JP2001115272A - HOT DIP Zn-Al SERIES PLATED STEEL SHEET EXCELLENT IN CORROSION RESISTANCE AND BLACKENING RESISTANCE - Google Patents
HOT DIP Zn-Al SERIES PLATED STEEL SHEET EXCELLENT IN CORROSION RESISTANCE AND BLACKENING RESISTANCEInfo
- Publication number
- JP2001115272A JP2001115272A JP29756499A JP29756499A JP2001115272A JP 2001115272 A JP2001115272 A JP 2001115272A JP 29756499 A JP29756499 A JP 29756499A JP 29756499 A JP29756499 A JP 29756499A JP 2001115272 A JP2001115272 A JP 2001115272A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- corrosion resistance
- resistance
- 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
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
- C23C28/02—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 only coatings only including layers of metallic material
- C23C28/023—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 only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—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 only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based 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
- C23C28/02—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 only coatings only including layers of metallic material
- C23C28/021—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 only coatings only including layers of metallic material including at least one metal alloy layer
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (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、耐食性と耐黒変性
に優れた溶融Ｚｎ−Ａｌ系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 coated steel sheet having excellent corrosion resistance and blackening resistance.
【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耐食性を高める
ためクロメート処理され、その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−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−ト処理材に
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、耐黒変性向上への要望が高かった。
溶融Ｚｎ−Ａｌ系めっき鋼板は溶融Ｚｎめっき鋼板より
耐食性が優れているが、未塗装状態あるいは加工後に塗
装を施す場合、耐食性をさらに高めるため、溶融Ｚｎめ
っき鋼板の場合と同様にクロメ−ト処理する場合が多
い。クロメ−ト処理をすれば未処理材に比べ耐食性は改
善されるが、黒変に対する耐性は通常の溶融Ｚｎめっき
鋼板のそれと大差ないため、優れた耐食性と耐黒変性を
兼備する溶融Ｚｎ−Ａｌ系めっき鋼板の開発が望まれて
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 order to increase corrosion resistance. After being packed as a coil or a cut plate 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 generation of white rust is significantly prevented by the chromate treatment, but in the rainy season with high humidity, blackening (black rust) may occur on the chromate treated material, Since the value is remarkably reduced, there has been a high demand for improved blackening resistance.
Hot-dip Zn-Al-based steel sheets have better corrosion resistance than hot-dip Zn-coated steel sheets, but when they are unpainted or coated after processing, they are subjected to the same chromating treatment as in the case of hot-dip Zn-coated steel sheets to further increase the corrosion resistance. Often do. Although the corrosion resistance is improved by the chromate treatment as compared with the untreated material, the resistance to blackening is not much different from that of a normal hot-dip galvanized steel sheet. Therefore, the molten Zn-Al which has both excellent corrosion resistance and blackening resistance is provided. The development of a system-plated steel sheet was desired.
【０００３】黒変を抑制するための措置として、例え
ば、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−処
理しＮｉやＣｏを付着させる方法（特公平３−４９９８
２号公報）、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（特公平５−３３３１１
号公報）などが開示されており、いずれの場合も、これ
らの溶液で処理した後、めっき面の黒変を助長するとさ
れているクロメ−ト処理を行っても、めっき面は黒変し
にくいとされている。ところが、溶融Ｚｎ−Ａｌ系合金
めっき鋼板は、更なる耐食性向上のためにはクロメ−ト
処理で代表される後処理皮膜形成が必要であり、そのた
め鋼板の処理は黒変抑制処理とクロメ−ト処理の２工程
となり、余分な設備費がかかってしまう難点があった。As a measure for suppressing black discoloration, for example, a method of immersing or spraying a zinc-based alloy-plated steel sheet with Ni ions, Co ions or a mixed solution of both to attach Ni or Co (Japanese Patent Publication No. 3-4998
No. 2), a method of spraying an aqueous solution containing a hydroxide of Co, a hydroxide of Fe, or both on a plating surface at 100 ° C. or higher to form an oxide film (Japanese Patent Publication No. 5-33311).
In any case, the plating surface is hardly blackened even if it is treated with these solutions and then subjected to chromate treatment which is considered to promote blackening of the plating surface. It has been. However, a hot-dip Zn-Al-based alloy-plated steel sheet requires a post-treatment film formation, such as a chromate treatment, in order to further improve the corrosion resistance. There was a problem that the number of processes was two and extra equipment cost was required.
