JPS5912756B2 - Highly corrosion resistant dissimilar multi-layer plated steel sheet for can manufacturing - Google Patents

Description

【発明の詳細な説明】 本発明は製缶用素材としての塗装耐食性、缶胴接合性、
特にシーム溶接性及び２ピース缶成形性に優れた低コス
トの製缶用表面処理鋼板に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides coating corrosion resistance, can body bondability,
In particular, the present invention relates to a low-cost surface-treated steel sheet for making cans that has excellent seam weldability and two-piece can formability.

製缶用表面処理鋼板としては、一般に電気銅メッキ（以
下ブリキと称す）と電解クロム酸処理鋼板（以下ＴＦＳ
−ＣＴと称す）が知られている。Surface-treated steel sheets for can manufacturing generally include electrolytic copper plated (hereinafter referred to as tinplate) and electrolytic chromic acid treated steel sheets (hereinafter referred to as TFS).
-CT) is known.

このうちブリキは製缶用表面処理鋼板として最も一般的
なものであり最も広く用いられている。その用途として
はブリキを裸のまま又は塗装を施した後錫の耐食性を生
かして、魚肉、スープ、果実等いわゆる食缶として使用
するほか、コーラ等炭酸飲料缶、果実ジュース缶等いわ
ゆる飲料缶又は１８を缶、ペール缶等にも広く使用され
ている。０ そして製缶方法としても、いわゆる３ピー
ス缶のみでなく、特に飲料缶等に多い２ピース缶の製造
にも錫の固体潤滑性を生して使用されている。Among these, tinplate is the most common and most widely used surface-treated steel sheet for can manufacturing. It is used as food cans for fish meat, soups, fruits, etc., as well as so-called beverage cans such as carbonated drink cans such as cola, fruit juice cans, etc. by taking advantage of the corrosion resistance of tin after tin is bare or painted. 18 is also widely used for cans, pails, etc. 0 As a can manufacturing method, tin is used not only for so-called 3-piece cans, but also for the manufacture of 2-piece cans, which are particularly common in beverage cans, taking advantage of the solid lubricity of tin.

これに対してＴＦＳ−ＣＴは比較的腐食性の少ない飲料
缶に主として用いられ、その他１８を缶、ぺ５−ル缶等
にも用いられているが製造方法としては３ピース缶のみ
であり、２ピース缶の製造には使用されていない。これ
はＴＦＳ−ＣＴの金属クロム、クロム水和酸化物を主体
とする非金属クロム層（以下オキサイドクロム層と称す
）が硬質でもフ０ ろいため、２ピース缶加工がむずか
しく、又２ピース缶加工後の耐食性が大巾に低下するか
らである。そして３ピース缶においても、缶胴接合方法
としてはいわゆる接着法が主体であり、したがつてシー
ム溶接する場合は表面のクロム層を研削除２５去する必
要がありー般的ではない。前述したように、従来のブリ
キ、ＴＦＳ−ＣＴの通常の用途及びその製造方法はそれ
ぞれの長所を生かし、ブリキは長期安定して保存する必
要性が大きな用途に主として使用され、又その製缶方３
０法としては接着法による製缶を除く３ピース缶及び２
ピース缶に製造される。On the other hand, TFS-CT is mainly used for beverage cans, which are relatively less corrosive, and is also used for 18 cans, pail cans, etc., but the manufacturing method is only for 3-piece cans. It is not used in the production of two-piece cans. This is because the metallic chromium and non-metallic chromium layer (hereinafter referred to as oxide chromium layer) mainly composed of chromium hydrated oxide of TFS-CT is hard but fluid, making it difficult to process two-piece cans. This is because the subsequent corrosion resistance will be greatly reduced. Even in the case of three-piece cans, the so-called adhesive method is the main method for joining the can body, and therefore, when seam welding is performed, it is necessary to remove the chromium layer on the surface by grinding, which is not common. As mentioned above, the conventional uses of tinplate and TFS-CT and their manufacturing methods take advantage of their respective strengths, and tinplate is mainly used for applications that require stable storage over a long period of time. 3
0 method includes 3-piece cans and 2 cans excluding cans made by adhesive method.
Manufactured in piece cans.

一方、ＴＦＳ−ＣＴは主として短期的な保存の用途に、
又製缶方法は主に接着法による３ピース缶の製造に使用
されていることは既に周知の通り３５である。On the other hand, TFS-CT is mainly used for short-term storage.
It is already well known that the can manufacturing method is mainly used to manufacture three-piece cans by adhesion.

