JP2018154913A - Black plated steel sheet excellent in scratch resistance - Google Patents
Black plated steel sheet excellent in scratch resistance Download PDFInfo
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Abstract
Description
本発明は、黒色めっき鋼板に関する。 The present invention relates to a black-plated steel sheet.
建築物の屋根材や外装材、家電製品、自動車などの分野では、意匠性などの観点から黒色の外観を有する鋼板のニーズが高まっている。鋼板の表面を黒色化する方法としては、鋼板の表面に黒色塗料を塗布して黒色塗膜を形成する方法がある。しかしながら、上記の分野では、耐食性の観点から溶融Ｚｎめっきや溶融Ａｌ含有Ｚｎ めっき、溶融Ａｌ、Ｍｇ含有Ｚｎめっきなどのめっきを施しためっき鋼板が使用されることが多く、これらのめっき鋼板の表面は金属光沢のある銀白色の色調を有している。したがって、黒色塗料の塗布により意匠性の高い黒色外観を得るためには、塗膜を厚くして下地色を隠蔽しなければならず、塗装コストが高くなってしまう。また、このように塗膜を厚くすると、スポット溶接などの抵抗溶接を行うことができなくなってしまうという問題もある。 In the fields of building roofing materials, exterior materials, home appliances, automobiles, and the like, there is an increasing need for steel plates having a black appearance from the viewpoint of design and the like. As a method for blackening the surface of a steel plate, there is a method of forming a black coating film by applying a black paint to the surface of the steel plate. However, in the above fields, plated steel sheets plated with hot-dip Zn plating, hot-dip Al-containing Zn plating, hot-melt Al, Mg-containing Zn plating, etc. are often used from the viewpoint of corrosion resistance. Has a silvery white color with metallic luster. Therefore, in order to obtain a black appearance with high designability by applying a black paint, the coating film must be thickened to conceal the base color, resulting in high coating costs. Further, when the coating film is thick in this way, there is a problem that resistance welding such as spot welding cannot be performed.
黒色塗膜を形成せずに、めっき鋼板の金属光沢および銀白色の色調を遮蔽する方法としては、めっき層そのものを黒色化する方法が提案されている（ 例えば、特許文献１参照）。特許文献１ には、溶融Ａｌ含有Ｚｎめっき鋼板に高温の水蒸気を２４時間以上吹き付けて、めっき層表層に薄い黒色皮膜を形成する方法が開示されている。特許文献１に記載の黒色めっき鋼板では、黒色化促進元素としてＭｇやＣｕ、Ｂｉなどをめっき層に含有させている。しかしながら、黒色化促進元素の含有量が１％を超えると、Ｚｎの酸化が抑制されるため、黒色化の促進効果が却って減少すると説明されている。 As a method for shielding the metallic luster and silver-white color tone of the plated steel sheet without forming a black coating film, a method of blackening the plating layer itself has been proposed (see, for example, Patent Document 1). Patent Document 1 discloses a method of forming a thin black film on the surface of the plating layer by spraying high-temperature water vapor on a molten Al-containing Zn-plated steel sheet for 24 hours or more. In the black plated steel sheet described in Patent Document 1, Mg, Cu, Bi, or the like is included in the plating layer as a blackening promoting element. However, it is described that when the content of the blackening promoting element exceeds 1%, the oxidation of Zn is suppressed, and thus the blackening promoting effect is decreased.
特許文献１に記載の黒色めっき鋼板には、めっき層の全厚さに亘って黒色化するとめっき層が脆化して密着性が低下してしまうため、厚い黒色皮膜を形成できないという問題がある。このため、加工などによりめっき層の表面に傷が付くと、めっき層自体の色である銀白色が露出して表面外観を損ねてしまうため、当該黒色めっき鋼板は強度の加工や高圧なで相手材が接触した場合の疵付きに耐えないものである。 The black-plated steel sheet described in Patent Document 1 has a problem in that when the black color is formed over the entire thickness of the plating layer, the plating layer becomes brittle and adhesiveness decreases, so that a thick black film cannot be formed. For this reason, if the surface of the plating layer is scratched by processing or the like, the silver white that is the color of the plating layer itself is exposed and the surface appearance is impaired. It cannot withstand the wrinkles when the material comes into contact.
