JPH0881761A - Zn-mg alloy plated steel sheet and production thereof - Google Patents
Zn-mg alloy plated steel sheet and production thereofInfo
- Publication number
- JPH0881761A JPH0881761A JP24335894A JP24335894A JPH0881761A JP H0881761 A JPH0881761 A JP H0881761A JP 24335894 A JP24335894 A JP 24335894A JP 24335894 A JP24335894 A JP 24335894A JP H0881761 A JPH0881761 A JP H0881761A
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- Japan
- Prior art keywords
- layer
- concentration
- alloy
- steel sheet
- alloy layer
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐食性，耐パウダリン
グ性，密着性，スポット溶接性，耐変色性等に優れたＺ
ｎ−Ｍｇ合金めっき鋼板及びその製造方法に関する。BACKGROUND OF THE INVENTION The present invention is a Z excellent in corrosion resistance, powdering resistance, adhesion, spot weldability, discoloration resistance and the like.
The present invention relates to an n-Mg alloy plated steel sheet and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】鋼板の耐食性を向上させるため、従来か
ら各種の表面処理が採用されている。なかでも、代表的
な表面処理方法であるＺｎめっきには、主として電気め
っき法，溶融めっき法等が採用されている。耐食性の向
上に対する要求は年々高まる傾向にあり、これに伴って
溶融めっき法，電気めっき法等において種々の改良が提
案されている。溶融めっき法でＺｎめっき鋼板の耐食性
を向上させようとすると、Ｚｎめっき層の付着量を増加
させることが先ず考えられる。しかし、製造面から付着
量の上限が制約されるため、付着量の増加によって耐食
性の向上を図ることには限界がある。また、付着量の増
加、すなわちめっき層の厚膜化は、めっき鋼板をプレス
成形するときにカジリ，フレーキング等の欠陥を発生さ
せる原因になり易い。2. Description of the Related Art Various surface treatments have been conventionally used to improve the corrosion resistance of steel sheets. Among them, electroplating, hot dipping and the like are mainly used for Zn plating which is a typical surface treatment method. The demand for improved corrosion resistance tends to increase year by year, and various improvements have been proposed in hot dipping, electroplating, and the like. When attempting to improve the corrosion resistance of a Zn-plated steel sheet by the hot dip coating method, it is first thought that the amount of the Zn-plated layer deposited is increased. However, since the upper limit of the adhered amount is limited from the manufacturing aspect, there is a limit in improving the corrosion resistance by increasing the adhered amount. Further, an increase in the amount of adhesion, that is, an increase in the thickness of the plated layer, tends to cause defects such as galling and flaking when press-forming the plated steel sheet.
【０００３】電気めっき法で同様に高付着量のめっき層
を形成しようとすると、ラインスピードを遅くすること
が必要になり、生産性が著しく損なわれる。そこで、電
気めっき法では、Ｚｎ−Ｎｉ系等のＺｎ合金めっきを施
すことによって耐食性の向上を図っている。しかし、Ｚ
ｎ−Ｎｉ合金めっき層は、硬質で脆いため、成形時にめ
っき層に割れや欠け等の欠陥を発生させ易い。このよう
な欠陥がめっき層に発生すると、欠陥部を介して下地鋼
が露出するため、めっき層本来の性能が発揮されず、欠
陥部を起点とした腐食が進行する。以上のような背景か
ら、高耐食性のＺｎ系合金めっき鋼板を蒸着で製造する
ことが試みられている。なかでも、Ｚｎ−Ｍｇ合金めっ
きは、優れた防食作用を有する。たとえば、特開昭６４
−１７８５３号公報では、０．５〜４０重量％のＭｇを
含むＺｎ−Ｍｇ合金めっき層を形成することを開示して
いる。また、Ｚｎ−Ｍｇ合金めっき層と下地鋼との間に
Ｚｎ，Ｎｉ，Ｃｕ，Ｍｇ，Ａｌ，Ｆｅ，Ｃｏ，Ｔｉ等の
中間層を介在させるとき、めっき層の密着性及び加工性
が向上することが特開平２−１４１５８８号公報で紹介
されている。If an electroplating method is used to form a plating layer having a high adhesion amount, it is necessary to slow down the line speed, and productivity is significantly impaired. Therefore, in the electroplating method, Zn-Ni-based Zn alloy plating is applied to improve the corrosion resistance. But Z
Since the n-Ni alloy plating layer is hard and brittle, defects such as cracks and chips are likely to occur in the plating layer during molding. When such a defect occurs in the plating layer, the underlying steel is exposed through the defect portion, so that the original performance of the plating layer is not exhibited and corrosion starting from the defect portion proceeds. From the background described above, it has been attempted to produce a Zn-based alloy plated steel sheet having high corrosion resistance by vapor deposition. Among them, Zn-Mg alloy plating has an excellent anticorrosion effect. For example, JP-A-64
Japanese Patent Laid-Open No. 17853 discloses forming a Zn-Mg alloy plating layer containing 0.5 to 40% by weight of Mg. Further, when an intermediate layer of Zn, Ni, Cu, Mg, Al, Fe, Co, Ti or the like is interposed between the Zn-Mg alloy plating layer and the base steel, the adhesion and workability of the plating layer are improved. This is introduced in Japanese Patent Laid-Open No. 2-141588.