ところが最近錫の価格上昇にともない製缶コスト低減及
び資源保護の立場から、ブリキの錫薄メツキ化、そして
錫薄メツキ化にともなう耐食性の劣化を補うためにブリ
キの裸使用にかわり塗装使用・＼の転換が行われ、又従
来ブリキを使用してきた用途にＴＦＳ−ＣＴを使用する
場合も増加して来つつある。However, with the recent rise in the price of tin, from the perspective of reducing can manufacturing costs and conserving resources, tin plating has become thinner, and in order to compensate for the deterioration in corrosion resistance that comes with thinner tin plating, paint has been used instead of bare tin. The use of TFS-CT in applications where tinplate has traditionally been used is also increasing.

一方製缶方法としても２ピース缶の生産割合が増加し、
Ｐｂ規制等社会的要請から３ピース缶も従来のハンダに
よる缶胴接合方法からシーム溶接による方法・＼と変化
している。まずブリキの錫薄メッキ化であるが、現在実
用的には錫付着量が片面当り２．８ｔ／イ前後のものが
あり、この程度の錫付着量が２ピース缶成形における錫
の固体潤滑性を充分に発揮できる下限であると云われて
おり、３ピース缶にしても２ピース缶にしても、耐食性
を補うために３ピース缶の場合は製缶前に、又２ピース
缶は製缶後に塗装して使用する場合がほとんどである。
つぎにブリキのＴＦＳ−ＣＴ化であるが、もちろん周知
のように、ＴＦＳ−ＣＴはその使用に当つては全面塗装
されることが前提となり、用途としては果実ジユーズの
ように腐食性が大きなものや鉄イオンの溶出を極度にき
らうような内容物の場合の使用は好ましくない。On the other hand, the production rate of two-piece cans has increased as a can manufacturing method.
Due to social demands such as Pb regulations, 3-piece cans have also changed from the conventional method of joining can bodies using solder to seam welding. First of all, tin plating is thinly plated with tin.Currently, in practical use, the amount of tin adhesion is around 2.8t/a per side, and this amount of tin adhesion is sufficient for the solid lubricity of tin in two-piece can molding. It is said that this is the lower limit at which the cans can be sufficiently exhibited, and whether the can is a 3-piece can or a 2-piece can, in order to compensate for corrosion resistance, it is necessary to In most cases, it is painted and used afterwards.
Next is the conversion of tinplate to TFS-CT, but of course, as is well known, TFS-CT requires that the entire surface be coated before use, and is intended for highly corrosive materials such as fruit juices. It is not preferable to use it when the content is such that the elution of iron ions or iron ions is extremely difficult.

さらにＴＦＳ−ＣＴの製缶方法においては近年その消費
が増加している２ピース缶の生産が不可能となる等ブリ
キのＴＦＳ−ＣＴ化には問題が多い。従つて主として製
缶コストの低減のため、従来のブリキと同等以上の裸耐
食性、塗装耐食性、缶腸成形成、特にシーム溶接性及び
２ピース缶成形性に優れた低コストの製缶用表面処理鋼
板の開発が各方面から要請され、本発明者等はこれに応
え（て、これ等の品質要求を全て満足する全く新しい製
缶用表面処理鋼板の開発に成功し、製缶用異種重層メツ
キ鋼板の名称で先に特願昭５６−６１７６７号で出願を
行つた。Furthermore, there are many problems in converting tinplate to TFS-CT, such as the inability to produce two-piece cans, the consumption of which has been increasing in recent years, in the TFS-CT can manufacturing method. Therefore, mainly to reduce can manufacturing costs, we developed a low-cost surface treatment for can manufacturing that has corrosion resistance equivalent to or better than conventional tinplate, coating corrosion resistance, can forming, especially seam weldability, and two-piece can forming. The development of steel sheets has been requested from various quarters, and in response to these requests, the present inventors have succeeded in developing a completely new surface-treated steel sheet for can manufacturing that satisfies all of these quality requirements. An application was previously filed in Japanese Patent Application No. 56-61767 under the name of steel plate.

