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JP2001115273A - HOT DIP Zn-Al SERIES PLATED STEEL SHEET EXCELLENT IN SECULAR BLACKENING RESISTANCE - Google Patents

HOT DIP Zn-Al SERIES PLATED STEEL SHEET EXCELLENT IN SECULAR BLACKENING RESISTANCE

Info

Publication number
JP2001115273A
JP2001115273A JP29756399A JP29756399A JP2001115273A JP 2001115273 A JP2001115273 A JP 2001115273A JP 29756399 A JP29756399 A JP 29756399A JP 29756399 A JP29756399 A JP 29756399A JP 2001115273 A JP2001115273 A JP 2001115273A
Authority
JP
Japan
Prior art keywords
steel sheet
hot
dip
plated steel
weight
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.)
Pending
Application number
JP29756399A
Other languages
Japanese (ja)
Inventor
Shiro Fujii
史朗 藤井
Ikuro Yamaoka
育郎 山岡
Kazumi Nishimura
一実 西村
Akira Tanaka
暁 田中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Original Assignee
Nippon Steel Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Steel Corp filed Critical Nippon Steel Corp
Priority to JP29756399A priority Critical patent/JP2001115273A/en
Publication of JP2001115273A publication Critical patent/JP2001115273A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322Coatings 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
    • C23C28/3225Coatings 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 with at least one zinc-based layer
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings 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
    • C23C28/345Coatings 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

PROBLEM TO BE SOLVED: To produce a hot dip Zn-Al series plated steel sheet excellent in secular blackening resistance. SOLUTION: As to this hot dip Zn-Al series plated steel sheet excellent in secular blackening resistance, in a hot dip Zn-Al series plated steel sheet having a plating layer containing, by weight, 0.1 to 70% Al, and the balance Zn with inevitable impurities, the surface of the plating layer is provided with a film layer containing one or two or more kinds among boric acid and borate compounds by 0.01 to 5 g/m2.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、耐経時黒変性に優
れた溶融Zn−Al合金めっき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 hot-dip Zn-Al alloy-plated steel sheet having excellent resistance to blackening over time.

【0002】[0002]

【従来の技術】最近、建材、土木分野において、未塗装
状態あるいは加工後に塗装を施した溶融Znめっき鋼板
が使用されるが、これらの鋼板の多くはクロメート処理
された状態でコイルあるいは切り板のままで梱包されて
一定期間、倉庫等に保管された後に各種部材に加工され
て使用される。これらの保管中、クロメート処理によっ
て白錆の発生は顕著に防止されるが、湿度の高い梅雨時
等には、クロメート処理材に経時黒変(黒錆)が生じる
ことがあり、商品価値を著しく低下させることから、耐
経時黒変性向上への要望が高かった。溶融Zn−Alめ
っき鋼板は、溶融Znめっき鋼板より耐食性の優れた鋼
板であるが、クロメート処理の有無に関わらず黒変に対
する耐性は通常の溶融Znめっき鋼板と大差なく、改善
が望まれていた。
2. Description of the Related Art Recently, in the field of building materials and civil engineering, hot-dip galvanized steel sheets which have been unpainted or coated after processing are used. Most of these steel sheets are subjected to chromate treatment in the form of coils or cut sheets. After being packed as it is and stored in a warehouse or the like for a certain period of time, it is processed into various members and used. During storage, the occurrence of white rust is significantly prevented by the chromate treatment. However, during the rainy season when the humidity is high, the chromate-treated material may undergo blackening over time (black rust), significantly increasing the commercial value. There is a high demand for improvement of blackening resistance over time because of lowering. The hot-dip Zn-Al coated steel sheet is a steel sheet having better corrosion resistance than the hot-dip Zn-coated steel sheet. However, the resistance to blackening regardless of the presence or absence of the chromate treatment is not much different from that of the normal hot-dip Zn-coated steel sheet, and improvement is desired. .

