JPH05295590A - Manufacture of surface treated steel sheet - Google Patents
Manufacture of surface treated steel sheetInfo
- Publication number
- JPH05295590A JPH05295590A JP4128201A JP12820192A JPH05295590A JP H05295590 A JPH05295590 A JP H05295590A JP 4128201 A JP4128201 A JP 4128201A JP 12820192 A JP12820192 A JP 12820192A JP H05295590 A JPH05295590 A JP H05295590A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- tin
- plating
- electroplating
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、鋼板の表面に均一且
つ緻密な錫電気メッキ層を有する表面処理鋼板、特に、
缶用表面処理鋼板を製造するための方法に関するもので
ある。より詳しくは、移動中の鋼板の少なくとも１つの
表面に電気メッキにより錫メッキ層を形成する工程を有
し、その工程で電気メッキ中に鋼板に超音波振動を付与
する表面処理鋼板の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated steel sheet having a uniform and dense tin electroplating layer on the surface of the steel sheet, and particularly,
The present invention relates to a method for producing a surface-treated steel sheet for cans. More specifically, the present invention relates to a method for producing a surface-treated steel sheet, which has a step of forming a tin-plated layer on at least one surface of a moving steel sheet by electroplating, in which ultrasonic vibration is applied to the steel sheet during electroplating. It is a thing.
【０００２】[0002]
【従来の技術】表面処理鋼板の製造工程、特に、電気メ
ッキによって錫メッキ層を形成する工程を有する缶用表
面処理鋼板の製造において、主として現在工業的に用い
られているのは、フェロスタンライン、ハロゲンライン
およびアルカリラインの３つのライン形式である。これ
らのラインの途中の、鋼板に連続的に錫電気メッキを施
こすための施設には、竪型または横型のメッキ槽（電解
槽）が使用されている。このような表面処理鋼板の製造
工程によって、鋼板の表面に良好な錫メッキ層を形成す
るためには、メッキ槽中のメッキ液の濃度、温度、電流
密度および通電パスの回数等を細かく管理することが必
要である。2. Description of the Related Art Ferrostanline is mainly used industrially in the process of producing a surface-treated steel sheet, particularly in the production of a surface-treated steel sheet for a can having a step of forming a tin plating layer by electroplating. , Halogen line and alkali line. Vertical or horizontal plating baths (electrolytic baths) are used in facilities for continuously performing tin electroplating on steel plates in the middle of these lines. In order to form a good tin-plated layer on the surface of the steel plate by such a manufacturing process of the surface-treated steel plate, the concentration of the plating solution in the plating bath, the temperature, the current density, the number of energization paths, etc. are finely controlled. It is necessary.
【０００３】通常、表面処理鋼板の製造工程において
は、目標とする錫メッキの付着量に応じて電流密度を算
出し、この電流密度において所望の良好な錫メッキ層が
得られるように、メッキ液の濃度および温度条件を管理
する。Usually, in the process of manufacturing a surface-treated steel sheet, the current density is calculated according to the target amount of tin plating deposited, and the plating solution is used so that a desired good tin plating layer can be obtained at this current density. Control the concentration and temperature conditions of.
【０００４】しかしながら、メッキ液の条件を変更して
錫電気メッキを行なったとしても、良好な錫メッキ層を
得ることができる電流密度の範囲は広くない。このため
目標メッキ付着量の変更および鋼板の移動速度の変動に
対応させて、電流密度が適正な範囲内に入るようにする
ためには、通電するメッキ槽の数を変更しなければなら
ない。即ち、例えば、作業する電流密度が高くなる場合
には、これを下げるために、通電するメッキ槽の数を増
加し、これにより電流密度を下げ、かくして、メッキ液
の条件を最適条件と合致するようにしなければならな
い。However, even if tin electroplating is performed by changing the conditions of the plating solution, the range of current density at which a good tin plating layer can be obtained is not wide. Therefore, in order to keep the current density within an appropriate range in response to the change in the target amount of plating deposition and the change in the moving speed of the steel sheet, the number of plating tanks to be energized must be changed. That is, for example, when the working current density is high, the number of plating baths to be energized is increased in order to reduce the current density, thereby lowering the current density, and thus the plating solution conditions are matched with the optimum conditions. Must be done.
