JPS63199897A - Tinned steel sheet having superior red rust resistance and production thereof - Google Patents

Tinned steel sheet having superior red rust resistance and production thereof

Info

Publication number
JPS63199897A
JPS63199897A JP3153987A JP3153987A JPS63199897A JP S63199897 A JPS63199897 A JP S63199897A JP 3153987 A JP3153987 A JP 3153987A JP 3153987 A JP3153987 A JP 3153987A JP S63199897 A JPS63199897 A JP S63199897A
Authority
JP
Japan
Prior art keywords
tin
steel sheet
red rust
nickel
rust resistance
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
Application number
JP3153987A
Other languages
Japanese (ja)
Other versions
JP2646542B2 (en
Inventor
Naoyuki Oba
直幸 大庭
Yoshinori Yomura
吉則 余村
Takayoshi Shimomura
下村 隆良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Engineering Corp
Original Assignee
NKK Corp
Nippon Kokan Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NKK Corp, Nippon Kokan Ltd filed Critical NKK Corp
Priority to JP62031539A priority Critical patent/JP2646542B2/en
Publication of JPS63199897A publication Critical patent/JPS63199897A/en
Application granted granted Critical
Publication of JP2646542B2 publication Critical patent/JP2646542B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PURPOSE:To efficiently produce a tinned steel sheet having superior red rust resistance by tinning a steel sheet, subjecting it to reflow treatment and simultaneously electrodepositing Ni and chromium oxide by cathodic electrolysis. CONSTITUTION:A steel sheet is tinned by >=2.8g/m<2> and subjected to reflow treatment. Cathodic electrolysis is then carried out in a chromating soln. contg. about 0.01-1.0mol/l Ni ions to simultaneously electrodeposit Ni and chromium oxide on the tinned surface. The Ni content in the resulting coating layer is restricted to 1-30mg/m<2> per one side. Thus, a tinned steel sheet having im proved red rust resistance is obtd. while the thickness of the Sn layer is about 1/3 of the conventional thickness.

Description

【発明の詳細な説明】 「発明の目的」 (産業上の利用分野) 本発明は、耐赤錆性に優れた錫めっき鋼板およびその製
造法に関するものである。
DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Field of Industrial Application) The present invention relates to a tin-plated steel sheet with excellent red rust resistance and a method for producing the same.

(従来の技術) 通常、錫めっき鋼板は、原板の脱脂、酸洗等の前処理を
行なった後、錫めっきが施され、次いで電気的な加熱に
よるリフロー処理を施すことにより、錫めっき特有の金
属光沢を有する製品となるが、塗料の密着性、耐食性を
より向上せしめるために、クロメート処理液による陰極
処理が施されるのが普通である。
(Prior art) Usually, tin-plated steel sheets are tin-plated after performing pre-treatments such as degreasing and pickling of the original sheet, and then subjected to reflow treatment using electrical heating to achieve the unique properties of tin plating. Although the product has a metallic luster, it is usually cathodically treated with a chromate treatment solution to further improve the adhesion and corrosion resistance of the paint.

しかし、この陰極処理、例えば#311処理等の場合に
は、クロムオキサイドが均一に付着せず局所的に偏在し
て析出することが知られている。
However, in the case of this cathodic treatment, for example, #311 treatment, it is known that chromium oxide does not adhere uniformly but precipitates locally unevenly.

(東洋鋼板、23、l 976/77、PL7〜28)
更に、缶蓋用鍋めっき鋼板等の場合は外観が重視される
ことから、無塗装で使用されることがあるが、めっき表
面の粗さの大きい、凹凸の激しい板を使用する場合には
、鋼板の表面が完全に錫で被覆されていない場合もあり
、例えば缶詰製造時におけるレトルト殺菌処理の際、水
滴が付着することにより赤錆の発生を看ることがある。
(Toyo Kohan, 23, l 976/77, PL7-28)
Furthermore, in the case of pot-plated steel sheets for can lids, appearance is important, so they are sometimes used unpainted, but when using plates with highly uneven plating surfaces, In some cases, the surface of the steel plate is not completely coated with tin, and for example, during retort sterilization treatment during the production of canned goods, red rust may develop due to water droplets adhering to the steel plate.

