is an evaluation result of the property, anti-sulfur blackening property and plating bath stability.

Figure 0006468059
Figure 0006468059

表1は、Zn−Niめっき組成を変化させた場合の結果である。浴組成が本発明の範囲内である場合には、本発明の範囲内のZn−Niめっき層が得られ、いずれの性能も良好であることが分かる。一方、浴組成が本発明の範囲を外れる場合には、いずれかの性能が劣ることが分かる。図1に、めっき浴組成とめっき中のNi含有率を図示し、図2に、△b*に及ぼすめっき中のNi含有率の影響を図示した。Ni含有率が5%以上である場合、△b*は2以下となって、耐黄変性は良好である。但し、NiイオンとZnイオンの合計が40kg/mである場合には、Zn−Niめっきの電流効率が低く、その付着量が少ないため、△b*が2超過となり、耐黄変性に劣る。 Table 1 shows the results when the Zn—Ni plating composition is changed. When the bath composition is within the range of the present invention, a Zn—Ni plating layer within the range of the present invention is obtained, and it can be seen that all the performances are good. On the other hand, if the bath composition is outside the scope of the present invention, it can be seen that either performance is inferior. FIG. 1 illustrates the plating bath composition and the Ni content during plating, and FIG. 2 illustrates the effect of the Ni content during plating on Δb *. When the Ni content is 5% or more, Δb * is 2 or less, and yellowing resistance is good. However, when the total of Ni ions and Zn ions is 40 kg / m 3 , the current efficiency of Zn—Ni plating is low and the amount of adhesion is small, so Δb * exceeds 2 and is inferior in yellowing resistance. .

Figure 0006468059
Figure 0006468059

表2は、Snめっき層の付着量を変化させた場合の結果である。Snめっき層の付着量が本発明の範囲内である場合、いずれの性能も良好であることが分かる。一方、Snめっき層の付着量が本発明の範囲を下回る場合には、耐食性が劣ることが分かる。Snめっき層の付着量が本発明の範囲を超える場合は、いずれの性能も良好であるが、経済性の観点からは、好ましくない。   Table 2 shows the results when the adhesion amount of the Sn plating layer is changed. When the adhesion amount of the Sn plating layer is within the range of the present invention, it can be seen that both performances are good. On the other hand, when the adhesion amount of the Sn plating layer is below the range of the present invention, it can be seen that the corrosion resistance is inferior. When the adhesion amount of the Sn plating layer exceeds the range of the present invention, all the performances are good, but it is not preferable from the viewpoint of economy.

Figure 0006468059
Figure 0006468059

表3は、電流密度を変化させた場合の結果である。電流密度が本発明の範囲内である場合には、本発明の範囲内のめっきが得られ、いずれの性能も良好であることが分かる。一方、電流密後が本発明の範囲を外れる場合には、いずれかの性能が劣ることが分かる。図3に、めっき中のNi含有率に及ぼす電流密度の影響を図示した。   Table 3 shows the results when the current density is changed. When the current density is within the range of the present invention, plating within the range of the present invention is obtained, and it can be seen that all the performances are good. On the other hand, if the current density is outside the scope of the present invention, it can be seen that either performance is inferior. FIG. 3 illustrates the effect of current density on the Ni content during plating.

Figure 0006468059
Figure 0006468059

表4は、めっき浴の液温を変えた場合の結果である。液温を25℃以上70℃以下とすることで、液温が上記範囲外である場合と比較して、液の安定性が向上することが分かる。   Table 4 shows the results when the temperature of the plating bath was changed. It can be seen that by setting the liquid temperature to 25 ° C. or more and 70 ° C. or less, the stability of the liquid is improved as compared with the case where the liquid temperature is out of the above range.

Figure 0006468059
Figure 0006468059

表5は、Snめっき層に対する加熱溶融処理をしない場合の結果である。加熱溶融処理をしない場合においても、いずれの性能も問題なく良好であることが分かる。   Table 5 shows the results obtained when the Sn plating layer is not heat-melted. It can be seen that even when the heat-melting treatment is not performed, all the performances are satisfactory without problems.

Figure 0006468059
Figure 0006468059

表6は、塩化物浴から陰極電解した場合の結果である。塩化物浴から得たNi,Znを含むZn−Niめっきにおいても、いずれの性能も問題なく良好であることが分かる。   Table 6 shows the results of cathodic electrolysis from a chloride bath. It can be seen that even in Zn-Ni plating containing Ni and Zn obtained from a chloride bath, all the performances are satisfactory without problems.

以上のように、本発明に係るNiとZnを主体とするZn−Niめっき層を形成させた本発明のSnめっき鋼板は、耐黄変性、塗膜密着性、耐硫化黒変性に優れることが明らかとなった。   As described above, the Sn-plated steel sheet of the present invention on which the Zn—Ni plating layer mainly composed of Ni and Zn according to the present invention is formed is excellent in yellowing resistance, coating film adhesion, and sulfurization blackness resistance. It became clear.