【０００５】特に、高電流密度で錫電気メッキする場合
において、良好な錫メッキ層が得られる限界電流密度
は、通常、フェロスタンラインで約30ASD （アンペアス
ケアーデシ）、ハロゲンラインで約60ASD 、アルカリラ
インで約7ASD程度に過ぎず、一般に小さい。また、無理
に高電流密度で錫電気メッキを行なうと、錫の析出形態
がデンドライト状の電析形態となる。そのため、メッキ
後外観は灰色を呈し、メッキ被膜は密着性が悪く、溶融
加熱処理を行なっても光沢が得られない。更に、電流密
度を高くしても電解効率の著しい低下を生じ錫が電析し
なくなる。Particularly, in the case of tin electroplating at a high current density, the limiting current density at which a good tin plating layer can be obtained is usually about 30 ASD (ampere care deci) on the ferrostane line, about 60 ASD on the halogen line, and the alkaline line. It is only about 7 ASD on the line and is generally small. Further, when tin electroplating is forcibly performed at a high current density, the tin deposition form becomes a dendrite-like electrodeposition form. Therefore, after plating, the appearance is gray, the adhesion of the plated coating is poor, and no gloss is obtained even after the melt heat treatment. Further, even if the current density is increased, the electrolysis efficiency is remarkably reduced, and tin is not electrodeposited.
【０００６】[0006]
【発明が解決しようとする課題】上述したように、従
来、錫電気メッキラインにおいては、１パス当たりの錫
メッキ層の付着量を高くすることができないため、多数
のメッキ槽（通電タンク）が必要となる。このため、製
造設備が大きくなり、設備コストおよびライン維持費が
大きくなるという問題があった。As described above, in the conventional tin electroplating line, since the amount of the tin plating layer deposited per pass cannot be increased, a large number of plating tanks (energization tanks) are required. Will be needed. Therefore, there is a problem that the manufacturing facility becomes large, and the facility cost and the line maintenance cost increase.
【０００７】このように、高電流密度で錫電気メッキの
操業を行なえない理由は、錫電気メッキ液中の錫イオン
の輸率が低く、電気メッキを行っている最中に鋼板の表
面に大きな拡散層がつくられるため、すぐに限界電流密
度に達してしまうことにある。As described above, the reason why tin electroplating cannot be performed at a high current density is that the transport number of tin ions in the tin electroplating solution is low, and the surface of the steel sheet is large during electroplating. Since the diffusion layer is formed, the limit current density is reached soon.
【０００８】錫電気メッキ中に鋼板の表面につくられる
拡散層の大きさを小さくし、高電流密度で操業を行なう
ための方法として、例えば、メッキ液をノズルから噴射
するような噴流条件下で電解を行なう方法が既に知られ
ている（以下、「先行技術１」という）。しかしなが
ら、先行技術１のみで、100 ＡＳＤを超えるような高電
流密度で錫メッキを行なうためには、例えば、５〜10m/
sec を超えるような高速噴流が必要であり、このため巨
大で高価な噴流設備を設置する必要がある。更に、噴流
の制御も困難である。このように、先行技術１のみで、
100 ＡＳＤを超えるような高電流密度で錫メッキを行な
うためには、設備コスト、操業面で困難である。As a method for reducing the size of the diffusion layer formed on the surface of the steel sheet during tin electroplating and performing the operation at a high current density, for example, under a jet flow condition in which a plating solution is jetted from a nozzle. A method of performing electrolysis is already known (hereinafter referred to as "prior art 1"). However, in order to perform tin plating at a high current density exceeding 100 ASD with only the prior art 1, for example, 5 to 10 m /
A high-speed jet that exceeds sec is required, and therefore a huge and expensive jet facility must be installed. Furthermore, it is difficult to control the jet flow. In this way, only in Prior Art 1,
It is difficult to perform tin plating at a high current density exceeding 100 ASD in terms of equipment cost and operation.
【０００９】錫電気メッキに関するものではないが、特
開昭54-95,941 号公報および特開昭54-109、039 号公報
に、電解クロム酸処理鋼板を製造するときに、鋼板に超
音波振動を付与する技術が開示されている（以下、「先
行技術２」という）。Although not related to tin electroplating, in JP-A-54-95,941 and JP-A-54-109,039, ultrasonic vibration is applied to a steel plate when producing a steel plate treated with electrolytic chromic acid. The technology to be given is disclosed (hereinafter referred to as "prior art 2").
【００１０】しかしながら、先行技術２は、過付着した
不要クロメートの溶解を、鋼板に超音波振動を付与する
ことによって促進するもので、上述した錫電気メッキが
有する問題点を解決するものではない。[0010] However, the prior art 2 accelerates the dissolution of unnecessary chromate that is excessively adhered by applying ultrasonic vibration to the steel sheet, and does not solve the above-mentioned problems of tin electroplating.
