JPH06108286A - High workability nickel-tin plated steel strip - Google Patents
High workability nickel-tin plated steel stripInfo
- Publication number
- JPH06108286A JPH06108286A JP4280449A JP28044992A JPH06108286A JP H06108286 A JPH06108286 A JP H06108286A JP 4280449 A JP4280449 A JP 4280449A JP 28044992 A JP28044992 A JP 28044992A JP H06108286 A JPH06108286 A JP H06108286A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- nickel
- tin
- plated
- amount
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Electroplating Methods And Accessories (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は深絞り加工性、ＤＩ成形
性に優れた表面処理鋼帯または鋼板（以下両者を含めて
鋼帯という。）に関し、より詳しくはアルカリ液を封入
する容器、例えばアルカリマンガン電池やニッケルカド
ミウム電池などの電池用途に適し、しかも加工性に優れ
たニッケル−錫めっき鋼帯に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated steel strip or steel sheet having excellent deep drawability and DI formability (hereinafter referred to as "steel strip including both"), and more specifically, a container for enclosing an alkaline solution, For example, the present invention relates to a nickel-tin plated steel strip which is suitable for battery applications such as alkaline manganese batteries and nickel cadmium batteries and has excellent workability.
【０００２】[0002]
【従来の技術】従来、アルカリマンガン電池や、ニッケ
ルカドミウム電池などの強アルカリ液を封入する容器
は、冷延鋼帯を電池ケースにプレス加工し、その後バレ
ルめっきすることにより製造されてきた。あるいはニッ
ケルめっき鋼帯を電池ケースにプレス加工する方法が採
用されてきた。しかし、バレルめっき法では生産性が低
く非能率で、めっき厚のばらつきが大きいという問題が
あった。したがって冷延鋼帯にめっきするニッケルめっ
き鋼帯がバレルめっき法に替わって広く使われるように
なってきた。ところで、アルカリマンガン電池やニッケ
ルカドミウム電池容器などの電池用途に、ニッケルめっ
き鋼帯が多く使用される理由は次の理由である。すなわ
ち、これらの電池は主として強アルカリ性の水酸化カリ
ウムなどを電解液としているため、アルカリ性電解液に
対する耐腐食性の点でニッケルめっきが優れているこ
と、電池を外部端子に接続する場合安定した接触抵抗を
ニッケルは有していること、さらには各構成部品から電
池に組立てられる際スポット溶接が行われるが、ニッケ
ルめっき鋼帯はスポット溶接性にも優れているからであ
る。また、ニッケルめっきは次の観点からもその必要性
がある。即ち、アルカリマンガン電池を例として述べる
と、電池ケースに鉄板を用いる場合、鉄が電池のアルカ
リ電解液中に溶出し、これが陽極の亜鉛粒の表面に析出
して、亜鉛の自己放電を誘発する原因とされている。従
ってニッケルめっき鋼帯はアルカリ液を電解液とする電
池ケース材料として好適に用いられてきたのである。2. Description of the Related Art Conventionally, a container for enclosing a strong alkaline liquid such as an alkaline manganese battery or a nickel cadmium battery has been manufactured by pressing a cold rolled steel strip into a battery case and then barrel plating. Alternatively, a method of pressing a nickel-plated steel strip into a battery case has been adopted. However, the barrel plating method has the problems of low productivity, inefficiency, and large variations in plating thickness. Therefore, nickel-plated steel strip for plating cold-rolled steel strip has been widely used instead of the barrel plating method. By the way, the reason why nickel-plated steel strips are often used for battery applications such as alkaline manganese batteries and nickel-cadmium battery containers is as follows. That is, since these batteries mainly use strong alkaline potassium hydroxide etc. as the electrolytic solution, nickel plating is excellent in terms of corrosion resistance to alkaline electrolytic solution, and stable contact when connecting the battery to external terminals. This is because nickel has resistance, and further, spot welding is performed when the components are assembled into a battery, but the nickel-plated steel strip is also excellent in spot weldability. Further, there is a need for nickel plating from the following viewpoint. That is, taking an alkaline manganese battery as an example, when an iron plate is used for the battery case, iron is eluted in the alkaline electrolyte of the battery, and this is deposited on the surface of the zinc particles of the anode to induce self-discharge of zinc. It is supposed to be the cause. Therefore, the nickel-plated steel strip has been suitably used as a battery case material using an alkaline solution as an electrolytic solution.
【０００３】[0003]
【発明が解決すべき課題】電池製造においては、電池容
量増加の方法として、材料の薄肉化が一層図られるよう
になり、ＤＩ（drawing and ironing ）加工法も用いら
れるようになった（特開昭６０−１８００５８号公報等
参照）。前記ＤＩ加工法は電池ケースの側面より底面が
厚く、耐圧強度の面で有利な成形法と考えられる。さら
に筒型のアルカリマンガン電池は従来電池ケース、正極
端子、負極端子の３ピースより、密閉缶に構成されてい
たが、コスト低減の観点から正極端子と電池ケースを一
体とした凸部一体形の電池ケースと負極端子の２ピース
形に変わりつつある。しかし、前記ＤＩ加工法を利用し
て前述の凸部一体形の電池ケースの製造においては、ニ
ッケルめっき鋼帯に求められる材料特性は極めて厳しい
ものとなる。即ち、前記ＤＩ加工法においては、缶側面
の厚みは底面の約１／２の板厚になり、さらに、凸付き
一体形の電池ケースに仕上げるための、２段の段付き加
工成形が加わるため、凸部一体形の深絞り加工時にコー
ナー部が破断する頻度が高く、生産性を阻害することに
なる。このため軟質で深絞り特性に優れる非時効性極低
炭素鋼の適用と相まって、材質面改善や耐食性向上の観
点から、冷延鋼板にニッケルめっき後、熱処理する方法
が提案されている。しかし、これらの対策では厳しい加
工条件に十分には対応できず、さらに格段の加工性の向
上が求められている。また、近年電池の使用される用途
が多岐にわたるようになるにつれ、従来ニッケルめっき
の接触抵抗で十分機能していたものが問題視されるよう
になってきた。即ち、電池両極での接触荷重が、ごく軽
負荷のものから高負荷のものまで広範囲に及ぶようにな
った。このため、より安定で且つ低い電気接触抵抗を有
した電池ケースが求められるようになってきた。電気接
触抵抗が高いと、正または負極端子と相手側接触面との
接触電圧が高くなり、その影響を受けて電池寿命が短く
なるという問題が生じてきた。このように、電池の軽量
化や高容量化の要求に伴い、材料素材であるニッケルめ
っき鋼帯に求められる要求性能はより厳しくなってき
た。即ち、前述のように電池ケース薄肉化の要求と厳し
い加工法とが広く適用されるようになり、従来のニッケ
ルめっき鋼帯では缶製造技術の進歩に追随できないとい
う問題点があった。そこで本発明は、封入アルカリ液に
対する電池ケースの耐食性を損なわずに、しかも電池ケ
ース成形性を向上させる好適な材料を提供するものであ
り、ケース内面は耐アルカリ腐食性を保持し、ケース外
面は電気接触性能を向上させ、さらに優れた加工性能を
有することを特徴とする表面処理鋼帯を提供することを
