JPS60262975A - Surface treated steel sheet having superior weldability and its manufacture - Google Patents
Surface treated steel sheet having superior weldability and its manufactureInfo
- Publication number
- JPS60262975A JPS60262975A JP11770484A JP11770484A JPS60262975A JP S60262975 A JPS60262975 A JP S60262975A JP 11770484 A JP11770484 A JP 11770484A JP 11770484 A JP11770484 A JP 11770484A JP S60262975 A JPS60262975 A JP S60262975A
- Authority
- JP
- Japan
- Prior art keywords
- chromium
- tin
- metallic
- steel sheet
- plating
- 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
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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、溶接性、特にシーム溶接性に優れ、かつ缶用
素材として充分な耐食性を有する表面処理鋼板およびそ
の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surface-treated steel sheet having excellent weldability, particularly seam weldability, and sufficient corrosion resistance as a material for cans, and a method for manufacturing the same.
食缶用の素材としては、従来一般にぶりさと称される錫
めっき鋼板が広く用いられて来た。この缶胴の接合方式
としては、以前は半田による接合方式が採用されていた
が、半田に含まれる鉛の毒性の問題から、近年、純錫半
田が使用されるようになった。しかし、純錫半田は接合
時の濡れ性が劣ることから半田接合の技術上の問題があ
り、更に高価な純錫半田を使用することにより製造コス
トの上昇の問題があった。As a material for food cans, tin-plated steel sheets, commonly referred to as yellowtail, have been widely used. Previously, solder was used to join these can bodies, but due to the toxicity of lead contained in solder, pure tin solder has come to be used in recent years. However, pure tin solder has poor wettability during bonding, which poses technical problems in solder bonding, and furthermore, the use of expensive pure tin solder increases manufacturing costs.
一方、近年、食品容器は、例えばポリエチレン、アルミ
ニウム、ガラス、紙などの低価格競合材料の進出に直面
しており、上記の如き高価な錫を付着量２．８〜１１．
２ ｇ／ｒｎ’の如く厚くめっきしたぶりき缶は、製造
コストが高いので、耐食性には格段すぐれた特性を有し
ているとはいえ、苦しい競合的立場を強いられてきた。On the other hand, in recent years, food containers have been faced with the introduction of low-priced competing materials such as polyethylene, aluminum, glass, and paper, and the amount of expensive tin deposited is 2.8 to 11.
Since tin cans plated as thick as 2 g/rn' are expensive to manufacture, they have been forced into a difficult competitive position, although they have excellent corrosion resistance.
ぶりき缶の上記欠点を解消する目的で、最近半田接合法
に代って、缶胴を電気抵抗溶接によって接合する方式が
発展し、普及するようになってきた。そのためには、電
気抵抗溶接に適した材料が必要である。In order to eliminate the above-mentioned drawbacks of tin cans, a method of joining can bodies by electric resistance welding has recently been developed and become popular in place of the solder joining method. This requires materials suitable for electric resistance welding.
従来から用いられている缶用材料としては、上記ぶりき
のほかに、クロムタイプのティンフリースチールがある
。これは電解クロメート処理を施し、表面に金属クロム
とクロム水和酸化物層を形成したものであるが、表面に
存在する厚いクロム水和酸化物が高抵抗であるために溶
接性が悪く、溶接部の強度不足を生じ、経済性にはすぐ
れているが、溶接缶用素材としては適当でない。In addition to the above-mentioned tin, chrome-type tin-free steel is a conventionally used material for cans. This is an electrolytic chromate treatment that forms a layer of metallic chromium and hydrated chromium oxide on the surface, but the thick hydrated chromium oxide on the surface has high resistance, resulting in poor weldability. Although it is economically efficient, it is not suitable as a material for welded cans.
その他、従来の缶用材料がいずれも溶接缶用素材として
不適切であることから、種々の試みが提案されている０
例えば、アメリカのナショナルスチール社によって発表
された「ニッケルライ・ト」に代表されるニッケルめっ
き鋼板があるが、これは、鋼板上に約０．５８／ｎｆの
目付量のニッケルめっきを施した上、表面に在来のクロ
メート処理を施したもので、塗料の密着性が劣り、また
３０■／ｓｉｎ以上の高速溶接での溶接性が劣るために
、用いられるに至っていない。In addition, since all conventional can materials are inappropriate as materials for welded cans, various attempts have been proposed.
For example, there is a nickel-plated steel sheet represented by "Nickelite" released by the American National Steel Company. , which has been subjected to conventional chromate treatment on its surface, has poor paint adhesion and poor weldability at high speed welding of 30 .mu./sin or higher, so it has not been used.
更に他の一つは、アメリカのジョーンズ参ローリン中ス
チール社によって発表された「ティンアロイ」に代表さ
れるものである。これは、約０．ｌｌｉ ＄／ｎｆの薄
目付の錫めっきを溶鍋処理した後、在来のクロメート処
理をしたものであるが、耐錆性、塗料の密着性、溶接性
ともに不充分である。Still another type is ``Tin Alloy'' released by the American Jones Rollin Steel Company. This is approximately 0. Tin plating with a thin coating weight of $/nf was subjected to hot pot treatment and then conventional chromate treatment, but the rust resistance, paint adhesion, and weldability were insufficient.