【００１１】また、連続錫電気メッキ工程において、超
音波を使用する技術についての、公知の知見はない。Further, there is no known knowledge about the technique of using ultrasonic waves in the continuous tin electroplating process.
【００１２】従って、この発明の目的は、均一で緻密な
錫の電着が得られ、このような良好な錫メッキ層が得ら
れる電流密度範囲を従来よりも広くすることができ、１
パス当たりの可能メッキ付着量が大であり、メッキ槽の
数が少なくてすむ、操業の容易な錫電気メッキ鋼板の製
造方法を提供することにある。Therefore, the object of the present invention is to obtain a uniform and dense electrodeposition of tin, and to widen the current density range in which such a good tin plating layer can be obtained, as compared with the prior art.
It is an object of the present invention to provide a method for manufacturing a tin electroplated steel sheet which has a large amount of depositable plating per pass, requires a small number of plating tanks, and is easy to operate.
【００１３】[0013]
【課題を解決するための手段】我々は、錫電気メッキに
おいて、電流密度範囲を従来よりも広くしても、均一で
緻密な錫の電着が得られ、１パス当たりの可能メッキ付
着量も大であり、そして、メッキ槽の数が少なくてす
む、表面処理鋼板の製造方法を得るために、鋭意研究を
重ねた。その結果、錫電気メッキ中において、鋼板に超
音波振動を付与すれば、高電流密度は勿論のこと、低電
流密度においても均一で緻密な錫メッキ層が得られ、適
正メッキ電流密度範囲が著しく広がることを知見した。We have found that in tin electroplating, even if the current density range is wider than before, a uniform and dense electrodeposition of tin can be obtained, and the possible plating deposition amount per pass is also increased. In order to obtain a method for producing a surface-treated steel sheet which is large and requires a small number of plating baths, intensive studies have been conducted. As a result, if ultrasonic vibration is applied to the steel plate during tin electroplating, a uniform and dense tin plating layer can be obtained not only at high current density but also at low current density, and the appropriate plating current density range is remarkably high. I found that it spreads.
【００１４】この発明は上述の知見に基づいてなされた
ものである。この発明は、錫電気メッキ液を使用し、前
記錫電気メッキ液を通って移動中の鋼板に電気メッキを
施して前記鋼板の少なくとも１つの表面上に錫メッキ層
を形成する工程を有する表面処理鋼板、特に、缶用表面
処理鋼板の製造方法において、前記鋼板の移動速度を１
ｍ／分以上とし、電気メッキ中に、鋼板の表面から20mm
離れた位置での超音波発振強度に換算して0.001 WATT／
cm2 から100 WATT／cm2 の範囲内の強度を有し且つ10Hz
から10MHz の範囲内の周波数を有する超音波振動を前記
鋼板に付与することに特徴を有するものである。The present invention was made based on the above findings. The present invention relates to a surface treatment including a step of using a tin electroplating solution and electroplating a steel sheet moving through the tin electroplating solution to form a tin plating layer on at least one surface of the steel sheet. In the method for producing a steel sheet, particularly a surface-treated steel sheet for cans, the moving speed of the steel sheet is set to 1
m / min or more, 20 mm from the surface of the steel plate during electroplating
0.001 WATT / converted to ultrasonic oscillation intensity at a remote location
with intensity in the range of cm 2 to 100 WATT / cm 2 and 10 Hz
It is characterized in that ultrasonic vibration having a frequency in the range from 1 to 10 MHz is applied to the steel sheet.
【００１５】次に、この発明を詳細に説明する。この発
明の対象となるのは、その途中に錫電気メッキ工程を有
する表面処理鋼板の連続メッキ製造工程である。本発明
において、電気メッキ中に鋼板に超音波振動を付与する
のは、光沢電流密度範囲を広げ、より均一で緻密な錫の
電着を得るためである。錫電気メッキは、錫電気メッキ
液を使用し、前記錫電気メッキ液を通って移動中の鋼板
に電気メッキを施して前記鋼板の少なくとも１つの表面
上に錫メッキ層を形成するという工程からなり、この超
音波振動の付与は、錫電気メッキ槽（電解槽）におい
て、錫電気メッキ中（錫電気メッキを行なう時）に同時
に行なう。Next, the present invention will be described in detail. The object of the present invention is a continuous plating manufacturing process of a surface-treated steel sheet having a tin electroplating process in the middle thereof. In the present invention, ultrasonic vibration is applied to the steel sheet during electroplating in order to widen the range of gloss current density and obtain a more uniform and dense electrodeposition of tin. Tin electroplating comprises the steps of using a tin electroplating solution to electroplate a steel sheet moving through the tin electroplating solution to form a tin plating layer on at least one surface of the steel sheet. The ultrasonic vibration is simultaneously applied in the tin electroplating bath (electrolytic bath) during tin electroplating (when tin electroplating is performed).
