JPH1171699A - Steel sheet for welded can having high-speed seam weldability after high-temperature short-time coating and baking - Google Patents
Steel sheet for welded can having high-speed seam weldability after high-temperature short-time coating and bakingInfo
- Publication number
- JPH1171699A JPH1171699A JP23265597A JP23265597A JPH1171699A JP H1171699 A JPH1171699 A JP H1171699A JP 23265597 A JP23265597 A JP 23265597A JP 23265597 A JP23265597 A JP 23265597A JP H1171699 A JPH1171699 A JP H1171699A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- tin plating
- layer
- steel sheet
- granular
- 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.)
- Withdrawn
Links
Classifications
-
- 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
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
-
- 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
- C23C28/3455—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 with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、塗料を高温短時間
で焼き付ける際に、錫が十分に残存し、良好な高速シー
ム溶接性を有する溶接缶用鋼板に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a steel plate for a welding can which has sufficient tin remaining when a paint is baked at a high temperature for a short time and has good high-speed seam weldability.
【０００２】[0002]
【従来の技術】金属容器は、缶胴と缶底が一体化し、イ
ージーオープンエンドとの２つの部分からなる２ピース
缶と、缶胴、缶底、イージーオープンエンドの３つの部
分からなる３ピース缶の２種類に大別される。さらに、
３ピース缶は缶胴の接合法によって、溶接缶と接着缶と
に分類される。溶接缶は、３ピース缶の缶胴を接合する
方法としてシーム溶接法を用いて製胴するものである。2. Description of the Related Art A metal container has a can body and a can bottom integrated with each other and has a two-piece can having an easy open end and a three-piece can having a can body, a can bottom and an easy open end. It is roughly divided into two types of cans. further,
Three-piece cans are classified into welded cans and adhesive cans according to the method of joining the can bodies. The welding can is produced by using a seam welding method as a method for joining the three-piece can bodies.
【０００３】溶接缶は、ス−ドロニック社が開発した高
速ワイヤーシーム溶接法が世界中に広まるにつれて、従
来の半田缶に代わりその生産が増大した。溶接缶は、現
在、３ピース缶の代表的な缶種といっても過言ではな
い。従来より、溶接缶用材料としては、特公昭５６−１
６９７８９号公報にみられるニッケルめっき鋼板、特公
昭６２−１４２４０号公報にみられる薄錫めっき鋼板等
が高速シーム溶接可能な材料として広く使用されてき
た。[0003] As the high-speed wire seam welding method developed by Sudronic has spread throughout the world, the production of welding cans has increased in place of conventional solder cans. It is no exaggeration to say that welding cans are currently a representative can type of three-piece cans. Conventionally, as a material for welding cans,
A nickel-plated steel sheet shown in Japanese Patent No. 69789, a thin tin-plated steel sheet shown in Japanese Patent Publication No. 62-14240, and the like have been widely used as materials capable of high-speed seam welding.
【０００４】[0004]
【発明が解決しようとする課題】これらの材料は、開発
当初は十分に実用性能を満足していたが、最近では製缶
会社での使われ方がより過酷なものとなったため、大幅
な性能向上を要請されている。製缶会社での材料の使わ
れ方が大きく変化したのは、缶コスト低減のための材料
のゲージダウンが進められたことと、塗装工程の合理化
が進められたことの２点である。従来、塗装工程は切り
板での塗装が主流であったが、生産性の向上を狙い、コ
イルコーティングが実現された。切り板塗装では２００
℃前後の温度で１０〜２０分の時間で焼き付けるもので
ある。これに対し、コイルコーティングでは、材料はコ
イルで供給され、ストリップにロールで塗装後２６０〜
２９０℃の高温で２０秒弱の短時間で塗料を焼き付ける
ものである。At the beginning of development, these materials sufficiently satisfied the practical performance, but recently the use of these materials by canning companies has become more severe, so that their performance has been greatly increased. Improvements have been requested. There are two major changes in how materials are used by canning companies: the reduction of material gauges to reduce can costs and the streamlining of the coating process. Conventionally, in the painting process, coating with a cut plate has been the mainstream, but coil coating has been realized with the aim of improving productivity. 200 for cutting board painting
It is to be baked at a temperature of about ℃ for 10 to 20 minutes. On the other hand, in coil coating, the material is supplied in a coil, and after coating on a strip with a roll,
The coating is baked at a high temperature of 290 ° C. in a short time of less than 20 seconds.
【０００５】上述のように、材料の使われ方が大きく変
化したために、上記の材料は次のような問題を抱えるよ
うになった。まず、ニッケルめっき鋼板は、コイルコー
ティングでの高温短時間塗装焼き付けには十分に対応で
きるが、表面の接触抵抗が比較的高いため、材料の板厚
が薄くなると、十分な接合強度を有し、かつスプラッシ
ュ（溶融した鉄の飛び出し）の発生が少ない適正溶接電
流範囲が狭くなり、実用に供する事が難しくなってく
る。一方、薄錫めっき鋼板は、金属錫の融点が低く、軟
質であるため溶接性が良好なのでゲージダウンにはある
程度対応できるが、コイルコーティングの高温短時間塗
装焼き付けにより錫の合金化が従来の切り板塗装焼き付
けよりも大幅に進むため、残存する金属錫が少なくな
り、溶接性の低下を招いている。良好な高速シーム溶接
性を確保するには、塗装焼き付け後に合金化していない
金属錫を確保することが必須条件である。この金属錫を
塗装焼き付け後に残存させるためにこれまで多くの努力
がなされたが、コイルコーティングでの高温短時間塗装
焼き付けでも金属錫が残存するという溶接缶用材料はま
だ開発されていない。[0005] As described above, since the usage of the material has changed greatly, the above-mentioned material has the following problems. First, nickel-plated steel sheets can sufficiently cope with high-temperature and short-time paint baking with coil coating, but because the contact resistance of the surface is relatively high, when the sheet thickness of the material becomes thin, it has sufficient bonding strength, In addition, the appropriate welding current range in which the generation of splash (moulded iron jumps out) is small, and the practical welding range becomes difficult. On the other hand, thin tin-plated steel sheets have a low melting point of metallic tin and are soft and have good weldability, so they can cope with gauge down to some extent. Since the process proceeds significantly more than the plate coating baking, the amount of remaining metallic tin is reduced, resulting in a decrease in weldability. In order to secure good high-speed seam weldability, it is an essential condition to secure unalloyed metal tin after paint baking. Many efforts have been made to make this metallic tin remain after baking, but a material for a welding can in which metallic tin remains even after high-temperature and short-time baking in coil coating has not yet been developed.
【０００６】本発明は、高温短時間の塗装焼き付け条件
でも錫の合金化が進行せず、高速シーム溶接性に十分な
金属錫を確保できる高速溶接性に優れた溶接缶用鋼板の
提供を目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a steel plate for a welding can which is excellent in high-speed weldability in which tin alloying does not progress even under conditions of high-temperature and short-time paint baking and which can secure sufficient metal tin for high-speed seam weldability. And
【０００７】[0007]
【課題を解決するための手段】発明者らは、錫の融点を
超えるような塗料の高温短時間塗装焼き付けでも、錫が
十分に残存するための、錫めっきの形態を鋭意検討した
結果、めっき界面における錫が粒状であれば地鉄との合
金反応が起こりにくくなることを見いだし、さらに、粒
状錫めっきのみでは鋼板全面を被覆しないため、鋼板の
露出部をなくし耐食性を向上させる目的で層状錫めっき
を粒状錫めっきの上に設けることを想到した。図１は本
発明の溶接缶用鋼板のめっき層の積層状態を図示した断
面模式図である。コイルコーティングでの高温短時間焼
き付け後に、良好な高速シーム溶接性を有する本発明の
溶接缶用鋼板は、基板５上に粒状錫めっき１を有し、そ
の上に層状錫めっき２、更に、その上層に金属クロム層
３と水和酸化クロム層４を有することを特徴とする。Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the form of tin plating so that tin can sufficiently remain even at high temperature and short time baking of a paint exceeding the melting point of tin. It has been found that if the tin at the interface is granular, the alloy reaction with the base iron is unlikely to occur.Furthermore, the granular tin plating alone does not cover the entire surface of the steel sheet. It has been conceived that the plating is provided on the granular tin plating. FIG. 1 is a schematic cross-sectional view illustrating the state of lamination of plated layers of a steel plate for a welding can according to the present invention. The steel plate for a welding can of the present invention having good high-speed seam weldability after high-temperature short-time baking with coil coating has a granular tin plating 1 on a substrate 5, a layered tin plating 2 thereon, and a It has a metal chromium layer 3 and a hydrated chromium oxide layer 4 as an upper layer.
【０００８】すなわち、本願発明の要旨は以下のとおり
である。 （１）鋼板上に、粒状錫めっき、その上に層状錫めっ
き、さらに、その上層に金属クロム層と水和酸化クロム
層を有することを特徴とする高温短時間塗装焼き付け後
の高速シーム溶接性に優れた溶接缶用鋼板。 （２）前記粒状錫めっきの粒径が、０．２〜１０μｍで
あり、かつ、その数が１ｍｍ2 当たり１×１０3 〜１×
１０6 個であることを特徴とする前記（１）に記載の溶
接缶用鋼板。That is, the gist of the present invention is as follows. (1) High-speed seam weldability after high-temperature and short-time paint baking, characterized by having granular tin plating on a steel sheet, layered tin plating thereon, and a metal chromium layer and a hydrated chromium oxide layer thereon Excellent steel plate for welding cans. (2) The particle size of the granular tin plating is 0.2 to 10 μm, and the number thereof is 1 × 10 3 to 1 × per 1 mm 2.
The steel plate for a welding can according to the above (1), wherein the number is 10 6 .
【０００９】（３）全錫めっき量が、２００〜１５００
ｍｇ／ｍ2 であることを特徴とする前記 （１）または
（２）に記載の溶接缶用鋼板。 （４）２〜１５ｍｇ／ｍ2 の金属クロム層とクロム換算
で２〜２０ｍｇ／ｍ2の水和酸化クロム層を有すること
を特徴とする前記（１）〜（３）のいずれかに記載の溶
接缶用鋼板。(3) The total tin plating amount is 200 to 1500
mg / m 2 , wherein the steel sheet for a welding can according to the above (1) or (2), (4) The method according to any one of the above (1) to (3), which has a chromium metal layer of 2 to 15 mg / m 2 and a hydrated chromium oxide layer of 2 to 20 mg / m 2 in terms of chromium. Steel plate for welding cans.
【００１０】[0010]
【発明の実施の形態】以下に本発明について詳細に説明
する。まず発明の基板としての鋼板は、通常容器用に用
いられるものでよく、特に限定するものではない。本発
明のポイントは、高温短時間の塗装焼き付け後、錫が十
分に残存するための錫の形態にある。通常の錫めっき鋼
板では、高温短時間の塗装焼き付け時に金属錫は殆ど合
金化してしまい、高速シーム溶接に必須な金属錫が十分
に残存しないという結果になる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, the steel sheet as the substrate of the present invention may be one usually used for containers, and is not particularly limited. The point of the present invention lies in the form of tin so that the tin remains sufficiently after baking at high temperature and short time. In a normal tin-plated steel sheet, when tin is baked at a high temperature for a short time, the metal tin is almost alloyed, resulting in that the metal tin essential for high-speed seam welding does not sufficiently remain.
【００１１】種々の検討を重ねた結果、錫の融点を超え
るような塗料の高温短時間塗装焼き付けでも、錫が十分
に残存するためには、錫めっきの形態が粒状であればよ
いことが判明した。あらかじめ錫を粒状の形態をとらせ
ることにより、鋼板と錫めっきの界面から粒状錫の頂上
までの距離を長くすることができる。この様にすると、
鋼板と金属錫の相互拡散に伴う原子の実質的移動距離が
長くなるため、錫の合金化が抑制される。As a result of various studies, it has been found that the tin plating should be in a granular form in order for tin to remain sufficiently even after baking at a high temperature for a short time at a temperature exceeding the melting point of tin. did. By preliminarily forming tin in a granular form, the distance from the interface between the steel sheet and the tin plating to the top of the granular tin can be increased. In this case,
Since the substantial movement distance of the atoms due to the interdiffusion between the steel sheet and the metallic tin increases, the alloying of tin is suppressed.
【００１２】粒状錫の粒径が０．２μｍ未満では、鋼板
と錫めっきの界面から粒状錫の頂上までの距離が十分で
なく、高温での焼き付け後に金属錫を残存させるのは難
しい。また、粒状錫の粒径が１０μｍを越えるような粗
大粒となると、錫めっきと鋼板との密着性が低下するの
で好ましくない。また、粒状錫の個数が１ｍｍ2 当たり
１×１０3 個未満になると溶接時の接点が減るために、
溶接性が悪化し、１ｍｍ2 当たり１×１０6 個を越える
と粒状錫の粒径も小さくなるために金属錫の残存が難し
くなる。以上の理由から粒状錫の粒径を０．２μｍ〜１
０μｍとし、かつ、その数を１ｍｍ2 当たり１×１０3
〜１×１０6 個と規制する。If the particle size of the granular tin is less than 0.2 μm, the distance from the interface between the steel sheet and the tin plating to the top of the granular tin is not sufficient, and it is difficult to leave metallic tin after baking at a high temperature. Further, if the particle size of the granular tin exceeds 10 μm, it is not preferable because the adhesion between the tin plating and the steel sheet is reduced. Also, if the number of granular tin is less than 1 × 10 3 per 1 mm 2 , the number of contacts at the time of welding decreases,
When the weldability deteriorates and the number of particles exceeds 1 × 10 6 per 1 mm 2 , the particle size of the granular tin becomes small, so that it becomes difficult to leave metallic tin. For the above reasons, the particle size of the granular tin is 0.2 μm to 1 μm.
0 μm and the number is 1 × 10 3 per mm 2
Restrict to ~ 1 × 10 6 .
【００１３】粒状錫の形成方法については、本発明は、
特に限定するものではないが、例えば、錫めっき法とし
て一般的な電解析出法の電解浴において、Ｓｎ2+の濃度
を通常よりも低くし、光沢剤を添加せずに、低電流密度
で電解めっきする方法が、粒状錫の形成には適してい
る。このようにすると、平滑な錫めっきではなく、「め
っきやけ」の状態となるので粒状錫が得られ、さらに、
形成された粒状錫の粒径は、電流密度の増加にともない
減少する傾向があるので、この方法によれば粒状錫の粒
径や密度の制御も比較的容易である。With regard to the method of forming particulate tin, the present invention provides:
Although not particularly limited, for example, in an electrolytic bath of a general electrolytic deposition method as a tin plating method, the concentration of Sn 2+ is made lower than usual, without adding a brightener, and at a low current density. The electrolytic plating method is suitable for forming the granular tin. In this case, granular tin is obtained because it is in a state of “plating burnt” instead of smooth tin plating.
Since the particle size of the formed particulate tin tends to decrease as the current density increases, the control of the particle size and density of the particulate tin is relatively easy according to this method.
【００１４】粒状錫めっきのみでは鋼板全面を被覆しな
いため、鋼板の露出部をなくし耐食性を向上させる目的
で層状錫めっきを粒状錫めっきの上に設ける。また、粒
状錫めっき量と層状錫めっき量の和である全錫めっき量
が、２００ｍｇ／ｍ2 未満の場合は錫の形態を粒状とし
た場合でも、高温での塗装焼き付け後に金属錫を残存さ
せるのは難しく、１５００ｍｇ／ｍ2 を越えると、高速
シーム溶接に必要な金属錫が残存する効果が飽和すると
ともに経済的に不利である。以上の理由から全錫めっき
量を２００〜１５００ｍｇ／ｍ2 と規制する。Since only the granular tin plating does not cover the entire surface of the steel sheet, layered tin plating is provided on the granular tin plating for the purpose of eliminating the exposed portion of the steel sheet and improving the corrosion resistance. When the total tin plating amount, which is the sum of the amount of granular tin plating and the amount of layered tin plating, is less than 200 mg / m 2 , metallic tin remains after baking paint at a high temperature even when the form of tin is granular. If it exceeds 1500 mg / m 2 , the effect of remaining metallic tin necessary for high-speed seam welding is saturated and is economically disadvantageous. For the above reasons, the total tin plating amount is regulated to 200 to 1500 mg / m 2 .
【００１５】また、錫めっき後にリフロー処理を行った
場合でも、粒状錫の形態は損なわれないので、リフロー
処理の有無は特に限定するものではない。さらに、錫め
っき層の上層に良好な塗料密着性を確保するという目的
で金属クロム層と水和酸化クロム層を設ける。錫めっき
鋼板の塗料密着性は、電解クロム鋼板に比べて一般に良
くないといわれている。この理由は、保管時あるいは塗
装焼き付け時に脆い錫酸化膜層が生成し、それが凝集破
壊を起こすからである。錫酸化膜層の成長を防ぐために
は、金属錫の表面を金属クロム層で被覆することが有効
である。錫めっき層上の金属クロム量が２ｍｇ／ｍ2 未
満の場合は、錫表面の被覆が十分でなく保管時あるいは
塗装焼き付け時に錫酸化膜層が成長し、良好な塗料密着
性を確保することが難しい。一方、金属クロムが１５ｍ
ｇ／ｍ2 を越える場合は、良好な塗料密着性を確保する
という効果が飽和する。また、水和酸化クロム層ほどで
はないが、金属クロムは、高融点で硬質のため、高速シ
ーム溶接性という観点からも１５ｍｇ／ｍ2 を越えない
ことが望ましい。[0015] Even if the reflow treatment is performed after the tin plating, the presence or absence of the reflow treatment is not particularly limited because the form of the granular tin is not impaired. Further, a metal chromium layer and a hydrated chromium oxide layer are provided on the tin plating layer for the purpose of ensuring good paint adhesion. It is generally said that tin-plated steel sheets have poor paint adhesion compared to electrolytic chromium steel sheets. The reason for this is that a brittle tin oxide film layer is formed during storage or baking, which causes cohesive failure. In order to prevent the growth of the tin oxide film layer, it is effective to cover the surface of metal tin with a metal chromium layer. If the amount of metallic chromium on the tin plating layer is less than 2 mg / m 2 , the tin surface coating is not sufficient, and the tin oxide film layer grows during storage or baking of paint, and good paint adhesion can be secured. difficult. On the other hand, metal chrome is 15m
If it exceeds g / m 2 , the effect of securing good paint adhesion is saturated. Although not as high as the hydrated chromium oxide layer, chromium metal has a high melting point and is hard, so that it does not exceed 15 mg / m 2 from the viewpoint of high-speed seam weldability.
【００１６】金属クロム層の上層には水和酸化クロム層
が存在するが、これは塗料との界面での良好な密着性を
確保するために必要である。水和酸化クロム層が２ｍｇ
／ｍ 2 未満では、良好な密着性を確保するのが困難であ
る。又、水和酸化クロム層が２０ｍｇ／ｍ2 を越える場
合は、シーム溶接性が劣化し、溶接缶が高速で製缶でき
なくなる。これらの理由から、水和酸化クロムの量を２
〜２０ｍｇ／ｍ2 と規制する。A hydrated chromium oxide layer is formed on the metal chromium layer.
Is present, which provides good adhesion at the interface with the paint.
Necessary to secure. 2mg hydrated chromium oxide layer
/ M TwoBelow, it is difficult to ensure good adhesion.
You. In addition, the hydrated chromium oxide layer is 20 mg / mTwoA place to cross
The seam weldability deteriorates, and the
Disappears. For these reasons, the amount of hydrated chromium oxide is
~ 20mg / mTwoAnd regulate.
【００１７】このようにして、コイルコーティング等の
高温短時間で塗料を焼き付ける塗装方法でも、良好な高
速シーム溶接性を発揮する溶接缶用鋼板が得られる。[0017] In this manner, even with a coating method of baking a paint at a high temperature for a short time, such as a coil coating, a steel sheet for a welding can exhibiting good high-speed seam weldability can be obtained.
【００１８】[0018]
【実施例】以下、本発明の実施例について述べる。板厚
０．１９ｍｍの容器用鋼板を、８０℃で３％水酸化ナト
リウム中で電解脱脂し、常温で１０％硫酸中で電解酸洗
を行い、鋼板表面を活性化させた。その後に浴温５０℃
で２価錫イオン濃度１５ｇ／ｌ、硫酸濃度４０ｇ／ｌ、
光沢剤無添加の電解浴から粒状錫を形成させた。粒状錫
の粒径とめっき量は、電解時の電流密度と供給クーロン
数で制御した。その後、光沢添加剤を含むフェノールス
ルホン酸錫めっき浴中で層状錫めっきを行い所定の金属
錫量となるようにした。錫めっき後、フラックスを塗布
せず速やかに抵抗加熱によりリフロー処理を行った。そ
して、温度５０℃のクロム酸１００ｇ／ｌ、硫酸１ｇ／
ｌの水溶液中で電解し、金属クロム層と水和酸化クロム
層を形成させた。金属クロム、水和酸化クロム量とも電
流密度と供給クーロン数で調整するとともに、水和酸化
クロム量については電解終了後、水洗までの溶解時間を
調整して制御した。Embodiments of the present invention will be described below. A 0.19 mm thick steel plate for a container was electrolytically degreased in 3% sodium hydroxide at 80 ° C. and electrolytically pickled in 10% sulfuric acid at room temperature to activate the steel plate surface. Then the bath temperature is 50 ℃
With a divalent tin ion concentration of 15 g / l, a sulfuric acid concentration of 40 g / l,
Granular tin was formed from the electrolytic bath without the brightener. The particle size and the amount of plating of the granular tin were controlled by the current density and the number of supplied coulombs during electrolysis. Thereafter, layered tin plating was performed in a tin phenolsulfonate plating bath containing a gloss additive so as to obtain a predetermined amount of metal tin. After the tin plating, a reflow treatment was immediately performed by resistance heating without applying a flux. Then, at a temperature of 50 ° C., chromic acid 100 g / l, sulfuric acid 1 g /
1 in an aqueous solution to form a metal chromium layer and a hydrated chromium oxide layer. Both the amounts of chromium metal and hydrated chromium oxide were adjusted by the current density and the number of coulombs supplied, and the amount of hydrated chromium oxide was controlled by adjusting the dissolution time from completion of electrolysis to washing with water.
【００１９】このようにして作製した本発明例とあわせ
て作製した比較例を表１に示す。ここで、粒状錫の粒径
は走査型電子顕微鏡により１０００〜５０００倍の観察
で求めるとともに、画像処理を行い単位面積当たりの個
数を求めた。錫量は蛍光Ｘ線法にて測定した。また、ク
ロム量については全クロム量を蛍光Ｘ線法で測定した
後、ｐＨを１０に調整した炭酸ナトリウム水溶液中で陽
極電解し、残ったクロム量を蛍光Ｘ線法で測定し水和酸
化クロム量とした。金属クロム量は、全クロム量から水
和酸化クロム量を差し引いて求めた。Table 1 shows a comparative example produced in combination with the present invention thus produced. Here, the particle size of the granular tin was determined by observation at a magnification of 1000 to 5000 with a scanning electron microscope, and image processing was performed to determine the number per unit area. The tin amount was measured by a fluorescent X-ray method. Regarding the amount of chromium, the total amount of chromium was measured by a fluorescent X-ray method, followed by anodic electrolysis in an aqueous solution of sodium carbonate adjusted to pH 10, and the amount of residual chromium was measured by a fluorescent X-ray method to determine the amount of chromium oxide hydrate. Amount. The amount of chromium metal was determined by subtracting the amount of hydrated chromium oxide from the total amount of chromium.
【００２０】これらの発明例と比較例の性能を以下の項
目で評価した。 （１）溶接性 各種の発明例と比較例の試験片を２７５℃まで１８秒で
昇温させ、その後に２１０℃で１０分、１９０℃で２０
分の追い焼きを行った。その後にワイヤースピード７０
ｍ／分の高速シーム溶接機でラップ代０．４ｍｍで溶接
し、適正溶接電流範囲を求めた。適正溶接電流範囲は、
スプラッシュが発生しない溶接電流を上限とし、溶接部
を引き裂くピール試験において十分な接合強度が得られ
る溶接電流を下限として求めた。表１に溶接性を評価し
た結果を示すが、評価基準は以下の基準によった。The performances of these invention examples and comparative examples were evaluated by the following items. (1) Weldability The test pieces of various invention examples and comparative examples were heated to 275 ° C. in 18 seconds, and then heated at 210 ° C. for 10 minutes and at 190 ° C. for 20 minutes.
I made a minute post-baking. After that, wire speed 70
Welding was performed with a lap margin of 0.4 mm using a high-speed seam welder of m / min, and an appropriate welding current range was determined. The proper welding current range is
The welding current at which no splash was generated was taken as the upper limit, and the welding current at which sufficient joining strength was obtained in the peel test for tearing the welded portion was found as the lower limit. Table 1 shows the results of evaluating the weldability, and the evaluation criteria were based on the following criteria.
【００２１】 ◎：適正溶接電流範囲が十分に広く、良好な溶接性を有
するレベル。 ○：適正溶接電流範囲は狭いが、実用的には問題ないレ
ベル。 △：適正溶接電流範囲が狭く、実用に供する事ができな
いレベル。 ×：適正溶接電流範囲が存在しないレベル。 （２）塗装耐食性 各種の発明例と比較例の試験片に缶用のエポキシフェノ
ール系塗料を６０ｍｇ／ｄｍ2 塗布し、その後２７５℃
まで１８秒で昇温させ、その後に２１０℃で１０分、１
９０℃で２０分の追い焼きを行った。その後に５０×５
０ｍｍにカットし、端面を裏面をラッカーでシールし
た。塗装面にカッターで鉄面に達するクロスカット傷を
入れ、試験片を作製した。作製した試験片を大気開放下
で１．５％クエン酸と１．５％塩化ナトリウム混合水溶
液５００ｍｌ中に浸漬し、５０℃で９６時間放置した。
試験後速やかに試験片を取り出し、テーピング剥離を行
い、塗装後の耐食性を評価した。評価結果を表１に示す
が、評価基準は以下の基準によった。A: A level having a sufficiently wide appropriate welding current range and good weldability. ：: The appropriate welding current range is narrow, but there is no practical problem. Δ: Level where the appropriate welding current range is narrow and cannot be put to practical use. ×: Level where no appropriate welding current range exists. (2) Paint corrosion resistance 60 mg / dm 2 of an epoxy phenol paint for cans was applied to test pieces of various invention examples and comparative examples, and then 275 ° C.