この先願発明の要旨とするところは、鋼板の表裏にまず
ニツケルメ Ｑツキを施したあと、一方のニツケルメツ
キ層の表面にのみ錫メツキを重層させ、更にクロム処理
層を両面に設けることにより、表裏異種メツキ層となし
たものであり、鋼板の表裏の性能の違いを利用すれば使
用する用途は広まり、表裏異種重層メ ４ツキという全
く新規なメツキ組成を持つた有用な新発明である。しか
るに、この出願では、ニツケル又は錫メツキ上にクロム
処理層を設ける訳であるが、このクロみ処理層の処理方
法及びクロム処理層の組成について特に限定していない
ために特に耐食性にバラツキを生じる欠点があつた。The gist of this prior invention is that after first applying nickel plating to the front and back sides of a steel plate, tin plating is overlaid only on the surface of one of the nickel plating layers, and a chromium treatment layer is further provided on both sides. This is a useful new invention that has a completely new plating composition of 4 different multi-layered platings, which can be used in a wide variety of applications by taking advantage of the difference in performance between the front and back sides of a steel plate. However, in this application, a chromium-treated layer is provided on nickel or tin plating, but there are no particular limitations on the treatment method for this chromium-treated layer or the composition of the chromium-treated layer, which results in variations in corrosion resistance. There were flaws.

本発明者等はこの耐食性のバラツキの原因について種々
研究を重ねた結果、クロム処理層を電解クロム処理に限
定すれば、耐食性はもとより塗装密着性をも更に向上す
ることができることを知見したものである。即ち、本発
明は前記した前出願の製缶用異種重層メツキの後処理層
として新たに電解クロム処理層を設け、さらに電解クロ
ム処理層の組成を、ト層から片面当り０．１〜２０７７
Ｖ／ｄの金属クロム層と、それぞれ片面当り金属クロム
換算で１〜１０７７Ｖ／ｗ？の結晶性クロム酸化物層と
非晶性クロム水和酸化物層を形成した全く新規な構成を
もつた高耐食性製缶用異種重層メツキ鋼板である。今、
本発明の新表面処理鋼板の皮膜構造を模式的に図示する
と図面のようになる。As a result of various studies on the causes of this variation in corrosion resistance, the inventors of the present invention have found that if the chromium treatment layer is limited to electrolytic chromium treatment, not only corrosion resistance but also paint adhesion can be further improved. be. That is, the present invention provides a new electrolytic chromium-treated layer as a post-treatment layer for the dissimilar multi-layer plating for can manufacturing of the previous application, and further changes the composition of the electrolytic chromium-treated layer from 0.1 to 2077 per side from the first layer.
V/d metal chromium layer and 1 to 1077 V/w in terms of metal chromium per side, respectively? This is a highly corrosion-resistant dissimilar multi-layer galvanized steel sheet for can manufacturing, which has a completely new structure in which a crystalline chromium oxide layer and an amorphous chromium hydrated oxide layer are formed. now,
The film structure of the new surface-treated steel sheet of the present invention is schematically illustrated as shown in the drawing.

図中１はメツキ素材となる冷延鋼板、２はニツケルメツ
キ層でメツキ方法は特に限定せず、電気メッキ、化学メ
ツキ等が用いられる。In the figure, reference numeral 1 indicates a cold-rolled steel plate serving as a plating material, and reference numeral 2 indicates a nickel plating layer.The plating method is not particularly limited, and electroplating, chemical plating, etc. may be used.

３は錫メツキ層でこれもメツキ方法は特に限定せず、電
気メッキ、化学メツキどちらでも良いが、電気メツキ法
が経済的である。3 is a tin plating layer, and the plating method for this layer is not particularly limited either, and either electroplating or chemical plating may be used, but the electroplating method is economical.

４，５，６はそれぞれ１回又は数回の電解クロム処理に
よつて得られる金属クロム層、結晶性クロム酸化物層、
非晶性クロム水和酸化物層であり、形成方法は３層同時
に行つても良いし、別々に行つても良い。4, 5, and 6 are metallic chromium layers, crystalline chromium oxide layers, and crystalline chromium oxide layers obtained by electrolytic chromium treatment once or several times, respectively.
These are amorphous chromium hydrated oxide layers, and the formation method for the three layers may be performed simultaneously or separately.

６はブリキ、ＴＦＳ−ＣＴ表面に通常形成される油膜層
である。6 is an oil film layer normally formed on the surface of tinplate, TFS-CT.