【0003】経時黒変を抑制するための措置として、例
えば、特公平3−49982号公報に開示されている亜
鉛系合金めっき鋼板をNiイオン、Coイオンあるいは
その両者の混合溶液で浸漬処理またはスプレー処理しN
iやCoを付着させる方法、特公平5−33311号公
報に開示されているCoの水酸化物、Feの水酸化物あ
るいは両者を含む水溶液を100℃以上のめっき面にス
プレーして酸化皮膜を形成させる方法などが公知であ
る。いずれの場合も、これらの溶液で処理した後、めっ
き面の経時黒変は少し抑制されるものの、必ずしもその
効果は十分ではなかった。
As a measure for suppressing blackening with time, for example, a zinc-based alloy-coated steel sheet disclosed in Japanese Patent Publication No. 3-49982 is immersed or sprayed with a solution of Ni ions or Co ions or a mixed solution of both. Processing N
The method of attaching i or Co, the hydroxide of Co disclosed in Japanese Patent Publication No. 5-33311, the hydroxide of Fe, or an aqueous solution containing both is sprayed on the plating surface at 100 ° C. or more to form an oxide film. A method for forming the film is known. In each case, after treatment with these solutions, blackening over time of the plated surface was slightly suppressed, but the effect was not always sufficient.

【0004】[0004]

【発明が解決しようとする課題】本発明は、前記のよう
な従来技術の問題点を解決して、耐経時黒変性の優れた
溶融Zn−Al合金めっき鋼板を提供することを目的と
している。
SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a hot-dip Zn-Al alloy-plated steel sheet having excellent resistance to blackening over time.

【0005】[0005]

【課題を解決するための手段】発明者らは、めっき表面
に少量の黒変防止成分を均一に分布させることにより優
れた耐経時黒変性を発現するZn−Al合金めっき鋼板
を開発すべく、種々検討した。その結果、鋼板の後処理
工程でめっき表面に経時黒変性抑制成分として硼酸およ
び硼酸塩化合物む薄膜を形成させれば良好な耐経時黒変
性が得られることを見出し本発明を完成させたものであ
って、その要旨とするところは、 (1)重量%で、Al:0.1〜70重量%を含有し、
残部Znおよび不可避不純物よりなるめっき層を有する
溶融Zn−Al系めっき鋼板であって、めっき層の表面
に、硼酸、硼酸塩化合物のうち1種または2種以上含有
する皮膜層を0.01〜5g/m2 有することを特徴と
する耐経時黒変性に優れた溶融Zn−Al系めっき鋼
板。
Means for Solving the Problems The inventors of the present invention have developed a Zn-Al alloy plated steel sheet which exhibits excellent anti-aging blackening by uniformly distributing a small amount of a blackening preventing component on the plating surface. Various studies were made. As a result, it has been found that good temporal blackening resistance can be obtained by forming a thin film containing boric acid and a borate compound as a temporal blackening inhibiting component on a plating surface in a post-treatment step of a steel sheet, and completed the present invention. Therefore, the gist of the invention is as follows: (1) By weight%, Al: 0.1 to 70% by weight,
A hot-dip Zn—Al-based plated steel sheet having a plating layer composed of a balance of Zn and unavoidable impurities, wherein a coating layer containing one or more of boric acid and a borate compound on a surface of the plating layer is 0.01 to 0.01%. A hot-dip Zn-Al-based plated steel sheet excellent in blackening resistance over time, characterized by having 5 g / m 2 .