【００１６】鋼板に超音波振動を付与する方法として、
下記に示す、鋼板に超音波を発振する方法、に示
す、鋼板を直接振動する方法等を使用すればよい。 超音波発振装置の外部発振子を、メッキ槽の内周面
あるいは電極に取り付け、または、外部発振子を錫電気
メッキ液中に設け、そして、鋼板に向けて超音波を発振
する。 外部発振子をコンダクターロールに取り付け、コン
ダクターロールを介して鋼板に直接超音波振動を付与す
る。As a method of applying ultrasonic vibration to a steel sheet,
The method of oscillating ultrasonic waves on the steel sheet shown below, the method of directly vibrating the steel sheet, or the like may be used. An external oscillator of the ultrasonic oscillator is attached to the inner peripheral surface of the plating tank or the electrode, or an external oscillator is provided in the tin electroplating solution, and ultrasonic waves are oscillated toward the steel plate. An external oscillator is attached to the conductor roll, and ultrasonic vibration is applied directly to the steel plate via the conductor roll.
【００１７】発振する超音波の周波数は、10Hzから10MH
z の範囲内とすべきである。上記範囲外では、超音波の
発振効果が得られない。即ち、周波数が10Hz未満では、
錫が鋼板表面に均一に付着しない。一方、周波数が10MH
z 超では、超音波の減衰が著しく、超音波が鋼板の表面
まで達しない。The frequency of the oscillating ultrasonic wave is from 10 Hz to 10 MH
Should be in the range of z. Outside the above range, the ultrasonic wave oscillating effect cannot be obtained. That is, if the frequency is less than 10Hz,
Tin does not evenly adhere to the steel plate surface. On the other hand, the frequency is 10MH
Above z, ultrasonic waves are significantly attenuated and do not reach the surface of the steel sheet.
【００１８】鋼板に付与する超音波の強度は、鋼板の表
面から20mm離れた位置での超音波の発振強度に換算し
て、0.001 WATT／cm2 から100 WATT／cm2 の範囲内とす
べきである。超音波の強度が0.001 WATT／cm2 未満で
は、キャビテーションが発生せず鋼板表面の攪拌効果が
得られない。一方超音波の強度が100 WATT／cm2 を超え
ると、超音波吸収によるメッキ液（電解溶液）等の発熱
が激しく実用的でない。The intensity of ultrasonic waves applied to the steel sheet should be within the range of 0.001 WATT / cm 2 to 100 WATT / cm 2 in terms of the ultrasonic wave oscillation intensity at a position 20 mm away from the surface of the steel sheet. Is. If the ultrasonic intensity is less than 0.001 WATT / cm 2 , cavitation does not occur and the stirring effect on the surface of the steel sheet cannot be obtained. On the other hand, when the ultrasonic wave intensity exceeds 100 WATT / cm 2 , the plating solution (electrolytic solution) and the like generate heat due to ultrasonic wave absorption and are not practical.
【００１９】この発明の製造方法は、鋼板に超音波振動
を付与する本発明錫電気メッキ工程の前後に、錫電気メ
ッキ以外の、他の一種以上、例えば、ニッケル、鉄、亜
鉛、クロム、コバルトまたは燐などの単一種のメッキ工
程あるいはこれらの二種以上の合金メッキ工程、電解ク
ロム酸処理あるいはその他の化成処理、または、リフロ
ー等の熱処理等を含む。The production method of the present invention is one or more other than tin electroplating, for example, nickel, iron, zinc, chromium, cobalt before and after the tin electroplating step of the present invention in which ultrasonic vibration is applied to the steel sheet. Alternatively, a single-type plating process of phosphorus or the like or an alloy plating process of two or more types of these, electrolytic chromic acid treatment or other chemical conversion treatment, or heat treatment such as reflow is included.
