JPS6233314B2 - - Google Patents
Info
- Publication number
- JPS6233314B2 JPS6233314B2 JP56188083A JP18808381A JPS6233314B2 JP S6233314 B2 JPS6233314 B2 JP S6233314B2 JP 56188083 A JP56188083 A JP 56188083A JP 18808381 A JP18808381 A JP 18808381A JP S6233314 B2 JPS6233314 B2 JP S6233314B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- plating layer
- galvanized steel
- zinc
- composite
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Description
本発明は塗装性に優れた複合亜鉛メツキ鋼板の
製造法に関する。
一般に、亜鉛メツキ鋼板はその耐蝕性が優れて
いるため高腐蝕環境下にさらされる場所に広く使
用されている。そして、近年、自動車の防錆対策
のために種々の亜鉛系メツキ鋼板が塗装されて使
用されるようになつた。この場合少くとも下塗り
として電着塗装をして使用されるため亜鉛系メツ
キ鋼板は、裸の耐蝕性の外に塗布後の耐蝕性、塗
装密着性が重要となつてきている。
従来の方法により製造された電気亜鉛メツキ鋼
板、溶融亜鉛メツキ鋼板では塗膜の二次密着性に
難があり、また、合金化溶融亜鉛メツキ鋼板の塗
膜の二次密着性は非合金メツキ鋼板に比し改善さ
れているが、冷間圧延鋼板に比してやや劣る。更
にこの鋼板は連結溶融メツキラインで製造される
ため鋼板の加工性、メツキ付着性の均一性、薄目
付への対応等の面で電気亜鉛メツキに比べ劣つて
いる。そのため、従来から良く知られているZn
−Fe合金電気メツキ法によつて、合金化溶融亜
鉛メツキと略同等のFe含有量のZn−Fe合金電気
メツキ鋼板を製造しているが、合金溶融亜鉛メツ
キと同じく塗膜の二次密着性は冷間圧延鋼板には
及ばないのである。
本発明は上記したように従来法により製造され
たメツキ鋼板の種々の問題点を解決したものであ
つて、耐蝕性で、かつ、装装性に優れた複合亜鉛
メツキ鋼板を製造する方法を提供するものであ
る。
本発明に係る塗装性に優れた複合亜鉛メツキ鋼
板の製造法の特徴とするところは、冷間圧延鋼板
を脱脂酸洗した後、亜鉛の硫酸塩、塩化物を主成
分として含有し、かつ、Co、Ni、Mo、Cr、
Mn、Ｗの硫酸塩、塩化物の中から選んだ１種、
又は、２種以上を含む硫酸塩、塩化物の水溶液か
らなるメツキ浴にて、上記冷間圧延鋼板にCo、
Ni、Mo、Cr、Mn、Ｗの中から選んだ１種、又
は、２種以上の成分を0.1〜20％含む残部亜鉛よ
りなるメツキ層を電気メツキにより形成し、次い
で、このメツキ鋼板を300℃〜550℃の温度に加熱
することのにある。
本発明に係る塗装性に優れた複合亜鉛メツキ鋼
板の製造法について、以下、詳細に説明する。
本発明に係る塗装性に優れた複合亜鉛メツキ鋼
板の製造法において、メツキ層の亜鉛を主成分と
して、Co、Ni、Mo、Cr、Mn、Ｗの１種、又
は、２種以上を0.1〜20％含有させるのは、亜鉛
自体の耐蝕性に加えてCo、Ni、Mo、Cr、Mn、
Ｗが含有されることによつて、さらに耐蝕性が良
くなるものであり、これらCo、Ni、Mo、Cr、
Mn、Ｗの含有量が0.1％未満であると耐蝕性は劣
り、また、20％を越えて含有しても耐蝕性はそれ
程向上しなく不経済である。そして、これらの
Co、Ni、Mo、Cr、Mn、Ｗは0.1〜20％の範囲内
では上記したように耐蝕性は向上させるけれども
塗装性、特に、二次密着性についてはやや不充分
である。
従つて、本発明に係る塗装性に優れた複合亜鉛
メツキ鋼板の製造法においては、上記した亜鉛を
主成分として、Co、Ni、Mo、Cr、Mn、Ｗの１
種、又は、２種以上を0.1〜20％含有するメツキ
層を形成した鋼板を、300℃〜550℃の温度に加熱
して塗装性を改善するのである。しかして、この
ように加熱処理を行なうことにより、上記のメツ
キ層中に基体の鋼板の鉄が拡散して、Zn−Fe−
Ｘ（上記したCo、Ni、Mo、Cr、Mn、Ｗから選
んだ１種、又は、２種以上の成分）の系の合金メ
ツキ層となるので、塗装性、特に、二次密着性が
向上するのである。そして加熱温度が300℃未満
では鉄がメツキ層中の拡散による合金化が充分で
なく、また、550℃を越えるとメツキ層中の亜鉛
の蒸発が多くなるのである。
このメツキ層中に鋼板からの鉄の拡散による合
金化について、図面により具体的に説明すると、
第１図ａ，ｂは従来より行なわれている２層メツ
キの場合の模型図で、第１図ａは鋼板上にNiを
メツキし、その上にZnをメツキした場合を示
し、第１図ｂは加熱後の鋼板のFe、Ni、Znの分
布状態を示す模型図で、塗装性に影響を与える
Feがメツキ層表面に合金化されにくいので、即
ち、Znが多いので塗装後の二次密着性は悪いの
である。
第２図は本発明に係る塗装性に優れた複合亜鉛
メツキ鋼板の製造法の場合の模型図であり、第２
図ａはメツキ層がNi含有Zn合金の例であるが
（他の含有成分でも同じである。）、これを、300℃
〜550℃の温度で加熱すると、第２図ｂに示すよ
うなZn、Ni、Feの合金化した状態となつて、メ
ツキ層表面に合金化して存在するFe分が多いの
で、塗装後の二次密着性が著しく向上するのであ
る。
よつて、同じような複合亜鉛合金メツキ層を有
するメツキ鋼板であつても上記したように、メツ
キ層の合金化の態様が異なるので塗装性において
格段の相違があることがわかる。
以下、本発明に係る塗装性に優れた複合亜鉛メ
ツキ鋼板の製造法の実施例について比較例ととも
に具体的に説明する。
実施例
冷間圧延鋼板を脱脂酸洗後、第１表に示す条件
によつて電気メツキ、及び、加熱処理を行なつ
た。
第２表に、メツキ層の含有成分、成分割合とそ
の性能について示す。
The present invention relates to a method for producing a composite galvanized steel sheet with excellent paintability. In general, galvanized steel sheets are widely used in locations exposed to highly corrosive environments because of their excellent corrosion resistance. In recent years, various types of zinc-plated steel sheets have come to be coated and used as rust prevention measures for automobiles. In this case, since zinc-plated steel sheets are used with at least an electrodeposition coating as an undercoat, corrosion resistance after coating and paint adhesion are becoming important in addition to bare corrosion resistance. Electrogalvanized steel sheets and hot-dip galvanized steel sheets manufactured