JPH09195082A - Electrogalvanized steel sheet excellent in plating appearance and manufacturing method thereof - Google Patents
Electrogalvanized steel sheet excellent in plating appearance and manufacturing method thereofInfo
- Publication number
- JPH09195082A JPH09195082A JP566196A JP566196A JPH09195082A JP H09195082 A JPH09195082 A JP H09195082A JP 566196 A JP566196 A JP 566196A JP 566196 A JP566196 A JP 566196A JP H09195082 A JPH09195082 A JP H09195082A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- bath
- plating
- electrogalvanized steel
- plating appearance
- 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.)
- Pending
Links
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電気亜鉛めっき鋼
板及びその製造方法に関し、特に家電用表面処理鋼板に
関するものである。TECHNICAL FIELD The present invention relates to an electrogalvanized steel sheet and a method for producing the same, and more particularly to a surface-treated steel sheet for household appliances.
【０００２】[0002]
【従来の技術】一般的に家電用亜鉛めっき鋼板はその外
観の鮮明さが要求されているため、めっき後に塗装が施
される。しかし、塗装後の外観は下地めっき表面外観の
影響を大きく受けるため、塗装後外観の鮮明さを満足さ
せるためには、塗装前のめっき表面の明度向上を図る必
要がある。2. Description of the Related Art Generally, zinc plated steel sheets for home appliances are required to have a clear appearance, and therefore they are coated after plating. However, the appearance after coating is greatly affected by the appearance of the surface of the base plating, and therefore, it is necessary to improve the brightness of the plating surface before coating in order to satisfy the sharpness of the appearance after coating.
【０００３】従来の電気亜鉛めっき処理鋼板の明度を向
上させる方法としては、有機化合物からなる光沢剤を添
加しためっき浴を用いて電気めっきをする方法が主流で
あった。例えば特許第 1318532号（特開昭５８−２１０
１８８号公報）では、β−アミノプロピオン酸の水溶性
誘導体を含む亜鉛めっき浴を用いて電気めっきすること
により、明度の向上を図っている。As a method for improving the brightness of a conventional electrogalvanized steel sheet, a method of electroplating using a plating bath to which a brightening agent made of an organic compound is added has been the mainstream. For example, Japanese Patent No. 1318532 (JP-A-58-210)
No. 188), the brightness is improved by electroplating using a zinc plating bath containing a water-soluble derivative of β-aminopropionic acid.
【０００４】[0004]
【発明が解決しようとする課題】一般的に有機系の添加
物は酸性のめっき浴中で分解する可能性があり、その場
合、添加剤の作用が変化するため、浴中で安定する添加
剤の開発が強く望まれていた。Generally, an organic additive may decompose in an acidic plating bath, in which case the action of the additive changes, so that the additive is stable in the bath. Was strongly desired.
【０００５】[0005]
【課題を解決するための手段】本発明の要旨は以下の通
りである。 （１）硫酸塩酸性亜鉛めっき処理浴において、浴中にＴ
ｌ（タリウム）を０．０１〜１０ppm 含有し、１０〜２
００Ａ／dm2 の電流密度により鋼板を電気亜鉛めっきし
て得られるめっき表面の明度がＬ値で７０以上であるこ
とを特徴とするめっき外観に優れた電気亜鉛めっき鋼
板。The gist of the present invention is as follows. (1) In a sulfuric acid / hydrochloric acid zinc plating treatment bath, T
Contains 0.01 to 10 ppm of l (thallium), 10 to 2
An electrogalvanized steel sheet excellent in plating appearance, characterized in that the lightness of the plated surface obtained by electrogalvanizing the steel sheet at a current density of 00 A / dm 2 is 70 or more in L value.
【０００６】（２）硫酸塩酸性亜鉛めっき処理浴におい
て、浴中にＴｌを０．０１〜１０ppm含有し、１０〜２
００Ａ／dm2 の電流密度により鋼板を電気亜鉛めっき
し、めっき表面の明度がＬ値で７０以上のめっき処理鋼
板を得ることを特徴とするめっき外観に優れた電気亜鉛
めっき鋼板の製造方法。(2) In the sulfuric acid / hydrochloric acid zinc plating treatment bath, 0.01 to 10 ppm of Tl is contained in the bath, and 10 to 2
A method for producing an electrogalvanized steel sheet excellent in plating appearance, which comprises electrogalvanizing a steel sheet with a current density of 00 A / dm 2 to obtain a plated steel sheet having a brightness of an L value of 70 or more.
【０００７】（３）亜鉛めっき処理浴中のＴｌの添加方
法として、硫酸タリウムまたは酢酸タリウムの添加によ
ることを特徴とする（２）記載のめっき外観に優れた電
気亜鉛めっき鋼板の製造方法。(3) The method for producing an electrogalvanized steel sheet having an excellent plating appearance according to (2), wherein Tl is added to the galvanizing bath by adding thallium sulfate or thallium acetate.
