JPS6191393A - Surface treated steel sheet for can having superior corrosion resistance - Google Patents
Surface treated steel sheet for can having superior corrosion resistanceInfo
- Publication number
- JPS6191393A JPS6191393A JP21397984A JP21397984A JPS6191393A JP S6191393 A JPS6191393 A JP S6191393A JP 21397984 A JP21397984 A JP 21397984A JP 21397984 A JP21397984 A JP 21397984A JP S6191393 A JPS6191393 A JP S6191393A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- alloy
- corrosion resistance
- plating
- steel sheet
- 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.)
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- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、鋼板表面kF@とNiからな□る合金層、旧
とSnからなる合金層、Sn層゛、クロ4メート被゛1
11J層とを順次81層してなる耐食性、に優れた缶用
、特に食缶、飲料缶用表面処理鋼板に関するものである
。 ・ ・(従来
技術とセの問題点)・ ゛ −・食缶用の素材とし
ては従来−・般にブリキと称されるSnめっき鋼板が広
く用いられて来た。この缶胴の゛接合方式とし−ては、
・以前は半田による接合方式が採用さ、れていたが、半
、田に含まれるpbの毒性の問題から近年、純Sn半田
が使用され°るようになった。しかし、純Sn半田は接
合時の濡れ性が劣ることから半田、接合の技術上の問題
があり、、更に高価な純Sn半田を使用することによる
製造コストの上昇の問9Nが・あった、−′、
ブリキ缶の上記欠点を解消する目的で、最近半田接合法
に代って缶胴を電気抵抗溶接によって接合する方式が発
展し。、普及するようになって来た0、そのためには電
気抵抗溶接に適した缶用素材が必要、fある−1−
・、 □、従来のブリキはSnを厚
くめっきしたもので、溶接性に必要な金m8nを十分に
有しており、優れた溶接性能を有している。DETAILED DESCRIPTION OF THE INVENTION The present invention provides an alloy layer consisting of kF@ and Ni on the surface of a steel sheet, an alloy layer consisting of nickel and Sn, a Sn layer,
The present invention relates to a surface-treated steel sheet for cans, particularly food cans and beverage cans, which has excellent corrosion resistance and is made of 81 successive 11J layers.・ ・(Prior art and problems) ゛ - Sn-plated steel sheets, commonly referred to as tinplate, have been widely used as materials for food cans. The joining method for this can body is as follows:
- In the past, solder was used for joining, but due to the toxicity of PB contained in solder and solder, pure Sn solder has come to be used in recent years. However, since pure Sn solder has poor wettability during bonding, there are technical problems with soldering and bonding, and there is also the problem of increased manufacturing costs due to the use of more expensive pure Sn solder. -', In order to eliminate the above-mentioned drawbacks of tin cans, a method has recently been developed in which can bodies are joined by electric resistance welding instead of solder joining. , it has become popular, and for that purpose, a material for cans suitable for electric resistance welding is needed.
・, □, Conventional tin plate is plated with a thick layer of Sn, has sufficient gold m8n necessary for weldability, and has excellent welding performance.
−11,近年食品1i!=は例えばポリエチレン、アル
・ミ、÷ラム、ガラス、紙などの低価格競合材料の進出
、4:直面しており、・上記の如き高価なSnを付着量
2.8〜11.2g/rn’の如く厚くめっきしたブリ
キ缶は製造コストが高いので、耐食性溶接性にすぐ載た
特性を有している・とはいえ、苦しい競合的立場を強い
られている。-11, Food 1i in recent years! =For example, the entry of low-priced competing materials such as polyethylene, aluminum, aluminum, ÷ram, glass, and paper. Thickly plated tin cans, such as ``Tin cans,'' are expensive to manufacture, so they are forced into a difficult competitive position, even though they have characteristics that are immediately superior to corrosion resistance and weldability.
コストを下げるためには、高価なSnを減らして薄目付
ブリキにすれば良いが、耐食性が著しく劣1化するので
実用に供することはできない。In order to reduce the cost, it is possible to reduce the amount of expensive Sn to make tinplate with a thinner coating, but the corrosion resistance deteriorates significantly and it cannot be put to practical use.
従来から用いられている缶用材料としては、上記ブリキ
の外にクロムタイプのティンフリースチール(以後TF
Sという)がある、これは電解クロメート処理を施し1
表面に金属クロムとクロム水利酸化物層を形成したもの
で安価な材料であるが、表面に存在する厚いクロム水利
酸化物層が高電気抵抗物質であるために溶接性が悪く溶
接部の強度不足を生じ、経済性には優れているが溶接缶
用素材としては適当でない。In addition to the tinplate mentioned above, chromium-type tin-free steel (hereinafter TF
S), which has been subjected to electrolytic chromate treatment 1
It is an inexpensive material with metal chromium and a chromium water-retention oxide layer formed on the surface, but the thick chromium water-retention oxide layer on the surface is a high electrical resistance material, resulting in poor weldability and lack of strength in the welded part. Although it is economically efficient, it is not suitable as a material for welded cans.