本発明は、かかる点に鑑みてなされたものであり、加工時や接触時の耐疵付き性に優れた黒色めっき鋼板を提供することを目的とする。 This invention is made | formed in view of this point, and it aims at providing the black plating steel plate excellent in the abrasion resistance at the time of a process or a contact.
本発明者は、Ａｌ：０．１〜２２.０質量％、Ｍｇ：０．１〜１０.０質量％を含み、かつＺｎ２Ｍｇ相がめっき層中に分布している溶融Ａｌ、Ｍｇ含有Ｚｎめっき鋼板を原板として使用し、かつこのめっき鋼板を密閉容器中で水蒸気と接触させることにより、上記課題を解決できることを見出し、さらに検討を加えて本発明を完成させた。 The present inventor contains Al: 0.1 to 22.0 mass%, Mg: 0.1 to 10.0 mass%, and a molten Al and Mg containing Zn 2 Mg phase distributed in the plating layer The present inventors have found that the above problem can be solved by using a Zn-plated steel plate as an original plate and bringing the plated steel plate into contact with water vapor in a sealed container, and further studied and completed the present invention.
すなわち、本発明は、以下の黒色めっき鋼板に関する。
［１］ Ａｌ：０．１〜２２.０質量％、Ｍｇ：０．１〜１０.０質量％を含み、かつＺｎの黒色酸化物がめっき層中に分布している溶融Ａｌ、Ｍｇ含有Ｚｎめっき層を有し、前記溶融Ａｌ、Ｍｇ含有Ｚｎめっき層表面の明度は、Ｌ＊ 値で６０ 以下であるとともに、ＪＩＳ Ｋ ６９０２の疵付き試験において疵発生のない最大荷重がＡｌ：０．１〜２２.０質量％、Ｍｇ：０．１〜１０.０質量％を含み、かつＺｎ２Ｍｇ相がめっき層中に分布している溶融Ａｌ、Ｍｇ含有Ｚｎめっき鋼板と比べて１．５倍以上である黒色めっき鋼板。
［２］前記Ｚｎの黒色酸化物は、前記溶融Ａｌ、Ｍｇ含有Ｚｎめっき層中にラメラ状に分布している、［１］に記載の黒色めっき鋼板。
［３］前記Ｚｎの黒色酸化物は、Ｚｎ２Ｍｇ相に由来するＺｎの酸化物である、［１］または［２］に記載の黒色めっき鋼板。
［４］ 前記溶融Ａｌ、Ｍｇ含有Ｚｎめっき層の上に無機系皮膜をさらに有する、［１］〜［３］のいずれか一項に記載の黒色めっき鋼板。
［５］ 前記溶融Ａｌ、Ｍｇ含有Ｚｎめっき層の上に有機系樹脂皮膜をさらに有する、［１］〜［３］のいずれか一項に記載の黒色めっき鋼板。
That is, this invention relates to the following black plating steel plates.
[1] Molten Al, Mg-containing Zn containing Al: 0.1 to 22.0 mass%, Mg: 0.1 to 10.0 mass%, and a black oxide of Zn being distributed in the plating layer The lightness of the surface of the molten Al, Mg-containing Zn plating layer having a plating layer is 60 or less in terms of L * value, and the maximum load that does not generate wrinkles in the wrinkle test of JIS K 6902 is Al: 0.1 ˜22.0 mass%, Mg: 0.1 to 10.0 mass%, and Zn 2 Mg phase is distributed in the plating layer 1.5 times compared with the molten Al and Mg-containing Zn plated steel sheet This is the black-plated steel sheet.
[2] The black-plated steel sheet according to [1], wherein the black oxide of Zn is distributed in a lamellar manner in the molten Al and Mg-containing Zn plating layer.
[3] The black plated steel sheet according to [1] or [2], wherein the black oxide of Zn is an oxide of Zn derived from a Zn 2 Mg phase.
[4] The black-plated steel sheet according to any one of [1] to [3], further including an inorganic coating on the molten Al and Mg-containing Zn plating layer.
