JP4051021B2 - Ni-plated steel sheet for battery cans - Google Patents
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- JP4051021B2 JP4051021B2 JP2003380854A JP2003380854A JP4051021B2 JP 4051021 B2 JP4051021 B2 JP 4051021B2 JP 2003380854 A JP2003380854 A JP 2003380854A JP 2003380854 A JP2003380854 A JP 2003380854A JP 4051021 B2 JP4051021 B2 JP 4051021B2
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- 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
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Description
本発明は、電池缶に用いられるメッキ鋼板素材に関し、更に詳しくは、電池缶の加工時の耐カジリ性、および耐食性、電池特性を改善しうる、メッキ鋼板素材に関するものである。 The present invention relates to a plated steel sheet material used for a battery can, and more particularly to a plated steel sheet material that can improve galling resistance, corrosion resistance, and battery characteristics during processing of the battery can.
一般に電池缶用の素材として、Ｎｉメッキされた鋼板が使用される。従来Ｎｉメッキは、缶に加工した後のいわゆるバレルメッキによって行われてきたが、缶内面へのＮｉメッキの付着が十分ではなく品質上の不安定性の問題があることから、先メッキ鋼板を缶に加工する方法に置き換わりつつある。先メッキ鋼板の場合、Ｎｉメッキ層が硬く延展性に乏しいことから、プレス加工性に劣り、また加工時にメッキが剥離して耐食性が劣化しやすい等の問題があった。 In general, a Ni-plated steel sheet is used as a material for a battery can. Conventionally, Ni plating has been carried out by so-called barrel plating after processing into a can, but since the Ni plating adheres to the inner surface of the can and is not sufficient, there is a problem of instability in quality. It is being replaced by the method of processing. In the case of a pre-plated steel sheet, since the Ni plating layer is hard and poor in spreadability, the press workability is inferior, and the plating is peeled off during processing and the corrosion resistance is liable to deteriorate.
この問題に対し、Ｎｉメッキ後熱処理することでメッキと地鉄の界面にＦｅ−Ｎｉ拡散層を形成して密着性を向上させると同時に、Ｎｉを再結晶、軟質化してメッキ層の延展性を向上させる方法が知られており、プレス加工性や耐食性は大幅に改善される（例えば特許文献１）。 To deal with this problem, heat treatment after Ni plating forms a Fe-Ni diffusion layer at the interface between the plating and the base iron to improve adhesion, and at the same time recrystallizes and softens Ni to increase the spreadability of the plating layer. A method of improving is known, and press workability and corrosion resistance are greatly improved (for example, Patent Document 1).
しかしながら、前述の従来技術では、Ｎｉメッキ層が再結晶、軟質化している結果として、電池製造過程において電池缶を高速搬送する際、電池缶外面どおしの接触における摺動性が必ずしも十分でなく、缶の流れ性が劣り生産性を悪化させる場合がある。また、プレス加工においても、金型との摺動性が十分でなく、プレス性を悪化させる場合もある。 However, in the above-described prior art, as a result of the Ni plating layer being recrystallized and softened, when the battery can is conveyed at high speed during the battery manufacturing process, the slidability in contact between the outer surfaces of the battery can is not always sufficient. In some cases, the flowability of the can is poor and the productivity is deteriorated. Also in the press working, the slidability with the mold is not sufficient, and the pressability may be deteriorated.
特許文献２では、Ｎｉメッキ後、更にＮｉ−Ｐ合金メッキを施して熱処理することにより、Ｆｅ−Ｎｉ拡散層と再結晶、軟質化したＮｉメッキ層の上層に更に硬質なＮｉ−Ｐ合金メッキ層を有する耐食性と耐疵つき性に優れたＮｉメッキ鋼板が示されている。 According to Patent Document 2, a Ni-P alloy plating layer that is harder on the Fe-Ni diffusion layer and the recrystallized and softened Ni plating layer by performing Ni-P alloy plating and heat treatment after Ni plating. A Ni-plated steel sheet having excellent corrosion resistance and scratch resistance is shown.