【０００４】[0004]
【発明が解決しようとする課題】高付着量のＺｎ−Ｍｇ
合金めっき鋼板では、プレス加工時にパウダリングが発
生し易い欠点がある。特に、Ｍｇ濃度の上昇に伴ってめ
っき層にＺｎ−Ｍｇの金属間化合物が多くなった場合、
Ｍｇの平均濃度が低いときでも下地側に金属間化合物が
存在する場合等において、この傾向が顕著になる。これ
は、Ｚｎ−Ｍｇ金属間化合物層が硬くて脆いためであ
り、高い延性をもつ下地鋼板の変形に追従できず、界面
剥離や亀裂を起こすことに原因がある。パウダリング
は、Ｍｇ濃度の低下によってめっき層に含まれる金属間
化合物の量を下げ、延性を高くすることによって解消さ
れる。しかし、Ｍｇ濃度の低下は、めっき層の防食作用
を低下させる。また、表面側のみを高Ｍｇ濃度にしても
耐パウダリング性が改善されるが、めっき層の表面がＭ
ｇ濃化によって黒色に変色し、めっき鋼板の商品価値を
下げる。しかも、めっき層表面の高Ｍｇ濃度は、溶接電
極に対するＭｇの拡散を促進させ、スポット溶接性を低
下させる。本発明は、このような問題を解消すべく案出
されたものであり、Ｚｎ−Ｍｇ合金めっき層を特定組成
の多層構造とすることにより、高Ｍｇ濃度に起因する欠
陥を抑制し、耐食性，耐パウダリング性，密着性，スポ
ット溶接性，耐変色性等に優れたＺｎ−Ｍｇ合金めっき
鋼板を得ること目的とする。Zn-Mg with high deposition amount
The alloy-plated steel sheet has a drawback that powdering is likely to occur during press working. In particular, when the Zn-Mg intermetallic compound increases in the plating layer as the Mg concentration increases,
Even when the average concentration of Mg is low, this tendency becomes remarkable when the intermetallic compound is present on the base side. This is because the Zn-Mg intermetallic compound layer is hard and brittle, and it cannot follow the deformation of the base steel sheet having high ductility and causes interfacial peeling or cracking. The powdering is eliminated by reducing the amount of the intermetallic compound contained in the plating layer by increasing the Mg concentration and increasing the ductility. However, the reduction of the Mg concentration reduces the anticorrosion effect of the plating layer. Also, even if only the surface side has a high Mg concentration, the powdering resistance is improved, but the surface of the plating layer is M
It will turn black due to thickening and reduce the commercial value of plated steel sheets. Moreover, the high Mg concentration on the surface of the plating layer promotes the diffusion of Mg to the welding electrode and reduces the spot weldability. The present invention has been devised to solve such a problem, and by forming the Zn-Mg alloy plating layer into a multilayer structure having a specific composition, suppresses defects caused by a high Mg concentration, and improves corrosion resistance, It is an object to obtain a Zn-Mg alloy plated steel sheet having excellent powdering resistance, adhesiveness, spot weldability, discoloration resistance and the like.
【０００５】[0005]
【課題を解決するための手段】本発明のＺｎ−Ｍｇ合金
めっき鋼板は、その目的を達成するため、図１に示す基
本的な層構成をもっている。下地鋼の表面にはＭｇ濃度
０．５重量％以下のＺｎ−Ｍｇ合金層があり、その上に
Ｍｇ濃度７重量％以上のＺｎ−Ｍｇ合金層及びＭｇ濃度
０．５重量％以下のＺｎ−Ｍｇ合金層が順次積層されて
いる。この基本層構成よりも高耐食性が要求される場
合、図２に示すように、Ｍｇ濃度０．５重量％以下のＺ
ｎ−Ｍｇ合金層とＭｇ濃度７重量％以上のＺｎ−Ｍｇ合
金層との間にＭｇ濃度２〜７重量％のＺｎ−Ｍｇ合金層
を設ける。Ｍｇ濃度７重量％以上のＺｎ−Ｍｇ合金層
は、高湿潤環境における耐食性を確保する観点から、Ｍ
ｇ含有量の上限を２０重量％にすることが好ましい。The Zn-Mg alloy plated steel sheet of the present invention has a basic layer structure shown in FIG. 1 in order to achieve the object. A Zn-Mg alloy layer having a Mg concentration of 0.5 wt% or less is present on the surface of the base steel, and a Zn-Mg alloy layer having a Mg concentration of 7 wt% or more and a Zn-Mg concentration of 0.5 wt% or less is formed on the Zn-Mg alloy layer. Mg alloy layers are sequentially stacked. When higher corrosion resistance than this basic layer structure is required, as shown in FIG. 2, Z with a Mg concentration of 0.5 wt% or less is used.
A Zn-Mg alloy layer having a Mg concentration of 2 to 7 wt% is provided between the n-Mg alloy layer and a Zn-Mg alloy layer having a Mg concentration of 7 wt% or more. The Zn-Mg alloy layer having a Mg concentration of 7 wt% or more is M from the viewpoint of ensuring corrosion resistance in a high-humidity environment.
The upper limit of the g content is preferably 20% by weight.
【０００６】蒸着時の雰囲気にＯ2 やＨ2 Ｏが含まれて
いると、鋼板表面が酸化され、めっき層の密着性が低下
する。また、表面活性化後に直ちに蒸着が行われず、鋼
板表面の汚染が予想される場合にあっても、めっき層の
密着性が低下する虞れがある。このような場合、鋼板表
面に対するＺｎ−Ｍｇ合金めっき層の密着性を図るた
め、図３又は図４に示すようにＺｎ−Ｆｅ合金層又はＺ
ｎ−Ｆｅ−Ｍｇ合金層を形成する。Ｚｎ−Ｆｅ合金層又
はＺｎ−Ｆｅ−Ｍｇ合金層は、それらによる成形時のパ
ウダリングを防止するため、層厚を０．５μｍ以下にす
ることが好ましい。また、Ｚｎ−Ｆｅ合金層又はＺｎ−
Ｆｅ−Ｍｇ合金層に含まれるＦｅ濃度は、通常６重量％
以上にする。If the atmosphere during vapor deposition contains O 2 or H 2 O, the surface of the steel sheet will be oxidized and the adhesion of the plating layer will decrease. Further, even if vapor deposition is not performed immediately after surface activation and the surface of the steel sheet is expected to be contaminated, the adhesion of the plating layer may be reduced. In such a case, in order to improve the adhesion of the Zn-Mg alloy plating layer to the surface of the steel sheet, as shown in FIG.
An n-Fe-Mg alloy layer is formed. The Zn—Fe alloy layer or the Zn—Fe—Mg alloy layer preferably has a layer thickness of 0.5 μm or less in order to prevent powdering during molding by the Zn—Fe alloy layer. In addition, a Zn-Fe alloy layer or Zn-
The Fe concentration contained in the Fe-Mg alloy layer is usually 6% by weight.
More than that.