目的とする。In the production of batteries, as a method for increasing the battery capacity, the material can be made thinner, and a DI (drawing and ironing) processing method has also been used. (See Japanese Patent Laid-Open No. 60-180058). The DI processing method is considered to be advantageous in terms of pressure resistance because the bottom surface is thicker than the side surface of the battery case. Further, the cylindrical alkaline manganese battery has conventionally been configured as a sealed can with three pieces of a battery case, a positive electrode terminal, and a negative electrode terminal, but from the viewpoint of cost reduction, the positive electrode terminal and the battery case are integrally formed into a convex portion. It is changing to a two-piece type with a battery case and a negative electrode terminal. However, the material properties required for the nickel-plated steel strip are extremely strict in the production of the battery case integrally formed with the convex portion by using the DI processing method. That is, in the DI processing method, the thickness of the side surface of the can is about half the thickness of the bottom surface, and further, two-step step forming is added to finish the battery case of the convex integrated type. The corners are frequently broken during deep drawing of the projection-integrated type, which hinders productivity. Therefore, in combination with the application of a non-aging ultra-low carbon steel that is soft and has excellent deep drawing characteristics, a method of nickel-plating a cold-rolled steel sheet and then heat-treating it has been proposed from the viewpoint of improving the material surface and improving the corrosion resistance. However, these measures cannot sufficiently cope with severe machining conditions, and further improvement in workability is required. In addition, as batteries have been used in various applications in recent years, what has conventionally been sufficiently functioning as the contact resistance of nickel plating has become a problem. That is, the contact load on both electrodes of the battery has come to be in a wide range from a very light load to a high load. Therefore, a more stable battery case having a low electric contact resistance has been demanded. When the electrical contact resistance is high, the contact voltage between the positive or negative electrode terminal and the contact surface on the other side becomes high, and the battery life is shortened due to the influence. As described above, along with the demand for lighter weight and higher capacity of batteries, the required performance required for the nickel-plated steel strip, which is a material, has become more severe. That is, as described above, the demand for thinner battery cases and strict processing methods have been widely applied, and there has been a problem that conventional nickel-plated steel strips cannot keep up with the progress of can manufacturing technology. Therefore, the present invention provides a suitable material that does not impair the corrosion resistance of the battery case with respect to the enclosed alkaline solution and further improves the battery case moldability. The inner surface of the case retains alkali corrosion resistance and the outer surface of the case is It is an object of the present invention to provide a surface-treated steel strip which has improved electrical contact performance and further has excellent processing performance.
【０００４】[0004]
【課題を解決するための手段】本発明は上記問題点を解
決するため、缶内面に相当する面にはニッケルめっきま
たはニッケルめっき後錫めっきをし、缶外面に相当する
面には錫めっきをしたニッケル−錫めっき鋼帯を提供す
る。すなわち、本発明の鋼板は次の特徴を有する。 （１）鋼板の一方の面には、めっき量５〜４０ｇ／ｍ2
のニッケルめっきが施されており、他方の面にはめっき
量２．８〜１７ｇ／ｍ2 の錫めっきが施されている。 （２）鋼板の一方の面には、めっき量５〜４０ｇ／ｍ2
のニッケルめっきが施されており、他方の面にはめっき
量２．８〜１７ｇ／ｍ2 の錫めっきが施されていて、か
つ前記ニッケルめっき層の一部が鉄−ニッケル合金層を
形成している。 （３）鋼板の一方の面には、めっき量５〜４０ｇ／ｍ2
のニッケルめっきが施されており、他方の面には、めっ
き量１〜１０ｇ／ｍ2 のニッケルめっきおよびめっき量
２．８〜１７ｇ／ｍ2 の錫めっきが施されている。 （４）鋼板の一方の面には、めっき量５〜４０ｇ／ｍ2
のニッケルめっきが施されており、他方の面には、めっ
き量１〜１０ｇ／ｍ2 のニッケルめっきおよびめっき量
２．８〜１７ｇ／ｍ2 の錫めっきが施されていて、かつ
前記両面のニッケルめっき層の一部が鉄−ニッケル合金
層を形成している。 （５）鋼板の一方の面には、めっき量５〜４０ｇ／ｍ2
のニッケルめっきが施されており、他方の面には、めっ
き量が１０ｇ／ｍ2 を超え４０ｇ／ｍ2 のニッケルめっ
きおよびめっき量１．７〜１７ｇ／ｍ2 の錫めっきが施
されている。 （６）鋼板の一方の面には、めっき量５〜４０ｇ／ｍ2
のニッケルめっきが施されており、他方の面には、めっ
き量が１０ｇ／ｍ2 を超え４０ｇ／ｍ2 のニッケルめっ
きおよびめっき量１．７〜１７ｇ／ｍ2 の錫めっきが施
されていて、かつ前記両面のニッケルめっき層の一部が
鉄−ニッケル合金層を形成している。In order to solve the above problems, the present invention uses nickel plating or nickel plating followed by tin plating on the surface corresponding to the inner surface of the can, and tin plating on the surface corresponding to the outer surface of the can. Provided nickel-tin plated steel strip. That is, the steel sheet of the present invention has the following features. (1) Plating amount 5-40g / m2 on one side of steel plate
Nickel plating is applied, and the other surface is tin plated with a plating amount of 2.8 to 17 g / m @ 2. (2) Plating amount 5-40g / m2 on one surface of the steel plate
Nickel plating is applied, and the other surface is plated with tin at a plating amount of 2.8 to 17 g / m @ 2, and a part of the nickel plating layer forms an iron-nickel alloy layer. There is. (3) One side of the steel plate has a plating amount of 5 to 40 g / m2
And nickel plating with a plating amount of 1 to 10 g / m @ 2 and tin plating with a plating amount of 2.8 to 17 g / m @ 2 are applied to the other surface. (4) Plating amount 5-40g / m2 on one side of the steel plate
Nickel plating is applied, the other surface is plated with nickel with a plating amount of 1 to 10 g / m2 and tin plating with a plating amount of 2.8 to 17 g / m2, and the nickel plating on both surfaces is performed. Part of the layer forms an iron-nickel alloy layer. (5) One side of the steel plate has a plating amount of 5 to 40 g / m2
Nickel plating is applied to the other surface, and the other surface is plated with nickel having a plating amount of more than 10 g / m @ 2 and 40 g / m @ 2 and tin plating having a plating amount of 1.7 to 17 g / m @ 2. (6) Plating amount 5-40g / m2 on one surface of the steel plate
Nickel plating is applied to the other surface, and the other surface is applied with nickel plating having a plating amount of more than 10 g / m 2 and 40 g / m 2 and tin plating having a plating amount of 1.7 to 17 g / m 2, and A part of the nickel plating layers on both sides forms an iron-nickel alloy layer.