電気抵抗溶接に適する缶用素材の具備すべき要件として
は溶接性と耐食性が優れたものであることが要求される
。この要件を具体的に説明すると、溶接の際に十分の溶
接強度があり、しかも溶接部にいわゆる「散り」などの
溶接欠陥を生じない適正溶接電流範囲を有していること
であり、また缶内容物に対して十分な耐食性を有してい
ることである。また溶接缶のほとんどは塗装して使用さ
れる。したがって塗膜の有する耐食性を有効に利用する
ことも重要であり優れた塗料密着性が必要である。Can materials suitable for electric resistance welding must have excellent weldability and corrosion resistance. To explain this requirement specifically, it is necessary to have sufficient welding strength during welding, and to have an appropriate welding current range that does not cause welding defects such as so-called "spatter" in the welded part. It must have sufficient corrosion resistance against the contents. Also, most welded cans are used after being painted. Therefore, it is important to effectively utilize the corrosion resistance of the paint film, and excellent paint adhesion is required.
(発明の目的〉
本発明の目的は、溶接缶用素材の上記従来の欠点を解消
し、上記溶接缶用素材として具備すべき上記要件を兼備
する食缶用素材を提供すやにある。(Object of the Invention) An object of the present invention is to eliminate the above-mentioned conventional drawbacks of materials for welded cans, and to immediately provide a material for food cans that satisfies the above-mentioned requirements that the material for welded cans should have.
すなわち1本発明は、鋼板表面に片面当り、厚さ10〜
5000人で、Ni/Fe+Niの重量比が0.02〜
0.90のFeとXiからなる合金層を有し、その上に
旧とSnからなる合金層を有し、その上にSn層を有し
、さらにその上にクロメート被膜層を有することを特徴
とする耐食性に優れた缶用表面処理鋼板を提供するもの
である。That is, 1 the present invention has a thickness of 10 to 10 mm per side on the steel plate surface.
5000 people, weight ratio of Ni/Fe+Ni is 0.02~
It is characterized by having an alloy layer consisting of 0.90 Fe and Xi, having an alloy layer consisting of old and Sn on top of that, having a Sn layer on top of that, and further having a chromate coating layer on top of that. The present invention provides a surface-treated steel sheet for cans with excellent corrosion resistance.
以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
Snは高価な金属であるが、溶接性、特に商業生産で最
も多く使われている30m/分以上の高速溶接性を得る
ために必要である。Although Sn is an expensive metal, it is necessary to obtain weldability, especially high-speed weldability of 30 m/min or more, which is most often used in commercial production.
すなわち、Snは柔らかく、かつ融点が低い金属である
ので、溶接時に容易に溶融して広がり、強固な接合部と
なるからである。That is, since Sn is a soft metal with a low melting point, it easily melts and spreads during welding, forming a strong joint.
Snは50mg/m″以上、好ましくはlooms/m
’以上あれば良好な高速溶接性が得られることを本発明
者らは既に知見している。しかしSnは高価な金属であ
るのでSnsをあまり多くするとコスト上不利となるの
で好ましくな□い。Sn is 50 mg/m'' or more, preferably rooms/m
The inventors of the present invention have already found that good high-speed weldability can be obtained if the temperature is higher than '. However, since Sn is an expensive metal, it is not preferable to increase the amount of Sns too much because it will be disadvantageous in terms of cost.
Sn自体は耐食性の良い金属であるがSnめっき層のみ
で用いようとすると、従来ブリキと同等か、あるいはそ
れ以上のSnめっき厚が必要となり実用的でない0通常
のブリキではSnめっき後にリフロー処理と称するSn
層の溶融処理を行って、FeSn2なる合金層を形成さ
せて耐食性を向上させている。 FeSn2合金層は柱
状晶から成る比較的粗な合金層であるため、量を多くし
なければ効果が十分でなく、安価な素材とするには不適
当である。Sn itself is a metal with good corrosion resistance, but if you try to use it only in the Sn plating layer, it will require a Sn plating thickness equal to or greater than that of conventional tinplates, which is impractical.Regular tinplates require reflow treatment after Sn plating. Sn
The layer is melted to form an alloy layer of FeSn2 to improve corrosion resistance. Since the FeSn2 alloy layer is a relatively coarse alloy layer consisting of columnar crystals, its effect is insufficient unless the amount is increased, making it unsuitable for use as an inexpensive material.