【０００７】これらのめっき鋼板は、鋼板表面にＺｎ蒸
着→Ｍｇ蒸着→Ｚｎ蒸着を順次行った後で加熱すること
によって形成される。或いは、蒸着割合を変えながら、
Ｚｎ及びＭｇを同時蒸着することによっても、必要とす
る層構成をもつＺｎ−Ｍｇ合金めっき層が形成される。
蒸着後の加熱温度，加熱時間等の条件を制御することに
より、必要とする厚みをもったＺｎ−Ｆｅ合金層又はＺ
ｎ−Ｆｅ−Ｍｇ合金層が下地鋼とめっき層との界面に形
成される。たとえば、５０秒以内の短時間加熱では加熱
温度を２７０〜３７０℃に、１時間以上の長時間加熱で
は加熱温度を１５０〜２５０℃に設定する。また、加熱
処理に代えて、蒸着終了時の鋼板温度が２７０〜３７０
℃となるように条件を設定することによっても、所定の
層構成をもったＺｎ−Ｍｇ合金めっき層を形成すること
ができる。蒸着法で形成されたＺｎ−Ｍｇ合金めっき層
には、通常、酸化したＭｇ濃化層が表面に存在する。初
期の耐食性が重視される用途ではＭｇ濃化層をそのまま
残しておくが、スポット溶接性が重視される用途や表面
の黒変色を防止する場合には、酸洗等によってＭｇ濃化
層を除去する。These plated steel sheets are formed by sequentially performing Zn vapor deposition → Mg vapor deposition → Zn vapor deposition on the steel sheet surface and then heating. Or while changing the deposition rate,
A Zn-Mg alloy plated layer having a required layer structure is also formed by simultaneous vapor deposition of Zn and Mg.
By controlling conditions such as heating temperature and heating time after vapor deposition, a Zn-Fe alloy layer or Z having a required thickness is obtained.
An n-Fe-Mg alloy layer is formed at the interface between the base steel and the plating layer. For example, the heating temperature is set to 270 to 370 ° C. for short time heating within 50 seconds, and the heating temperature is set to 150 to 250 ° C. for long time heating for 1 hour or more. Further, instead of the heat treatment, the steel plate temperature at the end of vapor deposition is 270 to 370.
The Zn-Mg alloy plating layer having a predetermined layer structure can also be formed by setting the conditions so that the temperature becomes ° C. The Zn-Mg alloy plated layer formed by the vapor deposition method usually has an oxidized Mg concentrated layer on its surface. The Mg-enriched layer is left as it is in applications where the initial corrosion resistance is important, but the Mg-enriched layer is removed by pickling or the like when the spot weldability is important or when black discoloration of the surface is to be prevented. To do.
【０００８】[0008]
【作用】本発明に従ったＺｎ−Ｍｇ合金めっき層は、中
心部にＭｇ濃度の高い部分があり、その上下にある層の
Ｍｇ濃度が低くなった多層構成をもっている。Ｍｇ濃度
が０．５重量％以下の低い層は、比較的溶出速度が大き
く、犠牲防食作用を呈し、疵付き部等における鋼板露出
部の赤錆発生を防止する。特に、初期の赤錆発生防止に
有効である。Ｍｇ濃度が７重量％以上と高い層は、耐食
性が高く、めっき層自体の腐食寿命を長くする。また、
Ｍｇ濃度が高い層から溶け出したＭｇは、防食性に優れ
たＺｎの腐食生成物であるＺｎＣｌ2・４Ｚｎ (ＯＨ)2や
Ｚｎ (ＯＨ)2の生成を促進させ、耐食性を向上させる。
Ｍｇ濃度が２〜７重量％と中間濃度のＺｎ−Ｍｇ合金層
は、低Ｍｇ濃度層と高Ｍｇ濃度層との中間の性質を示
し、更に耐食性を向上させる。このような各層の作用が
相乗的に働き、従来にない優れた耐食性が発揮される。The Zn-Mg alloy plated layer according to the present invention has a multi-layered structure in which the central portion has a high Mg concentration portion and the layers above and below it have a low Mg concentration. A layer having a low Mg concentration of 0.5% by weight or less has a relatively high elution rate, exhibits a sacrificial anticorrosion action, and prevents the occurrence of red rust on the exposed portion of the steel sheet in a flawed portion or the like. In particular, it is effective in preventing the occurrence of red rust in the initial stage. A layer having a high Mg concentration of 7% by weight or more has high corrosion resistance and prolongs the corrosion life of the plating layer itself. Also,
The Mg dissolved out from the layer having a high Mg concentration promotes the formation of ZnCl 2 .4Zn (OH) 2 and Zn (OH) 2 which are corrosion products of Zn having excellent corrosion resistance, and improves the corrosion resistance.
A Zn-Mg alloy layer having an Mg concentration of 2 to 7% by weight and an intermediate concentration exhibits intermediate properties between the low Mg concentration layer and the high Mg concentration layer, and further improves the corrosion resistance. The action of each layer works synergistically, and excellent corrosion resistance which has never been obtained is exhibited.
【０００９】めっきされた鋼板をプレス加工等で変形さ
せるとき、Ｍｇ濃度０．５重量％以下のＺｎ−Ｍｇ合金
層に延性があるため、ほとんど変形しない高Ｍｇ濃度の
Ｚｎ−Ｍｇ合金層と下地鋼との間の加工時における変形
量の差を吸収する。その結果、パウダリングの発生が抑
制される。めっき層の表層は、めっき後の鋼板を酸洗
し、表面の酸化したＭｇ濃化層を除去することによっ
て、スポット溶接時に溶接電極と接する面のＭｇ濃度が
０．５重量％以下になる。低Ｍｇ層は、溶接電極へのＭ
ｇ拡散を少なくし、スポット溶接性を向上させる。ま
た、表面に多量のＭｇが存在すると、Ｚｎの酸化物や水
酸化物が不飽和になり、黒変色が生じる。この黒変色
も、表層のＭｇ濃度を０．５重量％以下にすることによ
って防止できる。When the plated steel sheet is deformed by pressing or the like, since the Zn-Mg alloy layer having a Mg concentration of 0.5% by weight or less has ductility, the Zn-Mg alloy layer having a high Mg concentration which hardly deforms and the base Absorbs the difference in deformation amount between steel and steel during processing. As a result, the occurrence of powdering is suppressed. In the surface layer of the plating layer, the steel sheet after plating is pickled and the oxidized Mg concentrated layer on the surface is removed, so that the Mg concentration on the surface in contact with the welding electrode during spot welding becomes 0.5% by weight or less. Low Mg layer is M for welding electrode
Reduces g diffusion and improves spot weldability. In addition, when a large amount of Mg is present on the surface, the Zn oxide or hydroxide becomes unsaturated and black discoloration occurs. This black discoloration can also be prevented by setting the Mg concentration in the surface layer to 0.5% by weight or less.