[5] The black-plated steel sheet according to any one of [1] to [3], further including an organic resin film on the molten Al and Mg-containing Zn plating layer.
本発明によれば、意匠性に優れた黒色の外観を有し、かつ加工時や接触時の耐疵付き性に優れた黒色めっき鋼板を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, it can provide the black plated steel plate which has the black external appearance excellent in the designability, and was excellent in the scratch resistance at the time of a process or contact.
本発明の黒色めっき鋼板は、基材鋼板と、溶融Ａｌ、Ｍｇ含有Ｚｎめっき層（ 以下「めっき層」ともいう）とを有する。本発明の黒色めっき鋼板は、さらに、めっき層の上に無
機系皮膜または有機系樹脂皮膜を有していてもよい。
The black-plated steel sheet of the present invention has a base steel sheet and a molten Al, Mg-containing Zn plating layer (hereinafter also referred to as “plating layer”). The black-plated steel sheet of the present invention may further have an inorganic coating or an organic resin coating on the plating layer.
本発明の黒色めっき鋼板は、１）めっき層中にＺｎの黒色酸化物が分布していること、２）めっき層表面の明度がＬ＊値で６０以下（好ましくは４０以下、さらに好ましくは３５以下）であること、ＪＩＳ Ｋ ６９０２の疵付き試験において疵発生のない最大荷重が比較的高いことを特徴とする。めっき層表面の明度（Ｌ＊値）は、分光型色差計を用いて、ＪＩＳ Ｋ ５６００に準拠した分光反射測定法で測定される。 In the black-plated steel sheet of the present invention, 1) the black oxide of Zn is distributed in the plating layer, and 2) the brightness of the plating layer surface is 60 or less (preferably 40 or less, more preferably 35) in terms of L * value. And the maximum load without wrinkle generation in the wrinkle test of JIS K 6902 is relatively high. The lightness (L * value) on the surface of the plating layer is measured by a spectral reflection measurement method based on JIS K 5600 using a spectral color difference meter.
［基材鋼板］
基材鋼板の種類は、特に限定されない。たとえば、基材鋼板としては、低炭素鋼や中炭素鋼、高炭素鋼、合金鋼などからなる鋼板を使用することができる。良好なプレス成形性が必要とされる場合は、低炭素Ｔｉ添加鋼、低炭素Ｎｂ添加鋼などからなる深絞り用鋼板が基材鋼板として好ましい。また、Ｐ、Ｓｉ、Ｍｎなどを添加した高強度鋼板を用いてもよい。
[Base steel sheet]
The kind of base steel plate is not particularly limited. For example, as the base steel plate, a steel plate made of low carbon steel, medium carbon steel, high carbon steel, alloy steel, or the like can be used. When good press formability is required, a steel sheet for deep drawing made of low carbon Ti-added steel, low carbon Nb-added steel, or the like is preferable as the base steel sheet. Moreover, you may use the high strength steel plate which added P, Si, Mn, etc.
