JP2657750B2 - Manufacturing method of zinc-based electroplated steel sheet with excellent corrosion resistance - Google Patents

Manufacturing method of zinc-based electroplated steel sheet with excellent corrosion resistance

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Publication number
JP2657750B2
JP2657750B2 JP307393A JP307393A JP2657750B2 JP 2657750 B2 JP2657750 B2 JP 2657750B2 JP 307393 A JP307393 A JP 307393A JP 307393 A JP307393 A JP 307393A JP 2657750 B2 JP2657750 B2 JP 2657750B2
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JP
Japan
Prior art keywords
corrosion resistance
plating
steel sheet
zinc
coumarin
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.)
Expired - Fee Related
Application number
JP307393A
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Japanese (ja)
Other versions
JPH06212480A (en
Inventor
文男 山崎
芳雄 新藤
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.)
Nippon Steel Corp
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Nippon Steel Corp
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Priority to JP307393A priority Critical patent/JP2657750B2/en
Publication of JPH06212480A publication Critical patent/JPH06212480A/en
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Expired - Fee Related legal-status Critical Current

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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明は自動車、家電などに用い
られるCrを含有する耐食性に優れた亜鉛系電気めっき
鋼板の製造方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a zinc-containing electroplated steel sheet containing Cr and having excellent corrosion resistance, which is used in automobiles and home appliances.

【0002】[0002]

【従来の技術】電気亜鉛めっき鋼板は、自動車、家電、
建材用途を中心に広く使用さている。このうち、自動車
用途では、寒冷地帯における冬期の道路凍結防止用の散
布岩塩による車体腐食を防止するために、より高度な耐
食性が要求されている。亜鉛めっき鋼板の耐食性向上
は、亜鉛のめっき量(付着量)の増加で可能であるが、
これは溶接性や加工性の点で問題が多い。そこで亜鉛そ
のものの溶解を抑制し亜鉛めっきの寿命を延ばす方法と
して、多くの合金めっきが提案されている。中でもF
e、Ni、Coを合金成分として含有するZn系合金め
っきは、その良好な裸耐食性や塗装後耐食性が認めら
れ、実用化されている。また、特開昭61−27039
8号公報、特開昭62−54099号公報、特開平3−
120393号公報などに開示されているように、Zn
ないしZn系合金めっき中にCrを含有させる試みもな
されているが、耐食性においてZn−Ni合金めっきや
Zn−Fe合金めっきを凌駕するには到っていない。
2. Description of the Related Art Galvanized steel sheets are used in automobiles, home appliances,
Widely used mainly for building materials. Of these, in automobile applications, higher corrosion resistance is required in order to prevent vehicle body corrosion due to scattered rock salt for preventing road freezing in winter in cold regions. Corrosion resistance of galvanized steel sheet can be improved by increasing the amount of zinc plating (adhesion).
This has many problems in terms of weldability and workability. Therefore, many alloy platings have been proposed as a method of suppressing the dissolution of zinc itself and extending the life of zinc plating. Above all, F
Zn-based alloy plating containing e, Ni, and Co as alloy components is recognized for its good bare corrosion resistance and corrosion resistance after painting, and has been put to practical use. Further, Japanese Patent Application Laid-Open No. 61-27039
No. 8, JP-A-62-54099, JP-A-3-
As disclosed in JP-A-120393 and the like, Zn
Attempts have also been made to include Cr in the Zn-based alloy plating, but this has not been superior to Zn-Ni alloy plating or Zn-Fe alloy plating in corrosion resistance.

【0003】[0003]

【発明が解決しようとする課題】亜鉛と共にCrを析出
させる試みはCr3+やCr6+イオンを用いて従来から行
なわれているが、単純浴からは微量のCrが析出するの
みであり、Cr濃度や電流密度の増加によって数%のC
rを析出させても、良好な外観が得られないだけでな
く、加工性や電流効率の著しい低下を伴い工業的に有利
な方法はなかった。本発明は、上記問題点を解決し、C
rを含有する耐食性に優れた亜鉛系電気めっき鋼板の製
造方法を提供するものである。
Attempts to precipitate Cr together with zinc have conventionally been made using Cr 3+ or Cr 6+ ions, but only a small amount of Cr precipitates from a simple bath. Several% of C due to increase of Cr concentration and current density
Even when r is precipitated, not only good appearance is not obtained, but also there is no industrially advantageous method accompanied by remarkable reduction in workability and current efficiency. The present invention solves the above problems, and
An object of the present invention is to provide a method for producing a zinc-based electroplated steel sheet having excellent corrosion resistance containing r.