電気抵抗溶接に適する缶用素材の具備すべ！！要件とし
ては、溶接性と塗装後の耐食性がすぐれたものであるこ
とが要求される。この要件を具体的に説明すると、溶接
の際に充分の溶接強度があり、しかも溶接部にいわゆる
「散り」などの溶接欠陥を生じない適正電流範囲を有し
、缶内容物に対して塗装して用いた場合、塗膜の有する
耐食性を充分活かすことができる塗膜の密着性を有し、
更に不可避的に生ずる塗膜欠陥部においては、素材自体
のすぐれた耐食性によって腐食を防止できるものでなけ
ればならない。Be sure to have can materials suitable for electric resistance welding! ! The requirements are that it has excellent weldability and corrosion resistance after painting. To explain this requirement specifically, the welding strength is sufficient during welding, the welding area has an appropriate current range that does not cause welding defects such as "splatter", and the contents of the can are coated. When used as a coating, it has a coating film adhesion that can fully utilize the corrosion resistance of the coating film,
Furthermore, in the areas where coating film defects inevitably occur, corrosion must be prevented by the excellent corrosion resistance of the material itself.
本発明の目的は、溶接缶用素材の上記従来の欠点を解消
し、上記溶接缶用素材として具備すべき要件である溶接
性、塗装後耐食性、塗料密着性を兼備し、かつ安価な缶
用素材およびその製造方法を提供することにある。The purpose of the present invention is to eliminate the above-mentioned conventional drawbacks of welded can materials, to provide weldability, post-painting corrosion resistance, and paint adhesion, which are the requirements for welded can materials, and to provide an inexpensive can material. Our goal is to provide materials and methods of manufacturing them.
本発明の第１の態様によれば、鋼板上に目付量が５〜５
００＋ｓｇ／ｒｎ’の金属クロム層を有し、その上に塗
装焼付後に金属錫が残存するような一目付量の金属錫層
を有し、さらにその上にクロム水和酸化物あるいは金属
クロムとクロム水和酸化物から構成されるクロム換算で
３鳳ｇ／ｒｒ１′以上のクロメート被膜層を有すること
を特徴とする溶接性に優れた表面処理鋼板が提供される
。According to the first aspect of the present invention, the basis weight on the steel plate is 5 to 5.
It has a metallic chromium layer of 00+sg/rn', on top of which a metallic tin layer with a coating weight such that metallic tin remains after the paint is baked, and on top of that, chromium hydrated oxide or metallic chromium and chromium. A surface-treated steel sheet with excellent weldability is provided, which is characterized by having a chromate coating layer composed of a hydrated oxide and having a ratio of 3 g/rr1' or more in terms of chromium.
本発明の第２の態様によれば、清浄化処理を施した鋼板
表面にクロムめっきを施し、引き続いて塩酸、硫酸、シ
ュウ酸、酢酸を１種または２種以上含有する水溶液中で
陰極電解処理を行い１次いで錫めっきを施し、さらにク
ロム水和酸化物あるいは金属クロムとクロム水和酸化物
からなるクロメート被膜層を形成させることを特徴とす
る溶接性に優れた表面処理鋼板の製造方法が提供される
。According to the second aspect of the present invention, the surface of the steel plate that has been subjected to the cleaning treatment is chromium plated, and then cathodic electrolytic treatment is performed in an aqueous solution containing one or more of hydrochloric acid, sulfuric acid, oxalic acid, and acetic acid. Provided is a method for producing a surface-treated steel sheet with excellent weldability, which comprises first carrying out tin plating, and further forming a chromate coating layer consisting of hydrated chromium oxide or metallic chromium and hydrated chromium oxide. be done.
本発明の第３の態様によれば、清浄化処理を施した鋼板
表面にクロムめっきを施し、引き続いて塩酸、硫酸、シ
ュウ酸、酢酸を１種または２種以上含有し、かつ錫イオ
ンを含有する水溶液中で陰極電解処理を行い、次いで錫
めっきを施し、さらにクロム水和酸化物あるいは金属ク
ロムとクロム水和酸化物からなるクロメート被膜層を形
成させることを特徴とする溶接性に優れた表面処理鋼板
の製造方法が提供される。According to the third aspect of the present invention, chromium plating is applied to the surface of a steel plate that has been subjected to a cleaning treatment, and the surface is then coated with one or more of hydrochloric acid, sulfuric acid, oxalic acid, and acetic acid, and also contains tin ions. A surface with excellent weldability characterized by cathodic electrolytic treatment in an aqueous solution, followed by tin plating, and further formation of a chromate coating layer consisting of hydrated chromium oxide or metallic chromium and hydrated chromium oxide. A method of manufacturing a treated steel sheet is provided.
以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明者らは、缶用素材の電気抵抗溶接、特に近年、製
缶用溶接法として急速に普及しているところのスードロ
ニック溶接法に代表されるワイヤーシーム溶接に対する
溶接特性を調査検討した結果、金属錫が存在することに
より、良好なシーム溶接性能が得られることを見いだし
た。The present inventors investigated and examined the welding characteristics of electric resistance welding of can materials, particularly wire seam welding represented by sudronic welding, which has rapidly become popular as a welding method for can manufacturing in recent years. It has been found that the presence of metallic tin provides good seam welding performance.
すなわち、金属錫は融点が低いので溶接時に容易に溶融
し、溶接圧力によって広がり、鋼板同志の接触面積を広
げるとともに、金属同志の相互融合が容易となる。従っ
て、局所的な溶接電流集中による「散り」発生が起り難
く、また強固な溶接接合が形成されるので、広い適正溶
接電流範囲が得られるのである０通常の＃２５電気めっ
きぶりきは、広い適正溶接電流範囲を有しているが、こ
れは、約２．２ ｇ／ｒｒｆの金属錫を有しているから
である。That is, metal tin has a low melting point, so it easily melts during welding, spreads under welding pressure, expands the contact area between steel plates, and facilitates mutual fusion of metals. Therefore, "splash" due to local concentration of welding current is unlikely to occur, and a strong welding joint is formed, so a wide appropriate welding current range can be obtained. It has a suitable welding current range because it has about 2.2 g/rrf of metallic tin.