【０００４】また、Ｃｏイオンの黒変防止能をめっき中
に取り込むことを目的として、溶融Ｚｎ−Ｍｇ−Ａｌ−
Ｃｏの４元系合金めっき鋼板が提案されている（特公平
９−１４３６５８号公報）。黒変防止成分をめっき工程
で取り込むため工程増はないが、Ｃｏがめっき層全体に
分布するため、めっき表層部に所望の濃度のＣｏを分布
させるには相当な量のＣｏが必要となり、不経済であっ
た。[0004] Further, in order to incorporate the blackening preventing ability of Co ions during plating, molten Zn-Mg-Al-
A quaternary alloy plated steel sheet of Co has been proposed (Japanese Patent Publication No. 9-143658). Since the blackening preventing component is incorporated in the plating step, there is no increase in the process, but since Co is distributed over the entire plating layer, a considerable amount of Co is required to distribute the desired concentration of Co to the plating surface layer portion, which is unacceptable. It was economic.
【０００５】[0005]
【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、耐食性と耐黒変性の優
れた溶融Ｚｎ−Ａｌ系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-based alloy-coated steel sheet having excellent corrosion resistance and blackening resistance. I have.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、めっき鋼
板の後処理により優れた耐食性と耐黒変性を兼備するＺ
ｎ−Ａｌ系合金めっき鋼板を開発すべく、種々検討し
た。その結果、鋼板の後処理工程において、めっき表面
に形成する耐食性薄膜中に少量の黒変防止成分を均一に
分布させれば、製造工程を増やすことなく優れた耐食性
と耐黒変性が得られることを見出した。本発明は、この
ような知見をもとにして完成されたものであり、その要
旨とするところは、 （１）重量％で、Ａｌ：０．１〜７０％を含有し、残部
が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系のめっき鋼板であって、めっき層の表面
に、Ｃｏ化合物１種または２種以上を合計量で０．０１
〜８０重量％含有する皮膜層を有することを特徴とする
耐食性と耐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 Z steel having excellent corrosion resistance and blackening resistance by post-treatment of a plated steel sheet.
Various studies were conducted to develop an n-Al-based alloy plated steel sheet. As a result, in the post-processing step of steel sheet, if a small amount of anti-blackening component is uniformly distributed in the corrosion-resistant thin film formed on the plating surface, excellent corrosion resistance and blackening resistance can be obtained without increasing the number of manufacturing steps. Was found. The present invention has been completed based on such findings, and the gist thereof is as follows: (1) Al: 0.1 to 70% by weight, and the balance being Zn and A hot-dip Zn-Al-based plated steel sheet having a plated layer composed of unavoidable impurities, and one or more Co compounds in a total amount of 0.01 on the surface of the plated layer.
A hot-dip Zn-Al-based plated steel sheet having excellent corrosion resistance and blackening resistance, characterized by having a coating layer containing up to 80% by weight.
【０００７】（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
食性と耐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）に記載の耐食性と耐黒変性に優れた
溶融Ｚｎ−Ａｌ系めっき鋼板。 （４）皮膜層が、Ｔｉ，Ｚｒ，Ｃｒ，Ｍｏ，Ｗ，Ｍｎお
よび希土類元素のうち１種または２種以上の元素を含有
する金属系化合物、リン酸塩、亜リン酸塩、ケイ酸塩、
ニトロ化合物、シラン化合物、水性有機樹脂の１種また
は２種以上から形成されることを特徴とする前記（１）
〜（３）に記載の耐食性と耐黒変性に優れた溶融Ｚｎ−
Ａｌ系めっき鋼板である。(2) 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 corrosion resistance and blackening resistance. (3) The plating layer is, by weight%, Sn: 0.5 to 10%,
(1) or (2), wherein one or more of Sb: 0.05 to 1% and Pb: 0.05 to 1% are further contained. Hot-dip Zn-Al-based plated steel sheet. (4) The coating layer contains one or more of Ti, Zr, Cr, Mo, W, Mn and rare earth elements, a metal compound, a phosphate, a phosphite, and a silicate. ,
(1) characterized in that it is formed from one or more of a nitro compound, a silane compound and an aqueous organic resin.
(3) Fused Zn- excellent in corrosion resistance and blackening resistance described in (3).
It is an Al-based plated steel sheet.
【０００８】[0008]
【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。本発明においては、所定のＣｏ化合物、及
び腐食抑制皮膜の形成能を有する無機化合物や有機樹脂
を含む水溶性の金属表面処理剤で溶融Ｚｎ−Ａｌ系めっ
き面を処理することにより、該めっき面上にＣｏ化合物
が均一に分布した耐食性保護薄膜を形成させることが、
めっき鋼板の耐食性を改善しつつ、外観すなわち、湿潤
雰囲気中でのめっき層の耐黒変性を改善するための大き
な技術上のポイントである。Embodiments of the present invention will be described below in detail. In the present invention, the surface of the molten Zn-Al-based plating is treated with a predetermined Co compound, and a water-soluble metal surface treating agent containing an inorganic compound or an organic resin having an ability to form a corrosion inhibiting film. Forming a corrosion-resistant protective thin film on which a Co compound is uniformly distributed,
This is a major technical point for improving the corrosion resistance of the plated steel sheet and improving the appearance, that is, the blackening resistance of the plated layer in a humid atmosphere.