【０００５】[0005]
【作用】本発明の鋼帯を電池ケースなどに適用する場合
を例にとって、ケース内面側と、ケースの外面側とに分
けて説明する。 （缶内面）また、本発明ではケース内面側にニッケルめ
っきを行うが、そのめっき量は以下のようにして決定す
る（図１参照）。図１は、円筒絞り缶内（ケース内面に
ニッケルめっきが施してある。）に水酸化カリウム液を
入れ１２日間放置後の鉄溶出量を測定した結果を示す。
めっき量の異なった何種類かのめっき鋼板を作成し、絞
り加工で外形１３ｍｍ、高さ４９ｍｍの円筒缶を作り、
この中に水酸化カリウム溶液（濃度：８モル）を入れ、
温度６５℃、１２日間経過後の溶液中への鉄の溶出量を
測定した。なお鉄の溶出量を測定は、微量測定に適した
誘導結合プラズマ発光分光分析法を用いた。図１からニ
ッケルめっき量が５ｇ／ｍｍ2 未満になると鉄溶出量が
急激に増加し、電池ケースの耐久性を劣化させることが
わかる。一方、３２ｇ／ｍ2 を超えてもニッケルめっき
量の効果が顕著に現れず、且つ不経済である。したがっ
てニッケルめっき量は５ｇ〜３２ｇ／ｍｍ2 の範囲が好
ましい。なお、ニッケルめっき面も、ダル仕上げにした
方が好ましい。その理由は電池活物質（アルカリマンガ
ン電池の場合、二酸化マンガンが相当する。）との密着
力が高く、接触抵抗が低くなるため、自己放電率がより
低くなるからである。In the case where the steel strip of the present invention is applied to a battery case or the like, the case inner surface side and the case outer surface side will be described separately. (Inner surface of can) Further, in the present invention, nickel plating is performed on the inner surface of the case, and the plating amount is determined as follows (see FIG. 1). FIG. 1 shows the results of measuring the elution amount of iron after a potassium hydroxide solution was placed in a cylindrical squeezer (the case inner surface was nickel-plated) and left for 12 days.
We made several kinds of plated steel plates with different plating amounts, and made a cylindrical can with an outer diameter of 13 mm and a height of 49 mm by drawing.
Put potassium hydroxide solution (concentration: 8 mol) in this,
The elution amount of iron in the solution was measured after a lapse of 12 days at a temperature of 65 ° C. The elution amount of iron was measured by an inductively coupled plasma emission spectroscopic analysis method suitable for trace amount measurement. It can be seen from FIG. 1 that when the nickel plating amount is less than 5 g / mm @ 2, the iron elution amount rapidly increases and the durability of the battery case deteriorates. On the other hand, even if it exceeds 32 g / m @ 2, the effect of the amount of nickel plating does not remarkably appear, and it is uneconomical. Therefore, the nickel plating amount is preferably in the range of 5 g to 32 g / mm @ 2. The nickel-plated surface is also preferably dull-finished. The reason is that the self-discharge rate becomes lower because the contact strength with the battery active material (which corresponds to manganese dioxide in the case of alkaline manganese battery) is high and the contact resistance is low.
【０００６】（缶外面）錫めっきをケース外面側となる
ようにする理由は、錫めっきの安定した電気接触抵抗と
優れた加工性能からである（図２参照）。電気接触抵抗
について錫めっきが安定している理由は、めっき表層が
柔らかいことで電気接触抵抗を安定化させているものと
考えられる。冷延鋼板に錫めっきとニッケルめっきした
場合の表層硬度を比較測定したところ、錫めっき（めっ
き量１７ｇ／ｍ2 ）の場合、ＨＶ５ｇ荷重で、４５であ
るのに対し、ニッケルめっき（付着量１７ｇ／ｍ2 ）は
めっきのままで３０５あり、錫めっき表面より、ニッケ
ルめっきはめっき表層が硬いことが分かった。さらにニ
ッケルめっき後加熱温度５５０℃、均熱時間６時間の熱
処理を施し、ニッケルめっき後に軟質化熱処理した場合
でも、硬度は２１０を維持した。またニッケルめっきは
鉄など他の金属に比べて優れた電気接触抵抗を示すが、
それでも錫めっきに比べ、電気接触抵抗は高い。その理
由は、ニッケルめっき表層が酸化し電気抵抗の高いＮｉ
Ｏが形成されること、前記の如くニッケルめっき層が錫
めっき層に比較して硬いため、即ち変形抵抗が高いた
め、接触面積が錫めっきより小さいためと考えられる。
実際の電気接触抵抗を測定した結果を図２に示した。(Outer surface of can) The reason why the tin plating is arranged on the outer surface of the case is because of the stable electric contact resistance of the tin plating and the excellent processing performance (see FIG. 2). Regarding the electric contact resistance, it is considered that the reason why tin plating is stable is that the electric contact resistance is stabilized because the plating surface layer is soft. When the surface hardness of the cold-rolled steel sheet was tin-plated and nickel-plated, the tin-plating (plating amount: 17 g / m 2) was 45 under HV 5 g load. m2) was as-plated 305, and it was found that the nickel plating had a harder surface layer than the tin-plated surface. Further, the hardness was maintained at 210 even when a heat treatment was carried out after the nickel plating at a heating temperature of 550 ° C. for a soaking time of 6 hours and a softening heat treatment was performed after the nickel plating. Also, nickel plating shows superior electrical contact resistance compared to other metals such as iron,
However, the electrical contact resistance is higher than that of tin plating. The reason is that the nickel plating surface layer is oxidized and Ni has high electric resistance.
It is considered that O is formed and that the nickel plating layer is harder than the tin plating layer as described above, that is, the deformation resistance is high and the contact area is smaller than that of the tin plating layer.