【0004】[0004]

【課題を解決するための手段】本発明の要旨は、 (1)Crを含有する電気亜鉛めっき鋼板を製造するに
際し、Zn2+イオン、Cr3+イオン及びクマリンも
しくはその誘導体を0.1〜10g/1含有するめっき
浴を用いて、電気めっきを行なうことを特徴とする耐食
性に優れた亜鉛系電気めっき鋼板の製造方法。 (2)Crを含有する電気亜鉛めっき鋼板を製造するに
際し、Zn2+イオン、Cr3+イオン、クマリンもし
くはその誘導体を0.1〜10g/1、カチオンポリマ
ーおよび/またはポリオキシアルキレン誘導体を0.0
1〜20g/1含有するめっき浴を用いて、電気めっき
を行なうことを特徴とする耐食性に優れた亜鉛系電気め
っき鋼板の製造方法である。
The gist of the present invention is as follows: (1) In producing a galvanized steel sheet containing Cr, 0.1 to 10 g / kg of Zn 2+ ion, Cr 3+ ion and coumarin or a derivative thereof. 1. A method for producing a zinc-based electroplated steel sheet having excellent corrosion resistance, wherein electroplating is performed using a plating bath containing 1 . (2) In producing an electrogalvanized steel sheet containing Cr, Zn 2+ ion, Cr 3+ ion, coumarin or a derivative thereof is 0.1 to 10 g / 1 , and a cationic polymer and / or a polyoxyalkylene derivative is 0.0
This is a method for producing a zinc-based electroplated steel sheet having excellent corrosion resistance, wherein electroplating is performed using a plating bath containing 1 to 20 g / 1 .

【0005】[0005]

【作用】従来Zn2+イオンとCr3+ないしはCr6+イオ
ンからなる単純浴を使用しても微量のCrが析出するの
みであり、Cr濃度や電流密度の増加によって数%のC
rを析出させても、耐食性の向上代は小さく、また外観
や加工性の点で実用に耐えるめっきが得られなかった。
しかるに、Cr3+イオンを含む亜鉛系めっき浴中にクマ
リンもしくはクマリンの誘導体をCr析出促進剤として
添加することにより、この問題は解決され、多量のCr
を含む高度の耐食性を有するめっきが得られるようにな
る。この理由は、クマリンがCr3+イオンと錯体を形成
し、Zn2+イオンの析出を抑制しつつCr3+イオンの析
出を容易ならしめるためと推定される。クマリンもしく
はクマリンの誘導体の添加量は0.1〜10g/lが好
ましく、0.1g/l未満ではCr析出効果が十分では
なく、10g/lを超えるとめっき浴に溶解し難くなる
ので実用的ではない。ここで、クマリンとはC96 2
で示される有機化合物であり、
[Function] Conventional Zn2+Ion and Cr3+Or Cr6+Io
Traces of Cr precipitate even when using a simple bath made of
Only a few percent due to the increase in Cr concentration and current density.
Even if r is precipitated, the margin of improvement in corrosion resistance is small and the appearance
Plating that could withstand practical use in terms of workability was not obtained.
However, Cr3+Bear in zinc-based plating bath containing ions
Phosphorus or coumarin derivative as Cr precipitation accelerator
This problem can be solved by the addition of Cr.
Plating with high corrosion resistance
You. The reason is that coumarin is Cr3+Form a complex with ions
And Zn2+Cr while suppressing ion precipitation3+Ion deposition
It is presumed that it is easier to get out. Coumarin or
Is preferably 0.1 to 10 g / l of the coumarin derivative.
If less than 0.1 g / l, the effect of Cr precipitation is not sufficient.
If it exceeds 10 g / l, it is difficult to dissolve in the plating bath
So impractical. Here, coumarin is C9H6O Two
Is an organic compound represented by

【0006】[0006]

