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JP4844021B2 - Method for producing tin-plated steel strip - Google Patents

Method for producing tin-plated steel strip Download PDF

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JP4844021B2
JP4844021B2 JP2005182194A JP2005182194A JP4844021B2 JP 4844021 B2 JP4844021 B2 JP 4844021B2 JP 2005182194 A JP2005182194 A JP 2005182194A JP 2005182194 A JP2005182194 A JP 2005182194A JP 4844021 B2 JP4844021 B2 JP 4844021B2
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plating
steel strip
tin
bath
iron
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JP2007002287A (en
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京子 浜原
田中  匠
威 鈴木
浩樹 岩佐
健太郎 鈴木
慶 結城
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JFE Steel Corp
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Description

本発明は、複数のめっきセルを有する水平型電気めっきラインを用いた電気めっき金属帯の製造方法、および錫めっき鋼帯の製造方法に関する。   The present invention relates to a method for producing an electroplated metal strip using a horizontal electroplating line having a plurality of plating cells, and a method for producing a tin-plated steel strip.

電解質水溶液(めっき浴)中に金属帯を浸漬して電解によりめっき皮膜を形成する金属帯の電気めっきラインとして、金属帯が複数のめっきセル内を水平移動し、金属帯の片面ずつにめっき処理される水平型電気めっきラインがある。この電気めっきラインは比較的構造が単純なため、金属帯を高速で移動しながらめっき処理を施すことができるという利点がある。その代表的な例として、めっき浴にハロゲン浴を用い、鋼帯に錫めっき処理を施すハロゲン錫めっきラインが挙げられる。特に、ハロゲン錫めっきラインでは、めっき浴中の錫が空気中の酸素によって2価から4価に酸化されて溶解度の小さいハロゲン化物となって多量にスラッジとして発生するので、この多量のスラッジをめっきセル底に沈殿除去できる水平型のめっきセルが好適である。   As a metal band electroplating line in which a metal band is immersed in an aqueous electrolyte solution (plating bath) to form a plating film by electrolysis, the metal band moves horizontally in multiple plating cells and plating is performed on each side of the metal band. There is a horizontal electroplating line done. Since this electroplating line has a relatively simple structure, there is an advantage that the plating process can be performed while moving the metal strip at a high speed. A typical example is a halogen tin plating line in which a halogen bath is used as a plating bath and a steel strip is subjected to tin plating. In particular, in the halogen tin plating line, tin in the plating bath is oxidized from divalent to tetravalent by oxygen in the air to form a low-solubility halide, and a large amount of sludge is generated. A horizontal type plating cell that can precipitate and remove at the cell bottom is suitable.

一方、近年、環境問題がクロ−ズアップされる中で、ハロゲンイオンを含むスラッジの処理が困難となってきているため、ハロゲン錫めっきラインのハロゲン浴はメタンスルホン酸浴、硫酸浴、フェノールスルホン酸浴など酸性めっき浴へ切り替えられつつある。しかし、こうした酸性めっき浴ではpHが低いため、鋼帯からめっき浴中への鉄の溶出速度が速くなり、めっき浴中の鉄イオン濃度が高くなって、高生産性を可能にする高電流密度条件で電気錫めっきを行うとめっき均一性が劣化する(例えば、非特許文献1参照)。また、めっき浴中の鉄イオンの増加は錫イオンの酸化を促進し、スラッジ発生の原因にもなる。特に、上述したように、鋼帯が片面ずつめっき処理される水平型のめっきセルを用いた場合には、未めっきの鋼帯表面からの鉄の溶出が著しく、めっきの不均一性が助長されたり、多量のスラッジが発生することになる。すなわち、図3に模式的に示したように、水平型電気めっきラインでは、搬送ロール4により搬送される金属帯1は、めっきセル2中のアノード3に対向した表面からめっき皮膜が形成されるため、先にめっき皮膜の形成される金属帯1の表面(「A面」と呼ぶ)と反対側の表面(「B面」と呼ぶ)は、A面にめっき皮膜が形成されるまでめっきセル2のめっき浴に浸漬されたままになっているので、金属帯1が鋼帯の場合はB面からめっき浴中に多量の鉄が溶出することになる。   On the other hand, in recent years, as environmental problems have been closed up, it has become difficult to treat sludge containing halogen ions. It is being switched to an acidic plating bath such as a bath. However, because the pH of such acidic plating baths is low, the elution rate of iron from the steel strip into the plating bath is increased, and the iron ion concentration in the plating bath is increased, enabling high current density that enables high productivity. If electrotin plating is performed under the conditions, the plating uniformity deteriorates (for example, see Non-Patent Document 1). Moreover, the increase of the iron ion in a plating bath accelerates | stimulates the oxidation of a tin ion, and causes sludge generation. In particular, as described above, when using a horizontal type plating cell in which the steel strip is plated one side at a time, the elution of iron from the surface of the unplated steel strip is remarkable, and the unevenness of plating is promoted. Or a large amount of sludge is generated. That is, as schematically shown in FIG. 3, in the horizontal electroplating line, the metal strip 1 transported by the transport roll 4 is formed with a plating film from the surface facing the anode 3 in the plating cell 2. Therefore, the surface opposite to the surface of the metal strip 1 (referred to as “A surface”) on which the plating film is first formed (referred to as “B surface”) is plated until the plating film is formed on the A surface. Since the metal strip 1 is still immersed in the plating bath 2, a large amount of iron is eluted from the B surface into the plating bath when the metal strip 1 is a steel strip.