本発明者らは、溶接性と金属錫量の関係をさらに検討し
た結果、５０ｍｇ／ｒｒｌ’以上、好ましくは１００ｍ
ｇ／ｒｎ’以上の金属錫が存在すれば、４０〜６０ｍ／
分の高速溶接においても、実用上、十分な適正溶接電流
範囲が得られることを見いだした。The present inventors further investigated the relationship between weldability and the amount of metal tin, and found that the amount of tin is 50 mg/rrl' or more, preferably 100 m
If metallic tin of g/rn' or more is present, 40 to 60 m/rn'
It has been found that a suitable welding current range sufficient for practical use can be obtained even during high-speed welding of minutes.
従って、鋼板表面に５０ｍｇ／ｒｎ’の錫めっきを施せ
ば良好な溶接性が得られるはずであるが、実際には塗装
して溶接に供される場合が殆どである。Therefore, good weldability should be obtained by applying tin plating of 50 mg/rn' to the surface of a steel plate, but in reality, in most cases, the steel plate is coated and used for welding.
この場合、塗装後の焼付硬化処理により錫と素地鋼の鉄
とが合金化する０通常の焼付温度は１７０〜２２０℃で
あり、生成する鉄−錫合金はＦｅＳｎ２である。 Ｆｅ
Ｓｎ２は融点が高いため、金属錫の有していた溶接性向
上効果は合金化によって失われてしまう。従って、良好
な溶接性を得るためには、焼付処理によって合金化する
量を見込んで余分に錫をめっきしなければならず、不経
済である。In this case, the normal baking temperature at which tin and the iron of the base steel are alloyed by baking hardening treatment after painting is 170 to 220°C, and the produced iron-tin alloy is FeSn2. Fe
Since Sn2 has a high melting point, the effect of improving weldability that metallic tin had is lost by alloying. Therefore, in order to obtain good weldability, it is necessary to plate excess tin to account for the amount that will be alloyed by baking, which is uneconomical.
そこで、本発明者らは、焼付処理による錫と素地鉄との
合金化を抑制する方法を種々検討した結果、素地鋼と錫
との間に金属クロムを存在させることにより、鉄−錫合
金の生成を顕著に抑制できることを新規に見いだした。Therefore, the present inventors investigated various methods of suppressing the alloying of tin and base iron by baking treatment, and found that by making metallic chromium exist between base steel and tin, iron-tin alloy We have newly discovered that the formation of these substances can be significantly suppressed.
第１図は下地金属Ｃｒｉと焼付（２１０℃Ｘ２０分）で
生成する合金中のＳｎ量の関係を示すもので、これより
、金属クロムの介在による鉄−錫合金生成抑制効果が顕
著であることがよくわかる。また、金属クロムは、それ
自体、耐食性に優れた金属であり、鉄−錫合金の生成を
抑制すると同時に耐食性をも向上させる二重の効果を有
するのである。Figure 1 shows the relationship between the base metal Cri and the amount of Sn in the alloy formed by baking (210°C x 20 minutes), which shows that the presence of metallic chromium has a remarkable effect of suppressing the formation of iron-tin alloys. I understand very well. Moreover, metallic chromium itself is a metal with excellent corrosion resistance, and has the dual effect of suppressing the formation of iron-tin alloy and improving corrosion resistance at the same time.
すなわち、鋼板にクロムめっきを施した後、錫めっきを
施すことにより、高価な錫を有効に活用することができ
、また、同時に耐食性も向上するのである。That is, by applying tin plating to a steel plate after chromium plating, expensive tin can be used effectively, and corrosion resistance is also improved at the same time.
最上層に金属錫を形成することは良好な溶接性をもたら
すものであるが、塗装焼付時に表面に錫酸化物が生成す
るため、塗料密着性が十分でない。Forming metallic tin on the top layer provides good weldability, but tin oxide is generated on the surface during paint baking, resulting in insufficient paint adhesion.
これに対し、表面にクロム水和酸化物あるいは金属クロ
ムとクロム水和酸化物からなるクロメート被膜層を形成
させることにより、塗料密着性が向−しし、また、塗装
後嗣食性も向上する。特に金属クロムとクロム水和酸化
物からなるクロメート被膜層の場合、塗料密着性の向上
効果が顕著であり、腐食性の強い缶内容物に対しても優
れた塗装後嗣食性を示す。On the other hand, by forming a chromate coating layer consisting of hydrated chromium oxide or metallic chromium and hydrated chromium oxide on the surface, paint adhesion is improved and the corrosion resistance after painting is also improved. In particular, in the case of a chromate coating layer consisting of metallic chromium and chromium hydrated oxide, the effect of improving paint adhesion is remarkable, and it exhibits excellent post-painting corrosion resistance even for highly corrosive can contents.
クロム水和酸化物は塗料密着性・耐食性を向上させるが
、高電気抵抗物質であるので、多量に存在すると溶接性
を阻害する。従って、クロム水和酸化物はある一定量以
下にしなければならない。Chromium hydrated oxide improves paint adhesion and corrosion resistance, but since it is a high electrical resistance substance, its presence in large amounts impedes weldability. Therefore, the amount of chromium hydrate must be kept below a certain level.