【０００９】本発明におけるめっき層の組成は、Ａｌを
０．１〜７０重量％含有し、残部が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働きが
ある。Ａｌが０．１重量％未満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。一方、７０重量％を超える場合はめっ
き浴の融点が高くなるため、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 has a function of improving the plating adhesion between the plating layer and the base steel sheet and improving the corrosion resistance. If the Al content is less than 0.1% by weight, the adhesion of the plating 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. On the other hand, if 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.
【００１０】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重量％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
原因となり、逆に耐黒変性を低下させる。Ｓｉは、０．
１重量％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Ｆｅ−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。[0010] In addition, the following elements may be selectively added. Mg significantly improves the corrosion resistance of the plating layer when added in an amount of 0.1% by weight 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 to cause a deterioration in quality, and conversely, the blackening resistance is reduced. Si is 0.
Addition of 1% by weight or more has the effect of improving the corrosion resistance of the plating layer and suppressing the Fe-Zn alloying reaction and the Fe-Al alloying reaction between the plating layer and the base steel sheet.
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.
【００１１】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。Ｎ
ｉ，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。[0011] 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. N
i and Fe may enter the plating bath as unavoidable impurities, but are preferably adjusted to be less than 0.1% by weight, respectively.
【００１２】溶融Ｚｎ−Ａｌ系合金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、溶融Ｚｎ−Ａｌ
系めっき鋼板の表面外観品位向上のため、被めっき鋼板
を加熱前にアルカリ脱脂、酸洗、湯洗等を行い、表面汚
れをあらかじめ除去してもよい。As a method for producing a hot-dip Zn—Al-based alloy-coated steel sheet, a steel sheet to be plated is annealed and heated in a non-oxidizing furnace-reducing furnace method or a total reducing furnace method, then immersed and pulled into a hot-dip plating bath and then subjected to a gas wiping method. Or a method in which the surface of a steel plate to be plated is coated with Ni undercoating, heated by electric current, and then hot-dip similarly. In addition, molten Zn-Al
In order to improve the surface appearance quality of the system-plated steel sheet, the steel sheet to be plated may be subjected to alkali degreasing, pickling, washing with hot water or the like before heating to remove surface stains in advance.
【００１３】本発明において皮膜層中に分散するＣｏ化
合物は、皮膜形成能を有する無機化合物や水性有機樹脂
が溶解あるいは分散した水溶液に溶解あるいは微細分散
するものであれば、特に限定しないが、Ｃｏの塩類、水
酸化物、酸化物、錯化合物から選ばれた１種または２種
以上の化合物が好ましい。これらのうちＣｏの塩類とし
ては、水への溶解性または分散性が比較的良好な硝酸コ
バルト、酢酸コバルト、塩化コバルト、臭化コバルト、
炭酸コバルト、燐酸コバルト、チオシアン酸コバルト、
硫酸コバルト等から選ばれた１種または２種以上の化合
物であることがより好ましい。In the present invention, the Co compound dispersed in the film layer is not particularly limited as long as it is dissolved or finely dispersed in an aqueous solution in which an inorganic compound having a film forming ability or an aqueous organic resin is dissolved or dispersed. And one or more compounds selected from salts, hydroxides, oxides and complex compounds of the above. Among these, salts of Co include cobalt nitrate, cobalt acetate, cobalt chloride, cobalt bromide having relatively good solubility or dispersibility in water,
Cobalt carbonate, cobalt phosphate, cobalt thiocyanate,
More preferably, it is one or more compounds selected from cobalt sulfate and the like.
【００１４】また、Ｃｏの錯化合物としては、例えばヘ
キサアンミンコバルト（ＩＩＩ）イオン、トリス（エチ
レンジアミン）コバルト（ＩＩＩ）イオン等のようなＣ
ｏ3+の錯体、テトラクロロコバルト（ＩＩ）イオン、ア
クアトリクロロコバルト（ＩＩ）イオン等のようなＣｏ
2+の錯体、トリス（２，２−ジピリジル）コバルト
（Ｉ）イオン等のようなＣｏ+ の錯体、コバルトカルボ
ニルのような酸化数０のＣｏ錯体が挙げられるが、錯体
が水に溶解あるいは微細分散するものであれば、錯化剤
（配位子）を特に限定しない。上記のＣｏ（ＩＩＩ）、
Ｃｏ（ＩＩ）、Ｃｏ（Ｉ）錯イオンの対アニオンとして
は、硝酸イオン、酢酸イオン、塩化物イオン、臭化物イ
オン、炭酸イオン、燐酸イオン、亜燐酸イオン、チオシ
アン酸イオン等を用いる。The complex compounds of Co include, for example, C.sub.2 such as hexaamminecobalt (III) ion and tris (ethylenediamine) cobalt (III) ion.