本発明者らは、Ni−5n合金めっきを用いることによ
り少量で優れた耐食性が得られることを既に知見してい
る。The present inventors have already found that by using Ni-5n alloy plating, excellent corrosion resistance can be obtained with a small amount.
本発明者らは特願昭59−001094 r高速溶接性
、耐食性に優れたシーム溶接缶用表面処理鋼板」にて旧
−Sn合金めっきを用いたSn/Ni−9n合金2層め
っき鋼板を開示しているが1本発明者らは、この後Ni
−9n合金層について更に詳しい検討を行った結果、旧
−Sn合金めっき層と上層のSnめっき層とはめっき後
経過時間とともに室温で合金化が起こり、7〜10日間
で平衡状態に達することが分った。すなわち、旧−Sn
合金めっきはNiSn、旧3 Sna 、 Ni3 S
n2のいずれかの構造、あるいはこれらが混ざり合った
構造となっているが、上層のSnめっき層と合金化して
原子比Ni:Sn= l : 3にほぼ等しい組成の合
金となることが分った。The present inventors disclosed a Sn/Ni-9n alloy double-layer plated steel sheet using old-Sn alloy plating in Japanese Patent Application No. 59-001094 ``Surface treated steel sheet for seam welded cans with excellent high-speed weldability and corrosion resistance''. However, the present inventors subsequently discovered that Ni
A more detailed study of the -9n alloy layer revealed that the old -Sn alloy plating layer and the upper Sn plating layer undergo alloying at room temperature over time after plating, and reach an equilibrium state within 7 to 10 days. I understand. That is, old-Sn
Alloy plating is NiSn, former 3Sna, Ni3S
n2 structure or a mixture of these structures, it was found that when alloyed with the upper Sn plating layer, an alloy with a composition approximately equal to the atomic ratio Ni:Sn=l:3 was found. Ta.
この現象はSn/NiZ層めっきについても同様に起こ
ることが知られている。すなわち、1979年のTra
nsactions of the Ir+gtitu
te of )IetalFinishing Vol
57のP、J、にd!と C,A、 Mackalに
よる論文rBarrier Layers Again
st DiffusionJに述べられているところに
よればXiめっき層とSnめっき層は100℃以下にお
いて旧Sr+3なる合金を形成する。It is known that this phenomenon similarly occurs in Sn/NiZ layer plating. That is, in 1979, Tra
nsactions of the Ir+gtitu
te of ) Ietal Finishing Vol.
57 P, J, ni d! and the paper Barrier Layers Again by C. A. Mackal.
According to st Diffusion J, the Xi plating layer and the Sn plating layer form an alloy of prior Sr+3 at temperatures below 100°C.
したがってXl−Sn合金めつき1.あるいは旧めっき
の上層にSnめっきを行った場合、めっき後保管してい
る間に上記合金化が進み、原子比旧:5n71:3にほ
ぼ等しい合金層となる。この合金層は緻密で優れた耐食
性を有していることが分った。Therefore, Xl-Sn alloy plating 1. Alternatively, when Sn plating is performed on the upper layer of the old plating, the alloying progresses during storage after plating, resulting in an alloy layer having an atomic ratio of approximately 5n71:3. It was found that this alloy layer was dense and had excellent corrosion resistance.
本発明者らはさらに室温以宅の温度における合金化、す
なわち加熱処理した場合の合金化について検討を行った
結果温度が高くなる&Ni3 Sn4を主体とし午合金
となり、qらに温度が高くなそと稟地鉄との合金化が起
こりFe(Xi)−5n2型の合金となることが分?た
。これらの合金層はいずれも緻密で優れた耐食性を有し
、室温で形成されや合金とほぼ同1等の性能である。The present inventors further investigated alloying at a temperature higher than room temperature, that is, alloying when heat treated. As a result, the alloy becomes an alloy mainly composed of &Ni3Sn4, and the higher the temperature, the higher the temperature. It was found that alloying occurs between Fe(Xi)-5n2-type alloy and ferrous iron. Ta. All of these alloy layers are dense and have excellent corrosion resistance, and their performance is almost the same as that of an alloy formed at room temperature.