［溶融Ａｌ、Ｍｇ含有Ｚｎめっき層］
本発明の黒色めっき鋼板の原板としては、Ａｌ：０．１〜２２.０質量％、Ｍｇ：０．１〜１０.０質量％を含み、かつＺｎ２Ｍｇ相がめっき層中に分布している溶融Ａｌ、Ｍｇ含有Ｚｎめっき層を有する溶融Ａｌ、Ｍｇ含有Ｚｎめっき鋼板が使用される。より好ましくは、さらにめっき層の金属組織としてＡｌの単独相を含有する溶融Ａｌ、Ｍｇ含有Ｚｎめっき層を有する溶融Ａｌ、Ｍｇ含有Ｚｎめっき鋼板が使用される。ここで「Ａｌの単独相」とは共晶組織が形成されていないＡｌ相を意味する。たとえば、Ａｌの単独相は、初晶のＡｌ相である。ＡｌおよびＭｇは、Ｚｎ系めっき鋼板の耐食性を向上させる元素であるが、本発明においては、後述するように黒色化のために必須の元素である。Ａｌ含有量またはＭｇ含有量が上記範囲の下限値より小さい場合、十分な耐食性が得られない。一方、上限値より大きい場合は、めっき鋼板製造の際にめっき浴表面に酸化物（ドロスの発生が過多となり、美麗なめっき鋼板が得られない。
[Molded Al, Mg-containing Zn plating layer]
As an original plate of the black plated steel plate of the present invention, Al: 0.1 to 22.0% by mass, Mg: 0.1 to 10.0% by mass, and Zn 2 Mg phase is distributed in the plating layer. A molten Al / Mg-containing Zn-plated steel sheet having a molten Al / Mg-containing Zn plating layer is used. More preferably, a molten Al containing a single phase of Al as a metal structure of the plated layer, a molten Al having a Mg-containing Zn plated layer, or a Mg-containing Zn plated steel sheet is used. Here, “single phase of Al” means an Al phase in which no eutectic structure is formed. For example, the Al single phase is a primary Al phase. Al and Mg are elements that improve the corrosion resistance of the Zn-based plated steel sheet, but are essential elements for blackening in the present invention, as will be described later. When the Al content or the Mg content is smaller than the lower limit of the above range, sufficient corrosion resistance cannot be obtained. On the other hand, when it is larger than the upper limit, an oxide (drosse is excessively generated on the surface of the plating bath during the production of the plated steel sheet, and a beautiful plated steel sheet cannot be obtained.
上記組成の溶融Ａｌ、Ｍｇ含有Ｚｎめっき層は、Ａｌ／Ｚｎ／Ｚｎ２Ｍｇの三元共晶組
織を含む。三元共晶組織中のＺｎ２Ｍｇ相は、Ｚｎ−Ｍｇの二元系平衡状態図におけるＺｎが約８４重量％の点付近に存在する金属間化合物相であり、めっき層全体にラメラ状に分布している。ただし、めっき層の断面を観察した場合、Ａｌ／Ｚｎ／Ｚｎ２Ｍｇの三元共晶組織が断面全体に占める割合は、めっき組成によって異なる。Ｚｎ−Ａｌ−Ｍｇの三元系においては、Ａｌが４質量％ 付近、Ｍｇが３質量％付近が共晶組成であるため、めっき組成がこの組成に近い場合にはＡｌ／Ｚｎ／Ｚｎ２Ｍｇの三元共晶組織は８０％ほどの面積率を示し、めっき断面において最も広い面積を示す相となる。しかし、組成が共晶組成から離れるほど面積率は減少し、Ａｌ／Ｚｎ／Ｚｎ２Ｍｇの三元共晶組織よりも他の相が面積率としては最大となることもある。また、めっき組成によっては、溶融Ａｌ、Ｍｇ含有Ｚｎめっき層は、さらに初晶のＡｌ相を含んでいる。
The molten Al, Mg-containing Zn plating layer having the above composition includes a ternary eutectic structure of Al / Zn / Zn 2 Mg. The Zn 2 Mg phase in the ternary eutectic structure is an intermetallic compound phase in the vicinity of the point where Zn is about 84% by weight in the Zn-Mg binary equilibrium diagram, and the entire plating layer is lamellar. Distributed. However, when the cross section of the plating layer is observed, the proportion of the Al / Zn / Zn 2 Mg ternary eutectic structure in the entire cross section varies depending on the plating composition. In the Zn—Al—Mg ternary system, Al is about 4% by mass, and Mg is about 3% by mass of eutectic composition. Therefore, when the plating composition is close to this composition, Al / Zn / Zn 2 Mg The ternary eutectic structure shows an area ratio of about 80%, and becomes a phase showing the widest area in the plated section. However, the area ratio decreases as the composition moves away from the eutectic composition, and the phase other than the ternary eutectic structure of Al / Zn / Zn 2 Mg may become the maximum as the area ratio. Further, depending on the plating composition, the molten Al and Mg-containing Zn plating layer further contains an Al phase of primary crystal.