【0006】(2)めっき層が、重量%で、Mg:0.
1〜30%、Si:0.1〜5%の1種または2種を、
さらに含有することを特徴とする前記(1)に記載の耐
経時黒変性に優れた溶融Zn−Al系めっき鋼板。 (3)めっき層が、重量%で、Sn:0.5〜10%、
Sb:0.05〜1%、Pb:0.05〜1%の1種ま
たは2種以上を、さらに含有することを特徴とする前記
(1)または(2)に記載の耐経時黒変性に優れた溶融
Zn−Al系めっき鋼板。 (4)皮膜層が、Cr,Si,Ni,Co,Znのうち
1種または2種以上の元素を含む、無機化合物、有機樹
脂あるいは無機化合物と有機樹脂の両方より形成される
ことを特徴とする前記(1)〜(3)のいずれかに記載
の耐経時黒変性に優れた溶融Zn−Al系めっき鋼板で
ある。
(2) When the plating layer is composed of Mg: 0.1% by weight.
1 to 30%, one or two kinds of Si: 0.1 to 5%,
The hot-dip Zn-Al-based plated steel sheet according to the above (1), further comprising: (3) The plating layer is, by weight%, Sn: 0.5 to 10%,
One or more of Sb: 0.05 to 1% and Pb: 0.05 to 1% are further contained. Excellent hot-dip Zn-Al plated steel sheet. (4) The coating layer is formed of an inorganic compound, an organic resin, or both an inorganic compound and an organic resin, containing one or more of Cr, Si, Ni, Co, and Zn. The hot-dip Zn—Al-based plated steel sheet according to any one of the above (1) to (3), which is excellent in blackening resistance over time.

【0007】[0007]

【発明の実施の形態】以下、本発明の実施の形態を詳細
に説明する。本発明の要点は、溶融Zn−Al系めっき
面上に皮膜形成能を有する無機化合物や有機樹脂を用い
て硼酸および硼酸塩化合物を含有する皮膜を形成させる
ことで、めっき外観すなわち、湿潤雰囲気中でのめっき
表面の耐経時黒変性に優れた溶融Zn−Alめっき鋼板
を提供することにある。
Embodiments of the present invention will be described below in detail. The gist of the present invention is to form a film containing boric acid and a borate compound on a hot-dip Zn-Al-based plating surface using an inorganic compound or an organic resin having a film forming ability, so that plating appearance, that is, in a wet atmosphere To provide a hot-dip Zn-Al-plated steel sheet having excellent resistance to blackening over time of the plating surface.

【0008】本発明におけるめっき層組成は、Alを
0.1〜70重量%を含有し、残部Znおよび不可避不
純物からなるものとする。Alは、めっき層と素地鋼板
間のめっき密着性を改善し、耐食性を向上させる。Al
が0.1重量%以下ではめっき密着性が低下する。ま
た、溶融めっき浴中でのFe−Zn系金属間化合物を形
成し、めっき浴中ドロスが多量に発生し品質低下の原因
となる。70重量%を超える場合はめっき浴の融点が高
くなる為、めっき浴中機器の溶損、加熱コスト増大等の
問題が生じる。
The composition of the plating layer in the present invention contains 0.1 to 70% by weight of Al, and the balance consists of Zn and unavoidable impurities. Al improves plating adhesion between the plating layer and the base steel sheet, and improves corrosion resistance. Al
Is less than 0.1% by weight, the plating adhesion decreases. In addition, an Fe-Zn-based intermetallic compound is formed in a hot-dip plating bath, and a large amount of dross is generated in the plating bath, which causes a deterioration in quality. When the content exceeds 70% by weight, the melting point of the plating bath becomes high, so that problems such as erosion of equipment in the plating bath and increase in heating cost occur.

【0009】これに加え、以下の元素を選択的に添加し
ても良い。Mgは、0.1%以上の添加でめっき層の耐
食性を大幅に向上させる。しかし、30重量%を超えて
添加しても、その効果は飽和するばかりでなく、酸化物
となりめっき浴面に黒色ドロスが発生し品質低下の原因
となる。Siは、0.1%以上の添加で、めっき層の耐
食性を向上させると共にめっき層と素地鋼板の間でのF
e−Zn合金化反応およびFe−Al合金化反応を抑制
する効果がある。しかし、Siを5重量%を超えて添加
してもその効果が飽和するばかりでなく、ドロス発生量
が増大し品質低下の原因となる。
In addition, the following elements may be selectively added. Mg significantly improves the corrosion resistance of the plating layer when added at 0.1% or more. However, even if it is added in excess of 30% by weight, the effect is not only saturated, but also becomes an oxide, and black dross is generated on the plating bath surface, which causes quality deterioration. Si is added in an amount of 0.1% or more to improve the corrosion resistance of the plating layer and to reduce F between the plating layer and the base steel sheet.
This has the effect of suppressing the e-Zn alloying reaction and the Fe-Al alloying reaction. However, even if Si is added in excess of 5% by weight, the effect is not only saturated, but also the amount of dross generated increases, which causes quality deterioration.