【００１０】[0010]
本発明に従っためっき鋼板の作製 めっき原板として、Ｃ：０．００２重量％，Ｓｉ：０．
０２重量％，Ｍｎ：０．２１重量％，Ｐ：０．００７重
量％，Ｓ：０．００１重量％，Ｔｉ：０．０７６重量
％，Ａｌ：０．０３１重量％の組成を持ち、板厚０．８
ｍｍの鋼板を使用した。めっき原板をＮ2 −５０％Ｈ2
ガス雰囲気中で還元加熱することにより表面の酸化膜を
除去した後、真空室にセットした。真空室は、ポンプで
排気しながら露点−６０℃のＮ2 ガスを導入し、Ｎ2 分
圧を５×１０-2トールに維持した。この真空室内で、次
の手順で蒸着した。Ｚｎ→Ｍｇ→Ｚｎの順番で蒸着し、
トータルで片面当り１００ｇ／ｍ2 の蒸着量に設定し、
最初に蒸着するＺｎ量と最後に蒸着するＺｎ量を同一に
した。これにより、中心付近のＭｇ濃度が最も高い層で
は約１０重量のＭｇ濃度となり、上下層のＭｇ濃度は
０．５重量％以下になった。また、中間にある層のＭｇ
濃度は、約４重量％であった。Production of Plated Steel Sheet According to the Present Invention As a plating original plate, C: 0.002% by weight, Si: 0.
02% by weight, Mn: 0.21% by weight, P: 0.007% by weight, S: 0.001% by weight, Ti: 0.076% by weight, Al: 0.031% by weight, and a plate thickness. 0.8
A mm steel plate was used. Plate the plating base plate with N 2 -50% H 2
After removing the oxide film on the surface by reducing and heating in a gas atmosphere, it was set in a vacuum chamber. In the vacuum chamber, N 2 gas having a dew point of −60 ° C. was introduced while exhausting with a pump, and the N 2 partial pressure was maintained at 5 × 10 −2 Torr. In this vacuum chamber, vapor deposition was performed by the following procedure. Zn → Mg → Zn is deposited in this order,
Set a total deposition amount of 100 g / m 2 per side,
The amount of Zn deposited first and the amount of Zn deposited last were the same. As a result, the Mg concentration near the center was about 10 wt% in the highest Mg concentration, and the Mg concentration in the upper and lower layers was 0.5 wt% or less. In addition, the Mg in the middle layer
The concentration was about 4% by weight.
【００１１】下地鋼とめっき層との界面にＺｎ−Ｆｅ合
金層又はＺｎ−Ｆｅ−Ｍｇ合金層がある３層構造（図
３）又は５層構造（図４）のめっき鋼板を製造する場
合、２００℃に保持した鋼板表面にＺｎ→Ｍｇ→Ｚｎの
順番で蒸着した後、真空室を７００トールのＮ2 で満た
し、５〜１０秒間加熱した。加熱温度は、３層構造（図
３）のめっき層を形成する場合には２７０〜３３０℃、
５層構造（図４）のめっき層を形成する場合には３３０
〜３７０℃とした。これにより、Ｚｎ−Ｆｅ合金層又は
Ｚｎ−Ｆｅ−Ｍｇ合金層は、約０．２μｍの厚みとなっ
た。また、蒸着割合を変化させながらＺｎ及びＭｇを同
時に蒸着することにより、図１及び図２に示す層構成を
もった片面当りのＺｎ付着量が１００ｇ／ｍ2 のＺｎ−
Ｍｇ合金めっき層を形成した。このとき、蒸着時の鋼板
を板温１２０℃に保持した。なお、蒸着後に、加熱処理
は行わなかった。When a plated steel sheet having a three-layer structure (FIG. 3) or a five-layer structure (FIG. 4) having a Zn--Fe alloy layer or a Zn--Fe--Mg alloy layer at the interface between the base steel and the plating layer is produced, After vapor deposition in the order of Zn → Mg → Zn on the surface of the steel sheet kept at 200 ° C., the vacuum chamber was filled with 700 Torr of N 2 and heated for 5 to 10 seconds. The heating temperature is 270 to 330 ° C. when a plating layer having a three-layer structure (FIG. 3) is formed,
330 when forming a 5-layer structure (FIG. 4) plating layer
Was set to 370 ° C. As a result, the Zn-Fe alloy layer or the Zn-Fe-Mg alloy layer had a thickness of about 0.2 μm. In addition, by simultaneously depositing Zn and Mg while changing the deposition rate, the amount of Zn deposited on one surface having the layer structure shown in FIGS. 1 and 2 is 100 g / m 2 Zn-.
A Mg alloy plating layer was formed. At this time, the steel plate during vapor deposition was kept at a plate temperature of 120 ° C. Note that heat treatment was not performed after vapor deposition.