Co such as a complex of o 3+ , tetrachlorocobalt (II) ion, aquatrichlorocobalt (II) ion, etc.
A 2+ complex, a Co + complex such as tris (2,2-dipyridyl) cobalt (I) ion and the like, and a Co complex having an oxidation number of 0 such as cobalt carbonyl can be mentioned. The complexing agent (ligand) is not particularly limited as long as it disperses. Co (III) above,
As a counter anion of Co (II) or Co (I) complex ion, nitrate ion, acetate ion, chloride ion, bromide ion, carbonate ion, phosphate ion, phosphite ion, thiocyanate ion, etc. are used.
【００１５】皮膜層中に分散するＣｏ化合物の合計量は
皮膜全体の０．０１〜８０重量％、望ましくは０．１〜
５０重量％とするのがよい。Ｃｏ化合物の含有量が０．
０１重量％未満では、皮膜中に分散するＣｏ化合物の濃
度が希薄となり十分な耐黒変性が得られない。一方、８
０重量％を超えるとＣｏ化合物の黒変抑制効果が飽和す
るだけでなく、皮膜中でＣｏ化合物の均一分散が困難と
なる。皮膜層は、金属系化合物、リン酸塩、亜リン酸
塩、ケイ酸塩、ニトロ化合物、シラン化合物、水性有機
樹脂の１種または２種以上から形成するのがよい。The total amount of the Co compound dispersed in the coating layer is 0.01 to 80% by weight, preferably 0.1 to 80% by weight of the whole coating.
The content is preferably 50% by weight. When the content of the Co compound is 0.
If the amount is less than 01% by weight, the concentration of the Co compound dispersed in the film becomes so low that sufficient blackening resistance cannot be obtained. On the other hand, 8
If the content exceeds 0% by weight, not only the blackening inhibiting effect of the Co compound is saturated, but also it becomes difficult to uniformly disperse the Co compound in the film. The coating layer is preferably formed from one or more of a metal compound, a phosphate, a phosphite, a silicate, a nitro compound, a silane compound, and an aqueous organic resin.
【００１６】皮膜層を形成する金属系化合物としては、
例えば、塗布型クロメ−トの基剤として広く用いられて
いるクロム酸塩やフッ化クロム等を主成分とするＣｒ系
化合物、フルオロチタン酸等のチタン酸を主成分とする
化合物並びに該化合物に更にＶ化合物を添加したもの、
フルオロジルコニウム酸等のジルコニウム酸を主成分と
する化合物並びに該化合物に更にＣｅやＶの化合物を添
加したもの、モリブデン酸、タングステン酸あるいは過
マンガン酸を含む各種の酸素酸化合物、Ｃｅ、Ｌａ、Ｙ
等の希土類元素の塩を主成分とする化合物等が挙げられ
る。The metal-based compound forming the film layer includes
For example, a Cr-based compound mainly containing chromate or chromium fluoride, a compound mainly containing titanic acid such as fluorotitanic acid, which is widely used as a base material of a coating type chromate, and a compound containing such a compound. What further added a V compound,
Compounds containing zirconic acid as a main component such as fluorozirconic acid, and compounds obtained by further adding Ce or V compounds to the compounds, various oxygen compounds including molybdic acid, tungstic acid or permanganic acid, Ce, La, Y
And the like, whose main component is a salt of a rare earth element.
【００１７】皮膜層を形成するリン酸塩としては、例え
ば、リン酸亜鉛、リン酸カルシウム、リン酸バリウム、
縮合リン酸アルミニウム等、亜リン酸塩としては、例え
ば、亜リン酸亜鉛、亜リン酸バリウム、亜リン酸マグネ
シウム、亜リン酸マンガン等、ケイ酸塩としては、例え
ば、Ｎａ2 Ｏ・ｘＳｉＯ2 （ｘ＝２または３）の組成の
重合体等、ニトロ化合物としては、例えば、亜硝酸ナト
リウムで代表される亜硝酸塩等、シラン化合物として
は、例えば、トリメトキシシリル基を有するシランカッ
プリング剤等が挙げられる。Examples of the phosphate forming the coating layer include zinc phosphate, calcium phosphate, barium phosphate, and the like.
Phosphites such as condensed aluminum phosphate include, for example, zinc phosphite, barium phosphite, magnesium phosphite, manganese phosphite, and silicates include, for example, Na 2 O.xSiO 2 Examples of the nitro compound such as a polymer having a composition of (x = 2 or 3) and the like include nitrite represented by sodium nitrite, and examples of the silane compound include a silane coupling agent having a trimethoxysilyl group. Is mentioned.