The result of measuring the actual electrical contact resistance is shown in FIG.
【０００８】図２から、測定荷重が低いほど電気接触抵
抗は高く、測定荷重の増加にともなって低い電気接触抵
抗値を示す。これは荷重が高いほど接触面積が増加する
こと、表面の酸化被膜の破壊によるものと考えられる。
しかし、接触負荷荷重の大小にかかわらず、錫めっき付
着量が０．５ｇ／ｍ2 以上になると電気接触抵抗が安定
することがわかる。したがって、電気接触抵抗が安定の
観点からの錫めっき付着量の下限は０．５ｇ／ｍ2 とす
る。なおここで電気接触抵抗の測定方法は以下のように
して行った。交流４端子法で接触子を鍮棒の先端を１Ｒ
に加工した面に金めっきを施したものを使用し、印加電
流は１０ｍｍＡとし、接触荷重を２００ｇおよび１００
０ｇの一定荷重下で測定した。From FIG. 2, the lower the measuring load, the higher the electrical contact resistance, and the lower the electrical contact resistance value as the measuring load increases. It is considered that this is because the contact area increases as the load increases and the oxide film on the surface is destroyed.
However, it can be seen that the electrical contact resistance becomes stable when the tin plating adhesion amount becomes 0.5 g / m 2 or more, regardless of the contact load. Therefore, the lower limit of the amount of tin plating deposited is 0.5 g / m 2 from the viewpoint of stable electrical contact resistance. Here, the measuring method of the electrical contact resistance was performed as follows. AC 4 terminal method, the contactor is a brass rod tip 1R
The processed surface is plated with gold, the applied current is 10 mmA, and the contact load is 200 g and 100
It was measured under a constant load of 0 g.
【０００９】次に、ケース外面側に錫めっきを行う他の
理由は、ＤＩ加工や凸付き加工など厳しい成形加工に対
しても優れた加工性能を有するからである。錫は、軟ら
かく展延性に富み、常温でも再結晶するため、鉄やニッ
ケルなどのように加工硬化しない。さらに低融点金属
（融点２３２℃）であるため、厳しい深絞り加工やＤＩ
加工時にプレスダイとの接触面で温度が上がった場合、
錫めっき層がより潤滑効果を示すため、被加工物の加工
性能を著しく向上させる。殊に加工性能に及ぼすポンチ
側とダイ側を考えた場合、ダイ側の方がより加工性能に
影響する。このことは、本発明が片面錫めっきであり、
しかも電池ケースなど電池部品の外側になるよう成形す
るため、ダイ側面と錫めっき面が接触し好都合となる。
加工成形性の観点からの錫めっき量の下限は、缶の割れ
発生数度合いから決定される。すなわち、錫めっき量が
少ないと、ブランク径の大きな板の絞り加工ができず
に、缶成形時に割れが発生する。図３に錫めっき量を変
えて加工成形性を調査した結果を示す。図３の結果から
錫めっき量が１．７ｇ／ｍ2 以上の場合は良好な成形が
できたが、１．７ｇ／ｍ2 未満の場合には、缶に割れが
発生した。なお、缶の加工成形は以下のようにして行っ
た。ポンチ径５７．０ｍｍ、ダイス径５７．６４ｍｍ、
パンチおよびダイラジアス２ｍｍ、しわ押さえ５００Ｋ
ｇにてブランク径１２０ｍｍでカップ絞りを行った。一
方、錫めっき量が１７ｇ／ｍ2 を超えても技術的改善は
みられず、経済的観点より上限は１７ｇ／ｍ2 とする。
よって、前記電気接触抵抗、絞り性および経済性を勘案
すると錫めっき量は１．７〜１７ｇ／ｍ2 が適正範囲と
なる。なお、錫めっきはめっき後、リフロー処理（錫溶
融処理）と、めっきのままのノーリフローの方法がある
が、本発明では両方法どちらを用いても構わない。しか
しより好ましくは、ノーリフロー処理後に、調質圧延を
行う方法がより好ましい。その理由は、プレス加工時に
めっき表面の潤滑油の保持性が、錫めっき層表面がより
平滑面になっているリフロー処理の場合より優れている
からである。Next, another reason for performing tin plating on the outer surface of the case is that it has excellent processing performance even for severe forming processing such as DI processing and convex processing. Since tin is soft and rich in ductility, and recrystallizes even at room temperature, it does not work harden like iron and nickel. Furthermore, since it is a low melting point metal (melting point 232 ° C), it requires severe deep drawing and DI.
If the temperature rises on the contact surface with the press die during processing,
Since the tin-plated layer exhibits a more lubricating effect, it significantly improves the processing performance of the work piece. Especially when considering the punch side and the die side that affect the processing performance, the die side affects the processing performance more. This means that the present invention is single-sided tin plating,
Moreover, since the molding is performed outside the battery parts such as the battery case, the side surface of the die and the tin-plated surface come into contact with each other, which is convenient.
The lower limit of the tin plating amount from the viewpoint of workability is determined by the number of cracks in the can. That is, when the tin plating amount is small, a plate having a large blank diameter cannot be drawn, and cracks occur during can forming. Fig. 3 shows the results of investigation of workability by changing the tin plating amount. From the results shown in FIG. 3, when the tin plating amount was 1.7 g / m @ 2 or more, good molding could be achieved, but when the tin plating amount was less than 1.7 g / m @ 2, the can cracked. The cans were processed and molded as follows. Punch diameter 57.0 mm, die diameter 57.64 mm,
Punch and die radius 2mm, wrinkle retainer 500K
The cup was drawn with a blank diameter of 120 mm at g. On the other hand, even if the tin plating amount exceeds 17 g / m2, no technical improvement is observed, and the upper limit is set to 17 g / m2 from the economical viewpoint.
Therefore, in consideration of the electric contact resistance, drawability and economy, the tin plating amount is in the proper range of 1.7 to 17 g / m 2. Note that tin plating includes a reflow treatment (tin melting treatment) after plating and a non-reflow method as it is, but either method may be used in the present invention. However, more preferably, the method of performing temper rolling after the no-reflow treatment is more preferable. The reason is that the retention of the lubricating oil on the plating surface during press working is better than in the case of the reflow treatment in which the surface of the tin plating layer is smoother.