【0010】Sn,Sb,Pbは、めっき表面にスパン
グル模様を生成させる必要がある場合に添加する。Sn
は、0.5重量%以上の添加でその効果が現れるが、1
0重量%を超える添加にてその効果は飽和する。Sb,
Pbは、それぞれ、0.05重量%以上の添加でその効
果が現れるが、1重量%を超えて添加してもその効果は
飽和する。さらに、Tiは、めっき層の耐食性向上とめ
っき組織を微細化させる効果を持つので、効果の現れる
0.01重量%以上を添加しても良い。しかし、5重量
%を超えて添加してもその効果は飽和するばかりでな
く、ドロス発生量が増大し品質低下の原因となる。
[0010] Sn, Sb and Pb are added when it is necessary to form a spangle pattern on the plating surface. Sn
Is effective when added at 0.5% by weight or more.
The effect saturates with the addition exceeding 0% by weight. Sb,
Pb has its effect when added in an amount of 0.05% by weight or more, but its effect is saturated even when it is added in an amount exceeding 1% by weight. Further, Ti has an effect of improving the corrosion resistance of the plating layer and miniaturizing the plating structure, so that 0.01% by weight or more of the effect may be added. However, even if it is added in excess of 5% by weight, the effect is not only saturated, but also the amount of dross generated increases and causes quality deterioration.

【0011】Ni,Feは、めっき浴に不可避的不純物
として入る場合があるが、それぞれ0.1重量%未満と
なるよう調整することが好ましい。溶融Zn−Al系め
っき鋼板の製造方法として、被めっき鋼板を無酸化炉−
還元炉方式もしくは全還元炉方式にて焼鈍加熱した後、
溶融めっき浴に浸漬引き上げ後ガスワイピング法にて所
定のめっき付着量に連続的に溶融めっきする方法、もし
くは被めっき鋼板の表面にNi下地めっきを施し通電加
熱した後、同様に溶融めっきする方法が適用できる。ま
た、更には溶融Zn−Al系めっき鋼板の表面外観品位
を向上の為、被めっき鋼板を加熱前にアルカリ脱脂、酸
洗、湯洗等々を行い表面の汚れを予め除去しても良い。
Ni and Fe may enter the plating bath as unavoidable impurities, but are preferably adjusted to be less than 0.1% by weight, respectively. As a method for producing a hot-dip Zn-Al-based plated steel sheet, a steel sheet to be plated is subjected to a non-oxidizing furnace.
After annealing and heating in a reduction furnace method or a total reduction furnace method,
A method of continuously hot-dip plating to a predetermined coating weight by gas wiping after dipping and pulling in a hot-dip plating bath, or a method of hot-dip plating with Ni undercoating on the surface of the steel sheet to be plated and then hot-dip similarly Applicable. Further, in order to improve the surface appearance quality of the hot-dip Zn-Al-based plated steel sheet, the steel sheet to be plated may be subjected to alkali degreasing, pickling, washing with hot water, etc. before heating to remove stains on the surface in advance.