これらの合金層は少量で優れた一幸性を示すが、地鉄が
露出した場合Feの溶出5を促進する。すな抄ち、こ1
れらの合金は通常ブリキのFeSn2合金に比べても電
位的に責であり、、’4m的に卑なFsとの電位差が太
きく、Feの溶解が促進されるのである。したがってピ
ンホールにおける地鉄の露出、あるいは傷が入った場合
の地鉄の露出等があると、 Feの溶解が速く進行し穴
あき缶になる恐れがある0、
これに対し1本発明者らは、上記合金層と地鉄との間に
両者の中間の電位を示すFeとXiからなる合金層を設
けることによりFeの溶解を抑制できることを新規に見
い出し1本発明に到達したもので委る・ ・
なお、先行技術として特開昭57−23091 r溶接
缶用容器用−板とそρ製造法」、特開昭57−87,1
98:r高耐食性表面処理鋼板」、特開昭58−737
92 r容舅用メー、キ鋼板の製造方法」に開示されて
いるところに実Qlf、、これらは全てNiめ7き上1
.C5nめっきを施した2層めっき鋼板であり、2層め
っきにしたことによるピンホールの減少および熱処理さ
れた際にできるNiとSnの合金の耐食性の良さについ
て記されているが、ピンホールあるいは傷菱からのFe
溶出に、ついては何ら考慮されていない。Although these alloy layers exhibit excellent stability in small amounts, they promote Fe elution 5 when the base iron is exposed. Sunashōchi, Ko 1
These alloys have a lower potential than the FeSn2 alloy normally used in tinplate, and have a large potential difference with the less base Fs, which promotes the dissolution of Fe. Therefore, if the base metal is exposed through a pinhole or is scratched, there is a risk that the dissolution of Fe will proceed rapidly and result in a can with holes. have newly discovered that the dissolution of Fe can be suppressed by providing an alloy layer consisting of Fe and Xi exhibiting an intermediate potential between the above-mentioned alloy layer and the base iron, and the present invention has been achieved.・ ・ As a prior art, JP-A-57-23091 ``R Welded Can Container - Method for Manufacturing Plate and Ri'', JP-A 57-87, 1
98:r High Corrosion Resistance Surface Treated Steel Sheet”, JP-A-58-737
92 ``Method for manufacturing steel plates for cylindrical shafts'', these are all made of Ni grade 7 and 1
.. It is a two-layer plated steel sheet with C5n plating, and it is written that the two-layer plating reduces pinholes and that the alloy of Ni and Sn that is formed during heat treatment has good corrosion resistance. Fe from diamond
No consideration was given to elution.
また、特開昭5j−1,Q?!14. r高耐食性マ、
ト仕上げ製缶用表面処理−春」・、・特開昭5..8−
20・7388「プツト仕上げ製缶用表面処理鋼板」に
開示されているところによれば、NiまたはXl−Sn
合、金の上にSnめっきを施したもの、で・、実・施例
によれば通常ブリキ並の厚目付を対斂としでいるが1.
薄目付にした場、合について9記遁はなく、ピンホール
あるいは傷等からのFe溶出、県ついては全く考慮され
ていなり0、。Also, JP-A-5J-1, Q? ! 14. r High corrosion resistance ma,
``Surface Treatment for Finishing Can Making - Spring''... JP-A-5. .. 8-
According to the disclosure in 20.7388 “Surface treated steel sheet for puttu finish can making”, Ni or Xl-Sn
It is a metal plated with Sn plating on gold, and according to the examples, it is usually made with a thickness as thick as tin plate, but 1.
When using a thin basis weight, there is no 9-point equation, and no consideration is given to Fe elution from pinholes or scratches, etc.
これに対し、本発明鋼1板は、ピンホールあるいは傷等
からのFe溶出を極力抑えることを特徴としたFeとI
liからなる合金層と、QiとSnからなる合金層とS
n層の3層構造からなり、さらにり!メート被lI層を
設けてなる耐章性暢優れた缶用鋼板であつ−て、上記発
明とは製品の1構成、技術思想が全く異なったものであ
る。 ′・さて、本発明において
、鋼板表面にIsとNiからなる合金層を設ける目的は
3りンホー、ルあるいは傷等からのFe溶出の抑制であ
る。 FeとNiからなる合金層の厚さはlO〜5・0
00人、好ましくは10.9〜3000人である。Fe
−旧合令層の厚さ2.を10〜5000人に限定する理
由は、10λ以下ではFe1llff1.を・抑制する
効果が不十分であり、590、Q^以上2千な・るとF
e溶出を抑制する効果は十分であるが1.合金層が硬く
、かつ脆くなるため、クラックが入り易くなりクラック
からのFe溶出が起こるからで、ある、 FeとNiの
合金組成は重量比?Ni/ (、Fs+N1)−〒(!