【００２０】本発明の錫電気メッキ浴としては、第１錫
イオンを主成分とするものであればどのようなメッキ浴
でも使用可能である。このような錫電気メッキ浴とし
て、例えば、下記からに記載のメッキ浴がある。酸
性錫電気メッキ浴として下記からがある。 ベンゼンスルホン酸、メタンスルホン酸、トルエンス
ルホン酸、フェノールスルホン酸等の有機スルホン酸を
主成分として含むメッキ浴。 塩酸、ホウフッ酸、フッ化水素酸および硫酸の１種ま
たは２種以上と、ポリエチレングルコール、ポリオキシ
エチレンナフトールおよびポリエチレンナフトールスル
ホン酸等の光沢添加剤の１種または２種以上と、第１錫
イオンとを主成分として含むメッキ浴。 上記からに示す電気メッキ浴に、メッキ特性向上
のために必要に応じて、各種有機物、金属イオンを添加
させたメッキ浴。アルカリ性電気メッキ浴として下記
およびがある。 第２錫イオンと苛性ソーダとを主成分として含むメッ
キ浴。 上記に示すメッキ浴に、メッキ特性向上のために必
要に応じて、各種有機物、金属イオンを添加させたメッ
キ浴。As the tin electroplating bath of the present invention, any plating bath containing stannous tin as a main component can be used. Examples of such tin electroplating baths include the plating baths described below. The following are acidic tin electroplating baths. A plating bath containing an organic sulfonic acid such as benzene sulfonic acid, methane sulfonic acid, toluene sulfonic acid, phenol sulfonic acid as a main component. One or more of hydrochloric acid, borofluoric acid, hydrofluoric acid and sulfuric acid, and one or more of luster additives such as polyethylene glycol, polyoxyethylene naphthol and polyethylene naphthol sulfonic acid, and stannous tin A plating bath containing ions as the main component. A plating bath in which various organic substances and metal ions are added to the electroplating baths described above as needed to improve the plating characteristics. The following are the alkaline electroplating baths. A plating bath containing stannic ions and caustic soda as main components. A plating bath in which various organic substances and metal ions are added to the above-mentioned plating bath as needed to improve the plating characteristics.
【００２１】鋼板の移動速度は、１ｍ／分（mpm ）以上
とする。移動速度が１mpm 未満では、錫電気メッキ液の
対流効果がなく、鋼板表面への錫イオンの連続供給が困
難であり、メッキ層の密着不良、電解効率の低下、色調
不良などを生じる。The moving speed of the steel sheet is 1 m / min (mpm) or more. If the moving speed is less than 1 mpm, there is no convection effect of the tin electroplating solution, and it is difficult to continuously supply tin ions to the surface of the steel sheet, resulting in poor adhesion of the plating layer, deterioration of electrolytic efficiency, and poor color tone.
【００２２】[0022]
【実施例】次に、この発明を実施例により詳細に説明す
る。錫電気メッキ槽内に、鋼板に超音波振動を付与する
ための超音波発振装置を取り付けた。即ち、電極の横ま
たは電極反対面に、超音波発振装置の外部発振子として
の外部発振板を取り付け、鋼板の表面に向けて超音波を
発振可能とした。アノードとしては、可溶性の錫アノー
ドを用いた。必要に応じて電極を取り替えることによ
り、電解長さを調整した。使用した錫電気メッキ浴は、
下記に示すフェロスタンライン浴（以下、「Ａ浴」とい
う）、ハロゲンライン浴（以下、「Ｂ浴」という）また
はアルカリライン浴（以下、「Ｃ浴」という）であっ
た。 Ａ浴： Sn2+ 30g/l 、 Sn4+ ＜ 1g/l 遊離酸 (H2SO4 換算) 20g/l 添加剤 ＜10g/l 温度 45℃。 Ｂ浴： 塩化第１錫 75g/l 、 フッ化ナトリウム 25g/l フッ化水素カリウム 50g/l 塩化ナトリウム 45g/l Sn2+ 36g/l Sn4+ 1g/l pH 2.7 添加剤 1 〜2 g/l 温度 65℃。 Ｃ浴： Sn4+ 30g/l 、 Sn2+ ＜ 1g/l NaOH 15g/l 添加剤 ＜10g/l 温度 85℃。Next, the present invention will be described in detail with reference to Examples. An ultrasonic oscillating device for applying ultrasonic vibration to the steel plate was installed in the tin electroplating bath. That is, an external oscillating plate as an external oscillator of the ultrasonic oscillating device was attached to the side of the electrode or the surface opposite to the electrode so that ultrasonic waves could be oscillated toward the surface of the steel plate. A soluble tin anode was used as the anode. The electrolysis length was adjusted by replacing the electrodes as needed. The tin electroplating bath used is
It was a ferrostan line bath (hereinafter referred to as "A bath"), a halogen line bath (hereinafter referred to as "B bath") or an alkaline line bath (hereinafter referred to as "C bath") shown below. Bath A: Sn 2+ 30g / l, Sn 4+ <1g / l free acid (H 2 SO 4 equivalent) 20g / l Additive <10g / l Temperature 45 ° C. Bath B: stannous chloride 75 g / l, sodium fluoride 25 g / l potassium hydrogen fluoride 50 g / l sodium chloride 45 g / l Sn 2+ 36 g / l Sn 4+ 1 g / l pH 2.7 Additives 1-2 g / l l Temperature 65 ℃. Bath C: Sn 4+ 30g / l, Sn 2+ <1g / l NaOH 15g / l Additive <10g / l Temperature 85 ° C.