【0012】本発明において上記溶融Zn−Alめっき
表面に、硼酸および硼酸塩化合物を1種または2種以上
含有する皮膜を0.01〜5g/m2 形成させる。硼酸
および硼酸塩化合物を含有させることでめっき表面の酸
化が抑制され結果として耐経時黒変性の改善効果が得ら
れる。ここで、硼酸塩化合物とは、例えば、硼酸亜鉛、
硼酸ナトリウム、硼酸リチウム、テトラフルオロ硼酸、
硼酸アンモニウム等が適用できる。皮膜量は0.01〜
5g/m2 形成させる。0.01g/m2 未満では十分
な耐経時黒変性改善効果が得られない。5g/m2 を超
える場合は効果が飽和するばかりでなく製造コスト高と
なるので好ましくない。なお、被膜量の測定方法は、硼
酸及び硼酸塩化合物を塗布・乾燥する前後の重量変化を
測定する方法、めっき層を酸溶解して、硼素の含有量を
原子吸光法、IPC法等で測定し、硼酸および硼酸塩化
合物の付着量を測定する方法などがある。
In the present invention, a coating containing one or more of boric acid and a borate compound is formed on the surface of the hot-dip Zn—Al plating in an amount of 0.01 to 5 g / m 2 . By containing boric acid and a borate compound, oxidation of the plating surface is suppressed, and as a result, an effect of improving blackening resistance over time can be obtained. Here, borate compounds include, for example, zinc borate,
Sodium borate, lithium borate, tetrafluoroborate,
Ammonium borate or the like can be applied. Coating amount is 0.01 ~
5 g / m 2 is formed. If it is less than 0.01 g / m 2 , a sufficient effect of improving blackening resistance over time cannot be obtained. If it exceeds 5 g / m 2 , the effect is not only saturated, but also the production cost increases, which is not preferable. In addition, the measuring method of the coating amount is a method of measuring a weight change before and after applying and drying boric acid and a borate compound, and dissolving an acid in a plating layer and measuring a boron content by an atomic absorption method, an IPC method, or the like. However, there is a method of measuring the amount of boric acid and borate compound attached.

【0013】更に、皮膜層は、Cr,Si,Ni,C
o,Znの1または2種以上の元素を含む無機化合物、
有機樹脂あるいは無機化合物と有機樹脂の両方により構
成されることが好ましい。Cr,Si,Ni,Co,Z
nの1または2種以上の元素を含む無機化合物とは、特
に規定するものではないが、これらの元素の酸化物、水
酸化物、リン酸塩、酢酸塩、炭酸塩、硫酸塩、硝酸塩、
ニトロ化合物、シラン化合物等が挙げられる。例えば塗
布型クロメートに一般的に使用されている酸化クロム、
水酸化クロム、ケイ酸塩化合物(例えばコロイダルシリ
カ)等、従来の黒変防止剤として使用されている水酸化
コバルト、リン酸コバルト、酢酸コバルト、水酸化ニッ
ケル、リン酸ニッケル、酢酸ニッケル等が適用できる。
Further, the coating layer is made of Cr, Si, Ni, C
an inorganic compound containing one or more elements of o and Zn;
It is preferable to be composed of both an organic resin or an inorganic compound and an organic resin. Cr, Si, Ni, Co, Z
The inorganic compound containing one or more elements of n is not particularly limited, but includes oxides, hydroxides, phosphates, acetates, carbonates, sulfates, nitrates, and the like of these elements.
Examples include nitro compounds and silane compounds. For example, chromium oxide generally used for coating type chromate,
Cobalt hydroxide, cobalt phosphate, cobalt acetate, nickel hydroxide, nickel phosphate, nickel acetate, etc., which are used as conventional anti-blackening agents, such as chromium hydroxide and silicate compounds (for example, colloidal silica) are applied. it can.

【0014】また、有機樹脂としては、アクリル系、ポ
リウレタン系、ポリエステル系、エポキシ系の各種溶剤
系および水溶系樹脂が挙げられる。水溶系樹脂は水に溶
解または分散できるように分子鎖に各種の親水性基を導
入したもの、あるいは乳化重合や重合後の界面活性剤処
理によりエマルジョンを形成させたもの等が挙げられ
る。本発明における皮膜は、その目的を損なわない範囲
で、各種の有機及び無機の化合物、樹脂などを含んでい
ても差し支えない。これらの例としては、腐食抑制剤、
界面活性剤、無機潤滑剤、樹脂ワックス、顔料、染料、
架橋剤等が挙げられる。なお、無機化合物と有機樹脂の
両方を用いる場合は、無機化合物および有機樹脂を単に
混合しても、反応により化合させてもよい。
Examples of the organic resin include acrylic, polyurethane, polyester and epoxy solvent-based and water-based resins. Examples of the water-soluble resin include a resin in which various hydrophilic groups are introduced into a molecular chain so that the resin can be dissolved or dispersed in water, or a resin in which an emulsion is formed by emulsion polymerization or treatment with a surfactant after polymerization. The film in the present invention may contain various organic and inorganic compounds, resins and the like as long as the purpose is not impaired. Examples of these include corrosion inhibitors,
Surfactant, inorganic lubricant, resin wax, pigment, dye,
Crosslinking agents and the like can be mentioned. When both an inorganic compound and an organic resin are used, the inorganic compound and the organic resin may be simply mixed or combined by a reaction.