、02〜0.90が好ましい、このti比が0.02未
構で琲(イ)旧による合金化の効果がなくな7tFa4
出を抑制する効果が不十分となり、 、0.、(、!1
0を、こ木ると(ロ)合金の電位が貴なXiに近くなり
卑なFeの溶出を抑制する効果が無くなるからである・
、1゛、゛、・、I
Fv−Njからなφ合金層を形成させる方法としては、
工業的に次のいずれの方法によるも差支えない、
゛ 、i□・
(a)II板表面にNiめつきを施した後、非醜化性雰
囲気中で熱処理し、てNiすつきを全て鋼中に拡散させ
る方法。In contrast, the steel sheet 1 of the present invention is characterized by suppressing Fe elution from pinholes or scratches as much as possible.
An alloy layer consisting of li, an alloy layer consisting of Qi and Sn, and an alloy layer consisting of S
Consisting of a 3-layer structure with n layers, it is even more! This steel plate for cans is provided with a mate layer and has excellent chamfer resistance, and is completely different from the above-mentioned invention in terms of product structure and technical concept. '-Now, in the present invention, the purpose of providing an alloy layer consisting of Is and Ni on the surface of the steel sheet is to suppress the elution of Fe from holes, holes, scratches, etc. The thickness of the alloy layer consisting of Fe and Ni is lO~5.0
00 people, preferably 10.9 to 3000 people. Fe
- Thickness of the former Gorei layer 2. The reason for limiting the number of people to 10 to 5,000 is that Fe1llff1. below 10λ. The effect of suppressing is insufficient, and if it is 590, Q^ or more, 2,000 F.
e The effect of suppressing elution is sufficient, but 1. This is because the alloy layer becomes hard and brittle, making it easier to crack and causing Fe to be leached from the cracks.What is the alloy composition of Fe and Ni in weight ratio? Ni/ (,Fs+N1)−〒(!
, 02 to 0.90 is preferable; if this Ti ratio is not set at 0.02, the effect of alloying due to oxidation disappears and 7tFa4
The effect of suppressing the output becomes insufficient, and 0. ,(,!1
This is because if 0 is reduced, (b) the potential of the alloy approaches noble Xi, and the effect of suppressing the elution of base Fe is lost.
, 1゛,゛,..., I As a method for forming a φ alloy layer made of Fv-Nj,
Industrially, any of the following methods may be used:
゛, i□・ (a) A method in which the surface of the II plate is plated with Ni, and then heat treated in a non-degrading atmosphere to completely diffuse the Ni plating into the steel.
(bBl板表面にFe−Ni合金めつきを施した後、非
酸化性雰囲気中で熱処理してFe−Ni合金めっきの一
部もしくは全部を鋼中に拡散させる方法。(a method in which Fe-Ni alloy plating is applied to the surface of bBl plate and then heat-treated in a non-oxidizing atmosphere to diffuse part or all of the Fe-Ni alloy plating into the steel.
(c)鋼板表面にFe−Ni合金めっきを施す方法。(c) A method of applying Fe-Ni alloy plating to the surface of a steel plate.
これらの方法をそれぞれ単独もしくは2種以上組合わせ
てもよい、これらの方法によって深さ方向に種々の組成
を有するFeとXiからなる合金層を形成させることが
できる。These methods may be used alone or in combination of two or more, and alloy layers made of Fe and Xi having various compositions in the depth direction can be formed by these methods.
本発明ではと記Fe−Ni合金層の上に耐食性の優れた
N1とSnからなる合金層を設ける。In the present invention, an alloy layer made of N1 and Sn and having excellent corrosion resistance is provided on the Fe--Ni alloy layer.
N1とSnからなる合金層の量の好ましい範囲は20〜
1500mg/rn’であり、特に溶接缶用としてより
好ましい範囲は20〜400mg/m″である。Xl−
Sn合金の量が20sx/lo’未満では(ハ)耐食性
を向上させる効果が不十分であり、1500ss/rr
I′をこえると(ニ)耐食性を向上される効果が飽和し
てしまい、不経済となるからtある。旧とSnの組成比
は特に限定しないが、好ましくは!ia)比Sn/(N
i+5n)= 0.5ONO,95である。このt量比
が0.50未満では(ホ)合金層が硬くなり、加工によ
ってクラックが入り易く、0.95をこえると(へ)
Snが多くなり不経済となるからである。The preferred range of the amount of the alloy layer consisting of N1 and Sn is 20~
1500 mg/rn', and a more preferable range is 20 to 400 mg/m'', especially for welded cans.Xl-
If the amount of Sn alloy is less than 20ss/lo', (c) the effect of improving corrosion resistance is insufficient;
If it exceeds I', (d) the effect of improving corrosion resistance will be saturated and it will become uneconomical. The composition ratio of old and Sn is not particularly limited, but preferably! ia) Ratio Sn/(N
i+5n)=0.5ONO,95. If this t ratio is less than 0.50, (e) the alloy layer becomes hard and tends to crack during processing, and if it exceeds 0.95 (f)
This is because the amount of Sn increases and becomes uneconomical.