【００１８】また、水性有機樹脂としては、水溶性樹脂
のほか、水不溶性樹脂がエマルジョンやサスペンジョン
などの形で水中に微分散された状態になり得るもの（水
分散性樹脂）も含める。このような水性樹脂として使用
できる樹脂としては、例えば、ポリオレフィン系樹脂、
アクリル系樹脂、ポリウレタン系樹脂、ポリカーボネー
ト系樹脂、ポリエステル系樹脂、エポキシ系樹脂、フェ
ノール系樹脂、その他の加熱硬化型の樹脂などを例示で
き、架橋可能な樹脂であることがより好ましい。これら
の水性樹脂の２種類以上を混合して用いてもよい。水性
樹脂として使用できる樹脂に共通に見られる構造は、例
えば、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、乳化重合や重合後の乳化処理
によりエマルジョンを形成したものを例示できる。The aqueous organic resin includes not only a water-soluble resin but also a resin (a water-dispersible resin) in which a water-insoluble resin can be finely dispersed in water in the form of an emulsion or a suspension. As a resin that can be used as such an aqueous resin, for example, a polyolefin resin,
An acrylic resin, a polyurethane resin, a polycarbonate resin, a polyester resin, an epoxy resin, a phenol resin, and other heat-curable resins can be exemplified, and a crosslinkable resin is more preferable. Two or more of these aqueous resins may be used as a mixture. Structures commonly found in resins that can be used as aqueous resins include, for example, those in which various hydrophilic groups are introduced into the molecular chain so that they can be dissolved or dispersed in water, and emulsions formed by emulsion polymerization or emulsification after polymerization. Can be exemplified.
【００１９】本発明でＺｎ−Ａｌ系合金めっき上に形成
される皮膜は、上記の腐食抑制皮膜の形成能を有する化
合物を、合計量で２０重量％以上、望ましくは５０重量
％以上含む。皮膜形成能を有する成分が２０重量％未満
では、Ｃｏ化合物を担持し均一に分散できるような皮膜
が得られない。本発明において、めっき上に形成される
皮膜の付着量は特に限定しないが、金属系化合物を主た
る構成成分とする皮膜では、Ｃｏを含む金属換算で１〜
３００ｍｇ／ｍ2 、他の無機系化合物を主たる構成成分
とする皮膜では、皮膜層に分散するＣｏ化合物を含め
０．１〜５ｇ／ｍ2 、有機樹脂を主たる構成成分とする
皮膜では、皮膜層に分散するＣｏ化合物を含め０．３〜
５ｇ／ｍ2 の範囲にするのが好ましい。The film formed on the Zn-Al-based alloy plating in the present invention contains, in total, 20% by weight or more, preferably 50% by weight or more, of the above compounds having the ability to form a corrosion inhibiting film. If the component having the ability to form a film is less than 20% by weight, a film capable of supporting and uniformly dispersing a Co compound cannot be obtained. In the present invention, the adhesion amount of the film formed on the plating is not particularly limited, but in the case of a film containing a metal-based compound as a main component, it is 1 to 1 in terms of a metal containing Co.
300 mg / m 2 , in the case of a film mainly composed of another inorganic compound, 0.1 to 5 g / m 2 including a Co compound dispersed in the film layer, and in the case of a film mainly composed of an organic resin, a film layer 0.3 to including the Co compound dispersed in
It is preferred to be in the range of 5 g / m 2 .
【００２０】付着量が、金属系化合物を主たる構成成分
とする皮膜におけるＣｏを含む金属換算で、１ｍｇ／ｍ
2 未満、他の無機系化合物を主たる構成成分とする皮膜
で０．１ｇ／ｍ2 未満、有機樹脂を主たる構成成分とす
る皮膜で０．３ｇ／ｍ2 未満の場合、耐食性が不十分と
なるおそれがある。一方、それぞれ３００ｍｇ／ｍ2、
５ｇ／ｍ2 、５ｇ／ｍ2 を超えると、皮膜が不均一とな
り外観に問題が出たり、コストアップが懸念される。The coating amount is 1 mg / m 2 in terms of a metal containing Co in a film containing a metal compound as a main constituent.
In the case of less than 2, less than 0.1 g / m 2 for a film mainly composed of another inorganic compound, and less than 0.3 g / m 2 for a film mainly composed of an organic resin, the corrosion resistance becomes insufficient. There is a risk. On the other hand, each was 300 mg / m 2 ,
Exceeds 5g / m 2, 5g / m 2, and out a problem with the appearance coating becomes uneven, the cost is concerned.
【００２１】本発明において、めっき面上への皮膜形成
の方法としては、溶融めっき後のめっき表面が１００℃
以上の温度にあるうちに、Ｃｏ化合物と皮膜形成成分を
含む水系表面処理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℃を下
回る温度に冷却した後、Ｃｏ化合物と皮膜形成成分を含
む水系表面処理浴へのめっき鋼板のディップ、該表面処
理液のロールコート、バーコート、刷毛塗り、あるいは
スプレ−等の後、熱風などにより加熱乾燥あるいは反応
させることにより行うが、他の方法で塗布、皮膜形成さ
せてもよく、ここで掲げた方法に限定されない。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。In the present invention, as a method of forming a film on a plating surface, the plating surface after hot-dip plating is 100 ° C.