【００２３】焼鈍を施こし、次いで、調質圧延を施こし
た、0.20mmの厚さを有する冷延鋼板に対して、通常の脱
脂および酸洗処理を施こした。次いで、このような冷延
鋼板の少なくとも１つの表面に、鋼板に超音波振動を付
与しながら錫電気メッキを施こした。錫電気メッキの付
着量は、1.1 g/m2から11.2g/m2（♯10から♯100 ）の範
囲内とした。このような条件で錫電気メッキした後、錫
メッキ層が形成された錫メッキ鋼板に対して表層の溶融
加熱処理 (リフロー処理) を行なった。このようにし
て、本発明の範囲内の錫電気メッキ鋼板の供試体（以
下、「本発明供試体」という） No.１から51を調製し
た。比較のため、鋼板に超音波振動の付与を行なわずに
錫電気メッキを施こし、本発明の範囲外の錫電気メッキ
鋼板の供試体（以下、「比較用供試体」という） No.１
から３を調製した。更に、比較のため、鋼板に超音波振
動の付与は行なったものの、超音波周波数、超音波強度
および鋼板の移動速度のいずれかが本発明範囲を外れて
いる本発明の範囲外の錫電気メッキ鋼板の供試体（以
下、「比較用供試体」という） No.４から21を調製し
た。The cold-rolled steel sheet having a thickness of 0.20 mm, which had been annealed and then temper-rolled, was subjected to conventional degreasing and pickling treatments. Then, tin electroplating was applied to at least one surface of such a cold rolled steel sheet while applying ultrasonic vibration to the steel sheet. The amount of tin electroplating deposited was in the range of 1.1 g / m 2 to 11.2 g / m 2 (# 10 to # 100). After electroplating tin under these conditions, the surface of the tin-plated steel sheet on which the tin-plated layer was formed was subjected to a heating treatment (reflow treatment). In this way, tin electroplated steel sheet specimens (hereinafter referred to as "present invention specimens") Nos. 1 to 51 within the scope of the present invention were prepared. For comparison, a tin electroplated steel sheet outside the scope of the present invention was subjected to tin electroplating without applying ultrasonic vibration (hereinafter referred to as “comparative specimen”) No. 1
To 3 were prepared. Further, for comparison, although ultrasonic vibration was applied to the steel sheet, any one of the ultrasonic frequency, the ultrasonic intensity, and the moving speed of the steel sheet is outside the scope of the present invention. Tin electroplating outside the scope of the present invention. Steel plate specimens (hereinafter referred to as "comparative specimens") Nos. 4 to 21 were prepared.
【００２４】本発明供試体 No.１から３および比較用供
試体 No.１から３の電解効率を調べおよびリフロー処理
後の錫メッキ層の表面の状態を観察し、適正な光沢を有
する通常のブリキと同等の光沢が得られたか否かを判断
基準として、通常のブリキと同等の光沢が得られた電流
密度の範囲（以下、「光沢電流密度範囲」という）を調
べた。その結果を、表１に示す。表１には、錫電気メッ
キ浴組成、超音波強度、超音波周波数および鋼板の移動
速度を併せて示す。The electrolysis efficiencies of the test samples No. 1 to 3 of the present invention and the test samples No. 1 to 3 for comparison were examined, and the state of the surface of the tin-plated layer after the reflow treatment was observed. The range of the current density (hereinafter, referred to as “gloss current density range”) in which the gloss equivalent to that of a normal tin plate was obtained was examined with reference to whether or not the gloss equivalent to that of a tin plate was obtained. The results are shown in Table 1. Table 1 also shows the tin electroplating bath composition, ultrasonic intensity, ultrasonic frequency, and steel plate moving speed.
【００２５】[0025]
【表１】 [Table 1]
【００２６】表１から明らかなように、超音波振動の付
与を行なった本発明供試体 No.１から３は、超音波振動
の付与を行なわなかった比較用供試体 No.１から３と比
較して、光沢電流密度範囲が広いことがわかる。As is apparent from Table 1, the specimens No. 1 to 3 of the present invention to which the ultrasonic vibration was applied are compared with the comparative specimens No. 1 to 3 to which the ultrasonic vibration was not applied. It can be seen that the gloss current density range is wide.