本発明では、まず鋼板上に金属クロムめっきを施すが、
この金属クロムの効果は塗装焼付時の鉄−錫合金化の抑
制と耐食性の向上である。金属クロムは５ＩＩｇ／ｒｒ
＋′でも鉄−錫合金化を抑制するが、めっき操業上の変
動を考慮すると２０ｍｇ／ｒｎ’以上にしておく方が望
ましい。金属クロム量は多いほど鉄−錫合金化抑制効果
が大きく、耐食性も向上するが、５００＋ｓｇ／ｍ″以
上になると鉄−錫合金化抑制効果のみならず、耐食性向
上効果も飽和してしまい、不経済となるばかりでなく、
クロムめっき層に電着応力によるクラックが入り易くな
るので好ましくない。In the present invention, metal chromium plating is first applied on a steel plate, but
The effect of this metallic chromium is to suppress iron-tin alloying during paint baking and improve corrosion resistance. Metal chromium is 5IIg/rr
+' also suppresses iron-tin alloying, but considering fluctuations in plating operations, it is preferable to set the content to 20 mg/rn' or more. The higher the amount of metallic chromium, the greater the effect of suppressing iron-tin alloying and the improvement of corrosion resistance, but when it exceeds 500+sg/m'', not only the effect of suppressing iron-tin alloying but also the effect of improving corrosion resistance is saturated, resulting in poor Not only is it economical, but
This is not preferable because the chromium plating layer is likely to crack due to electrodeposition stress.
したがって、金属クロムめっき量は５〜５００ｍｇ／ゴ
で良いが、好ましくは２０〜３００ ｍｇ／ゴの範囲で
ある。Therefore, the amount of metal chromium plating may be from 5 to 500 mg/g, but preferably from 20 to 300 mg/g.
鋼板上に金属クロムめっきを施す方法は任意であり、公
知の電気めっき法、例えば無水クロム酸を主成分としＳ
Ｏ４２−、Ｆ−を適量添加した水溶液中で陰極電解する
方法等を用いれば良い。The method of applying metal chromium plating on the steel plate is arbitrary, and the known electroplating method, for example, S
A method such as cathodic electrolysis in an aqueous solution containing an appropriate amount of O42- and F- may be used.
本発明では金属クロム層の上に錫めっきを施すが、電気
めっき法によりめっきされた金属クロムの表面にはクロ
ム水和酸化物が存在するので、このままでは満足な錫め
っきを施すことができない、すなわち、通常工業的に行
なわれている電気クロムめっきは、Ｃｒ６＋イオンを電
気化学的に金属クロムまで還元するのであるが、周知の
如＜ Ｃｒ６”イオンは３価クロムの水和酸化物を経由
して金属クロムまで還元されるので、めっき表面には常
にクロム水和酸化物が残存しており、このクロム水和醸
化物が錫めっきを防げるのである。このクロム水和酸化
物が残存している状態で電気錫めっきを施しても、粉末
状のめっきか、密着力の乏しいめっき層しか得られない
。In the present invention, tin plating is applied on the metallic chromium layer, but since hydrated chromium oxide is present on the surface of the metallic chromium plated by electroplating, it is not possible to perform tin plating satisfactorily as it is. In other words, in the electrochromium plating that is normally carried out industrially, Cr6+ ions are electrochemically reduced to metallic chromium, but as is well known, Cr6'' ions are reduced through the hydrated oxide of trivalent chromium. Since tin metal is reduced to metallic chromium, chromium hydrated oxide always remains on the plating surface, and this chromium hydrated product can prevent tin plating.This chromium hydrated oxide remains. Even if electroplating is performed in this state, only a powdery plating or a plating layer with poor adhesion will be obtained.
したがって、電気錫めっきを施すためには、電気クロム
めっき後に、このクロム水和酸化物を除去しなければな
らない、このクロム水和酸化物を除去する方法としては
、熱アルカリで溶解させる方法やＮａ０）Ｉ水溶液、り
ん酸緩衝溶液、硼酸＊＊溶液等の溶液中で陽極電解によ
り溶解させる方法が知られている。Therefore, in order to perform electrotin plating, this chromium hydrated oxide must be removed after electrochromium plating. Methods for removing this chromium hydrated oxide include dissolving it with hot alkali and Na0 ) A method of dissolving the compound by anodic electrolysis in a solution such as an aqueous solution of I, a phosphate buffer solution, or a boric acid** solution is known.
熱アルカリで溶解させる方法では、アルカリ不溶性のク
ロム醸化物が残存し、満足な錫めっきを施すことができ
ない、また陽極電解処理では金属クロムも溶解し、金属
クロムが溶解消失するまでクロム水和酸化物が残存する
ので、本発明鋼板の製造に用いることはできない。In the method of dissolving with a hot alkali, alkali-insoluble chromium compounds remain, making it impossible to provide satisfactory tin plating.Also, in anodic electrolytic treatment, metallic chromium is also dissolved, and chromium hydrates and oxidizes until the metallic chromium dissolves and disappears. Since some substances remain, it cannot be used for manufacturing the steel sheet of the present invention.