又、缶詰用錫めっき鋼板の場合は、前述のレトルト処理
以外でも、例えば夏季の高温高湿の場合には、シート状
に重ねたままで、輸送中もしくは貯蔵中に赤錆を発生す
ることがある。一方、化成処理皮膜量の増大により赤錆
の発生をおさえる方法も検討されているが、例えば前述
の#311処理の場合には、赤錆の発生は少なくなるが
、ケミカルスティンと呼ぶ表面欠陥が生ずることが知ら
れている。そこで最近は特に缶蓋外面用等には、赤錆防
止のために錫めっき量を増加する傾向にあるが、これは
高価な錫の使用量を増大せしめることになり好ましいこ
とではない。
In addition, in the case of tin-plated steel sheets for canned goods, red rust may occur during transportation or storage while stacking sheets in the form of sheets, even when the steel sheets are not subjected to the above-mentioned retort treatment, for example, in the case of high temperature and high humidity in the summer. On the other hand, methods of suppressing the occurrence of red rust by increasing the amount of chemical conversion coating are being considered, but for example, in the case of the #311 treatment described above, the occurrence of red rust is reduced, but surface defects called chemical stains occur. It has been known. Recently, there has been a tendency to increase the amount of tin plating, especially for the outer surface of can lids, to prevent red rust, but this is not desirable because it increases the amount of expensive tin used.

(発明が解決しようとする問題点) 本発明は、上述したような錫めっき鋼板の現状に鑑み創
案されたものであり、錫めっき量を増大せしめることな
く、赤錆の発生を防止するためにクロメート処理の際に
、少量のニッケルイオンを添加することにより、耐赤錆
性に優れた錫めっき鋼板を得ると共に効率的な該鋼板の
製造法を提供することを目的とするものである。
(Problems to be Solved by the Invention) The present invention was devised in view of the current state of tin-plated steel sheets as described above, and in order to prevent the occurrence of red rust without increasing the amount of tin plating, the present invention The purpose of this invention is to obtain a tin-plated steel sheet with excellent red rust resistance by adding a small amount of nickel ions during treatment, and to provide an efficient method for producing the steel sheet.

「発明の構成」 (問題点を解決する手段) 前述の目的を達成するために、本発明者等は、(1) 
 2.8 g/m以上の錫めっき層上に、ニッケルとク
ロムオキサイドが混在した被覆層を有し、且つ該被覆層
中のニッケル含有量が片面当り1〜30mg/rrrで
あることを特徴とする耐赤錆性に優れた錫めっき鋼板。
"Structure of the invention" (Means for solving the problem) In order to achieve the above-mentioned purpose, the inventors have (1)
It has a coating layer containing a mixture of nickel and chromium oxide on a tin plating layer of 2.8 g/m or more, and the nickel content in the coating layer is 1 to 30 mg/rrr per side. Tin-plated steel sheet with excellent red rust resistance.

(2)鋼板に錫めっきをした後、リフロー処理を施し、
次いでニッケルイオンを含むクロメート処理液を用いて
陰極電解を行ない前記錫めっき面にニッケルとクロムオ
キサイドを同時に電着させることを特徴とする耐赤錆性
に優れた錫めっき銅板の製造方法。
(2) After tin-plating the steel plate, perform reflow treatment,
A method for manufacturing a tin-plated copper plate with excellent red rust resistance, characterized in that cathodic electrolysis is then performed using a chromate treatment solution containing nickel ions to simultaneously electrodeposit nickel and chromium oxide on the tin-plated surface.

を芸に提案する。Suggest to the art.

(作用) 従来技術で触れたように赤錆の発生を防止するため最近
は錫めっきの厚物が増加する傾向にあり、例えば缶蓋外
面の錫めっき量を8.4g/rr?とし、内面は塗装し
て用いることが多いため、2.8g/m′のめっき量と
するものが散見されるが、本発明では耐赤錆性が優れて
いるので缶蓋外面用等でもめっき量の下限を2.8g/
m2とすることができる。
(Function) As mentioned in the conventional technology, there is a recent tendency to increase the thickness of tin plating in order to prevent the occurrence of red rust.For example, the amount of tin plating on the outer surface of can lids has been increased to 8.4 g/rr? Since the inner surface is often painted and used, some products have a plating amount of 2.8 g/m', but the present invention has excellent red rust resistance, so the plating amount can be reduced even for the outer surface of can lids, etc. Lower limit of 2.8g/
m2.

本願発明の特徴の1つとするところは、錫めっき後のク
ロメート処理液にニッケルイオンを添加し、陰極処理に
よって錫めっき面に形成される被覆層中にニッケルを存
在せしめることである。錫や、ニッケルは腐蝕電位が鉄
よりも高く、鉄に対する被覆の効果についてはニッケル
は錫と同等の働きをし、又、腐食することがあっても赤
錆とはならないのでニッケルを利用する意義がある。
One of the features of the present invention is that nickel ions are added to the chromate treatment solution after tin plating, so that nickel is present in the coating layer formed on the tin-plated surface by cathodic treatment. Tin and nickel have a higher corrosion potential than iron, and nickel has the same effect as tin when it comes to coating iron, and even if it corrodes, it does not turn into red rust, so there is no point in using nickel. be.

第1図は、本発明による被覆を形成せしめた錫めっき鋼
板の断面構造を示したものであり、第2図に示す従来の
錫めっき鋼板の断面構造と異なり鉄地が表面に露出する
ことなく、クロメート被覆層中にニッケルが混在してい
る。
Figure 1 shows the cross-sectional structure of a tin-plated steel plate on which the coating according to the present invention has been formed, and unlike the cross-sectional structure of the conventional tin-plated steel plate shown in Figure 2, the iron base is not exposed on the surface. , nickel is mixed in the chromate coating layer.

本発明者等の研究によれば、クロメート被覆層中に存在
するニッケルの量は、1.0■/rI?以下では表面を
均一に覆うことは困難であり、耐赤錆性の効果は期待で
きず、好ましくは2.0■/M〜101mg/m2の間
であり、30mg/m2の付着量となった場合にはぶり
きとしての金属光沢が失われ黄色味を帯びてくる。これ
はニッケル自体の色である黄色−薄桃色に起因するもの
であり、外観が悪くなり好ましくない。従って本発明の
耐赤錆性に優れた錫めっき鋼板としては、錫めっき量は
2.8g/m2以上の錫めっき、を施したものを原板と
し、この上にニッケルとクロムオキサイドからなる被覆
層を形成せしめたものとなるが、該被覆層中に含有され
るニッケル含有量は片面当り1〜30mg/m2の範囲
に限定されたものとなる。
According to the research conducted by the present inventors, the amount of nickel present in the chromate coating layer is 1.0/rI? If the coating amount is below, it is difficult to uniformly cover the surface, and the effect of red rust resistance cannot be expected.The coating amount is preferably between 2.0μ/M and 101mg/m2, and when the coating amount is 30mg/m2. It loses its metallic luster and takes on a yellowish tinge. This is due to the yellow-pink color of nickel itself, which is undesirable as it gives a poor appearance. Therefore, the tin-plated steel sheet of the present invention with excellent red rust resistance uses a base plate with a tin plating amount of 2.8 g/m2 or more, and a coating layer of nickel and chromium oxide is applied on top of this. However, the nickel content contained in the coating layer is limited to a range of 1 to 30 mg/m 2 per side.

尚、上述のニッケル析出量を得るためにはクロメート処
理溶液中にニッケルイオンとして0、O1モル/l〜1
.0モル/1の濃度範囲が好ましく、ニッケルイオンの
量が多くなると同じ電気量を与えても析出量が増えてく
る。ニッケル、クロムオキサイドは同時に電着するので
、クロメート処理に際しては予め電着量など設定してお
(必要がある。
In addition, in order to obtain the above-mentioned amount of nickel precipitation, nickel ions should be added to the chromate treatment solution from 0 to 1 mol/l.
.. A concentration range of 0 mol/1 is preferable, and as the amount of nickel ions increases, the amount of precipitation increases even if the same amount of electricity is applied. Since nickel and chromium oxide are electrodeposited at the same time, it is necessary to set the amount of electrodeposition in advance during chromate treatment.

又、クロメート処理液中に5〜50g/lのホウ酸を添
加しておくとニッケルとクロムオキサイドが均一析出す
る効果がある。最適な範囲は5〜10g/lである。ホ
ウ酸は溶解度が小さいので、前述の50g/j2は略、
溶解度の上限である。本発明による錫めっき鋼板は缶用
として最適であるが、耐食性に優れているので汎用性が
あることは云うまでもない。
Furthermore, adding 5 to 50 g/l of boric acid to the chromate treatment solution has the effect of uniformly precipitating nickel and chromium oxide. The optimum range is 5-10 g/l. Since boric acid has low solubility, the above 50g/j2 is approximately
This is the upper limit of solubility. The tin-plated steel sheet according to the present invention is most suitable for use in cans, but it goes without saying that it has excellent corrosion resistance and is therefore versatile.

(実施例) 実施例−1 鋼帯をアルカリ脱脂および酸洗の後、錫めっき2.8g
/mを施し、抵抗加熱法によりリフローした。次いで重
クロム酸ソーダ0.1モル/1+硫酸ニッケル0.01
モル/1中で4c/dm”の陰極電解処理を施し、ニッ
ケルとクロムオキサイドを同時に電着せしめた。
(Example) Example-1 After alkali degreasing and pickling of a steel strip, 2.8g of tin plating was applied.
/m and reflowed by resistance heating method. Then sodium dichromate 0.1 mol/1 + nickel sulfate 0.01
A cathodic electrolytic treatment of 4 c/dm'' in mol/1 was performed to simultaneously electrodeposit nickel and chromium oxide.

実施例−2 硫酸ニッケルの使用量を、0.1モル/7!とした以外
は実施例−1と同一条件で処理。
Example-2 The amount of nickel sulfate used was 0.1 mol/7! Processed under the same conditions as Example-1 except for the following.

実施例−3 クロメート処理液にホウ酸を30g/lを添加した以外
は実施例−1と同一条件で処理。
Example 3 A treatment was carried out under the same conditions as in Example 1, except that 30 g/l of boric acid was added to the chromate treatment solution.

実施例−4 硫酸ニッケルを0.1モル/l、ホウ酸を30g/lと
した他は実施例−1と同一条件で処理。
Example-4 Processed under the same conditions as Example-1 except that nickel sulfate was 0.1 mol/l and boric acid was 30 g/l.

実施例−5 陰極電解処理を8c/dm”とした以外は実施例−3と
同一条件で処理。
Example-5 Processed under the same conditions as Example-3 except that the cathode electrolytic treatment was changed to 8 c/dm''.

実施例−6 陰極電解処理を8c/dm”とした以外は実施例−4と
同一条件で処理。
Example-6 Processed under the same conditions as Example-4 except that the cathode electrolytic treatment was 8c/dm''.

比較例−1 銅帯をアルカリ脱脂および酸洗の後、錫めっき2.8g
/%を施し、抵抗加熱法によりリフローした。次いで重
クロム酸ソーダ0.1モル/l中で4c/d@”の陰極
電解処理を施し、クロムオキサイドを電着せしめた。
Comparative Example-1 After alkali degreasing and pickling of copper strip, 2.8g of tin plating was applied.
/% and reflowed by resistance heating method. Next, cathodic electrolysis treatment of 4 c/d@'' was performed in 0.1 mol/l of sodium dichromate to electrodeposit chromium oxide.

比較例−2 錫めっき量を8.4g/rrfとした以外は比較例−1
と同一条件で処理。
Comparative example-2 Comparative example-1 except that the tin plating amount was 8.4 g/rrf
Processed under the same conditions.

比較例−3 陰極電解処理を16 c /dm2とした以外は比較例
−2と同一条件で処理。
Comparative Example-3 Processed under the same conditions as Comparative Example-2 except that the cathode electrolytic treatment was performed at 16 c/dm2.

比較例−4 陰極電解処理をlc/dm”とした以外は実施例−4と
同一条件で処理。
Comparative Example-4 Processed under the same conditions as Example-4 except that the cathode electrolytic treatment was changed to lc/dm''.

比較例−5 陰極電解処理を16 c /dmzとした以外は実施例
−4と同一条件で処理。
Comparative Example-5 Processed under the same conditions as Example-4 except that the cathode electrolytic treatment was performed at 16 c/dmz.

実施例−7 錫めっき量を8.4g/n(とした以外は実施例−1と
同一条件で処理したもの。
Example-7 Processed under the same conditions as Example-1 except that the amount of tin plating was 8.4 g/n.

次表は、前述の本発明の実施例の全て、並びに比較例の
全てについて塩水噴霧試験(JISZ2371 :3.
5 fir)を行なった耐赤錆性の試験結果を示すもの
である。
The following table shows the salt spray test (JISZ2371:3.
5 fir) is shown.

この表からも分るように、本発明による場合には、従来
の錫めっき鋼板と同等のクロムオキサイド量であっても
、ニッケル析出量が1mg/m2以上の範囲であれば、
錫めっき量が8.4g/rrrもしくは2.8g/rr
rであっても、従来の錫めっき銅板(8,4g/rrr
もしくは2.8g/rrr)よりも優れた耐錆性(耐赤
錆性)が得られ且つ外観も優れている。
As can be seen from this table, in the case of the present invention, even if the amount of chromium oxide is equivalent to that of conventional tin-plated steel sheets, if the amount of nickel precipitation is in the range of 1 mg/m2 or more,
Tin plating amount is 8.4g/rrr or 2.8g/rr
r, conventional tin-plated copper plate (8.4g/rrr
or 2.8 g/rrr), and the appearance is also excellent.

一方、従来の錫めっき鋼板は、錫めっき量が2.8g/
m2の場合はもちろん8.4g/rrfの場合であって
も耐錆性は充分ではない。錫めっき量が8.4g/mで
クロメート処理の際の処理電気量アップによる場合のみ
耐錆性は良好となっているが、外観はケミカルスティン
の発生により劣化している。被覆中にニッケルを含んで
いても化成処理電気量が少なくその析出量が1■/r+
(未満の場合には、耐錆性は充分ではない。一方ニッケ
ルの析出量が30■/rrlを越えた場合には耐錆性は
良いが、色調は黄色味を帯び、且つケミカルスティンが
発生し外観は著しく悪くなっている。
On the other hand, conventional tin-plated steel sheets have a tin plating amount of 2.8g/
Not only in the case of m2 but also in the case of 8.4 g/rrf, the rust resistance is not sufficient. Rust resistance is good only when the amount of tin plating is 8.4 g/m and the amount of electricity processed during chromate treatment is increased, but the appearance is deteriorated due to the generation of chemical stain. Even if the coating contains nickel, the amount of electricity required for chemical conversion treatment is small and the amount of nickel deposited is 1■/r+
(If the amount is less than 30 μ/rrl, the rust resistance will not be sufficient. On the other hand, if the amount of nickel precipitation exceeds 30 μ/rrl, the rust resistance will be good, but the color will be yellowish and chemical stain will occur.) However, the appearance has deteriorated significantly.

「発明の効果」 本発明により得られた錫めっき鋼板は、錫めっき量が2
.8g/rdであっても優れた耐赤錆性を有しており、
例えば昨今レトルト処理用缶蓋の外面側としての8.4
g/rrrの市販の錫めっき鋼板に比較した場合には1
/3の厚みで足りることになるので、耐赤錆性の向上と
共に製造コストの削減に関する点でも又、製造方法が極
めて単純且つ簡単な点も含めて極めて有益な発明という
べきである。
"Effects of the Invention" The tin-plated steel sheet obtained by the present invention has a tin plating amount of 2.
.. It has excellent red rust resistance even at 8g/rd,
For example, recently, 8.4
1 when compared to a commercially available tin-plated steel sheet of g/rrr.
Since a thickness of /3 is sufficient, this invention is extremely useful in terms of improving red rust resistance and reducing manufacturing costs, as well as the fact that the manufacturing method is extremely simple and easy.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図は本発明の錫めっき鋼板の被膜の断面構造を示し
第2図は従来の錫めっき鋼板の被膜の断面構造を示す。 l:ニッケルとクロムオキサイドの混在層2:酸化錫を
主・体とした層 3:錫層 4:鉄−錫合金層 5:鉄地 6:クロムオキサイドを主体とする層 第 1rlA 第 2  圓 手続補正書(山谷) 昭和 614.8   日
FIG. 1 shows a cross-sectional structure of a coating on a tin-plated steel sheet according to the present invention, and FIG. 2 shows a cross-sectional structure of a coating on a conventional tin-plated steel sheet. l: Mixed layer of nickel and chromium oxide 2: Layer mainly composed of tin oxide 3: Tin layer 4: Iron-tin alloy layer 5: Iron base 6: Layer mainly composed of chromium oxide 1st rlA 2nd round procedure Amendment (Yamaya) Showa 614.8

Claims (2)

【特許請求の範囲】[Claims] (1)2.8g/m^2以上の錫めっき層上に、ニッケ
ルとクロムオキサイドが混在した被覆層を有し、且つ該
被覆層中のニッケル含有量が片面当り1〜30mg/m
^2であることを特徴とする耐赤錆性に優れた錫めっき
鋼板。
(1) It has a coating layer containing a mixture of nickel and chromium oxide on a tin plating layer of 2.8 g/m^2 or more, and the nickel content in the coating layer is 1 to 30 mg/m per side.
A tin-plated steel sheet with excellent red rust resistance characterized by ^2.
(2)鋼板に錫めっきをした後、リフロー処理を施し、
次いでニッケルイオンを含むクロメート処理液を用いて
陰極電解を行ない、前記錫めっき面にニッケルとクロム
オキサイドを同時に電着させることを特徴とする耐赤錆
性に優れた錫めっき鋼板の製造方法。
(2) After tin-plating the steel plate, perform reflow treatment,
A method for producing a tin-plated steel sheet with excellent red rust resistance, characterized in that cathodic electrolysis is then performed using a chromate treatment solution containing nickel ions to simultaneously electrodeposit nickel and chromium oxide on the tin-plated surface.
JP62031539A 1987-02-16 1987-02-16 Tin-plated steel sheet excellent in red rust resistance and method for producing the same Expired - Fee Related JP2646542B2 (en)

Priority Applications (1)

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JP62031539A JP2646542B2 (en) 1987-02-16 1987-02-16 Tin-plated steel sheet excellent in red rust resistance and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62031539A JP2646542B2 (en) 1987-02-16 1987-02-16 Tin-plated steel sheet excellent in red rust resistance and method for producing the same

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JPS63199897A true JPS63199897A (en) 1988-08-18
JP2646542B2 JP2646542B2 (en) 1997-08-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004306839A (en) * 2003-04-09 2004-11-04 Mitsubishi Heavy Ind Ltd Ship

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5579891A (en) * 1978-12-14 1980-06-16 Toyo Kohan Co Ltd Preparation of tin plated steel sheet

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5579891A (en) * 1978-12-14 1980-06-16 Toyo Kohan Co Ltd Preparation of tin plated steel sheet

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004306839A (en) * 2003-04-09 2004-11-04 Mitsubishi Heavy Ind Ltd Ship

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JP2646542B2 (en) 1997-08-27

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