【００２７】次に、本発明供試体 No.４から51および比
較用供試体 No.４から21の電解効率およびリフロー処理
後の色調を調べた。その結果を表２、表３に示す。電解
効率が80％以上の値を示せば、実用的な操業が行なえる
条件を有していると評価した。リフロー処理後の色調の
評価は、リフロー処理後の錫メッキ層の表面の状態を観
察し、適正な光沢を有する通常のブリキと同等の光沢が
得られたか否かで判断した。通常のブリキと同等の光沢
が得られているものを○印、通常のブリキと同等の光沢
が得られていないものを×印とした。表２、表３には、
錫電気メッキ浴組成、電解電流密度、超音波強度、超音
波周波数および鋼板の移動速度を併せて示す。また、表
２中、表３中の超音波強度の値は、鋼板表面から20mmの
位置での超音波発振強度に換算して求めた。Next, the electrolysis efficiency and the color tone after the reflow treatment of the test samples No. 4 to 51 of the present invention and the test samples No. 4 to 21 for comparison were examined. The results are shown in Tables 2 and 3. It was evaluated that if the electrolysis efficiency shows a value of 80% or more, the condition for practical operation can be achieved. The color tone after the reflow treatment was evaluated by observing the state of the surface of the tin-plated layer after the reflow treatment and judging whether or not a gloss equivalent to that of a normal tin plate having an appropriate gloss was obtained. Those with a gloss equivalent to that of ordinary tinplate were marked with a circle, and those without a gloss equivalent to that of a regular tinplate were marked with x. In Table 2 and Table 3,
The tin electroplating bath composition, electrolytic current density, ultrasonic intensity, ultrasonic frequency, and steel plate moving speed are also shown. In addition, the values of the ultrasonic wave in Tables 2 and 3 were converted into ultrasonic wave intensities at a position 20 mm from the surface of the steel sheet.
【００２８】[0028]
【表２】 [Table 2]
【００２９】[0029]
【表３】 [Table 3]
【００３０】表２、表３から明らかなように、本発明供
試体 No.４から51は、比較用供試体No.４から21より
も、幅広い操業条件で良好な錫電気メッキ鋼板が得られ
ることがわかる。As is clear from Tables 2 and 3, specimens Nos. 4 to 51 of the present invention produce better tin electroplated steel sheets under a wider range of operating conditions than specimens No. 4 to 21 for comparison. I understand.
【００３１】これに対して、超音波の周波数が、この発
明の範囲外の比較用供試体 No.６、７、12、13、18およ
び19は、超音波による鋼板表面の攪拌効果が得られず、
電解効率が悪く、錫メッキ層の表面の状態も悪かった。On the other hand, the comparative samples Nos. 6, 7, 12, 13, 18 and 19 in which the frequency of the ultrasonic waves is outside the range of the present invention have the effect of stirring the surface of the steel sheet by ultrasonic waves. No
The electrolysis efficiency was poor, and the surface condition of the tin plating layer was also poor.
【００３２】超音波の強度が0.0005WATT/cm2または０WA
TT/cm2とこの発明の範囲を外れて低い比較用供試体 No.
４、10、16および比較用供試体 No.９、15、21は、電解
効率が悪く、錫メッキ層の表面の状態も悪かった。The ultrasonic intensity is 0.0005 WATT / cm 2 or 0 WA
Specimen No. for comparison which is low outside the range of TT / cm 2 and this invention
Nos. 4, 10, 16 and Comparative Samples Nos. 9, 15, 21 had poor electrolysis efficiency and the surface condition of the tin plating layer was also poor.
【００３３】超音波の強度が、この発明の範囲を外れて
高い比較用供試体 No.５、11および17は、発熱による錫
電気メッキ液の温度上昇により、電解効率が悪く、錫メ
ッキ層の表面の状態も悪かった。The comparative specimens Nos. 5, 11 and 17 in which the ultrasonic wave intensity is out of the range of the present invention have poor electrolysis efficiency due to the temperature rise of the tin electroplating solution due to heat generation, and the tin plating layer The surface condition was also bad.
【００３４】鋼板の移動速度が、この発明の範囲を外れ
て低い比較用供試体 No.８、14および20は、超音波によ
る鋼板表面の攪拌効果が得られず、電解効率が悪く、錫
メッキ層の表面の状態も悪かった。The comparative specimens Nos. 8, 14 and 20 in which the moving speed of the steel sheet was out of the range of the present invention, the stirring effect of the steel sheet surface by ultrasonic waves was not obtained, the electrolysis efficiency was poor, and the tin plating was not performed. The surface condition of the layers was also poor.