While at the above temperature, a method of spray-coating and evaporating and drying an aqueous surface treating solution containing a Co compound and a film-forming component to form a film, and after hot-dip plating the plating surface is cooled to a temperature lower than 100 ° C. Dip of a plated steel sheet into an aqueous surface treatment bath containing a compound and a film-forming component, roll-coat, bar-coat, brush-coat, or spray the surface treatment solution, and then heat dry or react with hot air or the like. However, the coating and film formation may be performed by other methods, and the method is not limited to the methods listed here. 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. These include, for example, corrosion inhibitors, surfactants, inorganic lubricants, resin waxes, pigments, dyes, crosslinking agents, and the like.
【００２２】[0022]
【実施例】以下、本発明を実施例及び比較例によってよ
り具体的に説明するが、本発明はこれらの実施例により
限定されるものではない。 （実施例１）めっき付着量１００〜１３０ｇ／ｍ2 、め
っき組成はＡｌが０．２〜５５重量％、Ｍｇが０〜２６
重量％、Ｓｉが０〜２重量％、Ｓｎが０〜５重量％、Ｓ
ｂが０〜０．１５重量％、Ｐｂが０〜０．１５重量％で
残部Ｚｎからなる、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、腐食抑制皮膜形成成分と
してクロム酸１０ｇ／ｌとシリカ１０または４０ｇ／ｌ
を含み、耐黒変性発現成分として硝酸コバルト、酢酸コ
バルト、チオシアン酸コバルトのいずれか１種を５また
は２５ｇ／ｌ含む表面処理液を調製し、めっき表面にス
プレー後、皮膜中のＣｒ量が概ね３０ｍｇ／ｍ2 となる
ようにロール絞りし、１００℃にて熱風乾燥した。形成
皮膜中のＣｏ化合物含量は、９．１〜５５．６重量％で
ある。飽和蒸気を噴霧した湿潤雰囲気中（温度：９８
℃、ＲＨ：９５％以上）にこれらの試験板を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、EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. (Example 1) Amount of plating: 100 to 130 g / m 2 , plating composition: 0.2 to 55% by weight of Al, 0 to 26 of Mg
Wt%, Si is 0-2 wt%, Sn is 0-5 wt%, S
A hot-dip Zn-Al-based alloy-plated steel sheet shown in Table 1 was produced, where b is 0 to 0.15% by weight, Pb is 0 to 0.15% by weight, and the balance is Zn. Then, 10 g / l of chromic acid and 10 or 40 g / l of silica are used as components for forming a corrosion inhibiting film.
And a surface treatment solution containing 5 or 25 g / l of any one of cobalt nitrate, cobalt acetate, and cobalt thiocyanate as a blackening resistance developing component. After spraying the plating surface, the amount of Cr in the coating is substantially reduced. The roll was squeezed to 30 mg / m 2 and dried with hot air at 100 ° C. The Co compound content in the formed film is 9.1 to 55.6% by weight. In a humid atmosphere sprayed with saturated steam (temperature: 98
(RH, RH: 95% or more) for 5 hours, and the blackened state of the film-formed surface was visually determined. The criterion is
【００２３】 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、評点３以上を合格とした。また、各試験板につい
てＪＩＳ−Ｚ２３７１に準拠した塩水噴霧試験を行い、
２４０時間後の白錆発生面積を測定することにより耐食
性を判定した。判定基準は、Rating 5 No black discoloration 4 Whitish change 3 About gray 2 Black change from black grey 1 Complete black discoloration, and a score of 3 or more was judged as acceptable. In addition, a salt spray test based on JIS-Z2371 was performed for each test plate,
The corrosion resistance was determined by measuring the white rust generation area after 240 hours. The criterion is
【００２４】 評点５ 白錆発生なし ４ 白錆発生面積５％未満 ３ 白錆発生面積５％〜２５％未満 ２ 白錆発生面積２５％〜５０％未満 １ 白錆発生面積５０％以上 とし、評点４以上を合格とした。比較のため、Ｃｏ化合
物を含まない皮膜についても同様に処理を行い、黒変状
態と白錆発生状態を判定した（比較例Ｎｏ．４０〜５
０）。結果をまとめて表１に示す。Rating 5 No white rust generation 4 White rust generation area less than 5% 3 White rust generation area 5% to less than 25% 2 White rust generation area 25% to less than 50% 1 White rust generation area 50% or more A score of 4 or more was accepted. For comparison, a film containing no Co compound was similarly treated to determine a blackened state and a white rusted state (Comparative Examples Nos. 40 to 5).