特許文献３では、缶外面の最表層に光沢Ｎｉ層あるいは、光沢Ｎｉ−Ｃｏ合金メッキ層を有する電池缶用メッキ鋼板が示されており、良好な摺動性が得られる。
しかしながら、前記の特許文献２、３の鋼板を使用して成形した電池缶は、加工時に「ヘアライン状」のカジリ痕が発生し、耐食性が悪化したり、金型寿命が低下しやすいといった問題があった。また、貯蔵後の極端子部の接触抵抗値が高く、電池特性を悪化させやすいといった問題もあった。
Patent Document 3 discloses a plated steel sheet for battery cans having a bright Ni layer or a bright Ni—Co alloy plating layer as the outermost layer on the outer surface of the can, and good slidability is obtained.
However, battery cans formed using the steel sheets of Patent Documents 2 and 3 described above have problems such as “hairline-shaped” galling marks generated during processing, resulting in deterioration in corrosion resistance and a reduction in mold life. there were. In addition, there is a problem that the contact resistance value of the electrode terminal part after storage is high and the battery characteristics are easily deteriorated.
そこで本発明は、加工時の耐カジリ性、および耐食性、電池特性を改善しうるＮｉメッキ鋼板および電池缶の提供を目的とする。 Then, this invention aims at provision of the Ni plating steel plate and battery can which can improve the galling resistance at the time of a process, corrosion resistance, and a battery characteristic.
課題で述べたような加工時の耐カジリ性、および耐食性、電池特性の改善のためには、特定のメッキ層構成を採用し、特に缶外面になる面のメッキ層状態の制御が重要である。 In order to improve galling resistance, corrosion resistance, and battery characteristics as described in the topic, it is important to adopt a specific plating layer configuration, and in particular to control the plating layer state on the outer surface of the can. .
すなわち本発明の要旨とするところは、次の通りである。
（１） 電池缶外面に相当する面にＦｅ−Ｎｉ拡散層を有し、更にその上層に光沢添加剤または半光沢添加剤含有Ｎｉメッキ層を有し、かつその表面粗度Ｒａが０．１μｍ以上１μｍ以下かつＲｍａｘが１μｍ以上１０μｍ以下であり、
上記Ｆｅ−Ｎｉ拡散層の付着量は、Ｎｉとして５〜４５ｇ／ｍ ２ であり、
上記光沢添加剤または半光沢添加剤含有Ｎｉメッキ層の付着量が、０．５〜２０ｇ／ｍ 2 であることを特徴とする電池缶用Ｎｉメッキ鋼板。
（２） 電池缶内面に相当する面にＦｅ−Ｎｉ拡散層、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層を有することを特徴とする上記（１）に記載の電池缶用Ｎｉメッキ鋼板。
（３） 上記（１）または（２）に記載のＮｉメッキ鋼板を用いてなることを特徴とする電池缶。
That is, the gist of the present invention is as follows.
(1) It has a Fe—Ni diffusion layer on the surface corresponding to the outer surface of the battery can, and further has a gloss additive or semi-gloss additive-containing Ni plating layer on the upper layer, and its surface roughness Ra is 0.1 μm. 1 μm or less and Rmax is 1 μm or more and 10 μm or less,
The adhesion amount of the Fe—Ni diffusion layer is 5 to 45 g / m 2 as Ni ,
The Ni-plated steel sheet for battery cans , wherein the adhesion amount of the gloss additive or semi-gloss additive-containing Ni plating layer is 0.5 to 20 g / m 2 .
(2) The surface of the battery can corresponding to the inner surface of the battery can has an Fe—Ni diffusion layer, or an Fe—Ni diffusion layer and an Ni plating layer that is recrystallized and softened on the Fe—Ni diffusion layer. Ni-plated steel sheet for battery cans.
(3) A battery can comprising the Ni-plated steel sheet according to (1) or (2).