本発明者らは、このクロム水和酸化物を効率よく除去す
る方法を種々検討した結果、塩酸、硫酸、シュウ酸、酢
酸を１種または２種以上含有する水溶液中、もしくは塩
酸、硫酸、シュウ酸、酢酸を１種または２種以上含有し
、かつ錫イオンを含有する水溶液中で陰極電解すること
により、効率よくクロム水和酸化物が除去できることを
新規に見いだした。塩酸、硫酸、シュウ酸、酢酸を１種
または２種以上含有する水溶液を用いる場合、全酸濃度
は３０〜２００ｇ／４１であれば良く、陰極電解は浴温
度２０〜８０℃、電流密度１〜５０Ａ／ｄｒｎ’で実施
できる。塩酸、硫酸、シュウ酸、酢酸を１種または２種
以上含有し、かつ錫イオンを含有する水溶液を用いる場
合は、クロム水利酸化物を除去すると同時に錫めっきを
施すことができて便利である。１例をあげれば、水溶液
中の全酸濃度は３０〜２００ ｇ ／ ｌ、錫イオン濃
度は０．０５〜２０ｇ／見で良く、陰極電解は浴温度２
０〜８０℃、電流密度１〜５０ Ａ／ｄｍ’テ実施でき
る０本発明では、塩酸、硫酸、シュウ酸、酢酸を１種ま
たは２種以上含有する水溶液、もしくは塩酸、硫酸、シ
ュウ酸、酢酸を１種または２種以上含有し、かつ錫イオ
ンを含有する水溶液中で陰極電解処理した後、電気錫め
っきを施す。The present inventors investigated various methods for efficiently removing this hydrated chromium oxide, and found that it is possible to remove chromium hydrated oxide in an aqueous solution containing one or more of hydrochloric acid, sulfuric acid, oxalic acid, or acetic acid, or in an aqueous solution containing one or more of hydrochloric acid, sulfuric acid, oxalic acid, or acetic acid. It has been newly discovered that chromium hydrated oxide can be efficiently removed by cathodic electrolysis in an aqueous solution containing one or more acids and acetic acid and tin ions. When using an aqueous solution containing one or more of hydrochloric acid, sulfuric acid, oxalic acid, and acetic acid, the total acid concentration may be 30 to 200 g/41, and the cathode electrolysis is performed at a bath temperature of 20 to 80°C and a current density of 1 to 1. It can be carried out at 50A/drn'. When using an aqueous solution containing one or more of hydrochloric acid, sulfuric acid, oxalic acid, and acetic acid and also containing tin ions, it is convenient because tin plating can be performed at the same time as removing chromium water-containing oxide. For example, the total acid concentration in the aqueous solution may be 30 to 200 g/l, the tin ion concentration may be 0.05 to 20 g/l, and cathodic electrolysis may be performed at a bath temperature of 2.
In the present invention, an aqueous solution containing one or more of hydrochloric acid, sulfuric acid, oxalic acid, acetic acid, or hydrochloric acid, sulfuric acid, oxalic acid, acetic acid After cathodic electrolytic treatment in an aqueous solution containing one or more types of and tin ions, electrolytic tin plating is performed.
錫めっきは良好な溶接性を得るために施すもので、塗装
焼付後の金属錫が５０１ｇ／ｒｎ’以上、好ましくは１
００ｍｇ／ｍ’以−Ｌ残存する様に、下地金属クロム量
とのかね合いて任意に錫めっき量を決めれば良い、錫め
っき量は多すぎても特に不都合なことはないが、安価な
素材とするためには１０００■ｇ／ｒｎ’以下にしてお
くことが望ましい。Tin plating is applied to obtain good weldability, and the metal tin after baking is 501 g/rn' or more, preferably 1
The amount of tin plating can be arbitrarily determined in consideration of the amount of chromium on the base metal so that less than 00 mg/m'-L remains. Too much tin plating is not particularly inconvenient, but it is a cheap material. In order to achieve this, it is desirable to keep it below 1000 g/rn'.
したがって、錫めっき量の好ましい範囲は５０〜１００
０ｍｇ／ｒｎ’テある。Therefore, the preferred range of tin plating amount is 50 to 100
There is 0mg/rn'te.
錫めっきは通常の電気錫めっき方法を用いれば良い、ま
た前述のクロムめっき後の塩酸、硫酸、シュウ酸、酢酸
を１種または２種以上含有し、かつ錫イオンを含有する
水溶液中での陰極電解処理で必要量の錫をめっきしても
良く、通常の電気錫めっき方法と並用しても良い。Tin plating may be carried out by using a normal electrolytic tin plating method, or by using a cathode in an aqueous solution containing one or more of hydrochloric acid, sulfuric acid, oxalic acid, or acetic acid and containing tin ions after the above-mentioned chromium plating. The required amount of tin may be plated by electrolytic treatment, or a normal electrolytic tin plating method may be used in parallel.
本発明では、錫めっき層の上に塗料密着性向上および塗
料密着性向上を目的として、クロム水和酸化物あるいは
金属クロムとクロム水和酸化物からなるクロメート被膜
層を施す、クロム水利酸化物の量は、十分な塗料密着性
、塗装耐食性を得るためにクロム換算で３−ｇ／ｒｎ’
以上必要であり、より好ましくは５■ｇ／ｒｎ”以上で
ある。またクロム水和酸化物は高電気抵抗物質であるの
で、多量になると溶接性を阻害する。したがって、クロ
ム水和酸化物量はクロム換算で３０ｍ＋ｇ／ｍ″以下、
好ましくは２０腸ｇ／ｒｎ’以下にしておくことが望ま
しい。In the present invention, a chromate coating layer consisting of chromium hydrated oxide or metallic chromium and chromium hydrated oxide is applied on the tin plating layer for the purpose of improving paint adhesion and paint adhesion. The amount is 3-g/rn' in terms of chromium in order to obtain sufficient paint adhesion and paint corrosion resistance.
The amount of hydrated chromium oxide is more than 5 g/rn", and more preferably 5 g/rn" or more. Also, since hydrated chromium oxide is a substance with high electrical resistance, a large amount impedes weldability. Therefore, the amount of hydrated chromium oxide is Less than 30m+g/m'' in chrome conversion,
It is desirable to keep it preferably below 20 intestinal g/rn'.
クロメート被膜中の金属クロムは３１ｇ／ｒｎ’以上で
顕著な塗料密着性向上効果を示す、クロメート被膜中の
金属クロムは多いほど塗料密着性、耐食性が向上するが
、２０ｍｇ／ｒ＋ｉ’以上では塗料密着性、耐食性向上
効果が飽和してしまい、不経済となるので望ましくない
。The metallic chromium in the chromate film exhibits a remarkable effect of improving paint adhesion when it is 31 g/rn' or more.The more metallic chromium in the chromate film, the better the paint adhesion and corrosion resistance, but at 20 mg/r+i' or more, the paint adhesion increases This is not desirable because the effect of improving properties and corrosion resistance becomes saturated and becomes uneconomical.