【化1】 Embedded image

【0007】クマリンの誘導体とはクマリン酸、クマル
酸、あるいはこれらのエステル類などを含む。クマリン
とその誘導体は単独、もしくは複合で用いられてよい。
めっき浴中には、これらクマリン類の他にさらにカチオ
ンポリマーあるいはポリオキシアルキレン誘導体を添加
してもよく、これにより外観品位を向上させることがで
き、また、Cr析出に対してもより有利である。これら
の添加量は0.01〜20g/lが好ましく、0.01
g/l未満では上記効果が不足し、20g/lを超える
とCr析出効果が飽和する。カチオンポリマーとポリオ
キシアルキレン誘導体は、何れか一方を用いてもよい
し、両方を用いてもよい。
[0007] Coumarin derivatives include coumaric acid, coumaric acid, and esters thereof. Coumarin and its derivatives may be used alone or in combination.
In the plating bath, a cationic polymer or a polyoxyalkylene derivative may be further added in addition to these coumarins, whereby the appearance quality can be improved, and it is more advantageous for Cr precipitation. . The addition amount of these is preferably 0.01 to 20 g / l,
If the amount is less than g / l, the above effect is insufficient, and if it exceeds 20 g / l, the Cr precipitation effect is saturated. Either the cationic polymer or the polyoxyalkylene derivative may be used, or both may be used.

【0008】カチオンポリマーとしては、次に示す4級
アミン塩の重合物が好ましく、特にポリアミンスルホン
(PASと略)及びポリアミン(PAと略)が効果的で
ある。この理由としては、アミン基による陰極面への吸
着作用とスルホン基へのCr 3+イオンの配位結合が寄与
していると推定される。平均分子量としては102〜1
6が好ましい。
[0008] As the cationic polymer, the following quaternary
Polymers of amine salts are preferred, especially polyamine sulfones
(Abbreviated as PAS) and polyamine (abbreviated as PA) are effective
is there. The reason for this is that amine groups absorb
Adhesion and Cr on sulfone groups 3+Coordination bond of ion contributes
It is estimated that The average molecular weight is 10Two~ 1
06Is preferred.

【0009】[0009]

【化2】 Embedded image

【0010】[0010]

【化3】 Embedded image

【0011】[0011]

【化4】 Embedded image

【0012】R1、R2は低級アルキル基を示し、XはC
-、HSO4 -、H2PO4 - 、R−SO3 -(RはC1〜C
4のアルキル基)、NO3 -のアニオンを示す。 この
他、1、2、3級アミンのポリマーも前述の4級アミン
ポリマーには及ばないが効果がある。
R 1 and R 2 each represent a lower alkyl group;
l -, HSO 4 -, H 2 PO 4 -, R-SO 3 - (R is C 1 -C
4 alkyl), NO 3 - shows the anion. In addition, polymers of primary, secondary and tertiary amines are effective, although they are inferior to the above-mentioned quaternary amine polymers.

【0013】ポリオキシアルキレン誘導体は、R2−O
−(R1−O)n−Hで示される有機化合物である。平均
分子量としては、102 〜106 が好ましい。このう
ち、特にポリエチレングリコール(PEGと略)HO−
(CH2−CH2−O)n−Hが有効である。
The polyoxyalkylene derivative is represented by R 2 —O
It is an organic compound represented by-(R 1 -O) n -H. The average molecular weight, 10 2 to 10 6 are preferred. Among them, polyethylene glycol (abbreviated as PEG) HO-
(CH 2 —CH 2 —O) n -H is effective.

【0014】図1には上記Cr析出促進剤の添加量とめ
っき層中のCr含有率の関係、図2には上記Cr析出促
進剤の添加量と得られためっき皮膜の外観の関係を示
す。Cr析出促進剤添加量以外の条件、すなわち、めっ
き浴組成、めっき条件は一定である。クマリン0.1g
/l未満ではCr含有率は1%であるが、0.1g/l
以上になるとCr含有率は5%以上になる。また、カチ
オンポリマーの1例としてPASを1g/l添加する
と、Cr含有率はクマリン単独の場合に比較して増加す
る傾向にあり、かつ光沢のある均一な外観が得られるよ
うになる。
FIG. 1 shows the relationship between the amount of the Cr deposition accelerator added and the Cr content in the plating layer, and FIG. 2 shows the relationship between the amount of the Cr deposition accelerator added and the appearance of the plating film obtained. . The conditions other than the amount of the Cr precipitation accelerator added, that is, the plating bath composition and the plating conditions are constant. Coumarin 0.1g
/ L, the Cr content is 1%, but 0.1 g / l
Above this, the Cr content becomes 5% or more. When 1 g / l of PAS is added as an example of the cationic polymer, the Cr content tends to increase as compared with the case of using coumarin alone, and a glossy uniform appearance can be obtained.

【0015】めっき浴の種類は特に制約されないが、硫
酸塩浴、塩化物浴、これらの混合浴が望ましい。金属イ
オン濃度については、Zn2+イオン、Cr3+イオン、鉄
族金属2価イオンの合計で30〜200g/lが好まし
い。30g/l未満では高電流密度でイオンの供給不足
となりやすく、結果的にめっき焼けを生じやすい。20
0g/lを超えると、ドラッグアウトによるイオンの浪
費が無視できなくなると共に、液温が低くなった場合の
結晶化の懸念を生じる。その他のめっき条件について
は、特に制約されるものではないが、pH0.5〜3、
浴温40〜70℃、液流速1m/min以上、電流密度
20A/dm2以上が好ましい範囲であり、目的とする
めっき組成、電流効率を考慮して最適な条件を採用する
ことができる。めっき浴中には、Na+、NH4 + などの
電導度助剤、耐食性をさらに向上させるためのSi
2、TiO2、Al23などの酸化物粒子、BaCrO
4などのクロム酸塩粒子を添加してもよく、本発明の製
造方法に本質的な支障はない。
The type of the plating bath is not particularly limited, but a sulfate bath, a chloride bath, and a mixed bath thereof are desirable. The metal ion concentration is preferably 30 to 200 g / l in total of Zn 2+ ions, Cr 3+ ions, and iron group metal divalent ions. If it is less than 30 g / l, the supply of ions tends to be insufficient at a high current density, and as a result, burning of the plating tends to occur. 20
If it exceeds 0 g / l, waste of ions due to drag-out cannot be ignored, and crystallization may occur when the liquid temperature is lowered. Although other plating conditions are not particularly limited, pH 0.5 to 3,
The preferred ranges are a bath temperature of 40 to 70 ° C., a liquid flow rate of 1 m / min or more, and a current density of 20 A / dm 2 or more, and optimal conditions can be adopted in consideration of a desired plating composition and current efficiency. In the plating bath, conductivity aids such as Na + and NH 4 + , Si for further improving corrosion resistance,
Oxide particles such as O 2 , TiO 2 , Al 2 O 3 , BaCrO
Chromate particles such as 4 may be added, and there is no essential hindrance to the production method of the present invention.

【0016】かくしてCrと鉄族金属を含有する電気亜
鉛めっき鋼板を製造することができるが、めっき層中の
Cr含有率については、5〜30%が好ましい。5%未
満でも亜鉛めっきに比較すれば耐食性の向上は認められ
るが、5%以上になると亜鉛めっきはもとよりZn−N
i、Zn−Feなどの合金めっきを上回る高耐食性を発
揮し、例えば塩水噴霧試験を500時間以上行なっても
容易に赤錆は発生しない。この理由は、CrはZnとの
共存下では不動態化せずZnとともに犠牲防食作用を発
揮するが、めっき表面に形成される腐食生成物は難溶性
の保護皮膜として機能し、めっき層内部への腐食因子の
侵入を抑制するためと推定される。Cr含有率が30%
を超えると、加工性が低下するため、好ましくない。ま
た、Cr析出促進剤であるクマリンもしくはクマリンの
誘導体ないしはカチオンポリマーやポリオキシアルキレ
ン誘導体をめっき層中に微量共析させても差し支えな
く、5%以下の共析率ならば緻密で均一なめっき層が形
成され成形性に有利である。
Thus, an electrogalvanized steel sheet containing Cr and an iron group metal can be manufactured, but the Cr content in the plating layer is preferably 5 to 30%. Even if less than 5%, an improvement in corrosion resistance is recognized in comparison with zinc plating, but if it is 5% or more, not only zinc plating but also Zn-N
It exhibits higher corrosion resistance than alloy plating of i, Zn-Fe, etc., and does not easily generate red rust even if, for example, a salt spray test is performed for 500 hours or more. The reason is that Cr does not passivate in the coexistence with Zn and exhibits sacrificial corrosion protection together with Zn, but the corrosion products formed on the plating surface function as a hardly soluble protective film and enter the plating layer. It is presumed to suppress the invasion of corrosion factors. 30% Cr content
If it exceeds, the workability is lowered, which is not preferred. In addition, coumarin or a derivative of coumarin or a cationic polymer or a polyoxyalkylene derivative, which is a Cr precipitation accelerator, may be co-deposited in a trace amount in the plating layer. Are formed, which is advantageous for moldability.