本発明によって、加工時の耐カジリ性、および耐食性、電池特性を改善しうるＮｉメッキ鋼板の提供が可能となった。上記本発明の電池缶用Ｎｉメッキ鋼板を用いてなる電池缶は、カジリ外観、耐食性、および接触抵抗に優れた性質を有するものである。 According to the present invention, it is possible to provide a Ni-plated steel sheet that can improve galling resistance, corrosion resistance, and battery characteristics during processing. The battery can using the Ni-plated steel sheet for battery can of the present invention has excellent properties in terms of galling appearance, corrosion resistance, and contact resistance.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明においては、少なくとも電池缶の外面となる面に、Ｆｅ−Ｎｉ拡散層を有し、更にその上層に光沢添加剤含有Ｎｉメッキ層または半光沢添加剤含有Ｎｉメッキ層を有することが必要である。更にその表面粗度Ｒａは０．１μｍ以上１μｍ以下かつＲｍａｘは１μｍ以上１０μｍ以下であることが必要である。 In the present invention, it is necessary to have an Fe-Ni diffusion layer on at least the outer surface of the battery can, and further to have a gloss additive-containing Ni plating layer or a semi-gloss additive-containing Ni plating layer as an upper layer. is there. Furthermore, the surface roughness Ra needs to be 0.1 μm or more and 1 μm or less, and Rmax needs to be 1 μm or more and 10 μm or less.
Ｆｅ−Ｎｉ拡散層は、プレス時の耐カジリ性と耐食性を確保するために必須である。その望ましい付着量は、Ｎｉとして５〜４５ｇ／ｍ2であり、５ｇ／ｍ2未満では耐食性が不足しやすく、４５ｇ／ｍ2超でも効果が飽和して不経済である。 The Fe—Ni diffusion layer is essential to ensure galling resistance and corrosion resistance during pressing. Its desired adhesion amount is 5~45g / m 2 as Ni, is less than 5 g / m 2 the corrosion resistance tends to lack, 45 g / m 2 exceeds even effect is uneconomical saturated.
前記のＦｅ−Ｎｉ拡散層の上層に、光沢添加剤含有Ｎｉメッキ層または半光沢添加剤含有Ｎｉメッキ層を有し、かつその表面粗度Ｒａが０．１μｍ以上１μｍ以下かつＲｍａｘが１μｍ以上１０μｍ以下であれば、優れた耐カジリ性と良好な接触抵抗も得ることができる。 The upper layer of the Fe—Ni diffusion layer has a bright additive-containing Ni plating layer or a semi-bright additive-containing Ni plating layer, and has a surface roughness Ra of 0.1 μm to 1 μm and an Rmax of 1 μm to 10 μm. If it is below, excellent galling resistance and good contact resistance can also be obtained.
特に、そのメカニズムは明らかでないが、湿潤環境下で経時しても接触抵抗の悪化はきわめて少ない。ここで前述の表面粗度については、鋼板最終製品としての粗度Ｒａが０．１μｍ以上１μｍ以下かつＲｍａｘが１μｍ以上１０μｍ以下であれば良く、この条件を満たす限りにおいては、冷間圧延後の原板の段階で調整された粗度であってもかまわないし、光沢添加剤含有Ｎｉメッキ層または半光沢添加剤含有Ｎｉメッキ層を施す前、あるいは後のいずれの段階で付与されたものであっても構わない。 In particular, the mechanism is not clear, but the contact resistance is very little deteriorated even with time in a humid environment. Here, as for the surface roughness described above, the roughness Ra as the steel sheet final product may be 0.1 μm or more and 1 μm or less and Rmax may be 1 μm or more and 10 μm or less. The roughness may be adjusted at the stage of the original plate, and may be applied before or after applying the Ni plating layer containing the gloss additive or the Ni plating layer containing the semi-gloss additive. It doesn't matter.
前記の光沢添加剤含有Ｎｉメッキ層または半光沢添加剤含有Ｎｉメッキ層の付着量は、０．５ｇ／ｍ2以上が望ましく、これ未満では耐カジリ性の改善効果が低い場合がある。また、上限としては、特に限定されないが、経済的な観点から、２０ｇ／ｍ2程度以下が望ましい。 The adhesion amount of the gloss additive-containing Ni plating layer or the semi-gloss additive-containing Ni plating layer is desirably 0.5 g / m 2 or more, and if it is less than this, the effect of improving galling resistance may be low. The upper limit is not particularly limited, but is preferably about 20 g / m 2 or less from an economic viewpoint.