クロメート被膜は、クロム水和酸化物のみで構成する場
合、無水クロム酸、クロム酸塩、重クロム酸塩の水溶液
あるいはこれらの混合水溶液を用い、浸漬法、スプレー
法、陰極電解法のいずれかの方法で形成させれば良い。When the chromate film is composed only of hydrated chromium oxide, it can be formed by dipping, spraying, or cathodic electrolysis using an aqueous solution of chromic anhydride, chromate, dichromate, or a mixed aqueous solution of these. It may be formed using a method.
また、金属クロムとクロム°水和酸化物から構成される
クロメート被膜を形成させるには、上記の水溶液に陰イ
オン（ＳＯ４２−、Ｆ−等）を適量添加した浴を用い陰
極電解処理を行えば良く、陰極電解条件（電流密度、浴
温度、液濃度等）を適切に選択することにより、金属ク
ロムとクロム水和酸化物を任意に形成させることができ
る。In addition, in order to form a chromate film composed of metallic chromium and chromium hydrated oxide, cathodic electrolysis can be performed using a bath in which an appropriate amount of anions (SO42-, F-, etc.) is added to the above aqueous solution. By appropriately selecting cathodic electrolysis conditions (current density, bath temperature, liquid concentration, etc.), metallic chromium and chromium hydrated oxide can be formed as desired.
次に本発明の実施例および比較例について説明する。Next, examples and comparative examples of the present invention will be described.
〔実施例１〕
通常のブリキ・ＴＦＳ用原板を電解脱脂、酸洗した後、
ＣｒＯ３２５０ｇ／ ｌ、）１２ ＳＯ４１，５ｇ／又
、Ｎａ２ ＳｉＦ ６５ ｇ／ ｌの浴を用い、浴温度
５０℃、電流密度５０Ａ／ｄｒｎ’で陰極電解処理を行
い、１００ｍｇ／ｍ″の金属クロムをめっきした。その
後、直ちにＨＣｌ１００ｇ／ｉの浴中で４０℃、１０
Ａ／ｄｒｌｆで陰極電解処理を行い、引き続いてハロゲ
ン浴を用いて１２０ｍｇ／ｒｎ’の錫めっきを行った。[Example 1] After electrolytically degreasing and pickling a regular tinplate/TFS plate,
Using a bath containing 250 g/l of CrO3, 1.5 g/l of SO4, and 65 g/l of Na2 SiF, cathode electrolysis was performed at a bath temperature of 50°C and a current density of 50 A/drn', and 100 mg/m'' of metallic chromium was plated. Thereafter, it was immediately heated at 40°C in a bath containing 100 g/i of HCl for 10
Cathodic electrolysis treatment was performed using A/drlf, followed by tin plating at 120 mg/rn' using a halogen bath.
さらに引き続いて３０ ｇ ／ ｌの重クロム融ナトリ
ウム浴を用いて電流密度５ Ａ／ｄｒｎ′でクロメート
処理を行った。Subsequently, chromate treatment was carried out using a 30 g/l sodium dichromate bath at a current density of 5 A/drn'.
〔実施例２〕
通常のブリキｅＴＦＳ用原板を電解脱脂、酸洗した後、
Ｃｒ０３２００ ｇ／ ｌ、Ｈ２ＳＯ４１，０ｇ／文、
Ｎａ２ ＳｉＦ ６ ５．５ｇ／ ｌ（Ｄ浴を用い、浴
温度５０℃、電流密度５０Ａ／ｄｒｎ’で陰極電解処理
を行い、６０ｍｇ／ｒｎ’の金属クロムをめっきした。[Example 2] After electrolytically degreasing and pickling a regular tin plate for eTFS,
Cr03200 g/l, H2SO41,0g/liter,
Na2SiF6 5.5g/l (using a D bath, cathode electrolytic treatment was performed at a bath temperature of 50°C and a current density of 50A/drn', and 60mg/rn' of metallic chromium was plated.
その後、直ちにＨＣ：Ｉ １００ ｇ／ｌ、５ｎＣＩ２
５ ｇ ／ ｆＬの浴中で４５℃、！ ＯＡ／ｄｒｎ’
で陰極電解処理を行い、引き続いてハロゲン浴を用いて
４００腸ｇ／ｒｎ’の錫めっきを行った。さらに引き続
いてＣｒ０３１５ｇ／又、Ｈ２Ｓｏ、 ０．１２ｇ／交
の浴を用いて電流密度２０Ａ／ｄｒｎ’でクロメート処
理を行った。Then immediately HC:I 100 g/l, 5nCI2
45 °C in a 5 g/fL bath,! OA/drn'
A cathodic electrolytic treatment was carried out, followed by tin plating at 400 g/rn' using a halogen bath. Subsequently, chromate treatment was performed at a current density of 20 A/drn' using a bath containing 315 g of Cr0 and 0.12 g of H2So.