XiとSnからなる合金層を形成させる方法としては工
業的に次のいずれの方法によるも差支えない。As a method for forming an alloy layer consisting of Xi and Sn, any of the following methods may be used industrially.
(a)lliまたはNi−Sn合金めっきを行った後さ
らにSnめっきを施し、特に加熱することなく室温で経
時させてNiとSnからなる合金層とSn層とを同時に
形成させる方法。(a) A method in which an alloy layer consisting of Ni and Sn and a Sn layer are simultaneously formed by applying Sn plating after performing lli or Ni-Sn alloy plating, and aging at room temperature without particular heating.
(b) NiまたはXl−Sn合金めっきを行った後さ
らにSnめっきを施し、Snの融点以下の温度で短時間
加熱処理し、N1とSnからなる合金層とSn層とを同
時に形成させる方法。(b) A method in which after Ni or Xl-Sn alloy plating is performed, Sn plating is further applied, and heat treatment is performed for a short time at a temperature below the melting point of Sn to simultaneously form an alloy layer consisting of N1 and Sn and a Sn layer.
本発明ではXl−Sn合金層の上にsJI層を設ける。In the present invention, an sJI layer is provided on the Xl-Sn alloy layer.
Sn層の目的は溶接性であり、50+g/m′以上、好
ましくは100mg/m’以上であれば良い、 Sn層
が50mg/m″未満では(ト)十分な溶接性が得られ
ないからである。The purpose of the Sn layer is weldability, and it is sufficient if it is 50+g/m' or more, preferably 100mg/m' or more.If the Sn layer is less than 50mg/m', (g) sufficient weldability cannot be obtained. be.
塗装して使用される場合、塗装後の焼付処理によりSn
の合金化が起るので、この合金化の分を見込んで5nI
kを決めれば良い、BBち、塗装後に50ax/ln’
以上、好ましくはLooms/rn’以上金属S+層が
存在する様に5allを決めれば良い* sniには特
に上限はないが、安価な素材とするにめには。When used after painting, Sn is removed by baking treatment after painting.
Since alloying occurs, 5nI is taken into consideration for this alloying.
Just decide k, BBchi, 50ax/ln' after painting
As mentioned above, 5all should be determined so that the metal S+ layer is preferably Looms/rn' or more.* There is no particular upper limit for sni, but in order to use an inexpensive material.
1000層g/rn’以下にしておくことが9ましい。It is preferable to keep it to 1000 layers g/rn' or less.
本発明鋼板は安価な溶接缶用素材を目的としているが、
Sn量を従来ブリキ並みに厚くして高耐食性のブリキ
として使用しても良い。Although the steel plate of the present invention is intended as an inexpensive material for welded cans,
It may be used as a highly corrosion-resistant tinplate by increasing the amount of Sn to the same thickness as conventional tinplate.
本発明では、SnNの上に塗料密着性、塗装後耐食性の
向上を目的としてクロメート被MFJを設ける。In the present invention, chromated MFJ is provided on SnN for the purpose of improving paint adhesion and post-painting corrosion resistance.
クロメート被膜はクロム水利酸化物のみで構成されても
良く、また金属クロムとクロム水利酸化物とから構成さ
れても良い。The chromate coating may be composed only of chromium water-conserving oxide, or may be composed of metallic chromium and chromium water-conserving oxide.
クロメート被膜は高電気抵抗物質であるので。Because chromate coating is a high electrical resistance material.
溶接缶として用いる場合は良好な溶接性をするにはクロ
メート被RQ量は305g/rn’以下にしておくこと
が望ましい。When used as a welded can, it is desirable to keep the RQ amount of chromate at 305 g/rn' or less in order to achieve good weldability.
〈実施例)
次に本発明を実施例および比較例につき具体的にXQr
lIする。<Example> Next, the present invention will be described in detail with reference to Examples and Comparative Examples.
I will do it.
(実施例1)
一冷延鋼板を電解脱脂した後、XiめっきもしくはFe
−旧合金めっきを行い、引き続いて10%−+90%N
2のガス雰囲気中で加熱処理を行ってFaとNiからな
る合金層を形成させた。さらに1%のスキンパスを行っ
た後、電解脱脂、酸洗を行い。(Example 1) After electrolytically degreasing a cold rolled steel sheet, Xi plating or Fe plating was applied.