【0015】皮膜形成の方法としては、溶融めっき後の
めっき表面が100℃以上の温度にある内に、硼酸およ
び硼酸塩化合物の水溶液もしくは硼酸および硼酸塩化合
物含有する無機もしく有機皮膜形成塗液をスプレー塗布
して蒸発乾燥させ皮膜化する方法、溶融めっき後めっき
表面が100℃以下迄冷却した後、めっき表面にスプレ
ー塗布、浸漬塗布、ロール塗布等を行った後、熱風等に
より加熱乾燥させ皮膜を形成させる方法等が適用でき
る。また、めっき表面に硼酸および硼酸塩化合物含有無
機もしく有機皮膜を1段処理にて形成しても良いし、硼
酸および硼酸塩化合物を1種または2種以上含有する水
溶液を塗布乾燥させた後、その上層に無機および有機皮
膜を形成する2段処理により形成しても良い。
As a method for forming a film, an aqueous solution of boric acid and a borate compound or a coating solution for forming an inorganic or organic film containing boric acid and a borate compound while the plating surface after hot-dip plating is at a temperature of 100 ° C. or higher. Spray coating and evaporation and drying to form a film. After hot-dip plating, the plating surface is cooled down to 100 ° C or less, spray coating, dip coating, roll coating, etc. are performed on the plating surface, and then heated and dried with hot air or the like. A method of forming a film or the like can be applied. Further, an inorganic or organic film containing boric acid and a borate compound may be formed on the plating surface by one-step treatment, or after an aqueous solution containing one or more boric acid and a borate compound is applied and dried. Alternatively, it may be formed by a two-step process of forming an inorganic and organic film on the upper layer.

【0016】[0016]

【実施例】以下、本発明を実施例にり具体的に説明す
る。めっき付着量100〜130g/m2 、めっき層の
構成元素として、Zn、Al、Mg、Si、Sn、S
b、Pbを、表1に示す濃度にて含む、表1に示す溶融
Zn−Al系合金めっき鋼板を製造した。次いで、めっ
き表面に硼酸および硼酸塩化合物を含む無機化合物皮
膜、有機樹脂被膜もしくは無機化合物/有機樹脂複合被
膜を1段処理法もしくは2段処理法にて形成した。作成
したサンプルは飽和蒸気を噴霧した湿潤雰囲気中(温
度:98℃、RH:95%以上)に、5時間暴露し、皮
膜形成面の黒変状態を目視により判定した。判定基準は
DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to embodiments. The plating adhesion amount is 100 to 130 g / m 2 , and Zn, Al, Mg, Si, Sn, S
A hot-dip Zn-Al-based alloy-plated steel sheet shown in Table 1 containing b and Pb at the concentrations shown in Table 1 was produced. Next, an inorganic compound film containing boric acid and a borate compound, an organic resin film or an inorganic compound / organic resin composite film was formed on the plating surface by a one-step treatment method or a two-step treatment method. The prepared sample was exposed for 5 hours in a humid atmosphere (temperature: 98 ° C., RH: 95% or more) sprayed with saturated steam, and the blackening state of the film-formed surface was visually determined. The criterion is