電池缶の内面となる面には、前述の外面となる面と同じ構成をとることももちろん可能であり、また違う構成とすることも可能である。違う構成とする場合には、Ｆｅ−Ｎｉ拡散層、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層を有することが、耐食性、電池特性の点から望ましい。 Of course, the inner surface of the battery can may have the same configuration as the outer surface, or may have a different configuration. In the case of a different configuration, it is desirable from the viewpoint of corrosion resistance and battery characteristics to have an Fe—Ni diffusion layer, or an Fe—Ni diffusion layer and an Ni plating layer recrystallized and softened thereon.
以上の状態を得るためには、Ｎｉメッキ、拡散処理、光沢添加剤または半光沢添加剤含有Ｎｉメッキ、の順で処理し、圧延による粗度調整はこのいずれの工程間にあっても良い。以下では、Ｎｉメッキ、拡散処理、光沢添加剤または半光沢添加剤含有Ｎｉメッキ、圧延による粗度調整、の順で処理する場合を例として、その条件について各工程毎に以下説明する。 In order to obtain the above state, Ni plating, diffusion treatment, gloss additive or semi-gloss additive-containing Ni plating are processed in this order, and the roughness adjustment by rolling may be between these steps. In the following, the conditions will be described for each step as an example in the case of Ni plating, diffusion treatment, gloss additive or semi-gloss additive-containing Ni plating, and roughness adjustment by rolling.
（メッキ下地鋼板）下地鋼板はＮｉメッキを施すことができるものであれば特に限定はないが、電池ケース用に加工に供されることを考慮すると、極低炭素鋼にＴｉ，Ｎｂ等を単独または複合添加したものや、低炭素Ａｌキルド鋼やＢ添加低炭素鋼等が好ましい。また、冷間圧延後の未再結晶の鋼板でも、再結晶焼鈍後の鋼板でも更に調質圧延後の鋼板でも用いることが出来るが、本発明においてはＦｅ−Ｎｉ拡散層の存在が必須であるので、Ｎｉメッキ後に拡散処理と下地鋼板の再結晶焼鈍を同時に行うことが経済的観点から好ましい。この観点から、下地鋼板としては冷間圧延後の未再結晶の鋼板を用いるのが本発明における最も有利な実施形態である。 (Plating base steel plate) The base steel plate is not particularly limited as long as it can be Ni-plated, but considering that it is used for processing for battery cases, Ti, Nb, etc. are used alone in ultra-low carbon steel. Alternatively, composite additions, low carbon Al killed steel, B-added low carbon steel, and the like are preferable. In addition, although it can be used for a non-recrystallized steel sheet after cold rolling, a steel sheet after recrystallization annealing, or a steel sheet after temper rolling, the presence of a Fe-Ni diffusion layer is essential in the present invention. Therefore, it is preferable from an economical viewpoint that the diffusion treatment and the recrystallization annealing of the base steel sheet are simultaneously performed after the Ni plating. From this viewpoint, the most advantageous embodiment of the present invention is to use a non-recrystallized steel sheet after cold rolling as the base steel sheet.
（メッキ前処理）Ｎｉメッキを施すための前処理であれば、何ら限定はなく、通常の処理（脱脂、酸洗等）を行えばよい。 (Pre-plating treatment) There is no limitation as long as it is a pre-treatment for performing Ni plating, and normal treatment (degreasing, pickling, etc.) may be performed.
（Ｎｉメッキ）Ｎｉメッキは、無光沢Ｎｉメッキ浴を用いることが耐食性の観点から望ましい。具体的には、ｗａｔｔ浴を例示できる。Ｎｉメッキの付着量は、外面になる面、内面になる面で同一でもよいし、差厚でもよい。 (Ni plating) For Ni plating, it is desirable to use a matte Ni plating bath from the viewpoint of corrosion resistance. Specifically, a watt bath can be illustrated. The adhesion amount of the Ni plating may be the same on the outer surface or the inner surface, or may be a differential thickness.