- Old alloy plating, followed by 10% - +90% N
Heat treatment was performed in the gas atmosphere of No. 2 to form an alloy layer consisting of Fa and Ni. After a further 1% skin pass, electrolytic degreasing and pickling were performed.
旧めっきもしくはXi’−Sn合金めっきを行い、引き
続いてSiめっきを行い、さらにクロメート処理を行っ
た後10日間室温で経時させた。Old plating or Xi'-Sn alloy plating was performed, followed by Si plating, and further chromate treatment, followed by aging at room temperature for 10 days.
(実施例2)
ブリキ原板を電解脱脂、酸洗した後、Fe−X1合
□−金めつきを行い、引き続いてIli
もしくはXl−Sn合□
金めつきを行い、さらに引き続いてSnめっきを行
・い、さらにクロメート処理を行った。(Example 2) After electrolytically degreasing and pickling a tin plate, Fe-X1
□-Gold plating followed by Ili
Or perform Xl-Sn alloy □ gold plating, and then perform Sn plating.
・I also performed chromate treatment.
この後10日間室温で経時させた。Thereafter, the mixture was allowed to stand at room temperature for 10 days.
(比較@l)
ブリキ原板を電解脱脂、酸洗した後N1もしくはXl−
Sn合金めっきを行い、引き続いてSnめっきを行い、
さらにクロメート処理を行った。この後10日間室温で
経時させた。(Comparison @l) After electrolytically degreasing and pickling the tin plate, N1 or Xl-
Sn alloy plating is performed, followed by Sn plating,
Furthermore, chromate treatment was performed. Thereafter, the mixture was allowed to stand at room temperature for 10 days.
(比較例2) 。(Comparative Example 2)
ブリキ原板、を電解脱脂、酸洗をした後Snめっきを行
い、さらにクロメート処理を行った。The original tin plate was electrolytically degreased, pickled, Sn-plated, and further chromate-treated.
実施例および比較例で用いた各めっき浴の組成は次□の
如くである。 ・
(Niめっき浴)
NiSO4e6H20’ 250g/1Ni
C交2 や61420 45g/1)13
BO330g1文
((Fe−Xi金合金っき浴)
F@CJLz ・41420 20〜230g/IL
、旧CJL2・61420 30〜300g/
!L83 BO325g/又
−Ni−3n合金□めっき浴)
旧CIL2命61420 250g/4So C
1z ・2)120 50x/1
’ N)In”HF2”
戸 08イ、見<<Snめっき
浴)
Sn Cn2・2H2060x/R
aHF2
・Na F
Na 0文 50g1文’N
a2Cr20y *2 H2O: 30 gelあ
るいは □
’CrO315g/fL ’
H2翁−0,12g/見
見上上ように処理した鋼板の性能を以下の方法 ;でズ
τ価した。。The composition of each plating bath used in Examples and Comparative Examples is as follows.・ (Ni plating bath) NiSO4e6H20' 250g/1Ni
C-cross 2 and 61420 45g/1) 13
BO330g1 sentence ((Fe-Xi gold alloy plating bath) F@CJLz ・41420 20-230g/IL
, old CJL2・61420 30-300g/
! L83 BO325g/Ni-3n alloy □ plating bath) Old CIL2 life 61420 250g/4So C
1z ・2) 120 50x/1
'N)In"HF2"
Door 08 I, see << Sn plating bath) Sn Cn2・2H2060x/R aHF2 ・Na F Na 0 sentence 50g 1 sentence'N
a2Cr20y *2 H2O: 30 gel or □ 'CrO315g/fL' H2O-0.12g/Appearance The performance of the steel plate treated as above was evaluated by the following method. .
(1) 溶接性−
上記鋼板を、塗装後の焼付−理を模して210 ′℃×
20分の熱処神を行った後、溶接速度□40■を分、接
胴加圧力40kxf、オーI(−チー2プ0.4mmで
シーム溶接を行い、「散り」を発生せず、力)つ十分−
な強度を有す暮ナゲ1トが形成される溶接型−流範囲(
適正溶接電流範囲)を求め、次の如く評価した。(1) Weldability - The above steel plate was heated to 210'°C to simulate the baking process after painting.
After heat treatment for 20 minutes, seam welding was performed at a welding speed of □40cm, contact pressure of 40kxf, and OI (-cheap 0.4mm) without causing any "splashing". ) enough
The welding type - flow range (
The appropriate welding current range) was determined and evaluated as follows.
第 1 表
(2)塗装後耐食性
上記鋼板にエポキシフェノール系塗料を50■2/df
fI’ I!装し、210℃XIO分×2回焼付した後
、鋭利なナイフで地鉄に達するクロスカットを入れ1.