めっき浴中への鉄の溶出を防止する方法として、酸性の錫めっき浴を用い、錫の電析開始前に鋼帯をめっき液に浸漬する、いわゆるプレディップ時に鋼帯をカソードとして、アノードとの間に0.03〜1A/dm2の電流を流して錫の電析を僅かに起こした状態にして、めっき浴中への鉄の溶出を防止する方法が開示されている(特許文献1参照)。また、鋼帯を連続式電気めっき設備により亜鉛または亜鉛合金めっきあるいは亜鉛または亜鉛合金をベースとした微粒子分散めっきを施す際に、鉄以外の導電性物質を用いて鋼帯に予め導電性皮膜を形成して、その後の亜鉛または亜鉛合金めっき工程において鉄の溶出を防止する方法も開示されている(特許文献2参照)。
特開平10-237685号公報 特開平5-106085号公報 George A. Federman et al: “5th International Tinplate Conference” (Industrial Tin Research Institute), 1992, P.88-98
As a method of preventing the elution of iron into the plating bath, an acidic tin plating bath is used, and the steel strip is immersed in a plating solution before the start of tin electrodeposition. A method of preventing the elution of iron into the plating bath by allowing a current of 0.03 to 1 A / dm 2 to flow between them to cause slight electrodeposition of tin is disclosed (see Patent Document 1). . In addition, when a steel strip is subjected to zinc or zinc alloy plating or fine particle dispersion plating based on zinc or zinc alloy using a continuous electroplating facility, a conductive coating is previously applied to the steel strip using a conductive material other than iron. There is also disclosed a method for preventing the elution of iron in the subsequent zinc or zinc alloy plating step (see Patent Document 2).
Japanese Patent Laid-Open No. 10-237685 Japanese Patent Laid-Open No. 5-106085 George A. Federman et al: “5th International Tinplate Conference” (Industrial Tin Research Institute), 1992, P.88-98

しかしながら、特許文献1に記載された方法を水平型電気めっきラインに適用して、第1番目のめっきセルで錫の電析が鋼帯表面に僅かに起こった状態にしても、その電析はアノードに対向した鋼帯表面でしか起こらないので、それとは反対側の鋼帯表面からの鉄の溶出は避けられない。また、特許文献2に記載された方法では、電気めっきラインの前にプレめっき装置を設置して導電性皮膜を形成する必要があり、製造コストの増大や生産性の低下を招く。   However, even if the method described in Patent Document 1 is applied to a horizontal electroplating line and tin electrodeposition occurs slightly on the surface of the steel strip in the first plating cell, the electrodeposition is Since it only occurs on the steel strip surface facing the anode, iron elution from the steel strip surface on the opposite side is inevitable. In addition, in the method described in Patent Document 2, it is necessary to install a pre-plating apparatus before the electroplating line to form a conductive film, resulting in an increase in manufacturing cost and a decrease in productivity.

本発明は、水平型電気めっきラインを用い、製造コストの増大や生産性の低下を招くことなく、めっき浴中への金属帯を構成する金属の溶出を防止できる電気めっき金属帯の製造方法、および錫めっき鋼帯の製造方法を提供することを目的とする。   The present invention is a method for producing an electroplated metal strip that uses a horizontal electroplating line and can prevent elution of the metal constituting the metal strip into the plating bath without causing an increase in production cost or a decrease in productivity, And it aims at providing the manufacturing method of a tin plating steel strip.