（熱拡散処理）不活性ガスまたは還元性のガス雰囲気中で熱処理して、Ｆｅ−Ｎｉ拡散層を形成する。具体的には、７００〜８５０℃程度の温度で均熱時間２０〜６０ｓｅｃ程度の処理を行う。この際、Ｎｉメッキ量が１０ｇ／ｍ2程度以上であれば、条件にもよるが、Ｆｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層が形成される。本発明においては、少なくとも缶外面になる面には、Ｆｅ−Ｎｉ拡散層が必須で、その上層に再結晶軟質化されたＮｉ層が存在することは耐かじり性の点で好ましくないため、熱処理条件を調整する必要がある。なお、下地鋼板として未再結晶鋼板を使用している時は、ここでの熱処理を鋼板の再結晶温度以上とすることで熱拡散処理と鋼板の再結晶焼鈍を同時に行うことができる。 (Thermal diffusion treatment) Heat treatment is performed in an inert gas or reducing gas atmosphere to form an Fe—Ni diffusion layer. Specifically, the treatment is performed at a temperature of about 700 to 850 ° C. for a soaking time of about 20 to 60 seconds. At this time, if the Ni plating amount is about 10 g / m 2 or more, although depending on conditions, an Fe—Ni diffusion layer and a recrystallized Ni plating layer formed thereon are formed. In the present invention, an Fe-Ni diffusion layer is indispensable at least on the outer surface of the can, and the presence of a recrystallized and softened Ni layer on the upper layer is not preferable in terms of galling resistance. It is necessary to adjust the conditions. In addition, when the non-recrystallized steel plate is used as the base steel plate, the heat diffusion treatment and the recrystallization annealing of the steel plate can be performed at the same time by setting the heat treatment here to the recrystallization temperature or higher of the steel plate.
（光沢添加剤または半光沢添加剤含有Ｎｉメッキ）本メッキに先だって、通常の前処理（脱脂、酸洗等）を必要に応じて行う。光沢添加剤または半光沢添加剤含有Ｎｉメッキは、通常のＮｉメッキ浴、例えばｗａｔｔ浴に市販の光沢添加剤または半光沢添加剤を含有させた浴で処理する。本メッキは必要とする面にのみ通電して形成すれば良い。 (Gloss Additive or Semi-Gloss Additive-Containing Ni Plating) Prior to the main plating, normal pretreatment (degreasing, pickling, etc.) is performed as necessary. The bright additive or semi-bright additive-containing Ni plating is processed in a conventional Ni plating bath, for example, a bath containing a commercially available bright additive or semi-bright additive. The plating may be formed by energizing only the necessary surface.
（調質圧延）圧延によって表面粗度を調整する。最終製品の表面粗度ＲａおよびＲｍａｘが所定の値になるように、適度な粗さのロールを用いて行えば良い。表裏等粗度であっても、異粗度であってもよく、用途に応じてロールの粗度を調整して圧延することができる。 (Temperature rolling) The surface roughness is adjusted by rolling. What is necessary is just to perform using the roll of moderate roughness so that surface roughness Ra and Rmax of a final product may become predetermined value. Roughness such as front and back surfaces or different roughness may be used, and rolling can be performed by adjusting the roughness of the roll according to the application.
以下に実施例によって本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail by way of examples.
（実施例１〜６）ならびに（比較例１〜５）を示す。 (Examples 1-6) and (Comparative Examples 1-5) are shown.