【００１２】以上の各めっき鋼板を０．５％ＨＣｌ水溶
液で酸洗し、表面のＭｇ濃化層を除去した。酸洗後のめ
っき鋼板は、十分に水洗した。得られためっき鋼板を観
察したところ、表１に示す層構成をもつめっき層となっ
ていた。各めっき鋼板の特性を調査した。耐食性は、Ｊ
ＩＳ Ｚ２３７１に準拠した塩水噴霧試験を行い、赤錆
発生時間で評価した。パウダリング性は、高さ４ｍｍ，
Ｒ＝０．５ｍｍのビードを付けた金型に試験片を挟み、
金型への加圧力５００ｋｇｆ及び引抜き速度２００ｍ／
分で金型から試験片を引き抜くド−ロービード試験を行
い、発生したパウダリングの量で評価した。スポット溶
接性は、単相交流型の溶接機に先端径４．５ｍｍのＣＦ
型Ｃｕ−１％Ｃｒ電極を装着し、連続溶接が可能な打点
数によって評価した。黒変色は、温度５０℃及び相対湿
度６０％の促進試験機の中に試験片を１０００時間放置
し、試験前後の明度差ΔＬ* によって評価した。試験結
果を示す表１から明らかなように、本発明に従った３層
構造又は５層構造をもつＺｎ−Ｍｇ合金めっき鋼板は、
耐食性，耐パウダリング性，スポット溶接性，耐黒変色
性の何れにおいても優れていた。また、図３及び図４の
構造をもつめっき層が形成されたものでは、Ｈ2 ＯやＯ
2 が数十ｐｐｍ存在する酸化性の雰囲気で蒸着した場合
でも、めっき層の密着性が良好であった。The above plated steel sheets were pickled with a 0.5% HCl aqueous solution to remove the Mg concentrated layer on the surface. The plated steel sheet after pickling was thoroughly washed with water. When the obtained plated steel sheet was observed, it was a plated layer having the layer structure shown in Table 1. The characteristics of each plated steel sheet were investigated. Corrosion resistance is J
A salt spray test according to IS Z2371 was performed, and the time of occurrence of red rust was evaluated. The powdering property is 4mm in height,
Place the test piece in a mold with a bead of R = 0.5 mm,
Pressing force to the mold is 500kgf and drawing speed is 200m /
The draw-bead test of pulling out the test piece from the mold in minutes was performed, and the amount of powdering generated was evaluated. Spot weldability is a single-phase AC welding machine with a CF of 4.5 mm tip diameter.
A Cu-1% Cr type electrode was attached, and evaluation was made by the number of spots at which continuous welding was possible. The black discoloration was evaluated by allowing the test piece to stand in an accelerated tester at a temperature of 50 ° C. and a relative humidity of 60% for 1000 hours and measuring the difference in lightness ΔL * before and after the test. As is clear from Table 1 showing the test results, the Zn-Mg alloy plated steel sheet having a three-layer structure or a five-layer structure according to the present invention is
It was excellent in all of corrosion resistance, powdering resistance, spot weldability, and black discoloration resistance. Further, in the case where the plating layer having the structure of FIGS. 3 and 4 is formed, H 2 O or O
Even when vapor deposition was carried out in an oxidizing atmosphere in which several tens of ppm of 2 existed, the adhesion of the plating layer was good.
【００１３】[0013]
【表１】 [Table 1]
【００１４】比較例１ 同じめっき原板を１２０℃に保持し、Ｚｎ及びＭｇの同
時蒸着によって、片面当りの付着量が１００ｇ／ｍ2 で
均一組成をもつＺｎ−Ｍｇ合金めっき層を形成した。 比較例２ 鋼板温度を２００℃に保持し、Ｚｎ→Ｍｇの順に蒸着し
た後、２７０〜３３０℃に加熱することによって、下層
がＭｇ濃度０．５重量％以下のＺｎ−Ｍｇ合金層，上層
がＭｇ濃度１０重量％のＺｎ−Ｍｇ合金層からなる２層
構造のＺｎ−Ｍｇ合金めっき鋼板をも作製した。このと
き、付着量を片面当り１００ｇ／ｍ2 （めっき厚みとし
て約０．２μｍ）に設定し、界面にＺｎ−Ｆｅ合金層又
はＺｎ−Ｆｅ−Ｍｇ合金層が形成されるように温度管理
した。Comparative Example 1 The same original plating plate was held at 120 ° C., and Zn and Mg were co-evaporated to form a Zn—Mg alloy plating layer having a uniform composition with an adhesion amount per one side of 100 g / m 2 . Comparative Example 2 A steel sheet temperature was kept at 200 ° C., vapor deposition was carried out in the order of Zn → Mg, and thereafter heating was carried out at 270 to 330 ° C., whereby the lower layer was a Zn—Mg alloy layer having a Mg concentration of 0.5 wt% or less, and the upper layer was A Zn-Mg alloy plated steel sheet having a two-layer structure composed of a Zn-Mg alloy layer having a Mg concentration of 10% by weight was also produced. At this time, the amount of adhesion was set to 100 g / m 2 per side (plating thickness was about 0.2 μm), and the temperature was controlled so that a Zn—Fe alloy layer or a Zn—Fe—Mg alloy layer was formed at the interface.
【００１５】比較例３ 片面当り１００ｇ／ｍ2 の付着量でＭｇ→Ｚｎの順に蒸
着し、２７０〜３３０℃に加熱することにより、Ｍｇ濃
度約１０重量％の下層とＭｇ濃度０．５重量％の上層か
らなる２層構造のＺｎ−Ｍｇ合金めっき鋼板を作製し
た。 比較例４ 鋼板温度を９０℃に保持し、Ｚｎ蒸着→Ｚｎ，Ｍｇ同時
蒸着→Ｚｎ蒸着を順次行い、下層からＺｎ層，Ｍｇ濃度
約１０重量％のＺｎ−Ｍｇ合金層及びＺｎ層の３層が積
層したＺｎ−Ｍｇ合金めっき鋼板を作製した。この場合
も、付着量を片面当り１００ｇ／ｍ2 に設定した。めっ
き層表面にあるＭｇ濃化層を除去するため、各めっき鋼
板を０．５％ＨＣｌ水溶液で１０秒間酸洗し、十分に水
洗した。得られたＺｎ−Ｍｇ合金めっき鋼板について、
同様な特性調査試験を行った結果を表２に示す。Comparative Example 3 Mg → Zn was vapor-deposited in the order of 100 g / m 2 on one side and heated to 270 to 330 ° C. to form a lower layer with a Mg concentration of about 10 wt% and a Mg concentration of 0.5 wt%. A Zn-Mg alloy plated steel sheet having a two-layer structure consisting of the upper layer was prepared. Comparative Example 4 While maintaining the steel plate temperature at 90 ° C., Zn vapor deposition → Zn, Mg simultaneous vapor deposition → Zn vapor deposition were sequentially performed, and a Zn layer, a Zn—Mg alloy layer having a Mg concentration of about 10 wt%, and a Zn layer were formed in three layers from the lower layer. To prepare a Zn-Mg alloy plated steel sheet. Also in this case, the adhesion amount was set to 100 g / m 2 per side. In order to remove the Mg concentrated layer on the surface of the plated layer, each plated steel sheet was pickled with a 0.5% HCl aqueous solution for 10 seconds and then sufficiently washed with water. About the obtained Zn-Mg alloy plated steel sheet,
Table 2 shows the results of a similar characteristic investigation test.