5%NaCJLと1.5%クエン酸の混合溶液中に55
℃で96時間浸漬した後、腐食状況を、クロスカット部
のテープ剥離による塗膜剥離幅とクロスカット部からの
Fs溶出量で評価した。Table 1 (2) Corrosion resistance after painting The above steel plate was coated with epoxy phenol paint at 50cm2/df.
fI' I! After baking at 210°C for XIO minutes twice, use a sharp knife to make a cross cut that reaches the base metal.1.
55 in a mixed solution of 5% NaCJL and 1.5% citric acid.
After immersion at ℃ for 96 hours, the corrosion status was evaluated by the width of the coating peeled off from the cross-cut portion by tape peeling and the amount of Fs eluted from the cross-cut portion.
゛ 上記鋼板についての諸性能を示した表2力)
ら明らかなように、本発明鋼板は優れた溶接性を有し、
比較例に対しより優れた塗装後耐食性を有していること
が分る。゛ Table 2 shows various performances of the above steel sheets)
As is clear from the above, the steel plate of the present invention has excellent weldability,
It can be seen that it has better corrosion resistance after painting than the comparative example.
〈発明の効果)
本発明においては、鋼板上に特番こF@−Ni合金層、
Ni−Sn合金層、SnP+およびクロメート層を形成
し、特にFe−X1合金層の厚さを10〜5000人、
Ni/(旧◆F@)のt量比を0.02〜0.30とす
ることにより、特に上記表面処理層にピンホール、傷な
どが生じた時にもF@の溶出のない、すなわち耐食性が
すぐれた缶用表面処理鋼板が得られる。<Effects of the invention> In the present invention, a special F@-Ni alloy layer,
Form Ni-Sn alloy layer, SnP+ and chromate layer, especially the thickness of Fe-X1 alloy layer is 10 to 5000,
By setting the t ratio of Ni/(former ◆F@) to 0.02 to 0.30, there is no elution of F@ even when pinholes, scratches, etc. occur in the surface treatment layer, that is, corrosion resistance. A surface-treated steel sheet for cans with excellent properties can be obtained.
Claims (1)
Fe+Niの重量比が0.02〜0.30のFeとNi
からなる合金層を有し、その上にNiとSnからなる合
金層を有し、その上にSn層を有し、さらにその上にク
ロメート被膜層を有することを特徴とする耐食性に優れ
た缶用表面処理鋼板。Ni/Ni/
Fe and Ni with a Fe+Ni weight ratio of 0.02 to 0.30
A can with excellent corrosion resistance, characterized in that it has an alloy layer consisting of Ni and Sn, an Sn layer thereon, and a chromate coating layer thereon. Surface treated steel plate for use.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21397984A JPS6191393A (en) | 1984-10-12 | 1984-10-12 | Surface treated steel sheet for can having superior corrosion resistance |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21397984A JPS6191393A (en) | 1984-10-12 | 1984-10-12 | Surface treated steel sheet for can having superior corrosion resistance |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6191393A true JPS6191393A (en) | 1986-05-09 |
JPH0340115B2 JPH0340115B2 (en) | 1991-06-17 |
Family
ID=16648233
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21397984A Granted JPS6191393A (en) | 1984-10-12 | 1984-10-12 | Surface treated steel sheet for can having superior corrosion resistance |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6191393A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002275641A (en) * | 2001-03-21 | 2002-09-25 | Kawasaki Steel Corp | Surface treated steel sheet |
WO2007091732A2 (en) * | 2006-02-09 | 2007-08-16 | Nippon Steel Corporation | Tinned steel sheet excellent in corrosion resistance |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57200592A (en) * | 1981-06-04 | 1982-12-08 | Kawasaki Steel Corp | Manufacture of surface treated steel plate for welded can |
-
1984
- 1984-10-12 JP JP21397984A patent/JPS6191393A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57200592A (en) * | 1981-06-04 | 1982-12-08 | Kawasaki Steel Corp | Manufacture of surface treated steel plate for welded can |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002275641A (en) * | 2001-03-21 | 2002-09-25 | Kawasaki Steel Corp | Surface treated steel sheet |
WO2007091732A2 (en) * | 2006-02-09 | 2007-08-16 | Nippon Steel Corporation | Tinned steel sheet excellent in corrosion resistance |
WO2007091732A3 (en) * | 2006-02-09 | 2008-03-27 | Nippon Steel Corp | Tinned steel sheet excellent in corrosion resistance |
Also Published As
Publication number | Publication date |
---|---|
JPH0340115B2 (en) | 1991-06-17 |
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