by conventional methods have difficulty in secondary adhesion of coating films, and the secondary adhesion of coating films on alloyed hot-dip galvanized steel sheets is lower than that of non-alloyed galvanized steel sheets. However, it is slightly inferior to cold-rolled steel sheets. Furthermore, since this steel sheet is manufactured on a connected hot-dip plating line, it is inferior to electrolytic galvanizing in terms of workability of the steel sheet, uniformity of plating adhesion, ability to handle thin coatings, etc. Therefore, the conventionally well-known Zn
- Zn-Fe alloy electroplated steel sheets with approximately the same Fe content as alloyed hot-dip galvanizing are manufactured using the Fe alloy electroplating method, but the secondary adhesion of the coating film is the same as that of alloyed hot-dip galvanizing. is not as good as that of cold-rolled steel sheets. The present invention solves the various problems of galvanized steel sheets manufactured by conventional methods as described above, and provides a method for manufacturing composite galvanized steel sheets that are corrosion resistant and have excellent mounting properties. It is something to do. The manufacturing method of the composite galvanized steel sheet with excellent paintability according to the present invention is characterized in that after degreasing and pickling a cold-rolled steel sheet, it contains zinc sulfate and chloride as main components, and Co, Ni, Mo, Cr,
One type selected from Mn, W sulfates and chlorides,
Alternatively, the above cold rolled steel sheet may be coated with Co,
A plating layer containing 0.1 to 20% of one or more components selected from Ni, Mo, Cr, Mn, and W with the remainder being zinc is formed by electroplating, and then this plated steel sheet is heated to 300% by electroplating. It is to be heated to a temperature between ℃ and 550℃. The method for manufacturing a composite galvanized steel sheet with excellent paintability according to the present invention will be described in detail below. In the method for manufacturing a composite galvanized steel sheet with excellent paintability according to the present invention, zinc in the plating layer is the main component, and one or more of Co, Ni, Mo, Cr, Mn, and W is added in an amount of 0.1 to 0. The 20% content is due to the corrosion resistance of zinc itself, as well as Co, Ni, Mo, Cr, Mn,
Corrosion resistance is further improved by containing W, and these Co, Ni, Mo, Cr,
If the content of Mn or W is less than 0.1%, the corrosion resistance will be poor, and if the content exceeds 20%, the corrosion resistance will not improve much and it will be uneconomical. And these
Co, Ni, Mo, Cr, Mn, and W within the range of 0.1 to 20% improve corrosion resistance as described above, but are somewhat insufficient in terms of paintability, especially secondary adhesion. Therefore, in the method of manufacturing a composite galvanized steel sheet with excellent paintability according to the present invention, one of Co, Ni, Mo, Cr, Mn, and W is used, with the above-mentioned zinc as the main component.
A steel plate on which a plating layer containing 0.1 to 20% of the seeds or two or more kinds is formed is heated to a temperature of 300°C to 550°C to improve paintability. However, by performing the heat treatment in this way, the iron of the base steel plate is diffused into the above plating layer, and the Zn-Fe-