本発明の黒色めっき鋼板の溶融Ａｌ、Ｍｇ含有Ｚｎめっき鋼板のめっき層内に分布しているＺｎ２Ｍｇ相は、ここまではＡｌ／Ｚｎ／Ｚｎ２Ｍｇ三元共晶組織を形成する相である場合について説明したが、本発明のめっき層組成において、Ａｌ／Ｚｎ２Ｍｇ二元共晶組織、またはＺｎ／Ｚｎ２Ｍｇ二元共晶組織を形成する相として現れることもある。これらに由来するＺｎ２Ｍｇ相であっても、共晶組織を形成するＺｎ２Ｍｇ相であれば、本発明の効果を奏する。 The Zn 2 Mg phase distributed in the plated layer of the molten Al and Mg-containing Zn plated steel sheet of the black plated steel sheet of the present invention is a phase that forms an Al / Zn / Zn 2 Mg ternary eutectic structure so far. As described above, in the plating layer composition of the present invention, it may appear as a phase forming an Al / Zn 2 Mg binary eutectic structure or a Zn / Zn 2 Mg binary eutectic structure. Even Zn 2 Mg phase derived from these, if Zn 2 Mg phase to form a eutectic structure, the effects of the present invention.
なお、本願明細書では、酸化物と水和酸化物とを総称して酸化物と称する。また、本願明細書において、めっき層中の各成分の含有量の値は、めっき層に含まれる各金属成分の質量をめっき層に含まれる全金属の質量で除したものを百分率で表したものである。すなわち、酸化物に含まれる酸素および水の質量は、めっき層中の成分として含まれない。したがって、水蒸気処理の際に金属成分の溶出が起こらない場合、水蒸気処理の前後においてめっき層中の各成分の含有量の値は変化しない。 In the present specification, oxides and hydrated oxides are collectively referred to as oxides. In the present specification, the content value of each component in the plating layer is expressed as a percentage obtained by dividing the mass of each metal component contained in the plating layer by the mass of all metals contained in the plating layer. It is. That is, the mass of oxygen and water contained in the oxide is not included as a component in the plating layer. Therefore, when the elution of the metal component does not occur during the steam treatment, the value of the content of each component in the plating layer does not change before and after the steam treatment.
溶融Ａｌ、Ｍｇ含有Ｚｎめっき層は、例えば、Ａｌ：０．１〜２２.０質量％、Ｍｇ：０．１〜１０.０質量％、残部：Ｚｎおよび不可避不純物からなるものを用いることが可能である。また、基材鋼板とめっき層との密着性を向上させるために、基材鋼板とめっき層との界面におけるＡｌ−Ｆｅ合金層の成長を抑制できるＳｉを０.００５質量％〜２.０質量％ の範囲でめっき層に添加してもよい。Ｓｉの濃度が２.０質量％を超えると、黒色化を阻害するＳｉ系酸化物がめっき層表面に生成してしまうおそれがある。また、Ｔｉ、Ｂ、Ｔｉ−Ｂ合金、Ｔｉ含有化合物またはＢ含有化合物をめっき層に添加してもよい。これらの化合物の添加量は、Ｔｉが０.００１質量％〜０.１質量％の範囲内となるように、Ｂが０.０００５質量％〜０.０４５質量％の範囲内となるように設定することが好ましい。ＴｉまたはＢを過剰量添加すると、めっき層に析出物を成長させるおそれがある。なお、めっき層中へのＴｉ、Ｂ、Ｔｉ−Ｂ合金、Ｔｉ含有化合物または 含有化合物の添加は、水蒸気処理による黒色化にほとんど影響を与えない。 As the molten Al and Mg-containing Zn plating layer, for example, a layer composed of Al: 0.1 to 22.0 mass%, Mg: 0.1 to 10.0 mass%, balance: Zn and inevitable impurities can be used. It is. Moreover, in order to improve the adhesiveness of a base steel plate and a plating layer, Si which can suppress the growth of the Al-Fe alloy layer in the interface of a base steel plate and a plating layer is 0.005 mass%-2.0 mass. % May be added to the plating layer. If the Si concentration exceeds 2.0 mass%, there is a possibility that a Si-based oxide that inhibits blackening may be generated on the surface of the plating layer. Further, Ti, B, Ti—B alloy, Ti-containing compound or B-containing compound may be added to the plating layer. The amount of these compounds added is set so that Ti is in the range of 0.001% to 0.1% by mass and B is in the range of 0.0005% to 0.045% by mass. It is preferable to do. If an excessive amount of Ti or B is added, there is a possibility that precipitates grow on the plating layer. Note that the addition of Ti, B, Ti-B alloy, Ti-containing compound or containing compound into the plating layer has little effect on the blackening by the steam treatment.