〔実施例３〕
通常のブリキ・ＴＦＳ用原板を電解脱脂、酸洗した後、
Ｃｒ０３１８０ ｇ／ ｌ、 Ｈ２ＳＯ４１，８ｇ／見
の浴を用い、浴温度５５℃、電流密度２０＾／ｄｍ’で
陰極電解処理を行い、２０ｍｇ／ｒｎ’の金属クロムを
めっきした。その後、直ちにＨＣｌ１２０ｇ／ｌ、５ｎ
ＣＩ２２ ｇ ／ ｌの浴中で５０℃、２０Ａ／ｄｒｎ
’で陰極電解処理を行い、引き続いてフェロスタン浴を
用いて７００ｍｇ／ｌｎ’の錫めっきを行なった。さら
に引き続いてＣｒ０３３０ｇ／文、）１２ ＳＯ４０，
２７ｇ ／見の浴を用いて電流密度２５Ａ／ｄｍ？でク
ロメート処理を行った。[Example 3] After electrolytically degreasing and pickling a regular tinplate/TFS plate,
Using a bath containing 180 g/l of Cr03 and 1.8 g/ml of H2SO4, cathodic electrolysis treatment was performed at a bath temperature of 55° C. and a current density of 20^/dm', and 20 mg/rn' of metallic chromium was plated. Immediately thereafter, HCl 120g/l, 5n
50°C, 20A/drn in a CI22 g/l bath
A cathodic electrolytic treatment was carried out using ', followed by tin plating at 700 mg/ln' using a ferrostane bath. Furthermore, Cr0330g/text, )12 SO40,
27g/current density 25A/dm using a viewing bath? Chromate treatment was performed.
〔実施例４〕
通常のブリキ・ＴＦＳ用原板を電解脱脂、酸洗した後、
Ｃｒ０３２５０ ｇ／ｌ、）ｌ ２ ＳＯ４１，５ｇ／
ｌ、）ｌａ２ ＳｉＦ ６ ５．０ｇ ／ ｌの浴を用
い、浴温度５０℃、電流密度５０Ａ／ｄｒｎ’で陰極電
解処理を行い１００腸ｇ／ｍｌの金属クロムをめっきし
た。[Example 4] After electrolytically degreasing and pickling a regular tinplate/TFS plate,
Cr03250 g/l, )l 2 SO41,5g/
Using a bath containing 5.0 g/l of la2 SiF 6 , cathodic electrolysis treatment was performed at a bath temperature of 50° C. and a current density of 50 A/drn' to plate 100 g/ml of metallic chromium.
その後直ちにＨＣＩ １００ ｇ／ ｌ 、 ５ｎＣ１
２５ｇ／ｌの浴中で５０℃、１０ Ａ／ｄｄで陰極電解
処理を行い３００ｍｇ／ｒｎ’の錫めっきを行った。Immediately thereafter HCI 100 g/l, 5nC1
Cathodic electrolysis treatment was carried out at 50° C. and 10 A/dd in a 25 g/l bath, and tin plating was performed at 300 mg/rn'.
さらに引き続いてＣｒ０３１５ｇ／ｆＬ、 ）Ｉ ２５
Ｏ４０，１２ｇ／ｌの浴を用いて電流密度２０Ａ／ｄｒ
ｎ’でクロメート処理を行った。Furthermore, Cr0315g/fL, )I 25
Current density 20A/dr using O40, 12g/l bath
Chromate treatment was performed on n'.
〔比較例１〕
通常のブリキ−ＴＦＳ用原板を電解脱脂、酸洗した後、
ハロゲン浴を用いて５００鵬ｇ／ｒｎ’の錫めっきを行
った。引き続いて３０ｇ／ｆＬの重クロム酸ナトリウム
浴を用いて電流密度５ Ａ／ｄｍ″でクロメート処理を
行った。[Comparative Example 1] After electrolytically degreasing and pickling a regular tin plate for TFS,
Tin plating was carried out at 500 g/rn' using a halogen bath. Subsequently, chromate treatment was carried out using a 30 g/fL sodium dichromate bath at a current density of 5 A/dm''.
〔比較例２〕
通常のブリキ・ＴＦＳ用原板を電解脱脂、酸洗した後、
フェロスタン浴を用いて８００重８／ｍｌの錫めっきを
行った。引き続いてＣｒＯ３１５ｇ／文、 Ｈ２ＳＯ４
０，１８ｇ／交の浴を用いて電流密度１０ Ａ／ｄｒｒ
？でクロメート処理を行った。[Comparative Example 2] After electrolytically degreasing and pickling a regular tin plate/TFS plate,
Tin plating was performed at 800 weights/ml using a ferrostane bath. Subsequently, CrO315g/unit, H2SO4
Current density 10 A/drr using a bath of 0.18 g/drr
? Chromate treatment was performed.
上記の処理をした各鋼板の性能を以下の方法で評価した
。The performance of each steel plate treated as described above was evaluated by the following method.
（１）溶接性評価
溶接速度４０鵬／分、接胴加圧力４０にｇｆ、オーバー
ラツプ幅０．４１でシーム溶接を行い、「散り」を発生
せず、かつ十分な強度を有する接合が形成される溶接電
流範囲（適正溶接電流範囲）をめた。(1) Evaluation of weldability Seam welding was performed at a welding speed of 40 min/min, contact force of 40 gf, and overlap width of 0.41, and a joint with sufficient strength was formed without causing "splashing". The welding current range (appropriate welding current range) was determined.
尚、溶接前に塗装焼付処理を想定して各鋼板ヶ２１０℃
Ｘ２０分処理した。In addition, each steel plate should be heated to 210°C assuming that it will be painted and baked before welding.
It was treated for 20 minutes.
（２）塗料密着性評価
エポキシフェノール系塗料を５０■ｇ／ゴ塗装、焼付け
た後、１．５％ＮａＣ１と１．５％クエン酸の混合溶液
中に５５℃で９６時間浸漬し、クロスカットテープ剥離
試験で塗料の密着性を評価した。(2) Paint adhesion evaluation After applying 50 g of epoxy phenol paint and baking it, it was immersed in a mixed solution of 1.5% NaCl and 1.5% citric acid at 55°C for 96 hours, and then cross-cut. Paint adhesion was evaluated using a tape peel test.