0). The results are summarized in Table 1.
【００２５】[0025]
【表１】 [Table 1]
【００２６】（実施例２）めっき面上の皮膜形成成分と
して、高酸価変性アクリル樹脂の水分散化物（樹脂固形
分２５重量％、アニオン性）、あるいは自己乳化型のポ
リウレタン樹脂エマルジョン（樹脂固形分２５重量％、
アニオン性）のいずれか１種を２００〜４００ｇ／ｌ含
み、耐黒変性発現成分として硝酸コバルト、炭酸コバル
ト、燐酸コバルトのいずれか１種を３または２０ｇ／ｌ
含む表面処理液を調製した。実施例１で調製した溶融Ｚ
ｎ−Ａｌ系合金めっき鋼板にこれらの処理液をスプレー
後、エアナイフ絞りによりト−タルの皮膜付着量が概ね
１ｇ／ｍ2 となるようにした。形成皮膜中のＣｏ化合物
含量は、２．９〜２８．６重量％であった。実施例１と
同様の黒変、白錆発生の促進試験を行い、皮膜形成面の
黒変状態と耐食性をそれぞれ５段階評点により判定し
た。比較のため、Ｃｏ化合物を含まない皮膜も調製し、
同様に黒変状態と耐食性を判定した（比較例Ｎｏ．９０
〜１００）。また、比較のため、水性樹脂１２ｇ／ｌ
（樹脂固形分３ｇ／ｌ）、Ｃｏ化合物２０ｇ／ｌの処理
液も調製し、ディップにより本発明のＣｏ化合物の含量
を逸脱するＣｏ化合物含量約８７％の皮膜形成を試みた
が、めっき表面上にＣｏ化合物が均一に分散する皮膜を
作れなかった（比較例Ｎｏ．１０１、１０２）。結果を
まとめて表２に示す。(Example 2) A water-dispersed product of a high acid value-modified acrylic resin (resin solid content 25% by weight, anionic) or a self-emulsifying polyurethane resin emulsion (resin solid 25% by weight,
Anionic) in an amount of 200 to 400 g / l, and 3 or 20 g / l of any one of cobalt nitrate, cobalt carbonate, and cobalt phosphate as a blackening resistance developing component.
A surface treatment solution was prepared. Melt Z prepared in Example 1
After spraying these treatment liquids on an n-Al-based alloy-plated steel sheet, the total film adhesion amount was adjusted to approximately 1 g / m 2 by air knife drawing. The Co compound content in the formed film was 2.9 to 28.6% by weight. A test for accelerating the generation of blackening and white rust similar to that in Example 1 was performed, and the blackening state and corrosion resistance of the film-formed surface were each evaluated by a five-point scale. For comparison, a film containing no Co compound was also prepared,
Similarly, the blackened state and the corrosion resistance were determined (Comparative Example No. 90).
~ 100). Also, for comparison, an aqueous resin 12 g / l
(Resin solid content 3 g / l), a treatment solution of Co compound 20 g / l was also prepared, and a coating with a Co compound content of about 87% which deviated from the Co compound content of the present invention was tried by dipping. Could not form a film in which the Co compound was uniformly dispersed (Comparative Examples Nos. 101 and 102). Table 2 summarizes the results.
【００２７】[0027]
【表２】 [Table 2]
【００２８】表１および２から明らかなように、本発明
の実施例Ｎｏ．１〜３９、５１〜８９で得ためっき鋼板
は、耐食性と耐黒変性の両方が優れている。これに対
し、めっき面上に形成された皮膜に所定量のＣｏ化合物
が含まれない場合（比較例Ｎｏ．４０〜５０、９０〜１
０２）は、本発明鋼板に比較し耐黒変性が劣る。As is clear from Tables 1 and 2, Example No. The plated steel sheets obtained in 1 to 39 and 51 to 89 are excellent in both corrosion resistance and blackening resistance. On the other hand, when the film formed on the plated surface does not contain a predetermined amount of the Co compound (Comparative Examples Nos. 40 to 50 and 90 to 1).
No. 02) is inferior in blackening resistance to the steel sheet of the present invention.
【００２９】[0029]
【発明の効果】本発明のめっき鋼板は、優れた耐食性と
耐黒変性を発現するだけでなく、その製造において、め
っき表面の黒変防止処理を従来の後処理（耐食性等を高
める処理）工程の中で行えるため、工程増がなく余分な
設備費がかからない。また、少量のＣｏ化合物を、後処
理工程で形成される腐食抑制皮膜中に均一に分散できる
ため、原材料費のアップが殆どなく効果的に黒変を抑制
できる。そのため、本発明によるめっき鋼板及びその製
造方法は、建材、土木、車体等で後処理が必要な用途に
極めて有用である。The plated steel sheet of the present invention not only exhibits excellent corrosion resistance and blackening resistance, but also uses a conventional post-treatment (treatment for increasing corrosion resistance, etc.) in the production of the plated steel sheet to prevent blackening of the plating surface. Since there is no need for additional processes, no extra equipment costs are required. Further, since a small amount of the Co compound can be uniformly dispersed in the corrosion-inhibiting film formed in the post-treatment process, the blackening can be effectively suppressed with almost no increase in raw material costs. Therefore, the plated steel sheet and the method for producing the same according to the present invention are extremely useful for applications requiring post-treatment in building materials, civil engineering, car bodies, and the like.