【００１０】（請求項３〜６の発明）なお、缶外面の耐
食性をより向上させる観点から、ケース外面になる面に
も錫めっき前に下地めっき処理としてニッケルめっきを
行うことがより好ましいが、この場合のニッケルめっき
のめっき量は１〜１０ｇ／ｍ2 とする場合と、１０ｇ／
ｍ2 を超えて４０ｇ／ｍ2 以下とする場合がある。その
理由はニッケルめっきのめっき量が１〜１０ｇ／ｍ2 で
は十分な耐食性が確保できないため、錫めっきで補う必
要があるからである。一方、ニッケルめっきのめっき量
が１０ｇ／ｍ2 を超えると、ニッケルめっきで耐食性が
確保できるため、錫めっき量を減少させることができる
からである。したがって、めっき量１〜１０ｇ／ｍ2 の
ニッケルめっきが施されている場合には、錫めっき量は
２．８〜１７ｇ／ｍ2 の錫めっきを施す必要がある。ま
た、めっき量が１０ｇ／ｍ2 を超え４０ｇ／ｍ2 のニッ
ケルめっきが施されている場合には、錫めっき量は１．
７〜１７ｇ／ｍ2 でよい。この根拠は塩水噴霧試験をお
こなって耐食性を調査した（図４に示す）図４の領域Ａ
（請求項３および４）、領域Ｂ（請求項５および６）に
おいては十分な耐食性が得られたが、領域Ｃでは耐食性
が劣り、領域Ｄでは加工性が十分でない。(Inventions 3 to 6) From the viewpoint of further improving the corrosion resistance of the outer surface of the can, it is more preferable to perform nickel plating as a base plating treatment on the surface which will be the outer surface of the case before tin plating. In this case, the nickel plating amount is 1 to 10 g / m 2 and 10 g / m 2
It may exceed 40 m / m2 and exceed m2. The reason is that if the nickel plating amount is 1 to 10 g / m @ 2, sufficient corrosion resistance cannot be ensured, and it is necessary to supplement with tin plating. On the other hand, if the nickel plating amount exceeds 10 g / m @ 2, the corrosion resistance can be secured by the nickel plating, and the tin plating amount can be reduced. Therefore, when nickel plating with a plating amount of 1 to 10 g / m @ 2 is applied, it is necessary to apply tin plating with a tin plating amount of 2.8 to 17 g / m @ 2. Further, when the plating amount exceeds 10 g / m 2 and the nickel plating amount is 40 g / m 2, the tin plating amount is 1.
It may be 7 to 17 g / m @ 2. The reason for this is that the salt spray test was conducted to investigate the corrosion resistance (shown in FIG. 4). Area A in FIG.
Sufficient corrosion resistance was obtained in (claims 3 and 4) and region B (claims 5 and 6), but in region C the corrosion resistance was poor and in region D the workability was not sufficient.
【００１１】次に、本発明の高加工性ニッケル−錫めっ
き鋼帯の製造方法を詳述する。 （鋼板）めっき原板としては、通常低炭素アルミキルド
鋼が用いられる。さらにニオブ、チタンを添加し非時効
性極低炭素鋼（炭素量：０．００３％以下）から製造さ
れた冷延鋼帯も用いられる。通常、冷延後、電解清浄、
焼鈍、調質圧延した鋼帯をめっき原板とするが、冷延後
の鋼板をそのままニッケルめっきの原板とする場合もあ
る。この場合は冷延後にニッケルめっきを行った後、引
き続き鋼素地を再結晶焼鈍する工程と、ニッケルめっき
層を熱拡散処理させる工程とを同時に行う方法である。Next, the method for producing the highly workable nickel-tin plated steel strip of the present invention will be described in detail. (Steel plate) As a plating original plate, low carbon aluminum killed steel is usually used. Further, cold-rolled steel strips made of non-aging ultra-low carbon steel (carbon content: 0.003% or less) to which niobium and titanium are added are also used. Usually, after cold rolling, electrolytic cleaning,
The annealed and temper-rolled steel strip is used as a plating original plate, but the cold-rolled steel plate may be used as it is as a nickel plating original plate. In this case, after cold rolling, nickel plating is performed, and subsequently, a step of recrystallizing and annealing the steel substrate and a step of thermally diffusing the nickel plating layer are simultaneously performed.
【００１２】（ニッケルめっき）前記めっき原板をアル
カリ電解脱脂、水洗、硫酸または塩酸酸洗（電解または
浸漬）、水洗の前処理を行った後、ニッケルめっきを行
う。ニッケルめっきの浴は本発明では、ワット浴、スル
ファミン酸浴、塩化浴など公知のめっき浴のいずれであ
っても構わない。さらにニッケルめっきの種類には、無
光沢めっき、半光沢めっき並びに光沢めっきがあるが、
硫黄含有有機物を添加した光沢めっき以外の、無光沢ま
たは半光沢めっきが本発明では好適に適用される。光沢
めっきの場合、めっき層が硬いため加工時の表面割れが
より多く発生し耐食性を阻害するとともに、ニッケルめ
っき後に熱処理すると、硫黄を含有するためめっき層が
脆化し耐食性を損なうからである。(Nickel Plating) The above plating original plate is subjected to alkaline electrolytic degreasing, water washing, sulfuric acid or hydrochloric acid pickling (electrolysis or dipping), and water washing pretreatment, and then nickel plating. In the present invention, the nickel plating bath may be any known plating bath such as a Watts bath, a sulfamic acid bath, or a chloride bath. Furthermore, the types of nickel plating include matte plating, semi-gloss plating and bright plating,
Matte or semi-bright plating other than bright plating to which a sulfur-containing organic substance is added is preferably applied in the present invention. This is because in the case of bright plating, since the plating layer is hard, more surface cracks are generated during processing to inhibit corrosion resistance, and when heat treatment is performed after nickel plating, the plating layer becomes brittle and deteriorates corrosion resistance because it contains sulfur.
【００１３】（熱処理）ニッケルめっきのままでも本発
明の効果は得られるが、より耐食性を向上させる方法と
して、ニッケルめっき後熱処理する方法も好適に用いら
れる。即ちニッケルめっき後熱処理を施すことによりニ
ッケルめっき層が軟質化し、加工時にめっき層でのクラ
ック発生量が低減されるからである。熱処理条件として
は、非酸化性雰囲気ガス内で加熱温度４５０〜８５０
℃、加熱時間３０秒〜１５時間の範囲で処理される。鋼
帯を熱処理する方法としては箱型焼鈍法と連続焼鈍法と
があるが、本発明ではそのいずれの方法によってもよ
く、箱型焼鈍法では（４５０〜６５０）℃×（５〜１５
時間）で処理され、連続焼鈍法では高温、短時間即ち
（６００〜８５０）℃×（３０秒〜５分）の熱処理条件
が好ましい。(Heat Treatment) Although the effect of the present invention can be obtained even with nickel plating as it is, a method of heat treatment after nickel plating is also suitably used as a method of further improving corrosion resistance. That is, the heat treatment after nickel plating softens the nickel plating layer and reduces the amount of cracks generated in the plating layer during processing. As heat treatment conditions, a heating temperature of 450 to 850 in a non-oxidizing atmosphere gas is used.