なお、第１図では鋼板の上面側に錫メツキ層３があり、
その下側−には錫メツキ層が無いメツキ組成を示したも
のであるが、鋼板の上下面即ち表裏いずれに錫メツキ層
があつてもよい。次に本発明の限定理由を説明する。In addition, in Fig. 1, there is a tin plating layer 3 on the upper surface side of the steel plate.
Although a plating composition is shown in which there is no tin plating layer on the lower side, there may be a tin plating layer on the top and bottom surfaces of the steel plate, that is, on either the front or back sides. Next, the reasons for the limitations of the present invention will be explained.

まず通常の方法で表面清浄化した鋼板両面にニツケルメ
ツキをする際、ニツケルメツキ層の厚みは片面当り１０
ワ／ｗ？以上を要する。これはニツケノしメツキ厚みが
１０ｎｉ／Ｒｉ？に満たないと上層の錫メツキ又は塗膜
の欠陥部を補えないため耐食性の劣化につながる。ニツ
ケルメツキ層の上限を片面当り５０００７７Ｖ／ｄと限
定したのは片面当り５０００巧／Ｒｉ？以上となるとコ
スト的に不利となるばかりか、缶胴接合法としてシーム
溶接性を採用する際のシーム溶接性の劣化につながるの
で、片面当り１０ｍｆ／７ｒ１′から５０００７７？／
ｄの範囲に限定したものであるが、ニツケルメツキ法と
して電気メツキ法を採用する場合は当然ニツケルメツキ
として鋼板の表裏の差厚メツキを行うことも本発明の範
囲に含まれる。次に錫メツキ層を前記ニツケルメツキ層
の片面のみに上乗せする際片面当り５０〜１１０００〜
／信に限定した理由は錫メツキ量が５０巧／ｄ以下では
耐食性向上にほとんど寄与せず、又次工程であるリフロ
ー工程又は製缶時の塗料焼付工程で錫がほとんどニツケ
ル又は合金化し表面色調を悪くすることから５０巧／Ｒ
ｒｉ′以上必要であり、又１１０００１／７ｒ？以上で
はコスト的に不利になることから錫メツキ量は５０７Ｖ
／ｄ〜１１０００巧／Ｒｒｉ′に限定される。First, when applying nickel plating to both sides of a steel plate whose surface has been surface-cleaned using the usual method, the thickness of the nickel plating layer is 10 mm per side.
Wa/w? The above is required. Is this Nitsukeno's thickness 10ni/Ri? If it is less than that, it will not be possible to compensate for defects in the upper tin plating or coating, leading to deterioration in corrosion resistance. The reason why the upper limit of the Nickel Mekki layer was limited to 500077V/d per side was 5000V/Ri per side? If it is more than that, it will not only be disadvantageous in terms of cost, but also lead to deterioration of seam weldability when seam weldability is adopted as the can body joining method. /
Although it is limited to the range of d, when an electroplating method is adopted as the nickel plating method, it is also within the scope of the present invention to perform differential thickness plating on the front and back of the steel plate as the nickel plating method. Next, when a tin plating layer is placed on only one side of the nickel plating layer, it is 50 to 11,000 per side.
The reason why the tin plating amount is less than 50 T/d hardly contributes to improvement of corrosion resistance, and in the next process, reflow process or paint baking process during can manufacturing, most of the tin becomes nickel or alloy, and the surface color changes. 50 Takumi/R from making things worse.
ri' or more is required, and 110001/7r? The amount of tin plating is 507V because the above is disadvantageous in terms of cost.
/d~11000/Rri'.

次に本発明の特徴の第１点である錫メツキを鋼板の両面
にメツキせず片面のみに限定した理由は、単に錫量削減
という経済的なものだけではなく、ニツケルメツキ単層
、及び錫一ニツケル２層それぞれの特徴を製缶材料とし
て有効に利用するという点にある。Next, the reason why tin plating, which is the first feature of the present invention, is limited to only one side of the steel plate instead of plating both sides is not only for the economical reason of reducing the amount of tin, but also for the single layer of nickel plating and the single layer of tin plating. The point is that the characteristics of each of the two layers of nickel are effectively utilized as a can-making material.