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） 4K044 AA02 AB02 BA06 BA10 BA17 BA19 BA21 BC02 CA11 CA16Continued on the front page (72) Inventor Kazumi Nishimura 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Corporation Technology Development Division (72) Akira Tanaka 1st Kimitsu, Kimitsu-shi, Chiba Nippon Steel Corporation F-term (reference) in Kimitsu Works 4K044 AA02 AB02 BA06 BA10 BA17 BA19 BA21 BC02 CA11 CA16
Claims (4)
し、残部が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系のめっき鋼板であって、めっき
層の表面に、Ｃｏ化合物１種または２種以上を合計量で
０．０１〜８０重量％含有する皮膜層を有することを特
徴とする耐食性と耐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 having a weight percent of Al: 0.1 to 70% and a balance of Zn and unavoidable impurities. A hot-dip Zn-Al-based steel sheet having excellent corrosion resistance and blackening resistance, comprising a coating layer containing 0.01 to 80% by weight of one or more Co compounds in total.
ることを特徴とする請求項１に記載の耐食性と耐黒変性
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 corrosion resistance and blackening resistance.
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
食性と耐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 plated steel sheet according to claim 1 or 2, which is excellent in corrosion resistance and blackening resistance.
Ｗ，Ｍｎおよび希土類元素のうち１種または２種以上の
元素を含有する金属系化合物、リン酸塩、亜リン酸塩、
ケイ酸塩、ニトロ化合物、シラン化合物、水性有機樹脂
の１種または２種以上から形成されることを特徴とする
請求項１〜３に記載の耐食性と耐黒変性に優れた溶融Ｚ
ｎ−Ａｌ系めっき鋼板。4. The coating layer is made of Ti, Zr, Cr, Mo,
A metal-based compound containing one or more of W, Mn and rare earth elements, a phosphate, a phosphite,
4. The molten Z having excellent corrosion resistance and blackening resistance according to claim 1, wherein the molten Z is formed from one or more of a silicate, a nitro compound, a silane compound and an aqueous organic resin.
n-Al-based plated steel sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29756499A JP2001115272A (en) | 1999-10-20 | 1999-10-20 | HOT DIP Zn-Al SERIES PLATED STEEL SHEET EXCELLENT IN CORROSION RESISTANCE AND BLACKENING RESISTANCE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29756499A JP2001115272A (en) | 1999-10-20 | 1999-10-20 | HOT DIP Zn-Al SERIES PLATED STEEL SHEET EXCELLENT IN CORROSION RESISTANCE AND BLACKENING RESISTANCE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001115272A true JP2001115272A (en) | 2001-04-24 |
Family
ID=17848188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29756499A Pending JP2001115272A (en) | 1999-10-20 | 1999-10-20 | HOT DIP Zn-Al SERIES PLATED STEEL SHEET EXCELLENT IN CORROSION RESISTANCE AND BLACKENING RESISTANCE |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001115272A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160027319A (en) * | 2014-08-28 | 2016-03-10 | 주식회사 포스코 | Zn alloy plated steel sheet having excellent anti-corrosion and good surface apperance and method for manufacturing the same |
| KR20180122731A (en) * | 2016-04-29 | 2018-11-13 | 아르셀러미탈 | Press hardening method |
-
1999
- 1999-10-20 JP JP29756499A patent/JP2001115272A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160027319A (en) * | 2014-08-28 | 2016-03-10 | 주식회사 포스코 | Zn alloy plated steel sheet having excellent anti-corrosion and good surface apperance and method for manufacturing the same |
| KR101639877B1 (en) * | 2014-08-28 | 2016-07-15 | 주식회사 포스코 | Zn alloy plated steel sheet having excellent anti-corrosion and good surface apperance and method for manufacturing the same |
| KR20180122731A (en) * | 2016-04-29 | 2018-11-13 | 아르셀러미탈 | Press hardening method |
| KR102025538B1 (en) * | 2016-04-29 | 2019-09-26 | 아르셀러미탈 | Press hardening method |
| KR20190111146A (en) * | 2016-04-29 | 2019-10-01 | 아르셀러미탈 | A press hardening method |
| KR102319215B1 (en) * | 2016-04-29 | 2021-10-29 | 아르셀러미탈 | A press hardening method |
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