（３）塗料密着性評価
エポキシフェノール系塗料を５０璽ｇ／ｒｎ’塗装焼付
けた後、トマトジュース中に５５℃で２週間浸漬し、板
面の腐食状態で塗装後の耐食性を評価した。(3) Evaluation of paint adhesion After applying 50 g/rn' of epoxy phenol paint and baking it, it was immersed in tomato juice at 55°C for 2 weeks, and the corrosion resistance after painting was evaluated based on the corroded state of the board surface.
上記の各鋼板についての諸計画を示した表１カ）ら明ら
かなように、本発明鋼板は優れた溶接性、塗料密着性、
塗装後耐食性を示す。As is clear from Table 1(a) showing various plans for each of the above steel plates, the steel plates of the present invention have excellent weldability, paint adhesion,
Shows corrosion resistance after painting.
第１図は下地金属Ｃｒ量と焼付処理（２１０”０×２０
分）で生成する合金中のＳｎ量の関係を示すグラフであ
る。
第１図Figure 1 shows the base metal Cr content and baking treatment (210"0 x 20
2 is a graph showing the relationship between the amount of Sn in the alloy produced in Figure 1
Claims (3)
クロム層を有し、その上に塗装焼付後に金属錫が残存す
るような目付量の金属錫層を有し、さらにその上にクロ
ム水和酸化物あるいは金属クロムとクロム水和酸化物か
ら構成されるクロム換算で３鵬ｇ／ｒｎ’以上のクロメ
ート被膜層を有することを特徴とする溶接性に優れた表
面処理鋼板。(1) It has a metallic chromium layer with a basis weight of 5 to 500 g/ln' on the steel plate, and on top of that a metallic tin layer with a basis weight such that metallic tin remains after baking the paint, and A surface-treated steel sheet with excellent weldability, characterized in that it has a chromate coating layer composed of chromium hydrated oxide or metallic chromium and chromium hydrated oxide and has a chromium equivalent of 3 g/rn' or more.
し、引き続いて塩酸、硫酸、シュウ酸、酢酸を１種また
は２種以上含有する水溶液中で陰極電解処理を行い、次
いで錫めっきを施し、さらにクロム水和酸化物あるいは
金属りａムとクロム水和酸化物からなるクロメート被膜
層を形成させることを特徴とする溶接性に優れた表面処
理鋼板の製造方法。(2) Chrome plating is applied to the surface of the steel sheet that has undergone cleaning treatment, followed by cathodic electrolysis treatment in an aqueous solution containing one or more of hydrochloric acid, sulfuric acid, oxalic acid, and acetic acid, and then tin plating is applied. A method for producing a surface-treated steel sheet with excellent weldability, which further comprises forming a chromate coating layer consisting of chromium hydrated oxide or metal aluminum and chromium hydrated oxide.
し、引き続いて塩酸、硫酸、シュウ酸、酢酸を１種また
は２種以上含有し、かつ錫イオンを含有する水溶液中で
陰極電解処理を行い、次いで錫めっきを施し、さらにク
ロム水和酸化物あるいは金属クロムとクロム水和酸化物
からなるクロメート被膜層を形成させることを特徴とす
る溶接性に優れた表面処理鋼板の製造方法。(3) Chromium plating is applied to the surface of the steel plate that has undergone cleaning treatment, and then cathodic electrolysis treatment is performed in an aqueous solution containing one or more of hydrochloric acid, sulfuric acid, oxalic acid, and acetic acid, and also containing tin ions. A method for manufacturing a surface-treated steel sheet with excellent weldability, which comprises the steps of: tin-plating, and further forming a chromate coating layer consisting of hydrated chromium oxide or metallic chromium and hydrated chromium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11770484A JPS60262975A (en) | 1984-06-08 | 1984-06-08 | Surface treated steel sheet having superior weldability and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11770484A JPS60262975A (en) | 1984-06-08 | 1984-06-08 | Surface treated steel sheet having superior weldability and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60262975A true JPS60262975A (en) | 1985-12-26 |
| JPH0368949B2 JPH0368949B2 (en) | 1991-10-30 |
Family
ID=14718241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11770484A Granted JPS60262975A (en) | 1984-06-08 | 1984-06-08 | Surface treated steel sheet having superior weldability and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60262975A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0565688A (en) * | 1991-09-06 | 1993-03-19 | Nkk Corp | Production of double layered electrolytically chromated steel sheet |
| JPH06346253A (en) * | 1993-06-11 | 1994-12-20 | Hitachi Cable Ltd | Metallic strip for tube making and metallic tube and cable using the strip |
| KR20020050383A (en) * | 2000-12-21 | 2002-06-27 | 이구택 | A producing process for surface-treated steel sheet with superior weldability |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57110685A (en) * | 1980-12-29 | 1982-07-09 | Nippon Steel Corp | Chrome plated steel plate of superior weldability and its production |
| JPS60190597A (en) * | 1984-03-09 | 1985-09-28 | Toyo Kohan Co Ltd | Surface treated steel sheet for welded can and its production |
-
1984
- 1984-06-08 JP JP11770484A patent/JPS60262975A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57110685A (en) * | 1980-12-29 | 1982-07-09 | Nippon Steel Corp | Chrome plated steel plate of superior weldability and its production |
| JPS60190597A (en) * | 1984-03-09 | 1985-09-28 | Toyo Kohan Co Ltd | Surface treated steel sheet for welded can and its production |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0565688A (en) * | 1991-09-06 | 1993-03-19 | Nkk Corp | Production of double layered electrolytically chromated steel sheet |
| JPH06346253A (en) * | 1993-06-11 | 1994-12-20 | Hitachi Cable Ltd | Metallic strip for tube making and metallic tube and cable using the strip |
| KR20020050383A (en) * | 2000-12-21 | 2002-06-27 | 이구택 | A producing process for surface-treated steel sheet with superior weldability |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0368949B2 (en) | 1991-10-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |