JP3890700B2 - Plated steel sheet for welding cans - Google Patents
Plated steel sheet for welding cans Download PDFInfo
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- JP3890700B2 JP3890700B2 JP27870097A JP27870097A JP3890700B2 JP 3890700 B2 JP3890700 B2 JP 3890700B2 JP 27870097 A JP27870097 A JP 27870097A JP 27870097 A JP27870097 A JP 27870097A JP 3890700 B2 JP3890700 B2 JP 3890700B2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【0001】
【発明の属する技術分野】
この発明は、主として缶の内面側が無塗装で使用される18リットル缶やペール缶等の溶接缶胴として用いられる溶接缶用のめっき鋼板、とりわけ研削処理によって被膜を除去することなく、溶接を行うことのできる溶接缶用めっき鋼板に関するものである。
【0002】
【従来の技術】
18リットル缶やペール缶の缶胴には、ぶりきや電解クロム酸処理鋼板等が用いられている。中でもぶりきは、Snめっき層が厚いために耐食性および溶接性に優れる反面、Snの使用量が多いために高価であり、また省資源の観点からも好ましくない。一方、電解クロム酸処理鋼板はSnを使用しないために、低コストで無塗装での耐食性に優れる反面、鋼板の被膜表面のクロム水和酸化物層が絶縁性であることから、そのまま溶接することが困難であり、事前に溶接部の表面を研削する必要がある。この研削処理において発生する研削粉は、作業環境を悪化する他溶接後の缶に付着するため、特に食品用途の缶で問題視される。そこで、かような問題を解決するための様々な試みが行われてきた。
【0003】
例えば、特公平3− 69999号公報では、鋼板表面に、40〜150 mg/m2の金属Cr層および金属Cr換算で5〜25mg/m2の非金属Cr層からなりかつ金属Crの一部が突起している被膜を形成することが、提案されている。この提案によって、確かに溶接性は向上するが、金属Crの一部を突起させたために、金属Cr層の薄い部分が局部的に生じて耐食性が劣化することが問題として残る。
【0004】
また、特公平5−27720 号公報では、鋼板表面に、45〜90mg/m2の平滑に析出させた金属Cr層と、Crとして1〜10mg/m2の難溶性のCr水和酸化物層とを形成することが提案されている。しかしながら、溶接性は不十分であり、しかもCr水和酸化物層の厚みを従来対比で減少させたために、耐食性が劣化することも問題となる。
【0005】
従って、耐食性を損なうことなく、電解クロム酸処理鋼板の溶接性を改善するためには、やはり鋼板表面に微量でもSnを有することが必要であることから、特公平2−16397 号公報では、鋼板表面に50〜900 mg/m2のSn層を有し、その上に7〜100 mg/m2の金属Cr層およびCr換算で5〜50mg/m2の非金属Cr層を有し、さらにSn層によって被覆されない、円換算で直径0.5 〜20μm の鋼板露出部が存在する鋼板が、提案されている。
【0006】
ここでは、Snめっき後にSnを加熱溶融、いわゆるリフローしてもしなくても良いとされているが、Snめっき後にリフローを行うと、もともとSn量が少ない上に、リフロー時に金属Sn量が減少し、さらに塗装焼き付け処理によってさらに減少し、溶接性は不十分なものとなる。
一方、Snめっき後にリフローしない場合は、確かに溶接性の改善効果があるものの、Snめっき層と素地鋼との間の密着性が著しく低下することが問題となる。
【0007】
さらに、特公平6−96790 号公報では、鋼板表面に径が0.2 〜2.0 μm および高さ0.1 μm 以上のSn粒からなる、20〜200 mg/m2のSn層を有し、その上に30〜150 mg/m2の金属Cr層およびCr換算で2〜40mg/m2の非金属Cr層を有する鋼板が提案されている。この提案によれば、確かに溶接性改善の点では一定の効果が得られるが、この場合もSnめっきの密着性が悪いという問題は依然として解決されていない。
【0008】
また、飲料缶や食缶の分野で既に実用化されている、溶接缶用の極薄Snめっき鋼板を、ガロン缶に適用することも検討されている。このような極薄Snめっき鋼板の製造方法については、例えば特開昭60−17099 号公報や同63−93894 号公報に開示されている。すなわち、特開昭60−17099 号公報には、鋼板上に第1層としてFe−Ni合金層を形成し、Snめっきを行った後にリフローによりFe−Sn−Ni合金層を含む第2層を形成し、さらに電解クロメート処理によりCr換算で5〜20mg/m2の範囲の金属Cr及びクロム水和酸化物からなる被膜を形成することが記載されている。また、特開昭63−93894 号公報では、両面にFe−Sn−Ni系合金層を有する鋼板の製缶後に缶外面側となる面に、塗装印刷後の残存金属Sn量が0.05g/m2以下となるようなSnめっき層と、その上に10〜30mg/m2の金属Cr及びCr換算で3〜15mg/m2の範囲のクロム水和酸化物からなるクロメート層とを有し、製缶後に缶内面側となる面には、塗装印刷後の残存金属Sn量が0.2 〜1.0 g/m2以下となるようなSnめっき層と、その上に3〜10mg/m2の金属CrとCr換算で3〜15mg/m2の範囲のクロム水和酸化物からなるクロメート層とを有する缶用鋼板について記載されている。
【0009】
【発明が解決しようとする課題】
これらの技術は、飲料缶や食缶の分野では既に実用化されており、ガロン缶に適用した場合にも溶接部の研削無しで十分な溶接性を与えることから、溶接性の点では問題がないと言える。しかしながら、これらの技術はあくまでも飲料缶や食缶への適用を目的とし、缶内外面ともに塗装して用いることを前提としたものであるから、缶内面側を無塗装で使用した場合に、耐食性の点で問題が残る。とりわけ、アルカリ性の溶液を缶の内容物とする場合、上記Fe−Sn−Ni合金層を有する鋼板では、Snが急速に溶解し褐色に変色するという、顕著な問題があった。
【0010】
この発明は、Fe−Sn−Ni層を有する鋼板における、無塗装での耐食性及び耐変色性に優れ、かつめっき密着性が良好である、無研削での溶接が可能なめっき鋼板を提供しようとするものである。
【0011】
【課題を解決するための手段】
すなわち、この発明は、鋼板の少なくとも片面に、Fe−Sn−Ni合金層及びSn層を有し、さらに鋼板両面の最外側を、金属Cr層およびクロム水和酸化物層からなる表面被膜で覆って成るものであり、鋼板の前記 Fe − Sn − Ni 合金層及び Sn 層を有する一方の面を覆う表面被膜は、付着量が30mg/m2をこえて200 mg/m2以下の金属Cr層及び付着量がCr換算で3〜25mg/m2のクロム水和酸化物層から成り、無塗装で使用され、前記鋼板の他方の面を覆う表面被膜は、金属Cr層の付着量が5〜100mg/m2であることを特徴とする溶接缶用めっき鋼板(ただし、鋼板の両面にFe−Ni−Sn合金層、その上層に金属Sn層、最上層にクロメート層を有し、鋼板の缶内面となる面の全Sn量が 1.0 〜 2.0g/m 2 、金属Cr量が 10 〜 40mg/m 2 、クロム水和酸化物量がCr換算で2 mg/m 2 以上であり、鋼板の缶外面となる面の全Sn量が 0.2 〜 0.8g/m 2 、クロム水和酸化物量がCr換算で2 mg/m 2 以上であり、さらに両面の金属Crとクロム水和酸化物の合計量がCr換算で 45mg/m 2 以下である塗装密着性に優れた溶接缶用めっき鋼板を除く)である。
【0013】
また、上記めっき鋼板において、Sn層の付着量X(mg/m2)、Fe−Sn−Ni合金層中のSn量Y(mg/m2)及び同Ni量Z(mg/m2)が、下記(1)〜(3)式を満足することが、実施に当たりより好ましい。
記
100 ≦X≦800 ----(1)
200 ≦X+Y≦1500 ----(2)
0.01≦Z/(Y+Z)≦0.5 ----(3)
【0014】
【発明の実施の形態】
上述したように、缶内面側を無塗装で使用する用途において、例えばアルカリ性の溶液を缶内容物とする場合、Fe−Sn−Ni合金層を有するSn系の鋼板を缶胴に用いると、Snが急速に溶解し表面が褐色に変色するという問題が生じる。そこで、発明者等は、アルカリ性溶液中でのSnの溶解を防止する手立てを種々検討した結果、鋼板表面のSn層上に設けた金属Cr層及びクロム水和酸化物層から成る表面被膜(以下、単に表面被膜と示す)、特に缶内面側となる鋼板の一方の面の表面被膜において、その金属Cr層の付着量を増加するのが有効であることが判明した。
【0015】
飲料缶や食缶への適用を想定した従来の技術では、表面被膜中の金属Cr量は最大で30mg/m2である。この理由としては、第1に、表面被膜中の金属Crの作用として塗料密着性の向上を期待するからであり、この塗料密着性を向上する効果は金属Cr量が30mg/m2に近づくと飽和するため、それ以上の金属Crを析出させることは不経済であったからである。第2の理由として、Sn層上に析出する金属Cr量が増加すると、塗装焼き付け時に起こるSnと地鉄との間の合金化が促進され、塗装後に残存するSn量が少なくなるために、溶接性が劣化するという問題があった。
【0016】
しかるに、この発明では、金属Crの作用として、とりわけアルカリ性溶液中でのSnの溶解を防止することが重要であり、その為には主に缶内面側となる鋼板の一方の面の表面被膜における、金属Cr層の付着量を35mg / m 2 以上200 mg/m2以下とする必要があり、さらに望ましくは60〜120 g/m2に調整することで良好な品質が得られる。
すなわち、金属Cr層の付着量が35mg / m 2 未満では、Sn溶解を抑制する効果が十分でなく、一方200 mg/m2をこえると、この効果が飽和するために、経済的な観点から200 mg/m2を上限とした。
【0017】
なお、この発明に従って金属Cr量を増加することは溶接性の観点からは不利であるが、この発明で主な対象とする缶外面側のみが塗装され、内面側が無塗装で使用される缶では、缶の内外面を塗装する場合に比べて塗装焼き付け回数が少ない為に、塗装後にSnが残存しやすいことから、十分な溶接性を与えることができる。
【0018】
さらに、この発明においては、主に缶内面側となる鋼板の一方の面の表面被膜にCr換算で3〜25mg/m2の付着量のクロム水和酸化物層が必要であり、さらに望ましくは6〜15mg/m2の付着量とする。すなわち、クロム水和酸化物層の付着量が3mg/m2未満では、塗料の密着性が不十分になり、一方25mg/m2以上では塗料密着性に対する効果が飽和すると共に外観が劣化するため、3〜25mg/m2の付着量とする。また、残る缶外面側となる鋼板の他方の面にも、塗料密着性を確保するために金属Cr層およびクロム水和酸化物層から成る表面被膜を設ける必要がある。なお、この他方の分に形成する表面被膜における金属Cr層及びクロム水和酸化物層の付着量は、上記した一方の面のそれと同程度でよいが、金属Cr層については、主に塗料密着性を考慮すればよいから、後述のとおり付着量を少なくすることが可能である。
【0019】
また、上記のめっき鋼板において、Sn層の付着量X(mg/m2)、Fe−Sn−Ni合金層中のSn量Y(mg/m2)及び同Ni量Z(mg/m2)が、下記(1)〜(3)式を満足することが、好ましい。
記
100 ≦X≦800 ----(1)
200 ≦X+Y≦1500 ----(2)
0.01≦Z/(Y+Z)≦0.5 ----(3)
【0020】
すなわち、無研削での溶接性を確保するために鋼板表面に微量のSnが必要であり、製缶メーカーでの溶接時に、鋼板上に50mg/m2以上のSn層が存在する必要があると考えられる。なお、Sn層とは合金化していないSnからなる。ここで、製缶時に溶接に先立ち塗装が行われる場合は、焼き付け時にSn層と鋼板との間の合金化が起こり、Snの残存量は焼き付け前のSn量より少なくなる。従って、この発明においては、塗装焼き付けによる合金化のためのSnの減少を考慮して、溶接性を確保するために、上記式(1)に示す通り付着量(X):100 〜800 mg/m2のSn層を設けることが好ましく、より好ましくは付着量を200 〜400 mg/m2とする。すなわち、Sn層の付着量(X)が100 mg/m2未満では、溶接時に残存するSn量が50mg/m2未満となり溶接が不十分になるためであり、Sn層の付着量(X)が800 mg/m2を超えると溶接性は十分であるが、経済的な観点から望ましくない。
【0021】
さらに、Sn層の下地として、Fe−Sn−Ni合金層が必要である。通常のぶりきでは、耐食性を向上させる為にSnと鋼板との間にFe−Sn合金層が設けられるが、この発明のようにSn量が少ない場合には、合金層に、耐食性向上とともに、塗装焼き付け時に起こる素地鋼とSnとの合金化を抑制するためのバリヤーとしての効果が期待される。そのためには、合金中に微量のNiを含有して緻密な合金層を形成することが有利である。勿論、このバリヤー効果を向上させるためには、合金層は厚いほど望ましいが、一定値以上ではその効果は飽和してしまう。以上の観点から、上記式(2)に示す通りFe−Sn−Ni合金層中に含まれるSn量(Y)は、合金化せずに残存するSn層付着量(X)との総和(X+Y)として200 〜1500mg/m2が好適であり、より好ましくは300 〜800 mg/m2である。
【0022】
一方、Fe−Sn−Ni合金中層中に含有されるNi量(Z)は、合金中のSn量との兼ね合いで決定され、上記式(3)に示す通り合金中のNiとSnとの総和(Z+Y)に対する重量比で0.01〜0.5 とすることが好適であり、より好ましくは0.05〜0.3 とする。この重量比が0.01未満では、Niを含有することにより合金層を緻密化する効果が薄れ、バリヤー効果の向上が望めないためであり、0.5 をこえるとSnとNiとの間の合金化が進むために、塗装焼き付け時のSnの合金化をむしろ促進するようになる。
【0023】
また、この発明においては、鋼板両面の金属Cr層およびクロム水和酸化物層から成る表面被膜を異なるものにすることも可能である。この理由は、一般に無塗装での耐食性を要求されるのは缶の内面側であり、この缶内面となる鋼板の一方の面の表面被膜中の金属Cr量を35mg / m 2 以上200 mg/m2以下とすることが必要であるが、缶外面側の他方の面は塗装されるため、十分な塗装密着性さえ確保できれば良いからである。このような見地から、他方の面の表面被膜は、金属 Cr 層の付着量が5〜 100mg / m 2 及びクロム水和酸化物層の付着量が Cr 換算で2 mg / m 2 以上とする。
【0024】
この発明のめっき鋼板は、各種製造方法によって得ることができ、その代表的な方法としては、以下の<A法>及び<B法>が有利に適合する。
<A法>
未焼鈍の冷延鋼板にNiめっきを行い、その後焼鈍して鋼板表面にNi拡散層を形成したのち、調質圧延を施す。かくして得られためっき原板に、Snめっき後リフロー処理を行うことによって、Sn層及びFe−Sn−Ni合金層を形成する。次いで、無水クロム酸を主として、硫酸や弗化物等の助剤を含有するクロメート浴中において陰極電解することにより、所定の付着量の金属Cr層及びクロム水和酸化物層を形成する方法。
【0025】
<B法>
焼鈍及び調質圧延済みの冷延鋼板にNiめっきを行い、その後Snめっき及びリフロー処理を行うことによって、Sn層及びFe−Sn−Ni合金層を形成する。さらに、無水クロム酸を主として、硫酸や弗化物等の助剤を含有するクロメート浴中において陰極電解することにより、所定の付着量の金属Cr層及びクロム水和酸化物層を形成する方法。
【0026】
【実施例】
〔供試材作成法〕
<A法> 板厚0.33mmの未焼鈍鋼板にワット浴を用いてNiめっきを行い、その後10%H2 +90%N2 のHNX ガス雰囲気中で焼鈍した鋼板に、圧下率1.5 %の調質圧延を施し、さらにハロゲン浴を用いてSnめっき後リフロー処理を行うことによって、Sn層及びFe−Sn−Ni合金層を形成した。さらに、無水クロム酸:60g/L及び流酸0.6 g/Lのクロメート浴中で陰極電解することにより、金属Cr層及びクロム水和酸化物層を形成した。
【0027】
<B法> 焼鈍及び調質圧延済みの冷延鋼板にワット浴を用いてNiめっきを行い、その後ハロゲン浴を用いてSnめっき後リフロー処理を行うことによって、Sn層及びFe−Sn−Ni合金層を形成した。さらに、無水クロム酸:60g/L及び硫酸0.6 g/Lのクロメート浴中で陰極電解することにより、金属Cr層及びクロム水和酸化物層を形成した。
【0028】
上記の方法により各種の付着量のめっき鋼板を作製し、各めっき鋼板について、次に示す各種の品質評価を行った。
〔品質評価方法〕
<耐内容物耐食性試験> 50mm×40mm試験片に切り出した供試材の一方の面S1 (逆の他方の面をS2 とする)を、半分から上が気相部及び下が液相部となるように、ガラス容器中に浸漬し、容器に蓋をして密閉した後、55℃の恒温室内に14日間放置したのち、その腐食状況を観察した。
【0029】
<溶接性> ガス炉を用いて170 ℃×10分間の空焼きを行った後に、JIS−G3303の電解剥離法に準拠してS1 表面Sn付着量を測定して溶接性の指標とした。そして、空焼き後の残存Sn付着量が50mg/m2未満の場合:×、空焼き後の残存Sn付着量が50mg/m2〜100 mg/m2の場合:Δ、空焼き後の残存Sn付着量が100 mg/m2をこえる場合:○として、判定した。
【0030】
<塗料密着性> 供試材のS2 面にエポキシフェノール系塗料を塗装し、10mm×100 mmに切断した、2枚の試験片について、その塗装面同士をナイロンフィルムにて熱圧着した後、引張り試験機にてTピール試験を行った。そして、剥離界面を観察し、塗膜及びフィルムでの凝集破壊の場合は○、供試材と塗膜との間に界面がある場合は×、両者の混合の場合はΔとした。
【0031】
上記の各評価結果を、鋼板の被膜構成とともに、表1に示す。
なお、表中のSnめっき量、Fe−Sn−Ni合金層中のSn量、Niめっき量の値より、この発明で規定した上述の式(1)〜(3)における、X,Y及びZの値を求められる。すなわち、Xの値はSnめっき量から合金層中のSn量を差し引くことにより、X+Yの値はSnめっき量そのものであり、Zの値はNiめっき量そのものであり、Z/(Z+Y)は、合金層中のSn量及びNiめっき量の和で割り付けることにより求められる。
【0032】
【表1】
【0033】
表1から、実施例1、実施例2及び実施例4,6,7は、何れも耐食性、溶接性及び塗料密着性が共に十分なものであることがわかる。実施例3では、Sn量が少ないために耐食性と溶接性がやや劣化しているが、塗料密着性は十分である。実施例8は、S2 面のCr付着量が少ないために塗料密着性がやや劣化しているが、耐食性と溶接性は良好である。これに対して、比較例1はS1 面の金属Cr量が不十分であるために、耐食性に問題があり、比較例2はNiが含まれていないために溶接性が不十分であり、そして比較例3はS1 面及びS2 面金属Cr及びクロム水和酸化物量が不十分であるために、耐食性に難があると共に塗料未着性も不十分となった。
【0034】
【発明の効果】
この発明によれば、特にアルカリ性の内容物に対して缶内面側を未塗装で使用した場合においても、十分な耐食性を発揮し、しかも研削処理を施さずとも十分な溶接性を備える、溶接缶用めっき鋼板を提供することができる。[0001]
BACKGROUND OF THE INVENTION
This invention is a plated steel plate for a welding can used as a welding can body, such as an 18 liter can or a pail can, which is mainly used without coating the inner surface side of the can. The present invention relates to a plated steel plate for a welding can.
[0002]
[Prior art]
Tins and electrolytic chromic acid-treated steel sheets are used for the can bodies of 18 liter cans and pail cans. Above all, tinplate is excellent in corrosion resistance and weldability because of the thick Sn plating layer, but is expensive because of the large amount of Sn used, and is not preferable from the viewpoint of resource saving. On the other hand, since the electrolytic chromate-treated steel sheet does not use Sn, it is excellent in corrosion resistance without coating at low cost. On the other hand, the chromium hydrated oxide layer on the coating surface of the steel sheet is insulative, so it should be welded as it is. It is difficult to grind the surface of the welded portion in advance. Since the grinding powder generated in this grinding process adheres to the can after welding, which deteriorates the working environment, it is regarded as a problem particularly in food cans. Therefore, various attempts have been made to solve such problems.
[0003]
For example, Kokoku 3 In 69999 discloses, on the surface of the steel sheet, 40 to 150 mg / m 2 of the metal Cr layer and a metal Cr terms become non-metallic Cr layer of 5 to 25 mg / m 2 and a portion of the metal Cr It has been proposed to form a film in which is projected. Although the weldability is certainly improved by this proposal, since a part of the metal Cr is protruded, a thin portion of the metal Cr layer is locally generated and the corrosion resistance deteriorates.
[0004]
Further, in Kokoku 5-27720 discloses, on the surface of the steel sheet, 45~90Mg / metal Cr layer with a smooth precipitation of m 2, 1-10 mg / m sparingly soluble Cr hydrous oxide layer of 2 as Cr It has been proposed to form However, the weldability is inadequate and the thickness of the Cr hydrated oxide layer is reduced as compared with the conventional case, so that the corrosion resistance deteriorates.
[0005]
Thus, without impairing the corrosion resistance, in order to improve the weldability of the electrolytic chromic acid treated steel sheet, again since it is necessary to have a Sn even a trace amount on the surface of the steel sheet, in Kokoku 2-16397, JP-steel has a Sn layer of 50 to 900 mg / m 2 on the surface, have a non-metallic Cr layer of 5 to 50 mg / m 2 on at 7 to 100 mg / m 2 of the metal Cr layer and Cr in terms of its further A steel plate that is not covered by the Sn layer and has an exposed steel plate portion having a diameter of 0.5 to 20 μm in terms of a circle has been proposed.
[0006]
Here, it is said that Sn does not have to be heated and melted after Sn plating, so-called reflow, but if reflow is performed after Sn plating, the amount of Sn is reduced and the amount of metal Sn is reduced during reflow. Further, it is further reduced by the paint baking process, and the weldability becomes insufficient.
On the other hand, in the case where reflow is not performed after Sn plating, although there is an effect of improving weldability, there is a problem that the adhesion between the Sn plating layer and the base steel is remarkably lowered.
[0007]
Further, Japanese Patent Publication No. 6-96790 has a Sn layer of 20 to 200 mg / m 2 composed of Sn grains having a diameter of 0.2 to 2.0 μm and a height of 0.1 μm or more on the surface of the steel plate, and 30 A steel sheet having a metallic Cr layer of ˜150 mg / m 2 and a non-metallic Cr layer of 2 to 40 mg / m 2 in terms of Cr has been proposed. According to this proposal, it is possible to obtain a certain effect in terms of improving the weldability. However, in this case as well, the problem of poor adhesion of Sn plating has not been solved.
[0008]
In addition, the application of ultra-thin Sn-plated steel sheets for welded cans already in practical use in the field of beverage cans and food cans to gallon cans is also under consideration. Such a method for producing an ultrathin Sn-plated steel sheet is disclosed in, for example, Japanese Patent Application Laid-Open Nos. 60-17099 and 63-93894. That is, in JP-A-60-17099, a second layer including an Fe—Sn—Ni alloy layer is formed by reflow after forming an Fe—Ni alloy layer as a first layer on a steel plate. In addition, it is described that a film made of metal Cr and chromium hydrated oxide in a range of 5 to 20 mg / m 2 in terms of Cr is formed by electrolytic chromate treatment. Further, in Japanese Patent Laid-Open No. 63-93894, the amount of residual metal Sn after coating printing is 0.05 g / m on the surface which becomes the outer surface side of a steel plate having a Fe—Sn—Ni alloy layer on both sides. A Sn plating layer of 2 or less and a chromate layer made of 10-30 mg / m 2 of metal Cr and chromium hydrated oxide in the range of 3-15 mg / m 2 in terms of Cr, On the inner surface of the can after making the can, an Sn plating layer with a residual metal Sn amount of 0.2 to 1.0 g / m 2 or less after coating and printing, and 3 to 10 mg / m 2 of metallic Cr on the Sn plating layer And a steel plate for cans having a chromate layer made of chromium hydrated oxide in the range of 3 to 15 mg / m 2 in terms of Cr.
[0009]
[Problems to be solved by the invention]
These technologies have already been put to practical use in the field of beverage cans and food cans, and even when applied to gallon cans, they give sufficient weldability without grinding the welded part, so there is a problem in terms of weldability. I can say no. However, these technologies are only intended for use in beverage cans and food cans, and are based on the premise that both the inner and outer surfaces of the can are painted. The problem remains in terms of. In particular, when an alkaline solution is used as the contents of the can, the steel sheet having the Fe—Sn—Ni alloy layer has a significant problem that Sn rapidly dissolves and turns brown.
[0010]
The present invention is to provide a plated steel sheet that is excellent in corrosion resistance and discoloration resistance without coating in a steel sheet having a Fe-Sn-Ni layer and that has good plating adhesion and can be welded without grinding. to that it is also of the.
[0011]
[Means for Solving the Problems]
That is, the present invention has a Fe—Sn—Ni alloy layer and a Sn layer on at least one surface of a steel plate, and further covers the outermost surfaces of both surfaces of the steel plate with a surface coating composed of a metal Cr layer and a chromium hydrated oxide layer. an adult shall Te, wherein the steel sheet Fe - Sn - Ni alloy layer and the surface coating over one surface having a Sn layer, the adhesion amount is more than the 30mg / m 2 200 mg / m 2 or less of the metal Cr layer and coating weight consists hydrated chromium oxide layer of 3~25mg / m 2 of Cr terms are used in unpainted surface coating covering the surface of the other side of the steel sheet, the amount of deposition of the metal Cr layer Plated steel sheet for welding cans characterized by being 5 to 100 mg / m 2 (however, it has a Fe—Ni—Sn alloy layer on both sides of the steel sheet, a metal Sn layer on the upper layer, and a chromate layer on the uppermost layer) The total Sn amount on the inner surface of the can is 1.0 to 2.0 g / m 2 , the metal Cr amount is 10 to 40 mg / m 2 , and the chromium hydrate oxide amount is 2 m in terms of Cr. g / m 2 or more, the total Sn content on the outer surface of the steel plate is 0.2 to 0.8 g / m 2 , the amount of chromium hydrated oxide is 2 mg / m 2 or more in terms of Cr , and metal on both sides The total amount of Cr and chromium hydrated oxide is 45 mg / m 2 or less in terms of Cr , except for the plated steel sheet for welding cans, which has excellent coating adhesion .
[0013]
Moreover, in the said plated steel plate, Sn layer adhesion amount X (mg / m 2 ), Sn amount Y (mg / m 2 ) and Ni amount Z (mg / m 2 ) in the Fe—Sn—Ni alloy layer In practice, it is more preferable that the following expressions (1) to (3) are satisfied.
Record
100 ≦ X ≦ 800 ---- (1)
200 ≦ X + Y ≦ 1500 ---- (2)
0.01 ≦ Z / (Y + Z) ≦ 0.5 ---- (3)
[0014]
DETAILED DESCRIPTION OF THE INVENTION
As described above, in an application in which the inner surface of the can is used without coating, for example, when an alkaline solution is used as the can content, when a Sn-based steel plate having an Fe-Sn-Ni alloy layer is used for the can body, Sn Will dissolve rapidly and the surface will turn brown. Therefore, as a result of various studies on the means for preventing the dissolution of Sn in an alkaline solution, the inventors have found that a surface coating (hereinafter referred to as a metal chrome layer and a chromium hydrated oxide layer provided on the Sn layer on the steel sheet surface). It was found that it is effective to increase the adhesion amount of the metallic Cr layer particularly in the surface coating on one surface of the steel plate on the inner surface side of the can.
[0015]
In the conventional technology assumed to be applied to beverage cans and food cans, the maximum amount of metallic Cr in the surface coating is 30 mg / m 2 . The reason for this is that, firstly, improvement of paint adhesion is expected as an effect of metal Cr in the surface coating, and this effect of improving paint adhesion is when the amount of metal Cr approaches 30 mg / m 2. This is because it was uneconomical to deposit more metal Cr because of saturation. The second reason is that if the amount of Cr metal deposited on the Sn layer increases, alloying between Sn and ground iron, which occurs during paint baking, is promoted, and the amount of Sn remaining after painting decreases, so welding There was a problem that the property deteriorated.
[0016]
However, in the present invention, it is important to prevent the dissolution of Sn in the alkaline solution, particularly as an effect of the metallic Cr, and for that purpose, in the surface coating on one surface of the steel sheet which is mainly the inner surface of the can. In addition, the adhesion amount of the metal Cr layer needs to be 35 mg / m 2 or more and 200 mg / m 2 or less, and more preferably, good quality can be obtained by adjusting to 60 to 120 g / m 2 .
In other words, if the amount of deposited metal Cr layer is less than 35 mg / m 2 , the effect of suppressing Sn dissolution is not sufficient, while if it exceeds 200 mg / m 2 , this effect is saturated, so from an economical viewpoint. The upper limit was 200 mg / m 2 .
[0017]
Although it is disadvantageous from the viewpoint of weldability to increase the amount of metallic Cr according to the present invention, in the can used only on the outer surface side of the can, which is the main object of the present invention, and the inner surface side is used without coating. Since the number of times of coating baking is smaller than when the inner and outer surfaces of the can are coated, Sn is likely to remain after coating, so that sufficient weldability can be provided.
[0018]
Further, in the present invention, a chromium hydrated oxide layer having an adhesion amount of 3 to 25 mg / m 2 in terms of Cr is required on the surface coating on one surface of the steel sheet mainly on the inner surface of the can, and more preferably the amount of adhered 6~15mg / m 2. That is, when the adhesion amount of the chromium hydrated oxide layer is less than 3 mg / m 2 , the adhesion of the paint becomes insufficient, while when it exceeds 25 mg / m 2 , the effect on the paint adhesion is saturated and the appearance deteriorates. 3 to 25 mg / m 2 . Further, it is necessary to provide a surface coating composed of a metal Cr layer and a chromium hydrated oxide layer on the other surface of the steel plate which is the remaining outer surface of the can in order to ensure paint adhesion. The adhesion amount of the metal Cr layer and the chromium hydrated oxide layer in the surface coating formed on the other side may be the same as that of the one surface described above. Therefore, the amount of adhesion can be reduced as described later.
[0019]
In the above plated steel sheet, the Sn layer adhesion amount X (mg / m 2 ), the Sn amount Y (mg / m 2 ) and the Ni amount Z (mg / m 2 ) in the Fe—Sn—Ni alloy layer However, it is preferable that the following expressions (1) to (3) are satisfied.
Record
100 ≦ X ≦ 800 ---- (1)
200 ≦ X + Y ≦ 1500 ---- (2)
0.01 ≦ Z / (Y + Z) ≦ 0.5 ---- (3)
[0020]
In other words, a small amount of Sn is necessary on the surface of the steel sheet in order to ensure weldability without grinding, and it is necessary that a Sn layer of 50 mg / m 2 or more exists on the steel sheet during welding at a can manufacturer. Conceivable. The Sn layer is made of Sn that is not alloyed. Here, when coating is performed prior to welding during can making, alloying between the Sn layer and the steel plate occurs during baking, and the remaining amount of Sn becomes smaller than the Sn amount before baking. Therefore, in the present invention, in order to secure weldability in consideration of Sn reduction due to alloying by paint baking, the adhesion amount (X) as shown in the above formula (1): 100 to 800 mg / It is preferable to provide an m 2 Sn layer, and more preferably, the adhesion amount is 200 to 400 mg / m 2 . That is, if the Sn layer adhesion amount (X) is less than 100 mg / m 2 , the amount of Sn remaining during welding is less than 50 mg / m 2 , resulting in insufficient welding. If it exceeds 800 mg / m 2 , the weldability is sufficient, but this is not desirable from an economic point of view.
[0021]
Furthermore, an Fe—Sn—Ni alloy layer is required as a base for the Sn layer. In normal tinting, a Fe-Sn alloy layer is provided between Sn and a steel plate to improve corrosion resistance.If the amount of Sn is small as in the present invention, the alloy layer has improved corrosion resistance. It is expected to be effective as a barrier to suppress alloying between the base steel and Sn that occurs during paint baking. For this purpose, it is advantageous to form a dense alloy layer containing a small amount of Ni in the alloy. Of course, in order to improve this barrier effect, the thicker the alloy layer, the better. However, the effect is saturated at a certain value or more. From the above viewpoint, the Sn amount (Y) contained in the Fe—Sn—Ni alloy layer as shown in the above formula (2) is the sum (X + Y) of the Sn layer adhesion amount (X) remaining without being alloyed. ) as 200 ~1500mg / m 2 are preferred, more preferably 300 ~800 mg / m 2.
[0022]
On the other hand, the amount of Ni (Z) contained in the Fe-Sn-Ni alloy middle layer is determined in consideration of the amount of Sn in the alloy, and the sum of Ni and Sn in the alloy as shown in the above formula (3). The weight ratio with respect to (Z + Y) is preferably 0.01 to 0.5, and more preferably 0.05 to 0.3. If the weight ratio is less than 0.01, the effect of densifying the alloy layer is reduced by containing Ni, and the improvement of the barrier effect cannot be expected, and if it exceeds 0.5, alloying between Sn and Ni proceeds. Therefore, the alloying of Sn at the time of paint baking is rather promoted.
[0023]
In the present invention, the surface coating composed of the metal Cr layer and the chromium hydrated oxide layer on both surfaces of the steel sheet can be made different. The reason for this is that the inner surface of the can is generally required to have corrosion resistance without coating, and the amount of metallic Cr in the surface coating on one side of the steel plate that forms the inner surface of the can is 35 mg / m 2 or more and 200 mg / Although it is necessary to set it to m 2 or less, since the other surface on the outer surface side of the can is coated, it is only necessary to ensure sufficient coating adhesion. From such a viewpoint, the surface coating on the other surface has a metal Cr layer adhesion amount of 5 to 100 mg / m 2 and a chromium hydrated oxide layer adhesion amount of 2 mg / m 2 or more in terms of Cr .
[0024]
The plated steel sheet of the present invention can be obtained by various manufacturing methods, and the following <Method A> and <Method B> are advantageously adapted as typical methods.
<Method A>
Ni plating is applied to an unannealed cold-rolled steel sheet, and then annealed to form a Ni diffusion layer on the surface of the steel sheet, followed by temper rolling. An Sn layer and an Fe—Sn—Ni alloy layer are formed by performing a reflow treatment after Sn plating on the plating original plate thus obtained. Next, a method of forming a metal Cr layer and a chromium hydrated oxide layer having a predetermined adhesion amount by cathodic electrolysis in a chromate bath mainly containing chromic anhydride and auxiliary agents such as sulfuric acid and fluoride.
[0025]
<Method B>
An annealed and temper-rolled cold-rolled steel sheet is subjected to Ni plating, and then Sn plating and reflow treatment are performed to form a Sn layer and a Fe—Sn—Ni alloy layer. Furthermore, a method of forming a metal Cr layer and a chromium hydrated oxide layer having a predetermined adhesion amount by cathodic electrolysis in a chromate bath mainly containing chromic anhydride and auxiliary agents such as sulfuric acid and fluoride.
[0026]
【Example】
[Sample preparation method]
<Method A> An unannealed steel sheet with a thickness of 0.33 mm was Ni-plated using a watt bath, and then tempered to a steel sheet annealed in a HNX gas atmosphere of 10% H 2 + 90% N 2 with a reduction rate of 1.5%. The Sn layer and the Fe—Sn—Ni alloy layer were formed by rolling and performing a reflow treatment after Sn plating using a halogen bath. Further, a metal Cr layer and a chromium hydrated oxide layer were formed by cathodic electrolysis in a chromate bath of chromic anhydride: 60 g / L and flowing acid 0.6 g / L.
[0027]
<Method B> By performing Ni plating on a cold-rolled steel sheet that has been annealed and temper-rolled using a watt bath, and then performing a reflow treatment after Sn plating using a halogen bath, the Sn layer and the Fe-Sn-Ni alloy A layer was formed. Further, a metal Cr layer and a chromium hydrated oxide layer were formed by cathodic electrolysis in a chromate bath of chromic anhydride: 60 g / L and sulfuric acid 0.6 g / L.
[0028]
By the above method, plated steel sheets with various adhesion amounts were produced, and the following various quality evaluations were performed on each plated steel sheet.
[Quality evaluation method]
<Content corrosion resistance test> One side S 1 of the specimen cut into a 50 mm × 40 mm test piece (the other opposite side is S 2 ), from the half to the gas phase part and below is the liquid phase After being immersed in a glass container so that it becomes a part, the container was covered and sealed, and then left in a constant temperature room at 55 ° C. for 14 days, and then the state of corrosion was observed.
[0029]
<Weldability> After air baking at 170 ° C. for 10 minutes using a gas furnace, the S 1 surface Sn adhesion amount was measured in accordance with the electrolytic peeling method of JIS-G3303, and used as an index of weldability. And, when the remaining Sn adhesion amount after baking is less than 50 mg / m 2 : ×, when the remaining Sn adhesion amount after baking is 50 mg / m 2 to 100 mg / m 2 : Δ, remaining after baking When the Sn adhesion amount exceeded 100 mg / m 2 : judged as ○.
[0030]
<Paint adhesion> painted epoxy phenolic paint S 2 side of the test material was cut into 10 mm × 100 mm, for the two test pieces, after thermocompression bonding the coated surface with each other by a nylon film, A T peel test was conducted with a tensile tester. Then, the peeling interface was observed, and in the case of cohesive failure in the coating film and the film, it was evaluated as ◯, when there was an interface between the test material and the coating film, and when the both were mixed, Δ.
[0031]
Each evaluation result is shown in Table 1 together with the coating composition of the steel sheet.
From the values of Sn plating amount in the table, Sn amount in the Fe—Sn—Ni alloy layer, and Ni plating amount, X, Y and Z in the above formulas (1) to (3) defined in the present invention The value of is obtained. That is, the value of X is obtained by subtracting the amount of Sn in the alloy layer from the amount of Sn plating, the value of X + Y is the amount of Sn plating itself, the value of Z is the amount of Ni plating itself, and Z / (Z + Y) is It is obtained by assigning by the sum of the Sn amount and the Ni plating amount in the alloy layer.
[0032]
[Table 1]
[0033]
From Table 1, it can be seen that Example 1, Example 2 and Examples 4, 6 and 7 are all sufficient in corrosion resistance, weldability and paint adhesion. In Example 3, since the amount of Sn is small, the corrosion resistance and weldability are slightly deteriorated, but the paint adhesion is sufficient. In Example 8, although the adhesion amount of the paint is slightly deteriorated due to the small amount of Cr deposited on the S 2 surface, the corrosion resistance and weldability are good. On the other hand, Comparative Example 1 has a problem in corrosion resistance because the amount of metal Cr on the S 1 surface is insufficient, and Comparative Example 2 has insufficient weldability because it does not contain Ni. and Comparative example 3 in order S 1 side and S 2 side metallic Cr and hydrated chromium oxide content is insufficient, becomes paints arrive resistance even insufficient with a difficulty in corrosion resistance.
[0034]
【The invention's effect】
According to the present invention, a welded can that exhibits sufficient corrosion resistance and has sufficient weldability without being subjected to grinding treatment even when the inner surface of the can is used uncoated with alkaline content. A plated steel sheet can be provided.
Claims (2)
記
100 ≦X≦800 ----(1)
200 ≦X+Y≦1500 ----(2)
0.01≦Z/(Y+Z)≦0.5 ----(3)In claim 1, the Sn layer adhesion amount X (mg / m 2 ), the Sn amount Y (mg / m 2 ) and the Ni amount Z (mg / m 2 ) in the Fe-Sn-Ni alloy layer are as follows: A plated steel sheet for a welding can characterized by satisfying the expressions (1) to (3).
Record
100 ≦ X ≦ 800 ---- (1)
200 ≦ X + Y ≦ 1500 ---- (2)
0.01 ≦ Z / (Y + Z) ≦ 0.5 ---- (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP27870097A JP3890700B2 (en) | 1997-10-13 | 1997-10-13 | Plated steel sheet for welding cans |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP27870097A JP3890700B2 (en) | 1997-10-13 | 1997-10-13 | Plated steel sheet for welding cans |
Publications (2)
Publication Number | Publication Date |
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JPH11117094A JPH11117094A (en) | 1999-04-27 |
JP3890700B2 true JP3890700B2 (en) | 2007-03-07 |
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JP27870097A Expired - Fee Related JP3890700B2 (en) | 1997-10-13 | 1997-10-13 | Plated steel sheet for welding cans |
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JP (1) | JP3890700B2 (en) |
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1997
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