【００１６】[0016]
【表２】 [Table 2]
【００１７】表２の結果から明らかなように、比較例の
めっき鋼板は、耐食性，耐パウダリング性，スポット溶
接性及び黒変性の何れにおいても劣っていた。特に表層
までＭｇ濃度が高い比較例１，２では、明度変化 (ΔＬ
*)が大きく、良好な表面状態が維持されなかった。比較
例３のめっき鋼板は、表層のＭｇ濃度が低いものの、パ
ウダリングが多量に発生し、加工性に劣っていた。As is clear from the results shown in Table 2, the plated steel sheets of Comparative Examples were inferior in any of corrosion resistance, powdering resistance, spot weldability and blackening. In particular, in Comparative Examples 1 and 2 in which the Mg concentration is high up to the surface layer, the brightness change (ΔL
* ) Was large and a good surface condition was not maintained. The plated steel sheet of Comparative Example 3 had a low Mg concentration in the surface layer, but suffered a large amount of powdering and was inferior in workability.
【００１８】[0018]
【発明の効果】以上に説明したように、本発明のＺｎ−
Ｍｇ合金めっき鋼板は、下地鋼と高Ｍｇ濃度のＺｎ−Ｍ
ｇ合金層との間に延性のある低Ｍｇ濃度のＺｎ−Ｍｇ合
金層を介在させることにより、高Ｍｇ濃度のＺｎ−Ｍｇ
合金層の耐食性を維持し、且つ硬質な高Ｍｇ濃度のＺｎ
−Ｍｇ合金層と下地鋼との間で加工時に生じる変形量の
差を低Ｍｇ濃度のＺｎ−Ｍｇ合金層で吸収している。こ
れにより、Ｚｎ−Ｍｇ合金めっき層本来の高耐食性が活
用され、加工性が良好なめっき鋼板が得られる。しか
も、表層のＭｇ濃度が低下しているので、スポット溶接
性も向上しためっき鋼板となる。As described above, according to the present invention, the Zn-
Mg alloy plated steel sheet is a base steel and Zn-M with high Mg concentration.
By interposing a ductile Zn-Mg alloy layer having a low Mg concentration with the g alloy layer, a Zn-Mg having a high Mg concentration is formed.
Zn with a high Mg concentration that maintains the corrosion resistance of the alloy layer and is hard
The difference in the amount of deformation generated during working between the -Mg alloy layer and the base steel is absorbed by the Zn-Mg alloy layer having a low Mg concentration. Thereby, the high corrosion resistance inherent in the Zn-Mg alloy plating layer is utilized, and a plated steel sheet having good workability can be obtained. Moreover, since the Mg concentration in the surface layer is reduced, the plated steel sheet has improved spot weldability.
【図１】 ３層構造をもつＺｎ−Ｍｇ合金めっき層FIG. 1 is a Zn-Mg alloy plating layer having a three-layer structure.
【図２】 ５層構造をもつＺｎ−Ｍｇ合金めっき層FIG. 2 Zn-Mg alloy plating layer having a five-layer structure
【図３】 下地鋼とめっき層との界面にＺｎ−Ｆｅ合金
層又はＺｎ−Ｆｅ−Ｍｇ合金層を形成させた３層構造の
Ｚｎ−Ｍｇ合金めっき層FIG. 3 is a Zn-Mg alloy plating layer having a three-layer structure in which a Zn-Fe alloy layer or a Zn-Fe-Mg alloy layer is formed at the interface between the base steel and the plating layer.
【図４】 下地鋼とめっき層との界面にＺｎ−Ｆｅ合金
層又はＺｎ−Ｆｅ−Ｍｇ合金層を形成させた５層構造の
Ｚｎ−Ｍｇ合金めっき層FIG. 4 is a Zn-Mg alloy plating layer having a five-layer structure in which a Zn-Fe alloy layer or a Zn-Fe-Mg alloy layer is formed at the interface between the base steel and the plating layer.
【手続補正書】[Procedure amendment]
【提出日】平成７年２月７日[Submission date] February 7, 1995
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】[0010]
【実施例】 本発明に従っためっき鋼板の作製 めっき原板として、Ｃ：０．００２重量％，Ｓｉ：０．
０２重量％，Ｍｎ：０．２１重量％，Ｐ：０．００７重
量％，Ｓ：０．００１重量％，Ｔｉ：０．０７６重量
％，Ａｌ：０．０３１重量％の組成を持ち、板厚０．８
ｍｍの鋼板を使用した。めっき原板をＮ2 −５０％Ｈ2
ガス雰囲気中で還元加熱することにより表面の酸化膜を
除去した後、真空室にセットした。真空室は、ポンプで
排気しながら露点−６０℃のＮ2 ガスを導入し、Ｎ2 分
圧を５×１０-2トールに維持した。この真空室内で、次
の手順で蒸着した。Ｚｎ→Ｍｇ→Ｚｎの順番で蒸着し、
トータルで片面当り１００ｇ／ｍ2 の蒸着量に設定し、
最初に蒸着するＺｎ量と最後に蒸着するＺｎ量を同一に
した。Example Production of plated steel sheet according to the present invention As a plating original plate, C: 0.002% by weight, Si: 0.