【０００８】（４）亜鉛めっき処理浴中のＴｌの添加方
法として、Ｐｂ合金中にＴｌを０．１〜１０wt％含有す
るＰｂ系陽極を使用し、電極の溶解と共にＴｌを供給す
ることを特徴とする（２）記載のめっき外観に優れた電
気亜鉛めっき鋼板の製造方法。(4) As a method of adding Tl to the galvanizing bath, a Pb-based anode containing 0.1 to 10 wt% of Tl in a Pb alloy is used, and Tl is supplied together with melting of the electrode. (2) A method for producing an electrogalvanized steel sheet having an excellent plating appearance according to (2).
【０００９】[0009]
【発明の実施の形態】以下、本発明者らが行った実験結
果に基づいて本発明を説明する。 （１） Ｚｎ電気めっき Ｚｎ2+（３０〜１００ g/l）−Ｈ2 ＳＯ4 （１０〜５０
g/l）系ベースめっき浴中にＴｌ2 （ＳＯ4 ）3 を添加
してめっきし、亜鉛めっき浴中のＴｌ濃度を０〜１６pp
m に変化させ、めっき付着量は２０ g/m2 とした。電流
密度は１０〜２００Ａ／dm2 の範囲とする。１０Ａ／dm
2 未満であると不めっきが発生する場合があり、２００
Ａ／dm2 超であるとめっき焼けむらが発生する場合があ
る。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below based on the results of experiments conducted by the present inventors. (1) Zn electroplating Zn 2+ (30-100 g / l) -H 2 SO 4 (10-50
g / l) -based base plating bath with Tl 2 (SO 4 ) 3 added to plate the Tl concentration in the zinc plating bath from 0 to 16 pp
The coating amount was changed to m and the coating weight was set to 20 g / m 2 . The current density is in the range of 10 to 200 A / dm 2 . 10 A / dm
If it is less than 2 , non-plating may occur, and 200
If it is more than A / dm 2 , uneven plating burning may occur.
【００１０】（２） 皮膜特性評価 めっき後鋼板表面の明度（Ｌ値）を測定した。Ｌ値はＪ
ＩＳ Ｚ8730色差表示方法のハンターの色素式における
明度指数を用いた。図１はめっき浴中Ｔｌ濃度とめっき
表面Ｌ値との関係を示した図表である。図１から、めっ
き浴中Ｔｌ濃度が増加するほど得られためっき鋼板表面
Ｌ値も増加するが、Ｔｌ濃度が１０ppm 付近でＬ値は変
化しなくなる。従って、Ｔｌ濃度を０．０１〜１０ppm
にすることで、効率よく明度の優れた亜鉛めっき鋼板を
得ることができる。(2) Evaluation of coating properties The lightness (L value) of the steel sheet surface after plating was measured. L value is J
The lightness index in Hunter's dye formula of the IS Z8730 color difference display method was used. FIG. 1 is a chart showing the relationship between the Tl concentration in the plating bath and the L value of the plating surface. From FIG. 1, as the Tl concentration in the plating bath increases, the obtained L surface value of the plated steel sheet also increases, but the L value does not change when the Tl concentration is around 10 ppm. Therefore, the Tl concentration should be 0.01-10ppm
By doing so, a galvanized steel sheet having excellent brightness can be efficiently obtained.
【００１１】（３） 塗装後外観評価 めっき後ボンデライジング処理を施し、更に白色塗装を
行い、外観の評価を行った。 ボンデライジング皮膜：２ g/m2 白色塗装 ：２μｍ アミラック＃１０００（関西ペイント製） 評価基準 ×：下地めっき色が透過して塗装後外観ではっきり見える △：下地めっき色が透過して塗装後外観でやや見える ○：下地めっき色が塗装後外観で見えない(3) Evaluation of Appearance after Coating Appearance was evaluated by performing a bonderizing treatment after plating and then performing white coating. Bonderizing film: 2 g / m 2 White coating: 2 μm Amylak # 1000 (manufactured by Kansai Paint) Evaluation criteria ×: Undercoating color penetrates and is clearly visible after coating △: Undercoating color penetrates and appearance after coating Somewhat visible .: Undercoating color is not visible after painting.
【００１２】図２は、白色塗装後外観とめっき表面Ｌ値
との関係を示した図表である。図２から、Ｌ値が７０未
満になると下地めっき色が透過して塗装後外観ではっき
り見えるため、優れた塗装後外観を得るためにはめっき
表面のＬ値は７０以上が必要である。FIG. 2 is a chart showing the relationship between the appearance after white coating and the L value of the plating surface. From FIG. 2, when the L value is less than 70, the underlying plating color is transmitted and can be clearly seen in the appearance after coating. Therefore, in order to obtain an excellent appearance after coating, the L value of the plating surface must be 70 or more.