To 210 ° C. for 10 minutes,
After-baking was performed at 90 ° C. for 20 minutes. Then 50 × 5
It was cut to 0 mm, and the end face was sealed on the back face with lacquer. A cross-cut wound reaching the iron surface was made on the painted surface with a cutter to prepare a test piece. The prepared test piece was immersed in a mixed aqueous solution of 1.5% citric acid and 1.5% sodium chloride in 500 ml under the atmosphere and left at 50 ° C. for 96 hours.
The test piece was taken out immediately after the test, subjected to taping peeling, and the corrosion resistance after coating was evaluated. The evaluation results are shown in Table 1. The evaluation criteria were as follows.
【００２２】 ○：クロスカット部近傍で塗膜剥離がなく、その他の塗
装部でも点状腐食の認められないレベル。 △：クロスカット部近傍の塗膜が０．２〜０．５ｍｍ剥
離しており、その他の塗装部にも点状の腐食が若干認め
られる。 ×：クロスカット部近傍の塗膜が０．５ｍｍ以上剥離
し、その他の塗装部にも多くの点状腐食が認められる。：: No peeling of the coating film near the cross cut portion, and no point corrosion is observed in other coating portions. Δ: The coating film in the vicinity of the cross cut portion was peeled off by 0.2 to 0.5 mm, and a little point-like corrosion was also observed in other coating portions. X: The coating film in the vicinity of the cross cut portion was peeled by 0.5 mm or more, and many spot-like corrosions were also observed in other coated portions.
【００２３】（３）実缶試験 各種の発明例と比較例の試験片に缶用のエポキシフェノ
ール系塗料を溶接部を除いて６０ｍｇ／ｄｍ2 塗布し、
その後２７５℃まで１８秒で昇温させ、その後に２１０
℃で１０分、１９０℃で２０分の追い焼きを行った。そ
の後に、ワイヤースピード７０ｍ／分の高速シーム溶接
機でラップ代０．４ｍｍで溶接し、溶接部はオルガノゾ
ル系塗料で補修し、溶接缶の胴を作製した。(3) Actual can test An epoxy phenol paint for cans was applied at 60 mg / dm 2 to the test pieces of various invention examples and comparative examples, except for welded parts.
Thereafter, the temperature was raised to 275 ° C. in 18 seconds,
Post-baking was performed at 10 ° C. for 10 minutes and at 190 ° C. for 20 minutes. Thereafter, welding was performed with a lap margin of 0.4 mm using a high-speed seam welding machine with a wire speed of 70 m / min, and the weld was repaired with an organosol-based paint to produce a welded can body.
【００２４】胴をダブルネックイン加工するとともにア
ルミ製のイージーオープンエンドを巻き締め、内容物と
してコーヒーとオレンジジュースを充填し、電解クロム
酸処理鋼板の塗装板で作製した蓋を巻き締めた。このよ
うにして、作製した実缶を３８℃で１２ヶ月間保管し、
鉄の内容物中への溶出量を測定した。測定結果を表１に
示す。The body was double-necked and the aluminum easy open end was tightly wound, filled with coffee and orange juice as contents, and a lid made of a coated plate of electrolytic chromic acid-treated steel sheet was tightly wound. The actual can thus prepared is stored at 38 ° C. for 12 months,
The amount of iron eluted into the contents was measured. Table 1 shows the measurement results.
【００２５】[0025]
【表１】 [Table 1]
【００２６】鉄の溶出量は、コーヒーに関しては、０．
５ｐｐｍ以下を良好とし、オレンジジュースに関しては
０．８ｐｐｍ以下を良好とした。表１の総合的評価から
明らかなように、本発明の溶接缶用鋼板は、錫の融点を
超えるような高温で塗料を焼き付けるような場合でも、
実用上十分良好な高速シーム溶接性を有し、塗装後の耐
食性についても良好な性能が確保されている。The amount of iron eluted is 0.1 for coffee.