すなわちその主眼は缶の種類に応じた要求性能、すなわ
ちニツケル単独層では得られない錫層を重層したために
得る長所、具体的に云えは錫自身持つている絞り性及び
耐食性に優れている点と錫−ニツケルの２層となした結
果得られる無塗装の耐食性、塗装性及び塗装後の耐食性
の良い点にある。次に本発明の特徴の第２点である両面
に施す電解クロム被覆層の構造を下層から順に片面当り
０．１〜２０巧／ｄの金属クロム層とそれぞれ片面当り
金属クロム換算で１〜１０巧／ｄの結晶性クロム酸化物
層と非晶性クロム水和酸化物層の３層構造となした理由
は、金属クロム層−が０．１ｍｑ／Ｒｒ？以下では、メ
ツキ層のピンホールのシーリング効果が少なく、又製缶
用塗料を塗装後使用する場合塗料密着性が劣ることから
０．１巧／Ｒｉ？′以上必要であり、又２０７ｒ！Ｆｉ
／ｄ以上ではシーム溶接性及びハンダ性等劣化すること
から２０巧／ｄ以下に限定される。In other words, the main focus is on the required performance depending on the type of can, that is, the advantages obtained by layering a tin layer that cannot be obtained with a single layer of nickel, specifically the excellent drawability and corrosion resistance that tin itself has. The two layers of tin and nickel provide good corrosion resistance without painting, paintability, and corrosion resistance after painting. Next, the structure of the electrolytic chromium coating layer applied to both sides, which is the second feature of the present invention, is as follows: Starting from the bottom layer, the metal chromium layer has a thickness of 0.1 to 20 per d/d, and the metal chromium layer has a thickness of 1 to 10 per d in terms of metal chromium per side. The reason for the three-layer structure of a crystalline chromium oxide layer and an amorphous chromium hydrated oxide layer is that the metal chromium layer is 0.1 mq/Rr? Below, the sealing effect of the pinholes in the plating layer is small, and if the paint for can making is used after painting, the paint adhesion is poor, so 0.1 Taku/Ri? ' or more is required, and 207r! Fi
If it exceeds /d, seam weldability and solderability deteriorate, so it is limited to 20/d or less.

又、結晶性クロム酸化物及び非晶性クロム水和酸化物は
同様に１巧／ｄ以下では耐食性、塗膜密着性が劣化し、
１０巧／ｄ以上ではシーム溶接性、ハンダ性等が劣化す
ることから、それぞれ片面当り１巧／Ｒｒｉ″〜１０７
７ＺＶ／ｄの範囲に限定される。なお、後処理である電
解タロム処理層の形成方法は通常無水クロム酸を主剤と
し、ＳＯ４及びＨＳを助剤とした電解液中で、すでにニ
ツケル（両面）及ひ錫（片面）メツキ処理を終つた鋼板
を陰極として電解することにより、同時に前記３種のク
ロム層を形成させても良いし、最初に金属クロム層を電
解メツキしさらに該金属クロム層上に２回目の電解処理
により結晶性クロム酸化物と非晶性クロム水和酸化物層
を設けることも出来る。In addition, when crystalline chromium oxide and amorphous chromium hydrate oxide are less than 1/d, corrosion resistance and coating adhesion deteriorate.
If the seam weldability, solderability, etc. are deteriorated if the seam weldability and solderability are higher than 10 taku/d, the seam weldability, solderability, etc. will be deteriorated.
Limited to a range of 7ZV/d. In addition, the method of forming the electrolytic tarom treatment layer, which is a post-treatment, is usually carried out in an electrolytic solution containing chromic anhydride as the main ingredient and SO4 and HS as auxiliary agents. The above three types of chromium layers may be simultaneously formed by electrolyzing a steel plate as a cathode, or the metal chromium layer may be electrolytically plated first, and then crystalline chromium may be formed on the metal chromium layer by a second electrolytic treatment. Oxide and amorphous chromium hydrated oxide layers can also be provided.

要するに電解処理により下層から順に金属クロム層、結
晶性クロム酸化物層、非晶性クロム水和酸化物層の順に
形成出来れば良く、特に電解処理法についての限定は行
わない。なお、本発明と同種の電解クロム処理層である
金属クロム層、結晶性クロム酸化物層及び非晶性クロム
水和酸化物層を有したものが、例えば特公昭５２−３２
６２０号公報に記載されている。In short, the electrolytic treatment method is not particularly limited as long as it can form a metal chromium layer, a crystalline chromium oxide layer, and an amorphous chromium hydrated oxide layer in this order from the bottom layer by electrolytic treatment. Note that a layer having a metal chromium layer, a crystalline chromium oxide layer, and an amorphous chromium hydrated oxide layer, which are electrolytic chromium treatment layers of the same type as the present invention, is disclosed in, for example, Japanese Patent Publication No. 52-32.
It is described in Publication No. 620.