【００１３】次に、Ｔｌの供給方法を説明する。めっき
浴に硫酸タリウムまたは酢酸タリウムのような薬剤を直
接添加する方法が一般的であるが、この方法では手間が
かかるし、浴濃度の調整も困難である。そこで、それら
の問題を解消できるＰｂ−Ｔｌ系電極を用いるＴｌ供給
方法について説明する。Next, a method of supplying Tl will be described. A method of directly adding a chemical such as thallium sulfate or thallium acetate to the plating bath is generally used, but this method takes time and adjustment of the bath concentration is difficult. Therefore, a Tl supply method using a Pb-Tl system electrode that can solve these problems will be described.
【００１４】（４） Ｐｂ−Ｔｌ系電極によるＴｌの供
給方法 電極には不溶性電極として一般的であるＰｂ合金系電極
を使用する。Ｐｂ合金系のＴｌ以外の合金化金属は特に
定めないが、ここではＰｂ−２％Ｉｎ−１％Ａｇ−Ｔｌ
電極を用いた結果について説明する。電極中のＴｌ含有
率を０〜１４wt％まで２wt％おきに変化させて、それぞ
れ２０日間電気めっきした後の浴中Ｔｌ濃度の測定を行
った。ただし、浴中Ｔｌ濃度は電極使用後１０日前後で
飽和する。(4) Method of supplying Tl by Pb-Tl type electrode As the electrode, a Pb alloy type electrode which is generally used as an insoluble electrode is used. Although alloying metals other than Pb alloy-based Tl are not particularly specified, here, Pb-2% In-1% Ag-Tl is used.
The results using the electrodes will be described. The Tl content in the electrode was changed every 2 wt% from 0 to 14 wt% and the Tl concentration in the bath was measured after electroplating for 20 days. However, the Tl concentration in the bath saturates around 10 days after the electrode was used.
【００１５】図３は、電極中のＴｌ含有率と浴中飽和Ｔ
ｌ濃度との関係を示した図表である。図３から、電極中
のＴｌ含有率が増加し、１０wt％付近でＴｌ濃度が１０
ppmに達するため、本発明の浴中Ｔｌ濃度を満足させる
には、電極中のＴｌ含有率を１０wt％以下にすることが
必要である。ただし、電極中のＴｌ含有率が０．１wt％
未満であると、浴中へのＴｌの供給不足になる可能性が
ある。FIG. 3 shows the Tl content in the electrode and the saturated T in the bath.
It is a chart showing the relationship with 1 concentration. From FIG. 3, the Tl content in the electrode increased, and the Tl concentration was 10% at around 10 wt%.
Since it reaches ppm, it is necessary to set the Tl content in the electrode to 10 wt% or less in order to satisfy the Tl concentration in the bath of the present invention. However, the Tl content in the electrode is 0.1 wt%
If it is less than the range, there is a possibility of insufficient supply of Tl in the bath.
【００１６】また、Ｔｌは高価であるため、必要なＴｌ
濃度に応じて電極中のＴｌ含有率の調整をすればよい。
従って、Ｐｂ−Ｔｌ系電極を用いることで、薬剤の投入
をすることなくＴｌの添加及びＴｌ濃度調節が可能であ
る。Since Tl is expensive, the required Tl
The Tl content in the electrode may be adjusted according to the concentration.
Therefore, by using the Pb-Tl system electrode, it is possible to add Tl and adjust the Tl concentration without introducing a drug.
【００１７】[0017]
【発明の効果】硫酸塩酸性亜鉛めっき処理浴において、
浴中にＴｌを０．０１〜１０ppm 含有し、１０〜２００
Ａ／dm2 の電流密度により鋼板を電気亜鉛めっきするこ
とによって、めっき表面の明度がＬ値で７０以上である
電気亜鉛めっき鋼板を製造することができる。更に、亜
鉛めっき処理浴中のＴｌの添加方法として、Ｐｂ合金中
にＴｌを０．１〜１０wt％含有するＰｂ系陽極を使用
し、電極の溶解と共にＴｌを供給することで、薬剤の投
入をすることなくＴｌの添加及びＴｌ濃度調節が可能で
ある。INDUSTRIAL APPLICABILITY In a sulfuric acid / hydrochloric acid zinc plating bath,
0.01 to 10 ppm of Tl is contained in the bath, 10 to 200
By electrogalvanizing a steel sheet with a current density of A / dm 2, an electrogalvanized steel sheet having an L value of 70 or more on the plated surface can be manufactured. Furthermore, as a method for adding Tl in the galvanizing bath, a Pb-based anode containing 0.1 to 10 wt% of Tl in a Pb alloy is used, and Tl is supplied together with the melting of the electrode, so that the chemical agent is introduced. It is possible to add Tl and adjust the Tl concentration without doing so.