板厚０．２５ｍｍのＮｂ−Ｔｉ−Ｓｕｌｃ鋼（未再結晶鋼板）を原板とし、無光沢Ｎｉメッキ→拡散処理→半光沢添加剤含有Ｎｉメッキ→調質圧延の手順でサンプルを製造した。無光Ｎｉメッキは、無光沢ワット浴（硫酸ニッケル：３５０ｇ／リットル＋塩化ニッケル：７０ｇ／リットル＋ホウ酸：４５ｇ／リットル）によって行った。拡散処理は、連続焼鈍炉にて無酸化条件で８００℃均熱４０ｓｅｃの条件で行った（この条件を表１中「ｓｔｄ」と表記）。拡散処理後のＮｉメッキ層の状態をＧＤＳおよび断面観察により観察し、表１中に示した（「Ａ」はＦｅ−Ｎｉ拡散層を、「Ｂ」はＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化したＮｉメッキ層が存在する状態であることを示す）。半光沢添加剤含有Ｎｉメッキは、先の無光沢ワット浴（硫酸ニッケル：３５０ｇ／リットル＋塩化ニッケル：７０ｇ／リットル＋ホウ酸：４５ｇ／リットル）に市販のアセチレン系半光沢添加剤を添加した浴で行った。なお、半光沢添加剤入Ｎｉメッキに先だって、５％ＮａＯＨによる脱脂処理、つづけて５％硫酸水溶液により表面活性化処理を行った。調質圧延は、２スタンド圧延機にて、各種粗度のロールを用い、ドライ圧延した。なお、無光沢Ｎｉメッキ、半光沢添加剤入Ｎｉメッキそれぞれの付着量は表１に示すとおりである。また最終製品の表面粗度ＲａおよびＲｍａｘも表１に示すとおりである。 A sample was manufactured in the order of matte Ni plating → diffusion treatment → semi-gloss additive-containing Ni plating → temper rolling using Nb—Ti—Sulc steel (non-recrystallized steel plate) having a thickness of 0.25 mm as an original plate. Non-light Ni plating was performed by a matte Watt bath (nickel sulfate: 350 g / liter + nickel chloride: 70 g / liter + boric acid: 45 g / liter). The diffusion treatment was performed in a continuous annealing furnace under non-oxidizing conditions and at 800 ° C. soaking for 40 seconds (this condition is expressed as “std” in Table 1). The state of the Ni plating layer after the diffusion treatment was observed by GDS and cross-sectional observation, and are shown in Table 1 (“A” represents the Fe—Ni diffusion layer, “B” represents the Fe—Ni diffusion layer and its upper layer). This indicates that there is a Ni-plated layer softened in crystal). Semi-gloss additive-containing Ni plating is a bath obtained by adding a commercially available acetylenic semi-gloss additive to the previous matte watt bath (nickel sulfate: 350 g / liter + nickel chloride: 70 g / liter + boric acid: 45 g / liter). I went there. Prior to Ni plating with a semi-gloss additive, a degreasing treatment with 5% NaOH was performed, followed by a surface activation treatment with a 5% sulfuric acid aqueous solution. The temper rolling was dry-rolled using a roll having various roughnesses in a two-stand rolling mill. In addition, the adhesion amounts of the matte Ni plating and the semi-gloss additive-added Ni plating are as shown in Table 1. Table 1 also shows the surface roughness Ra and Rmax of the final product.
（実施例７）
半光沢添加剤含有Ｎｉメッキに替わり、光沢添加剤入Ｎｉメッキを行う以外は、先の例と同一に処理した。光沢添加剤含有Ｎｉメッキは、無光沢ワット浴（硫酸ニッケル：３５０ｇ／リットル＋塩化ニッケル：７０ｇ／リットル＋ホウ酸：４５ ｇ／リットル）に市販の含窒素系光沢添加剤を添加した浴で行った。無光沢Ｎｉメッキ、光沢添加剤入Ｎｉメッキそれぞれの付着量は表１に示すとおりである。
(Example 7)
Instead of the semi-gloss additive-containing Ni plating, the same treatment as in the previous example was performed except that Ni plating with gloss additive was performed. Gloss additive-containing Ni plating is performed in a bath obtained by adding a commercially available nitrogen-containing gloss additive to a matte watt bath (nickel sulfate: 350 g / liter + nickel chloride: 70 g / liter + boric acid: 45 g / liter). It was. Table 1 shows the adhesion amounts of the matte Ni plating and the Ni plating with gloss additive.