上記の目的は、複数のめっきセルを有する水平型電気めっきラインを用いて金属帯に電気めっき処理を施して電気めっき金属帯を製造するに当り、複数のめっきセルのうち少なくとも第1番目のめっきセルで金属帯の両面に電気めっき処理を施すことを特徴とする電気めっき金属帯の製造方法により達成される。   The above object is to produce an electroplated metal strip by subjecting a metal strip to electroplating using a horizontal electroplating line having a plurality of plating cells, and at least the first plating of the plurality of plating cells. This is achieved by a method for producing an electroplated metal strip, characterized in that electroplating is performed on both sides of the metal strip in a cell.

メタンスルホン酸錫めっき浴またはフェノールスルホン酸錫めっき浴を用いる複数のめっきセルを有する水平型電気錫めっきラインを用いて鋼帯に電気錫めっき処理を施して電気錫めっき鋼帯を製造する場合には、複数のめっきセルのうち少なくとも第1番目のめっきセルで前記鋼帯の両面に、錫付着量を鋼帯の片面当り0.02〜0.3g/m 2 とする電気錫めっき処理を施すことが必要である。 When manufacturing an electrotin-plated steel strip by subjecting the steel strip to electrotin plating using a horizontal electrotin plating line having a plurality of plating cells using a tin methane sulfonate plating bath or a phenol sulfonate tin plating bath Requires at least the first plating cell of a plurality of plating cells to be subjected to electrotin plating treatment on both surfaces of the steel strip so that the amount of tin adhered is 0.02 to 0.3 g / m 2 per one surface of the steel strip. It is.

本発明により、水平型電気めっきラインを用いて電気めっき金属帯を製造するに当り、製造コストの増大や生産性の低下を招くことなく、めっき浴中への金属帯を構成する金属の溶出を防止できるようになった。なお、この発明は、特に、電気錫めっき鋼帯の製造に好適である。   According to the present invention, in producing an electroplated metal strip using a horizontal electroplating line, the metal constituting the metal strip can be eluted into the plating bath without causing an increase in production cost or a decrease in productivity. It became possible to prevent. The present invention is particularly suitable for the production of an electrotin-plated steel strip.

本発明である電気めっき金属帯の製造方法は、図1に一例として模式的に示した水平型電気めっきラインにより実現できる。既存の第1番目のめっきセル2に、先にめっき皮膜の形成される金属帯1のA面とは反対側のB面にもめっき皮膜が形成できるように、新たにアノード3を設置し、第1番目のめっきセル2でB面にもめっき皮膜を形成すれば、その後のめっきセル2で金属帯1が直接めっき浴に接触することがなくなるので、金属帯1を構成する金属、すなわち金属帯1が鋼帯の場合は鉄のめっき浴への溶出が防止されることになる。また、既存のめっきセル2にアノード3を設置するだけなので、製造コストの増大や生産性の低下を招くことはない。本発明の目的を達成するために、第1番目のめっきセル2で金属帯1の両面にめっき皮膜を形成することは必須であるが、第2番目以降のめっきセル2にも新たにアノード3を設置し、両面にめっき皮膜を形成できるようにしても全く問題ない。一度に金属帯1の両面にめっき皮膜を形成できるめっきセル2が増えるので、めっきセル2のトータル個数を減少でき設備のコンパクト化や低コスト化を図れる。   The method for producing an electroplated metal strip according to the present invention can be realized by a horizontal electroplating line schematically shown as an example in FIG. In the existing first plating cell 2, an anode 3 is newly installed so that a plating film can also be formed on the B surface opposite to the A surface of the metal band 1 where the plating film is formed first. If a plating film is also formed on the B surface in the first plating cell 2, the metal band 1 does not come into direct contact with the plating bath in the subsequent plating cell 2, so the metal constituting the metal band 1, that is, the metal When band 1 is a steel band, elution of iron into the plating bath is prevented. In addition, since the anode 3 is simply installed in the existing plating cell 2, there is no increase in manufacturing cost or productivity. In order to achieve the object of the present invention, it is essential to form plating films on both surfaces of the metal strip 1 in the first plating cell 2, but the anode 3 is newly added to the second and subsequent plating cells 2. There is no problem even if a plating film can be formed on both sides. Since the number of plating cells 2 that can form plating films on both sides of the metal strip 1 at the same time increases, the total number of plating cells 2 can be reduced and the equipment can be made more compact and the cost can be reduced.