02% by weight, Mn: 0.21% by weight, P: 0.007% by weight, S: 0.001% by weight, Ti: 0.076% by weight, Al: 0.031% by weight, and a plate thickness. 0.8
A mm steel plate was used. Plate the plating base plate with N 2 -50% H 2
After removing the oxide film on the surface by reducing and heating in a gas atmosphere, it was set in a vacuum chamber. In the vacuum chamber, N 2 gas having a dew point of −60 ° C. was introduced while exhausting with a pump, and the N 2 partial pressure was maintained at 5 × 10 −2 Torr. In this vacuum chamber, vapor deposition was performed by the following procedure. Zn → Mg → Zn is deposited in this order,
Set a total deposition amount of 100 g / m 2 per side,
The amount of Zn deposited first and the amount of Zn deposited last were the same.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１１】下地鋼とめっき層との界面にＺｎ−Ｆｅ合
金層又はＺｎ−Ｆｅ−Ｍｇ合金層がある３層構造（図
３）又は５層構造（図４）のめっき鋼板を製造する場
合、２００℃に保持した鋼板表面にＺｎ→Ｍｇ→Ｚｎの
順番で蒸着した後、真空室を７００トールのＮ2 で満た
し、５〜１０秒間加熱した。加熱温度は、３層構造（図
３）のめっき層を形成する場合には２７０〜３３０℃、
５層構造（図４）のめっき層を形成する場合には３３０
〜３７０℃とした。これにより、Ｚｎ−Ｆｅ合金層又は
Ｚｎ−Ｆｅ−Ｍｇ合金層は、約０．２μｍの厚みとなっ
た。これにより、中心付近のＭｇ濃度が最も高い層では
約１０重量％のＭｇ濃度となり、上下層のＭｇ濃度は
０．５重量％以下になった。また、中間にある層のＭｇ
濃度は、約４重量％であった。また、蒸着割合を変化さ
せながらＺｎ及びＭｇを同時に蒸着することにより、図
１及び図２に示す層構成をもった片面当りのＺｎ付着量
が１００ｇ／ｍ2 のＺｎ−Ｍｇ合金めっき層を形成し
た。各層の濃度は、先のもの（図３，４）と同じにし
た。このとき、蒸着時の鋼板を板温１２０℃に保持し
た。なお、蒸着後に、加熱処理は行わなかった。 ─────────────────────────────────────────────────────
When a plated steel sheet having a three-layer structure (FIG. 3) or a five-layer structure (FIG. 4) having a Zn--Fe alloy layer or a Zn--Fe--Mg alloy layer at the interface between the base steel and the plating layer is produced, After vapor deposition in the order of Zn → Mg → Zn on the surface of the steel sheet kept at 200 ° C., the vacuum chamber was filled with 700 Torr of N 2 and heated for 5 to 10 seconds. The heating temperature is 270 to 330 ° C. when a plating layer having a three-layer structure (FIG. 3) is formed,
330 when forming a 5-layer structure (FIG. 4) plating layer
It was set to ˜370 ° C. As a result, the Zn-Fe alloy layer or the Zn-Fe-Mg alloy layer had a thickness of about 0.2 μm. As a result, the Mg concentration in the highest Mg concentration near the center was about 10% by weight, and the Mg concentrations in the upper and lower layers were 0.5% by weight or less. In addition, the Mg in the middle layer
The concentration was about 4% by weight. Further, by simultaneously depositing Zn and Mg while changing the deposition rate, a Zn—Mg alloy plating layer having a layer structure shown in FIGS. 1 and 2 and having a Zn deposition amount on one side of 100 g / m 2 is formed. did. The concentration of each layer was the same as the previous one (FIGS. 3 and 4). At this time, the steel plate during vapor deposition was kept at a plate temperature of 120 ° C. Note that heat treatment was not performed after vapor deposition. ─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成７年８月３０日[Submission date] August 30, 1995
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１４】比較例１ 同じめっき原板を１２０℃に保持し、Ｚｎ及びＭｇの同
時蒸着によって、片面当りの付着量が１００ｇ／ｍ２で
均一組成をもつＺｎ−Ｍｇ合金めっき層を形成した。 比較例２ 鋼板温度を２００℃に保持し、Ｚｎ→Ｍｇの順に蒸着し
た後、２７０〜３３０℃に加熱することによって、下層
がＭｇ濃度０．５重量％以下のＺｎ−Ｍｇ合金層，上層
がＭｇ濃度１０重量％のＺｎ−Ｍｇ合金層からなる２層
構造のＺｎ−Ｍｇ合金めっき鋼板をも作製した。このと
き、付着量を片面当り１００ｇ／ｍ２に設定し、界面に
Ｚｎ−Ｆｅ合金層又はＺｎ−Ｆｅ−Ｍｇ合金層が形成さ
れるように温度管理した。Comparative Example 1 The same original plating plate was held at 120 ° C., and Zn and Mg were co-evaporated to form a Zn—Mg alloy plating layer having a uniform composition with an adhesion amount per one side of 100 g / m 2 . Comparative Example 2 A steel sheet temperature was kept at 200 ° C., vapor deposition was carried out in the order of Zn → Mg, and thereafter heating was carried out at 270 to 330 ° C., whereby the lower layer was a Zn—Mg alloy layer having a Mg concentration of 0.5 wt% or less, and the upper layer was A Zn-Mg alloy plated steel sheet having a two-layer structure composed of a Zn-Mg alloy layer having a Mg concentration of 10% by weight was also produced. At this time, the adhesion amount was set to 100 g / m 2 on one side, and the temperature was controlled so that the Zn—Fe alloy layer or the Zn—Fe—Mg alloy layer was formed at the interface.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 三尾野 忠昭 大阪府堺市石津西町５番地 日新製鋼株式 会社鉄鋼研究所内 (72)発明者 斎藤 実 大阪府堺市石津西町５番地 日新製鋼株式 会社鉄鋼研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadaaki Miono 5 Ishizu Nishimachi, Sakai City, Osaka Prefecture Nisshin Steel Co., Ltd. Steel Research Laboratories (72) Minor Saito 5 5 Ishizu Nishimachi, Sakai City, Osaka Nisshin Steel Co., Ltd. Company Steel Research Institute
Claims (4)
合金層，Ｍｇ濃度７重量％以上のＺｎ−Ｍｇ合金層及び
Ｍｇ濃度０．５重量％以下のＺｎ−Ｍｇ合金層が順次積
層されているＺｎ−Ｍｇ合金めっき鋼板。1. A Zn-Mg having a Mg concentration of 0.5% by weight or less.