［黒色酸化物］
本発明の黒色めっき鋼板は、そのめっき層中に分布しているＺｎの黒色酸化物を含有する。ここで、めっき層中とは、めっき層表面とめっき層内部の両方を含む。
[Black oxide]
The black-plated steel sheet of the present invention contains Zn black oxide distributed in the plating layer. Here, in the plating layer includes both the surface of the plating layer and the inside of the plating layer.
本発明の黒色めっき鋼板では、Ｚｎ２Ｍｇ相に由来するＺｎの黒色酸化物がラメラ状に分布している（初晶Ａｌ相に由来するＡｌの黒色酸化物については後述する）。Ｚｎの黒色酸化物が生成する機構は、以下のように考えられる。 In the black plated steel sheet of the present invention, the black oxide of Zn derived from the Zn 2 Mg phase is distributed in a lamellar shape (the black oxide of Al derived from the primary Al phase will be described later). The mechanism of the formation of Zn black oxide is considered as follows.
上述の溶融Ａｌ、Ｍｇ含有Ｚｎめっき鋼板を密閉容器中で水蒸気に接触させると、まずめっき層表面の酸化皮膜がＨ２Ｏと反応して水和酸化物に変化するとともに、この酸化物層を通過したＨ２Ｏがめっき層中の金属と反応する。このとき、三元共晶組織を構成するＺｎ２Ｍｇ相に含まれるＺｎが優先的に酸化する。時間の経過とともに、Ｚｎ２Ｍｇ相に含まれるＺｎの酸化はめっき層の深さ方向に進行する。水蒸気雰囲気で酸素ポテンシャルが低下しているため、Ｚｎ酸化物の近傍に存在する、酸素との反応性の高いＭｇは、Ｚｎ酸化物から酸素を奪ってＭｇ酸化物となる。このため、Ｚｎ酸化物は、非化学量論組成で酸素欠乏型の酸化物に変化するものと考えられる。このように酸素欠乏型の酸化物が生成すると、その欠陥準位に光がトラップされるため、酸化物が黒色外観を呈することになる。したがって、本発明の黒色めっき鋼板では、特許文献１の黒色めっき鋼板とは異なり、めっき層中のＭｇの含有量が多いほど黒色化が促進される。一方、Ｚｎ相に含まれるＺｎは、酸化反応の進行が遅く、その大部分が金属のまま残存する。結果として、本発明により得られる黒色めっき鋼板のめっき層は、Ｚｎ２Ｍｇ相に由来するＺｎの黒色酸化物がラメラ状に分布する金属組織となる。 When the above-mentioned molten Al, Mg-containing Zn-plated steel sheet was brought into contact with water vapor in a sealed container, the oxide film on the surface of the plating layer first reacted with H2O to change to a hydrated oxide, and passed through this oxide layer. H2O reacts with the metal in the plating layer. At this time, Zn contained in the Zn 2 Mg phase constituting the ternary eutectic structure is preferentially oxidized. Over time, the oxidation of Zn contained in the Zn 2 Mg phase proceeds in the depth direction of the plating layer. Since the oxygen potential is lowered in the water vapor atmosphere, Mg having high reactivity with oxygen existing in the vicinity of the Zn oxide takes oxygen from the Zn oxide and becomes Mg oxide. For this reason, the Zn oxide is considered to change into an oxygen-deficient oxide having a non-stoichiometric composition. When an oxygen-deficient oxide is generated in this way, light is trapped in the defect level, and the oxide exhibits a black appearance. Therefore, unlike the black-plated steel sheet of Patent Document 1, the black-plated steel sheet of the present invention promotes blackening as the Mg content in the plating layer increases. On the other hand, the Zn contained in the Zn phase has a slow oxidation reaction, and most of it remains as a metal. As a result, the plated layer of the black plated steel sheet obtained by the present invention has a metal structure in which the black oxide of Zn derived from the Zn 2 Mg phase is distributed in a lamellar shape.