The treatment is performed at a temperature of 30 ° C. for 30 seconds to 15 hours. As a method for heat-treating a steel strip, there are a box-type annealing method and a continuous annealing method. In the present invention, either method may be used, and in the box-type annealing method, (450 to 650) ° C. × (5 to 15)
In the continuous annealing method, the heat treatment condition of high temperature, short time, that is, (600 to 850) ° C. × (30 seconds to 5 minutes) is preferable.
【００１４】（錫めっき）ニッケルめっき後、引き続い
て、ケース外側相当面に錫めっきを施す。当該錫付着量
は、錫めっきに先立って施されるニッケルめっきが下地
に施してあるか否かにより、錫めっきの規定範囲は異な
る。浴組成は通常用いられている酸性浴、アルカリ浴が
あるが、本発明においては硫酸第１錫浴あるいはフェノ
ールスルフォン酸浴を用いる。なお、缶用材料などの使
用される錫めっきの方法は、脱脂、酸洗、錫めっき、リ
フロー（錫溶融処理）、ケミカル処理の工程で製造され
る場合が一般的であるが、本発明においても同様の方法
が適用される。しかし、ＤＩ加工の如く、より厳しい加
工条件の場合は、ワックス潤滑保持性が良いノーリフロ
ー（錫溶融処理なし）の方が望ましい。(Tin Plating) After nickel plating, subsequently, tin plating is applied to the outer surface of the case. The tin deposition amount varies depending on whether the nickel plating applied prior to the tin plating is applied to the base or not, the specified range of the tin plating. The bath composition includes an acidic bath and an alkaline bath which are usually used, but in the present invention, a stannous sulfate bath or a phenol sulfonic acid bath is used. Note that the tin plating method used for can materials and the like is generally manufactured by steps of degreasing, pickling, tin plating, reflow (tin melting treatment), and chemical treatment. A similar method applies. However, under more severe processing conditions such as DI processing, it is preferable to use no reflow (without tin melting treatment), which has good wax lubricity retention.
【００１５】（調質圧延）加工性能を損なうことなく表
面をより光沢美麗化する方法として、錫めっき後、調質
圧延する方法も用いられる。この方法は、錫めっきした
後錫溶融処理しないで、圧下率２乃至３％以下でブライ
トワークロールにより軽圧延するものである。本方法に
より、錫溶融しない場合の鈍く白っぽい錫めっき層や鈍
い金属光沢を呈したニッケルめっき層は、光沢のある美
麗な表面外観となる。さらに仕上げ研摩したワークロー
ルを用いて圧延すれば、金属光沢を呈した銀白色のきれ
いな表面外観を得ることができる。調質圧延において表
裏のめっきの種類が異なり表面の摩擦係数が異なるため
鋼帯に反りを生じる場合には、調質圧延後レベラー装置
を通すことにより反りを矯正することができる。(Quench rolling) As a method of making the surface more glossy without impairing the processing performance, a method of temper rolling after tin plating is also used. In this method, lightly rolling is performed by a bright work roll with a rolling reduction of 2 to 3% or less without performing tin melting treatment after tin plating. By this method, the dull whitish tin-plated layer without tin melting and the nickel-plated layer exhibiting a dull metallic luster have a glossy and beautiful surface appearance. Further, if it is rolled using a work roll that has been subjected to finish polishing, it is possible to obtain a clean silver-white surface appearance having a metallic luster. When the steel strip is warped due to different types of plating on the front and back sides during temper rolling and the surface friction coefficient is different, the warping can be corrected by passing it through a leveler device after temper rolling.
【００１６】[0016]
【実施例】以下に実施例によって、本発明をさらに詳細
に説明する。板厚０．２５ｍｍの冷延→焼鈍済みの低炭
素アルミキルド鋼板をめっき原板とした。鋼化学組成は
下記の通りである（重量％）。 Ｃ：０．０４％，Ｍｎ：０．２１％，Ｓｉ：０．０１
％，Ｐ：０．０１３％，Ｓ：０．０１０％，Ａｌ：０．
０６４％，Ｎ：０．００３８％ 上記鋼板を、アルカリ電解脱脂（苛性ソーダ：３０ｇ／
ｌ，陽極処理：５Ａ／ｄｍ2 ×１０秒，陰極処理：５Ａ
／ｄｍ2 ×１０秒，浴温：７０℃）、硫酸酸洗（硫酸：
５０ｇ／ｌ，浴温：３０℃，２０秒浸漬）を行った後、
下記の条件でニッケルめっきを行った。 浴組成 ： 硫酸ニッケル ３２０ ｇ／ｌ 塩化ニッケル ４０ ｇ／ｌ ほう酸 ３０ ｇ／ｌ ラウリル硫酸ソーダ ０．５ ｇ／ｌ 浴温度 ： ５５±２ ℃ ｐＨ ：
４．１〜４．６ 攪拌 ： 空気攪拌 電流密度 ：１０ Ａ／ｄｍ2 アノード ：ニッケルペレット（チタンバスケットにニ
ッケルペレット充填） 上記の条件で、片面及び両面に無光沢ニッケルめっきを
行い、その厚みを上記条件で電解時間を変化させて、ニ
ッケルめっき厚を変化させた。ニッケルめっき後、熱処
理する場合、水素：６．５％，残部：窒素ガス，露点：
−４０℃の保護ガスを用いて、均熱温度：５５０℃，均
熱時間：６時間の熱処理を行った。ニッケルめっきに引
き続き、下記の硫酸第一錫めっき浴を用いて錫めっきを
行った。 浴組成 ： 硫酸第一錫 ３０ ｇ
／ｌ （Ｓ++） フェノールスルフォン酸 ６０ ｇ／ｌ エトキシ化αナフトール ５ ｇ／ｌ 浴温度 ： ５０±２ ℃ 電流密度 ： ２０Ａ／ｄｍ2 アノード：
錫板 めっきは、電解時間を変えて付着量を変化させ、抵抗加
熱により、鋼帯を２７０℃に加熱し、溶錫して光沢を賦
与した。さらに錫めっき層の酸化膜成長による黄変を抑
制するために、通常のブリキの製造に適用される化学処
理を行った。 処理浴：重クロム酸ソーダ ３０ｇ／ｌ 浴温 ：４５ ℃ 陰極電解：５Ａ／ｄｍ2 ×５秒 以上の条件で、試料を作成した。それぞれの試料を用い
て、塩水噴霧試験、アルカリ液鉄溶出量、電気接触抵抗
を測定した。塩水噴霧試験はＪＩＳ Ｚ−２３７１に基
づき、噴霧時間２時間の結果を示す。耐食性は直角折り
曲げ試験片で評価した（○：良い，×：劣る）。表１の
結果から本発明範囲である実施例１から１３は、塩水噴
霧試験、アルカリ液鉄溶出量、電気接触抵抗、加工性の
何れの結果も極めて良好な結果を示した。一方、比較例
１４から１９は本発明の範囲を外れるので、何れも良好
な結果が得られなかった。The present invention will be described in more detail with reference to the following examples. A cold-rolled and annealed low-carbon aluminum killed steel plate having a plate thickness of 0.25 mm was used as a plating original plate. The chemical composition of steel is as follows (% by weight). C: 0.04%, Mn: 0.21%, Si: 0.01
%, P: 0.013%, S: 0.010%, Al: 0.