【0017】[0017]

【実施例】冷延鋼板を、アルカリ脱脂し、5%硫酸水溶
液で酸洗した後、表1及び表2に示す条件で電気めっき
を行なった。Cr析出促進剤のうち、カチオンポリマー
としては平均分子量1万のPA、平均分子量3500の
PAS、ポリオキシアルキレン誘導体としては平均分子
量1500のPEGを用いた。めっき浴としては硫酸塩
浴を用い、めっき付着量は20g/m2とした。こうし
て得られためっき組成と耐食性、外観の評価を表2に示
す。耐食性は塩水噴霧試験(JIS Z2371に準
拠)を500時間行ない、以下の要領で判定した。
EXAMPLE A cold-rolled steel sheet was degreased with alkali and pickled with a 5% aqueous sulfuric acid solution, and then electroplated under the conditions shown in Tables 1 and 2. Among the Cr precipitation accelerators, PA having an average molecular weight of 10,000 and PAS having an average molecular weight of 3500 were used as the cationic polymer, and PEG having an average molecular weight of 1500 was used as the polyoxyalkylene derivative. As a plating bath, a sulfate bath was used, and the coating weight was 20 g / m 2 . Table 2 shows the plating compositions, corrosion resistance, and appearance evaluations thus obtained. The corrosion resistance was determined by performing a salt spray test (according to JIS Z2371) for 500 hours and performing the following procedure.

【0018】◎:赤錆発生1%以下 ○:赤錆発生10
%以下 △:赤錆発生50%以下 ×:赤錆発生50%超 めっき外観については、めっき表面の光沢度(JIS Z 87
41 GS (60°)、黒色ガラス板基準値93)を測定
し、以下の要領で判定した。 ◎:光沢度30以上 ○:光沢度20以上 △:光沢度10以
上 ×:光沢度10未満
:: Red rust generation 1% or less :: Red rust generation 10
%: Red rust generation 50% or less X: Red rust generation 50% or less For the plating appearance, the glossiness of the plating surface (JIS Z 87
41 G S (60 °), black glass plate standard value 93) were measured, and judged in the following manner. ◎: Gloss 30 or more ○: Gloss 20 or more △: Gloss 10 or more ×: Gloss less than 10

【0019】表1、表2において、比較例1はめっき浴
にクマリンが少ないために、Crの析出量が少なく耐食
性が不良である。比較例2は比較例1と同一のめっき浴
組成で電流密度を高くしてCrを析出させたが、十分な
Cr含有率が得られていないため、耐食性が不足すると
共に、外観も不良である。比較例3はZn−Ni合金め
っきであり、外観は良好なものの耐食性は本発明例を下
回る。これらに対して、本発明例は何れもCr含有率5
%以上のめっきが得られ、耐食性、外観共に良好であ
る。また本発明例5〜11はクマリン類とカチオンポリ
マーもしくはポリオキシアルキレン誘導体を併用した例
であるが、本発明例1〜4のクマリン類単独使用の例に
比し、外観が一段と向上しCr含有率も高くなる結果が
得られた。
In Tables 1 and 2, Comparative Example 1 has a small amount of chromium in the plating bath, and thus has a small amount of deposited Cr and poor corrosion resistance. In Comparative Example 2, Cr was deposited by increasing the current density with the same plating bath composition as Comparative Example 1, but a sufficient Cr content was not obtained, so that the corrosion resistance was insufficient and the appearance was poor. . Comparative Example 3 is a Zn-Ni alloy plating, and although the appearance is good, the corrosion resistance is lower than that of the present invention. On the other hand, all of the examples of the present invention have a Cr content of 5%.
% Of plating is obtained, and both corrosion resistance and appearance are good. Examples 5 to 11 of the present invention are examples in which a coumarin is used in combination with a cationic polymer or a polyoxyalkylene derivative, but the appearance is further improved and the content of Cr is higher than those of examples 1 to 4 of the present invention in which coumarins are used alone. The result was that the rate was high.