Since it is an alloy plating layer of X (one or more components selected from the above-mentioned Co, Ni, Mo, Cr, Mn, and W), paintability, especially secondary adhesion, is improved. That's what I do. If the heating temperature is less than 300°C, iron will not be sufficiently alloyed by diffusion in the plating layer, and if it exceeds 550°C, a large amount of zinc in the plating layer will evaporate. The alloying caused by the diffusion of iron from the steel plate into this plating layer will be explained in detail with reference to the drawings.
Figures 1a and b are model diagrams of conventional two-layer plating. Figure 1a shows a case where Ni is plated on a steel plate and Zn is plated on top of that. b is a schematic diagram showing the distribution of Fe, Ni, and Zn in the steel plate after heating, which affect paintability.
Since Fe is difficult to alloy on the surface of the plating layer, that is, there is a large amount of Zn, the secondary adhesion after painting is poor. FIG. 2 is a schematic diagram of the method for manufacturing a composite galvanized steel sheet with excellent paintability according to the present invention.
Figure a shows an example in which the plating layer is made of a Ni-containing Zn alloy (the same is true for other contained components).
When heated at a temperature of ~550°C, Zn, Ni, and Fe become alloyed as shown in Figure 2b, and since there is a large amount of alloyed Fe present on the surface of the plating layer, the second layer after painting becomes Next, adhesion is significantly improved. Therefore, it can be seen that even though plated steel sheets have similar composite zinc alloy plating layers, there are significant differences in paintability because the manner of alloying of the plating layers is different, as described above. Hereinafter, examples of the method for manufacturing a composite galvanized steel sheet with excellent paintability according to the present invention will be specifically described along with comparative examples. Example After degreasing and pickling a cold rolled steel plate, it was electroplated and heat treated under the conditions shown in Table 1. Table 2 shows the components contained in the plating layer, the component ratios, and their performance.
【表】【table】
【表】【table】
【表】【table】
【表】
第２表において、（注１）、（注２）、（注）は次
のことを示している。
（注１） 塩水噴霧試験24時間後の赤錆発生率
（注２） 塩水噴霧試験500時間後のスクラツチ部
からのフクレ幅の1/2（mm）
（注３） ３コート塗装板を41℃の温水に240時間
浸漬後、２mmのゴバン目100ケを切りテーピン
グ後剥離したゴバン目数
以上説明したように、本発明に係る塗装性に優
れた複合亜鉛メツキ鋼板の製造法は上記の構成を
有しているものであるから、耐蝕性に優れ、さら
に、塗装性、特に、二次密着性に極めて優れた複
合亜鉛メツキ鋼板を得ることができる。[Table] In Table 2, (Note 1), (Note 2), and (Note) indicate the following. (Note 1) Rate of occurrence of red rust after 24 hours of salt spray test (Note 2) 1/2 (mm) of blistering width from scratch after 500 hours of salt spray test (Note 3) 3-coat painted board heated to 41℃ After immersing in hot water for 240 hours, 100 2mm gobs were cut and taped.The number of gobs peeled off.As explained above, the method for manufacturing a composite galvanized steel sheet with excellent paintability according to the present invention has the above configuration. Therefore, it is possible to obtain a composite galvanized steel sheet which has excellent corrosion resistance and also has extremely excellent paintability, especially secondary adhesion.