以上、本発明の好適な実施形態について詳細に説明したが、本発明はかかる例に限定されない。本発明の属する技術の分野における通常の知識を有する者であれば、特許請求の範囲に記載された技術的思想の範疇内において、各種の変更例または修正例に想到し得ることは明らかであり、これらについても、当然に本発明の技術的範囲に属するものと了解される。   As mentioned above, although preferred embodiment of this invention was described in detail, this invention is not limited to this example. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.

以上のように、NiとZnを主体とするZn−Niめっき層を形成させた本発明のSnめっき鋼板は、従来のクロメート処理を必要とせずに、耐黄変性、塗膜密着性、耐硫化黒変性に優れることから、環境にやさしい缶用材料として、食缶、飲料缶などに広く用いることができ、産業上の利用価値が極めて高いものである。
As described above, the Sn-plated steel sheet of the present invention in which a Zn—Ni plating layer mainly composed of Ni and Zn is formed does not require the conventional chromate treatment, and is resistant to yellowing, coating adhesion, and sulfidation resistance. Since it is excellent in blackening, it can be widely used for food cans, beverage cans and the like as an environmentally friendly can material, and has a very high industrial utility value.

Claims (6)

鋼板の少なくとも片面に、SnをSn換算量として片面当たり2.8g/m以上15g/m以下含有するSnめっき層が形成されたSnめっき鋼板上に、質量%で、Niを5%以上75%以下含有し、残部がZn及び不純物からなるZn−Niめっき層が、片面当たり0.05g/m以上0.5g/m以下の付着量で形成された、Snめっき鋼板。 On at least one side of the steel sheet , Sn is contained in an amount of mass% on a Sn-plated steel sheet on which an Sn plating layer containing Sn in an amount of 2.8 g / m 2 or more and 15 g / m 2 or less per one surface as Sn equivalent amount is formed. more than 5% to 75% contain less, the balance being Zn-Ni plated layer consisting of Zn and impurities, formed by two or more 0.5 g / m 2 or less of coating weight per side 0.05 g / m, Sn-plated steel sheet . 前記Zn−Niめっき層におけるNi含有率が、質量%で、10%以上55%以下である、請求項1に記載のSnめっき鋼板。   The Sn-plated steel sheet according to claim 1, wherein the Ni content in the Zn-Ni plated layer is 10% to 55% by mass. 前記Zn−Niめっき層におけるNi含有率が、質量%で、10%以上30%以下である、請求項1又は2に記載のSnめっき鋼板。   The Sn plating steel plate according to claim 1 or 2 whose Ni content in said Zn-Ni plating layer is 10% or more and 30% or less by mass%. 前記Snめっき層と前記鋼板との間に、SnとFeとの合金層を有する、請求項1〜3の何れか1項に記載のSnめっき鋼板。   The Sn plated steel sheet according to any one of claims 1 to 3, further comprising an alloy layer of Sn and Fe between the Sn plated layer and the steel sheet. 鋼板の少なくとも片面に、SnをSn換算量として片面当たり2.8g/m以上15g/m以下含有するSnめっき層が形成されたSnめっき鋼板を、
NiイオンとZnイオンとを含み、Niイオン濃度が質量%で20%以上95%以下であり、かつ、NiイオンとZnイオンの合計が50kg/m以上250kg/m以下である水溶液中で、
電流密度0.1A/dm以上150A/dm以下の条件で電解する、Snめっき鋼板の製造方法。
On at least one surface of the steel sheet, the S n, the Sn plated steel sheet Sn plating layer is formed containing 2.8 g / m 2 or more 15 g / m 2 or less per one side as Sn in terms of amount,
In an aqueous solution containing Ni ions and Zn ions, the Ni ion concentration being 20% to 95% by mass, and the total of Ni ions and Zn ions being 50 kg / m 3 to 250 kg / m 3 ,
Electrolysis at a current density of 0.1 A / dm 2 or more 150A / dm 2 the following conditions, the production method of the Sn-plated steel sheet.
鋼板の少なくとも片面に、SnをSn換算量として片面当たり2.8g/m以上15g/m以下含有するSnめっき層と、当該Snめっき層と鋼板との間に位置するSnとFeとの合金層と、が形成されたSnめっき鋼板を、
NiイオンとZnイオンとを含み、Niイオン濃度が質量%で20%以上95%以下であり、かつ、NiイオンとZnイオンの合計が50kg/m以上250kg/m以下である水溶液中で、
電流密度0.1A/dm以上150A/dm以下の条件で電解する、Snめっき鋼板の製造方法。
On at least one surface of the steel sheet, the S n, and the Sn plating layer containing 2.8 g / m 2 or more 15 g / m 2 or less per one side as Sn in terms of weight, and Sn which is located between said Sn plating layer and the steel sheet An Sn-plated steel sheet on which an alloy layer with Fe is formed,
In an aqueous solution containing Ni ions and Zn ions, the Ni ion concentration being 20% to 95% by mass, and the total of Ni ions and Zn ions being 50 kg / m 3 to 250 kg / m 3 ,
Electrolysis at a current density of 0.1 A / dm 2 or more 150A / dm 2 the following conditions, the production method of the Sn-plated steel sheet.
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