図2に、本発明の方法を実施するための水平型電気めっきラインの別の例を模式的に示す。このラインでは、従来の水平型電気めっきラインの第1番目のめっきセル2の前に、新たに金属帯1の両面にめっき皮膜を形成可能なたて型のめっきセル2が設けられている。特に、2組のアノード3で金属帯1の両面にめっき皮膜を形成できるようになっているので、めっき効率の向上を図れるばかりでなく、めっき付着量を多くできるので金属帯1を構成する金属の溶出をより確実に防止できる。めっきセル2を1個増設する必要があるが、B面へのめっき皮膜形成用のめっきセル2を減らすことができるので、製造コストの増大や生産性の低下を招くことはない。   FIG. 2 schematically shows another example of a horizontal electroplating line for carrying out the method of the present invention. In this line, a vertical plating cell 2 capable of forming a plating film on both sides of the metal strip 1 is newly provided before the first plating cell 2 of the conventional horizontal electroplating line. In particular, since two sets of anodes 3 can form plating films on both sides of the metal strip 1, not only can the plating efficiency be improved, but the amount of plating can be increased, so the metal constituting the metal strip 1 Can be more reliably prevented. Although it is necessary to add one plating cell 2, it is possible to reduce the number of plating cells 2 for forming a plating film on the B surface, so that there is no increase in manufacturing cost or productivity.

こうした水平型電気めっきラインで錫めっき鋼帯を製造するとき、本発明の方法は、上述のようなめっき浴中への鉄の溶出が著しいメタンスルホン酸浴、硫酸浴、フェノールスルホン酸浴などpHの低い酸性めっき浴を用いる場合に特に効果的である。なお、鉄の溶出が少ないpHの高いハロゲン浴に対しても有効であることは言うまでもない。   When producing a tin-plated steel strip in such a horizontal electroplating line, the method of the present invention is effective in the pH of a methanesulfonic acid bath, sulfuric acid bath, phenolsulfonic acid bath, etc., in which iron elution into the plating bath is significant. This is particularly effective when an acidic plating bath having a low resistance is used. Needless to say, the present invention is also effective for a halogen bath with high pH and low elution of iron.

また、第1番目のめっきセルにおける錫付着量を、鋼帯の片面当り0.02〜0.3g/m2とすることが鉄の溶出防止により効果的である。鋼帯からめっき浴への鉄の溶出量は10g/l以下とすることが好ましく、5g/l以下とすることがより好ましい。メタンスルホン酸錫めっき浴を用いる場合は、鋼帯の片面当り0.02g/m2以上の錫付着量となるように第1番目のめっきセルで両面めっきすれば鉄の溶出量を10g/l以下にでき、鋼帯の片面当り0.2g/m2以上の錫付着量となるようにすれば鉄の溶出量を5g/l以下にできる。なお、鋼帯の片面当り0.3g/m2を超える錫付着量となるようにすると設備コストの増大となる可能性が生じる。 In addition, it is effective for preventing the elution of iron that the tin adhesion amount in the first plating cell is 0.02 to 0.3 g / m 2 per one surface of the steel strip. The amount of iron eluted from the steel strip into the plating bath is preferably 10 g / l or less, and more preferably 5 g / l or less. When using a tin methane sulfonate plating bath, the amount of iron leaching is 10 g / l or less if both sides are plated in the first plating cell so that the amount of tin attached is 0.02 g / m 2 or more per side of the steel strip. If the amount of tin adhered is 0.2 g / m 2 or more per side of the steel strip, the elution amount of iron can be reduced to 5 g / l or less. If the amount of tin deposited exceeds 0.3 g / m 2 per side of the steel strip, the equipment cost may increase.