第１図ａ，ｂは従来法の複合メツキ層の模型
図、第２図ａ，ｂは本発明に係る塗装性に優れた
複合亜鉛メツキ鋼板の製造法による複合メツキ層
の模型図である。
FIGS. 1a and 1b are schematic diagrams of a composite plating layer produced by the conventional method, and FIGS. 2a and 2b are schematic diagrams of a composite plating layer produced by the method of manufacturing a composite galvanized steel sheet with excellent paintability according to the present invention.
Claims (1)
塩、塩化物を主成分として含有し、かつ、Co、
Ni、Mo、Cr、Mn、Ｗの硫酸塩、塩化物の中から
選んだ１種、又は、２種以上を含む硫酸塩、塩化
物の水溶液からなるメツキ浴にて、上記冷間圧延
鋼板にCo、Ni、Mo、Cr、Mn、Ｗの中から選ん
だ１種、又は、２種以上の成分を0.1〜20％含む
残部亜鉛よりなるメツキ層を電気メツキにより形
成し、次いで、このメツキ鋼板を300℃〜550℃の
温度に加熱することを特徴とする塗装性に優れた
複合亜鉛メツキ鋼板の製造法。1 After degreasing and pickling a cold rolled steel sheet, it contains zinc sulfate and chloride as main components, and Co,
The above cold rolled steel sheet is coated in a plating bath consisting of an aqueous solution of sulfates and chlorides containing one or more selected from sulfates and chlorides of Ni, Mo, Cr, Mn, and W. A plating layer containing 0.1 to 20% of one or more components selected from Co, Ni, Mo, Cr, Mn, and W with the balance being zinc is formed by electroplating, and then this plated steel sheet A method for producing a composite galvanized steel sheet with excellent paintability, which is characterized by heating the steel to a temperature of 300°C to 550°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18808381A JPS5891163A (en) | 1981-11-24 | 1981-11-24 | Manufacture of composite zinc plated steel plate with superior suitability to coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18808381A JPS5891163A (en) | 1981-11-24 | 1981-11-24 | Manufacture of composite zinc plated steel plate with superior suitability to coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5891163A JPS5891163A (en) | 1983-05-31 |
| JPS6233314B2 true JPS6233314B2 (en) | 1987-07-20 |
Family
ID=16217399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18808381A Granted JPS5891163A (en) | 1981-11-24 | 1981-11-24 | Manufacture of composite zinc plated steel plate with superior suitability to coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5891163A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0715153B2 (en) * | 1987-12-17 | 1995-02-22 | 新日本製鐵株式会社 | Zinc-chromium multi-layer electroplated steel sheet |
| JPH0788598B2 (en) * | 1989-03-28 | 1995-09-27 | 新日本製鐵株式会社 | Multi-layer zinc-chrome plated steel sheet |
| JPH0361396A (en) * | 1989-07-27 | 1991-03-18 | Nkk Corp | Production of double-layer plated steel sheet excellent in electrodeposition coating property capable of preventing generation of bubbly defect in electrodeposition coating film |
| JPH0689473B2 (en) * | 1990-04-25 | 1994-11-09 | 新日本製鐵株式会社 | Anti-corrosion steel plate with excellent corrosion resistance |
| JPH0791669B2 (en) * | 1990-08-01 | 1995-10-04 | 新日本製鐵株式会社 | Anticorrosion steel plate with excellent corrosion resistance |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56293A (en) * | 1979-06-18 | 1981-01-06 | Toyo Kohan Co Ltd | Production of dark color zinc electroplated steel plate |
-
1981
- 1981-11-24 JP JP18808381A patent/JPS5891163A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5891163A (en) | 1983-05-31 |
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