しかしながらこの公報の表面被覆鋼板の基体鋼板はメツ
キ処理されていない鉄板であり、この鉄面上にクロムメ
ツキされるものでいわゆる錫なし鋼板の分野で使われる
材料であり、本発明のようにニツケル一錫の異種重層メ
ツキ上にクロムメツキされるものとはそのメツキ組成を
異にし、第２表従来例２ＴＦＳ−ＣＴの例に示す如く、
耐食性及びシーム溶接性の点でもはるかに優れたもので
、その目的及び構成効果とも全く異つた新規な表面処理
鋼板である。本発明の新表面処理鋼板の耐食性が良好で
あることを示すため、従来ブリキの耐食性評価値として
一般に用いられているＡＴＣ値、ＩＳＶ値の測定結果を
説明する。However, the base steel plate of the surface-coated steel plate in this publication is an unplated iron plate, and the steel surface is plated with chrome, which is a material used in the field of so-called tin-free steel plates. The plating composition is different from that in which chrome plating is applied on top of a multilayer plating of different types of tin, as shown in the example of Conventional Example 2TFS-CT in Table 2.
It is a new surface-treated steel sheet that has far superior corrosion resistance and seam weldability, and has a completely different purpose and structural effect. In order to show that the new surface-treated steel sheet of the present invention has good corrosion resistance, the measurement results of ATC value and ISV value, which are conventionally used as evaluation values for corrosion resistance of tinplate, will be explained.

ＡＴＣ値、ＩＳ値ともＳｎ−Ｎｉ重層面について通常の
方法で測定した結果で第１表に示す。比較として従来の
ブリキ＃２５（片面Ｓｎ付着量２．７７／ｄ）、＃１０
０（片面Ｓｎ付着量１１７／７ｒｉ′）の測定結果を合
せて示す。注）１）ＡＴＣ試験 ＡＴＣ試験（ＡｌｌＯｙ−ＴｉｎＣＯｕｐｌｅＴｅｓｔ
）は酸性缶詰の耐食性を評価する有効な試験で、ジユー
ズ中で合金層と錫を連結しその間に流れる微弱な電流を
ＡＴＣ電流として測定するもの。Both the ATC value and the IS value were measured on the Sn--Ni multilayer surface using a conventional method, and are shown in Table 1. For comparison, conventional tin plate #25 (Sn adhesion amount on one side 2.77/d) and #10
0 (one-sided Sn adhesion amount 117/7ri') is also shown. Note) 1) ATC test ATC test (AllOy-TinCOupleTest
) is an effective test for evaluating the corrosion resistance of acidic canned goods. It connects an alloy layer and tin in a juice box and measures the weak current flowing between them as the ATC current.

２）ＩＳＶ試験 鉄溶出試験（ＲＯｎＳＯｌｕｔｉＯｎＴｅｓｔ）は、ブ
リキの耐食試験の一つで腐食液にある濃度の硫酸を用い
錫が鋼よりわずかに陽極的であるような状態で試験する
。2) ISV test The iron leaching test (ROnSOlutiOnTest) is one of the corrosion resistance tests for tinplate, and is tested using sulfuric acid at a certain concentration in the corrosive liquid under conditions such that tin is slightly more anodic than steel.

第１表に示すように、本発明例は従来例と比較しＡＴＣ
，ＩＳ各試験値共に良好である。As shown in Table 1, the example of the present invention has a higher ATC than the conventional example.
, IS test values are both good.

さらに本発明の特徴の第２点である電解クロム被覆層を
金属クロム層、結晶性クロム酸化物層及び非晶性クロム
水和酸化物層の３層構造としたことによつて、従来ブリ
キにおいて通常行われている重クロム酸ソーダ中におけ
る陰極電解処理によつて得られるクロメート処理層では
裸の耐食性、塗装耐食性及び塗料密着性等が不十分であ
つた点を改めて、各特性を著しく向上させることが可能
となり、本発明の特徴あるメツキ被覆系、すなわち片面
にニツケル単層、片面にニツ，ゲル一錫重層というメツ
キ被覆系を設けたことと相まつて、従来得られなかつた
高性能を得ることができるものである。Furthermore, the electrolytic chromium coating layer, which is the second feature of the present invention, has a three-layer structure of a metal chromium layer, a crystalline chromium oxide layer, and an amorphous chromium hydrated oxide layer. The conventional chromate treatment layer obtained by cathodic electrolysis in sodium dichromate was insufficient in bare corrosion resistance, paint corrosion resistance, paint adhesion, etc., and now each property has been significantly improved. This, together with the unique plating system of the present invention, that is, a single layer of nickel on one side and a multilayer of nickel and gel on the other side, allows us to achieve high performance that was previously unobtainable. It is something that can be done.