A Zn-Mg alloy plated steel sheet in which an alloy layer, a Zn-Mg alloy layer having a Mg concentration of 7% by weight or more, and a Zn-Mg alloy layer having a Mg concentration of 0.5% by weight or less are sequentially stacked.
合金層，Ｍｇ濃度２〜７重量％のＺｎ−Ｍｇ合金層，Ｍ
ｇ濃度７重量％以上のＺｎ−Ｍｇ合金層，Ｍｇ濃度７重
量％以上のＺｎ−Ｍｇ合金層，Ｍｇ濃度２〜７重量％の
Ｚｎ−Ｍｇ合金層及びＭｇ濃度０．５重量％以下のＺｎ
−Ｍｇ合金層が順次積層されているＺｎ−Ｍｇ合金めっ
き鋼板。2. Zn-Mg having a Mg concentration of 0.5% by weight or less.
Alloy layer, Zn-Mg alloy layer with Mg concentration of 2 to 7% by weight, M
Zn-Mg alloy layer with g concentration of 7 wt% or more, Zn-Mg alloy layer with Mg concentration of 7 wt% or more, Zn-Mg alloy layer with Mg concentration of 2-7 wt%, and Zn with Mg concentration of 0.5 wt% or less
-A Zn-Mg alloy plated steel sheet in which Mg alloy layers are sequentially laminated.
Ｚｎ−Ｆｅ−Ｍｇ合金層が形成されている請求項１又は
２記載のＺｎ−Ｍｇ合金めっき鋼板。3. The Zn—Mg alloy plated steel sheet according to claim 1, wherein a Zn—Fe alloy layer or a Zn—Fe—Mg alloy layer is formed at the interface with the base steel.
し、次いで加熱することを特徴とする請求項１〜３の何
れかに記載のＺｎ−Ｍｇ合金めっき鋼板の製造方法。4. The method for producing a Zn—Mg alloy plated steel sheet according to claim 1, wherein Zn, Mg and Zn are sequentially vapor-deposited on the steel sheet and then heated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24335894A JP3640688B2 (en) | 1994-09-12 | 1994-09-12 | Zn-Mg alloy plated steel sheet and manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24335894A JP3640688B2 (en) | 1994-09-12 | 1994-09-12 | Zn-Mg alloy plated steel sheet and manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0881761A true JPH0881761A (en) | 1996-03-26 |
| JP3640688B2 JP3640688B2 (en) | 2005-04-20 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24335894A Expired - Fee Related JP3640688B2 (en) | 1994-09-12 | 1994-09-12 | Zn-Mg alloy plated steel sheet and manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3640688B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0730045A2 (en) * | 1995-02-28 | 1996-09-04 | Nisshin Steel Co., Ltd. | Steel sheet with Zn-Mg binary coating layer excellent in corrosion resistance and manufacturing method thereof |
| US9744743B2 (en) | 2012-12-26 | 2017-08-29 | Posco | Zn—Mg alloy plated steel sheet, and method for manufacturing same |
| WO2018124649A1 (en) * | 2016-12-26 | 2018-07-05 | 주식회사 포스코 | Zinc alloy plated steel having excellent weldability and corrosion resistance |
| CN111527235A (en) * | 2017-12-26 | 2020-08-11 | Posco公司 | Multilayer zinc alloy plated steel material having excellent spot weldability and corrosion resistance |
| US10988845B2 (en) | 2016-12-22 | 2021-04-27 | Posco | Plated steel sheet having multilayer structure and manufacturing method therefor |
| US11136651B2 (en) | 2016-12-23 | 2021-10-05 | Posco | Zn-Mg alloy plated steel material having excellent corrosion resistance and plating adhesion |
-
1994
- 1994-09-12 JP JP24335894A patent/JP3640688B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0730045A2 (en) * | 1995-02-28 | 1996-09-04 | Nisshin Steel Co., Ltd. | Steel sheet with Zn-Mg binary coating layer excellent in corrosion resistance and manufacturing method thereof |
| EP0730045A3 (en) * | 1995-02-28 | 1997-09-17 | Nisshin Steel Co Ltd | Steel sheet with Zn-Mg binary coating layer excellent in corrosion resistance and manufacturing method thereof |
| US5747111A (en) * | 1995-02-28 | 1998-05-05 | Nisshin Steel Co., Ltd. | Steel sheet coated with Zn-Mg binary coating layer excellent in corrosion resistance and manufacturing method thereof |
| US9744743B2 (en) | 2012-12-26 | 2017-08-29 | Posco | Zn—Mg alloy plated steel sheet, and method for manufacturing same |
| US10988845B2 (en) | 2016-12-22 | 2021-04-27 | Posco | Plated steel sheet having multilayer structure and manufacturing method therefor |
| US11136651B2 (en) | 2016-12-23 | 2021-10-05 | Posco | Zn-Mg alloy plated steel material having excellent corrosion resistance and plating adhesion |
| WO2018124649A1 (en) * | 2016-12-26 | 2018-07-05 | 주식회사 포스코 | Zinc alloy plated steel having excellent weldability and corrosion resistance |
| EP3561147A4 (en) * | 2016-12-26 | 2020-03-25 | Posco | Zinc alloy plated steel having excellent weldability and corrosion resistance |
| US11208716B2 (en) | 2016-12-26 | 2021-12-28 | Posco | Multi-layered zinc alloy plated steel having excellent spot weldability and corrosion resistance |
| US11649542B2 (en) | 2016-12-26 | 2023-05-16 | Posco Co., Ltd | Multi-layered zinc alloy plated steel having excellent spot weldability and corrosion resistance |
| CN111527235A (en) * | 2017-12-26 | 2020-08-11 | Posco公司 | Multilayer zinc alloy plated steel material having excellent spot weldability and corrosion resistance |
| US11414743B2 (en) | 2017-12-26 | 2022-08-16 | Posco | Multilayered zinc alloy plated steel material having excellent spot weldability and corrosion resistance |
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| Publication number | Publication date |
|---|---|
| JP3640688B2 (en) | 2005-04-20 |
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