（比較例６）
板厚０．２５ｍｍのＮｂ−Ｔｉ−Ｓｕｌｃ鋼（再結晶鋼板）を原板とし、５％ＮａＯＨ水溶液による脱脂処理および５％硫酸水溶液による表面活性化処理を行った後、光沢添加剤入Ｎiメッキを行い、更に調質圧延を行った。光沢添加剤入Ｎiメッキは先の実施例７と同様に行った。調質圧延は、先の例（実施例１〜６および比較例１〜３）と同一に行った。
(Comparative Example 6)
Nb-Ti-Sulc steel (recrystallized steel plate) with a thickness of 0.25 mm is used as a base plate, and after degreasing with 5% NaOH aqueous solution and surface activation treatment with 5% sulfuric acid aqueous solution, Ni plating with gloss additive is applied. Then, temper rolling was performed. The bright additive-added Ni plating was performed in the same manner as in Example 7. The temper rolling was performed in the same manner as the previous examples (Examples 1 to 6 and Comparative Examples 1 to 3).
（性能評価方法）
耐かじり性；幅３０ｍｍ長さ３００ｍｍの試験片に防錆油（ノックスラスト５３０）を塗油し、ＳＫＤ１１平面金型で荷重１トンにて圧着し、２００ｍｍ／ｍｉｎの速度で引きぬいた。５本連続で行い、５本面の表面（外面になる面）を目視およびＳＥＭ拡大（×１０００）観察によりヘアライン状のかじり痕有無を観察した。かじり無を「○」、極軽微なかじりありを「△」、かじりありを「×」と評価した。
(Performance evaluation method)
Anti-galling property: A test piece having a width of 30 mm and a length of 300 mm was coated with rust-preventing oil (Knox Last 530), crimped with a SKD11 flat mold at a load of 1 ton, and pulled at a speed of 200 mm / min. Five lines were continuously formed, and the presence or absence of galling traces in a hairline shape was observed by visual observation and SEM enlargement (× 1000) observation on the surface of the five surfaces (surface to be the outer surface). No galling was evaluated as “◯”, very slight galling was evaluated as “△”, and galling was evaluated as “×”.
耐食性；鋼板サンプルをプレス加工し、通常のＬＲ０６型アルカリマンガン電池用の缶を製造し、正極端子部外面を上に向けて、塩水噴霧試験（ＪＩＳ−Ｚ−２３７１）を３時間行い、赤錆発生状況を目視観察した。錆皆無を「○」、極軽微な錆（点状錆が５個まで）ありを「△」、錆ありを「×」と評価した。 Corrosion resistance: Pressed steel plate samples to produce cans for ordinary LR06 type alkaline manganese batteries, and the salt spray test (JIS-Z-2371) was conducted for 3 hours with the positive electrode terminal outer surface facing upward, generating red rust The situation was visually observed. No rust was evaluated as “◯”, extremely light rust (up to 5 spot-like rust) was evaluated as “△”, and rust was evaluated as “×”.
接触抵抗；鋼板サンプルをプレス加工し、通常のＬＲ０６型アルカリマンガン電池用の缶を製造し、６０℃９５％ＲＨに２０日間放置した後、山崎精機研究所製電気接点シュミレータＣＲＳ−１を用い、荷重１００ｇにて正極端子部外面の接触抵抗を測定した。１０ｍΩ未満を「○」、１０ｍΩ以上２０ｍΩ未満を「△」、２０ｍΩ以上を「×」と評価した。以上の評価結果を表１に示す。表１に示すように、本発明の実施例では良好な耐かじり性、耐食性、接触抵抗が得られた。
Contact resistance: A steel plate sample was pressed, a can for an ordinary LR06 type alkaline manganese battery was produced, and left at 60 ° C. and 95% RH for 20 days, and then an electrical contact simulator CRS-1 manufactured by Yamazaki Seiki Laboratories was used. The contact resistance of the positive electrode terminal part outer surface was measured with a load of 100 g. Less than 10 mΩ was evaluated as “◯”, 10 mΩ or more and less than 20 mΩ was evaluated as “Δ”, and 20 mΩ or more was evaluated as “×”. The above evaluation results are shown in Table 1. As shown in Table 1, good galling resistance, corrosion resistance, and contact resistance were obtained in the examples of the present invention.