064%, N: 0.0038% The above steel sheet was subjected to alkaline electrolytic degreasing (caustic soda: 30 g /
1, anodization: 5A / dm2 x 10 seconds, cathodic treatment: 5A
/ Dm2 x 10 seconds, bath temperature: 70 ° C, sulfuric acid pickling (sulfuric acid:
50 g / l, bath temperature: 30 ° C., 20 seconds immersion)
Nickel plating was performed under the following conditions. Bath composition: Nickel sulfate 320 g / l Nickel chloride 40 g / l Boric acid 30 g / l Sodium lauryl sulfate 0.5 g / l Bath temperature: 55 ± 2 ° C. pH:
4.1-4.6 Agitation: Air agitation Current density: 10 A / dm2 Anode: Nickel pellets (titanium basket filled with nickel pellets) Matte nickel plating was performed on one side and both sides under the above conditions, and the thickness was adjusted to the above value. The nickel plating thickness was changed by changing the electrolysis time depending on the conditions. When heat-treated after nickel plating, hydrogen: 6.5%, balance: nitrogen gas, dew point:
Using a protective gas at -40 ° C, heat treatment was performed at a soaking temperature of 550 ° C and a soaking time of 6 hours. Subsequent to nickel plating, tin plating was performed using the following stannous sulfate plating bath. Bath composition: Stannous sulfate 30 g
/ L (S ++) Phenolsulfonic acid 60 g / l Ethoxylated α-naphthol 5 g / l Bath temperature: 50 ± 2 ° C Current density: 20 A / dm2 Anode:
In the tin plate plating, the amount of adhesion was changed by changing the electrolysis time, and the steel strip was heated to 270 ° C. by resistance heating and molten tin was added to impart gloss. Furthermore, in order to suppress the yellowing due to the oxide film growth of the tin plating layer, the chemical treatment applied to the production of ordinary tin plates was performed. Treatment bath: sodium dichromate 30 g / l Bath temperature: 45 ° C. Cathodic electrolysis: 5 A / dm 2 × 5 seconds A sample was prepared under the above conditions. Using each sample, the salt spray test, the amount of iron elution from alkaline solution, and the electrical contact resistance were measured. The salt spray test is based on JIS Z-2371, and shows the results of a spray time of 2 hours. The corrosion resistance was evaluated by a right-angled bending test piece (○: good, ×: inferior). From the results of Table 1, Examples 1 to 13, which are within the scope of the present invention, showed extremely good results in all of the salt spray test, the amount of alkali solution iron elution, the electrical contact resistance, and the workability. On the other hand, Comparative Examples 14 to 19 were out of the scope of the present invention, and thus no good results were obtained.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【発明の効果】本発明のめっき鋼板は深絞り加工性、Ｄ
Ｉ成形性に優れ、アルカリ液を封入する容器、例えばア
ルカリマンガン電池やニッケルカドミウム電池などの電
池用途に適し、しかも加工性に優れている。すなわち、
封入アルカリ液に対する電池ケースの耐食性を損なわず
に、しかも電池ケース成形性を向上させることができ
る。さらにケース内面は耐アルカリ腐食性を保持し、ケ
ース外面は電気接触性能を向上させ、優れた加工性能を
有する表面処理鋼帯提供することができる。The plated steel sheet of the present invention has a deep drawing workability, D
It has excellent moldability, is suitable for battery applications such as containers containing an alkaline solution, such as alkaline manganese batteries and nickel cadmium batteries, and has excellent processability. That is,
It is possible to improve the battery case moldability without impairing the corrosion resistance of the battery case against the enclosed alkaline solution. Further, it is possible to provide a surface-treated steel strip which has alkali corrosion resistance on the inner surface of the case, has improved electrical contact performance on the outer surface of the case, and has excellent processing performance.
【図１】ニッケルめっき量を変化させた場合の鉄溶出量
の測定結果を示す。FIG. 1 shows the measurement results of the iron elution amount when the nickel plating amount was changed.
【図２】錫めっき量を変化させた場合の電気接触抵抗の
測定結果を示す。FIG. 2 shows the measurement results of electrical contact resistance when the tin plating amount was changed.
【図３】錫めっき量を変化させた場合の缶成形時の割れ
発生数度合いを示す。FIG. 3 shows the number of cracks generated during can forming when the tin plating amount is changed.
【図４】本発明の缶内面相当面のめっき量の関係説明
図。FIG. 4 is an explanatory view of the relationship between the plating amount of the surface corresponding to the inner surface of the can of the present invention.
Claims (6)
ｇ／ｍ2 のニッケルめっきが施されており、他方の面に
はめっき量２．８〜１７ｇ／ｍ2 の錫めっきが施されて
いる高加工性ニッケル−錫めっき鋼帯。1. A plating amount of 5 to 40 on one surface of a steel sheet.
Highly workable nickel-tin plated steel strip which is g / m2 nickel plated and the other surface is tin plated with a plating amount of 2.8 to 17 g / m2.
ｇ／ｍ2 のニッケルめっきが施されており、他方の面に
はめっき量２．８〜１７ｇ／ｍ2 の錫めっきが施されて
いて、かつ前記ニッケルめっき層の一部が鉄−ニッケル
合金層を形成している高加工性ニッケル−錫めっき鋼
帯。2. A plating amount of 5 to 40 on one surface of the steel sheet.
g / m2 of nickel plating is applied, the other surface is plated with tin of 2.8 to 17 g / m2, and a part of the nickel plating layer is an iron-nickel alloy layer. Highly workable nickel-tin plated steel strip being formed.