【００３５】[0035]
【発明の効果】以上説明したように、この発明によれ
ば、従来の超音波振動を付与しない錫電気メッキと比較
して電流密度範囲が最高で10倍近くも広がり、より均一
で緻密な錫の電着が得られるとともに、１パス当たりで
可能なメッキの付着量も広がり、メッキ槽の数も少なく
てすみ、設備コスト、維持費の低減をはかることができ
る、表面処理鋼板の製造方法が得られ、かくして、工業
上有用な効果が得られる。As described above, according to the present invention, as compared with the conventional tin electroplating which does not apply ultrasonic vibration, the current density range is expanded up to about 10 times, and the tin is more uniform and dense. The method for producing a surface-treated steel sheet is capable of achieving the electrodeposition of, the spread of the amount of plating possible per pass, the number of plating tanks is small, and the equipment cost and maintenance cost can be reduced. Thus, industrially useful effects can be obtained.
Claims (2)
ッキ液を通って移動中の鋼板に電気メッキを施して前記
鋼板の少なくとも１つの表面上に錫メッキ層を形成する
工程を有する表面処理鋼板の製造方法において、 前記鋼板の移動速度を１ｍ／分以上とし、電気メッキ中
に、鋼板の表面から20mm離れた位置での超音波発振強度
に換算して0.001 WATT／cm2 から100 WATT／cm2 の範囲
内の強度を有し且つ10Hzから10MHz の範囲内の周波数を
有する超音波振動を前記鋼板に付与することを特徴とす
る表面処理鋼板の製造方法。1. A surface comprising the step of using a tin electroplating solution and electroplating a steel sheet moving through the tin electroplating solution to form a tin plating layer on at least one surface of the steel sheet. In the method for producing a treated steel sheet, the moving speed of the steel sheet is set to 1 m / min or more, and 0.001 WATT / cm 2 to 100 WATT converted into ultrasonic oscillating intensity at a position 20 mm away from the surface of the steel sheet during electroplating. A method for producing a surface-treated steel sheet, which comprises applying to the steel sheet an ultrasonic vibration having an intensity in the range of / cm 2 and a frequency in the range of 10 Hz to 10 MHz.
ある請求項１記載の方法。2. The method according to claim 1, wherein the surface-treated steel sheet is a surface-treated steel sheet for cans.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12820192A JP3206101B2 (en) | 1992-04-21 | 1992-04-21 | Manufacturing method of surface treated steel sheet |
| US08/038,529 US5391290A (en) | 1992-04-21 | 1993-03-29 | Method for continuously tin-electroplating metal strip |
| EP93106316A EP0567042A1 (en) | 1992-04-21 | 1993-04-19 | Method for continuously tin-electroplating metal strip |
| KR1019930006680A KR950014642B1 (en) | 1992-04-21 | 1993-04-21 | Method for continuously tin-electroplating metal strip |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12820192A JP3206101B2 (en) | 1992-04-21 | 1992-04-21 | Manufacturing method of surface treated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05295590A true JPH05295590A (en) | 1993-11-09 |
| JP3206101B2 JP3206101B2 (en) | 2001-09-04 |
Family
ID=14978972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12820192A Expired - Fee Related JP3206101B2 (en) | 1992-04-21 | 1992-04-21 | Manufacturing method of surface treated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3206101B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256998A (en) * | 1993-03-05 | 1994-09-13 | Shimada Phys & Chem Ind Co Ltd | Agitation method of plating solution |
| EP0890658A2 (en) * | 1997-06-11 | 1999-01-13 | Reynolds Tech Fabricators, Incorporated | Megasonic plating system |
| JP2018053274A (en) * | 2016-09-26 | 2018-04-05 | 千住金属工業株式会社 | Metal body and method for producing metal body |
-
1992
- 1992-04-21 JP JP12820192A patent/JP3206101B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256998A (en) * | 1993-03-05 | 1994-09-13 | Shimada Phys & Chem Ind Co Ltd | Agitation method of plating solution |
| EP0890658A2 (en) * | 1997-06-11 | 1999-01-13 | Reynolds Tech Fabricators, Incorporated | Megasonic plating system |
| EP0890658A3 (en) * | 1997-06-11 | 1999-03-10 | Reynolds Tech Fabricators, Incorporated | Megasonic plating system |
| JP2018053274A (en) * | 2016-09-26 | 2018-04-05 | 千住金属工業株式会社 | Metal body and method for producing metal body |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3206101B2 (en) | 2001-09-04 |
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