【図１】めっき浴中Ｔｌ濃度とめっき表面Ｌ値との関係
を示す図表。FIG. 1 is a chart showing the relationship between Tl concentration in a plating bath and L value of a plating surface.
【図２】白色塗装後外観とめっき表面Ｌ値との関係を示
す図表。FIG. 2 is a chart showing the relationship between the appearance after white coating and the plating surface L value.
【図３】電極中のＴｌ含有率と浴中飽和Ｔｌ濃度との関
係を示す図表。FIG. 3 is a chart showing the relationship between the Tl content in the electrode and the saturated Tl concentration in the bath.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 井上 郁也 君津市君津１番地 新日本製鐵株式会社君 津製鐵所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ikuya Inoue 1 Kimitsu, Kimitsu City Nippon Steel Corporation Kimitsu Steel Works
Claims (4)
浴中にＴｌ（タリウム。以下同じ）を０．０１〜１０pp
m 含有し、１０〜２００Ａ／dm2 の電流密度により鋼板
を電気亜鉛めっきして得られるめっき表面の明度がＬ値
で７０以上であることを特徴とするめっき外観に優れた
電気亜鉛めっき鋼板。1. In a sulfuric acid / hydrochloric acid zinc plating treatment bath,
0.01 to 10 pp of Tl (Thallium, same below) in the bath
An electrogalvanized steel sheet containing m and having an L value of 70 or more in terms of brightness of a plated surface obtained by electrogalvanizing a steel sheet at a current density of 10 to 200 A / dm 2 , which is excellent in plating appearance.
浴中にＴｌを０．０１〜１０ppm 含有し、１０〜２００
Ａ／dm2 の電流密度により鋼板を電気亜鉛めっきし、め
っき表面の明度がＬ値で７０以上のめっき処理鋼板を得
ることを特徴とするめっき外観に優れた電気亜鉛めっき
鋼板の製造方法。2. A sulfuric acid-hydrochloric acid zinc plating treatment bath,
0.01 to 10 ppm of Tl is contained in the bath, 10 to 200
A method for producing an electrogalvanized steel sheet having an excellent plating appearance, which comprises electrogalvanizing a steel sheet with a current density of A / dm 2 to obtain a plated steel sheet having a brightness of an L value of 70 or more.
して、硫酸タリウムまたは酢酸タリウムの添加によるこ
とを特徴とする請求項２記載のめっき外観に優れた電気
亜鉛めっき鋼板の製造方法。3. The method for producing an electrogalvanized steel sheet excellent in plating appearance according to claim 2, wherein Tl is added to the galvanizing bath by adding thallium sulfate or thallium acetate.
して、Ｐｂ合金中にＴｌを０．１〜１０wt％含有するＰ
ｂ系陽極を使用し、電極の溶解と共にＴｌを供給するこ
とを特徴とする請求項２記載のめっき外観に優れた電気
亜鉛めっき鋼板の製造方法。4. A method of adding Tl to a galvanizing bath, wherein Pb contains 0.1 to 10 wt% of Tl in Pb alloy.
The method for producing an electrogalvanized steel sheet having excellent plating appearance according to claim 2, wherein a b-type anode is used and Tl is supplied together with the melting of the electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP566196A JPH09195082A (en) | 1996-01-17 | 1996-01-17 | Electrogalvanized steel sheet excellent in plating appearance and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP566196A JPH09195082A (en) | 1996-01-17 | 1996-01-17 | Electrogalvanized steel sheet excellent in plating appearance and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09195082A true JPH09195082A (en) | 1997-07-29 |
Family
ID=11617300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP566196A Pending JPH09195082A (en) | 1996-01-17 | 1996-01-17 | Electrogalvanized steel sheet excellent in plating appearance and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09195082A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008240036A (en) * | 2007-03-26 | 2008-10-09 | Kobe Steel Ltd | Electrogalvanized steel sheet excellent in stain resistance and production method thereof |
| US12497708B2 (en) | 2019-12-20 | 2025-12-16 | Posco Co., Ltd | Electrogalvanized steel sheet having superb whiteness and method for manufacturing same |
-
1996
- 1996-01-17 JP JP566196A patent/JPH09195082A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008240036A (en) * | 2007-03-26 | 2008-10-09 | Kobe Steel Ltd | Electrogalvanized steel sheet excellent in stain resistance and production method thereof |
| US12497708B2 (en) | 2019-12-20 | 2025-12-16 | Posco Co., Ltd | Electrogalvanized steel sheet having superb whiteness and method for manufacturing same |
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