ｇ／ｍ2 のニッケルめっきが施されており、他方の面に
は、めっき量１〜１０ｇ／ｍ2 のニッケルめっきおよび
めっき量２．８〜１７ｇ／ｍ2 の錫めっきが施されてい
る高加工性ニッケル−錫めっき鋼帯。3. A plating amount of 5 to 40 on one surface of the steel sheet.
Highly workable nickel with g / m2 nickel plating and the other surface with nickel plating with a plating amount of 1-10 g / m2 and tin plating with a plating amount of 2.8-17 g / m2. -Tinned steel strip.
ｇ／ｍ2 のニッケルめっきが施されており、他方の面に
は、めっき量１〜１０ｇ／ｍ2 のニッケルめっきおよび
めっき量２．８〜１７ｇ／ｍ2 の錫めっきが施されてい
て、かつ前記両面のニッケルめっき層の一部が鉄−ニッ
ケル合金層を形成している高加工性ニッケル−錫めっき
鋼帯。4. A plating amount of 5 to 40 on one surface of a steel plate.
g / m2 nickel plating is applied, and the other surface is plated with nickel plating with a plating amount of 1-10 g / m2 and tin plating with a plating amount of 2.8-17 g / m2. A highly workable nickel-tin plated steel strip in which a part of the nickel plated layer of 1. forms an iron-nickel alloy layer.
ｇ／ｍ2 のニッケルめっきが施されており、他方の面に
は、めっき量が１０ｇ／ｍ2 を超え４０ｇ／ｍ2 のニッ
ケルめっきおよびめっき量１．７〜１７ｇ／ｍ2 の錫め
っきが施されている高加工性ニッケル−錫めっき鋼帯。5. A plating amount of 5 to 40 on one surface of the steel sheet.
g / m2 nickel plating is applied, and the other surface is plated with a plating amount of more than 10 g / m2, 40 g / m2 nickel plating and a plating amount of 1.7 to 17 g / m2 tin plating. Highly workable nickel-tin plated steel strip.
ｇ／ｍ2 のニッケルめっきが施されており、他方の面に
は、めっき量が１０ｇ／ｍ2 を超え４０ｇ／ｍ2 のニッ
ケルめっきおよびめっき量１．７〜１７ｇ／ｍ2 の錫め
っきが施されていて、かつ前記両面のニッケルめっき層
の一部が鉄−ニッケル合金層を形成している高加工性ニ
ッケル−錫めっき鋼帯。6. A plating amount of 5 to 40 on one surface of a steel plate.
g / m2 nickel plating is applied, and the other surface is plated with a plating amount of over 10 g / m2, 40 g / m2 nickel plating and a plating amount of 1.7 to 17 g / m2 tin plating. A highly workable nickel-tin plated steel strip in which a part of the nickel plated layers on both sides forms an iron-nickel alloy layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4280449A JP2534604B2 (en) | 1992-09-26 | 1992-09-26 | Highly workable nickel-tin plated steel strip for battery cases |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4280449A JP2534604B2 (en) | 1992-09-26 | 1992-09-26 | Highly workable nickel-tin plated steel strip for battery cases |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8021600A Division JP2784746B2 (en) | 1996-01-16 | 1996-01-16 | Battery case |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06108286A true JPH06108286A (en) | 1994-04-19 |
| JP2534604B2 JP2534604B2 (en) | 1996-09-18 |
Family
ID=17625218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4280449A Expired - Fee Related JP2534604B2 (en) | 1992-09-26 | 1992-09-26 | Highly workable nickel-tin plated steel strip for battery cases |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2534604B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0725453A4 (en) * | 1993-10-22 | 1996-08-21 | ||
| WO1998015673A1 (en) * | 1996-10-09 | 1998-04-16 | Toyo Kohan Co. Ltd. | Surface treated steel sheet and method of manufacturing the same |
| EP1003230A1 (en) * | 1996-09-03 | 2000-05-24 | TOYO KOHAN Co., Ltd | Surface-treated steel plate for battery case, battery case and battery using the case |
| US6127064A (en) * | 1997-08-29 | 2000-10-03 | Sumitomo Electric Industries, Ltd. | Jar can for secondary battery |
| JP2006172876A (en) * | 2004-12-15 | 2006-06-29 | Sii Micro Parts Ltd | Alkaline battery and its manufacturing method |
| JP2009263699A (en) * | 2008-04-23 | 2009-11-12 | Toyota Motor Corp | METHOD OF MANUFACTURING PLATED BASE MATERIAL HAVING Sn PLATED LAYER |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04154995A (en) * | 1990-10-12 | 1992-05-27 | Nkk Corp | Multi-ply ni plated steel sheet for di can and its production |
| JPH04154996A (en) * | 1990-10-12 | 1992-05-27 | Nkk Corp | Ni plated steel sheet for di can and its production |
-
1992
- 1992-09-26 JP JP4280449A patent/JP2534604B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04154995A (en) * | 1990-10-12 | 1992-05-27 | Nkk Corp | Multi-ply ni plated steel sheet for di can and its production |
| JPH04154996A (en) * | 1990-10-12 | 1992-05-27 | Nkk Corp | Ni plated steel sheet for di can and its production |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0725453A4 (en) * | 1993-10-22 | 1996-08-21 | ||
| EP1003230A1 (en) * | 1996-09-03 | 2000-05-24 | TOYO KOHAN Co., Ltd | Surface-treated steel plate for battery case, battery case and battery using the case |
| EP1003230A4 (en) * | 1996-09-03 | 2000-05-24 | Toyo Kohan Co Ltd | Surface-treated steel plate for battery case, battery case and battery using the case |
| US6270922B1 (en) | 1996-09-03 | 2001-08-07 | Toyo Kohan Co., Ltd. | Surface-treated steel plate for battery case, battery case and battery using the case |
| WO1998015673A1 (en) * | 1996-10-09 | 1998-04-16 | Toyo Kohan Co. Ltd. | Surface treated steel sheet and method of manufacturing the same |
| US6127064A (en) * | 1997-08-29 | 2000-10-03 | Sumitomo Electric Industries, Ltd. | Jar can for secondary battery |
| JP2006172876A (en) * | 2004-12-15 | 2006-06-29 | Sii Micro Parts Ltd | Alkaline battery and its manufacturing method |
| JP2009263699A (en) * | 2008-04-23 | 2009-11-12 | Toyota Motor Corp | METHOD OF MANUFACTURING PLATED BASE MATERIAL HAVING Sn PLATED LAYER |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2534604B2 (en) | 1996-09-18 |
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