【0020】[0020]

【表1】 [Table 1]

【0021】[0021]

【表2】 [Table 2]

【0022】[0022]

【発明の効果】以上述べた如く、本発明は、特定の添加
剤をめっき浴に仕込むことにより、従来困難であった電
気亜鉛めっき中へのCrの共析を可能とし、耐食性に極
めて優れた電気亜鉛めっき鋼板を製造するものである。
したがって、自動車車体用途を中心に高耐食性が要求さ
れる防錆鋼板を製造する上で極めて効果的である。
As described above, according to the present invention, by adding a specific additive to a plating bath, it is possible to co-deposit Cr into electrogalvanized plating, which has been difficult in the past, and to achieve extremely excellent corrosion resistance. It is for producing electrogalvanized steel sheets.
Therefore, it is extremely effective in producing a rust-preventive steel sheet requiring high corrosion resistance mainly for an automobile body.

【図面の簡単な説明】[Brief description of the drawings]

【図1】めっき浴中へのクマリン及びPASの添加量と
めっき層中のCr含有率の関係を示す図、
FIG. 1 is a diagram showing the relationship between the amount of coumarin and PAS added to a plating bath and the Cr content in a plating layer;

【図2】めっき浴中へのクマリン及びPASの添加量と
得られためっき皮膜の外観との関係を示す図である。
FIG. 2 is a graph showing the relationship between the amount of coumarin and PAS added to a plating bath and the appearance of a plating film obtained.

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 Crを含有する電気亜鉛めっき鋼板を製
造するに際し、Zn2+イオン、Cr3+イオン、及び
クマリンもしくはその誘導体を0.1〜10g/1含有
するめっき浴を用いて、電気めっきを行なうことを特徴
とする耐食性に優れた亜鉛系電気めっき鋼板の製造方
法。
When producing an electrogalvanized steel sheet containing Cr, electroplating is performed using a plating bath containing Zn 2+ ions, Cr 3+ ions, and coumarin or a derivative thereof at 0.1 to 10 g / 1. A method for producing a zinc-based electroplated steel sheet having excellent corrosion resistance.
【請求項2】 Crを含有する電気亜鉛めっき鋼板を製
造するに際し、Zn2+イオン、Cr3+イオン、クマ
リンもしくはその誘導体を0.1〜10g/1、カチオ
ンポリマーおよび/またはポリオキシアルキレン誘導体
0.01〜20g/1含有するめっき浴を用いて、電
気めっきを行なうことを特徴とする耐食性に優れた亜鉛
系電気めっき鋼板の製造方法。
2. When producing a galvanized steel sheet containing Cr, 0.1 to 10 g / 1 of Zn 2+ ion, Cr 3+ ion, coumarin or a derivative thereof, and 0 to 10 g of a cationic polymer and / or a polyoxyalkylene derivative. A method for producing a zinc-based electroplated steel sheet having excellent corrosion resistance, wherein electroplating is performed using a plating bath containing 0.1 to 20 g / 1 .
JP307393A 1993-01-12 1993-01-12 Manufacturing method of zinc-based electroplated steel sheet with excellent corrosion resistance Expired - Fee Related JP2657750B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP307393A JP2657750B2 (en) 1993-01-12 1993-01-12 Manufacturing method of zinc-based electroplated steel sheet with excellent corrosion resistance

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP307393A JP2657750B2 (en) 1993-01-12 1993-01-12 Manufacturing method of zinc-based electroplated steel sheet with excellent corrosion resistance

Publications (2)

Publication Number Publication Date
JPH06212480A JPH06212480A (en) 1994-08-02
JP2657750B2 true JP2657750B2 (en) 1997-09-24

Family

ID=11547172

Family Applications (1)

Application Number Title Priority Date Filing Date
JP307393A Expired - Fee Related JP2657750B2 (en) 1993-01-12 1993-01-12 Manufacturing method of zinc-based electroplated steel sheet with excellent corrosion resistance

Country Status (1)

Country Link
JP (1) JP2657750B2 (en)

Also Published As

Publication number Publication date
JPH06212480A (en) 1994-08-02

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