5 ppm or less was determined to be good, and for orange juice, 0.8 ppm or less was determined to be good. As is clear from the comprehensive evaluation in Table 1, the steel sheet for a welding can of the present invention is suitable for baking paint at a high temperature exceeding the melting point of tin.
It has good high-speed seam weldability for practical use and good corrosion resistance after painting.
【００２７】[0027]
【発明の効果】本発明の溶接缶用鋼板は、鋼板上に粒状
の錫めっき、その上に層状錫めっき、金属クロム層と水
和酸化クロム層を有しているので、錫の融点を超えるよ
うな高温で塗料を焼き付けるような場合でも、実用上十
分良好な高速シーム溶接性を有し、塗装後の耐食性につ
いても良好な性能が確保されている。したがって、本発
明は工業的に、非常に価値の高い発明であるといえる。The steel plate for a welding can of the present invention has a granular tin plating on a steel plate, a layered tin plating thereon, a metal chromium layer and a hydrated chromium oxide layer, so that the melting point of tin is exceeded. Even when the paint is baked at such a high temperature, it has practically sufficiently good high-speed seam weldability and good corrosion resistance after painting. Therefore, it can be said that the present invention is an industrially very valuable invention.
【図１】本発明の溶接缶用鋼板を示す図である。FIG. 1 is a view showing a steel plate for a welding can of the present invention.
１…粒状錫めっき ２…層状錫めっき ３…金属クロム層 ４…水和酸化クロム層 ５…基板 1: Granular tin plating 2: Layered tin plating 3: Metal chromium layer 4: Hydrated chromium oxide layer 5: Substrate
フロントページの続き (72)発明者 平野 茂 福岡県北九州市戸畑区飛幡町１−１ 新日 本製鐵株式会社八幡製鐵所内Continued on the front page (72) Inventor Shigeru Hirano 1-1 Niwahata-cho, Tobata-ku, Kitakyushu-shi, Fukuoka Nippon Steel Corporation Inside Yawata Works
Claims (4)
錫めっき、さらに、その上層に金属クロム層と水和酸化
クロム層を有することを特徴とする高温短時間塗装焼き
付け後の溶接缶用鋼板。1. A welding can after high-temperature and short-time paint baking, characterized in that it has granular tin plating on a steel sheet, layered tin plating thereon, and further has a metal chromium layer and a hydrated chromium oxide layer thereon. For steel plate.
０μｍであり、かつ、その数が１ｍｍ2 当たり１×１０
3 〜１×１０6 個であることを特徴とする請求項１に記
載の溶接缶用鋼板。2. The particle size of the granular tin plating is 0.2-1.
It is 0 .mu.m, and the number is 1 mm 2 per 1 × 10
The steel plate for a welding can according to claim 1, wherein the number is 3 to 1 x 10 < 6 >.
／ｍ2 であることを特徴とする請求項１または２に記載
の溶接缶用鋼板。3. The total tin plating amount is 200 to 1500 mg.
/ M 2. The steel sheet for a welding can according to claim 1 or 2, wherein
ロム換算で２〜２０ｍｇ／ｍ2 の水和酸化クロム層を有
することを特徴とする請求項１〜３のいずれかに記載の
溶接缶用鋼板。4. The welding according to claim 1, wherein the welding has a chromium metal layer of 2 to 15 mg / m 2 and a hydrated chromium oxide layer of 2 to 20 mg / m 2 in terms of chromium. Steel plate for cans.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23265597A JPH1171699A (en) | 1997-08-28 | 1997-08-28 | Steel sheet for welded can having high-speed seam weldability after high-temperature short-time coating and baking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23265597A JPH1171699A (en) | 1997-08-28 | 1997-08-28 | Steel sheet for welded can having high-speed seam weldability after high-temperature short-time coating and baking |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1171699A true JPH1171699A (en) | 1999-03-16 |
Family
ID=16942716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23265597A Withdrawn JPH1171699A (en) | 1997-08-28 | 1997-08-28 | Steel sheet for welded can having high-speed seam weldability after high-temperature short-time coating and baking |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1171699A (en) |
-
1997
- 1997-08-28 JP JP23265597A patent/JPH1171699A/en not_active Withdrawn
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