以上に本発明の具体的実施例について述べる。Specific embodiments of the present invention will be described above.

実施例通常の方法で冷延鋼板に脱脂、酸洗を行い、（１
）に示す条件で鋼板両面に電気ニツケルメツキを行い、
次に（２）に示す条件で鋼板片面のみに電気錫メツキを
行つたのち（３），（４）に示す条件で鋼板両面に電解
クロムメツキ処理を行い、次に通常の方法でＤＯＳの油
膜を形成した。Example A cold-rolled steel plate was degreased and pickled in the usual manner.
) Electric nickel plating was applied to both sides of the steel plate under the conditions shown in
Next, electrolytic tin plating is applied to only one side of the steel plate under the conditions shown in (2), then electrolytic chrome plating is applied to both sides of the steel plate under the conditions shown in (3) and (4), and then the DOS oil film is removed using the usual method. Formed.

で処理するという２回処理法。This is a two-step processing method.

なお本発明例の比較として片面当り錫付着量２７００〜
／Ｒｉ？，クロメート被覆量（浸漬法）１５７７？／信
（金属クロム換算）のブリキ（以下＃２５ブリキと称す
）及び片面当り金属クロム量１００７Ｖ／Ｄ，クロム酸
化物量１２７Ｖ／ｄ（金属クロム換算）のＴＦＳ−ＣＴ
を使用した。In addition, as a comparison with the present invention example, the amount of tin deposited per one side is 2700 ~
/Ri? , Chromate coverage (immersion method) 1577? / TFS-CT (hereinafter referred to as #25 tinplate) with a metal chromium content of 1007 V/D and a chromium oxide content of 127 V/d (metal chromium equivalent) per side.
It was used.

以上述べた条件にて本発明例、比較例及び従来例を以下
に示すような各種試験に供し、その性能を評価した。Examples of the present invention, comparative examples, and conventional examples were subjected to various tests as shown below under the conditions described above, and their performances were evaluated.

（Ａ） ＵＣＣ（ア゛ンダーカツトフイルムコロージヨ
ン）テストエポキシフエノール塗料をＳｎ／Ｎｉ重層被
覆側に４５Ｔ１１９／Ｄｍ２塗布し、２０５℃ＸｌＯ分
の焼付、さらに１８０℃ＸｌＯ分の追加焼付を行い塗装
した面にナイフスクラツチを入れた後、腐食液（１．５
％クエン酸−１．５％食塩等の混合液、ＣＯ２ガス飽和
）中に浸漬し、５０℃で３日間保定した後、スクラツチ
部をテープ剥離してスクラツチ周辺部の腐食状態を判定
した。(A) UCC (Under Cut Film Corrosion) Test Epoxy phenol paint was applied to the Sn/Ni multilayer coated side with 45T119/Dm2, baked at 205°C for XlO, and additionally baked at 180°C for XlO. After making a knife scratch on the surface, apply a caustic solution (1.5
% citric acid - 1.5% common salt, etc., saturated with CO2 gas) and maintained at 50° C. for 3 days, the scratched portion was peeled off with tape and the state of corrosion around the scratched portion was determined.

なお比較例、従来例共上記と全く同じ条件でテストした
。Note that both the comparative example and the conventional example were tested under exactly the same conditions as above.

８腐食液浸漬テスト 囚と同一条件でエポキシフエノール塗料をＳｎ／Ｎｉ重
層被覆側に塗装した塗装板に、エリクセン試験機で４ｗ
ｆｔの押し出し加工したものと曲げＲ２ｗｎに折り曲げ
た後１ｋ９Ｘ５０ｃｍの衝撃加工を加えたものの２種の
サンプルを（イ）脱気した６と同じ腐食液，（ロ）１０
０％オレンジジュース，（ハ）コカコーラのそれぞれの
液中に浸漬し、密封した後、５０℃で１４日間保定後の
表面腐食状態を判定した。8. Under the same conditions as those used in the corrosive liquid immersion test, a painted board with epoxy phenol paint applied to the Sn/Ni multilayer coated side was subjected to 4w using an Erichsen tester.
Two types of samples, one that was extruded and one that was subjected to impact processing of 1k9 x 50cm after being bent to R2wn, were mixed with (a) the same corrosive liquid as in 6 which was degassed, (b) 10
After being immersed in 0% orange juice and (iii) Coca-Cola and sealed, the surface corrosion state was determined after being kept at 50° C. for 14 days.