本発明の電池缶用Ｎｉメッキ鋼板は、耐かじり性、耐食性、および接触抵抗に優れ、電池缶の外観、耐食性、電池特性、を改善しうるものであるから、一次電池、二次電池等の電池缶に用いることができる。 Since the Ni-plated steel sheet for battery cans of the present invention is excellent in galling resistance, corrosion resistance, and contact resistance, and can improve the appearance, corrosion resistance, and battery characteristics of battery cans, such as primary batteries and secondary batteries. It can be used for battery cans.
Claims (3)
上記Ｆｅ−Ｎｉ拡散層の付着量は、Ｎｉとして５〜４５ｇ／ｍ ２ であり、
上記光沢添加剤または半光沢添加剤含有Ｎｉメッキ層の付着量が、０．５〜２０ｇ／ｍ 2 であることを特徴とする電池缶用Ｎｉメッキ鋼板。 It has a Fe-Ni diffusion layer on the surface corresponding to the outer surface of the battery can, and further has a gloss additive or semi-bright additive-containing Ni plating layer on its upper surface, and its surface roughness Ra is 0.1 μm or more and 1 μm or less. And Rmax is 1 μm or more and 10 μm or less ,
The adhesion amount of the Fe—Ni diffusion layer is 5 to 45 g / m 2 as Ni ,
Adhesion amount of the gloss additive or semi-gloss additive-containing Ni plating layer, Ni-plated steel sheet for a battery can, which is a 0.5 to 20 g / m 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20120130076A (en) | 2010-01-08 | 2012-11-28 | 도요 고한 가부시키가이샤 | Ni-plated steel sheet with excellent pressability for battery can |
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| JP4818755B2 (en) * | 2006-03-02 | 2011-11-16 | 新日本製鐵株式会社 | Steel plate for welding can |
| JP4612573B2 (en) * | 2006-03-24 | 2011-01-12 | 新日本製鐵株式会社 | Method for producing multilayer Ni diffusion plated steel sheet |
| JP5102977B2 (en) * | 2006-05-31 | 2012-12-19 | Ｆｄｋエナジー株式会社 | Plated steel plate for battery cans, battery cans, batteries, alkaline batteries |
| JP2008041527A (en) * | 2006-08-09 | 2008-02-21 | Matsushita Electric Ind Co Ltd | Battery can, and battery using it |
| JP5108356B2 (en) * | 2007-03-30 | 2012-12-26 | Ｆｄｋエナジー株式会社 | Metal parts for batteries, manufacturing method thereof, batteries |
| JP4995140B2 (en) * | 2008-04-25 | 2012-08-08 | 新日本製鐵株式会社 | Ni-plated steel sheet for containers, container manufactured thereby, and method for manufacturing the same |
| US8734961B2 (en) | 2009-06-09 | 2014-05-27 | Toyo Kohan Co., Ltd. | Nickel-plated steel sheet and process for producing battery can using the nickel-plated steel sheet |
| US8795846B2 (en) | 2009-08-26 | 2014-08-05 | Toyo Kohan Co., Ltd. | Ni-plated steel sheet for battery can having excellent press formability |
| CN102822387B (en) | 2010-03-25 | 2014-12-31 | 新日铁住金株式会社 | Steel sheet for vessel having excellent corrosion resistance |
| EP2607522B1 (en) | 2010-08-18 | 2016-10-26 | Nippon Steel & Sumitomo Metal Corporation | Steel sheet for can with excellent corrosion resistance |
| JP5593167B2 (en) * | 2010-08-26 | 2014-09-17 | Ｆｄｋエナジー株式会社 | Alkaline battery |
| TWI451005B (en) * | 2011-04-07 | 2014-09-01 | Nippon Steel & Sumitomo Metal Corp | Ni containing surface treated steel sheet for can and producing method thereof |
| TWI488980B (en) | 2012-10-15 | 2015-06-21 | Nippon Steel & Sumitomo Metal Corp | Steel sheet for container and manufacturing method thereof |
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