また、めっき層中にＡｌの初晶が存在する場合は、より短時間でめっき層内部にＺｎの
黒色酸化物が進行する。Ａｌは、ＺｎおよびＭｇと比較してＨ２Ｏとの反応性が高い。したがって、金属Ａｌは、高温の水蒸気と接触すると、速やかに酸化物となる。初晶Ａｌ相に含まれるＡｌが速やかに酸化した後は、その下側に位置するＺｎ２Ｍｇ相に含まれるＺｎの酸化がめっき層の深さ方向に進行する。このように初晶Ａｌ相などのＡｌの単独相は、めっき層内部のＺｎの酸化を促進するための「パス」となる。結果として、めっき層中に初晶Ａｌ相などのＡｌの単独相が存在する場合は、より短時間でめっき層内部にＺｎの黒色酸化物が形成される。同様に三元共晶中のＡｌもＺｎの酸化を促進させる「パス」となっているものと推測される。
Further, when an Al primary crystal is present in the plating layer, Zn black oxide proceeds in the plating layer in a shorter time. Al is more reactive with H2O than Zn and Mg. Therefore, when metal Al comes into contact with high-temperature water vapor, it quickly becomes an oxide. After the Al contained in the primary crystal Al phase is rapidly oxidized, the oxidation of Zn contained in the Zn 2 Mg phase located therebelow proceeds in the depth direction of the plating layer. Thus, the single phase of Al such as the primary crystal Al phase becomes a “pass” for promoting the oxidation of Zn inside the plating layer. As a result, when an Al single phase such as primary crystal Al phase is present in the plating layer, Zn black oxide is formed inside the plating layer in a shorter time. Similarly, it is presumed that Al in the ternary eutectic is also a “pass” for promoting the oxidation of Zn.
［無機系皮膜および有機系樹脂皮膜］
本発明の黒色めっき鋼板のめっき層の表面には、無機系皮膜または有機系樹脂皮膜が形成されていてもよい。無機系皮膜および有機系樹脂皮膜は、黒色めっき鋼板の耐食性や耐カジリ性（黒色外観の保持性）などを向上させる。皮膜の成分については、特に限定されるものではない。
[Inorganic film and organic resin film]
An inorganic coating or an organic resin coating may be formed on the surface of the plating layer of the black-plated steel sheet of the present invention. The inorganic coating and the organic resin coating improve the corrosion resistance and galling resistance (retainability of black appearance) of the black-plated steel sheet. The components of the film are not particularly limited.
本発明の黒色めっき鋼板は、めっき層中に非常に硬いＺｎの酸化物が存在するため加工時や接触時に疵が発生しにくい構造となっている。特に針状の相手材が接触した場合には、局所的に接触力が強くなり、この状態で相手材が移動すると引っ掻き疵が発生するが、前述のように硬いＺｎの酸化物によって、その引っ掻き疵の発生が抑制されることになり、これによって加工や接触の以前の良好な外観を保つことができる。また、本発明の黒色めっき鋼板は、塗膜を形成していないため、通常の溶融Ａｌ、Ｍｇ含有Ｚｎめっき鋼板と同様にスポット溶接をすることも可能である。 The black-plated steel sheet of the present invention has a structure in which wrinkles are unlikely to occur during processing or contact because a very hard Zn oxide is present in the plating layer. In particular, when a needle-shaped mating material comes into contact, the contact force becomes locally strong, and when the mating material moves in this state, scratches are generated. As described above, the scratching is caused by the hard Zn oxide. Generation | occurrence | production of wrinkles will be suppressed and this can maintain the favorable external appearance before a process and contact. Moreover, since the black plating steel plate of this invention has not formed the coating film, it is also possible to carry out spot welding similarly to a normal molten Al and Mg containing Zn plating steel plate.