金属帯として、鋼帯または亜鉛帯を用い、鋼帯にはアルカリ電解脱脂とこれに引き続く硫酸酸洗からなる前処理を、また、亜鉛帯にはアルカリ電解脱脂のみの前処理を行った後、図1〜3の水平型電気めっきラインにより、表1に示すめっき金属を、表1に示すめっき浴で連続的にめっき処理を施す試験1〜9を行った。このとき、図1と図2を用いて第1番目のめっきセルで金属帯の両面にめっき皮膜を形成した試験1〜7では、片面当りのめっき付着量を表1のように変化させた。そして、30日間連続めっき後の第2番目のめっきセルにおけるめっき浴中の金属帯を構成する金属、すなわち鋼帯の場合は鉄、亜鉛帯の場合は亜鉛の濃度を測定した。   As a metal strip, a steel strip or a zinc strip is used. The steel strip is subjected to pretreatment consisting of alkaline electrolytic degreasing and subsequent sulfuric acid pickling, and the zinc strip is pretreated only with alkaline electrolytic degreasing. Tests 1 to 9 were performed in which the plating metals shown in Table 1 were continuously plated in the plating bath shown in Table 1 using the horizontal electroplating line shown in FIGS. At this time, in Tests 1 to 7 in which plating films were formed on both surfaces of the metal strip in the first plating cell with reference to FIGS. 1 and 2, the plating adhesion amount per one surface was changed as shown in Table 1. And the density | concentration of the metal which comprises the metal band in the plating bath in the 2nd plating cell after 30-day continuous plating, ie, the iron in the case of a steel strip, and the zinc in the case of a zinc strip was measured.

結果を表1に示す。本発明例である試験2、3、5、6、7では、30日間連続めっき後のめっき浴中の鉄の濃度は15g/l以下と低く、鉄のめっき浴中への溶出が防止されている。特に、片面当りのめっき付着量を0.02g/m2以上にすることにより、めっき浴中の鉄の濃度を10g/l以下と著しく低くすることができる。 The results are shown in Table 1. In Tests 2 , 3 , 5 , 6 , and 7 , which are examples of the present invention, the concentration of iron in the plating bath after continuous plating for 30 days is as low as 15 g / l or less, and elution of iron into the plating bath is prevented. Yes. In particular, by making the coating weight per piece surface to 0.02 g / m 2 or more, the concentration of iron in the plating bath may be less remarkably low 10 g / l.

一方、従来の方法でめっき処理を施した比較例の試験8、9では、めっき浴中の鉄または亜鉛の濃度は30g/l以上と高く、鉄や亜鉛のめっき浴中への溶出が著しい。   On the other hand, in tests 8 and 9 of comparative examples in which plating treatment was performed by the conventional method, the concentration of iron or zinc in the plating bath was as high as 30 g / l or more, and the elution of iron or zinc into the plating bath was remarkable.

Figure 0004844021
Figure 0004844021

本発明を実施するための水平型電気めっきラインの一例を模式的に示す図である。It is a figure which shows typically an example of the horizontal type electroplating line for implementing this invention. 本発明を実施するための水平型電気めっきラインの別の例を模式的に示す図である。It is a figure which shows typically another example of the horizontal type electroplating line for implementing this invention. 従来の水平型電気めっきラインの一例を模式的に示す図である。It is a figure which shows typically an example of the conventional horizontal type electroplating line.

符号の説明Explanation of symbols

1 金属帯
2 めっきセル
3 アノード
4 搬送ロール
1 Metal strip
2 Plating cell
3 Anode
4 Transport roll

Claims (1)

メタンスルホン酸錫めっき浴またはフェノールスルホン酸錫めっき浴を用いる複数のめっきセルを有する水平型電気錫めっきラインを用いて鋼帯に電気錫めっき処理を施して電気錫めっき鋼帯を製造するに当り、前記複数のめっきセルのうち少なくとも第1番目のめっきセルで前記鋼帯の両面に、錫付着量を鋼帯の片面当り0.02〜0.3g/m2とする電気錫めっき処理を施すことを特徴とする錫めっき鋼帯の製造方法。 In producing an electrotin-plated steel strip by subjecting the steel strip to electrotin plating using a horizontal electrotin plating line having a plurality of plating cells using a tin methane sulfonate plating bath or a phenol sulfonate tin plating bath. The tin plating amount is 0.02 to 0.3 g / m 2 per one side of the steel strip on both surfaces of the steel strip in at least the first plating cell among the plurality of plating cells, A method for producing a tin-plated steel strip.
JP2005182194A 2005-06-22 2005-06-22 Method for producing tin-plated steel strip Expired - Fee Related JP4844021B2 (en)

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