【0017】 評点5 黒変全くなし 4 白っぽく変化 3 灰色程度 2 黒灰色から黒変化 1 完全黒変 とし、3以上の評点を合格とした。比較のため、硼酸も
しくは硼酸塩化合物皮膜を形成しない材料についても同
様に処理を行い黒変状態を判定した(比較例No.22
〜32)。結果をまとめて表1に示す。表1から明らか
なように、本発明の実施例No.1〜21で得ためっき
鋼板は、耐経時黒変性が優れている。これに対し、めっ
き表面上に硼酸及び硼酸塩化合物を含有する皮膜を形成
しなかった比較例No.22〜32は、耐経時黒変性が
劣る。
Rating 5 No black discoloration 4 Change whitish 3 About gray 2 Black change from black grey 1 Complete black discoloration, and a score of 3 or more was considered acceptable. For comparison, a material which did not form a boric acid or borate compound film was treated in the same manner to determine a blackened state (Comparative Example No. 22).
~ 32). The results are summarized in Table 1. As is clear from Table 1, Example No. 1 of the present invention. The plated steel sheets obtained in Nos. 1 to 21 have excellent blackening resistance over time. On the other hand, in Comparative Example No. in which a film containing boric acid and a borate compound was not formed on the plating surface. Nos. 22 to 32 are inferior in aging blackening resistance.

【0018】[0018]

【表1】 [Table 1]

【0019】[0019]

【発明の効果】従来、主として建材用途分野においては
溶融Zn−Al系めっき鋼板を長期間使用した際の経時
黒変による外観低下問題が深刻であった。本発明の溶融
Zn−Al系めっき鋼板は優れた耐経時黒変性を有する
ことから、この問題を解決することができ産業上極めて
高い価値を有するといえる。
Conventionally, in the field of building materials, the problem of appearance deterioration due to blackening with time when a hot-dip Zn-Al-based plated steel sheet is used for a long time has been serious. Since the hot-dip Zn—Al-based plated steel sheet of the present invention has excellent blackening resistance with time, it can be said that this problem can be solved and has extremely high value in industry.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 西村 一実 千葉県富津市新富20−1 新日本製鐵株式 会社技術開発本部内 (72)発明者 田中 暁 千葉県君津市君津1番地 新日本製鐵株式 会社君津製鐵所内 Fターム(参考) 4K027 AA05 AA22 AB05 AB44 AB48 4K044 AA02 AB02 BA10 BA18 BA21 BB03 BC02 CA11 CA53  ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kazumi Nishimura 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Corporation Technology Development Division (72) Inventor Akira Tanaka 1 Kimitsu, Kimitsu-shi, Chiba New Japan F-term in Kimitsu Works (reference) 4K027 AA05 AA22 AB05 AB44 AB48 4K044 AA02 AB02 BA10 BA18 BA21 BB03 BC02 CA11 CA53