板厚１.２ｍｍのＳＰＣＣを基材として、めっき層の厚みが１０μｍの溶融Ａｌ、Ｍｇ含有Ｚｎめっき鋼板を作製した。めっき成分は、Ａｌが６．０質量％、Ｍｇが３．０質量％、Ｚｎが９１質量％とした。前記めっき鋼板を水蒸気と接触させて黒色化処理を行った。水蒸気と接触させる条件は、温度１２０℃、相対湿度８５％、酸素濃度３％、処理時間２０時間である。 Using SPCC having a plate thickness of 1.2 mm as a base material, a molten Al / Mg-containing Zn-plated steel plate having a plating layer thickness of 10 μm was prepared. The plating components were 6.0 mass% for Al, 3.0 mass% for Mg, and 91 mass% for Zn. The plated steel sheet was brought into contact with water vapor to perform blackening treatment. The conditions for contact with water vapor are a temperature of 120 ° C., a relative humidity of 85%, an oxygen concentration of 3%, and a treatment time of 20 hours.
上記の黒色化処理しためっき鋼板（以下、黒色めっき鋼板という）と黒色化処理していないめっき鋼板（以下、めっき鋼板という）を用いて、黒色めっき鋼板のめっき層表面の明度（Ｌ＊値）の測定と、疵付き試験を行なった。
黒色めっき鋼板のめっき層表面の明度（Ｌ＊値）は、分光型色差計を用い、ＪＩＳ Ｋ ５６００に準拠した分光反射測定法で測定した。
疵付き試験は、ＪＩＳ Ｋ ６９０２の疵付き試験に準拠し、先端が４５°であるダイヤモンド製の接触針を黒色めっき鋼板のめっき層表面に押付けて疵を付け、目視により疵付きの有無を判定した。
Using the above-mentioned blackened plated steel sheet (hereinafter referred to as black plated steel sheet) and non-blackened plated steel sheet (hereinafter referred to as plated steel sheet), the lightness (L * value) of the plating layer surface of the black plated steel sheet Measurement and a wrinkle test were performed.
The brightness (L * value) of the plating layer surface of the black-plated steel sheet was measured by a spectral reflection measurement method based on JIS K 5600 using a spectral color difference meter.
The wrinkle test conforms to the wrinkle test of JIS K 6902, and a diamond contact needle with a 45 ° tip is pressed against the surface of the plating layer of the black-plated steel plate to make a wrinkle and visually check for wrinkles. did.
黒色めっき鋼板のめっき層表面の明度（Ｌ＊値）は、３２であった。 The brightness (L * value) of the plating layer surface of the black-plated steel sheet was 32.
また、疵付け試験を行った結果、めっき鋼板では接触針の加圧力が０．３Ｎで疵が発生したが、黒色めっき鋼板で疵が発生した加圧力は０．６Ｎであった。 Further, as a result of the brazing test, wrinkles were generated when the applied pressure of the contact needle was 0.3 N in the plated steel sheet, but the applied pressure where wrinkles were generated in the black plated steel sheet was 0.6 N.
本発明では、表面の明度Ｌ＊値が６０以下で、耐疵付き性に優れた黒色めっき鋼板であり、建築物の屋根材や外装材、家電製品、自動車などの意匠性が必要な部品に好適に用いることができる。
In the present invention, the surface brightness L * value is 60 or less, and it is a black-plated steel sheet having excellent scratch resistance, and is used for parts that require design such as building roofing materials, exterior materials, home appliances, and automobiles. It can be used suitably.
Claims (5)
The black plated steel sheet according to any one of claims 1 to 3, further comprising an organic resin film on the molten Al, Mg-containing Zn plating layer.
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| WO2013160973A1 (en) * | 2012-04-25 | 2013-10-31 | 日新製鋼株式会社 | Black-plated steel sheet |
| JP2013227622A (en) * | 2012-04-25 | 2013-11-07 | Nisshin Steel Co Ltd | Plated black steel plate |
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| WO2013160973A1 (en) * | 2012-04-25 | 2013-10-31 | 日新製鋼株式会社 | Black-plated steel sheet |
| JP2013227622A (en) * | 2012-04-25 | 2013-11-07 | Nisshin Steel Co Ltd | Plated black steel plate |
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