（Ｏ塗膜密着性テスト ６と同一条件でエポキシフエノール塗料をＳｎ／Ｎｉ重
層被覆側及びＮｉ単層被覆側に塗装した塗装板をそのま
ま（１次密着性）、又３％食塩溶液中に浸漬し１２５℃
×９０分レトルト後（２次密着性）及び（４）のＵＣＣ
テスト後（ＵＣＣ後密着性）、２ｗｍ間隔のコバン目を
ナイフで入れテープ剥離することによつて評価した。(A coated plate coated with epoxy phenol paint on the Sn/Ni multilayer coated side and the Ni single layer coated side under the same conditions as O paint film adhesion test 6 was immersed as it is (primary adhesion) or in a 3% salt solution. 125℃
× After 90 minutes retort (secondary adhesion) and UCC of (4)
After the test (adhesion after UCC), evaluation was made by inserting ridges with a knife at 2wm intervals and peeling off the tape.

比較例、従来例共上記と全く同じ条件でテストした。Both the comparative example and the conventional example were tested under exactly the same conditions as above.

９缶外面耐錆性テスト 缶外面用熱硬化性アクリル塗料をＮｉ単層被覆側に塗装
した塗装面にナイフでスクラツチを入れた後、５０℃、
湿度９８％の湿潤テスターに６ｈかけ、そして３０℃、
湿度８０％の恒温炉湿テスターで１ケ月間保定した後の
スクラツチ部の発錆状態でもつて評価した。9 Can External Rust Resistance Test A thermosetting acrylic paint for the exterior of cans was applied to the Ni single-layer coated side. After scratching with a knife,
Placed in a humidity tester at 98% humidity for 6 hours, then at 30°C.
The rusting state of the scratched portion was also evaluated after being kept in a constant temperature oven humidity tester at 80% humidity for one month.

［Ｆ］ シーム溶接性 シーム溶接機を使用して同腫の板を０．４ｍ巾で重ね合
せ、加圧力５０ｋ９／Ｃｄ、又２次側の溶接電流４．５
ｋＡの条件でシーム溶接し、シーム溶接部の強度を衝撃
テストで、又シーム溶接部の外観は目視で評価した。[F] Seam welding Using a seam welding machine, the same tumor plates were overlapped in a width of 0.4 m, and the welding force on the secondary side was 50 k9/Cd, and the secondary side welding current was 4.5.
Seam welding was performed under kA conditions, and the strength of the seam weld was evaluated by an impact test, and the appearance of the seam weld was evaluated visually.

なお本評価は無塗装の板で行つた。以上囚〜５の評価結
果を第２表に示す。This evaluation was conducted using an unpainted board. Table 2 shows the evaluation results for cases 5 to 5 above.

Claims (1)

【特許請求の範囲】[Claims] １ 表面清浄化した鋼板の両面下層に片面当り１０〜５
０００ｍｇ／ｍ＾２を有するニッケルメッキ層を設け、
片側面のみの該ニッケル層上に５０〜１１０００ｍｇ／
ｍ＾２の電気錫メッキ層を設け、更にその上層鋼板両面
に電解クロム処理層を設けてなり、この電解クロム処理
層が下層から順に片面当り０．１〜２０ｍｇ／ｍ＾２の
金属クロム層とそれぞれ片面当り金属クロム換算で１〜
１０ｍｇ／ｍ＾２の結晶性クロム酸化物層と非晶性クロ
ム水和酸化物層を形成した高耐食性製缶用異種重層メッ
キ鋼板。1. 10 to 5 per side on the lower layer of both sides of the surface-cleaned steel plate.
Provided with a nickel plating layer having 000mg/m^2,
50-11000mg/on the nickel layer on only one side
An electrolytic tin plating layer of m^2 is provided, and an electrolytic chromium treatment layer is further provided on both sides of the upper steel plate, and this electrolytic chromium treatment layer is a metallic chromium layer of 0.1 to 20 mg/m^2 per side in order from the bottom layer. and 1 to 1 in terms of metal chromium per side, respectively.
A highly corrosion-resistant dissimilar multi-layer plated steel sheet for can manufacturing, which has a crystalline chromium oxide layer and an amorphous chromium hydrated oxide layer of 10 mg/m^2.