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】 重量%で、Al:0.1〜70重量%を
含有し、残部Znおよび不可避不純物よりなるめっき層
を有する溶融Zn−Al系めっき鋼板であって、めっき
層の表面に、硼酸、硼酸塩化合物のうち1種または2種
以上含有する皮膜層を0.01〜5g/m2 有すること
を特徴とする耐経時黒変性に優れた溶融Zn−Al系め
っき鋼板。
1. A hot-dip Zn—Al-based coated steel sheet containing, by weight%, Al: 0.1 to 70% by weight and having a plating layer consisting of a balance of Zn and unavoidable impurities. boric acid, one or molten Zn-Al-based plated steel sheet excellent in blackening time with lapse, characterized in that a coating layer containing 2 or more with 0.01-5 g / m 2 of the borate compound.
【請求項2】 めっき層が、重量%で、 Mg:0.1〜30%、 Si:0.1〜5%の1種または2種を、さらに含有す
ることを特徴とする請求項1に記載の耐経時黒変性に優
れた溶融Zn−Al系めっき鋼板。
2. The plating layer according to claim 1, wherein the plating layer further contains one or two of Mg: 0.1 to 30% and Si: 0.1 to 5% by weight. A hot-dip Zn-Al-based plated steel sheet having excellent blackening resistance over time according to the description.
【請求項3】 めっき層が、重量%で、 Sn:0.5〜10%、 Sb:0.05〜1%、 Pb:0.05〜1%の1種または2種以上を、さらに
含有することを特徴とする請求項1または2に記載の耐
経時黒変性に優れた溶融Zn−Al系めっき鋼板。
3. The plating layer further contains one or more of Sn: 0.5 to 10%, Sb: 0.05 to 1%, and Pb: 0.05 to 1% by weight. The hot-dip Zn-Al-based steel sheet according to claim 1 or 2, wherein the steel sheet is excellent in blackening resistance over time.
【請求項4】 皮膜層が、Cr,Si,Ni,Co,Z
nのうち1種または2種以上の元素を含む、無機化合
物、有機樹脂あるいは無機化合物と有機樹脂の両方によ
り形成されることを特徴とする請求項1〜3のいずれか
に記載の耐経時黒変性に優れた溶融Zn−Al系めっき
鋼板。
4. The coating layer is made of Cr, Si, Ni, Co, Z
4. The black according to any one of claims 1 to 3, wherein the black is formed of an inorganic compound, an organic resin, or both an inorganic compound and an organic resin containing one or more elements of n. Hot-dip Zn-Al-based plated steel sheet with excellent modification.
JP29756399A 1999-10-20 1999-10-20 HOT DIP Zn-Al SERIES PLATED STEEL SHEET EXCELLENT IN SECULAR BLACKENING RESISTANCE Pending JP2001115273A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003031684A1 (en) * 2001-09-28 2003-04-17 Bo Shin Ro Surface treating agent for zinc or zinc alloy and method for surface treatment
JP2004068075A (en) * 2002-08-06 2004-03-04 Jfe Steel Kk Hot-dip zn-al-mg plated steel sheet superior in workability and corrosion resistance, and manufacturing method therefor
JP2009091652A (en) * 2007-09-19 2009-04-30 Nippon Steel Corp HOT DIP Mg-Al-BASED ALLOY PLATED STEEL MEMBER
JP2011026632A (en) * 2009-07-21 2011-02-10 Jfe Steel Corp Hot-dip galvanized steel
JP2011026630A (en) * 2009-07-21 2011-02-10 Jfe Steel Corp Hot-dip galvanized steel pipe and method for manufacturing hot-dip galvanized material
JP2015214747A (en) * 2014-04-23 2015-12-03 Jfeスチール株式会社 MOLTEN Al-Zn-BASED PLATED SHEET STEEL, AND PRODUCTION METHOD THEREOF
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003031684A1 (en) * 2001-09-28 2003-04-17 Bo Shin Ro Surface treating agent for zinc or zinc alloy and method for surface treatment
JP2004068075A (en) * 2002-08-06 2004-03-04 Jfe Steel Kk Hot-dip zn-al-mg plated steel sheet superior in workability and corrosion resistance, and manufacturing method therefor
JP2009091652A (en) * 2007-09-19 2009-04-30 Nippon Steel Corp HOT DIP Mg-Al-BASED ALLOY PLATED STEEL MEMBER
JP2011026632A (en) * 2009-07-21 2011-02-10 Jfe Steel Corp Hot-dip galvanized steel
JP2011026630A (en) * 2009-07-21 2011-02-10 Jfe Steel Corp Hot-dip galvanized steel pipe and method for manufacturing hot-dip galvanized material
JP2015214747A (en) * 2014-04-23 2015-12-03 Jfeスチール株式会社 MOLTEN Al-Zn-BASED PLATED SHEET STEEL, AND PRODUCTION METHOD THEREOF
WO2018139619A1 (en) 2017-01-27 2018-08-02 新日鐵住金株式会社 Plated steel
KR20190099064A (en) 2017-01-27 2019-08-23 닛폰세이테츠 가부시키가이샤 Plated steels
US10982303B2 (en) 2017-01-27 2021-04-20 Nippon Steel Corporation Coated steel product
KR20220089152A (en) * 2020-12-21 2022-06-28 주식회사 포스코 Black color plated sheet and manufacturing method thereof
WO2022139421A1 (en) * 2020-12-21 2022-06-30 주식회사 포스코 Black color plated steel sheet, and manufacturing method thereof
KR102438477B1 (en) 2020-12-21 2022-08-31 주식회사 포스코 Black color plated sheet and manufacturing method thereof

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